U.S. patent application number 12/216531 was filed with the patent office on 2008-11-06 for rubber compound for tire tread and method for the preparation thereof.
This patent application is currently assigned to MICHELIN RECHERCHE ET TECHNIQUE S.A.. Invention is credited to Jean-Luc Cabioch, Laurent Coissieux, Jean-Michel Favrot, Franck Varagniat.
Application Number | 20080275160 12/216531 |
Document ID | / |
Family ID | 32749534 |
Filed Date | 2008-11-06 |
United States Patent
Application |
20080275160 |
Kind Code |
A1 |
Cabioch; Jean-Luc ; et
al. |
November 6, 2008 |
Rubber compound for tire tread and method for the preparation
thereof
Abstract
A crosslinkable or crosslinked rubber composition is described
which includes a diene elastomer having a mass content of cyclic
vinyl units of greater than 15%, and which may be used to form a
tire tread. Also described is a tire tread and a tire incorporating
the tread. The composition contains a linear or branched diene
elastomer derived from at least one conjugated diene, and a
reinforcing filler. The elastomer has cyclic vinyl units according
to a mass content of greater than or equal to 15% and a
number-average molecular weight of from 30,000 to 350,000 g/mol.
The elastomer may be obtained by anionic polymerization of one or
more monomers including a conjugated diene in an inert hydrocarbon
solvent with a catalytic system including an organolithium
initiator and a polar agent with several heteroatoms. The reaction
may be performed batchwise where the polar agent:initiator molar
ratio is greater than 8, or continuously where the polar
agent:initiator molar ratio is greater than or equal to 3.
Inventors: |
Cabioch; Jean-Luc;
(Chateaugay, FR) ; Coissieux; Laurent;
(Clermont-Ferrand, FR) ; Favrot; Jean-Michel;
(Cournon d'Auvergne, FR) ; Varagniat; Franck;
(Ceyrat, FR) |
Correspondence
Address: |
BUCHANAN, INGERSOLL & ROONEY PC
POST OFFICE BOX 1404
ALEXANDRIA
VA
22313-1404
US
|
Assignee: |
MICHELIN RECHERCHE ET TECHNIQUE
S.A.
Granges-Paccot
CH
|
Family ID: |
32749534 |
Appl. No.: |
12/216531 |
Filed: |
July 7, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11183912 |
Jul 19, 2005 |
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12216531 |
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PCT/EP04/00280 |
Jan 16, 2004 |
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11183912 |
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Current U.S.
Class: |
523/150 |
Current CPC
Class: |
C08K 3/36 20130101; C08K
3/36 20130101; C08F 297/044 20130101; C08C 19/44 20130101; C08F
36/04 20130101; C08F 36/04 20130101; C08F 4/48 20130101; B60C
1/0016 20130101; C08L 15/00 20130101 |
Class at
Publication: |
523/150 |
International
Class: |
C08J 5/14 20060101
C08J005/14 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 20, 2003 |
FR |
03/00743 |
Claims
1. A crosslinkable or crosslinked rubber composition comprising a
linear or branched diene elastomer resulting from at least one
conjugated diene, and a reinforcing filler, wherein said elastomer
comprises cyclic vinyl units according to a mass content of greater
than or equal to 15% and having a number-average molecular weight
ranging from 30,000 to 350,000 g/mol.
2. The crosslinkable or crosslinked rubber composition according to
claim 1, wherein said number-average molecular weight falls within
a range of from 60,000 to 350,000 g/mol.
3. The crosslinkable or crosslinked rubber composition according to
claim 2, wherein said number-average molecular weight falls within
a range of from 100,000 to 300,000 g/mol.
4. The crosslinkable or crosslinked rubber composition according to
claim 1, wherein said mass content of cyclic vinyl units is greater
than or equal to 20%.
5. The crosslinkable or crosslinked rubber composition according to
claim 1, wherein said elastomer comprises a mass fraction of units
resulting from conjugated dienes of greater than 30%.
6. The crosslinkable or crosslinked rubber composition according to
claim 5, wherein said elastomer is a 1,3-butadiene homopolymer or a
copolymer of 1,3-butadiene and a vinyl aromatic comonomer.
7. The crosslinkable or crosslinked rubber composition according to
claim 1, wherein said elastomer is present in a quantity of greater
than or equal to 50 parts by weight per hundred parts of
elastomer(s).
8. The crosslinkable or crosslinked rubber composition according to
claim 7, wherein said elastomer is present in a quantity equal to
100 phr.
9. The crosslinkable or crosslinked rubber composition according to
claim 1, wherein said reinforcing filler comprises an inorganic
reinforcing filler.
10. The crosslinkable or crosslinked rubber composition according
to claim 9, wherein the mass fraction of said inorganic reinforcing
filler is greater than or equal to 50%.
11. The crosslinkable or crosslinked rubber composition according
to claim 10, wherein the mass fraction of said inorganic
reinforcing filler is equal to 100%.
12. The crosslinkable or crosslinked rubber composition according
to claim 9, wherein the inorganic reinforcing filler is silica.
13. The crosslinkable or crosslinked rubber composition according
to claim 1, wherein said elastomer is branched by means of a
starring agent.
14. The crosslinkable or crosslinked rubber composition according
to claim 13, where the starring agent is tris
(2,4-di-tert-butylphenyl) phosphate.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a division of pending application
Ser. No. 11/183,912 filed Jul. 19, 2005, which is a continuation of
PCT Application No. PCT/EP2004/000280, filed Jan. 16, 2004,
published in French on Aug. 5, 2004 as WO 2004/065478, which claims
priority of French Application No. 03/00743, filed Jan. 20, 2003,
the contents of these applications being incorporated herein by
reference in their entirety.
BACKGROUND
[0002] 1. Field of the Invention
[0003] The present invention relates to a crosslinkable or
crosslinked rubber composition which comprises a diene elastomer
having a mass content of cyclic vinyl units of greater than 15%,
and which may be used to form a tire tread. The invention also
relates to such a tread and to such a tire incorporating said
tread.
[0004] 2. Description of Related Art
[0005] A conjugated diene monomer, such as butadiene, may be
incorporated into a polymer obtained anionically in the form
cis-1,4, trans-1,4 or -1,2 (vinyl linkages).
[0006] Anionic polymerization reactions are conventionally
initiated by an organolithium compound in the presence of a
hydrocarbon solvent and one or more conjugated diene monomers. The
elastomers produced by these reactions have a low average mass
content of vinyl linkages, generally being between 8% and 15%. In
order to obtain elastomers having a given glass transition
temperature (Tg), it is known to add to the polymerization medium a
polar agent, which also has the effect of significantly increasing
the average content of these linkages. This content may then reach
90%, for example.
[0007] U.S. patent specifications U.S. Pat. No. 5,620,939, U.S.
Pat. No. 5,906,956 and U.S. Pat. No. 6,140,434 disclose anionic
polymerization processes which are performed batchwise, are
intended to increase the content of vinyl linkages in a diene
elastomer which may be a polybutadiene, a styrene-butadiene
copolymer or a polyisoprene. Furthermore, these documents indicate
that the diene elastomers so obtained are usable in rubber
compositions for tire treads, whether associated with carbon black
or with silica. These batch polymerization processes are carried
out at a temperature of between 30 and 100.degree. C. and they in
particular involve the use of catalytic systems comprising: [0008]
a polar agent comprising one or more heteroatoms, such as
tetrahydrofuran (THF) or tetramethylethylenediamine (TMEDA), [0009]
an organolithium initiator, such as n-butyllithium, and [0010] an
alkali metal salt of an aliphatic or alicyclic alcohol, such as
sodium tert.-amylate or sodium mentholate.
[0011] More precisely, in its Examples, document U.S. Pat. No.
5,620,939 discloses molar ratios of [(salt:initiator), (salt:polar
agent), (polar agent:initiator)] which are equal to [1; 0.33; 3],
[2; 0.66; 3], [3; 1; 3], [0.5; 0.17; 3], [1; 0.5; 2] and [1; 0.2;
5].
