This invention relates to a novel class of polymeric compositions which have molecular weights ranging from 300 to 3000 and are the reaction product of (a) an alkyl or cycloalkyl substituted diphenyldiamine and (b) a conjugated or nonconjugated diene. The polymeric diphenyldiamine compounds are particularly useful as an antiozonant in diene containing polymers.

BACKGROUND OF THE INVENTION 
As known to those skilled in the art, degradation of rubber from ozone 
manifests itself by (a) cracks appearing perpendicular to the stress in 
the rubber and (b) the appearance of a silvery film or frosting on the 
surface of the article. The attack of ozone is purely a surface 
phenomenon. The function of the antiozonant depends on its migration to 
the surface of the rubber article where the battle against the ozone 
attack can occur. 
Conventional diphenyldiamine antiozonants, such as 
N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamines, are widely used in 
the protection of rubber. Whereas use of these diphenyldiamine 
antiozonants have in the past proved quite satisfactory, recent 
developments in rubber technology has resulted in rubber products with 
extended service lives and, therefore, require commensurate protection 
from ozonolysis. These recent developments are particularly apparent in 
tires. Therefore, there exists a need for new and improved antiozonants 
offering extended protection from ozonolysis of rubber. 
SUMMARY OF THE INVENTION 
The present invention relates to polymeric antiozonant compositions and 
their use in a diene containing polymer. The polymeric antiozonant 
compositions have a molecular weight ranging from about 300 to about 3,000 
and are derived from the polymerization reaction between (a) a 
diphenyldiamine and (b) at least one conjugated or nonconjugated diene 
compound. The polymerization is conducted in the presence of an acid 
catalyst. 
DETAILED DESCRIPTION OF THE INVENTION 
The present invention relates to a polymeric composition useful as an 
antiozonant which comprises a polymer having a molecular weight ranging 
from about 300 to about 3,000 and is the polymeric reaction product of 
(a) a diphenyldiamine of the formula: 
##STR1## 
wherein R is a radical selected from the group consisting of an alkyl 
having from 3 to 16 carbon atoms and a cycloalkyl having from 5 to 12 
carbon atoms: and 
(b) at least one diene selected from the group comprising (1) conjugated 
dienes consisting of 1,3-butadiene, isoprene, chloroprene, 
2-ethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, cyclopentadiene, 
piperylene: and (2) nonconjugated dienes consisting of 1,4-pentadiene, 
1,4-hexadiene, ethyldiene norbornene, 1,4-diisopropenylbenzene, 
1,3-diisopropenylbenzene, 1,4-di-.alpha.-ethylvinylbenzene, 
1,3-di-.alpha.-ethylvinylbenzene, 
1-isopropenyl-4-.alpha.-ethylvinylbenzene, 
1-isopropenyl-3-.alpha.-ethylvinylbenzene, 
1-.alpha.-ethylvinyl-4-.alpha.'-isopropylvinylbenzene, 
1-.alpha.-ethylvinyl-3-.alpha.'-isopropylvinylbenzene, 
1,4-di-.alpha.-isopropylvinylbenzene, 
1,3-di-.alpha.-isopropylvinylbenzene, limonene, vinylcyclohexene, 
cyclooctadiene, dicyclopentadiene and 1,5,9-cyclododecatriene. 
There is also disclosed a composition comprising (1) a diene containing 
polymer and (2) a polymeric antiozonant having a molecular weight ranging 
from about 300 to about 3,000 and comprises the polymeric reaction product 
of 
(a) a diphenyldiamine of the formula: 
##STR2## 
wherein R is a radical selected from the group consisting of an alkyl 
having from 3 to 16 carbon atoms and a cycloalkyl having from 5 to 12 
carbon atoms: and 
(b) at least one diene selected from the group comprising (1) conjugated 
dienes consisting of 1,3-butadiene, isoprene, chloroprene, 
cyclopentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene and 
piperylene: and (2) nonconjugated dienes consisting of 1,4-pentadiene, 
1,4-hexadiene, ethylidene norbornene, 1,4-diisopropenylbenzene, 
1,3-diisopropenylbenzene, 1,4-di-.alpha.-ethylvinylbenzene, 
1,3-di-.alpha.-ethylvinylbenzene, 
1-isopropenyl-4-.alpha.-ethylvinylbenzene, 
1-isopropenyl-3-.alpha.-ethylvinylbenzene, 
1-.alpha.-ethylvinyl-4-.alpha.'-isopropylvinylbenzene, 
1-.alpha.-ethylvinyl-3-.alpha.'-isopropylvinylbenzene, 
1,4-di-.alpha.-isopropylvinylbenzene, 
1,3-di-.alpha.-isopropylvinylbenzene, limonene, vinylcyclohexene, 
cyclooctadiene, dicyclopentadiene and 1,5,9-cyclododecatriene. 
