EP0000385B1 - Durch Wärme härtbare Zusammensetzungen bestehend aus Polyarylacetylenen und substituierten Polyphenylenoxyden und durch ihre Härtung erhaltene Harze - Google Patents

Durch Wärme härtbare Zusammensetzungen bestehend aus Polyarylacetylenen und substituierten Polyphenylenoxyden und durch ihre Härtung erhaltene Harze Download PDF

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Publication number
EP0000385B1
EP0000385B1 EP78100334A EP78100334A EP0000385B1 EP 0000385 B1 EP0000385 B1 EP 0000385B1 EP 78100334 A EP78100334 A EP 78100334A EP 78100334 A EP78100334 A EP 78100334A EP 0000385 B1 EP0000385 B1 EP 0000385B1
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composition
prepolymer
poly
fluidizer
phenylene oxide
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French (fr)
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EP0000385A1 (de
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James Edwin French
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Hercules LLC
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Hercules LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C08L65/02—Polyphenylenes
    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L49/00—Compositions of homopolymers or copolymers of compounds having one or more carbon-to-carbon triple bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/312—Non-condensed aromatic systems, e.g. benzene

Definitions

  • thermosetting compositions and thermoset resins therefrom. More particularly, the invention relates to such compositions and resins based on certain poly(arylacetylene)s and poly(phenylene oxide)s:
  • compositions of GB-PS 1398 142 can be cured simply by heating, and this operation need not be carried out under pressure, since there is no gas evolution during the curing step.
  • thermoset resins having significant thermal stability and desirable flexural properties. Nevertheless, it was recognized that it would be desirable for these resins to have even greater oxidative thermal stability, and it was found, in accordance with US-PS 3,931,093, that the addition of a phenol-aldehyde resin to the thermosetting compositions of GB-PS 1,398,142 decreased the oxidative weight loss of the cured compositions on exposure to high temperatures over an extended period of time.
  • thermosetting compositions comprising a polyacetylenically unsaturated prepolymer and a phenol-aldehyde resin.
  • the prepolymer is a polymer of at least one polyacetylenically substituted aromatic compound, such as diethynylbenzene, and has a number average molecular weight of about 900 to about 12,000 and contains about 5 to about 20% by weight of terminal acetylenic groups.
  • thermosetting compositions which comprise from 5 to 30% by weight of a poly(2,6 - dialkyl - 1,4 - phenylene oxide) and from 70 to 95% by weight of a polymer composition comprising a prepolymer of at least one polyacetylenically substituted aromatic compound, said prepolymer having a number average molecular weight of from 900 to 12,000, as determined by vapor pressure osmometry, a ratio of aromatic protons to olefinic protons greater than 2.4:1, preferably greater than 7.5:1, and preferably as high as 38:1, and containing from 5 to 20% terminal acetylenic groups by weight of the prepolymer.
  • the amount of the poly - (2,6 - dialkyl - 1,4 - phenylene oxide) preferably is from 10 to 20% by weight of the thermosetting composition, and the corresponding amount of the polymer composition is from 80 to 90% by weight of the thermosetting composition.
  • the polymer composition preferably contains a fluidizer for the prepolymer component.
  • the poly(2,6 - dialkyl - 1,4 - phenylene oxide) additives used in accordance with this invention perform a different function from that of the phenol-aldehyde resins of US-PS 3,931,093, and the results obtained in accordance with this invention not only were unexpected, since the poly(2,6 - dialkyl - 1,4 - phenylene oxides) by themselves degrade rapidly at temperatures from 230° to 260°C., but also could certainly not have been predicted from US-PS 3,931,093.
  • thermoset resins of this invention are prepared in two stages.
  • a polymer composition is formed from a polyacetylenically unsaturated prepolymer of a polyacetylenically substituted aromatic compound, and there preferably is incorporated into this composition a fluidizer for the prepolymer.
  • the polymer composition is combined with a poly(2,6 - dialkyl - 1,4 - phenylene oxide), and the resulting thermosetting composition then can be fabricated and heated, whereby resinification takes place.
