U.S. patent application number 15/770902 was filed with the patent office on 2018-11-01 for modifer, modified and conjugated diene-based polymer and rubber composition including 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, Hyo Jin Bae, Woo Jin Cho, Heung Yeal Choi, Hee Jung Jeon, Suk Youn Kang, Kyoung Hwan Oh.
Application Number | 20180312669 15/770902 |
Document ID | / |
Family ID | 61000855 |
Filed Date | 2018-11-01 |
United States Patent
Application |
20180312669 |
Kind Code |
A1 |
Kang; Suk Youn ; et
al. |
November 1, 2018 |
MODIFER, MODIFIED AND CONJUGATED DIENE-BASED POLYMER AND RUBBER
COMPOSITION INCLUDING THE SAME
Abstract
The present invention provides a modifier, a modified and
conjugated diene-based polymer which is modified using the same,
and a rubber composition including the modified and conjugated
diene-based polymer, and more particularly, a modifier which
includes a compound represented by Formula 1 and is capable of
improving the mixing properties between a conjugated diene-based
polymer and a filler, a modified and conjugated diene-based polymer
which is modified using the same, and a rubber composition
including the modified and conjugated diene-based polymer.
Inventors: |
Kang; Suk Youn; (Daejeon,
KR) ; Bae; Hyo Jin; (Daejeon, KR) ; Jeon; Hee
Jung; (Daejeon, KR) ; Ahn; Jeong Heon;
(Daejeon, KR) ; Choi; Heung Yeal; (Daejeon,
KR) ; Oh; Kyoung Hwan; (Daejeon, KR) ; Cho;
Woo Jin; (Daejeon, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
LG Chem, Ltd. |
Seoul |
|
KR |
|
|
Assignee: |
LG Chem, Ltd.
Seoul
KR
|
Family ID: |
61000855 |
Appl. No.: |
15/770902 |
Filed: |
June 30, 2017 |
PCT Filed: |
June 30, 2017 |
PCT NO: |
PCT/KR2017/006995 |
371 Date: |
April 25, 2018 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08C 19/44 20130101;
C08F 36/04 20130101; C08C 19/22 20130101; C08L 15/00 20130101; C08F
4/44 20130101; C08K 3/06 20130101; C08K 5/09 20130101; C08F 236/06
20130101; C08C 19/25 20130101; C08K 2003/2296 20130101; C08F 236/08
20130101; C08F 8/42 20130101; C08F 4/42 20130101; C08L 9/00
20130101; C08K 5/3412 20130101; C07F 7/10 20130101; C08K 5/549
20130101; C08F 2500/17 20130101; C08F 136/06 20130101; C08F 4/545
20130101; C08F 136/06 20130101; C08F 2/06 20130101; C08L 15/00
20130101; C08L 91/00 20130101; C08K 3/04 20130101; C08L 15/00
20130101; C08L 91/00 20130101; C08K 3/04 20130101; C08K 5/3437
20130101; C08K 3/22 20130101; C08K 5/09 20130101; C08K 3/06
20130101; C08K 5/47 20130101; C08K 5/31 20130101 |
International
Class: |
C08L 9/00 20060101
C08L009/00; C08F 236/08 20060101 C08F236/08; C08F 4/42 20060101
C08F004/42 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 4, 2016 |
KR |
10-2016-0084112 |
Oct 31, 2016 |
KR |
10-2016-0143545 |
Claims
1. A modifier comprising a compound represented by the following
Formula 1: ##STR00008## in Formula 1, R.sup.1 to R.sup.3 are each
independently a trivalent hydrocarbon group which is substituted
with at least one substituent selected from the group consisting of
a halogen group, an alkyl group of 1 to 20 carbon atoms, a
cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 30
carbon atoms, and --R.sup.6COOR.sup.7; or an unsubstituted divalent
hydrocarbon group of 1 to 10 carbon atoms, where all R.sup.1 to
R.sup.3 are not the trivalent hydrocarbon group; or the divalent
hydrocarbon group, at the same time, R.sup.4 is a single bond, an
alkylene group of 1 to 20 carbon atoms, or a cycloalkylene group of
3 to 20 carbon atoms, R.sup.5 is a silyl group which is
unsubstituted or substituted with an alkyl group of 1 to 20 carbon
atoms; halogen; a cyano group; or --COR.sup.8, R.sup.6 is a single
bond, an alkylene group of 1 to 20 carbon atoms, or a cycloalkylene
group of 3 to 20 carbon atoms, R.sup.7 is an alkyl group of 1 to 20
carbon atoms, or a cycloalkyl group of 3 to 20 carbon atoms, and
R.sup.8 is one selected from the group consisting of an alkoxy
group of 1 to 10 carbon atoms, an aryl group of 6 to 30 carbon
atoms, a heteroaryl group of 2 to 30 carbon atoms, a
heterocycloalkyl group of 2 to 10 carbon atoms, a heteroamine group
of 2 to 10 carbon atoms, and a disilylamino group of 3 to 10 carbon
atoms.
2. The modifier of claim 1, wherein in Formula 1, R.sup.1 to
R.sup.3 are each independently a trivalent hydrocarbon group which
is substituted with --R.sup.6COOR.sup.7; or an unsubstituted
divalent hydrocarbon group of 1 to 10 carbon atoms, where all
R.sup.1 to R.sup.3 are not the trivalent hydrocarbon group; or the
divalent hydrocarbon group, at the same time, R.sup.4 is a single
bond, or an alkylene group of 1 to 20 carbon atoms, R.sup.5 is a
silyl group which is substituted with an alkyl group of 1 to 20
carbon atoms; halogen; a cyano group; or --COR.sup.8, R.sup.6 is a
single bond, R.sup.7 is an alkyl group of 1 to 20 carbon atoms, and
R.sup.8 is one selected from the group consisting of an alkoxy
group of 1 to 10 carbon atoms, an aryl group of 6 to 30 carbon
atoms, a heteroaryl group of 2 to 30 carbon atoms, a
heterocycloalkyl group of 2 to 10 carbon atoms, a heteroamine group
of 2 to 10 carbon atoms, and a disilylamino group of 3 to 10 carbon
atoms.
3. The modifier of claim 1, wherein the compound represented by
Formula 1 is a compound represented by the following Formula 2:
##STR00009## in Formula 2, R.sup.1 and R.sup.3 are each
independently a trivalent hydrocarbon group which is substituted
with at least one substituent selected from the group consisting of
a halogen group, an alkyl group of 1 to 20 carbon atoms, a
cycloalkyl group of 3 to 20 carbon atoms, and an aryl group of 6 to
30 carbon atoms; or an unsubstituted divalent hydrocarbon group of
1 to 10 carbon atoms, R.sup.2 is a trivalent hydrocarbon group
which is substituted with --R.sup.6COOR.sup.7, R.sup.4 and R.sup.6
are single bonds, R.sup.7 is an alkyl group of 1 to 20 carbon
atoms, or a cycloalkyl group of 3 to 20 carbon atoms, and R.sup.9
to R.sup.11 are each independently hydrogen, or an alkyl group of 1
to 20 carbon atoms.
4. The modifier of claim 3, wherein the compound represented by
Formula 2 is one selected from the group consisting of the
compounds represented by the following Formulae 2-1 to 2-3:
##STR00010##
5. A modified and conjugated diene-based polymer, comprising a
functional group derived from the modifier according to claim
1.
6. The modified and conjugated diene-based polymer of claim 5,
wherein the modified and conjugated diene-based polymer has
molecular weight distribution of 2.0 to 3.5.
7. The modified and conjugated diene-based polymer of claim 5,
wherein the modified and conjugated diene-based polymer has a
mooney viscosity (MV) of 20 to 70 at 100.degree. C.
