EP3634941A1 - Compounds and mixtures with antidegradant and antifatigue efficacy and compositions including said compounds - Google Patents
Compounds and mixtures with antidegradant and antifatigue efficacy and compositions including said compoundsInfo
- Publication number
- EP3634941A1 EP3634941A1 EP18733019.6A EP18733019A EP3634941A1 EP 3634941 A1 EP3634941 A1 EP 3634941A1 EP 18733019 A EP18733019 A EP 18733019A EP 3634941 A1 EP3634941 A1 EP 3634941A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- compound
- mixture
- compounds
- hydrogen
- 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.)
- Pending
Links
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- 239000000203 mixture Substances 0.000 title claims description 133
- 230000002929 anti-fatigue Effects 0.000 title description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 21
- -1 polymethylene group Polymers 0.000 claims abstract description 16
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 5
- 229920001971 elastomer Polymers 0.000 claims description 31
- 238000009472 formulation Methods 0.000 claims description 30
- 239000000806 elastomer Substances 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 239000000314 lubricant Substances 0.000 claims description 10
- 239000000446 fuel Substances 0.000 claims description 9
- 239000002816 fuel additive Substances 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 12
- 125000002877 alkyl aryl group Chemical group 0.000 abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 62
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- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
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- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
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- BHKKSKOHRFHHIN-MRVPVSSYSA-N 1-[[2-[(1R)-1-aminoethyl]-4-chlorophenyl]methyl]-2-sulfanylidene-5H-pyrrolo[3,2-d]pyrimidin-4-one Chemical compound N[C@H](C)C1=C(CN2C(NC(C3=C2C=CN3)=O)=S)C=CC(=C1)Cl BHKKSKOHRFHHIN-MRVPVSSYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
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- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- VCHOFVSNWYPAEF-UHFFFAOYSA-N 1-(3-acetylphenyl)ethanone Chemical compound CC(=O)C1=CC=CC(C(C)=O)=C1 VCHOFVSNWYPAEF-UHFFFAOYSA-N 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- SKBBQSLSGRSQAJ-UHFFFAOYSA-N 1-(4-acetylphenyl)ethanone Chemical compound CC(=O)C1=CC=C(C(C)=O)C=C1 SKBBQSLSGRSQAJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005932 reductive alkylation reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 238000012306 spectroscopic technique Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
-
- 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
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/04—Systems containing only non-condensed rings with a four-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- the present invention relates generally to compounds with antidegradant and antifatigue efficacy that are useful as an additive for vulcanized rubber articles, vulcanizable elastomeric formulations, lubricants, fuels, fuel additives and other compositions which require such efficacy or in compositions which are themselves useful as compositions to impart such efficacy.
- Antidegradants useful in the manufacture of articles formed from elastomers, plastics and the like require a very specific combination of qualities that can be difficult to achieve. While the antidegradants must obviously have commercially acceptable efficacy, they must also exhibit that efficacy over prolonged periods of time associated with use of the article, particularly at exposed surfaces of the article where degradation from environmental factors such as light, oxygen and ozone primarily occurs. Just as important to the protection of surface exposed components, efficacy in protecting imbedded components of composite materials from the effects of oxidative aging and repetitive mechanical action are critically important. The antidegradants must achieve these results while not negatively impacting other additives' efficacy or desirable characteristics in the final article.
- antidegradants which provide or improve the mechanical fatigue life after an article has been in service, aged oxidatively or by exposure to ozone are highly valued since these will inherently improve the useful mechanical service life of article. Consequently, elastomeric articles which undergo repeated mechanical flexure, extension, or compression during service would greatly benefit from such a discovery.
- the present invention relates to compounds represented by the formula I:
- X 1 , X 2 , X 3 and X 4 are each selected from the group consisting of alkyl, aryl, alkylaryl groups and hydrogen; or wherein X 1 , X 2 , X 3 and X 4 are each hydrogen or methyl;
- each of R 1 , R 2 , R 3 , and R 4 are hydrogen.
