EP1259665B1 - Carbonisation de materiaux fibreux cellulosiques en presence d'un compose organosilicie - Google Patents

Carbonisation de materiaux fibreux cellulosiques en presence d'un compose organosilicie Download PDF

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Publication number
EP1259665B1
EP1259665B1 EP00985407A EP00985407A EP1259665B1 EP 1259665 B1 EP1259665 B1 EP 1259665B1 EP 00985407 A EP00985407 A EP 00985407A EP 00985407 A EP00985407 A EP 00985407A EP 1259665 B1 EP1259665 B1 EP 1259665B1
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EP
European Patent Office
Prior art keywords
units
carbonization
organosilicon compound
cellulosic fibrous
fibrous materials
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.)
Expired - Lifetime
Application number
EP00985407A
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German (de)
English (en)
French (fr)
Other versions
EP1259665A2 (fr
Inventor
Pierre Olry
Hervé PLAISANTIN
Sylvie Loison
René PAILLER
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.)
Safran Ceramics SA
Original Assignee
SNECMA Propulsion Solide SA
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Application filed by SNECMA Propulsion Solide SA filed Critical SNECMA Propulsion Solide SA
Publication of EP1259665A2 publication Critical patent/EP1259665A2/fr
Application granted granted Critical
Publication of EP1259665B1 publication Critical patent/EP1259665B1/fr
Anticipated expiration legal-status Critical
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Classifications

    • 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
    • D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
    • 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
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/14—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with organic compounds, e.g. macromolecular compounds

