WO1992010351A1 - A method for preparing a conductive plastic product and a mould for performing the method - Google Patents

A method for preparing a conductive plastic product and a mould for performing the method Download PDF

Info

Publication number
WO1992010351A1
WO1992010351A1 PCT/FI1991/000385 FI9100385W WO9210351A1 WO 1992010351 A1 WO1992010351 A1 WO 1992010351A1 FI 9100385 W FI9100385 W FI 9100385W WO 9210351 A1 WO9210351 A1 WO 9210351A1
Authority
WO
WIPO (PCT)
Prior art keywords
mould
polymer
conductor
doping agent
dopable
Prior art date
Application number
PCT/FI1991/000385
Other languages
English (en)
French (fr)
Inventor
Timo Kokkonen
Toivo Kärnä
Jukka Laakso
Esko Savolainen
Original Assignee
Neste Oy
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 Neste Oy filed Critical Neste Oy
Publication of WO1992010351A1 publication Critical patent/WO1992010351A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0013Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fillers dispersed in the moulding material, e.g. metal particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/88Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced
    • B29C70/882Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced partly or totally electrically conductive, e.g. for EMI shielding
    • B29C70/885Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced partly or totally electrically conductive, e.g. for EMI shielding with incorporated metallic wires, nets, films or plates
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124Intrinsically conductive polymers
    • H01B1/127Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2995/00Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0003Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular electrical or magnetic properties, e.g. piezoelectric
    • B29K2995/0005Conductive

