U.S. patent application number 09/780340 was filed with the patent office on 2002-02-28 for process for preparing polymer by using copper compound.
This patent application is currently assigned to Sekisui Chemical Co., LTD. Invention is credited to Shibayama, Koichi.
Application Number | 20020026031 09/780340 |
Document ID | / |
Family ID | 23397766 |
Filed Date | 2002-02-28 |
United States Patent
Application |
20020026031 |
Kind Code |
A1 |
Shibayama, Koichi |
February 28, 2002 |
Process for preparing polymer by using copper compound
Abstract
The present inventors has its objects to provide a
polymerization catalyst component, a copper compound which can
easily be synthesized and is stable. The present invention is
related to a method of producing a polymer which comprises using a
copper compound represented by the general formula CuXn, LCuXn or
L(L')CnXn (wherein L and L' each represents a ligand, X represents
a halogen atom or an alkoxy, thioxy, allyloxy, amino, secondary
amino, tertiary amino, cyano, nitro, alkyl or allyl group, and n
represents an integer of 0 to 2) as a catalyst and/or
polymerization initiator in polymerizing a vinyl monomer whose
polarity value e, when expressed in terms of absolute value, is not
more than 1.5.
Inventors: |
Shibayama, Koichi;
(Otsu-shi, JP) |
Correspondence
Address: |
Connolly Bove Lodge & Hutz LLP
Suite 800
1900 M Street, N.W.
Washington
DC
20036-3425
US
|
Assignee: |
Sekisui Chemical Co., LTD
Osaka
JP
|
Family ID: |
23397766 |
Appl. No.: |
09/780340 |
Filed: |
February 12, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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09780340 |
Feb 12, 2001 |
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09355528 |
Sep 23, 1999 |
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Current U.S.
Class: |
528/327 ;
526/154; 526/164; 528/328; 528/354; 528/355; 528/356; 528/357;
528/359; 528/362; 528/363; 528/364; 528/480; 528/485; 528/487 |
Current CPC
Class: |
C08F 4/54 20130101; C08F
2500/03 20130101; C08F 110/02 20130101; C08F 10/02 20130101; C08F
110/02 20130101; C08F 10/02 20130101 |
Class at
Publication: |
528/327 ;
528/328; 528/354; 528/355; 528/359; 528/356; 528/357; 528/485;
528/480; 528/487; 528/363; 528/362; 528/364; 526/154; 526/164 |
International
Class: |
C08F 006/00 |
Claims
1. A method of producing a polymer which comprises using a copper
compound represented by the general formula LCuXna or L(L')CuXnb
(wherein L and L' each represents a N-coordination compound
selected from the group consisting of bisoxazoline, substituted
bisoxazoline, an amidinato compound and a diimine represented by
the general formula R.sup.3N.dbd.CR.sup.4CR.sup.5.dbd.NR.sup.6
(wherein R.sup.3, R.sup.4, R.sup.5 and R.sup.6 each represents
independently an alkyl, allyl, an aryl, a hydrogen atom, or a
halogen atom; or at least one group of R.sup.3 and R.sup.4, R.sup.4
and R.sup.5, and R.sup.5 and R.sup.6 is combined and represents a
cyclic group with the next carbon and/or nitrogen atom), or a O-
and N-coordination compound; X represents a halogen atom or an
alkoxy, thioxy, allyloxy, amino, secondary amino, tertiary amino,
cyano, nitro, alkyl or allyl group; na represents an integer of 1
to 2; and nb represents an integer of 0 to 2) as a catalyst and/or
polymerization initiator in polymerizing a vinyl monomer whose
polarity value e, when expressed in terms of absolute value, is not
more than 1.5.
2. A method of producing a polymer which comprises using a copper
compound represented by the general formula LCuXna or L(L')CuXnb
(wherein L and L' each represents a N-coordination compound
selected from the group consisting of bisoxazoline, substituted
bisoxazoline, an amidinato compound and a diimine represented by
the general formula R.sup.3N.dbd.CR.sup.4CR.sup.5.dbd.NR.sup.6
(wherein R.sup.3, R.sup.4, R.sup.5 and R.sup.6 each represents
independently an alkyl, allyl, an aryl, a hydrogen atom, or a
halogen atom; or at least one group of R.sup.3 and R.sup.4, R.sup.4
and R.sup.5, and R.sup.5 and R.sup.6 is combined and represents a
cyclic group with the next carbon and/or nitrogen atom), or a O-
and N-coordination compound; X represents a halogen atom or an
alkoxy, thioxy, allyloxy, amino, secondary amino, tertiary amino,
cyano, nitro, alkyl or allyl group; na represents an integer of 1
to 2; and nb represents an integer of 0 to 2) as a catalyst and/or
polymerization initiator in polymerizing a compound capable of
polymerizing by a ring-opening reaction.
3. The method of producing a polymer using a copper compound
according to claim 1 or 2, wherein the copper compound is used
together with one or more organometallic compounds selected from
the group consisting of aluminoxanes, organoaluminum compounds
represented by the general formula AlR.sub.mZ.sub.3-m (wherein R
represents a hydrocarbon group containing 1 to 20 carbon atoms, Z
represents a hydrogen or halogen atom or an alkoxy, allyloxy or
siloxy group, and m is an integer of 0 to 3), boron-containing
Lewis acids and boron-containing ionic compounds.
4. The method of producing a polymer using a copper compound
according to claim 1, wherein the vinyl monomer is an
.alpha.-substituted olefin.
5. The method of producing a polymer using a copper compound
according to claim 1, wherein the vinyl monomer is a (meth)acrylic
ester.
6. The method of producing a polymer using a copper compound
according to claim 2, wherein the compound capable of polymerizing
by a ring-opening reaction is a lactone.
7. The method of producing a polymer using a copper compound
according to claim 1 or 2, wherein at least one of L and L' in the
copper compound represented by the general formula LCuXna or
L(L')CuXnb is the N-coordination compound.
8. The method of producing a polymer using a copper compound
according to claim 7, wherein the N-coordination compound is the
amidinato compound.
9. The method of producing a polymer using a copper compound
according to claim 8, wherein the amidinato compound is
N,N'-dimethylamidinato, N,N'-diethylamidinato,
N,N'-diisopropylamidinato, N,N'-di-t-butylamidinat- o,
N,N'-ditrifluoromethylamidinato, N,N'-diphenylamidinato,
N,N'-di-substituted phenylamidinato,
N,N'-ditrimethylsilylamidinato, N,N'-dimethylbenzamidinato,
N,N'-diethylbenzamidinato, N,N'-diisopropylbenzamidinato,
N,N'-di-t-butylbenzamidinato, N,N'-ditrifluoromethylbenzamidinato,
N,N'-diphenylbenzamidinato, N,N'-ditrimethylsilylbenzamidinato, or
N,N'-di-substituted phenylbenzamidinato.
10. The method of producing a polymer using a copper compound
according to claim 9, wherein the amidinato compound is
N,N'-ditrimethylsilylbenzamidi- nato.
