EP0372622A2 - Acrylvorläufer für Kohlenstoffasern und Verfahren zur Herstellung derselben - Google Patents

Acrylvorläufer für Kohlenstoffasern und Verfahren zur Herstellung derselben Download PDF

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Publication number
EP0372622A2
EP0372622A2 EP89203017A EP89203017A EP0372622A2 EP 0372622 A2 EP0372622 A2 EP 0372622A2 EP 89203017 A EP89203017 A EP 89203017A EP 89203017 A EP89203017 A EP 89203017A EP 0372622 A2 EP0372622 A2 EP 0372622A2
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EP
European Patent Office
Prior art keywords
acrylic
temperature
stretching
spinneret
solvent
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
Application number
EP89203017A
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English (en)
French (fr)
Other versions
EP0372622A3 (de
EP0372622B1 (de
Inventor
Franco Tasselli
Franco Cognigni
Renato Di Bonito
Armando Mariano
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ENICHEM FIBRE SpA
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ENICHEM FIBRE SpA
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Application filed by ENICHEM FIBRE SpA filed Critical ENICHEM FIBRE SpA
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Publication of EP0372622A3 publication Critical patent/EP0372622A3/de
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    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent

Definitions

  • This invention relates to a wet spinning process for acrylonitrile copolymers in a polar solvent solution, in particular dimethylacetamide, for producing an acrylic yarn of high mechanical characteristics suitable for conversion into carbon fibres (C. F.)
  • acrylic yarns suitable for conversion into carbon fibres are known and widely described in the patent and scientific literature.
  • Such yarns are generally known as "acrylic precursors for carbon fibres" because of their specific use.
  • the methods mostly used for producing acrylic precursors are mainly the wet spinning of solutions of suitable acrylic polymers in organic or inorganic solvents.
  • the organic solvents mostly used include polar compounds of high solvent power towards acrylic polymers, such as dimethylformamide, dimethylacetamide, dimethyl sulphoxide, ethylene carbonate etc.
  • Widely used inorganic solvents include aqueous sodium thiocyanate solutions, aqueous zinc chloride solutions and concentrated aqueous nitric acid solutions.
  • This consists of maintaining the spinneret not in immediate contact with the coagulating bath, so that the dope leaving the spinneret has to pass a few millimetres through the air before being immersed in the bath. This process enables a high spinneret stretch to be obtained.
  • the polymers most widely used for forming the solutions used in those spinning processes of the known art for the preparation of carbon fibre acrylic precursors are those which contain one or more monomer units of the following list: methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, itaconic acid etc., copolymerized with the acrylonitrile.
  • acrylic precursors are generally obtained having a maximum tenacity of 50-55 cN/tex and generally containing defects, this having a certain importance with regard to the characteristics of the carbon fibres deriving from them.
  • the defects depend on the type of spinning process used.
  • metal residues such as sodium and zinc
  • the metal residues contained in the acrylic precursor prejudice the proper progress of the acrylic fibre carbonization stage and lessen the oxidation resistance of the carbon fibre obtained thereby.
  • the maximum tenacity attainable in fibres produced by spinning processes in inorganic solvents is 50-55 cN/tex even when air stretching at the exit from the spinneret is used as described in the aforesaid USA patents plus extra stretching after the fibre consolidation as stated.
  • the spinning processes for acrylic polymer solutions in organic solvents generally produce acrylic precursors in which the structural characteristic are generally worse that for the same precursors obtained from solutions in an inorganic solvent because of the presence of possibly large cavities (macrovoids).
  • these latter generally have an irregular cross-section in the shape of a bean or kidney instead of a circular cross-­section which would provide better mechanical properties for the fibre, and would therefore allow more uniform progress of the oxidation process which precedes the carbonization stage in the production of carbon fibres.
  • the acrylic precursor of the present invention is further characterised by a compact fibre structure free of flaws, a regular filament count, a constant count of the various filaments and good separation between them.
