U.S. patent application number 15/554894 was filed with the patent office on 2018-02-15 for catalyst composition for preparing conjugated diene-based polymer and conjugated diene-based polymer prepared using the same.
This patent application is currently assigned to LG Chem, Ltd.. The applicant listed for this patent is LG Chem, Ltd.. Invention is credited to Jeong Heon Ahn, Hee Jung Jeon, Suk Youn Kang, Dong Hui Kim, Yu Ra Lee, Suk Joon Yoo.
Application Number | 20180044452 15/554894 |
Document ID | / |
Family ID | 57797297 |
Filed Date | 2018-02-15 |
United States Patent
Application |
20180044452 |
Kind Code |
A1 |
Kang; Suk Youn ; et
al. |
February 15, 2018 |
CATALYST COMPOSITION FOR PREPARING CONJUGATED DIENE-BASED POLYMER
AND CONJUGATED DIENE-BASED POLYMER PREPARED USING THE SAME
Abstract
The present invention provides a catalyst composition including
a functionalizing agent of the following Formula 1 together with a
rare earth metal compound, an alkylating agent, and a halogen
compound, having good catalytic activity and polymerization
reactivity and useful for the preparation of a conjugated
diene-based polymer having high linearity and excellent
processability, and a conjugated diene-based polymer prepared using
the catalyst composition. (X.sub.1).sub.a--Si--(X.sub.2).sub.4-a,
[Formula 1] In Formula 1, a, X.sub.1, and X.sub.2 are the same as
defined in the disclosure.
Inventors: |
Kang; Suk Youn; (Daejeon,
KR) ; Jeon; Hee Jung; (Daejeon, KR) ; Kim;
Dong Hui; (Daejeon, KR) ; Yoo; Suk Joon;
(Daejeon, KR) ; Ahn; Jeong Heon; (Daejeon, KR)
; Lee; Yu Ra; (Daejeon, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
LG Chem, Ltd. |
Seoul |
|
KR |
|
|
Assignee: |
LG Chem, Ltd.
Seoul
KR
|
Family ID: |
57797297 |
Appl. No.: |
15/554894 |
Filed: |
June 24, 2016 |
PCT Filed: |
June 24, 2016 |
PCT NO: |
PCT/KR2016/006801 |
371 Date: |
August 31, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08F 4/08 20130101; C08F
2410/01 20130101; C08F 8/32 20130101; C08F 36/04 20130101; C08F
210/12 20130101; C08K 5/544 20130101; C08F 136/06 20130101; C08K
5/57 20130101; C08F 4/545 20130101; C08F 8/42 20130101; C08K 5/0091
20130101; C08L 9/00 20130101; B60C 1/00 20130101; C08F 4/609
20130101; C08F 136/04 20130101; C08F 36/06 20130101; C08F 4/545
20130101; C08F 236/06 20130101; C08F 230/04 20130101 |
International
Class: |
C08F 136/06 20060101
C08F136/06 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 24, 2015 |
KR |
10-2015-0089906 |
Dec 22, 2015 |
KR |
10-2015-0184237 |
Claims
1. A catalyst composition for preparing a conjugated diene-based
polymer, the catalyst composition comprising: a functionalizing
agent of the following Formula 1; a rare earth metal compound; an
alkylating agent; and a halogen compound, wherein the
functionalizing agent is contained in 1 equivalent to 20
equivalents based on 1 equivalent of the rare earth metal compound:
(X.sub.1).sub.a--Si--(X.sub.2).sub.4-a, [Formula 1] in Formula 1, a
is an integer of 1 to 3, X.sub.1 and X.sub.2 are each independently
selected from the group consisting of a hydrogen atom, monovalent
C.sub.1-20 hydrocarbon, --OR, and a covalent bonding functional
group, where at least one of X.sub.1 and X.sub.2 includes the
covalent bonding functional group, where R is selected from the
group consisting of a hydrogen atom, C.sub.1-20 alkyl, C.sub.3-20
cycloalkyl, C.sub.6-20 aryl, C.sub.7-20 alkylaryl, C.sub.7-20
arylalkyl and a covalent bonding functional group, and the covalent
bonding functional group is a functional group containing a
carbon-carbon double bond.
2. The catalyst composition for preparing a conjugated diene-based
polymer of claim 1, wherein the covalent bonding functional group
is selected from the group consisting of C.sub.2-20 alkenyl and
(meth)acryl.
3. The catalyst composition for preparing a conjugated diene-based
polymer of claim 1, wherein the covalent bonding functional group
is selected from the group consisting of vinyl, allyl, methallyl,
butenyl, pentenyl, hexenyl and (meth)acryl.
4. The catalyst composition for preparing a conjugated diene-based
polymer of claim 1, wherein the functionalizing agent comprises one
selected from the group consisting of the following Formulae 2a to
2k, or a mixture of at least two thereof: ##STR00020## in Formulae
2a to 2k, Me means methyl, nBu means n-butyl, Ph means phenyl, and
OEt means ethoxy.
5. The catalyst composition for preparing a conjugated diene-based
polymer of claim 1, wherein X.sub.1 and X.sub.2 in Formula 1 are
each independently selected from the group consisting of linear or
branched C.sub.1-6 alkyl, vinyl, allyl, and methallyl, where at
least one of X.sub.1 and X.sub.2 is selected from the group
consisting of vinyl, allyl, and methallyl.
6. The catalyst composition for preparing a conjugated diene-based
polymer of claim 1, wherein the rare earth metal compound comprises
a neodymium compound of the following Formula 3: ##STR00021## in
Formula 3, R.sub.1 to R.sub.3 are each independently a hydrogen
atom, or linear or branched C.sub.1-12 alkyl.
7. The catalyst composition for preparing a conjugated diene-based
polymer of claim 6, wherein the neodymium compound is Formula 3, in
which R.sub.1 is linear or branched C.sub.6-8 alkyl, and R.sub.2
and R.sub.3 are each independently linear or branched C.sub.2-6
alkyl.
8. The catalyst composition for preparing a conjugated diene-based
polymer of claim 1, wherein the neodymium compound comprises one
selected from the group consisting of Nd(2,2-diethyl
decanoate).sub.3, Nd(2,2-dipropyl decanoate).sub.3, Nd(2,2-dibutyl
decanoate).sub.3, Nd(2,2-dihexyl decanoate).sub.3, Nd(2,2-dioctyl
decanoate).sub.3, Nd(2-ethyl-2-propyl decanoate).sub.3,
Nd(2-ethyl-2-butyl decanoate).sub.3, Nd(2-ethyl-2-hexyl
decanoate).sub.3, Nd(2-propyl-2-butyl decanoate).sub.3,
Nd(2-propyl-2-hexyl decanoate).sub.3, Nd(2-propyl-2-isopropyl
decanoate).sub.3, Nd(2-butyl-2-hexyl decanoate).sub.3,
Nd(2-hexyl-2-octyl decanoate).sub.3, Nd(2,2-diethyl
octanoate).sub.3, Nd(2,2-dipropyl octanoate).sub.3, Nd(2,2-dibutyl
octanoate).sub.3, Nd(2,2-dihexyl octanoate).sub.3,
Nd(2-ethyl-2-propyl octanoate).sub.3, Nd(2-ethyl-2-hexyl
octanoate).sub.3, Nd(2,2-diethyl nonanoate).sub.3, Nd(2,2-dipropyl
nonanoate).sub.3, Nd(2,2-dibutyl nonanoate).sub.3, Nd(2,2-dihexyl
nonanoate).sub.3, Nd (2-ethyl-2-propyl nonanoate).sub.3 and
Nd(2-ethyl-2-hexyl nonanoate).sub.3, or a mixture of at least two
thereof.
9. The catalyst composition for preparing a conjugated diene-based
polymer of claim 1, wherein the alkylating agent comprises an
organoaluminum compound of the following Formula 4:
Al(R).sub.z(X).sub.3-z, [Formula 4] in Formula 4, R is each
independently a hydrocarbyl group; or a heterohydrocarbyl group
comprising at least one heteroatom selected from the group
consisting of a nitrogen atom, an oxygen atom, a boron atom, a
silicon atom, a sulfur atom and a phosphor atom in a hydrocarbyl
structure, X is each independently selected from the group
consisting of a hydrogen atom, a halogen atom, a carboxyl group, an
alkoxy group, and an aryloxy group, and Z is an integer of 1 to
3.
10. The catalyst composition for preparing a conjugated diene-based
polymer of claim 1, wherein 20 equivalents or less of the
functionalizing agent is included based on 1 equivalent of the rare
earth metal compound.
11. The catalyst composition for preparing a conjugated diene-based
polymer of claim 1, wherein from 5 moles to 200 moles of the
alkylating agent is included based on 1 mole of the rare earth
metal compound.
12. The catalyst composition for preparing a conjugated diene-based
polymer of claim 1, wherein from 1 mole to 20 moles of the halogen
compound is included based on 1 mole of the rare earth metal
compound.
13. The catalyst composition for preparing a conjugated diene-based
polymer of claim 1, further comprising one or both selected from
the group consisting of a diene-based monomer and an aliphatic
hydrocarbon-based solvent.
14. A conjugated diene-based polymer prepared by using the catalyst
composition according to claim 1, the conjugated diene-based
polymer has a mooney viscosity of 10 MU to 90 MU at 100.degree. C.
and a polydispersity of 3.4 or less.
15. The conjugated diene-based polymer of claim 14, wherein a
functional group derived from a functionalizing agent of the
following Formula 1 is comprised in a polymer:
(X.sub.1).sub.a--Si--(X.sub.2).sub.4-a [Formula 1] in Formula 1, a
is an integer of 1 to 3, X.sub.1 and X.sub.2 are each independently
selected from the group consisting of a hydrogen atom, monovalent
C.sub.1-20hydrocarbon, --OR, and a covalent bonding functional
group, where at least one of X.sub.1 and X.sub.2 includes the
covalent bonding functional group, where R is selected from the
group consisting of a hydrogen atom, C.sub.1-20 alkyl, C.sub.3-20
cycloalkyl, C.sub.6-20 aryl, C.sub.7-20 alkylaryl, C.sub.7-20
arylalkyl, and a covalent bonding functional group, and the
covalent bonding functional group is a functional group containing
a carbon-carbon double bond.
16. A method for preparing a conjugated diene-based polymer, the
method comprising: polymerizing conjugated diene-based monomers
using the catalyst composition according to claim 1.
17. A rubber composition comprising the conjugated diene-based
polymer according to claim 14.
18. A tire part manufactured by using the rubber composition
according to claim 17.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims the benefit of priority based
on Korean Patent Application Nos. 2015-0089906, filed on Jun. 24,
2015, and 2015-0184237, filed on Dec. 22, 2015, the entire contents
of which are incorporated herein by reference.
TECHNICAL FIELD
[0002] The present invention relates to a catalyst composition for
preparing a conjugated diene-based polymer and a conjugated
diene-based polymer prepared using the same.
BACKGROUND ART
[0003] According to the gradual increase in demand for a rubber
composition in various manufacturing fields for tires, impact
resistant polystyrene, the sole of shoes, golf balls, etc., the
value of conjugated diene-based polymer which is a synthetic
rubber, specifically, a butadiene-based polymer is increasing as an
alternative material to natural rubber of which the produced amount
is insufficient.
[0004] Meanwhile, in a conjugated diene-based polymer, linearity
and the degree of branching greatly affect the physical properties
of the polymer. In particular, with a decrease in linearity or an
increase in the degree of branching, the dissolution rate and
viscosity properties of the polymer increase, and as a result, the
processability of the polymer is improved. However, if the degree
of branching of the polymer is excessively large, molecular weight
distribution is broadened, and the mechanical properties of the
polymer, which influence the abrasion resistance, cracking
resistance or repellency of a rubber composition may rather be
deteriorated. In addition, the linearity and the degree of
branching of the conjugated diene-based polymer, specifically, the
butadiene-based polymer are highly dependent on the amount of
cis-1,4 bonds contained in the polymer. If the amount of cis-1,4
bonds contained in the conjugated diene-based polymer increases,
the linearity may increase. As a result, the polymer has good
mechanical properties, thereby increasing the abrasion resistance,
cracking resistance and repellency of a rubber composition.