8. A method for preparing a modified and conjugated diene-based
polymer, the method comprising: a modification step of reacting a
conjugated diene-based polymer comprising an organometal part
activated from a lanthanide series rare earth element catalyst
composition with a modifier comprising a compound represented by
the following Formula 1: ##STR00011## in Formula 1, R.sup.1 to
R.sup.3 are each independently a trivalent hydrocarbon group which
is substituted with at least one substituent selected from the
group consisting of a halogen group, an alkyl group of 1 to 20
carbon atoms, a cycloalkyl group of 3 to 20 carbon groups, an aryl
group of 6 to 30 carbon atoms, and --R.sup.6COOR.sup.7; or an
unsubstituted divalent hydrocarbon group of 1 to 10 carbon atoms,
where all R.sup.1 to R.sup.3 are not the trivalent hydrocarbon
group; or the divalent hydrocarbon group, at the same time, R.sup.4
is a single bond, an alkylene group of 1 to 20 carbon atoms, or a
cycloalkylene group of 3 to 20 carbon atoms, R.sup.5 is a silyl
group which is unsubstituted or substituted with an alkyl group of
1 to 20 carbon atoms; halogen; a cyano group; or --COR.sup.8,
R.sup.6 is a single bond, an alkylene group of 1 to 20 carbon
atoms, or a cycloalkylene group of 3 to 20 carbon atoms, R.sup.7 is
an alkyl group of 1 to 20 carbon atoms, or a cycloalkyl group of 3
to 20 carbon atoms, and R.sup.8 is one selected from the group
consisting of an alkoxy group of 1 to 10 carbon atoms, an aryl
group of 6 to 30 carbon atoms, a heteroaryl group of 2 to 30 carbon
atoms, a heterocycloalkyl group of 2 to 10 carbon atoms, a
heteroamine group of 2 to 10 carbon atoms, and a disilylamino group
of 3 to 10 carbon atoms.
9. The method for preparing a modified and conjugated diene-based
polymer of claim 8, further comprising prior to the modification
step, a step of performing polymerization reaction of a conjugated
diene-based monomer using a catalyst composition comprising a
lanthanide series rare earth element-containing compound in a
polymerization solvent to prepare a conjugated diene-based polymer
having an activated organometal part.
10. The method for preparing a modified and conjugated diene-based
polymer of claim 9, wherein the catalyst composition comprises the
lanthanide series rare earth element-containing compound, an
alkylating agent and a halogen compound.
11. The method for preparing a modified and conjugated diene-based
polymer of claim 9, wherein the lanthanide series rare earth
element-containing compound comprises a neodymium compound
represented by the following Formula 3: ##STR00012## in Formula 3,
R.sub.a to R.sub.c are each independently hydrogen, or an alkyl
group of 1 to 12 carbon atoms, where all R.sub.a to R.sub.c are not
hydrogen, at the same time.
12. The method for preparing a modified and conjugated diene-based
polymer of claim 9, wherein the catalyst composition further
comprises a conjugated diene-based monomer.
13. The method for preparing a modified and conjugated diene-based
polymer of claim 8, wherein the conjugated diene-based polymer
comprising the activated organometal part is a conjugated
diene-based polymer comprising a terminal activated organometal
part.
14. The method for preparing a modified and conjugated diene-based
polymer of claim 8, wherein the conjugated diene-based polymer
comprising the activated organometal part is a neodymium catalyzed
butadiene-based polymer comprising a repeating unit derived from an
1,3-butadiene monomer.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims the benefit of priority based
on Korean Patent Application Nos. 10-2016-0084112, filed on Jul. 4,
2016, and 10-2016-0143545, filed on Oct. 31, 2016, the entire
contents of which are incorporated herein by reference.
TECHNICAL FIELD
[0002] The present invention relates to a modifier used for the
modification of a modified and conjugated diene-based polymer, and
more particularly, to a modifier which has excellent affinity with
a filler and may improve mixing properties of a conjugated
diene-based polymer, a modified and conjugated diene-based polymer
which is modified using the same, and a rubber composition
including the modified and conjugated diene-based polymer.
BACKGROUND ART
[0003] With the growing concern of energy savings and environmental
problems increases, the decrease of a fuel consumption ratio of an
automobile is being required. As a method of fulfill the
requirement, a method for decreasing exothermic properties of tires
by using an inorganic filler such as silica and carbon black in a
rubber composition for forming tires, has been suggested, but
dispersion of the inorganic filler in the rubber composition was
not easy and defects of degrading the physical properties of the
rubber composition such as abrasion resistance, cracking resistance
and processability were rather generated.
[0004] In order to solve such defects, a method for modifying a
polymerization active part of a conjugated diene-based polymer
which is obtained by anionic polymerization using an organolithium
with a functional group which is capable of interacting with an
inorganic filler has been developed as a method for increasing
dispersibility of an inorganic filler such as silica and carbon
black in a rubber composition. Particularly, a method for modifying
a polymerization active terminal of a conjugated diene-based
polymer using a tin-based compound, a method of introducing an
amino group, or a modification method using an alkoxysilane
derivative, etc., has been suggested.
[0005] However, if a rubber composition using a modified and
conjugated diene-based polymer which has been modified by the
above-described method is prepared, low exothermic properties may
be secured, but effects of improving physical properties of the
rubber composition such as abrasion resistance, processability, or
the like are insufficient.
[0006] In another method, in a living polymer which is obtained via
coordination polymerization using a catalyst including a lanthanide
series rare earth element compound, a method for modifying a living
active terminal by a specific coupling agent or a modifier has been
developed. However, in a conventionally known catalyst including a
lanthanide series rare earth element compound, the activity of the
living terminal thus produced is weak, and the modification rate of
the terminal is low, and the effects of improving the physical
properties of the rubber composition is insignificant.
DISCLOSURE OF THE INVENTION
Technical Problem
[0007] The present invention has been devised in consideration of
the above-mentioned problems, and an object of the present
invention is to provide a modifier which has excellent affinity
with a filler and is capable of improving the mixing properties of
a conjugated diene-based polymer.
[0008] In addition, other objects of the present invention are to
provide a modified and conjugated diene-based polymer which is
modified by the modifier and has improved mixing properties between
a polymer and a filler, and a method for preparing the same.
[0009] In addition, other objects of the present invention are to
provide a rubber composition and a tire including the modified and
conjugated diene-based polymer.
Technical Solution
[0010] To solve the above-described tasks, according to an
embodiment of the present invention, there is provided a modifier
including a compound represented by the following Formula 1:
##STR00001##
[0011] in Formula 1, R.sup.1 to R.sup.3 may be each independently a
trivalent hydrocarbon group which is substituted with at least one
substituent selected from the group consisting of a halogen group,
an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to
20 carbon atoms, an aryl group of 6 to 30 carbon atoms, and
--R.sup.6COOR.sup.7; or an unsubstituted divalent hydrocarbon group
of 1 to 10 carbon atoms, where all R.sup.1 to R.sup.3 may not be
the trivalent hydrocarbon group; or the divalent hydrocarbon group,
at the same time, R.sup.4 may be a single bond, an alkylene group
of 1 to 20 carbon atoms, or a cycloalkylene group of 3 to 20 carbon
atoms, R.sup.5 may be a silyl group which is unsubstituted or
substituted with an alkyl group of 1 to 20 carbon atoms; halogen; a
cyano group; or --COR.sup.8, R.sup.6 may be a single bond, an
alkylene group of 1 to 20 carbon atoms, or a cycloalkylene group of
3 to 20 carbon atoms, R.sup.7 may be an alkyl group of 1 to 20
carbon atoms, or a cycloalkyl group of 3 to 20 carbon atoms, and
R.sup.8 may be one selected from the group consisting of an alkoxy
group of 1 to 10 carbon atoms, an aryl group of 6 to 30 carbon
atoms, a heteroaryl group of 2 to 30 carbon atoms, a
heterocycloalkyl group of 2 to 10 carbon atoms, a heteroamine group
of 2 to 10 carbon atoms and a disilylamino group of 3 to 10 carbon
atoms.
[0012] In addition, according to other embodiments of the present
invention, there are provided a modified and conjugated diene-based
polymer including a functional group derived from the modifier, and
a method for preparing the same.
[0013] Further, according to other embodiments of the present
invention, there are provided a rubber composition and a tire
including the modified and conjugated diene-based polymer.
Advantageous Effects
[0014] According to the present invention, a modifier which has
excellent affinity with a filler and is capable of improving mixing
properties of a conjugated diene-based polymer is provided, and
further, a modified and conjugated diene-based polymer which is
modified by the modifier and has improved mixing properties between
a polymer and a filler, a method for preparing the same, and a tire
including the same, are provided.