11. The method of producing a polymer using a copper compound
according to claim 7, wherein the N-coordination compound is the
diimine represented by the general formula
R.sup.3N.dbd.CR.sup.4CR.sup.5.dbd.NR.sup.6 (wherein R.sup.3,
R.sup.4, R.sup.5 and R.sup.6 each represents independently an
alkyl, allyl, an aryl, a hydrogen atom, or a halogen atom; or at
least one group of R.sup.3 and R.sup.4, R.sup.4 and R.sup.5, and
R.sup.5 and R.sup.6 is combined and represents a cyclic group with
the next carbon and/or nitrogen atom).
12. The method of producing a polymer using a copper compound
according to claim 11, wherein the diimine is represented by the
general formula R.sup.3N.dbd.CR.sup.4CR.sup.5.dbd.NR.sup.6 (wherein
each R.sup.3 and R.sup.6 is an aryl, each R.sup.4 and R.sup.5 is a
hydrogen atom, a halogen atom, an alkyl, allyl, or an aryl; or
R.sup.4 and R.sup.5 are combined and represents a cyclic
hydrocarbon with the next carbon atoms).
13. The method of producing a polymer using a copper compound
according to claim 1 or 2, wherein at least one of L and L' in the
copper compound represented by the general formula LCuXna or
L(L')CuXnb is the O- and N-coordination compound.
14. The method of producing a polymer using a copper compound
according to claim 13, wherein the O- and N-coordination compound
is 8-quinolinol or substituted 8-quinolinol.
Description
TECHNICAL FIELD
[0001] The present invention relates to a method of producing a
polymer using a copper compound.
PRIOR ART
[0002] A poly-.alpha.-substituted olefin derived from an
.alpha.-substituted olefin of the general formula
CH.sub.2.dbd.CY.sup.1E (wherein Y.sup.1 represents a phenyl or
substituted phenyl group and E represents a hydrogen atom or an
alkyl group) by polymerization has so far been produced by various
methods. Industrially, it is produced by adding a radical generator
to a monomer and carrying out radical polymerization. However, the
polymer produced by this method has a fairly broad molecular weight
distribution and, because of inclusion of a low-molecular-weight
polymer, it is poor in heat resistance.
[0003] On experimental scale, it can be obtained also by anionic
polymerization, cationic polymerization or group transfer
polymerization, for instance. Recently, a method of producing a
highly stereoregular poly-.alpha.-substituted olefin has been
proposed and has attracted attention which comprises polymerizing
an .alpha.-substituted olefin of the general formula
CH.sub.2.dbd.CY.sup.2H (wherein Y.sup.2 represents a phenyl or
substituted phenyl group) using, as a polymerization catalyst
component, a transition metal complex alone or a combination of a
transition metal complex and an organoaluminum compound [Nobuhide
Ishihara et al.: The Society of Polymer Science, Japan, Preprints,
35, 240 (1986); Japanese Kokai Publication Hei-03-72504].
[0004] A poly-.alpha.-substituted olefin derived from an
.alpha.-substituted olefin of the general formula
CH.sub.2.dbd.CY.sup.3Z (wherein Y.sup.3 represents a cyano group
and Z represents a hydrogen atom or an alkyl group) by
polymerization has so far been produced by various methods.
Industrially, it is produced by radical polymerization with a
radical generator added to a monomer.
[0005] As a method of polymerization by which the molecular weight
and molecular weight distribution can be controlled, there have
been proposed, on the laboratory level, anionic polymerization,
coordination polymerization and group transfer polymerization, for
instance. To be concrete, a highly stereoregular
poly-.alpha.-substituted olefin was produced from a monomer of the
general formula CH.sub.2.dbd.CHY.sup.3 (wherein Y.sup.3 represents
a cyano group) by a production method using an aluminum metal
compound and a transition metal compound as polymerization
catalysts (Japanese Kokai Publication Hei-01-79206) and a precision
polymer having a narrow molecular weight distribution was produced
by a polymerization reaction using an organic rare earth metal
complex as a catalyst component [Akira Nakamura et al.: 43rd
Meeting of The Society of Polymer Science, Japan (May 26, 1994),
II-3-08].
[0006] Recently, a lactone polymer has attracted attention as
biodegradable plastics.
[0007] As regards the polymerization of a lactone, anionic
polymerization, coordination polymerization and group transfer
polymerization, among others, have been proposed, on the laboratory
level, as a polymerization method capable of controlling the
molecular weight and molecular weight distribution. More
specifically, there may be mentioned the method comprising carrying
out polymerization using an aluminum-porphyrin complex as a
polymerization initiator [Macromolecules, 14, 166 (1981)] and the
method comprising using an aluminum-porphyrin complex and a Lewis
acid having a bulky substituent as a polymerization initiator
(Japanese Kokai Publication Hei-04-323204), among others.
[0008] A vinyl monomer has so far been polymerized by various
methods. Most of the methods employed in industry comprise adding a
radical generator to a vinyl monomer and carrying out radical
polymerization under high temperature and high pressure conditions.
Recently, anionic polymerization, coordination polymerization and
group transfer polymerization, for instance, have been proposed, on
the laboratory level, as polymerization methods by which the
molecular weight and molecular weight distribution can be
controlled.
[0009] However, the compounds used in such catalyst systems are
generally unstable against oxygen and/or moisture and readily
decomposable and, further, require a number of reaction steps for
their synthesis. In addition, their instability makes their
synthesis difficult, leading to low yields and, as a result, they
constitute expensive catalyst systems.
[0010] On the other hand, as for the metal in the transition metal
complex used in the catalyst systems, titanium, zirconium, hafnium
and the like, which are group IV transition elements, hence early
transition metals, are generally used. Recently, nickel, palladium
and the like, which are group X transition elements, hence late
transition metals, have also been used in spite of their rather
decreased reactivity [e g. JACS, 117 (23), 6414 (1995)].
[0011] The complex containing copper as the nucleus has an
advantage in that it has good stability and can be synthesized with
ease. Because of its low activity due to its stability, however, it
has never been studied as a polymerization catalyst. Only recently,
the present inventors found and reported that a copper complex can
be used as a catalyst for polymerization of carbodiimide, which is
a highly polar monomer, to give a living polymer [Macromolecules,
30, 3159 (1997)].
[0012] However, a copper complex has never been applied as a
polymerization catalyst for a monomer of relatively low polarity
which requires reactivity.
SUMMARY OF THE INVENTION
[0013] The object of the present invention is to provide a method
of producing a polymer using, as a polymerization catalyst, a
copper compound which can easily be synthesized and is stable.
[0014] The present inventors have succeeded in solving the problems
discussed above by using, as a polymerization catalyst component, a
copper compound which can easily be synthesized and is stable.
[0015] The method of producing a polymer using a copper compound in
accordance with a first aspect of the present invention
(hereinafter referred to as "first invention") comprises using a
copper compound represented by the general formula CuXn, LCuXn or
L(L')CuXn (wherein L and L' each represents a ligand, X represents
a halogen atom or an alkoxy, thioxy, allyloxy, amino, secondary
amino, tertiary amino, cyano, nitro, alkyl or allyl group, and n
represents an integer of 0 to 2) as a catalyst and/or
polymerization initiator in polymerizing a vinyl monomer whose
polarity value e, when expressed in terms of absolute value, is not
more than 1.5.