[0012] In its Examples, document U.S. Pat. No. 5,906,956 discloses
the following values for said molar ratios: [2; 1; 2], [0.5; 1;
0.5], [0.25; 0.08; 3], [0.5; 0.17; 3], [1; 0.33; 3], [1; 0.66; 3],
[3; 1; 3], [0.5; 0.17; 3], [1; 0.5; 2] and [1; 0.2; 5].
[0013] In its Examples, document U.S. Pat. No. 6,140,434 discloses
the following values for said molar ratios: [0.25; 0.03; 8], [0.25;
0.05; 5], [0.25; 0.08; 3], [0.25; 0.25; 1], [0.25; 0.5; 0.5],
[0.15; 0.05; 3], [0.5; 0.17 ; 3], [1; 0.33; 3] and [0.25; 0.13;
2].
[0014] Independently of raising the content of vinyl linkages in
these elastomers, the attempt has in the past been made to form
cyclic structures of the vinylcyclopentane type in diene elastomers
obtained anionically. [0015] One solution for forming these cyclic
structures involves performing post-polymerization reactions, for
example by treating the elastomers with Lewis acids. [0016] Another
solution may involve forming these cyclic structures directly
during anionic polymerization by performing said polymerization
continuously with a low monomer concentration in the reaction
medium and using a specific catalytic system.
[0017] In its examples of embodiment, US patent specification U.S.
Pat. No. 3,966,691 describes a process for cyclizing butadiene in
the polymerization medium, which involves using a catalytic system
comprising an initiator consisting of n-butylsodium and an
activator consisting of tetramethylethylenediamine (TMEDA). A
lithium alkoxide is optionally added to the polymerization medium
to accelerate polymerization.
[0018] Polymerization is performed continuously at a temperature of
between -20.degree. C. and 150.degree. C., and the polybutadienes
obtained have a mass content of cyclic structures of greater than
40%, but a number-average molecular weight of no more than 2,000
g/mol.
[0019] The articles "G. Quack, L. J. Fetters, Macromolecules, Vol
11, no. 2, pp.369-373, (1978)" and "A. R. Luxton, M. E. Burrage, G.
Quack, L. J. Fetters, Polymer, Vol 22, pp.382- 386" also describe
continuous cyclization processes in the polymerization medium,
which involve using catalytic systems comprising an organolithium
initiator, such as n-butyllithium, and a polar agent consisting of
TMEDA (reference may be made to page 383, right hand column of the
last-cited document for a description of the cyclization
mechanism).
[0020] The polymerizations are performed at temperatures of between
30 and 90.degree. C. and the polybutadienes obtained have a mass
content of vinylcyclopentane cycles of at least 18%, but a
number-average molecular weight of no more than 5,000 g/mol.
[0021] One major drawback of these polymerization processes is thus
the very low value of the number-average molecular weight of the
diene elastomers obtained, which means that these elastomers cannot
be used to form the elastomeric matrix of a rubber tire tread
composition.
SUMMARY OF THE INVENTION
[0022] The object of the present invention is to overcome this
drawback, and said object is achieved in that the applicants have
surprisingly discovered that linear or branched diene elastomers
arising from at least one conjugated diene and comprising both
cyclic vinyl units in a mass content of greater than or equal to
15% and a number-average molecular weight of from 30,000 to 350,000
g/mol, may advantageously be used, thanks to their relatively high
molecular weight and their elevated content of cyclic vinyl units,
to form all or part of the elastomeric matrix of a crosslinkable or
crosslinked rubber composition which may be used to form a tire
tread and which in particular furthermore comprises a reinforcing
filler.
[0023] The applicants have in fact just unexpectedly discovered
that tire tread type compositions based on these elastomers with a
high cyclic vinyl unit content have in particular, in the
crosslinked state, hysteresis losses and moduli of elongation which
are entirely of the same order as those exhibited by known tread
compositions based on diene elastomers containing no cyclic vinyl
units, these latter compositions otherwise being identical.
DETAILED DESCRIPTION OF THE INVENTION
[0024] Advantageously, the rubber composition according to the
invention is such that the elastomer with cyclic vinyl units which
it comprises has a number-average molecular weight of from 60,000
to 350,000 g/mol and, even more advantageously, of from 100,000 to
300,000 g/mol.
[0025] According to an advantageous example of embodiment of the
invention, the rubber composition according to the invention is
such that said elastomer has a mass content of cyclic vinyl units
of greater than or equal to 20%.
[0026] The cyclic vinyl units of said elastomer according to the
invention are of the vinylcycloalkane type, and they are of the
following generic formula:
##STR00001##
[0027] The diene elastomer of the composition according to the
invention preferably comprises a mass fraction of units derived
from conjugated dienes which is greater than 30% and may be any
homopolymer or copolymer obtained by polymerization: [0028] of a
conjugated diene monomer having from 4 to 12 carbon atoms or of two
or more of these conjugated diene monomers together, or
alternatively [0029] of one or more of these conjugated diene
monomers with one or more vinyl aromatic compounds each having from
8 to 20 carbon atoms.
[0030] Suitable conjugated diene monomers are, in particular,
1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di-(C1 to --C5
alkyl)-1,3-butadienes such as 2,3-dimethyl-1,3-butadiene,
2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene,
2-methyl-3-isopropyl-1,3-butadiene, an aryl-1,3-butadiene,
1,3-pentadiene and 2,4-hexadiene.
[0031] Suitable vinyl aromatic compounds are, for example, styrene,
ortho-, meta- and para-methylstyrene, the commercial mixture
"vinyltoluene", para-tert.-butylstyrene or divinylbenzene. It will
be noted that styrene is preferably used.
[0032] Preferably, in the process according to the invention,
1,3-butadiene and/or isoprene are used as the conjugated diene
monomer(s), while styrene is used as the vinyl aromatic monomer in
order to obtain copolymers of butadiene/isoprene (BIR),
styrene/butadiene (SBR), styrene/isoprene (SIR) or
butadiene/styrene/isoprene (SBIR).
[0033] Even more preferably, said elastomer consists of a
homopolymer of 1,3-butadiene (BR) or a copolymer of 1,3-butadiene
and a vinyl aromatic comonomer.
[0034] In this latter case, 1,3-butadiene and styrene may be
copolymerized to obtain an SBR having at least 70% by weight of
butadiene and at most 30% by weight of styrene and, preferably, at
least 90% of butadiene and at most 10% of styrene.
[0035] In this preferred case where the elastomer comprising cyclic
vinyl units is a BR or an SBR, it will be noted that this elastomer
may advantageously have a zero or low content of styrene (as is the
case for BR and SBR, respectively), a monomer which is relatively
expensive in comparison with butadiene, so consequently giving rise
to a reduced overall cost for obtaining the composition according
to the invention, while still imparting to said composition
substantially the same properties in the crosslinked stake
(hysteresis losses, moduli and glass transition temperature) as
those imparted by a known SBR with a higher styrene content, thanks
to the high cyclic vinyl unit content in the BR or SBR according to
the invention, which has the effect of offsetting this relative
shortfall in styrene unit content.
[0036] The diene elastomers obtained by the processes according to
the invention may subsequently be branched (i.e. coupled or
starred) or not.
[0037] Very particularly suitable starring agents are
trichloromethylsilane, tetrachloromethylsilane, diphenyl carbonate
or, even more preferably, tris(2,4-di-tert.-butylphenyl) phosphite,
such as is described in US patent specification U.S. Pat. No.
6,384,164 in the name of the Applicants.
