U.S. patent application number 09/836511 was filed with the patent office on 2001-08-23 for polymeric dicyclopentadiene/limonene resin.
This patent application is currently assigned to The Goodyear Tire & Rubber Company. Invention is credited to Keith, Denise Jeannette, Segatta, Thomas Joseph, Wideman, Lawson Gibson.
Application Number | 20010016636 09/836511 |
Document ID | / |
Family ID | 22930464 |
Filed Date | 2001-08-23 |
United States Patent
Application |
20010016636 |
Kind Code |
A1 |
Wideman, Lawson Gibson ; et
al. |
August 23, 2001 |
Polymeric dicyclopentadiene/limonene resin
Abstract
This invention relates to a novel class of polymeric resins
which have a softening point ranging from about 50.degree. C. to
about 220.degree. C. and a molecular weight ranging from about 500
to about 42,000. The resins consist essentially of the polymers
which result from the polymerization reaction between
dicyclopentadiene and limonene. The polymeric resins are
particularly useful in improving traction of the rubber when used
in tire treads.
Inventors: |
Wideman, Lawson Gibson;
(Hudson, OH) ; Segatta, Thomas Joseph; (Copley,
OH) ; Keith, Denise Jeannette; (Akron, OH) |
Correspondence
Address: |
The Goodyear Tire & Rubber Company
Department 823
1144 East Market Street
Akron
OH
44316-0001
US
|
Assignee: |
The Goodyear Tire & Rubber
Company
|
Family ID: |
22930464 |
Appl. No.: |
09/836511 |
Filed: |
April 17, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09836511 |
Apr 17, 2001 |
|
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09246391 |
Feb 9, 1999 |
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6245873 |
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Current U.S.
Class: |
526/283 ;
526/335; 526/336; 526/340.3 |
Current CPC
Class: |
C08L 21/00 20130101;
C08L 2666/06 20130101; C08F 236/20 20130101; C08F 232/08 20130101;
C08L 21/00 20130101 |
Class at
Publication: |
526/283 ;
526/335; 526/336; 526/340.3 |
International
Class: |
C08F 036/00 |
Claims
What is claimed is:
1. A resin composition consisting essentially of a polymer which is
the reaction product of the polymerization reaction between
dicyclopentadiene and limonene, said resin having a softening point
ranging from about 50 to about 220.degree. C. and a molecular
weight ranging from about 500 to about 42,000.
2. A resin composition comprising a blend of two or more resins,
wherein each resin consists essentially of the polymer which is the
reaction product of the polymerization reaction between
dicyclopentadiene and limonene and each resin has a is softening
point ranging from about 50 to about 220.degree. C. and a molecular
weight ranging from about 500 to about 42,000.
3. The resin composition of claim 1 wherein the blend comprises
four individual resins.
4. The resin composition of claim 2 wherein said blend comprises
three individual resins.
5. The resin composition of claim 1 wherein said composition
consists essentially of the polymerization reaction product of from
about 10 to about 1 moles of dicyclopentadiene and from about 1 to
about 10 moles of limonene.
6. The resin composition of claim 2 wherein each resin is the
polymerization reaction product of from about 1 to about 2 moles of
dicyclopentadiene and from about 2 to about 1 moles of
limonene.
7. The resin composition of claim 3 wherein the first resin has a
softening point ranging from about 55 to about 75.degree. C., the
second resin has a softening point ranging from about 80 to about
131.degree. C., the third resin has a softening point ranging from
about 126 to about 168.degree. C., and the fourth resin has a
softening point ranging from about 168 to about 195.degree. C.
8. The resin composition of claim 4 wherein the first resin has a
softening point ranging from about 134 to about 156.degree. C., the
second resin has a softening point ranging from about 138 to about
180.degree. C., and the third resin has a softening point ranging
from about 188 to about 208.degree. C.
9. The resin composition of claim 3 wherein the first resin has a
molecular weight ranging from about 500 to about 15,000, the second
resin has a molecular weight ranging from about 700 to about
15,000, the third resin has a molecular weight ranging from about
3,000 to about 15,000, and the fourth resin has a molecular weight
ranging from about 4,000 to about 15,000.
10. The resin composition of claim 4 wherein the first resin has a
molecular weight ranging from about 700 to about 24,000, the second
resin has a molecular weight ranging from about 700 to about
36,000, and the third resin has a molecular weight ranging from
about 700 to about 42,000.
11. The resin composition of claim 1 wherein said polymerization is
conducted in the presence of a catalyst.
12. The resin composition of claim 11 wherein said catalyst is
selected from the group consisting of H.sub.2SO.sub.4, HCl,
H.sub.3PO.sub.4, HClO.sub.4, BF.sub.3, BCl.sub.3, AlCl.sub.3,
AlBr.sub.3, SnCl.sub.4, ZnCl.sub.2, SbCl.sub.3, and etherates of
said acid catalyst.
13. The resin composition of claim 1 wherein said polymerization is
a thermal polymerization.
14. A rubber stock comprising (1) a rubber selected from the group
consisting of natural rubber, rubbers derived from a diene monomer
or mixtures thereof, and (2) a polymeric resin composition
consisting essentially of the reaction product of the
polymerization between dicyclopentadiene and limonene, said resin
having a softening point ranging from about 50 to about 220.degree.
C., and an average molecular weight ranging from about 500 to about
42,000.