Definitions

  • the subject of the present invention is a process for carbonizing cellulosic fibrous materials, in the presence of at least one organosilicon compound; this, to obtain fibrous carbon materials. Said carbonization can be carried out both continuously and discontinuously.
  • the carbon fibrous materials obtained can in turn be heat treated (especially graphitized) to generate fibers having the desired properties.
  • Carbon fibers with a cellulose precursor were the first carbon fibers manufactured in the world. Starting from such cellulosic precursors, Edison in the late 19th century, obtained filaments for his incandescent lamps (US Patent 223,898).
  • Polyacrylonitrile has however proven for a long time a more suitable precursor for obtaining high-strength and high-modulus carbon fibers, more particularly intended for reinforcements of composite materials.
  • ex-viscose carbon fibers have been used since 1955 in the manufacture of carbon / phenolic resin composites, used as thermal protection for propellants. These fibers, low modulus, have a restricted thermal conductivity.
  • the manufacture of these fibers requires a special rayon type precursor: a rayon with a disoriented crystalline texture (R. BACON, Carbon Fibers from Rayon Precursors, in Chemistry and Physics of Carbon, 1973, Vol. 2, Marcel Dekker, New-York and P. OLRY, 14 th Biennal Conference on Carbon, 1979).
  • Said organosilicon product has been described therein as an oligomer chosen from polydimethylphenylallylsilanes, polysiloxanes, polymethylsiloxanes, polysilazanes and polyaluminoorganosiloxanes. In fact, its exact nature is not really specified.
  • the originality of the present invention lies in the selection of specific organosilicon compounds - additives for carbonization of cellulosic fibrous materials - which are particularly effective.
  • Said compounds have been found to be very effective in improving the properties of the carbon fibers obtained after carbonization, this with any type of charred cellulosic materials (rayon, fibrans, in particular commercial); and, that said carbonization is carried out continuously or discontinuously.
  • the intervention of said compounds constitutes an undeniable advantage for the implementation of batch and continuous carbonizations, it proves to be essential for the continuous carbonization of certain substrates (it makes said continuous carbonization of said substrates possible. substrates).
  • the present invention therefore relates to the use of a particular family of organosilicon compounds in said context.
  • This reinforcement with the additives of the invention, is of remarkable intensity. It makes it possible to counter shrinkage during carbonization and even to stretch the fibers (up to 50%) without breaking them, which ensures an orientation of the texture of said fibers and a reduction or rearrangement of the internal pores. It made it possible to obtain, with any type of cellulose (celluloses with solvent, spokes for tires in particular), filaments which have resistances of the order of 1,500 to 2,000 MPa and modules of the order of 70 to 110 GPa.
  • organosilicon compounds selected in the context of the present invention is that of oligomers and silicone resins, as defined above.
  • Said family in fact comprises two sub-families, on the one hand, that of the oligomers of partially hydrolysed organic silicates, volatile at temperatures of use and on the other hand, that of resins, products solid at room temperature, deposited by impregnation, advantageously in solution in a solvent.
  • Said oligomers and resins have a number average molecular weight of between 500 and 10,000, advantageously between 2,500 and 5,000. Generally, for oligomers, a number average molecular weight of between 500 and 2,000, more generally between 500 and 1000 and for resins, a number average molecular weight of between 1,000 and 10,000, more generally between 2,000 and 10,000.
  • Said oligomers and resins have in their chemical structure the units of formulas SiO, and SiO x R y (OR ') z , as defined above.
  • the units of formula SiO 4 are said to be units Q 4 .
  • alkyl radicals R and / or R '(in the formula SiO x R y (OR') z ) are advantageously lower C 1 -C 4 alkyl radicals, very advantageously methyl or ethyl radicals, of particularly preferably methyl radicals.
  • organosilicon compounds of this family (itself made up of the subfamily of oligomers and that of resins, as defined above), oligomers and resins are very particularly preferred within the framework of the present invention. , as specified below.
  • the organosilicon compound involved is a resin known as MQ resin, consisting of units of formula SiO 4 (units Q 4 ), units of formula SiO 3 -OH (units Q 3 ) and units of formula O-Si-R 3 (units M).
  • MQ resin consisting of units of formula SiO 4 (units Q 4 ), units of formula SiO 3 -OH (units Q 3 ) and units of formula O-Si-R 3 (units M).
  • MQ resin consisting of units of formula SiO 4 (units Q 4 ), units of formula SiO 3 -OH (units Q 3 ) and units of formula O-Si-R 3 (units M).
