IE914415A1 - Crosslinked poly(organosilylhydrazines) and process for¹their preparation - Google Patents

Crosslinked poly(organosilylhydrazines) and process for¹their preparation

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Publication number
IE914415A1
IE914415A1 IE441591A IE441591A IE914415A1 IE 914415 A1 IE914415 A1 IE 914415A1 IE 441591 A IE441591 A IE 441591A IE 441591 A IE441591 A IE 441591A IE 914415 A1 IE914415 A1 IE 914415A1
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IE
Ireland
Prior art keywords
formula
organosilylhydrazine
poly
units
nitrogen
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Application number
IE441591A
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Atochem
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Application filed by Atochem filed Critical Atochem
Publication of IE914415A1 publication Critical patent/IE914415A1/en

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Classifications

    • 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
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • 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
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
    • C04B35/589—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained from Si-containing polymer precursors or organosilicon monomers
    • 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
    • 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
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/10—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing aluminium

Abstract

The invention relates to the field of ceramics and more precisely of crosslinked precursors. These precursors are poly(organosilylhydrazines) crosslinked with a metallic reactant. These crosslinked products produce a high yield of ceramic after pyrolysis.

Description

This invention relates to the field of ceramic precursors and in particular to crosslinked poly(organosilylhydrazines).
In the present description the term 5 poly(organosilylhydrazine) is employed to denote a compound containing a plurality of units of formula =Si-N-N-.
I I I US Patent 4,730,026 describes polymers containing repeat units |— R | I --Si - N-I I — R R — a and at least one bridge of formula -MR'n-, the said bridge or bridges being attached to the nitrogen atoms of the repeat units, and the symbol M representing a metal chosen from groups III A, II Β, IV B and II A of the Periodic Table. The polymers used in the preparation of these crosslinked polymers are organosilazanes and, by way of example, the patent specification mentions poly(1,1dimethylsilazane) or a polymerised silazane derived from cyclic methylsilazane. In general, these various polymers are prepared from a halosilane and ammonia or an amine. - 3 According to the present invention, there are provided crosslinked polymers comprising a plurality of units of formula I Si - N - N (I) and at least one bridge of formula -MRn- (II), in which at least two of the available valencies of the silicon and nitrogen atoms form bonds between the repeat units of a single chain, at least one of the available valencies of a nitrogen atom of a unit crosslinks with a nitrogen atom of another unit by means of an -MRn- bridge, and each of the other valencies of the silicon and nitrogen atoms bears a hydrogen atom or an alkyl, alkenyl, cycloalkyl or aryl radical containing up to 24 carbon atoms, and in which M represents an element from group III A, II Β, IV B or II A of the Periodic Classification of the elements, n represents a number equal to or lower than the valency of M - 2, and each R group, which may be the same or different when n is greater than 1, represents a hydrogen or halogen atom and preferably chlorine, an alkyl radical containing from 1 to 6 carbon atoms, an amino, mono- or dialkylamino radical, or an aryl, alkylaryl or aralkyl radical containing up to 18 carbon atoms.
The invention also provides a process for the - 4 preparation of a crosslinked polymer as defined above, which process comprises reacting a polymer containing a plurality of units of formula I with a compound of formula MRX, in which M and R are as defined above and x is the valency of M, and which compound is capable of binding or deprotonating and binding the nitrogen atoms of units of formula I.
