EP1680269A1 - Procede pour produire un materiau plastique a haute resistance et utilisation de ce materiau plastique - Google Patents

Procede pour produire un materiau plastique a haute resistance et utilisation de ce materiau plastique

Info

Publication number
EP1680269A1
EP1680269A1 EP04790646A EP04790646A EP1680269A1 EP 1680269 A1 EP1680269 A1 EP 1680269A1 EP 04790646 A EP04790646 A EP 04790646A EP 04790646 A EP04790646 A EP 04790646A EP 1680269 A1 EP1680269 A1 EP 1680269A1
Authority
EP
European Patent Office
Prior art keywords
plastic material
stretching
plastic
fixing
crosslinking
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Withdrawn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
EP04790646A
Other languages
German (de)
English (en)
Inventor
Thomas Paier
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.)
Poloplast GmbH and Co KG
Original Assignee
Poloplast GmbH and Co KG
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 Poloplast GmbH and Co KG filed Critical Poloplast GmbH and Co KG
Publication of EP1680269A1 publication Critical patent/EP1680269A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/04—After-treatment of articles without altering their shape; Apparatus therefor by wave energy or particle radiation, e.g. for curing or vulcanising preformed articles
    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
    • 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
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/02—Thermal after-treatment
    • 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
    • B29C2035/0827—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 UV radiation
    • 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
    • B29C2035/0844—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 X-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
    • 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
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material

Definitions

  • the invention relates to a method for producing a high-strength plastic material, the use of such a plastic material for producing a high-strength hollow body, a plastic hollow body made of the material described and fibers, strips, profiles, films, filaments, semi-finished products and composite materials made from this material.
  • the prior art also knows dimensionally resettable objects made of plastic, for example shrink films, shrink tubes or the like.
  • the plastic material is stretched and then cross-linked. Subsequent heating causes shrinkage due to the shape change memory of the plastic material.
  • this process is not prevented by the method according to the invention.
  • the described dimensionally resettable objects are thus designed with regard to their material in such a way that a shape change memory is impressed on them.
  • the mechanical properties, in particular the strength values are again in the order of magnitude of the plastic material originally used (base polymer).
  • the invention has for its object to provide a method for producing a high-strength plastic material which provides high strengths and physical values of the plastic with simple and inexpensive applicability. Furthermore, the task is based on creating a high-strength plastic component.
  • the plastic or plastic material is first stretched with thermal fixation, subsequently this is additionally crosslinked.
  • the plastic material is brought into the desired pre-shape, for example by extrusion. This is followed by stretching the plastic material. As a result, the molecules are oriented so that an oriented structure results. After stretching, the plastic material is fixed and crosslinked, and fixing can take place during crosslinking, before crosslinking or after crosslinking. By fixing which one too annealing, the amorphous parts of the plastic material relax while the crystallites are retained in their orientation. For this purpose, the plastic material is preferably held, clamped or prevented from changing its shape. If this stretched or stretched material is then fixed or tempered, a very uniform lamellar structure of the crystallites is created.
  • the slats are aligned perpendicular to the direction of fixation. Since fixing leads to the fact that restoring forces from the amorphous part are missing after fixing, tempering or relaxing, the plastic product is dimensionally stable even at higher temperatures. There is therefore no shrinking. The higher temperatures described here extend to the fixing temperature.
  • the stretched or stretched material was tempered or fixed without preventing it from changing its shape, the original, disordered structure that was present before stretching or stretching would be restored. This process leads to the shrinkage of the material already described in connection with the prior art.
  • the stretching can take place uniaxially or multi-axially.
  • the degree of stretching and the direction of stretching can be adapted to the respective geometry of the plastic material and the desired physical properties.
  • the plastic material according to the invention can be thread-like, strip-like or foil-like, but there are also many other geometric shapes.
  • the thermal fixation is preferably carried out by heating the plastic material to a temperature below the crystallite melting temperature and above the use temperature of the plastic part.
  • the plastic material is under tension or is mechanically clamped and prevented from changing its shape, so that the stresses introduced by the stretching process are reduced. According to the invention, this is particularly important in order to exclude the shrinking process described above in connection with the prior art.
  • the crosslinking is preferably carried out according to the invention with the introduction of energetic radiation.
  • Networking can take place with or without the addition of a kicker.
  • a kicker can be, for example, DCP (dicumyl peroxide) or TAIC (triallyl isocyanurate).
  • Other crosslinkers (radical formers, catalysts) are also possible.
  • the crosslinking by means of energetic radiation can take place, for example, by means of UV radiation, IR radiation, X-ray radiation or the like.
  • the radiation can be specifically matched to the plastic material, for example a polymer and / or the kicker, in order to activate them accordingly, as is known from photocrosslinking. It is preferred if the polymer itself is not damaged. Such damage is avoided in particular if the kickers are added to the plastics material in a suitable manner.
  • the dosing of the kicker can preferably take place in accordance with the amorphous or crystalline portion of the plastic material and the desired degree of crosslinking. This ensures that the crosslinking process is precisely controlled and that the crystalline areas of the stretched plastic material are not disturbed or destroyed.
  • PE polyethylene
  • thermoplastic blend mixture
  • 3 shows a representation in the subsequently networked state
  • 4 shows a diagram of a material according to the invention showing different parameters during different manufacturing stages
  • Fig. 6 is a diagram, analogous to Fig. 5, for a material according to the prior art, which is used for a shrink article with dimensional recovery.
  • the stretching of partially crystalline polymers creates crystalline zones which have the shape of needle crystals and / or have single-crystal platelets stacked one behind the other. Immediately after the stretching process, tensions due to stretching are still present in the amorphous areas. In the subsequent thermal fixation, these are reduced to such an extent that the finished plastic material remains largely dimensionally stable.
  • a shrinkage of 0% is ideally generated.
  • there may still be a slight shrinkage with regard to the dimensional stability of the plastic material to be achieved according to the invention which is ⁇ 2.5%, in the worst case ⁇ 5%.
  • Such a partially crystalline structure is shown in the simplified representation in FIG. 1. During the crystallization, the kickers are deposited at the phase boundaries.
  • FIG. 3 In the crosslinking of the polymer and / or the kicker shown in FIG. 3 by the initiated chemical reaction, for example by introducing energetic radiation, the amorphous regions in which the kicker has accumulated are crosslinked between and with the crystals. This state is shown in Fig. 3.
  • the networked points are identified by reference number 3. It goes without saying that the representation of FIGS. 1 to 3 only shows the processes very schematically and is only used for general explanation.
  • crosslinking reaction can also take place in the crystalline regions of the plastic material.
  • the plastic material according to the invention can be used, for example, for the production of hollow bodies, in particular tubular hollow bodies.
  • a plastic hollow body of this type is distinguished in particular by high strength properties in comparison to the plastic hollow bodies known from the prior art.
  • the crystalline regions are each illustrated with reference number 1, while the amorphous regions are indicated with reference number 2.
  • the plastic material according to the invention is thus characterized in that the crystallites are crosslinked together with the amorphous regions across the phase boundaries and the plastic material does not have any significant memory and shrinkage (shrinkage) takes on the smallest possible value. This significantly improves the physical properties. There is a significant increase in the overall strength, the temperature resistance increases and the impact strength is significantly increased. These improvements in physical values occur particularly normal (perpendicular) to the direction of stretching.
  • the tendency to splices is also reduced, which otherwise can be very pronounced in the case of highly stretched plastic fibers due to the morphology.
  • FIG. 4 shows a schematic diagram, in which different elasticity modules for a material sample according to the invention are shown in different process steps.
  • different elasticity modules for a material sample according to the invention are shown in different process steps.
  • A sample in the unstretched state
  • B sample in the stretched state
  • C sample in the stretched and crosslinked state.
  • the lh modulus of elasticity was measured on a typical cross-linkable HD-PE (polyethylene) material.
  • the degree of stretching was 400%. It can clearly be seen which significant increase in the modulus of elasticity results from the crosslinking (state C).
  • FIG. 5 shows a temperature module curve for stretching, fixing and crosslinking, the solid line illustrating the respective modulus values, while the dashed line represents the temperature curve.
  • FIG. 5 shows particularly clearly which increase in the modulus of elasticity is experienced by networking (see also FIG. 4). This modulus of elasticity is used up to the application area, i.e. until the plastic material is used.
  • FIG. 6 shows a representation analogous to FIG. 5, the same material having the corresponding parameters being processed in order to produce a shrink article as described in the introduction in connection with the prior art.
  • the same data as for the comparison sample in FIG. 5 were used.
  • the stretching temperature was 80 ° C
  • the activation took place at 120 ° C.
  • the crosslinking dose was 60 kGy. It is particularly clear here that the modulus of elasticity remains constant over the entire processing process, so that there is no increase in the modulus of elasticity or other mechanical values.