- the present invention relates to a compositions and mixtures including a compound represented by the formula I:
- X 1 , X 2 , X 3 and X 4 are each selected from the group consisting of alkyl, aryl, alkylaryl groups and hydrogen; or wherein X1 , X2, X3 and X4 are each hydrogen or methyl;
- R 1 , R 2 , R 3 , and R 4 are each selected from the group consisting of alkyl, aryl, alkylaryl groups and hydrogen; or wherein R 1 , R 2 , R 3 , and R 4 are each selected from the group consisting of propyl, ethyl, methyl or hydrogen; and wherein one of R 1 and R 2 , and one of R 3 and R 4 may optionally be bridged by a polymethylene group;
- each of R 1 , R 2 , R 3 , and R 4 are hydrogen.
- the present invention is directed to an antidegradant composition including the compounds of the present invention.
- the present invention is directed to a lubricant composition including the compounds of the present invention.
- the present invention is directed to a vulcanizable elastomeric formulation including the compounds of the present invention.
- the present invention is directed to a vulcanized elastomeric rubber article with at least one component formed from a vulcanizable elastomeric formulation of the present invention.
- the compounds of the present invention have surprisingly demonstrated antidegradant and antifatigue agent efficacies and accordingly are particularly useful in imparting resistance to crack propagation, degradation and the many manifestations thereof in a variety of applications.
- the compound of the present invention When utilized as a component in vulcanizable elastomeric formulations for forming vulcanized rubber articles, and specifically in vehicle tires and their components, the compound of the present invention has demonstrated a particularly desirable and surprising combined efficacy against oxidative degradation, ozonative degradation and resistance against fatigue and crack propagation that is superior to the combination heretofore achieved by prior art materials. Further advantages and areas of applicability will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the spirit and scope of the present invention.
- Antidegradant refers to a material that inhibits degradation
- compositions, formulation or article to which it is added or applied are examples of a composition, formulation or article to which it is added or applied.
- Antifatigue agent refers to a material that improves the flex fatigue resistance of a composition, formulation or article to which it is added or applied after a period of in-service application time whereby the composition, formulation or article is subjected to thermal, oxidative, ozone and mechanical degradative forces.
- Antioxidant refers to a material that inhibits oxidative degradation of a composition, formulation or article to which it is added or applied.
- Antiozonant refers to a material that inhibits ozone exposure degradation of a composition, formulation or article to which it is added or applied.
- Elastomer means any polymer which after vulcanization (or crosslinking) and at room temperature can be stretched under low stress to at least twice its original length and, upon immediate release of the stress, will return with force to approximately its original length, including without limitation rubber.
- Vulcanizable Elastomeric Formulation means a composition that includes an elastomer and that is capable of vulcanization when placed under vulcanization conditions.
- the present invention is directed to a compound represented by the formula I:
- Non-limiting examples of the compound of the present invention according to formula I include N,N'-(ethane-1 ,2-diyl)bis(N- phenylbenzene-1 ,4-diamine); N,N'-(butane-2,3-diyl)bis(N-phenylbenzene-1 ,4- diamine); N,N'-(octane-1 ,8-diyl)bis(N-phenylbenzene-1 ,4-diamine); N,N'-(1 ,4- phenylenebis(methylene))bis(N-phenylbenzene-1 ,4-diamine); N,N'-(1 ,3- phenylenebis(methylene))bis(N-phenylbenzene-1 ,4-diamine); N,N'-(1 ,4- phenylenebis(ethane-1 ,1 -diyl))bis(N-phenylbenzen
- the present invention relates to pounds represented by the formula I:
- X 1 , X 2 , X 3 and X 4 are each independently hydrogen or methyl; wherein R 1 , R 2 , R 3 , and R 4 are each independently selected from the group consisting of propyl, ethyl, methyl or hydrogen, and wherein one of R 1 and R 2 , and one of R 3 and R 4 may optionally be bridged by a polymethylene group to form a cycloalkyl;
- each of R 1 , R 2 , R 3 , and R 4 are hydrogen.
