EP1539849A1 - Expandierbare polyamidzusammensetzung und daraus abgeleiteter polyamidschaumstoff - Google Patents

Expandierbare polyamidzusammensetzung und daraus abgeleiteter polyamidschaumstoff

Info

Publication number
EP1539849A1
EP1539849A1 EP03760760A EP03760760A EP1539849A1 EP 1539849 A1 EP1539849 A1 EP 1539849A1 EP 03760760 A EP03760760 A EP 03760760A EP 03760760 A EP03760760 A EP 03760760A EP 1539849 A1 EP1539849 A1 EP 1539849A1
Authority
EP
European Patent Office
Prior art keywords
polyamide
composition according
composition
compound
temperature
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Withdrawn
Application number
EP03760760A
Other languages
English (en)
French (fr)
Inventor
Jean-Marie Bernard
Jean-François BRIOIS
Eric Roche
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Operations SAS
Original Assignee
Rhodia Polyamide Intermediates SAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Rhodia Polyamide Intermediates SAS filed Critical Rhodia Polyamide Intermediates SAS
Publication of EP1539849A1 publication Critical patent/EP1539849A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/281—Monocarboxylic acid compounds
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/60—Polyamides or polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/02—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by the reacting monomers or modifying agents during the preparation or modification of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers

Definitions

  • the present invention relates to an expandable polyamide composition and a polyamide foam obtained from this composition, as well as to a process for obtaining the foam.
  • Synthetic foams are used in many fields, such as thermal or sound insulation, upholstery etc.
  • Structural foams are rigid foams composed of a low density core and a skin whose density is close to that of the polymer making up the matrix. These foams can be used as lightweight structures in the aeronautics or automotive fields for example.
  • Non-structural foams can be flexible or rigid.
  • Rigid foams are used in the field of thermal insulation (the gas present in the cells acts as an insulator).
  • Flexible foams are used in the field of furniture and upholstery, for their compressibility and cushioning properties, in the field of packaging due to their low weight, as well as in the field of insulation.
  • phonic foams with open porosity have the particularity of absorbing certain frequencies).
  • thermoplastic polymer foams such as polystyrene, PVC, polyethylene, polypropylene foams, etc. It is known to inject gases under pressure into the polymer in the molten state.
  • foams using a chemical reaction releasing gas, such as carbon dioxide.
  • a chemical reaction releasing gas such as carbon dioxide.
  • polyurethane foams obtained by reaction between isocyanates, polyols and water leading to the formation of polyurethane with release of carbon dioxide.
  • Polyamide foams can also be obtained chemically, by bringing together isocyanates and lactams as well as bases to activate the anionic polymerization.
  • the present invention provides another chemical route for producing polyamide foams, from an expandable composition comprising a compound comprising at least one isocyanate function, a polyamide and a compound comprising at least one acid function.
  • the preparation of the composition and of the foam is simple, the foam is obtained in situ without the need for the introduction of external compounds, and directly from the composition.
  • the process for preparing the foam allows in particular the control of the foaming reaction. This process is also flexible: in fact foams of diverse and varied nature and properties can be easily obtained by this process, in particular by the appropriate choice of the nature and characteristics of the polyamide of the composition.
  • the invention proposes, in a first object, an expandable composition comprising at least the following compounds:
  • A a compound comprising at least one isocyanate function
  • B a polyamide
  • the invention provides in a second object a process for preparing a polyamide foam from an expandable composition as described above, comprising at least the steps following: a) heating the composition to a temperature at least equal to 80 ° C. b) stabilizing the honeycomb structure obtained The invention finally provides a polyamide foam obtained from the process described above
  • the term “acid function” means any acid function which can, by reaction with an isocyanate function, allow the release of gaseous evolution, generally of carbon dioxide; by way of example, mention may be made of the carboxylic acid, phosphoric, sulfonic functions, etc. However, the carboxylic acid functions are preferred.
  • the term “acid function” also means functions derived from the acid function, such as the acid anhydride, acid chloride, ester, etc. function.
  • Compound C of the composition comprises at least one acid function.
  • the polyamide of invention B generally also comprises carboxylic acid functions; these functions can be present at the terminal ends of the polyamide, and / or distributed along the polyamide chain.
  • the acid functions along the polyamide chain in particular can be introduced to the polycondensation using a comonomer such as an aminodiacide for example, or by functionalization for example of the amide bonds by reaction with an acid aldehyde in particular.
  • Compound A can also include acid functions, in particular carboxylic acid.
  • the expandable composition of the invention comprises a respective amount of acid functions and isocyanate functions adapted to the evolution of gas, in particular of the desired carbon dioxide and therefore to the density of the foam which it is desired to obtain from the composition. expandable.
  • the acid functions can be provided by compound C alone, by polyamide B alone, by compound A alone, by any two of these compounds A, B and C, or by the three compounds A, B and C.
  • the polyamide B of the invention is a polyamide of the type of those obtained by polycondensation from dicarboxylic acids and diamines, or of the type of those obtained by polycondensation of lactams and / or amino acids.
  • the polyamide B of the invention can be a mixture of polyamides of different types and / or of the same type, and / or copolymers obtained from different monomers corresponding to the same type and / or to different types of polyamide.
  • the polyamide has a number of moles of acid functions greater than the number of moles of amine functions, generally speaking in this case a polyamide having an excess of acidic end groups.
  • the polyamide B of the invention can be an oligomer.
  • the molecular weight by number of the polyamide of the invention is advantageously greater than or equal to 1000 g / mol, preferably greater than or equal to 3000 g / mol.
  • polyamide 6 As an example of a polyamide which may be suitable for the invention, mention may be made of polyamide 6, polyamide 6.6, polyamide 11, polyamide 12, polyamides 4.6; 6.10; 6.12; 12.12, 6.36; semi-aromatic polyamides, polyphthalamides obtained from terephthalic and / or isophthalic acid such as the polyamide sold under the trade name AMODEL, their copolymers and alloys.
  • the polyamide is chosen from polyamide 6, polyamide 6.6, their mixtures and copolymers.
  • the polyamide of the invention is a linear polyamide.
  • the polyamide of the invention comprises star or H macromolecular chains, and where appropriate linear macromolecular chains.
  • the polymers comprising such star or H macromolecular chains are for example described in the documents FR 2 743