  • the present invention also relates to the acrylic fibres produced by the method and the carbon fibres deriving from them by oxidation and subsequent carbonization, in accordance with the well known processes of the state of the art.
  • the spinning process is of the wet type comprising the use of solutions of an acrylic polymer of the type described hereinafter in a suitable polar solvent.
  • the acrylic polymer solutions are carefully purified of any impurities which may be present by filtration through two or three napped cotton cloths or metal meshes having mesh apertures of 5-10 microns, and are then fed to the spinning section.
  • Spinning is carried out by spinnerets containing between 3000 and 40000 orifices, with a capillary diameter variable between 120 and 180 microns, and immersed in the coagulating bath.
  • the process is characterised essentially by the coagulation stage, which is conducted under such bath temperature, time and composition conditions as to obtain at the end of the process an acrylic yarn having the aforesaid characteristics and tenacity values which have never been encountered in acrylic fibres forming part of the known art.
  • the yarns leaving the spinneret are passed into a coagulating bath maintained at a temperature of between 15 and 35°C and consisting of a binary solvent-non solvent mixture in which the solvent is that of the acrylic polymer solution and the non-solvent is water.
  • the binary solvent-non solvent mixture has a rigorously controlled composition with a solvent content of between 78 and 82% by weight, and preferably a solvent content which is a fixed value within this range and strays from this value by not more than ⁇ 0.5%.
  • the stretch in the spinneret during coagulation is 1.5-5 times the solution extrusion rate through the spinneret orifices.
  • the yarn passes about a roller rotating at a peripheral speed of 4-10 m/minute and is stretched in air by passage about a second roller rotating at a peripheral speed of between 1.5 and 3.5 times that of the preceding roller.
  • the yarn is then washed in countercurrent with demineralized water at a temperature of between 20°C and 50°C and is again stretched in a water bath maintained at a temperature of between 95 and 99°C.
  • the subsequent stages in the wet spinning process according to the present invention comprise lubrication, consisting of passing the yarn through a bath containing a lubricant and an antistatic agent, drying by passage over rollers heated to a temperature of between 120 and 150°C and preferably between 130 and 140°C, and further stretching to the extent of 1.2-1.5 times and thermal stabilization by contact with hot rollers or heating elements heated to 140-180°C.
  • the yarn collection rate on the bobbins is between 50 and 80 m/minute.
  • the fibres obtained by the spinning process according to the present invention have perfectly round cross-sections and an extremely compact structure free of flaws.
  • acrylic polymers which are most widely used in preparing polymer solutions for feeding to the spinnerets are acrylonitrile copolymers (ACN) with one or more acrylic monomers such as acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, acrylates and methacrylates in general, itaconic acid and other ethylenically unsaturated monomers able to copolymerize with acrylonitrile.
  • ACN acrylonitrile copolymers
  • the preferred copolymers are those of high acrylonitrile content (acrylonitrile content exceeding 90%).
  • copolymers are those of high ACN content containing some percentage (1-10 % by weight) of monomers containing the carboxyl function, such as acrylic acid, methacrylic acid, itaconic acid etc.
  • the most suitable polymers include acrylonitrile-acrylic acid copolymers containing 94-98% of acrylonitrile, and acrylonitrile-­methylacrylate-acrylic acid terpolymers containing from 94-97% of acrylonitrile, 1-3% of acrylic acid and 1-5% of methylacrylate.
  • copolymers are prepared by the usual radical polymerization methods well known to the expert of the art.
  • the acrylic solutions of the said copolymers are formed by dissolving them in a polar solvent of high solvent power.
  • polar solvent of high solvent power Those particularly preferred are dimethylformamide, dimethylacetamide and dimethylsulphoxide.
  • the polymer concentration in the spinning solution is a function of its molecular weight.
  • the specific application of the "acrylic precursors" produced by the method according to the present invention is the production of carbon fibres by carbonization methods well known in the state of the art.