[0005] Accordingly, various methods for preparing a conjugated
diene-based polymer are being studied and developed to increase the
amount of cis-1,4 bonds in a conjugated diene-based polymer and
increase linearity and such that the conjugated diene-based polymer
will have appropriate processability at the same time.
[0006] Particularly, a method of preparing a butadiene-based
polymer using a compound of a rare earth metal such as neodymium
and an alkylating agent in group I to group III, particularly, a
polymerization catalyst of a composite metal composed of methyl
aluminoxane has been developed. However, a polymer obtainable by
the method has an insufficiently high amount of cis-1,4 bonds, and
an insufficiently small amount of vinyl, such that the improving
effect of physical properties is still insufficient.
[0007] As an another method, a method of preparing a
butadiene-based polymer having a high amount of cis-1,4 bonds using
a polymerization catalyst including a rare earth metal compound, an
alkylating agent in group I to group III, and an ionic compound
composed of non-coordinating anions and cations, has been
developed. In the method, Nd(OCOCCl.sub.3).sub.3 is used as the
rare earth metal compound, but the polymerization activity of the
metal compound is low, and the amount of vinyl bonds of the
butadiene polymer is large, such that a rubber composition
including the butadiene-based polymer prepared by the method
attained an insufficient improvement of physical properties when
compared to a rubber composition including the conventional
butadiene-based polymer. In addition, the butadiene-based polymer
prepared by the method has a large amount of vinyl bonds and wide
molecular weight distribution.
[0008] As another method, a method of preparing a butadiene-based
polymer having a large amount of cis-1,4 bonds using a
polymerization catalyst composed of a rare earth metal salt
composed of a halogen atom-containing component and aluminoxane,
has been developed. However, a specific catalyst such as neodymium
bis(trichloroacetate) (versatic acid), etc. is used, such that the
polymerization activity of a neodymium salt is low, and industrial
applicability is low.
[0009] Therefore, the development of a method of preparing a
conjugated diene-based polymer which has high linearity and is
capable of showing excellent processability, is required.
DISCLOSURE OF THE INVENTION
Technical Problem
[0010] A first task for solving of the present invention is to
provide a catalyst composition has excellent catalytic activity,
useful in the preparation of a conjugated diene-based polymer
having high linearity and narrow molecular weight distribution.
[0011] A second task for solving of the present invention is to
provide a conjugated diene-based polymer prepared using the
catalyst composition, and a method for preparing the same.
[0012] A third task for solving of the present invention is to
provide a rubber composition including the conjugated diene-based
polymer prepared by using the catalyst composition, and a tire part
manufactured from the rubber composition.
Technical Solution
[0013] That is, according to an embodiment of the present
invention, there is provided a catalyst composition for preparing a
conjugated diene-based polymer including a functionalizing agent of
the following Formula 1, a rare earth metal compound, an alkylating
agent, and a halogen compound, wherein the functionalizing agent is
included in 1 equivalent to 20 equivalents based on 1 equivalent of
the rare earth metal compound:
(X.sub.1).sub.a--Si--(X.sub.2).sub.4-a [Formula 1]
[0014] in Formula 1,
[0015] a is an integer of 1 to 3,
[0016] X.sub.1 and X.sub.2 are each independently selected from the
group consisting of a hydrogen atom, monovalent C.sub.1-20
hydrocarbon, --OR, and a covalent bonding functional group, where
at least one of X.sub.1, and X.sub.2 includes the covalent bonding
functional group, where R is selected from the group consisting of
a hydrogen atom, C.sub.1-20 alkyl, C.sub.3-20 cycloalkyl,
C.sub.6-20 aryl, C.sub.7-20 alkylaryl, C.sub.7-20 arylalkyl, and a
covalent bonding functional group, and
[0017] the covalent bonding functional group is a functional group
containing a carbon-carbon double bond.
[0018] In addition, according to another embodiment of the present
invention, there is provided a conjugated diene-based polymer
prepared by using the catalyst composition and having a mooney
viscosity of 10 MU to 90 MU at 100.degree. C. and a polydispersity
of 3.4 or less.
[0019] In addition, according to a further another embodiment of
the present invention, there is provided a method for preparing a
conjugated diene-based polymer, including performing a
polymerization reaction of conjugated diene-based monomers using
the catalyst composition.
[0020] Further, according to a further another embodiment of the
present invention, there are provided a rubber composition
including the conjugated diene-based polymer, and a tire part
manufactured by using the rubber composition.
Advantageous Effects
[0021] Since the catalyst composition for preparing a conjugated
diene-based polymer according to the present invention includes a
functionalizing agent which is capable of providing a functional
group which may make a covalent bond during preparing a conjugated
diene-based polymer, high catalytic activity and polymerization
reactivity are shown, and a conjugated diene-based polymer having
high linearity and excellent processability and physical properties
may be prepared when preparing a conjugated diene-based polymer
using the catalyst composition.
BEST MODE FOR CARRYING OUT THE INVENTION
[0022] Hereinafter, the present invention will be described in more
detail in order to assist the understanding of the present
invention.
[0023] It will be understood that words or terms used in the
specification and claims shall not be interpreted as the meaning
defined in commonly used dictionaries. It will be further
understood that the words or terms should be interpreted as having
a meaning that is consistent with their meaning of the technical
idea of the invention, based on the principle that an inventor may
properly define the meaning of the words or terms to best explain
the invention.
[0024] The term "preforming" used in the present disclosure means
pre-polymerization in a catalyst composition for preparing a
conjugated diene-based polymer. In particular, when a catalyst
composition for preparing a conjugated diene-based polymer
including a rare earth metal compound, an alkylating agent
including an aluminum compound, and a halogen compound, includes
diisobutyl aluminum hydride (hereinafter, DIBAH) as the aluminum
compound, a small amount of a monomer such as butadiene is included
together to decrease the production possibility of diverse
catalytically active species. Accordingly, the pre-polymerization
of butadiene in the catalyst composition for preparing a conjugated
diene-based polymer is performed prior to the polymerization
reaction for preparing a conjugated diene-based polymer, and this
process is referred to as preforming.
[0025] In addition, the term "premixing" used in the present
disclosure means a homogenously mixed state of each of constituting
components without being polymerized in a catalyst composition.
[0026] In addition, the terms "catalyst composition" used in the
present disclosure mean a simple mixture of constituting
components, diverse composites caused by physical or chemical
attraction, or a chemical reaction product of constituting
components.
[0027] In the present invention, a functionalizing agent including
a covalent bonding functional group such as an allyl group in a
molecule is used during preparing a catalyst composition for
forming a conjugated diene-based polymer, and the structural
stability of a catalytically active species may be improved, the
catalytic activity and reactivity of the catalyst composition may
be increased, and a conjugated diene-based polymer having high
linearity and excellent processability and physical properties may
be prepared.
[0028] Catalyst Composition
[0029] The catalyst composition for conjugated diene polymerization
according to an embodiment of the present invention includes (a) a
functionalizing agent, (b) a rare earth metal compound, (c) an
alkylating agent, and (d) a halogen compound. Hereinafter, each
component will be explained in detail.
[0030] (a) Functionalizing Agent
[0031] The functionalizing agent in the catalyst composition for
conjugated diene polymerization according to an embodiment of the
present invention is a silane (Si)-based compound including at
least one covalent bonding functional group containing a
carbon-carbon double bond. The covalent bonding functional group is
a functional group containing a carbon-carbon double bond such as
vinyl, allyl, methallyl, and (meth)acryl, and may improve catalytic
activity by the reaction with a neodymium compound which is
activated by an alkylating agent in the catalyst composition,
thereby stabilizing a catalytically active species and increasing
the reactivity thereof.
[0032] In addition, since the functionalizing agent includes Si as
a central element, the activity of a catalyst composition may be
further increased, and as a result, a conjugated diene-based
polymer having narrow molecular weight distribution may be prepared
during preparing a conjugated diene-based polymer.
[0033] Particularly, the functionalzing agent may be a compound of
the following Formula 1:
(X.sub.1).sub.a--Si--(X.sub.2).sub.4-a [Formula 1]
[0034] in Formula 1,
[0035] a is an integer of 1 to 3,
[0036] X.sub.1 and X.sub.2 are each independently selected from the
group consisting of a hydrogen atom, monovalent C.sub.1-20
hydrocarbon, --OR, and a covalent bonding functional group, where
at least one of X.sub.1, and X.sub.2 includes the covalent bonding
functional group, where R is selected from the group consisting of
a hydrogen atom, C.sub.1-20 alkyl, C.sub.3-20 cycloalkyl,
C.sub.6-20 aryl, C.sub.7-20 alkylaryl, C.sub.7-20 arylalkyl, and a
covalent bonding functional group, and
[0037] the covalent bonding functional group is a functional group
containing a carbon-carbon double bond.
[0038] In addition, in Formula 1, if a relation of a >1 is
satisfied, a plurality of X.sub.1 may be the same or different.
Also, if a relation of 4-a>1 is satisfied in Formula 1, a
plurality of X.sub.2 may be the same or different.
[0039] Particularly, in Formula 1, X.sub.1 and X.sub.2 may be each
independently selected from the group consisting of a hydrogen
atom, monovalent C.sub.1-20hydrocarbon, --OR (in this case, R is
selected from the group consisting of a hydrogen atom, C.sub.1-20
alkyl, C.sub.3-20 cycloalkyl, C.sub.6-20 aryl, C.sub.7-20
alkylaryl, C.sub.7-20 arylalkyl, and a covalent bonding functional
group), and a covalent bonding functional group.
[0040] In this case, the monovalent hydrocarbon group may be
particularly, linear or branched C.sub.1-20 alkyl such as methyl,
ethyl and propyl; C.sub.3-20 cycloalkyl such as cyclopropyl,
cyclobutyl, and cyclopentyl; C.sub.6-20 aryl such as phenyl; and
C.sub.7-20 arylalkyl or C.sub.7-20 alkylaryl as the combination
thereof.
[0041] In addition, the covalent bonding functional group may be
alkenyl or (meth)acryl, and in this case, the alkenyl may be
particularly, C.sub.2-20 alkenyl, more particularly, C.sub.2-12
alkenyl, and further more particularly, C.sub.2-6 alkenyl. More
particularly, the covalent bonding functional group may be selected
from the group consisting of vinyl, allyl, methallyl, butenyl,
pentenyl, hexenyl and (meth)acryl, and the covalent bonding
functional group may be allyl in consideration of remarkable
improving effect of catalytic activity and polymerization
reactivity when applied to a catalyst composition. Meanwhile, in
the present invention, (meth)acryl means the inclusion of acryl and
methacryl.
[0042] In addition, X.sub.1 and X.sub.2 may be each independently
substituted with at least one substituent selected from the group
consisting of linear or branched C.sub.1-20 alkyl, C.sub.3-20
cycloalkyl, and C.sub.6-30 aryl.
[0043] More particularly, X.sub.1 and X.sub.2 may be each
independently selected from the group consisting of a hydrogen
atom, alkyl, alkoxy, vinyl, allyl, methallyl, and (meth)acryl, and
wherein the alkyl may be linear or branched C.sub.1-20 alkyl, more
particularly, linear or branched C.sub.1-6alkyl, and the alkoxy may
be linear or branched C.sub.1-20 alkoxy, more particularly, linear
or branched C.sub.1-6 alkoxy. Here, in Formula 1, at least one of
X.sub.1 and X.sub.2 is a covalent bonding functional group
containing a double bond in a molecule such as vinyl, allyl,
methallyl, and (meth)acryl.
[0044] Particularly, the functionalizing agent may be selected from
the group consisting of the compounds of the following Formulae 2a
to 2k:
##STR00001##
[0045] In Formulae 2a to 2k, Me means methyl, nBu means n-butyl, Ph
means phenyl, and OEt means ethoxy.
