WO1982003080A1 - Article en resine phenolique moulee stable a la chaleur - Google Patents

Article en resine phenolique moulee stable a la chaleur Download PDF

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Publication number
WO1982003080A1
WO1982003080A1 PCT/US1981/000253 US8100253W WO8203080A1 WO 1982003080 A1 WO1982003080 A1 WO 1982003080A1 US 8100253 W US8100253 W US 8100253W WO 8203080 A1 WO8203080 A1 WO 8203080A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
percent
acrylonitrile
aldehyde
phenol
Prior art date
Application number
PCT/US1981/000253
Other languages
English (en)
Inventor
Electric Co General
Michael Dean Bertolucci
John Rudolf Bartolomucci
Original Assignee
Gen Electric
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Gen Electric filed Critical Gen Electric
Priority to EP19810901736 priority Critical patent/EP0073191A4/fr
Priority to JP50217881A priority patent/JPS58500568A/ja
Priority to BR8108979A priority patent/BR8108979A/pt
Priority to PCT/US1981/000253 priority patent/WO1982003080A1/fr
Publication of WO1982003080A1 publication Critical patent/WO1982003080A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/12—Condensation polymers of aldehydes or ketones
    • C04B26/122—Phenol-formaldehyde condensation polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols

Definitions

  • thermoset plastics and to thermosetting plastic compositions. More particularly, it relates to a molded thermoset article containing a phenol-aldehyde resin, an acrylonitrile-butadiene copolymer, and a silicate mineral in fiber or particulate form; and to thermosetting molding compositions containing a thermosettable phenol-aldehyde prepolymer, an acrylonitrile-butadiene copolymer and a silicate mineral in fiber or particulate form.
  • Phenolic-aldehyde resins are generally highly brittle low impact strength products of limited compatibility with other plastics. Plasticizers have been employed with these products to increase the flexibility, but increased flexibility has resulted in the diminution of other properties and processing difficulties. For example, to obtain any significant degree of flexibility relatively large amounts of up to or more than equal parts of glycols or glycerine must be used which diminishes the product strength and induces sweating out of the glycol and glycerine during the heat curing cycle. Further, plasticization by crosslinking with unsaturated thermoplastic polymers like polyvinylbutyral or compatible elastomers has not bees wholly satisfactory because of the lowered heat and solvent resistance of the resulting mixtures. These mixtures have improved impact strength, but still lack suitable flexibility. Furthermore, unsaturated oils like tung oil, even in substzntial amounts as resin modifiers, fail to provide sufficient flexibility.
  • finely divided fillers such as wood flour and walnut shell flour
  • wood flour and walnut shell flour adversely affects their heat resistance, dimensional stability and does little to improve impact strength.
  • long fibered fillers such as paper flock, cotton flock or sisal fiber
  • it has adequate impact strength but remains deficient in heat resistance and dimensional stability.
  • the surface qualities of the molded product are unsatisfactory for many applications.
  • a molded product made from phenolic-aldehyde resins which has good impact strength, good heat resistance, good dimensional stability, good hot rigidity, high flexural modulus, good surface appearance, and good heat stability, i.e., the ability to retain its properties upon exposure to heat.
  • the present invention provides such a molded article and a molding composition for making such an article.
  • the present invention is based on the discovery that a phenolic molded article containing a phenolic resin, an acrylonitrile-butadiene copolymer, and a silicate mineral, either in puulate or fiber form, possess good impact strength, good heat resistance, good dimensional stability, good hot rigidity, high flexural modulus, good surface appearance, and good heat stability.
  • one embodiment of this invention is a phenolic molded article containing a phenolic resin, an acrylonitrilebutadiene copolymer, and a silicate mineral.
  • Another embodiment of the present invention is a phenolic molding composition containing a phenolic thermcsettiag resin, an acrylonitrilebutadiene copolymer, and a silicate mineral.
  • the molded article of the present invention comprises from about 20 to about 70 percent by weight of a phenolic resin.
  • the phenolic resin may be a one- or two-stage phenolic resin.
  • the two-stage phenolic resins, the novolak resins are well known and may in general be the condensation product of a phenol, such as phenol itself, the cresols, xylenols, cresylic acid or resorcinol or mixtures thereof, and an amount of an aldehyde such as formaldehyde, acetaldehyde, furfural and the like insufficient to cause complete crosslinking, or cure, and in which an acid or basic catalyst may be used to promote the reaction.
  • thermosettable resin produced by this reaction is mixed with an amount of curing agent, such as hexamethylenetetramine, to cause the mixture to harden and cure to an infusible, insoluble state when subjected to heat or to heat and pressure.
  • a resin might be, for example, the reaction product of phenol and formaldehyde in the ratio of 0.85 mole of formaldehyde per mole of phenol, with sulfuric acid as the catalyst.
