U.S. patent application number 13/600687 was filed with the patent office on 2013-06-06 for arborescent polymers and process for making same.
This patent application is currently assigned to LANXESS, INC.. The applicant listed for this patent is Gabor Kaszas, Kevin Kulbaba, Judit Puskas. Invention is credited to Gabor Kaszas, Kevin Kulbaba, Judit Puskas.
Application Number | 20130144021 13/600687 |
Document ID | / |
Family ID | 39136652 |
Filed Date | 2013-06-06 |
United States Patent
Application |
20130144021 |
Kind Code |
A1 |
Kaszas; Gabor ; et
al. |
June 6, 2013 |
ARBORESCENT POLYMERS AND PROCESS FOR MAKING SAME
Abstract
The present invention relates to arborescent polymers and to a
process for making same. In one embodiment, the present invention
relates to arborescent polymers formed from at least one inimer and
at least one isoolefin that have been end-functionalized with a
polymer or copolymer having a low glass transition temperature
(T.sub.g), and to a process for making such arborescent polymers.
In another embodiment, the present invention relates to arborescent
polymers formed from at least one inimer and at least one isoolefin
that have been end-functionalized with less than about 5 weight
percent end blocks derived from a polymer or copolymer having a
high glass transition temperature (T.sub.g), and to a process for
making such arborescent polymers.
Inventors: |
Kaszas; Gabor; (Akron,
OH) ; Puskas; Judit; (Akron, OH) ; Kulbaba;
Kevin; (London, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Kaszas; Gabor
Puskas; Judit
Kulbaba; Kevin |
Akron
Akron
London |
OH
OH |
US
US
CA |
|
|
Assignee: |
; LANXESS, INC.
Sarnia
OH
The University of Akron
Akron
|
Family ID: |
39136652 |
Appl. No.: |
13/600687 |
Filed: |
August 31, 2012 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
12439034 |
May 7, 2010 |
8258230 |
|
|
PCT/US07/19280 |
Aug 31, 2007 |
|
|
|
13600687 |
|
|
|
|
60841757 |
Sep 1, 2006 |
|
|
|
Current U.S.
Class: |
526/265 |
Current CPC
Class: |
C08L 53/00 20130101;
C08L 53/00 20130101; C08F 236/08 20130101; C08F 297/08 20130101;
C08F 210/12 20130101; C08F 290/042 20130101; C08F 293/00 20130101;
C08F 210/12 20130101; C08L 53/00 20130101; C08F 236/08 20130101;
C08L 2666/02 20130101; C08L 2666/04 20130101; C08F 2500/03
20130101 |
Class at
Publication: |
526/265 |
International
Class: |
C08F 236/08 20060101
C08F236/08 |
Claims
1. An end-functionalized arborescent polymer comprising: an
arborescent elastomeric polymer having two or more branching points
and a low glass transition temperature (T.sub.g); and less than
about 5 weight percent end blocks derived from a polymer or
copolymer having a high glass transition temperature (T.sub.g).
2. The end-functionalized arborescent polymer of claim 1, wherein
the end-functionalized arborescent polymer exhibits thermoplastic
elastomeric properties.
3. The end-functionalized arborescent polymer of claim 1, wherein
the arborescent elastomeric polymer comprises an arborescent
polyisoolefin core.
4. The end-functionalized arborescent polymer of claim 1, wherein
the arborescent elastomeric polymer is formed from at least one
inimer of Formula I: A-B (I) wherein A is: ##STR00009## wherein B
is: ##STR00010## R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and
R.sub.6 are each independently selected from the group consisting
of hydrogen, halogens, linear or branched C.sub.1 to C.sub.10
alkyls and C.sub.5 to C.sub.5 aryls; or R.sub.1, R.sub.2 and
R.sub.3 are hydrogen; and R.sub.4, R.sub.5 and R.sub.6 are each
independently selected from the group consisting of hydrogen,
hydroxyl, bromine, chlorine, fluorine, iodine, ester
(--O--C(O)--R.sub.7), peroxide (--OOR.sub.7), and --O--R.sub.7,
wherein R.sub.7 is unsubstituted linear or branched C.sub.1 to
C.sub.20 alkyl, unsubstituted linear or branched C.sub.1 to
C.sub.10 alkyl, substituted linear or branched C.sub.1 to C.sub.20
alkyl, substituted linear or branched C.sub.1 to C.sub.10 alkyl,
aryl group having from 2 to about 20 carbon atoms, aryl group
having from 9 to 15 carbon atoms, substituted aryl group having
from 2 to about 20 carbon atoms or substituted aryl group having
from 9 to 15 carbon atoms; or any one of R.sub.4, R.sub.5 and
R.sub.6 is chlorine or fluorine and any remaining R.sub.4, R.sub.5
and R.sub.6 are independently selected from unsubstituted linear or
branched C.sub.1 to C.sub.20 alkyls, unsubstituted linear or
branched C.sub.1 to C.sub.10 alkyls, substituted linear or branched
C.sub.1 to C.sub.20 alkyls and substituted linear or branched
C.sub.1 to C.sub.10 alkyls; or any two of R.sub.4, R.sub.5 and
R.sub.6 together form an epoxide and a remaining R group is either
hydrogen, unsubstituted linear or branched C.sub.1 to C.sub.10
alkyl, or substituted linear or branched C.sub.1 to C.sub.10
alkyl.
5. The end-functionalized arborescent polymer of claim 6, wherein
the inimer of Formula (I) comprises either an aryl or alkyl group
joining A and B.
6. The end-functionalized arborescent polymer of claim 6, wherein
the inimer of Formula (I) comprises a benzene ring joining A and
B.
7. The end-functionalized arborescent polymer of claim 6, wherein
the inimer of Formula (I) comprises a linkage of Formula (II):
##STR00011## wherein n is an integer in the range of 1 to about 12;
joining A and B.
8. The end-functionalized arborescent polymer of claim 6, wherein
the arborescent elastomeric polymer is formed from at least one
inimer selected from the group consisting of
4-(2-hydroxyisopropyl)styrene, 4-(2-methoxyisopropyl)styrene,
4-(1-methoxyisopropyl)styrene, 4-(2-chloroisopropyl)styrene,
4-(2-acetoxyisopropyl)styrene, 2,3,5,6-tertamethyl-4-(2-hydroxy
isopropyl)styrene, 3-(2-methoxyisopropyl)styrene,
4-(epoxyisopropyl)styrene, 4,4,6-trimethyl-6-hydroxyl-1-heptene,
4,4,6-trimethyl-6-chloro-1-heptene,
4,4,6-trimethyl-6,7-epoxy-1-heptene,
4,4,6,6,8-pentamethyl-8-hydroxyl-1-nonene,
4,4,6,6,8-pentamethyl-8-chloro-1-nonene,
4,4,6,6,8-pentamethyl-8,9-epoxy-1-nonene,
3,3,5-trimethyl-5-hydroxyl-1-hexene,
3,3,5-trimethyl-5-chloro-1-hexene,
3,3,5-trimethyl-5-6-epoxy-1-hexene,
3,3,5,5,7-pentamethyl-7-hydroxyl-1-octene,
3,3,5,5,7-pentamethyl-7-chloro-1-octene, and
3,3,5,5,7-pentamethyl-7,8-epoxy-1-octene.
9. The end-functionalized arborescent polymer of claim 6, wherein
the arborescent elastomeric polymer is formed from at least one of
4-(2-methoxyisopropyl)styrene or 4-(epoxyisopropyl)styrene.
10. The end-functionalized arborescent polymer of claim 1, wherein
the arborescent elastomeric polymer is formed from at least one
isoolefin of Formula (III): ##STR00012## wherein R.sub.9 is C.sub.1
to C.sub.4 alkyl.
11. The end-functionalized arborescent polymer of claim 1, wherein
the arborescent elastomeric polymer is formed from isobutylene or
2-methyl-1-butene.
12. The end-functionalized arborescent polymer of claim 1, wherein
the high glass transition temperature end-blocks comprise one or
more diene monomer selected from the group consisting of
butadiene-1,3; 2-methylbutadiene-1,3; 2,4-dimethylbutadiene-1,3;
piperyline; 3-methylpentadiene-1,3; hexadiene-2,4;
2-neopentylbutadiene-1,3; 2-methlyhexadiene-1,5;
2,5-dimethyhexadiene-2,4; 2-methylpentadiene-1,4;
2-methylheptadiene-1,6; cyclopentadiene; methylcyclopentadiene;
cyclohexadiene; 1-vinyl-cyclohexadiene; and mixtures thereof.
13. The end-functionalized arborescent polymer of claim 1, wherein
the high glass transition temperature end-blocks comprise monomeric
units derived from monomers selected from the group consisting of
isoprene, monovinylidiene arenes, and co-polymers and combinations
thereof.
14. The end-functionalized arborescent polymer of claim 17, wherein
the monovinylidiene arene monomer is selected from the group
consisting of styrene, p-methylstyrene, p-tert-butylstyrene,
p-chlorostyrene, indene and mixtures thereof.
15. The end-functionalized arborescent polymer of claim 1, wherein
the high glass transition temperature end-blocks comprise less than
about 5 weight percent monovinylidiene arene content.
16. The end-functionalized arborescent polymer of claim 1, wherein
the high glass transition temperature end-blocks have a number
average molecular weight of less than about 10,000 g/mol.
17. The end-functionalized arborescent polymer of claim 1, wherein
the end-functionalized arborescent polymer is crosslinked or cured
to provide a vulcanized article.
Description
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation application of U.S.
patent application Ser. No. 12/439,034, filed Feb. 26, 2009,
pending, which is a 371 national phase application of International
PCT Application No. PCT/US2007/019280, filed Aug. 31, 2007,
abandoned, which claims the benefit of U.S. Provisional Application
No. 60/841,757, filed Sep. 1, 2006, abandoned, the entirety of all
of these applications being incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to arborescent polymers and to
a process for making same. In one embodiment, the present invention
relates to arborescent polymers formed from at least one inimer and
at least one isoolefin that have been end-functionalized with a
polymer or copolymer having a low glass transition temperature
(T.sub.g), and to a process for making such arborescent polymers.
In another embodiment, the present invention relates to arborescent
polymers formed from at least one inimer and at least one isoolefin
that have been end-functionalized with less than about 5 weight
percent end blocks derived from a polymer or copolymer having a
high glass transition temperature (T.sub.g), and to a process for
making such arborescent polymers. In still another embodiment, the
present invention relates to arborescent polymers formed from at
least one inimer and at least one isoolefin that have been
end-functionalized, where such polymers have a saturated core and
one or more unsaturated end-functionalized portions. In still
another embodiment, the present invention relates to arborescent
polymers that exhibit phase separation even though such polymers
would normally fall within the weakly separated or homogeneous
portion of a standard polymer phase diagram.
BACKGROUND OF THE INVENTION
[0003] Over the last several decades, the development of novel
butyl-based elastomers has been limited by the complexity of the
methyl chloride (MeCl) slurry process. The current butyl process
demands high purity feeds and a diluent (e.g., MeCl), as well as
the use of extremely low temperatures (less than -90.degree. C.).
The polymerization is very rapid (close to diffusion control) and
utilizes a Lewis acid initiator complex with either water or protic
activator, further complicating the catalyst makeup and dosing of
the reactors. Fouling of the reactors is also a problem in such a
slurry process, resulting in reduced production rates caused by the
frequent cleaning of the reactors. These factors make the current
synthesis of new butyl polymers both costly and unforgiving.
[0004] Additionally, it is the extremely high rate of
polymerization of isobutene that limits control of the
polymerization process and polymer structure. The polymer
precipitates from the commercially used diluent, methyl chloride.
This prevents any further manipulation of the molecular structure.
Very few co-monomers can be incorporated along with isobutylene,
and in relatively low concentration as they typically cause rate
depression, chain transfer and, in the case of dienes, branching
and cyclization. In addition, all co-monomers increase the glass
transition temperature (T.sub.g), resulting in less desirable low
temperature properties.
