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WO1991009066A1 - Resines et mousses a haute teneur en carbone - Google Patents

Resines et mousses a haute teneur en carbone Download PDF

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Publication number
WO1991009066A1
WO1991009066A1 PCT/US1990/007518 US9007518W WO9109066A1 WO 1991009066 A1 WO1991009066 A1 WO 1991009066A1 US 9007518 W US9007518 W US 9007518W WO 9109066 A1 WO9109066 A1 WO 9109066A1
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Prior art keywords
prepolymer
foaming
viscosity modifier
composition
foaming composition
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Inventor
Larry K. Truesdale
Gerald Fleming
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Hyperion Catalysis International Inc
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Hyperion Catalysis International Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2349/00—Characterised by the use of homopolymers or copolymers of compounds having one or more carbon-to-carbon triple bonds; Derivatives of such polymers

Definitions

  • the invention features a foaming composition that includes (a) a foaming agent; (b) an aromatic polyacetylenically unsaturated prepolymer; and (c) a viscosity modifier for modifying the flow properties of said prepolymer having one or more acetylenic groups available for reacting with the prepolymer.
  • the foaming agent, prepolymer, and viscosity modifier are chosen such that at the decomposition temperature of the foaming agent, the viscosity of the composition is sufficient to permit molding and foaming.
  • the amount of viscosity modifier is no greater than 20% by weight, more preferably between 8 and 20% by weight.
  • the viscosity modifier has a softening point less than 150°C.
  • oligomers having a lower degree of polymerization than the prepolymer. These oligomers may also have the same chemical composition as the prepolyme
  • Preferred prepoly er ⁇ include the cyclotrimerized product of an aromatic diacetylene (e.g., diethynylbenzene, bis(ethynylphenyl)ether, or bis(ethynylphenyi)ether) and an aryl or alkyl monoacetylene (e.g., phenylacetylene) or acetylene. Also preferred are prepolymers which are the .
  • aromatic diacetylene e.g., diethynylbenzene, bis(ethynylphenyl)ether, or bis(ethynylphenyi)ether
  • an aryl or alkyl monoacetylene e.g., phenylacetylene
  • prepolymers which are the .
  • cyclotrimerized products of a) an aliphatic diacetylene having the formula HC ⁇ C-CH -C CH where n is an integer between 2 and 10, inclusive (e.g., 1,4-pentadiyne) and an aryl or alkyl monoacetylene (e.g., phenylacetylene) or acetylene; b) diacetylene and an aryl or alkyl monoacetylene (e.g., phenylacetylene) or acetylene, and c) an aromatic diacetylene (e.g., diethynylbenzene, 4, '-diethynyldiphenylmethane, or bis(ethynylphenyl)ether) or aliphatic diacetylene (as recited above, e.g., 1,4-pentadiyne) and an aryl or alkyl nitrile (e.g
  • Preferred foaming agents include azodicarbona ide, p-toluenesulfonyl hydrazide, and 4,4'-oxybisbenzenesulfonyl hydrazide.
  • Particularly preferred foaming compositions • include those in which the foaming agent is azodicarbonamide, the prepolymer is the cyclotrimerized product of diethynylbenzene and phenylacetylene, and the viscosity modifier is diphenylbutadiyne; those in which the foaming agent is azodicarbonamide, the prepolymer is the cyclotrimerized product of diethynylbenzene and phenylacetylene, and the viscosity modifier is 4,4 '-diethynyldiphenylmethane; and those in which the foaming agent is azodicarbonamide, the prepolymer is the cyclotrimerized product of diethynylbenzene and phen
  • the invention also features a process for . preparing a foam that includes taking the above-described foaming-composition and molding it to form a shaped article under-reaction conditions, including " temperature and pressure, sufficient to decompose the foaming agent, thereby causing foaming of the composition, and to cause the acetylenic groups of the viscosity modifier to react with the prepolymer.
  • the foaming composition is preferably formed by ball milling the foaming agent, prepolymer, and viscosity modifier to form a homogeneous powder.
  • the molding step preferably takes place at a temperature below about
  • 3 preferably have densities less than 0.2 g/cm (more preferably between 0.01 and 0.2 g/cm , more preferably
  • the compressive strength of the foam preferably is at least 100 psi in the temperature range 0 - 500°F.
  • the compressive strength preferably does not vary by more than 5% upon exposure to moisture.
  • the foams are lightweight, chemically inert, and thermally stable (below 600°F in air). They are also moisture resistant and thus dimensionally stable, even at elevated temperatures. Similarly, they exhibit good compressive strength, even at elevated temperatures. They are also readily prepared at relatively low temperatures; thus, crosslinking of the prepolymer to form an infusible solid is avoided.
  • the invention also features novel polyacetylenically unsaturated prepolymers and thermoset resins prepared from them, and processes for preparing these materials, including cyclotrimerization catalysts. Controlling the molecular weight of the ' product through selection of the proper solvent and the discovery of catalysts whose activity is not highly sensitive to monomer concentration enables steady. state (and thus continuous) polymerization. Moreover, soluble oligomers that result during preparation of the prepolymer can be recycled and used to prepare more prepolymer.