[0016] Preferably, the method of producing a polymer comprises
using a copper compound represented by the general formula LCuXna
or L(L')CuXnb (wherein L and L' each represents a N-coordination
compound selected from the group consisting of bisoxazoline,
substituted bisoxazoline, an amidinato compound and a diimine
represented by the general formula
R.sup.3N.dbd.CR.sup.4CR.sup.5.dbd.NR.sup.6 (wherein R.sup.3,
R.sup.4, R.sup.5 and R.sup.6 each represents independently an
alkyl, allyl, an aryl, a hydrogen atom, or a halogen atom; or at
least one group of R.sup.3 and R.sup.4, R.sup.4 and R.sup.5, and
R.sup.5 and R.sup.6 is combined and represents a cyclic group with
the next carbon and/or nitrogen atom), or a O- and N-coordination
compound; X represents a halogen atom or an alkoxy, thioxy,
allyloxy, amino, secondary amino, tertiary amino, cyano, nitro,
alkyl or allyl group; na represents an integer of 1 to 2; and nb
represents an integer of 0 to 2) as a catalyst and/or
polymerization initiator in polymerizing a vinyl monomer whose
polarity value e, when expressed in terms of absolute value, is not
more than 1.5.
[0017] The method of producing a polymer using a copper compound in
accordance with a second aspect of the present invention
(hereinafter referred to as "second invention") comprises using a
copper compound represented by the general formula CuXn, LCuXn or
L(L')CuXn (wherein L and L' each represents a ligand, X represents
a halogen atom or an alkoxy, thioxy, allyloxy, amino, secondary
amino, tertiary amino, cyano, nitro, alkyl or allyl group, and n
represents an integer of 0 to 2) as a catalyst and/or
polymerization initiator in polymerizing a compound capable of
polymerizing by a ring-opening reaction.
[0018] Preferably, the method of producing a polymer comprises
using a copper compound represented by the general formula LCuXna
or L(L')CuXnb (wherein L and L' each represents a N-coordination
compound selected from the group consisting of bisoxazoline,
substituted bisoxazoline, an amidinato compound and a diimine
represented by the general formula
R.sup.3N.dbd.CR.sup.4CR.sup.5.dbd.NR.sup.6 (wherein R.sup.3,
R.sup.4, R.sup.5 and R.sup.6 each represents independently an
alkyl, allyl, an aryl, a hydrogen atom, or a halogen atom; or at
least one group of R.sup.3 and R.sup.4, R.sup.4 and R.sup.5, and
R.sup.5 and R.sup.6 is combined and represents a cyclic group with
the next carbon and/or nitrogen atom), or a O- and N-coordination
compound; X represents a halogen atom or an alkoxy, thioxy,
allyloxy, amino, secondary amino, tertiary amino, cyano, nitro,
alkyl or allyl group; na represents an integer of 1 to 2; and nb
represents an integer of 0 to 2) as a catalyst and/or
polymerization initiator in polymerizing a compound capable of
polymerizing by a ring-opening reaction.
[0019] The method of producing a polymer using a copper compound in
accordance with a third aspect of the present invention
(hereinafter referred to as "third invention") comprises using the
copper compound together with one or more organometallic compounds
selected from the group consisting of aluminoxanes, organoaluminum
compounds represented by the general formula AlR.sub.mZ.sub.3-m
(wherein R represents a hydrocarbon group containing 1 to 20 carbon
atoms, Z represents a hydrogen or halogen atom or an alkoxy,
allyloxy or siloxy group, and m is an integer of 0 to 3),
boron-containing Lewis acids and boron-containing ionic compounds
in the first or second invention.
DETAILED DESCRIPTION OF THE INVENTION
[0020] In the following, the present invention is described in
detail.
[0021] The vinyl monomer to be used in the present invention
includes those which have a reactive double bond within the
molecule and whose polarity value e, when expressed in terms of
absolute value, is not more than 1.5.
[0022] The above-mentioned polarity value e is a value indicating
the electron density at a double bond site. When there is an
electron flow into the double bond, the polarity shows a negative
value and, when an electron is being pulled by a substituent, it
shows a positive value [Kobunshi Kagaku no Kiso; edited by The
Society of Polymer Science, Japan, published by Tokyo Kagaku
Dojin).
[0023] When the above polarity value e exceeds 1.5, the vinyl
monomer is excessively high in polarity, so that the copper complex
catalyst, in particular in a system in which an organometallic
compound is used as a promoter, is deactivated and the
polymerization reaction can no longer proceed successfully.
[0024] As the vinyl monomer whose polarity value e is not more than
1.5 in absolute value, there may be mentioned, for example,
olefins; .alpha.-substituted olefins; (meth)acrylic esters; and
monomers having a carbon-nitrogen double bond or a carbon-nitrogen
triple bond. These may be used singly or two or more of them may be
used in combination or copolymerized. In the case of
copolymerization, random copolymerization and block
copolymerization are both possible.
[0025] Said olefin has at least one carbon-carbon double bond
within the molecule. Examples are such .alpha.-olefins as ethylene,
propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and
4-methyl-1-pentene; and dienes such as butadiene.
[0026] The .alpha.-substituted olefin mentioned above may be
represented by the general formula CH.sub.2.dbd.CY.sup.1E (wherein
Y.sup.1 represents a phenyl or substituted phenyl or cyano group
and E represents a hydrogen atom or an alkyl group) and, as
examples, there may be mentioned styrene, .alpha.-methylstyrene,
.alpha.-ethylstyrene, o-methylstyrene, p-methylstyrene,
o-chlorostyrene, p-chlorostyrene, o-bromostyrene, p-bromostyrene,
p-nitrostyrene, o-methoxystyrene, p-methoxystyrene, acrylonitrile,
methacrylonitrile and the like.
[0027] Among said (meth)acrylic esters, those of the general
formula CH.sub.2.dbd.C(R.sup.1)COOR.sup.2 [wherein R.sup.1 is a
hydrogen atom or a methyl group (in the case of acrylic esters, it
is a hydrogen atom and, in the case of methacrylic esters, it is a
methyl group) and R.sup.2 is a univalent group selected from among
aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and
hydrocarbon groups containing a functional group such as halogen,
amine or ether] may be used efficiently. Specific examples include,
but are not limited to, methyl (meth) acrylate, ethyl
(meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate,
n-butyl (meth) acrylate, isobutyl (meth)acrylate, sec-butyl
(meth)acrylate, t-butyl (meth)acrylate, isoamyl (meth)acrylate,
n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl
(meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate,
n-tridecyl (meth)acrylate, myristyl (meth)acrylate, cetyl
(meth)acrylate, stearyl (meth)acrylate, allyl (meth)acrylate, vinyl
(meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate,
2-naphthyl (meth)acrylate, 2,4,6-trichlorophenyl (meth)acrylate,
2,4,6-tribromophenyl (meth)acrylate, isobornyl (meth)acrylate,
2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate,
diethylene glycol monomethyl ether (meth)acrylate, polyethylene
glycol monomethyl ether (meth)acrylate, polypropylene glycol
monomethyl ether (meth)acrylate, tetrahydrofurufuryl
(meth)acrylate, 2,3-dibromopropyl (meth)acrylate, 2-chloroethyl
(meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate,
hexafluoroisopropyl (meth)acrylate, glycidyl (meth)acrylate,
3-trimethoxysilylpropyl (meth)acrylate, 2-diethylaminoethyl
(meth)acrylate, 2-dimethylaminoethyl (meth)acrylate,
t-butylaminoethyl (meth)acrylate, and the like.