  • acrylic precursors produced by the method of the present invention enables carbon fibres having excellent mechanical characteristics to be obtained, while using thermal oxidation temperatures for the acrylic fibres (this being a well known stage in the carbonization process) which are relatively low and for shorter times.
  • an acrylic precursor consisting of an acrylonitrile (ACN) - methylacrylate (MA) - acrylic acid (AA) terpolymer containing 94% of ACN, 2% of AA and 4% of MA, processed in a carbon fibre production plant by way of a first oxidation stage in air at a temperature of 220-240°C and two carbonization stages in an inert environment (nitrogen) with a maximum temperature of 1500°C, resulted in carbon fibres with the following characteristics: Tenacity ⁇ 3.5 GPa Modulus 220-270 Pa Elongation 1-1.7% Density 1.75-1.78 Carbon percentage 95-96%
  • the feed rates were such as to satisfy the following ratios: Monomer composition: 94.5% ACN, 3.5% MA, 2% AA; Catalysts: 0.6% of sodium hydroxylamine sulphonate and 1.5% of sodium bisulphite on the monomers; Aqueous H2SO4 solution such as to maintain the reaction pH at 2.5; Ratio H2O/monomers: 5.5/1; Total reaction time 9 hours; Reaction temperature 55°C; Conversion 92%; MD 1800.
  • the polymer obtained in the form of a slurry, was filtered through a rotary filter, washed with deionized water until the salts (catalyst residues) had completely disappeared, and dried in a fluidized bed drier.
  • the polymer was dispersed in DMAc at -7°C; the polymer slurry was then transformed into a solution by heating in a plate heat exchanger at 88°C.
  • the polymer solution obtained containing 23% of solids, was carefully filtered in a filter press through suitable filter cloths consisting of cotton linters (1st stage), 20 micron aperture metal cloth (2nd stage), and 10 micron aperture metal cloth (3rd stage).
  • the polymer solution from the filtration stage was then spun in a wet spinning plant under the following spinning conditions: - Temperature of polymer solution at spinneret inlet 50°C. - Circular spinneret 80 mm diameter with 6000 orifices of 150 microns in diameter. - Coagulating bath consisting of an aqueous 80% solution of dimethylacetamide maintained at 24°C. - Collection rate after coagulation 5 metres/minute. - Stretch in spinneret 2.4 - Stretch in air through two pairs of rollers, stretching 2.5 times. - Countercurrent washing in 4 stages with deionized water at 45-­50°C. - Stretch in water at 98°C, stretching 4 times.
  • the characteristics of the obtained fibre were as follows: Overall count 7,200 dtex Filament count 1.2 dtex Tenacity 70 cN/tex Elongation 13% H2O regain 100°C 10% Finish percentage 0.3% Sodium 100 ppm Filament cross-section circular Voids after coagulation 0 Flaws in finished fibre 0 (see photographs, enclosures 1 and 2: cross-sections through final fibre).
  • Example 1 The polymer solution of Example 1 was spun under the following spinning conditions: - Spinneret 6000 orifices, orifice diameter 52 microns. - Coagulating bath: aqueous 50% solution of dimethylacetamide maintained at 45°C. - Collection rate after coagulation 7 metres/minute. - Stretch in spinneret 0.67 - Stretch in air, not possible. - Countercurrent washing as in Example 1. - Stretch in water at 98°C, 7 times (the maximum possible). - Lubrication, drying, extra stretching and collection as in Example 1.
  • the fibre characteristics were as follows: Overall count 7,200 dtex Filament count 1.2 dtex Tenacity 55 cN/tex Elongation 14% H2O regain 100°C 11% Finish percentage 0.3% Sodium 110 ppm Filament cross-section kidney shaped Voids after coagulation, number/mm 10-30 Flaws in finished fibre, number/mm 5-10 (see photographs, enclosures 3 and 4: cross-sections through final fibre).
  • the fibres produced in Examples 1 and 2 are both converted into carbon fibres in an industrial plant operating under the following conditions: Feed 200 bobbins Oxidation in two furnaces operating in 4 stages, ie 220, 230, 235, 240°C Stretch under oxidation 5% 1st carbonization stage in N2 at 900°C 2nd carbonization stage in N2 at 1400°C Surface treatment by electrolysis with an ammonium bicarbonate solution. Lubrication by aqueous epoxy resin dispersion Drying at 150°C.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Fibers (AREA)
  • Artificial Filaments (AREA)
EP89203017A 1988-12-02 1989-11-28 Acrylvorläufer für Kohlenstoffasern und Verfahren zur Herstellung derselben Revoked EP0372622B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT2283688 1988-12-02
IT8822836A IT1227677B (it) 1988-12-02 1988-12-02 Precursore acrilico per fibre di carbonio e procedimento per ottenerlo