- compositions including the compounds represented by formula I above, as further elaborated below.
- R may be such that C may be equal to 3, that is a propylene group such that a pentylene group is bonded to each of the adjacent nitrogen atoms, or may be branched such that adjacent carbons are bonded to the carbons depicted adjacent the R group, while a third carbon is bonded only to one of the two carbons bonded to those adjacent the R group, that is an isopropylene group.
- R 2 , R 3 , and R 4 are each independently selected from the group consisting of propyl, ethyl, methyl or hydrogen.
- R 1 , R 2 , R 3 , and R 4 may all be hydrogen, or may all be methyl, or may all be ethyl or propyl, or may be a mixture of any of these.
- one of R 1 and R 2 may be methyl and the other hydrogen, and one of R 3 and R 4 may be methyl and the other hydrogen.
- one of R 1 and R 2 , and one of R 3 and R 4 may optionally be bridged by a polymethylene group to form a cycloalkyi group.
- the compounds of the present invention may include a substituted or unsubstituted cycloalkyi such as cyclobutane, cyclopropane, or cyclohexane, or cycloheptane, or cyclooctane, in which two of R 1 , R 2 , R 3 , and R 4 may comprise methylene groups linked to the cycloalkyls or may each form a carbon of the cyclic alkyl itself.
- Non-limiting cycloalkyls that may be present in the compounds of formula II include cyclohexane, cyclohexane dimethanol.
- Diols useful to form such compounds containing cyclic alkyls also thus include, without limitation, cyclohexanediol, cyclohexanedimethanol.
- dicarbonyls useful to obtain such compounds include cyclohexanedione and cyclohexane dialdehyde.
- Non-limiting examples of the compounds of the present invention according to formula I thus include N,N'-(ethane-1 ,2-diyl)bis(N- phenylbenzene-1 ,4-diamine) and N,N'-(butane-2,3-diyl)bis(N-phenylbenzene- 1 ,4-diamine), as depicted above.
- the compounds of the present invention may be prepared from a polyalcohol starting material through a hydrogen autotransfer procedure using a homogenous or heterogeneous catalyst (see e.g. Guillena, et.al. Chem. Rev. 2010, 110, 161 1 for a general description of the mechanism).
- the compounds of interest can also be prepared from a polycarbonyl starting material using a heterogeneous transition metal catalyst in the presence of hydrogen.
- Precursors for compounds of the present invention, the compounds of the present invention and methods for their manufacture are illustrated by the following examples, which are not intended in any way to limit the spirit or scope of the present invention.
- Example 1 Preparation of Precursor (N,N',N,N')-N,N'-(ethane-1 ,2- diylidene)bis(N-phenylbenzene-1 ,4-diamine)
- DIBAL-H (122 g, 25 wt. % in toluene) was slowly cannulated into a 1 L round-bottom flask that contained THF (102 mL). Then the di-imine 1 (20.0 g, 50.2 mmol) was carefully added at ambient temperature. After the addition was complete, the mixture was heated to 60 °C and allowed to react for 19.25 hours. Then the reaction was cooled using an ice-water bath to ca. 5- 10 °C, at which point a saturated solution of NaK tartrate was added drop wise until the reaction mixture formed a gel. At that point, 250 mL of the NaK tartrate solution was quickly added, followed by 500 mL of EtOAc.
- the catalyst was clarified by passing the mixture through a plug of celite, using a minimal amount of DMF/EtOH (1 10 g DMF, 140 g of EtOH) to rinse the bottle and cake.
- the homogeneous mixture was transferred to a 1 L round-bottom flask with magnetic stir bar.
- 750 g of water was added via pressure-equalizing dropping funnel over a 40 minute period with vigorous stirring.
- the precipitated solids were filtered through a 1 micron glass fiber disc and washed with 2.5L of water.
