EP0110953A4 - Compositions de caoutchouc contenant des oxydes de furazane aromatiques. - Google Patents

Compositions de caoutchouc contenant des oxydes de furazane aromatiques.

Info

Publication number
EP0110953A4
EP0110953A4 EP19830902018 EP83902018A EP0110953A4 EP 0110953 A4 EP0110953 A4 EP 0110953A4 EP 19830902018 EP19830902018 EP 19830902018 EP 83902018 A EP83902018 A EP 83902018A EP 0110953 A4 EP0110953 A4 EP 0110953A4
Authority
EP
European Patent Office
Prior art keywords
rubber
furazan
oxide
lower hydrocarbyl
vulcanizate
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
EP19830902018
Other languages
German (de)
English (en)
Other versions
EP0110953A1 (fr
Inventor
Walter R Hausch
Daniel F Graves
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bridgestone Firestone Inc
Original Assignee
Firestone Tire and Rubber Co
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 Firestone Tire and Rubber Co filed Critical Firestone Tire and Rubber Co
Publication of EP0110953A1 publication Critical patent/EP0110953A1/fr
Publication of EP0110953A4 publication Critical patent/EP0110953A4/fr
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber

Definitions

  • This invention relates to uncured rubber compositions and filled vulcanizates made therefrom. More particularly, it relates to such compositions exhibiting improved properties and containing aromatic furazan oxides. It also relates to methods of improving the processability, green strength and viscosity properties of uncured rubber compositions and articles made from the vulcanizates, such as tires, and methods of improving the rolling resistance and running temperatures of such tires.
  • uncured rubber compositions comprising at least one rubber having an unsaturated carbon chain and minor, property-improving, amounts of at least one aromatic furazan oxide of a partial formula
  • compositions wherein the depicted carbon atoms are part of a fused aromatic ring, are improved in processability and/or green strength.
  • Such compositions may also exhibit desirably
  • SUBSTITUTE SHEET reduced viscosity and other beneficial properties.
  • the invention includes methods of improving processability, enhancing green strength and reducing viscosity of uncured compositions by adding aromatic furazan oxides to them. Liquid rubber compositions are also within the scope of the invention.
  • a filled vulcanizate made by vulcanizing a composition comprising at least one rubber having an unsaturated carbon chain, filler and a minor, cured property-improving amount of at least one aromatic furazan oxide of the partial formula
  • depicted carbon atoms are part of, a second, single aromatic ring, is improved in filler interaction, hysteresis, modulus, compression set and resiliency.
  • Rubber articles and portions thereof made from such vulcanizates such as tires, hoses, belts, treads, sidewalls and the like are also within the scope of the invention as are methods for reducing the rolling resistance and running temperatures of such tires.
  • the rubber compositions of the first aspect of this invention are not cured, that is, they are uncured and not vulcanized. In some instances, they contain curing agents (systems) and thus are capable of being cured. In other words, they are vulcanizable. In other instances, the compositions of this invention do not contain curing agents, either because they are
  • the invention includes uncured rubber compositions containing aromatic furazan oxides whether or not they contain, in addition, curing agents, and whether or not they are intermediates to which curing agents are to be added.
  • Said curing agents when present, are of the conventional type such as sulfur-or peroxide-based curing systems and the like. They are used in conventional amounts and incorporated in the uncured compositions of this invention by known techniques and procedures.
  • Fillers may be, and often are present as is known to those skilled in the art. Typical fillers include carbon black in its various forms, glass, silica, talc and similar finely divided mineral materials.
  • the rubbers used in the uncured compositions of this invention have unsaturated carbon chains. That is, their polymer backbones contain a significant amount of unsaturation, in contrast to the pendent or vinyl saturation as found in some other types of rubbers. Typically, the chains of such unsaturated rubbers have at least about 20% of their carbon to carbon bonds as unsaturated bonds. Characterization of rubber as having unsaturated carbon chains it well-known in the art as shown by ANSI/ASTM Standard D 1418-79A where unsaturated-chain rubbers are referred to as R rubbers. Class R rubbers include natural rubber and various synthetic rubbers derived at least partly from diolefins.
  • OMPI__ The following is a non-exclusive list of R class rubbers which can be used in the compositions of the present invention:
  • PSB Polyridine-styrene-butadiene SBR--Styrene-butadiene SCR--Styrene-chloroprene SIR--Styrene-isoprene rubbers.
  • compositions where the rubber is NR, IR, BR,
  • NR includes both heava and guayule rubber as well as mixtures thereof.
  • compositions of the present aspect of this invention can also contain materials used in conventional rubber formulations such as antioxidants, accelerators, retarders, promoters and the like in addition to the curing systems and fillers noted above. It should be noted, however, that it is sometimes desirable to choose such materials with care since they may interact with the essential furazan oxides.
