USRE25260E - Stabilizing diene rubbers with the reac- - Google Patents
Stabilizing diene rubbers with the reac- Download PDFInfo
- Publication number
- USRE25260E USRE25260E US25260DE USRE25260E US RE25260 E USRE25260 E US RE25260E US 25260D E US25260D E US 25260DE US RE25260 E USRE25260 E US RE25260E
- Authority
- US
- United States
- Prior art keywords
- para
- meta
- ortho
- grams
- phenethyl
- Prior art date
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- Expired
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- 229920001971 elastomer Polymers 0.000 title description 26
- 239000005060 rubber Substances 0.000 title description 22
- 150000001993 dienes Chemical class 0.000 title description 7
- 230000000087 stabilizing Effects 0.000 title description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 58
- -1 methyl phenethyl Chemical group 0.000 description 39
- 239000000203 mixture Substances 0.000 description 31
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- CBCKQZAAMUWICA-UHFFFAOYSA-N P-Phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000004587 chromatography analysis Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000005336 cracking Methods 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 7
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 7
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229940035422 Diphenylamine Drugs 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 5
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N 4-Aminobiphenyl Chemical group C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 4
- SRTHRWZAMDZJOS-UHFFFAOYSA-N Lithium hydride Chemical compound [H-].[Li+] SRTHRWZAMDZJOS-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 230000003078 antioxidant Effects 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atoms Chemical group C* 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 4
- 229920000126 Latex Polymers 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 229920001195 polyisoprene Polymers 0.000 description 3
- BZKBCQXYZZXSCO-UHFFFAOYSA-N sodium hydride Chemical compound [H-].[Na+] BZKBCQXYZZXSCO-UHFFFAOYSA-N 0.000 description 3
- 240000002027 Ficus elastica Species 0.000 description 2
- 240000008528 Hevea brasiliensis Species 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 150000004986 phenylenediamines Chemical class 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000003068 static Effects 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-Tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 description 2
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 1-ethenyl-4-methylbenzene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-Chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 description 1
- FZHNODDFDJBMAS-UHFFFAOYSA-N 2-ethoxyethenylbenzene Chemical compound CCOC=CC1=CC=CC=C1 FZHNODDFDJBMAS-UHFFFAOYSA-N 0.000 description 1
- VHOQXEIFYTTXJU-UHFFFAOYSA-N 2-methylbuta-1,3-diene;2-methylprop-1-ene Chemical compound CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 1
- LBKFFSWAYMTCLQ-UHFFFAOYSA-N 4-N-phenyl-1-N-(2-phenylethyl)benzene-1,4-diamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NCCC1=CC=CC=C1 LBKFFSWAYMTCLQ-UHFFFAOYSA-N 0.000 description 1
- 235000019687 Lamb Nutrition 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N Lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N Sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 210000000538 Tail Anatomy 0.000 description 1
- YMOONIIMQBGTDU-SREVYHEPSA-N [(Z)-2-bromoethenyl]benzene Chemical compound Br\C=C/C1=CC=CC=C1 YMOONIIMQBGTDU-SREVYHEPSA-N 0.000 description 1
- UHRMSMOCULMYMJ-VURMDHGXSA-N [4-[(Z)-2-nitroprop-1-enyl]phenyl] thiocyanate Chemical compound [O-][N+](=O)C(/C)=C\C1=CC=C(SC#N)C=C1 UHRMSMOCULMYMJ-VURMDHGXSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000111 anti-oxidant Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 230000003197 catalytic Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000008079 hexane Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000000630 rising Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000008096 xylene Substances 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
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
Definitions
- This invention relates to the preservation of xidiza'ble compositions such as rubbers and petroleum products and, more particularly, to the provision and use of a new class of N-aralkyl N-phenyl phenylene diamines which are useful as age resistors for the various oxidiz able rubbers and petroleum products.
- Unsaturated materials such as rubbers and gasoline are subject to deterioration from many sources, such as sunlight, ozone, atmospheric oxygen, the presence of heavy metals, etc. Both cured and uncured natural and synthetic elastomers are subject to such deterioration. Deterioration in cured stocks of rubber may vary with the type of stock, the state of cure and the amount of surface exposed. Also, the temperature of the oxidizable compositions is an important factor in deterioration. An ideal antioxidant or antiozonant would be one which would protect the oxidizable compound from deterioration regardless of time, physical state of the oxidizable compound, and regardless of use. Since no such general antioxidant or antiozonant has been discovered, compromises must be made in the selection of an age resistor for a particular use.
- N-aralkyl N'-phenyl phenylene diamines In the practice of the invention, oxidizabl compositions are protected from deterioration by means of N- aralkyl N'-phenyl phenylene diamines.
- the N-aralkyl N'-phenyl phenylene diamines of this invention can be further described as N-aralkyl N'-phenyl phenylene diamines conforming to the following structure:
- R is an aralkyl radical
- R' is a radical selected from hydrogen, alkyl radicals, alkoxy radicals, and halogen radicals
- R" is a radical selected from hydrogen, alkyl radicals, alk-oxy radicals, and halogen radicals.
- the alkyl radicals may be primary, secondary, or tertiary and may contain from 1 to 9 carbon atoms.
- the alkoxy radicals may also contain from 1 to 9 carbon atoms in addition to the oxygen.
- the halogen radicals may be any of the halogens such as fluorine, chlorine and bromine.
