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
  • C04B35/515—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
  • C04B35/56—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 carbides or oxycarbides
  • C04B35/565—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 carbides or oxycarbides based on silicon carbide
  • C04B35/571—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 carbides or oxycarbides based on silicon carbide 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

Definitions

• the present invention relates to organosilicon polymers having recurring silylene-1,3-butadiyne units.
• the invention relates to reaction products of hexachloro-1,3-butadiene and n- butyllithium followed by quenching with certain dichlorosilanes to provide useful polymers that have good film-forming properties, at least one of which can be pulled into fibers, all of which are thermally converted into silicon carbide with a high ceramic yield, and many of which offer attractive candidates for electrical conduction and non-linear optical properties.
• the polymers are prepared in high yield, in a single-pot economical reaction, which uses
• This invention relates to silylene- and
• disilylene-1,3-butadiyne polymers The polymers are prepared by reacting hexachloro-1,3-butadiene with n- butyllithium, followed by quenching with RR'SiCl 2 to produce silylene-1,3-butadiyne polymers or followed by quenching with ClR 2 SiSiR 2 Cl to form disilylene- 1,3-butadiyne polymers.
• This invention involves preparation of two different, but distinctly related, organosilicon polymers.
• the first has a recurring silylene-1,3- butadiyne unit, and the second has a recurring disilylene-1,3-butadiyne unit.
• the first group of polymers have a recurring silylene-1,3-butadiyne unit of the formula:
• R and R' represent an organic moiety and "X" is an integer of from 20 to 500.
• Type A polymers hereinafter referred to, from time to time, as a "Type A" polymers.
• the second group of polymers that are prepared in accordance with this invention have a recurring disilylene-1,3-butadiyne unit of the following formula: TYPE B
• Type A silylene- polymer is formed, or a Type B disilylene- polymer is formed depends upon the quenching reaction and whether or not it uses for the quench RR'SiCl 2 (Type A polymers) or ClR 2 SiSiR 2 Cl (Type B polymers).
• RR'SiCl 2 Type A polymers
• ClR 2 SiSiR 2 Cl Type B polymers
• R can be any organic moiety, but is preferably selected from the group consisting of hydrogen, C 1 to C 20 alkyl, C 6 to C 20 aryl, and C 7 to C 20 alkylaryl.
• R is selected from the group consisting of hydrogen and C 1 to C 5 .
• R is either hydrogen or methyl. Hydrogen and methyl are most preferred because these will provide the highest yield of silicon carbide upon heating.
• the polymers of this invention whether Type A polymers or Type B polymers, generally have a
• the average molecular weight on a weight average basis is generally around 20,000.
• the number of recurring units in the polymer will vary from as little as 20 up to 500, but preferably will have an average chain length within the range of from about 200 to about 300 recurring units. Further the details of the polymer, the polymer characterization and structure will be given in the examples and after a description of the process of the invention.
• the amount of BuLi employed should be a stoichiometric amount
• the molar ratio of n-butyllithium to hexachloro-1,3-butadiene should be about 4:1.
• the second step reaction of the process is carried on in the same pot and is referred to as a quenching reaction. It is represented by Equation 2 below.
• Type A polymer or a Type B polymer simply dependent upon whether it is quenched with RR'SiCl 2 or ClR 2 SiSiR 2 Cl.
• This quenching reaction step, as well as the reaction with n-butyllithium is preferably conducted in the presence of an organic solvent.
• Preferred solvents are tetrahydro-furan, diethyl ether, benzene and hexane.
• the initial reaction, that is the combination of the hexachloro-1,3-butadiene and the n-butyllithium can be conducted at room temperature or lower
• the reaction since the reaction is exothermic it has been found convenient, although not essential, that the reaction be initiated at dry ice temperatures, -78oC, with gradual addition of the hexachloro-1, 3-butadiene to the n-butyllithium over a period of time, for example 5-20 minutes, with stirring. Then the dry ice bath can be removed and the mixture allowed to warm to room temperature. This same repetition of cooling followed by warming can be accomplished in the addition of the silylene or disilylene compound to form the Type A or Type B polymers. Generally speaking, the reaction may be run at any temperature between -78°C and room temperature. The reaction also does not appear to be time dependent since it goes fairly rapidly. Generally, the qualities of the polymers produced appears to be better when temperatures below room temperature are employed, followed by gradual warm up.
• the R moiety of the polymers can be selected from hydrogen, C 1 to C 20 alkyl, C 6 to C 20 aryl and C 7 to C 20 alkylaryl.
• R and R' may be the same or
• dichlorodimethylsilane (Me 2 SiCl 2 ) was added in a dropwise fashion over a 5 minute period.
• the polymer thus obtained was soluble in halogenated hydrocarbons (e.g., chloroform) and aromatics (e.g., benzene) but insoluble in alcohols and aliphatic hydrocarbons (e.g. hexane).
• halogenated hydrocarbons e.g., chloroform
• aromatics e.g., benzene
• alcohols and aliphatic hydrocarbons e.g. hexane
• GPC M w from ca. 3,000-100,000 with the maximum at ca. 20,000.
• Melting Point Does not melt. Above 90oC converts to a black, infusible, insoluble material by way of crosslinking.
• Thermogravimetric Analysis (TGA) : Weight loss, monitored to 1,100oC, was 18%. Monitoring the evolved gas revealed it to be initially methane and later H 2 . Thermal decomposition is essentially complete by 800oC.
• disilylenedi-acetylene polymers undergo crosslinking above 90oC (without melting) to produce infusible, insoluble materials.
• the polymer powders are pressed into shapes and then fired, the shapes are retained and extremely strong ceramic material is obtained.
• These polymers are excellent candidates for nonlinear optical materials. Heating these polymers up to 1,300oC while monitoring by X-ray powder diffraction revealed only the 111,220 and 311 lines of -silicon carbide.
• Type A polymers were prepared using the exact procedure earlier described.
• R R' equals phenyl or methyl, and mixed R's, wherein R is phenyl and R' is methyl.
• R is phenyl and R' is methyl.
• Each of these was characterized in the manner given above, each was formed in high yield, and had molecular weights within the range herein specified. Only those polymers which had at least one phenyl substituent on silicon pulled fibers of good quality, and these polymers also produced the best quality films.
• the Type B polymer prepared had R equals methyl. Both steps performed satisfactorily and the overall reaction afforded good polymer yields.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Ceramic Engineering (AREA)
• Materials Engineering (AREA)
• Structural Engineering (AREA)
• Manufacturing & Machinery (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Silicon Polymers (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 1989
  • 1989-05-16 US US07/352,825 patent/US4965332A/en not_active Expired - Fee Related
• 1990
  • 1990-05-16 JP JP2508233A patent/JPH03502712A/ja active Granted
  • 1990-05-16 EP EP19900908792 patent/EP0429601A4/en not_active Ceased
  • 1990-05-16 WO PCT/US1990/002711 patent/WO1990014381A1/en not_active Ceased
  • 1990-05-16 CA CA002016947A patent/CA2016947A1/en not_active Abandoned

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