WO2011070081A1 - Copolymères d'acrylonitrile-silazane, en particulier sous forme fibreuse, procédé de production et utilisation desdits polymères - Google Patents

Copolymères d'acrylonitrile-silazane, en particulier sous forme fibreuse, procédé de production et utilisation desdits polymères Download PDF

Info

Publication number
WO2011070081A1
WO2011070081A1 PCT/EP2010/069196 EP2010069196W WO2011070081A1 WO 2011070081 A1 WO2011070081 A1 WO 2011070081A1 EP 2010069196 W EP2010069196 W EP 2010069196W WO 2011070081 A1 WO2011070081 A1 WO 2011070081A1
Authority
WO
WIPO (PCT)
Prior art keywords
acrylonitrile
silazane
fibers
different
copolymer
Prior art date
Application number
PCT/EP2010/069196
Other languages
German (de)
English (en)
Other versions
WO2011070081A8 (fr
Inventor
Monika Bauer
Daniel Decker
Guenther Motz
Original Assignee
Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
Clariant International Ltd
Universität Bayreuth
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 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V., Clariant International Ltd, Universität Bayreuth filed Critical Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
Priority to JP2012542542A priority Critical patent/JP5636060B2/ja
Priority to US13/514,795 priority patent/US9096702B2/en
Priority to RU2012128553/04A priority patent/RU2012128553A/ru
Priority to KR1020127017836A priority patent/KR20130006593A/ko
Priority to CN201080056191.3A priority patent/CN102844342B/zh
Priority to EP10787475.2A priority patent/EP2510024B1/fr
Publication of WO2011070081A1 publication Critical patent/WO2011070081A1/fr
Publication of WO2011070081A8 publication Critical patent/WO2011070081A8/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • C04B35/62272—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on non-oxide ceramics
    • C04B35/62277—Fibres based on carbides
    • C04B35/62281—Fibres based on carbides based on silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • C04B35/62272—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on non-oxide ceramics
    • C04B35/62286—Fibres based on nitrides
    • C04B35/62295—Fibres based on nitrides based on silicon nitride
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62802—Powder coating materials
    • C04B35/62805—Oxide ceramics
    • C04B35/6281—Alkaline earth metal oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/62—Nitrogen atoms
    • 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
    • D01D5/08—Melt 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
    • D01F6/28—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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
    • C04B2235/483—Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5208—Fibers
    • C04B2235/5264—Fibers characterised by the diameter of the fibers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C04B2235/6021—Extrusion moulding