  • said resin MQ has n, patterns Q 4 , n, patterns Q 3 and n 3 patterns M, with advantageously: 2 ⁇ n 1 ⁇ 70 3 ⁇ n 2 ⁇ 50 3 ⁇ n 3 ⁇ 50, and a number average molecular weight of between 2,500 and 5,000.
  • Resins of this type are commercially available.
  • the organosilicon compound intervening is chosen from the oligomers of a partially hydrolyzed organic silicate, advantageously chosen from the oligomers of a partially hydrolyzed alkyl silicate, and preferably chosen from the oligomers of partially hydrolyzed ethyl silicate.
  • a partially hydrolyzed ethyl silicate oligomer in particular that of an oligomer of this type, produced on a large scale by the silicone industry, is particularly recommended.
  • TEOS 40 and in particular marketed by the company BAYER under the reference TES 40.
  • TEOS 28 tetraethylorthosilicate
  • the commercial product is in fact a mixture of ethyl silicate (1 SiO 4 tetrahedron, 1 silicon atom per molecule) and oligomers of said silicate which contain up to 9 SiO 4 tetrahedra, including those of the ends of molecules which have SiO 3 -OH units (Q 3 units ). Said product gradually distills from room temperature to 500 ° C.
  • TEOS 40 and / or similar compounds is an integral part of the present invention.
  • organosilicon compounds selected according to the invention it is now proposed to describe, in no way limiting, their mode of intervention. In fact, two modes of intervention are recommended, depending on the nature of said compound.
  • non-volatile compound ie which remains largely solid and / or liquid, at temperatures close to 400 ° C
  • the cellulosic fibrous materials such organosilicon compounds (of such an organosilicon compound or of at least two such organosilicon compounds), which are not volatile, said compounds are therefore generally used in solution in a solvent; solvent, such as perchlorethylene, which is easily removed before carbonization.
  • solvent such as perchlorethylene
  • Such a film-forming agent is advantageously chosen from silicone oils, of suitable viscosity (said viscosity generally being between 500 and 10,000 mPa.s, advantageously between 500 and 5,000 mPa.s).
  • Such oils can in particular correspond to one or the other of the formulas below (-Si (CH 3 ) 2 -O) n or (-Si (CH 3 ) 2 -O-Si (C 5 H 6 ) 2 -O) n .
  • Such oils depolymerize around 400 ° C and a priori play no role in the chemical reinforcement of the surface of the fibers. However, they avoid the bridging of the filaments by the pyrolysis products of the cellulose (tars), bridging which could lead to embrittlement of the threads.
  • non-volatile organosilicon compounds in mixture with a film-forming agent (advantageously chosen from non-reactive and reactive silicone oils), in solution in a solvent.
  • Such a film-forming agent is generally used at a rate of 10 to 50% by weight relative to the weight of organosilicon compound (s) (non-volatile (s)).
  • organosilicon compound (s) involved is (are) volatile (s) (ie that it (s) distills (s), quantitatively, well below 400 ° C), it is not possible to impregnate the substrate to be carbonized.
  • the cellulosic fibrous materials are charred in the presence of its (their) vapor.
  • the carbonization is in fact implemented, at least in part, advantageously at least in its first phases, in the presence of such (such) volatile organosilicon compound (s).
  • the said compound (s) generally intervene in an inert gas.
  • the organosilicon compounds, selected according to the invention intervene, of course, in an effective amount, generally at a rate of 1 to 10% by weight, relative to the weight of cellulosic materials. It is advisable to put enough to observe the expected effect but not too much because then one can observe an undesirable bonding effect. Those skilled in the art are able to optimize the amount of intervention of the organosilicon compounds whose use is recommended in the context of the process of the invention.
  • organosilicon compounds could be further enhanced by the joint intervention of a mineral additive.
  • the cellulosic fibrous materials are thus also impregnated, before their carbonization, with at least one mineral additive, acid or Lewis base.
  • Said mineral additive can in particular be chosen from halides, sulphates and phosphates of ammonium, sodium, urea and their mixtures.
  • carbonization is initiated in an atmosphere which contains hydrogen chloride (HCl gas).
  • Said atmosphere generally contains said hydrogen chloride, diluted in air or nitrogen.
  • HCl gas hydrogen chloride
  • Said first step is generally carried out between 100 and 250 ° C. She can in fact be more precisely qualified as a relaxation stage - dehydration, preliminary to carbonization proper.
  • the additives of the invention are advantageously used, both in carbonization processes used batchwise and in carbonization processes used continuously. We have seen that they made possible the implementation of certain carbonizations continuously (carbonizations that it was only possible to implement, according to the prior art, discontinuously).