  • the polyamide of the invention is a copolyamide having a statistical tree structure.
  • copolyamides of statistical tree structure and their process for obtaining are described in particular in document WO 99/03909.
  • the polyamide of the invention can also be a composition comprising a linear polyamide and a star, H and / or tree polyamide as described above.
  • the polyamide of the invention can also be a composition comprising a hyperbranched copolyamide of the type of those described in document WO 00/68298.
  • the polyamide may optionally include other functions such as ester, and / or urea, and / or carbonate, and / or ether, etc. functions.
  • Compound A of the invention is a compound comprising at least one isocyanate function, it may be a mixture of compounds comprising at least one isocyanate function. According to a preferred embodiment of the invention, the compound A is a polyisocyanate. By polyisocyanate is meant a compound comprising at least two isocyanate functions.
  • polyisocyanates which may be suitable are isophorone diisocyanate, 1, 3- and 1, 4-cyclohexane diisocyanate, 1, 2-ethylene diisocyanate, 1, 4- tetramethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 2,2,4 and 2,4,4-trimethyl-1, 6-hexamethylene diisocyanate, 1, 12-dodecane diisocyanate, .alpha.,. alpha.
  • isocyanurate trimers such as Tolonate HDT® from the company Rhodia, biurets such as tolonate HDB® from the company RHODIA.
  • isocyanate oligomers are the oligomers is aliphatic ocyanates such as isophorone diisocyanate dimer or trimer, asymmetric hexamethylene diisocyanate trimer, as well as derivatives of high functionality and low viscosity hexamethylene diisocyanate, and norbomene diisocyanate dimers and trimers.
  • the polyisocyanate is a mixture of polyisocyanate compounds of average functionality of between 2 and 8 (limits included), preferably of functionality between 3 and 7 (limits included). Functionality is defined as the number of isocyanate functions carried by each of the constituent molecules of the mixture.
  • polyisocyanate mixtures that may be mentioned are isocyanurate trimers such as hexamethylene diisocyanate trimer (HDT), isophorone diisocyanate trimer (IPDT) standard, the average functionality of which is approximately 3.5. It is also possible to use the polyisocyanate isocyanurate derivatives of toluene diisocyanate (TDI) or of methane diphenyl isocyanate (MDI).
  • the polyisocyanate is a diisocyanate, that is to say a polyisocyanate comprising two isocyanate functions, or a triisocyanate, that is to say a polyisocyanate comprising three isocyanate functions.
  • the polyisocyanate is an isocyanurate.
  • the compound A comprising at least one isocyanate function is different from a prepolymer or a polymer.
  • the isocyanate functions of compound A are wholly or partly protected by a protective group, generally linked to the isocyanate function by covalent bond.
  • the protected polyisocyanate of the invention is preferably a polyisocyanate of formula (II) below:
  • lactams such as caprolactam or dodecalactam may be mentioned; oxymes such as 2-butanonoxime, pyruvatoxime, acetonoxime or benzophenoxime; optionally substituted heterocyclic compounds such as derivatives of pyrazole, triazole, imidazole, benzotriazole or their alkyl derivatives such as dimethyl pyrazole, methyl pyrazole, dimethyl triazole, 2 ethyl or propyl imidazole; alcohols or phenols and their derivatives such as tert-butanol, methanol, ethanol, phenol, para or ortho hydroxybenzoic acids or their (cyclo) alkyl esters, dialkyl malonate, hydroxamic acids etc.
  • oxymes such as 2-butanonoxime, pyruvatoxime, acetonoxime or benzophenoxime
  • optionally substituted heterocyclic compounds such as derivatives of pyrazole, triazole, imidazo
  • a particular case of protection of the isocyanate functions is the case of uretidine diones which consists in protecting the isocyanate function by itself.
  • the isocyanate functions can also be protected in the form of N acylurea by reaction of the isocyanate functions with amide functions, the latter possibly being those of polyamide.
  • Protected polyisocyanates are liquid compounds or solid formulations. In general these formulations do not contain solvents.
  • the protective groups of the invention are preferably lactams and more preferably caprolactam.
  • the polyisocyanate compounds may optionally include other functions such as urea and / or biuret bonds, and or carbamate and / or allophanate and / or ester and / or carbonates and / or ether.
  • the temperature of "deprotection" of the isocyanate functions of compound A is greater than or equal to the melting or softening temperature of polyamide B.
  • the temperature of “Deprotection” of the isocyanate functions of compound A is the temperature at which the cleavage of the covalent bond between the protective group and the isocyanate function is observed, and beyond which the isocyanate function is again free and reactive.
  • the “deprotection” temperature of the isocyanate functions varies in particular as a function of the nature of the protective group; the choice of the protective group can therefore be adapted, for example to the melting point of the polyamide B chosen for the composition.
  • the softening temperature of the polyamide is the temperature from which the polyamide is deformed when a given stress is applied to it.
  • the protection of the isocyanate functions of compound A is generally carried out prior to the preparation of the composition of the invention. It can however also be used during the preparation of the composition of the invention, for example by introduction of the protective group at the time of bringing the constituents of the composition into contact.
  • isocyanate function of compound A within the meaning of the invention is understood to mean both the isocyanate functions protected by a protective group and the unprotected isocyanate functions. For example, when talking about the number of moles of isocyanate functions of compound A, if these functions are protected by a protective group or a mixture of protective groups, it will be the number of moles of isocyanate functions protected.