[0005] The present butyl process is 65 year old technology, and the
previously mentioned limitations are a few of the main reasons for
the development and commercialization of few new grades of
butyl-based elastomers during the past 60 years. Furthermore, all
of the new butyl-based elastomers, with the exception of star
branched regular butyl, are manufactured by post-polymerization
modification. This is typically carried out by dissolving the
already precipitated base polymer in a hydrocarbon solvent and,
following modification, isolating the polymer again via steam
coagulation for finishing. Given this process, the production of
these new butyl-based elastomers requires a significant amount of
energy, and thus production thereof is very inefficient and
costly.
[0006] Additionally, butyl-type (polyisobutylene-based) polymers
find a wide range of uses in such areas as biomedical applications
(e.g., stents and implants), tire applications (e.g., innerliners),
food-related packaging applications, pharmaceutical closures and in
various sealant applications.
[0007] As such, there is a need in the art for a process that
permits the production of butyl-type polymers having controlled
architecture, molecular weight, molecular distribution, branching,
co-monomer distribution, and/or co-monomer sequencing, that is
accomplished by independent control of the polymerization and
initiation steps, as well as control of the overall polymerization
rate.
SUMMARY OF THE INVENTION
[0008] The present invention relates to arborescent polymers and to
a process for making same. In one embodiment, the present invention
relates to arborescent polymers formed from at least one inimer and
at least one isoolefin that have been end-functionalized with a
polymer or copolymer having a low glass transition temperature
(T.sub.g), and to a process for making such arborescent polymers.
In another embodiment, the present invention relates to arborescent
polymers formed from at least one inimer and at least one isoolefin
that have been end-functionalized with less than about 5 weight
percent end blocks derived from a polymer or copolymer having a
high glass transition temperature (T.sub.g), and to a process for
making such arborescent polymers. In still another embodiment, the
present invention relates to arborescent polymers formed from at
least one inimer and at least one isoolefin that have been
end-functionalized, where such polymers have a saturated core and
one or more unsaturated end-functionalized portions. In still
another embodiment, the present invention relates to arborescent
polymers that exhibit phase separation even though such polymers
would normally fall within the weakly separated or homogeneous
portion of a standard polymer phase diagram.
[0009] In one embodiment, the present invention relates to an
end-functionalized arborescent polymer comprising: an arborescent
elastomeric polymer portion having two or more branching points,
the arborescent elastomeric polymer block having a low
glass-transition temperature (T.sub.g); and one or more
end-functionalized portions, wherein one or more end-functionalized
portions terminate at least one of the two or more branches of the
arborescent elastomeric polymer portion of the end-functionalized
arborescent polymer.
[0010] In another embodiment, the present invention relates to an
end-functionalized arborescent polymer comprising the reaction
production of at least one inimer and at least one isoolefin,
wherein the end-functionalized arborescent polymer has been
end-functionalized with less than about 5 weight percent end blocks
derived from a polymer or copolymer having a high glass transition
temperature (T.sub.g).
[0011] In still another embodiment, the present invention relates
to an end-functionalized arborescent polymer comprising the
reaction production of at least one inimer and at least one
isoolefin, where the end-functionalized arborescent polymer has a
saturated core and one or more unsaturated end-functionalized
portions.
[0012] In still another embodiment, the present invention relates
to an arborescent polymer comprising the reaction product of at
least one inimer and at least one isoolefin, wherein the
arborescent polymer exhibits phase separation even though such
polymers would normally fall within the homogeneous portion of a
standard polymer phase diagram.
[0013] In still another embodiment, the present invention relates
to an end-functionalized arborescent polymer comprising the
reaction product of at least one inimer and at least one isoolefin,
wherein the end-functionalized polymer contains from about 0.5 to
about 50 weight percent end blocks derived from a polymer or
copolymer having a low T.sub.g.
[0014] In still another embodiment, the present invention relates
to an end-functionalized arborescent polymer comprising the
reaction product of at least one inimer and at least one isoolefin,
wherein the end-functionalized arborescent polymer has been
end-functionalized with a low T.sub.g homo or copolymer that
contains isoprene or any other cationically polymerizable
monomer.
[0015] In still another embodiment, the present invention relates
to an end-functionalized arborescent polymer comprising the
reaction product of at least one inimer and at least one isoolefin,
wherein the end-functionalized arborescent polymer further
comprises at least one filler.
[0016] In still another embodiment, the present invention relates
to an end-functionalized arborescent polymer comprising the
reaction product of at least one inimer and at least one isoolefin,
wherein the end-functionalized arborescent polymer can be
crosslinked and/or cured to form a butyl rubber.
[0017] In still another embodiment, the present invention relates
to an end-functionalized thermoplastic elastomeric arborescent
polymer comprising the reaction product of at least one inimer and
at least one isoolefin, wherein the end-functionalized
thermoplastic elastomeric arborescent polymer are reinforced with
one or more fillers and wherein the one or more fillers
preferentially interact with the end-functionalized portions of the
end-functionalized thermoplastic elastomeric arborescent
polymer.
[0018] In still another embodiment, the present invention relates
to an end-functionalized thermoplastic elastomeric arborescent
polymer comprising the reaction product of at least one inimer and
at least one isoolefin, wherein the end-functionalized portions of
such polymers have a number average molecular weight of less than
about 10,000 g/mol.
[0019] In still another embodiment, the present invention relates
to a method for producing an end-functionalized arborescent polymer
composition comprising the steps of: (A) combining at least one
inimer compound with at least one isoolefin compound in a suitable
solvent to form a inimer/isoolefin mixture; (B) adding to the
inimer/isoolefin mixture at least one Lewis acid halide to form a
polymerization reaction mixture; (C) causing the polymerization
reaction mixture of Step (B) to undergo polymerization to produce a
polymer product; (D) subjecting the polymer product to an
end-functionalization reaction to yield an end-functionalized
polymer product; and (E) recovering the end-functionalized polymer
product.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] FIG. 1 is a graph depicting torque curves of a raw polymer
(06DNX001 RP) in accordance with the present invention and a filled
polymer (06DNX001 with carbon black) in accordance with the present
invention;
[0021] FIG. 2 is a graph depicting the torque and temperature
increases during mixing for an arborescent polymer of the present
invention (06DNX001) and a commercial grade butyl (RB402);
[0022] FIG. 3 is a graph depicting plots for stress versus
elongation for a green polymer according to the present invention
with 60 phr N234 carbon black (06DNX001 with 60 phr N234) and a
green regular grade butyl with 60 phr N234 carbon black (RB402 with
60 phr N234);
[0023] FIG. 4 is a graph depicting plots for stress versus
elongation for a raw polymer according to the present invention
(06DNX130 RP) and a regular grade butyl (RB301);
[0024] FIG. 5 is a graph depicting torque and temperature increases
during mixing for an arborescent polymer in accordance with one
embodiment of the present invention (06DNX130) and a commercial
grade butyl (RB402);
[0025] FIG. 6 is a graph depicting plots for stress versus
elongation for a polymer according to the present invention with 60
phr N234 carbon black (06DNX130 with 60 phr N234) and a regular
grade butyl with 60 phr N234 carbon black (RB402 with 60 phr
N234);
[0026] FIG. 7 is a graph depicting storage modulus versus cure time
for a sulfur cure of an arborescent polymer (06DNX130) formed in
accordance with the present invention, where the polymer contains
60 phr of N234 carbon black;
[0027] FIG. 8 is a graph depicting storage modulus versus cure time
for a peroxide cure of an arborescent polymer (06DNX130) formed in
accordance with the present invention, where the polymer contains
60 phr of N234 carbon black;
[0028] FIG. 9 is a graph depicting plots for stress versus
elongation for the cured polymers of FIGS. 7 and 8;
[0029] FIG. 10 is a graph depicting a plot of storage modulus
versus cure time obtained for an arborescent polymer composition in
accordance with one embodiment of the present invention, where the
polymer (06DNX130) contains 100 parts of N234 carbon black and the
plot is obtained at a temperature of 166.degree. C.;
[0030] FIG. 11 is a graph depicting torque and temperature
increases during mixing for an arborescent polymer in accordance
with one comparative example of the present invention (06DNX090)
and an arborescent polymer in accordance with one embodiment of the
present invention (06DNX130);
[0031] FIG. 12 is a graph depicting plots of storage modulus versus
temperature phase angle versus temperature for an arborescent
polymer (06DNX030) formed in accordance with one embodiment of the
present invention;
[0032] FIG. 13 is a graph depicting plots for stress versus strain
for the samples (06DNX030) prepared in accordance with one
embodiment of the present invention;
[0033] FIG. 14 is a graph depicting plots of storage modulus versus
temperature for a raw polymer (06DNX030) formed in accordance with
one embodiment of the present invention and for a polymer
(06DNX030) formed in accordance with one embodiment of the present
invention mixed with 60 phr N234 carbon black;
[0034] FIG. 15 is a graph depicting plots for stress versus
elongation for a polymer according to the present invention with 60
phr N234 carbon black (06DNX030 with carbon black) and a raw
polymer (06DNX030) formed in accordance with one embodiment of the
present invention;
[0035] FIG. 16 is a graph depicting plots for stress versus
elongation for a polymer according to the present invention with 60
phr N234 carbon black (06DNX110 mixed with 60 phr N234) and a raw
polymer (06DNX110) formed in accordance with one embodiment of the
present invention;
[0036] FIG. 17 is a graph depicting plots for stress versus
elongation for a polymer according to the present invention with 60
phr N234 carbon black (06DNX110 mixed with 60 phr N234) and a raw
polymer (06DNX110) formed in accordance with one embodiment of the
present invention;
[0037] FIG. 18 is a graph depicting a degradation study comparison
a comparison between arbPIB-PMS-OH with and without carbon
black;
[0038] FIG. 19 is a graph depicting plots for stress versus
elongation for raw polymer samples PB402, an arborescent copolymer
with 0.4 mol percent CPD formed in accordance with the present
invention (Example 8, raw polymer) and an arborescent copolymer
with 1.7 mole percent CPD formed in accordance with the present
invention (Example 9, raw polymer);
[0039] FIG. 20 is a graph depicting plots for stress versus
elongation for PB402 with 60 phr N234 carbon black, an arborescent
copolymer with 0.4 mole percent CPD formed in accordance with the
present invention filled with N234 (Example 8 with 60 phr N234),
and the arborescent copolymer with 1.7 mole percent CPD formed in
accordance the present invention filled with N234 (Example 9 with
60 phr N234); and
[0040] FIGS. 21A and 21B are DSC data from an arb-CPD polymer
formed in accordance with the present invention (Example 8, raw
polymer) and arb-CPD according to the present invention that
contains 60 phr carbon black (Example 8 with 60 phr N234).
DETAILED DESCRIPTION OF THE INVENTION
[0041] The present invention relates to arborescent polymers and to
a process for making same. In one embodiment, the present invention
relates to arborescent polymers formed from at least one inimer and
at least one isoolefin that have been end-functionalized with a
polymer or copolymer having a low glass transition temperature
(T.sub.g), and to a process for making such arborescent polymers.
In another embodiment, the present invention relates to arborescent
polymers formed from at least one inimer and at least one isoolefin
that have been end-functionalized with less than about 5 weight
percent end blocks derived from a polymer or copolymer having a
high glass transition temperature (T.sub.g), and to a process for
making such arborescent polymers. In still another embodiment, the
present invention relates to arborescent polymers formed from at
least one inimer and at least one isoolefin that have been
end-functionalized, where such polymers have a saturated core and
one or more unsaturated end-functionalized portions. In still
another embodiment, the present invention relates to arborescent
polymers that exhibit phase separation even though such polymers
would normally fall within the weakly separated or homogeneous
portion of a standard polymer phase diagram.
[0042] In still another embodiment, the present invention relates
to arborescent polymers formed from at least one inimer and at
least one isoolefin that have been end-functionalized with about
0.5 to about 50 weight percent end blocks derived from a polymer or
copolymer having a low T.sub.g. In another instance, polymers
according to this embodiment, have from about 1 to about 40 weight
percent end-blocks, or about 2 to about 30 weight percent end
blocks, or about 3 to about 20 weight percent end blocks, or even
from about 1 to about 25 weight percent end blocks. Here, as well
as elsewhere in the specification and claims, individual range
limits may be combined to form additional ranges.