[0028] The above-mentioned monomer containing a carbon-nitrogen
double bond or a carbon-nitrogen triple bond is, for example, alkyl
isocyanates and alkyl isocyanides.
[0029] As the above-mentioned compound capable of polymerizing
through a ring-opening reaction, there may be mentioned cyclic
ester compounds, cyclic epoxide compounds and the like and, more
specifically, lactone compounds such as .beta.-propiolactone,
.alpha.-methyl-.beta.-propiolacto- ne, .alpha.,
.alpha.'-dimethyl-.beta.-propiolactone,
.alpha.-vinyl-.beta.-propiolactone, .gamma.-butyrolactone,
.delta.-valerolactone and .epsilon.-caprolactone, and propylene
oxide. These may be used singly or two or more of them may be used
in combination.
[0030] For obtaining a polymer from the above-mentioned vinyl
monomer or the compound capable of polymerizing through a
ring-opening reaction in the production method of the present
invention, a copper compound is used as a catalyst either alone or
incombination with an organometallic compound.
[0031] Said copper compound is represented by the general formula
CuXn, LCuXn or L(L')CuXn, preferably, by the general formula LCuXna
or L(L')CuXnb.
[0032] In the above formulas, L and L' each represents a ligand and
X represents a halogen atom or an alkoxy, thioxy, allyloxy, amino,
secondary amino, tertiary amino, cyano, nitro, alkyl or allyl
group, preferably a halogen atom such as chlorine or bromine; an
alkoxy group such as methoxy, ethoxy, isopropoxy or t-butoxy; or a
tertiary amino group such as dimethylamino or diethylamino n is an
integer of 0 to 2. na is an integer of 1 to 2. nb is an integer of
0 to 2.
[0033] The ligands L and L' are not particularly restricted but may
be involved in coordinate bonding through the unpaired electron of
an N, S, O or P atom occurring in the ligand structure or through a
cyclopentadienyl group. More specifically, mention may be made of
N-coordination, such as coordination with an amine, secondary
alkylamine, tertiary alkylamine or an diimine, or amidinato
coordination; and O-coordination such as coordination with an
alkoxy or aryloxy group, among others.
[0034] As the N-coordination compound, there may be mentioned, for
example, bipyridine, substituted bipyridine, bisoxazoline,
substituted bisoxazoline; diimines represented by the general
formula R.sup.3N.dbd.CR.sup.4CR.sup.5.dbd.NR.sup.6 (wherein
R.sup.3, R.sup.4, R.sup.5 and R.sup.6 each represents independently
an alkyl, alkyl, an aryl, a hydrogen atom, or a halogen atom; or at
least one group of R.sup.3 and R.sup.4, R.sup.4 and R.sup.5, and
R.sup.5 and R.sup.6 is combined and represents a cyclic group with
the next carbon and/or nitrogen atom); and amidinato compounds
exemplified by N,N'-di-substituted amidinato such as
N,N'-dimethylamidinato, N,N'-diethylamidinato,
N,N'-diisopropylamidinato, N,N'-di-t-butylamidinat- o,
N,N'-ditrifluoromethylamidinato, N,N'-diphenylamidinato,
N,N'-di-substituted phenylamidinato and
N,N'-ditrimethylsilylamidinato, and N,N'-di-substituted
benzamidinato such as N,N'-dimethylbenzamidinato,
N,N'-diethylbenzamidinato, N,N'-diisopropylbenzamidinato,
N,N'-di-t-butylbenzamidinato, N,N'-ditrifluoromethylbenzamidinato,
N,N'-diphenylbenzamidinato, N,N'-ditrimethylsilylbenzamidinato and
N,N'-di-substituted phenylbenzamidinato.
[0035] In the general formula
R.sup.3N.dbd.CR.sup.4CR.sup.5.dbd.NR.sup.6 of the diimine, the
alkyl of R.sup.3, R.sup.4, R.sup.5 and R.sup.6 is exemplified by an
alkyl having 1 to 6 carbon atoms such as methyl, ethyl, n-propyl,
isopropyl, n-butyl, t-butyl, pentyl, and hexyl. The aryl is
exemplified by phenyl, biphenyl, and the like. The above alkyl,
allyl, and aryl may be substituted by alkyl having 1 to 4 carbon
atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and
t-butyl; alkoxy, and the like. The halogen atom is exemplified by
fluorine, chlorine, bromine, and iodine. The cyclic group is, for
example, a cyclic hydrocarbon by combining R.sup.4 and R.sup.5 with
the next carbon atoms and a heterocycle by combining R.sup.4 and
R.sup.4, or R.sup.5 and R.sup.6 with the next carbon and nitrogen
atoms. The cyclic hydrocarbon is exemplified by mono- di- or
tri-cyclic hydrocarbon having 4-, 5- or 6-membered ring as each
ring, and the like. The heterocycle is exemplified by mono-, di- or
tri-heterocycle having 4-, 5- or 6-membered ring as each ring, and
the like. Apart of carbon atoms of the cyclic group may be
substituted by at least one or nitrogen atom(s), sulfur atom(s),
oxygen atom(s), and silicon atom(s).
[0036] The diimine of the general formula
R.sup.3N.dbd.CR.sup.4CR.sup.5.db- d.NR.sup.6 (wherein each R.sup.3
and R.sup.6 is an aryl, each R.sup.4 and R.sup.5 is a hydrogen
atom, a halogen atom, an alkyl, allyl, or an aryl; or R.sup.4 and
R.sup.5 are combined and represents a cyclic hydrocarbon with the
next carbon atoms) is preferable. The diimine of the above general
formula, wherein each R.sup.3 and R.sup.6 is an aryl and R.sup.4
and R.sup.5 are combined and represents a cyclic hydrocarbon with
the next carbon atoms, is more preferable. Particularly, each
R.sup.3 and R.sup.6 is preferable to be a phenyl substituted by
alkyl having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl,
isopropyl, n-butyl, and t-butyl on its o- and/or m-position(s).
[0037] As the O-coordination compound with an alkoxy or aryloxy
group, the O-coordination compound which coordinates with both O
and N atoms of the compound at the same time, namely the O- and
N-coordination compound, is preferable. As the O- and
N-coordination compound, there may be mentioned, for example,
8-quinolinol, and the 8-quinolinol may be substituted.