- the aralkyl radicals may be derived from unsaturated 'aralkyl compositions such as styrene, substituted styrenes, e.g. styrenes substituted in the ring with alkyl radicals having from 1 to 9 carbon atoms, alkoxy radicals having from '1 to 9 carbon atoms, halogens, nitro groups; vinyl toluene; etc.
- unsaturated 'aralkyl compositions such as styrene, substituted styrenes, e.g. styrenes substituted in the ring with alkyl radicals having from 1 to 9 carbon atoms, alkoxy radicals having from '1 to 9 carbon atoms, halogens, nitro groups; vinyl toluene; etc.
- N-aralkyl N'-phenyl phenylene diamines which are useful in the practice of this invention are:
- N-phenethyl-N'-phenyl-para-phenylene-diamine N-(ortho, meta or para methyl phenethyl)-N'-phenylpara-phenylene diamine N-(ortho, meta or para ethyl phenethyl)-N'-phenyl-paraphenylene diamine N-(ortho, meta or para methoxy phenethyl)-N'-phenylpara-phenylene diamine N-(ortho, meta or para ethoxy phenethyl)-N-phenylpara-phenylene diamine N-(ortho, meta or para chloro phenethyl)-N'phenylpara-phenylene diamine N-(ortho, meta or para bromo phenethyl)-N-phenylpara-phenylene diamine N-(ortho, meta or para cyclohexyl phenethyl)-N-phen
- meta or para ethyl phenyl)-pana-phenylene diamine N-(ortho, meta or para methoxy phenet'hyl)-N'-(ortho, meta or para ethyl phenyD-para-phenylene diamine N-(ortho, meta or para ethoxy phenethyl)-N-(ortho, meta or para ethyl phenyl)-para-phenylene diamine N-(ortho, meta or para chloro phenethyl)-N'-(ortho, meta or para ethyl phenyD-para-phenylene diamine N-(ortho, meta or para bromo phenethyl)-N-(ortho, meta or para ethyl henyD-para-pheuylene diamine N-(ortho, meta or para cyclohexyl phenethyl)-N'-(ortho,
- N-aralkyl N-phenyl phenylene diamines of this invention may be made by reacting a phenylene diarnme with an aralkyl composition.
- a phenylene diamine composition Illustrative of the phenylene diamines which may be used to provide the compositions of this invention are:
- para-phenylene diamines have been used to illustrate the invention but the ortho or meta isomers may also be used.
- aralkyl compositions which may be used are: styrene; ortho, meta or para methyl styrene; ortho, meta or para ethyl styrene; ortho, meta or para methoxy styrene; ortho, meta or para ethoxy styrene; ortho, meta or para chloro styrene; ortho, meta or para bromo styrene; ortho, meta or para nitro styrene; etc.
- the aralkyl compositions and phenylene diamines are customarily reacted in the presence of a catalyst.
- the alkali metals such as sodium, potassium, lithium, etc., may be used, sodium being preferred.
- the hydrides and amides of the alkali metals may also be used to catalyze the reaction.
- the catalyst may be present in a catalytic amount ranging from a trace, e.g., 0.01% by weight, to about 5.0% by weight, based on the weight of the reactants. Tests have indicated that about 0.05 to about 0.25% by weight of catalyst is preferred.
- the temperature of reaction is not critical, it is preferred to complete the reactions of this invention within a temperature range of about 125 C. to 250 C. For best results, a temperature ranging from about 170 C. to 200 C. is preferred.
- EXAMPLE 1 Three hundred eighty-six grams of para-amino diphenyl amine were charged to a one liter flask equipped with stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet. The flask was flushed with nitrogen and a slow stream was passed in during the reaction. Heating was begun and 4 grams of freshly cut sodium were added. At 175 C., 230 grams of styrene were added dropwise during a period of 2% hours while the temperature rose to 198 C. The reaction mixture was heated an additional 2% hours at 190-200 C. It was allowed to cool and 300 milliliters of benzene followed by milliliters of water were added.
- EXAMPLE 2 One hundred eighty-four grains of para-amino d-iphenyl amine were heated to C. under a slow stream of dry nitrogen which was maintained during the reaction. Four grams of a 50% sodium dispersion in xylene were added and at C. 115 grams of styrene were started in dropwise. It was added over a three-hour period with the temperature rising to C. and then dropping back to 158 C. The mixture was heated for 20 hours after the addition of the styrene during which time the temperature gradually rose to C. The mixture was allowed to cool after which 200 milliliters of benzene followed by 5 milliliters of water were added.
- the mixture was refluxed one hour, a water trap inserted and refluxing continued until no further water was collected.
- the mixture was filtered and stripped to 205 C. pot temperature at 19 millimeters pressure.
- a 30 gram sample was removed and analyzed by chromatography, giving a 54.4% yield of the N-phenethyl-N'-phenyl-para-phenylene diamine.
- the remainder was distilled and 137 grams of product obtained having a boiling point of 205210 C. at 0.2 millimeter pressure and a melting point of 58-64 C. This corresponds to a 53.5% yield.