As can be appreciated after having read the present application, by forming 
a polymeric diphenyldiamine it is believed that the mobility of 
diphenyldiamine moiety to migrate to the surface of the host rubber is 
reduced and therefore a longer period of antiozonant availability is 
provided. In addition, by using a mixture of polymeric diphenyldiamines 
which vary in molecular weights, one provides a somewhat "time release" 
effect controlled by the difference of mobility of each polymeric 
antiozonant within the host polymer. 
As mentioned above, a diphenyldiamine of the above formula is used to 
prepare the polymeric compositions of the present invention. With respect 
to the above formula, R may consist of an alkyl having a total of from 
about 3 to about 16 carbon atoms or a cycloalkyl having from 5 to 12 
carbon atoms. Preferably, R is an alkyl having 3 to 8 carbons or a 
cycloalkyl having 6 carbon atoms. Representative of diphenyldiamines which 
may be suitable for use in preparation of the compositions of the present 
invention include N-phenyl-N'-isopropyl-p-phenylenediamine, 
N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine, and 
N-phenyl-N'-(1-methylheptyl)-p-phenylenediamine to name a few. The most 
preferred diphenyldiamine is 
N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine. Many of the above 
diphenyldiamines are commercially available. For example, 
N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine is commercially 
available from Monsanto Company of St. Louis, Mo. under the designation 
Santoflex 13. N-phenyl-N'-isopropyl-p-phenylenediamine is commercially 
available from Pennwalt Corporation of Buffalo, N.Y. under the designation 
Anto 3H, from Monsanto Company of St. Louis, Mo. under the designation 
Santoflex IP and from Mobay Chemical Corporation of Pittsburgh, Pa. under 
the designation Vulkanox 4010NA. N-phenyl-N'-cyclohexyl-p-phenylenediamine 
is commercially available from Uniroyal Inc. of New York, N.Y. under the 
designation Flexzone 6H. 
The polymeric compositions of the present invention are derived from at 
least one conjugated or nonconjugated diene. Examples of conjugated dienes 
which may be used include 1,3-butadiene, isoprene, chloroprene, 
2-ethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 
cyclopentadiene or mixtures thereof. Examples of nonconjugated dienes 
which may be used include 1,4-pentadiene, 1,4-hexadiene, ethylidene 
norbornene, 1,4-diisopropenylbenzene, 1,3-diisopropenylbenzene, 
1,4-di-.alpha.-ethylvinylbenzene, 1,3-di-.alpha.-ethylvinylbenzene, 
1-isopropenyl-4-.alpha.-ethylvinylbenzene, 
1-isopropenyl-3-.alpha.-ethylvinylbenzene, 
1-.alpha.-ethylvinyl-4-.alpha.'-isopropylvinylbenzene, 
1-.alpha.-ethylvinyl-3-.alpha.'-isopropylvinylbenzene, 
1,4-di-.alpha.-isopropylvinylbenzene, 
1,3-di-.alpha.-isopropylvinylbenzene, limonene, vinylcyclohexene, 
cyclooctadiene, dicyclopentadiene, 1,5,9-cyclododecatriene or mixtures 
thereof. In addition a mixture of conjugated and nonconjugated dienes may 
be used. The preferred dienes for use in preparation of the present 
invention are isoprene, piperylene, 1,4-diisopropenylbenzene and 
1,3-diisopropenylbenzene. 
The terms "polymeric compound" and "polymer" when used to describe the 
compositions of the present invention are intended to only include those 
molecules which contain a monomeric unit derived from the diphenyldiamine 
and diene and where at least one of the monomeric units derived from the 
diphenyldiamine or diene is repeated. Therefore, the compounds formed by 
the reaction of a single diphenyldiamine molecule and a single diene 
molecule are not polymeric as the term is used herein. The term monomeric 
unit means a structure that occurs in a polymeric compound and which 
differs from the structure of diphenyldiamine or diene compound due to 
changes resulting from molecular reorientation during the linking to the 
adjacent structure. These changes may include addition to a double bond or 
the addition or removal of a hydrogen atom from the diphenyldiamine or 
diene. 