[0038] According to a preferred feature of the invention, said
diene elastomer according to the invention is obtained by anionic
polymerization of one or more monomers comprising at least one
conjugated diene monomer, comprising the reaction, in an inert
aliphatic or alicyclic hydrocarbon solvent, of the monomer or
monomers with a catalytic system comprising an organolithium
initiator and a polar agent comprising several heteroatoms, the
reaction being performed:
[0039] (1) either batchwise, the (polar agent:initiator) molar
ratio being in this case greater than 8,
[0040] (2) or continuously, the (polar agent:initiator) molar ratio
being in this case greater than or equal to 3,
[0041] which, in said case (1), makes it possible to prepare a
linear diene elastomer having both a mass content of cyclic vinyl
units of greater than or equal to 15% and a number-average
molecular weight (Mn) ranging from 10,000 g/mol to 60,000 g/mol,
and, [0042] in said case (2), makes it possible to prepare a linear
diene elastomer having both a mass content of cyclic vinyl units of
greater than or equal to 15% and a weight Mn ranging from 10,000
g/mol to 300,000 g/mol, it being possible to achieve Mn values of
greater than or equal to 100,000 on condition that an alkali metal
salt of an aliphatic or alicyclic alcohol is incorporated into said
catalytic system, such that the system simultaneously satisfies the
following three conditions: [0043] (i) the (polar agent:initiator)
molar ratio is greater than or equal to 3. [0044] (ii) the
(salt:initiator) molar ratio falls within a range of from 0.01 to
2, and [0045] (iii) the (salt:polar agent) molar ratio falls within
a range of from 0.001 to 0.5.
[0046] Organolithium initiators usable in this catalytic system
according to the invention which may be mentioned are monolithiated
compounds comprising an aliphatic or alicyclic hydrocarbon group
having from 1 to 10 carbon atoms, such as n-butyllithium
(hereinafter abbreviated to n-BuLi), sec-butyllithium,
tert.-butyllithium, n-propyllithium, amyllithium, cyclohexyllithium
or phenylethyllithium.
[0047] The quantity of initiator which is used to form the
catalytic system is preferably between 0.002 and 0.01 mol per kg of
monomer(s).
[0048] Polar agents comprising two or more heteroatoms (atoms of
oxygen or nitrogen) usable in this catalytic system according to
the invention which may be mentioned are "multidentate" polar
agents, such as diethers and diamines, for example
tetramethylethylenediamine (TMEDA), dimethoxyethane (DME),
diethylcarbitol (DEC), triethylene glycol dimethyl ether (or
"triglyme"), tetraethylene glycol dimethyl ether (or "tetraglyme"),
or dipiperidinoethane.
[0049] This polar agent is used to form the catalytic system
according to the invention in a content of between 300 and 30000
parts per million parts by weight of reaction medium (ppm) and,
preferably, at a content of between 500 and 3000 ppm.
[0050] It will be noted that polar agents comprising a single
heteroatom ("monodentate" agents), such as monoamines and
monoethers, for example tetrahydrofuran (THF), are not suitable for
carrying out the processes according to the invention since they do
not allow the above-stated mass content of cyclic vinyl units in
the diene elastomer to be obtained.
[0051] It will be noted that, unlike processes performed by means
of known catalytic systems, the above-stated processes (1) or (2)
according to the invention (batch or continuous) make it possible
to obtain linear diene elastomers having molecular weights Mn of
greater than 10,000 g/mol.
[0052] It will be noted that said process (2), which comprises
anionic polymerization in a stirred continuous reactor of at least
one conjugated diene monomer by the reaction, in an inert aliphatic
or alicyclic hydrocarbon solvent, of the monomer or monomers with a
catalytic system comprising said organolithium initiator and said
polar agent comprising two or more heteroatoms, such that said
relationship (i) is met, advantageously makes it possible to obtain
linear elastomers with weights Mn of greater than or equal to
60,000 g/mol, or even of greater than or equal to 100,000 g/mol in
the event that said salt is incorporated into the catalytic system,
such that said system additionally satisfies the above-stated
conditions (ii) and (iii).
[0053] This continuous process (2) according to the invention
including the use of said salt is a preferred embodiment of the
present invention, because it makes it possible to obtain diene
elastomers having both very high molecular weights relative to the
known prior art and a mass content of cyclic vinyl units of greater
than or equal to 20%.
[0054] It will also be noted that the processes (1) and (2)
according to the invention advantageously make it possible to
control the molecular weight distribution of the diene elastomers
obtained, which have a relatively low polydispersity index Ip (less
than 3).
[0055] In relation to said batch process (1) according to the
invention, which is characterized by a (polar agent:initiator)
molar ratio value of greater than 8, this ratio is advantageously
greater than or equal to 10 and, even more advantageously, greater
than or equal to 15. It may, for example, be decided to restrict
the value of this molar ratio to 100.
[0056] In relation to said continuous process (2) according to the
invention, which is characterized by said condition (i) and
optionally said conditions (ii) and (iii), the (polar
agent:initiator) molar ratio is advantageously greater than or
equal to 5 and, even more advantageously, this molar ratio is
greater than or equal to 10. It may, for example, be decided to
restrict the value of this molar ratio to 100.
[0057] Still more advantageously, in order to obtain linear diene
elastomers of molecular weights Mn specifically greater than or
equal to 100,000 g/mol by said continuous process (2), the
catalytic systems according to the invention are such that the
(polar agent:initiator) molar ratio is greater than or equal to 15,
which represents very large quantities of polar agent in these
catalytic systems relative to the quantities used in known
catalytic systems. It may, for example, be decided to select a
value of 15 to 40 for this molar ratio.
[0058] Alkali metal salts of an aliphatic or alicyclic alcohol
usable in these processes which are preferably used are those, the
alcohol of which comprises from 3 to 12 carbon atoms and, even more
preferably, from 3 to 8 carbon atoms.
[0059] Advantageously, a sodium or potassium salt of an aliphatic
alcohol is used, such as sodium tert.-butylate, sodium
tert.-amylate or sodium isopentylate, or alternatively a sodium or
potassium salt of an alicyclic alcohol, such as a dialkylated
sodium cyclohexanolate, for example sodium mentholate.
[0060] According to one preferred feature of the invention, the
catalytic system used in said continuous process (2) including said
salt (characterized by said conditions (i), (ii) and (iii)) is such
that the (salt:polar agent) molar ratio falls within a range of
from 0.001 to 0.1.
[0061] According to another preferred feature of the invention, the
catalytic system used in this continuous process (2) is such that
the (salt:initiator) molar ratio falls within a range of from 0.01
to 0.6. According to a first example of embodiment of this
preferred feature, this ratio falls within a range of from 0.01 to
0.2 and, according to a second example of embodiment, this ratio
falls within a range of from 0.3 to 0.6.
[0062] This range of from 0.01 to 0.2 for the (salt:initiator)
molar ratio is particularly suitable for obtaining, by the
continuous process (2) according to the invention, linear
elastomers of a molecular weight Mn of greater than or equal to
100,000 g/mol and having a mass content of cyclic vinyl units which
is greater than or equal to 15%, advantageously greater than or
equal to 20%.
[0063] The range of from 0.3 to 2 and, preferably, of from 0.3 to
0.6, for this (salt:initiator) molar ratio is particularly suitable
for obtaining, by the continuous process (2) according to the
invention, linear elastomers of a molecular weight Mn of less than
or equal to 30,000 g/mol and having a mass content of cyclic vinyl
units which is greater than or equal to 35%, advantageously greater
than or equal to 40%.
[0064] Generally, it will furthermore be noted that the mass
content of vinyl units in the diene elastomers obtained by the
processes according to the invention is between 40% and 65%.
[0065] Inert hydrocarbon solvents usable in the processes according
to the invention which may be mentioned are aliphatic or alicyclic
solvents such as pentane, hexane, the commercial mixture of
hexane/methylcyclohexane, heptane, methylcyclohexane or
cyclohexane.
[0066] It will be noted that aromatic solvents, such as toluene,
are not usable.
[0067] Of course, the compositions of the invention may contain a
single diene elastomer comprising cyclic vinyl units such as that
stated above or a mixture of several of these diene elastomers.
[0068] This or these diene elastomer(s) comprising a mass content
of cyclic vinyl units greater than 15% may be used alone in the
composition according to the invention, or be used in a blend with
any other elastomer conventionally used in tires, such as natural
rubber or a blend based on natural rubber and a synthetic
elastomer, or alternatively another diene elastomer which is
optionally coupled and/or starred or alternatively partially or
entirely functionalised.