15. The rubber stock of claim 14 wherein said rubber derived from a
diene monomer or mixtures thereof is selected from the group
comprising natural rubber, polyisoprene, polybutadiene,
polychloroprene, copolymers of isoprene and butadiene, copolymers
of styrene and butadiene, copolymers of acrylonitrile and
butadiene, copolymers of acrylonitrile and isoprene and blends
thereof.
16. The rubber stock of claim 14 wherein said polymeric resin
composition is present in an amount ranging from about 5 to about
50 parts per hundred parts of rubber.
17. The rubber stock of claim 16 wherein said polymeric resin
composition is present in an amount ranging from about 10 to about
25 parts per hundred parts of rubber.
18. The rubber stock of claim 14 wherein the resin composition
comprises a blend of four individual resins.
19. The rubber stock of claim 14 wherein said resin composition
comprises a blend of three individual resins.
20. The rubber stock of claim 18 wherein the first resin has a
softening point ranging from about 55 to about 75.degree. C., the
second resin has a softening point ranging from about 80 to about
131.degree. C., the third resin has a softening point ranging from
about 126 to about 168.degree. C., and the fourth resin has a
softening point ranging from about 168 to about 195.degree. C.
21. The rubber stock of claim 19 wherein the first resin has a
softening point ranging from about 135 to about 156.degree. C., the
second resin has a softening point ranging from about 138 to about
180.degree. C., and the third resin has a softening point ranging
from about 188 to about 208.degree. C.
22. The rubber stock of claim 18 wherein the first resin has a
molecular weight ranging from about 500 to about 15,000, the second
resin has a molecular weight ranging from about 700 to about
15,000, the third resin has a molecular weight ranging from about
3,000 to about 15,000, and the fourth resin has a molecular weight
ranging from about 4,000 to about 15,000.
23. The rubber stock of claim 19 wherein the first resin has a
molecular weight ranging from about 700 to about 24,000, the second
resin has a molecular weight ranging from about 700 to about
36,000, and the third resin has a molecular weight ranging from
about 700 to about 42,000.
24. A pneumatic tire having a tread comprised of (1) a rubber
selected from the group consisting of natural rubber, rubbers
derived from a diene monomer or mixtures thereof, and (2) a
polymeric resin composition consisting essentially of the reaction
product of the polymerization between dicyclopentadiene and
limonene, said resin having a softening point ranging from about 50
to about 220.degree. C., and an average molecular weight ranging
from about 500 to about 42,000.
25. The pneumatic tire of claim 24 wherein said rubber derived from
a diene monomer or mixtures thereof is selected from the group
comprising natural rubber, polyisoprene, polybutadiene,
polychloroprene, copolymers of isoprene and butadiene, copolymers
of styrene and butadiene, copolymers of acrylonitrile and
butadiene, copolymers of acrylonitrile and isoprene and blends
thereof.
26. The pneumatic tire of claim 24 wherein said polymeric resin
composition is present in an amount ranging from about 5 to about
50 parts per hundred parts of rubber.
27. The pneumatic tire of claim 26 wherein said polymeric resin
composition is present in an amount ranging from about 10 to about
25 parts per hundred parts of rubber.
28. The pneumatic tire of claim 24 wherein the resin composition
comprises a blend of four individual resins.
29. The pneumatic tire of claim 24 wherein said resin composition
comprises a blend of three individual resins.
30. The pneumatic tire of claim 28 wherein the first resin has a
softening point ranging from about 55 to about 75.degree. C., the
second resin has a softening point ranging from about 80 to about
131.degree. C., the third resin has a softening point ranging from
about 126 to about 168.degree. C., and the fourth resin has a
softening point ranging from about 168 to about 195.degree. C.
31. The pneumatic tire of claim 29 wherein the first resin has a
softening point ranging from about 135 to about 156.degree. C., the
second resin has a softening point ranging from about 138 to about
180.degree. C., and the third resin has a softening point ranging
from about 188 to about 208.degree. C.
32. The pneumatic tire of claim 28 wherein the first resin has a
molecular weight ranging from about 500 to about 15,000, the second
resin has a molecular weight ranging from about 700 to about
15,000, the third resin has a molecular weight ranging from about
3,000 to about 15,000, and the fourth resin has a molecular weight
ranging from about 4,000 to about 15,000.
33. The pneumatic tire of claim 29 wherein the first resin has a
molecular weight ranging from about 700 to about 24,000, the second
resin has a molecular weight ranging from about 700 to about
36,000, and the third resin has a molecular weight ranging from
about 700 to about 42,000.
Description
BACKGROUND OF THE INVENTION
[0001] This invention relates to a polymeric resin which is the
reaction product of the polymerization reaction between
dicyclopentadiene and limonene. Use of the polymeric resins of the
present invention in a rubber tire stock improves the traction and
handling of the tire.
SUMMARY OF THE INVENTION
[0002] The present invention relates to a polymeric
dicyclopentadiene/limonene resin. The polymeric resins of the
present invention have softening points ranging from about
50.degree. C. to about 220.degree. C., and a molecular weight of
from about 500 to about 42,000. The present invention also includes
a blend of dicyclopentadiene/limonene resins and rubber stocks
containing the dicyclopentadiene/limonene resin.
DETAILED DESCRIPTION OF THE INVENTION
[0003] The present invention relates to a polymeric resin
consisting essentially of the reaction product of the
polymerization reaction between dicyclopentadiene and limonene and
having a softening point ranging from about 50.degree. C. to about
220.degree. C. and a molecular weight ranging from about 500 to
about 42,000.