Definitions

  • the present invention relates to copolymers of acrylonitrile and silazanes which contain at least one organically polymerizable double bond, in particular a
  • the copolymers are because of their content of silicon,
  • Nitrogen and carbon atoms e.g. as fire protection materials or as starting materials for pyrolyzed systems of composition SiCN
  • the materials can be present in any form, in particular in the form of fibers.
  • the pyrolyzed products have the properties of ceramics and are e.g. in the form of fibers or
  • ceramic matrices used as reinforcing elements in components that are exposed to or resist high temperatures and / or corrosive media.
  • Pamphlets also the possibility polysilazanes with ketenes, thioketenes,
  • Carbodiimide or CS2 implement. Concrete examples of this or even
  • SiC ceramic fibers are often synthesized starting from silanes / polysilanes. However, this synthetic route is not free from difficulties. So must for
  • melt spinning process More often, a melt spinning process is used. Particularly disadvantageous here, however, is the need to cure the polymer fibers by means of electron irradiation, for which extremely high doses of about 20 MGy are required.
  • the object of the invention is to find a suitable for the field of flame and fire protection material that can be processed into stable moldings, such as self-supporting fibers. In preferred embodiments, it should undergo pyrolysis, in particular in the form of stable fibers, in order to obtain materials of the composition SiC, SiN or SiCN.
  • silazanes generally refers to compounds which contain the group R 1 R 2 R 3 Si-N (R 4 ) SiR 5 R 6 R 7 .
  • a very simple member of this group is the disilazane, H 3 Si-NH-SiH 3 .
  • Cyclic and linear silazanes include or consist of -Si (R 1 R 2 ) -N (R 3 ) - structural units. Starting from the basic structures, a large number of silazanes has been developed whose substituents on the silicon can be, for example, in addition to hydrogen, alkyl, alkenyl or aryl and their substituents on the nitrogen, in addition to hydrogen, alkyl or aryl. There are oligomeric and polymeric structures, including incorporation of additional groups such as urea groups, as well as various rings and multiple rings.
  • Copolymerize addition polymerization catalysts to polymers which typically remain soluble in the reaction solvent used eg, DMF or other solvent suitable for acrylonitrile.
  • the copolymers are usually soluble in the same solvents as acrylonitrile and polyacrylonitrile. After removal of the solvent, they are in solid form at room temperature, however, become highly viscous liquid as the temperature increases.
  • the melt has viscoelastic properties and can be drawn into fibers accordingly. These can be further crosslinked after cooling and possibly stretching with electron irradiation and thus rendered infusible or converted into a thermoset state. Pyrolysis of the fibers may follow such post-curing of the fibers.
  • the copolymerization proceeds according to the scheme:
  • n 0, 1, 2, 3 or any higher number
  • R the substituent in the silazane used, generally corresponding to R 2 of the formulas (I) to (III) below.
  • Suitable reactants for the acrylonitrile are all monomeric, oligomeric or polymeric silazanes having one or more silicon-bonded alkenyl groups.
  • oligomeric silazanes are understood to mean silazanes having 2 to 10 silicon atoms. Polymeric silazanes are therefore those having at least 1 1 silicon atoms.
  • the usable silazanes or oligo- / polysilazanes have the general formula (I)
  • R 2 is alkenyl
  • R 3 is hydrogen or straight-chain, branched or cyclic, substituted or - preferably - unsubstituted alkyl, the same alkenyl as R 2 or a
  • R 2 and R 3 are the same or different and straight-chain, branched or
  • alkenyl is cyclic, substituted or, preferably, unsubstituted alkyl, alkenyl, aryl, arylalkyl, alkylaryl, alkenylaryl or arylalkenyl, wherein each of the
  • Substituents R 2 and R 3 in the case of n and / or o greater than 1 in different Units may have a different meaning, but preferably has the same meaning
  • radical R 3 and at least one radical R 3 - all or each part of the radicals R 3 and R 3 together may represent an unsubstituted or substituted, straight-chain or branched alkylene group having preferably 2 bridging carbon atoms, where appropriate, the remaining part of Radicals R 3 and R 3 have the meaning given under (a),
  • R 4 and R 4 are alkyl having preferably 1 to 4 carbon atoms, phenyl or hydrogen, where several radicals R 4 and / or R 4 in a silazane molecule may be identical or different,
  • R 1 and R 5 are the same or different and may have the same meaning as R 2 or R 3 , wherein R 5 may also mean Si (R 1 ) (R 2 ) (R 3 ), or R 1 and R 5 together represent a single bond,
  • R 6 is Si (R 2 ) (R 2 ' ) -XR 7 -Si (R 2 ) q (OR 2' ) 3- q, where X is either O or NR 4 , R 7 is a single bond or a substituted or preferably represents unsubstituted, straight-chain, branched or cyclic alkylene group and q can be 0, 1, 2 or 3,
  • P is an alkylene group having 1 to 12 carbon atoms, preferably ethylene, m and p are independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or an integer between 1 1 and 25,000, preferably between 1 1 and 200 mean and
  • n and o independently of one another denote 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or an integer between 1 1 and 25 000, preferably between 1 1 and 200,
  • the units set in square brackets are preferably randomized, in other cases instead blockwise and, if appropriate, evenly in each case
  • Molecule can be distributed.
  • units in the context of the definition of the silazanes of the formulas (I) to (III) refers to the in each case set in an angular bracket and with an amount of these units in the molecule indicating index (m, n %) provided parts of the molecule.
  • R 2 in the formulas (I) to (III) is a vinyl group.
  • R 3 is more preferably alkyl, in this embodiment, very particularly preferably methyl or ethyl.
  • n in the formulas 1 to 3 is at least 1, they are in each case one
  • Silicon atom of the corresponding units bonded substituents (R 2 and R 3 ) independently of the first preferred embodiment preferably selected as follows: an alkyl radical in combination with a hydrogen atom, another alkyl radical, an alkenyl radical, preferably a vinyl radical, or a phenyl radical.
  • the alkyl or alkenyl radicals in the formulas (I) to (III) have 1 to 6 carbon atoms. Methyl, ethyl and vinyl radicals are particularly preferred.
  • the aryl, arylalkyl, alkylaryl, alkenylaryl or arylalkenyl radicals have from 5 to 12 carbon atoms. Phenyl and styryl radicals are particularly preferred. This embodiment is particularly preferred in combination with the first embodiment.
  • R 4 and / or R 4 are alkyl, in particular methyl.
  • Materials produced carbon fibers should have superior properties.
  • R 2 , R 3 , R 2 and R 3 are preferably selected from alkyl, in particular from 1 to 8 carbon atoms.
  • the substituents R 2 , R 3 , R 2 and R 3 carry fluorine atoms. This embodiment is particularly preferred in combination with the fourth embodiment.
  • the index o is 0.
  • the index m is in each case 0.
  • R 1 and R 5 together form a single bond.
  • This embodiment is particularly preferred for compounds of formula (I) wherein the index o is zero and, optionally, the index m is also zero.
  • o is 0 and m and n are greater than 1 and are preferably between 2 and 25,000, in particular between 2 and 200.
  • m and n may be the same or different. Additionally or alternatively, the m and n units may be randomized or evenly distributed. They may be arranged in blocks or not in blocks.
