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WO2013056705A1 - Procédé de fabrication d'objets à partir de polyamide réticulé par irradiation - Google Patents

Procédé de fabrication d'objets à partir de polyamide réticulé par irradiation Download PDF

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Publication number
WO2013056705A1
WO2013056705A1 PCT/DE2012/100325 DE2012100325W WO2013056705A1 WO 2013056705 A1 WO2013056705 A1 WO 2013056705A1 DE 2012100325 W DE2012100325 W DE 2012100325W WO 2013056705 A1 WO2013056705 A1 WO 2013056705A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyamide
raw material
radiation
takes place
crosslinking
Prior art date
Application number
PCT/DE2012/100325
Other languages
German (de)
English (en)
Inventor
Michel Gschwendtner
Franziska WEICHELT
Original Assignee
Minervius Gmbh
Hülsmann, Ralf
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 Minervius Gmbh, Hülsmann, Ralf filed Critical Minervius Gmbh
Publication of WO2013056705A1 publication Critical patent/WO2013056705A1/fr

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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
    • 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
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/085—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using gamma-ray
    • 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
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
    • B29C2035/0877—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation using electron radiation, e.g. beta-rays
    • 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
    • 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
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • 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

Definitions

  • the invention relates to a process for the production of articles from radiation-crosslinked polyamide.
  • irradiation crosslinking (hereinafter also referred to as irradiation) is understood here as meaning a generally known process for modifying polymers with the aid of ionizing radiation.
  • EP 1 966 280 A1, US 2008/0207782 A1 and US Pat. No. 4,444,816 each describe processes for radiation cross-linking of polyamides.
  • the radiation crosslinking takes place in each case after the object to be produced has already been formed from a raw material.
  • the result of this is that the process of radiation crosslinking has to be matched to the respective geometry of the object, which makes the process technically complex.
  • the invention has for its object to provide a process engineering easy to be performed method for the production of articles of irradiated polyamide.
  • the process for the production of articles made of radiation-crosslinked polyamide has the following process steps, which are listed in chronological order: a) Radiation crosslinking of a polyamide In the solid state, and b) transforming the radiation-crosslinked polyamide raw material into a final product.
  • Raw materials e.g. in the form of granules, pellets, flakes, beads or powders can be used. Subsequently, the shaping takes place, i. the transformation of the cross-linked raw material into the desired
  • polyamide polymers whose repeating units possess the amide group as a characteristic feature. This includes both homopolyamides and copolyamides. Under
  • Homopolyamides are understood to mean polyamides which can be described by a single repeating unit.
  • Copolyamides are understood to mean polyamides which can be described by different repeating units.
  • polyamides also includes polyamide blends, i. blends of various types of polyamides (e.g., PA6 / PA66 blends) as well as blends of polyamide and others
  • Polymers e.g., polystyrene / polyamide blends or acrylonitrile-butadiene-styrene (ABS) / polyamide blends.
  • the radiation crosslinking takes place in the presence of a crosslinking additive.
  • the crosslinking additive may be solid, liquid or be gaseous and contains at least one multiple bond.
  • solid or liquid crosslinking additives they must be introduced into the polyamide raw material before the irradiation by melt mixing / compounding.
  • particularly suitable solid / liquid crosslinking additives are triallyl cyanurate or triallyl isocyanurate.
  • the crosslinking additive can be used in concentrations of 0.01 - 20%.
  • the irradiation can be in the presence of oxygen
  • Reacting polyamides via a peroxide radical mechanism with oxygen molecules from the air to form new polar functional groups e.g.
  • gaseous crosslinking additive can be added directly during the irradiation, during the irradiation diffuse into the polyamide and crosslink there with the polyamide. This method is preferable because an additional compounding step of polyamide and crosslinking additive is omitted here and the associated disadvantages, e.g. Chain degradation of the polyamide during compounding, be reduced. Examples of gaseous
  • Crosslinking additives are ethylene or acetylene.
  • Radiation crosslinking occurs at a temperature at which the polyamide raw material is in the solid phase (ie, solid state).
  • the starting polymer may be in the form of granules, pellets, flakes, spheres or powders.
  • the radiation crosslinking takes place under ambient pressure.
  • the irradiation takes place at a temperature below the crystalline melting temperature of the
  • the amorphous regions are preferably branched / partially crosslinked, while the crystalline regions remain largely unchanged. In this way, the processability of the crosslinked polyamide is largely retained.
  • Irradiation is by means of ionizing radiation, i. possible
  • Irradiation sources are in particular electron radiation, gamma radiation or X-radiation, but preferably electron radiation.
  • the irradiation dose should be between 0.1 and 500 kGy, preferably in the range of 1 to 60 kGy; the choice of irradiation dose depends on the type of polyamide, the additive content and / or the desired degree of crosslinking.
  • the polyamide raw material is crosslinked to a gel content of 0.01 to 10%.
  • This preferred degree of crosslinking is well below the usual degrees of crosslinking (gel content 60-70%) and allows a simple and simple further processing / transformation of the irradiated polyamide.
  • Polyamide obtained only the above-mentioned low degree of crosslinking (gel content of 0.01 -10%), so that the material also after the
  • End products can be molded.
  • products that have been chemically crosslinked or radiation-crosslinked after shaping are no longer deformable or recyclable.
  • a reshaping of the irradiated polyamide can in particular by an extrusion process or a
  • the samples are irradiated in a gamma-irradiation facility at a dose of 8.0 kGy, then annealed at 80 ° C for 8 hours and finally cooled to room temperature.
  • the long lived polyamide radicals formed during irradiation may continue to react with the crosslinking additive.
  • the tempering process changes the color of PA6.10 granules from colorless to slightly pink, to PA6 or from colorless to slightly yellow.
  • the mechanical and theological properties of the modified PA6.10 are compared with those of the untreated PA6.10. Significant increase in complex viscosity due to branching reactions after radiation modification can be observed.
  • the sample is irradiated in a gamma irradiation facility at a dose of 16 kGy, then annealed at 80 ° C for 8 hours and finally cooled to room temperature. During annealing, a color change from colorless to pink can be detected.
  • the mechanical and theological properties of the modified PA6.6T are compared with those of the untreated PA6.6T. There may be a slight increase in complex viscosity due to branching / crosslinking after radiation modification. The injection pressure with which the tension rods are produced for the investigation of the mechanical properties does not change almost as a result of the radiation modification, i.
  • the modified PA6.6T can be processed into a final product (tension rods) without having to make any changes to the machine. By radiation modification, a slight increase in tensile strength and a reduction in elongation at break can be observed.
  • a compound of 1% by weight of triallyl cyanurate in polyamide PA12 is prepared, extruded into a water bath and then cut into pellets (granulated). After drying, about 500 g of the granules are each packed in a gas-impermeable bag. After vacuuming, the bags are filled with an inert gas (nitrogen) until the external and internal pressures are equalized.
  • the samples are irradiated with high-energy electrons from an electron irradiation facility (10 MeV) at room temperature with a surface dose of 4, 16 or 24 kGy. Subsequently, a part of the samples is annealed at 80 ° C for 8 hours, the other part is not annealed.
  • the mechanical and thermal properties of the modified polyamides are compared with those of the untreated polyamide PA12 and an improvement in the mechanical and thermal properties can be observed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un procédé de fabrication d'objets à partir de polyamide réticulé par irradiation, comportant les étapes suivantes données dans leur ordre d'exécution dans le temps: a) réticulation par irradiation d'une matière brute de polyamide à l'état solide; et b) façonnage de la matière brute de polyamide réticulée par irradiation pour former un produit fini.
PCT/DE2012/100325 2011-10-20 2012-10-19 Procédé de fabrication d'objets à partir de polyamide réticulé par irradiation WO2013056705A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011054629.4 2011-10-20
DE102011054629A DE102011054629A1 (de) 2011-10-20 2011-10-20 Verfahren zur Herstellung von Gegenständen aus strahlenvernetztem Polyamid

Publications (1)

Publication Number Publication Date
WO2013056705A1 true WO2013056705A1 (fr) 2013-04-25

Family

ID=47278631

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE2012/100325 WO2013056705A1 (fr) 2011-10-20 2012-10-19 Procédé de fabrication d'objets à partir de polyamide réticulé par irradiation

Country Status (2)

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DE (1) DE102011054629A1 (fr)
WO (1) WO2013056705A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202020103707U1 (de) * 2020-06-26 2021-09-28 Edscha Engineering Gmbh Laufrolle, insbesondere für eine Schiebetür