- EXAMPLE 3 One hundred eighty-four grams of para-amino diphenyl amine were melted down in a 1 liter fiask under a slow stream of dry nitrogen which was maintained during the reaction. Two grams of sodium were added and at 100 C. 115 grams of styrene were added dropwise during a period of 25 minutes during which the temperature rose to 163 C. The temperature rose to C. in three hours and was maintained at 190 C.i2 for an additional four hours. The mixture was cooled, and 200 milliliters of benzene followed by 5 milliliters of water were added. The mixture was refluxed for one hour. The mixture contained 483 grams of solution from which a 5 gram sample was removed.
- EXAMPLE 4 One hundred eighty-four grams of para-amino diphenylamine were heated to 180 C. under a slow stream of dry nitrogen which was maintained during the remainder of the reaction. Styrene was added until reflux was maintained at that temperature. Then 0.5 gram of freshly cut sodium was added and styrene addition continued to maintain the reaction at 180 Q12 for seven hours. This required 186 grams of styrene. The mixture was cooled and 200 milliliters of benzene were added followed by 2 milliliters of water. This mixture was refluxed for one hour. There were 562 grams of solution. Chromatographic analysis showed a 72.8% yield of N-[alpha-Ilphenethyl N-phenyl-para-phenylene diamine.
- EXAMPLE 5 One hundred eighty-four grams of par'a-amino-diphenylamine were melted down in a 1 liter flask under a slow stream of dry nitrogen which was maintained during the reaction. At 100 C., 0.1 gram of lithium hydride was added, and styrene started in dropwise. In 15 minutes, the temperature was at 180 C. and styrene addition was adjusted to give reflux at this temperature. One hour after initial addition of lithium hydride, 0.1 gram more was added. The mixture was then kept at 180 C. *-2 for six hours by styrene addition. This required 135 grams of styrene. After cooling, 200 milliliters of benz'ene were added, followed by 100 milliliters of water. The mixture was then refluxed for one hour, resulting in 467 grams of solution. Chromatographic analysis of this solution showed the yield to be 12.5%
- EXAMPLE 7 One hundred eight-four grams of para-amino-diphenylamine were melted in a 1 liter flask under a stream of dry nitrogen which was maintained during the reaction. At 80 C., 2 grams of potassium were added and at 100 C. 135 grams of styrene were added during a period of five minutes. The temperature rose to 159 C. in 25 minutes when refluxing began. In two hours it was at 190 C. and was kept at 190 C.:2 for an additional seven hours. The mixture was cooled to 80 C. after which 200 milliliters of benzene were added followed by 5 milliliters of water. The mixture was refluxed for one hour. This gave 499 grams of solution. Chromatographic analysis of the solution showed the yield to be 59.2%.
- EXAMPLE 8 One hundred eighty-four grams of para-amino-diphenylamine were heated to 180 C. in a 1 liter flask under a slow stream of dry nitrogen which was maintained during the reaction. Enough styrene was added to cause reflux at that temperature. 1 gram of sodium amide was added and heating continued for 6.5 hours. Styrene was added to maintain reflux at 180 C.i2 C., requiring a total of 116 grams during the reaction. After cooling, 200 milliliters of benzene and 5 milliters of Water were add-ed. The mixture was refluxed for one hour. This gave 492 grams of solution. Chromatographic analysis of the solution gave an 11.1% content of N-phenethyl-N'- phenyl-para-phenylene diamine. This was an 18.9% yield.
- EXAMPLE 9 One hundred eighty-four grams of para-amino-diphenylamine were melted in a 1 liter flask under a slow stream of dry nitrogen which was maintained during the reaction. At 90 C, 1 gram of sodium hydride, suspended in mineral oil, was added and the styrene started in dropwise. 'In 20 minutes the temperature was 180 C. and was kept there :3 for six hours by styrene addition. One hundred eighty-six grams of styrene were required. After cooling, 200 milliliters of benzene were added followed by 10 milliliters of water and the solution refluxed for one hour. This gave 578 grams of solution. From chromatographic analysis of the solution, the yield was 719% of N-phenethyl N-phenyl-para-phenylene diamine.
- EXAMPLE 10 One hundred eighty-four grams of para-amino-diphenylamine were heated to 110 C. in a 1 liter flask and 3 grams of sodium were added. At 140 C., 130 grams of vinyl toluene were added dropwise in 2 /2 hours with temperature at about 170-185" C. The mixture was heated an additional half hour after which milliliters of alcohol were added during cooling. This was followed by 250 milliliters of benzene. The solution was filtered warm and distilled. Ninety-six grams of N-methyl-phenethyl-N-phenyl para-phenylene diamine were obtained having a boiling point of 225-230 C., and a melting point of 5760 C. This was a 31.8% yield.
- EXAMPLE 11 One hundred eighty-four grams of para-amino-diphenylamine were heated to C. and six grams of sodium.
- EXAMPLE 12 One hundred eighty-four grams of para-amino-diphenylamine were heated to 90 C. after which 2 grams of sodium were added. At 130 C., 20 milliliters of styrene were added followed by dropwise addition during the following hour at l85 C. A total of 108 grams of styrene were added. The mixture was heated an additional hour at l75-l85 C. After cooling, 50 milliliters of alcohol were added. The mixture was then stripped up to C. pot temperature at 25 millimeters pressure. Two hundred forty-five grams remained. Chromatographic analysis showed this to be 54.7% yield of N- phenethyl-N'-phenyl-p-phenylene diamine. This corresponds to a yield of 46.5%.