[0043] In yet another embodiment, the present invention relates to
arborescent polymers formed from at least one inimer and at least
one isoolefin that have been end-functionalized with about 0.5 to
about 5 weight percent end blocks derived from a polymer or
copolymer having a high glass transition temperature (T.sub.g). In
another instance, polymers according to this embodiment, have from
about 1 to about 4 weight percent end blocks, or even from about
1.5 to about 3.5 weight percent end blocks. In another instance,
polymers according to this embodiment, are end-functionalized with
styrene or a styrene derivative having a high glass transition
temperature.
[0044] In still yet embodiment, the present invention relates to
arborescent polymers that have one or more end-functionalized
portions, or even two or more end-functionalized portions (i.e.,
branch-like appendages). Regarding the end-functionalized portions,
such portions can be formed from the same, similar, or different,
or even any combination thereof, end blocks, where such end blocks
are derived from a polymer or copolymer having either a high glass
transition temperature (T.sub.g) or a low glass transition
temperature (T.sub.g).
[0045] In the present invention, a polymer or copolymer having a
low glass transition temperature is defined to be a polymer or
copolymer having a glass transition temperature of less than about
40.degree. C., or less than about 35.degree. C., or less than about
30.degree. C., or even less than about 25.degree. C. In another
embodiment, a polymer or copolymer having a low glass transition
temperature is defined to be a polymer or copolymer having a glass
transition temperature less than about room temperature (i.e.,
25.degree. C.). It should be noted that the previously stated
ranges are intended to encompass any polymers and/or copolymers
that have a glass transition temperature that falls below one of
the previously stated thresholds.
[0046] Conversely, a polymer or copolymer having a high glass
transition temperature is defined to be a polymer or copolymer
having a glass transition temperature of more than about 40.degree.
C., or more than about 45.degree. C., or more than about 50.degree.
C., or more even more than about 100.degree. C. It should be noted
that the previously stated ranges are intended to encompass any
polymers and/or copolymers that have a glass transition temperature
that falls above one of the previously stated thresholds.
[0047] Additionally, in the specification and claims the word
polymer is used generically and encompasses regular polymers (i.e.,
homopolymers) as well as copolymers, block copolymers, random block
copolymers and terpolymers.
[0048] In still another embodiment, the present invention relates
to arborescent polymers formed from at least one inimer and at
least one isoolefin that have been end-functionalized with a low
T.sub.g homo or copolymer that contains isoprene or any other
cationically polymerizable monomer.
[0049] In yet another embodiment, the present invention relates to
arborescent polymers that that have been end-functionalized and
further include at least one filler, where such polymers have been
formed from at least one inimer and at least one isoolefin. An
exemplary reaction scheme for producing polymers according to this
embodiment is shown below where each F represents one or more
functional end blocks according to the present invention that
preferentially interact with one more filler particles.
##STR00001##
[0050] In still another embodiment, the present invention relates
to arborescent polymers formed from at least one inimer and at
least one isoolefin that have been end-functionalized with a
copolymer or homopolymer containing functional groups derived from
a diene or diene derivative, or blocks of polydiene and polydiene
derivatives. In another instance, the polymers of this embodiment,
or other various embodiments disclosed herein, can be subjected to
a bromination step.
[0051] In still another embodiment, the present invention relates
to arborescent polymers formed from at least one inimer and at
least one isoolefin that have been end-functionalized with about
0.5 to about 5 weight percent end blocks derived from a styrene or
a styrene derivative, or blocks containing polystyrene or its
derivatives.
[0052] In yet another embodiment, the present invention relates to
end-functionalized arborescent polymers where such polymers can be
crosslinked and/or cured to form a butyl rubber, where the rubber
can optionally contain one or more fillers. In another instance,
the polymers of this embodiment can be subjected to a halogenation
step (e.g., a bromination or chlorination step).
[0053] In yet another embodiment, the present invention relates to
end-functionalized thermoplastic elastomeric arborescent polymers
that are reinforced with one or more fillers, where the one or more
fillers preferentially interact with the end-functionalized
portions of such arborescent polymers.
[0054] In still another embodiment, the present invention relates
to end-functionalized thermoplastic elastomeric arborescent
polymers formed from at least one inimer and at least one
isoolefin, wherein the end-functionalized portions of such polymers
have a number average molecular weight of less than about 10,000
g/mol, less than about 7,500 g/mol, less than about 6,000 g/mol, or
even less than about 5,000 g/mol.
Inimers:
[0055] Initially, self-condensing monomers combine features of a
monomer and an initiator and the term "inimer" (IM) is used
describe such compounds. If a small amount of a suitable inimer is
copolymerized with, for example, isobutylene, arborescent
polyisobutylenes can be synthesized. Formula (I) below details the
nature of the inimer compounds that can be used in conjunction with
the present invention. In Formula (I) A represents the
polymerizable portion of the inimer compound, while B represents
the initiator portion of the inimer compound.
A-B (I) [0056] where A is
[0056] ##STR00002## [0057] where B is
##STR00003##
[0057] In Formula (I), R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5
and R.sub.6 are each, in one embodiment, independently selected
from hydrogen, linear or branched C.sub.1 to C.sub.10 alkyl, or
C.sub.5 to C.sub.8 aryl. In another embodiment, R.sub.1, R.sub.2,
and R.sub.3 are all hydrogen. In another embodiment, R.sub.4,
R.sub.5 and R.sub.6 are each independently selected from hydrogen,
hydroxyl, bromine, chlorine, fluorine, iodine, ester
(--O--C(O)--R.sub.7), peroxide (--OOR.sub.7), and --O--R.sub.7
(e.g., --OCH.sub.3 or --OCH.sub.2.dbd.CH.sub.3). With regard to
R.sub.7, R.sub.7 is an unsubstituted linear or branched C.sub.1 to
C.sub.20 alkyl, an unsubstituted linear or branched C.sub.1 to
C.sub.10 alkyl, a substituted linear or branched C.sub.1 to
C.sub.20 alkyl, a substituted linear or branched C.sub.1 to
C.sub.10 alkyl, an aryl group having from 2 to about 20 carbon
atoms, an aryl group having from 9 to 15 carbon atoms, a
substituted aryl group having from 2 to about 20 carbon atoms, a
substituted aryl group having from 9 to 15 carbon atoms. In one
embodiment, where one of R.sub.4, R.sub.5 and R.sub.6 either a
chlorine or fluorine, the remaining two of R.sub.4, R.sub.5 and
R.sub.6 are independently selected from an unsubstituted linear or
branched C.sub.1 to C.sub.20 alkyl, an unsubstituted linear or
branched C.sub.1 to C.sub.10 alkyl, a substituted linear or
branched C.sub.1 to C.sub.20 alkyl, a substituted linear or
branched C.sub.1 to C.sub.10 alkyl. In still another embodiment,
any two of R.sub.4, R.sub.5 and R.sub.6 can together form an
epoxide.
[0058] In one embodiment, portions A and B of inimer compound (I)
are joined to one another via a benzene ring. In one instance,
portion A of inimer compound (I) is located at the 1 position of
the benzene ring while portion B is located at either the 3 or 4
position of the benzene ring. In another embodiment, portions A and
B of inimer compound (I) are joined to one another via the linkage
shown below in Formula (II):
##STR00004##
where n is an integer in the range of 1 to about 12, or from 1 to
about 6, or even from 1 to about 3. In another embodiment, n is
equal to 1 or 2.
[0059] In another embodiment, for isobutylene polymerization B can
be a tertiary ether, tertiary chloride, tertiary methoxy group or
tertiary ester. Very high molecular weight arborescent PIBs can be
synthesized using the process of the present invention with inimers
such as 4-(2-hydroxy-isopropyl)styrene and
4-(2-methoxy-isopropyl)styrene.
[0060] Exemplary inimers for use in conjunction with the present
invention include, but are not limited to,
4-(2-hydroxyisopropyl)styrene, 4-(2-methoxyisopropyl)styrene,
4-(1-methoxyisopropyl)styrene, 4-(2-chloroisopropyl)styrene,
4-(2-acetoxyisopropyl)styrene, 2,3,5,6-tertamethyl-4-(2-hydroxy
isopropyl)styrene, 3-(2-methoxyisopropyl)styrene,
4-(epoxyisopropyl)styrene, 4,4,6-trimethyl-6-hydroxyl-1-heptene,
4,4,6-trimethyl-6-chloro-1-heptene,
4,4,6-trimethyl-6,7-epoxy-1-heptene,
4,4,6,6,8-pentamethyl-8-hydroxyl-1-nonene,
4,4,6,6,8-pentamethyl-8-chloro-1-nonene,
4,4,6,6,8-pentamethyl-8,9-epoxy-1-nonene,
3,3,5-trimethyl-5-hydroxyl-1-hexene,
3,3,5-trimethyl-5-chloro-1-hexene,
3,3,5-trimethyl-5-6-epoxy-1-hexene,
3,3,5,5,7-pentamethyl-7-hydroxyl-1-octene,
3,3,5,5,7-pentamethyl-7-chloro-1-octene, or
3,3,5,5,7-pentamethyl-7,8-epoxy-1-octene. In one embodiment, the
inimer of the present invention is selected from
4-(2-methoxyisopropyl)styrene or 4-(epoxyisopropyl)styrene.
[0061] In still another embodiment, the inimer utilized in
conjunction with the present invention has a formula according to
one of those shown below:
##STR00005##
wherein X corresponds to a functional organic group from the series
--CR.sup.1.sub.2Y, where Y represents OR, Cl, Br, I, CN, N.sub.3 or
SCN and R.sup.1 represents H and/or a C.sub.1 to C.sub.20 alkyl,
and Ar represents C.sub.6H.sub.4 or C.sub.10H.sub.8.
Isoolefin:
[0062] Formula (III) details the nature of the isoolefin compounds
that can be used in conjunction with the present invention.
##STR00006##
where R.sub.9 is C.sub.1 to C.sub.4 alkyl group such as methyl,
ethyl or propyl. In one embodiment, the compound according to
Formula (III) is isobutylene (i.e., isobutene) or
2-methyl-1-butene.
[0063] In one embodiment, 4-(2-methoxyisopropyl)styrene or
4-(epoxyisopropyl)styrene is used as the inimer and isobutylene as
the isoolefin, as will be described in detail below, to yield an
arborescent polymer as shown below in Scheme 1.
##STR00007##
Using the process of the present invention, the structure of
arborescent polymers (e.g., arborescent polyisobutylenes) can be
varied within a wide range. For example, arborescent polymers
according to the present invention can be controlled via the molar
ratios of inimer and monomer (e.g., isobutylene) added to the
polymerization charge. For example, decreasing the concentration of
inimer relative to the concentration of isobutylene monomer in the
feed will result in longer chains with reduced degrees of
branching. Conversely, increasing the concentration of inimer
relative to the amount of isobutylene leads to the formation of a
polymer with a highly branched structure having shorter arm
lengths. Scheme 1 above illustrates the result of these two
scenarios. Further alteration of the arborescent core can be
achieved by the sequential addition of inimer and/or monomer
throughout the polymerization process. For example a "pom-pom"-like
polymer architecture results by first making a structure shown on
the left side of Scheme 1 followed by the sequential addition of
both inimer and monomer.
[0064] Distinct changes in the rheological properties of a polymer
formed in accordance with the present invention are made possible
by changes in the chain architecture. Arborescent polyisobutylenes
(PIB) formed in accordance with the present invention have reduced
shear sensitivity due to the branched structure, and reduced
viscosity compared to linear polymers of equivalent chain length.
More specifically, the use of arborescent PIBs in rubber compound
formulations have been shown to produce materials with increased
green strength, reduced cold flow, and reduced die swell.
[0065] In another embodiment, the arborescent polymers of the
present invention can be functionalized with co-monomers which can
provide useful chemical properties to the PIB template. For
example, the main PIB backbone can be synthesized and then the
addition of the co-monomer at the later stages of the
polymerization can provide end blocks on the growing arms of the
macromolecule. Scheme 2 below represents a functionalized
arborescent polymer made in accordance with the present invention,
as will be detailed below.