  • the vulcanizates of the present invention also contain fillers of the conventional type such as carbon black in its many forms, clays, talc, pyrophyllite, silica and other inorganic, finely divided materials.
  • fillers of the conventional type such as carbon black in its many forms, clays, talc, pyrophyllite, silica and other inorganic, finely divided materials.
  • they contain conventional curing systems and agents, such as sulfur, antioxidants, accelerators, retarders, coupling agents, promoters and the like. It should be noted, however, that it. is sometimes desirable to take care in choosing such materials since they may interact with the furazan oxides.
  • furazan oxides used in both the vulcanizable and vulcanized (cured) compositions of this invention are fused aromatic, that is, they have an aromatic ring fused to the N-oxidized heterocyclic furazan ring. They are of the partial formula
  • depicted carbon atoms are part of a fused, single aromatic ring.
  • This aromatic ring can be carbocyclic such as a benzene ring or it may be heterocyclic, such as a pyridine ring. It can be the only additional ring in the furazan compound, or it can be part of a linked or fused ring system. It is only necessary that both depicted carbon atoms be part of the same aromatic ring.
  • furazan oxides useful in the vulcanizable and cured compositions of this invention are those that can be represented by the formulae
  • lower hydrocarbyl refers to groups of carbon and hydrogen having eight or less carbon atoms such as methyl, ethyl, butyl, pentyl, heptyl, octyl (all isomers) .
  • Linking atoms or groups include ether, thio ether, sulfoxide, sulfone, amine, methylene and the like (including simple covalent bonds such as found in biphenyl) and the other linking groups shown in U.S.
  • Hydrocarbyl- oxa, hydrocarbyl this and mixed hydrocarbyl oxa-thia substitutents are also possible where the hydrocarbyl groups are typically lower alkylene moieties. Such are often made from glycols, dithiols, epoxides and episulfides. Often the furazan oxide is a benzofurazan oxide of the formula
  • the furazan oxide is benzofurazan oxide or the methyl or methoxy analog thereof.
  • furazan oxides particulary those containing relatively large amounts of nitrogen and oxygen, such as benzotri (furazan oxide) and 4, 6-di (nitro) benzofurazan oxide, are prone to rapid decomposition to the point of explosions; all may be physiologically active to varying degrees. Therefore, care in their handling and use should be exercised.
  • the vulcanizable compositions of the present invention can be prepared by conventional techniques using various types of mills, blenders and mixers known to the art.
  • the cured compositions can be made by the same techniques followed by curing.
  • the amount of furazan oxide used is a property-improving amount, such as an amount which will improve the processability of the composition and, in certain instances, its green strength and viscosity properties.
  • Processability properties are those related to the ease and efficiency of mixing, mastication and handling of a rubber composition in its unvulcanized, that is, uncured state. They include viscosity and often the speed and efficiency with which various other components are dispersed in the rubber.
  • Similar amounts are used in the cured compositions to improve such vulcanizate properties as filler interaction, modulus, resiliency, hysteresis, rolling resistance, running temperature and the like.
  • this property-improving amount will range from about 0.1 to 10 parts per 100 parts (by weight) rubber (phr) .
  • the furazan oxide will be used in an amount ranging from 0.5-5 phr.
  • the temperatures used in formulating the rubber compositions of this invention range from ambient to those normally used in the art, such as 75 degrees to 175 degrees or ambient, say 20°, to those conventionally used such as 150° to 200°. In its broader aspects, the formulations can be made from about 20 degrees to 220 degrees. Although in many instances, narrower temperature ranges such as about 50 degrees to 190 degrees are employed.
  • fillers, promoters, curing agents and other conventional rubber additives are also often included in these precured mixtures in conventional amounts.
  • the vulcanizates of this invention are prepared by curing the furazan oxide containing compositions under conditions of temperature and time customarily used in the art, and the invention is not significantly dependent on such curing variables.
  • the rubber and filler (or pigment) are first mixed and then the mixture treated with furazan oxide before curing.
  • Other sequences can also be used but it is essential to have the rubber, filler (pigment) and furazan oxide intimately combined before vulcanization.
  • compositions of the present invention are improved processability, enhanced green strength and in some instances reduced viscosity.
  • Compositions containing substantial amounts (greater than 50 percent) of NR, IR or CR show improved processability and enhanced green strength.