- test compounds were cured for 80 minutes at 275 F. and tested as follows:
- test strips By exposing test strips at 15% elongation to approximate 100 p.p.m. of ozone for ten minutes (rapid ozone test).
- Moderate to severe cracking Moderate cracking Slight Cracking Severe Cracking. Motigrate cracking.
- the compounds were tested in inhibited catalytically cracked gasoline using the oxygen bomb induction period method (ASTM Standard Test D525). The following results were obtained using 0.025 gram of the'compounds per liter of gasoline.
- Antiozonant Induction period, minutes None 739 R.P. vinyl toluene and para-amino diphenylamine 1,206 N methylphenethyl-N'-phenyl-para-phenylene diamine 1,150 R.P. styrene and para-amino diphenyl amine 1,224 N-phenethyl N phenyl-para-phenylene diamine- 1,223
- the rubbers which can be protected by the products of this invention are the oxidizable rubbery polymers of conjugated dienes which include natural rubber and the various synthetic diene rubbers which are similar to natural rubber in their aging characteristics, such as polychloroprene; butyl rubber, which is a polymerization product of a major proportion of a mono olefin, such as isobutylene, and a minor proportion of a multi olefin, such as butadiene or isoprene; the rubbery copolymers of butadiene and styrene which may contain from 50 to 75% by weight of butadiene; the rubbery copolymers of butadiene and acrylonitrile and polyisoprene.
- conjugated dienes which include natural rubber and the various synthetic diene rubbers which are similar to natural rubber in their aging characteristics, such as polychloroprene
- butyl rubber which is a polymerization product of a major proportion of a mono o
- the products of the invention are useful as age resistors for raw rubbers in latex form, coagulated rubber latices or vulcanized rubbers, and may be present in an amount of from 0.25 to 8.0% by weight, based on the weight of the rubber, although it is generally preferred to use from 0.5 to 4.0% by Weight, based on the Weight of rubber.
- the antioxidants of this invention can be incorporated into rubber in any customary manner. They may be added in the form of physical mixtures or in the form of emulsions using any of the known emulsifiers such as monovalent metal hydroxides, fatty acids, organic They may be added to the rubber in the form of latex, or they may be milled into coagu lated rubber in the usual manner.
- hydrocarbons which can beprotccted by the products of this invention can be described as catalytica'lly cracked, thermally cracked gasoline or blends thereof.
- Higher boiling fractions such as kerosene, fuel oil, and diesel oils are also included within the scope of this invention.
- the compounds of this invention can be used to stabilize the highly refined hydrocarbons by adding about 001% to 0.1% by weight of 'the'antioxidant to the highly refined hydrocarbons.
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Description
United States Patent Ofi ice Re. 25,260 Reissued Oct. 16, 1962 STABILIZING DIENE RUBBERS WITH THE REAC- TION PRODUCT OF P-AMINO DIPHENYLEN- AMINE AND STYRENE Farris H. Wilson, Jr., Cuyahoga Falls, Ohio, assignorto The Goodyear Tire & Rubber Company, Akron, Ohio, a corporation of Ohio N Drawing. Original No. 2,984,646, dated May 16, 1961, Ser. No. 725,487, Apr. 1, 1958. Application for reissue Jan. 10, 1962, Ser. No. 166,001
2 Claims. (Cl. 260-45.9)
Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.
This invention relates to the preservation of xidiza'ble compositions such as rubbers and petroleum products and, more particularly, to the provision and use of a new class of N-aralkyl N-phenyl phenylene diamines which are useful as age resistors for the various oxidiz able rubbers and petroleum products.
Unsaturated materials such as rubbers and gasoline are subject to deterioration from many sources, such as sunlight, ozone, atmospheric oxygen, the presence of heavy metals, etc. Both cured and uncured natural and synthetic elastomers are subject to such deterioration. Deterioration in cured stocks of rubber may vary with the type of stock, the state of cure and the amount of surface exposed. Also, the temperature of the oxidizable compositions is an important factor in deterioration. An ideal antioxidant or antiozonant would be one which would protect the oxidizable compound from deterioration regardless of time, physical state of the oxidizable compound, and regardless of use. Since no such general antioxidant or antiozonant has been discovered, compromises must be made in the selection of an age resistor for a particular use.
It is an object of the present invention to provide antioxidant and antiozonant compositions which are capable of protecting various oxidizable rubbers and petroleum products for extended periods of time. It is another object of this invention to provide N-aralkyl N-phenyl phenylene diamines which are capable of protecting various oxidizable rubbers and petroleum products from deterioration from oxygen, ozone, and/or sunlight.
In the practice of the invention, oxidizabl compositions are protected from deterioration by means of N- aralkyl N'-phenyl phenylene diamines. The N-aralkyl N'-phenyl phenylene diamines of this invention can be further described as N-aralkyl N'-phenyl phenylene diamines conforming to the following structure:
wherein R is an aralkyl radical, R' is a radical selected from hydrogen, alkyl radicals, alkoxy radicals, and halogen radicals and wherein R" is a radical selected from hydrogen, alkyl radicals, alk-oxy radicals, and halogen radicals. The alkyl radicals may be primary, secondary, or tertiary and may contain from 1 to 9 carbon atoms. The alkoxy radicals may also contain from 1 to 9 carbon atoms in addition to the oxygen. The halogen radicals may be any of the halogens such as fluorine, chlorine and bromine. The aralkyl radicals may be derived from unsaturated 'aralkyl compositions such as styrene, substituted styrenes, e.g. styrenes substituted in the ring with alkyl radicals having from 1 to 9 carbon atoms, alkoxy radicals having from '1 to 9 carbon atoms, halogens, nitro groups; vinyl toluene; etc.