- the solids were transferred to a 1 L Erienmeyer flask and stirred with a stir bar in ca. 750 imL of H2O for 4 hrs.
- the solids were once again filtered and washed with additional H2O.
- Example 4 Preparation of Precursor (N,N')-N,N'-(butane-2,3- diylidene)bis(N-phenylbenzene-1 ,4-diamine), or 4,4-(((2E,3E)-butane-2,3- diylidene)bis(azaneylylidene))bis(N-phenylaniline)
- Example 5 Alternative Preparation of 4,4-(((2E,3E)-butane-2,3- diylidene)bis(azaneylylidene))bis(N-phenylaniline), or ( ⁇ , ⁇ ')- ⁇ , ⁇ '- (butane-2,3-diylidene)bis(N-phenylbenzene-1 ,4-diamine)
- LiAIH 4 (7.40 g, 1995 mmol) was carefully added to THF (162 mL) in a 1 L round-bottom flask.
- Di-imine 3 (20.4 g, 48.7 mmol) was carefully added to the solution. After the addition was complete, the reaction was refluxed for 4 hrs. After this time, the mixture was cooled using an ice water bath and then carefully quenched by the drop wise addition of water (25 mL) followed by drop wise addition of 15% NaOH (50 mL). An additional 150 mL of water was added to the mixture and then stirred overnight. After filtration, the brown liquid was concentrated under reduced pressure using a rotary evaporator.
- the catalyst was clarified by passing the mixture through a plug of celite. The volatiles were removed under reduced pressure using a rotary evaporator.
- 1 H NMR (500 MHz, DMSO-d6) ⁇ 7.49 (bs, 4H, major isomer), 7.47 (bs, 2H, minor isomer), 7.10 (m, 4H), 6.92-6.86 (m, 4H), 6.79 (m, 4H), 6.64-6.55 (m, 6H), 5.07 (d, 2H, major isomer), 4.92 (d, 2H, minor isomer), 3.51 (m, 4H), 1 .15 (d, 6H, major isomer), 1 .1 1 (d, 6H, minor isomer).
- Example 9 Preparation of a mixture of N,N'-(ethane-1 ,2-diyl)bis(N- phenylbenzene-1 ,4-diamine) Compound 2 and N-1 ,3-dimethylbutyl-N'- phenyl-p-phenylenediamine (6PPD)
- DIBAL-H (101 g, 25 wt.% in toluene) was slowly cannulated into a 1 L round-bottom flask that contained THF (86 mL). Then the di-imine 6 (20.0 g, 42.9 mmol) was carefully added at ambient temperature. After the addition was complete, the mixture was heated to 60 °C and allowed to react for 19 hours (after 3 hours of reaction time, additional DIBAL-H (20.0 g, 25 wt. % in toluene) was added). Then the reaction was cooled using an ice-water bath to ca. 5-10 °C, at which point a saturated solution of NaK tartrate was added drop wise until the reaction mixture formed a gel.
- the solids were then placed in a flask with a stir bar and vigorously stirred with additional water. After filtration, the solids were then vigorously stirred in heptane (200 mL). The solids were filtered and washed with some additional heptane. The light-gray solid was placed in a 45 °C vacuum oven with nitrogen sweep (17.45 g of isolated product). ICP analysis: 397 ppm aluminum. The solids were re-dissolved in EtOAc:THF (1 :1 ). The mixture was passed through a short plug of silica gel. The plug was rinsed with additional EtOAc:THF. The volatiles were then removed under reduced pressure.
- DIBAL-H (98.0 g, 25 wt.% in toluene) was slowly cannulated into a 1 L round-bottom flask that contained THF (106 mL). Then the di-imine 8 (24.7 g, 52.8 mmol) was carefully added at ambient temperature. After the addition was complete, the mixture was heated to 60 °C and allowed to react for 17.5 hours. Then the reaction was cooled using an ice-water bath to ca. 5- 10 °C, at which point a saturated solution of NaK tartrate was added drop wise until the reaction mixture formed a gel. At that point, 650 mL of the NaK tartrate solution was quickly added, followed by 500 mL of EtOAc.