The invention further provides a crosslinkable composition consisting of a mixture before reaction of one or more polymers containing a plurality of units of formula I with a compound MRX.
Furthermore, the invention provides ceramic material resulting from pyrolysis of a crosslinked polymer according to the invention.
In formula I the substituents which may be carried by the silicon and nitrogen atoms may suitably be chosen from alkyl radicals such as methyl, ethyl, propyl or butyl, alkenyl radicals such as vinyl and allyl, and aryl radicals such as phenyl, tolyl, xylyl or naphthyl. Particularly preferred however are the products containing units of formula I in which a nitrogen atom carries a hydrogen atom and/or the silicon atom carries a hydrogen atom or a vinyl substituent.
The polysilylhydrazines of formula I do not per se form a subject of the present invention and their preparation is described, for example, in European Patent - 5 Application published under no. 351,262. The present invention also applies to the polymers comprising units of formula I in combination with I I ...
-Si-0- and/or -Si-OH units, the preparation of which is I I described in European Patent Application published under no. 327,773. The content of the abovementioned two European applications is to be considered as forming part of the present specification.
The compound of formula MRX may be chosen from a broad class of products capable of permitting the formation of a bond between the units of formula I from one chain to another, via the nitrogen atoms of the units.
Among the elements of groups III A, II Β, IV B and II A those particularly preferred are B, Al, Zn, Cd, Ti, Zr, Hf and Mg. In the compounds of formula MRX, R preferably represents H, Cl, -CH3, -C2H5, -C6H5, -C2H4NH2, -C4H8-C6H5, -NH2, -NHR' and -NR'2, wherein R' represents an alkyl or aryl radical as referred to for R.
The compound of formula MRX is preferably chosen from the group consisting of Al(C2H5)3, B(C2H5)3, BH3, A1(CH3)3, Zn(C2H5)2, Mg(C4H9)2, A1C13, Ti[N(C2H5)2]4, A1(C2H5)2NH2, ZrCH2C(CH3)2C6H5, (CH3)2A1C1 and CH3A1C12.
The reaction of the polymer containing the plurality of units of formula I with the compound MRX can be carried out without any solvent, particularly when the - 6 polymer is in the liquid or solid state and the compound MRX is in the liquid or gaseous state. When this is not the case, and more generally, the reaction can be carried out in a solvent medium.
By way of illustration of the solvents which can be employed there can be mentioned in particular halogenated compounds such as methylene chloride, dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran, tetrahydropyran and 1,4-dioxane, aliphatic hydrocarbons such as pentane or hexane, and aromatic hydrocarbons such as benzene, toluene and xylene.
Generally speaking, the reaction can be carried out at a temperature of between -40°C and 200°C. The duration of the reaction can, particularly as a function of the temperature chosen, range from a few tens of minutes to several hours or even hundreds of hours.
In the preparation of the crosslinked polymers in accordance with the invention the reactants (compound containing a plurality of units of formula I and compound MRX) are generally used in quantities such that the silicon/element M molar ratio is between 1 and 100 and preferably between 3 and 40.
The crosslinked products according to the invention can be in various physical states ranging from viscous liquids to solids.
Pyrolysis of the crosslinked polymers according to the invention carried out at a temperature which is generally between 850°C and 1200°C results in a yield of ceramic (pyrolysis residue content) which is markedly higher than that obtained from a compound solely containing units of formula I.