  • Compound C comprising at least one acid function is preferably a polyacid, that is to say a compound comprising at least two acid functions. Mixtures of different C compounds can be used.
  • Compound C can also be a compound comprising an acid function and another function, reactive with the carboxylic or amine function of the polyamide, mention may therefore be made, as an example of a reactive function, of the primary or secondary amine functions, alcohols, sulfhydrides, etc. .
  • a reactive function of the primary or secondary amine functions, alcohols, sulfhydrides, etc.
  • citric acid As an example of such compound C, mention may be made of citric acid.
  • the preferred reactive functions are the primary or secondary amino functions.
  • Compound C of the invention is preferably a dicarboxylic acid. Mention may be made, as an example of a dicarboxylic acid, of adipic acid, dodecanedioic acid, terephthalic acid, etc.
  • the expandable composition of the invention may also comprise, in addition to compounds A, B, and C, blowing agents which will make it possible to amplify the foaming phenomenon during the preparation of the foam from the composition.
  • blowing agents are known to those skilled in the art.
  • the expandable composition of the invention may also comprise other additives useful for the subsequent preparation of the foam, such as surfactants, nucleators such as talc, plasticizers, etc. These additives are known to those skilled in the art.
  • the composition may also include reinforcing fillers such as glass fibers, matifiers such as titanium dioxide or zinc sulfide, pigments, dyes, heat or light stabilizers, bioactive agents, anti-fouling agents, antistatic agents, flame retardants, high or low density fillers etc. This list is not exhaustive.
  • composition of the invention comprising compounds A, B, and C. It is possible, for example, to produce an intimate mixture of the powders of the various compounds. It is also possible to introduce compounds A and C into the polyamide
  • the mixing can for example be carried out in an extrusion device.
  • Polyamide B can also be in the form of granules, which are coated with compounds A and C.
  • Another mode of preparation of the composition suitable in the context of the invention is the pasting of the various compounds.
  • the composition When the composition is prepared using an extrusion device for example, it can then be put into the form of granules. These granules can then be used as such or for example be ground in the form of powder - of suitable particle size - prior to the preparation of foam from the expandable composition.
  • the particle size of the composition in powder form is advantageously less than or equal to 1 mm, preferably less than or equal to 500 ⁇ m.
  • composition of the invention can also be presented or be in the form of a liquid or a gel for example, using any means known to those skilled in the art.
  • the temperature used during the preparation of the composition is preferably lower than the “deprotection” temperature of the isocyanate functions.
  • the invention relates to a process for preparing a polyamide foam from an expandable composition as described above, comprising at least the following steps: a) heating the composition to a temperature at least equal at 80 ° C b) stabilize the honeycomb structure obtained
  • step a) The temperature of step a) must be sufficient for there to be a reaction between the isocyanate functions and the carboxylic acid functions of the composition, as well as a gaseous evolution generally of carbon dioxide and the formation of a cellular structure. .
  • the temperature and the kinetics of the decarboxylation reaction are dependent on the nature of the various constituents of the foam, that is to say of the compounds A, B and C, and on the presence or absence of catalysts. In general this temperature is at least equal to 80 ° C.
  • the temperature during step a) is higher than the melting or softening temperature of polyamide B.
  • Step a) is generally carried out in the molten state.
  • An extrusion device can be used during this step.
  • step a) varies depending on the device used.
  • a catalyst or a mixture of catalysts can be used during this step.
  • a catalyst can for example be used to accelerate the deprotection kinetics or lower the deprotection temperature of the isocyanate functions of compound A.
  • Mention may be made, as example of catalyst, of metal derivatives such as those of tin (such as tin dibutyldilaurate), zinc (such as zinc octoate), bismuth, tertiary amines such as diazabicyclooctane (DABCO), diazabicycloundecene (DBU).
  • DABCO diazabicyclooctane
  • DBU diazabicycloundecene
  • Another catalyst can be used to accelerate the reaction for decarboxylation of the carbamic anhydride and of the acid obtained by reaction of the acid function with the isocyanate function; by way of example, mention may be made of tertiary amines such as diazabicyclooctane (DABCO), diazabicycloundecene (DBU), triethylamine.
  • DABCO diazabicyclooctane
  • DBU diazabicycloundecene
  • triethylamine triethylamine
  • step a) is greater than or equal to the temperature of "deprotection" of the isocyanate functions of compound A.
  • Pore-forming agents can be introduced during step a), as well as surfactants, nucleating agents such as talc, plasticizers, etc.
  • Other compounds can also be introduced during step a), such as reinforcing fillers such as glass fibers, matifiers such as titanium dioxide or zinc sulfide, pigments, dyes, heat stabilizers or light, bioactive agents, antifouling agents, antistatic agents, flame retardants etc. This list is not exhaustive.
  • Step b) of stabilization of the alveolar structure can be obtained for example by chemical route -by crosslinking of the polyamide- and / or by physical route -for example by cooling to a temperature lower than or equal to the glass transition temperature or polyamide melting.