BEST NODE FOR CARRYING OUT THE INVENTION
[0015] Hereinafter, the present invention will be described in more
detail to assist the understanding of the present invention.
[0016] It will be understood that words or terms used in the
description and claims of the present invention 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.
[0017] The modifier according to an embodiment the present
invention may include a compound represented by the following
Formula 1:
##STR00002##
[0018] in Formula 1, R.sup.1 to R.sup.3 may be each independently a
trivalent hydrocarbon group which is substituted with at least one
substituent selected from the group consisting of a halogen group,
an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to
20 carbon atoms, an aryl group of 6 to 30 carbon atoms, and
--R.sup.6COOR.sup.7; or an unsubstituted divalent hydrocarbon group
of 1 to 10 carbon atoms, where all R.sup.1 to R.sup.3 may not be
the trivalent hydrocarbon group; or the divalent hydrocarbon group,
at the same time, R.sup.4 may be a single bond, an alkylene group
of 1 to 20 carbon atoms, or a cycloalkylene group of 3 to 20 carbon
atoms, R.sup.5 may be a silyl group which is unsubstituted or
substituted with an alkyl group of 1 to 20 carbon atoms; halogen; a
cyano group; or --COR.sup.8, R.sup.6 may be a single bond, an
alkylene group of 1 to 20 carbon atoms, or a cycloalkylene group of
3 to 20 carbon atoms, R.sup.7 may be an alkyl group of 1 to 20
carbon atoms, or a cycloalkyl group of 3 to 20 carbon atoms, and
R.sup.8 may be one selected from the group consisting of an alkoxy
group of 1 to 10 carbon atoms, an aryl group of 6 to 30 carbon
atoms, a heteroaryl group of 2 to 30 carbon atoms, a
heterocycloalkyl group of 2 to 10 carbon atoms, a heteroamine group
of 2 to 10 carbon atoms and a disilylamino group of 3 to 10 carbon
atoms.
[0019] Unless otherwise defined in the present invention,
"trivalent hydrocarbon group which is substituted with a
substituent" may mean a hydrocarbon group which is substituted with
total trivalence from a bond (divalence) in an N atom-containing
ring and a bond (monovalence) with the defined substituent, or the
substituted trivalent hydrocarbon group may be a trivalent
hydrocarbon group of 1 to 10, or 1 to 5 carbon atoms which form a
ring together with an N atom, excluding the carbon number of the
defined substituent.
[0020] In addition, unless otherwise defined in the present
invention, "single bond" may mean a single covalent bond itself,
which does not include a separate atom or molecular group.
[0021] In addition, unless otherwise defined in the present
invention, "silyl group unsubstituted or substituted with an alkyl
group of 1 to 20 carbon atoms" may mean one selected from the group
consisting of an unsubstituted monovalent silyl group and di- to
tetra-valent silyl group substituted with the alkyl group.
[0022] The modifier according to the present invention may be the
compound represented by Formula 1 itself, or may include another
compound which may modify a conjugated diene-based polymer together
with the compound represented by Formula 1.
[0023] In addition, the modifier according to the present invention
includes a cyclized tertiary amine derivative as the compound
represented by Formula 1, and in a conjugated diene-based polymer,
particularly, a conjugated diene-based polymer having an active
organometal part, the modifier may modify the conjugated
diene-based polymer by imparting a conjugated diene-based polymer
with a functional group via a substitution or addition reaction
with the active organometal part.
[0024] Meanwhile, the modifier according to an embodiment of the
present invention includes a functional group which is capable of
improving affinity with a filler in a molecule, and mixing
properties between a polymer and a filler may be improved. Further,
by including a cyclized tertiary amine derivative as described
above, the modifier may prevent the agglomeration between fillers
in a rubber composition and may improve the dispersibility of a
filler. In an embodiment, if silica which is a kind of an inorganic
filler is used as a filler, agglomeration may be easily arise
between hydroxide groups present on the surface of the silica due
to a hydrogen bond, but the cyclized tertiary amino group may
inhibit the hydrogen bond between hydroxide groups of the silica,
thereby improving the dispersibility of the silica. As described
above, the modifier has a structure which may maximize the mixing
properties of a modified and conjugated diene-based polymer, and a
modified and conjugated diene-based polymer having excellent
balance of mechanical properties of a rubber composition such as
abrasion resistance and processability may be efficiently
prepared.
[0025] According to an embodiment of the present invention, in
Formula 1, R.sup.1 to R.sup.3 may be each independently a trivalent
hydrocarbon group which is substituted with --R.sup.6COOR.sup.7; or
an unsubstituted divalent hydrocarbon group of 1 to 10 carbon
atoms, where all R.sup.1 to R.sup.3 may not be the trivalent
hydrocarbon group; or the divalent hydrocarbon group, at the same
time, R.sup.4 may be a single bond, or an alkylene group of 1 to 20
carbon atoms, R.sup.5 may be a silyl group which is substituted
with an alkyl group of 1 to 20 carbon atoms; halogen; a cyano
group; or --COR.sup.8, R.sup.6 may be a single bond, R.sup.7 may be
an alkyl group of 1 to 20 carbon atoms, and R.sup.8 may be one
selected from the group consisting of an alkoxy group of 1 to 10
carbon atoms, an aryl group of 6 to 30 carbon atoms, a heteroaryl
group of 2 to 30 carbon atoms, a heterocycloalkyl group of 2 to 10
carbon atoms, a heteroamine group of 2 to 10 carbon atoms, and a
disilylamino group of 3 to 10 carbon atoms.
[0026] According to an embodiment of the present invention, the
compound represented by Formula 1 may be a compound represented by
the following Formula 2:
##STR00003##
[0027] in Formula 2, R.sup.1 and R.sup.3 may be each independently
a trivalent hydrocarbon group which is substituted with at least
one substituent selected from the group consisting of a halogen
group, an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group
of 3 to 20 carbon atoms, and an aryl group of 6 to 30 carbon atoms;
or an unsubstituted divalent hydrocarbon group of 1 to 10 carbon
atoms, R.sup.2 may be a trivalent hydrocarbon group which is
substituted with --R.sup.6COOR.sup.7, R.sup.4 and R.sup.6 may be
single bonds, R.sup.7 may be an alkyl group of 1 to 20 carbon
atoms, or a cycloalkyl group of 3 to 20 carbon atoms, and R.sup.9
to R.sup.11 may be each independently hydrogen, or an alkyl group
of 1 to 20 carbon atoms.
[0028] In another embodiment, in Formula 2, R.sup.1 and R.sup.3 may
be each independently an unsubstituted divalent hydrocarbon group
of 1 to 10 carbon atoms, R may be a trivalent hydrocarbon group
which is substituted with --R.sup.6COOR.sup.7, R.sup.4 and R.sup.6
may be single bonds, R.sup.11 may be an alkyl group of 1 to 20
carbon atoms, and R.sup.9 to R.sup.11 may be each independently an
alkyl group of 1 to 20 carbon atoms.
[0029] In a particular embodiment, the compound represented by
Formula 2 may be one selected from the group consisting of the
compounds represented by the following Formulae 2-1 to 2-3:
##STR00004##
[0030] The modified and conjugated diene-based polymer according to
an embodiment of the present invention may include a functional
group derived from the modifier. Particularly, the modified and
conjugated diene-based polymer may be prepared by modifying a
conjugated diene-based polymer with the modifier.
[0031] The conjugated diene-based polymer may be a butadiene
homopolymer such as polybutadiene, or a butadiene copolymer such as
a butadiene-isoprene copolymer.
[0032] In a particular embodiment, the conjugated diene-based
polymer may include from 80 to 100 wt % of a 1,3-butadiene monomer
derived repeating unit, and selectively 20 wt % or less of other
conjugated diene-based monomer derived repeating unit which is
copolymerizable with 1,3-butadiene. Within the ranges, effects of
not degrading the content of 1,4-cis bonds in a polymer may be
attained. In this case, the 1,3-butadiene monomer may include
1,3-butadiene or the derivatives thereof such as 1,3-butadiene,
2,3-dimethyl-1,3-butadiene, and 2-ethyl-1,3-butadiene, and the
other conjugated diene-based monomer which is copolymerizable with
1,3-butadiene may include 2-methyl-1,3-pentadiene, 1,3-pentadiene,
3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene,
2,4-hexadiene, or the like, where one or a compound of at least two
thereof may be used.