Representative N-aralkyl N'-phenyl phenylene diamines Which are useful in the practice of this invention are:
N-phenethyl-N'-phenyl-para-phenylene-diamine N-(ortho, meta or para methyl phenethyl)-N'-phenylpara-phenylene diamine N-(ortho, meta or para ethyl phenethyl)-N'-phenyl-paraphenylene diamine N-(ortho, meta or para methoxy phenethyl)-N'-phenylpara-phenylene diamine N-(ortho, meta or para ethoxy phenethyl)-N-phenylpara-phenylene diamine N-(ortho, meta or para chloro phenethyl)-N'phenylpara-phenylene diamine N-(ortho, meta or para bromo phenethyl)-N-phenylpara-phenylene diamine N-(ortho, meta or para cyclohexyl phenethyl)-N-phenylpara-phenylene diamine N-(ortho, meta or para methyl phenethyl)-N'-(ortho,
meta or para tolyl) para-phenylene diamine N-(ortho, meta or para ethyl phenethyl)-N'-(ortho,
meta or para tolyl) para-phenylene diamine N (ortho, meta or para methoxy phenethyl)-'N'-(ortho,
meta or para tolyl) para-phenylene diamine N-(ortho, meta or para ethoxy phenethyl)-N-(ortho,
meta or para tolyl) para-phenylene diamine N-(ortho, meta or para chloro pbenethyl)-N'-(ortho,
meta or para tolyl) para-phenylene diamine N (,ortho, meta or para bromo phenethyl)-N-(ortho,
meta or para tolyl) para-phenylene diamine N-(phenethyl)-N'-(orth0, meta or para tolyl) para-phenylene-diamine N-phenethyl-N'dortho, meta or para ethyl phenyl)-paraphenylene diamine N-(ortho, meta or para methyl phenethyl)-N'-(ortho,
meta or para ethyl phenyl)-pana-phenylene diamine N-(ortho, meta or para methoxy phenet'hyl)-N'-(ortho, meta or para ethyl phenyD-para-phenylene diamine N-(ortho, meta or para ethoxy phenethyl)-N-(ortho, meta or para ethyl phenyl)-para-phenylene diamine N-(ortho, meta or para chloro phenethyl)-N'-(ortho, meta or para ethyl phenyD-para-phenylene diamine N-(ortho, meta or para bromo phenethyl)-N-(ortho, meta or para ethyl henyD-para-pheuylene diamine N-(ortho, meta or para cyclohexyl phenethyl)-N'-(ortho, meta or para ethyl phenyl)-para-phenylene diamine N-(ortho, meta or para methyl phenethyl)-N'-(ortho, meta or para methoxy phenyD-para-phenylene diamine N-(ortho, meta or para ethyl phenethyl)-N'-(ortho, meta or para methoxy phenyl)-para-phenylene diamine N-(ortho, meta or para methoxy phenethyl)-N'-(ortho, meta or para methoxy phenyl)para-pheny1ene diamine N-(ortho, meta or para-ethoxy phenethyl)-N'-(ortho, meta or para methoxy phenyl) para-phenylene diamine N-(ortho, meta or para chloro phenethyl)-N'-(ortho,
meta or para methoxy phenyl) para-phenylene diamine N-(ortho, meta or para bromo phenethyl)-N-(ortho, meta or para methoxy phenyl) para-phenylene diamine N-(ortho, meta or para cyclohexyl phenethyl)-N'-(ortho, meta or para methoxy phenyl) para-phenylene diamine N-phenethyl-N'-phenyl-2 or 3 methyl-para-phenylene diamine N-(ortho, meta or para methylphenethyl-N'-phenyl-2 or 3 methyl-para-p-henylene diamine N-phenethyl N-ortho-meta or para tolyl-Z or 3 methylpara-phenylene diamine N-phenethy1-N'-phenyl-2 or 3 methoxy-para phenylene diamine N-(ortho, meta or para methyl phenethyl)-N-phenyl-2 or 3 methoxy-para-phenylene diamine N-phenethyl-N'-tolyl-2 or 3 methoxy-para-phenylene diamine The para-phenylene diamines have been used to illustrate the invention but the ortho or meta derivatives may also be used.
The N-aralkyl N-phenyl phenylene diamines of this invention may be made by reacting a phenylene diarnme with an aralkyl composition. Illustrative of the phenylene diamines which may be used to provide the compositions of this invention are:
N-phenyl-para-phenylene diamine N-tolyl-para-phenylene diamine N -ethylphenyl-para-phenylene diamine N-chlorophenyl-para-phenylene diamine N-bromophenyl-para-phenylene diamine N-rnethoxyphenyl-para-phenylene diamine N-ethoxyphenyl-para-phenylene diamine N-phenyl-(2 or 3 methyl)-para-phenylene diamine N-tolyl-(2 or 3 methyD-para-phenylene diamine N-phenyl-( 2 or 3 methoxy)-para-phenylene diamine, etc.