  • n and o in the formula (I) have the meaning zero and R 5 has the meaning Si (R 1 ) (R 2 ' ) (R 3' ).
  • the individual bond stains in these examples may in particular be alkyl, very particularly preferably methyl, but may also be hydride or partly alkyl and partly hydride.
  • m in the formula (I) has the meaning 1, 2, 3, 4, 5 or an integer between 6 and 50, while n and o are zero, or it is a mixture of various of these silazanes.
  • the substituents R 1 and R 5 may be the same or different and have the same meaning as R 3 , wherein R 5 may also mean Si (R 1 ) (R 2 ) (R 3 ). If appropriate, this or these silazanes can also be present, in particular, in a mixture with silazanes in which R 1 and R 5 together form a single bond.
  • o in the formula (I) is zero, while m and n are the same or different and mean between 2 and 200-25,000.
  • the substituents R 1 and R 5 may be the same or different and have the same meaning as R 3 , wherein R 5 may also mean Si (R 1 ) (R 2 ) (R 3 ). If appropriate, this or these silazanes may also be present, in particular, in a mixture with silazanes in which R 1 and R 5 together form a
  • oligomers / polymers examples are the following oligomers / polymers: the units in square brackets being randomized in the molecules, possibly in blocks and in other cases uniformly arranged in the molecules
  • n and o are 0, m is 2, 3, 4, 5, 6, 7, 8, 9, 10 or an overlying number, and R 1 and R 5 Together they represent a single bond.
  • m and n are respectively 2, 3, 4, 5, 6, 7, 8, 9, 10 or an overlying number, and R 1 and R 5 are together a single bond.
  • Molecules randomized or blockwise, in some cases evenly distributed, m- or n-fold, or in the case of the last-shown formula together (m + n) -fold in the specified ratio to each other, but the molecules are present in closed chain form.
  • This variant can be used in particular in a mixture with
  • halosilanes having at least one Si-H bond alone and / or in combination with di- or trihalosilanes are reacted in an excess of liquid, anhydrous ammonia and left in this medium for a longer time, they form in the ammonium halide salt formed by the resulting ammonium halide salt the corresponding acid become more acidic environment over time by reaction of Si-H bonds polymerization products in which the indices m, n and o have a higher value and / or a different ratio than before, possibly catalyzed by the presence of dissolved and ionized ammonium halide.
  • Polymerization products can be obtained by the action of sodium dissolved in ammonia.
  • monomeric or oligomeric / polymeric silazanes of formula (I) wherein o is zero can be reacted with amino or hydroxy containing alkoxysilanes, for example, 3-aminopropyltriethoxysilane.
  • ABSE Benzyl ether styrene
  • N-alkyl substituted silazanes are readily preparable by those skilled in the art by reacting the corresponding halosilanes with alkylamines, e.g. in US 4,935,481 and US 4,595,775.
  • the quantitative ratio of silazane used to acrylonitrile used is in principle not critical.
  • the molar proportions of silazane to acrylonitrile may range from 100: 1 to 1: 100. Proportions of 4: 1 to 1:20 have proved favorable.
  • the molar proportion of silazane is preferably no greater than that of acrylonitrile.
  • the reaction takes place in a common solvent for the components.
  • the customary for the polymerization of acrylonitrile solvents such as DMF, 1, 3-dioxolan-2-one, dimethylacetamide or DMSO can be used. It becomes a common catalyst for radical polymerizations, in particular
  • Polyadditions added.
  • the reaction is usually carried out at elevated temperature, for example at 40 ° C to 100 ° C (or at the reflux temperature of the solvent); It is usually completed after a few hours.
  • the materials according to the invention are exclusively from acrylonitrile and silazane. However, it is also possible that they contain other additives.
  • Suitable additives are, for example, organic substances (monomers or other organic molecules) which can be copolymerized with acrylonitrile.
  • these additives should usually make up not more than 20 wt .-%, based on the proportion of the sum of acrylonitrile and organic molecule.
  • the organic substance or substances are preferably admixed to or introduced into the same solution into which the other components are introduced in order to effect the polymerization.
  • the material may contain one or more fillers, which are preferably inorganic in nature, but may also be organically modified, e.g. to facilitate a Einpolymermaschine.
  • the filler may be added as needed in an amount of up to about 60% by weight, based on the weight of the material. Preferred are amounts of up to
  • the filler is preferably added before the solvent is separated.
  • the material of the present invention can be made into any shape. However, it is preferably used for the production of fibers or is in the form of fibers.
  • the solvent is separated from the obtained polymer solution (or polymer suspension if a filler has been added).
  • the product is usually solid at room temperature. If the temperature is increased, a viscoelastic melt of interconnected polymer molecules is formed. In many cases, the softening point is above 100 ° C.
  • fibers are drawn, preferably by extrusion through a die head containing a larger number of nozzles. Preferably, the nozzle cross-section is about
  • the fibers are then cooled and thereby preferably stretched, the diameter being significantly lower; in a continuous fiber production, they are then preferably wound up.
  • the resulting fibers are suitable for processing in textile materials, e.g. Weaving, entangling, laying, or for incorporation in polymer compositions as
  • Verstarkungsmittel are particularly interesting for use in fire protection, as they fire-retardant due to the high content of silicon and nitrogen
  • the fibers can be converted by pyrolysis into ceramic fibers.
  • the polymer fiber obtained from the melt is first made infusible by conventional methods, for example by irradiation with electron beams.
  • doses in the range of approx. 200 KGy are generally sufficient.
  • the pyrolysis is preferably carried out under oxygen-free inert gas, for example argon.
  • the reaction conditions gas atmosphere, temperature
  • the reaction conditions can be chosen so that the ratio of silicon to nitrogen to carbon in the product is approximately maintained (but usually the carbon content decreases slightly, because some methane can form).
  • SiCN ceramic fibers These may optionally be converted to SiC or SiN fibers by known means, e.g. by heating the fibers to at least 1450 ° C to form SiC, or by pyrolysis in one
  • Ratio 1 1 Under a nitrogen atmosphere, 1.59 g (8.6 mol) of DVTMDS, 0.91 g (17.2 mmol) of ACN and 2.5 g of dimethylformamide (DMF) in a three-necked flask equipped with a reflux condenser with bubble counter, gas inlet and magnetic stirrer, To this mixture is added 37.5 mg of azoisobutyronitrile (AIBN), and
  • the polymer obtained by polymerizing a vinylsilazane with acrylonitrile is freed from the solvent and heated until a viscous melt is formed. This is pressed through a nozzle plate with several hundred nozzles with diameters of 200 or 300 ⁇ . The resulting filaments sink in a room at normal room temperature with gravity down. The fiber ends are taken, and the fiber bundle is wound under tension on a rotating roller, wherein the fibers are stretched to a thickness of about 10-30 ⁇ .
  • Example 5 The fibers of Example 5 are exposed to electron irradiation of 200 KGy. Then they are thermosetting and can not be more