[0033] According to an embodiment of the present invention, the
conjugated diene-based polymer may be a conjugated diene-based
polymer including an organometal part, which is derived from a
catalyst composition including a lanthanide series rare earth
element-containing compound, that is, activated from a catalyst,
particularly, a neodymium catalyzed butadiene-based polymer
including a 1,3-butadiene monomer derived repeating unit.
[0034] In the present invention, the activated organometal part of
the conjugated diene-based polymer may be an activated organometal
part at the terminal of the conjugated diene-based polymer
(activated organometal part at the terminal of a molecular chain),
an activated organometal part in a main chain, or an activated
organometal part in a side chain. Among them, in case of obtaining
an activated organometal part of the conjugated diene-based polymer
by anionic polymerization or coordination anionic polymerization,
the activated organometal part may be a terminal activated
organometal part.
[0035] In addition, the modified and conjugated diene-based polymer
according to an embodiment of the present invention may have
optimized properties of molecular weight distribution, mooney
viscosity, etc. to improve the balance of physical properties of a
rubber composition, including viscoelasticity, tensile properties
and processability via the control of the conditions of a catalyst
composition, polymerization, etc. during the preparation
thereof.
[0036] Particularly, the modified and conjugated diene-based
polymer may have narrow molecular weight distribution (Mw/Mn) of
2.0 to 3.5. If applied to a rubber composition within this range,
effects of improving tensile properties and viscoelasticity may be
achieved. The molecular weight distribution may be, for example,
from 2.5 to 3.5, from 2.5 to 3.2, or from 2.6 to 3.0.
[0037] In the present invention, the molecular weight distribution
of a modified and conjugated diene-based polymer may be calculated
from a ratio (Mw/Mn) of a weight average molecular weight (Mw) to a
number average molecular weight (Mn). In this case, the number
average molecular weight (Mn) is a common average of an individual
polymer molecular weight, which is obtained by measuring the
molecular weights of n polymer molecules, obtaining the total of
the molecular weights and dividing the total by n. The weight
average molecular weight (Mw) shows molecular weight distribution
of a polymer composition. All molecular weight average values may
be expressed by gram per mol (g/mol). In addition, each of the
weight average molecular weight and the number average molecular
weight may mean a polystyrene converted molecular weight analyzed
by gel permeation chromatography (GPC).
[0038] The modified and conjugated diene-based polymer according to
an embodiment of the present invention may satisfy the
above-described molecular weight distribution conditions, and at
the same time, may have a weight average molecular weight (Mw) of
3.times.10.sup.5 to 1.5.times.10.sup.6 g/mol, and a number average
molecular weight (Mn) of 1.0.times.10.sup.5 to 5.0.times.10.sup.5
g/mol. If applied to a rubber composition within the ranges,
tensile properties may be excellent and processability may be good,
and workability of the rubber composition may be improved and
mulling and kneading may become easy, thereby achieving excellent
mechanical properties and excellent balance of the physical
properties of the rubber composition. The weight average molecular
weight may be, for example, from 5.times.10.sup.5 to
1.2.times.10.sup.6 g/mol, or from 5.times.10.sup.5 to
8.times.10.sup.5 g/mol, and the number average molecular weight may
be, for example, from 1.5.times.10.sup.5 to 3.5.times.10.sup.5
g/mol, or from 2.0.times.10.sup.5 to 2.7.times.10.sup.5 g/mol.
[0039] More particularly, if the modified and conjugated
diene-based polymer according to an embodiment of the present
invention satisfies the conditions of the molecular weight
distribution together with the weight average molecular weight (Mw)
and the number average molecular weight at the same time, and when
applied to a rubber composition, tensile properties,
viscoelasticity and processability of the rubber composition may be
excellent, and the balance between the physical properties may be
excellent.
[0040] In addition, the modified and conjugated diene-based polymer
according to an embodiment of the present invention may have mooney
viscosity (MV) of 20 to 70 at 100.degree. C. With the mooney
viscosity in the range, even better processability may be attained.
The mooney viscosity at 100.degree. C. may be, for example, from 40
to 70, from 40 to 65, or from 42 to 55.
[0041] In the present invention, the mooney viscosity may be
measured by using a mooney viscometer, for example, MV2000E of
Monsanto Co., Ltd. using Large Rotor at a rotor speed of 2.+-.0.02
rpm at 100.degree. C. 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, Platen was operated for measurement.
[0042] The modified and conjugated diene-based polymer according to
an embodiment of the present invention may be prepared by a
preparation method including a modification step of reacting a
conjugated diene-based polymer including an organometal part from
activated from a lanthanide series rare earth element catalyst
composition with a modifier including a compound represented by
Formula 1.
[0043] In a particular embodiment, in order to react the activated
organometal part of the conjugated diene-based polymer with the
modifier for the preparation of the modified and conjugated
diene-based polymer, the conjugated diene-based polymer used may
preferably have living properties or pseudo living properties.
Coordination anionic polymerization may be used as the
polymerization reaction of the polymer having such living
properties.
[0044] According to an embodiment of the present invention, the
method for preparing a modified and conjugated diene-based polymer
may further include a step of preparing a conjugated diene-based
polymer having an activated organometal part via polymerization
reaction of conjugated diene-based monomers in a polymerization
solvent using a catalyst composition including a lanthanide series
rare earth element-containing compound prior to the modification
step.
[0045] In the catalyst composition, the lanthanide series rare
earth element-containing compound may be a compound including one
or two or more elements among the rare earth elements having atomic
number of 57 to 71 in the periodic table such as neodymium,
praseodymium, cerium, lanthanum and gadolinium, particularly, a
compound including neodymium.
[0046] In another embodiment, the lanthanide series rare earth
element-containing compound may be a salt which is soluble in a
hydrocarbon solvent, such as the carboxylate, alkoxide,
.beta.-diketone complex, phosphate and phosphite of the lanthanide
series rare earth element, particularly, a neodymium-containing
carboxylate.
[0047] The hydrocarbon solvent may be a saturated aliphatic
hydrocarbon of 4 to 10 carbon atoms including butane, pentane,
hexane, heptane, etc.; a saturated alicyclic hydrocarbon of 5 to 20
carbon atoms including cyclopentane, cyclohexane, etc.; an aromatic
hydrocarbon including mono-olefins such as 1-butene and 2-butene,
benzene, toluene, xylene, etc.; or a halogenated hydrocarbon
including methylene chloride, chloroform, trichloroethylene,
perchloroethylene, 1,2-dichloroethane, chlorobenzene, bromobenzene,
chlorotoluene, etc.
[0048] According to an embodiment of the present invention, the
lanthanide series rare earth element-containing compound may
include a neodymium compound represented by the following Formula
3:
##STR00005##
[0049] in Formula 3, R.sub.a to R.sub.c are each independently
hydrogen, or an alkyl group of 1 to 12 carbon atoms, where all
R.sub.a to R.sub.c are not hydrogen at the same time.
[0050] In a particular embodiment, the neodymium compound may be at
least one selected from the group consisting of
Nd(neodecanoate).sub.3, Nd(2-ethylhexanoate).sub.3, 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),
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-t-butyl 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.
[0051] In another embodiment, the lanthanide series rare earth
element-containing compound may particularly be a neodymium
compound of Formula 3 wherein R.sub.a is a linear or branched alkyl
group of 4 to 12 carbon atoms, R.sub.b and R.sub.c are each
independently hydrogen or an alkyl group of 2 to 8 carbon atoms,
where both R.sub.b and R.sub.c are not hydrogen at the same time,
in consideration of excellent solubility in a polymerization
solvent without fear of oligomerization, conversion ratio into a
catalyst active species, and consequent improving effects of
catalyst activity.
[0052] In a more particular embodiment, in Formula 3, R.sub.a may
be a linear or branched alkyl group of 6 to 8 carbon atoms, R.sub.b
and R.sub.c may be each independently hydrogen or an alkyl group of
2 to 6 carbon atoms, where R.sub.b and R.sub.c may not be hydrogen
at the same time, and particularly embodiments may include 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-t-butyl 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. Among the compounds, 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.