The molar ratio of the diphenyldiamine to diene in the polymer may vary 
depending on the desired ratio in the final polymeric product. For 
example, the molar ratio of the diphenyldiamine to diene as starting 
material may range from about 1:10 to about 10:1. The preferred molar 
ratio of diphenyldiamine to diene may range from about 5:1 to 1:5 as 
starting material. The most preferred ratio ranges from about 2:1 to 1:2. 
As to the final product, the molar ratio of polymeric units derived from 
the diphenyldiamine to diene may range from about 8:1 to 1:8. The 
preferred molar ratio of diphenyldiamine to diene in the final product 
ranges from about 1:2 to 2:1 with a range of from about 1.1:1 to 1:1.1 
being particularly preferred. 
The polymerization reaction between the diphenyldiamine and the diene is 
conducted in the presence of an acid catalyst. Examples of acid catalysts 
that may be used include Bronsted acid and Lewis acid type catalysts. Such 
known acid catalysts include H.sub.2 SO.sub.4, HCl, H.sub.3 PO.sub.4 ; 
metal halides such as BF.sub.3, BCl.sub.3, AlCl.sub.3, AlBr.sub.3, 
SnCl.sub.4, ZnCl.sub.2, SbCl.sub.3 and their etherates. The choice of a 
particular catalyst is dependent upon many factors including the melting 
or boiling points of the reactants, desired rate of reaction, solvent, and 
pressure and temperature limitations of the production equipment, etc. 
When higher yields are desired, the metal halides or their etherates may 
be utilized. The preferred acid catalysts are BF.sub.3 and AlCl.sub.3. The 
most preferred catalyst is BF.sub.3 and its etherate. 
The polymerization reaction may be carried out neat (without solvent) at or 
above the melting points of the reactants or can be carried out in the 
presence of a solvent. The solvent may be an aliphatic C.sub.6 -C.sub.12 
hydrocarbon, an aromatic or haloaromatic (C.sub.6 to C.sub.9) hydrocarbon, 
or a C.sub.6 to C.sub.9 aliphatic halohydrocarbon. Examples of suitable 
solvents are hexane, heptane, benzene, toluene, xylene and chlorobenzene. 
The preferred solvents are toluene and xylene. 
The polymerization reaction may be conducted under a variety of operating 
conditions. The reaction pressure may vary and range from 1 atm to about 
100 atm with a pressure of from about 2 atm to about 10 atm being 
preferred. The reaction temperature may range from about 25.degree. to 
220.degree. C. with the preferred range being from about 140.degree. to 
190.degree. C. 
Depending on the reactivity of the reactants, amount of catalyst, reaction 
pressure and reaction temperature, the reaction time may vary. Generally 
speaking, the reaction time ranges from about 1 to about 8 hours. 
In addition to the diphenyldiamine compound and diene, other compounds may 
be present during the polymerization reaction. For example, many feed 
streams containing the desired diene may also include other hydrocarbons. 
Examples of such hydrocarbons include 1,5-dimethyl-5-vinyl-1-cyclohexene, 
1-methyl-4-isopropenyl-1-cyclohexene, 1,4-dimethyl-4-vinyl-1-cyclohexene, 
1-methyl-5-isopropenyl-1-cyclohexene, 2,5-dimethyl-1,5-cyclooctadiene, 
1,5-dimethyl-1,5-cyclooctadiene, 2-methyl-2-butene, butenes, pentenes and 
hexenes. 
The reaction product of the polymerization reaction will generally include 
a mixture of compounds. These compounds may include simple alkylated 
diphenyldiamines (not polymeric), and a variety of polymers with varying 
molecular weights. 
The molecular weight of the polymeric compounds of the present invention 
may vary. For example, when the reactants are 1,3-butadiene and 
N-phenyl-N'-isopropyl-p-phenylenediamine, the molecular weight may be as 
low as 334. On the other hand, the molecular weight may be as high as 
3000. Preferably, the molecular weight ranges from about 350 to about 3000 
with a range of from about 500 to about 2000 being particularly preferred. 
The above molecular weights are as determined by gel permeation 
chromatography. 