[0069] It will be noted that the improvement in the properties of
the rubber composition according to the invention will be all the
greater, the lower is the proportion of said conventional
elastomer(s) in the composition according to the invention.
[0070] Advantageously, the composition according to the invention
comprises said elastomer with cyclic vinyl units in a quantity of
greater than or equal to 50 phr (phr: parts by weight per hundred
parts of elastomer(s)) and, even more advantageously, in a quantity
of greater than or equal to 70 phr (this or these conventional
elastomer(s) then being present in the composition according to the
invention in a quantity of less than or equal to 50 phr or
alternatively of less than or equal to 30 phr, respectively).
[0071] According to a preferred embodiment of the invention, said
composition comprises said elastomer with cyclic vinyl units in a
quantity equal to 100 phr.
[0072] As indicated previously, the composition according to the
invention also comprises a reinforcing filler in a quantity which
may vary from 50 to 150 phr.
[0073] According to a first example of embodiment of the invention,
said reinforcing filler comprises an inorganic reinforcing filler
in a mass fraction preferably ranging from 50% to 100%.
[0074] In the present application, "inorganic reinforcing filler"
is understood to mean in known manner an inorganic or mineral
filler, whatever its colour and its origin (natural or synthetic),
also referred to as "white" filler or sometimes "clear" filler in
contrast to carbon black, this inorganic filler being capable, on
its own, without any means other than an intermediate coupling
agent, of reinforcing a rubber composition intended for the
manufacture of tires, in other words which is capable of replacing
a conventional tire-grade carbon black filler in its reinforcement
function.
[0075] Advantageously, the entirety or at the very least a majority
proportion of said inorganic reinforcing filler is silica
(SiO.sub.2). The silica used may be any reinforcing silica known to
the person skilled in the art, in particular any precipitated or
pyrogenic silica having a BET surface area and a CTAB specific
surface area both of which are less than 450 m.sup.2/g, even if
highly dispersible precipitated silicas are preferred.
[0076] Preferably, a silica is used which has BET or CTAB specific
surface areas which both range from 80 m.sup.2/g to 260
m.sup.2/g.
[0077] In the present specification, the BET specific surface area
is determined in known manner, in accordance with the method of
Brunauer, Emmett and Teller described in "The Journal of the
American Chemical Society", vol. 60, page 309, February 1938, and
corresponding to Standard AFNOR-NFT-45007 (November 1987); the CTAB
specific surface area is the external surface area determined in
accordance with the same Standard AFNOR-NFT-45007 of November
1987.
[0078] "Highly dispersible silica" is understood to mean any silica
having a very substantial ability to disagglomerate and to disperse
in an elastomeric matrix, which can be observed in known manner by
electron or optical microscopy on thin sections. Non-limitative
examples of such preferred highly dispersible silicas which may be
mentioned are the silicas Ultrasil 7000 and Ultrasil 7005 from
Degussa, the silicas Zeosil 1165MP, 1135MP and 1115MP from Rhodia,
the silica Hi-Sil EZ150G from PPG, the silicas Zeopol 8715, 8745
and 8755 from Huber, and treated precipitated silicas such as, for
example, the aluminium-"doped" silicas described in application
EP-A-735 088.
[0079] The physical state in which the inorganic reinforcing filler
is present is immaterial, whether it be in the form of a powder,
microbeads, granules or alternatively balls. Of course, "inorganic
reinforcing filler" is also understood to mean mixtures of
different inorganic reinforcing fillers, in particular of highly
dispersible silicas such as described above.
[0080] Other, non-limitative examples of inorganic reinforcing
fillers which may be used are: [0081] aluminas (of formula
Al.sub.2O.sub.3), such as the highly dispersible aluminas which are
described in European Patent Specification EP-A-810 258, or
alternatively [0082] aluminium hydroxides, such as those described
in International Patent Specification WO-A-99/28376.
[0083] Also suitable are reinforcing inorganic fillers comprising
carbon blacks modified by silica, such as, although this is not
limiting, the fillers sold by CABOT under the name "CRX 2000",
which are described in international patent specification
WO-A-96/37547.
[0084] According to a second example of embodiment of the
invention, said reinforcing filler comprises carbon black in a mass
fraction of from 50% to 100%. Any carbon blacks conventionally used
in tires and particularly in the treads of such tires are suitable,
in particular HAF, ISAF and SAF type blacks. Carbon blacks N1115,
N134, N234, N339, N347 and N375 may be mentioned in non-limitative
manner.
[0085] Said reinforcing filler may comprise a blend of said
inorganic reinforcing filler with carbon black, the mass fraction
of carbon black in said reinforcing filler preferably being
selected less than or equal to 50%.
[0086] For example, black/silica blends or blacks partially or
entirely covered with silica are suitable to form the reinforcing
filler.
[0087] The rubber composition according to the invention may
furthermore comprise, in conventional manner, an inorganic
reinforcing filler/elastomeric matrix bonding agent (also referred
to as coupling agent), the function of which is to ensure
sufficient chemical and/or physical bonding (or coupling) between
said inorganic filler and the matrix, while facilitating the
dispersion of this inorganic filler within said matrix.
[0088] A "coupling" agent is more precisely understood to mean an
agent capable of establishing a sufficient chemical and/or physical
connection between the filler under consideration and the
elastomer, while facilitating the dispersion of this filler within
the elastomeric matrix; such a coupling agent, which is at least
difunctional, has, for example, the simplified general formula
"Y-T-X", in which: [0089] Y represents a functional group ("Y"
function) which is capable of bonding physically and/or chemically
with the inorganic filler, such a bond being able to be
established, for example, between a silicon atom of the coupling
agent and the surface hydroxyl (OH) groups of the inorganic filler
(for example, surface silanols in the case of silica); [0090] X
represents a functional group ("X" function) which is capable of
bonding physically and/or chemically with the elastomer, for
example by means of a sulfur atom; [0091] T represents a group
making it possible to link Y and X.
[0092] The coupling agents must in particular not be confused with
simple agents for covering the filler in question which, in known
manner, may comprise the Y function which is active with respect to
the filler but are devoid of the X function which is active with
respect to the elastomer.
[0093] Such coupling agents, of variable effectiveness, have been
described in a very large number of documents and are well-known to
the person skilled in the art. In fact, it is possible to use any
known coupling agent which is known to or likely to ensure, in the
diene rubber compositions usable for the manufacture of tires,
effective bonding or coupling between an inorganic reinforcing
filler such as silica and a diene elastomer, such as, for example,
organosilanes, in particular polysulfurized alkoxysilanes or
mercaptosilanes, or alternatively polyorganosiloxanes bearing the
aforementioned X and Y functions.
[0094] Silica/elastomer coupling agents in particular have been
described in a large number of documents, the best known being
difunctional alkoxysilanes, such as polysulfurized
alkoxysilanes.
[0095] In particular, polysulfurized alkoxysilanes, which are
referred to as "symmetrical" or "asymmetrical" depending on their
specific structure, are used, such as those described in patents
U.S. Pat. No. 3 842 111, U.S. Pat. No. 3 873 489, U.S. Pat. No. 3
978 103, U.S. Pat. No. 3 997 581, U.S. Pat. No. 4 002 594, U.S.
Pat. No. 4 072 701, U.S. Pat. No. 4 129 585, or in the more recent
patents or patent applications U.S. Pat. No. 5 580 919, U.S. Pat.
No. 5 583 245, U.S. Pat. No. 5 650 457, U.S. Pat. No. 4 663 358,
U.S. Pat. No. 5 663 395, U.S. Pat. No. 5 663 396, U.S. Pat. No. 5
674 932, U.S. Pat. No. 5 675 014, U.S. Pat. No. 5 684 171, U.S.
Pat. No. 5 684 172, U.S. Pat. No. 5 696 197, U.S. Pat. No. 5 708
053, U.S. Pat. No. 5 892 085, EP-A-1 043 357, which describe such
known compounds in detail.