  • Thermally stable, chemically inert, low density foams are prepared from a foaming composition that includes a) a foaming agent, b) an aromatic (e.g., containing one or more aromatic rings) polyacetylenically unsaturated prepolymer, and c) a viscosity modifier (present in an amount between 8 and 20% by weight).
  • a foaming agent i.e. the temperature at which it decomposes to form a gas that causes foaming
  • a viscosity modifier present in an amount between 8 and 20% by weight.
  • the particular materials are chosen such that at the decomposition temperature of the foaming agent (i.e. the temperature at which it decomposes to form a gas that causes foaming) , the viscosity of the composition is sufficient to permit molding and foaming.
  • the viscosity modifier is generally a solid at room temperature that softens or melts in the range of the decomposition temperature of the foaming agent. At this temperature, however, the prepolymer is normally present as a solid or highly viscous liquid; thus, it cannot be efficiently molded or foamed at this temperature. At higher temperatures, however, the prepolymer cures, forming an insoluble, infusible solid that cannot be shaped.
  • the purpose of the viscosity modifier is to soften the prepolymer and reduce-its viscosity to the point where it can flow and fill the mold at the decomposition temperature of the foaming - agent.
  • the reduced viscosity also allows the gas released by the foaming agent to be trapped in the curing prepolymer, thereby resulting in uniform foaming throughout the prepolymer (as opposed to escaping from the interior of the prepolymer).
  • the acetylenic groups of the viscosity modifier also react with the residual acetylenic groups of the prepolymer during molding so that the viscosity modifier becomes part of the final foam; thus, it does not have to be removed following molding, nor will it leach out of the foam or impair the foam's chemical and physical properties in use.
  • the foaming agent may be conveniently introduced as a thermally unstable powder, uniformly mixed into the prepolymer and viscocity modifier.
  • particulate sizes of the foaming agent powder are small to affect a uniform evolution of gas during the cure and hence, a uniformly foamed product.
  • the density of the foams is controlled.
  • the first step in preparing the foams involves preparation of the prepolymer. Various prepolymers may be synthesized and used to produce foams having advantageous properties as will be discussed further below.
  • the prepolymer, viscosity modifier, and foaming agent are intimately mixed, for example, in a ball mill to form a homogeneous powder. Finally, the mixture is discharged into a mold and heated.
  • the heating step includes heating for a period of time at a temperature below the optimum cure temperature, but high enough such that the viscosity modifier softens and reduces the viscosity of the mixture, e.g., about 130°C.
  • This initial heating forms a uniform mixture of lower viscosity.
  • the mixture is then brought to a higher temperature, e.g., about about 200°.C at which the foaming agent decomposes and the in.al foam. roduct i-s. formed.
  • the foam may be carbonized by a high temperature cure (e.g., at 1000°C) to form a hard, glassy, carbon foam for electrical applications.
  • a high temperature cure e.g., at 1000°C
  • the foams are useful in a variety of applications, including composite structures where a combination of low density and dimensional stability at elevated temperatures are needed.
  • the following examples are illustrative of the formation of foams.
  • Example 1 The following example illustrates preparation of a foam forming composition in the form of a powder.
  • a prepolymer prepared according to Example 8, below Into a 000 ball mill jar was placed 23.00 g of a prepolymer prepared according to Example 8, below, 2.68 g of diphenylbutadiyne (viscosity modifier), and 1.07 g of azodicarbonamide (foaming agent).
  • To the mixture was added stainless steel media to fill the jar 2/3 full.
  • the jar was capped and turned on a roller mill at 180 rpm for 18 hrs.
  • the mixture was removed from the jar and the resin was scraped from the wall of the jar and ground in a mortar with a pestle.
  • the fine powder was transferred to a bottle, affording 24.34 g of recovered foaming composition.
  • Example 2 The ' - following example illustrates preparation of a ' foaming " composition in ' the form of a powder.
  • a 000 ceramic ball mill jar was placed 18.09 g of a prepolymer prepared according to Example 8, 2.12 g of diethynyldiphenyl methane (viscosity modifier), and .85 g of azodicarbonamide (foaming agent). Enough stainless steel media were placed in the jar to fill the jar 2/3 full. The capped jar was turned on a roller mill at 180 rpm. The sides of the jar were scraped down after 1 hour, 4 hours, and 20 hours. The jar was turned a total of 28 hours.
  • Example 3 The following example illustrates the formation of foam using the foaming composition discussed in Example 1.
  • a 1" x 3" compression mold was sprayed with mold release agent.
  • a 1" x 3" piece of 3 mil porous glass-Teflon cloth was then placed in the mold, followed by 2.63 g of foaming composition and a 1" x 3" piece of non-porous glass-Teflon cloth.
  • the top half of the mold was placed in the cavity and the mold was placed in preheated carver press and pressurized in the range of 10,000 to 0 psi.
  • the top half of the mold served to compact the mixture to a uniform thickness.
  • the top was removed and the nonporous cloth was removed.
  • the taffy-like mixture was then compacted with a spatula, after which the moid -(with- a flat steel plate cover) was returned to the press- -and- eheated to a mold temperature of 127°C.