Rubber stocks comprising diene containing polymers subject to ozonolysis 
may be protected with the compositions of the present invention. Examples 
of diene containing polymers include substituted and unsubstituted, 
saturated and unsaturated, natural and synthetic polymers. The natural 
polymers include natural rubber in its various forms, e.g., pale crepe and 
smoked sheet, and balata and gutta percha. The synthetic polymers include 
those prepared from a single monomer (homopolymer) or a mixture of two or 
more copolymerizable monomers (copolymer) wherein the monomers are 
combined in a random distribution or block form. The monomers may be 
substituted or unsubstituted and may possess one or more double bonds, for 
example, diene monomers, both conjugated and nonconjugated, and 
monoolefins including cyclic and acyclic monoolefins, especially vinyl and 
vinylidene monomers Examples of conjugated dienes are 1,3-butadiene, 
isoprene, chloroprene, 2-ethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene 
and piperylene. Examples of nonconjugated dienes are 1,4-pentadiene, 
1,4-hexadiene, 1,5-hexadiene, dicyclopentadiene, 1,5-cyclooctadiene and 
ethylidene norbornene. Examples of acyclic monoolefins are ethylene, 
propylene, 1-butene, isobutylene, 1-pentene and 1-hexene. Examples of 
cyclic monoolefins are cyclopentene, cyclohexene, cycloheptene, 
cyclooctene and 4-methyl-cyclooctene. Examples of vinyl monomers are 
styrene, acrylonitrile, acrylic acid, ethylacrylate, vinyl chloride, 
butylacrylate, methyl vinyl ether, vinyl acetate and vinyl pyridine. 
Examples of vinylidene monomers are .alpha.-methylstyrene, methacrylic 
acid, methyl methacrylate, itaconic acid, ethyl methacrylate, glycidyl 
methacrylate and vinylidene chloride. Representative examples of the 
synthetic polymers used in the practice of this invention are 
polychloroprene: homopolymers of a conjugated 1,3-diene such as isoprene 
and butadiene, and in particular, polyisoprenes and polybutadienes having 
essentially all of their repeat units combined in a cis-1,4-structure: 
copolymers of a conjugated 1,3-diene such as isoprene and butadiene with 
up to 50 percent by weight of at least one copolymerizable monomer 
including ethylenically unsaturated monomers such as styrene or 
acrylonitrile; butyl rubber, which is a polymerization product of a major 
proportion of a monoolefin and a minor proportion of a diolefin such as 
butadiene or isoprene: polyurethanes containing carbon to carbon double 
bonds: and polymers and copolymers of monoolefins containing little or no 
unsaturation, such as polyethylene, polypropylene, ethylene propylene 
copolymers and terpolymers of ethylene, propylene and a nonconjugated 
diene such as dicyclopentadiene, 1,4-hexadiene and ethylidene norbornene. 
The rubber compounds preferably protected by this invention are 
cis-1,4-polyisoprene (natural or synthetic), polybutadiene, 
polychloroprene and the copolymers of isoprene and butadiene, copolymers 
of acrylonitrile and butadiene, copolymers of acrylonitrile and isoprene, 
copolymers of styrene and butadiene and blends thereof. 
The amount of polymeric antiozonants that may be used in the diene 
containing polymers may vary and depend on the polymer to be protected, 
the particular polymeric antiozonant, desired protection and the like. 
Generally speaking, the polymeric antiozonant is used in amounts of from 
0.1 to 10 parts per hundred parts (phr) of diene polymer. Preferably, the 
polymeric antiozonant is used in amounts of from about 1 to about 7 phr, 
with a range of from about 2 to about 5 phr being particularly preferred. 
The polymeric antiozonants may be incorporated in the diene containing 
polymer by conventional mixing procedures, for example, by adding them in 
a Banbury mixer or by adding them to the rubber on a mill. With liquid or 
low melting solid polymeric antiozonants, no special precautions are 
necessary for obtaining good dispersions. However, when using higher 
melting polymeric antiozonants, it is recommended that they be ground to a 
fine powder, preferably 70 micrometer particle size or less to ensure 
adequate dispersion. Such powders may be treated to suppress dust, for 
example, by the addition of oil, or they can be mixed with a binder, for 
example, a polymer latex, and formed into granules or pellets containing 
up to 5% by weight of binder. They can also be formulated as 
predispersions or masterbatch in a diene polymer, which predispersions may 
contain, for example, from 15 to 50% by weight of polymer. 