  • the method of the invention is thus implemented continuously.
  • the cellulosic fibrous material may in particular be in the form of threads or textile surfaces (fabrics, knits, felts, nonwovens, unidirectional sheets, unidirectional ribbons, etc.).
  • Said cellulosic fibrous material may in particular consist of any type of rayon and fibranne.
  • the process of the invention is, in this respect, particularly interesting: it leads, implemented with products, available on the market, of wide distribution, to fibrous carbon materials, of high quality. According to the prior art, such high quality materials could only be obtained from cellulosic fibrous materials of very specific types.
  • This pyrolysis carried out batchwise in the context of the example, may well be carried out continuously.
  • the carbon filaments extracted from the wire have a resistance of 1,125 MPa and a module of 40 GPa for a diameter of 5.8 ⁇ m.
  • the shrinkage during carbonization is 40%.
  • the carbonization yield is 16%.
  • the impregnation is carried out by passing the wire through a 2.5% by weight solution of the solution of the MQ resin mixture and non-reactive siloxane oil in perchlorethylene. After elimination of the perchlorethylene, the wire is pyrolyzed under a tension of 0.53 N (54 gf) according to the thermal profile specified in Example 1.
  • the carbon filaments extracted from the wire have a resistance of 1,800 MPa and a module of 66 GPa, for a diameter of 4.4 ⁇ m.
  • the elongation during carbonization is 7.1%.
  • the carbonization yield is 16.1%.
  • a mesophase cellulose yarn (tensile strength 100 cN / tex), manufactured according to the teaching of patent application EP-A-0 179 822 (Michelin), of 1,900 dtex (average filament diameter 12, 5 ⁇ m), is desensed, impregnated with the organosilicon additive as in Example 2, and pyrolyzed under a tension of 0.39 N (40 gf) according to the thermal profile specified in Example 1.
  • the carbon filaments extracted from the wire have a resistance of 1,800 MPa and a modulus of 100 GPa.
  • the diameter is 3.8 ⁇ m and the elongation, during charring, is 52%.
  • the carbonization yield is 17.3%.
  • the tetraethylorthosilicate used is that sold by the company Bayer under the reference TES 40.
  • the carbon filaments extracted from the wire have a resistance of 930 MPa and a module of 38 GPa, for a diameter of 5.5 ⁇ m.
  • the carbonization shrinkage, along the fiber axis, is 38%.
  • the carbonization yield is 14.5%.
  • a cellulose yarn identical to that of Example 1 is desensed and then impregnated with the organosilicon additive as in Example 1. It is then also impregnated with 8% by weight of NH 4 Cl by passage through an aqueous solution with 13% by weight of said NH 4 Cl.
  • the wire is dried at 100 ° C for 30 min and the excess NH 4 Cl is removed by rinsing for a few seconds with distilled water.
  • Said wire is dried at 100 ° C for 1 hour then undergoes pyrolysis up to 1200 ° C as in Example 1.
  • the tensile strength of the carbon filaments extracted from said carbonized wire is 1,200 MPa and their modulus of 45 GPa, for a diameter of 8.3 ⁇ m.
  • the shrinkage during carbonization is 32.3%.
  • the carbonization yield is 30%.
  • a cellulose yarn identical to that of Example 1 is desensed and then impregnated with the organosilicate additive as in Example I. It is then pyrolyzed according to the thermal profile of Example 1, but replacing the step at 170 ° - 90 min in air in a step at 170 ° - 90 min in HCl / N 2 mixture (1: 1).
  • the breaking strength of the carbon filaments extracted from said carbonized wire is 1350 MPa, their modulus of 50 GPa, their diameter of 8.6 ⁇ m.
  • the shrinkage during carbonization is 31.5%.
  • the carbonization yield is 27%.
  • a cellulose yarn identical to that of Example 1 is desensitized with perchlorethylene and then, without impregnation with the polysiloxane additive, it is pyrolyzed according to the thermal profile indicated in said Example 1.
  • the breaking strength of the carbon filaments extracted from the wires obtained is only 660 MPa, their modulus is 38 GPa.
  • the diameter of said filaments is 5.8 ⁇ m.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Inorganic Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Silicon Polymers (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Woven Fabrics (AREA)
EP00985407A 1999-12-06 2000-12-05 Carbonisation de materiaux fibreux cellulosiques en presence d'un compose organosilicie Expired - Lifetime EP1259665B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9915329 1999-12-06
FR9915329A FR2801907B1 (fr) 1999-12-06 1999-12-06 Carbonisation de materiaux fibreux cellulosiques en presence d'un compose organosilicie
PCT/FR2000/003389 WO2001042544A2 (fr) 1999-12-06 2000-12-05 Carbonisation de materiaux fibreux cellulosiques en presence d'un compose organosilicie