The following Examples further illustrate the invention: Examples 1 to 11 The following starting poly(organosilylhydrazines) are employed in these examples: CH3 I A -/ Si - NH - N / I I ch3 CH - CHo I B -f- Si - NH - N -)I I ch3 CH3 I C-fSi-NH-Nf I I H These polymers are prepared by reaction of the corresponding chlorosilanes [(CH3)2SiCl2, (CH2=CH)CH3SiCl2 and CH3SiHCl2] with hydrazine under the following - 8 conditions: PRODUCT A The reaction takes place in a jacketed reactor fitted with a thermometer, a stirring system, a condenser (15°C) and a nitrogen inlet. After purging the reactor with nitrogen, 600 ml of toluene, 2.5 moles of triethylamine and 1 mole of (CH3)2SiCl2 are poured into it at 15°C. With the reactor being stirred and cooled with water at 15°C, 1.25 moles of hydrazine are poured into it at a constant rate over 90 min. After this addition the temperature of the reaction mixture is brought to 70°C for 6 hours and finally, with gentle stirring, to 15°C for 15 hours. The precipitate is filtered off, is washed with 900 ml of toluene under nitrogen pressure, and the clear solution is collected. The solvent and the residual volatile reactants are removed with the aid of a rotary evaporator at 60°C at a pressure which is gradually reduced from 150 mm of mercury to 0.5 mm of mercury at the end of evaporation. g of a viscous liquid product are finally collected.
PRODUCT B The reaction takes place in a jacketed reactor fitted with a thermometer, a stirring system, a condenser (15°C) and a nitrogen inlet. After purging the reactor with nitrogen 600 ml of toluene, 2.4 moles of triethylamine and 1 mole of CH3SiCHCH2Cl2 are poured into it at 15°C. With the reactor being stirred and cooled with water at 15°C, - 9 1.2 moles of hydrazine are poured into it at a constant rate over 60 min. After this addition the temperature of the reaction mixture is brought to 70°C for 6 hours and finally, with gentle stirring, to 15°C for 15 hours. The precipitate is filtered off, is washed with 900 ml of toluene under nitrogen pressure and the clear solution is collected. The solvent and the residual volatile reactants are removed with the aid of a rotary evaporator at 60°C at a pressure which is gradually reduced to 150 mm of mercury down to 0.5 mm of mercury at the end of evaporation. 88 g of a viscous liquid product are finally collected.
PRODUCT C The reaction takes place in a jacketed reactor fitted with a thermometer, a stirring system, a condenser (15°C) and a nitrogen inlet. After purging the reactor with nitrogen 600 ml of toluene, 2.4 moles of triethylamine and 1 mole of CH3SiHCl2 are poured into it at 15°C. With the reactor being stirred and cooled with water at 15°C, 1.2 moles of hydrazine are poured into it at a constant rate over 60 min. After this addition the temperature of the reaction mixture is brought to 70°C for 6 hours and finally, with gentle stirring, to 15°C for 15 hours. The precipitate is filtered off, is washed with 900 ml of toluene under nitrogen pressure and the clear solution is collected. The solvent and the residual volatile reactants are removed with the aid of a rotary evaporator at 60°C at - 10 a pressure which is gradually reduced to 150 mm of mercury down to 0.5 mm of mercury at the end of evaporation. 51 g of a solid liquid product are finally collected.
The reactants employed are the following: a - A1(C2H5)3 b - NH2A1(C2H5)2 c - Ti[N(C2H5)2]4 d - (CH3)2A1C1 In all these examples methylene chloride is 10 employed as solvent and the reaction is carried out at room temperature.
The pyrolysis of the crosslinked product and of the starting material (control) is carried out under argon at 1000°C.
The following are shown in the table which follows: - the starting polymer (A, B or C) - the reactant (a, b, c or d) - the Si/M molar ratio (M = element) - the physical characteristics of the crosslinked 20 product (appearance, solubility in hexane) - the residual content (pyrolysis yield) of the crosslinked product - the residual content of the starting polymer (control).
Ex. Starting polymer Reactant Si/M molar ratio Physical charac- terlstics Pyrolysis lOOO’C X residual content Crosslinked product Control 1 A a 5 soluble viscous 25 2 2 Λ a 2 wax - poorly soluble 45 2 3 B a 5 insoluble solid 67 58 4 C a 6 solid 75 62 5 A b 16 poorly soluble , very viscous 9 2 6 B b 4 wax - poorly soluble 65 58 7 C b 18 Insoluble powder 78 62 8 A c 23 insoluble powder 29 2 9 B c 17 insoluble powder 74 58 10 C c 23 insoluble powder 85 62 11 A d 5 soluble viscous 15 2