[0038] The copper compound mentioned above may occur as the dimer
or trimer or binuclear complex of a compound of the general formula
CuXn, LCuXn or L(L')CuXn, preferably of the general formula LCuXna
or L(L')CuXnb, which contains two or more copper atoms per
molecule.
[0039] In many instances, these complexes occur in the monomer form
in the solution or in the monomer at the time of reaction, although
they occur as dimers, trimers or binuclear complexes in their solid
state. They can be used in the present invention if said monomer
state corresponds to the general formula CuXn, LCuXn or L(L')CuXn,
preferably the general formula LCuXna or L(L')CuXnb.
[0040] The above copper compound can be synthesized in an easy and
simple manner from an inexpensive copper halide, for example copper
chloride. When the synthesis of copper(II) amidinato complexes,
namely the N-coordination compounds mentioned above, is taken as an
example, they can be synthesized, for example, by adding an
equivalent amount of an amidine compound to anhydrous copper(II)
chloride and stirring the mixture in a dry organic solvent at
ordinary temperature for several hours.
[0041] In many instances, the copper compound thus synthesized is
relatively stable against oxygen and moisture. In particular,
bivalent copper complexes, such as
N,N'-dimethylbenzamidinato-copper(II) complex, can remain stable
even in 100% dry oxygen, while the corresponding titanium complexes
are decomposed in an atmosphere containing oxygen at a
concentration of about 1%. Therefore, they can be handled very
easily as compared with transition metal compounds such as titanium
and zirconium compounds.
[0042] The above copper compound may be used singly or two or more
of them may be used in combination.
[0043] It may be used also in a form diluted with a hydrocarbon or
a halogenated hydrocarbon or the like.
[0044] The above copper compound may be used in a form supported on
a granular carrier.
[0045] Useful as the granular carrier is, for example, an inorganic
carrier such as SiO.sub.2, Al.sub.2O.sub.3, MgO, CaO, TiO.sub.2,
ZnO and MgCl.sub.2; and a resin such as polyethylene, polypropylene
and styrene-divinylbenzene copolymers.
[0046] Suitable as the organometallic compound to be used in
combination with the copper compound is at least one member
selected from the group consisting of aluminoxane, organoaluminum
compounds represented by the general formula AlR.sub.mZ.sub.3-m
(wherein R represents a hydrocarbon group containing 1 to 20 carbon
atoms, Z represents a hydrogen or halogen atom or an alkoxy,
allyloxy or siloxy group, and m is an integer of 0 to 3),
boron-containing Lewis acids and boron-containing ionic
compounds.
[0047] Among the above organometallic compounds, aluminoxanes are
compounds represented by the general formula
R.sup.1(Al(R.sup.1)--O).sub.- pAlR.sup.1.sub.2 or the general
formula (1) given below.
[0048] In each formula, R.sup.1 represents a hydrocarbon group
containing 1 to 3 carbon atoms, and p represents an integer not
less than 2. 1
[0049] Among the above aluminoxane, methylaluminoxane in which
R.sup.1 is a methyl group and p is not less than 5 are preferred,
and those in which p is not less than 10 are more preferred. Such
aluminoxanes are commercially available generally in the form of
toluene solutions.
[0050] As regards the method of producing them, the direct reaction
of trialkylaluminums with water and the reaction with metal salt
hydrates are known.
[0051] As the organoaluminum compound represented by the above
general formula AlR.sub.mZ.sub.3-m, there may be mentioned various
species. More specifically, there may be mentioned
trialkylaluminums such as trimethylaluminum, triethylaluminum,
truisopropylaluminum, triisobutylaluminum and trioctylaluminum;
alkenylaluminums such as isoprenylaluminum; dialkylaluminum
monochlorides such as dimethylaluminum chloride, diethylaluminum
chloride, diisopropylaluminum chloride, diisobutylaluminum chloride
and dioctylaluminum chloride; alkylaluminum sesquichloride such as
methylaluminum sesquichloride, ethylaluminum sesquichloride,
isopropylaluminum sesquichloride, isobutylaluminum sesquichloride
and octylaluminum sesquichloride; alkylalminum dichlorides such as
methylaluminum dichloride, ethylaluminum dichloride,
isopropylaluminum dichloride, isobutylaluminum dichloride and
octylaluminum dichloride; alkoxy group-containing aluminum
compounds such as methoxydiethylaluminum,
diisopropoxymethylaluminum and triisopropoxyaluminum; and so
forth.
[0052] As the boron-containing Lewis acid among the above
organometallic compounds, there may be mentioned compounds
represented by the general formula BR.sup.2.sub.3 wherein R.sup.2
represents a phenyl group, which may optionally have a substituent
such as a fluorine atom, a methyl group, a trifluoromethyl group or
the like, or represents a fluorine atom. Specific examples are
trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron,
tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron,
tris(pentafluorophenyl)boron, tris(p-tolyl)boron,
tris(o-tolyl)boron, and tris(3,5-dimethylphenyl)boron- . Among
these, tris(pentafluorophenyl)boron is preferred.
[0053] As the boron-containing ionic compound among the above
organometallic compounds, there may be mentioned, for example,
trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts,
dialkylammonium salts and triarylphosphonium salts.
[0054] As specific examples, there may be mentioned
trialkyl-substituted ammonium salts such as triethylammonium
tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron,
tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium
tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron,
tributylammonium tetra(pentafluorophenyl)boron, tripropylammonium
tetra(o,p-dimethylphenyl- )boron, tributylammonium
tetra(m,m-dimethylphenyl)boron, tributylammonium
tetra(p-trifluoromethylphenyl)boron and tri(n-butyl)ammonium
tetra(o-tolyl)boron; N,N-dialkylanilinium salts such as
N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium
tetra(phenyl)boron and N,N,2,4,6-pentamethylanilinium
tetra(phenyl)boron; dialkylammonium salts such as
di(1-propyl)ammonium tetrapentafluorophenylboron and
dicyclohexylammonium tetra(phenyl)boron; triarylphosphonium salts
such as triphenylphosphonium tetra(phenyl)boron and
tri(dimethylphenyl)phosphonium tetra(phenyl)boron; and the like.
Further examples are triphenylcarbenium
tetrakis(pentafluorophenyl)borona- te, N,N-dimethylanilinium
tetrakis(pentafluorophenyl)borate, ferrocenium
tetra(pentafluorophenyl)borate and the like.
[0055] Further, such anion salts as listed below may also be
mentioned as examples of the boron-containing ionic compounds [in
the ionic compounds listed below, the counter ion is typically
given as, but is not limited to, tri(n-butyl)ammonium]. Such salts
of anions include, for example, bis[tri(n-butyl)ammonium]
nonaborate, bis[tri(n-butyl)ammonium] decaborate,
bis[tri(n-butyl)ammonium] undecaborate, bis[tri(n-butyl)ammonium]
dodecaborate, bis[tri(n-butyl)ammonium] decachlorodecaborate,
bis[tri(n-butyl)ammonium] dodecachlorododecaborate,
tri(n-butyl)-ammonium 1-carbadecaborate, tri(n-butyl)ammonium
1-carbaundecaborate, tri(n-butyl)ammonium 1-carbadodecaborate,
tri(n-butyl)ammonium 1-trimethylsilyl-1-carbadecaborate,
tri(n-butyl)ammonium bromo-1-carbadodecaborate and, further, borane
and carborane complexes; carborane anion salts; carboranes and
carborane salts, for instance.