  • Improved processability of uncured rubber formulations is often desirable because it permits savings in energy and time while compounding and subsequent processing of the rubber by techniques such as calendering, milling, remilling, extrusion and the like. Such savings are important in the current period of shortages and rising costs.
  • processability is an inclusive term used also to describe the decreased viscosity and/or high green strength such as found in the compositions of this invention.
  • NR, IR and CR containing compositions show viscosity reductions of about 20 Mooney units for about 0.5-1.5 phr furazan oxide with accompanying increases in green strength of about 20-100 psi.
  • Similar levels of furazan oxide in synthetic rubbers such as, for example, SBR show Mooney viscosity increases of about 10 units while when peak green strength is increased about 5-50 psi.
  • With higher levels of furazan oxides e.g. 2-5 phr
  • the extreme in viscosity reduction can be reached with liquefaction of NR and IR.
  • Such liquid rubbers are useful in sealants and as processing aids where they are combined with other types of rubber to aid in plasticizing rubber.
  • Liquid rubbers also known as depolymerized rubber (DPR)
  • DPR depolymerized rubber
  • maximum viscosity reductions can usually be achieved by adjusting the concentrations of the furazan oxide and the antioxidant or radial trapping materials (fillers) in a given rubber composition.
  • an internal mixer such as a Brabender or small size Banbury mixer
  • the usual technique was to add various materials, often in portions, to the mixer and continue mixing for the indicated time period. Further additions followed by mixing are then made to the masterbatches thus prepared.
  • the standard technique was according to the following schedule:
  • the uncured masterbatch was then immediately banded and sheeted on a small twin roll mill set at 60 gauge. Mooney viscosities were measured using the large rotor in a four minute cycle at 100 degrees. This procedure was used to make masterbatches from NR (Hevea) and SBR (trade name Duradene, available from The Firestone Tire & Rubber Company, Akron, Ohio, USA) .
  • a series of typical tire belt skim formulations were prepared using 100 percent natural rubber containing zinc oxide (5 phr), stearic acid (2 phr), carbon black (40 • parts) and varying amounts and types of furazan oxides. Each was mixed 5 minutes and dropped at 143°.
  • the additives used and results were as follows
  • stocks IA and IB both of which contained furazan oxides, exhibited decreased Mooney viscosities and, at the same time, increased green strengths.
  • EXAMPLE TWO A SBR-based passenger tire tread stock composition was prepared containing about 60 phr carbon black and conventional amounts of zinc oxide, stearic oxide and a waxy antioxidant. A similar formulation containing in addition 1.0 phr benzofurazan oxide was prepared under comparable conditions. The Mooney viscosity
  • a NR composition was prepared containing about 40 parts ISAF black, about 20 parts Hi-sil silica and conven ⁇ tional amounts of zinc oxide, antioxidants, softener, resin, sulfenamide accelerator, sulfur and retarder.
  • An essentially identical composition was prepared containing, in addition, 1 phr benzofurazan oxide.
  • the control had a Mooney viscosity of 64.4 and the furazan oxide formula ⁇ tion, a viscosity of 49.0.
  • 1.0 part furazan oxide causes a 15 unit decrease in viscosity under identical mixing conditions.
  • EXAMPLE 5(B) A similar series of rubber compounds based on SBR was prepared containing methyl benzofurazan oxide and, in some instances, Santoflex 13. In the absence of the latter, a steady increase in viscosity is observed. When antioxidant is also present, a steady decrease in viscosity resulted as shown by the data in Table 5B.
  • a series of vulcanizates was prepared using a conventional carbon black containing forumulation and sulfur based curing system.
  • the vulcanizates also contained about 20 parts Hi-Sil silica and conventional amounts of zinc oxide, antioxidants, softener, resin, sulfenamide accelerator, sulfur and retarder.
  • the first (the control) contained no promoter, the second 0.6 phr Nitrol (Monsanto Chem Co.) and the third 1.0 phr benzo ⁇ furazan oxide. Nitrol is a known promoter and was used at its recommended level. Evaluation data for each vulcani ⁇ zate are shown in Table I.
  • Clearly the benzofurazanoxide- containing vulcanizate is superior in most properties and exhibits no significant deficiencies in any property.
  • Typical truck tire tread vulcanizates were prepared from grade B natural rubber filled with silica (about 80 parts phr Hi-Sil) and containing conventional amounts of silane coupling agent, plasticizer, antioxi ⁇ dants, processing oil, sulfur, accelerator retarder, resin
  • a series of typical tread stocks was prepared from synthetic rubber according to a typical tread stock recipe calling for about 60 parts carbon black.
  • the control contained no additive and Examples 3A and 3B contained one phr of methoxy benzofurazan oxide and benzo- furazan oxide, respectively.
  • Each stock was cured in the usual manner and the vulcanizate specimens evaluated in a number of standard tests. As can be seen from the data in Table III, the stocks containing the benzofurazan oxides showed superior properties.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

