EP3523351A1 - Composition polymérisable - Google Patents

Composition polymérisable

Info

Publication number
EP3523351A1
EP3523351A1 EP17771471.4A EP17771471A EP3523351A1 EP 3523351 A1 EP3523351 A1 EP 3523351A1 EP 17771471 A EP17771471 A EP 17771471A EP 3523351 A1 EP3523351 A1 EP 3523351A1
Authority
EP
European Patent Office
Prior art keywords
polymerizable composition
sodium
fibers
component
caprolactamate
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Withdrawn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
EP17771471.4A
Other languages
German (de)
English (en)
Inventor
Michael Witt
Dominic Fuchs
Michaela FRANK
Dirk Steinhilber
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.)
Lanxess Deutschland GmbH
Original Assignee
Lanxess Deutschland GmbH
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 Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Publication of EP3523351A1 publication Critical patent/EP3523351A1/fr
Withdrawn legal-status Critical Current

Links

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
    • 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
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/16—Preparatory processes
    • C08G69/18—Anionic polymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7812—Nitrogen containing -N-C=0 groups containing amide groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/12—Olefin polymerisation or copolymerisation
    • B01J2231/127—Anionic (co)polymerisation

Definitions

  • the present invention relates to a polymerizable composition containing as cyclic amides a special mixture of caprolactam and laurolactam, their preparation and their use for the production of polyamide, in particular a fiber-reinforced composite material with polyamide matrix characterized in that only a small volume shrinkage occurs in the polymerization.
  • lactams allow very rapid conversion of an activated lactam melt to a polyamide.
  • Polyamides belong to the class of thermoplastics and thus exhibit different properties than other commercial casting compounds based on epoxy resins, phenolic resins or polyurethane systems, which lead either to thermosets or to crosslinked polymers.
  • Thermoplastics are particularly easy to recycle at the end of a component's life cycle.
  • a lactam is usually mixed together with at least one catalyst and at least one activator and the caprolactam melt so activated can subsequently be polymerized.
  • volume shrinkage of polyamides of caprolactam or laurolactam in each case about 15%. Particularly serious is this disadvantage in cast-over components, such as cables or engine parts, as it can easily lead to tensions or even cracks under stress. Accordingly, the range of applications of a pure cast PA6 or cast PA12 polymerization is limited. Volume shrinkage of the polymerizing lactam melt is also a challenge in the case of the RIM PA 6 process with continuous fiber reinforcement. For example, in the case of polymerization in closed cavities, volume shrinkage may cause the matrix to be behind the fiber surface of the textile fabric previously inserted into the cavity.
  • Caprolactam is generally used as a scale product for casting and RIM polymerization.
  • the caprolactam which is solid at room temperature is brought to its melting point of 69 ° C. and then heated further to a polymerization temperature of about 150 ° C. Increasing the temperature of the melt from 69 to 150 ° C reduces the density of the melt.
  • volume shrinkage is generally related to all three factors, ie to the shrinkage experienced by the hot, liquid lactam melt by polymerization and crystallization, and in addition to the volume reduction induced by the cooling of the polymer to room temperature. Volume shrinkage is generally associated with a proportional increase in density and is determined as follows:
  • volume shrinkage in percent (1 - density of the polymerizable composition at 150 ° C / density of the resulting polymer at room temperature, 23 ° C) x100.
  • the volume reduction by polymerization and crystallization are crucial for the later quality of the component.
  • the component is subsequently removed from the mold directly at the polymerization temperature and then cooled down, the dimensions of the component change, but voids no longer form on cooling.