The rubber stocks may include reinforcing carbon blacks, pigments such as 
titanium dioxide and silicon dioxide, metal oxide activators such as zinc 
oxide and magnesium oxide, stearic acid, hydrocarbon softeners and 
extender oils, amine, ether and phenolic antioxidants, phenylenediamine 
antidegradants and tackifiers. The preferred phenylenediamine 
antidegradants which may be used in addition to the polymeric antiozonant 
include N-phenyl-N'-isopropyl-p-phenylenediamine, 
dicumyl-p-phenylenediamines or mixtures thereof. The stocks may also 
contain prevulcanization inhibitors but in many stocks their use is 
unnecessary.

EXAMPLE 1 
Into a 1-liter flask equipped with a thermometer, a heating mantle, reflux 
condenser and nitrogen balloon was charged 130 grams 
N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (0.485 mole) and 85 
grams (0.538 mole) of 1,3-diisopropenylbenzene. The mixture was heated to 
about 120.degree. C. to dissolve the components with occasional stirring. 
The reaction mixture was cooled to about 75.degree. C. and 18.2 grams of 
boron trifluoride etherate was added via syringe where a mild exotherm to 
about 80.degree. C. was observed. The reaction pot was heated to 
160.degree.-170.degree. C for 15 hours. The mixture was cooled, dissolved 
in 500 ml toluene, and washed with aqueous NaOH solution (12 grams NaOH in 
200 ml water). The product was dried 16 hours at 100.degree. C. in a 
vacuum oven to a constant weight. Analysis by GPC showed 34.8% by weight 
of the mixture had a molecular weight of 2062, 22.4% by weight of the 
mixture had a molecular weight of 1399, 25.9% by weight of the mixture had 
a molecular weight of 900, 4.1% by weight of the mixture had a molecular 
weight of 700, 8.2% by weight of the mixture had a molecular weight of 604 
and 4.0% by weight of the mixture had a molecular weight of 519. 
EXAMPLE 2 
A reaction was carried out under the conditions of Example 1, except 
1,4-diisopropenylbenzene was substituted for the 1,3-diisopropylbenzene 
and the reaction mixture was heated to 160.degree. C. for 3 hours after 
addition of the catalyst. Analysis by GPC showed 34.2% by weight of the 
mixture had a molecular weight of 1690, 36.2% by weight of the mixture had 
a molecular weight of 999, 8.5% by weight of the mixture had a molecular 
weight of 689, 15.5% by weight of the mixture had a molecular weight of 
544, 3.0% by weight of the mixture had a molecular weight of 412 and 1.3% 
by weight of the mixture had a molecular weight of 368. 
EXAMPLE 3 
A reaction was carried out under the conditions of Example 1, except 65.3 
grams (0.96 mole) of isoprene was substituted for the 
1,3-diisopropylbenzene and the reaction mixture was heated to 40.degree. 
C. when the catalyst was added. The flask was heated to 150.degree. C. for 
8 hours after the catalyst was added. Analysis by GPC showed 9.5% by 
weight of the mixture had a molecular weight of 530, 20.4% by weight of 
the mixture had a molecular weight of 369 and 67.5% by weight of the 
mixture had a molecular weight of 338. 
EXAMPLE 4 
A reaction was carried out under the conditions of Example 1, except 
limonene (73.4 grams, 0.54 mole) was substituted for the 
1,3-diisopropenylbenzene. At about 75.degree. C. when the catalyst was 
added, an exotherm to about 90.degree. C. was observed. The flask was 
heated to 170.degree. C. for 8 hours. GPC analysis showed 2.9% by weight 
of the mixture had a molecular weight of 525, 15.8% by weight of the 
mixture had a molecular weight of 409, 18.2% by weight of the mixture had 
a molecular weight of 382 and 63.1% by weight of the mixture had a 
molecular weight of 337. 
EXAMPLE 5 
A reaction was carried out under the conditions of Example 1, except 50 
grams (0.72 mole) of a 1.35 molar ratio of piperylene to 2-methyl-2-butene 
was substituted for the 1,3-diisopropenylbenzene. The catalyst was added 
at about 40.degree. C. and the mixture heated to 160.degree. C. for 4 
hours. GPC analysis showed 12.5% with a molecular weight of 726 and 87.5% 
with a molecular weight of 450. 