  • the thermosettable resin so produced may then be mixed with hexamethylenetetramine, for example, in the ratio of 16 parts by weight of hexamethylenetetramine per 100 parts by weight of the novolak resin, to produce the final resin capable of being completely cured under beat or heat and pressure.
  • Typical of the two-stage resins suitable for use in the present invention are those prepared by placing one mole of phenol into a reactor with 1% by weight concentrated sulfuric acid and heating to a temperature of 97o-100oC. While maintaining the temperature, 0.75 mole of formaldehyde as a 37% aqueous solution is slowly added, over a period of 30-60 minutes, using heat and vacuum, the reaction product then is dehydrated until a temperature of 120o-130oC is reached at 27-28 inches of vacuum. The resin product is then cooled and ground with 14-18 parts by weight of hexamethylenetetramine per 100 parts by weight of resin with the resulting ground mixture being typical of the two-stage molding resin useful in the composition of this invention.
  • the one-stage phenolic resins, the resole resins are well known and may in general be the condensation product of a phenol, such as phenol itself, the cresol's, xylenols, cresylic acid or resorcinol or mixtures thereof, and an amount of an aldehyde such as formaldehyde, acetaldehyde, furfural and the like, which is sufficient to cause crosslinking or cure-when subjected to heat or heat and pressure.
  • An alkaline catalyst may be used to promote the reaction.
  • the product of this reaction is thermosetting without the addition of hardening or curing agents.
  • An illustrative example of the production of a one-stage resin is the reaction of phenol with formaldehyde in the ratio of 1.5 moles of formaldehyde per mole of phenol, with caustic soda 'as the catalyst.
  • Exemplifying the one-stage resins found suitable for the present invention are those prepared by reacting one mole of phenol with a solution of formaldehyde in the presence of a 0.5-2 percent by weight based on the phenol of a hydroxide catalyst (sodium, calcium, barium, etc.) to yield a ratio of 1.0 to 1.3 moles of formaldehyde to one mole of phenol.
  • the reaction is carried out by heating slowly (30-60 minutes ⁇ to a temperature of 70o-100oC and holding at that temperature for another 30-60 minutes to carry out the condensation step.
  • the resin product is recovered by dehydrating while heating under vacuum and then cooling.
  • the phenol resin component is present in the molded article in amounts generally ranging from about 20 to about 70 weight percent, preferably from about 25 to about 55 weight percent, more preferably from about 30 to about 50 weight percent, and most preferably from about 35 to about 45 percent by weight.
  • the acrylonitrile-butadiene elastomers which are used as essential constituents of the molded articles are well known and are generally the eopolymerization products of acrylonitrile and butadiene monomers.
  • Preferred acrylonitrile-butadiene copolymers are those formed from butadiene and acrylonitrile monomers wherein the weight ratio of butadiene monomers to acrylonitrile monomers is in the range of from about 95:5 to about 15:85.
  • the acrylonitrile-butadiene constituent is present in the molded article in from .about 3 to about 25 percent by weight, preferably from about 4 to about 20 weight percent by weight, more preferably from about 5 to about 15 percent by weight, and most preferably from about 8 to about 12 percent by weight.
  • the silicate minerals which are used as essential constituents of the molded article ar e also well known and are selected from glass, both glass fibers and particulate glass, the alkali and alkaline earth metal silicates, aluminum silicate, and mixtures thereof.
  • Illustrative of the alkali and alkaline earth metal silicates are sodium silicate, potassium silicate, magnesium silicate, calcium silicate and lithium silicate.
  • the silicate mineral constituent may comprise only one silicate mineral, i.e., glass, or a mixture of two or more silicates, i.e., glass and calcium silicate or calcium silicate and aluminum silicate.
  • One particularly useful silicate constituent contains a mixture of glass and calcium silicate in a weight ratio of 1:1.
  • a particularly useful calcium silicate is a silane modified calcium silicate which contains a minor amount, i.e., from about 0.5 to about 2 weight percent, of silane and a major amount, i.e., from about 93 to about 99.5 weight percent, of calcium silicate.
  • the silicate mineral constituent is present in the molded article in from about 15 to about 70 weight percent, preferably from about 20 to about 65 weight percent, more preferably from about 30 to about 60 weight percent, and most preferably from about 40 to 50 weight percent.
  • the molded article may also optionally include other materials such as dyes, pigments, fillers, lubricants and the like, all of which are well known in the art.
  • the acrylonitrile- butadiene copolymer and the silicate mineral are added to the phenol-aldehyde resin prepolymer prior to the compounding of the resin into a molding composition.
  • the novolak resin is used as the resin component.