  • thermoset resins in any desired shape, since those thermosetting compositions containing the prepolymer, a fluidizer for the prepolymer and the poly(2,6 - dialkyl - 1,4 - phenylene oxide) are readily formed into any desired shape, and these molded, or otherwise formed, articles can then be cured by heating and will retain their shape.
  • the first stage in the preparation of the thermoset resins of this invention includes the formation of a prepolymer from at least one polyacetylenically substituted aromatic compound.
  • the polyacetylenically substituted aromatic compound used to prepare these prepolymers can be any aromatic compound containing two or more acetylene groups, that is, two carbons linked by a triple bond. These groups may be attached to the same aromatic ring or to different aromatic rings in the compound.
  • Those compounds containing at least one external acetylenic group are preferred since these are the most reactive.
  • those compounds containing only internal acteylenic groups are used in admixture with a compound containing at least one ethynyl group.
  • Exemplary of the polyacetylenically substituted aromatic compounds are m-diethynylbenzene and p-diethynylbenzene; the diethynyl toluenes; the diethynyl xylenes; 9,10-diethynylanthracene; diethynylbiphenyl; 9,10-diethynylphenanthrene; 4,4' - diethynyl - transazobenzene; di-(ethynylphenyl)ether; 2,3,5,6 - tetrachloro - 1,4 - diethynylbenzene; diphenyl-diacetylene (i.e., diphenylbutadiyne); dibenzyldiacetylene; di - p - tolyldiacetylene; di - a - naphthyldiacetylene 1 - chloro -
  • the polyacetylenically substituted aromatic compounds may be characterized as containing two to three acetylenic groups and one to seven aromatic rings, which rings are selected from the benzene, naphthalene, anthracene and phenanthrene rings and mixtures thereof.
  • Monoacetylenically substituted aromatic compounds such as phenylacetylene, biphenylacetylene and diphenylacetylene may be used in admixture with the polyacetylenically substituted aromatic compounds in the preparation of the prepolymers.
  • Representative of such an admixture is that of diethynylbenzene with phenylacetylene.
  • the diethynylbenzene component may be m-diethynylbenzene, p-diethynylbenzene or mixtures thereof.
  • the phenylacetylene component enters the resulting copolymer at approximately one-half the rate of the diethynylbenzene component.
  • considerable variation in the composition of the reaction mixture is possible in producing copolymers containing from 10 to 45% by weight of phenylacetylene-derived units.
  • the prepolymerization reaction is carried out by heating the monomeric polyacetylenically substituted aromatic compound with an aromatization catalyst to effect polycyclotrimerization of the monomer.
  • the reaction can be carried out in bulk or in the presence of an inert diluent.
  • Any inert diluent can be used, as, for example, ethers such as 1,2-dimethoxyethane, dioxane and tetrahydrofuran, ketones such as acetone, or aromatic hydrocarbons such as benzene, toluene and xylene.
  • the amount of diluent used is not critical and generally will be such as to form a concentration of the polyacetylenically substituted aromatic compound in the diluent of from 2 to 50%. Obviously, larger or smaller amounts of the diluent can be used.
  • the temperature during the polymerization reaction will be from 55°C. to 250°C., and more preferably from 80°C. to 150°C. The reaction desirably is carried out in an inert atmosphere.
  • an aromatization catalyst is a catalyst that promotes the formation of an aromatic ring by the cyclization of three acetylene groups.
  • Preferred aromatization catalysts are nickel catalysts such as nickel bis(acrylonitrile), nickel bis(acraldehyde), nickel carbonyl bis(triphenylphosphine), nickel cyanide bis(triphenylphosphine) and nickel acetylacetonate in combination with triphenylphosphine.
  • the Group IV-B metal halides such as titanium tetrachloride in combination with diethylaluminum chloride,.
  • the Group V-B metal halides such as the niobium pentahalides and tantalum pentahalides also may be used as catalysts.
  • the amount of the catalyst used can be varied widely but generally will be from 0.5 to 5% of the monomer by weight.