EXAMPLE 6 
A one-liter flask containing 260 grams (0.97 mole) of 
N-phenyl-N'-1,3-dimethylbutyl)-p-phenylenediamine and 170 grams (1.07 
mole) of 1,3-diisopropenylbenzene) was heated to about 120.degree. C. with 
stirring under nitrogen to dissolve the 
N-phenyl-N'-(1,3-dimethybutyl)-p-phenylenediamine. The flask was cooled to 
about 95.degree. C. and 20 ml of fresh boron trifluoride etherate was 
slowly added via a syringe. A mild exotherm of about 5.degree. C. was 
noted. The flask was heated to 180.degree. C. with stirring for 16 hours. 
The flask was cooled to about 100.degree. C. and 500-1000 ml of toluene 
were added with stirring to dissolve the product. The product was washed 
with 12 grams of NaOH dissolved in about 100 ml of water with stirring. 
The wash solution was colored and drawn off the bottom of the vessel. 
About 200 ml of water was then added to aid removing any excess NaOH 
solution. Sodium chloride was added to help separate the phases. The 
aqueous portion was also drawn off the bottom of the vessel. The product 
in the toluene solution was filtered through anhydrous sodium sulfate to 
dry and prevent bumping during stripping (vacuum) of the solvent and 
lights at greater than 110.degree. C. A melting range of 
45.degree.-51.degree. C. from a black shiny solid was found. GPC analysis 
showed 31.3% with a molecular weight of 3280, 21.6% with a molecular 
weight of 2140, 26.5% with a molecular weight of 1195, 8.5% with a 
molecular weight of 632, 8.6% with a molecular weight of 450 and 2.2% with 
a molecular weight of 349. 
EXAMPLE 7 
A one-liter 3-neck round bottom flask was fitted with a reflux condenser, 
thermometer and means of agitation. The system was slowly flushed with 
nitrogen and charged with 260 grams (0.97 mole) of 
N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine and 131 grams of washed 
isoprene. The reaction mixture was sealed under a nitrogen balloon and 
heated to reflux to dissolve the 
N-phenyl-N'-(1,3-dimethyl-butyl)-p-phenylenediamine and isoprene. 20 ml of 
BF.sub.3 etherate catalyst was injected after several minutes of reflux 
and stirring via a dry syringe. Heat was applied to the flask and reflux 
continued as the flask was allowed to slowly heat up. The flask 
temperature of 175.degree.-180.degree. C. was achieved after 2-3 hours and 
held for 4 hours. The flask was then cooled to about 100.degree. C. and 
500 ml of toluene were added with stirring. The reactor contents were 
stirred for about 15 minutes as the reactor temperature was allowed to 
drop to about 70.degree. C. An aqueous solution of 12 grams of NaOH in 200 
ml of water was added to a 3-liter separatory funnel. The reactor contents 
were also transferred to the separatory funnel and the contents shaken. 
The lower aqueous layer was drawn off and replaced with 200 ml of fresh 
water. The separatory funnel was shaken and the lower aqueous layer 
separated. The dark product was semi-solid in nature and can be poured out 
of the containment vessel, however, a bit easier if heated. GPC analysis 
showed 21.5% had a molecular weight of 825 and 78.5% had a molecular 
weight of 449. 
EXAMPLE 8 
A reaction was carried out under the conditions of Example 7, except 130 
grams of a mixture of piperylene/2-methyl-2-butene was substituted for the 
isoprene. The molar ratio of piperylene:2-methyl-2-butene was 1.35:1. GPC 
analysis showed 12.5% with a molecular weight of 726 and 87.5% with a 
molecular weight of 450. 
EXAMPLE 9 
A one-liter round bottom flask containing 260 grams (0.97 mole) of 
N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine and 170 grams (1.07 
mole) of 1,3-diisopropenyl-benzene was heated to 120.degree. C. with 
stirring under nitrogen to dissolve the 
N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine. The flask and contents 
were allowed to cool to about 70.degree. C. with a nitrogen sparge slowly 
bubbling into the dark solution. The nitrogen line was removed and quickly 
replaced with a BF.sub.3 gas line attached to a gross-tared lecture bottle 
of BF.sub.3 gas. The BF.sub.3 gas was allowed to bubble into the solution 
with intermittent addition. The amount of BF.sub.3 gas added to the flask 
was monitored by disconnecting the BF.sub.3 line from the lecture bottle 
and weighing. A partially deflated nitrogen balloon was attached to the 
flask to monitor BF.sub.3 gas that did not stay in solution, however, no 
appreciable inflating of the balloon was observed. The pot temperature 
appeared to climb about 10.degree. to 13.degree. C. After addition of the 
BF.sub.3, the pot temperature was raised to 175.degree.-180.degree. C. as 
quickly as practical with stirring under nitrogen. A total of 16 hours 
reaction time at 175.degree.-180.degree. C. was completed, but the 
reaction was cooled at 4-hour intervals for taking sample for HPLC 
analysis. The HPLC analyses show essentially complete reaction to the 
desired polymers by 8-12 hours residence time and the product distribution 
is almost identical to that in Example 6. 