[0096] Particularly suitable for implementing the invention,
without the definition below being limitative, are symmetrical
polysulfurized alkoxysilanes which satisfy the following general
formula (I):
(I) Z--A--Sn--A--Z , in which: [0097] n is an integer from 2 to 8
(preferably from 2 to 5); [0098] A is a divalent hydrocarbon
radical (preferably C.sub.1-C.sub.18 alkylene groups or
C.sub.6-C.sub.12 arylene groups, more particularly C.sub.1-C.sub.10
alkylenes, in particular C.sub.1-C.sub.4 alkylenes, in particular
propylene); [0099] Z corresponds to one of the formulae below:
##STR00002##
[0099] in which: [0100] the radicals R.sup.1, which may or may not
be substituted, and may be identical or different, represent a
C.sub.1-C.sub.18 alkyl group, a C.sub.5-C.sub.18 cycloalkyl group,
or a C.sub.6-C.sub.18 aryl group (preferably C.sub.1-C.sub.6 alkyl,
cyclohexyl or phenyl groups, in particular C.sub.1-C.sub.4 alkyl
groups, more particularly methyl and/or ethyl). [0101] the radicals
R.sup.2, which may or may not be substituted, and may be identical
or different, represent a C.sub.1-C.sub.18 alkoxyl group or
C.sub.5-C.sub.18 cycloalkoxyl group (preferably C.sub.1-C8 alkoxyl
groups or C.sub.5-C.sub.8 cycloalkoxyl groups, more preferably
C.sub.1-C.sub.4 alkoxyl groups, more particularly methoxyl and/or
ethoxyl).
[0102] In the case of a mixture of polysulfurized alkoxysilanes
corresponding to the formula (I) above, in particular conventional
commercially available mixtures, it will be understood that the
mean value of "n" is a fractional number, preferably varying
between 2 and 5.
[0103] Polysulfurized alkoxysilanes which may more particularly be
mentioned are polysulfides (in particular disulfides, trisulfides
or tetrasulfides) of
bis(alkoxyl(C.sub.1-C.sub.4)-alkyl(C.sub.1-C.sub.4)silylalkyl(C.sub.1-C.s-
ub.4)), such as for example bis(3-trimethoxysilylpropyl) or
bis(3-triethoxysilylpropyl) polysulfides. Of these compounds,
bis(3-triethoxysilylpropyl) tetrasulfide, abbreviated TESPT, of the
formula [(C.sub.2H.sub.5O).sub.3Si(CH.sub.2).sub.3S.sub.2].sub.2,
or bis(triethoxysilylpropyl) disulfide, abbreviated TESPD, of the
formula [(C.sub.2H.sub.5O).sub.3Si(CH.sub.2).sub.3S].sub.2 are in
particular used. TESPD is sold, for example, by Degussa under the
names Si266 or Si75 (in the latter case, in the form of a mixture
of disulfide (75% by weight) and of polysulfides), or alternatively
by Witco under the name Silquest A1589. TESPT is sold, for example,
by Degussa under the name Si69 (or X50S when supported at a content
of 50 wt. % on carbon black) or alternatively by the company Osi
Specialties under the name Silquest A1289 (in both cases, a
commercial mixture of polysulfides with an average value of n
approaching 4). Tetrasulfurised monoalkoxysilanes, such as
monoethoxydimethylsilylpropyl tetrasulfide (abbreviated to MESPT),
which are the subject matter of international patent application
PCT/EP02/03774 in the name of the applicants, may also be
mentioned.
[0104] The compositions according to the invention also comprise,
in addition to said elastomeric matrix, said reinforcing filler and
optionally said bonding agent, all or part of the other
constituents and additives normally used in rubber compositions,
such as plasticisers, pigments, antioxidants, antiozonant waxes, a
crosslinking system based on sulfur and/or peroxide and/or
bismaleimides, one or more covering agents for the inorganic
reinforcing filler such as alkylalkoxysilanes, polyols, amines or
amides.
[0105] The compositions according to the invention may be prepared
by carrying out a first thermomechanical working phase of the
constituents of the composition, with the exception of the
crosslinking system and at a maximum temperature of between
130.degree. C. and 200.degree. C., followed by a second mechanical
working phase carried out at a temperature below said maximum
temperature of the first phase and during which said crosslinking
system is incorporated.
[0106] The above-stated, and further, features of the present
invention are disclosed in greater detail in the following
description of several exemplary embodiments of the invention,
which are stated by way of illustrative, non-limiting examples.
Characterization of the Synthesised Elastomers
[0107] SEC (size exclusion chromatography) was used to determine
the molecular weights and the polydispersity indices of the
elastomers. According to this technique, the macromolecules are
separated physically according to their respective sizes when
swollen, in columns filled with a porous stationary phase.
[0108] A chromatograph sold under the name "WATERS" and under the
model "150C" is used for the aforementioned separation. A set of
two "WATERS" columns is used, the type being "STYRAGEL HT6E".
[0109] DSC (differential scanning calorimetry) was used to measure
the glass transition temperatures (Tg) of the elastomers obtained.
[0110] Furthermore, carbon-13 nuclear magnetic resonance
(.sup.13C-NMR) was used to determine the microstructural
characteristics of the elastomers obtained. The details of this
characterization are explained below.
[0111] .sup.13C-NMR analyses are performed using a "Bruker AM250"
spectrometer. The nominal frequency of carbon 13 is 62.9 MHz. To
ensure quantitative results, the spectra are recorded without the
"nuclear Overhauser effect" (NOE). Spectral width is 240 ppm. The
impulse angle used is a 90.degree. impulse with a duration of 5
.mu.s. Low power decoupling and a wide proton band are used to
eliminate scalar .sup.1H-.sup.13C coupling during .sup.13C
acquisition. The sequence repetition time is 4 seconds. The number
of transients accumulated to increase the signal/noise ratio is
8192. The spectra are calibrated against the CDCl.sub.3 band at 77
ppm.
[0112] Interpretation of the NMR spectra of SBR and BR has been the
subject matter of many publications in the literature, for example
the following documents: [0113] (1) Q.-T. Pham, R. Petiaud, H.
Waton, M.-F. Llauro-Darricades, Proton and Carbon NMR Spectra of
Polymers, Penton Press, London (1991). [0114] (2) Sato H.,
Ishikawa, T., Takebayashi K., Tanaka Y., Macromolecules, 22,
1748-1753, (1989). [0115] (3) Harwood, H., J. Rubber Chem.
Technology, 55, 769-806, (1982). [0116] (4) Kobayashi E., Furakawa
J., Ochiai M., Tsujimoto T, European Polym. J., 19, 871-875,
(1983). [0117] (5) Jiao S., Chen X., Hu L., Yan B., Chinese J.
Polym. Sci., 8, 17-24, (1990). [0118] (6) Quack G., Fetters L. J.,
Macromolecules, 11, no. 2, 369-373, (1978).
[0119] In particular, vinylcyclopentane type structures were
revealed and assigned in document (6) above.
[0120] The microstructures revealed for SBR and BR are as
follows:
##STR00003##
[0121] The table below summarises the chemical shifts corresponding
to the various carbon atoms of these structures in the unsaturated
carbon zone.
TABLE-US-00001 Chemical Assignments Structure - shifts No. of
carbon observed 145-140.6 V-3, VCP-6 116.6-113.2 V-4 126.5-124.9
S-6 132.9-126.9 S-4, S-5, S-7, S-8 C-2, C-3, T-2, T-3 145-140.6
V-3, VCP-6 147.1-145 S-3 113.2-111 VCP-7
The cis/trans ratio in the diene moiety is determined in the
aliphatic portion of the spectrum on the basis of assignments which
are familiar to the person skilled in the art (see documents (1) to
(5) above).