  • Crosslinking of the polyamide can be carried out using crosslinking agents known to those skilled in the art. They are generally compounds comprising at least two reactive functions with the acid and / or amino functions of the polyamide. Generally, these compounds comprise at least three reactive functions. Examples of crosslinking agents that may be mentioned include carbonylbislactams such as carbonylbiscaprolactam, bisoxazine, bisoxazoline. These crosslinking agents are preferably introduced during the preparation of the composition to be expanded.
  • the foam structure obtained can be shaped into granules which can be melted or not subsequently, or shaped by molding for example.
  • the invention relates to polyamide foams obtained by the process described above.
  • the foams obtained according to this process advantageously have a density less than or equal to 0.5 g / cm 3 , preferably less than or equal to 0.3 g / cm 3
  • Compound B2 copolyamide 6 / 6.6 (60/40) of relative viscosity measured in 90% formic acid at 25 ° C of 120 ml / g
  • Compound B3 copolyamide 6 / 6.6 (60/40) of relative viscosity measured in 90% formic acid at 25 ° C of 140 ml / g
  • Compound A1 isophorone diisocyanate trimer (IPDT) whose isocyanate functions are protected by ⁇ -caprolactam, having an isocyanate titer of 3200 meq / kg.
  • IPDT isophorone diisocyanate trimer
  • Compound A2 mixture of isophorone diisocyanate (IPDI) and isophorone diisocyanate trimer (IPDT), the isocyanate functions of which are protected by ⁇ -caprolactam, sold by the company Bayer under the reference Crelan LS2256®
  • Compound D1 talc (magnesium silicate) sold by the company Luzenac Europe under the reference Mistron Vapor RP6®, having a particle size of 7 ⁇ m.
  • Compoose D2 silica marketed by the company Rhodia under the reference Tixosil 365® and with an average particle size of 3.5 ⁇ m.
  • compositions prepared are detailed in Table 1. The proportions are indicated in percentages by weight in the composition.
  • Composition E is obtained by mixing the various compounds in a BRABENDER single-screw extruder, having a length / diameter ratio equal to 20.
  • the extrusion conditions are as follows:
  • the extruded composition is cooled in water to room temperature. It has a density of 1.1.
  • the composition is coarsely ground until a particle size of 1-2 mm is obtained.
  • composition E is replaced by compound A1 alone in Example 1, the density of the test piece obtained is 1.1.
  • composition E 10 g of composition E as obtained in Example 1 (with a particle size of 1-2 mm) are freeze-ground until a powder with an average particle size of 300 ⁇ m is obtained. 3 g of this composition is placed in a pyrex mold previously coated with release agent. The mold is heated at a temperature of 190 ° C for 30 min in a fan oven. A rigid expanded polyamide specimen of density 0.2 is thus obtained. Cell distribution is of the closed type, and is fairly regular. The size of the cells varies between 0.1 and 0.2 mm in diameter.
  • composition F The various compounds of composition F are mixed in the form of a powder, then the mixture obtained is freeze-ground until a powder with a particle size of less than 300 ⁇ m is obtained. Homogenization is carried out during the grinding process. 3 g of this composition are then placed in a pyrex mold previously coated with release agent. The mold is heated at a temperature of 190 ° C for 30 min in a fan oven. A semi-rigid expanded polyamide specimen of density 0.2 is thus obtained. Cell distribution is of the closed type, and is fairly regular. The size of the cells varies between 0.1 and 0.2 mm in diameter.
  • composition F The different compounds of composition F are mixed in the form of a powder, then the mixture obtained is freeze-ground until a powder with a particle size of less than 300 ⁇ m is obtained. Homogenization is carried out during the grinding process.
  • composition H The various compounds of composition H are mixed in the form of a powder, then the mixture obtained is freeze-ground until a powder with a particle size of less than 300 ⁇ m is obtained. Homogenization is carried out during the grinding process. 3 g of this composition are then placed in a pyrex mold previously coated with release agent. The mold is heated at a temperature of 190 ° C for 40 min in a fan oven. A 0.25 density polyamide expanded specimen is thus obtained. Cell distribution is closed, and it is regular. The size of the cells varies between 0.1 and 0.2 mm in diameter. The Young's modulus of the test piece obtained is measured on a series of 4 cylindrical test pieces with a diameter of 26.5 mm and a thickness of 15.8 mm. The measurement is carried out using the INSTRON 1185 device under the following conditions:
  • FIG. 1 represents the stress-displacement curve corresponding to the test piece of composition H
  • the average modulus measured is 43.4 MPa.
  • Composition J is obtained by mixing the various compounds in a BUSS 46 co-kneader equipped with a submerged head cut.
  • the extrusion conditions are as follows:
  • the nozzle temperature is maintained at 240 ° C.
  • a 0.45 density plate (skin included) is obtained.
  • Example 7 Composition K is obtained by mixing the various compounds in a BUSS 46 co-kneader equipped with a submerged head cut.
  • the extrusion conditions are as follows:
  • Polyamide balls "ready to foam” with a diameter of 1.5mm are thus obtained. These balls are then fed into a Billion Stabilog injection press equipped with a “plate” mold of dimension 85x85x5 mm with central direct injection.
  • the temperature profile on the heating elements is as follows: supply zone 165 ° C-165 ° C-190 ° C. The nozzle temperature is maintained at 240 ° C.
  • a 0.45 density plate (skin included) is obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Polyamides (AREA)
EP03760760A 2002-06-21 2003-06-20 Expandierbare polyamidzusammensetzung und daraus abgeleiteter polyamidschaumstoff Withdrawn EP1539849A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0207714A FR2841253B1 (fr) 2002-06-21 2002-06-21 Composition polyamide expansible et mousse polyamide obtenue a partir de cette composition
FR0207714 2002-06-21
PCT/FR2003/001900 WO2004000908A1 (fr) 2002-06-21 2003-06-20 Composition polyamide expansible et mousse polyamide obtenue a partir de cette composition_______________________________________