The para-phenylene diamines have been used to illustrate the invention but the ortho or meta isomers may also be used.
The aralkyl compositions which may be used are: styrene; ortho, meta or para methyl styrene; ortho, meta or para ethyl styrene; ortho, meta or para methoxy styrene; ortho, meta or para ethoxy styrene; ortho, meta or para chloro styrene; ortho, meta or para bromo styrene; ortho, meta or para nitro styrene; etc.
In the practice of this invention, the aralkyl compositions and phenylene diamines are customarily reacted in the presence of a catalyst. The alkali metals such as sodium, potassium, lithium, etc., may be used, sodium being preferred. In addition, the hydrides and amides of the alkali metals may also be used to catalyze the reaction. The catalyst may be present in a catalytic amount ranging from a trace, e.g., 0.01% by weight, to about 5.0% by weight, based on the weight of the reactants. Tests have indicated that about 0.05 to about 0.25% by weight of catalyst is preferred.
Although the temperature of reaction is not critical, it is preferred to complete the reactions of this invention within a temperature range of about 125 C. to 250 C. For best results, a temperature ranging from about 170 C. to 200 C. is preferred.
The invention may be further illustrated by means of the following examples which are not intended as limitations on the scope of the invention:
EXAMPLE 1 Three hundred eighty-six grams of para-amino diphenyl amine were charged to a one liter flask equipped with stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet. The flask was flushed with nitrogen and a slow stream was passed in during the reaction. Heating was begun and 4 grams of freshly cut sodium were added. At 175 C., 230 grams of styrene were added dropwise during a period of 2% hours while the temperature rose to 198 C. The reaction mixture was heated an additional 2% hours at 190-200 C. It was allowed to cool and 300 milliliters of benzene followed by milliliters of water were added. The mixture was refluxed for one hour and then a water trap was inserted. Refluxing was continued until no further water was collected. The solution was filtered while still warm and then distilled, giving 315 grams of N-phenethyl- '-phenyl-paraphenylene diamine having a boiling point of 215-220 C. at 0.35 millimeter and a melting point of 5763 C. This represents a 54.5% yield. By recrystallization from hexane, a light crystalline solid having a melting point of 68-70 C. was obtained. This recrystallized product was substantially pure N-beta-phenethyl-N'-phenyl-para-phenylene diamine.
EXAMPLE 2 One hundred eighty-four grains of para-amino d-iphenyl amine were heated to C. under a slow stream of dry nitrogen which was maintained during the reaction. Four grams of a 50% sodium dispersion in xylene were added and at C. 115 grams of styrene were started in dropwise. It was added over a three-hour period with the temperature rising to C. and then dropping back to 158 C. The mixture was heated for 20 hours after the addition of the styrene during which time the temperature gradually rose to C. The mixture was allowed to cool after which 200 milliliters of benzene followed by 5 milliliters of water were added. The mixture was refluxed one hour, a water trap inserted and refluxing continued until no further water was collected. The mixture was filtered and stripped to 205 C. pot temperature at 19 millimeters pressure. A 30 gram sample Was removed and analyzed by chromatography, giving a 54.4% yield of the N-phenethyl-N'-phenyl-para-phenylene diamine. The remainder was distilled and 137 grams of product obtained having a boiling point of 205210 C. at 0.2 millimeter pressure and a melting point of 58-64 C. This corresponds to a 53.5% yield.
EXAMPLE 3 One hundred eighty-four grams of para-amino diphenyl amine were melted down in a 1 liter fiask under a slow stream of dry nitrogen which was maintained during the reaction. Two grams of sodium were added and at 100 C. 115 grams of styrene were added dropwise during a period of 25 minutes during which the temperature rose to 163 C. The temperature rose to C. in three hours and was maintained at 190 C.i2 for an additional four hours. The mixture Was cooled, and 200 milliliters of benzene followed by 5 milliliters of water were added. The mixture was refluxed for one hour. The mixture contained 483 grams of solution from which a 5 gram sample was removed. This sample was analyzed by chromatography and gave a 55.2% yield. The remainder of the solution was filtered and stripped of volatiles up to C. pot temperature at 20 millimeters pressure, leaving a residue of 262 grams. This was analyzed by chromatography and gave a 54.8% yield of N-[alphaII-phenethyl N'-phenyl-para-phenylene diamine.
EXAMPLE 4 One hundred eighty-four grams of para-amino diphenylamine were heated to 180 C. under a slow stream of dry nitrogen which was maintained during the remainder of the reaction. Styrene was added until reflux was maintained at that temperature. Then 0.5 gram of freshly cut sodium was added and styrene addition continued to maintain the reaction at 180 Q12 for seven hours. This required 186 grams of styrene. The mixture was cooled and 200 milliliters of benzene were added followed by 2 milliliters of water. This mixture was refluxed for one hour. There were 562 grams of solution. Chromatographic analysis showed a 72.8% yield of N-[alpha-Ilphenethyl N-phenyl-para-phenylene diamine.