Claims (8)

1. comprising a A crosslinked poly(organosilylhydrazine) plurality of units of formula I Si - N - N (I) 5 and at least one bridge of formula -MR n -, in which at least two of the available valencies of the silicon and nitrogen atoms form bonds between the repeating units of a single chain, at least one of the available valencies of a nitrogen atom of a unit crosslinks with a nitrogen atom of 10 another unit by means of an -MR n - bridge, and each of the other valencies of the silicon and nitrogen atoms bears a hydrogen atom or an alkyl, alkenyl, cycloalkyl or aryl radical containing up to 24 carbon atoms, and in which M represents an element from group III A, II Β, IV B or II A 15 of the Periodic Classification of the elements, n represents a number equal to or lower than the valency of M - 2, and each R group, which may be the same or different when n is greater than 1, represents a hydrogen or halogen atom, an alkyl radical containing from 1 to 6 carbon atoms, 20 an amino, mono- or dialkylamino radical, or an aryl, alkylaryl or aralkyl radical containing up to 18 carbon atoms.
2. A poly(organosilylhydrazine) according to Claim 1, in which, in the units of formula I, a nitrogen - 13 atom carries a hydrogen atom and/or the silicon atom carries a hydrogen atom or a vinyl substituent.
3. A poly(organosilylhydrazine) according to Claim 1 or 2, in which, in the formula -MR n -, M represents 5 an element chosen from the group consisting of B, Al, Zn, Cd, Ti, Zr, Hf and Mg.
4. A poly(organosilylhydrazine) according to any of the preceding claims, in which, in the formula -MR n -, R represents chlorine. 10 5. A poly(organosilylhydrazine) according to Claim 1 substantially as described herein. 6. A process for the preparation of a poly(organosilylhydrazine) according to any preceding Claim, which process comprises reacting a polymer 15 containing a plurality of units of formula I with a compound of formula MR X , in which M and R are as defined in Claim 1 and x is the valency of M, and in which the compound MR X is capable of binding or deprotonating and binding the nitrogen atoms of units of formula I. 20 7. A process according to Claim 6, in which the compound MR X is chosen from the group consisting of A1(C 2 H 5 ) 3 , B(C 2 H 5 ) 3 , BH 3 , A1(CH 3 ) 3 , Zn(C 2 H 5 ) 2 , Mg(C 4 H 9 ) 2 , A1C1 3 , Ti[N(C 2 H 5 ) 2 ] 4 , A1(C 2 H 5 ) 2 NH 2 , ZrCH 2 C(CH 3 ) 2 C 6 H 5 and (CH 3 ) 2 A1C1. 25 8. A process for the preparation of a poly(organosilylhydrazine) according to Claim 1 - 14 substantially as described herein. 9. A process for the preparation of a crosslinked poly(organosilylhydrazine) substantially as described in any one of the Examples.
5. 10. A poly(organosilylhydrazine) according to Claim 1 prepared by the process claimed in any one of Claims 6 to 9. 11. A crosslinkable composition comprising a polymer containing a plurality of units of formula I and a
6. 10 compound of formula MR X , in which the symbols of formula I and of the formula MR X are as defined in Claim 1.
7. 12. Ceramic material obtained by pyrolysis of a crosslinked poly(organosilylhydrazine) as claimed in any one of Claims 1 to 5 and 10.
8. 15 13. Ceramic material according to Claim 12 substantially as described in any one of the Examples.
IE441591A 1990-12-19 1991-12-18 Crosslinked poly(organosilylhydrazines) and process for¹their preparation IE914415A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR9015924A FR2670789A1 (en) 1990-12-19 1990-12-19 POLY (ORGANOSILYLHYDRAZINES) RETICLES AND PROCESS FOR THE PREPARATION THEREOF.

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IE914415A1 true IE914415A1 (en) 1992-07-01

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EP (1) EP0493995A1 (en)
JP (1) JPH04339826A (en)
KR (1) KR920012194A (en)
CN (1) CN1063292A (en)
AU (1) AU8984791A (en)
CA (1) CA2058018A1 (en)
FR (1) FR2670789A1 (en)
IE (1) IE914415A1 (en)
IL (1) IL100395A0 (en)
NO (1) NO914980L (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2703040B1 (en) * 1993-03-23 1995-05-12 Atochem Elf Sa Process for the preparation of powder for ceramic nitride and / or metallic carbide and / or metalloid by flash pyrolysis and the powder thus obtained.
US6228794B1 (en) 1997-03-14 2001-05-08 University Of Iowa Research Foundation Cationic group 13 complexes incorporating bidentate ligands as polymerization catalysts
US5777120A (en) * 1997-03-14 1998-07-07 University Of Iowa Research Foundation Cationic aluminum alkyl complexes incorporating amidinate ligands as polymerization catalysts

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4730026A (en) * 1986-09-30 1988-03-08 E. I. Du Pont De Nemours And Company Cross-linked organosilazane polymers
US5032551A (en) * 1988-03-05 1991-07-16 Toa Nenryo Kogyo Kabushiki Kaisha Silicon nitride based ceramic fibers, process of preparing same and composite material containing same
US4886860A (en) * 1988-03-23 1989-12-12 Toa Nenryo Kogyo Kabushiki Kaisha Polymetalosilazane and process for preparing same

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AU8984791A (en) 1992-06-25
NO914980D0 (en) 1991-12-17
CA2058018A1 (en) 1992-06-20
KR920012194A (en) 1992-07-25
EP0493995A1 (en) 1992-07-08
IL100395A0 (en) 1992-09-06
JPH04339826A (en) 1992-11-26
CN1063292A (en) 1992-08-05
FR2670789A1 (en) 1992-06-26
FR2670789B1 (en) 1993-02-26
NO914980L (en) 1992-06-22

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