Des compositions de caoutchouc non-polymérisées contenant des oxydes de furazane aromatiques fusionnés présentent une aptitude améliorée au traitement et une viscosité réduite. Des oxydes de furazane utiles ont les deux carbones de l'anneau furazane comme faisant partie d'un anneau aromatique fusionné et comprennent l'oxyde de benzofurazane et ses analogues de méthyle et de méthoxy. Des améliorations à l'aptitude au traitement, à la résistance au vert et à la liquéfaction de NR peuvent être obtenues en utilisant ces oxydes de furazane dans des compositions de caoutchouc non-polymérisées. Des produits de vulcanisation de caoutchouc plein contenant des oxydes de furazane aromatiques présentent de nombreuses propriétés améliorées telles qu'une interaction accrue entre le matériau de remplissage et le caoutchouc et une hystérèse réduite. Des oxydes de furazane utiles ont les deux carbones de l'anneau de furazane comme partie d'un anneau aromatique fusionné. Des exemples caractéristiques sont l'oxyde de benzofurazane et ses analogues de méthyle et de méthoxy. Des pneumatiques fabriqués à partir des produits de vulcanisation de l'invention ont des températures de roulement plus faibles et une résistance au roulis améliorée.
EP19830902018 1982-05-20 1983-05-09 Compositions de caoutchouc contenant des oxydes de furazane aromatiques. Ceased EP0110953A4 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US38019482A 1982-05-20 1982-05-20
US38019382A 1982-05-20 1982-05-20
US380193 1982-05-20
US380194 1982-05-20