[0046] More particularly, the functionalizing agent may be Formula
1, in which X.sub.1 and X.sub.2 may be each independently selected
from the group consisting of linear or branched C.sub.1-6 alkyl,
vinyl, allyl, and methallyl, where at least one of X.sub.1 and
X.sub.2 may be vinyl, allyl, or methallyl.
[0047] The functionalizing agent of Formula 1 may be used by using
a common synthesis reaction. In an embodiment, the functionalizing
agent of Formula 1 may be prepared by the reaction as in the
following Reaction 1. The following Reaction 1 is only an
embodiment for explaining the present invention, and the present
invention is not limited thereto.
##STR00002##
[0048] (b) Rare Earth Metal Compound
[0049] In the catalyst composition for conjugated diene
polymerization according to an embodiment of the present invention,
the rare earth metal compound is activated by an alkylating agent
and then reaction with a reactive group of the functionalizing
agent is performed to form a catalytically active species for the
polymerization of a conjugated diene.
[0050] As the rare earth metal compound, any one used for the
preparation of a common conjugated diene-based polymer may be used,
without specific limitation. Particularly, the rare earth metal
compound may be a compound including one or at least two of rare
earth metals of atomic numbers of 57 to 71 such as lanthanum,
neodymium, cerium, gadolinium and praseodymium, and more
particularly, a compound including one or at least two selected
from the group consisting of neodymium, lanthanum and gadolinium
may be used.
[0051] In addition, the rare earth metal compound may be rare earth
metal-containing carboxylates (for example, neodymium acetate,
neodymium acrylate, neodymium methacrylate, neodymium acetate,
neodymium gluconate, neodymium citrate, neodymium fumarate,
neodymium lactate, neodymium maleate, neodymium oxalate, neodymium
2-ethylhexanoate, neodymium neodecanoate, etc.), organic phosphates
(for example, neodymium dibutyl phosphate, neodymium dipentyl
phosphate, neodymium dihexyl phosphate, neodymium diheptyl
phosphate, neodymium dioctyl phosphate, neodymium bis(1-methyl
heptyl)phosphate, neodymium bis(2-ethylhexyl)phosphate, neodymium
didecyl phosphate, etc.), organic phosphonates (for example,
neodymium butyl phosphonate, neodymium pentyl phosphonate,
neodymium hexyl phosphonate, neodymium heptyl phosphonate,
neodymium octyl phosphonate, neodymium (1-methylheptyl)phosphonate,
neodymium (2-ethylhexyl)phosphonate, neodymium decyl phosphonate,
neodymium dodecyl phosphonate, neodymium octadecyl phosphonate,
etc.), organic phosphinates (for example, neodymium butyl
phosphinate, neodymium pentyl phosphinate, neodymium hexyl
phosphinate, neodymium heptyl phosphinate, neodymium octyl
phosphinate, neodymium (1-methyl heptyl)phosphinate, neodymium
(2-ethylhexyl)phosphinate, etc.), carbamates (for example,
neodymium dimethyl carbamate, neodymium diethyl carbamate,
neodymium diisopropyl carbamate, neodymium dibutyl carbamate,
neodymium dibenzyl carbamate, etc.), dithio carbamates (for
example, neodymium dimethyldithio carbamate, neodymium
diethyldithio carbamate, neodymium diisopropyl dithio carbamate,
neodymium dibutyldithio carbamate, etc.), xanthogenates (for
example, neodymium methyl xanthogenate, neodymium ethyl
xanthogenate, neodymium isopropyl xanthogenate, neodymium butyl
xanthogenate, neodymium benzyl xanthogenate, etc.),
.beta.-diketonates (for example, neodymium acetylacetonate,
neodymium trifluoroacetyl acetonate, neodymium hexafluoroacetyl
acetonate, neodymium benzoyl acetonate, etc.), alkoxides or
allyloxides (for example, neodymium methoxide, neodymium ethoxide,
neodymium isopropoxide, neodymium phenoxide, neodymium nonyl
phenoxide, etc.), halides or pseudo halides (neodymium fluoride,
neodymium chloride, neodymium bromide, neodymium idodide, neodymium
cyanide, neodymium cyanate, neodymium thiocyanate, neodymium azide,
etc.), oxyhalides (for example, neodymium oxyfluoride, neodymium
oxychloride, neodymium oxybromide, etc.), or organic rare earth
metal compounds including at least one rare earth metal-carbon bond
(for example, Cp.sub.3Ln, Cp.sub.2LnR, Cp.sub.2LnCl, CpLnCl.sub.2,
CpLn (cyclooctatetraene), (C.sub.5Me.sub.5).sub.2LnR, LnR.sub.3,
Ln(allyl).sub.3, Ln(allyl).sub.2Cl, etc., where Ln is a rare earth
metal element, and R is hydrocarbyl as defined above), etc. and may
include any one or a mixture of at least two thereof.
[0052] More particularly, the rare earth metal compound may be a
neodymium compound of the following Formula 3:
##STR00003##
[0053] In Formula 3, R.sub.1 to R.sub.3 are each independently a
hydrogen atom, or a linear or branched C.sub.1-12 alkyl group.
[0054] As described above, in the case where the neodymium compound
of Formula 3 includes a carboxylate ligand containing an alkyl
group having various lengths of at least two carbons at an a
position as a substituent, sterical change may be induced around a
neodymium central metal to block the tangle between compounds, and
as a result, oligomerization is restrained, and a conversion ratio
into an active species is high. Such a neodymium compound has a
high solubility in a polymerization solvent.
[0055] More particularly, the rare earth metal compound may be a
neodymium compound of Formula 3, in which R.sub.1 is a linear or
branched C.sub.6-12 alkyl group, and R.sub.2 and R.sub.3 are each
independently a hydrogen atom, or a linear or branched C.sub.2-6
alkyl group, where R.sub.2 and R.sub.3 are not hydrogen atoms at
the same time.
[0056] More particularly, in the neodymium compound of Formula 3,
R.sub.8 may be linear or branched C.sub.6-8 alkyl, and R.sub.2 and
R.sub.3 may be each independently linear or branched C.sub.2-6
alkyl. As described above, when R.sub.1 is an alkyl group of 6 or
more carbon atoms, and R.sub.2 and R.sub.3 are alkyl groups of 2 or
more carbon atoms, the deterioration of conversion efficiency to
catalytically active species may be further improved without fear
of oligomerization during a polymerization process, and excellent
catalytic activity may be shown.
[0057] More particularly, the neodymium compound may be at least
one selected from the group consisting of Nd(2,2-diethyl
decanoate).sub.3, Nd(2,2-dipropyl decanoate).sub.3, Nd(2,2-dibutyl
decanoate).sub.3, Nd(2,2-dihexyl decanoate).sub.3, Nd(2,2-dioctyl
decanoate).sub.3, Nd(2-ethyl-2-propyl decanoate).sub.3,
Nd(2-ethyl-2-butyl decanoate).sub.3, Nd(2-ethyl-2-hexyl
decanoate).sub.3, Nd(2-propyl-2-butyl decanoate).sub.3,
Nd(2-propyl-2-hexyl decanoate).sub.3, Nd(2-propyl-2-isopropyl
decanoate).sub.3, Nd(2-butyl-2-hexyl decanoate).sub.3,
Nd(2-hexyl-2-octyl decanoate).sub.3, Nd(2,2-diethyl
octanoate).sub.3, Nd(2,2-dipropyl octanoate).sub.3, Nd(2,2-dibutyl
octanoate).sub.3, Nd(2,2-dihexyl octanoate).sub.3,
Nd(2-ethyl-2-propyl octanoate).sub.3, Nd(2-ethyl-2-hexyl
octanoate).sub.3, Nd(2,2-diethyl nonanoate).sub.3, Nd(2,2-dipropyl
nonanoate).sub.3, Nd(2,2-dibutyl nonanoate).sub.3, Nd(2,2-dihexyl
nonanoate).sub.3, Nd(2-ethyl-2-propyl nonanoate).sub.3 and
Nd(2-ethyl-2-hexyl nonanoate).sub.3, or a mixture of at least two
thereof. In addition, in consideration of excellent solubility in a
polymerization solvent without fear of oligomerization, excellent
conversion ratio to the catalytically active species and consequent
improving effect of catalytic activity, the neodymium compound may
be at least one selected from the group consisting of
Nd(2,2-diethyl decanoate).sub.3, Nd(2,2-dipropyl decanoate).sub.3,
Nd(2,2-dibutyl decanoate).sub.3, Nd(2,2-dihexyl decanoate).sub.3,
and Nd(2,2-dioctyl decanoate).sub.3, or a mixture of at least two
thereof.
[0058] In addition, the neodymium compound may have a solubility of
about 4 g or more per 6 g a non-polar solvent at room temperature
(23.+-.5.degree. C.). In the present invention, the solubility of
the neodymium compound means the degree of clear dissolution
without generating turbid phenomenon. Through such a high
solubility, excellent catalytic activity may be attained.
[0059] (c) Alkylating Agent
[0060] In the catalyst composition for conjugated diene
polymerization according to an embodiment of the present invention,
the alkylating agent is an organometallic compound which is capable
of delivering a hydrocarbyl group to another metal and plays the
role of a co-catalyst. Any alkylating agents used for the
preparation of a common diene-based polymer may be used as the
alkylating agent, without specific limitation.
[0061] Particularly, the alkylating agent is soluble in a non-polar
solvent, particularly, a non-polar hydrocarbon-based solvent, and
may be an organometallic compound including a bond between a
cationic metal such as metals in group 1, 2, or 3 with carbon, or a
boron-containing compound. More particularly, the alkylating agent
may be at least one selected from the group consisting of an
organoaluminum compound, an organomagnesium compound, and an
organolithium compound, or a mixture of at least two thereof.
[0062] In the alkylating agent, the organoaluminum compound may be,
particularly, a compound of the following Formula 4:
Al(R).sub.z(X).sub.3-z, [Formula 4]
[0063] In Formula 4,
[0064] R is each independently a monovalent organic group which is
combined with an aluminum atom via a carbon atom, and may be a
hydrocarbyl group such as C.sub.1-20 alkyl, C.sub.3-20 cycloalkyl,
C.sub.2-20 alkenyl, C.sub.3-20 cycloalkenyl, C.sub.6-20 aryl,
C.sub.7-20 arylalkyl, C.sub.7-20 alkylaryl, allyl, and C.sub.2-32
alkynyl; or a heterohydrocarbyl group containing at least one
heteroatom selected from the group consisting of a nitrogen atom,
an oxygen atom, a boron atom, a silicon atom, a sulfur atom, and a
phosphor atom in place of carbon in a hydrocarbyl structure,
[0065] X is each independently selected from the group consisting
of a hydrogen atom, a halogen group, a carboxyl group, an alkoxy
group and an aryloxy group,
[0066] z is an integer of 1 to 3.
[0067] More particularly, the organoaluminum compound may include
dihydrocarbylaluminum hydride such as diethylaluminum hydride,
di-n-propylaluminum hydride, diisopropylaluminum hydride,
di-n-butylaluminum hydride, diisobutylaluminum hydride (DIBAH),
di-n-octylaluminum hydride, diphenylaluminum hydride,
di-p-tolylaluminum hydride, dibenzylaluminum hydride,
phenylethylaluminum hydride, phenyl-n-propylaluminum hydride,
phenylisopropylaluminum hydride, phenyl-n-butylaluminum hydride,
phenylisobutylaluminum hydride, phenyl-n-octylaluminum hydride,
p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride,
p-tolylisopropylaluminum hydride, p-tolyl-n-butylaluminum hydride,
p-tolylisobutylaluminum hydride, p-tolyl-n-octylaluminum hydride,
benzylethylaluminum hydride, benzyl-n-propylaluminum hydride,
benzylisopropylaluminum hydride, benzyl-n-butylaluminum hydride,
benzylisobutylaluminum hydride and benzyl-n-octylaluminum hydride;
hydrocarbylaluminum dihydride such as ethylaluminum dihydride,
n-propylaluminum dihydride, isopropylaluminum dihydride,
n-butylaluminum dihydride, isobutylaluminum dihydride, and
n-octylaluminum dihydride, or the like.
