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WO1994011173A1 - Procede de fabrication de corps moules en polylactide par extrusion ou par moulage par compression - Google Patents

Procede de fabrication de corps moules en polylactide par extrusion ou par moulage par compression Download PDF

Info

Publication number
WO1994011173A1
WO1994011173A1 PCT/EP1993/003225 EP9303225W WO9411173A1 WO 1994011173 A1 WO1994011173 A1 WO 1994011173A1 EP 9303225 W EP9303225 W EP 9303225W WO 9411173 A1 WO9411173 A1 WO 9411173A1
Authority
WO
WIPO (PCT)
Prior art keywords
polylactide
amorphous
extrusion
preform
molded bodies
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.)
Ceased
Application number
PCT/EP1993/003225
Other languages
German (de)
English (en)
Inventor
Hans-Josef Sterzel
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to JP6511731A priority Critical patent/JPH08502935A/ja
Priority to EP94901813A priority patent/EP0669866A1/fr
Publication of WO1994011173A1 publication Critical patent/WO1994011173A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • B29B11/00—Making preforms
    • B29B11/06—Making preforms by moulding the material
    • B29B11/12—Compression moulding

Definitions

  • Poly-L-lactide, poly-D-lactide and their copolymers are known. They are compostable polymers, the decomposition of which does not result in non-natural degradation products, but only biomass and carbon dioxide. Because of this behavior, polylactide has great potential, especially in the packaging sector.
  • Polylactides can also be produced entirely from renewable raw materials: L-lactide, D-lactide, DL-lactide or mixtures thereof are obtained from lactic acid and ring-opening to high-molecular products and polymerized while maintaining the asymmetric carbon atom.
  • the homopolymeric D- and L-lactides have melting points around 175 ° C, the tensile modulus at room temperature is 3,000 N / mm 2 , the weight average molecular weights being 50,000 to 200,000 g / mol.
  • the glass transition temperature is 50 ° C.
  • polylactides have a disadvantage for conventional injection molding processing: they crystallize so slowly that cooling times of up to several minutes are required in order to obtain partially crystalline moldings with appropriate dimensional stability above the glass transition temperature. The long cooling time is also needed to avoid sticking in the mold.
  • polylactides can be made more tensile by one-dimensional orientation (DE 16 42 112, DE 16 42 111, DE 14 92 427). Fibers are extruded and stretched at temperatures from 60 to 150 ° C up to ten times their original length.
  • Such fibers are commonly used as surgical sutures.
  • the object is achieved by processing polylactides by compression molding or extrusion molding, the mass flowing and oriented in several directions in a temperature range from 60 to 150 ° C. and spontaneous crystallization occurring.
  • the crystallization therefore takes place in fractions of a second, while it takes place in the range of minutes without the presence of flow and orientation.
  • amorphous preforms or semi-finished amorphous products are produced by extrusion or injection molding when the melt is cooled to below 30 ° C.
  • This amorphous preforms or the amorphous semifinished product is at temperatures of 60 to 150 ° C within 1 to 3 min. heated.
  • the temperature conditions are set so that the material does not crystallize.
  • the heating can take place via electrical heat radiators as well as by contacting with a heating liquid such as water, ethylene glycol, glycerol or high-boiling petroleum ether or by means of a warm air stream.
  • the semi-finished product is then brought into a mold with a temperature of 60 to 150 ° C., preferably the same temperature as that of the semi-finished product, and the mold is then closed.
  • the mass of the semi-finished product is chosen so that the finished molded part just fills the mold.
  • the increase in density due to crystallization is taken into account.
  • the finished molded part can be removed from the mold within a few seconds. 5
  • the processing of polylactide according to the invention allows the production of complex objects with high heat resistance and high solvent resistance within economically short cycle times.
  • a poly-L-lactide with an inherent viscosity of 1.59 is used, measured as a 0.1% solution in chloroform at 25 ° C.
  • the amorphous density of the material, measured on a quenched injection molded part, mold temperature 20 ° C., is 1.25 g / cm 3 .
  • the material was pre-dried at 120 ° C for 15 to 20 hours at a pressure of less than 10 mbar.
  • the processing itself was carried out under argon coverage in order to avoid degradation of the molar mass by oxidation and / or hydrolysis.
  • the melt temperature was 25 205 ° C.
  • Poly-lactide is melted in the plasticizing unit of an injection molding machine and then injected into a mold for the production of cups, lower diameter 45 mm, upper diameter 58 mm, height 56 mm, wall thickness 1.5 mm.
  • the cup weighs 20.4 g.
  • the mold surface temperature is varied between 90 and 130 ° C.
  • the shortest demolding time is 4.1 min. at a mold surface temperature of 110 ° C.
  • a crystalline fraction of approximately 20% is measured as the quotient of the area of the crystalline X-ray peak to the total area.
  • the modulus of elasticity is 2,900 N / mm 7 .
  • polylactide is melted and then injected into a mold cooled to 20 ° C., after 20 seconds. Cycle time to obtain a disk-shaped amorphous preform with a diameter of 37.3 mm, a height of 15 mm and a weight of 20.5 g.
  • the preform is in boiling water within 30 seconds. heated to 100 ° C. It is then placed in the middle of a press die heated to 100 ° C. The stamp is then lowered, likewise at a temperature of 100 ° C., in order to obtain a molded part corresponding to the cup from Example 1.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