[0053] More particularly, in Formula 3, R.sub.a may be a linear or
branched alkyl group of 6 to 8 carbon atoms, and R.sub.b and
R.sub.c may be each independently an alkyl group of 2 to 6 carbon
atoms.
[0054] As described above, the neodymium compound represented by
Formula 3 includes a carboxylate ligand including an alkyl group
with various lengths with 2 or more carbon atoms as a substituent
at an .alpha.-position and may induce steric change around a
neodymium central metal to block tangling phenomenon between
compounds, thereby achieving the effects of restraining
oligomerization. In addition, such neodymium compound has high
solubility with respect to a polymerization solvent and decreases
the ratio of neodymium which has difficulty in converting into a
catalyst active species and is positioned at the central part,
thereby achieving the effects of a high conversion ratio into a
catalyst active species.
[0055] In another embodiment, the weight average molecular weight
(Mw) of the neodymium compound represented by Formula 3 may be from
600 to 2,000 g/mol. With the weight average molecular weight in the
range, excellent catalyst activity may be shown stably.
[0056] In addition, the solubility of the lanthanide series rare
earth element-containing compound may be, for example about 4 g or
more with respect to 6 g of a nonpolar solvent at room temperature
(25.degree. C.). In the present invention, the solubility of the
neodymium compound means the degree of clear dissolution without
turbidity, and such high solubility may serve excellent catalyst
activity.
[0057] The lanthanide series rare earth element-containing compound
may be used, for example, in an amount of 0.1 to 0.5 mmol, more
particularly, 0.1 to 0.2 mmol based on 100 g of the conjugated
diene-based monomer. Within this range, catalyst activity is high,
an appropriate catalyst concentration is obtained, and effects of
omitting a deliming process are attained.
[0058] The lanthanide series rare earth element-containing compound
may be used, for example, as a reactant type with a Lewis base. The
reactant improves the solubility with respect to the solvent of the
lanthanide series rare earth element-containing compound by the
Lewis base and gives effects of storing stably for a long time. The
Lewis base may be used, for example, in a ratio of 30 mol or less,
or 1 to 10 mol based on 1 mol of the rare earth element. The Lewis
base may be, for example, acetylacetone, tetrahydrofuran, pyridine,
N,N-dimethylformamide, thiophene, diphenyl ether, triethylamine, an
organophosphorous compound, or monohydric or dihydric alcohol.
[0059] The catalyst composition may include, for example, a
lanthanide series rare earth element-containing compound, an
alkylating agent and a halogen compound.
[0060] The alkylating agent may play the role of a co-catalyst as
an organometal compound which may transport a hydrocarbyl group to
other metal, particularly, may be an organometal compound which is
soluble in a nonpolar solvent and which contains a metal-carbon
bond, such as an organoaluminum compound, an organomagnesium
compound, an organolithium compound, etc.
[0061] The organoaluminum compound may be, for example, at least
one selected from the group consisting of an alkylaluminum such as
trimethylaluminum, triethylaluminum, tri-n-propylaluminum,
triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum,
tri-t-butylaluminum, tripentylaluminum, trihexylaluminum,
tricyclohexylaluminum, and trioctylaluminum; a
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
hydrogen; and a hydrocarbylaluminum dihydride such as ethylaluminum
dihydride, n-propylaluminum dihydride, isopropylaluminum dihydride,
n-butylaluminum dihydride, isobutylaluminum dihydride, and
n-octylaluminum dihydride.
[0062] The organomagnesium compound may be, for example, an
alkylmagnesium compound such as diethylmagnesium,
di-n-propylmagnesium, diisopropylmagnesium, dibutylmagnesium,
dihexylmagnesium, diphenylmagnesium and dibenzylmagnesium.
[0063] The organolithium compound may be, for example, an
alkyllithium compound such as n-butyllithium.
[0064] The alkylating agent may use at least one selected from the
group consisting of the organoaluminum compounds, the
organomagnesium compounds and the organolithium compounds,
particularly, diisobutylaluminum hydride (DIBAH) which may play the
role of a molecular weight controlling agent during performing
polymerization reaction. In another embodiment, the alkylating
agent may be used in an amount of 1 to 100 mol, or 3 to 20 mol
based on 1 mol of the lanthanide series rare earth
element-containing compound.
[0065] The halogen compound may be at least one selected from the
group consisting of an aluminum halogen compound; an inorganic
halogen compound obtained by substituting aluminum in the aluminum
halogen compound with boron, silicon, tin or titanium; and an
organohalogen compound such as a t-alkylhalogen compound (alkyl of
4 to 20 carbon atoms).
[0066] Particular examples of the inorganic halogen compound may be
at least one selected from the group consisting of dimethylaluminum
chloride, diethylaluminumchloride (DEAC), dimethylaluminum bromide,
diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum
fluoride, methylaluminum dichloride, ethylaluminum dichloride,
methylaluminum dibromide, ethylaluminum dibromide, methylaluminum
difluoride, ethylaluminum difluoride, methylaluminum
sesquichloride, ethylaluminum sesquichloride, isobutylaluminum
sesquichloride, methylmagnesium chloride, methylmagnesium bromide,
methylmagnesium iodide, ethylmagnesium chloride, ethylmagnesium
bromide, butylmagnesium chloride, butylmagnesium bromide,
phenylmagnesium chloride, phenylmagnesium bromide, benzylmagnesium
chloride, trimethyltin chloride, trimethyltin bromide, triethyltin
chloride, triethyltin bromide, di-t-butyltin dichloride,
di-t-butyltin dibromide, dibutyltin dichloride, dibutyltin
dibromide, tributyltin chloride and tributyltin bromide.
[0067] In another embodiment, the organohalogen compound may be at
least one selected from the group consisting of t-butyl chloride,
t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride,
benzyl bromide, chloro-di-phenylmethane, bromo-di-phenylmethane,
triphenylmethyl chloride, triphenylmethylbromide, benzylidene
chloride, benzylidene bromide, methyltrichlorosilane,
phenyltrichlorosilane, dimethyldichlorosilane,
diphenyldichlorosilane, trimethylchlorosilane, benzoyl chloride,
benzoyl bromide, propionyl chloride, propionyl bromide, methyl
chloroformate and methyl bromoformate.
[0068] The halogen compound may be, for example, at least one
selected from the group consisting of the inorganic halogen
compounds and the organohalogen compounds, and in another
embodiment, may be used in an amount of 1 to 20 mol, 1 to 5 mol, or
2 to 3 mol based on 1 mol of the lanthanide series rare earth
element-containing compound.
[0069] In another embodiment, the alkylating agent and the halogen
compound may include a lanthanide series rare earth
element-containing compound which has been alkylated and
chlorinated in advance, and in this case, a conversion ratio may be
further improved.
[0070] According to an embodiment of the present invention, the
catalyst composition may further include the conjugated diene-based
monomer which is used in the present polymerization reaction.
[0071] As described above, if a portion of the conjugated
diene-based monomer used in the present polymerization reaction is
premixed with the catalyst composition and is used in a preforming
catalyst composition type, catalyst activity may be improved, and
further, the conjugated diene-based polymer thus prepared may be
stabilized.
[0072] In the present invention, the term "preforming" may mean
pre-polymerization in a catalyst system due to the addition of
butadiene if a catalyst composition, that is, a catalyst system
including a lanthanide series rare earth element-containing
compound, an alkylating agent and a halogen compound includes
diisobutylaluminum hydride (DIBAH), etc., and a small amount of a
conjugated diene-based monomer such as butadiene is added to
decrease the possibility of producing diverse catalyst active
species with DIBAH. In addition, the term "premix" may mean a
uniformly mixed state of each compound without performing
polymerization in a catalyst system.
[0073] Particular examples of the conjugated diene monomer may be
at least one selected from the group consisting of 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 and 2,4-hexadiene. The amount of the
conjugated diene-based monomer used for the preparation of the
catalyst composition may be a portion within the total amount range
used of the conjugated diene-based monomer used for the
polymerization reaction, particularly, from 1 to 100 mol, from 10
to 50 mol, or from 20 to 40 mol based on 1 mol of the lanthanide
series rare earth element-containing compound.