  • the reaction is essential to stop the reaction prior to complete conversion of the monomer. If the reaction is allowed to go to completion, the product is an insoluble, infusible material that cannot be plastic formed, nor can it be fluidized with a fluidizer and then plastic formed. Hence, the reaction is generally stopped at a monomer conversion above 30% and below 90%, and preferably at a monomer conversion of from 50% to 90%.
  • prepolymer having a number average molecular weight of from 900 to 12,000, avoid the production of very high molecular weight materials which are of essentially no use in the production of plastic formed articles, and at the same time retain in the prepolymer from 5 to 20% terminal acetylene groups by weight of the prepolymer for reaction in the second stage of the thermoset resin preparation.
  • the prepolymers are soluble in aromatic hydrocarbons, ketones and ethers.
  • the method by which the polymerization reaction is stopped and the prepolymer is isolated will depend in large measure on the method used in preparing the prepolymer and on the monomer or monomers used in its preparation. If a monomer of comparatively high volatility is used in preparation of the prepolymer, then any of such a monomer remaining in the prepolymer should be removed to avoid foaming and void formation in the plastic forming and curing steps used in the preparation of the thermoset resin in the second stage reaction. This removal can be effected by vacuum evaporation or steam distillation of the polymerization reaction mixture, or the reaction mixture can be mixed with a diluent which is a solvent for the monomer and a non-solvent for the prepolymer.
  • the prepolymer can be separated, as by filtration, and the monomer, any prepolymer remaining in solution, and the diluents can be recovered and recycled in the process.
  • Suitable diluents for precipitating the prepolymer are methanol, ethanol and isopropanol, and aliphatic hydrocarbons or mixtures thereof such as petroleum ether, pentane, hexane or heptane.
  • thermosetting compositions of this invention may not have the flow properties required for plastic forming at temperatures below the cure temperature for these compositions. Therefore, it ordinarily is desirable in the practice of this invention to include a fluidizer for the prepolymer in the thermosetting composition, thereby making it possible to produce a composition that will have sufficient flow to permit plastic forming and that, when further heated after plastic forming, will cure to produce a thermoset resin.
  • fluidizer used in accordance with this invention is that represented by the acetylenic fluidizers disclosed in the aforementioned GB-PS 1398 142. These fluidizers are mono- or polyacetylenically substituted aromatic compounds having a melting point below 185°C. and a boiling point above 250°C., or a vapor pressure at 125°C. of less than 20 mm.
  • acetylenic fluidizers are beta-naphthyl acetylene, biphenylacetylene, 4 - ethynyl - transazobenzene, diphenylacetylene, di - m - tolylacetylene, di - o - tolylacetylene, bis(4-ethylphenyl)acetylene, bis(3,4-dimethyl)acetylene, bis(4-chlorophenyl)acetylene, phenyl benzoyl acetylene, beta-naphthyl- phenylacetylene, di(alpha-naphthyl)acetylene, 1,4-diethynylnaphthalene, 9,10-diethynylanthracene, 4,4'-diethynylbiphenyl, 9,10-diethynylphenanthrene, 4,4' - diethyn
  • Another type of fluidizer which can be used in accordance with this invention is that represented by certain aromatic organic compounds having specified structure and physical characteristics. For the sake of convenience, these compounds may at times be referred to herein as aromatic fluidizers. These compounds are described in GB-PS 1435 305. In general, these compounds are characterized by containing at least two six-membered aromatic rings, said rings being condensed with each other or coupled with each other directly or through a single oxygen, sulfur, nitrogen or phosphorus atom or through a methylene, dimethylmethylene, ethylene, vinylene or keto group. These compounds or mixtures thereof are additionally characterized by containing no crystalline organic phase at 220°C., having a viscosity of less than 20 centipoises at 220°C.
  • the fluidizer compounds may be used either individually or in admixture with each other.