  • the steel cover and a sheet of porous teflon-glass cloth were placed over the mold cavity and the mold was placed into a carver press preheated to around 200°C.
  • the mold was then heated to 219°C over 28 minutes.
  • the sample was removed from the mold while hot after 28 minutes.
  • the resulting product had a density of 0.1416 g/cm 3 .
  • Example 4 The following illustrates formation of a foam using the foaming composition of Example 1.
  • a 1" x 3" compression mold was sprayed with mold release agent and a 1" x 3" piece of 3 mil porous Teflon cloth was placed in the mold, followed by 2.37 g of foaming composition according to Example 1 and a 1" x 3" piece of non-porous glass-teflon cloth.
  • the mold was assembled and heated to 127°C - 8 minutes.
  • the mold was then removed from the press, the upper half of the mold • removed, and the nonporous cloth peeled off the softened and consolidated resin.
  • the flat lower half of the mold was then returned to the press and heated to 126°C; the resin was then compacted with a spatula to force more resin into the corners and edges prior to foaming.
  • Example 5 The procedure of Example 3 was followed using
  • a 1" x 3" compression mold was sprayed with Teflon mold release agent before a 1" x 3" piece of porous glass-Teflon cloth was placed in the bottom of the mold. The mold was then charged with 2.66 g of foaming composition. A piece of 1" x 3" non-porous glass-Teflon cloth was placed on the lower half. The mold was placed in a Carver Press with preheated platens. After 5 minutes, the mold temperature was
  • the mold was then disassembled and the nonporous cloth removed. The mixture was then returned to the press and reheated. When the mold temperature reached
  • the mold was transferred to a press with platens heated to 212°C. After 67 minutes, the sample was removed from the hot mold. The resulting foam had a
  • foaming agents examples include azodicarbonomide, p-toluensulfonyl hydrazide, and 4, 4'- oxybisbenzenesulf ⁇ yl hydrazide.
  • Viscosity Modifiers Acetylenically substituted compounds that can be used to modify the viscosity of the prepolymer and are reactive (copolymerizable) with the prepolymer can be any mono- or polyacetylenically substituted compound, which can be the same of different from the compound used to prepare the prepolymer, provided that this acetylenically substituted compound softens at about the temperature at which the foaming agent decomposes.
  • It may be aromatic (e.g., containing one or aromatic rings) or aliphatic having the general formula HC ⁇ C-CH -C ⁇ CH where n is an integer between 2 and 12, inclusive.
  • aromatic compounds include diphenylbutadiyne, 4, 4'- diethynyldiphenyl methane, and bis(ethynylphenyl)ether.
  • aliphatic compounds include 1,4-pentadiyne.
  • oligomers having a lower degree of polymerization (and thus a lower molecular weight and softening temperature) than the prepolymer. These oligomers may also have the same chemical composition as the prepolymer.
  • viscosity modifiers can be found in U.S. Patent No. 4,097,400 to Jabloner, entitled “Polyarylacetylenes and Thermoset Resins Therefrom", the entire contents of which are hereby incorporated by reference.
  • betanaphthylacetylene biphenylacetylene, 4-ethynyltrans-azobenzene, diphenylacetylene, di-m-tolylacetylene, di-o-tolylacetylene, bis(4-ethylphenyl) cetylene, bis(4-chlorophenyl)acetylene, phenylbenzoylacetylene, be anaphthylphenylacetylene, di( lpha-naphthyl)acetylene, 1,4-diethynylnaphthalene, 9, lO-diethynyl-anth-r-acene, 4,4'-di-ethynylbiphenyl, 9,10-diethynylphenanthrene, 4, '-diethynyl-transazobenzene, 4,4'-diethynyldiphenylether, 2,3,5,6-tetrach
  • Example 7 A 12 liter, 4-neck round bottom flask was equipped with a mechanical stirrer, a thermometer, a subsurface oxygen inlet, and an air cooled condenser. To the flask was added 648 g of crude concentrate of the soluble portion from the preparation of the prepolymer prepared in Example 8, described below. Analysis of the concentrate indicated it contained 193 g of phenylacetylene, 59 g of diethynylbenzene, and 210 g of hexanes-soluble, low molecular weight oligomer. To the flask, was also added 115 g of phenylacetylene, 150 g of diethynylbenzene, 10 g of the prepolymer prepared in
  • Example 8 501 g of pepidine, 5 liters of acetone, and 90 g of copper(I)chloride. The green mixture was stirred while oxygen was bubbled through the liquid. A gentle exotherm was observed during the first five hours. The reaction was stirred overnight before the solids were removed by filtration. The filtrate was concentrated on a rotary evaporator ( ⁇ 60°C), affording a thick, black oil with particuiates. The oil was diluted with 300 ml acetone, 1200 ml toluene, and then filtered. The filtrate was rinsed twice with 1 liter of water, twice with 1 liter of 1 N HCL, 1 liter of saturated " sodium " bicarbonate, and twice with 750 ml of brine.