Publications (2)

Publication Number Publication Date
EP1259665A2 EP1259665A2 (fr) 2002-11-27
EP1259665B1 true EP1259665B1 (fr) 2004-04-28

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EP00985407A Expired - Lifetime EP1259665B1 (fr) 1999-12-06 2000-12-05 Carbonisation de materiaux fibreux cellulosiques en presence d'un compose organosilicie

Country Status (12)

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US (1) US7226639B2 (ja)
EP (1) EP1259665B1 (ja)
JP (1) JP4651256B2 (ja)
AT (1) ATE265560T1 (ja)
AU (1) AU2183401A (ja)
BR (1) BR0016124B1 (ja)
DE (1) DE60010343T2 (ja)
FR (1) FR2801907B1 (ja)
MX (1) MXPA02005624A (ja)
RU (1) RU2256013C2 (ja)
UA (1) UA72780C2 (ja)
WO (1) WO2001042544A2 (ja)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2801906B1 (fr) * 1999-12-06 2002-03-01 Snecma Carbonisation de materiaux fibreux cellulosiques en presence d'un compose organosilicie
ATE361383T1 (de) * 2004-12-07 2007-05-15 Snecma Propulsion Solide Verfahren zur herstellung von garnen oder faserblättern aus kohlenstoff ausgehend von einem cellulosematerial
JP4936478B2 (ja) * 2009-01-14 2012-05-23 前田 俊克 炭素化布帛の製造方法及び炭素化布帛
JP5271887B2 (ja) * 2009-05-08 2013-08-21 国防科学研究所 ライオセル系炭素繊維及び炭素織物の製造方法
RU2459893C1 (ru) * 2011-03-18 2012-08-27 Общество с ограниченной ответственностью Научно-производственный центр "УВИКОМ" (ООО НПЦ "УВИКОМ") Способ получения углеродного волокнистого материала
RU2490378C1 (ru) * 2012-03-23 2013-08-20 Общество с ограниченной ответственностью Научно-производственный центр "УВИКОМ" (ООО НПЦ "УВИКОМ") Способ получения углеродного волокнистого материала
KR101285702B1 (ko) * 2012-09-03 2013-07-12 국방과학연구소 섬유강화 복합재료
CA2987025C (en) 2015-06-11 2023-06-13 Stora Enso Oyj A fiber and a process for the manufacture thereof

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JPS5540687B2 (ja) * 1971-10-04 1980-10-20
DE2320825C2 (de) * 1973-04-25 1983-11-17 Deutsches Wollforschungsinstitut an der Rheinisch-Westfälischen Technischen Hochschule Aachen, 5100 Aachen Verfahren zum Carbonisieren von Cellulosematerialien
FR2421982A1 (fr) * 1978-04-03 1979-11-02 Saint Gobain Composition d'ensimage et fibres de verre traitees a l'aide de cette composition
JPS5950188B2 (ja) * 1979-07-18 1984-12-06 麒麟麦酒株式会社 ガラス容器の擦り傷遮蔽用組成物
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Also Published As

Publication number Publication date
FR2801907A1 (fr) 2001-06-08
JP2003516478A (ja) 2003-05-13
UA72780C2 (en) 2005-04-15
MXPA02005624A (es) 2004-09-10
US7226639B2 (en) 2007-06-05
DE60010343D1 (de) 2004-06-03
DE60010343T2 (de) 2005-05-04
ATE265560T1 (de) 2004-05-15
JP4651256B2 (ja) 2011-03-16
BR0016124A (pt) 2002-11-19
FR2801907B1 (fr) 2002-03-01
AU2183401A (en) 2001-06-18
EP1259665A2 (fr) 2002-11-27
RU2256013C2 (ru) 2005-07-10
BR0016124B1 (pt) 2012-01-10
WO2001042544A2 (fr) 2001-06-14
US20020182139A1 (en) 2002-12-05
RU2002115274A (ru) 2004-01-10
WO2001042544A3 (fr) 2001-12-27

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