EXAMPLE 5 One hundred eighty-four grams of par'a-amino-diphenylamine were melted down in a 1 liter flask under a slow stream of dry nitrogen which was maintained during the reaction. At 100 C., 0.1 gram of lithium hydride was added, and styrene started in dropwise. In 15 minutes, the temperature was at 180 C. and styrene addition was adjusted to give reflux at this temperature. One hour after initial addition of lithium hydride, 0.1 gram more was added. The mixture was then kept at 180 C. *-2 for six hours by styrene addition. This required 135 grams of styrene. After cooling, 200 milliliters of benz'ene were added, followed by 100 milliliters of water. The mixture was then refluxed for one hour, resulting in 467 grams of solution. Chromatographic analysis of this solution showed the yield to be 12.5%
5 EXAMPLE 6 One hundred eight-four grams of para-amino-diphenylamine were melted in a 1 liter flask under a slow stream of dry nitrogen which was maintained during the reaction. At 100 C., 0.5 gram of lithium amide was added and styrene addition begun. In 20 minutes, the temperature was 180 C. and the styrene addition was adjusted to hold at 180 :4 with refluxing for seven hours. This required 93 grams of styrene. After cooling, 200 milliliters of benzene were added, followed by 10 milliliters of water, after which the mixture was then refluxed for one hour. This gave 471 grams of solution. Chromatographic analysis of this solution showed the yield to be 25.5%.
EXAMPLE 7 One hundred eight-four grams of para-amino-diphenylamine were melted in a 1 liter flask under a stream of dry nitrogen which was maintained during the reaction. At 80 C., 2 grams of potassium were added and at 100 C. 135 grams of styrene were added during a period of five minutes. The temperature rose to 159 C. in 25 minutes when refluxing began. In two hours it was at 190 C. and was kept at 190 C.:2 for an additional seven hours. The mixture was cooled to 80 C. after which 200 milliliters of benzene were added followed by 5 milliliters of water. The mixture was refluxed for one hour. This gave 499 grams of solution. Chromatographic analysis of the solution showed the yield to be 59.2%.
EXAMPLE 8 One hundred eighty-four grams of para-amino-diphenylamine were heated to 180 C. in a 1 liter flask under a slow stream of dry nitrogen which was maintained during the reaction. Enough styrene was added to cause reflux at that temperature. 1 gram of sodium amide was added and heating continued for 6.5 hours. Styrene was added to maintain reflux at 180 C.i2 C., requiring a total of 116 grams during the reaction. After cooling, 200 milliliters of benzene and 5 milliters of Water were add-ed. The mixture was refluxed for one hour. This gave 492 grams of solution. Chromatographic analysis of the solution gave an 11.1% content of N-phenethyl-N'- phenyl-para-phenylene diamine. This was an 18.9% yield.
EXAMPLE 9 One hundred eighty-four grams of para-amino-diphenylamine were melted in a 1 liter flask under a slow stream of dry nitrogen which was maintained during the reaction. At 90 C, 1 gram of sodium hydride, suspended in mineral oil, was added and the styrene started in dropwise. 'In 20 minutes the temperature was 180 C. and was kept there :3 for six hours by styrene addition. One hundred eighty-six grams of styrene were required. After cooling, 200 milliliters of benzene were added followed by 10 milliliters of water and the solution refluxed for one hour. This gave 578 grams of solution. From chromatographic analysis of the solution, the yield was 719% of N-phenethyl N-phenyl-para-phenylene diamine.
EXAMPLE 10 One hundred eighty-four grams of para-amino-diphenylamine were heated to 110 C. in a 1 liter flask and 3 grams of sodium were added. At 140 C., 130 grams of vinyl toluene were added dropwise in 2 /2 hours with temperature at about 170-185" C. The mixture was heated an additional half hour after which milliliters of alcohol were added during cooling. This was followed by 250 milliliters of benzene. The solution was filtered warm and distilled. Ninety-six grams of N-methyl-phenethyl-N-phenyl para-phenylene diamine were obtained having a boiling point of 225-230 C., and a melting point of 5760 C. This was a 31.8% yield.
EXAMPLE 11 One hundred eighty-four grams of para-amino-diphenylamine were heated to C. and six grams of sodium.
were added. At C., 130 grams of vinyl toluene were added dropwise during a 2% hour period with the temperature at 180-191 C. The mixture was heated an additional hour at -19l C. After cooling, 10 milliliters of absolute alcohol were added followed by 5 milliliters of water. Five hundred milliliters of benzene were added and then 100 milliliters of distillate were taken off. The solution was filtered and stripped to 200 C. pot temperature at 0.8 millimeter pressure. One hundred ten grams of a dark solid remained which had a melting point of 5055 C.
EXAMPLE 12 One hundred eighty-four grams of para-amino-diphenylamine were heated to 90 C. after which 2 grams of sodium were added. At 130 C., 20 milliliters of styrene were added followed by dropwise addition during the following hour at l85 C. A total of 108 grams of styrene were added. The mixture was heated an additional hour at l75-l85 C. After cooling, 50 milliliters of alcohol were added. The mixture was then stripped up to C. pot temperature at 25 millimeters pressure. Two hundred forty-five grams remained. Chromatographic analysis showed this to be 54.7% yield of N- phenethyl-N'-phenyl-p-phenylene diamine. This corresponds to a yield of 46.5%.
The following formulation was used to test the materials as antiozonants:
The test compounds were cured for 80 minutes at 275 F. and tested as follows:
1) By exposing test strips at 15% elongation to approximate 100 p.p.m. of ozone for ten minutes (rapid ozone test).