[0056] Furthermore, such metal carborane salts and metal borane
anions as listed below may also be mentioned as examples of said
boron-containing ionic compound [in the ionic compounds listed
below, the counter ion is typically given as, but is not limited
to, tri(n-butyl)ammonium].
[0057] Said metal carborane salt and metal borane anion include,
among others, tri(n-butyl)ammonium
bis(nonahydrido-1,3-dicarbanonaborate) cobaltate(III),
tri(n-butyl)ammonium bis(undecahydrido-7,8-dicarbaundecab- orate)
ferrate(III), tri(n-butyl)ammonium
bis(undecahydrido-7,8-dicarbaund- ecaborate) cobaltate(III),
tri(n-butyl)ammonium bis(undecahydrido-7,8-dica- rbaundecaborate)
nickelate(III), tri(n-butyl)ammonium
bis(undecahydrido-7,8-dicarbaundecaborate) cuprate(III), and the
like.
[0058] In the catalyst system in the present invention, there may
be incorporated, when necessary, an electron-donating compound such
as ethyl benzoate. The addition of such a compound may sometimes
lead to a marked increase in polymerizing activity.
[0059] The details of the polymerization mechanisms in the
production method of the present invention are not clear. It is
presumable, however, that the copper compound serves as a catalyst
and/or polymerization initiator and that the interaction between
the copper compound alone or the copper compound and organometallic
compound, on one hand, and the vinyl monomer or the compound
capable of polymerizing through a ring-opening reaction
(hereinafter, collectively referred to as "monomer") on the other
accelerates the coordination and insertion reactions of the
monomer.
[0060] The above copper compound alone or the copper compound and
organometallic compound may be added to the reaction system before,
simultaneously with, or after monomer introduction, but preferably
before monomer introduction. The polymerization technique and
conditions, among others, are not particularly restricted. The
polymerization may be carried out continuously or
noncontinuously.
[0061] The polymerization for obtaining the above polymers is
preferably carried out in an inert gas atmosphere. Useful as said
inert gas are nitrogen, helium and argon, among others.
[0062] The solvent to be used in the polymerization includes, among
others, halogenated hydrocarbons such as methylene chloride,
chloroform, carbon tetrachloride and dichloroethane; hydrocarbons
such as benzene, toluene and xylene; tetrahydrofuran, dioxane,
dimethylformamide and the like. It is also possible to carry out
the polymerization without using any solvent.
[0063] The polymerization temperature is preferably within the
range from the melting point of the solvent used to the boiling
point thereof. If under pressurization, the polymerization can be
carried out within a wider temperature range extending to a higher
temperature than the boiling point at ordinary pressure.
[0064] For example, even at room temperature, polymers with a
narrow molecular weight distribution can be obtained.
[0065] To be concrete, it is generally preferred that the
polymerization temperature be -20.degree. C. to 200.degree. C.,
more preferably 0.degree. C. to 120.degree. C. As for the
polymerization pressure, it is generally preferred that it be
within the range of atmospheric pressure to 100 kg/cm.sup.2, more
preferably from atmospheric pressure to 50 kg/cm.sup.2.
[0066] In cases where the copper compound is used alone as the
catalyst, it is generally preferred that it be used in an amount of
about 0.00005 to 0.5 millimole, more preferably about 0.0001 to
0.05 millimole, as calculated on the copper atom basis, per liter
of polymerization volume.
[0067] In cases where the copper compound and organometallic
compound are combinedly used as the catalyst, the copper compound
is preferably used in the same amount as in the case of single use
of the copper compound and, as regards the organometallic compound,
it is generally preferred that when it is an aluminum compound, it
be used in an amount of about 1 to 10,000 moles, more preferably 10
to 5,000 moles, as calculated on the aluminum atom basis, per mole
of the copper atom in the copper compound. In the case of a
boron-containing Lewis acid or ionic compound, it is generally
preferred that it be used in an amount of 1 to 500 moles, more
preferably 1 to 100 moles, as calculated on the boron atom basis,
per mole of the copper atom in said copper compound.
[0068] The molecular weight of the product polymer can be
controlled by modifying the polymerization temperature and other
conditions or by other known means, for example the use of
hydrogen.
[0069] By using such a polymerization catalyst as mentioned above,
it is possible to obtain polymers excellent in composition
distribution in the same manner as in the case of using other
transition metal complex catalysts. Actually, it can be confirmed
by polymer analysis by gel permeation chromatography (GPC) that the
polymers obtained by the production method of the present invention
have a molecular weight distribution (Mw/Mn) as narrow as 1.1 to
3.5, indicating the progress of polymerization in a precisely
controlled manner.
BEST MODES FOR CARRYING OUT THE INVENTION
[0070] The following examples illustrate the present invention in
further detail. However, these examples are by no means limitative
of the scope of the present invention.
EXAMPLE 1
[0071] (1) Synthesis of Copper Compounds
[0072] In the following, unless otherwise specified, dried and
distilled reagents were used.
Synthesis of N,N'-ditrimethylsilylbenzamidinatocopper(II)
compound
[0073] {circle over (1)} Synthesis of
N,N,N'-tris(trimethylsilyl)benzamidi- ne
[0074] A fully argon-substituted 250-ml Schlenk flask was charged
with 40 ml of tetrahydrofuran and cooled to -78.degree. C. To this
flask was added 10 ml of 1,1,1,3,3,3-hexamethyldisilazane, and 30.5
ml of a commercial 1.6 M n-butyllithium solution in hexane was
added dropwise over 20 minutes. After 30 minutes of stirring, 4.9
ml of benzonitrile was added dropwise over 10 minutes.
[0075] Then, the temperature of the system was returned to ordinary
temperature, then stirring was performed for 10 hours, the solvent
was then distilled off under reduced pressure, 50 ml of toluene was
added to the solid remaining in the flask, and 12.2 ml of
trimethylsilyl chloride was added dropwise. Further, the flask was
equipped with a condenser, the mixture was heated under reflux for
10 hours and then filtered, and the solvent was distilled off from
the filtrate under reduced pressure to give the desired product.
The desired product was purified by vacuum distillation, whereupon
11 g of N,N,N'-tris(trimethylsilyl)benzamidine was obtained as
white crystals.