  • the phenol and aldehyde are first reacted in the presence of heat and a catalyst to form a prepolymer; the prepolymer is ground and a suitable curing agent, such as hexamethylenetetramine, is added thereto; the mixture of the curing agent and prepolymer is further ground to powder form; the powdered mixture of prepolymer and curing agent is then mechanically mixed, in an extruder or roll system, with the acrylonitrile-butadiene copolymer and silicate mineral to form the molding composition; and this molding composition is fed into a molding apparatus wherein, by the application of heat, the prepolymer is cured to the phenol novolak resin.
  • a suitable curing agent such as hexamethylenetetramine
  • Another method of making the novolak resin containing molded article comprises using a liquid phenol-aldehyde prepolymer.
  • the liquid prepolymer obtained by reacting the phenol and aldehyde in the presence of a catalyst and heat is blended with a curing agent with the silicate mineral and acrylonitrile-butadiene copolymer, in an extruder or roll system, to form the molding composition; and the molding composition is fed to a molding apparatus wherein the orepolymer is cured, by the application of heat, to the ahenol novolak resin.
  • the resole resin is used as the phenolic resin component of the molded article
  • the phenol and aldehyde are partially reacted in the presence of heat and a catalyst to form, a prepolymer.
  • the prepolymer is then ground to powder form; the powdered prepolymer is then mechanically mixed, in an extruder or roll system, with the silicate mineral and the acrylonitrile-butadiene copolymer to form a molding composition; and this molding composition is then molded in a molding apparatus wherein the prepolymer is cured, through the application of heat, i.e., further condensed and crosslinked, to form the phenol resole resin.
  • prepolymer when used herein, it is meant to include the further curable, i.e., further crosslinkable or thermosettable, partial condensation product of a phenol and an aldehyde.
  • curing or thermosetting occurs by further application of heat to the partial condensation product of a phenol and an aldehyde.
  • further curing or thermosetting occurs by heating the partial condensation product of a phenol and aldehyde in the presence of a curing agent such as hexamethylenetetramine.
  • another embodiment of the present invention comprises a molding composition
  • a molding composition comprising a prepolymer of a phenolic resin. specifically a prepolymer of a novolak or resole resin, an acrylonitrile-butadiene copolymer, and a silicate mineral.
  • the phenolic resin prepolymer component is present in the molding composition in amounts generally ranging, in percent by weight. the prepolymer is cured, by the application of heat, to the phenol novolak resin.
  • the resole resin is used as the phenolic resin component of the molded article
  • the phenol and aldehyde are partially reacted in the presence of heat and a catalyst to form a prepolymer.
  • the prepolymer is then ground to powder form; the powdered prepolymer is then mechanically mixed, in an extruder or roll system, with the silicate mineral and the acrylonitrile-butadiene copolymer to form a molding composition; and this molding composition is then molded in a molding apparatus wherein the prepolymer is cured, through the application of heat, i.e., further condensed and crosslinked, to form the phenol resole resin.
  • prepolymer when used herein, it is meant to include the further curable, i.e., further crosslinkable or thermosettable, partial condensation product of a phenol and an aldehyde.
  • curing or thermosetting occurs by further application of heat to the partial condensation product of a phenol and an aldehyde.
  • further curing or thermosetting occurs by heating the partial condensation product of a phenol and aldehyde in the presence of a curing agent such as hexamethylenetetramine.
  • another embodiment of the present invention comprises a molding composition
  • a molding composition comprising a prepolymer of a phenolic resin, specifically a prepolymer of a novolak or resole resin, an acrylonitrile-butadiene copolymer, and a silicate mineral.
  • the phenolic resin prepolymer component is present in the molding composition in amounts generally ranging, in percent by weight, from about 20 to about 70 percent, preferably from .about 25 to about 55 percent, more preferably from about 30 to about 50 percent, and most preferably from about 35 to about 45 percent.
  • the acrylonitrile-butadiene copolymer component of the molding composition is generally present, in percent by weight, from 3 to about 25 percent, preferably from about 4 to about 20 percent, more preferably from about 5 to about 15 percent, and most preferably from about 8 to about 12 percent.
  • the silicate mineral component of the molding composition is generally present, in percent by weight, in from about 15 to about 70 percent, preferably from about 20 to about 65 percent, more preferably from about 30 to about 60 percent, and most preferably from about 40 to about 50 percent.
  • the molding composition may also optionally include other materials such as dyes, pigments, fillers, lubricants and the like, all of which are well known in the art.
  • the molding compositions are molded into various shapes using conventional molds, molding conditions and techniques of operation. PREFERRED EMBODIMENT OF THE INVENTION
  • This example illustrates a molded article outside the scope of the instant invention molded from a molding composition containing a typical two-stage phenolic thermosetting molding resin and silicate minerals but not containing the acrylonitrile-butadiene copolymer.