- DIBAL-H 134 g, 25 wt.% in toluene
- THF 81 mL
- the di-imine 10 (20.0 g, 40.4 mmol) was carefully added at ambient temperature.
- the reaction was cooled using an ice-water bath to ca. 5-10 °C, at which point a saturated solution of NaK tartrate was added drop wise until the reaction mixture formed a gel.
- 500 mL of the NaK tartrate solution was quickly added, followed by 500 mL of EtOAc.
- the biphasic mixture was vigorously stirred overnight. The mixture was then transferred to a 1 -L separatory funnel, and the layers were then separated. The organics were washed with a 10% NaOH solution (1 10 mL) and then water (200 mL x 2). The organics were dried with Na2SO4. The mixture was then filtered. The solids were suspended in heptane (ca. 250 mL) and vigorously stirred. The solids were collected by filtration and then dried in a 50 ° C vacuum oven with nitrogen sweep. The product was isolated as a tan powder (17.8 g, 88% yield). ICP analysis : 1 1 ppm aluminum.
- Example 17 Preparation of Precursor (N,N',N,N')-N,N'-(1 ,3- phenylenebis(ethan-1 -yl-1 -ylidene))bis(N-phenylbenzene-1 ,4-diamine)
- Example 18 N,N'-(1 ,3-phenylenebis(ethane-1 ,1-diyl))bis(N- phenylbenzene-1 ,4-diamine)
- DIBAL-H 99.0 g, 25 wt.% in toluene
- THF 99.0 mL
- the di-imine 12 (24.5 g, 49.4 mmol) was carefully added at ambient temperature.
- the mixture was heated to 60 °C and allowed to react for 17.5 hours.
- the reaction was cooled using an ice-water bath to ca. 5-10 °C, at which point a saturated solution of NaK tartrate was added drop wise until the reaction mixture formed a gel.
- Example 19 N-methylated mixture of N-phenyl-N-(1-(4-(1-((4- (phenylamino)phenyl)amino)ethyl)phenyl)ethyl)benzene-1 ,4-diamine
- Compound 1 1 are also effective antidegradants within the scope of the present invention, Compound 11 (51 .2 g, 103 mmol) was placed in a 2-necked 1 L rb flask with overhead stirrer and then dissolved in acetone (0.50 M, 206 mL).
- the compounds of the present invention may also be synthesized by a catalytic reductive alkylation method from a polycarbonyl starting material and involving a heterogeneous transition metal catalyst in the presence of hydrogen. Examples of this method are provided below.
- OIT oxidative induction time
- Oxygen is then introduced to the sample cell and the length of time before the onset of degradation, as seen by the initiation of an endothermic process in the DSC trace, is measured.
- N- (1 ,3-Dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD) and N-(1 ,4- dimethylpentyl)-N'-phenyl-p-phenylenediamine (7PPD) known antidegradant additives for rubber that are commercially available from Eastman Chemical Company under the trademark Santoflex ® , were also tested as controls for OIT. The results are listed in the following table:
- Oxidative Induction Time measured at 150°C
- the compounds of the present invention demonstrate surprisingly excellent antioxidant performance that compares well to 6PPD and 7PPD and indicates utility in fuels, lubes, tires and other applications that can benefit from a highly active antioxidant compound).
- liquid nitrile rubber 1312LV, Zeon Chemicals L.P., Louisville, KY
- THF THF
- the antidegradants formed in examples 2 and 1 1 were each added to separate amounts of liquid nitrile rubber solution such that the samples each contained 1 weight % concentrations of antidegradant based on the weight of nitrile rubber.
- 600 microliters of each antidegradant-containing composition was placed on a ZnSe horizontal attenuated total reflectance crystal trough plate (HATR) and dried under a stream of nitrogen to create a thin film of each composition for testing.