[0068] In addition, the organoaluminum compound may include
aluminoxanes.
[0069] The aluminoxane may be prepared by reacting trihydrocarbyl
aluminum-based compounds with water, and may particularly be linear
aluminoxanes of the following Formula 5a or circular aluminoxanes
of the following Formula 5b:
##STR00004##
[0070] In Formulae 5a and 5b, R is a monovalent organic group which
is combined with an aluminum atom via a carbon atom and is the same
as the above-defined R, x and y are each independently an integer
of 1 or more, particularly, 1 to 100, and more particularly, an
integer of 2 to 50.
[0071] More particularly, the aluminoxane may be, methylaluminoxane
(MAO), modified methylaluminoxane (MAO), ethylaluminoxane,
n-propylaluminoxane, isopropylaluminoxane, butylaluminoxane,
isobutylaluminoxane, n-pentylaluminoxane, neopentylaluminoxane,
n-hexylaluminoxane, n-octylaluminoxane, 2-ethylhexylaluminoxane,
cyclohexylaluminoxane, 1-methylcyclopentylaluminoxane,
phenylaluminoxane or 2,6-dimethylphenyl aluminoxane, and any one or
a mixture of at least two thereof may be used.
[0072] In addition, in the aluminoxane compound, the modified
methylaluminoxane is obtained by substituting the methyl group of
the methylaluminoxane with a modifier (R), particularly, a
C.sub.2-20 hydrocarbon group, and particularly, may be a compound
of the following Formula 6:
##STR00005##
[0073] In Formula 6, R is the same as defined above, and each of m
and n may be an integer of 2 or more. In addition, in Formula 2, Me
means a methyl group.
[0074] More particularly, R in the above Formula 6 may be linear or
branched C.sub.2-20 alkyl, C.sub.3-20 cycloalkyl, C.sub.2-20
alkenyl, C.sub.3-20 cycloalkenyl, C.sub.6-20 aryl, C.sub.7-20
arylalkyl, C.sub.7-20 alkylaryl, allyl, or C.sub.2-20 alkynyl, and
more particularly, may be linear or branched C.sub.2-10 alkyl such
as ethyl, isobutyl, hexyl and octyl, and even more particularly,
may be isobutyl.
[0075] More particularly, the modified methylaluminoxane may be
obtained by substituting about 50 mol % to 90 mol % of the methyl
group of the methylaluminoxane with the hydrocarbon group. When the
amount of the hydrocarbon group substituted in the modified
methylaluminoxane is in the range, alkylation may be promoted, and
catalytic activity may increase.
[0076] Such modified methylaluminoxane may be prepared by a common
method, and particularly, may be prepared using trimethylaluminum
and an alkylaluminum other than trimethylaluminum. In this case,
the alkylaluminum may be triisobutylaluminum, triethylaluminum,
trihexylaluminum, or trioctylaluminum, and any one or a mixture of
at least two thereof may be used.
[0077] Meanwhile, an organomagnesium compound as the alkylating
agent includes at least one magnesium-carbon bond, and may be a
magnesium compound dissoluble in a non-polar solvent, specifically,
a non-polar hydrocarbon-based solvent. Particularly, the
organomagnesium compound may be a compound of the following Formula
7a:
Mg(R).sub.2 [Formula 7a]
[0078] In Formula 7a, R is each independently a monovalent organic
group and is the same as the above defined R.
[0079] More particularly, the organomagnesium compound of Formula
7a may be an alkylmagnesium compound such as diethylmagnesium,
di-n-propylmagnesium, diisopropylmagnesium, dibutylmagnesium,
dihexylmagnesium, diphenylmagnesium, and dibenzylmagnesium.
[0080] In addition, the organomagnesium compound may be a compound
of the following Formula 7b:
RMgX [Formula 7b]
[0081] In Formula 7b, R is a monovalent organic group and is the
same as the above defined R, and X is selected from the group
consisting of a hydrogen atom, a halogen group, a carboxyl group,
an alkoxy group and an aryloxy group.
[0082] More particularly, the organomagnesium compound of Formula
7b may be a hydrocarbyl magnesium hydride such as methyl magnesium
hydride, ethyl magnesium hydride, butyl magnesium hydride, hexyl
magnesium hydride, phenyl magnesium hydride, and benzyl magnesium
hydride; a hydrocarbyl magnesium halide such as methyl magnesium
chloride, ethyl magnesium chloride, butyl magnesium chloride, hexyl
magnesium chloride, phenyl magnesium chloride, benzyl magnesium
chloride, methyl magnesium bromide, ethyl magnesium bromide, butyl
magnesium bromide, hexyl magnesium bromide, phenyl magnesium
bromide, and benzyl magnesium bromide; a hydrocarbyl magnesium
carboxylate such as methyl magnesium hexanoate, ethyl magnesium
hexanoate, butyl magnesium hexanoate, hexyl magnesium hexanoate,
phenyl magnesium hexanoate, and benzyl magnesium hexanoate; a
hydrocarbyl magnesium alkoxide such as methyl magnesium ethoxide,
ethyl magnesium ethoxide, butyl magnesium ethoxide, hexyl magnesium
ethoxide, phenyl magnesium ethoxide, and benzyl magnesium ethoxide;
or a hydrocarbyl magnesium aryloxide such as methyl magnesium
phenoxide, ethyl magnesium phenoxide, butyl magnesium phenoxide,
hexyl magnesium phenoxide, phenyl magnesium phenoxide, and benzyl
magnesium phenoxide.
[0083] In addition, as the alkylating agent, an alkyl lithium of
R--Li as an organolithium compound (in this case, R is linear or
branched C.sub.1-20 alkyl, and more particularly, linear C.sub.1-8
alkyl) may be used. More particularly, methyllithium, ethyllithium,
isopropyllithium, n-butyllithium, sec-butyllithium, t-butyllithium,
isobutyllithium, pentyllithium, isopentyllithium, etc. may be used,
and any one or a mixture of at least two thereof may be used.
[0084] Among the above compounds, an alkylating agent used in the
present invention may be specifically, DIBAH which may play the
role of a molecular weight controlling agent during
polymerization.
[0085] In addition, the alkylating agent may be the modified
methylaluminoxane in consideration of improving catalytic activity
and reactivity by using aliphatic hydrocarbon-based solvents of a
single phase as a solvent system used during preparing a catalyst
composition.
[0086] (d) Halogen Compound
[0087] In the catalyst composition for conjugated diene
polymerization according to an embodiment of the present invention,
the kind of the halogen compound is not specifically limited, but
any halogenating agents used in the preparation of a common
diene-based polymer may be used without specific limitation.
[0088] Particularly, the halogen compound may be a diatomic
halogen, an interhalogen compound, a hydrogen halide, an organic
halide, a nonmetal halide, a metal halide, or an organometallic
halide, etc., and any one or a mixture of at least two thereof may
be used. Among them, in consideration of the improvement of
catalytic activity and consequent improving effect of reactivity,
the halogen compound may be one selected from the group consisting
of an organic halide, a metal halide and an organometallic halide,
or a mixture of at least two thereof.
[0089] More particularly, the diatomic halogen may include
fluorine, chlorine, bromine, or iodine.
[0090] The interhalogen compound may particularly include iodine
monochloride, iodine monobromide, iodine trichloride, iodine
pentafluoride, iodine monofluoride, iodine trifluoride, etc.
[0091] In addition, the hydrogen halide may particularly include
hydrogen fluoride, hydrogen chloride, hydrogen bromide, or hydrogen
iodide.
[0092] In addition, the organic halide may particularly include
t-butyl chloride (t-BuCl), t-butyl bromide, allyl chloride, allyl
bromide, benzyl chloride, benzyl bromide, chloro-di-phenylmethane,
bromo-di-phenylmethane, triphenylmethyl chloride, triphenylmethyl
bromide, benzylidene chloride, benzylidene bromide,
methyltrichlorosilane, phenyltrichlorosilane,
dimethyldichlorosilane, diphenyldichlorosilane,
trimethylchlorosilane (TMSCl), benzoyl chloride, benzoyl bromide,
propionyl chloride, propionyl bromide, methyl chloroformate, methyl
bromoformate, iodomethane, diiodomethane, triiodomethane (also
referred to as "iodoform"), tetraiodomethane, 1-iodopropane,
2-iodopropane, 1,3-diiodopropane, t-butyl iodide,
2,2-dimethyl-1-iodopropane (also referred to as "neopentyl
iodide"), allyl iodide, iodobenzene, benzyl iodide, diphenylmethyl
iodide, triphenylmethyl iodide, benzylidene iodide (also referred
to as "benzal iodide"), trimethylsilyl iodide, triethylsilyl
iodide, triphenylsilyl iodide, dimethyldiiodosilane,
diethyldiiodosilane, diphenyldiiodosilane, methyltriiodosilane,
ethyltriiodosilane, phenyltriiodosilane, benzoyl iodide, propionyl
iodide, methyl iodoformate, or the like.
[0093] In addition, the nonmetal halide may particularly include
phosphorus trichloride, phosphorus tribromide, phosphorus
pentachloride, phosphorus oxychloride, phosphorus oxybromide, boron
trifluoride, boron trichloride, boron tribromide, silicon
tetrafluoride, silicon tetrachloride (SiCl.sub.4), silicon
tetrabromide, arsenic trichloride, arsenic tribromide, selenium
tetrachloride, selenium tetrabromide, tellurium tetrachloride,
tellurium tetrabromide, silicon tetraiodide, arsenic triiodide,
tellurium tetraiodide, boron triiodide, phosphorus triiodide,
phosphorus oxyiodide or selenium tetraiodide.
[0094] The metal halide may particularly include tin tetrachloride,
tin tetrabromide, aluminum trichloride, aluminum tribromide,
antimony trichloride, antimony pentachloride, antimony tribromide,
aluminum trifluoride, gallium trichloride, gallium tribromide,
gallium trifluoride, indium trichloride, indium tribromide, indium
trifluoride, titanium tetrachloride, titanium tetrabromide, zinc
dichloride, zinc dibromide, zinc difluoride, aluminum triiodide,
gallium triiodide, indium triiodide, titanium tetraiodide, zinc
diiodide, germanium tetraiodide, tin tetraiodide, tin diiodide,
antimony triiodide or magnesium diiodide.
[0095] The organometallic halide may particularly include
dimethylaluminum chloride, diethylaluminum chloride,
dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum
fluoride, diethylaluminum fluoride, methylaluminum dichloride,
ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum
dibromide, methylaluminum difluoride, ethylaluminum difluoride,
methylaluminum sesquichloride, ethylaluminum sesquichloride (EASC),
isobutylaluminum sesquichloride, methylmagnesium chloride,
methylmagnesium bromide, ethylmagnesium chloride, ethylmagnesium
bromide, n-butylmagnesium chloride, n-butylmagnesium bromide,
phenylmagnesium chloride, phenylmagnesium bromide, benzylmagnesium
chloride, trimethyltin chloride, trimethyltin bromide, triethyltin
chloride, triethyltin bromide, di-t-butyltin dichloride,
di-t-butyltin dibromide, di-n-butyltin dichloride, di-n-butyltin
dibromide, tri-n-butyltin chloride, tri-n-butyltin bromide,
methylmagnesium iodide, dimethylaluminum iodide, diethylaluminum
iodide, di-n-butylaluminum iodide, diisobutylaluminum iodide,
di-n-octylaluminum iodide, methylaluminum diiodide, ethylaluminum
diiodide, n-butylaluminum diiodide, isobutylaluminum diiodide,
methylaluminum sesquiiodide, ethylaluminum sesquiiodide,
isobutylaluminum sesquiiodide, ethylmagnesium iodide,
n-butylmagnesium iodide, isobutylmagnesium iodide, phenylmagnesium
iodide, benzylmagnesium iodide, trimethyltin iodide, triethyltin
iodide, tri-n-butyltin iodide, di-n-butyltin diiodide,
di-t-butyltin diiodide, or the like.