  • the formulation employed was as follows: Percent by Weight
  • Silicate Minerals (a 1:1 weight 56. 5 ratio of glass to silane modified calcium silicate ⁇
  • the above ingredients were comixed on a conventional roll-mill system and molded into test samples using a pressure of about 1,000 psi and a temperature of about 165oC for about one minute.
  • EXAMPLE 2 This example illustrates a molded article outside the scope of the instant invention molded from a molding composition containing a typical two-stage phenolic thermosetting molding resin and acrylonitrile-butadiene copolymer but not containing the silicate minerals.
  • the formulation employed was as follows:
  • the above ingredients were comixed on a conventional roll-mill system and molded into test samples using a pressure of about 1,000 psi and a temperature of about 165oC for about one minute.
  • EXAMPLE 3 This example illustrates a molded article outside the scope of the instant invention molded from a molding composition containing a typical two-stage phenolic thermosetting molding resin and the silicate minerals but containing Elvaloy (an ethylene vinyl acetate copolymer sold by E.I. DuPont de Nemours and Company) in place of the acrylonitrile-butadiene copolymer.
  • Elvaloy an ethylene vinyl acetate copolymer sold by E.I. DuPont de Nemours and Company
  • the formulation employed was as follows: Percent by Weicht
  • Silicate Minerals (a 1:1 weight ratio of glass to silane modified calcium silicate)
  • the above ingredients were comixed on a conventional roll-mill system and molded into test samples using a pressure of about 1,000 psi and a temperature of about 165oC for about 1 minute.
  • EXAMPLE 4 This example illustrates a molded article of the present invention molded from a molding composition containinc a typical two-stage phenolic thermosetting molding resin, acrylonitrile-butadiene copolymer, and the silicate minerals.
  • the formulation employed was as follows:
  • Silicate Minerals (a 1:1 weight 46.5 ratio of class to silane modified calcium silicate)
  • the above ingredients were comixed on a conventional roll-mill system and molded into test samples using a pressure of about 1,000 psi and a temperature of about 165oC for about cse minute.
  • test specimens comprising a 4 inch diameter by 1/3 inch thick disc were subjected to a Drop Ball Imoact Test.
  • the disc was placed in a dropped ball impact tester and the center of the disc was struck with a 1/2-pound weight. The weight was dropped repeatedly from a height sequentially raised in 1-inch increments and the point at which the specimen shattered was recorded.
  • test specimens one-half inch wide and one-half inch thick were subjected to the Izod impact test.
  • the Izod impact test was performed in accordance with the ASTM standards D256-A. Briefly, the specimen is notched and placed in a holder and a fixed pendulum swings down and breaks the sample. The value of the energy expended in breaking the specimen expressed in ft. lbs. /in. of notch is recorded.
  • test specimens 1/4" ⁇ 1/2" ⁇ 5" were tested for flexural strength, both before and after heat aging, according to ASTM standard D-790.
  • phenolic molded articles containing both the acrylonitrile-butadiene copolymer and the silicate mineral exhibit an increase in impact strength, heat distortion temperature, and flexural strength after exposure to heat, over those phenolic molded articles which do not contain the combination of both the acrylonitrile-butadiene. copolymer and silicate mineral.
  • the flexural strength of the article of Example 4 is greater than the initial flexural strength of the molded article of Example 4, which contains both the acrylonitrile-butadiene copolymer and the silicate mineral, the flexural strength of the article of Example 4 continually increases upon exposure to heat until after being heated for 5 hours at 350oF and for an additional 43 hours at 450 oF, it is greater than both the initial and identically heat aged flexural strengths of the article of Example 1.
  • Table I clearly illustrates the criticality of the presence of both the acrylonitrile-butadiene copolymer and the silicate mineral in obtaining a phenolic article having improved properties, particularly improved heat stability.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Article en resine phenolique moulee stable a la chaleur comprenant, en pourcentages ponderaux. environ 20 a 70% d'une resine phenolique, environ 3 a 25% d'un elastomere d'acrylonitrile butadiene et environ 15 a 70% d, un silicate mineral. Composition de moulage comprenant, en pourcentages ponderaux, environ 20 a 70% en poids d'une resine thermodurcissable de phenol-aldehyde, environ 3 a 25% en poids d'un elastomere d'acrylonitrile butadiene, et environ 15 a 70% en poids d'un silicate mineral.
PCT/US1981/000253 1981-03-02 1981-03-02 Article en resine phenolique moulee stable a la chaleur WO1982003080A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP19810901736 EP0073191A4 (fr) 1981-03-02 1981-03-02 Article en resine phenolique moulee stable a la chaleur.
JP50217881A JPS58500568A (ja) 1981-03-02 1981-03-02 熱に安定なフエノ−ル樹脂成形物
BR8108979A BR8108979A (pt) 1981-03-02 1981-03-02 Artigo moldado de resina fenolica estavel ao calor
PCT/US1981/000253 WO1982003080A1 (fr) 1981-03-02 1981-03-02 Article en resine phenolique moulee stable a la chaleur