Publications (1)

Publication Number Publication Date
EP1539849A1 true EP1539849A1 (de) 2005-06-15

Family

ID=29719944

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03760760A Withdrawn EP1539849A1 (de) 2002-06-21 2003-06-20 Expandierbare polyamidzusammensetzung und daraus abgeleiteter polyamidschaumstoff

Country Status (10)

Country Link
US (1) US8946314B2 (de)
EP (1) EP1539849A1 (de)
JP (1) JP4303201B2 (de)
CN (1) CN100480295C (de)
AU (1) AU2003255684A1 (de)
CA (1) CA2490519A1 (de)
FR (1) FR2841253B1 (de)
RU (1) RU2326897C2 (de)
TW (1) TWI287550B (de)
WO (1) WO2004000908A1 (de)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1906223A (zh) * 2004-01-06 2007-01-31 三井化学聚氨酯株式会社 热固性聚酰胺发泡体及其用途、以及热固性聚酰胺的制造方法
DE102008000352A1 (de) * 2008-02-20 2009-08-27 Rhein Chemie Rheinau Gmbh Gusspolyamid-Herstellung unter Verwendung spezieller Aktivatoren
FR2945540B1 (fr) * 2009-05-15 2012-06-08 Rhodia Operations Procede de preparation de mousse polyamide et mousse susceptible d'etre obtenue par ce procede
PL2563850T5 (pl) * 2010-04-27 2022-08-29 Basf Se Spienialny granulat poliamidowy
US9427900B2 (en) * 2010-11-12 2016-08-30 Basf Se Composite component comprising a polymer phase and a foamed phase, and processes for producing the same
JP2012149150A (ja) * 2011-01-18 2012-08-09 Natoko Kk 不透明膜形成用液状組成物、不透明膜及びこれを形成する方法
ES2638316T3 (es) * 2012-06-29 2017-10-19 Imerys Talc Europe Eficacia de nucleación del talco en el comportamiento espumante y estructura celular de espumas con base en polímeros
FR2993270B1 (fr) * 2012-07-12 2015-08-07 Rhodia Operations Procede de moussage chimique en presence de charges de renfort
PL3255075T3 (pl) 2013-03-06 2020-06-29 Ege Kimya Sanayi Ve Ticaret A.Ş. Uretanowane polimery zawierające kobalt do suszenia na powietrzu powłok, farb i tuszy na bazie polimerów
BR112016009327B1 (pt) 2013-10-29 2022-01-11 Performance Polyamides, Sas Composição de poliamida espumável, seu método de produção, espuma, seu uso, e veículo motorizado
JP6431546B2 (ja) * 2014-09-30 2018-11-28 積水化成品工業株式会社 樹脂複合体
JP6530812B2 (ja) * 2015-10-27 2019-06-12 ▲済▼南▲聖▼泉集団股▲フン▼有限公司Ｊｉｎａｎ Ｓｈｅｎｇｑｕａｎ Ｇｒｏｕｐ Ｓｈａｒｅ Ｈｏｌｄｉｎｇ Ｃｏ．， Ｌｔｄ． グラフェン構造を有するポリウレタン樹脂を含む複合ポリウレタンフォーム、その製造方法及び用途
CA3005173A1 (en) 2015-11-13 2017-05-18 Ege Kimya San. Ve Tic. A. S. Metal-bearing urethanized polymer soluble in a low-volatile organic compound solvent
JP7003115B2 (ja) * 2016-09-06 2022-02-04 コンストラクション リサーチ アンド テクノロジー ゲーエムベーハー 採鉱における空洞を充填するための火炎伝播しないポリアミドフォーム
TWI647253B (zh) * 2016-12-29 2019-01-11 大東樹脂化學股份有限公司 利用芳香族氨甲酸酯透過異氰酸鹽作為前驅物之經催化熱反應路徑以製備醯胺或聚醯胺的方法及由芳香胺製備芳香族氨甲酸酯前驅物的方法
JP7317106B2 (ja) 2018-09-28 2023-07-28 ダウ グローバル テクノロジーズ エルエルシー ポリアミド発泡体の調製
CN111100445B (zh) * 2018-10-25 2022-07-12 中国石油化工股份有限公司 一种聚酰胺组合物及其制备方法和应用