Publications (3)

Publication Number Publication Date
EP0372622A2 true EP0372622A2 (de) 1990-06-13
EP0372622A3 EP0372622A3 (de) 1991-04-10
EP0372622B1 EP0372622B1 (de) 1995-04-12

Family

ID=11201004

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89203017A Revoked EP0372622B1 (de) 1988-12-02 1989-11-28 Acrylvorläufer für Kohlenstoffasern und Verfahren zur Herstellung derselben

Country Status (7)

Country Link
EP (1) EP0372622B1 (de)
KR (1) KR920007111B1 (de)
AT (1) ATE121146T1 (de)
DE (1) DE68922190T2 (de)
ES (1) ES2070897T3 (de)
IL (1) IL92521A (de)
IT (1) IT1227677B (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005052223A2 (fr) * 2003-11-27 2005-06-09 Moskovsky Gosudarstvenny Universitet Imeni M.V. Lomonosova Procede de fabrication de fibre
IT202100029576A1 (it) 2021-11-23 2023-05-23 Montefibre Mae Tech S R L Processo di produzione di fibre acriliche ad alta velocità e relativo apparato

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101148428B1 (ko) * 2009-12-31 2012-05-23 주식회사 효성 탄소섬유용 폴리아크릴로니트릴계 전구체 섬유의 제조방법
KR101239424B1 (ko) * 2010-12-30 2013-03-06 주식회사 효성 탄소섬유 전구체의 제조방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5239455B2 (de) * 1973-07-23 1977-10-05
EP0044534A2 (de) * 1980-07-23 1982-01-27 Hoechst Aktiengesellschaft Hochmodul-Polyacrylnitrilfäden und -fasern sowie Verfahren zu ihrer Herstellung
US4349523A (en) * 1977-04-05 1982-09-14 Toray Industries, Inc. Process for producing carbon fiber of improved oxidation resistance
EP0223199A2 (de) * 1985-11-18 1987-05-27 Toray Industries, Inc. Verfahren zur Herstellung von Kohlenstoffasern mit hoher Festigkeit und hohem Elastizitätsmodul
EP0255109A2 (de) * 1986-07-28 1988-02-03 Mitsubishi Rayon Co., Ltd. Verfahren zur Herstellung von Acrylfasern mit hohen Fasereigenschaften

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5239455B2 (de) * 1973-07-23 1977-10-05
US4349523A (en) * 1977-04-05 1982-09-14 Toray Industries, Inc. Process for producing carbon fiber of improved oxidation resistance
EP0044534A2 (de) * 1980-07-23 1982-01-27 Hoechst Aktiengesellschaft Hochmodul-Polyacrylnitrilfäden und -fasern sowie Verfahren zu ihrer Herstellung
EP0223199A2 (de) * 1985-11-18 1987-05-27 Toray Industries, Inc. Verfahren zur Herstellung von Kohlenstoffasern mit hoher Festigkeit und hohem Elastizitätsmodul
EP0255109A2 (de) * 1986-07-28 1988-02-03 Mitsubishi Rayon Co., Ltd. Verfahren zur Herstellung von Acrylfasern mit hohen Fasereigenschaften

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005052223A2 (fr) * 2003-11-27 2005-06-09 Moskovsky Gosudarstvenny Universitet Imeni M.V. Lomonosova Procede de fabrication de fibre
WO2005052223A3 (fr) * 2003-11-27 2005-07-21 Univ Moskovsk Procede de fabrication de fibre
IT202100029576A1 (it) 2021-11-23 2023-05-23 Montefibre Mae Tech S R L Processo di produzione di fibre acriliche ad alta velocità e relativo apparato
EP4187002A1 (de) 2021-11-23 2023-05-31 Montefibre Mae Technologies S.R.L. Hochgeschwindigkeitsverfahren zur herstellung von acrylfasern und entsprechende vorrichtung

Also Published As

Publication number Publication date
EP0372622A3 (de) 1991-04-10
DE68922190T2 (de) 1995-09-07
IT8822836A0 (it) 1988-12-02
IL92521A (en) 1992-08-18
EP0372622B1 (de) 1995-04-12
ES2070897T3 (es) 1995-06-16
DE68922190D1 (de) 1995-05-18
KR900010088A (ko) 1990-07-06
IL92521A0 (en) 1990-08-31
IT1227677B (it) 1991-04-23
KR920007111B1 (ko) 1992-08-24
ATE121146T1 (de) 1995-04-15

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