  • a polymerizable composition which comprises a) a cyclic amide containing a mixture of laurolactam and caprolactam, the amount of laurolactam being from 10 to 35% by weight, in particular from 20 to
  • the volume shrinkage in the polymerization of the composition according to the invention is significantly reduced compared to pure caprolactam.
  • cyclic amides while a mixture containing caprolactam and laurolactam is used, wherein the cyclic amides in the polymerizable composition according to the invention, preferably to more than 95 wt .-%, in particular more than 98 wt .-% of caprolactam and laurolactam.
  • Mixtures of different lactams for adhesive applications are already known from DE3730504 C1.
  • the activator of component b) is preferably such activators based on blocked aliphatic isocyanates, preferably disocyanates, in particular isophorone diisocyanate (IPDI) or preferably those of the formula OCN- (CH 2 ) 4 -2o-NCO, in particular butylene diisocyanate, hexamethylene diisocyanate ( HDI), octamethylene diisocyanate, decamethylene diisocyanate, undecamethylene diisocyanate or dodecamethylene diisocyanate. Particularly preferred is blocked hexamethylene diisocyanate (HDI).
  • lactam is preferred, in particular caprolactam-blocked diisocyanate.
  • differently blocked polyisocyanates can also be used in a mixture.
  • Caprolactam is particularly preferably blocked HDI, N, N'-hexane-1,6-diylbis (hexahydro-2-0X0-1H-azepine-1-carboxamide), CAS No .: 5888-87-9.
  • the mass ratio of the cyclic amides of component a) to the blocked isocyanate of component b) can be varied within wide limits and is generally from 1: 1 to 10000: 1, preferably from 5: 1 to 2000: 1, particularly preferably 20: 1 to 1000: 1.
  • the catalyst c) for the polymerization, in particular anionic polymerization of the cyclic amides is preferably at least one selected from the group consisting of sodium caprolactamate, potassium caprolactamate, bromide magnesium caprolactamate, chloride magnesium caprolactamate, magnesium bis-caprolactamate, sodium hydride, sodium, Sodium hydroxide, sodium methoxide, sodium ethanolate, sodium propanolate, sodium butanolate, potassium hydride, potassium hydroxide, potassium methoxide, potassium ethanolate, potassium propoxide and potassium butoxide, preferably from the group consisting of sodium hydride, sodium and sodium caprolactamate, more preferably sodium caprolactamate.
  • the molar ratio of the cyclic amides a) to catalyst c) can be varied within wide limits. It is generally 1: 1 to 10000: 1, preferably 5: 1 to 1000: 1, particularly preferably 1: 1 to 500: 1.
  • the polymerizable composition according to the invention preferably contains from 50 to 100% by weight of components a) to c), preferably from 80 to 100% by weight, in particular from 90 to 100%, particularly preferably from 95 to 100%, based on the total weight of the composition.
  • composition according to the invention particularly preferably contains an activator of component b) based on a caprolactam-blocked hexamethylene diisocyanate and, as a catalyst of component b), sodium caprolactamate.
  • activator of component b) based on a caprolactam-blocked hexamethylene diisocyanate and, as a catalyst of component b), sodium caprolactamate.
  • the polymerizable composition of the present invention may contain one or more polymers, which polymer may in principle be selected from polymers obtained in the polymerization of the polymerizable composition of the present invention, various polymers and polymer blends thereof.
  • the polymerizable composition according to the invention may also contain filler. Fillers, especially particulate fillers, can have a wide range of particle sizes, ranging from dusty to coarse particles. Suitable fillers are organic or inorganic fillers and / or fibrous materials.
  • inorganic fillers such as kaolin, chalk, wollastonite, talc, calcium carbonate, silicates, titanium dioxide, zinc oxide, graphite, graphenes, glass particles, eg glass beads
  • nanoscale fillers such as carbon nanotubes, carbon black, nanoscale sheet silicates, nanoscale aluminum oxide (Al 2 0 3 ) and nanoscale titanium dioxide (Ti0 2 ) are used.
  • one or more fibers can be used. These are preferably selected from known inorganic reinforcing fibers such as boron fibers, glass fibers, carbon fibers, silica fibers, ceramic fibers and basalt fibers, organic reinforcing fibers such as aramid fibers, polyester fibers, nylon fibers, polyethylene fibers and natural fibers such as wood fibers, flax fibers, hemp fibers and sisal fibers.