  • the resulting dark brown liquid was filtered through a glass fiber filter to remove some finely suspended solids before mixing with 100 g of anhydrous magnesium sulfate and 20 g of norite. Filtration through celite afforded a dark brown solution which was concentrated under vacuum, initially at 60°C and 20 mm Hg and finally at 75°C for 30 minutes at 0.5 mm. A total of 525 g of the oligomeric product was obtained as a dark brown oil.
  • the prepolymers are fusible aromatic polymers having unreacted acetylene groups; these acetylene groups may be internal or external. They generally have a number average molecular weight less than about 15,000.
  • the prepolymers are synthesized by cyclotrimerization of various acetylenic species in the presence of a catalyst.
  • Suitable prepolymers for the formation of foams include those synthesized by reaction of an aromatic diacetylene (e.g., diethynylbenzene and phenylacetylene) or aliphatic diacetylene (e.g., 1, -pentadiyne) and an aryl or alkyl monoacetylene (e.g., phenylacetylene or l-decyne), diacetylene and an aryl or alkyl monoacetylene (e.g., phenylacetylene), an aromatic diacetylene (e.g., diethynylbenzene) and an aryl or alkyl nitrile (e.g., benzonitrile) , or by reaction of various functionalized starting materials to produce functionalized prepolymers having various properties, all of which are further discussed below, along with specific examples.
  • Acetylene itself may also be used instead of the aliphatic or aromatic mono
  • polyacetylenically substituted aromatic compounds useful- in- preparing the prepolymers include m- and p-diethynylbenzenes; diethynyl toluenes; diethynylxylenes; 9,10-diethynylphenanthrene;
  • Example 8 A 2 liter reactor.equipped with a mechanical stirrer, a dry ice condenser, a thermometer, an addition funnel, and a vacuum take-off was purged with argon before 600 ml of deoxygenated hexanes was added. Argon was bubbled through the solvent overnight. In a separate flask, a solution of 31.01 g (.304 moles) of phenylacetylene, 19.59 g (.155 moles) of I, " 3-diethynylbenzene, -and “ 3.78 g (.0315 moles) of mesit-ylene in 150 ml hexanes was deoxygenated with argon overnight before it was charged into the addition funnel.
  • the catalyst was prepared in another flask by charging 0.156 g (0.61 mmol) of nickel acetylacetonate and 0.739 g (2.42 mmol) of tri-o-tolylphosphine into 20 ml of toluene.
  • the solution was deoxygenated overnight with argon. In all cases, the overnight deoxygenations were done to expedite start-up the next day.
  • the hexanes in the reactor were treated with 1.6 mmol of diisobutylaluminum hydride in hexanes and the reactor was placed under reduced pressure (82 mm Hg) and held constant. The hexanes cooled to 8°C. To the hexanes was added 10% of the acetylene mixture. The catalyst solution was activated by adding 2.42 mmol of diisobutylaluminum hydride in hexanes and after five minutes one half of the catalyst mixture was added to the reactor. During the next 30 minutes the remaining monomers were slowly added, followed by the remaining catalyst. The reaction was maintained at reduced pressure for 6 1/2 hours before it was returned to atmospheric pressure by introducing argon into the reactor.
  • the solution was stirred, cooled to 15°C, and deoxygenated for 4 hours with argon.
  • To thenickel-phosphine solution was added 1.460 liter of diisobutylaluminum hydride while maintaining the temperature below 25°C.
  • Ten percent of the acetylene mixture was transferred to the 200 gallon reactor, followed by half of the catalyst mixture. The remaining acetylene mixture was added over a two hour period while maintaining the reaction temperature below 10°C. The second half of the catalyst mixture was added an hour later when the exotherm began to subside.
  • the reaction was monitored by gas chromatography periodically throughout the addition of the reagents and thereafte .
  • transition metal 0 halides which, either alone or in combination with a trialkylalane or dialkylaluminum halide, effect the cyclotrimerization of phenylacetylene.
  • lanthanide elements with similar ability.
  • a broad range of prepolymer types are available due to changes in molecular weight, residual ethynyl group content, and variation in the 1,2,4- versus 1,3,5-isomer distribution of the 0 cyclotrimerization. With many of these catalysts no linear oligomerization of the acetylene occurs.
  • metal halides will cyclotrimerize phenylacetylene: nickel fluoride, 5 cobalt chloride, chromium chloride, molybdenum chloride, tungsten chloride, vanadium trichloride, niobium pentachloride, bis(cyclopentadienyl) niobium dichloride, tantalum pentachlo ide, titanium tetrachloride, cyclopentadienyltitanium trichloride, bis(cyclopentadienyl)titanium dichloride, zirconium tetrachloride, bis(cyclopentadienyl)zirconium dichloride, and bis(cyclopentadienyl)hafnium dichloride.
  • nickel fluoride 5 cobalt chloride
  • chromium chloride molybdenum chloride
  • tungsten chloride vanadium trichloride
  • Niobium and tantalum pentachloride both are also active cyclotrimerization catalysts for phenylacetylene but in the presence of diethyl.aluminum chloride, a different catalyst is present as indicated by the differing 1,2,4- to 1,3,5-selectivity ratios produced. " Furthermore, niobium and tantalum pentahalides can be modified by the addition of alkoxides, phenoxides, or mercaptides. Niobium tetrachloride and niobium trichloride have also been shown to be active catalysts.