[0004] In addition, the present invention relates to a resin
composition comprising a blend of two or more polymeric resins
wherein each resin consists essentially of the reaction product of
the polymerization reaction between dicyclopentadiene and limonene.
Alternatively, the blend can be formed in-situ; that is, the
reaction temperature may be raised during the polymerization to
increase the molecular weight distribution and broaden the
softening point.
[0005] In addition, there is disclosed a pneumatic tire having a
tread comprised of a rubber stock comprising (1) a rubber selected
from the group consisting of natural rubber, rubber derived from a
diene monomer or mixtures thereof, and (2) a polymeric resin
composition consisting essentially of the reaction product of the
polymerization reaction between dicyclopentadiene and limonene;
said resin having a softening point ranging from about 50 to about
220.degree. C. and a molecular weight ranging from about 500 to
about 42,000.
[0006] There is also disclosed a rubber stock comprising (1) a
rubber selected from the group consisting of natural rubber, rubber
derived from a diene monomer or mixtures thereof, and (2) a
polymeric resin composition consisting essentially of the reaction
product of the polymerization reaction between dicyclopentadiene
and limonene; said resin having a softening point ranging from
about 50 to about 220.degree. C. and a molecular weight ranging
from about 500 to about 42,000.
[0007] The terms "polymeric compound" and "polymer" when used to
describe the resins of the present invention are intended to only
include those molecules which contain a monomeric unit derived from
dicyclopentadiene and limonene and where at least one of the
monomeric units derived from the dicyclopentadiene or limonene is
repeated. Therefore, the compounds formed by the reaction of a
single dicyclopentadiene molecule and a single limonene 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 dicyclopentadiene or limonene 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
dicyclopentadiene or limonene.
[0008] The molar ratio of the dicyclopentadiene to limonene in the
polymerization reaction may vary, depending on the desired
properties of the final polymeric product. For example, the molar
ratio of the dicyclopentadiene to limonene as starting material may
range from about 1:10 to about 10:1. The preferred molar ratio of
dicyclopentadiene to limonene 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 dicyclopentadiene to limonene may range from about
8:1 to 1:8. The preferred molar ratio of dicyclopentadiene to
limonene in the final product ranges from about 1:3 to 3:1 with a
range of from about 2.1:1 to 1:2.1, being particularly
preferred.
[0009] The polymerization reaction between the dicyclopentadiene
may be a thermal (no catalyst) polymerization, or catalyzed, i.e.,
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.2SO.sub.4, HCl, H.sub.3PO.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 factors including the melting
or boiling points of the reactants, desired rate of reaction,
solvent, and pressure and temperature limitation 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
AlCl.sub.3.
[0010] In the catalyzed polymerization process, the amount of
catalyst may range from about 0.1 to about 20 weight percent of
catalyst based on the total weight of reactants to be polymerized.
Preferably, a range of from about 3 to about 5 weight percent of
catalyst is preferred. The optimum concentration of catalyst
depends on the nature of the solvent, if any, which effects the
solubility of the catalyst as well as on the stirring efficiency
inside the polymerization reactor. High catalyst concentration
reduces the resin molecular weight distribution and, therefore,
limits the amount of feed additive required for controlling the
resin molecular weight.
[0011] 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-C.sub.9) hydrocarbon, or a C.sub.6-C.sub.9 aliphatic
halohydrocarbon. Examples of suitable solvents include hexane,
heptane, cyclohexane, benzene, toluene, xylene, and chlorobenzene.
The preferred solvents are hexane and cyclohexane.
[0012] The polymerization reaction may be conducted under a variety
of operating conditions. The reaction pressure may vary and range
from about one atmosphere to about 100 atmospheres with a pressure
of from about two atmospheres to about ten atmospheres being
preferred. The reaction temperature may range from about 0 to
100.degree. C. with a preferred range being from about 30 to
50.degree. C.
[0013] 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 varies from
about 1 to about 8 hours.
[0014] The molecular weight distribution of the polymeric resin of
the present invention may range from about 500 to about 42,000. In
a particularly preferred embodiment of the present invention, the
resin composition comprises a blend of two or more individual
polymeric resins each one of which is the reaction product of a
polymerization reaction between dicyclopentadiene and limonene.
Each individual polymeric resin preferably differs from the other
by having a different molecular weight range. Generally speaking,
all of the polymeric resins will exhibit some lower molecular
weight values, however, not all of the individual resins may
include the higher molecular values. In the alternative, all of the
resins may have distributions that vary by their lower molecular
values with the high molecular weight value relatively being the
same. For example, when the resin blend comprises three individual
polymeric resins, the first resin may have a molecular weight
ranging from about 700 to about 24,000, the second resin may have a
molecular weight ranging from about 700 to about 36,000, and the
third resin may have a molecular weight ranging from about 700 to
about 42,000.
[0015] In accordance to another embodiment of the present
invention, the resin composition may comprise a blend of four
individual resins. In accordance with this embodiment, the first
resin may have a molecular weight ranging from about 500 to about
15,000, the second resin may have a molecular weight ranging from
about 700 to about 15,000, the third resin may have a molecular
weight ranging from about 3,000 to about 15,000, and the fourth
resin may have a molecular weight ranging from about 4,000 to about
15,000.