[0074] The above-described catalyst composition may be prepared,
for example, by injecting the lanthanide series rare earth
element-containing compound, the alkylating agent, the halogen
compound, and selectively the conjugated diene-based monomer into
an organic solvent one by one and mixing. In this case, the organic
solvent may be a nonpolar solvent which has no reactivity with the
constituent components of the catalyst composition. Particularly,
the organic solvent may use at least one selected from the group
consisting of an aliphatic hydrocarbon-based solvent such as
pentane, hexane, isopentane, heptane, octane, and isooctane; a
cycloaliphatic hydrocarbon-based solvent such as cyclopentane,
methylcyclopentane, cyclohexane, methylcyclohexane, and
ethylcyclohexane; and an aromatic hydrocarbon-based solvent such as
benzene, toluene, ethylbenzene, and xylene. Particular example of
the organic solvent may include an aliphatic hydrocarbon solvent
such as hexane.
[0075] According to an embodiment of the present invention, the
polymerization reaction of a conjugated diene-based polymer using
the catalyst composition may be conducted by radical
polymerization, particularly, bulk polymerization, solution
polymerization, suspension polymerization, or emulsion
polymerization, more particularly, solution polymerization. In
another embodiment, the polymerization reaction may be conducted by
any one of a batch type method or a continuous type method. In a
particular embodiment, the polymerization reaction for preparing
the conjugated diene-based polymer may be conducted by injecting a
conjugated diene-based monomer to the catalyst composition and
reacting in an organic solvent.
[0076] In another embodiment, the polymerization reaction for
preparing the conjugated diene-based polymer may be conducted in an
organic solvent. The organic solvent may be additionally added to
the amount used for the preparation of the catalyst composition,
and in this case, the organic solvent may be the same as that
explained above. In addition, in case of using the organic solvent,
the concentration of the monomer may be from 3 to 80 wt %, or from
10 to 30 wt %.
[0077] According to an embodiment of the present invention,
additives including a reaction terminator for finishing
polymerization reaction, such as polyoxyethylene glycol phosphate;
and an antioxidant such as 2,6-di-t-butyl p-cresol may be further
used during conducting polymerization reaction for preparing the
conjugated diene-based polymer. Besides, additives for facilitating
solution polymerization, particularly, a chelating agent, a
dispersant, a pH controlling agent, a deoxidizer, or an oxygen
scavenger may be selectively further used.
[0078] In another embodiment, the polymerization reaction for
preparing the conjugated diene-based polymer may be conducted at 20
to 200.degree. C., or 20 to 100.degree. C. for 15 minutes to 3
hours, or 30 minutes to 2 hours. Within the ranges, the reaction
may be easily controlled, the polymerization reaction rate and
efficiency may be excellent, and the content of cis-1,4 bond of the
conjugated diene-based polymer thus prepared may be high. In
addition, the polymerization reaction for preparing the conjugated
diene-based polymer may preferably avoid the inclusion of a
compound having deactivation function, such as oxygen, water and
carbon dioxide in a polymerization reaction system to prevent the
deactivation of a catalyst composition including a lanthanide
series rare earth element-containing compound and a polymer.
[0079] The polymerization reaction for preparing the conjugated
diene-based polymer may be quenched by adding an isopropanol
solution of 2,6-di-t-butyl-p-cresol (BHT), etc. to the
polymerization reaction system. Then, desolvation treatment such as
steam stripping for decreasing the partial pressure of solvents via
supplying vapor, or a vacuum drying process may be selectively
further conducted.
[0080] As a result of the polymerization reaction, a conjugated
diene-based polymer including an organometal part which is
activated from a catalyst including the lanthanide series rare
earth element-containing compound, more particularly, a neodymium
catalyzed conjugated diene-based polymer including a 1,3-butadiene
monomer unit is produced, and the conjugated diene-based polymer
thus prepared may have pseudo living properties.
[0081] Meanwhile, in the modification step in the preparation of
the modified and conjugated diene-based polymer according to an
embodiment of the present invention, the modifier is added in a
stoichiometric quantity or more with respect to the active
organometal part of the conjugated diene-based polymer to the
conjugated diene-based polymer which is prepared by the
above-described preparation process, to perform the reaction with
the activated organometal part which is combined with the polymer.
In this case, the modifier may be used in an amount of 0.1 to 20
mol, or 0.5 to 10 mol based on 1 mol of the lanthanide series rare
earth element-containing compound used during preparing the
conjugated diene-based polymer having the activated organometal
part. The modification reaction may be, for example, conducted via
solution reaction or solid reaction, particularly, solution
reaction. In another embodiment, the modification reaction may be
conducted by using a batch type reactor, or by a continuous type
using a multi-step continuous type reactor or an in-line
blender.
[0082] In another embodiment, the modification reaction may be
performed in the same temperature and pressure conditions as those
in a common polymerization reaction, and particularly, may be
performed at a temperature of 20 to 100.degree. C. Within this
range, effects of not increasing the viscosity of the polymer and
not deactivating the activated terminal of the polymer may be
achieved.
[0083] The preparation method of the modified and conjugated
diene-based polymer according to an embodiment of the present
invention may further include precipitation and separation
processes with respect to the modified and conjugated diene-based
polymer thus prepared. Filtering, separating and drying processes
with respect to the precipitated modified and conjugated
diene-based polymer may follow common methods.
[0084] As described above, by the preparation method of the
modified and conjugated diene-based polymer according to an
embodiment of the present invention, a modified and conjugated
diene-based polymer having narrow molecular weight distribution and
excellent physical properties, particularly, a neodymium catalyzed
butadiene-based polymer may be prepared.
[0085] The rubber composition according to an embodiment of the
present invention may include the modified and conjugated
diene-based polymer.
[0086] In a particular embodiment, the rubber composition may
include the modified and conjugated diene-based polymer in an
amount of 10 wt % or more, or 10 to 100 wt %, and within this
range, the improving effects of excellent abrasion resistance,
crack resistance and ozone resistance the rubber composition may be
achieved.
[0087] In another embodiment, the rubber composition may further
include a rubber component in an amount of 90 wt % or less based on
the total weight of the rubber composition together with the
modified and conjugated diene-based polymer. Specifically, the
rubber composition may further include the rubber component in an
amount of 1 to 900 parts by weight based on 100 parts by weight of
the modified and conjugated diene-based copolymer.
[0088] The rubber component may be a natural rubber or a synthetic
rubber, particularly, at least one selected from the group
consisting of a natural rubber (NR) including cis-1,4-polyisoprene;
a modified natural rubber which is obtained by modifying or
purifying a common natural rubber, such as an epoxidized natural
rubber (ENR), a deproteinized natural rubber (DPNR), and a
hydrogenated natural rubber; and a synthetic rubber such as a
styrene-butadiene copolymer (SBR), a polybutadiene (BR), a
polyisoprene (IR), a butyl rubber (IIR), an ethylene-propylene
copolymer, a polyisobutylene-co-isoprene, a neoprene, a
poly(ethylene-co-propylene), a poly(styrene-co-butadiene), a
poly(styrene-co-isoprene), a
poly(styrene-co-isoprene-co-butadiene), a
poly(isoprene-co-butadiene), a
poly(ethylene-co-propylene-co-diene), a polysulfide rubber, an
acryl rubber, a urethane rubber, a silicone rubber, an
epichlorohydrin rubber, a butyl rubber, a halogenated butyl
rubber.
[0089] In another embodiment, the rubber composition may further
include 10 parts by weight or more, or 10 to 120 parts by weight of
a filler based on 100 parts by weight of the modified and
conjugated diene-based polymer.
[0090] The filler may particularly be silica, graphite or carbon
black.