  • Preferred catalysts include niobium pentachloride modified with lithium tert-butyl ercaptide, titanium tetrachloride-diethylaluminum chloride, and cyclopentadienyltitanium trichloride-diethylaluminum chloride.
  • polymers with molecular weights over 10 AMU and with essentially no residual ethynyl groups have been prepared using titanium tetrachloride and diethylaluminum chloride.
  • Lower molecular weight resins, i.e., with average molecular weight ⁇ 2,000 and with large amounts of residual ethynyl groups can be prepared for example using cyclopentandienyl titanium trichloride and diethylaluminum chloride.
  • Alkylacetylenes and diaryldiacetylenes may also be used to prepare prepolymers from a mixture of alkyl and/or arylacetylenes and polyacetylenically substituted aromatics.
  • the very high selectivity for cyclotrimerization exhibited by these catalysts enables the synthesis of polymers containing only minor amounts of linear oligomers (i.e. vinyl protons) under mild conditions and can be used to prepare polycyclotrimerized polyphenylene polymers.
  • the catalysts involve the reduction of transition metal salts of 1,3-dicarbonyl compounds with aluminum hydrides.
  • the activity and selectivity of the catalysts is, in general, dependent on the metal, added ligands, and reaction conditions. With some metals, other reductants such as sodium naphthalide or triisobutylaluminum may be used.
  • the catalyst systems make polyphenylene polymers which contain residual ethynyl groups.
  • the catalysts are prepared by reducing the transition metal compound with a dialkylaluminum hydride or trialkyl aluminum compound.
  • the transition metal compounds usually contain 1,3 dicarbonyl anionic ligand ⁇ such as acetylacetonates .
  • nickel(II)acetylacetonate is reduced in the presence of a triaryl phosphine with two molar equivalents of diisobutylaluminum hydride at or below room temperature, an active catalyst for the cyclotrimerization of acetylenes is obtained.
  • the catalyst activity is a function of the phosphine chosen, with ortho-substituted phosphines often providing the highest activity and selectivity.
  • aryl phosphines substituted at the ⁇ -ortho position with methyl or methoxy groups are more active than unsubstituted phosphines, which are more active than arylphosphites, which are more active than alkylphosphines.
  • the catalyst prepared at -20°C from one molar equivalent of nickel acetylacetonate, two molar equivalents of diisobutylaluminum hydride, and four molar equivalents of tri-o-tolylphosphine will catalytically cyclotrimerize phenylacetylenes to a mixture of 1,2,4- and 1,3,5-triphenylbenzene in which the former isomer predominates 45 to 1. Only trace amounts of dimer and linear trimer are produced. Catalysts prepared with the less active phosphorous ligands require higher reaction temperatures and afford products of lower isometric purity and lower selectivity for cyclotrimer compared to the linear oligomer.
  • a broad range of prepolymer types can be prepared by controlling the- reaction time and temperatures, the amount and type of ligands, the reaction medium, and the order and ratio of feedstock addition.
  • prepolymers of low molecular weight with cure energies of about 100-300 J/g can be selectively produced.
  • Aliphatic hydrocarbons or alcoholic solvents can be used for controlling properties since the polyphenylene resins can be - precipitated from the reaction media at the appropriate- conversion.
  • ' - Prepolymer processability is also a -function of the isomer selectivity of the cyclotrimerization catalyst. Since the relative amounts of 1,2,4- and 1,3,5-isomers can be varied by changing the reaction temperature, catalyst metal and the ligands around the catalyst, this provides an additional tunable variable to optimize resin properties and processability.
  • Catalysts which afford particularly high selectivity for cyclotrimerization compared to linear oligomerization for preparing prepolymers from phenylacetylene and diethynylbenzene include the following:
  • Nickel acetylacetonates reduced with diisobutylaluminum hydride or triisobutylaluminum in the presence of phosphines of phosphites.
  • Titanocene dichloride reduced with diisobutylaluminum hydride.
  • the catalysts can be used without prior treatment, by introducing them into the reaction vessel under an inert atmosphere, such as argon, either directly as solids, or solutions in aromatic solvents, such a toluene, followed by the introduction of the acetylene compounds to be polymerized.
  • an inert atmosphere such as argon
  • aromatic solvents such as a toluene
  • the same reaction is extendable to diacetylene and acetylene and to other mono-substituted acetylenes besides phenylacetylene, and to other diacetylene molecules (i.e., in which two acetylenic functions are linked by an organic fragment).
  • the catalyst is also expected to exhibit some activity in the similar reaction of disubstituted acetylenes and diacetylenes.
  • the reaction proceeds at room temperature or below.
  • the products are very clean, containing little, if any, linear polymer. They do contain sufficient amounts of terminal acetylenes to provide enough cure so that shape retention is possible upon molding. Curing occurs at about 150-170°C, preceded and accompanied by softening and melting.
  • polycyclotrimerization that yield final polymers with modified properties.
  • These functionalized polymers can contain residual, unreacted ethynyl groups and can be used as thermoset resins.