(2) Exposing 6 inch tapered wedge samples, stretched to l530% elongation, to direct sunlight on the roof (static weathering test described in an article by J. H. Fielding, India Rubber World, vol. 115, pages 802-805, 1947), and
(3) Exposing 6 inch tapered wedge samples, stretched to 10-21% elongation, to direct sunlight on the roof while flexing the samples 58 times a minute in a flexing machine (kinetic weathering test described in an article by I. H. Fielding, India Rubber World, vol. 115, pages 802-805, 1947).
The following results were obtained:
Antiozonant Rapid Ozone Static 3 month Kinetic 1 month RP-vinyl toluene and para-amino-diphenyl amine.
N methylphenethyl N phenyl-para-phenylene diamine (Product of Example 1).
RP-styrene and para-aminodiphenyl amine N-phenethy1-N-phenyl-paraphenylene diamine.
Severe cracking.- Slighit cracking" Very slight cracking. d0
Moderate to severe cracking; Moderate cracking Slight Cracking Severe Cracking. Motigrate cracking.
N 0 cracks Slight cracking. do Do.
soaps, etc.
The compounds were tested in inhibited catalytically cracked gasoline using the oxygen bomb induction period method (ASTM Standard Test D525). The following results were obtained using 0.025 gram of the'compounds per liter of gasoline.
Antiozonant: Induction period, minutes None 739 R.P. vinyl toluene and para-amino diphenylamine 1,206 N methylphenethyl-N'-phenyl-para-phenylene diamine 1,150 R.P. styrene and para-amino diphenyl amine 1,224 N-phenethyl N phenyl-para-phenylene diamine- 1,223
The rubbers which can be protected by the products of this invention are the oxidizable rubbery polymers of conjugated dienes which include natural rubber and the various synthetic diene rubbers which are similar to natural rubber in their aging characteristics, such as polychloroprene; butyl rubber, which is a polymerization product of a major proportion of a mono olefin, such as isobutylene, and a minor proportion of a multi olefin, such as butadiene or isoprene; the rubbery copolymers of butadiene and styrene which may contain from 50 to 75% by weight of butadiene; the rubbery copolymers of butadiene and acrylonitrile and polyisoprene.
The products of the invention are useful as age resistors for raw rubbers in latex form, coagulated rubber latices or vulcanized rubbers, and may be present in an amount of from 0.25 to 8.0% by weight, based on the weight of the rubber, although it is generally preferred to use from 0.5 to 4.0% by Weight, based on the Weight of rubber.
The antioxidants of this invention can be incorporated into rubber in any customary manner. They may be added in the form of physical mixtures or in the form of emulsions using any of the known emulsifiers such as monovalent metal hydroxides, fatty acids, organic They may be added to the rubber in the form of latex, or they may be milled into coagu lated rubber in the usual manner.
The various highly refined hydrocarbons which can beprotccted by the products of this invention can be described as catalytica'lly cracked, thermally cracked gasoline or blends thereof. Higher boiling fractions such as kerosene, fuel oil, and diesel oils are also included within the scope of this invention.
The compounds of this invention can be used to stabilize the highly refined hydrocarbons by adding about 001% to 0.1% by weight of 'the'antioxidant to the highly refined hydrocarbons.
While certain representative embodiments and de tails have been shown for thepurpose of illustrating the invention, it will be apparent to those skilled in this art that various changes and modifications may be made therein Without departing from the spirit or scope of the invention.
I claim:
[1. An oxidizable rubbery polymer of a conjugated diene containing from 0.25 to 8.0% by Weight, based on the weight of rubber, of N-alpha-phenethyl-N'-phenylpara-phenylene diamine] 2. An oxidizable rubbery polymer of a conjugated diene containing from 0.25 to 8.0% by weight, based on the weight of rubber, 0f N-betw-phenethyl-N-phenyl-paraphenylene diamine.
3. An oxidizdble rubbery polymer of a conjugated diene containing from 0.25 to 8.0% by weight, based on the weight 0 rubber, 0f the reaction product obtained by reacting para-aminodiphenyl amine with styrene at a temperature between and 250 C. and in the presence of a condensation catalyst selected from the group consisting of alkali metals, alkali metal hydrides and alkali metal amides.
References Cited in the file of this patent or the original patent UNITED STATES PATENTS 2,067,686 Semon Ian. 12, 1937 2,494,059 Ruggles Jan. 10, 1950' 2,810,709 Eby Oct. 22, 1957 2,813,124 Rice NOV. 12, 1957 2,822,395 Dent Feb. 4, 1958 2,835,705 Lamb et a1. May 20, 1958 2,838,471 Peterson et a1. June 10, 1958 FOREIGN PATENTS 1,140,433 France July 22, 1957
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3502615A (en) * | 1967-01-25 | 1970-03-24 | Universal Oil Prod Co | Synergistic antiozonant mixture and use thereof in rubber |
EP0041915A1 (en) * | 1980-06-09 | 1981-12-16 | The Goodyear Tire & Rubber Company | Styrylated amine antioxidants |
-
0
- US US25260D patent/USRE25260E/en not_active Expired
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3502615A (en) * | 1967-01-25 | 1970-03-24 | Universal Oil Prod Co | Synergistic antiozonant mixture and use thereof in rubber |
EP0041915A1 (en) * | 1980-06-09 | 1981-12-16 | The Goodyear Tire & Rubber Company | Styrylated amine antioxidants |
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