CN1243554A - Manufacture of elongate members - Google Patents
Manufacture of elongate members Download PDFInfo
- Publication number
- CN1243554A CN1243554A CN98801838A CN98801838A CN1243554A CN 1243554 A CN1243554 A CN 1243554A CN 98801838 A CN98801838 A CN 98801838A CN 98801838 A CN98801838 A CN 98801838A CN 1243554 A CN1243554 A CN 1243554A
- Authority
- CN
- China
- Prior art keywords
- thing
- polymer
- elongation
- elongation thing
- oxidation
- 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.)
- Granted
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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/08—Chemical 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/18—Monocomponent 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon 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
- D01F9/22—Carbon 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
-
- 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
- C08J2333/00—Characterised 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
- C08J2333/18—Homopolymers or copolymers of nitriles
- C08J2333/20—Homopolymers or copolymers of acrylonitrile
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Toxicology (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Fibers (AREA)
- Artificial Filaments (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
A melt article, e.g. a fibre or film, of fusible acrylonitrile polymer can be 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
TECHNICAL FIELD OF THE INVENTION
The present invention relates to elongation thing, and relate to their oxidation, carbonization and graphitization based on acrylonitrile polymer.
Background technology
Acrylonitrile polymer is well-known, at for example Encyclopaedia of Polymer Science andEngineering, Volume 1 (Wiley-Interscience, 1985) 426 page heads are in the article of " Acrylic Fibers " description to be arranged all for " AcrylonitrilePolymers's " with 334 page heads.Polyacrylonitrile polymer is defined as: the polymer that contains at least 85% (weight) acrylonitrile monemer unit.The modified polypropene nitrile polymer is defined as: the polymer that contains 40-85% (weight) acrylonitrile monemer unit.Many acrylonitrile polymers, comprise most of acrylic fiber polymer, when heating, cannot not be molten, and can only decompose can not fusion.Known processes such as such polymer can adopt that wet method or dry method are extruded become elongation thing, for example fiber.These technologies comprise that the polymer solution that will be dissolved in the suitable solvent is expressed to respectively in coagulating bath or the evaporitic environment.We know that also can under the dry spinning condition plasticizer be extruded, be taken off then to the acrylonitrile polymer of plasticizing makes the elongation thing.We also know some fusible acrylonitrile polymers, and at for example patent US-A-5, describes to some extent in 106,925 and US-A-5,286,828 people such as (two pieces all be) Curatolo.Its content is here introduced for your guidance.Fusible acrylonitrile polymer like this can melt extrude, and forms the elongation thing under the temperature that is lower than their decomposition temperatures.Generally speaking, such polymer can be by wet spinning, also available dry spinning technology extrusion molding.
Carbon fiber is well-known, and at for example Encyclopaedia of Polymer Science and Engineering, Volume 2 (Wiley-Interscience, 1985) 640 page heads are to describe to some extent in the article of " Carbon Fibers ".Carbon fiber is made through the control thermal decomposition by for example fibrous acrylonitrile polymer of organic matter precursor.The thermal decomposition of acrylonitrile polymer generally includes a series of pyrolysis step.The first step can be called stabilization step or oxidation, pre-oxidation or thermal cure step, in air under low relatively temperature usually 200-450 ℃ carry out.Oxidized fibre thermal conversion through 1000-2000 ℃ of temperature in inert atmosphere becomes carbon fiber (carbonization), perhaps can the heating through being higher than 2500 ℃ of temperature carry out graphitization in inert atmosphere.
For making the elongation thing, melt extrusion technology has certain superiority than dry method and wet method extruding technology, shows especially on the relative simplicity of equipment needed thereby.In addition, known melt extrusion technology usually than wet method and the easier production of dry method extruding technology by modification cross section pass the bar of extruding with modification cross section of extrusion molding.Yet the fusible acrylonitrile polymer that melt extrudes is not easy thermal decomposition to form oxidation, carbonization or graphitization product.Such polymer is being lower than meeting fusion under its temperature that oxidation can take place.
Explanation of the present invention
The invention provides the method for making the elongation thing, comprise the steps:
(1) fusible acrylonitrile polymer is melt extruded making the elongation thing, and with it as characterization step.
(2) will extend this polymer in the thing and carry out crosslinkedly, give its not meltability thus.
The elongation thing can adopt film or adopt the form of fiber preferably.
Be used for suitable fusible acrylonitrile polymer of the present invention and their manufacturing, melt extrude method, description is arranged in 106,925 and US-A-5,286,828 at for example patent US-A-5.Fusible acrylonitrile polymer contains the acrylonitrile monemer unit of at least 50% (weight) usually.
Cross-linking step (2) can realize in many ways.For example, the elongation thing of extruding can be exposed in the ionisation radiation crosslinked to cause.Perhaps with causing that the crosslinked chemical reagent of acrylonitrile polymer handles the elongation thing, for example ammonia, hydrazine, primary amine or secondary amine.In addition, fusible acrylonitrile polymer can also contain the monomeric unit of the crosslinkable groups except that nitrile group, for example olefinic or oh group.In this case, the elongation thing that melt extrudes can cause under the condition that crosslinkable groups is reacted, make cross-linking reaction takes place in the bar, make the elongation thing be exposed to ultraviolet radiation when for example containing ethylenic group, or make elongation thing etherificate during hydroxyl group or react with the bifunctional reagent.Be careful before melt extruding and during extruding and avoid over-crosslinked, because this can influence the physical property that melt extrudes the elongation thing unfriendly.Thereby crosslinkable groups should have sufficient heat endurance with undue crosslinked during preventing to melt extrude.In addition, also can make acrylonitrile polymer contain potential crosslinkable groups.For example can contain tert-butyl group vinyl ether monomers unit, be used to provide potential crosslinkable groups.Ether group can melt extrude posthydrolysis generation hydroxy methylene group as crosslinkable groups.