  • the functional groups can be the point of attachment of other molecules, including polymers, to prepare a wide spectrum of graft polymers. Such systems could provide better strength, thermal stability, chemical inertness to the ' grafted polymers, and improved composite properties.
  • the polymer prepared from diethynylbenzene, phenylacetylene and 3-methyl-3-buten-l-yne contains isopropenyl groups off the aromatic backbones which can be involved in olefin polymerizations with substrates such as ethylene, styrene, butadiene, etc.
  • the prepolymer may also be modified with a variety of electrophilic agents such as peracids, halogens, ozone, etc., allowing grafting of a wide variety of substrates to the functionalized polyphenylene resin.
  • polyphenylene polymers containing carboethoxy groups can be converted to acids, acid halides, amides, or alcohols, or transesterified.
  • Additional functional groups can be introduced through the incorporation of mono or polyethynyl silanes where the other substituents attached to the silicon atom contain the functionality.
  • the silanes could be - polymeric and. other metals or metalloids could be substituted for silicon.
  • thermosets adhesives
  • potting compounds dielectrics
  • Example 10 The following illustrates preparation of carboxy and functionalized branched polyphenylene prepolymers by cyclotrimerization.
  • a mixture of phenylacetylene (10 parts), 3-ethynylmethylbenzoate (10 parts), 1,3-diethynylbenzene (20 parts) and toluene (360 parts) are mixed in a reaction vessel.
  • the mixture is catalytically cyclotrimerized to yield a mixture of branched polyphenylene prepolymers containing methoxy carbonyl substituents.
  • Example 11 The following illustrates a preparation of 2-hydroxyethoxycarbonyl functionalized branched polyphenylene prepolymer.
  • the branched polyphenylene prepolymers containing methoxy carbonyl groups (as prepared in Example 10) are stirred with excess ethylene glycol and 0.05 parts sodium methoxide at about 110°C. Methyl alcohol distills off, and the reaction is worked up to yield a mixture of branched polyphenylene prepolymers containing 2-hydroxyethoxyca ' rbonyl substituents.
  • Example 12 The following illustrates preparation of 3-amino-propylamino carbonyl functionalized branched polyphenylene preopolymers.
  • the branched polyphenylene prepolymers containing methoxycarbonyl groups (1 part, prepared as in Example 10) are stirred with excess l, ' 3-diaminopropynyl solvent. Methyl alcohol distills off, and the reaction is worked up to yield a mixture of branched ' polyphenylene prepolymers containing 3-aminopropylaminocarbonyl substituents.
  • Example 13 The following illustrates the preparation of sodium carboxylate functionalized branched polyphenylene prepolymers by hydrolysis of the corresponding ester.
  • a carboxy ester-functionalized branched polyphenylene prepolymer (prepared, for example, as in Example 12), is dissolved in a solvent and treated with excess sodium hydroxide and a phase transfer catalyst. The reaction is worked up to yield a mixture of branched polyphenylene prepolymers containing sodium carboxylate substituents.
  • Example 14
  • the following illustrates the preparation of branched polyphenylene prepolymers containing hydroxy methyl substituents.
  • the branched polyphenylene prepolymers containing methoxycarbonyl groups are reacted with lithium aluminum hydride in tetrahydrofuran solvent.
  • the reaction mixture is worked up to yield branched polyphenylene prepolymers containing hydroxymethyl substituents.
  • Example 15 The following illustrates preparation of branched polyphenylene prepolymers containing hydroxy substituents.
  • 1,3-diethynylbenzene (20 parts); and toluene (360 parts) are mixed in a reactor vessel.
  • the mixture is catalytically cyclotrimerized to yield branched ⁇ polyphenylene prepolymers containing acetoxy substituents.
  • This material is then treated with aqueous caustic and phase transfer catalyst, and branched polyphenylene prepolymers containing hydroxy groups are isolated.
  • Example 16 The following illustrates preparation of branched polyphenylene prepolymers containing glycidylether substitutents .
  • Branched polyphenylene- prepolymers containing hydroxy substituents are treated with excess epichlorohydrin, and worked up to yield branched polyphenylene prepolymers containing glycidylether substituents.
  • the prepolymers may be prepared by polycyclotrimerizing a diacetylene with an aryl or alkyl nitrile. In general, the prepolymers are more basic and polar than the polyphenylene polymers and should be useful where these properties are desired.
  • the polyphenylene polymers include pyridyl rings and can be prepared with residual unreacted ethynyl groups. These polymers can also be used to form thermoset resins having excellent thermal and chemical stability and are 5 particularly useful for composites, adhesives, membrane materials, and thin film barriers.
  • cobalt catalysts can be used to prepare pyridyl containing polyphenylene polymers by cocyclotrimerizing bis(ethynyl)-compounds with aryl and
  • alkyl nitriles To control the residual ethynyl group content, the degree of crosslinking, the pyridine content, and the processability of the polymer, a monoacetylene, such as phenylacetylene, may also be added to the monomer feed. Cure energies greater than
  • Polymers may be prepared from nitrile containing monomers such as cyanobenzene, dicyanobenzene, cyanopyridine, cyanothiophene, perfluorocyanobenzene, dicyanomethane, and cyanoacetamide.