[0016] The blend may be formed in-situ or mechanically blended.
[0017] The resin composition of the present invention has a
softening point ranging from about 50 to about 220. For the
purposes of the present invention, the term "softening point" is
used to describe the temperature range from when wetting occurs in
a capillary melting point tube to where the resin is completely
liquid. Representative of suitable equipment to determine the
relative softening point is a Thomas-Hoover Melting Point apparatus
equipped with a silicon oil bath. In accordance with the embodiment
of the present invention when the resin composition comprises a
blend of three individual resins, the first resin may have a
softening point ranging from about 134 to about 156.degree. C., the
second resin may have a softening point ranging from about 138 to
about 180.degree. C., and the third resin may have a softening
point ranging from about 188 to about 208.degree. C. In accordance
with the embodiment of the present invention where the blend
comprises four individual resins, the first resin may have a
softening point ranging from about 55 to about 75.degree. C., the
second resin may have a softening point ranging from about 80 to
about 131.degree. C., the third resin may have a softening point
ranging from about 126 to about 168.degree. C., and the fourth
resin may have a softening point range of about 168 to about
195.degree. C.
[0018] Rubber stocks containing natural rubber or rubbers derived
from a diene monomer may be modified with the resin compositions of
the present invention. Examples of rubbers derived from a diene
monomer include substituted and unsubstituted, saturated and
unsaturated, 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) when the monomers
are combined in the random distribution or block form. In addition
to the diene monomers, other monomers may be used. Of all the
monomers that may be used, 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; and 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; and 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.
[0019] The rubber compounds which may be modified by the resins of
the present invention are preferably 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,
butadiene and isoprene, copolymers of styrene and butadiene and
blends thereof.
[0020] The amount of polymeric resins that may be used with the
diene containing polymers may vary and depend on the polymer to be
modified, the particular polymeric resin, the desired degree of
modification and the like. Generally speaking, the polymeric resin
is used in amounts ranging from about 5 to about 50 parts per
hundred (phr) of diene polymer. Preferably, the polymeric resin is
used in amounts of from about 5 to about 25 phr, with a range of
from about 10 to about 25 phr being particularly preferred.
[0021] The polymeric resins 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. Preferably, when the polymeric resins have higher
molecular weights, it is recommended that they be ground to a fine
powder to insure 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 granules
or pellets containing up to 5 percent by weight of a binder. They
can also be formulated as pre-dispersions or masterbatched in a
diene rubber stock, which pre-dispersions may contain, for example,
from 15 to 50 percent by weight of the polymeric resin.
[0022] Similar to vulcanizing conventional rubber stocks, the
rubber stocks containing the polymeric resins need a sulfur
vulcanizing agent. Examples of suitable sulfur vulcanizing agents
include elemental sulfur (free sulfur) or sulfur donating
vulcanizing agents, for example, an amine disulfide, polymeric
polysulfide or sulfur olefin adducts. Preferably, the sulfur
vulcanizing agent is elemental sulfur. The amount of sulfur
vulcanizing agent will vary depending on the components of the
rubber stock and the particular type of sulfur vulcanizing agent
that is used. Generally speaking, the amount of sulfur vulcanizing
agent ranges from about 0.1 to about 8 phr with a range of from
about 1.5 to about 6 being preferred.
[0023] Conventional rubber additives may be incorporated in the
rubber stock of the present invention. The presence of a sulfur
vulcanizing agent and conventional additives are not considered to
be an aspect of this invention. The additives commonly used in
rubber stocks include fillers, plasticizers, curatives, processing
oils, retarders, antiozonants, antioxidants and the like. The total
amount of filler that may be used may range from about 45 to about
130 phr being preferred. Fillers include silicas, clays, calcium
carbonate, calcium silicate, titanium dioxide and carbon black.
Preferably, at least a portion of the filler is carbon black.
Plasticizers, oils or mixtures thereof are conventionally used in
amounts ranging from about 2 to about 150 phr with a range of about
5 to about 130 phr being preferred. The amount of plasticizer used
will depend upon the softening effect desired. Examples of suitable
plasticizers include aromatic extract oils, petroleum softeners
including asphaltenes, saturated and unsaturated hydrocarbons and
nitrogen bases, coal tar products, cumarone-indene resins and
esters such as dibutylphthalate and tricresyl phosphate. Examples
of oils are commonly known as highly aromatic process oil, process
soybean oil and highly paraffinic process oil. Materials used in
compounding which function as an accelerator-activator includes
metal oxides such as zinc oxide, magnesium oxide and litharge which
are used in conjunction with acidic materials such as fatty acid,
for example, stearic acid, oleic acid, murastic acid, and the like.
The amount of the metal oxide may range from about 1 to about 10
phr with a range of from about 2 to about 8 phr being preferred.
The amount of fatty acid which may be used may range from about
0.25 phr to about 5.0 phr with a range of from about 0.5 phr to
about 2 phr being preferred.