Work-up was started by cooling the reaction pot to about 100.degree. C., 
and adding 500-1000 ml of toluene with stirring. After dissolution, the 
pot temperature was maintained above 70.degree. C. as 200 ml of water 
containing 12 grams of NaOH is added and agitated. The organic/aqueous 
phase separation occurs very quickly when the temperature is maintained 
hot. The aqueous layer is drawn off the bottom, and 200 ml of water is 
added to complete the wash. The pH of the wash water remains basic as 
determined with the indicator paper. The toluene is then stripped at about 
100.degree.-110.degree. C. under reduced pressure. The molten ZONE (MP 
about 54.degree. C.) can be poured or allowed to flow from the reactor. 
EXAMPLE 10 
Rubber compositions containing natural rubber, cis-polybutadiene 
(BUDENE.RTM. 1207), carbon black, processing aids and a sulfur accelerated 
cure system typical of a tire sidewall were prepared in a BR Banbury using 
two separate stages of addition. The sulfur and accelerator were added to 
the Banbury in the second stage, whereas the processing aids were added to 
the first pass along with the rubbers and carbon black. Different amounts 
of antiozonant, antioxidant or the product of Example 6 were added during 
the first stage of mixing. Table I sets out the vulcanizate properties of 
the rubber compounds. The only difference in composition of the rubber 
compounds is indicated in Table I. The static ozone resistance of 
compounds E and F are superior to the other compounds listed in the table. 
These compounds contain molar equivalent amounts of the product of Example 
6 as compared to the antiozonant Santoflex 13. The dynamic ozone 
resistance of Compound F is also superior to Compound D, which directly 
compares the product of Example 6 to Santoflex 13. These results clearly 
illustrate the superior ozone protection of the polymeric diphenyldiamine. 
EXAMPLE 11 
Rubber compositions containing natural rubber, cis-polybutadiene 
(BUDENE.RTM. 1207), carbon black, processing aids and a sulfur accelerated 
cure system typical of a tire sidewall were prepared in a BR Banbury using 
the procedure outlined in Example 10. Table II sets out the vulcanizate 
properties of rubber compounds comparing the product of Example 2 with 
Santoflex 13 at molar equivalent levels. The results show improved flex 
cut growth for the product of Example 2 containing compound and also 
improved static ozone resistance. 
EXAMPLE 12 
Rubber compositions containing natural rubber, cis-polybutadiene 
(BUDENE.RTM. 1207), carbon black, processing aids and a sulfur accelerated 
cure system typical of a tire sidewall were prepared in a BR Banbury using 
the procedure outlined in Example 10. Table III sets out the vulcanizate 
properties of rubber compounds comparing Santoflex 13 with a polymeric 
diphenyldiamine prepared from isoprene, the product of Example 7. The 
polymeric diphenyldiamine gave improved static ozone resistance when 
compared to the control containing Santoflex 13. 
EXAMPLE 13 
Rubber compositions containing natural rubber, cis-polybutadiene 
(BUDENE.RTM. 1207), carbon black, processing aids and a sulfur accelerated 
cure system typical of a tire sidewall were prepared in a BR Banbury using 
the procedure outlined in Example 10. Table IV sets out the vulcanizate 
properties of rubber compounds comparing Santoflex 13 to the polymeric 
diphenyldiamine prepared in Example 8 (from PIPS/2M2B) and a blend of the 
two. The polymeric diphenyldiamine containing PIPS/2M2B shows better 
static ozone resistance on original and aged samples and improved cyclic 
ozone resistance after preaging of the samples. 