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Silicon Polymers (AREA)
  • Inorganic Fibers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne un copolymère qui est obtenu par réaction d'acrylonitrile ou d'un mélange d'acrylonitrile et d'une molécule organique qui peut être copolymérisée avec un acrylonitrile, avec au moins un silazane monomère, oligomère et/ou polymère, le silazane renfermant au moins une double liaison vinylique. Le copolymère peut être mis sous forme fibreuse et/ou rendu non fusible. L'utilisation de copolymères sous forme fibreuse, permet de produire des fibres céramiques par pyrolyse.
PCT/EP2010/069196 2009-12-09 2010-12-08 Copolymères d'acrylonitrile-silazane, en particulier sous forme fibreuse, procédé de production et utilisation desdits polymères WO2011070081A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP2012542542A JP5636060B2 (ja) 2009-12-09 2010-12-08 特には繊維形態での、アクリロニトリル−シラザン共重合体、その調製方法及びその使用
US13/514,795 US9096702B2 (en) 2009-12-09 2010-12-08 Acrylonitrile-silazane copolymers, especially in fiber form, process for preparation thereof and use thereof
RU2012128553/04A RU2012128553A (ru) 2009-12-09 2010-12-08 Сополимер акрилонитрила и силазана, в частности, в форме волокон, способ его получения и применения
KR1020127017836A KR20130006593A (ko) 2009-12-09 2010-12-08 특히 섬유 형태의 아크릴로니트릴-실라잔 공중합체, 이와 같은 공중합체의 제조 방법 그리고 이와 같은 공중합체의 용도
CN201080056191.3A CN102844342B (zh) 2009-12-09 2010-12-08 尤其是纤维形态的丙烯腈-硅氮烷共聚物、其制备方法及其用途
EP10787475.2A EP2510024B1 (fr) 2009-12-09 2010-12-08 Copolymères d'acrylonitrile-silazane, en particulier sous forme fibreuse, procédé de production et utilisation desdits polymères