- HATR ZnSe horizontal attenuated total reflectance crystal trough plate
- a control sample using commercially available 6PPD antidegradant was also formed by (i) creating a composition containing 6PPD antidegradant in the liquid nitrile rubber 10% solution with 6PPD in an amount of 1 % by weight based on the weight of nitrile rubber and (ii) forming a thin film of the control composition as described above.
- Each thin film sample was then subjected to ozonolysis in a polystyrene chamber kept thermally equilibrated at 40 °C in a Shel Lab Model CE5F oven (Shel Lab, Cornelius, OR.) with ozone generated using a A2Z Ozone Inc. (Louisville, KY) model MP-1000 ozone generator.
- the ozonolysis reaction was allowed to proceed for 100 minutes under an ozone concentration of approximately 5 ppm.
- the infrared spectra were recorded using a Perkin- Elmer Spectrum-2 spectrophotometer.
- the extent of ozonolysis reaction relative to 6PPD was determined as the ratio of the 1725 cnr 1 /2237 cm -1 absorbance ratio for the test materials divided by the ratio of the 1725 cnr 1 /2237 cm 1 absorbance for 6PPD.
- Table 2 The extent of ozonolysis reaction relative to 6PPD was determined as the ratio of the 1725 cnr 1 /2237 cm -1 absorbance ratio for the test materials divided by the ratio of the 1725 cnr 1 /2237 cm 1 absorbance for 6PPD.
- the antidegradants of the present invention reduced the relative extent of ozonolysis after 100 minutes by about 60% as compared to 6PPD.
- the compounds of the present invention therefore are shown to demonstrate surprisingly excellent antiozonant performance that is superior to currently commercial antidegradants and indicates utility in applications that can benefit from a highly active antiozonant compound.
- antidegradant masterbatches of the compositions set forth in Table 3 below were prepared, with two items including compounds of the present invention as antidegradant (specifically the compounds of examples 2 and 1 1 above) one control item including conventional 6PPD antidegradant; and a second control including 4,4',4"-tris(1 ,3-dimethylbutylamino)triphenylamine (compound IV-a described in U.S. Patent No. 8,833,417) as antidegradant.
- Masterbatches were prepared using a Kobelco Inc. 1 .6L banbury style mixer equipped with 4-wing H style rotors set to a rotor speed of 25 rpm.
- a DeltaTherm Delta T system Model AB431 S temperature controller was used to control the mixer temperature to 80 °C. Material weights in the proportions given in Table 3 were determined to fill 74% of the mixing chamber volume. Carbon black, ZnO, stearic acid, antidegradant and 1 /3 of the rubber were added to the mixer and the ram was set to close the mixer, the start the mix time was taken when the ram was in the closed position. After 30 seconds of mixing, the ram was raised and 1 /3 of the rubber was added, again the ram was set to close. After an additional 30 seconds of mixing after the ram closed, the final 1 /3 of the rubber was added and the ram closed. The rotor speed was adjusted to 65 rpm and the ingredients were mixed until the mixer thermocouple sensor registered 170 °C. The total time required for these steps was approximately 5 minutes. The temperature of the composition measured immediately after discharge was ⁇ 170 °C.
- a conventional vulcanizing agent polymeric sulfur
- a conventional vulcanization accelerator N,N'-Dicyclohexyl-2-benzothiazole sulfonamide (DCBS)
- DCBS N,N'-Dicyclohexyl-2-benzothiazole sulfonamide
- vulcanized elastomeric article samples for testing, the vulcanizable elastomeric formulations were then sheeted on a two roll mill to a thickness of 2 to 3 millimeters.
- sheets were cut, pressed and vulcanized in a mold for 60 minutes at 140 °C to form 6 test samples from each formulation.
- the vulcanized items were then aged for 25 days at 77 °C and 40% relative humidity. Subsequent to aging, the samples were tested at 100% strain in conformance to ASTM D4482-1 1 .
