Process for producing olefin living polymer

Details Process for producing olefin living polymer Process for producing olefin living polymer

2001-11-08

2004-09-07

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S134000, C526S160000, C526S170000, C526S943000, C526S348200, C526S348600, C526S348800, C526S351000, C526S352000

Reexamination Certificate

active

06787617

ABSTRACT:

TECHNICAL FIELD
The present invention relates to a process for preparing olefinic living polymers, and more particularly to a process for preparing olefinic living polymers which can be converted into terminal-functionalized polymers and block copolymers having a narrow molecular weight distribution.
BACKGROUND ART
Regarding living polymerization of olefins, there are reported production of syndiotactic polypropylene (PP) ([r] not more than 0.8) having a molecular weight distribution (Mw/Mn) of 1.05 to 1.4 using V(acac)
3
/R
2
AlX catalyst, wherein acac is acetylacetonato, R is ethyl or isobutyl group and X is Cl or Br, in Macromolecules, 12, 814(1979); production of living polymers of ethylene or 1-hexene using Me
2
Si(2-SiMe
3
-4-tBu-C
5
H
2
)
2
Sm(THF)
2
catalyst.without cocatalyst, wherein Me is methyl group, tBu is t-butyl group and THF is tetrahydrofuran, in Shokubai, 37, 205(1995); production of living polymers of C
6
to C
10
&agr;-olefins having a Mw/Mn ratio of not more than 1.1 at room temperature using [(2,6-iPr
2
C
6
H
3
)N(CH
2
)
3
N(2,6-iPr
2
C
6
H
3
)]TiMe
2
/B(C
6
F
5
)
3
catalyst, wherein iPr is isopropyl group and Me is methyl group, in J. Am. Chem. Soc., 118, 10008(1996); living polymerization of &agr;-olefins having 3 to 18 carbon atoms in a low concentration at a temperature of not more than 0° C. in the presence of a catalyst system consisting of a bulky aryl group-containing diimine complex of Ni represented by the formula:
wherein Ar is 2,6-diisopropylphenyl group, in J. Am. Chem. Soc., 118, 11664(1996); production of atactic living polymer of 1-hexene having a Mw/Mn ratio of not more than 1.1 at 0° C. using a catalyst consisting of a tri-coordination type diamide complex of Zr ([NON]ZrMe
2
complex) and B(C
6
F
5
)
3
wherein [NON]ZrMe
2
complex is a compound of the formula:
in J. Am. Chem. Soc., 119, 3830(1997); and production of syndiotactic living polypropylene of [r] about 0.65 at low temperatures using [tBuNSiMe
2
Flu]TiMe
2
/B(C
6
F
5
)
3
catalyst, wherein tBu is t-butyl group, Me is is methyl group and Flu is
in Polym. Prepr., Japan, 46, 1601(1997); cf. Kobunshi, Vol. 47, February, 74-77(1998).
Also, JP-A-5-503546 discloses production of a multi-block copolymer having a molecular weight distribution of 1.4 to 1.8 by bringing a first olefin component into contact with a catalyst which is a reaction product of a metallocene component such as a bis(cyclopentadienyl)titanium, zirconium or hafnium derivative (first component) with a second component having a cation capable of donating a proton and a compatible non-coordinating anion, at a temperature of −5 to +10° C. to produce a first living polymer and then adding a second monomer to copolymerize with the first polymer.
Further, JP-A-9-500150 discloses production of a block copolymer or tapered copolymer having a molecular weight distribution of 1.35 to 4.1 by copolymerizing at least one olefinic monomer at a temperature of −5 to +10° C. using a catalyst which is a reaction product of a cyclopentadienyl Group IV-B metal component with an alumoxane or a compatible non-coordinating anion wherein Ti, Zr and Hf are exemplified as the Group IV-B metal.
On the other hand, it is reported in Macromelecules, 31, 3184(1998) that living polymerization of propylene or 1-hexene takes place at −50° C. in the presence of [tBuNSiMe
2
Flu]TiMe
2
catalyst.
For example, however, in case of using the [(2,6-iPr
2
C
6
H
3
)N(CH
2
)
3
N(2,6-iPr
2
C
6
H
3
)]TiMe
2
/B(C
6
F
5
)
3
catalsyt or the bulky aryl group-containing diimine Ni complex/methylaluminoxane catalyst mentioned above, problems are encountered that these catalysts are complicated and are hard to prepare and the obtained polymers are poor in regularity. The production of syndiotactic living polymers at low temperatures using the above-mentioned [tBuNSiMe