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009059777A DE102009059777A1 (de) 2009-12-09 2009-12-09 Acrylnitril-Silazan-Copolymere, insbesondere in Faserform, Verfahren zu deren Herstellung und ihre Verwendung
DE102009059777.8 2009-12-09

Publications (2)

Publication Number Publication Date
WO2011070081A1 true WO2011070081A1 (fr) 2011-06-16
WO2011070081A8 WO2011070081A8 (fr) 2012-06-28

Family

ID=43466467

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/069196 WO2011070081A1 (fr) 2009-12-09 2010-12-08 Copolymères d'acrylonitrile-silazane, en particulier sous forme fibreuse, procédé de production et utilisation desdits polymères

Country Status (8)

Country Link
US (1) US9096702B2 (fr)
EP (1) EP2510024B1 (fr)
JP (1) JP5636060B2 (fr)
KR (1) KR20130006593A (fr)
CN (1) CN102844342B (fr)
DE (1) DE102009059777A1 (fr)
RU (1) RU2012128553A (fr)
WO (1) WO2011070081A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9371423B2 (en) 2013-07-09 2016-06-21 General Electric Company Methods and apparatus for crosslinking a silicon carbide fiber precursor polymer
US10508056B1 (en) * 2015-05-19 2019-12-17 General Electric Company Method to form silicon carbide fibers by single stage pyrolysis of polysilazane precursors