- the relative aged fatigue performance is reported in Table 5 below as the ratio of average of six samples of the present invention to the average of 6 control samples of 6-PPD containing material.
- the articles formed from vulcanizable elastomeric formulations of the present invention demonstrate surprisingly excellent resistance to fatigue and crack propagation that is markedly better than the articles formed using conventional 6PPD antidegradant.
- the compounds of the present invention accordingly impart highly desirable levels of anti-fatigue resistance and are therefore efficacious anti-fatigue agents.
- the present invention is directed to a composition that includes at least one compound of the present invention as described above.
- the specific amount of the compound of the present invention that is included in the composition may vary widely depending on the intended use application for the composition. It will be understood by one of ordinary skill the art that the composition of the present invention can include one or more compounds of the present invention such that the concentration of each individual compound necessary to achieve the desired antidegradant efficacy is lower. Further, other known antidegradant additives may be included in the composition such that a reduced amount of the compound of the present invention may be required to achieve the total desired antidegradant efficacy.
- the composition of a present invention is a vulcanizable elastomeric formulation.
- the vulcanizable elastomeric formulation of the present invention includes at least one elastomer and the compound of the present invention.
- the compound of the present invention is present in the vulcanizable elastomeric formulation in an amount of from 0.1 to 20.0 parts, preferably from 0.1 to 5.0 parts, per 100 parts elastomer.
- the elastomer in the vulcanizable elastomeric formulation may be any vulcanizable unsaturated hydrocarbon elastomer known to one skilled in the art.
- These elastomers may include without limitaton natural rubber or any synthetic rubber, for example diene containing elastomers such as polymers formed from butadiene; isoprene; or combinations of styrene and butadiene, or styrene and isoprene, or styrene, butadiene and isoprene; or polymers formed from ethylene, propylene and diene monomers such as ethylidene norbonadiene or 1 ,5-hexadiene.
- the vulcanizable elastomeric formulation may optionally also include other additives conventionally used in rubber processing, such as processing/flow aids, extenders, plasticizers, resins, adhesion promoters, bonding agents, buffers, fillers, pigments, activators, prevulcanization inhibitors, acid retarders, accelerators, fatty acids, zinc oxide, or other compounding ingredients or additives to further enhance the characteristics and/or improve the performance of the vulcanizable elastomeric formulation or the vulcanized elastomeric article from which it is formed
- Suitable accelerators may include, but not be limited to guanidines, thiazoles, sulfenamides, sulfenimides, dithiocarbamates, xanthates, thiurams, and combinations or mixtures thereof.
- the vulcanizable elastomeric formulation of the present invention is useful in the manufacture of vulcanized elastomeric articles such as rubber belts and hoses, windshield wiper blades, vehicle tires and components thereof such as the tread, shoulder, sidewall and innerliner. Accordingly, in another aspect, the present invention is directed to a vulcanized elastomeric article with at least one component formed from the vulcanizable elastomeric formulation of the present invention. In one particular embodiment, the vulcanized elastomeric article is a vehicle tire and the tire component is a sidewall.
- the present invention in a general aspect is directed to a composition including the compound of the present invention.
- the composition is an antidegradant composition with utility and efficacy for inhibition of degradation of a composition, formulation or article to which it is added or applied.
- the antidegradant composition of the present invention therefore includes the compound of the present invention and optionally a carrier for the compound.
- Suitable carriers are substantially inert with respect to the compound and include waxes, oils, or solids such as carbon black or silica.
- the composition of the present invention has a separate primary utility or functionality (such as a coating, lubricant, oil, fuel additive or fuel composition) and includes a functional ingredient and the compound of the present invention as a component.
- the functional ingredient is typically a degradable material such as a hydrocarbon but may also include other degradable materials.
- This embodiment therefore encompasses for example, a lubricant composition that includes a lubricant as the functional ingredient and the compound of the present invention.