  • Other materials may be present in small amounts, if they do not detract from the desirable characteristics of the fluidizing compounds and if the mixture meets the specified physical properties requirements. For example, small amounts of volatile materials, can be tolerated in mixtures with higher boiling materials, without causing void formation in the compositions during cure. Also, higher melting materials can be tolerated in admixture with other compounds which will depress the melting point of the mixture to the desired temperature.
  • the fluidizer compound acts on the prepolymer to produce a plastic formable composition. It is believed that in part it acts as a plasticizer, making it possible to shape the prepolymer, and in part that it may undergo a partial reaction with the prepolymer. In any event, the actylenic fluidizers, unlike ordinary plasticizers, react with the prepolymer when the plastic formed composition is cured and hence become a part of the final thermoset resin.
  • the amount of fluidizer incorporated in the polymer composition comprising the prepolymer can be varied over a wide range, but from a practical standpoint will generally be from 2% to 70% by weight of the prepolymer.
  • the amount of fluidizer in the thermosetting composition will be from 1% to 29%, and the corresponding amount of prepolymer will be from 69% to 41 %.
  • the amount of fluidizer in the thermosetting composition will be from 2% to 39%, and the corresponding amount of prepolymer will be from 93% to 56% by weight.
  • the amount of fluidizer will be from 5% to 40% ' by weight of the prepolymer.
  • the fluidizer can be incorporated in the polymer composition in a variety of ways.
  • One of the simplest methods is to mix the prepolymer and fluidizer in a diluent that is a solvent for the two materials and which is preferably low boiling for ease in removing the diluent after the mixing operation.
  • the mixing operation can be carried out at any convenient temperature, generally at room temperature.
  • Suitable diluents for this purpose are chlorinated hydrocarbons, such as methylene chloride and dichloroethane, and aromatic hydrocarbons, such as benzene and toluene. Such diluents can be removed by evaporation after adequate mixing has been achieved.
  • the unreacted portion does not need to be removed from the prepolymer and can act as all or part of the fluidizer in the thermosetting composition.
  • the poly(2,6 - dialkyl - 1,4 - phenylene oxide) component of the compositions of this invention also can be combined in a number of ways with the polymer composition comprising the prepolymer.
  • the solvent technique just described for incorporation of the fluidizers may be used. This method can be particularly efficient if a fluidizer is employed, since both the fluidizer and the poly(2,6 - dialkyl - 1,4 - phenylene oxide) can be incorporated into the thermosetting composition at the same time.
  • An interesting variation of the solvent technique is one in which the thermosetting composition is isolated by water precipitation.
  • the poly(2,6 - dialkyl - 1,4 - phenylene oxide) and a fluidizer such as diphenylamine may be dissolved in hot tetrahydrofuran and the resulting solution cooled to 50°C.
  • the prepolymer component then may be dissolved in the solution and the solution subsequently slowly added to an excess of water with vigorous stirring.
  • the precipitated composition then may be isolated by filtration and dried, usually in a vacuum oven at a temperature of 45°C.
  • thermosetting compositions of this invention are well known in the art. These polymers and the process of producing them are described, for example, in US-PS 3,306,874 and US-PS 3,306,875.
  • the particular polymers used in accordance with this invention are those in which the alkyl substituents contain one to three carbon atoms.
  • the preferred polymer for the purposes of this invention is poly(2,6 - dimethyl - 1,4 - phenylene oxide).
  • the number average molecular weight of these polymers generally will be in the range of from 15,000 to 75,000, preferably from 20,000 to 50,000, corresponding to an intrinsic viscosity of from 0.5 to 1.0.
  • thermosetting composition fillers, pigments, antioxidants and other desired additives.
  • additives are readily incorporated at the time the other components of the thermosetting composition are combined with each other.
  • Exemplary of the materials that can be incorporated are organic and inorganic fibrous materials such as graphite, glass, asbestos, metal, metal oxide, metal carbide, boron, boron carbide, boron nitride and silicon carbide fibers, and particulate reinforcements such as glass beads, metal oxides, metal carbonates, clay, talc, silica, diatomaceous earth, carbon, graphite, molybdenum sulfide and powdered fluorocarbon resins.
  • the amount of filler incorporated in the thermosetting composition can be varied widely, but generally will be from 1 to 95 percent by weight of the filled composition.
  • compositions so obtained can be divided by any desired means into suitably sized pieces for subsequent fabrication operations.
  • the compositions can be ground to fine powders and converted into pellets convenient for utilization in subsequent operations by compacting under pressure at room temperature or at a somewhat elevated temperature.
  • These thermosetting compositions are stable and can be stored at room temperature.
  • thermosetting compositions of this invention will flow on heating and remain sufficiently fluid so that the compositions can be shaped by conventional plastic forming such as extrusion, compression, transfer and injection molding, calendering and forging.
  • plastic forming such as extrusion, compression, transfer and injection molding, calendering and forging.
  • shapes such as sheets, pipes, rods and wire coatings can be made by extrusion.
  • Sheets can in subsequent operations be further modified in form as by embossing or thermoforming. More complex shapes can be made by molding operations.
  • Coatings can be prepared by application of solutions of the thermosetting compositions of this invention in solvents such as tetrahydrofuran.
  • the temperature employed in plastic forming and related operations can be varied widely, the preferred temperature being dependent on the amount of fluidizer when one is employed, the molecular weight of the prepolymer, the amount of the poly(2,6 - dialkyl - 1,4 - phenylene oxide), the type and amount of any filler or reinforcing agent present, the fabrication method, the pressure employed, and the amount of curing desired during the fabrication operation. Temperatures as low as 40°C. can be used, or as high as 200°C., but generally will be within the range of from 90°C. to 165°C.
  • thermosetting composition resolidifies.
  • low temperatures are employed to avoid much change in the flow properties of the composition during its fabrication.
  • transfer or compression molding it may be desirable to fabricate the material at an elevated temperature so that curing of the material occurs during the shaping operation.
  • the temperature at which the thermosetting composition is heated to effect further polymerization which can be referred to as the curing operation, can be varied widely and will depend on such factors as the components of the thermosetting composition and the size and shape of the fabricated article. In general, the conditions for effecting the cure will range from several hours at a temperature of 100°C. to a few minutes at a temperature of 300°C. Alternatively, a fabricated article can be used in its only partially cured form, and curing can be effected during use at an elevated temperature.
  • thermosetting compositions containing an acetylenic fluidizer The reaction that takes place during the curing of those thermosetting compositions containing an acetylenic fluidizer involves a copolymerization reaction between the prepolymer and the acetylenic fluidizer, which reaction may effect some cross-linking of the prepolymer.
  • reaction during curing primarily is one of further polymerization of the prepolymer.
  • the thermoset resins so produced are hard, stiff, strong, abrasion resistant, infusible and insoluble. They retain strength, stiffness and insolubility at elevated temperatures, are stable to exposure at elevated temperatures for extended periods, and are resistant to oxidative attack at elevated temperature.
  • thermosetting compositions of this invention are resistant to chemical attack by strong acids and concentrated alkali and are resistant to swelling by organic solvents at elevated temperatures.
  • the inclusion of the poly(2,6 - dialkyl - 1,4 - phenylene oxide) in the thermosetting compositions of this invention provides thermoset resins having improved flexural properties and markedly improved strength retention upon oxidative aging at elevated temperatures.
  • This combination of properties was quite unexpected, since the poly(2,6 - dialkyl - 1,4 - phenylene oxide)s rapidly degrade at elevated temperatures such as from about 230° to about 260°C.
  • at high temperatures in air there is a synergistic interaction of the components of the thermoset resins, resulting in lower stress concentrations which, in turn, decrease cracking and prevent undue loss of strength.
  • thermosetting compositions of this invention are useful as thermosetting binder resins for glass, carbon, asbestos, graphite, alumina, silicon carbide, boron nitride and boron fibers, and for particulate materials such as molybdenum sulfide and powdered fluorocarbon resins, and in the preparation of moldings to be used in high temperature environments, as for example, turbine blades for jet engines, aeroplane wing edges, ablative coatings for space reentry vehicles, bearings, grinding wheels, brake linings and clutch facings.