[0096] In addition, the catalyst composition for preparing a
conjugated diene polymer according to an embodiment of the present
invention may include a non-coordinating anion-containing compound
or a non-coordinating anion precursor compound together with the
halogen compound instead of the halogen compound.
[0097] Particularly, in the non-coordinating anion-containing
compound, the non-coordinating anions may be anions not forming a
coordination bond with the active center of a catalyst system due
to steric hindrance and having a sterically large volume, and may
be tetraarylborate anions or tetraarylborate fluoride anions. In
addition, the non-coordinating anion-containing compound may
include carbonium cations such as triaryl carbonium cations;
ammonium cations such as N,N-dialkyl anilinium cations, or counter
cations such as phosphonium cations together with the
non-coordinating anions. More particularly, the non-coordinating
anion-containing compound may be triphenylcarbonium
tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium
tetrakis(pentafluorophenyl)borate, triphenylcarbonium
tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,
N,N-dimethylanilinium
tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, or the like.
[0098] In addition, as the non-coordinating anion precursor, a
triaryl boron compound (BR.sub.3, where R is a strongly electron
withdrawing aryl group such as a pentafluorophenyl group and a
3,5-bis(trifluoromethyl)phenyl group) may be used as a compound
capable of forming non-coordinating anions under reaction
conditions.
[0099] The catalyst composition for forming a conjugated
diene-based polymer according to an embodiment of the present
invention may further include a diene-based monomer in addition to
the above-described components.
[0100] The diene-based monomer may be mixed with a catalyst for
polymerization and form a premixing type catalyst, or may be
polymerized with components in a catalyst for polymerization,
specifically an alkylating agent such as DIBAH to form a preforming
type catalyst. In case of conducting such preforming
polymerization, catalytic activity may be improved, and a
conjugated diene-based polymer thus prepared may be further
stabilized.
[0101] Particularly, as the diene-based monomer, any one used for
the preparation of a common conjugated diene-based polymer may be
used, without specific limitation.
[0102] Particularly, the diene-based monomer may be 1,3-butadiene,
isoprene, 1,3-pentadiene, 1,3-hexadiene,
2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene,
2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene,
4-methyl-1,3-pentadiene, 2,4-hexadiene, or the like, and any one or
a mixture of at least two thereof may be used.
[0103] The catalyst composition for forming a conjugated
diene-based polymer according to an embodiment of the present
invention may further include a reaction solvent in addition to the
above-described components.
[0104] The reaction solvent may particularly be a non-polar solvent
having no reactivity with the components constituting the catalyst.
Particularly, linear, branched or circular aliphatic
C.sub.5-20hydrocarbon such as n-pentane, n-hexane, n-heptane,
n-octane, n-nonane, n-decane, isohexane, isopentane, isooctane,
2,2-dimethylbutane, cyclopentane, cyclohexane, methylcyclopentane
and methylcyclohexane; a mixture solvent of aliphatic
C.sub.5-20hydrocarbon such as petroleum ether, petroleum spirits,
and kerosene; or an aromatic hydrocarbon-based solvent such as
benzene, toluene, ethylbenzene, and xylene, and any one or a
mixture of at least two thereof may be used. More particularly, the
non-polar solvent may be linear, branched or circular aliphatic
C.sub.5-20 hydrocarbon or a mixture solvent of aliphatic
hydrocarbon, and more particularly, n-hexane, cyclohexane, or a
mixture thereof may be used.
[0105] In addition, the reaction solvent may be appropriately
selected according to the kind of the materials constituting the
catalyst composition, specifically, the alkylating agent.
[0106] In particular, an alkylaluminoxane such as methylaluminoxane
(MAO) and ethylaluminoxane as the alkylating agent is not easily
dissolved in an aliphatic hydrocarbon-based solvent, and an
aromatic hydrocarbon-based solvent may be appropriately used.
[0107] In addition, in the case where modified methylaluminoxane is
used as the alkylating agent, an aliphatic hydrocarbon-based
solvent may be appropriately used. In this case, a single solvent
system may be attained together with an aliphatic hydrocarbon-based
solvent such as hexane, which is mainly used as a polymerization
solvent, the polymerization reaction may be more favorable. In
addition, the aliphatic hydrocarbon-based solvent may promote
catalytic activity, and reactivity may be further improved due to
such catalytic activity.
[0108] The above-described constituting components in the catalyst
composition may form a catalytically active species via the
interaction therebetween. Accordingly, the catalyst composition
according to an embodiment of the present invention may include by
optimally combining the amounts of the constituting components so
as to show even better catalytic activity and excellent
polymerization reactivity.
[0109] Particularly, the catalyst composition may include 20
equivalents or less of the functionalizing agent based on 1
equivalent of the rare earth metal compound. If the amount of the
functionalizing agent is greater than 20 equivalents, unreacted
functionalizing agent may remain to induce side reactions. More
particularly, the functionalizing agent may be included in an
amount of 3 equivalent to 7 equivalents based on 1 equivalent of
the rare earth metal compound.
[0110] In addition, the catalyst composition may include the
alkylating agent in an amount of 5 moles to 200 moles based on 1
mole of the rare earth metal compound. If the amount of the
alkylating agent is less than 5 molar ratio, activation effect with
respect to the rare earth metal compound may be insignificant, and
if the amount is greater than 200 molar ratio, the control of
catalyst reaction during preparing a polymer is not easy, and it is
apprehended that an excessive amount of the alkylating agent may
induce side reactions. More particularly, the catalyst composition
may include the alkylating agent in an amount of 5 moles to 20
moles based on 1 mole of the rare earth metal compound, and may
include 5 moles to 10 moles in consideration of the remarkable
improving effect of processability.
[0111] In addition, the catalyst composition may include 1 mole to
20 moles, and may more particularly include 2 moles to 6 moles of
the halogen compound based on 1 mole of the rare earth metal
compound. If the amount of the halogen compound is less than 1
molar ratio, the generation of a catalytically active species is
insufficient, and catalytic activity may be deteriorated. If the
amount is greater than 20 molar ratio, the control of catalyst
reaction is not easy, and the excessive amount of the halogen
compound may induce side reactions.
[0112] In addition, if the catalyst composition further includes
the diene-based monomer, the catalyst composition may particularly
further include 1 equivalent to 50 equivalents, and more
particularly, 20 equivalents to 35 equivalents of the diene-based
monomer based on 1 equivalent of the rare earth metal compound.
[0113] In addition, if the catalyst composition further includes
the reaction solvent, the catalyst composition may further include
the reaction solvent in an amount of 20 moles to 20,000 moles, and
more particularly, 100 moles to 1,000 moles based on 1 mole of the
rare earth metal compound.
[0114] The catalyst composition having the above-described
constitution may be prepared by mixing the functionalizing agent,
the rare earth metal compound, the alkylating agent, the halogen
compound, and selectively the conjugated diene monomer and the
reaction solvent by a common method.
[0115] In an embodiment, a premixing type catalyst composition may
be prepared by adding a functionalizing agent, a rare earth metal
compound, an alkylating agent, a halogen compound and selectively a
conjugated diene monomer to a reaction solvent one by one or
simultaneously, and then, mixing.
[0116] In an another embodiment, a preforming type catalyst
composition may be prepared by mixing a functionalizing agent, a
rare earth metal compound, an alkylating agent and a halogen
compound to a reaction solvent, adding a conjugated diene monomer,
and preforming.
[0117] In this case, to promote the generation of a catalytically
active species, the mixing and polymerizing processes may be
conducted in a temperature range of 0.degree. C. to 60.degree. C.,
and in this case, heat treatment may be conducted simultaneously to
fulfill the temperature conditions.
[0118] More particularly, the catalyst composition may be prepared
by mixing a rare earth metal compound, an alkylating agent, a
reaction solvent and selectively a conjugated diene monomer, first
heat treating at a temperature of 10.degree. C. to 60.degree. C.,
adding a halogen compound to the mixture thus obtained, and second
heat treating in a temperature range of 0.degree. C. to 60.degree.
C.
[0119] In the catalyst composition prepared by the above-described
preparation method, a catalytically active species is formed by the
interaction of constituting components.
[0120] As described above, due to the use of the functionalizing
agent, the catalyst composition of the present invention may
produce a catalytically active species having better catalytic
activity and polymerization reactivity when compared to the
conventional composition. As a result, a conjugated diene-based
polymer having even higher linearity and processability may be
prepared.
[0121] In particular, the catalyst composition having the
above-described components may show the degree of a catalytic
activity of 10,000 kg [polymer]/mol[Nd].h or more during the
polymerization in a temperature range of 20.degree. C. to
90.degree. C. for 5 minutes to 60 minutes. In the present
invention, the degree of catalytic activity is a value obtained
from the injection molar ratio of the rare earth metal compound
with respect to the total amount obtained of the conjugated
diene-based polymer thus prepared.
[0122] Conjugated Diene Polymer
[0123] According to another embodiment of the present invention, a
conjugated diene-based polymer prepared using the catalyst
composition, and a method of preparing the same are provided.
[0124] The conjugated diene-based polymer according to an
embodiment of the present invention may be prepared by the
polymerization reaction of a conjugated diene-based monomer
according to a typical preparation method of a conjugated
diene-based polymer except for using the catalyst composition for
conjugated diene polymerization.
[0125] In this case, the polymerization reaction may be conducted
by a bulk polymerization, a solution polymerization, a suspension
polymerization or an emulsion polymerization, and may be also
conducted by a batch method, a continuous method and a
semi-continuous method. More particularly, a method may be
appropriately selected and conducted among the polymerization
methods according to the kind of the functionalizing agent used in
the catalyst composition.
[0126] In this case, the polymerization reaction may be conducted
by various methods such as a bulk polymerization, a solution
polymerization, a suspension polymerization and an emulsion
polymerization, and may be also conducted by a batch method, a
continuous method and a semi-continuous method. More particularly,
a method may be appropriately selected and conducted among the
polymerization methods according to the kind of the functionalizing
agent used in the catalyst composition. In an embodiment, in the
case where the functionalizing agent included in the catalyst
composition is a Si compound, a batch type polymerization method
may be used.
[0127] Particularly, in the case where the solution polymerization
is used for the preparation, the conjugated diene polymer according
to an embodiment of the present invention may be prepared by
injecting a diene-based monomer to the catalyst composition for
polymerization in a polymerization solvent, and performing
reaction.
[0128] As the conjugated diene-based monomer, any one used for
preparing a common conjugated diene-based polymer may be used,
without specific limitation. The diene-based monomer may
particularly be 1,3-butadiene, isoprene, 1,3-pentadiene,
1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene,
2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene,
4-methyl-1,3-pentadiene, 2,4-hexadiene, etc., and any one or a
mixture of at least two thereof may be used. More particularly, the
conjugated diene-based monomer may be 1,3-butadiene.
[0129] In addition, other monomers capable of being copolymerized
with the diene monomer may be further used during the
polymerization reaction in consideration of the physical properties
of the diene polymer finally prepared.
[0130] The other monomers may particularly include an aromatic
vinyl monomer such as styrene, p-methylstyrene,
.alpha.-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene,
ethylvinylbenzene, divinylbenzene, 4-cyclohexylstyrene, and
2,4,6-trimethylstyrene, and any one or a mixture of at least two
thereof may be used. The other monomers may be used in an amount of
20 wt % or less based on the total amount of the monomers used in
the polymerization reaction.
[0131] In this case, the diene-based monomer is used not such that
the total amount used for the preparation of a diene-based polymer
is dissolved in a non-polar solvent, but such that a portion of the
total amount is dissolved in a polymerization solvent and
polymerized, and then injected in installments according to the
polymerization conversion ratio in once or more times,
particularly, in twice or more times, and more particularly, in
twice to four times.