[0091] The silica may be, for example, wet silica (hydrated
silicate), dry silica (anhydrous silicate), calcium silicate,
aluminum silicate, or colloid silica. More particularly, the filler
may be wet silica which has the most significant improving effects
of destruction characteristics and compatible effects of wet grip
characteristics, and in this case, a silane coupling agent may be
used together for the improvement of reinforcing and low exothermic
properties. The silane coupling agent may particularly include, for
example, at least one selected from the group consisting of
bis(3-triethoxysilylpropyl)tetrasulfide,
bis(3-triethoxysilylpropyl)trisulfide,
bis(3-triethoxysilylpropyl)disulfide,
bis(2-triethoxysilylethyl)tetrasulfide,
bis(3-trimethoxysilylpropyl)tetrasulfide,
bis(2-trimethoxysilylethyl)tetrasulfide,
3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane,
2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane,
3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide,
3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide,
2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide,
3-trimethoxysilylpropylbenzothiazolyltetrasulfide,
3-triethoxysilylpropylbenzolyltetrasulfide,
3-triethoxysilylpropylmethacrylatemonosulfide,
3-trimethoxysilylpropylmethacrylatemonosulfide,
bis(3-diethoxymethylsilylpropyl)tetrasulfide,
3-mercaptopropyldimethoxymethylsilane,
dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide,
and dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and more
particularly, the silane coupling agent may be
bis(3-triethoxysilylpropyl)polysulfide or
3-trimethoxysilylpropylbenzothiazyltetrasulfide in consideration of
the improving effect of reinforcing properties.
[0092] The silane coupling agent may be used in an amount of 1 to
20 parts by weight, or 5 to 15 parts by weight based on 100 parts
by weight of silica, and within this range, the effects of the
coupling agent may be sufficiently shown, and the gelation of a
rubber component may be prevented.
[0093] The carbon black may, for example, have a nitrogen
adsorption specific surface area of 20 to 250 m/g (measured based
on N2SA, JIS K 6217-2:2001), and within this range, effects of
excellent processability and reinforcing performance are achieved.
In another embodiment, the carbon black may have a dibutylphthalate
oil absorption (DBP) of 80 to 200 cc/100 g, and within this range,
effects of excellent processability and reinforcing performance are
achieved.
[0094] The filler may include an inorganic filler of at least one
metal, metal oxide, or metal hydroxide selected from aluminum,
magnesium, titanium, calcium and zirconium. Particular example of
the inorganic filler may be at least one selected from the group
consisting of .gamma.-alumina, .alpha.-alumina, alumina-hydrate
(Al.sub.2O.sub.3.H.sub.20), aluminum hydroxide [Al(OH).sub.3],
aluminum carbonate [Al.sub.2(CO %).sub.2], magnesium hydroxide
[Mg(OH).sub.2], magnesium oxide (MgO), magnesium carbonate (MgCO),
talc (3MgO.4SiO.sub.2.H.sub.2O), attapulgite
(5Mg0.8SiO.sub.2.9H.sub.2O), titanium white (TiO), titanium black,
calcium oxide (CaO), calcium hydroxide [Ca(OH).sub.2], magnesium
aluminate (MgO.Al.sub.2O.sub.3), clay (Al.sub.2O.sub.3.2SiO.sub.2),
kaoline (Al.sub.2O.sub.3.2Si0.sub.2.2H.sub.2O), calcium silicate
(Ca.sub.2.SiO.sub.4, etc.), aluminum calcium silicate
(Al.sub.2O.sub.3.CaO.2SiO.sub.2, etc.), calcium magnesium silicate
(CaMgSiO.sub.4), calcium carbonate (CaCO.sub.3), zirconium oxide
(ZrO.sub.2), zirconium hydroxide [ZrO(OH).sub.2nH.sub.2O],
zirconium carbonate [Zr(CO.sub.3).sub.2] and crystalline alumino
silicate. If the carbon black and the inorganic filler are mixed
and used, the mixing weight ratio may be 95:5 to 5:95 in
consideration of the improving effects of performance.
[0095] The rubber composition may be, for example, sulfur
crosslinkable, and so may further include a vulcanizing agent. The
vulcanizing agent may be particularly a sulfur powder and may be
included in an amount of 0.1 to 10 parts by weight based on 100
parts by weight of the rubber component. With the amount used in
the above range, elasticity and strength required for a vulcanized
rubber composition may be secured, and at the same time, a low fuel
consumption ratio may be attained.
[0096] The rubber composition may further include various additives
used in a common rubber industry in addition to the above
components, particularly, a vulcanization accelerator, a process
oil, a plasticizer, an antiaging agent, a scorch preventing agent,
a zinc white, stearic acid, a thermosetting resin, or a
thermoplastic resin. The vulcanization accelerator may particularly
include thiazole-based compounds such as 2-mercaptobenzothiazole
(M), dibenzothiazyldisulfide (DM), and
N-cyclohexyl-2-benzothiazylsulfenamide (CZ), or guanidine-based
compounds such as diphenylguanidine (DPG). The vulcanization
accelerator may be included in an amount of 0.1 to 5 parts by
weight based on 100 parts by weight of the rubber component.
[0097] The process oil acts as a softener in a rubber composition
and may particularly include a paraffin-based, naphthene-based, or
aromatic compound. More particularly, an aromatic process oil may
be used in consideration of tensile strength and abrasion
resistance, and a naphthene-based or paraffin-based process oil may
be used in consideration of hysteresis loss and properties at low
temperature. The process oil may be included in an amount of 100
parts by weight or less based on 100 parts by weight of the rubber
component. With the above-described amount in the range, the
deterioration of tensile strength and low exothermic properties
(low fuel consumption ratio) of a vulcanized rubber may be
prevented.
[0098] The antiaging agent may particularly include a condensate of
amines and ketones at a high temperature, such as
N-isopropyl-N'-phenyl-p-phenylenediamine,
N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine,
6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, and
poly-2,2,4-trimethyl-1,2-dihydroquinoline (TMDQ). The antiaging
agent may be used in an amount of 0.1 to 6 parts by weight based on
100 parts by weight of the rubber component.
[0099] The rubber composition may be obtained by mulling using a
mulling apparatus such as a banbury mixer, a roll, and an internal
mixer according to a mixing prescription. In addition, a rubber
composition having low exothermic properties and excellent abrasion
resistance may be obtained by a vulcanization process after a
molding process.
[0100] Therefore, the rubber composition may be useful to the
manufacture of each member of a tire such as a tire tread, an under
tread, a side wall, a carcass coating rubber, a belt coating
rubber, a bead filler, a chafer, and a bead coating rubber, or to
the manufacture of rubber products in various industries such as a
dustproof rubber, a belt conveyor, and a hose.
BEST NODE FOR CARRYING OUT THE INVENTION
[0101] Hereinafter, the present invention will be explained in
particular referring to embodiments. However, the following
embodiments are only for the illustration of the present invention,
and the scope of the present invention is not limited thereto.
PREPARATION EXAMPLES
Preparation Example 1: Catalyst Composition 1
[0102] Into a hexane solution under nitrogen conditions, a
neodymium carboxylate compound was added, and diisobutylaluminum
hydride (DIBAH) and diethylaluminum chloride (DEAC) were injected
one by one such that a molar ratio of neodymium
compound:DIBAH:DEAC=1:9-10:2-3 and mixed to prepare a catalyst
composition. The catalyst composition thus prepared was instantly
used or used after storing at -30 to 20.degree. C. under nitrogen
conditions.
Preparation Example 2: Catalyst Composition 2
[0103] A pre-alkylated neodymium carboxylate compound purchased
from COMAR Chemical Co., Ltd. was used.
Preparation Example 3: Preparation of ethyl 1-(trimethylsilyl)
piperidine-4-carboxylate
[0104] To a solution of 2 g of ethyl piperidine-4-carboxylate
dissolved in dichloromethane (CH.sub.2Cl.sub.2), 1.77 ml of
triethylamine (Et.sub.3N) and 1.62 ml of trimethylsilyl chloride
(TMSCl) were added at 0.degree. C., and the reaction mixture was
stirred for 5 hours at 0.degree. C. Then, solvents in the produced
solution were evaporated under a reduced pressure, and the
remaining product was re-dissolved in hexane and filtered to obtain
a compound of the structure below. .sup.1H nuclear magnetic
resonance spectroscopic spectrum was observed.
##STR00006##
[0105] .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 4.11-4.08 (m, 2H),
.delta. 3.13-3.11 (m, 2H), .delta. 2.61-2.54 (m, 2H), .delta.