[0076] {circle over (2)} Synthesis of an
N,N'-ditrimethylsilylbenz-amidina- tocopper(II) compound
[0077] A fully argon-substituted 50-ml Schlenk flask was charged
with 1.3 g of the N,N,N'-tris(trimethylsilyl)benzamidine prepared
as mentioned above in {circle over (1)} and 0.28 g of anhydrous
copper chloride, and 15 ml of anhydrous acetonitrile (product of
Wako Pure Chemical Industries) was then added to give a homogeneous
solution. After the lapse of 15 hours, the solution was filtered,
the solvent was distilled off from the filtrate under reduced
pressure to give the desired product. The desired product was
recrystallized from a tetrahydrofuran/n-hexane mixed solvent to
give 0.65 g of the copper complex [compound represented by the
formula (2) given below; in formula (2), TMS represents a
trimethylsilyl group] as green crystals. Identification was
performed by IR and elemental analysis. 2
[0078] (2) Synthesis of Polyethylene
[0079] A 300-ml glass pressure vessel was purged with argon, and
then charged with 100 ml of toluene, followed by addition of 12 mg
of the N,N'-ditrimethylsilylbenzamidinatocopper(II) compound
prepared as described above in (1) and 5 ml of a 10% solution of
methylaluminoxane (product of Aldrich Chemical) in toluene. Then,
while introducing gaseous ethylene into the vessel and maintaining
the system inside at 1.1 kg/cm.sup.2, the polymerization was
carried out at 20.degree. C. for 24 hours. Thereafter, the reaction
was terminated by adding 150 ml of methanol to the reaction
solution, and the precipitate polymer was recovered, whereupon 1.5
g of polyethylene was obtained.
[0080] The polyethylene obtained was subjected to polymer analysis
by gel permeation chromatography (GPC) and differential scanning
calorimetry (DSC). o-Dichlorobenzene was used as the solvent for
GPC. The weight average molecular weight was 820,000 and the number
average molecular weight was 405,000, and the ratio of weight
average molecular weight to number average molecular weight
(Mw/Mn), an index indicating the molecular weight distribution, was
thus 2. The melting curve obtained by DSC showed a peak, namely
melting temperature, at 138.degree. C. No melting peak was observed
at 60.degree. C. or below.
EXAMPLE 2
[0081] Two grams (2 g) of polyethylene was obtained under the same
conditions as in Example 1 except that 10 ml of a 1 M solution of
triisobutylaluminum (product of Aldrich) in toluene was used in
lieu of 5 ml of the 10% solution of methylaluminoxane in
toluene.
[0082] The polyethylene obtained was evaluated in the same manner
as in Example 1. The weight average molecular weight was 715,000,
the number average molecular weight was 388,000, and the ratio of
weight average molecular weight to number average molecular weight
(Mw/Mn), an index indicating the molecular weight distribution, was
1.8.
[0083] The melting curve obtained by DSC showed a peak, namely
melting temperature, at 137.degree. C. Like Example 1, no melting
peak was observed at 60.degree. C. or below.
EXAMPLE 3
[0084] A 100-ml Schlenk flask was purged with argon and then
charged with 20 ml of toluene, followed by addition of 10 mg of the
N,N'-ditrimethylsilylbenzamidinatocopper(II) compound prepared in
Example 1 (1) and 5 ml of a 10% solution of methylaluminoxane
(product of Aldrich) in toluene. Then, 1 g of monomeric styrene was
introduced into the flask and the polymerization was carried out at
20.degree. C. for 72 hours. The reaction was then terminated by
addition of 30 ml of methanol, the catalyst residue was removed,
the product was dissolved in chloroform and the solution was poured
into an excess of n-hexane. The resulting precipitate polymer was
recovered, whereupon 0.39 g of polystyrene was obtained.
[0085] The polystyrene obtained was analyzed by gel permeation
chromatography (GPC) and nuclear magnetic resonance spectrometry
(NMR). Tetrahydrofuran was used as the solvent for GPC. The
polystyrene-equivalent weight average molecular weight and number
average molecular weight of the polymer obtained were 45,000 and
29,000, respectively, and the ratio of weight average molecular
weight to number average molecular weight (Mw/Mn), an index
indicating the molecular weight distribution, was 1.55.
Stereoregularity analysis by nuclear magnetic resonance
spectrometry (NMR) showed isotactic stereoregularity.
EXAMPLE 4
[0086] Polystyrene (0.35 g) was obtained under the same conditions
as in Example 3 except that 5 ml of a 1 M solution of
triisobutylaluminum (product of Aldrich) in toluene was used in
lieu of 5 ml of the 10% solution of methylaluminoxane in
toluene.
[0087] The polystyrene obtained was evaluated by GPC in the same
manner as in Example 1. The weight average molecular weight was
52,000, the number average molecular weight was 35,000, and the
ratio of weight average molecular weight to number average
molecular weight (Mw/Mn), an index indicating the molecular weight
distribution, was 1.49.
EXAMPLE 5
[0088] A 100-ml Schlenk flask was purged with argon and then
charged with 20 ml of toluene, followed by addition of 10 mg of the
N,N'-ditrimethylsilylbenzamidinatocopper(II) compound prepared in
Example 1 (1) and 5 ml of a 10% solution of methylaluminoxane
(product of Aldrich) in toluene. Then, 1.3 g of acrylonitrile was
introduced into the flask and the polymerization was carried out at
20.degree. C. for 24 hours. The reaction was then terminated by
addition of 30 ml of methanol. The catalyst residue was removed,
the reaction product was dissolved in dimethylformamide and the
solution was poured into an excess of isopropanol. The resulting
precipitate polymer was recovered, whereupon 0.89 g of
polyacrylonitrile was obtained.
[0089] The polyacrylonitrile obtained was evaluated by GPC in the
same manner as in Example 1. Dimethylformamide was used as the
solvent for GPC and, for obtaining an exact peak, it was used as a
0.1 M solution of lithium bromide. The polystyrene-equivalent
weight average molecular weight and number average molecular weight
of the polymer obtained were 155,000 and 102,000, respectively, and
the ratio of weight average molecular weight to number average
molecular weight (Mw/Mn), an index indicating the molecular weight
distribution, was 1.52.
EXAMPLE 6
[0090] Polystyrene (0.76 g) was obtained under the same conditions
as in Example 5 except that 5 ml of a 1 M solution of
triisobutylaluminum (product of Aldrich) in toluene was used in
lieu of 5 ml of the 10% solution of methylaluminoxane in
toluene.
[0091] The polystyrene obtained was evaluated by GPC in the same
manner as in Example 1. The weight average molecular weight was
112,000, the number average molecular weight was 81,000, and the
ratio of weight average molecular weight to number average
molecular weight (Mw/Mn), an index indicating the molecular weight
distribution, was 1.38.
EXAMPLE 7
[0092] A 100-ml Schlenk flask was purged with argon and then
charged with 10 ml of toluene, followed by addition of 30 mg of the
N,N'-ditrimethylsilylbenzamidinatocopper(II) compound prepared in
Example 1 (1) and 2 ml of a 10% solution of methylaluminoxane
(product of Aldrich) in toluene. Then, 1.2 g of
.epsilon.-caprolactone was introduced into the flask and the
polymerization was carried out at 30.degree. C. for 24 hours. The
reaction was then terminated by addition of 30 ml of methanol. The
catalyst residue was removed, the reaction product was dissolved in
dimethylformamide and the solution was poured into an excess of
isopropanol. The resulting precipitate polymer was recovered,
whereupon 1.11 g of poly(.epsilon.-caprolactone) was obtained.