[0132] In addition, the polymerization solvent may be a non-polar
solvent, and this solvent is the same as the solvent used in
advance for the preparation of a catalyst for polymerization.
[0133] The concentration of a monomer used in the polymerization
solvent is not specifically limited, and may be 3 wt % to 80 wt %,
and more particularly, 10 wt % to 30 wt %.
[0134] In addition, during the polymerization reaction, additives
may be further used, including a molecular weight controlling agent
such as trimethylaluminum, diisobutylaluminum hydride, and
trimethylsilane; a reaction terminator such as polyoxyethylene
glycol phosphate; and an antioxidant such as
2,6-di-t-butylparacresol. In addition, additives serving easy
solution polymerization, particularly, additives such as a
chelating agent, a dispersant, a pH controlling agent, a deoxidant,
and an oxygen scavenger may be selectively used.
[0135] In addition, the polymerization reaction may be conducted at
a temperature of 0.degree. C. to 200.degree. C., and more
particularly, 20.degree. C. to 100.degree. C.
[0136] In addition, the polymerization reaction may be performed in
the above temperature range until a conversion ratio of a
conjugated diene-based polymer reaches 100%, for 5 minutes to 1
hour, particularly, for 10 minutes to 2 hours.
[0137] From the result of the polymerization reaction, a conjugated
diene-based polymer is produced.
[0138] The conjugated diene-based polymer may be a rare earth metal
catalyzed conjugated diene-based polymer, which contains an active
organometallic part which is derived from the catalyst including a
rare earth metal compound, more particularly, a rare earth metal
catalyzed butadiene-based polymer containing a 1,3-butadiene
monomer unit, and more particularly, a neodymium catalyzed
butadiene-based polymer containing a 1,3-butadiene monomer unit. In
addition, the conjugated diene-based polymer may be a polybutadiene
composed of only 1,3-butadiene monomers.
[0139] The conjugated diene-based polymer produced by the
polymerization reaction may be dissolved in a polymerization
solvent, or may be obtained in a precipitated state. If the polymer
is dissolved in the polymerization solvent, precipitation may be
obtained by adding a lower alcohol such as methyl alcohol or ethyl
alcohol, or steam. Thus, the method of preparing a conjugated
diene-based polymer according to an embodiment of the present
invention may further include precipitation and separation
processes with respect to a conjugated diene-based polymer prepared
after the polymerization reaction. In this case, filtering,
separating and drying processes with respect to the precipitated
conjugated diene-based polymer may be conducted by a common
method.
[0140] As described above, in the method of preparing a conjugated
diene-based polymer according to an embodiment of the present
invention, a conjugated diene-based polymer having high linearity
and processability may be prepared by using a functionalizing agent
during preparing a catalyst composition.
[0141] Particularly, the conjugated diene-based polymer may include
a functional group derived from the functionalzing agent in a
molecule.
[0142] In addition, the conjugated diene-based polymer may be a
rare earth metal catalyzed diene-based polymer which contains an
active organometallic part which is derived from the catalyst
including a rare earth metal compound, more particularly, a rare
earth metal catalyzed butadiene-based polymer containing a
1,3-butadiene monomer unit, and more particularly, a neodymium
catalyzed butadiene-based polymer.
[0143] The conjugated diene-based polymer according to an
embodiment of the present invention may have narrow distribution of
molecular weight, i.e., have a polydispersity (PDI) of 3.4 or less,
which is a ratio (Mw/Mn) of a weight average molecular weight (Mw)
and a number average molecular weight (Mn). If the PDI of the
conjugated diene-based polymer is greater than 3.4, and the polymer
is applied in a rubber composition, mechanical properties such as
abrasion resistance and impact resistance may be deteriorated. More
particularly, the polydispersity of the conjugated diene-based
polymer may be 3.2 or less in consideration of remarkable improving
effect of the mechanical properties of the polymer according to the
control of polydispersity.
[0144] The conjugated diene-based polymer according to an
embodiment of the present invention may have a weight average
molecular weight (Mw) of 300,000 g/mol to 1,200,000 g/mol, and
particularly 400,000 g/mol to 1,000,000 g/mol. In addition, the
conjugated diene-based polymer according to an embodiment of the
present invention may have a number average molecular weight (Mn)
of 100,000 g/mol to 700,000 g/mol, and particularly 120,000 g/mol
to 500,000 g/mol.
[0145] If the conjugated diene-based polymer has a weight average
molecular weight of less than 300,000 g/mol and a number average
molecular weight of less than 100,000 g/mol, the elasticity of a
vulcanizate may decrease, hysteresis loss may increase, and
abrasion resistance may be degenerated. If the weight average
molecular weight is greater than 1,200,000 g/mol or the number
average molecular weight is greater than 700,000 g/mol,
processability may be deteriorated, the workability of a rubber
composition including the conjugated diene-based polymer may be
degenerated, and mixing and kneading may become difficult, and
thus, the sufficient improvement of the physical properties of a
rubber composition may become difficult. In the present invention,
each of the weight average molecular weight and the number average
molecular weight is conversion molecular weight with a polystyrene
standard, which is analyzed by gel permeation type chromatography
(GPC).
[0146] More particularly, when applied in a rubber composition and
in consideration of improving effect of the mechanical properties,
elasticity and processability of the rubber composition in balance,
the conjugated diene-based polymer according to an embodiment of
the present invention may preferably satisfy the polydispersity,
the weight average molecular weight and the number average
molecular weight conditions at the same time. Particularly, the
conjugated diene-based polymer has a ratio (Mw/Mn) of a weight
average molecular weight (Mw) and a number average molecular weight
(Mn) of 3.4 or less, a weight average molecular weight (Mw) of
300,000 g/mol to 1,200,000 g/mol, and a number average molecular
weight (Mn) of 100,000 g/mol to 700,000 g/mol, and more
particularly, a ratio (Mw/Mn) of a weight average molecular weight
(Mw) and a number average molecular weight (Mn) of 3.2 or less, a
weight average molecular weight (Mw) of 400,000 g/mol to 1,000,000
g/mol, and a number average molecular weight (Mn) of 120,000 g/mol
to 500,000 g/mol.
[0147] In addition, the conjugated diene-based polymer shows high
linearity due to the use of a functionalizing agent during the
preparation process thereof. Generally, with the increase of
linearity, a branching degree may decrease, and a solution
viscosity may increase. Particularly, when solution viscosity (SV)
is divided by mooney viscosity (MV) to obtain a value and the
corrected value thereof is referred to as linearity (SV/MV), the
linearity (SV/MV) of the conjugated diene-based polymer according
to an embodiment of the present invention may be 1 to 15, and more
particularly 3 to 13.
[0148] In addition, the mooney viscosity (ML1+4) of the conjugated
diene-based polymer at 100.degree. C. may be 10 MU to 90 MU, and
particularly, 20 MU to 80 MU. In addition, the solution viscosity
of the conjugated diene-based polymer may be 100 cP to 600 cP, and
particularly, 170 cP to 500 cP.
[0149] In the present invention, the mooney viscosity may be
measured, for example, by using MV2000E manufactured by Monsanto
Co., Ltd. using Large Rotor at 100.degree. C. at a rotor speed of
2.+-.0.02 rpm. In this case, a specimen used may be stood at room
temperature (23.+-.3.degree. C.) for 30 minutes or more, and
27.+-.3 g of the specimen may be collected and put in a die cavity,
and then, the mooney viscosity may be measured by operating Platen.
The unit of the mooney viscosity is a mooney unit (MU). In the
present invention, the solution viscosity (SV) was measured by the
same method for measuring the mooney viscosity, but the viscosity
of a polymer in 5% toluene at 20.degree. C. was measured.
[0150] More particularly, in consideration of remarkable improving
effect according to the control of the mooney viscosity and the
solution viscosity, the conjugated diene-based polymer according to
an embodiment of the present invention may have a mooney viscosity
(MV) at 100.degree. C. of 20 MU to 80 MU, a solution viscosity (SV)
of 100 cP to 600 cP, and a linearity (SV/MV) of 3 to 13.
[0151] In addition, the conjugated diene-based polymer according to
an embodiment of the present invention may have the cis content in
the conjugated diene-based polymer, when measured by Fourier
transform infrared spectroscopy, particularly, the cis-1,4 bond
content of 95% or more, and more particularly, 96% or more. In
addition, the vinyl bond content in the conjugated diene-based
polymer may be 1% or less. When the cis-1,4 bond content in a
polymer is high as described above, linearity may increase, and
when mixed in a rubber composition, the abrasion resistance and
cracking resistance of the rubber composition may be improved.
[0152] In addition, the conjugated diene-based polymer according to
an embodiment of the present invention has pseudo-living
properties. Accordingly, a polymer may be modified via the
modification process of the terminal thereof for functionalizing
using a functional group such as a group having an interaction with
an inorganic filler such as carbon black and silica. In this case,
the method of preparing a conjugated diene-based polymer according
to an embodiment of the present invention may further include a
modification process using a modifier with respect to the
conjugated diene-based polymer prepared as the result of a
polymerization reaction.
[0153] The modification process may be conducted by a common
modification method except for using the conjugated diene-based
polymer according to the present invention.
[0154] In addition, as the modifier, a compound which may impart a
polymer with the functional group or increase a molecular weight
via coupling during the reaction with a conjugated diene-based
polymer, may be used. Particularly, at least one functional group
selected from an azacyclopropane group, a ketone group, a carboxyl
group, a thiocarboxyl group, a carbonate group, a carboxylic
anhydride group, a metal carboxylate, an acid halide, an urea
group, a thiourea group, an amide group, a thioamide group, an
isocyanate group, a thioisocyanate group, a halo-isocyano group, an
epoxy group, a thioepoxy group, an imine group and an M-Z bond
(where M is selected from the group consisting of Sn, Si, Ge and P,
and Z is a halogen atom) may be included, and an activated proton
and an onium salt, which activate the activated organometallic
part, may not be included. More particularly, the terminal modifier
may be one selected from the group consisting of alkoxysilane, an
imine-containing compound, an ester, an ester-carboxylate metal
complex, an alkyl ester carboxylate metal complex, an aldehyde or
ketone, an amide, an isocyanate, an isothiocyanate, an imine and an
epoxide, or a mixture of at least two thereof. In an embodiment,
the modifier may be
(E)-N,N-dimethyl-4-((undecylimino)methyl)benzenamine. The terminal
modifier during a modification process may be used in an amount of
0.01 equivalents to 200 equivalents, and more particularly, 0.1
equivalents to 150 equivalents based on 1 equivalent of the rare
earth metal compound.
[0155] The conjugated diene-based polymer prepared via the
modification process includes a modifier derived functional group
in the polymer, particularly, at the terminal thereof.
Particularly, the modifier derived functional group may be at least
one selected from an azacyclopropane group, a ketone group, a
carboxyl group, a thiocarboxyl group, a carbonate group, a
carboxylic anhydride group, a metal carboxylate, an acid halide, an
urea group, a thiourea group, an amide group, a thioamide group, an
isocyanate group, a thioisocyanate group, a halo-isocyano group, an
epoxy group, a thioepoxy group, an imine group and an M-Z bond
(where M is selected from the group consisting of Sn, Si, Ge and P,
and Z is a halogen atom). By including such a modifier derived
functional group, good affinity with respect to an inorganic filler
such as carbon black and silica, which are used during preparing a
rubber composition, may be shown, and the dispersibility thereof
may be increased. As a result, the physical properties of a rubber
composition may be further improved. Therefore, according to
another embodiment of the present invention, a modified and
conjugated diene-based polymer is provided.
[0156] Rubber Composition
[0157] According to further another embodiment of the present
invention, a rubber composition including the conjugated
diene-based polymer is provided.
[0158] Particularly, the rubber composition may include 10 wt % to
100 wt % of the conjugated diene-based polymer and less than 90 wt
% of a rubber component. If the amount of the conjugated
diene-based polymer is less than 10 wt %, the improving effect of
the abrasion resistance, crack resistance, and ozone resistance of
the rubber composition may be insignificant.
