EP0110953A4 - RUBBER COMPOSITIONS CONTAINING AROMATIC FURAZANE OXIDES. - Google Patents
RUBBER COMPOSITIONS CONTAINING AROMATIC FURAZANE OXIDES.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
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 78
- 229920001971 elastomer Polymers 0.000 title claims abstract description 69
- 239000005060 rubber Substances 0.000 title claims abstract description 68
- JKFAIQOWCVVSKC-UHFFFAOYSA-N furazan Chemical compound C=1C=NON=1 JKFAIQOWCVVSKC-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 31
- OKEAMBAZBICIFP-UHFFFAOYSA-N 3-oxido-2,1,3-benzoxadiazol-3-ium Chemical compound C1=CC=CC2=[N+]([O-])ON=C21 OKEAMBAZBICIFP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 5
- 238000005096 rolling process Methods 0.000 claims abstract description 5
- 230000003993 interaction Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000945 filler Substances 0.000 claims description 22
- KKEBXNMGHUCPEZ-UHFFFAOYSA-N 4-phenyl-1-(2-sulfanylethyl)imidazolidin-2-one Chemical compound N1C(=O)N(CCS)CC1C1=CC=CC=C1 KKEBXNMGHUCPEZ-UHFFFAOYSA-N 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000006229 carbon black Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- -1 hydroxyl halogen Chemical class 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- SFDJOSRHYKHMOK-UHFFFAOYSA-N nitramide Chemical compound N[N+]([O-])=O SFDJOSRHYKHMOK-UHFFFAOYSA-N 0.000 claims description 4
- 229920005556 chlorobutyl Polymers 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 230000002708 enhancing effect Effects 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 230000001737 promoting effect Effects 0.000 claims 1
- 230000001965 increasing effect Effects 0.000 abstract description 6
- 230000003247 decreasing effect Effects 0.000 abstract description 5
- 239000003963 antioxidant agent Substances 0.000 description 15
- 235000006708 antioxidants Nutrition 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 239000002174 Styrene-butadiene Substances 0.000 description 9
- 230000003078 antioxidant effect Effects 0.000 description 9
- 229920003048 styrene butadiene rubber Polymers 0.000 description 9
- 241001441571 Hiodontidae Species 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 230000009467 reduction Effects 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- AWBOSXFRPFZLOP-UHFFFAOYSA-N 2,1,3-benzoxadiazole Chemical compound C1=CC=CC2=NON=C21 AWBOSXFRPFZLOP-UHFFFAOYSA-N 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229940073020 nitrol Drugs 0.000 description 3
- 238000010058 rubber compounding Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XYLFFOSVQCBSDT-UHFFFAOYSA-N 1,2-dinitrosobenzene Chemical class O=NC1=CC=CC=C1N=O XYLFFOSVQCBSDT-UHFFFAOYSA-N 0.000 description 2
- MTRATWQOBZWRTD-UHFFFAOYSA-N 4-methyl-1-oxido-2,1,3-benzoxadiazol-1-ium Chemical compound CC1=CC=CC2=[N+]([O-])ON=C12 MTRATWQOBZWRTD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 238000012668 chain scission Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- LOVYCUYJRWLTSU-UHFFFAOYSA-N 2-(3,4-dichlorophenoxy)-n,n-diethylethanamine Chemical compound CCN(CC)CCOC1=CC=C(Cl)C(Cl)=C1 LOVYCUYJRWLTSU-UHFFFAOYSA-N 0.000 description 1
- YHBBUAULQKLKMW-UHFFFAOYSA-N 4,6-dinitro-1-oxido-2,1,3-benzoxadiazol-1-ium Chemical compound C1=C([N+](=O)[O-])C=C([N+]([O-])=O)C2=NO[N+]([O-])=C21 YHBBUAULQKLKMW-UHFFFAOYSA-N 0.000 description 1
- BNDZZXBUJOTVKD-UHFFFAOYSA-N 4-methoxy-1-oxido-2,1,3-benzoxadiazol-1-ium Chemical compound COC1=CC=CC2=[N+]([O-])ON=C12 BNDZZXBUJOTVKD-UHFFFAOYSA-N 0.000 description 1
- 101100489581 Caenorhabditis elegans par-5 gene Proteins 0.000 description 1
- 229920010800 Duradene Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 241000221020 Hevea Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- FMGUJLASXUBMOP-UHFFFAOYSA-N N-Methyl-N,4-dinitrosoaniline Chemical compound O=NN(C)C1=CC=C(N=O)C=C1 FMGUJLASXUBMOP-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 241001495453 Parthenium argentatum Species 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000004662 dithiols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000010077 mastication Methods 0.000 description 1
- 230000018984 mastication Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- NLRKCXQQSUWLCH-UHFFFAOYSA-N nitrosobenzene Chemical compound O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000002081 peroxide group Chemical group 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000000063 preceeding effect Effects 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003553 thiiranes Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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.