2.34-2.32 (m, 1H), .delta. 1.74 (m, 2H), .delta. 1.42 (m, 2H),
.delta. 1.23-1.22 (m, 3H), .delta. 0.05-0.00 (m, 9H).
Preparation Example 4: Preparation of ethyl
1-(trimethylsilyl)piperidine-3-carboxylate
[0106] To a solution of 2 g of ethyl piperidine-3-carboxylate
dissolved in dichloromethane (CH.sub.2Cl.sub.2), 1.77 ml of
triethylamine (Et.sub.3N) and 1.62 ml of trimethylsilyl chloride
(TMSCl) were added at 0.degree. C., and the reaction mixture was
stirred for 3 hours at 0.degree. C. Then, volatile solvents were
removed under a reduced pressure, and the residue was filtered
twice using hexane. The filtered crude material was separated via
distillation under a reduced pressure to obtain a compound of the
structure below. .sup.1H nuclear magnetic resonance spectroscopic
spectrum was observed.
##STR00007##
[0107] .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 4.10-4.09 (m, 2H),
.delta. 3.19-3.17 (m, 1H), .delta. 2.93 (m, 1H), .delta. 2.79-2.72
(m, 1H), .delta. 2.54 (m, 1H), .delta. 2.24 (m, 1H), .delta.
1.94-1.92 (m, 1H), .delta. 1.63-1.58 (m, 2H), .delta. 1.28-1.21 (m,
4H), .delta. 0.00 (m, 9H).
EXAMPLES
Example 1: Preparation of Modified and Conjugated Diene-Based
Polymer
[0108] <Preparation of Butadiene Polymer>
[0109] To a completely dried reactor, vacuum and nitrogen were
alternately applied, and to the reactor in a vacuum state, 4.7 kg
of a mixture solution of 1,3-butadiene/hexane was injected and
Catalyst Composition 1 of Preparation Example 1 was added. Then,
polymerization reaction was performed at 60 to 90.degree. C. for 15
to 60 minutes to prepare a butadiene polymer including a terminal
activated aluminum part.
[0110] <Modification Reaction>
[0111] After finishing the polymerization reaction of
1,3-butadiene, a hexane solution including the modifier (1-10 eq.
based on catalyst) prepared in Preparation Example 3 was added to a
polybutadiene polymerization solution including an aluminum part
activated from the catalyst composition, and then was reacted for
30 to 60 minutes under the same temperature conditions as the
polymerization conditions. Then, a hexane solution including a
polymerization terminator was injected to terminate the reaction,
and a hexane solution including an antioxidant was injected to
prepare a modified butadiene-based polymer.
Example 2: Preparation of Modified and Conjugated Diene-Based
Polymer
[0112] A modified and conjugated diene-based polymer was prepared
by the same method as Example 1 except for using Catalyst
Composition 2 of Preparation Example 2 as a catalyst composition
during preparing a butadiene polymer and using the modifier
prepared in Preparation Example 4 as a modifier during modification
reaction.
Comparative Example 1
[0113] BR1208 (manufacturer, LG Chem, Ltd.) was used as unmodified
Nd--BR.
Comparative Example 2
[0114] CB24 (manufacturer, Lanxess Co.) was used as unmodified
Nd--BR.
EXPERIMENTAL EXAMPLES
Experimental Example 1
[0115] For the polymers before modification and the polymers after
modification in Examples 1 and 2, and the polymers of Comparative
Examples 1 and 2, modification or unmodification state, a number
average molecular weight (Mn), a weight average molecular weight
(Mw), molecular weight distribution (MWD), mooney viscosity (MV)
and solution viscosity were measured, respectively. [0116] Number
average molecular weight (Mn, .times.10.sup.5 g/mol), weight
average molecular weight (Mw, .times.10.sup.5 g/mol), and molecular
weight distribution (MWD): measured using gel permeation
chromatography for each of the polymers. [0117] Mooney viscosity
(MV) (ML1+4, @100.degree. C. and -S/R) (MU): measured by using
MV-2000E of Monsanto Co., Ltd. at 100.degree. C. using Large Rotor
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, Platen was operated and mooney viscosity was
measured while applying torque.
[0118] In addition, during measuring the mooney viscosity, the
change of the mooney viscosity shown with the release of the torque
was observed, and a -S/R value was determined from the gradient
value thereof. [0119] Solution viscosity (MU): viscosity of a
polymer in 5 wt % toluene was measured at 20.degree. C.
TABLE-US-00001 [0119] TABLE 1 Example Comparative Example Division
1 2 1 2 Catalyst Composition Prepa- Prepa- -- -- ration ration
Example 1 Example 2 Modifier Prepa- Prepa- -- -- ration ration
Example 3 Example 4 Before Mn 2.66 2.62 1.57 2.56 modification Mw
6.68 7.77 7.78 6.08 Mw/Mn 2.57 2.96 4.96 2.37 ML1 + 4 -- -- 45 45
-S/R -- -- 0.7274 0.5997 After Mn 2.49 2.64 -- -- modification Mw
6.94 7.88 -- -- Mw/Mn 2.78 2.99 -- -- ML1 + 4 47 52 -- -- -S/R
0.8215 0.9863 -- -- Solution 274 341 N/A 151 viscosity
[0120] In Table 1, N/A means unmeasurable.
[0121] As shown in Table 1, for the cases of Examples 1 and 2,
which were prepared according to the present invention, it was
found that the mooney viscosity and the weight average molecular
weight were increased and the molecular weight distribution was
increased after modification.
Experimental Example 2
[0122] With respect to 100 parts by weight of the modifier or
unmodified conjugated diene-based polymer of Example 1 or 2, or
Comparative Example 1 or 2, 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 white (ZnO), and 2 parts by
weight of stearic acid were mixed to prepare a rubber mixture. To
the rubber mixture thus prepared, 2 parts by weight of a sulfur
powder, 2 parts by weight of a vulcanization accelerator (CZ) and
0.5 parts by weight of a vulcanization accelerator (DPG) were
added, followed by vulcanizing at 160.degree. C. for 25 minutes to
manufacture a rubber specimen. With respect to the rubber specimen
thus manufactured, tensile properties, viscoelasticity and abrasion
resistance were evaluated.
[0123] In detail, with respect to the rubber specimen thus
manufactured, modulus when elongated by 300% (300% modulus
(M-300%), kgf/cm.sup.2), tensile strength (kgf/cm.sup.2) of a
vulcanized material, and elongation (%) of a vulcanized material
when broken were measured after vulcanizing at 150.degree. C. for
t90 minutes according to ASTM D412. In addition, each measured
value was indexed with respect to the measured value of Comparative
Example 2 of 100.
[0124] In addition, with respect to the rubber specimen,
viscoelasticity coefficient (tan .delta.) at 60.degree. C. was
measured with a frequency of 10 Hz and a deformation rate of 3%. In
addition, each measured value was indexed with respect to the
measured value of Comparative Example 2 of 100.
[0125] In addition, with respect to the rubber specimen, DIN
abrasion test was conducted according to ASTM D5963 and DIN wt loss
index (loss volume index: abrasion resistance index, Method A
(ARI.sub.A)) is shown together. The higher the index is, the better
the abrasion resistance is.
TABLE-US-00002 TABLE 2 Example Comparative Example Division 1 2 1 2
Modifier Prepa- Prepa- -- -- ration ration Example 3 Example 4
M-300% 100 98 83 97 M-300% index 104 101 86 100 T/S 184 182 166 177
T/S index 104 103 94 100 Elongation 485 491 523 484 Elongation
index 100 101 108 100 Tan .delta. @60.degree. C. 0.138 0.140 --
0.149 Tan .delta. @60.degree. C. index 108 106 83 100 DIN wt loss
index 106 99 -- 100
[0126] As shown in Table 2, different from Comparative Example 1
which shows degraded modulus when elongated by 300%, tensile
strength and viscoelasticity except for elongation when compared to
Comparative Example 2, it was found for Examples 1 and 2 in which
modification using a modifier according to the present invention
was conducted, that all of modulus when elongated by 300%, tensile
strength, and tensile properties and viscoelasticity of elongation
were excellent and further, it was found that abrasion resistance
was maintained to the same level as Comparative Example 2 or
improved.
* * * * *