[0159] In addition, the rubber component may particularly be
natural rubber (NR); or synthetic rubber such as a
styrene-butadiene copolymer (SBR), a hydrogenated SBR, a
polybutadiene (BR) having a low cis-1,4 bond content, a
hydrogenated BR, a polyisoprene (IR), butyl rubber (IIR), ethylene
propylene rubber, ethylene propylene diene rubber,
polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-propylene),
poly(styrene-co-butadiene), poly(styrene-co-isoprene),
poly(styrene-co-isoprene-co-butadiene),
poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene),
polysulfide rubber, acryl rubber, urethane rubber, silicone rubber,
and epichlorohydrin rubber, and any one or a mixture of at least
two thereof may be used.
[0160] In addition, the rubber composition may further include 10
parts by weight or more of a filler based on 100 parts by weight of
the rubber component. In this case, the filler may be carbon black,
starch, silica, aluminum hydroxide, magnesium hydroxide, clay
(hydrated aluminum silicate), etc., and any one or a mixture of at
least two thereof may be used.
[0161] In addition, to the rubber composition, a compounding agent
used in a common rubber industry such as a vulcanizing agent, a
vulcanization accelerator, an antiaging agent, a scorch preventing
agent, a softening agent, a zinc white, stearic acid and a silane
coupling agent may be appropriately selected and mixed in addition
to the rubber component and filler in a range of not hindering the
object of the present invention.
[0162] The rubber composition is prepared by using a catalyst
composition including a functionalizing agent, and includes a
conjugated diene-based polymer having excellent linearity and
processability, thereby exhibiting improved effects of abrasion,
viscoelasticity and processability in balance without leaning to
one side.
[0163] Accordingly, the rubber composition is useful for the
manufacture of various rubber molded articles such as tires for a
car, a truck (track) and a bus (for example, a tire tread, a
side-wheel, a sub-tread, a bead filler, a breaking member, etc.),
elastic parts of a tire stock, an O-ring, a profile, a gasket, a
film, a hose, a belt, the sole of shoes, dustproof rubber and a
window seal.
[0164] Hereinafter, the present invention will be explained in
particular referring to embodiments. However, it will be understood
that the embodiments of the present invention may have various
modifications, and the scope of the present invention should be
interpreted to be limited to the following embodiments. The
embodiments of the present invention are provided to more
completely explaining the present invention to a person having an
average knowledge in the art.
Preparation of Functionalizing Agent
Preparation Example 1: Preparation of Allyltrimethylsilane
##STR00006##
[0166] To a solution prepared by dissolving nMe.sub.3SiCl (3 g,
9.87 mmol) in Et.sub.2O at room temperature (23.+-.5.degree. C.), a
solution of allylMgBr (1.0 M, 30 mmol, 30 ml in Et.sub.2O) was
added dropwisely. The reaction mixture was stirred at room
temperature for 2 hours. After finishing the reaction, the solution
thus obtained was quenched using NaCl and extracted with diethyl
ether (Et.sub.2O). An organic layer thus separated was extracted
with Et.sub.2O and dried with MgSO.sub.4. Under a reduced pressure,
volatile solvents were removed, and the residual product was
separated via silica gel neutralized with Et.sub.3N and Et.sub.2O
to obtain allyltrimethylsilane as a functionalzing agent.
[0167] .sup.1H NMR (500 MHz, CDCl.sub.3) 5.78-5.74 (m, 1H),
4.86-4.82 (m, 2H), 1.53-1.50 (m, 2H), 0.00 (s, 9H).
Preparation Example 2: Preparation of Diallyldimethylsilane
##STR00007##
[0169] Mg (16 g, 693 mmol) and allyl bromide (allylBr) (52 ml, 600
mmol) were reacted in THF (500 ml) to prepare a THF solution of
allylMgBr. In an ice bath, a THF solution of Me.sub.2SiCl.sub.2
(9.06 g) was added dropwisely to the reaction solution, and a
reaction mixture was stirred at room temperature (23.+-.5.degree.
C.) for 2 hours. The temperature was elevated to 60.degree. C., and
stirring was performed overnight for 12 hours while keeping the
same temperature. After finishing the reaction, the reaction
product was poured into ice water and extracted with diethyl ether
(Et.sub.2O). An organic layer was washed with brine and dried with
Na.sub.2SO.sub.4. After removing solvents, the residual product was
filtered via silica gel or separated via suction distillation to
obtain diallyldimethylsilane as a functionalizing agent.
[0170] .sup.1H NMR (500 MHz, CDCl.sub.3) 5.82-5.73 (m, 2H),
4.86-4.83 (m, 4H), 1.54 (d, J=8.15 Hz, 4H), 0.00 (s, 6H).
Preparation Example 3: Preparation of Triallylmethylsilane
##STR00008##
[0172] In an ice bath, a THF solution of allylMgBr was added
dropwisely to a THF solution of MeSiCl.sub.3 (9.06 g, 7.12 ml, 60.6
mmol), and a reaction mixture was stirred at room temperature
(23.+-.5.degree. C.) for 2 hours. The temperature was elevated to
60.degree. C., and stirring was performed overnight for 12 hours
while keeping the temperature. After finishing the reaction, the
reaction product was poured into ice water and extracted with
diethyl ether (Et.sub.2O). An organic layer was washed with brine
and dried with Na.sub.2SO.sub.4. After removing solvents, the
residual product was filtered via silica gel or separated via
suction distillation to obtain diallyldimethylsilane as a
functionalizing agent.
[0173] .sup.1H NMR (500 MHz, CDCl.sub.3) 5.82-5.74 (m, 3H),
5.01-4.85 (m, 6H), 1.58 (d, J=13.1 Hz, 6H), 0.00 (s, 3H).
Preparation Example 4: Preparation of Triallylphenylsilane
##STR00009##
[0175] Triallylphenylsilane was prepared by conducting the same
method described in Preparation Example 3 except for using
PhSnCl.sub.3 instead of MeSiCl.sub.3 in Preparation Example 3.
[0176] .sup.1H NMR (500 MHz, CDCl.sub.3) 7.59-7.34 (m, 5H),
5.85-5.5 (m, 3H), 4.98-4.88 (m, 6H), 1.88 (d, J=10 Hz, 6H).
Preparation Example 5: Preparation of Tetraallylsilane
##STR00010##
[0178] At room temperature (23.+-.5.degree. C.), a THF solution of
allylMgBr (200 ml, 400 mmol, 2.0 M in THF) was added dropwisely to
a THF solution of SiCl.sub.4 (11 ml, 16.18 g, 95 mmol). A reaction
mixture was stirred at room temperature for 2 hours and refluxed
overnight for 12 hours. After finishing the reaction, the reaction
product was cooled to room temperature, poured into ice water and
extracted with diethyl ether (Et.sub.2O). A combined ethylene-based
extract was washed with water, dried with Na.sub.2SO.sub.4, and
concentrated. The residual product was separated via suction
distillation to obtain tetraallylsilane of a colorless oil
phase.
[0179] .sup.1H NMR (500 MHz, CDCl.sub.3) 5.83-5.75 (m, 4H),
4.92-4.87 (m, 8H), 1.61 (d, J=8.15, 8H).
Preparation Example 6: Preparation of Allyltriethoxysilane
##STR00011##
[0181] At room temperature (23.+-.5.degree. C.), a THF solution of
allylMgBr (100 ml, 100 mmol, 1.0 M in THF) was added dropwisely to
a THF solution of SiCl.sub.4 (11 ml, 16.18 g, 95 mmol). A reaction
mixture was stirred at room temperature for 2 hours, and EtOH (15
ml) and Et.sub.3N (15 ml) were additionally added dropwisely,
followed by stirring 2 hours for reaction. After finishing the
reaction, the reaction product was poured into ice water and
extracted with Et.sub.2O. A combined ethylene-based extract was
washed with water, dried with Na.sub.2SO.sub.4, and concentrated to
obtain allyltriethoxysilane.
[0182] .sup.1H NMR (500 MHz, CDCl.sub.3) 5.87-5.78 (m, 1H),
5.01-4.90 (m, 2H), 3.82 (q, J=10 Hz, 6H), 1.66 (d, J=10 Hz, 2H),
1.22 (t, J=10 Hz, 9H).
Preparation of Conjugated Diene-Based Polymer
Example 1
[0183] A neodymium compound of Nd(2,2-diethyl decanoate).sub.3
(concentration in hexane of 40 wt %) and the functionalizing agent
(i) which was prepared in Preparation Example 2 and had the
following structure (DAS, 5 equivalents based on 1 equivalent of
the neodymium compound) were injected to a hexane solvent. Then,
diisobutylaluminum hydride (DIBAH) and diethylaluminum chloride
(DEAC) were added one by one such that a molar ratio of neodymium
compound:DIBAH:DEAC=1:10:2.4 and mixed to prepare a catalyst
composition.
[0184] To a completely dried organic reactor, a vacuum state and a
nitrogen gas were alternately applied, and to a reactor in a vacuum
state, 4.7 kg of a mixture solution of 1,3-butadiene/hexane
(1,3-butadiene content=500 g) was added, the catalyst composition
prepared above was added, and a polymerization reaction was
performed at 70 for 60 minutes to prepare a butadiene polymer.
##STR00012##
Example 2
[0185] A butadiene polymer was prepared by conducting the same
method described in Example 1 except for using 5 equivalents of the
functionalizing agent (ii) (TAS) of a chemical formula which was
prepared in Preparation Example 5 as the functionalizing agent in
Example 1 based on 1 equivalent of the neodymium compound.
##STR00013##
Example 3
[0186] To a mixture solution of hexane and 1,3-butadiene (pBD), a
neodymium compound of Nd(2,2-diethyl decanoate).sub.3
(concentration in hexane=40 wt %), the functionalizing agent (i)
(DAS, 1 equivalent based on 1 equivalent of the neodymium
compound), diisobutylaluminum hydride (DIBAH), and diethylaluminum
chloride (DEAC) were injected one by one such that a molar ratio of
neodymium compound:DIBAH:DEAC=1:9.2:2.4, and mixed to prepare a
catalyst composition. In this case, equivalents of the
1,3-butadiene was used based on 1 equivalent of the neodymium
compound.
[0187] A butadiene polymer was prepared by conducting the same
method described in Example 1 except for using the catalyst
composition thus prepared.
Comparative Example 1
[0188] A neodymium compound of Nd(2,2-diethyl decanoate).sub.3
(concentration in hexane=40 wt %), diisobutylaluminum hydride
(DIBAH), and diethylaluminum chloride (DEAC) were injected to a
hexane solvent one by one such that the molar ratio of neodymium
compound:DIBAH:DEAC=1:10.1:2.4, and mixed to prepare a catalyst for
polymerization.
[0189] A butadiene polymer was prepared by conducting the same
method described in Example 1 except for using the catalyst for
polymerization thus prepared.
Comparative Example 2
[0190] A butadiene polymer (BR1208.TM., manufactured by LG
Chemicals Co., Ltd.) prepared by conducting the same method
described in Example 1 except for using nickel octoate instead of a
Nd-based catalyst and not using a functionalizing agent in Example
1, was used.
Experimental Example 1
[0191] The improvement of catalytic activity and the improving
effect of conversion ratio according to the use of the
functionalizing agent of the present invention when using a
butadiene-based polymer, were evaluated.
[0192] In detail, 89 mg (0.054 mmol) of a neodymium compound of
Nd(2,2-diethyl decanoate).sub.3, a functionalizing agent described
in the following Table 1, diisobutylaluminum hydride (DIBAH) (0.12
ml, 0.675 mmol), and diethylaluminum chloride (DEAC) (0.13 ml,
0.130 mmol) were added one by one to hexane, and mixed to prepare a
catalyst composition. To a completely dried organic reactor, a
vacuum state and a nitrogen gas were alternately applied, and to a
reactor in a vacuum state, 150 g of a mixture solution of
1,3-butadiene/hexane (1,3-butadiene content=22.5 g) was added, and
the prepared catalyst composition was added thereto, and then, a
polymerization reaction was performed at 70 for the time period
described in the following Table 1 to prepare a butadiene
polymer.