TABLE I 
__________________________________________________________________________ 
A B C D E F 
__________________________________________________________________________ 
Compound # 
Santoflex 13 (phr) 
0 0 3 3 0 0 
Wingstay .RTM. 100 (phr) 
0 1 0 1 0 1 
Product of Example 6 (phr) 
0 0 0 0 4.9 4.9 
Stress Strain 
Tensile Strength (MPa) 
13.9 
13.5 
13.5 
12.9 
13.7 
12.3 
Elongation at Break (%) 
620 590 620 585 660 600 
300% Modulus (MPa) 
5.8 6.0 5.7 5.9 5.3 5.2 
Static Ozone* 
25% Strain, 168 hours 
Original Samples F F D4 A4 0 0 
Preaged Samples (14 days @ 70.degree. C.) 
F F C4 B4 0 0 
Dynamic Ozone* 
25% Strain, 168 hours 
Original Samples F F F D4 F D3 
Preaged Samples (14 days @ 70.degree. C.) 
F F F F F C4 
__________________________________________________________________________ 
*Ozone Rating System 
0 = no cracking 
F = complete failure 
Number of cracks 
A = very few (less than 1/4 surface) 
B = few (1/4 to 1/2 surface) 
C = moderate (1/2 to 3/4 surface) 
D = heavy (3/4 to all surface) 
Size of Cracks 
1 = small (hairline) 
2 = medium 
3 = large 
4 = severe (open) 
TABLE II 
______________________________________ 
Santoflex 13 (phr) 3 0 
Wingstay .RTM. 100 (phr) 
1 1 
Product of Example 2 (phr) 
0 4.8 
Rheometer, 150.degree. C. 
Maximum Torque 34.9 33.1 
Minimum Torque 9.0 8.5 
t.sub.90, minutes 20.0 18.9 
t.sub.25, minutes 7.8 7.3 
Stress Strain 
Tensile Strength (MPa) 14.6 13.5 
Elongation at Break (%) 
540 540 
300% Modulus (MPa) 7.0 6.5 
DeMattia Flex 
Pierced (.08"), 6 hours flex 
1.5" .12" 
(Failure) 
Static Ozone, 25% Strain, 168 hours 
Original Samples D3 A4 
Preaged Samples (7 days @ 70.degree. C.) 
D3 B3 
Rebound (ASTM D1054) 
100.degree. C. (%) 67.2 64.8 
______________________________________ 
TABLE III 
______________________________________ 
Santoflex 13 (phr) 3 0 
Product of Example 7 (phr) 
0 3.75 
Rheometer, 150.degree. C. 
Maximum Torque 33.3 33.9 
Minimum Torque 9.4 9.0 
t.sub.90, minutes 23.5 20.2 
t.sub.2, minutes 8.0 6.7 
Stress Strain 
Tensile Strength (MPa) 
15.1 15.1 
Elongation at Break, (%) 
650 620 
300% Modulus (MPa) 5.8 6.2 
Rebound (ASTM D1054) 
100.degree. C. (%) 70.0 71.0 
Static Ozone 
25% Strain, 168 hours 
C3 A3 
______________________________________ 
TABLE IV 
______________________________________ 
Santoflex 13 (phr) 4 0 2 
Product of Example 8 (phr) 
0 4.8 2.4 
Stress Strain 
Tensile Strength (MPa) 
14.0 13.6 13.8 
Elongation at Break (%) 
520 520 520 
300% Modulus (MPa) 6.9 6.6 6.8 
Rebound 
100.degree. C. (%) 75.5 74.0 75.0 
Static Ozone, 25% Strain, 168 Hours 
Original Sample A3 0 0 
Preaged Samples (7 days @ 70.degree. C.) 
D2 B3 B3 
Cyclic Ozone 
Original 
72 hours 0 0 0 
216 hours 1-1 1-1 1-1 
Preaged** 
120 hours 1/2* 0 0 
192 hours 1-1 1/2* 1/2* 
288 hours Break 3-3 3-3 
384 hours -- Break Break 
______________________________________ 
*Edge 
**7 days at 70.degree. C. 
Cycle D3395using a cycled ozone on/off procedure 
Density 
0 = none 
1/2 = Edge 
1 = 1/8 surface 
2 = 3/8 surface 
3 = 5/8 surface 
4 = 3/4 surface 
Severity 
0 = None 
1 = .01 in. 
3 = .03 in. 
5 = .10 in. 
10 = .25 in. 
12 = +.25 in.