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GB2321215A - Cross-linked acrylonitrile precursors for carbon fibres - Google Patents

Cross-linked acrylonitrile precursors for carbon fibres Download PDF

Info

Publication number
GB2321215A
GB2321215A GB9700946A GB9700946A GB2321215A GB 2321215 A GB2321215 A GB 2321215A GB 9700946 A GB9700946 A GB 9700946A GB 9700946 A GB9700946 A GB 9700946A GB 2321215 A GB2321215 A GB 2321215A
Authority
GB
United Kingdom
Prior art keywords
cross
elongate member
acrylonitrile
polymer
melt
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Withdrawn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
GB9700946A
Other versions
GB9700946D0 (en
Inventor
David Mac Service
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.)
Courtaulds Fibres Holdings Ltd
Original Assignee
Courtaulds Fibres Holdings Ltd
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 Courtaulds Fibres Holdings Ltd filed Critical Courtaulds Fibres Holdings Ltd
Priority to GB9700946A priority Critical patent/GB2321215A/en
Publication of GB9700946D0 publication Critical patent/GB9700946D0/en
Priority to CA002278484A priority patent/CA2278484A1/en
Priority to EA199900666A priority patent/EA001275B1/en
Priority to EP98900898A priority patent/EP0953071A1/en
Priority to CN98801838A priority patent/CN1091809C/en
Priority to AU56708/98A priority patent/AU5670898A/en
Priority to KR1019997005821A priority patent/KR20000069731A/en
Priority to IL13067098A priority patent/IL130670A0/en
Priority to PCT/GB1998/000124 priority patent/WO1998031852A1/en
Priority to JP53393998A priority patent/JP2001508842A/en
Publication of GB2321215A publication Critical patent/GB2321215A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • D01F11/08Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/18Homopolymers or copolymers of nitriles
    • C08J2333/20Homopolymers or copolymers of acrylonitrile

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Toxicology (AREA)
  • Inorganic Fibers (AREA)
  • Artificial Filaments (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

A melt-extruded article, e.g. a fibre or film, a fusible acrylonitrile polymer is cross-linked to render it infusible. The thusly cross-linked article can be oxidised and subsequently carbonised or graphitised in similar manner to articles made by wet- or dry-extrusion of infusible acrylonitrile polymers.