Characterization of the Rubber Compositions Obtained:
[0122] Mooney viscosity: ML(1+4) at 100.degree. C. measured in
accordance with Standard ASTM D 1646. [0123] Moduli of elongation
ME10, ME100 and ME300 (at 10%, 100% and 300%, expressed in MPa)
measured in accordance with Standard ASTM D 412. [0124] SHORE A
hardness: measured in accordance with Standard ASTM D 2240, 1997.
[0125] Hysteresis losses (HL): measured in % by rebound at
60.degree. C. on sixth impact, according to relationship HL
(%)=100.times.(W.sub.0-W.sub.1)/W.sub.1, where W.sub.0=energy
supplied and W.sub.1=energy returned. [0126] Dynamic shear
properties: measured in accordance with Standard ASTM D 2231-71,
approved in 1977 (measurement as a function of the deformation
performed at 10 Hz with a peak-to-peak deformation ranging from
0.45 to 50%). The stated nonlinearity is the difference in the
shear moduli (MPa) between 0.15 and 50% deformation. Hysteresis is
stated by measurement of tan 6 at 7% deformation and at 23.degree.
C. in accordance with Standard ASTM D 2231-71. [0127] Dynamic
properties in compression: measurements as a function of
temperature performed at 10 Hz while the temperature is rising (at
a rate of 2.degree. C. per minute) with an applied stress of 12 N
and a ratio of dynamic force to static force of 1.25.
I. ELASTOMER SYNTHESIS EXAMPLES
1) Example 1
"Control": Preparation of a High Molecular Weight, Oil-Extended
"Control" Starred SBR 1 Containing no Vinylcyclopentane Structural
Units.
[0128] This SBR is produced continuously in a 14 liter perfectly
stirred reactor.
[0129] Toluene, butadiene, styrene, tetrahydrofuran and
dimethoxyethane are introduced into this reactor in quantities by
weight of 100:10.15:4.15:0.68:0.25 respectively. 200 .mu.mol of
n-BuLi per 100 g of monomers are introduced via the line inlet in
order to neutralise the protic impurities introduced by the various
constituents present in this line inlet. 150 .mu.mol of n-BuLi per
100 g of monomers are introduced at the reactor inlet.
[0130] The (polar agent:n-BuLi) molar ratio is approximately
569.
[0131] The various flow rates are adjusted such that the average
dwell time in the reactor is 40 minutes and the temperature is
maintained at 60.degree. C.
[0132] The conversion rate, which is measured on a sample taken at
the reactor outlet, is 87%, and the inherent viscosity of the
linear SBR obtained, which is measured at 0.1 g/dl in toluene, is
2.61 dl/g. A starring agent consisting of propylene glycol
carbonate is introduced at the reactor outlet, then this starred
SBR is subjected to antioxidant treatment with 0.2 phr of
2,2'-methylene-bis(4-methyl-6-tert.-butylphenol) and 0.2 phr of
N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine.
[0133] The mass Mn of this starred SBR 1 is 250,000 g/mol, and the
Ip index is 1.89.
[0134] This "control" SBR 1 has a mass content of styrene linkages
of 25%. As for the butadiene moiety, it has a mass content of vinyl
structural units of 58% and no vinylcyclopentane structural unit is
detected.
[0135] Prior to extension with oil, the Tg of this "control" SBR 1
according to the invention is -24.degree. C.
[0136] This Example clearly shows that an aromatic polymerization
solvent, such as toluene, is not suitable for obtaining cyclic
vinyl units in the high molecular weight diene elastomer
obtained.
[0137] This "control" SBR 1 is then extended according to
techniques known to the person skilled in the art with 37 parts by
weight of aromatic oil per 100 parts of elastomer.
2) Example 2
According to the Invention: Preparation of a High Molecular Weight,
Oil-Extended Starred SBR 2 According to the Invention
[0138] This SBR is produced continuously in a 14 liter perfectly
stirred reactor.
[0139] Cyclohexane, butadiene, styrene and
tetramethylethylenediamine are introduced into this reactor in
quantities by weight of 100:13.6:0.7:0.17 respectively (the
quantity of tetramethylethylenediamine in the reaction medium being
approximately 1500 ppm), and a solution of sodium tert.-amylate is
furthermore introduced in a sodium:active lithium ratio of 0.04.
300 .mu.mol of n-BuLi per 100 g of monomers are introduced via the
line inlet in order to neutralise the protic impurities introduced
by the various constituents present in the line inlet. 660 .mu.mol
of n-BuLi per 100 g of monomers are introduced at the reactor
inlet. The (TMEDA:n-BuLi) molar ratio is approximately 15.5.
[0140] The various flow rates are adjusted such that the average
dwell time in the reactor is 40 minutes and the temperature is
maintained at 80.degree. C.
[0141] The (sodium:tetramethylethylenediamine) molar ratio is
0.002.
[0142] The conversion rate, which is measured on a sample taken at
the reactor outlet, is 90%, and the inherent viscosity of the
linear SBR obtained, which is measured at 0.1 g/dl in toluene, is
2.30 dl/g. This linear SBR has a number-average molecular weight Mn
of 150,000 g/mol.
[0143] A starring agent comprising tris(2,4-di-tert-butylphenyl)
phosphite is introduced at the reactor outlet, then this starred
SBR is subjected to the antioxidant treatment of section 1) above.
This starred SBR 2 has a weight Mn of 260,000 g/mol and an Ip index
of 2.56.
[0144] The mass content of styrene linkages in this starred SBR 2
according to the invention is 6%. In the butadiene moiety, the mass
content of vinyl linkages is 57% and the mass content of
vinylcvclopentane units is 22%.
[0145] Prior to extension with oil, the Tg of this SBR 2 according
to the invention is -25.degree. C.
[0146] By incorporating an alkali metal salt of an aliphatic or
alicyclic alcohol into the catalytic system, polymerization
(carried out continuously with a (polar agent:initiator) molar
ratio of greater than 15) thus gives rise to a mass content of
cyclic vinyl units of greater than 20% for a linear elastomer of a
molecular weight of greater than 150,000 g/mol.
[0147] This starred SBR 2 according to the invention is then
extended according to techniques known to the person skilled in the
art with 37 parts by weight of aromatic oil per 100 parts of
elastomer.
3) Example 3
According to the Invention: Preparation of a High Molecular Weight,
Oil-Extended Starred BR According to the Invention
[0148] This polybutadiene (BR) according to the invention is
produced continuously under conditions identical to those described
in Example 2 above, except that 14.3 parts per hundred parts of
cyclohexane are introduced into the reactor, that no styrene is
introduced into the reactor and that 600 .mu.mol of n-BuLi per 100
g of monomers are introduced at the reactor inlet.
[0149] The (TMEDA:n-BuLi) molar ratio is approximately 17.1.
[0150] The conversion rate, which is measured on a sample taken at
the reactor outlet, is 92%, and the inherent viscosity of the
linear BR obtained, which is measured at 0.1 g/dl in toluene, is
1.86 dl/g. The molecular weight Mn of this linear BR is 130,000
g/mol.
[0151] As previously, the starring agent is introduced at the
reactor outlet before the starred BR is subjected to the same
antioxidant treatment as above.
[0152] This starred BR has a weight Mn of 181,000 g/mol and an Ip
index of 2.89.
[0153] This starred BR has a mass content of vinyl linkages of 56%
and a mass content of vinylcyclopentane units of 20%.
[0154] Prior to extension with oil, the Tg of this BR according to
the invention is -29.degree. C.
[0155] This Example also shows that, by incorporating an alkali
metal salt of an aliphatic or alicyclic alcohol into the catalytic
system, polymerization (carried out continuously with a (polar
agent:initiator) molar ratio of greater than 15) gives rise to a
mass content of cyclic vinyl units of greater than 20% with a
linear polybutadiene of a molecular weight of greater than 100,000
g/mol.
[0156] This starred BR according to the invention is extended
according to techniques known to the person skilled in the art with
35 parts by weight of aromatic oil per 100 parts of elastomer.
4) Example 4
According to the Invention: Preparation of a High Molecular Weight,
Non-Oil-Extended Starred SBR 4 According to the Invention
[0157] The polymer is produced continuously in a 0.8 liter
perfectly stirred reactor.