[0024] Accelerators may be used to control the time and/or
temperature required for vulcanization of the rubber stock. As
known to those skilled in the art, a single accelerator may be used
which is present in amounts ranging from about 0.2 to about 3.0
phr. In the alternative, combinations of two or more accelerators
may be used which consist of a primary accelerator which is
generally used in a larger amount (0.3 to about 3.0 phr), and a
secondary accelerator which is generally used in smaller amounts
(0.05 to about 1.50 phr) in order to activate and improve the
properties of the rubber stock. Combinations of these accelerators
have been known to produce synergistic effects on the final
properties and are somewhat better than those produced by use of
either accelerator alone. Delayed action accelerators also are
known to be used which are not affected by normal processing
temperatures and produce satisfactory cures at ordinary
vulcanization temperatures. Suitable types of accelerators include
amines, disulfides, guanidines, thioureas, thiazoles, thiurams,
sulfenamides, dithiocarbamates and the xanthates. Examples of
specific compounds which are suitable include zinc
diethyl-dithiocarbamate, 4,4'-dithiodimorpholine,
N,N-di-methyl-S-tert-butylsulfenyldithiocarbamat- e,
tetramethylthiuram disulfide, 2,2'-dibenzothiazyl disulfide,
butyraldehydeaniline mercaptobenzothiazole,
N-oxydiethylene-2-benzothiazo- lesulfenamide. Preferably, the
accelerator is a sulfenamide.
[0025] A class of compounding materials known as scorch retarders
are commonly used. Phthalic anhydride, salicyclic acid, sodium
acetate and N-cyclohexyl thiophthalimide are known retarders.
Retarders are generally used in an amount ranging from about 0.1 to
0.5 phr.
[0026] Preformed phenol-formaldehyde type resins may be used in the
rubber stock and are generally present in an amount ranging from
about 1.0 to about 5.0 phr, with a range of from about 1.5 to about
3.5 phr being preferred.
[0027] Conventionally, antioxidants and some times antiozonants,
hereinafter referred to as antidegradants, are added to rubber
stocks. Representative antidegradants include monophenols,
bisphenols, thiobisphenols, polyphenols, hydroquinone derivatives,
phosphites, thioesters, naphthyl amines,
diphenyl-p-phenylenediamines, diphenylamines and other diaryl amine
derivatives, para-phenylenediamines, quinolines and mixtures
thereof. Specific examples of such antidegradants are disclosed in
The Vanderbilt Rubber Handbook (1990), pages 282-286.
Antidegradants are generally used in amounts from about 0.25 to
about 5.0 phr with a range of from about 1.0 to about 3.0 phr being
preferred.
[0028] The mixing of the rubber composition can be accomplished by
methods known to those having skill in the rubber mixing art. For
example, the ingredients are typically mixed in at least two
stages; namely, at least one non-productive stage followed by a
productive mix stage. The final curatives including sulfur
vulcanizing agents are typically mixed in the final stage which is
conventionally called the "productive" mix stage in which the
mixing typically occurs at a temperature, or ultimate temperature,
lower than the mix temperature(s) than the preceding non-productive
mix stage(s). The rubber and polymeric resin are mixed in one or
more non-productive mix stages. The terms "non-productive" and
"productive" mix stages are well known to those having skill in the
rubber mixing art.
[0029] Vulcanization of the pneumatic tire of the present invention
is generally carried out at conventional temperatures ranging from
about 100.degree. C. to 200.degree. C. Preferably, the
vulcanization is conducted at temperatures ranging from about
110.degree. C. to 180.degree. C. Any of the usual vulcanization
processes may be used such as heating in a press or mold, heating
with superheated steam or hot air or in a salt bath.
[0030] The following examples are presented in order to illustrate
but not limit the present invention.
[0031] Cure properties were determined using a Monsanto oscillating
disc rheometer which was operated at a temperature of 150.degree.
C. and at a frequency of 11 hertz. A description of oscillating
disc rheometers can be found in the Vanderbilt Rubber Handbook
edited by Robert O. Ohm (Norwalk, Conn., R. T. Vanderbilt Company,
Inc., 1990), pages 554-557. The use of this cure meter and
standardized values read from the curve are specified in ASTM
D-2084. A typical cure curve obtained on an oscillating disc
rheometer is shown on page 555 of the 1990 edition of the
Vanderbilt Rubber Handbook.
[0032] In such an oscillating disc rheometer, compounded rubber
samples are subjected to an oscillating shearing action of constant
amplitude. The torque of the oscillating disc embedded in the stock
that is being tested that is required to oscillate the rotor at the
vulcanization temperature is measured. The values obtained using
this cure test are very significant since changes in the rubber or
the compounding recipe are very readily detected. It is obvious
that it is normally advantageous to have a fast cure rate.
[0033] In the following examples, the Flexsys Rubber Process
Analyzer (RPA) 2000 was used to determine dynamic mechanical
rheological properties. The curing conditions were 160.degree. C.,
1.667 Hz, 15.8 minutes and 0.7 percent strain. A description of the
RPA 2000, its capability, sample preparation, tests and subtests
can be found in these references. H A Pawlowski and J S Dick,
Rubber World, June 1992; J S Dick and H A Pawlowski, Rubber World,
January 1997; and J S Dick and J A Pawlowski, Rubber & Plastics
News, Apr. 26 and May 10, 1993.
[0034] The compounded rubber sample is placed on the bottom die.
When the dies are brought together, the sample is in a pressurized
cavity where it will be subjected to a sinusoidal oscillating
shearing action of the bottom die. A torque transducer connected to
the upper die measures the amount of torque transmitted through the
sample as a result of the oscillations. Torque is translated into
the shear modulus, G, by correcting for the die form factor and the
strain. The RPA 2000 is capable of testing uncured or cured rubber
with a high degree of repeatability and reproducibility. The tests
and subtests available include frequency sweeps at constant
temperature and strain, curing at constant temperature and
frequency, strain sweeps at constant temperature and frequency and
temperature sweeps at constant strain and frequency. The accuracy
and precision of the instrument allows reproducible detection of
changes in the compounded sample.