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3239489A (en) 1961-10-17 1966-03-08 Monsanto Co Poly-urea-silazanes and process of preparation
US4395460A (en) 1981-09-21 1983-07-26 Dow Corning Corporation Preparation of polysilazane polymers and the polymers therefrom
US4595775A (en) 1984-04-06 1986-06-17 Petrarch Systems, Inc. N-methylhydridosilazanes, polymers thereof, methods of making same and silicon nitrides produced therefrom
US4621383A (en) 1984-02-09 1986-11-11 Christopher Gendala Method and apparatus for inflating an article
WO1987005298A1 (fr) 1986-03-04 1987-09-11 Sri International Polysilazanes et compositions connexes, procedes et utilisations
US4929704A (en) 1988-12-20 1990-05-29 Hercules Incorporated Isocyanate- and isothiocyanate-modified polysilazane ceramic precursors
US4935481A (en) 1987-11-07 1990-06-19 Hoechst Aktiengesellschaft Polysilazanes, process for the preparation thereof, silicon nitride-containing ceramic materials which can be prepared therefrom, and the prepaation thereof
US6165551A (en) 1994-11-07 2000-12-26 Lanxide Technology Company, Lp Protective compositions and method of making same
US6329487B1 (en) 1999-11-12 2001-12-11 Kion Corporation Silazane and/or polysilazane compounds and methods of making
US6652978B2 (en) 2001-05-07 2003-11-25 Kion Corporation Thermally stable, moisture curable polysilazanes and polysiloxazanes
WO2006071907A1 (fr) * 2004-12-29 2006-07-06 3M Innovative Properties Company Compositions polymériques précéramiques polymérisables multiphotoniques
WO2006071914A2 (fr) * 2004-12-29 2006-07-06 3M Innovative Properties Company Compositions polymeres de preceramiques polymerisables monophotoniques et multiphotoniques

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3393218A (en) * 1964-05-18 1968-07-16 Monsanto Co Polymeric silazane compounds
DE3324834A1 (de) 1983-07-09 1985-01-17 Cassella Ag, 6000 Frankfurt Vernetztes copolymerisat, verfahren zu seiner herstellung und seine verwendung als sorptionsmittel
EP2024406B1 (fr) 2006-06-06 2012-08-01 Dow Corning Corporation Formule hybride silicone-acrylate et sa méthode de fabrication
CN105308078B (zh) * 2013-03-15 2017-06-30 联邦科学与工业研究组织 衍生自丙烯腈的聚合物

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3239489A (en) 1961-10-17 1966-03-08 Monsanto Co Poly-urea-silazanes and process of preparation
US4395460A (en) 1981-09-21 1983-07-26 Dow Corning Corporation Preparation of polysilazane polymers and the polymers therefrom
US4621383A (en) 1984-02-09 1986-11-11 Christopher Gendala Method and apparatus for inflating an article
US4595775A (en) 1984-04-06 1986-06-17 Petrarch Systems, Inc. N-methylhydridosilazanes, polymers thereof, methods of making same and silicon nitrides produced therefrom
WO1987005298A1 (fr) 1986-03-04 1987-09-11 Sri International Polysilazanes et compositions connexes, procedes et utilisations
US4935481A (en) 1987-11-07 1990-06-19 Hoechst Aktiengesellschaft Polysilazanes, process for the preparation thereof, silicon nitride-containing ceramic materials which can be prepared therefrom, and the prepaation thereof
US4929704A (en) 1988-12-20 1990-05-29 Hercules Incorporated Isocyanate- and isothiocyanate-modified polysilazane ceramic precursors
US5001090A (en) 1988-12-20 1991-03-19 Hercules Incorporated Silicon nitride ceramics from isocyanate- and isothiocyanate-modified polysilazanes
US5021533A (en) 1988-12-20 1991-06-04 Hercules Incorporated Crosslinkable poly(thio)ureasilazane composition containing a free radical generator
US6165551A (en) 1994-11-07 2000-12-26 Lanxide Technology Company, Lp Protective compositions and method of making same
US6329487B1 (en) 1999-11-12 2001-12-11 Kion Corporation Silazane and/or polysilazane compounds and methods of making
US6652978B2 (en) 2001-05-07 2003-11-25 Kion Corporation Thermally stable, moisture curable polysilazanes and polysiloxazanes
WO2006071907A1 (fr) * 2004-12-29 2006-07-06 3M Innovative Properties Company Compositions polymériques précéramiques polymérisables multiphotoniques
WO2006071914A2 (fr) * 2004-12-29 2006-07-06 3M Innovative Properties Company Compositions polymeres de preceramiques polymerisables monophotoniques et multiphotoniques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
S. KOKOTT; G. MOTZ: "Modifizierung des ABSE-Polycarbosilazans mit Multi-Walled Carbon Nanotubes zur Herstellung spinnfähiger Massen", MAT.-WISS. U. WERKSTOFFTECH., vol. 38, no. 11, 2007, pages 894 - 900