The not fusible polymer of crosslinked mistake is preferably the polymer that does not show any fusion tendency below 300 ℃ about.This just can adopt the common manufacturing technology of acrylonitrile elongation thing (comprising fiber), and the polymer of crosslinked mistake is carried out oxidation, thermal decomposition then.The present invention also provides a kind of method, and the method also comprises step (3): the elongation thing with crosslinked mistake under oxidizing condition carries out thermal decomposition, manufactures the acrylonitrile elongation thing of an oxidation thus.The present invention also provides a kind of method in addition, and the method also is included in the step (4) of under the anoxic condition elongation thing of this oxidation being carried out thermal decomposition except step (3), makes carbonization or graphited elongation thing thus.
Elongation thing by the crosslinked mistake of the fibers form of the inventive method manufacturing is suitable for making carbon fiber, as for example fire proofing and battery separator.
Claims (5)
1. the manufacture method of elongation thing comprises step (1): fusible acrylonitrile polymer is melt extruded to make the elongation thing and as the step (2) of feature: this polymer is carried out crosslinkedly in this elongation thing, give its non-melt thus.
2. the method for claim 1, also comprise step (3): this elongation thing of thermal decomposition behind this crosslinked polymer, thermal decomposition is carried out under the condition of oxidation, makes the elongation thing of oxidation thus.
3. method as claimed in claim 2 also comprises step (4): the elongation thing of this oxidation of thermal decomposition under the condition of anoxybiotic, make carbonization or graphited elongation thing thus.
4. as each described method among the claim 1-3, it is characterized in that extending thing is fiber.
5. will be used for making carbon fiber by the elongation thing that each described method in the claim 1 is made.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9700946A GB2321215A (en) | 1997-01-17 | 1997-01-17 | Cross-linked acrylonitrile precursors for carbon fibres |
| GB9700946.8 | 1997-01-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1243554A true CN1243554A (en) | 2000-02-02 |
| CN1091809C CN1091809C (en) | 2002-10-02 |
Family
ID=10806159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98801838A Expired - Fee Related CN1091809C (en) | 1997-01-17 | 1998-01-15 | Manufacture of elongate members |
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 (1)
| 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 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU3365400A (en) * | 1999-02-22 | 2000-09-14 | Standard Oil Company, The | 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 |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1033141A (en) * | 1962-04-17 | 1966-06-15 | Courtaulds Ltd | Process for modifying synthetic fibres |
| US3414498A (en) * | 1963-04-09 | 1968-12-03 | Toyo Rayon Co Ltd | Cross-linking of polymeric substances with acetylene and ionizing radiation |
| DE1929849C3 (en) * | 1969-06-12 | 1973-10-18 | Sigri Elektrographit Gmbh | Process for the production of carbon or graphite fibers |
| GB1283714A (en) * | 1969-07-09 | 1972-08-02 | Ici Ltd | Process for the production of carbon fibres |
| BE755579A (en) * | 1970-04-07 | 1971-03-01 | Sigri Elektrographit Gmbh | CARBON AND GRAPHITE FIBER MANUFACTURING PROCESS |
| 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 | Production of heat-resistant acrylonitrile yarn |
| 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 |
| US5436275A (en) * | 1993-11-30 | 1995-07-25 | Japan Exlan Company Limited | Porous acrylonitrile polymer fiber |
| 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 |
-
1997
- 1997-01-17 GB GB9700946A patent/GB2321215A/en not_active Withdrawn
-
1998
- 1998-01-15 EP EP98900898A patent/EP0953071A1/en not_active Withdrawn
- 1998-01-15 EA EA199900666A patent/EA001275B1/en not_active IP Right Cessation
- 1998-01-15 JP JP53393998A patent/JP2001508842A/en active Pending
- 1998-01-15 WO PCT/GB1998/000124 patent/WO1998031852A1/en not_active Application Discontinuation
- 1998-01-15 AU AU56708/98A patent/AU5670898A/en not_active Abandoned
- 1998-01-15 CA CA002278484A patent/CA2278484A1/en not_active Abandoned
- 1998-01-15 IL IL13067098A patent/IL130670A0/en unknown
- 1998-01-15 CN CN98801838A patent/CN1091809C/en not_active Expired - Fee Related
- 1998-01-15 KR KR1019997005821A patent/KR20000069731A/en not_active Application Discontinuation
Cited By (1)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0953071A1 (en) | 1999-11-03 |
| GB9700946D0 (en) | 1997-03-05 |
| CN1091809C (en) | 2002-10-02 |
| AU5670898A (en) | 1998-08-07 |
| WO1998031852A1 (en) | 1998-07-23 |
| CA2278484A1 (en) | 1998-07-23 |
| EA001275B1 (en) | 2000-12-25 |
| KR20000069731A (en) | 2000-11-25 |
| GB2321215A (en) | 1998-07-22 |
| IL130670A0 (en) | 2000-06-01 |
| EA199900666A1 (en) | 2000-02-28 |
| JP2001508842A (en) | 2001-07-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: ERCURDYS BRITISH LIMITED Free format text: FORMER OWNER: DENTHAL CO., LTD. Effective date: 20020322 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20020322 Address after: Derby County Applicant after: Ercurdys British Limited Address before: Derby County Applicant before: Searl & Co., Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |