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    • 专利摘要:
    The invention relates to thermosetting compositions which are blends of novel poly(arylacetylenes) and, as fluidizers, certain aromatic organic compounds containing at least two aromatic rings. The poly(arylacetylenes) are prepolymers of polyacetylenically substituted aromatic compounds, which prepolymers have a number average molecular weight of from about 900 to about 12,000 and contain from about 5 to 20% by weight of acetylenic groups. Diethynylbenzene is one of the preferred monomers used in preparation of the prepolymers. Representative of the compounds containing at least two aromatic rings are anthracene, phenanthrene and diphenylmethane. The compositions are curable by heat to produce thermoset resins which have very desirable physical properties at both normal and high temperatures.
    公开号:SU867317A3
    申请号:SU731979611
    申请日:1973-12-17
    公开日:1981-09-23
    发明作者:Клайд Кессна Младший Лоренс
    申请人:Геркулес Инкорпорейтед (Фирма)；
    IPC主号:
    专利说明:

    one
    The invention relates to heat-resistant thermosetting compositions and thermosetting resins based on them, and more specifically to such compositions and resins that are derived from acetylenic substituted aromatic compounds.
    High temperature resins, currently available, have various drawbacks that limit their use in many cases. One of the most frequently encountered is. The disadvantage is the release of volatile substances during the cure cycle, which makes it imperative that the cure cycle be carried out under pressure. For example, polyimides, when cured by vulcanization, release volatile components that cause the formation of gas bubbles tO or cavities in the cured resin, if significant pressure is not maintained during the curing operation. When the phenolic resins are cured, water is released, which also causes the formation of cavities if the curing reaction is not under pressure. Another of the disadvantages of previously known high temperature resins is their non-
    the ability to form into the required forms using conventional methods due to their poor flow characteristics.
    The known heat-resistant thermosetting composition comprising a polymer — polyphenylene; and an aromatic compound — benzened sulfonyl chloride.
    The disadvantages of the known composition are that in the course of its curing, volatile substances are released, and the temperature to which it must be heated to obtain the necessary fluidity is above 200 ° C.
    The purpose of the invention is to improve the technological properties of the composition.
    This goal is achieved in that the composition as a polymer contains polyacetylene with a number average molecular weight of 1010-9700, acetylenic unsaturation of 4.4-15% and a ratio of aromatic and olefinic protons of 5.5t1-30: 1, and as an aromatic compound - organic a compound containing at least two six-membered condensed with each other or connected to each other directly, through a heteroatom, through a hydrocarbon or keto group of aromatic rings with the following ratio of components, weight. h : Polyacetylene100 Aromatic Compound2-100 Thermosetting resins obtained by curing the thermosetting compositions of the present invention are characterized in that they are substantially free of aliphatic saturation and are predominantly aromatic in structure.  These thermosetting resins are further characterized by the presence of flexural strength. at least. 4,000.  pounds per square.  inch - (281.2 kg / cm) And the modulus of flexibility, at i-iepe, is about 350,000 psi.  inch (24605 kg / cm2).  Most resins are also characterized by retaining at least 35% of the indicated flexibility modulus. to a temperature of at least about in an inert atmosphere while retaining at least about 35% of the specified flexural and modulus resistance and at least about 80% of their weight when storing a sheet with a thickness of 30 mil (0.75 mm) per air at 270 ° C for 220 hours, and a loss of less than 20% Of the weight when they are heated in powder form to 500 s at a rate of 10 ° C per minute in an inert atmosphere.  The thermosetting resins of the present invention are prepared using a two-step process.  In the first stage, polyacetylene unsaturated prepolymers are prepared from polyacetylene substituted aromatic compounds.  At the second stage, the prepolymer in combination with at least one of the aromatic organic compounds containing at least two six-membered aromatic rings, taken as a flow agent, is treated and heated, whereby the formation of resin occurs.  Using these techniques, a thermosetting resin can be obtained in any desired form, since the mixture of a pre-sampler and an aromatic compound is easily molded into any desired form, and this molded or otherwise molded product can then be cured by heat and retains its shape.     The first stage is the preparation of thermo-reactive. The resins in the invention represent the formation of a prepolymer from at least one polyacetylene aromatic compound, the prepolymer is subsequently mixed in a second stage with an aromatic organic compound that gives fluidity, and the resulting thermosetting composition is then thermally processed and vulcanized .  The polyacetylene substituted aromatic compound used to prepare these prepolymers can be any aromatic compound containing two or more acetylene groups (t. e.  when two carbon atoms are connected by a triple bond) attached to the same aromatic ring or to different aromatic rings in the compound, knH mixtures of such compounds.  Acetylene groups can be internal, t. e.  acetylenic groups such as aryl-C-C-aryl, or they may be external, t. e.  ethynyl groups of the aryl-C-C-H type, or both types may be present in the polyacetylene compound.  Compounds containing at least one external acetylene group are preferred because they are the most reactive.  Typically, compounds containing only internal acetylenic groups are used in admixture with a compound containing at least one ethynyl group.  Examples of polyacetylenic substituted aromatic compounds are m- and p-diethinylbenzolols, diethyltin toluene) Diethynyl xylenes, 9,10-diethynyl anthracene, diethynylbiphenyl, 9-10-diethynylphenanthrene) 4, 4-diethynyl trans-azobenzene; di (ethynylphenyl) ether 2, 3, 5, 6-tetrachloro-. 1,4-diethylbenzene; diphenyldiacetylene (t. e.  diphenylbutadiene); Dibenzyl-diacetylenJ di-p-tolyldiacetylene; di-C1-naphthyldiacetylene J 1-chloro-2, 5-di-ethynylbenzene) 2,2-dichlorodiphenyl-diacetylene; 4,4 - di chlorine phenyl yl di acetylene,. 4,4 -dibrocciphenyl-diacetylene} 1,4,4-bis (phenylethynyl) benzene;  1, 3-bis (phenylethynyl) benzene; 9,10-bis- (phenylethynyl) anthracene, - 1,3,5-triethylenbenzene; 1,2,4-triethenylbenzene J 1,3,5-tris (phenylethynyl); 2, 4, 6-triphenylbenzene, 1,2,4-tris (phenylethynyl-3,5,6-triphenylbenzene, tris (ethynylphenyl benzene, etc.  Mono-acetylenic substituted aromatic compounds can also be used in the preparation of a pre-sample, such as, for example, phenylacetylene, biphenylacetylene and diphenyl acetylene.  As previously mentioned, mixtures of polyacetylene substituted aromatics can be used to prepare prepolymers.  A mixture of diethenylbenzene and diphenylbuttine is especially beneficial, with the latter component being about 30 to 75% by weight of the total resin.  The distiline component may be m-diethyl benzene, p. -diethenylbenzene or mixtures thereof.  The resulting copolymers contain about 30-75% by weight of units of pro-diphenyl butadiene, since the diphenyl-butadiene component is included in the copolymer to the same extent as the diethinyl benzene component.  Eons from polymers can be cured after displacement, with at least one of the aromatic flow agents of the present invention, to obtain a thermosetting resin having a prescribed strength and resistance to oxidation at high temperature.  In addition, the resins obtained from these copolymers have much higher elongation at break, about 1.1-1.8% compared with the corresponding resins originating from diethinylbenzene homopolymer, in which the elongation at break is less 1.0%.  Another successful mixture of diethinylben ash with phenylacetylene can be m-diethyl benzene, p-distinyl benzene or mixtures thereof.  In this case, the phenylacetylene component enters into copolymers of approximately half the power of the diethinylbenzene component.  Thus, upon receipt of copolymers containing from about 10 to 45% by weight of units derived from phenylacetylene, considerable variation in the composition of the reaction mixture is possible.  The resulting copolymers, when combined with at least one of the aromatic flow agents of the proposed invention, can be cured, giving thermosetting resins having the prescribed resistance properties to oxidation at high temperature.  In addition to TorOj, these resins are much better in bending resistance and modulus of flexibility compared to the corresponding resins prepared from diethyl benzene homopolymers.  The prepolymerization reaction is carried out by heating the polyacetyl substituted aromatic compound with a catech aromatization agent.  The reaction may be carried out in bulk or in the presence of an inert diluent.  Any inert diluent may be used, such as ethers, such as 1,2-dimethoxyethane, dioxane and tetrahydrofuran, ketones, such as acetone, or aromatic hydrocarbons, such as benzene, toluene, xylene, etc.  The amount of diluent used is not critical, it is usually used in such a quantity that the concentration of the polyacetylene substituted aromatic compound in the diluent is from 1 to 50%. Obviously, large amounts can be used.  To accomplish the desired cyclization reaction, any aromatization catalyst may be used.  By aromatization catalyst is meant a catalyst that stimulates the formation of an aromatic ring during the cyclization of three acetylene groups.  Preferred aromatization catalysts are nickel catalysts, such as nickel bis (acrylonitrile), nickel bis (acraldehyde) nickel bis (acraldehyde), nickel carbonyl bis (triphenyl phosphine), nickel cyanide bis triphenyl phosphine, acetyl acetone nickel in combination with triphenylphosphine and the halides of metals of the VB group, such as niobium pentahalides and tantalum pentagologenides.  The amount of katsshizator used may vary widely.  But it usually ranges from about 0.5% to about 95% by weight of the monomer.  J Polymerization is carried out by heating the polyacetylene monomer or a mixture of monomers with a catalyst to a temperature of from about 55 to about.  250 ° C, and more preferably from about 80 ° C to 150 ° C.  The reaction is preferably carried out in an inert atmosphere.  In carrying out the process, it is important to stop the reactivity before completion of the monomer conversion.  If the reaction is completed, the final product is highly cross-linked, insoluble, non-meltable material that cannot be plasticized and fluidized using the flow agents of the present invention.  Therefore, the reaction is usually stopped when the conversion reaches about more than 30% and less than 90%, and preferably at a monomer conversion of from about 50% to 90%.  Using this work, a prepolymer having an average molecular weight of from about 1010 to about 9700 can be obtained, avoiding the production of polymers with very high molecular weight, which are cross-linked and can no longer be used to obtain flat molding, and at the same time the time left in the prepolymer is at least about 5% and preferably about 4.4-15% of acetylene groups by weight of the prepolymer for the reaction in the second step of preparing a thermosetting resin. The prepolymers are soluble in aroma eskih hydrocarbons, ketones and esters.  The method by which the reaction Prepolymerisc. w stops, and the prepolymer is released, depends, of course, more on the method used to prepare the prepolymer, mono-mon or monomers used in the preparation, etc.  If a polyacetylene substituted aromatic monomer of high yield is used in polymer preparation, for example, a monomer having a boiling point below approximately; then any such monomer remaining in the prepolymer must be removed in order to avoid foaming and cavity formation during plastic molding and vulcanization used in the preparation of thermosetting resin in the second stage of the reaction.  This removal can be carried out by vacuum evaporation or steam distillation of the prepolymerization 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. .  In the latter case, the prepolymer can be separated, for example, by filtration, and the monomer, any amount of prepolymer remaining in the solution and the diluent, can be regenerated and recycled in the process.  Suitable diluents for precipitating the prepolymer are methanol, ethanol, and isopropanol, aliphatic hydrocarbons, and mixtures thereof, such as, for example, petroline ether, pentane, hexane, heptane and others. The prepolymers of the proposed shadow are unique polymers they are described and In the pending Harold Jab Lawner's application ,.  French Patent No. 1226314 filed February 12, 1973  In contrast to the acetylene polymers of the prior art, the present polymers can be used to prepare thermoreactive ones. resins having the desired properties described here It is well known that acetylene and substituted acetylenes, such as phenylacetylene, can polymerize but the polymers thus obtained are linear polymers, many of which have olefinic or acetylenic unsaturated bonds in the polymer chain.  It is also known that aliphatic compounds containing two or more acetylene groups can be polymerized, but again the polymer is linear contains acetylene unsaturation.  The prepollers for preparing the final thermosetting resin, as mentioned, usually have a ratio of aromatic protons to olefinic photons higher than about 2.4: 1, and preferably greater than about 7.5: 1.   The ratio of acetylenic, aromatic, and olefinic protons inherent in the prepolymer is determined with the help of the method of nuclear magnetic resonance when using deuterated acetone as solvent.  The areas under the peaks near 3.63 h, per million at 7.48 hours  on rel and under curve between 6. 83 and 5. 4 hours  per million  proportional to the amount of acetylenic, aromatic and olefinic protons, with the chemical shift values being measured by internal tetramethylsilane ethanol.  The amount of acetylene protons and the concentration of acetylene groups are quantified using an internal standard, nitroNjeTaHa, added in exact proportion to the prepolymer and giving a signal peak at 4.42 h.  on man.  Preparation of thermosetting composition.  The prepolymers described are high melting materials, and since this concerns many thermoforming techniques, it should be noted that the prepolymers do not have the flow properties required for ductile molding at temperatures below the aromatization polymerization reaction temperature.  In other words, if they are at a temperature of flow, the polymerization reaction proceeds in such a way that a non-meltable, insoluble and inappropriate product is formed.  In accordance with the invention, it has been found that by adding at least one of the aromatic compounds, the flow agents of the invention, it is possible to obtain a composition that has sufficient fluidity to allow plastic forming, and with further heating after plastic forming cross-linked through an acetylenic unsaturated bond in the prepolymer, giving a thermosetting resin.  Aromatic flow agents that can be used to modify the flow properties of a prepolymer do not impair the required stability at high temperature and the oxidation resistance properties of thermosetting resins, can be any aromatic organic compounds having a specific structure and physical characteristics.  Compounds or mixtures thereof must contain no more than 5% of the substance volatile at 240 ° C during distillation, in accordance with method AS. TM D20-56 in order to avoid excessive undesirable losses during evaporation during processing and thermal vulcanization.  In addition, the compounds or mixtures of the compounds should not contain a crystalline organic phase at 2 to 20 ° C to ensure compatibility with the prepolymer and then fluidize it.  The temperature at which the compounds or mixtures should not contain a crystalline organic phase is also an important factor due to the fact that this temperature should not be so high that i cause an excessive degree of curing of the prepolymer over the period of time required for the factory. thermosetting composition containing it.  Fluidizing compounds should also have a viscosity of less than 20 centipoise at 220 ° C and be technically stable and resistant to oxidation at high temperatures.  Compounds possessing e. these properties are further characterized by containing at least two six-membered aromatic rings that can be replaced by a methyl group, with the rings being condensed with each other or combined with each other directly or through one oxygen, sulfur, nitrogen or phosphorus atom or through methylene, dimethylene, ethylene, vinylene or keto group.  .  ; More specifically, the fluidizing compounds of the present invention are aromatic dihydrogen compounds containing two or more benzene or pyridine rings condensed with each other or conjugated to each other. or through the indicated atoms or groups acting to bond the rings to each other.  Examples of condensed ring aromatic compounds are anthracene, 1-methyl-anthracene, 2-methylanthracene, 1-methyl naphthalene, 2-methylne. phthaline, 1,4-dimethylnaphthalene, 2,3-dimethylnaphthalene, 2,6-dimethylnaphthalene, phenanthrene, 1-methylphenanthrene, 3-methylphenanthrene, pyrene, 3,4-benzopyrene, fluoranthene, 1-phenylnaphthalene, 2-phenylnaphthalene, acenaphthene, quinoline, isoquinoline, acridine, phenanthridine, phenazine, 2. , Diphenylquinoline, 2,4-diphenylquinoline and 2,2-dichinolyl.  All these compounds have a boiling point higher than about 240 ° C, which corresponds to a vapor pressure less than,. what about.  10 mm at 100 ° C / and a melting point of less than about.  Some of these compounds, for example, phenylnaphthalene, diphenylquinolones and 2,2-dichinolyl, are also compounds in. which aromatic rings match directly each other. with . a friend.  Additional representative compounds of this type are diphenyl, -2,2-dimethyldiphenyl, 3, 3-dimethyldiphenyl, 4,4-dimethyldiphenyl; 1,1-dinaphyl; 2, -2-dinaphthyl) 1 2-diphenylbenzene; 1,3-diphenylbenzene; 1,4-diphenylbenzene; 1; 2, 3-triphenylbenzene, - 1,3,5-triphenyl benzene; 2, 2-dipyridyl, 2,3-dipyridyl) 2,4-dipyridyl; 3,3-dipyridyl; 3,4-dip ridyl; 4,4-dipyridyl; 2,4-diphenylpyridyl; 2,6-diphenylpyridyl; 2, 3,6-triphenylpyridine; 2,4,5-three. fenylpyridine and 2,4,6-triphenylpyridine.  These compounds also all boil. pr temperature is higher than about.  240 ° C and melt at a temperature of less than about 220 ° C.  Finally, there are fluid compounds in which aromatic rings are combined with each other through an oxygen atom, sulfur, nitrogen or phosphorus atom, or through a methylene, vinylene or keto group.  Examples of compounds of this type are diphenyl ether; diphenylsulfide / diphenylsulfone triphenylamine; triphenylphosphine triphenylphosphine oxide; diphenylmethane; 2,2-diphenylpropane, 1,2-diphenyleth (N) stilbene and benzophenone.  The invention also includes compounds, such as diphenylene oxide, (cyphenylene sulfide, fluorene and flurrenone, which, in addition to the binding atom or ring group, are directly bound to each other in another molecule.  It should again.  note acenaphthene, in which aromatic rings not only condense with each other, but also combine with each other through an ethylene group.  All these compounds are characterized by having boiling points higher than about 24, and melting points lower than about 220 ° C.  Compounds - flow agents of the invention may be used either individually or in a mixture with each other. - Other substances may also be present in small quantities, if they do not impair the desired characteristics of the fluidizing compounds, and if the mixture meets the specified requirements for melting, viscosity, and volatility.  For example, the largest amounts of volatile materials can be introduced into the mixture in high-boiling substances, if they do not cause cavities, in the compositions during the curing time.  Also substances melting at temperatures above 220 ° C can be added in mixtures with other compounds that lower the melting point of the mixture below. Representatives of such high-melting compounds that are suitable in mixtures with other compounds are chrysene, perylene, coronene, benzipyrenes, picen, benzfluorenes, benzfluorantenes and carbazole.  Particularly suitable for use as flow agents are complex mixtures of high-boiling aromatic compounds present in high-boiling F1 stocks of coal tar and oil pitch.  In addition, the flow agents of the invention can be used in a mixture with the acetylene flow agents described and claimed in Harold Jablinter’s aforementioned joint application.  Representative such acetylenic flow agents are beta-naphthylacetylene, bipHNYL-acetylene 4-ethynyltrans-azobenzene; diphenylacetylene; di-m-tolyl acetylene di-o-tolyl acetylene bis-.  - and ethylphenyl) acetylene; bis- (3,4-dimethylphenyl) acetylene; bis- (4-hporpenyl) acetylene; phenyl benzoylacetylene; beta-iaftil-fennpacetylene} di (alphanaphthyl) -acetylene / 1,4-diethylnylaphthalene; 9,10-diethinyl anthracene; 4,4-diethylenbiphenyl 9,10-diethenlinfenanthre 4,4-diethynyl transazobeneol, 4,4-diethynyl trans-aerobenzo; 4,4 -diatyldiphenyl alcohol; 2,3,5,6-tetrachloro-1, 1,4-diethynylbenzene; diphenylbutasch di-p-tolyl-diace. tylen; dibenzyl-diacetylene; 2,2-dichlorodiphenyldyacetylene; 3,3-dichlorodiphenyl-diacetylene; di (alpha-naphthide) diaceti flax, diethyl diphenyl butadiene, etc.  Exactly how aromatic fluids of the disinfecting compounds act on the pre-polymers, giving plastic formulations, is not known.  Considers that they act as plasticizers, things are possible.  imparting a form to high-tensile prepolymers, but it is possible that they can also undergo a partial reaction with the prepolymer during extrusion.  In any case, such aromatic flow agents, unlike conventional plasticators, are resistant to precipitation from the cured resin at high temperatures and do not impair the excellent oxidation resistance of the resin. The amount of the aromatic flow agent introduced into the prepolymer can vary widely, but it is usually 1 about 20-100% by weight of the prepolymer, preferably about 10 to about 50% by weight, based on the prepolymer.  When used in conjunction with an acetylenic flow agent, the amount of aromatic flow agent is typically about 25-75% of the total weight of the flow agent.  The aromatic flow agent can be introduced into the prepolymer using a variety of methods.  One of the simplest methods is to mix the two components in a diluent which is a solvent for both of them and which is preferably low boiling for easy removal of the diluent after the blending operation. Suitable diluents for this purpose are methylene chloride, dichloroethane, acetone, methylstilketone, benzene toluene and others.  Such diluents can be removed after the proper mixing is achieved, by evaporation, distillation. and etc.  Mixing can be carried out at any convenient temperature, usually at room temperature.  WITH . On the other hand, if the monomer or monograms used to prepare the prepolymer have boiling points above about, the unreacted part need not be removed from the prepolymer and it can act as part of the flow agent in the thermosetting composition.  A filler may also be added to the thermosetting composition, and, pigments, antioxidants and other desired additives.  Such additives are easily added at the time of mixing the prepolymer and the aromatic flow agent when the mixing diluent is still present.  Examples of materials that can be injected are organic and inorganic fibrous materials, such as graphite, glass, asbestos, metals, metal oxides, metal carbides, boron, boron carbide, silicon carbide fibers, and particle enhancer, such as glass beads. , metal oxides, carbonate metals, clay, diatomaceous earth, and so on.  The amount of filler introduced into the thermosetting composition can vary widely, but it is usually from about 1 to about 95% by weight of the composition.  After removing the mixing diluent, the resulting plastic composition can be divided by any desired means into suitable size pieces for subsequent manufacturing operations.  Alternatively, the composition may be pulverized to a fine powder. and turn into tablets suitable for use in subsequent Operations by compressing under pressure at room temperature or at a slightly elevated temperature.  These thermosetting compositions are stable and can be stored at room temperature.  Getting thermosetting.  The prepolymer modified with the aromatic flow agent melts when heated and remains sufficiently liquid so that the composition can be molded using conventional plastic molding methods such as extrusion, compression, injection molding, transfer molding, chandriding, forging, etc.  For example, using extrusion, forms such as sheets, pipe bars, wire coatings can be made.  Sheets may be further modified in subsequent onepaiws, for example, by profiling or thermoforming.  With the help of operations & tions to pour in the form of Kyugut and more complex forms.  Temperature, . Used in plastic molding and related onepatpiHx can vary widely, with the preferred temperature depending on. the amount of aromatic flow agent used, the molecular weight of the prepapimer, the type and amount of filler or reinforcing agent.
    is present in the composition, fabrication method, applied pressure and degree of cross-linking required during the fabrication operation. Such low temperatures as about, or as high as, but usually they are in the range of - about can be used. As heating continues, above 90 ° C, and usually under a pressure of 15 to about 150,000 psi. an inch (1.05-105 kg / cm-) thermosetting composition re-hardens. In Operations such as extrusion or injection molding, which may be desirable to recycle waste, low temperatures are used to avoid large changes in flow properties of the composition during fabrication. In other operations, such as transfer casting or pressing, it may be desirable to fabricate a material at an elevated temperature so that it does. the time of the molding operation occurred cross-linking or curing of the material.
    After the fabrication and heating operation is above 90 ° C for a time sufficient to solidify the material, continuous application of pressure during subsequent vulcanization is not necessary. A further polymerization or crosslinking reaction to form an insoluble thermally stable resin does not entail the formation of any gaseous or volatile substances and, accordingly, no foaming or cavity formation. The manufactured article can then be converted to a thermosetting resin by additional heating.
    The temperature at which the thermosetting composition is heated to effect further polymerization and crosslinking, which may be referred to as curing temperature (curing), can vary widely and usually depends on factors such as the components of the thermosetting composition, size and shape of the fabricated product, and so on. d. Generally, the cure conditions range from a few hours at about 100 ° C to a few minutes at about. A fabricated product can be used in a partially vulcanized form, and vulcanization can be performed during use of the product at elevated temperatures.
    A reaction that takes place during the vulcanization of a thermosetting composition containing both an aromatic flow agent and an acetylene flow agent, results in a copolymerization between the prepolymer and the acetylene flow agent, and this
    the reaction at the same ca.-ioe time performs cross-linking of the prepolymer. Therefore, in this case, the final thermosetting resin can be defined as a copolymer of a prepolymer and an acetylene flow agent. In the case of casting a compositionj containing only an aromatic flow agent, the reaction during the vulcanization is primarily a further polymerization reaction of the prepolymer, and perhaps to some extent it is accompanied by a reaction of the prepolymer with an aromatic agent,
    Thermosetting resin obtained
    15 is thus solid, tough, durable, abrasion resistant, infusible and insoluble. These resins retain their strength and solubility at elevated temperatures,
    20 are stable to elevated temperatures for extended periods and resistant to oxidative deterioration at elevated temperatures. Their oxidative stability can be further improved by the introduction of stabilizers, such as ammonium biphosphate, calcium hypophosphate and acid butyl phosphate. They are highly resistant to the chemical attack of strong acids and concentrated alkalis. As indicated, these thermosetting resins are characterized by having a flexural strength of at least about 4000 pounds per square meter. an inch (281.2 kg / cm) and a modulus of flexibility of at least 350,000 psi. inch (24605 kg / cm). Most resins are also characterized by retaining at least the specified flexural strength of the modulus of flexibility and at least 80% of their weight when the sheet is 30 ml thick.
    0 (0.75 mm) is in the air for 220 hours, and less than 20% of its weight is lost when they are heated as a powder to 500 ° C. at a speed of 10 C / min in inert
    5 atmosphere. Obviously, these values can be significantly improved by adding fillers and other reinforcing additives.
    Under the terms bending strength
    0 (or bending resistance) and the modulus of flexibility are understood to be strength and modulus measured in accordance with ASTM D-790-70.
    New thermosetting compositions
    5 of the present invention are useful as thermosetting binding resins for glass, graphite, asbestos and boron fibers and in the preparation of castings intended for use at high ambient temperatures, such as jet turbine blades for jet engines, aircraft wing edges, gravity reducing coatings for space vehicles entering or returning to the dense atmosphere of an elephant,. bearings, grinding wheels, brake linings and clutch linings. The compositions are also useful as chemically resistant coatings. The following examples illustrate the preparation of prepolymers, thermosetting compositions, and thermosetting resins of the present invention. All parts and percentages are by weight unless otherwise indicated. Example. A mixture of 630 parts of methadiethylenbenzene and 70 parts of para-diethynylbenzene dissolved in 3077 parts of anhydrous benzene is loaded into a polymerization vessel. The solution was flushed with nitrogen and heated to reflux. Then, a mixture of the catalyst prepared by mixing 4.4 parts of nickel acetylacetonate and 8.8 hours of triphenylphosphine in 50 parts without water benzene was added to the solution heated to a reverse-cooling solution. After adding the initial portion, the other portions are added separately after one, two, and three hours. The solution is maintained at reflux temperature for a total of six and a quarter hours, during which time the monomer conversion is 85.6%. The prepolymer is then precipitated by adding the solution to its sevenfold volume of petroleum ether, and the yellow powder separated by filtration is 406 hours. The prepolymer contains 11.8% acetylene groups. Example 2. The molding composition is prepared by dissolving the prepolymer of example 1 and the flow agents of table. 1 in acetone with thorough mixing, the acetone solvent is then removed with a rotary pump. The composition is dried under vacuum for 16 hours at room temperature, followed by drying for 1 hour at. Using parallel-plate plastometry and temperature change at a rate of 10 C / min, the viscosity of the molding compositions is determined at different temperatures. The data obtained in this way are given in table. 1. These data show the fluidization properties of the aromatic flow agents listed in the table. Table 1
    Absent anthracene
    Fanantrin
    Anthracene + Diphenylbutadiene
    Phenanthrene + Diphenylbutadiene
    Diphenyl ether
    Diphenylsulfide
    13 2.5
    8.5 7.5 7
    0.04
    0.001 0.0005 0.0003
    ten
    0.3
    7
    four
    one
    30 10
    1 Example 3. The molding compositions prepared according to example 2 are molded and vulcanized, and the vulcanized samples are evaluated for their mechanical properties. My form was completely positive disk-shaped, having an inner diameter of one inch (2.5 cm). The form is loaded at room temperature with a sample of the molding composition and heated to. Pressure is then applied to compact the molding composition and to heat the food / liquid until the temperature reaches Anthracene.
    Phenanthrene + Silica
    Anthracene + Diphenylbutad
    Phenanthrene + Diphenylbutad
    Diphenylsulfide Silica
    Calcined diatomaceous earth (93-95% SiOj) is present in an amount equal in weight to the total weight of the prepolymer and the flow agent.
    Example 4. Disk samples prepared according to example 3 are evaluated for their functional oxidative stability. The disks are weighed, placed in a circulating air oven and kept at. After 220 hours, the disks are weighed again and the following results are obtained.
    ABOUT
    18
    43
    100
    43
    18
    1.050.000
    0.000 970.000 6.700 7.400
    1.020.000 4.000 350.000
    1.160.000
    6.300
    1,450,000
    14.200
    980.000
    9.160 1.800.000 9.140
    Example 5. Other disk samples prepared in accordance with Example 3 are ground into a fine powder (passing through a 100 mesh screen and evaluated for purely thermal stability. This involves testing samples for weight loss using a thermal gravimetric analysis when heated in nitrogen atmosphere to 500 ° C at a rate of temperature increase of 10 C / min. The following results were obtained
    -55
    60
    P. Example 9. The polymerization of Example 1 is essentially repeated, except that
    65 tignet 1700S. The formed disk is 20 mils thick (0.5 mm; then removed from the mold and cured at atmospheric pressure for three hours. The resistance and modulus of flexibility of the unfolded compositions are determined by measuring the forces required to cause deformation (deflection and The final damage of the test No. 1 samples. The obtained data as well as the pressure for casting used for the preparation of disc samples are presented in Table 2 Table 2
    a mixture of a catalyst containing 4, 7 h of nickel acetylacetonate and 9.3 parts of triphenylphosphine. This polymerization process is then repeated four times using double quantities of all components of the reaction mixture, and also one time repeated polymerization using an example of threefold quantities of all components. The total amount of monomer loaded in this last reaction is 2000 hours. The monomer conversion in these reactions is in the range of 87-89%. Example 8. The fluid agents of example 7 in the indicated quantities are also evaluated with a prepolymer measure b in the aging tests, examples 4 and 5. The following data were obtained Example 9. In a polymerization vessel filled with nitrogen, 71 hours were loaded diethyl benzene.
    The six reaction mixtures are then added to approximately six times the total volume of heptane compared to their total volume. The precipitated prepolymer is precipitated by filtration, and the amount is 3.6X2 h.
    Example 7. Following Examples 2 and 3, additional flow agents are evaluated using prepolymer 6. The resulting data is given in Table. 3 and 4.
    Table 3
    Table4 1.062 h, nickel acetylacetonate, 2.124 parts of triphenylphosphine and 737 parts of anhydrous dioxane. The clear, pale green solution is then heated under stirring to reflux and maintained in this way until the desired degree of conversion of 57% is reached. This is determined by periodically taking certain sample qualities, cooling the sample to room temperature, pouring it into 5 volumes of petroleum ether, drying and weighing the precipitate. When the desired conversion is achieved (lh 50 min), the reaction mixture is poured into 5 volumes of petroleum ether. A dark, tarry mass is precipitated. The surface layer is separated and filtered. The solids are allowed to dry in air, and then washed with petroleum ether and dried. The product thus obtained is a brown powder. It has an average molecular weight value of about 2,900. An NMR analysis, as indicated, shows. that the prepolymer has an aromatic proton to olefin proton ratio higher than 30: 1. The prepolymer contains 15.05 acetylene groups. The molding composition is prepared by mixing 50 parts of calcined diatomaceous earth containing 93-95% 510/2, which is pre-dried, heated before heating, and cooled under anhydrous conditions, 8.5 hours 1-phenylnaphthalene and 41.5 hours a prepared prepolymer, a sufficient amount of ac tone is added to dissolve the two organic substances and to achieve better mixing with the vehicle. The acetone is then evaporated in a stream of air and then under vacuum. The molding composition thus prepared is a fine powder of brown (cocoa) color. The form used to form these compositions is a 21/4 inch (20 cm - 0.63 cm) semi-positive disc shape. A disk of aluminum, 5.3 g of molding compositions and aluminum void are placed in a mold at room temperature. The inner part of the mold (punch) is inserted and the mold is placed in a preheated hydraulic press, and the temperature of the forming specimen is controlled with a thermocouple. The sample temperature increased to 275 ° С for 50 min when heated under a pressure of 1500 psi. inch (105.45 kg / cm. Heaters are turned off (final sample temperature is 280 ° C), the pressure is removed and the form is cooled. After 1 hour and 40 minutes the form is removed from the press and cooled with cold water. The hard and shiny brown disk formed in this way It has a density of 1.54, and Barcol's hardness (No. 935-1) 75. The flexibility properties determined here are: resistance 4,520 pounds per square inch (317.756 kg / cm) and a module 8600 pounds per square inch (60458 kg / s Example -10. A polymer vessel with a nitrogen atmosphere is loaded. 3.0 h. 4.4 -diethenylbiphenyl 0.15 including bis (triphenylphosphine) nickel-dicarbonyl and 100 parts of anhydrous dioxane. The solution is heated under a nitrogen atmosphere on a refluxed steam bath for 1 hour. During this time, about 65% of the monomer turns into a prepolymer having an average molecular weighing 3000. About 4 parts of diphenylmethane is added to the solution. The solution is then evaporated to dryness and dried under high vacuum .. A film is prepared from the yellow solid thus obtained, the solid is a mixture of 57% prepolymer, about 31% unreacted o monomer and 12% diphenylmotane, the film is prepared by heating this solid on a steel plate at 160 ° C, then cured under nitrogen at atmospheric pressure and 250 ° C for 4 hours. This film has a weight loss of only 10% when heated in air up to 500 ° С at a speed of 10 s / min. . Example 11. The prepolymerization of Example 10 is repeated. Except that the 4,4-diztinylb-g phenyl used in this example is replaced by di (4-cetinylphenyl ether) and the prepolymerization reaction time is 2 h. After the removal of dioxin a very viscous, sticky yellow substance is obtained which is a mixture of 60% prepolymer with an average molecular weight of about 2500 and 40% of unreacted monomer. Diphenyl ether is mixed into this sticky solid in an amount of 10% by weight based on weight sticky solid The resulting material is then g formed into a film according to Example 10 and hardened at 250 ° C for 4 hours, The cured film has an air weight loss when heated to 10 s / min at about 10%. 13. A prepolymer according to Example 9 is prepared using a mixture of 90% meta- and 10% para-diethynylbenzene; 0.26% nickel catcher as a monomer and polymerization is carried out until 80% conversion is achieved. The prepolymer had an average molecular weight of 5500, contained 12.8% acetylene groups, and had an aromatic proton to olefin proton ratio of 13: 1. Molding compositions are prepared from this prepolymer by mixing it with 25% by weight of diphenylmethane and additionally adding 1.1 parts to 100 parts of a mixture of acid butyl phosphate as a stabilizer for one of them. Discs 30-35 mils (0.75-0.875 mm) thick and one inch in diameter L2.5 cm) are prepared and cured by heating for 5 hours at. These discs are then heated in a Forced Air Furnace at 26 ° C. The results are shown in the table. There is a time for stabilizability of 10% loss of resin weight at 260 ° C, and butylphosate 2386 is exemplified. Example 14. In a reaction vessel blown with argon, 20 parts of 1-HLOR-2,5-diethylbenzene and 70 parts of benzene are placed. The contents of the vessel are stirred and heated to reflux. A solution of 0.05 parts of nickel acetylacetonate and 4.5 parts of benzene are added to the reaction mixture, followed by the addition of a solution of 0.15 parts of triphenylphosphine in 4.5 parts of benzene. The solution is heated to boiling point for 1.5 hours. At this temperature, about 80% of the monomer is converted to a prepolymer. The solution is cooled and poured into 5 volumes of methanol. The brown solid that has precipitated is filtered, washed and dried under vacuum. The polymer yield is 9.0 hours. The prepolymer has an average molecular weight of 7000, contains 11% acetylene groups, and the ratio of aromatic and olefinic protons is 6: 1. This prepolymer material is mixed with 1.8 parts of phenanthrene, molded at 150 ° C and cured at atmospheric pressure and 250 ° C for 2 hours. The resulting resin has a bending resistance. 5500 psi an inch (386, 65 kg / cm and a modulus of flexibility of 750,000 pounds per square inch (52725 kg / cm. Example 15). The prepolymer is prepared as in Example 9, the prepolymerization reaction being carried out until a monomer conversion of 90% is reached. The prepolymer having an average molecular weight 9700 and containing 9.5% acetylene groups, the ratio of aromatic and olefinic protons is 8: 1, mixed with 17% by weight of anthracene in benzene and benzene is then removed by evaporation. The mixture is molded into a picture frame at 140150 ° C for 6 minutes under a pressure of 6,000 psi (421.8 kg / cm) and eat, freeze at atmospheric pressure for 2 hours at 250 ° C. The resin has a flexural resistance of 6700 psi (471 kg / cm and a modulus of flexibility of 950000 pounds per sq. in. (66785 kg / cm -; repeated measurements of the modulus flexibility is carried out on this form with increasing temperature, ° C. Flexibility modulus (LUNTS per KB unic. inc. 42 inches. 920.000 Qo930 000: 145810.000 ..goal 000 ... 231780.000 -QQ760 000 326720.000 24 Example 16. Copolymer- The prepolymer of diethylbenzene and phenylacetylene is prepared by heating under reflux in benzene, into a polymerization OSUD charged 60 hours. 90:10 mixture of m- and p-dietinilbenzolov 60 hours. phenylacetylene, 600 parts of benzene and 2h. chlorobenzene. After heating to reflux temperature, 5 parts of a catalytic solution prepared by adding 0.34 parts of acetylacetonate and 0.6 parts of triphenylphosphine in 15 parts of benzene were added. After two hours, an additional 1C of this catalyst solution is added. After 4 hours analysis of gas-liquid chromatography shows that 74% of diethinylbenzene and 35% of phenylacetylene turned into a copolymer. The copolymer is precipitated by adding the amount of petroleum ether five times higher than its volume, and 26 parts of the polymer are recovered. This product has an average molecular weight of about 3000, an acetylene content of 8.9% and a ratio of aromatic protons to olefin of 5.5: 1. This prepolymer is used to prepare the molding composition at a pressure of 12% by weight of 1,3-diphenylbenzene, and the disks are molded using a molding temperature of 150 ° C for 6 minutes under a pressure of 2000 psig. inch (140, 6 kg / cm2), followed by vulcanization for 2 hours at 250 ° C at atmospheric pressure. Flexibility properties obtained: resistance 8000 psi. inch (562.4 kg / cm, module 975000 psi / sq. inch (68542.5 kg / cm -). Example 17. A prepolymer of diphenylbutadiene and p-diethylbenzene prepolymer is prepared in benzene solvent at reflux. 63 grams of diphenylbutadiene, 2 grams of diethylbenzene, 600 grams of benzene and 2 grams of chlorobenzene are loaded into a polymerization vessel. After heating at reflux, 2 grams of nickel acetylacetonate and 4 grams of triphenylphosphine at 20 grams are added. benzene .. After 1 hour, add 10 parts of diethinylbeneol. After 2 hours, add 10 hours of diethinylbenzo a and 2 parts of the catalytic ° ° solution. After 3 hours, add Q parts of diethinylbenzene and 4. parts of the catalyst solution of the fluorine.After a total reaction time of 7 hours, analysis of the gas by liquid chromatography showed the reaction mixture, which remained 10%. each of the monomer components. The solution was added to the kp: to 5 times the volume of methanol compared to its volume, and 77 parts of the copolymer precipitated. It had an acetylene content of 8.4% and an aromatic / olefinic hydrogen ratio of 8: 1 .
    A molding composition is prepared from this prepolymer with the addition of 12% by weight of phenanthridine and 1.0% by weight of acid butyl phosphate. The discs are formed using a molding temperature for 6 missions under a pressure of 2000 fonts per square meter. inch (140.6 KF / cM j followed by out-of-mold curing for 2 hours at atmospheric pressure, the flexibility of these hardened suits: resistance to 5200, module 750,000 pounds per square inch (365.56 and 52725 kg / cm 2 ).
    Example 18. A B-polymerization vessel filled with an argon atmosphere was charged with 60 parts of phenylacetylene, 54 parts of meta-diethylbenzene, 6 hours. para-diethynylbenzene, 422 parts of benzene and 0.3 parts of monochlrrbenzrl. The solution is heated under reflux with stirring, then 0.8 parts of triphenylphosphine and 0.4 parts of acet1 nickel acetate in benzene are added to the heated solution. The reaction is monitored by gas chromatography analysis. Three hours after the addition of the catalyst, 88.3% of diethylbenzene and 49.5% of phenylacetylene were consumed. The solution is cooled and poured into 7 volumes of petroleum ether. The precipitated powder is filtered, dried with fresh petroleum ether and dried under vacuum, the yield is 53 parts (46% light yellow copolymer. Calculations on the use of the monomer show that the copolymer contains, sol.%: Diethyl benzene - 64 and phenylacetylene - 36.
    From this prepolymer, a molding composition is prepared using 25% 2,2-dipyridyl as a flow agent. From this composition, formuyu disks when heated for b min under a pressure of 1000 psi. inch (703 kg / cm) and cured by heating for five hours at atmospheric pressure. The resulting product had an average flexural resistance of 11,300 psi. an inch (794.39 kg / cm) and an average modulus of flexibility of 1106,000 psi. inch (77751.8 kg / cm). When testing a sample using thermogravimetric analysis at a heating rate of 10 ° C / min to 500 ° C, the result of weight loss was 8%. A weight loss of 2.3% was observed when the sample was heated at 260 s for 220 hours during the oxidative test.
    Example 19. In Example 18, a copolymer is prepared from a reaction mixture containing 75 h, diphenylbu
    (tadiina, 22.5 parts of ta-diethylenebenzene, 2.5 parts of para-dithinylbenzene, 413 parts of dioxane, 0.3 parts of monochlorobenzene, 0.7 parts of triphenylphosphine and 0.3 hours of nickel cetyl acetonate. Consumption of diethylbenzrel - 100%, and diphenylbutadiene - 83.7%. A light-yellow copolymer product is obtained with a yield of 47%, containing 27.8 molar percent of diethylbenzene and 72.2 molar percent of diphenylbutadiene. Following the step 18, a molding composition is prepared using 2 , 2-dichinolyl as a flow agent. The viscosity of the compositions at X 10 pauses. The composition is molded and
    5 is cured. The cured product has an average flexural resistance of 7,250 psi. an inch (509.675 kg / cm) and an average modulus of flexibility of 425,000 psi. inch (29877.5 kg / cm J.
    0
    Example 20. The procedure of Example 19 is repeated, but 32.2 parts of diphenylbutadiene are used, 61 parts of methadiethinylbenzene and 6.8 parts of paradiethylenbenzene are used as monomer5. Noah mixture. The components of the catalyst are also reduced in quantity to 0.35 parts of triphenylphosphine and O ,, 15 parts of nickel acetylacetonate, the reaction time is one hour from the moment of addition of the catalyst. The copolymeric product contains 68.9 molar percent dizginylbenzene and 31.1 molar percent diphenylbutadiene. According to Example 18, a molding is prepared.
    5, the copolymer composition is molded and cured. An over-edema product has an average flexural strength of 6,250 psi. inch (439.375 kg / cm) and average
    0 flexibility module 355,000 psi inch (24956.5 kg / cm)
    Example 21. The procedure of Example 19 is repeated, but 2,2-dichinolyl is replaced by triphenyl phosphite as a flow agent. Cured product
    5 has an average flexural resistance of 7325 psi. an inch (515 kg / cm), and an average modulus of flexibility of 450,000 pounds per square kilometer. in. (31635 kg / cm2;.
    0
    Example 22 In accordance with Example 1, a prepolymer is prepared. Molding compositions are prepared from a diancé ipolymer by mixing it with 25% PS by weight of a number of flow agents. Table 5 lists the viscosities of these compositions in accordance with the procedure of Example 2, as well as the physical properties and oxidation stability of the cured products.
    0 Example 23. When using a prepolymer prepared from a 90:10 mixture of methadiethinylbeneode and para-diethynylbenzene, molding compositions are prepared in accordance with Example 1, and evaluated in accordance with Examples 2, 3, 4 and 5 using varying amounts of high-boiling aromatic coal tar and petroleum pitches as flow agents. Petroleum pitches are mixtures of high-boiling aromatic compounds produced during the high-temperature cracking of petroleum. Caman coal tar pitch is a mixture of high boiling aromatics extracted from coal tar, volatile components of coal tar removed during distillation, and phenolic and acidic materials, mainly separated during alkaline extraction.
    Table 5 These pitches contain a small amount of acids, phenols, alcohols, and non-aromatic unsaturated compounds, as shown by measurements of acid, hydroxyl, and bromine numbers. They do not contain a crystalline organic phase when heated to temperatures above. It is known that materials of this type contain mainly condensed ring aromatic compounds, such as naphthalene, methylnaphthalenes, thionaphthene, quinoline, anthracene, phenanthrene, methylanthracene, α-methylphenanthrene, pyrene, chrysene, benzpyrene, perylene, pycen, benzperylen and coronep and siren, and pyrene, chrysene, benzpyrene, perylene, pycen, benzpyrilylene and coronep and cipher, Dineni containing aromatic rings conjugated to each other, such as biphenyl, acenaphthene, carbazole, fuloren, diphenyl ether, fluorantrene, benzfluarenes and benzflouranthenes. The characteristics of the oil pitch and coal tar pitch are given in table. b. . T a b persons b Example 24. 15 parts of phenylacetylene, 13.5 methadiethinylbenzene, 1.5 parts of para-diethynylbenzene, 216 parts of methylisobutyl ketone and 0.075 parts of monochlorobenol are charged into an argon atmosphere polymerization tank. The solution is heated to 82 ° C while stirring, after which 0.2 parts of triphenylphosphine and 0.1 parts of nickel acetyl-acetonate in methylisobutyl ketone are further added to the heated solution. The reaction is monitored by gas-liquid chromatographic analysis. When the content of phenylacetylene in the copolymer is 30.9%, as determined by gas-liquid chromatographic analysis, the reaction is stopped by adding 1.5 volumes of methanol to the reaction mixture. The precipitated yellow copolymer product is then washed with fresh methanol and vacuum dried to obtain nine parts (30% Yield) of the product. The product has a quantitative average molecular weight of 1340 and contains 5.8% acetylene groups. The molding composition is prepared from the indicated copolymer, using 20% of the coal tar of Example 23 as a diluent. The composition is molded and cured in accordance with the technological procedure of example 3.
    em
    25
    100
    12
    25,100,200
    25,100
    25,100
    25,100
    T a
    faces
    13 6
    1000250
    1000 21 0.3
    116.5
    0.08
    0.080.07 8
    14029
    4 0.09
    7 0.06
    11 0.2
    26 0.8
    0,003 0,005
    2
    权利要求:
    Claims (1)
    [1]
    0.3 15 3 6 0.03 duct has a bending resistance of 1884 kg / cm (26,800 psi; and a bending modulus of 82966 kg / cm (1180000 psi). Example 25. Following the procedure of Example 24, receive a copolymer containing 22.1% by weight of phenylacetylene, at a yield of 60%. The copolymer has a quantitative average molecular weight of 1500 and contains 4g4% of acetylene groups. A forming composition containing a copolymer is prepared and cured as follows 24. Example. the product has a flexural strength of 1406.2 kg / cm (21,000 psi) and an average flexural modulus of 19578 5.5 kg / cm (2785000 pounds / inch. Example 26. In Example 24-: a copolymer is obtained, the contents are 30.9% by weight of phenylacetylene, when the yield is 24%. The copolymer has a quantitative average molecular weight 1010 9.1% acetylene groups. The molding composition containing the copolymer is prepared and cured in accordance with Example 24. The aperture product has an average flexural strength of 2032 kg / civr (pounds / inch) and the average is mo. The curvature of the bend is 2,09845.5 kg / cm (2,985,000 psi). The research results are summarized in table. 7 and .8. V Thus, the proposed composition hardens without isolation of volatile products and has a low yield stress, which facilitates the formation of products. The invention is a heat-resistant thermosetting composition comprising a polymer and an aromatic compound, distinguished with the fact that, in order to improve the technological properties of the composition, it contains polyacetylene with a number average molecular weight of 1010-9700, acetylene unsaturation 4.4-15 % and with
    Table 6 Values obtained with compositions containing a filler of calcined (calcined) diatomaceous earth, equal in weight to prepolymer plus flow agent. the ratio of aromatic and olefinic protons is 5.51-30: 1 ,. and as an aromatic compound, it is organic. . Chesic compound containing at least two six-membered condensed with each other or connected to each other directly, a heteroatom, through a hydrocarbon or keto group of the aromatic ring in the following ratio of components, parts by weight; Polyacetylene Aromatic compound Sources of information taken into account during the examination 1. British Polymer Journaf, 2, No. 6, 264, 1970 (prototype).
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    同族专利:
    公开号 | 公开日
    JPS4989744A|1974-08-27|
    AU6374773A|1975-06-19|
    GB1435305A|1976-05-12|
    FR2210632B1|1978-12-29|
    NL187315B|1991-03-18|
    AU469023B2|1976-01-29|
    SE407228B|1979-03-19|
    CA1016685A|1977-08-30|
    NL7317264A|1974-06-20|
    DE2359861C2|1981-11-26|
    FR2210632A1|1974-07-12|
    DE2359861A1|1974-06-27|
    BR7309878D0|1974-09-05|
    NL187315C|1991-08-16|
    US3882073A|1975-05-06|
    JPS5645939B2|1981-10-29|
    IT1008623B|1976-11-30|
    BE808640A|1974-03-29|
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    US8815381B2|2012-01-26|2014-08-26|The United States Of America, As Represented By The Secretary Of The Navy|Formation of boron carbide-boron nitride carbon compositions|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US316332A|US3882073A|1972-12-18|1972-12-18|Thermosetting compositions containing poly|
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