##STR00008##
In Scheme 2, the saw-tooth portions represent the functionalization
of the arborescent polymer shown on the right side of Scheme 1.
[0066] In the present invention, the end-functionalized portion of
the polymers disclosed herein can be derived, according to the
embodiments detailed above, from any suitable low or high glass
transition polymer. Suitable polymers for accomplishing the
end-functionalization of the present invention include, but are not
limited to, homo or copolymer of styrene or styrene derivatives,
including indene and its derivatives, diene or triene (conjugated
or other dienes such as isoprene, butadiene-1,3;
2-methylbutadiene-1,3; 2,4-dimethylbutadiene-1,3; piperyline;
3-methylpentadiene-1,3; hexadiene-2,4; 2-neopentylbutadiene-1,3;
2-methlyhexadiene-1,5; 2,5-dimegyhexadiene-2,4;
2-methylpentadiene-1,4; 2-methylheptadiene-1,6; cyclopentadiene;
methylcyclopentadiene; cyclohexadiene; 1-vinyl-cyclohexadiene; or
mixtures of two or more thereof), norbornadiene, and
.beta.-pinene.
[0067] Among the advantages made possible by the process of the
present invention is the ability to produce butyl-based polymer
compounds that possess increased filler affinity, have improved
processability characteristics, are able to be injection molded
(due in part to lower viscosities); increased tolerance to
peroxide-based curing, have a high degree of unsaturation, and
permit high temperature production of butyl-based polymer compounds
(e.g., at a temperature of about -40.degree. C.).
[0068] In one embodiment, the process according to the present
invention is carried out in an inert organic solvent or solvent
mixture in order that the polyisoolefin and the final polymer
product remain in solution. At the same time, the solvent also
provides a degree of polarity so that the polymerization process
can proceed at a reasonable rate. Suitable solvents include single
solvents such as n-butyl chloride. In another embodiment, a mixture
of a non-polar solvent and a polar solvent can be used. Suitable
non-polar solvents include, but are not limited to, hexane,
methylcyclohexane and cyclohexene. Suitable polar solvents include,
but are not limited to, ethyl chloride, methyl chloride and
methylene chloride. In one embodiment, the solvent mixture is a
combination of methylcyclohexane and methyl chloride, or even
hexane and methyl chloride. To achieve suitable solubility and
polarity it has been found that the ratio of the non-polar solvent
to the polar solvent on a weight basis should be from about 80:20
to about 40:60, from about 75:25 to about 45:55, from about 70:30
to about 50:50, or even about 60:40. Again, here, as well as
elsewhere in the specification and claims, individual range limits
may be combined.
[0069] The temperature range within which the process is carried
out is from about -20.degree. C. to about -100.degree. C., or from
about -30.degree. C. to about -90.degree. C., or from about
-40.degree. C. to about -85.degree. C., or even from about
-50.degree. C. to about -80.degree. C. The process of the present
invention is, in one embodiment, carried out using an about 1 to
about 30 percent polyisoolefin solution (weight/weight basis), or
even from about 5 to about 10 weight percent polyisoolefin
solution.
[0070] In order to produce the arborescent polymers of the present
invention it is, in one embodiment, necessary to use a co-initiator
(e.g., a Lewis acid halide). Suitable Lewis acid halides include,
but are not limited to, BCl.sub.3, BF.sub.3, AlCl.sub.3,
SnCl.sub.4, TiCl.sub.4, SbF.sub.5, SeCl.sub.3, ZnCl.sub.2,
FeCl.sub.3, VCl.sub.4, AlR.sub.nCl.sub.3-n, wherein R is an alkyl
group and n is less than 3, and mixtures thereof. In one
embodiment, titanium tetrachloride (TiCl.sub.4) is used as the
co-initiator.
[0071] The branched block copolymers of the present invention can
also be produced in a one-step process wherein the isoolefin is
co-polymerized with the initiator monomer in conjunction with the
co-initiator in a solution at a temperature of from about
-20.degree. C. to about -100.degree. C., or from about -30.degree.
C. to about -90.degree. C., or from about -40.degree. C. to about
-85.degree. C., or even from about -50.degree. C. to about
-80.degree. C. An electron donor and a proton trap are introduced,
followed by the addition of a pre-chilled solution of the
co-initiator in a non-polar solvent (e.g., hexane). The
polymerization is allowed to continue until it is terminated by the
addition of a nucleophile such as methanol.
[0072] In some embodiments, production of arborescent polymers in
accordance with the present invention necessitates the use of
additives such as electron pair donors to improve blocking
efficiency and proton traps to minimize homopolymerization.
Examples of suitable electron pair donors are those nucleophiles
that have an electron donor number of at least 15 and no more than
50 as tabulated by Viktor Gutmann in The Donor Acceptor Approach to
Molecular Interactions, Plenum Press (1978) and include, but are
not limited to, ethyl acetate, dimethylacetamide, dimethylformamide
and dimethyl sulphoxide. Suitable proton traps include, but are not
limited to, 2,6-ditertiarybutylpyridine,
4-methyl-2,6-ditertiarybutylpyridine and diisopropylethylamine.
[0073] In another embodiment, the arborescent polymers of the
present invention can also contain one or more fillers. Suitable
fillers include, but are not limited to, carbon black, silica,
starch, clays, nanoclays, carbon nanotubes, other silicon based
fillers, etc. In the case where one or more fillers are utilized in
conjunction with the present invention, the filler can be bound,
attached, captured and/or entrained by the end-functionalized
portion of the arborescent polymers of the present invention rather
than by the core portion thereof (e.g., the polyisobutylene
portion).
[0074] In yet another embodiment, the present invention provides a
rubber composition comprising at least one, optionally halogenated,
arborescent polymer, at least one filler and at least one
vulcanizing agent. In order to provide a vulcanizable rubber
compound, at least one vulcanizing agent or curing system has to be
added. The present invention is not limited to any one type of
curing system. An exemplary curing system is a sulfur curing
system. In such an instance, the amount of sulfur utilized in the
curing process can be in the range of from about 0.3 to about 2.0
phr (parts by weight per hundred parts of rubber). An activator,
for example zinc oxide, can also be used. If present, the amount of
activator ranges from about 0.5 parts to about 5 parts by
weight.
[0075] Other ingredients, for instance stearic acid, oils (e.g.,
Sunpar.RTM. of Sunoco), antioxidants, or accelerators (e.g., a
sulfur compound such as dibenzothiazyldisulfide (e.g.,
Vulkacit.RTM. DM/C of Bayer AG) can also be added to the compound
prior to curing. Curing (e.g., sulfur-based cure) is then effected
in a known manner. See, for instance, Chapter 2, The Compounding
and Vulcanization of Rubber, in Rubber Technology, Third Edition,
Chapman & Hall, 1995. This publication is hereby incorporated
by reference for its teachings relating to cure systems.
[0076] The vulcanizable rubber compound according to the present
invention can contain further auxiliary products for rubbers, such
as reaction accelerators, vulcanizing accelerators, vulcanizing
acceleration auxiliaries, antioxidants, foaming agents, anti-aging
agents, heat stabilizers, light stabilizers, ozone stabilizers,
processing aids, plasticizers, tackifiers, blowing agents,
dyestuffs, pigments, waxes, extenders, organic acids, inhibitors,
metal oxides, and activators such as triethanolamine, polyethylene
glycol, hexanetriol, etc. Such compounds, additives, and/or
products are known in/to the rubber industry. The rubber aids are
used in conventional amounts, which depend on the intended use.
Conventional amounts are, for example, from about 0.1 to about 50
phr. In one embodiment, the vulcanizable compound comprising a
solution blend further comprises in the range of about 0.1 to about
20 phr of one or more organic fatty acids as an auxiliary product.
In one embodiment, the unsaturated fatty acid has one, two or more
carbon double bonds in the molecule which can include about 10% by
weight or more of a conjugated diene acid having at least one
conjugated carbon-carbon double bond in its molecule. In another
embodiment, the fatty acids used in conjunction with the present
invention have from about 8 to about 22 carbon atoms, or even from
about 12 to about 18 carbon atoms. Suitable examples include, but
are not limited to, stearic acid, palmitic acid and oleic acid and
their calcium-, zinc-, potassium-, magnesium- and ammonium salts.
Furthermore up to about 40 parts of processing oil, or even from
about 5 to about 20 parts of processing oil, per hundred parts of
elastomer, can be present.
[0077] It may be advantageous to further add silica modifying
silanes, which give enhanced physical properties to silica or
silicious filler containing compounds. Compounds of this type
possess a reactive silylether functionality (for reaction with the
silica surface) and a rubber-specific functional group. Examples of
these modifiers include, but are not limited to,
bis(triethoxysilylpropyl)tetrasulfane,
bis(triethoxy-silylpropyl)disulfane, or thiopropionic acid
S-triethoxylsilyl-methyl ester. The amount of silica modifying
silane is in the range of from about 0.5 to about 15 parts per
hundred parts of elastomer, or from about 1 to about 10, or even
from about 2 to about 8 parts per hundred parts of elastomers. The
silica modifying silane can be used alone or in conjunction with
other substances which serve to modify the silica surface
chemistry.
[0078] The ingredients of the final vulcanizable rubber compound
comprising the rubber compound are often mixed together, suitably
at an elevated temperature that can range from about 25.degree. C.
to about 200.degree. C. Normally the mixing time does not exceed
one hour and a time in the range from about 2 to about 30 minutes
is usually adequate. Mixing is suitably carried out in an internal
mixer such as a Banbury mixer, or a Haake or Brabender miniature
internal mixer. A two roll mill mixer also provides a good
dispersion of the additives within the elastomer. An extruder also
provides good mixing, and permits shorter mixing times. It is
possible to carry out the mixing in two or more stages, and the
mixing can be done in different apparatus, for example one stage in
an internal mixer and one stage in an extruder. For compounding and
vulcanization see also: Encyclopedia of Polymer Science and
Engineering, Volume 4, p. 66 et seq. (Compounding) and Volume 17,
p. 666 et seq. (Vulcanization). This publication is hereby
incorporated by reference for its teachings relating to compounding
and vulcanization.
[0079] In still another embodiment, in the case where the
arborescent polymers of the present invention are
end-functionalized, the core portion (e.g., the polyisobutylene
portion) has no curable sites, whereas the end-functionalized
portion in this embodiment can have one or more curable sites. This
permits, among other things, for such arborescent polymers to
undergo peroxide cure without causing damage to the overall
arborescent polymer structure. Also possible, in such instances,
are the use of other cure systems such as sulfur-based cure systems
to obtain a cured composition in accordance with the present
invention.
[0080] The number average molecular weight (M.sub.n) polymers of
the present invention range from about 500 g/mol to about 2,000,000
g/mol; or from about 1,000 g/mol to about 1,500,000 g/mol; or from
about 10,000 g/mol to about 1,000,000 g/mol; or from about 20,000
g/mol to about 500,000 g/mol; or from about 50,000 g/mol to about
400,000 g/mol; or from about 70,000 g/mol to about 300,000 g/mol;
or even from about 80,000 g/mol to about 295,000 g/mol. In another
embodiment, the number average molecular weight (M.sub.n) polymers
of the present invention range from about 20,000 g/mol to about
300,000 g/mol. Again, here, as well as elsewhere in the
specification and claims, individual range limits may be
combined.
[0081] In one embodiment, the polymers of the present invention
have a narrow molecular weight distribution such that the ratio of
weight average molecular weight to number average molecular weight
(M.sub.w/M.sub.n) is in the range of about 1.0 to about 4.5, or
from about 1.1 to about 4.0, or from about 1.2 to about 3.5, or
from about 1.3 to about 3.0, or from about 1.4 to about 2.5, or
even from about 1.5 to about 2.0. In another embodiment, the
polymers of the present invention have a narrow molecular weight
distribution such that the ratio of weight average molecular weight
to number average molecular weight (M.sub.w/M.sub.n) is in the
range of 1.6 to about 2.4, or from about 1.7 to about 2.3, or from
about 1.8 to about 2.2, or from about 1.9 to about 2.1, or even
from about 1.5 to about 1.9.