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2995531A (en) * 1958-09-08 1961-08-08 Mobay Chemical Corp Stable coating compositions containing a polyisocyanate and a polyamide
DE1122697B (de) * 1960-05-06 1962-01-25 Bayer Ag Verfahren zur Herstellung von Schaumstoffen auf Isocyanatbasis
US3145825A (en) 1961-10-03 1964-08-25 Meyer Geo J Mfg Co Selective quantity ratio divider conveyor
GB1227146A (de) * 1968-03-29 1971-04-07
US4028287A (en) * 1972-04-27 1977-06-07 Bridgestone Tire Company Limited Process for continuous preparation of a foam polyamide
US4374976A (en) * 1977-10-25 1983-02-22 Blount David H Process for the production of polyamide silicate resinous products
SU1067014A1 (ru) * 1978-06-16 1984-01-15 Предприятие П/Я М-5885 Полимерна композици
US4444816A (en) * 1980-12-03 1984-04-24 Raychem Corporation Radiation cross-linking of polyamides
DE3628122A1 (de) * 1986-08-19 1988-03-03 Herberts Gmbh Fremdvernetzende bindemittelkombination, diese enthaltende waessriges ueberzugsmittel und dessen verwendung
DE3834859A1 (de) * 1988-10-13 1990-04-19 Basf Lacke & Farben Verfahren zur herstellung lagerstabiler schmelzklebelackloesungen sowie deren verwendung
DE3840817A1 (de) * 1988-12-03 1990-06-07 Bayer Ag Verfahren zur herstellung von formkoerpern aus polyurethanschaumstoffen und die nach diesem verfahren erhaltenen formkoerper
NZ234512A (en) * 1989-07-19 1992-05-26 Mitsui Toatsu Chemicals Polyols prepared by adding alkylene oxide onto a compound containing at least one ester and/or amide linkage; polyurethane resins and foams prepared therefrom
US5130382A (en) * 1990-03-30 1992-07-14 Texaco Chemical Company Hydroxy terminated polyoxypropylene polyamides
DE19514320A1 (de) * 1995-04-18 1996-10-24 Hoechst Ag Polyamidschäume
US5817425A (en) * 1995-07-21 1998-10-06 Toyo Boseki Kabushiki Kaisha Layered polyamide film and method for producing the same
CN1204346A (zh) * 1995-12-11 1999-01-06 巴斯福股份公司 制备任选含有增强材料、由多异氰酸酯聚合加成产物和内脱模剂的自脱模的致密或多孔模塑
US5891563A (en) * 1996-10-08 1999-04-06 Bridgestone/Firestone, Inc. Polyisocyanurate boards with reduced moisture absorbency and lower air permeability and related methods
DE19654179A1 (de) * 1996-12-23 1998-06-25 Basf Ag H-förmige Polyamide
FR2766197B1 (fr) * 1997-07-17 1999-09-03 Nyltech Italia Copolyamide thermoplastique, composition a base de ce copolyamide thermoplastique
FR2793252B1 (fr) * 1999-05-05 2001-07-20 Rhodianyl Copolyamide hyperbranche, composition a base de ce copolyamide hyperbranche et procede d'obtention de ce dernier
DE10040762A1 (de) * 2000-08-19 2002-03-07 Henkel Kgaa Formteile aus Dimerfettsäurefreie Polyamiden