Definitions

  • the invention relates to a method for preparing a conductive plastic product, in which method a conductor polymer to be doped or a mixture of such a polymer and a matrix plastic is led in a molten state into a mould.
  • the invention relates to a mould for realizing the method.
  • Conductive polymers may be prepared from organic polymers having long chains of conjugated double bonds.
  • the quantity of the silicon electrodes of double bonds can be affected by adding to the polymer certain doping agents, which either receive or donate electrons. Openings or extra electrons then arise in the polymer chain, which make the passage of electric current along the conjugated chain possible.
  • the conductivity of polymers can be adjusted depending on the doping agent content so that it covers nearly the entire conductivity range from insulators to metals.
  • Such conductive polymers have many interesting applications, e.g. EMI applications and ESD applications.
  • Conductive polymeric and organic conductors are generally speaking insoluble, it is not possible to melt or form them, and in certain cases, they are unstable against oxygen, moisture and high temperatures, due to which also doping at high temperatures has previously not succeeded. Until now, it has therefore not been possible to treat or form conductor polymers thermoplastically in any way. There are descriptions of the meltability of some single conductor polymers, but their conductivity has been very poor. After doping, the polymer is generally insoluble and it can no longer be formed, due to which doping has traditionally been performed subsequently after the forming of the polymer.
  • the doping of polymers thus occurs after the treatment, or after the formation of the product, e.g. with FeClg.
  • Such a method becomes very expens ⁇ ive because of special devices designed for doping, and furthermore, it is unprac ⁇ tical and non-pro-environmental, since toxic volatile gases spread to the environ ⁇ ment.
  • An earlier FI application 901632 by the applicant describes for the first time a method for preparing a conductive polymer product by doping, in which method doping occurs in connection with the treatment of the polymer or even before the treatment.
  • the purpose of the FI application 901632 is to provide a method for doping a conductor polymer, in which method the properties of the conductor polymer can be treated as desired, and which polymer is stable.
  • One of the treatment methods of plastic pieces is press moulding.
  • the leading of the plastic mass into the mould may occur in many different ways, whereof injection moulding or die-casting, as it is also called, is the most usual way.
  • Dimensionally stable, complex and exactly similar products may be prepared by injection moulding.
  • the machine is generally comprised of two main parts, which are an injection unit and a closing unit, which units are mounted on a common stand.
  • a worm screw rotates in the injection unit by the power of an electric or hydraulic motor.
  • the depth of the screw threads is at its highest at the initial end and decreases in the middle section and continues as small to the head of the screw, wherein there is located a check valve.
  • At the rear end of the cylinder casing there is located a feeding hole and on top of it a funnel.
  • the raw material is poured into the f nnel and the rotating screw draws the raw material along with it.
  • the plastic then melts due to the cylinder heating and friction.
  • the screw in the cylinder is in the front position.
  • the screw may move backwards simultaneously as it allows the molten plastic mass to pass.
  • At the front of the screw point there is formed a chamber, wherein the molten plastic turns.
  • At the front end of the chamber or at the cylinder cam there is a hole, which is either open or furnished with a valve.
  • the screw stops and the cam of the injection unit is run into an injection channel hole in the mould. For this purpose, there is an opening in the middle in a fixing plate of the die press.
  • a hydraulic cylinder providing an injection pressure, which by means of a conventional machine amounts to max. 1500-2000 bar.
  • the screw acts as a piston, since it is provided at its point with a check valve (a so-called ring), which prevents the molten mass from flowing back along the threads of the screw.
  • the plastic mass is injected at a very high pressure into the mould.
  • the maximum pressure of the injection unit is in the range of 500 bar.
  • Plastic mass is injected into the mould, and after it has sufficiently solidified, the mould is opened. The machine is then ready for the next cycle.
  • a free opening is arranged under the mould tables, from which opening the product may drop e.g. onto conveyor belt. Most machines are located horizontally for facilitating the removal of the piece.
  • the most economi- cal solution for a mould is a so-called natural mould, in which the division plane follows the circumference of the the largest projection of the press and the press readily in a solidified state slides out of the casing or away from the top of core.
  • the channel may be e.g. conical, and at its most simple, the channel continues as a cone onto the surface of the extruder and combines with it.
  • Special ejection systems are needed for the mould for ejecting the mould piece. A considerable quantity of heat enters the molten mass, which heat has to be conveyed away and cooled.
  • an external device e.g. cooling and tempering devices, since e.g. the temperature of the mould has to be maintained exactly constant and fairly high.
  • the injection mould has to be dimensioned to resist the injection pressure and the closing pressure without changing its form.
  • the maximum pressure provided by the injection unit is 1500-2000 bar, which is seldom needed.
  • the pressure decreases also in the channels and the mould cavities, but the mould has still to resist hundreds of bars. If there is at this place a part of an outward moving mould, it has to be locked mechanically or by means of a hydraulic cylinder, when the mould is closed.
  • the molten thermoplastic penetrates under pressure into gaps of less than 0.1 mm. (Cold-set and rubber penetrate into a still smaller gap.)
  • the mould parts important for the dimensions of the mould piece are generally prepared from tempered steel or hardened. The surfaces are some ⁇ times nitrated or hard-chromium plated, if the surface requirements are high.
  • the surfaces of the mould core have to correspond to the surface requirements of the product.
  • the moulds may have several cores or large mould pieces have several mass inlet points for ensuring a uniform filling. In these cases, the channel has to be divided into several branches.
  • a reference is made to a Finnish brochure "Properties, treatment methods and usage of plastics", Training Centre of Engineering Societies, INSKO, M.Sc.(Eng.) Mikael Boedeker).
  • thermoplasts may be moulded in a mould.
  • Two groups are generally men ⁇ tioned: general or mass plastics and technical plastics.
  • General plastics usually refer to plastics costing FIM 4-6,-/kg, e.g. LDPE (LD polyethylene), HPDE (HP polyethylene), PP (polypropylene), PS (polystyrene), SB (styrene butadiene) and PVC (polyvinyl chloride).
  • LDPE LD polyethylene
  • HPDE HP polyethylene
  • PP polypropylene
  • PS polystyrene
  • SB styrene butadiene
  • PVC polyvinyl chloride
  • the invention relates to a method for preparing conductive plastic products by doping a conductor polymer or a plastic mixture containing a conductor polymer in connection with the treatment of the product, when the treatment occurs by means of press moulding.
  • conductor polymer is also used for a dopable polymer, although it is not yet conductive before the doping.
  • the plastic product from an internally conductive polymer or from a mixture of such a polymer and a matrix plastic.
  • the conduc- tivity of the product may then be accurately adjusted for the application desired either by changing the composition of the polymer mixture or by modifying the doping degree.
  • the object of the invention is to provide a method, in which conductor polymers may be treated by injection moulding by timing the doping in connection with the treatment.
  • the inventive method is mainly characterized in that a doping agent is added to a molten dopable conductor polymer in the mould.
  • the first embodiment of the inventive mould is mainly characterized in that the mould contains pores, through which the doping agent is led into the core of the mould.
  • the second embodiment of the inventive mould is mainly characterized in that the mould contains channels leading into the core of the mould, through which channels the doping agent is led into the core of the mould.
  • An advantage of the invention is that the inventive doping method is extremely easy to realize.
  • An existing standard mould base may be used as the equipment with minor changes.
  • the invention utilizes the perception of the FI application 901632 that the doping can be performed by adding a doping agent to the conductor polymer when it is in a molten state and that the doping can be timed to occur in connection with the treatment.
  • the doping was performed when treating the product e.g. in connection with injection moulding, whereby the doping agent was added to an extruder before it was pressed into the mould.
  • This invention describes a new method for doping a conductor polymer in a molten state.
  • the doping agent can be brought to the conductor polymer or to the molten mixture formed by the conductor polymer and the matrix plastic in a different way, which embodiments are described subsequently in det.ail in connection with the figures.
  • the 7 actual doping occurs in the mould in connection with the treatment and during the shaping of the product and possibly thereafter.
  • the oxidizing and reducing doping agent can be a gas, (e.g. an iodine steam), a liquid (e.g. a liquid sulphonic acid) or a solid matter (e.g. a sulphonic acid having a suitable melting point).
  • a gas e.g. an iodine steam
  • a liquid e.g. a liquid sulphonic acid
  • a solid matter e.g. a sulphonic acid having a suitable melting point
  • the polymer used can be any melt-treatable dopable polymer, such as poly(3- octyl thiophene), and the matrix material can be any treatable polymer.
  • the invention can be utilized for preparing any plastic product having a potential conductivity.
  • Fig. 1 shows an inventive embodiment in connection with an applied injection moulding method, wherein a doping agent is added to a molten conductor polymer mixture to be doped when the mixture is in the mould.
  • Fig. 2 shows an inventive embodiment in connection with an applied injection moulding method, wherein a doping agent is added, via special channels in the mould, to a molten conductor polymer mixture when the mixture is in the mould.
  • a conductor polymer 1 or a mixture 2' of the conductor polymer and a matrix plastic 2 is added to a feeding funnel 6 of an injection-moulding machine 4.
  • the raw-material mixture is then melted by means of a feeding screw 7 and led along a channel 8 into a mould 9.
  • a liquid doping agent 3a and/or gaseos agent 3b is added to the molten conductor polymer mixture 2' to the mould 9, to a mould core 10.
  • the doping agent 3 is led into the mould 9 via a duct 12, and its supply is adjusted by means of a cylinder 13.
  • the raw-material 8 mixture is pressed in the mould core 10.
  • the mould piece is cooled and then removed in a manner known per se.
  • the inventive embodiment according to Fig. 2 otwerwise corresponds to the embodiment of Fig. 1, but the doping agent 3 is added to the molten conductor polymer mixture 2' via channels 11 in the mould 9.
  • the mould may also be formed porous (not shown).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Composite Materials (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
PCT/FI1991/000385 1990-12-14 1991-12-13 A method for preparing a conductive plastic product and a mould for performing the method WO1992010351A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI906167 1990-12-14
FI906167A FI90324C (fi) 1990-12-14 1990-12-14 Menetelmä sähköäjohtavan muovituotteen valmistamiseksi