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3228996A (en) * 1961-05-17 1966-01-11 Basf Ag Crosslinking linear high molecular weight polyamides with peroxides
EP0007114A1 (fr) * 1978-07-18 1980-01-23 Teijin Limited Feuille en polyamide aromatique et procédé pour sa fabrication
US4444816A (en) 1980-12-03 1984-04-24 Raychem Corporation Radiation cross-linking of polyamides
WO2000035992A1 (fr) * 1998-12-16 2000-06-22 Dsm N.V. Polyamide aleatoirement ramifie intrinsequement exempt de gel
US6656550B1 (en) * 1996-10-08 2003-12-02 Alan M. Zamore Dilatation device of uniform outer diameter
WO2004005026A1 (fr) * 2002-07-09 2004-01-15 Dsm Ip Assets B.V. Procede pour appliquer une couche de polyamide ramifie sur un substrat
US20050207931A1 (en) * 2004-03-21 2005-09-22 Toyota Motorsport Gmbh unknown
EP1865018A1 (fr) * 2005-03-30 2007-12-12 Mitsubishi Engineering-Plastics Corporation Pastille de resine reticulable en polybutene terephthalate a rayonnement ionisant
US20080207782A1 (en) 2005-01-18 2008-08-28 Paul Jacobs Polyamide Foams, Process to Make Them and Applications Thereof
EP1966280A1 (fr) 2005-12-23 2008-09-10 EMS-Chemie AG Matieres a mouler polyamide reticulables et elements moules ainsi fabriques
WO2009114715A2 (fr) * 2008-03-14 2009-09-17 Valspar Sourcing, Inc. Compositions pulvérulentes et procédés de fabrication d’objets à partir de celles-ci
WO2010142605A1 (fr) * 2009-06-12 2010-12-16 Rhodia Operations Polyamide de haute viscosite

Family Cites Families (3)

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Publication number Priority date Publication date Assignee Title
US4525257A (en) * 1982-12-27 1985-06-25 Union Carbide Corporation Low level irradiated linear low density ethylene/alpha-olefin copolymers and film extruded therefrom
TW275636B (fr) * 1991-06-21 1996-05-11 Himont Inc
DE102006041874B4 (de) * 2005-09-30 2014-06-18 Leibniz-Institut Für Polymerforschung Dresden E.V. Vorrichtung zur kontinuierlichen Modifizierung von Polymeren im fließfähigen Zustand mittels Elektronenstrahlung

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3228996A (en) * 1961-05-17 1966-01-11 Basf Ag Crosslinking linear high molecular weight polyamides with peroxides
EP0007114A1 (fr) * 1978-07-18 1980-01-23 Teijin Limited Feuille en polyamide aromatique et procédé pour sa fabrication
US4444816A (en) 1980-12-03 1984-04-24 Raychem Corporation Radiation cross-linking of polyamides
US6656550B1 (en) * 1996-10-08 2003-12-02 Alan M. Zamore Dilatation device of uniform outer diameter
WO2000035992A1 (fr) * 1998-12-16 2000-06-22 Dsm N.V. Polyamide aleatoirement ramifie intrinsequement exempt de gel
WO2004005026A1 (fr) * 2002-07-09 2004-01-15 Dsm Ip Assets B.V. Procede pour appliquer une couche de polyamide ramifie sur un substrat
US20050207931A1 (en) * 2004-03-21 2005-09-22 Toyota Motorsport Gmbh unknown
US20080207782A1 (en) 2005-01-18 2008-08-28 Paul Jacobs Polyamide Foams, Process to Make Them and Applications Thereof
EP1853655B1 (fr) * 2005-01-18 2010-02-10 Zotefoams Plc Mousses de polyamide, leur procede de fabrication et leurs applications
EP1865018A1 (fr) * 2005-03-30 2007-12-12 Mitsubishi Engineering-Plastics Corporation Pastille de resine reticulable en polybutene terephthalate a rayonnement ionisant
EP1966280A1 (fr) 2005-12-23 2008-09-10 EMS-Chemie AG Matieres a mouler polyamide reticulables et elements moules ainsi fabriques
WO2009114715A2 (fr) * 2008-03-14 2009-09-17 Valspar Sourcing, Inc. Compositions pulvérulentes et procédés de fabrication d’objets à partir de celles-ci
WO2010142605A1 (fr) * 2009-06-12 2010-12-16 Rhodia Operations Polyamide de haute viscosite

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DIETMAR DRUMMER, ANDREAS SEEFRIED: "Thermoformability of Radiation Cross Linked Polyamide 12", THERMOFORMING QUARTERLY, vol. 30, no. 4, 1 October 2011 (2011-10-01), pages 22 - 28, XP002693022 *

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