  • inorganic reinforcing fibers such as boron fibers, glass fibers, carbon fibers, silica fibers, ceramic fibers and basalt fibers
  • organic reinforcing fibers such as aramid fibers, polyester fibers, nylon fibers, polyethylene fibers and natural fibers such as wood fibers, flax fibers, hemp fibers and sisal fibers.
  • fibers are preferably used as continuous fibers, for example in the form of tapes, loops, woven or knitted fabrics. It is also possible to use a non-ordered fiber deposit, in particular in the form of mats, nonwovens or else cut fibers of different fiber length, in particular from 0.1 mm to several cm in length, preferably up to 5 cm in length.
  • the use of these fiber materials is preferably carried out only in the application of the polymerizable composition according to the invention for the production of a fiber-reinforced composite material according to the invention. Also in this case, shrinkage by the fibers, based on the total volume, is further reduced.
  • the polymerizable composition according to the invention may contain one or more further additives.
  • additives for example, stabilizers such as copper salts, dyes, antistatic agents, release agents, antioxidants, light stabilizers, PVC stabilizers, lubricants, release agents, blowing agents, and combinations thereof may be added.
  • stabilizers such as copper salts, dyes, antistatic agents, release agents, antioxidants, light stabilizers, PVC stabilizers, lubricants, release agents, blowing agents, and combinations thereof may be added.
  • additives are preferred in an amount of 0 to 5 wt .-%, preferably from 0 to 4 wt .-%, particularly preferably from 0 to 3.5 wt .-%, based on the total weight of the polymerizable composition.
  • the polymerizable composition may contain at least one additive, preferably in an amount of at least 0.01% by weight, based on the total weight of the polymerizable composition, more preferably at least 0.1% by weight, based on the total weight of the polymerizable composition , in particular of at least 0.5 wt .-%, based on the total weight of the polymerizable composition.
  • the polymerizable composition according to the invention contains as additive at least one impact modifier.
  • a polymeric compound is used as the impact modifier, it is added to the aforementioned polymers.
  • a polydiene polymer for example polybutadiene, polyisoprene
  • these preferably contain anhydride and / or epoxide groups.
  • the polydiene polymer has a glass transition temperature below 0 ° C., preferably below -10 ° C., particularly preferably below -20 ° C.
  • the polydiene polymer can be based on a polydiene copolymer with polyacrylates, polyethylene acrylates and / or polysiloxanes and prepared by the usual methods (e.g., emulsion polymerization, suspension polymerization, solution polymerization, gas phase polymerization).
  • the invention further relates to a process for the preparation of the polymerizable composition, which comprises bringing the mixture of cyclic amides of component a) into contact with at least one blocked polyisocyanate of component b) and at least one catalyst of component c) ,
  • components b) and c) are first mixed independently of one another in a). Only at a later time, generally immediately before the anionic polymerization, these individual mixtures are then mixed together.
  • the process is therefore preferably characterized in that an activator mixture comprising cyclic amides of component a) and at least one activator of component b) with a catalyst Q
  • a temperature is preferably selected which is equal to or greater than the melting point of the resulting mixture, in particular 70 to 160 ° C.
  • the mixing of the components can be carried out batchwise or continuously. Suitable devices for mixing the components are known in the art. For batch mixing, stirred tanks or kneaders are preferably used. Continuous mixing operations are preferably carried out in the extruder, as well as by static mixing elements, which are implemented in a mixing head or directly with in the tool, or by mixing by means of countercurrent injection.
  • the mixing device is preferably tempered.
  • Both the activator (s) and the catalyst (s) may also be used in the form of finished commercial products.