Publications (1)

Publication Number Publication Date
WO1992010351A1 true WO1992010351A1 (en) 1992-06-25

Family

ID=8531577

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI1991/000385 WO1992010351A1 (en) 1990-12-14 1991-12-13 A method for preparing a conductive plastic product and a mould for performing the method

Country Status (2)

Country Link
FI (1) FI90324C (fi)
WO (1) WO1992010351A1 (fi)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4177238A (en) * 1977-12-14 1979-12-04 Logic Devices, Inc. Fluid cooling of injection molded plastic articles
EP0160911A2 (de) * 1984-05-11 1985-11-13 Hoechst Aktiengesellschaft Polyacetylen-Formmasse, Verfahren zu ihrer Herstellung und ihre Verwendung
EP0168620A2 (de) * 1984-06-15 1986-01-22 Zipperling Kessler & Co (GmbH & Co) Verfahren zur Herstellung von verformbaren Polymerblends aus elektrisch leitfähigen organischen Polymeren sowie Verwendung der Polymerblends
US4623499A (en) * 1983-02-28 1986-11-18 Nihon Sekiso Kogyo Co., Ltd. Method for manufacture of shaped article of organic substance
WO1989001015A1 (en) * 1987-07-29 1989-02-09 Neste Oy Conductive plastic composites
US4818451A (en) * 1986-04-02 1989-04-04 Mitsubishi Yuka Badische Co., Ltd. Method of preparing a foamed molded article and blow-filling gun apparatus for use therein
EP0369442A2 (en) * 1988-11-16 1990-05-23 Aga Aktiebolag Method for regulation of the process conditions in a moulding tool
WO1991015859A1 (en) * 1990-03-30 1991-10-17 Neste Oy A method for preparing a conductive polymer