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
WOUS81/00253810302 1981-03-02
PCT/US1981/000253 WO1982003080A1 (fr) 1981-03-02 1981-03-02 Article en resine phenolique moulee stable a la chaleur

Publications (1)

Publication Number Publication Date
WO1982003080A1 true WO1982003080A1 (fr) 1982-09-16

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1981/000253 WO1982003080A1 (fr) 1981-03-02 1981-03-02 Article en resine phenolique moulee stable a la chaleur

Country Status (4)

Country Link
EP (1) EP0073191A4 (fr)
JP (1) JPS58500568A (fr)
BR (1) BR8108979A (fr)
WO (1) WO1982003080A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2142547A (en) * 1983-04-28 1985-01-23 Goodyear Tire & Rubber Simulated slate bed for a billiard table
FR2632317A1 (fr) * 1988-06-03 1989-12-08 Gewerk Keramchemie Matiere moulage thermodurcissable a base de resine phenolique, de type resol, pour la fabrication d'articles a resistance chimique
WO2007055723A3 (fr) * 2005-11-07 2007-07-05 Cisco Tech Inc Procede et appareil pour fournir une assertion d'identite cryptographique concernant un reseau telephonique public commute (pstn)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0192319B1 (fr) * 1985-01-22 1992-07-15 Mycogen Corporation Encapsulation cellulaire de pesticides biologiques