- This embodiment further encompasses a combustible fuel composition that includes a combustible fuel as the functional ingredient and the compound of the present invention.
- This embodiment further encompasses a fuel additive composition that includes a fuel additive as the functional ingredient and the compound of the present invention.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
- Lubricants (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US15/618,281 US10260017B2 (en) | 2015-12-22 | 2017-06-09 | Compounds and mixtures with antidegradant and antifatigue efficacy and compositions including said compounds |
PCT/US2018/033101 WO2018226373A1 (en) | 2017-06-09 | 2018-05-17 | Compounds and mixtures with antidegradant and antifatigue efficacy and compositions including said compounds |
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EP3634941A1 true EP3634941A1 (en) | 2020-04-15 |
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EP18733019.6A Pending EP3634941A1 (en) | 2017-06-09 | 2018-05-17 | Compounds and mixtures with antidegradant and antifatigue efficacy and compositions including said compounds |
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EP (1) | EP3634941A1 (en) |
JP (1) | JP2020523333A (en) |
KR (1) | KR20200017463A (en) |
CN (1) | CN110691769B (en) |
WO (1) | WO2018226373A1 (en) |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2905654A (en) | 1955-12-16 | 1959-09-22 | Firestone Tire & Rubber Co | N-phenyl-p-phenylenediamine as antiozonant for butadiene-styrene rubbery copolymer |
GB835826A (en) * | 1957-11-19 | 1960-05-25 | Firestone Tire & Rubber Co | Improvements relating to reaction products of hydrocarbon dihalides and substituted phenylenediamines and their use in rubber |
CA2598703A1 (en) | 2005-02-22 | 2006-08-31 | Polnox Corporation | Nitrogen and hindered phenol containing dual functional macromolecular antioxidants: synthesis , performances and applications |
FR2931158B1 (en) | 2008-05-15 | 2010-07-30 | Michelin Soc Tech | RUBBER COMPOSITION FOR PNEUMATIC INCORPORATING A NEW ANTI-OXIDANT SYSTEM |
US8987515B2 (en) | 2011-12-13 | 2015-03-24 | Chemtura Corporation | Cross products and co-oligomers of phenylenediamines and aromatic amines as antioxidants for lubricants |
US10294423B2 (en) * | 2013-11-22 | 2019-05-21 | Polnox Corporation | Macromolecular antioxidants based on dual type moiety per molecule: structures, methods of making and using the same |
JP6265832B2 (en) * | 2014-05-22 | 2018-01-24 | 株式会社ブリヂストン | Rubber composition, tire, amine compound and anti-aging agent |
JP6377954B2 (en) * | 2014-05-22 | 2018-08-22 | 株式会社ブリヂストン | Rubber composition, tire, bisphenyldiamine compound and anti-aging agent |
EP2952505B1 (en) * | 2014-06-05 | 2018-05-23 | China Petroleum & Chemical Corporation | A hindered phenol compound, preparation thereof and use thereof as an antioxidant |
US10287418B2 (en) * | 2015-12-22 | 2019-05-14 | Eastman Chemical Company | Compounds with antidegradant and antifatigue efficacy and compositions including said compounds |
-
2018
- 2018-05-17 KR KR1020207000515A patent/KR20200017463A/en not_active Application Discontinuation
- 2018-05-17 EP EP18733019.6A patent/EP3634941A1/en active Pending
- 2018-05-17 JP JP2019568098A patent/JP2020523333A/en active Pending
- 2018-05-17 WO PCT/US2018/033101 patent/WO2018226373A1/en active Application Filing
- 2018-05-17 CN CN201880038142.3A patent/CN110691769B/en active Active
Also Published As
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JP2020523333A (en) | 2020-08-06 |
KR20200017463A (en) | 2020-02-18 |
WO2018226373A8 (en) | 2019-01-03 |
WO2018226373A1 (en) | 2018-12-13 |
CN110691769B (en) | 2023-03-10 |
CN110691769A (en) | 2020-01-14 |
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