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4177238A (en) * 1977-12-14 1979-12-04 Logic Devices, Inc. Fluid cooling of injection molded plastic articles
US4623499A (en) * 1983-02-28 1986-11-18 Nihon Sekiso Kogyo Co., Ltd. Method for manufacture of shaped article of organic substance
EP0160911A2 (de) * 1984-05-11 1985-11-13 Hoechst Aktiengesellschaft Polyacetylen-Formmasse, Verfahren zu ihrer Herstellung und ihre Verwendung
EP0168620A2 (de) * 1984-06-15 1986-01-22 Zipperling Kessler & Co (GmbH & Co) Verfahren zur Herstellung von verformbaren Polymerblends aus elektrisch leitfähigen organischen Polymeren sowie Verwendung der Polymerblends
US4818451A (en) * 1986-04-02 1989-04-04 Mitsubishi Yuka Badische Co., Ltd. Method of preparing a foamed molded article and blow-filling gun apparatus for use therein
WO1989001015A1 (en) * 1987-07-29 1989-02-09 Neste Oy Conductive plastic composites
EP0369442A2 (en) * 1988-11-16 1990-05-23 Aga Aktiebolag Method for regulation of the process conditions in a moulding tool
WO1991015859A1 (en) * 1990-03-30 1991-10-17 Neste Oy A method for preparing a conductive polymer

Also Published As

Publication number Publication date
FI906167A0 (fi) 1990-12-14
FI90324C (fi) 1994-01-25
FI90324B (fi) 1993-10-15
FI906167A (fi) 1992-06-15

Similar Documents

Publication Publication Date Title
BR9916087B1 (pt) composiÇço para moldagem rotativa, processo para a produÇço de uma composiÇço de micropelotas para moldagem rotativa, e, processo para a preparaÇço de um produto moldado.
EP1018519A3 (en) Method of molding edible starch
US2469342A (en) Method and apparatus for molding plastics
GB1234639A (fi)
WO1992010352A1 (en) A method for preparing a conductive plastic product
RU2004133969A (ru) Устройство для прямого формования пластмассовых изделий
EP0783948A3 (en) Sequentially injected multi-component shuttle-stack injection molding
GB1218147A (en) Segment copolymers of 1,3-dienes and aromatic vinyl compounds
MXPA03002246A (es) Dispositivo de mezcla y procedimiento para la obtencion de compuestos de moldeo termoplasticamente transformables, especialmente cargas aditivadas.
WO1992010351A1 (en) A method for preparing a conductive plastic product and a mould for performing the method
JPH08112825A (ja) 医療製品およびその製法
EP1295903A3 (en) Polymeric material, molded product and methods for their production
US7862762B2 (en) Moulding of mouldable materials
US3536787A (en) Process for devolatilizing polymers
US3765816A (en) Apparatus for molding plastic
US3962387A (en) Method of injection molding a foamable thermoplastic material
TWI750771B (zh) 再生塑膠射出成型系統之射出機
CA2517366A1 (en) Method of removing molded natural resins from molds utilizing lifter bars
CA2285772A1 (en) Apparatus for the preparation of preforms in manufacturing plants for the production of bottles and containers or products of various kind
NL8501268A (nl) Werkwijze en inrichting voor het met koud spuitkanaal transfer-vormen.
SU1577999A1 (ru) Литьева форма дл изготовлени полимерных изделий
JPH05500533A (ja) 導電性ポリマーの調製方法
CN218985519U (zh) 一种注塑机辅助上料装置
KR20030012442A (ko) 사출 성형장치
SU1703478A1 (ru) Литьева форма дл изготовлени полимерных изделий

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU MC NL SE

122 Ep: pct application non-entry in european phase