2
Flu]TiMe
2
/B(C
6
F
5
)
3
catalyst has also the problems that syndiotactic polymers having a low stereoregularity are only obtained, and polymers having a high stereoregularity such as high syndiotacticity or high isotacticity, polymers rich in isotacticity or atactic polymers cannot be obtained, and that the structure of the catalyst is complicated and it is hard to prepare the catalyst.
Also, in case of using as a catalyst the reaction product of a metallocene component and a second component having a cation capable of donating a proton and a compatible non-coordinating anion, and in case of using as a catalyst a reaction product of a cyclopentadienyl Group IV-B metal component with an alumoxane or a compatible non-coordinating anion, it is not always possible to make the molecular weight distribution narrow or it is not always possible to efficiently obtain living polymers. In the field of using terminal-functionalized polymers or block copolymers, it has been desired to produce living polymers having a narrower molecular weight distribution or to more efficiently produce living polymers, from the viewpoint that polymers having a high rate of terminal functionalization or a high blocking efficiency.
Further, the living polymerization at −50° C. using [tBuNSiMe
2
Flu]TiMe
2
catalyst is not satisfactory in yield and molecular weight of the produced polymers.
DISCLOSURE OF INVENTION
The present inventors have found, as a result of making intensive study in order to solve the above problems of the prior art, that olefinic living polymers having a molecular weight distribution of not more than 1.3 can be prepared when olefinic monomers are polymerized at low temperatures using a catalyst comprising a hafnium or zirconium-containing compound having one or two cyclopentadienyl backbones, a borane or borate compound having a phenyl group which may be substituted, and optionally a specific alkylaluminum compound.
Thus, in accordance with an embodiment of the present invention, there is provided a process for preparing olefinic living polymers which comprises polymerizing an olefinic monomer having 2 to 20 carbon atoms at a polymerization temperature of −20 to −100° C. in the presence of a catalyst comprising:
(A-1) a hafnium-containing compound having one or two cyclopentadienyl backbones, and
(B) a borane compound (B-1) of the formula (I):
B(Ph)
3
  (I)
 wherein Ph is a phenyl group which may be substituted, or
a borate compound (B-2) of the formula (II):
B
−
(Ph)
4
X
+
  (II)
 wherein Ph is as defined above and X
+
is a cation, to produce a polymer having a molecular weight distribution (Mw/Mn) of 1 to 1.3.
Further, in accordance with another embodiment of the present invention, there is provided a process for preparing olefinic living polymers which comprises polymerizing an olefinic monomer having 2 to 20 carbon atoms, at a polymerization temperature of −60 to −100° C. in the presence of a catalyst comprising:
(A-2) a zirconium-containing compound having one or two cyclopentadienyl backbones, and
(B) a borane compound (B-1) of the formula (I):
B(Ph)
3
  (I)
 wherein Ph is a phenyl group which may be substituted, or
a borate compound (B-2) of the formula (II):
B
−
(Ph)
4
X
+
  (II)
 wherein Ph is as defined above and X
+
is a cation, to produce a polymer having a molecular weight distribution (Mw/Mn) of 1 to 1.3.
In the preparation of the catalyst, the hafnium-containing compound (A-1) and the zirconium-containing compound (A-2) may be used together. In this case, there is the case that living polymers having a bimodal molecular weight distribution are obtained.
The above-mentioned catalysts can be prepared by using the components (A) and (B) together with an aluminum compound (C) of the formula (III):
AlR
3−n
Y
n
  (III)
wherein R is a hydrocarbon group having 4 to 20 carbon atoms, Y is a halogen atom, an alkoxyl group, a trialkylsiloxy group, a di(trialkylsilyl)amino group or a trialkylsilyl group, and n is 0, 1 or 2. The aluminum

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