[0158] Cyclohexane, butadiene, styrene, tetramethylethylenediamine
are introduced into this reactor in quantities by weight of
100:13.15:1.13:0.29 respectively. 200 .mu.mol of n-BuLi per 100 g
of monomers are introduced via the line inlet in order to
neutralise the protic impurities introduced by the various
constituents present in this line inlet. 1200 .mu.mol of n-BuLi per
100 g of monomers are introduced at the reactor inlet.
[0159] The (TMEDA:n-BuLi) molar ratio is approximately 14.6.
[0160] The various flow rates are adjusted such that the average
dwell time in the reactor is 40 minutes and the temperature is
maintained at 80.degree. C.
[0161] The conversion rate, which is measured on a sample taken at
the reactor outlet, is 92%, and the inherent viscosity of the
linear SBR obtained, which is measured at 0.1 g/dl in toluene, is
1.35 dl/g. The molecular weight Mn of this linear SBR is 75,000
g/mol.
[0162] A starring agent comprising methyltrichlorosilane (400
.mu.mol per 100 g de monomers) is introduced at the reactor outlet,
then this starred SBR is subjected to the same antioxidant
treatment as previously.
[0163] The mass Mn of this starred SBR 4 is 120,000 g/mol, and the
Ip index is 1.89. The viscosity of this SBR 4 is 1.85 dl/g.
[0164] This SBR 4 has a content of styrene units of 8%, a mass
content of vinyl structural units of 51% and a mass content of
vinylcyclopentane structural units of 18%.
[0165] The Tg of this SBR 4 according to the invention is
-28.degree. C.
[0166] This Example shows that it is not necessary to incorporate
an alkali metal salt of an aliphatic or alicyclic alcohol into the
catalytic system in order to obtain, after polymerization (carried
out continuously with a (polar agent:initiator) molar ratio of
greater than 10), a mass content of cyclic vinyl units of greater
than 15% for a linear elastomer of a molecular weight Mn of between
50,000 and 100,000 g/mol.
5) Example 5
"Control": Preparation of a High Molecular Weight, Non-Oil-Extended
"Control" Starred SBR 5:
[0167] The SBR is prepared under conditions similar to those of
Example 4.
[0168] Cyclohexane, butadiene, styrene, tetramethylethylenediamine
are introduced into this reactor in quantities by weight of
100:10.6:3.7:0.02 respectively. 200 .mu.mol of n-BuLi per 100 g of
monomers are introduced via the line inlet in order to neutralise
the protic impurities introduced by the various constituents
present in this line inlet. 1200 .mu.mol of n-BuLi per 100 g of
monomers are introduced at the reactor inlet.
[0169] The various flow rates are adjusted such that the average
dwell time in the reactor is 40 minutes and the temperature is
maintained at 60.degree. C.
[0170] The conversion rate, which is measured on a sample taken at
the reactor outlet, is 92%, and the inherent viscosity of the SBR
obtained, which is measured at 0.1 g/dl in toluene, is 1.20 dl/g. A
starring agent comprising methyltrichlorosilane (400 .mu.mol per
100 g de monomers) is introduced at the reactor outlet, then this
starred SBR 5 is subjected to the same antioxidant treatment as
previously.
[0171] The mass Mn of this starred SBR 5 is 110,000 g/mol, and the
Ip index is 1.51. The viscosity of this SBR 5 is 1.56 dl/g.
[0172] This starred SBR 5 has a mass content of vinyl units of 52%
and a mass content of vinylcyclopentane units of 2.5%.
[0173] The content of styrene units in this SBR 5 is 25%.
[0174] The Tg of this SBR 5 is -28.degree. C.
II. RUBBER PROCESSING EXAMPLES:
1) First Comparative Example
[0175] In this Example, two rubber compositions 1 and 2 of the
passenger-car tire tread type, the reinforcing filler of which
consists of silica, are compared.
[0176] The first "control" composition 1 is based on the "control"
SBR 1 obtained in Example 1 of section I. above (this SBR 1 in
particular has a mass content of styrene linkages of 25%, and
contains no cyclic vinyl structural units).
[0177] The second composition 2 according to the invention is based
on the SBR 2 according to the invention obtained in Example 2 of
section I. above (this SBR 2 has a mass content of styrene linkages
of 6% and a mass content of cyclic vinyl structural units of
22%).
[0178] The formulation of each of the compositions 1 and 2 is as
follows (in phr: parts by weight per hundred parts of
elastomer):
TABLE-US-00002 Elastomer: SBR 1 or SBR 2 100 Silica (1) 80 Aromatic
oil "ENERFLEX 65" 37.5 Bonding agent (2) 6.4 ZnO 2.5 Stearic acid 2
Antioxidant (3) 1.9 Antiozone wax "C32ST" 1.5 Sulfur 1.1
Sulfenamide (4) 2 Diphenylguanidine 1.47 (1) = Silica "ZEOSIL 1165
MP" (sold by Rhodia) (2) = Bonding agent "Si69" (sold by Degussa)
(3) = N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (4) =
N-cyclohexyl-2-benzothiazylsulfenamide
[0179] Each composition is prepared according to the method
described in European Patent specification EP-A-501 227, it being
specified that a first thermomechanical working phase is performed
in two steps respectively lasting 4 and 5 minutes, at an average
paddle speed of 85 revolutions/minute in a mixer of approximately
400 cm.sup.3 until a maximum "dropping" temperature of 160.degree.
C. is reached, and a second mechanical working phase, which
includes incorporation of the vulcanization system, is performed on
an open mill at 30.degree. C.
[0180] Vulcanization is carried out at 150.degree. C. for 60
minutes.
[0181] The results are set forth in Table 1.
TABLE-US-00003 TABLE 1 COMPOSITION 1 ("control") 2 (invention) ML(1
+ 4) at 100.degree. C..sub."rubber" 67 55 Properties in the
non-vulcanized state: ML(1 + 4) at 100.degree. C..sub."mixture" 97
82 Properties in the vulcanized state: Shore 65 65 ME10 5.6 5.8
ME100 1.8 1.9 ME300 2.3 2.5 ME300/ME100 1.3 1.3 Losses at
60.degree. C. 24.3 27.3 Dynamic properties as a function of
deformation Delta G* at 23.degree. C. 3.11 3.54 Tan .delta. max. at
23.degree. C. 0.347 0.415 Dynamic properties as a function of
temperature Dynamic Tg (.degree. C.) -16 -11 Tan .delta. at Tg 0.75
0.77
[0182] With regard to the properties in the vulcanized state, it
will be noted that the properties of composition 2 according to the
invention are of the same order of magnitude as those of the
"control" composition 1.
[0183] In fact, the moduli at low and high deformations and the
hysteresis properties at low and high deformations (tan .delta.
max. at 23.degree. C. and losses at 60.degree. C., respectively) of
composition 2 are close to the corresponding moduli and hysteresis
properties of composition 1. The differences in hysteresis
properties observed at small (.DELTA.G*) and large (losses at
60.degree. C.) deformations between compositions 1 and 2 are mainly
due to the difference in dynamic Tg between these compositions. Had
the dynamic Tg been identical, these properties would have been
similar.
[0184] Furthermore, composition 2 according to the invention has a
"mixture" Mooney viscosity value which is 15 points lower than that
of the "control" composition 1.
[0185] It will also be noted that SBR 2 according to the invention,
which has a mass content of styrene linkages of only 6%, makes it
possible to impart to composition 2 according to the invention
practically the same properties in the vulcanized state as those
imparted to the "control" composition 1 by SBR 1, which has a mass
content of styrene linkages of 25%, thanks to the high content
(22%) of cyclic vinyl structural units which this SBR 2 comprises,
unlike SBR 1 which contains no such structural units.
2) Second Comparative Example
[0186] In this Example, two rubber compositions 1 and 3 of the
passenger-car tire tread type, the reinforcing filler of which
consists of silica, are compared.
[0187] The first "control" composition 1 is identical to that in
section II. 1) above.