Publications (2)

Publication Number Publication Date
EP0110953A1 EP0110953A1 (fr) 1984-06-20
EP0110953A4 true EP0110953A4 (fr) 1984-09-28

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP19830902018 Ceased EP0110953A4 (fr) 1982-05-20 1983-05-09 Compositions de caoutchouc contenant des oxydes de furazane aromatiques.

Country Status (10)

Country Link
EP (1) EP0110953A4 (fr)
KR (1) KR920001045B1 (fr)
AU (1) AU568502B2 (fr)
CA (1) CA1229940A (fr)
ES (1) ES8505699A1 (fr)
IT (1) IT1162863B (fr)
NO (1) NO163622C (fr)
PH (1) PH22898A (fr)
PT (1) PT76728B (fr)
WO (1) WO1983004031A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4557306A (en) * 1984-06-18 1985-12-10 The Firestone Tire & Rubber Company Carbon black-furazan oxide product and rubber compositions containing same
ZA854276B (en) * 1984-09-21 1986-01-29 Firestone Tire & Rubber Co Rubber compositions containing furazan oxides and transition metal salts
US4975497A (en) * 1984-09-21 1990-12-04 Bridgestone/Firestone, Inc. Rubber compositions containing furazan oxides and transition metal salts
US4570690A (en) * 1984-09-21 1986-02-18 The Firestone Tire & Rubber Company Mixing procedure for obtaining filled rubber vulcanizates containing aromatic furazan oxides
EP0195927B1 (fr) * 1985-03-18 1990-11-22 The Firestone Tire & Rubber Company Caoutchouc modifié à l'oxyde de furazane et compositions de caoutchouc contenant celui-ci
US4751271A (en) * 1985-03-18 1988-06-14 The Firestone Tire & Rubber Company Furazan oxide modified rubbers and rubber compositions containing same

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1542772A1 (de) * 1964-10-09 1970-03-26 Bayer Ag Mittel zum Schutz von Materialien gegen Schimmelbefall

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Publication number Priority date Publication date Assignee Title
US2905582A (en) * 1955-04-29 1959-09-22 Lord Mfg Co Method of bonding polyurethanes to rubbers
US2974120A (en) * 1957-12-23 1961-03-07 Monsanto Chemicals Rubber compositions and preparation thereof
US3931106A (en) * 1973-05-11 1976-01-06 Imperial Chemical Industries Limited Generation and use of dinitrile oxides
US3931121A (en) * 1974-11-11 1976-01-06 Basf Wyandotte Corporation Process for accelerating the curing of polymers with organo chloronitroso compounds
DE2534400A1 (de) * 1975-08-01 1977-02-17 Basf Ag Umweltfreundliche einbrennlacke
JPS52102231A (en) * 1975-12-29 1977-08-27 Kawaguchi Chemical Ind Inhibition of polymerization of aromatic vinyl compounds
JPS52133931A (en) * 1976-05-04 1977-11-09 Kawaguchi Chemical Ind Improved polymerization inhibition of aromatic vinyl compound
GB1586861A (en) * 1977-09-16 1981-03-25 Ici Ltd Polymers

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1542772A1 (de) * 1964-10-09 1970-03-26 Bayer Ag Mittel zum Schutz von Materialien gegen Schimmelbefall

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 76, no. 8, April 20, 1954, American Chemical Society (US), R.J. GAUGHRAN et al.: "Contribution to the chemistry of benzfuroxan and benzfurazan derivatives", pages 2233-2236. *

Also Published As

Publication number Publication date
KR920001045B1 (ko) 1992-02-01
EP0110953A1 (fr) 1984-06-20
AU1702983A (en) 1983-12-02
ES522553A0 (es) 1985-06-01
AU568502B2 (en) 1988-01-07
PT76728B (en) 1987-02-06
PT76728A (en) 1983-06-01
IT1162863B (it) 1987-04-01
IT8367550A0 (it) 1983-05-18
NO163622B (no) 1990-03-19
NO831760L (no) 1983-11-21
WO1983004031A1 (fr) 1983-11-24
NO163622C (no) 1990-06-27
KR840004920A (ko) 1984-10-31
PH22898A (en) 1989-01-19
ES8505699A1 (es) 1985-06-01
CA1229940A (fr) 1987-12-01

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