  • component b) there are caprolactam-blocked hexamethylene diisocyanate, for example commercially available under the name Brüggolen® C20 from Brüggemann or Addonyl® 8120 from Rhein Chemie Rheinau GmbH.
  • a solution of sodium caprolactamate in caprolactam can be used, e.g. Brüggolen ⁇ C10 from Brüggemann, which contains 17 to 19% by weight of sodium caprolactamate in caprolactam or addonyl KAT NL from Rhein Chemie Rheinau GmbH, which contains 18.5% by weight of sodium caprolactamate in caprolactam.
  • catalyst c) is also particularly suitable bromide magnesium caprolactamate, z. B. Brüggolen® C1 Brüggemann.
  • the polymerizable composition is preferably rapidly transferred into a cavity intended for polymerization.
  • Ratio can be combined to use the polymerizable composition according to the invention for the preparation of polymers with lower shrinkage.
  • the time required for the composition according to the invention to reach the polymerization temperature until solidification is preferably less than 10 minutes, preferably less than 5 minutes, in particular less than 1 minute.
  • the polymerizable composition should be processed quickly.
  • the invention further relates to a process for the preparation of a polymer matrix, characterized in that the polymerizable composition at a temperature of 120 to 200 ° C, preferably at 120 to 180 ° C, in particular at 140 to 160 ° C treated.
  • a cavity for example containing the electrical, current-carrying components of a cable harness or an electric motor, is potted with the polymerizable composition according to the invention and optionally polymerized by increasing the temperature.
  • the invention further relates to a process for producing a fiber composite material, characterized in that i) the polymerizable composition according to the invention or its individual components a), b) and c) brings into contact with fibers and ii) the resulting composition at a temperature of 120 to 200 ° C, preferably at 120 to 180 ° C, in particular at 140 to 160 ° C treated. 1 Q
  • the fibers can be brought into contact with the polymerizable composition in various ways.
  • inventive polymerizable composition or its individual components a), b) and c) are introduced in solid or liquid form and reinforced with fibers, preferably in the form of short fibers or in the form of textile reinforcing structures become.
  • the alternative 1, 2 or 3, wherein in a heatable, pressure-tight form fibers, in particular textile reinforcing structures are inserted.
  • the polymerizable composition is injected by means of overpressure of 1 to 150 bar and / or at a negative pressure of the mold (tool) of 10 to 900 mbar in the mold.
  • the polymerization takes place at the abovementioned temperatures. It arises directly in the form of the composite component.
  • a negative pressure is applied, preferably from 5 to 800 mbar and the polymerizable composition is sucked into the mold and polymerized after filling the mold with the polymerizable composition at the above-mentioned temperature ,
  • the polymerization is carried out in a conventional centrifugal casting process, wherein the polymerizable composition is introduced into the mold in solid or liquid form and the fibers are introduced in the form of short fibers or in the form of previously designed textile reinforcements.
  • the components and equipment used are substantially free of water, carbon dioxide and / or oxygen.
  • vacuum is applied to the closed mold cavity used before the melt is injected.
  • inert gas such as As nitrogen or argon.
  • Short fibers, long fibers, continuous fibers or mixtures thereof are preferably used in the process according to the invention as fibers.
  • short fibers have a length of 0.1 to 1 mm
  • long fibers a length of 1 to 50 mm
  • continuous fibers a length of greater than 50 mm.
  • Continuous fibers are used to produce the fiber-reinforced composite materials, preferably in the form of a textile structure, for. B. as woven, knitted or knitted fabrics, 1 ⁇
  • the above-mentioned textile fiber structures can be used in one or more layers and in different combinations with respect to textile fabrics, fiber types and their fiber quantities for component production. Preference is given to using scrims, multiaxial scrims, (multiaxial) scrims or fabrics which consist of two or more than two, preferably two to nine, layers.