[0188] The second composition 3 according to the invention is based
on the BR according to the invention obtained in Example 3 of
section I. above (this BR has a mass content of cyclic vinyl
structural units of 20%).
[0189] The formulation of each of the compositions 1 and 3 is as
follows (in phr: parts by weight per hundred parts of
elastomer):
TABLE-US-00004 Elastomer: SBR 1 or BR 100 Silica (1) 80 Aromatic
oil "ENERFLEX 65" 37.5 Bonding agent (2) 6.4 ZnO 2.5 Stearic acid 2
Antioxidant (3) 1.9 Antiozone wax "C32ST" 1.5 Sulfur 1.1
Sulfenamide (4) 2 Diphenylguanidine 1.47 (1) = Silica "ZEOSIL 1165
MP" (sold by Rhodia) (2) = Bonding agent "Si69" (sold by Degussa)
(3) = N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (4) =
N-cyclohexyl-2-benzothiazylsulfenamide
[0190] Each composition is prepared according to the method
described in European Patent specification EP-A-501 227, it being
specified that a first thermomechanical working phase is performed
in two steps respectively lasting 4 and 5 minutes, at an average
paddle speed of 85 revolutions/minute in a mixer of approximately
400 cm.sup.3 until a maximum "dropping" temperature of 160.degree.
C. is reached, and a second mechanical working phase, which
includes incorporation of the vulcanization system, is performed on
an open mill at 30.degree. C.
[0191] Vulcanization is carried out at 150.degree. C. for 60
minutes.
[0192] The results are set forth in Table 2.
TABLE-US-00005 TABLE 2 COMPOSITION 1 ("control") 3 (invention) ML(1
+ 4) at 100.degree. C..sub."rubber" 67 48 Properties in the
non-vulcanized state: ML(1 + 4) at 100.degree. C..sub."mixture" 97
71 Properties in the vulcanized state: Shore 65 65 ME10 5.6 5.8
ME100 1.8 1.9 ME300 2.3 2.5 ME300/ME100 1.3 1.3 Losses at
60.degree. C. 24.3 27.0 Dynamic properties as a function of
deformation Delta G* at 23.degree. C. 3.11 3.59 Tan .delta. max. at
23.degree. C. 0.347 0.405 Dynamic properties as a function of
temperature Dynamic Tg (.degree. C.) -16 -13 Tan .delta. at Tg 0.75
0.72
[0193] With regard to the properties in the vulcanized state, it
will be noted that the properties of composition 3 according to the
invention are of the same order of magnitude as those of the
"control" composition 1.
[0194] In fact, the moduli at low and high deformations and the
hysteresis properties at low and high deformations (tan .delta.
max. at 23.degree. C. and losses at 60.degree. C., respectively) of
composition 3 are close to the corresponding moduli and hysteresis
properties of composition 1. The differences in hysteresis
properties observed at small (.DELTA.G*) and large (losses at
60.degree. C.) deformations between compositions 1 and 3 are mainly
due to the difference in dynamic Tg and "rubber" Mooney values
between these compositions. Had the dynamic Tg and "rubber" Mooney
values been identical, these properties would have been
similar.
[0195] It will also be noted that the dynamic Tg of composition 3
according to the invention is very close to that of the "control"
composition 1.
[0196] Furthermore, composition 3 according to the invention has a
"mixture" Mooney viscosity value which is 26 points lower than that
of the "control" composition 1.
[0197] It will furthermore be noted that the BR according to the
invention, which by definition contains no styrene linkages, makes
it possible to impart to the composition 3 according to the
invention practically the same properties in the vulcanized state
as those imparted to the "control" composition 1 by SBR 1, which
has a mass content of styrene linkages of 25%, thanks to the high
content (20%) of cyclic vinyl structural units which this BR
comprises, unlike SBR 1 which contains no such structural
units.
3) Third Comparative Example
[0198] In this Example, two rubber compositions 4 and 5 of the
passenger-car tire tread type, the reinforcing filler of which
consists of silica, are compared.
[0199] The second composition 4 according to the invention is based
on the SBR 4 according to the invention obtained in Example 4 of
section I. above (this SBR 4 has a mass content of styrene linkages
of 8% and a mass content of cyclic vinyl structural units of
18%).
[0200] The second composition 5 according to the invention is based
on the SBR 5 according to the invention obtained in Example 5 of
section I. above (this SBR 5 has a mass content of styrene linkages
of 25% and a mass content of cyclic vinyl structural units of only
2.5%).
[0201] The formulation of each of the compositions 4 and 5 is as
follows
(in phr: parts by weight per hundred parts of elastomer):
TABLE-US-00006 Elastomer: SBR 4 or SBR 5 100 Silica (1) 60 Aromatic
oil "ENERFLEX 65" 20.5 Bonding agent (2) 4.8 ZnO 2.5 Stearic acid 2
Antioxidant (3) 1.9 Antiozone wax "C32ST" 1.5 Sulfur 1.1
Sulfenamide (4) 2 Diphenylguanidine 1.1 (1) = Silica "ZEOSIL 1165
MP" (sold by Rhodia) (2) = Bonding agent "Si69" (sold by Degussa)
(3) = N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (4) =
N-cyclohexyl-2-benzothiazylsulfenamide
[0202] Each composition is prepared according to the method
described in European Patent specification EP-A-501 227, it being
specified that a first thermomechanical working phase is performed
in two steps respectively lasting 4 and 5 minutes, at an average
paddle speed of 85 revolutions/minute in a mixer of approximately
400 cm.sup.3 until a maximum "dropping" temperature of 160.degree.
C. is reached, and a second mechanical working phase, which
includes incorporation of the vulcanization system, is performed on
an open mill at 30.degree. C.
[0203] Vulcanization is carried out at 150.degree. C. for 60
minutes.
[0204] The results are set forth in Table 3.
TABLE-US-00007 TABLE 3 COMPOSITION 4 (invention) 5 ("control") ML(1
+ 4) at 100.degree. C..sub."rubber" 43 43 Properties in the
non-vulcanized state: ML(1 + 4) at 100.degree. C..sub."mixture" 61
55 Properties in the vulcanized state: Shore 59.3 59.1 ME10 4.8 4.5
ME100 1.5 1.4 ME300 1.5 1.5 ME300/ME100 1.0 1.08 Losses at
60.degree. C. 35.0 35.1 Dynamic properties as a function of
deformation Delta G* at 23.degree. C. 1.45 1.15 Tan .delta. max. at
23.degree. C. 0.257 0.238 Dynamic properties as a function of
temperature Dynamic Tg (.degree. C.) -15 -15 Tan .delta. at Tg 1.11
1.19 E' at 50.degree. C. in MPa 5.5 5.7 E'' at 50.degree. C. in MPa
0.83 0.86
[0205] With regard to the properties in the vulcanized state, it
will be noted that the properties of composition 4 according to the
invention are similar to those of the "control" composition 5.
[0206] In fact, the moduli at low and high deformations and the
hysteresis properties at low and high deformations (tan .delta.
max. at 23.degree. C. and losses at 60.degree. C., respectively) of
composition 4 are close to the corresponding moduli and hysteresis
properties of composition 5.
[0207] It will also be noted that the dynamic properties (dynamic
Tg, in particular) of composition 4 according to the invention are
very close to those of the "control" composition 5.
[0208] Consequently, at identical dynamic Tg and "rubber" Mooney
values, the hysteresis properties observed at small (.DELTA.G*) and
large (losses at 60.degree. C.) deformations are similar for
compositions 4 and 5.
[0209] It will also be noted that SBR 4 according to the invention,
which has a mass content of styrene linkages of only 8%, makes it
possible to impart to composition 4 according to the invention
practically the same properties in the vulcanized state as those
imparted to the "control" composition 5 by SBR 5, which has a mass
content of styrene linkages of 25%, thanks to the high content
(18%) of cyclic vinyl structural units which this SBR 4 comprises,
unlike SBR 5 which contains only 2.5% of such structural units.
* * * * *