EXAMPLES
[0082] The following examples are descriptions of methods within
the scope of the present invention, and use of certain compositions
of the present invention as described in detail above. The
following examples fall within the scope of, and serve to
exemplify, the more generally described compositions, formulations
and processes set forth above. As such, the examples are not meant
to limit in any way the scope of the present invention.
[0083] Butyl polymers containing an arborescent butyl core and
chemically curable end-sequences are prepared as will be discussed
in detail below. All polymerizations are carried out in an MBraun
MB 15OB-G-I dry box.
[0084] Chemicals:
[0085] 4-(2-methoxy-isopropyl)styrene (p-methoxycumyl styrene,
pMeOCumSt) is synthesized, while isobutylene and methyl chloride
are used without further purification from a suitable production
unit. Isoprene (IP, 99.9% and available from Aldrich) is passed
through a p-tert-butylcatechol inhibitor remover column prior to
usage.
[0086] Test Methods:
[0087] The molecular weight and molecular weight distributions of
the polymers are determined by size exclusion chromatography (SEC).
The system consists of a Waters 515 HPLC pump, a Waters 2487 Dual
Absorbance Detector, a Wyatt Optilab Dsp Interferometric
Refractometer, a Wyatt DAWN EOS multi-angle light scattering
detector, a Wyatt Viscostar viscometer, a Wyatt QELS quasi-elastic
light scattering instrument, a 717plus autosampler and 6
Styragel.RTM. columns (HR1/2, HR1, HR3, HR4, HR5 and H6). The RI
detector and the columns are thermostated at 35.degree. C. and THF
freshly distilled from CaH.sub.2 is used as the mobile phase at a
flow rate of 1 ml/min. The results are analyzed using ASTRA
software (Wyatt Technology). Molecular weight calculation is
carried out using 100% mass recovery as well as 0.108 cm.sup.3/g
do/dc value.
[0088] HNMR measurements are conducted using a Bruker Avance 500
instrument and deuterated chloroform or THF as the solvent. Raw
polymer Mooney measurements are conducted at 125.degree. C. using a
MV 2000 rotational viscometer manufactured by Alpha Technology.
Mixing with carbon black is accomplished using a 75 cm.sup.3
Banbury type Brabender mixer.
[0089] Dynamic properties of all the samples are determined in
compression using Gabo Eplexor 150N. Test conditions: static
strain: 5%; max force: 20N; dynamic strain: 2%; max force: 10N;
frequency: 10 Hz; heating rate: 2.degree. C./min; and load between
measurements: preload. Stress strain measurements are done at
23.degree. C. using 500 mm/min crosshead speed on an Instron Model
1122 instrument.
[0090] In Example 1, inimer is added at a concentration of
1.14.times.10.sup.-3 mol/dm.sup.3. In Example 2, inimer is added at
a concentration of 2.27.times.10.sup.-3 mol/dm.sup.3.
Example 1
06DNX001
[0091] Polymerization is carried out in a 3 dm.sup.3 round shape
baffled glass reactor. The reactor is equipped with a glass stirrer
rod (mounted with a crescent shaped Teflon impeller) and a
thermocouple. To the reactor are added 0.35 grams of pMeOCumSt, 900
cm.sup.3 hexane (measured at room temperature), 600 cm.sup.3 methyl
chloride (measured at -95.degree. C.), 2 cm.sup.3
di-tert-butylpyridine (measured at room temperature) and 240
cm.sup.3 isobutylene (measured at -95.degree. C.). Polymerization
is started at -95.degree. C. by addition of a pre-chilled mixture
of 6 cm.sup.3 TiCl.sub.4 and 20 cm.sup.3 hexane (both measured at
room temperature). After 120 minutes of polymerization, a mixture
of 236 cm.sup.3 isoprene (measured at room temperature), 150
cm.sup.3 methyl chloride (measured at -95.degree. C.) and 0.5
cm.sup.3 di-tert-butylpyridine (measured at room temperature) is
added. Upon the addition of the isoprene charge, the viscous
solution turns into a two phase system. The solution is brought
back to a viscous solution by the addition of 150 cm.sup.3 hexane
(measured at room temperature and cooled to -95.degree. C.) at 130
minutes. At 135 minutes a pre-chilled mixture of 3 cm.sup.3
TiCl.sub.4 and 20 cm.sup.3 hexane (both measured at room
temperature) is added. Polymerization is terminated at 150 minutes
by the addition of 125 cm.sup.3 methanol containing 11 grams of
NaOH. During the polymerization, samples are taken using a cold
pipette and discharged into test tubes containing 10 cm.sup.3 of
methanol.
[0092] After the evaporation of methyl chloride, hexane is added to
the polymer solution and the solution is washed neutral with water.
The polymer product is isolated with steam coagulation and dried on
a hot mill to a constant weight. The dried weight of the polymer is
164.7 grams.
[0093] During polymerization, samples are withdrawn from the charge
using a cold pipette at different times and injected into vials
containing methanol. The molecular weights of these samples are
measured to illustrate the increase in molecular weight during
polymerization. The characteristics of various samples taken at
different time intervals are noted in Table 1.
TABLE-US-00001 TABLE 1 Reaction M.sub.n M.sub.w M.sub.z M.sub.w/
Sample Time dn/dc (g/mol) (g/mol) (g/mol) M.sub.n 06DNX001-1 10
0.098 70,300 82,700 101,300 1.18 06DNX001-2 20 0.107 94,400 145,300
471,400 1.54 06DNX001-3 40 0.114 175,700 292,200 551,000 1.66
06DNX001-4 80 0.108 267,300 536,300 1,152,000 2.01 06DNX001-5 115
0.114 246,800 562,700 1,301,000 2.28 06DNX001-6 132 0.109 288,200
662,600 1,567,000 2.30 06DNX001-7 150 0.11 295,000 717,800
1,778,000 2.43
[0094] In Table 1, the time column indicates the time at which
samples for testing are withdrawn from the above described
polymerization reaction.
[0095] HNMR analysis indicated that the amount of isoprene
incorporated into the polymer is 0.7 mole percent. The Mooney
viscosity of the finished product is determined to be 41.6
(1+8@125.degree. C.).
[0096] The cure activity of the sample is determined in the absence
and presence of carbon black. Tables 2 and 3 below show the
formulations used in parts per hundred parts of rubber. The cure is
measured at 166.degree. C. using an MDR made by Alpha Technology.
The test conditions are: 1.degree. arc, 1.7 Hz. FIG. 1 shows a
comparison between the torque curves of the raw polymer (06DNX001
RP) and a filled polymer (06DNX001 with carbon black).
TABLE-US-00002 TABLE 2 Polymer 100 Stearic Acid 1 Sulfur NBS 1.5
Vulkacit Merkapto MG/C (MBT) 0.5 Vulkacit Thiuram/C (D) 1 Zinc
Oxide 5
TABLE-US-00003 TABLE 3 Polymer 100 N234 60 Stearic Acid 1 Sulfur
NBS 1.5 Vulkacit Merkapto MG/C (MBT) 0.5 Vulkacit Thiuram/C (D) 1
Zinc Oxide 5
[0097] Next raw 06DNX001 polymer is mixed with 60 phr N234 carbon
black in a Banbury type Brabender mixer using a 78.8% fill factor.
The torque development and temperature increase during mixing is
significantly more pronounced than with typical and/or regular
butyl compositions. FIG. 2 is a graph depicting the torque and
temperature increases during mixing for an arborescent polymer of
the present invention (06DNX001) and a commercial grade butyl
(RB402). Maximum temperature, torque and specific energy of the
samples prepared in accordance with the present invention are
higher than that of the linear samples at the same or even at a
lower raw polymer Mooney viscosity. The torque of the arborescent
sample formed in accordance with the present invention also shows a
distinctive second peak as illustrated by FIG. 2. This is an
indication of improved filler dispersion (see N. Tokita and I.
Pliskin, Rubber Chem. & Technol., 46, 1166 (1973)). Butyl
rubber is known to mix poorly with carbon black. Typically, such a
butyl rubber does not have a distinctive second torque peak or such
a peak is very ill defined. Tokita divided a torque curve into
three regions (see N. Tokita and I. Pliskin, Rubber Chew. &
Technol., 46, 1166 (1973)). The first is the filler wetting region
located between the filler addition and the minimum of the power
curve, and the second is the dispersion region located between the
minimum of the power curve and just over the second power peak.
This region is followed by the mastication region. Generally
speaking, the higher the second torque peak the better the filler
dispersion. According to Tokita, improved filler dispersion is
expected to result in a lower Mooney viscosity, higher die swell
and mill shrinkage.
[0098] The sheeted out black mix shows unexpected strength at room
temperature indicating a strong reinforcement uncharacteristic to
regular butyl polymers. This is illustrated by the stress strain
curves of the carbon black mixes obtained using macro dumbbells cut
out from molded macro sheets. The molding is done at 160.degree. C.
FIG. 3 is a graph depicting plots for stress versus elongation for
a green polymer according to the present invention with 60 phr N234
carbon black (06DNX001 with 60 phr N234) and a green regular grade
butyl with 60 phr N234 carbon black (RB402 with 60 phr N234).
[0099] For comparison purposes the stress strain curve of the RB402
compound is included in FIG. 3. RB402 contains 97.2 mole percent
isobutylene and 2.2 mole percent isoprene. The arborescent sample
06DNX001 contains 99.3 mole percent isobutylene and 0.7 mole
percent isoprene. However, the molecular architecture is
drastically different as RB402 contains linear chains and the
isoprene moieties are scattered randomly along the chain.
Arborescent polymer 06DNX001 contains a branched PIB core and the
isoprene units are attached to the ends of the arms thereby forming
a localized high isoprene content isobutylene-isoprene copolymer.
While not wishing to be bound to any one theory, the localized
nature of 06DNX001 is believed to increase the polymer-filler
interactions.
Example 2
06DNX130
[0100] Polymerization is carried out in a 3 dm.sup.3 round shape
baffled glass reactor. The glass reactor is equipped with a glass
stirrer road (mounted with a crescent shaped Teflon impeller) and a
thermocouple. To the reactor are added 0.70 grams of pMeOCumSt, 900
cm.sup.3 hexane (measured at room temperature), 600 cm.sup.3 methyl
chloride (measured at -92.degree. C.), 2 cm.sup.3
di-tert-butylpyridine (measured at room temperature) and 240
cm.sup.3 isobutylene (measured at -92.degree. C.). Polymerization
is started by the addition of a pre-chilled mixture of 6 cm.sup.3
TiCl.sub.4 and 30 cm.sup.3 hexane (both measured at room
temperature). After 45 minutes of polymerization, a pre-chilled
mixture of 70 cm.sup.3 isoprene, 0.5 cm.sup.3
di-tert-butylpyridine, and 0.90 cm.sup.3 dimethyl acetamide (all
measured at room temperature) is added. To accelerate the reaction
a 1.0 molar solution of ethyl aluminum dichloride in hexane is
added in 10 cm.sup.3 increments at 45.5, 48 and 50.5 minutes.
Addition of the last increment resulted in 4.degree. C. temperature
rise indicating the onset of polymerization. Soon after that, the
solution started to climb up on the stirrer road indicating an
increase in viscosity. Polymerization is terminated at 60 minutes
by the addition of 125 cm.sup.3 methanol containing 11 grams of
NaOH.
[0101] After the evaporation of the methyl chloride, hexane is
added to the polymer solution and the solution is washed neutral
with water. Thereafter, 0.2 grams of Irganox 1076 is added to the
solution and the polymer is isolated by steam coagulation and dried
on a hot mill to a constant weight. The dried weight of the polymer
is 174.23 grams. According to HNMR measurement the amount of 1,4-P
enchainment is 2.6 mole percent. The Mooney viscosity of the
finished product is determined to be 30.6 (1+8@125.degree. C.).
[0102] The sheeted out raw polymer sample displays unexpected
strength (elasticity) at room temperature in spite of its low
Mooney viscosity at 125.degree. C. This observation is quantified
by green strength measurements. For this measurement micro
dumbbells are cut out from molded macro sheets of the raw polymers.
The green strength of the arborescent butyl is compared to a high
Mooney viscosity (52) regular butyl grade, RB301. FIG. 4 shows
plots for stress versus elongation for a raw polymer according to
the present invention (06DNX130 RP) and a regular grade butyl
(RB301). Increased green strength of the arborescent polymer of the
present invention over the linear commercial grade is clearly
demonstrated by the continuous rise of tensile strength with
elongation. In contrast, the higher Mooney viscosity linear butyl
displayed peak strength at about 250% elongation. Following this
peak, the linear butyl showed a gradual decrease in strength.
[0103] Raw polymer is mixed with 60 phr N234 carbon black in a
Banbury type Brabender mixer using 78.8% fill factor. The torque
development and temperature increase during mixing is significantly
more pronounced than with typical and/or regular butyl
compositions. FIG. 5 is a graph illustrating the torque and
temperature increases during mixing for the arborescent polymer of
the present invention (06DNX130) and a commercial grade butyl
(RB402). The Mooney viscosity of the RB402 sample is determined to
be 31.3 (1+8@125.degree. C.).
[0104] Maximum temperature, torque and specific energy of the
samples prepared in accordance with the present invention are
higher than that of the linear samples at the same or even at a
lower raw polymer Mooney viscosity. The torque of the arborescent
sample formed in accordance with the present invention also shows a
second peak as illustrated by FIG. 5. This is an indication of
improved filler dispersion. Butyl rubber is known to mix poorly
with carbon black. Typically, butyl rubber does not have a
distinctive second torque peak or it is very ill defined. Tokita
divided a torque curve into three regions (see N. Tokita and I.
Pliskin, Rubber Chew. & Technol., 46, 1166 (1973)). The first
is the filler wetting region located between the filler addition
and the minimum of the power curve, and the second is the
dispersion region located between the minimum of the power curve
and just over the second power peak. This region is followed by the
mastication region. Generally speaking, the higher the second
torque peak the better the filler dispersion. According to Tokita,
improved filler dispersion is expected to result in a lower Mooney
viscosity, higher die swell and mill shrinkage.
[0105] The sheeted out black mix shows unexpected strength at room
temperature indicating a strong reinforcement uncharacteristic to
regular butyl polymers. This is illustrated by the stress strain
curves of the carbon black mixes obtained using macro dumbbells cut
out from molded macro sheets. FIG. 6 shows plots for stress versus
elongation for a polymer according to the present invention with 60
phr N234 carbon black (06DNX130 with 60 phr N234) and a regular
grade butyl with 60 phr N234 carbon black (RB402 with 60 phr
N234).
[0106] Cure activity is demonstrated first using the formulation
outlined in Table 3 above. The recorded cure curve is shown in FIG.
7. Specifically, FIG. 7 is a graph depicting storage modulus versus
cure time for a sulfur cure of an arborescent polymer formed in
accordance with the present invention, where the polymer contains
60 phr of N234 carbon black. FIG. 8 illustrates/confirms that an
arborescent polymer according to one embodiment of the present
invention can be cured using peroxide. The cure is achieved by the
addition of 4 phr DiCuP 40.degree. C. and 2 phr HVA#2.
Specifically, FIG. 8 is a graph depicting storage modulus versus
cure time for a peroxide cure of an arborescent polymer formed in
accordance with the present invention, where the polymer contains
60 phr of N234 carbon black.
[0107] FIG. 9 is a graph depicting plots for stress versus
elongation for the cured polymers of FIGS. 7 and 8.
[0108] A sample of this example (06DNX130) is also mixed with 100
phr N234 carbon black in order to demonstrate the ability of an
arborescent polymer formed in accordance with the present invention
to absorb a high quantity of filler. After the mix a smooth
compound is obtained and no loose carbon black is detected in the
mixer. The mix is compounded with the curatives listed in Table 3,
using the indicated loading. FIG. 10 is a graph depicting a plot of
storage modulus versus cure time obtained for this composition at
166.degree. C.
Example 3
05DNX150
[0109] This is a comparative example designed to determine the
behavior of the arborescent PIB core.
[0110] Polymerization is carried out in a 5 dm.sup.3 round shape
baffled glass reactor. The glass reactor is equipped with a glass
stirrer road (mounted with a crescent shaped Teflon impeller) and a
thermocouple. To the reactor are added 0.7 grams of pMeOCumSt, 1800
cm.sup.3 methyl-cyclohexane (measured at room temperature), 1200
cm.sup.3 methyl chloride (measured at -95.degree. C.), 4 cm.sup.3
di-tert-butylpyridine (measured at room temperature) and 480
cm.sup.3 isobutylene (measured at -95.degree. C.). Polymerization
is started at -93.degree. C. by the addition of a pre-chilled
mixture of 11 cm.sup.3 TiCl.sub.4 and 40 cm.sup.3
methyl-cyclohexane (both measured at room temperature). After 85
minutes of polymerization, a mixture of 100 cm.sup.3 isoprene
(measured at room temperature), 250 cm.sup.3 of isobutylene
(measured at -95.degree. C.), and 250 cm.sup.3 methyl-cyclohexane
(measured at room temperature) is added. Polymerization is
terminated at 122 minutes by the addition of 125 cm.sup.3 methanol
containing 11 grams of NaOH. During the polymerization samples are
taken using a cold pipette. Samples are discharged into test tubes
containing 10 cm.sup.3 of methanol.
[0111] After the evaporation of methyl chloride, hexane is added to
the polymer solution and the solution is washed neutral with water.
The resulting polymer is isolated with steam coagulation and dried
on a hot mill to a constant weight. HNMR analysis indicates that
the amount of isoprene incorporated into the polymer is very low,
approximately 0.1 mole percent.
[0112] During polymerization, samples are withdrawn from the charge
using a cold pipette at different times and injected into vials
containing methanol. The molecular weights of these samples are
measured to illustrate the increase in molecular weight during
polymerization. The characteristics of various samples taken at
different time intervals are noted in Table 4.
TABLE-US-00004 TABLE 4 Reaction M.sub.n M.sub.w M.sub.z M.sub.w/
Sample Time dn/dc (g/mol) (g/mol) (g/mol) M.sub.n 05DNX150-1 25
0.114 86,800 119,500 182,300 1.38 05DNX150-2 52 0.114 190,300
355,100 969,100 1.87 05DNX150-3 75 0.117 254,500 529,600 1,229,000
2.08 05DNX150-4 90 0.111 289,600 624,700 1,478,000 2.16 05DNX150-5
100 0.111 295,300 617,100 1,414,000 2.09 05DNX150-6 110 0.111
293,100 622,000 1,384,000 2.12
[0113] In Table 4, the time column indicates the time at which
samples for testing are withdrawn from the above described
polymerization reaction.
Example 4
06DNX090
[0114] This is another comparative example designed to determine
the behavior of the arborescent PIB core.
[0115] Polymerization is carried out in a 3 dm.sup.3 round shape
baffled glass reactor. The glass reactor is equipped with a glass
stirrer road (mounted with a crescent shaped Teflon impeller) and a
thermocouple. To the reactor are added 0.7 grams of pMeOCumSt, 900
cm.sup.3 hexane (measured at room temperature), 600 cm.sup.3 methyl
chloride (measured at -95.degree. C.), 2 cm.sup.3
di-tert-butylpyridine (measured at room temperature) and 240
cm.sup.3 isobutylene (measured at -95.degree. C.). Polymerization
is started at -93.degree. C. by the addition of a pre-chilled
mixture of 6 cm.sup.3 TiCl.sub.4 and 30 cm.sup.3 methyl cyclohexane
(both measured at room temperature). Polymerization is terminated
at 121 minutes by the addition of 125 cm.sup.3 methanol containing
11 grams of NaOH. During the polymerization samples are taken using
a cold pipette. Samples are discharged into test tubes containing
10 cm.sup.3 of methanol.
[0116] After the evaporation of methyl chloride, hexane is added to
the resulting polymer solution and the solution is washed neutral
with water. The resulting polymer is isolated with steam
coagulation and dried on a hot mill to a constant weight. The dried
weight of the polymer is 164.54 grams.
[0117] FIG. 4, as discussed above, also illustrates that a polymer
according to the present invention in combination with 60 phr N234
carbon black (06DNX130 with 60 phr N234) behaves like a cured
elastomer. The black mix can be repeatedly remolded and upon
cooling down a new rubber-like article is obtained.
[0118] The following comparison proves that the arborescent nature
of the PIB core does not result in the improved torque development
during the mix or the observed TPE behavior of the black mix. FIG.
11 compares a mixing curve for an arborescent compound of Example 2
(06DNX130) with the mixing behavior of the arborescent PIB core of
this Example (06DNX090). Specifically, FIG. 11 is a graph depicting
torque and temperature increases during mixing for an arborescent
polymer in accordance with Example 4 of the present invention
(06DNX090) and an arborescent polymer in accordance with Example 2
of the present invention (06DNX130).
[0119] As can be seen in FIG. 11 the second large torque peak is
absent from the mixing curve of the arborescent PIB core
composition this Example (06DNX090). Also the temperature plateaus
out at an earlier time and stabilizes at a lower value during
mixing for the arborescent PIB core composition of this Example
(06DNX090) as compared to the arborescent compound of Example 2
(06DNX130).
Example 5a
06DNX030
[0120] Polymerization is carried out in a 3 dm.sup.3 round shape
baffled glass reactor. The glass reactor is equipped with a glass
stirrer rod (mounted with a crescent shaped Teflon impeller) and a
thermocouple. To the reactor are added 0.35 grams of pMeOCumSt, 900
cm.sup.3 hexane (measured at room temperature), 600 cm.sup.3 methyl
chloride (measured at -95.degree. C.), 2 cm.sup.3
di-tert-butylpyridine (measured at room temperature) and 240
cm.sup.3 isobutylene (measured at -95.degree. C.). Polymerization
is started at -93.degree. C. by the addition of a pre-chilled
mixture of 6 cm.sup.3 TiCl.sub.4 and 20 cm.sup.3 hexane (both
measured at room temperature). After 85 minutes of polymerization
time a pre-chilled mixture of 250 cm.sup.3 hexane, 70 cm.sup.3
pMeSt, 0.5 cm.sup.3 of di-tert-butyl-pyridine (all measured at room
temperature), 150 cm.sup.3 methyl chloride along with 120 cm.sup.3
isobutylene (measured at -95.degree. C.) is added. After 200
minutes of total polymerization time, the reaction is terminated by
the addition of 11 grams of NaOH dissolved in 125 cm.sup.3
methanol. During the polymerization samples are taken using a cold
pipette. Samples are discharged into test tubes containing 10
cm.sup.3 of methanol.
[0121] From independent rate measurements the unreacted isobutylene
in the reactor is calculated to be 4.9 grams at the moment of the
addition of pMeSt/IB mixture. Therefore the pMeSt content of the
monomer charge after addition of the monomer mixture is 24.8 mole
percent. After the evaporation of methyl chloride, hexane is added
to the polymer solution and the solution is washed neutral with
water. The resulting polymer is isolated with steam coagulation and
dried on a hot mill followed by molding in a press at 180.degree.
C. The dried weight of the polymer is 188.96 grams.
[0122] HNMR measurement indicated that the overall pMeSt content of
the resulting polymer is 4.5 mole percent or 9.5 weight
percent.
[0123] During polymerization, samples are withdrawn from the charge
using a cold pipette at different times and injected into vials
containing methanol. The molecular weights of these samples are
measured to illustrate the increase in molecular weight during
polymerization. The characteristics of various samples taken at
different time intervals are noted in Table 5.
TABLE-US-00005 TABLE 5 Reaction M.sub.w M.sub.n Sample Time (g/mol)
(g/mol) M.sub.w/M.sub.n 06DNX030-1 15 123,000 86,680 1.42
06DNX030-2 30 222,700 136,800 1.63 06DNX030-3 50 364,000 189,700
1.92 06DNX030-4 80 482,700 218,100 2.21 06DNX030-5 95 473,300
252,000 1.88 06DNX030-6 115 540,900 273,200 1.98 06DNX030-7 145
506,100 262,200 1.93
[0124] In Table 4, the time column indicates the time at which
samples for testing are withdrawn from the above described
polymerization reaction.
[0125] The glass transition temperature of the outer IB-co-pMeSt
sequences can not be detected by DSC. Dynamic testing of the raw
polymer also fails to show the glass transition temperature of the
outer segments (FIG. 12).
[0126] Raw polymer (06DNX030) is mixed with 60 phr N234 carbon
black in a Banbury type Brabender mixer using 78.8% fill factor.
Dynamic testing of the black mix reveals the presence of a rubbery
plateau (FIG. 14). Specifically, FIG. 14 is a graph depicting plots
of storage modulus versus temperature for a raw polymer (06DNX030)
formed in accordance with one embodiment of the present invention
and for a polymer (06DNX030) formed in accordance with one
embodiment of the present invention mixed with 60 phr N234 carbon
black.
[0127] The sheeted out black mix shows unexpected strength at room
temperature indicating a strong reinforcement uncharacteristic to
regular butyl polymers. This is illustrated by the stress strain
curves of the black mix obtained using macro dumbbells cut out from
molded macro sheets. Molding is done at 160.degree. C. FIG. 15 is a
graph depicting plots for stress versus elongation for a polymer
according to the present invention with 60 phr N234 carbon black
(06DNX030 with carbon black), and a raw polymer (06DNX030) formed
in accordance with one embodiment of the present invention. FIG. 15
illustrates that a molded article has a significant strength and it
behaves like a cured elastomer at room temperature.
Example 5b
06DNX030
[0128] Five mixes are formed by mixing 100 parts of Example 5a
(06DNX030) with 20 parts silica (Zeosil 1165 MP available from
Rhodia) in a Haake Buchler Rheocord System 40 drive unit equipped
with a 75 cc Rheomix mixer, without any compatibilizer additives.
For all the mixes a 73% fill factor is used. The mixer is heated to
130.degree. C. and is loaded at 20 rpm with the rubber followed by
the silica. Mixing is carried out at 100 rpm using a maximum of 5
minutes mixing time and the compound was dumped at 170.degree. C.
Sheets are compression molded at 180.degree. C. using a 63.6 mm by
63.6 mm by 1.26 mm square mold having a 10 mm wide slit on one side
for the overflow of excess material, and the following procedure:
samples are heated for 3 minutes in the mold and molded at the
specified temperature for 5 minutes using 30 tons ram force (5''
diameter ram). After five minutes the mold is transferred to a cold
press to cool the sample. Microdumbbell specimens are cut from the
sheet. FIG. 13 shows the stress-strain curves of this material. As
can be seen from FIG. 13, strong filler reinforcement occurs (from
8 to 16 MPa) in the samples made in accordance with this
Example.
Example 6
06DNX110
[0129] Polymerization is carried out in a 3 dm.sup.3 round shape
baffled glass reactor. The glass reactor is equipped with a glass
stirrer rod (mounted with a crescent shaped Teflon impeller) and a
thermocouple. To the reactor is added 0.7 grams of Epoxy Inimer,
900 cm.sup.3 hexane (measured at room temperature), 600 cm.sup.3
methyl chloride (measured at -95.degree. C.), 2 cm.sup.3
di-tert-butylpyridine (measured at room temperature) and 240
cm.sup.3 isobutylene (measured at -95.degree. C.). Polymerization
is started at -93.degree. C. by the addition of a pre-chilled
mixture of 6 cm.sup.3 TiCl.sub.4 and 30 cm.sup.3 hexane (both
measured at room temperature). After 67 minutes of polymerization
time a pre-chilled mixture of 250 cm.sup.3 hexane, 70 cm.sup.3
pMeSt, 1.0 cm.sup.3 of di-tert.-butyl-pyridine, 0.9 cm.sup.3 of
dimethyl acetamide (all measured at room temperature), 150 cm.sup.3
methyl chloride along with 120 cm.sup.3 isobutylene (measured at
-95.degree. C.) is added. After 160 minutes of total polymerization
time, the reaction is terminated by the addition of 11 grams of
NaOH dissolved in 125 cm.sup.3 of methanol. During the
polymerization, samples are taken using a cold pipette. Samples are
discharged into test tubes containing 10 cm.sup.3 of methanol.
[0130] From rate measurements, the unreacted isobutylene in the
reactor is calculated to be 19.2 grams at the moment of the
addition of pMeSt/IB mixture. Therefore the pMeSt content of the
monomer charge after addition of the monomer mixture is 22.2 mole
percent.
[0131] After the evaporation of methyl chloride, hexane is added to
the polymer solution and the solution is washed neutral with water.
The resulting polymer is isolated with steam coagulation and dried
on a hot mill followed by molding the polymer in a press at
180.degree. C. The dried weight of the polymer is 155.30 grams.
HNMR measurement indicates that the overall pMeSt content of the
resulting polymer is 2.3 mole percent or 4.8 weight percent. The
raw polymer is then mixed with 60 phr N234 carbon black. The black
mix displays a rubber-like behavior. A macro sheet is compression
molded at 160.degree. C. and the stress strain behavior is compared
to the raw polymer. FIG. 16 shows the recorded stress strain
curves. Specifically, FIG. 16 is a graph depicting plots for stress
versus elongation for a polymer according to the present invention
with 60 phr N234 carbon black (06DNX110 mixed with 60 phr N234) and
a raw polymer (06DNX110), formed in accordance with one embodiment
of the present invention.
Example 7
06DNX120
[0132] Polymerization is carried out in a 3 dm.sup.3 round shape
baffled glass reactor. The glass reactor is equipped with a glass
stirrer rod (mounted with a crescent shaped Teflon impeller) and a
thermocouple. To the reactor is added 0.7 grams of Epoxy Inimer,
900 cm.sup.3 hexane (measured at room temperature), 600 cm.sup.3
methyl chloride (measured at -95.degree. C.), 2 cm.sup.3
di-tert-butylpyridine (measured at room temperature) and 240
cm.sup.3 isobutylene (measured at -95.degree. C.). Polymerization
is started at -93.degree. C. by the addition of a pre-chilled
mixture of 6 cm.sup.3 TiCl.sub.4 and 30 cm.sup.3 hexane (both
measured at room temperature). After 37.5 minutes of polymerization
time a pre-chilled mixture of 250 cm.sup.3 hexane, 70 cm.sup.3
pMeSt, 1.0 cm.sup.3 of di-tert.-butyl-pyridine, 0.9 cm.sup.3 of
dimethyl acetamide (all measured at room temperature) and 150
cm.sup.3 methyl chloride along with 120 cm.sup.3 isobutylene
(measured at -95.degree. C.) is added. After 151 minutes of total
polymerization time, the reaction is terminated by the addition of
11 grams of NaOH dissolved in 125 cm.sup.3 of methanol. During the
polymerization, samples are taken using a cold pipette. Samples are
discharged into test tubes containing 10 cm.sup.3 of methanol.
[0133] From rate measurements, the unreacted isobutylene in the
reactor is calculated to be 51.3 grams at the moment of the
addition of pMeSt. Therefore, the pMeSt content of the monomer
charge after addition of the monomer mixture is 36.8 mole
percent.
[0134] After the evaporation of methyl chloride, hexane is added to
the polymer solution and the solution is washed neutral with water.
The resulting polymer is isolated with steam coagulation and dried
on a hot mill followed by molding the polymer in a press at
180.degree. C. The dried weight of the polymer is 156 grams. HNMR
measurement indicates that the overall pMeSt content of the
resulting polymer is 7.9 mole percent or 16.8 weight percent. The
raw polymer is then mixed with 60 phr N234 carbon black. The black
mix displays a rubber-like behavior. A macro sheet is compression
molded at 160.degree. C. and the stress strain behavior is compared
to the raw polymer.
[0135] FIG. 17 depicts the recorded stress strain curves for the
above samples. Specifically, FIG. 17 is a graph depicting plots for
stress versus elongation for a polymer according to the present
invention with 60 phr N234 carbon black (06DNX120 mixed with 60 phr
N234) and a raw polymer (06DNX120) formed in accordance with one
embodiment of the present invention. In this case the raw polymer
already displays thermoplastic elastomeric properties. However, 60
phr carbon black reinforces the material substantially, nearly
doubling its tensile strength.
[0136] In the 0.degree. C. to 200.degree. C. range,
T.sub.g=111.6.degree. C. This is characteristic of the
poly(paramethylstyrene) end blocks (PMS) measured on the raw
polymer (TA Instruments DSC, 10.degree. C./min heating rate, 10 mg
sample). The T.sub.g of the polymer filled with carbon black was
140.7.degree. C. The raw polymer is extracted with methyl ethyl
ketone, hexane and ethanol (Soxhlet extractor, 10 to 15 passes at
reflux temperature). There is no measurable weight loss after the
exhaustive extraction.
[0137] Samples of the raw and black-filled polymer are subjected to
biodegradation studies in vitro. Twelve discs (D=12 mm) are cut
from 1 mm thick sheets. A pH 7.4 Buffer solution is prepared with
DI water from Hydrion Chemvelopes -7.4+/-0.02 @ 25.degree. C.
buffer. A color indicator is added to show freshness of buffer.
Samples are placed into wells with 2 mL of buffer in each well. The
tray is placed in an incubator on a shaker (CAT 520) at motor level
2 (Selutec TECO 20), with the temperature set at 36.degree. C. The
experiment is carried out for 20 days, the buffer is changed every
Monday, Wednesday, and Friday and the mass is recorded. FIG. 18
shows the results based on a plot of swelling percentage versus
days of exposure for the samples noted above. No biodegradation is
observed, and the carbon-filled sample was more hydrophilic.
[0138] In vitro testing of response to bacteria is carried out as
follows: EF260506 and EF310506 samples (5 mm discs sterilized by
ethylene oxide) are placed on Agar containing human erythrocytes
(HE). The plates are inoculated with bacteria: first
bacteria--staphylococcus aureas (S.A.) at a 0.5 McF concentration
and at a 0.005 McF concentration, the second bacteria--MRSA at a
0.5 McF concentration and at a 0.005 McF concentration. A third
sample of each polymer is placed on Agar with no HE and S.A. is
added at 0.005 McF. The samples are placed in an incubator set at
35.degree. C. for 24 hours, then inhibition zones are measured and
photographs are taken. No inhibition zones are found around the
polymer disks.
[0139] In vivo biocompatibility studies are carried out by
implanting microdumbbells into rats. The samples are explanted
after 6 months. Excellent tissue interaction (no inflammation) is
observed.
Example 8
[0140] Polymerization is carried out in a 500 cm.sup.3 round shape
baffled glass reactor. The reactor is equipped with a glass stirrer
rod (mounted with a crescent shaped Teflon impeller) and a
thermocouple. To the reactor are added 0.07 grams of pMeOCumSt
inimer, 90 cm.sup.3 methylcyclohexane (measured at room
temperature), 60 cm.sup.3 methyl chloride (measured at -92.degree.
C.), 0.2 cm.sup.3 di-tert-butylpyridine (measured at room
temperature) and 24 cm.sup.3 isobutylene (measured at -92.degree.
C.). Polymerization is started at -92.degree. C. by addition of a
pre-chilled mixture of 0.6 cm.sup.3 TiCl.sub.4 and 3 cm.sup.3
methylcyclohexane (both measured at room temperature). After 45
minutes of polymerization, a mixture of 2 cm.sup.3 of
cyclopentadiene (measured at room temperature), 5 cm.sup.3 of
isobutylene, 10 cm.sup.3 methylcyclohexane (measured at room
temperature), and 0.2 cm.sup.3 di-tert-butylpyridine (measured at
room temperature). Upon the addition of the cyclopentadiene charge,
the solution turns light orange and increases in viscosity.
Polymerization is terminated at 54 minutes by the addition of 15
cm.sup.3 ethanol containing 1 gram of NaOH.