  • the fiber materials used as fibers preferably include those of inorganic minerals such as carbon, for example as low modulus carbon fibers or high modulus carbon fibers, silicate and non-silicate glasses of various kinds, boron, silicon carbide, metals, metal alloys, metal oxides, metal nitrides, metal carbides and silicates, as well as organic materials such as natural and synthetic polymers, for example, polyacrylonitriles, polyesters, polyamides, polyimides, aramids, liquid-crystal polymers, polyphenylene sulfides, polyether ketones, polyether ether ketones, polyether imides, cotton, cellulose and other natural fibers, for example, flax, sisal, kenaf, hemp, abaca.
  • inorganic minerals such as carbon
  • silicate and non-silicate glasses of various kinds, boron, silicon carbide, metals, metal alloys, metal oxides, metal nitrides, metal carbides and silicates
  • organic materials such as natural
  • high-melting materials for example glasses, carbon, aramids, liquid-crystal polymers, polyphenylene sulfides, polyether ketones, polyether ether ketones and polyetherimides; particularly preferred are glass fibers, carbon fibers, aramid fibers, steel fibers, ceramic fibers and / or other sufficiently temperature-resistant polymeric fibers or filaments which are hot do not dissolve activated melt.
  • Fibers can be used in an amount ranging from 5 to 65% by volume, based on the resulting fiber composite, corresponding to, for example, glass fibers 10 to 80% by weight, but preferably in the range of 45 to 65% Vol .-%, based on the fiber composite material, with particularly preferred fibers are glass fibers or carbon fibers.
  • the inventive method allows in conjunction with the reinforcing fibers in the polymerization very low volume shrinkage, low residual monomer contents 1 g of the lactams involved, a good impregnation of the reinforcing fibers, economically acceptable polymerization times and the formation of products with good mechanical properties.
  • the invention also relates to the use of the polymerizable composition according to the invention for potting processes, in particular for the fixation and / or mechanical protection of cable bundles or for potting parts of electric motors, which in particular include current-carrying components.
  • the above use is preferred if the polymerizable composition is used in the presence of fibers for producing a fiber composite material.
  • Addonyl 8120 180 g of a specified in Table 1 mixture of caprolactam and laurolactam are presented with 8.0 g Addonyl 8120 in a second three-necked flask.
  • Addonyl 8120 is a caprolactam-blocked hexamethylene diisocyanate on both sides, specifically N, N'-hexane-1,6-diylbis (hexahydro-2-oxo-1H-azepine-1-carboxamide), CAS No .: 5888 -87-9.
  • the contents of both flasks were melted in oil baths preheated to 150 ° C., then heated to 110 ° C. Subsequently, it was evacuated at this temperature for 10 minutes. Then both flasks were filled with nitrogen and the oil baths removed.
  • both melts were placed in an open beaker overgrown with nitrogen, and the melts were mixed with a glass stir bar; the beaker was heated with the aid of an oil bath heated to 160 ° C.
  • Shrinkage A density and thus volume change of the activated lactam melt molten at 150 ° C. in relation to the polymer formed at 23 ° C.
  • volume shrinkage in percent (1-density of the polymerizable lactam melt at 150 ° C. / density of the polymer obtained at room temperature 23 ° C.) ⁇ 100
  • Shrinkage B Density and thus volume change of the activated lactam melt molten at 150 ° C. in relation to the polymer formed at 150 ° C. as well (cooled to room temperature after preparation and heated again to 150 ° C. for density determination).
  • volume shrinkage in percent (1-density of the polymerizable lactam melt at 150 ° C. / density of the polymer obtained at 150 ° C.) ⁇ 100 Shrinkage A Shrinkage B
  • the volume shrinkage in the conversion of the activated caprolactam melt to the polymer at 150 ° C could be significantly reduced by the presence of up to about 30 wt .-% laurolactam. Higher Laurinlactamanmaschine (from 40 wt .-%) were no longer manageable with the procedure described.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyamides (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