[0035] The values reported for the storage modulus, (G'), loss
compliance (J") and tan delta are obtained from a strain sweep at
100.degree. C. and 1 Hz following the cure test. These properties
represent the viscoelastic response of a test sample to shear
deformation at a constant temperature and frequency.
[0036] The following examples are presented for the purposes of
illustrating and not limiting the present invention. All parts are
parts by weight unless specifically identified otherwise.
EXAMPLE 1
[0037] A one liter stainless steel autoclave was charged with 170
grams of washed and dried dicyclopentadiene, 80 grams of washed and
dried (+)-limonene and 100 milliliters of xylenes. The reactor was
flushed with nitrogen, sealed and heated to 270.degree. C. with
stirring. The reactor pressure peaked at 185 psig at 270.degree. C.
The reactor pressure began to drop as the temperature was
maintained at 270.degree. C. Within about 15 minutes, the pressure
dropped 20 to 30 psig. After one hour of residence time, the
reactor was cooled. The contents were transferred to a flask and
heated to about 170.degree. C., and the pressure on the surface of
the contents was reduced to about 25 inches of mercury vacuum. The
stripped resin was poured from the flask as molten material at
about 150.degree. C. A softening point from 55-75.degree. C. was
determined. The molecular weight range was determined to be 500 to
15,000.
EXAMPLE 2
[0038] The procedures of Example 1 were repeated except the
residence time at 270.degree. C. was two hours, instead of one
hour. The softening point for this polymeric resin ranged from
about 80 to 131.degree. C. The molecular weight range was
determined to be 700 to 15,000.
EXAMPLE 3
[0039] The procedures of Example 1 were repeated, except the
residence time at 270.degree. C. was 4 hours, and the polymeric
resin product had a softening point ranging from about 126.degree.
C. to 168.degree. C. The molecular weight range was determined to
be 3,000 to 15,000.
EXAMPLE 4
[0040] The procedures of Example 1 were repeated except the
residence time of 270.degree. C. was for 6 hours instead of one
hour, and the softening point for the resin ranged from about
168.degree. C. to 195.degree. C. The molecular weight range was
determined to be 4,000 to 15,000.
EXAMPLE 5
[0041] The dicyclopentadiene/limonene resin from Examples 1-4, were
combined by mixing 150 grams of each polymeric resin into a 2-liter
stainless steel beaker. A hot plate was used to melt the polymeric
resins and stirring gave a homogeneous mixture. The blend was
cooled to room temperature, and chipped into small granular pieces,
which exhibited an overall softening range of from about 78 to
173.degree. C. The product was an amber-color solid.
EXAMPLE 6
[0042] A three liter round bottom flask was fitted with a
mechanical stirrer, a constant temperature water bath, a
thermocouple and a dropping funnel. The flask was swept with
nitrogen and charged with 200 milliliters of cyclohexane containing
10 grams of anhydrous aluminum chloride. Stirring was started and
the water bath raised the temperature of the aluminum
chloride/cyclohexane suspension to 30.degree. C. The dropping
funnel was charged with a 170 grams of dicyclopentadiene that had
been washed with 6 percent aqueous sodium hydroxide inhibitor, but
not dried after a second washing with water, 80 grams of
(+)-limonene of technical grade from Eastman Kodak and 100
milliliters of cyclohexane. The feed stream was added as quickly as
possible with the reaction temperature maintained at
32.+-.2.degree. C. After about 25 minutes, all of the feed had been
added and the reaction temperature of 32.+-.2.degree. C. was
maintained for three hours with stirring. A solution of 200
milliliters of isopropanol and 600 milliliters of water was added
to the reaction mixture as the heat was removed. The
aqueous-organic mixture was stirred vigorously until all of the
catalyst had been hydrolyzed. The organic layer which contains a
suspended solid was separated and washed with two portions of 200
milliliters of water. The organic layer which contained the
suspended solid was dried in a drying oven at 150.degree. C. and 28
inches of mercury vacuum. The product softens or shows wetting in a
capillary melting point tube at 188 to about 208.degree. C. with a
molecular weight range of 700 to 40,000.
EXAMPLE 7
[0043] The reaction conditions and procedures of Example 6 were
repeated at 42.+-.2.degree. C. to give a resin that softens or
shows wetting in a capillary melting tube at 138 to 180.degree. C.
with a molecular weight range of 700 to 36,000.
EXAMPLE 8
[0044] Reaction conditions and procedures of Example 6 were
repeated except the reaction was conducted at 52.+-.2.degree. C. to
give a resin that softens or shows wetting in a capillary melting
point tube at 134 to 156.degree. C. with a molecular weight range
of 700 to 24,000.
EXAMPLE 9
[0045] The dicyclopentadiene/limonene resin from Examples 6, 7, and
8 were combined by mixing 75 grams of each polymeric resin into a
2-liter stainless steel beaker. A hot plate was used to liquify the
polymeric resins and stirring gave a homogeneous mixture. The blend
was cooled to room temperature, and chipped into small granular
pieces, which exhibited an overall softening range of from
132.degree. C. to 191.degree. C.