TABLE-US-00001 TABLE 1 Functionalizing agent Polymerization
Conversion Kind Amount time ratio Example 4 ##STR00014## (iii) 5 eq
30 min 98% Example 5 ##STR00015## (i) 5 eq 30 min 91% Example 6
Example 7 Example 8 ##STR00016## (iv) 5 eq 5 eq 5 eq 30 min 60 min
120 min 42.1% 58.4% 70.1% Example 9 Example 10 Example 11
##STR00017## (v) 5 eq 5 eq 5 eq 30 min 60 min 120 min 35.2% 49.3%
68.3% Example 12 ##STR00018## (vi) 5 eq 30 min 10% Example 13
##STR00019## (vii) 5 eq 30 min 25%
[0193] From the experimental results, the conversion to a butadiene
polymer became possible due to the use of the functionalizing agent
according to the present invention, and conversion ratio to a
butadiene polymer was increased with longer polymerization time. In
addition, when the reaction was conducted with the same amount for
the same polymerization time, a case where all functional groups
bonded to Si were polymerization reactive functional groups, or a
case where using a functionalizing agent including at least one
polymerization reactive functional group with alkyl (Examples 4 and
5) showed higher conversion ratio than cases where using
functionalizing agents having aryl or alkoxy (Examples 6 to 11). In
addition, similarly, a case where using a functionalizing agent
including allyl as a polymerization reactive functional group even
though including alkyl (Example 5) showed higher conversion ratio
when compared to a case where using a functionalizing agent
including allyl bonded via oxygen which is a heteroatom (Example
13).
Experimental Example 2
[0194] For the butadiene polymers prepared in Examples 1 to 3, and
Comparative Examples 1 and 2, various physical properties were
measured by the following methods, and the results are shown in
Table 2.
[0195] 1) Microstructure Analysis
[0196] The amounts of cis-1,4 bonds, vinyl bonds and trans bonds in
the prepared butadiene polymers were respectively measured by using
Fourier infrared spectroscopy and nuclear magnetic resonance
spectroscopy.
[0197] 2) Weight Average Molecular Weight (Mw), Number Average
Molecular Weight (Mn) and Polydispersity (PDI)
[0198] The weight average molecular weight (Mw), and the number
average molecular weight (Mn) of the prepared butadiene polymers
were measured by gel permeation chromatography (GPC), and
polydispersity (PDI, Mw/Mn) was calculated therefrom.
[0199] In particular, each of the butadiene-based polymers thus
prepared was dissolved in THF for 30 minutes under 40.degree. C.
conditions and loaded on gel permeation chromatography and flowed.
In this case, two columns of PLgel Olexis and one column of PLgel
mixed-C manufactured by Polymer Laboratories Co., Ltd. were used in
combination as columns. In addition, all newly replaced columns
were mixed bed type columns, and polystyrene (PS) was used as a GPC
standard material.
[0200] 3) Viscosity Properties
[0201] Mooney viscosity (MV, (ML1+4 @100.degree. C.) (MU): The
mooney viscosity (MV) for the butadiene-based polymers was measured
by using MV2000E manufactured by Monsanto Co., Ltd. using Large
Rotor at 100.degree. C. at a rotor speed of 2.+-.0.02 rpm. In this
case, a specimen used was stood at room temperature
(23.+-.3.degree. C.) for 30 minutes or more, and 27.+-.3 g of the
specimen was collected and put in a die cavity, and then, the
mooney viscosity was measured by operating Platen while applying
torque.
[0202] -S/R value: A -S/R value was determined from a gradient
value on the change of mooney viscosity, which was shown by the
release of the torque when measuring the mooney viscosity.
[0203] Solution viscosity (SV) was obtained by measuring viscosity
of a polymer in 5% toluene at 20.degree. C.
TABLE-US-00002 TABLE 2 Compar- Compar- ative ative Example Example
Example Example Example 1 2 1 2 3 Functionalizing -- -- DAS (5 eq)
TAS (5 eq) DAS (1 eq) + agent (amount) pBD (33 eq) Catalyst
Nd-based Ni-based Nd-based Nd-based Nd-based IR Microstructure
96.4/0.5/3.1 96.2/2.0/1.8 97.1/0.5/2.4 97.0/0.5/2.5 ND
(cis/vinyl/trans) (amount ratio) GPC Mn g/mol 2.49.E+05 1.57.E+05
2.62.E+05 2.51.E+05 ND Mw g/mol 8.47.E+05 7.78.E+05 7.99.E+05
7.00.E+05 ND Mw/Mn -- 3.41 4.96 3.05 2.78 ND MV ML1 + 4 MU 44.8
43.2 54.1 46.3 43.7 (@100.degree. C.) -S/R -- 0.5502 0.7651 0.6758
0.7142 0.6944 Solution viscosity 276.0 280.0 301.0 485.0 134.4 (SV)
(cP) SV/MV 6.16 6.48 5.56 10.5 3.08
[0204] In the above Table 2, ND means "not measured", and eq means
equivalent.
[0205] From the experimental results, with respect to the
microstructure, the butadiene polymers of Examples 1 to 3, which
were prepared using a functionalizing agent showed 97% or more of
the cis bond content and 0.5% or less of the vinyl bond content in
a polymer, and the butadiene polymers of Examples 1 to 3 showed
0.65 or more of a -S/R value and high linearity. In addition, with
respect to the molecular weight distribution, the butadiene polymer
of Examples 1 to 3, which were prepared using a functionalizing
agent showed a low PDI of 3.05 or less, more particularly, 2.78 to
3.05, and was found to show narrow molecular weight distribution.
In addition, with respect to viscosity properties, the butadiene
polymers of Examples 1 to 3, which were prepared using a
functionalizing agent had SV/MV in a range of 3.08 to 10.5.
[0206] In addition, the copolymer of Example 3, which was prepared
using a catalyst composition in which 1,3-butadiene was
additionally added as a conjugated diene-based monomer during
preparing the catalyst composition, showed markedly lower solution
viscosity and SV/MV when compared to those of Examples 1 and 2
using the same functionalizing agent. From the results, the
improvement of processability during preparing a rubber composition
may be expected.
[0207] Meanwhile, the butadiene polymer of Comparative Example 1,
which was prepared by the same method as Example 1 except for not
using a functionalizing agent, showed broader molecular weight
distribution and a lower -S/R value when compared to those of
Examples 1 to 3, which used a functionalizing agent. Accordingly,
the butadiene polymer of Comparative Example 1 showed
processability deterioration as shown in the following Table 3.
[0208] In addition, the butadiene polymer of Comparative Example 2,
which was prepared by not using a functionalizing agent and using a
nickel-based catalyst, showed a higher vinyl content and broader
molecular weight distribution when compared to those of Examples 1
to 3.
Experimental Example 3
[0209] Rubber specimens were manufactured using the butadiene
polymers prepared in Examples 1 to 3, and Comparative Examples 1
and 2, and abrasion properties, viscoelasticity and processability
were measured for the rubber specimens thus manufactured by the
following methods, and the results are shown in Table 3.
[0210] In particular, based on 100 parts by weight of the
butadiene-based polymers prepared in the above Examples 1 and 2 and
Comparative Example 1 as rubber raw materials, 70 parts by weight
of graphite, 22.5 parts by weight of a process oil, 2 parts by
weight of an antiaging agent (TMDQ), 3 parts by weight of zinc
oxide (ZnO), and 2 parts by weight of stearic acid were mixed to
prepare each rubber compound. To the rubber compound thus prepared,
2 parts by weight of sulfur, 2 parts by weight of a vulcanization
accelerator (CZ), and 0.5 parts by weight of a vulcanization
accelerator (DPG) were added, and vulcanization was performed at
160 for 25 minutes to manufacture a rubber specimen.
[0211] 1) Abrasion Properties
[0212] Loss volume index: ARI.sub.A (abrasion resistance index,
Method A) was measured according to a method specified in the
experimental standard of ASTM D5963, and was represented as an
index value. The higher the value was, the better the abrasion
properties was.
[0213] 2) Viscoelasticity
[0214] A dynamic mechanical analyzer of TA Co., Ltd. was used. A
Tan 5 value was measured by changing deformation with a frequency
of 10 Hz at each measurement temperature (-70.degree. C. to
70.degree. C.) with a twist mode. Payne effect was illustrated as a
difference between a minimum value and a maximum value between the
deformation of 0.28% to 40%. If the Payne effect was decreased,
dispersibility of a filler such as silica was improved. If the Tan
5 value at a low temperature of 0.degree. C. was increased, wet
traction was good, and if the Tan 5 value at a high temperature of
50.degree. C. to 70.degree. C. was decreased, hysteresis loss was
decreased, and low rolling resistance of a tire, i.e., a low fuel
consumption ratio became good.
[0215] 3) Processability
[0216] The surfaces of vulcanized rubber sheets (FMB) manufactured
using the butadiene polymers prepared in Examples 1 to 3 and
Comparative Examples 1 and 2 by the same method in Experimental
Example 1 were photographed by using a digital camera (sheet
width=20 cm).
[0217] Based on observed results, each result was scored as 1-4 by
representing near 1 when the surface state of a sheet was good and
the edge portion thereof was clean, and 4 when the surface state
was rough and the edge was not planar, to evaluate
processability.
TABLE-US-00003 TABLE 3 Comparative Comparative Example 1 Example 2
Example 1 Example 2 Example 3 Functionalizing -- -- DAS (5 eq) TAS
(5 eq) DAS (1 eq) + pBD agent (amount) Catalyst Nd-based Ni-based
Nd-based Nd-based Nd-based Tan .delta. @ 0.degree. C. 0.209 (112%)
0.208 (115%) 0.184 (103%) 0.183 (103%) 0.185 avg. Tan .delta. (@
0.164 (85%) 0.162 (88%) 0.146 (95%) 0.142 (97%) 0.147 50.degree.
C.-70.degree. C.) Loss volume index 100 89 105 105 107
Processability 4 1 3 3 2
[0218] In the above Table 3, eq means equivalent, and pBD means
mixed 1,3-butadiene during preparing a catalyst composition.
[0219] From the experimental results, the butadiene polymers
prepared in Examples 1 to 3 using a catalyst composition including
a functionalizing agent showed a higher loss volume index when
compared to that of Comparative Examples 1 and 2, and were found to
have better abrasion properties.
[0220] In addition, with respect to viscoelasticity, the butadiene
polymers of Examples 1 to 3, which were prepared using a catalyst
composition including a functionalizing agent, showed similar level
of a Tan 5 value at a low temperature of 0.degree. C. as those of
Comparative Examples 1 and 2, and was found to show equivalent
level of wet traction. In addition, a Tan 5 value at a high
temperature of 50.degree. C. to 70.degree. C. was further smaller
in general when compared to those of Comparative Examples 1 and 2,
and hysteresis loss was small, and low rolling resistance of a
tire, i.e., a low fuel consumption ratio was further improved.
[0221] In addition, in the vulcanized rubber specimen of the
butadiene polymer of Comparative Example 1, which was manufactured
using a catalyst composition not including a functionalizing agent,
surface roughness at both sides of a sheet was observed
considerably. On the contrary, the FMB sheets manufactured by using
the butadiene polymers of Examples 1 to 3 according to the present
invention showed smooth surface properties. Particularly in
Examples 1 and 2, in which a Sn-based functionalizing agent was
used, similar or better smooth surface properties were shown when
compared to the FMB sheet manufactured by using the nickel
catalyzed butadiene polymer of Comparative Example 2, which was
known to have good processability. From the results, the butadiene
polymer according to the present invention is expected to have good
processability when manufacturing a tire, etc.
[0222] From the experimental results, rubber compositions including
the butadiene polymer according to the present invention were found
to show improved effects of abrasion properties, viscoelasticity,
and processability in balance without leaning to one side when
compared to the rubber compositions of the comparative
examples.
* * * * *