Description

MANUFACTURE OF ELONGATE MEMBERS This invention relates to the manufacture of elongate members based on acrylonitrile polymers and to their oxidation, carbonisation and graphitisation.
Acrylonitrile polymers are well-known and are described for example in articles in Encyclopaedia of Polymer Science and Engineering, Volume 1 (Wiley-Interscience, 1985) entitled "Acrylonitrile Polymers", at page 426, and "Acrylic Fibers", at page 334. Acrylic polymers are defined as polymers which contain at least 85% by weight acrylonitrile monomer units. Modacrylic polymers are defined as polymers which contain 40 to 85% by weight acrylonitrile monomer units. Many acrylonitrile polymers, including a large proportion of acrylic polymers, are infusible and decompose without melting when they are heated. Processes are known by which such polymers can be processed into elongate members, for example fibres, using wet- or dry-extrusion techniques.
These involve the extrusion of a solution of the polymer in a suitable solvent into a coagulating bath or an evaporative atmosphere, respectively. Processes are also known whereby elongate members can be manufactured by extrusion of a plasticised acrylonitrile polymer under dry-spinning conditions, followed by removal of the plasticiser. Fusible acrylonitrile polymers are also known and are described for example in US-A-5,106,925 and US-A-5,286,828 (both Curatolo et al.), the contents of which are incorporated herein by way of reference. Such fusible acrylonitrile polymers can be melt-extruded to form an elongate member at temperatures below the temperature at which they decompose. In general, such polymers may alternatively be extruded by wet- and dry-spinning techniques.
Carbon fibres are well-known and are described for example in an article in Encyclopaedia of Polymer Science and Engineering, Volume 2 (Wiley-Interscience, 1S85) entitled "Carbon Fibers", at page 640. Carbon fibres are made by controlled pyrolysis of an organic precursor, for example an acrylonitrile polymer, in fibrous form. Pyrolysis of acrylonitrile polymers typically involves a number of pyrolysis steps. The first step, which may be called the stabilisation step or the oxidation, pre-oxidation or thermosetting step, is carried out at relatively low temperatures, typically in the range 200-450 C, usually in air. The oxidised fibre may then be converted to carbon fibre (carbonised) by heating in an inert atmosphere at 1000-2000'C, or it may be graphitised by heating in an inert atmosphere at temperatures in excess of 2500 C.
Melt-extrusion techniques have certain advantages over dry- and wet-extrusion techniques for the manufacture of elongate members, notably in the relative simplicity of the apparatus required. Furthermore, it is known that melt-extrusion often lends itself more readily to the production of extruded members of modified cross-section by extrusion though a die of modified cross-section than do wet- and dry-extrusion techniques. However, it will readily be appreciated that melt-extruded fusible acrylonitrile polymers cannot readily be pyrolysed to form oxidised, carbonised or graphitised articles. Such polymers melt below the temperature at which they can be oxidised.
The present invention provides a method for manufacturing an elongate member comprising the steps of (1) melt-extruding a fusible acrylonitrile polymer to produce an elongate member, and as characterising step (2) cross-linking said polymer in said elongate member, thereby rendering it infusible.
The elongate member may take the form of a film or preferably a fibre.
Suitable fusible acrylonitrile polymers for use in the invention and methods for their manufacture and melt-extrusion are described for example in US-A-5,106,925 and US-A-5,286,828. The fusible acrylonitrile polymer generally contains at least 50 percent by weight acrylonitrile monomer units.
The cross-linking step (2) may be effected in a variety of ways. For example, the extruded elongate member may be exposed to ionising radiation so as to induce cross-linking.
Alternatively, the elongate member may be treated with a chemical reagent which serves to induce cross-linking in acrylonitrile polymers, for example ammonia, hydrazine or a primary or secondary amine. Further alternatively, the fusible acrylonitrile polymer may comprise monomer units which possess a cross-linkable group other than the nitrile group, for example olefinic or hydroxyl groups.
Cross-linking may in such cases be induced in the melt-extruded elongate member by subjecting it to conditions which cause reaction of the cross-linkable group, for example in the case of an olefinic group exposure to W radiation or in the case of a hydroxyl group etherification or reaction with a bifunctional reagent. Care should be taken to avoid excessive cross-linking before and during the melt-extrusion step, because this may adversely affect the physical properties of the melt-extruded member. The cross-linkable group should accordingly possess sufficient thermal stability to resist excessive cross-linking during melt-extrusion. Further alternatively, the acrylonitrile polymer may comprise latent cross-linkable groups. For example, it may comprise t-butyl vinyl ether monomer units serving to provide latent cross-linkable groups, whereby the ether groups can be hydrolysed after melt-extrusion to yield hydroxymethylene groups as cross-linkable groups.
The cross-linked infusible polymer is preferably one which does not show any tendency to melt below about 300 C.
This permits the cross-linked polymer to be oxidised and subsequently pyrolysed using techniques generally known for acrylonitrile elongate members, including fibres. The invention further provides a method which further includes the step of (3) pyrolysing the cross-linked elongate member under oxidising conditions, thereby producing an oxidised acrylonitrile elongate member. The invention yet further provides a method which in addition to step (3) further includes the step of (4) pyrolysing said oxidised elongate member under anaerobic conditions, thereby producing a carbonised or a graphitised elongate member.
Cross-linked elongate members produced by the method of the invention in the form of fibres are suited to the manufacture of carbon fibres, for example for use in fire-retardant materials and in battery separators.

Claims (3)

1. A method for manufacturing an elongate member comprising the steps of (1) melt-extruding a fusible acrylonitrile polymer to produce an elongate member, and as characterising step (2) cross-linking said polymer in said elongate member, thereby rendering it infusible.
2. The method according to claim 1, further including the step (3) of pyrolysing said elongate member after crosslinking said polymer, said pyrolysing being carried out under oxidising conditions, thereby producing an oxidised elongate member.
3. The method according to claim 2, further including the step of (4) pyrolysing said oxidised elongate member under anaerobic conditions, thereby producing a carbonised or graphitised elongate member.
GB9700946A 1997-01-17 1997-01-17 Cross-linked acrylonitrile precursors for carbon fibres Withdrawn GB2321215A (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
GB9700946A GB2321215A (en) 1997-01-17 1997-01-17 Cross-linked acrylonitrile precursors for carbon fibres
JP53393998A JP2001508842A (en) 1997-01-17 1998-01-15 Manufacturing method of extension member
CN98801838A CN1091809C (en) 1997-01-17 1998-01-15 Manufacture of extensions
EA199900666A EA001275B1 (en) 1997-01-17 1998-01-15 Manufacture of elongate members
EP98900898A EP0953071A1 (en) 1997-01-17 1998-01-15 Manufacture of elongate members
CA002278484A CA2278484A1 (en) 1997-01-17 1998-01-15 Manufacture of elongate members
AU56708/98A AU5670898A (en) 1997-01-17 1998-01-15 Manufacture of elongate members
KR1019997005821A KR20000069731A (en) 1997-01-17 1998-01-15 Manufacture of elongate members
IL13067098A IL130670A0 (en) 1997-01-17 1998-01-15 Manufacture of elongate members
PCT/GB1998/000124 WO1998031852A1 (en) 1997-01-17 1998-01-15 Manufacture of elongate members

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB9700946A GB2321215A (en) 1997-01-17 1997-01-17 Cross-linked acrylonitrile precursors for carbon fibres