EXAMPLE 10
[0046] Three hundred parts of cyclohexane and 50 parts of anhydrous
aluminum chloride were placed into a reactor. While continuously
stirring the mixture, 600 parts of a hydrocarbon mixture was slowly
added to the reactor over a period of about 60 minutes. The
hydrocarbon mixture consisted of 30 percent inert hydrocarbons with
the remaining 70 percent by weight of the mixture comprising the
following resin forming components:
1 Component Percent Limonene 67.0 Dicyclopentadiene 33.0
[0047] The temperature of the reaction was maintained in a range of
about 250 to 30.degree. C. After an hour of agitation from the time
of final addition, the hydrocarbon mixture was added to
approximately 4,000 parts of a 25 percent solution of isopropyl
alcohol in water to neutralize and decompose the aluminum chloride.
The aqueous layer was removed and the resin solution washed with an
additional 4,000 parts of the alcohol/water blend.
[0048] The resulting resin solution was steam-distilled at a pot
temperature of about 235.degree. C. The resulting residual molten
resin was cooled to room temperature to provide an 85 percent yield
of a hard brittle pale yellow resin having a softening point of
110.degree. C. to 129.degree. C. Small molecule GPC analysis gives
a molecular weight distribution of 6.7 percent in the 9500 MW
range, 69.1 percent in the 1100 MW range, 6.5 percent in the 600 MW
range, 9.0 percent in the 450 MW range and 4.6 percent in the 330
MW range.
EXAMPLE 11
[0049] A rubber stock was prepared which consisted of styrene
butadiene rubber and conventional amounts of carbon black
antioxidant, sulfur and accelerator, fatty acid and zinc oxide. In
addition, each sample contained a highly aromatic processing oil,
highly paraffinic process oil and processed soybean oil. In Samples
1 and 3, the three oils were partially replaced with a polymeric
dicyclopentadiene/limonene resin. In this study, each of the four
polymeric resins prepared in accordance with Examples 1-4 was used
at the 6 and 12 phr level (total resin was 24 and 48 phr) and
compared with the control compounds. The table below provides the
relative amounts of the various oils and resins. In addition, the
properties of each of the resulting rubber stocks were tested nd
are listed in the table. The cured specimens of each rubber stock
were prepared by press curing the sample at 150.degree. C. for 28
minutes under 280 psi pressure with the exception of those
specimens used to test for Strebler, Zwick Rebound, Light Blow Out
and DIN Abrasion. The samples for testing for Strebler, Zwick
Rebound and Light Blow Out were cured for 38 minutes. The specimens
tested for DIN Abrasion were cured for 33 minutes.
2TABLE I Sample 1 2 3 4 Aromatic Processing Oil 22.00 30.00 14.00
30.00 Paraffinic Processing Oil 22.00 30.00 14.00 30.00 Process
Soybean Oil 22.00 30.00 14.00 30.00 Example 1 Resin 6.00 12.00
Example 2 Resin 6.00 12.00 Example 3 Resin 6.00 12.00 Example 4
Resin 6.00 12.00 Productive Tests: Rheometer MDR2000 @ 150.degree.
C. S'Min (dN-m) 2.7 2.4 3.1 2.6 T (1) 5.1 4.7 5.4 5.0 TC25 5.8 5.4
6.3 5.7 TC90 25.5 18.4 32.4 18.1 S'Max (dN-m) 10.0 10.1 10.4 10.5
Delta S' (dN-m) 7.3 7.4 7.2 8.0 S" @ S'MaX 2.7 2.1 3.2 2.4 TanD @
S'Max 0.27 0.21 0.31 0.23 Assigned Cures 28 28 28 28 Stress Strain
300% Modulus (MPa) 3.2 4.4 3.2 4.8 Tensile (MPa) 7.9 10.0 7.2 7.6
Elongation (%) 684 636 706 468 Rebound RT 11.5 12.1 12.7 12.5
100.degree. C. 20.8 29.3 17.3 30.0 Hardness RT 66.3 59.4 74.7 59.7
100.degree. C. 39.1 40.1 44.5 41.3 Strebler Normalized to 0.2" Avg
Force (N) 105 154 106 N/A 110 143 121 N/A Zwick Rebound 65.degree.
C. 15.8 20.0 14.2 17.4 95.degree. C. 19.0 25.0 14.8 23.8
120.degree. C. 22.6 31.0 17.8 30.6 150.degree. C. 28.0 37.8 24.2
36.8 Light Blow Out Temp (F.) 319 310 362 307 Time (Min) 23 27.5 18
15 DIN Abrasion Rating 274 279 282 278 MTS Dynamic Modulus E' (MPa)
5.8 5.4 7.0 6.0 Tan Delta 0.45 0.39 0.48 0.40 Autovibron at
60.degree. C. E' (MPa) 20.8 16.5 40.9 15.1 E" (MPa) 4.2 2.9 6.1 2.5
Tangent Delta 0.19 0.18 0.15 0.17 Autovibron at 100.degree. C. E'
(MPa) 11.8 9.6 17.5 9.0 E" (MPa) 3.2 1.6 3.5 1.4 Tangent Delta 0.19
0.17 0.20 0.16 Autovibron at 150.degree. C. E' (MPa) 10.4 8.0 14.1
7.5 E" (MPa) 1.8 1.1 2.7 .9 Tangent Delta 0.17 0.13 0.19 0.13
[0050] As one can see from the above data, the effect of using the
dicyclopentadiene/limonene resins in place of the aromatic
processing oil, paraffinic processing oil and processed soybean oil
was to increase the hysteresis (rebound, E", tangent delta) and low
strain stiffness (E', hardness) while reducing the cure state (300
percent modulus), cure rate (T25, T90) and tear (Strebler). The
dicyclopentadiene/limonene resins gave better storage modulus, loss
modulus and tangent delta throughout the temperature range of
60.degree. C. to 150.degree. C. It is this response with
temperature that provides enhanced traction and handling.