Landscapes
- 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)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US38019382A | 1982-05-20 | 1982-05-20 | |
US38019482A | 1982-05-20 | 1982-05-20 | |
US380193 | 1982-05-20 | ||
US380194 | 1995-01-30 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0110953A1 EP0110953A1 (en) | 1984-06-20 |
EP0110953A4 true EP0110953A4 (en) | 1984-09-28 |
Family
ID=27008923
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19830902018 Ceased EP0110953A4 (en) | 1982-05-20 | 1983-05-09 | RUBBER COMPOSITIONS CONTAINING AROMATIC FURAZANE OXIDES. |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0110953A4 (es) |
KR (1) | KR920001045B1 (es) |
AU (1) | AU568502B2 (es) |
CA (1) | CA1229940A (es) |
ES (1) | ES8505699A1 (es) |
IT (1) | IT1162863B (es) |
NO (1) | NO163622C (es) |
PH (1) | PH22898A (es) |
PT (1) | PT76728B (es) |
WO (1) | WO1983004031A1 (es) |
Families Citing this family (6)
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 |
US4570690A (en) * | 1984-09-21 | 1986-02-18 | The Firestone Tire & Rubber Company | Mixing procedure for obtaining filled rubber vulcanizates containing aromatic furazan oxides |
US4975497A (en) * | 1984-09-21 | 1990-12-04 | Bridgestone/Firestone, Inc. | Rubber compositions containing furazan oxides and transition metal salts |
ZA854276B (en) * | 1984-09-21 | 1986-01-29 | Firestone Tire & Rubber Co | Rubber compositions containing furazan oxides and transition metal salts |
DE3675670D1 (de) * | 1985-03-18 | 1991-01-03 | Firestone Tire & Rubber Co | Mit furazanoxid modifizierter kautschuk und diesen enthaltende kautschukmischungen. |
US4751271A (en) * | 1985-03-18 | 1988-06-14 | The Firestone Tire & Rubber Company | Furazan oxide modified rubbers and rubber compositions containing same |
Citations (1)
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 |
Family Cites Families (8)
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 |
-
1983
- 1983-05-09 EP EP19830902018 patent/EP0110953A4/en not_active Ceased
- 1983-05-09 AU AU17029/83A patent/AU568502B2/en not_active Ceased
- 1983-05-09 WO PCT/US1983/000697 patent/WO1983004031A1/en not_active Application Discontinuation
- 1983-05-13 CA CA000428063A patent/CA1229940A/en not_active Expired
- 1983-05-18 IT IT67550/83A patent/IT1162863B/it active
- 1983-05-18 NO NO831760A patent/NO163622C/no unknown
- 1983-05-19 PT PT76728A patent/PT76728B/pt unknown
- 1983-05-19 ES ES522553A patent/ES8505699A1/es not_active Expired
- 1983-05-19 KR KR1019830002203A patent/KR920001045B1/ko active IP Right Grant
- 1983-05-19 PH PH28930A patent/PH22898A/en unknown
Patent Citations (1)
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)
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 |
---|---|
WO1983004031A1 (en) | 1983-11-24 |
AU1702983A (en) | 1983-12-02 |
NO163622B (no) | 1990-03-19 |
ES522553A0 (es) | 1985-06-01 |
IT1162863B (it) | 1987-04-01 |
EP0110953A1 (en) | 1984-06-20 |
AU568502B2 (en) | 1988-01-07 |
PT76728B (en) | 1987-02-06 |
ES8505699A1 (es) | 1985-06-01 |
NO831760L (no) | 1983-11-21 |
CA1229940A (en) | 1987-12-01 |
KR840004920A (ko) | 1984-10-31 |
IT8367550A0 (it) | 1983-05-18 |
NO163622C (no) | 1990-06-27 |
PT76728A (en) | 1983-06-01 |
KR920001045B1 (ko) | 1992-02-01 |
PH22898A (en) | 1989-01-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4557306A (en) | Carbon black-furazan oxide product and rubber compositions containing same | |
US4778857A (en) | Uncured rubber compositions containing aromatic furazan oxides | |
US3419639A (en) | Ozone-resistant composition | |
US4570690A (en) | Mixing procedure for obtaining filled rubber vulcanizates containing aromatic furazan oxides | |
US4975497A (en) | Rubber compositions containing furazan oxides and transition metal salts | |
US4751271A (en) | Furazan oxide modified rubbers and rubber compositions containing same | |
CA1307608C (en) | Rubber compositions modified with benzimidazolinones | |
EP0289752A1 (en) | Rubber compositions modified with heterocyclic Di-N-oxides | |
US5023292A (en) | Tire compounds | |
WO1983004031A1 (en) | Uncured rubber compositions containing aromatic furazan oxides | |
CA1265298A (en) | Rubber compositions modified with sulfenamide derivatives | |
US3852251A (en) | Two-component accelerator system for vulcanizable rubbers | |
JPH1053667A (ja) | ポリマーコンパンドおよびそれらをハロゲン含有ゴムの加硫で用いる使用 | |
US5326828A (en) | Tetrabenzylthiuram disulfide/urea cured elastomeric composition | |
US4882394A (en) | Method for improving rubber cure rates | |
US3915943A (en) | Tire tread having low heat buildup | |
US3384613A (en) | Retardation of scorch in rubber compounds containing dicumyl peroxide as the vulcanizing agent | |
NZ204254A (en) | Uncured rubber compositions containing aromatic furazan oxides | |
JPH0240257B2 (es) | ||
EP0175062B1 (en) | Rubber compositions containing furazan oxides and transition metal salts | |
EP0195927B1 (en) | Furazan oxide modified rubbers and rubber compositions containing same | |
JP2003176379A (ja) | ゴム組成物 | |
CA1250678A (en) | Natural rubber containing compositions with increased tear strength | |
JPH02155937A (ja) | 減少したヒステリシス損を有する加硫ゴムの製造方法およびこれらの成形品 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19840118 |
|
AK | Designated contracting states |
Designated state(s): DE FR GB LU |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED |
|
18R | Application refused |
Effective date: 19900719 |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: GRAVES, DANIEL F. Inventor name: HAUSCH, WALTER R. |