  • the compositions also are useful as chemically resistant coatings and as temperature resistant adhesive and potting compounds.
  • thermosetting compositions and the thermoset resins of this invention. All parts and percentages are by weight unless otherwise indicated.
  • a polymerization vessel was charged with a mixture of 630 parts of meta-diethynylbenzene and 70 parts of paradiethynylbenzene dissolved in 3077 parts of anhydrous benzene.
  • the solution was sparged with nitrogen and heated to reflux temperature. There then was added to the refluxing solution in four approximately equal increments a catalyst mixture prepared by mixing 4.7 parts of nickel acetylacetonate and 9.3 parts of triphenylphosphine in 50 parts of anhydrous benzene. After addition of the initial increment, the others were separately added one, two and three hours later.
  • the solution was held at reflux temperature for a total of six and one-quarter hours, at which time the monomer conversion was 85.5%.
  • the prepolymer then was precipitated by adding the solution to seven times its volume of petroleum ether and the yellow powder, separated by filtration, amounted to 406 parts.
  • the prepolymer contained 11.8% acetylene groups.
  • the prepolymer used in this example was prepared by repeating the polymerization reaction of Example 1 several times. Monomer conversion in these reactions was in the range of 85­-89%. The reaction mixtures then were added to approximately six times their total volume of heptane, and the precipitated prepolymer was recovered by filtration.
  • a molding composition was prepared from 64.0 parts of the prepolymer, 16.0 parts of 1,4-diphenylbutadiyne as fluidizer and 20.0 parts of poly(2,6 - dimethyl - 1,4 - phenylene oxide) (number average molecular weight: 20,000).
  • the prepolymer and the fluidizer were dissolved in benzene, using approximately two milliliters of benzene per gram of solids.
  • the two benzene solutions then were blended with each other, after which the benzene solvent was removed using a rotary evaporator.
  • the residual composition was dried overnight at 45°C. under vacuum, ball milled for approximately six hours in a ceramic mill with ceramic balls and again dried at 45°C. overnight under vacuum.
  • a composition containing only the prepolymer and the 1,4-diphenylbutadiyne in the indicated amounts was prepared in the same way.
  • the resulting compositions then were formed into disks 890 p, (35 mils) thick and 2,54 cm (1 inch) in diameter by compression molding in a fully positive three-disk mold.
  • Each of the three sections of the mold was charged at room temperature with a sample of the composition and the mold was placed in a preheated press. Pressure was applied to consolidate the samples and then released. As the temperature of the mold approached 100°C., 422 kg/cm 2 (6,000 p.s.i.) pressure was applied and heating was continued to a mold temperature of 150°C.
  • the molded disks were removed from the mold, and, after cooling to room temperature, were cured at atmospheric pressure in a forced air oven programmed to heat up slowly from room temperature to 235°C. over a period of nine and one-half hours, hold at 235°C. for one-half hour and then cool to 55°C. over a period of five and one-quarter hours.
  • the flexural strength and flexural modulus of the cured compositions were determined by measurement of the forces required to cause deflection and ultimate failure of the disk specimens when these forces were applied at the unsupported centers of the specimens. The data obtained are given in Table I.
  • Molding compositions were prepared as in Example 2 except for use of diphenylamine (DPA) as the fluidizer in most of the compositions instead of diphenylbutadiyne (DPBD).
  • DPA diphenylamine
  • DPBD diphenylbutadiyne
  • the resulting compositions were formed into flex bars 12,7 x 1,27 x 0,32 cm (5" x 1/2" x 1/8") by compression molding in a three-bar mold.
  • the molding and curing conditions were generally the same as those used in Example 2, except the moldings usually were held for 15 minutes at pressure after the mold temperature reached 150°C. Prior to curing, the flex bars were cut in half to form bars 6,35 cm (two and one-half inches) in length.