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004000908A1 *

Also Published As

Publication number Publication date
JP2005530017A (ja) 2005-10-06
US20060167124A1 (en) 2006-07-27
AU2003255684A1 (en) 2004-01-06
TWI287550B (en) 2007-10-01
FR2841253A1 (fr) 2003-12-26
US8946314B2 (en) 2015-02-03
RU2326897C2 (ru) 2008-06-20
FR2841253B1 (fr) 2004-10-22
JP4303201B2 (ja) 2009-07-29
CA2490519A1 (fr) 2003-12-31
WO2004000908A1 (fr) 2003-12-31
RU2005101346A (ru) 2006-01-20
CN100480295C (zh) 2009-04-22
TW200413472A (en) 2004-08-01
CN1671763A (zh) 2005-09-21

Similar Documents

Publication Publication Date Title
EP1539849A1 (de) Expandierbare polyamidzusammensetzung und daraus abgeleiteter polyamidschaumstoff
EP2430084B1 (de) Verfahren zur herstellung von polyamidschaumstoff und nach dem verfahren herstellbarer schaumstoff
US8168260B2 (en) Cross-linkable thermoplastic polyurethanes
HU202564B (en) Process for producing stabilized polyisocyanates
EP2326681B1 (de) Modifiziertes polyamid, herstellungsverfahren dafür und aus dem polyamid erhaltener gegenstand
FR2527214A1 (fr) Procede de preparation d'une piece composite en matiere plastique cellulaire presentant des groupes urethannes ou isocyanurates, ou urethannes et isocyanurates
CN102428114A (zh) 用于制备碳二亚胺的方法
JPH09272726A (ja) ポリウレタン樹脂
FR2858623A1 (fr) Mousses polyurethannes, procede de fabrication et utilisation de ces mousses
JP4253253B2 (ja) 離型剤およびプラスチック成形部品の製造方法
TW201114793A (en) Sprayable elastomeric polyurethane foam and process for its production
FR2988394A1 (fr) Agent fluidifiant et procede utilisant cet agent
EP2448998B1 (de) Modifiziertes polyamid, herstellungsverfahren dafür und aus diesem polyamid hergestellter artikel
FR2764296A1 (fr) Composition de resine de polyurethane pour moulage en moule creux, produit obtenu a partir de celle-ci et procede de production de ce produit
EP1641608A2 (de) Verfahren zur herstellung von auf geschäumtem polymer basierenden perlen
EP3712196A1 (de) Verwendung von copolyamiden für die herstellung von zusammensetzungen mit einer stabilen steifigkeit unter einwirkung von temperatureffekten
FR2858622A1 (fr) Mousses polyurethane, polyester-polyols pour l'obtention des mousses et utilisation de ces mousses
EP0600774B1 (de) Mischungen von Polyisocyanaten zur Herstellung von weichen hochelastischen Polyurethan-Schaumstoffen
CH536864A (fr) Procédé de préparation d'une mousse de polyuréthane
HK1059274A (en) Carbodiimide composition for acoustically matching layer, process for producing a formed article for said layer and ultrasonic transducer using said formed article

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20041221

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20070126

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: RHODIA OPERATIONS

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20160726