Publications (2)

Publication Number Publication Date
GB9700946D0 GB9700946D0 (en) 1997-03-05
GB2321215A true GB2321215A (en) 1998-07-22

Family

ID=10806159

Family Applications (1)

Application Number Title Priority Date Filing Date
GB9700946A Withdrawn GB2321215A (en) 1997-01-17 1997-01-17 Cross-linked acrylonitrile precursors for carbon fibres

Country Status (10)

Country Link
EP (1) EP0953071A1 (en)
JP (1) JP2001508842A (en)
KR (1) KR20000069731A (en)
CN (1) CN1091809C (en)
AU (1) AU5670898A (en)
CA (1) CA2278484A1 (en)
EA (1) EA001275B1 (en)
GB (1) GB2321215A (en)
IL (1) IL130670A0 (en)
WO (1) WO1998031852A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000050675A1 (en) * 1999-02-22 2000-08-31 The Standard Oil Company Carbon fibers or sheets made from copolymers of acrylonitrile
US6630555B2 (en) 2001-11-06 2003-10-07 Lord Corporation Internally blocked organoborate initiators and adhesives therefrom

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101798392B (en) * 2009-12-11 2012-01-04 中国科学院上海应用物理研究所 Method for modifying polyacrylonitrile by using gamma ray irradiation

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1033141A (en) * 1962-04-17 1966-06-15 Courtaulds Ltd Process for modifying synthetic fibres
GB1054137A (en) * 1963-04-09 1967-01-04 Toyo Rayon Co Ltd Process for cross linking polymers
GB1260449A (en) * 1969-06-12 1972-01-19 Sigri Elektrographit Gmbh Improvements in or relating to the production of carbonfibres
GB1264763A (en) * 1970-04-07 1972-02-23 Sigri Elektrographit Gmbh Improvements in or relating to the production of carbon fibres
GB2285009A (en) * 1993-11-30 1995-06-28 Japan Exlan Co Ltd Porous acrylonitrile fibres

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1283714A (en) * 1969-07-09 1972-08-02 Ici Ltd Process for the production of carbon fibres
US3917776A (en) * 1970-12-12 1975-11-04 Mitsubishi Rayon Co Process for producing carbon fiber
GB1580529A (en) * 1975-10-24 1980-12-03 Nat Res Dev Polymers useful for producing carbon fibres
US4473372A (en) * 1983-05-12 1984-09-25 Celanese Corporation Process for the stabilization of acrylic fibers
JPS62149918A (en) * 1985-12-25 1987-07-03 Mitsubishi Rayon Co Ltd Manufacturing method of heat-resistant acrylonitrile fiber
US4921656A (en) * 1988-08-25 1990-05-01 Basf Aktiengesellschaft Formation of melt-spun acrylic fibers which are particularly suited for thermal conversion to high strength carbon fibers
US5509986A (en) * 1994-08-22 1996-04-23 The Dow Chemical Company Process for preparing an ignition resistant carbonaceous material comprising a melt blowing or spunbonding step, a radiation step and a carbonizing step

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1033141A (en) * 1962-04-17 1966-06-15 Courtaulds Ltd Process for modifying synthetic fibres
GB1054137A (en) * 1963-04-09 1967-01-04 Toyo Rayon Co Ltd Process for cross linking polymers
GB1260449A (en) * 1969-06-12 1972-01-19 Sigri Elektrographit Gmbh Improvements in or relating to the production of carbonfibres
GB1264763A (en) * 1970-04-07 1972-02-23 Sigri Elektrographit Gmbh Improvements in or relating to the production of carbon fibres
GB2285009A (en) * 1993-11-30 1995-06-28 Japan Exlan Co Ltd Porous acrylonitrile fibres

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000050675A1 (en) * 1999-02-22 2000-08-31 The Standard Oil Company Carbon fibers or sheets made from copolymers of acrylonitrile
US6630555B2 (en) 2001-11-06 2003-10-07 Lord Corporation Internally blocked organoborate initiators and adhesives therefrom
US6841635B2 (en) 2001-11-06 2005-01-11 Lord Corporation Internally blocked organoborate initiators and adhesives therefrom

Also Published As

Publication number Publication date
EA199900666A1 (en) 2000-02-28
CA2278484A1 (en) 1998-07-23
CN1091809C (en) 2002-10-02
AU5670898A (en) 1998-08-07
CN1243554A (en) 2000-02-02
IL130670A0 (en) 2000-06-01
EA001275B1 (en) 2000-12-25
WO1998031852A1 (en) 1998-07-23
GB9700946D0 (en) 1997-03-05
KR20000069731A (en) 2000-11-25
JP2001508842A (en) 2001-07-03
EP0953071A1 (en) 1999-11-03

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Legal Events

Date Code Title Description
WAP Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1)