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2540592A (en) * 1948-09-10 1951-02-06 Standard Oil Dev Co Plasticized phenolic resin blends
US2598289A (en) * 1949-06-09 1952-05-27 Us Rubber Co Composition of matter comprising a thermosetting cashew nut shell oil modified phenol-formaldehyde resin, a rubbery copolymer of butadiene and acrylonitrile, and diatomaceous earth
US2657185A (en) * 1948-08-19 1953-10-27 Standard Oil Dev Co Blends of elastomers with modified phenolic resins
US2935763A (en) * 1954-09-01 1960-05-10 Us Rubber Co Method of forming pellets of a synthetic rubber latex and a particulate resin
US3015568A (en) * 1958-05-12 1962-01-02 American Can Co Baked dough package
US3344094A (en) * 1965-01-21 1967-09-26 Johns Manville Dry mix friction material comprising butadiene acrylonitrile rubber, phenol formaldehyde resin and filler
US3474065A (en) * 1962-11-19 1969-10-21 Hooker Chemical Corp Phenolic resins for elastomeric compositions
US3586735A (en) * 1965-04-29 1971-06-22 Albert Ag Chem Werke Rubber mixtures reinforced by phenol novolac resins and process for preparing phenol novolac resins suitable therefor
US3702841A (en) * 1971-02-12 1972-11-14 Nasa Intumescent paint containing nitrile rubber
US4183841A (en) * 1965-07-16 1980-01-15 The United States Of America As Represented By The Secretary Of The Navy Filled composition containing phenol-aldehyde resin and butadiene-acrylonitrile polymer

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2459739A (en) * 1944-04-01 1949-01-18 Firestone Tire & Rubber Co Elastomeric copolymer mixed with phenol-aldehyde resin

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2657185A (en) * 1948-08-19 1953-10-27 Standard Oil Dev Co Blends of elastomers with modified phenolic resins
US2540592A (en) * 1948-09-10 1951-02-06 Standard Oil Dev Co Plasticized phenolic resin blends
US2598289A (en) * 1949-06-09 1952-05-27 Us Rubber Co Composition of matter comprising a thermosetting cashew nut shell oil modified phenol-formaldehyde resin, a rubbery copolymer of butadiene and acrylonitrile, and diatomaceous earth
US2935763A (en) * 1954-09-01 1960-05-10 Us Rubber Co Method of forming pellets of a synthetic rubber latex and a particulate resin
US3015568A (en) * 1958-05-12 1962-01-02 American Can Co Baked dough package
US3474065A (en) * 1962-11-19 1969-10-21 Hooker Chemical Corp Phenolic resins for elastomeric compositions
US3344094A (en) * 1965-01-21 1967-09-26 Johns Manville Dry mix friction material comprising butadiene acrylonitrile rubber, phenol formaldehyde resin and filler
US3586735A (en) * 1965-04-29 1971-06-22 Albert Ag Chem Werke Rubber mixtures reinforced by phenol novolac resins and process for preparing phenol novolac resins suitable therefor
US4183841A (en) * 1965-07-16 1980-01-15 The United States Of America As Represented By The Secretary Of The Navy Filled composition containing phenol-aldehyde resin and butadiene-acrylonitrile polymer
US3702841A (en) * 1971-02-12 1972-11-14 Nasa Intumescent paint containing nitrile rubber

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0073191A4 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2142547A (en) * 1983-04-28 1985-01-23 Goodyear Tire & Rubber Simulated slate bed for a billiard table
FR2632317A1 (fr) * 1988-06-03 1989-12-08 Gewerk Keramchemie Matiere moulage thermodurcissable a base de resine phenolique, de type resol, pour la fabrication d'articles a resistance chimique
WO2007055723A3 (fr) * 2005-11-07 2007-07-05 Cisco Tech Inc Procede et appareil pour fournir une assertion d'identite cryptographique concernant un reseau telephonique public commute (pstn)

Also Published As

Publication number Publication date
JPS58500568A (ja) 1983-04-14
EP0073191A4 (fr) 1983-08-23
EP0073191A1 (fr) 1983-03-09
BR8108979A (pt) 1983-01-25

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