Also Published As

Publication number Publication date
EP2510024B1 (fr) 2013-10-30
JP5636060B2 (ja) 2014-12-03
RU2012128553A (ru) 2014-01-20
US20120248641A1 (en) 2012-10-04
WO2011070081A8 (fr) 2012-06-28
CN102844342B (zh) 2015-11-25
KR20130006593A (ko) 2013-01-17
EP2510024A1 (fr) 2012-10-17
DE102009059777A1 (de) 2011-06-16
US9096702B2 (en) 2015-08-04
JP2013513683A (ja) 2013-04-22
CN102844342A (zh) 2012-12-26

Similar Documents

Publication Publication Date Title
EP2408846B1 (fr) Polymères hybrides de cyanates et de silazanes, leur procédé de production et leur utilisation
DE3805796C2 (de) Verfahren zur Herstellung von organischen Silazanpolymeren und Keramikmaterialien daraus
DE3719343C2 (de) Organische Silazanpolymere, Verfahren zu deren Herstellung und deren Verwendung
DE102008064372A1 (de) Polysilan-Polycarbosilane mit reduziertem Chlorgehalt auf Basis von Methylchlorpolysilanen sowie daraus hergestellte Spinnmassen und keramische Formkörper
DE2743843A1 (de) Borsiloxanpolymere und ein verfahren zu deren herstellung
DE102009056371A1 (de) Polysilan-Polycarbonsilane mit reduziertem Kohlenstoffgehalt auf Basis von Methylchlorpolysilanen sowie daraus hergestellte Keramiken
EP0375994B1 (fr) Procédé de préparation de polycarbosilanes; polycarbosilanes obtenus par ledit procédé
DE3444306C2 (de) Borsiliciumorganisches Polymeres und Herstellungsverfahren dafür
DE69023620T2 (de) Verfahren zur Herstellung eines fasermatrix-keramischen Verbundwerkstoffs.
EP2510024B1 (fr) Copolymères d'acrylonitrile-silazane, en particulier sous forme fibreuse, procédé de production et utilisation desdits polymères
DE102008018062A1 (de) Silicium-Bor-Kohlenstoff-Stickstoff-Keramiken und Vorläuferverbindungen, Verfahren zur salzfreien Polymerisation von RnHal3-nSi-X-BRmHal2-m
EP0659806B1 (fr) Polyborosilazanes précéramiques, leur procédé de préparation et produits céramiques à partir de ceux-ci
DE3877072T2 (de) Keramische stoffe.
EP2622044B1 (fr) Résines ä base d'un polyester insaturé et polysilazane et des produits thermodurcissable obtenus de celles-ci
EP1317462B1 (fr) Ceramiques a carbonitrure de silicium-bore et composes precurseurs, leurs procedes de preparation et leur utilisation
EP2945977B1 (fr) Polysilane de poids moleculaire eleve et procede de preparation correspondant pour la production de corps moules preceramiques
WO2012041933A1 (fr) Résines réactives et corps moulés et matières plates ou textiles réalisés à partir de celles-ci, comprenant des polysilazanes particulaires en tant qu'agents ignifugeants
DE4403839A1 (de) Präkeramische Polyborosilazane, Verfahren zu deren Herstellung sowie daraus erhaltenes keramisches Material
DE69104150T2 (de) Verfahren zur Herstellung von Polysilazanen und Verfahren zur Herstellung von keramischen Materialien.
DE4001246A1 (de) Polymere polysilazane, verfahren zu ihrer herstellung sowie deren verwendung
DE10104536A1 (de) Siliciumborcarbonitridkeramiken und Vorläuferverbindungen, Verfahren zu deren Herstellung und Verwendung
WO2014090934A1 (fr) Procede de synthese d'un polymere preceramique sans chlore pour la fabrication de corps moules ceramiques

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080056191.3

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10787475

Country of ref document: EP

Kind code of ref document: A1

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10787475

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 13514795

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2012542542

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 2010787475

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 6032/DELNP/2012

Country of ref document: IN

ENP Entry into the national phase

Ref document number: 20127017836

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2012128553

Country of ref document: RU