  • the diethynyl components include diethynylbenzene and
  • Example 17 The following is ' illustrative of the preparation of a pyridine containing prepolymer. Minor
  • the remaining contents of the addition funnel were added over a 2 hour period. Upon completion of the addition, 29% of the diethynylbenzene and 12% of the benzonitrile had been consumed. Two hours later the consumptions were 60 and 15%, respectively, and the catalyst Was inactive. The reaction was allowed to cool to room temperature overnight and was reheated the next morning. A second charge of 2.00 ml of catalyst was then added. An hour later the catalyst was inactive. Consumption of diethynylbenzene was 84% and benzonitrile was 18%. The reaction solution was cooled and dripped into 1500 ml of methanol. The yellow precipitate was rinsed twice with 300 ml of methanol before it was vacuum dried at 45°C for 16 hours to afford 52.66 g of yellow powder.
  • the prepolymer was compression molded by applying 670 lbs/in pressure to the powder in a mold and electrically heating the mold to 280°C. At 100°C the pressure had dropped to zero. At 160°C the pressure was re-applied to 330 lbs/in . After the mold reached 280°C, it was allowed to cool to 250°C under pressure before the.sample was removed hot. The coupon was then post-cured at 325°C for 17 hr under an , inert atmosphere. TGA analysis of a 120-170 mesh sample in air (50 ml/min) showed a %/hr weight loss at 316°C. Dynamic mechanical analysis showed a flexural modulus of 580 kp ⁇ i -at 50°C dropping to 410 dpsi at 325°C when heated at 5°/min under an inert atmosphere.
  • the number in parenthesis is the molar parts of the monomer mixed in the reaction.
  • Nitrogen content of the dry resin by combustion analysis.
  • the cure energy of the dry resin as determined by differential scanning calorimetry in sealed pans under the inert atmosphere. Curing generally occured between 150°C and 220°C at a heating rate of 10°/min.
  • PA phenylacetylene
  • DB 1,3-diethynylbenzene
  • DEE di-p-ethynylphenyl ether
  • a two-stage process for prepolymer formation involving polycyclotrimerization followed by oxi.dative ' coupling may also be used to produce prepolymers which contain manageable residual acetylene content.
  • the process calls for first preparing a resin with pendant acetylene groups via a cyclotrimerization polymerization.
  • the pendant acetylene groups are then oxidatively coupled either to each other or to other monomers, either mono- or difunctional, to give a higher molecular weight prepolymer (normally 10,000 to 100,000 AMW), which retains the acetylene content of the initial prepolymer and has desirable properties such as excellent crosslinking and high solubility.
  • difunctional acetylenes e.g., diethynyl benzene
  • difunctional acetylenes e.g., diethynyl benzene
  • monofunctional acetylenes e.g., acetylene, phenylacetylene
  • This moderate polyme ization may give, for example, a product with an average molecular weight of from ⁇ 350 to over 20,000 and with a pendant acetylene content of from ⁇ 0.5% to ⁇ 20%.
  • the cyclotrimerized polymer is then oxidatively coupled using a copper catalyst in the presence of a weak base (e.g., pyridine) and an oxidant (e.g., air, H 2 0 2 ) to give a higher molecular weight species which contains the same acetylene content.
  • a weak base e.g., pyridine
  • an oxidant e.g., air, H 2 0 2
  • Varying amounts of monofunctional acetylenes e.g., acetylene, phenylacetylene
  • difunctional acetylenes e.g., diethynyl benzene
  • difunctional acetylenes may be added to increase the average acetylene content or heteroatom containing difunctional acetylenes (e.g., diethynyl dipy idyl ether) to strengthen, toughen, stiffen, etc., the final resin.
  • difunctional acetylenes may be added with or without monofunctional acetylenes.
  • the final prepolymer is solvent processable and melt processable.
  • the high molecular weight (from -1000 to > 500,000) prepolymer contains a higher acetylene content per molecule than is available through a simple cyclotrimerization process and yet a manageable acetylene content, below the limit for uncontrolled cure.
  • the following examples are illustrative.
  • Example 18 The following illustrates the preparation of an oxidation coupled resin.
  • 20 g of resin (024-49) [Describe the resin], 100 mL of methylene chloride, 10 mL of pyridine, and 0.10g of cuprous chloride.
  • a polymerization solvent may be used in which the monomer is soluble but the polymer is not in order to control polymer molecular weight.
  • the solvent or mixture of solvents has the property that the monomers are soluble and the polymer of desired molecular weight is insoluble.
  • the molecular weight can be controlled but the extent of monomer consumption can be held at any level desired. In this way, polymerization- reactions may be run continuously. Soluble oligomers that result during preparation of the prepolymer can be recycled and used to prepare more prepolymer. Because catalyst may be occluded in the precipated prepolymer, make-up catalyst may have to be added.
  • the molecular weight o ' f the polymer obtained is due solely to the polarity of the solvent used and not - on the extent of reaction.
  • the solvent may be less polar than the polymer or more polar than the polymer .