L'invention concerne une composition polymérisable, comprenant a) un amide cyclique constitué d'un mélange de laurinlactame et de caprolactame, la quantité de laurinlactame s'élevant à 10 à 35 % en poids par rapport à la quantité totale d'amide cyclique, b) au moins un promoteur ainsi que c) au moins un catalyseur destiné à la polymérisation des amides cycliques.
EP17771471.4A 2016-10-07 2017-09-26 Composition polymérisable Withdrawn EP3523351A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP16192727.2A EP3305829A1 (fr) 2016-10-07 2016-10-07 Composition polymérisable
PCT/EP2017/074364 WO2018065260A1 (fr) 2016-10-07 2017-09-26 Composition polymérisable

Publications (1)

Publication Number Publication Date
EP3523351A1 true EP3523351A1 (fr) 2019-08-14

Family

ID=57123854

Family Applications (2)

Application Number Title Priority Date Filing Date
EP16192727.2A Withdrawn EP3305829A1 (fr) 2016-10-07 2016-10-07 Composition polymérisable
EP17771471.4A Withdrawn EP3523351A1 (fr) 2016-10-07 2017-09-26 Composition polymérisable

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP16192727.2A Withdrawn EP3305829A1 (fr) 2016-10-07 2016-10-07 Composition polymérisable

Country Status (5)

Country Link
US (1) US20200031996A1 (fr)
EP (2) EP3305829A1 (fr)
JP (1) JP2019531384A (fr)
CN (1) CN109790287A (fr)
WO (1) WO2018065260A1 (fr)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1360899A (en) * 1971-07-27 1974-07-24 Ceskoslovenska Akademie Ved Method of manufacturing polyamides by anionic polymerization and copolymerization of cyclic lactams
DE3730504C1 (en) 1987-09-11 1989-03-16 Atochem Werke Gmbh Copolyamides containing caprolactam and laurolactam, process for the preparation thereof and use thereof for heat-sealing textiles
JPH07707B2 (ja) * 1988-07-14 1995-01-11 東レ株式会社 ポリアミド発泡体の製造方法
DE19527154C2 (de) * 1995-07-25 2001-06-07 Inventa Ag Thermoplastisch verformbare Verbundwerkstoffe
FR2910900B1 (fr) * 2006-12-28 2010-08-20 Arkema France Procede de preparation de poudre de polyamide par polymerisation anionique
EP2570448A1 (fr) * 2011-09-13 2013-03-20 Basf Se Utilisation de polyéthylénimines dans la fabrication de polyamides
EP2666802A1 (fr) * 2012-05-22 2013-11-27 Rhein Chemie Rheinau GmbH Polyamide coulé, son procédé de fabrication et dýutilisation

Also Published As

Publication number Publication date
EP3305829A1 (fr) 2018-04-11
JP2019531384A (ja) 2019-10-31
US20200031996A1 (en) 2020-01-30
WO2018065260A1 (fr) 2018-04-12
CN109790287A (zh) 2019-05-21

Similar Documents

Publication Publication Date Title
EP2789641B1 (fr) Procédé de fabrication de compositions monomères et leur utilisation destinée à fabriquer un élément de formage en polyamide
EP0755966B1 (fr) Composites thermoplastiques thermoformables
EP2093246B1 (fr) Polymérisation anionique de lactames en utilisant des agents d'activation spéciaux
DE102010040027B4 (de) Verfahren zur Herstellung von faserverstärkten Gusspolyamid-Formkörpern
EP0791618B1 (fr) Procédé pour préparer des matériaux composites formables à chaud comprenant une matrice de polylactam
EP2957598A1 (fr) Composite contenant un matériau matriciel composé d'un polyamide amorphe et son utilisation
EP3257893B1 (fr) Demi-produit matrice/fibre
DE1520392A1 (de) Verstaerkte polymere Verbindungen und Verfahren zu deren Herstellung
EP2666805B1 (fr) Procédé de fabrication d'une matière première composite en fibres
EP3130622B1 (fr) Composition polymerisable
EP3405512B1 (fr) Composition polymérisable
WO2013050074A1 (fr) Procédé de fabrication de matériaux composites renforcés par des fibres
EP2870191B1 (fr) Catalyseurs pour la fabrication de polyamide de fusion, son procédé de fabrication et son utilisation
EP3523351A1 (fr) Composition polymérisable
EP0134992B1 (fr) Méthode de préparation de grands moulages en polyamide renforcé par des fibres
EP3445809B1 (fr) Composition polymérisable
DE102017216315B4 (de) Verbesserter faserverstärkter Verbundkunststoff und Verfahren zu dessen Herstellung
DE4328882A1 (de) Verfahren zur Herstellung von gefülltem und/oder verstärktem Gußpolyamid
WO2012163764A1 (fr) Nouvelle composition pour la production de polyamides coulés
EP0540066A2 (fr) Matériaux composite thermoplastique renforcé par des fibres, contenant des polyamides

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

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

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

17P Request for examination filed

Effective date: 20190507

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

18W Application withdrawn

Effective date: 20190712