[0141] After the evaporation of methyl chloride, hexane is added to
the polymer solution and the solution is washed neutral with water.
The polymer product is isolated with steam coagulation and dried in
an oven at 100.degree. C. under vacuum for 48 hours to remove
residual water. The isolated polymeric material was white in
appearance with a dry weight of 17.2 grams. The material was
completely soluble (gel-free) and is analyzed by HNMR and SEC. The
HNMR indicated that the cyclopentadiene content of the material is
0.4 mole percent. Table 6 below lists data relating to this
Example.
[0142] FIG. 19 depicts the recorded stress strain curves for the
unfilled materials. Specifically, FIG. 19 is a graph depicting
plots for stress versus elongation for raw polymer samples for
PB402 and for a polymer with 0.4 mole percent CPD. RB402 contains
97.2 mole percent polyisobutylene PIB and 2.2 mole percent isoprene
IP. The arborescent sample contains 99.6 mole percent isobutylene
and 0.4 mole percent cyclopentadiene. However, as with the previous
example, the molecular architecture is drastically different as
RB402 contains linear PIB chains and the unsaturated groups (IP)
are scattered randomly along the chain. The arborescent polymer of
the present example contains a branched PIB core and the
cyclopentadiene units are in the IB-co-CPD block attached to the
ends of the arms thereby forming a localized high cyclopentadiene
content in the copolymer. In FIG. 19, the materials show a yield
point and behave as predicted, without any filler.
[0143] The raw polymer from Example 8 is then mixed with 60 phr
N234 carbon black on a Brabender micro-mill with a roll temperature
of 45.degree. C. The sheeted out black mix shows unexpected
strength at room temperature as shown in FIG. 20, indicating a
strong reinforcement uncharacteristic to regular butyl polymers. To
help illustrate this effect, a comparative example using PB 402 (a
commercial grade of butyl) is prepared. A macro sheet is
compression molded at 130.degree. C. and the stress strain behavior
is compared. The arbPIB-CPD functionalized polymer of the invention
with only 0.4 mol % of cyclopentadiene (Example 8) provides
additional evidence of significant filler interaction, which is not
apparent in the linear PB402 sample.
[0144] FIG. 20 as discussed above, also illustrates that a polymer
according to the present invention in combination with 60 phr N234
carbon black (Example 10 with 60 phr N234) behaves like a cured
elastomer. However, the black mix can be repeatedly remolded and
upon cooling down a new rubber-like article is obtained (recyclable
rubber).
TABLE-US-00006 TABLE 6 Mole Percent Yield M.sub.n M.sub.w M.sub.z
M.sub.w/ CPD Sample (g) (kg/mol) (kg/mol) (kg/mol) M.sub.n (HNMR)
Example 8 17.2 216 486 1954 2.25 0.4
[0145] The glass transition temperature of the outer IB-co-CPD
sequences can not be detected by DSC for either the raw polymer or
the filled compound (FIGS. 21A and 21B).
Example 9
[0146] Polymerization is carried out in a 500 cm.sup.3 round shape
baffled glass reactor. The reactor is equipped with a glass stirrer
rod (mounted with a crescent shaped Teflon impeller) and a
thermocouple. To the reactor are added 0.07 grams of pMeOCumSt, 90
cm.sup.3 methylcyclohexane (measured at room temperature), 60
cm.sup.3 methyl chloride (measured at -92.degree. C.), 0.2 cm.sup.3
di-tert-butylpyridine (measured at room temperature) and 24
cm.sup.3 isobutylene (measured at -92.degree. C.). Polymerization
is started at -92.degree. C. by addition of a pre-chilled mixture
of 0.6 cm.sup.3 TiCl.sub.4 and 3 cm.sup.3 methylcyclohexane (both
measured at room temperature). After 45 minutes of polymerization,
a mixture of 5 cm.sup.3 of cyclopentadiene (measured at room
temperature), 2 cm.sup.3 of isobutylene, 10 cm.sup.3
methylcyclohexane (measured at room temperature), and 0.2 cm.sup.3
di-tert-butylpyridine (measured at room temperature). Upon the
addition of the cyclopentadiene charge, the solution turns light
orange and dramatically increases in viscosity. Polymerization is
terminated at 48 minutes by the addition of 15 cm.sup.3 ethanol
containing 1 gram of NaOH.
[0147] After the evaporation of methyl chloride, hexane is added to
the polymer solution and the solution is washed neutral with water.
The polymer product is isolated with steam coagulation and dried in
an oven at 100.degree. C. under vacuum for 48 hours to remove
residual moisture. The isolated polymeric material is white in
appearance with a dry weight of 16.5 grams. The material contains
low amounts of gel (approximately 1%) and therefore only the
soluble fraction is analyzed by HNMR and SEC. The HNMR indicated
that the cyclopentadiene content of the soluble fraction is 1.7
mole percent. The resulting data is shown below in Table 7.
[0148] FIG. 19 depicts the recorded stress strain curves for the
unfilled materials. Specifically, FIG. 19 is a graph depicting
plots for stress versus elongation for raw polymer samples. In this
example, the arborescent material contains 98.3 mole percent
isobutylene and 1.7 mole percent cyclopentadiene. However, as with
the previous example, the molecular architecture is drastically
different as RB402 contains linear PIB chains and the unsaturated
groups (IP) are scattered randomly along the chain. The arborescent
polymer of the present example contains a branched PIB core and the
cyclopentadiene units are in the IB-co-CPD block attached to the
ends of the arms thereby forming a localized high cyclopentadiene
content in the copolymer. In FIG. 19, the materials show a yield
point and behave as predicted, without any filler.
[0149] The raw polymer from this example (Example 9) is then mixed
with 60 phr N234 carbon black on a Brabender micro-mill with a roll
temperature of 45.degree. C. The sheeted out black mix shows
unexpected strength at room temperature as shown in FIG. 20,
indicating a strong reinforcement uncharacteristic to regular butyl
polymers. As before, this effect is illustrated by comparison with
PB 402 (a commercial grade of butyl). The arbPIB-CPD functionalized
polymer of the present invention, with 1.7 mole percent of
cyclopentadiene groups (Example 9), shows evidence of significant
filler interaction, which is not apparent in the linear PB402
sample.
[0150] FIG. 20 as discussed above, also illustrates that a polymer
according to the present invention in combination with 60 phr N234
carbon black (Example 9 with 60 phr N234) behaves like a cured
elastomer. However, the black mix can be repeatedly remolded and
upon cooling down a new rubber-like article is obtained (i.e.,
recyclable rubber).
TABLE-US-00007 TABLE 7 Mole Percent Yield M.sub.n M.sub.w M.sub.z
M.sub.w/ CPD Sample (g) (kg/mol) (kg/mol) (kg/mol) M.sub.n (HNMR)
Example 9 16.5 207 455 2759 2.20 1.7 (soluble fraction)
Example 10
[0151] Polymerization is carried out in a 500 cm.sup.3 round shape
baffled glass reactor. The reactor is equipped with a glass stirrer
rod (mounted with a crescent shaped Teflon impeller) and a
thermocouple. To the reactor are added 0.07 grams of pMeOCumSt
inimer, 90 cm.sup.3 hexane (measured at room temperature), 60
cm.sup.3 methyl chloride (measured at -92.degree. C.), 0.2 cm.sup.3
di-tert-butylpyridine (measured at room temperature) and 24
cm.sup.3 isobutylene (measured at -92.degree. C.). Polymerization
is started at -92.degree. C. by addition of a pre-chilled mixture
of 0.6 cm.sup.3 TiCl.sub.4 and 3 cm.sup.3 hexane (both measured at
room temperature). After 45 minutes of polymerization, a mixture of
7 cm.sup.3 of cyclopentadiene (measured at room temperature), 10
cm.sup.3 hexanes (measured at room temperature), 0.1 cm.sup.3
di-tert-butylpyridine (measured at room temperature), and 0.1
cm.sup.3 dimethylacetamide is added. Upon the addition of the
cyclopentadiene charge, the solution turns light orange and
dramatically increases in viscosity. Polymerization is terminated
at 48 minutes by the addition of 15 cm.sup.3 ethanol containing 1
gram of NaOH.
[0152] After the evaporation of methyl chloride, hexane is added to
the polymer solution and the solution is washed neutral with water.
The polymer product is isolated with steam coagulation and dried in
an oven at 100.degree. C. under vacuum for 48 hours to remove
residual water. The isolated polymeric material for example 10 is
white in appearance with a dry weight of 18.4 grams. The resulting
material contains a fraction of gel (approximately 48%) and
therefore only the soluble portion is fully characterized using
HNMR and SEC techniques. The resulting data is presented below in
Table 8. HNMR measurement indicates that the overall
cyclopentadiene content of the soluble fraction of the polymer is
3.5 mole percent.
TABLE-US-00008 TABLE 8 Mole Percent Yield M.sub.n M.sub.w M.sub.z
M.sub.w/ CPD Sample (g) (kg/mol) (kg/mol) (kg/mol) M.sub.n (HNMR)
Example 18.4 80 408 1288 5.1 3.5 10 (soluble fraction)
Example 11
[0153] Polymerization is carried out in a 500 cm.sup.3 round shape
baffled glass reactor. The reactor is equipped with a glass stirrer
rod (mounted with a crescent shaped Teflon impeller) and a
thermocouple. To the reactor are added 0.07 grams of pMeOCumSt
inimer, 90 cm.sup.3 hexane (measured at room temperature), 60
cm.sup.3 methyl chloride (measured at -92.degree. C.), 0.2 cm.sup.3
di-tert-butylpyridine (measured at room temperature) and 24
cm.sup.3 isobutylene (measured at -92.degree. C.). Polymerization
is started at -92.degree. C. by addition of a pre-chilled mixture
of 0.6 cm.sup.3 TiCl.sub.4 and 3 cm.sup.3 hexane (both measured at
room temperature). After 45 minutes of polymerization, a mixture of
7 cm.sup.3 of cyclopentadiene (measured at room temperature), 10
cm.sup.3 hexanes (measured at room temperature) and 0.1 cm.sup.3
di-tert-butylpyridine (measured at room temperature) is added. Upon
the addition of the cyclopentadiene charge, the solution turns
light orange and dramatically increases in viscosity.
Polymerization is terminated at 48 minutes by the addition of 15
cm.sup.3 ethanol containing 1 gram of NaOH.
[0154] After the evaporation of methyl chloride, hexane is added to
the polymer solution and the solution is washed neutral with water.
The polymer product is isolated with steam coagulation and dried in
an oven at 100.degree. C. under vacuum for 48 hours to remove
residual water. The isolated polymeric material for example 11 is
white in appearance with a dry weight of 19.0 grams. The resulting
material contains a fraction of gel (approximately 78%) and
therefore only the soluble portion is fully characterized using
HNMR and SEC techniques. The resulting data is presented below in
Table 9. HNMR measurement indicates that the overall
cyclopentadiene content of the soluble fraction of the polymer is 9
mole percent.
TABLE-US-00009 TABLE 9 Mole Percent Yield M.sub.n M.sub.w M.sub.z
M.sub.w/ CPD Sample (g) (kg/mol) (kg/mol) (kg/mol) M.sub.n (HNMR)
Example 19.0 184 776 1796 4.2 9.0 11 (soluble fraction)
[0155] Although not limited thereto, the compounds of the present
invention are useful in a variety of technical fields. Such fields
include, but are not limited to, biomedical applications (e.g., use
in stents), tire applications (e.g. use in innerliners),
food-related packaging applications, pharmaceutical closures and in
various sealant applications. With regard to the use of the
compounds of the present invention in various tire applications, in
such cases the compounds of the present invention can be further
"modified" by a halogenation step (e.g., a bromination or
chlorination step). Such halogenation processes are known to those
of skill in the art and are not reproduced herein for the sake of
brevity.
[0156] Although the invention has been described in detail with
particular reference to certain embodiments detailed herein, other
embodiments can achieve the same results. Variations and
modifications of the present invention will be obvious to those
skilled in the art and the present invention is intended to cover
in the appended claims all such modifications and equivalents.
* * * * *