  • a suitable less polar solvent would be a saturated hydrocarbon such as hexane, cyclohexane, octane or methylcyclohexane, or a mixture of a hydrocarbon and an aromatic solvent such as hexane and benzene or perfluorinated hydrocarbon.
  • a suitable solvent which is more polar than .the polymer might be lower ketones such as methyl ethyl ketone; other examples include ethyl acetate, alcohols such as methanol, ethanol, isopropanol; other examples are acetic acid or water or mixtures of these solvents either with each other or with a less polar solvent such as toluene.
  • Intermediate less polar solvents can be prepared by mixing these non-polar solvents with solvents which dissolve the polymers such as aromatic hydrocarbons, chlorinated solvents and oxygenated solvents.
  • Controlling the molecular weight of the polymer also enables control of the residual acetylene content of the resin.
  • the residual acetylene content is important in a thermoset resin in that it determines the degree of crosslinking in the final thermoset object which is produced and hence the physical and mechanical properties of the object.
  • the process of the invention affords control over the residual acetylene content without sacrificing the extent of monomer consumption in the resin preparation reaction.
  • Functional acetylenes may be polymerized either alone or with added monofunctional acetates. Very low molecular weight polymers may be recycled along with fresh difunctional acetylenes either with or without added monofunctional acetylenes. These polymerizations are conducted in a solvent or a mixture of solvents in which a polymer of desired molecular weight and therefore-corresponding desired residual acetylene content is insoluble.
  • Example 20 is illustrative.
  • the ethylcyclohexane solution from the first filtration was evaporated to give 91.9 g of an oil. It was calculated that the methylcyclohexane distillate contained 8 g of phenylacetylene and 5 g of diethynylbenzene. It was also calculated that the residue contained 9 g of phenylacetylene, 6 g of diethynylbenzene, and 54 g of a very low molecular weight polymer. The balance of the oil was solvent. Both recovered solvent and residual oil were recycled to a second batch of polymer along with 61.3 g of fresh phenylacetylene and 47.6 g of fresh diethynylbenzene. The total charge of polymer producing materials was 180 g-
  • the polymerization was run exactly as described above.
  • the prepolymer which precipitated from methylcyclohexane turned sticky upon warming to room temperature so it ' was immediately dissolved in 350 ml of tolueneN
  • the toluene solution of polymer was added over ⁇ 30 seconds to 3000 ml of methanol at room temperature with stirring. The mixture was stirred over a weekend and the polymer was then collected by filtration to afford 57.26 g of product after vacuum drying at room temperature.

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Abstract

L'invention se rapporte à des résines à haute teneur en carbone et à des procédés de préparation de ces résines, qui utilisent des compositions moussantes contenant: (a) un agent moussant, (b) un prépolymère aromatique sans saturation polyacétylénique, et (c) un modificateur de viscosité qui modifie les propriétés d'écoulement du prépolymère et qui comporte un ou plusieurs groupes acétyléniques pouvant entrer en réaction avec le prépolymère. L'agent moussant, le prépolymère et le modificateur de viscosité sont choisis de façon que, à la température de décomposition de l'agent moussant, la viscosité de la composition soit suffisante pour permettre les opérations de moulage et de moussage. Les groupes acétyléniques du modificateur de viscosité entrent en réaction avec les groupes acétyléniques résiduels du prépolymère pendant l'opération de moulage, de sorte que le modificateur de viscosité devient partie intégrante de la mousse finale, n'a pas à être retirer par la suite et ne se sépare pas par dissolution de la mousse ou n'altère pas ses propriétés chimiques ou physiques. Après le moulage la mousse peut être carbonisée pour produire une mousse au carbone utile dans des applications électriques.
PCT/US1990/007518 1989-12-15 1990-12-14 Resines et mousses a haute teneur en carbone Ceased WO1991009066A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100503432C (zh) * 2006-11-13 2009-06-24 同济大学 用芳基乙炔单体制备碳泡沫的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4026861A (en) * 1974-06-03 1977-05-31 Hercules Incorporated Thermosetting compositions containing poly(arylacetylenes)
US4097460A (en) * 1971-07-23 1978-06-27 Hercules Incorporated Poly(arylacetylenes) and thermoset resins therefrom
US4362680A (en) * 1980-03-21 1982-12-07 Showa Denko K.K. Process for production of molded articles of acetylene polymer
US4596684A (en) * 1981-07-30 1986-06-24 Toyo Rubber Chemical Industrial Corporation Method for manufacturing low density rubber foamed body

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4097460A (en) * 1971-07-23 1978-06-27 Hercules Incorporated Poly(arylacetylenes) and thermoset resins therefrom
US4026861A (en) * 1974-06-03 1977-05-31 Hercules Incorporated Thermosetting compositions containing poly(arylacetylenes)
US4362680A (en) * 1980-03-21 1982-12-07 Showa Denko K.K. Process for production of molded articles of acetylene polymer
US4596684A (en) * 1981-07-30 1986-06-24 Toyo Rubber Chemical Industrial Corporation Method for manufacturing low density rubber foamed body

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100503432C (zh) * 2006-11-13 2009-06-24 同济大学 用芳基乙炔单体制备碳泡沫的方法

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