  • the flexural properties of the cured compositions were determined using the special flex testing jig according to ASTM D - 790, Method I (three-point loading), Procedure A (0.01 in./in. strain rate). Testing was usually done at a 16:1 ratio of span:thickness. Normally, the span was 5,08 cm (two inches) and the crosshead speed was 0,127 cm (0.05 inch) per minute. The data given in Table II are in most instances the average of three measurements.
  • Example 3 Several of the cured compositions of Example 3 were subjected to oxidative aging in a forced air oven at 260°C. for a period of approximately 310 hours. After aging, the flexural properties of the compositions were determined following the procedure of Example 3. The data obtained are shown in

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Claims (8)

1. Wärmehärtbare Zusammensetzung aus einer Polymerzusammensetzung bestehend aus einem Vorpolymer von zumindest einer polyacetylenisch substituierten aromatischen Verbindung, wobei dieses Vorpolymer ein Zahlenmittel-Molekulargewicht von 900 bis 12.000 besitzt, ein Verhältnis von aromatischen Protonen zu olefinischen Protonen von größer als 2,4 und bezogen auf das Gewicht des Vorpolymers 5 bis 20% terminale Acetylengruppen aufweist, dadurch gekennzeichnet, daß ein Poly(2,6 - dialkyl - 1,4 - phenylenoxid), welches 1 bis 3 Kohlenstoffatome in den Alkylsubstituenten enthält, in der wärmehärtbaren Zusammensetzung enthalten ist, wobei die Mengen des Poly(2,6 - dialkyl - 1,4 - phenylenoxids) und der Polymerzusammensetzung enthaltend das Vorpolymer 5 bis 30 Gew.-% bzw. 70 bis 95 Gew.-% bezogen auf den Gesamtpolymergehalt der wärmehärtbaren Zusammensetzung betragen.
2. Zusammensetzung gemäß Anspruch 1, in welcher das Vorpolymer ein Polymer eines Diäthynylbenzols ist.
3. Zusammensetzung gemäß Anspruch 1, worin die Polymerzusammensetzung zusätzlich ein Fluidisierungsmittel für das Vorpolymer enthält.
4. Zusammensetzung gemäß Anspruch 3, worin das Fluidisierungsmittel Diphenylbutadiyn ist.
5. Zusammensetzung gemäß Anspruch 3, worin das Fluidisierungsmittel Diphenylamin ist.
6. Zusammensetzung gemäß Anspruch 1, worin das Poly(2,6 - dialkyl - 1,4 - phenylenoxid) Poly(2,6 - dimethyl - 1,4 - phenylenoxid) ist.
7. Zusammensetzung gemäß Anspruch 6, worin die Menge des Poly(2,6 - dimethyl - 1,4 - phenylenoxids) 10 bis 20 Gew.-% beträgt.
8. Wärmehärtbares Harz erhalten durch Hitzehärtung der Zusammensetzung gemäß Anspruch 1.
EP78100334A 1977-07-08 1978-07-07 Durch Wärme härtbare Zusammensetzungen bestehend aus Polyarylacetylenen und substituierten Polyphenylenoxyden und durch ihre Härtung erhaltene Harze Expired EP0000385B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US814053 1977-07-08
US05/814,053 US4144218A (en) 1977-07-08 1977-07-08 Thermosetting compositions containing a poly (arylacetylene) and a poly (phenylene oxide)

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EP0000385A1 EP0000385A1 (de) 1979-01-24
EP0000385B1 true EP0000385B1 (de) 1981-08-26

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EP78100334A Expired EP0000385B1 (de) 1977-07-08 1978-07-07 Durch Wärme härtbare Zusammensetzungen bestehend aus Polyarylacetylenen und substituierten Polyphenylenoxyden und durch ihre Härtung erhaltene Harze

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US (1) US4144218A (de)
EP (1) EP0000385B1 (de)
DE (1) DE2860977D1 (de)

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Also Published As

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US4144218A (en) 1979-03-13
EP0000385A1 (de) 1979-01-24
DE2860977D1 (en) 1981-11-19

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