EXAMPLE 12
[0051] In this example, various resins were evaluated in a rubber
compound.
[0052] Rubber compositions containing the materials set out in
Tables 2 and 3 were prepared in a BR Banbury.TM. mixer using two
separate stages of addition (mixing); namely, one non-productive
mix stage and one productive mix stage. The non-productive stage
was mixed for 3.5 minutes or to a rubber temperature of 160.degree.
C., whichever occurred first. The mixing time for the productive
stage was to a rubber temperature of 120.degree. C.
[0053] The rubber compositions are identified herein as Samples
1-3. Samples 1 and 2 are considered herein as controls without the
use of the resin used in the present invention being added to the
rubber composition. Samples 1 and 2 each contain commercially
available resins. Sample 3 is the resin prepared in Example 10.
[0054] The samples were cured at about 150.degree. C. for about 28
minutes.
[0055] Table 3 illustrates the behavior and physical properties of
the cured Samples 1-3.
[0056] Lab data reveals that the new DCPD/Limonene resin in fact
enhances the traction and durability properties simultaneously
without following the typical tradeoff as previously described.
Comparing the dynamic properties from the RPA 2000 and
stress-strain data (UTS) of the Coumarone-Indene and phenolic
resins, the typical tradeoff of sacrificing durability (lower G' at
40 percent strain, 300 percent modulus and tensile strength) for
improved dry traction (increased tan delta and loss compliance at
40 percent strain) is demonstrated. Control A (phenolic resin) is a
soft compound with high hysteresis. Control B (Coumarone-Indene
resin) is a stiff compound with low hysteresis.
[0057] The DCPD/Limonene resin versus the Control A shows that the
durability is significantly improved (G' at 40 percent strain, 300
percent modulus and tensile strength) and dry traction is
maintained (tan delta and J" at 40 percent). Control B represents a
typical effort to increase the durability of Control A through the
use of resins. The DCPD/Limonene resin versus the Control B shows
that the durability is only slightly reduced (G' at 40 percent
strain, 300 percent modulus and tensile strength) and the dry
traction is significantly improved (tan delta and J" at 40
percent).
3 TABLE 2 Ctrl Ctrl Samples 1 2 3 Non-Productive Emulsion SBR.sup.1
100 100 100 Carbon Black.sup.2 80.0 80.0 80.0 Aromatic Oil 37.5
37.5 37.5 Stearic Acid 2.0 2.0 2.0 Microcrystalline Wax 2.0 2.0 2.0
Zinc Oxide 3.0 3.0 3.0 Antioxidant.sup.3 1.0 1.0 1.0 Phenolic
Resin.sup.4 25.0 0 0 Coumarone Indene.sup.5 Resin 0 25.0 0 Resin of
Example 10 0 0 25.0 Productive Accelerators.sup.6 3.5 3.5 3.5
Accelerator.sup.7 0.25 0.25 0.25 Sulfur 0.95 0.95 0.95
[0058] .sup.1Emulsion SBR containing 40 percent styrene a Tg of
35.degree. C. and a base Mooney of 110 when oil extended (37.5 phr
oil) the Mooney was 48. The solution SBR was obtained from The
Goodyear Tire & Rubber Company. .sup.2I.sub.2122 and DBP=114
.sup.3Polymerized 1,2-dihydro-2,2,4-trimethylquinoline
.sup.4Unreactive phenol-formaldehyde resin having a melting point
of 106-114.degree. C. (Ring and Ball) which is commercially
available from Schenectady Chemical under the designation CRJ-418.
.sup.5Coumarone Indene Resin having a softening point of
100.degree. C. which is commercially available from Neville
Chemical under the designature Cumar.TM. R-13. .sup.6N-cyclohexyl
benzothiazole-2-sulfenamide .sup.7Tetramethyl thiuram disulfide
4 TABLE 3 Sample 1 2 3 Phenolic resin 25.0 0 0 Coumarone Indene
Resin 0 25.0 0 Resin of Example 10 0 0 25.0 RPA 2000, 15.8 min,
160.degree. C., 17% strain, 1.67 Hz T25 (min) 1.89 2.98 1.92 T90
(min) 9.3 9.7 9.7 Min Torque (dNm) 0.49 0.59 0.66 Max Torque (dNm)
1.76 2.28 2.28 Delta Torque (dNm) 1.27 1.69 1.62 RPA 2000, 1 Hz,
100.degree. C. G' 40% (KPa) 376 476 449 Tan Delta 40% 0.254 0.224
0.277 J" 40% 1/MPa 0.63 0.45 0.57 UTS, cure 28 minutes @
150.degree. C. 300% Modulus, MPa 3.5 4.1 3.6 Tensile Strength, MPa
13.2 15.8 14.7 Elongation, % 719 718 740 Zwick Rebound, 95.degree.
C. 29.8 35.6 29.8 Rebound 120.degree. C. 35.8 40.6 34
* * * * *