Selon un procédé de fabrication de corps moulés en polylactide, on chauffe un produit semi-fini amorphe en polylactide ou une ébauche amorphe compacte jusqu'à une température comprise entre 60 et 150 °C. L'ébauche reste amorphe et est ensuite extrudée dans un outil lui aussi chauffé jusqu'à une température comprise entre 60 et 150 °C, de sorte que le polylactide s'écoule suivant des axes multiples. Il est ainsi orienté et cristallisé.
PCT/EP1993/003225 1992-11-19 1993-11-18 Procede de fabrication de corps moules en polylactide par extrusion ou par moulage par compression Ceased WO1994011173A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP6511731A JPH08502935A (ja) 1992-11-19 1993-11-18 圧縮成形またはフローモールディングによるポリラクチド成形体の製造方法
EP94901813A EP0669866A1 (fr) 1992-11-19 1993-11-18 Procede de fabrication de corps moules en polylactide par extrusion ou par moulage par compression

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19924238997 DE4238997A1 (de) 1992-11-19 1992-11-19 Verfahren zur Herstellung von Polylactid-Formkörpern durch Formpressen oder Fließpressen
DEP4238997.6 1992-11-19

Publications (1)

Publication Number Publication Date
WO1994011173A1 true WO1994011173A1 (fr) 1994-05-26

Family

ID=6473242

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1993/003225 Ceased WO1994011173A1 (fr) 1992-11-19 1993-11-18 Procede de fabrication de corps moules en polylactide par extrusion ou par moulage par compression

Country Status (4)

Country Link
EP (1) EP0669866A1 (fr)
JP (1) JPH08502935A (fr)
DE (1) DE4238997A1 (fr)
WO (1) WO1994011173A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9732184B2 (en) 2014-07-29 2017-08-15 W. L. Gore & Associates, Inc. Process for producing articles formed from polylactic acid and articles made therefrom

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006131973A1 (fr) * 2005-06-09 2006-12-14 Sumitomo Heavy Industries, Ltd. Appareil de moulage pour articles moules par injection et procede de moulage

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0238076A2 (fr) * 1986-03-18 1987-09-23 Asahi Kasei Kogyo Kabushiki Kaisha Pièce façonnée en polymère orienté de tétrafluoroéthylène
WO1990011060A1 (fr) * 1989-03-17 1990-10-04 Zachariades Anagnostis E Procede de fabrication d'un produit en polyethylene a poids moleculaire ultra-eleve
US5007939A (en) * 1987-11-19 1991-04-16 Solvay & Cie (Societe Anonyme) Article made of lactic acid polymer capable of being employed particularly as a biodegradable prosthesis and process for its manufacture
EP0321176B1 (fr) * 1987-12-14 1995-02-08 JOHNSON & JOHNSON ORTHOPAEDICS INC. Elément thermoplastique à orientation moléculaire et procédé pour sa fabrication

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0238076A2 (fr) * 1986-03-18 1987-09-23 Asahi Kasei Kogyo Kabushiki Kaisha Pièce façonnée en polymère orienté de tétrafluoroéthylène
US5007939A (en) * 1987-11-19 1991-04-16 Solvay & Cie (Societe Anonyme) Article made of lactic acid polymer capable of being employed particularly as a biodegradable prosthesis and process for its manufacture
EP0321176B1 (fr) * 1987-12-14 1995-02-08 JOHNSON & JOHNSON ORTHOPAEDICS INC. Elément thermoplastique à orientation moléculaire et procédé pour sa fabrication
WO1990011060A1 (fr) * 1989-03-17 1990-10-04 Zachariades Anagnostis E Procede de fabrication d'un produit en polyethylene a poids moleculaire ultra-eleve

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9732184B2 (en) 2014-07-29 2017-08-15 W. L. Gore & Associates, Inc. Process for producing articles formed from polylactic acid and articles made therefrom
US9987773B2 (en) 2014-07-29 2018-06-05 W.L. Gore & Associates, Inc. Process for producing articles formed from polylactic acid and articles made therefrom
US10150232B2 (en) 2014-07-29 2018-12-11 W. L. Gore & Associates, Inc. Process for producing articles formed from polylactic acid and articles made therefrom

Also Published As

Publication number Publication date
DE4238997A1 (de) 1994-05-26
EP0669866A1 (fr) 1995-09-06
JPH08502935A (ja) 1996-04-02

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