Landscapes

  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

L'invention concerne un procédé servant à produire un matériau plastique à haute résistance et comprenant les étapes suivantes: production du matériau plastique, étirage du matériau plastique, fixage du matériau plastique et réticulation du matériau plastique. L'invention concerne également des corps creux en plastique ainsi que des produits en plastique produits selon le procédé de l'invention.
EP04790646A 2003-11-06 2004-10-19 Procede pour produire un materiau plastique a haute resistance et utilisation de ce materiau plastique Withdrawn EP1680269A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10351829 2003-11-06
PCT/EP2004/011831 WO2005046974A1 (fr) 2003-11-06 2004-10-19 Procede pour produire un materiau plastique a haute resistance et utilisation de ce materiau plastique

Publications (1)

Publication Number Publication Date
EP1680269A1 true EP1680269A1 (fr) 2006-07-19

Family

ID=34584905

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04790646A Withdrawn EP1680269A1 (fr) 2003-11-06 2004-10-19 Procede pour produire un materiau plastique a haute resistance et utilisation de ce materiau plastique

Country Status (2)

Country Link
EP (1) EP1680269A1 (fr)
WO (1) WO2005046974A1 (fr)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1308912A (en) * 1969-07-21 1973-03-07 Courtaulds Ltd Crimped polyamide yarn
SE8206483L (sv) * 1982-11-15 1984-05-16 Uponor Ab Sett for orientering av materialet i ror av plast
US4894107A (en) * 1985-05-16 1990-01-16 American National Can Company Process for making multiple layer polymeric films
JPS62148239A (ja) * 1985-12-23 1987-07-02 Matsushita Electric Works Ltd 延伸硬化組成物の製法
JPS6372709A (ja) * 1986-09-12 1988-04-02 Mitsubishi Cable Ind Ltd 水架橋ポリオレフイン成形品及びその製造方法
US5286762A (en) * 1988-07-23 1994-02-15 Idemitsu Kosan Company Limited Styrene-based polymer moldings and process for production thereof
JPH02253924A (ja) * 1989-03-28 1990-10-12 Unitika Ltd 耐熱性フッ素系重合体２軸配向フィルムおよびその製造方法
JPH02301419A (ja) * 1989-05-17 1990-12-13 Unitika Ltd 耐熱性ポリエステル２軸配向フィルム及びその製造方法
JP2003237822A (ja) * 2002-02-15 2003-08-27 Sekisui Jushi Co Ltd 熱可塑性樹脂バンドおよびその製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005046974A1 *

Also Published As

Publication number Publication date
WO2005046974A1 (fr) 2005-05-26

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