[0093] The poly(.epsilon.-caprolactone) obtained was evaluated by
GPC in the same manner as in Example 1. Chloroform was used as the
solvent for GPC. The polystyrene-equivalent weight average
molecular weight and number average molecular weight of the polymer
obtained were 32,600 and 25,200, respectively, and the ratio of
weight average molecular weight to number average molecular weight
(Mw/Mn), an index indicating the molecular weight distribution, was
1.29.
EXAMPLE 8
[0094] A 50-ml Schlenk flask was purged with argon and then charged
with 10 ml of toluene, followed by addition of 18.0 mg of the
N,N'-ditrimethylsilylbenzamidinatocopper(II) compound prepared in
Example 1 (1) and 0.5 ml of a 10% solution of methylaluminoxane
(product of Aldrich) in toluene. Then, 1.66 g of propylene oxide
was introduced into the flask and the polymerization was carried
out at 0.degree. C. for 24 hours. Thereafter, 30 ml of methanol was
added to the reaction mixture to thereby terminate the reaction,
the catalyst residue was removed, the solvent was distilled off
under reduced pressure, the remaining reaction product was added to
an excess of n-hexane, and the precipitate polymer was recovered,
whereupon 1.42 g of a propylene oxide polymer resulting from ring
opening was obtained.
[0095] The propylene oxide ring-opening polymer obtained was
evaluated by GPC in the same manner as in Example 1.
Tetrahydrofuran was used as the solvent for GPC. The
polystyrene-equivalent weight average molecular weight and number
average molecular weight of the polymer obtained were 249,000 and
140,900, respectively, and the ratio of weight average molecular
weight to number average molecular weight (Mw/Mn), an index
indicating the molecular weight distribution, was 1.77.
EXAMPLE 9
[0096] A 100-ml Schlenk flask was purged with argon and then
charged with 20 ml of toluene, followed by addition of 10 mg of a
commercial acetylacetonato compound of copper (II) and 2 ml of a
10% solution of methylaluminoxane (product of Aldrich) in toluene.
Then, 1.3 g of methyl methacrylate was introduced into the flask
and the polymerization was carried out at 30.degree. C. for 24
hours.
[0097] Thereafter, 30 ml of methanol was added to the reaction
mixture to thereby terminate the reaction, the catalyst residue was
removed, the remaining reaction product was dissolved in
chloroform, the solution was added to an excess of methanol, and
the precipitate polymer was recovered, whereupon 0.86 g of
poly(methyl methacrylate) was obtained.
[0098] The poly(methyl methacrylate) obtained was evaluated by GPC
in the same manner as in Example 1. Tetrahydrofuran was used as the
solvent for GPC. The polystyrene-equivalent weight average
molecular weight and number average molecular weight of the polymer
obtained were 35,000 and 28,500, respectively, and the ratio of
weight average molecular weight to number average molecular weight
(Mw/Mn), an index indicating the molecular weight distribution, was
1.23.
EXAMPLE 10
[0099] (1) Synthesis of a Copper Compound
[0100] Synthesis of a Complex of Copper(II) with 2 Molecules of
8-quinolinol
[0101] Commercial copper acetate (2.63 g) was dissolved in 300 ml
of an acetic acid/sodium acetate buffer solution (prepared by
blending equal volumes of 0.1 M aqueous solution of acetic acid and
0.1 M aqueous solution of sodium acetate).
[0102] To this solution was added 4 g of commercial 8-quinolinol,
and the mixture was stirred at ordinary temperature for 1 hour to
give a yellow-green precipitate. The thus-formed yellow-green
precipitate was collected by filtration, washed with distilled
water and dried under vacuum to give 4.4 g of a green-orange
compound (copper(II) complex with 2 molecules of 8-quinolinol)
representable by the formula (3) shown below. 3
[0103] (2) Synthesis of poly(n-butyl acrylate)
[0104] A 100-ml Schlenk flask was purged with argon and then
charged with 20 ml of toluene, followed by addition of 25 mg of the
copper(II) complex with 2 molecules of 8-quinolinol as prepared
above in (1) and 2 ml of a 10% solution of methylaluminoxane
(product of Aldrich) in toluene. Then, 2.3 g of n-butyl acrylate
was introduced into the flask and the polymerization was carried
out at 0.degree. C. for 24 hours. Thereafter, 30 ml of methanol was
added to the reaction mixture to thereby terminate the reaction,
the catalyst residue was removed, the reaction product was
dissolved in chloroform, the solution was added to an excess of
methanol, and the precipitate polymer was recovered, whereupon 2 g
of poly(n-butyl acrylate) was obtained.
[0105] The poly(n-butyl acrylate) obtained was evaluated by GPC in
the same manner as in Example 1. Tetrahydrofuran was used as the
solvent for GPC. The polystyrene-equivalent weight average
molecular weight and number average molecular weight were 80,100
and 57,000, respectively, and the ratio of weight average molecular
weight to number average molecular weight (Mw/Mn), an index
indicating the molecular weight distribution, was 1.41.
EXAMPLE 11
[0106] A 100-ml Schlenk flask was purged with argon and then
charged with 7 ml of toluene, followed by addition of 12 mg of the
copper(II) complex with 2 molecules of 8-quinolinol as prepared in
Example 10 (1) and 2 ml of a 10% solution of methylaluminoxane
(product of Aldrich) in toluene. Then, 1.3 g of methyl methacrylate
was introduced into the flask and the polymerization was carried
out at 30.degree. C. for 24 hours. Thereafter, 30 ml of methanol
was added to the reaction mixture to thereby terminate the
reaction, the catalyst residue was removed, the reaction product
was dissolved in chloroform, the solution was added to an excess of
methanol, and the precipitate polymer was recovered, whereupon 0.75
g of poly(methyl methacrylate) was obtained.
[0107] The poly(methyl methacrylate) obtained was evaluated by GPC
in the same manner as in Example 1. Tetrahydrofuran was used as the
solvent for GPC. Thepolystyrene-equivalent weight average molecular
weight and number average molecular weight were 19,800 and 15,200,
respectively, and the ratio of weight average molecular weight to
number average molecular weight (Mw/Mn), an index indicating the
molecular weight distribution, was 1.30.
EXAMPLE 12
[0108] A 50-ml Schlenk flask was purged with argon and then charged
with 34 ml of toluene, followed by addition of 10.8 mg of the
copper(II) complex with 2 molecules of 8-quinolinol as prepared in
Example 10 (1) and 0.5 ml of a 10% solution of methylaluminoxane
(product of Aldrich) in toluene. Then, 3.9 g of n-butyl acrylate
was introduced into the flask and the polymerization was carried
out at 0.degree. C. for 48 hours. Thereafter, 30 ml of methanol was
added to the reaction mixture to thereby terminate the reaction,
the catalyst residue was removed, the reaction product was
dissolved in chloroform, the solution was added to an excess of
methanol, and the precipitate polymer was recovered, whereupon 2.8
g of poly(n-butyl acrylate) was obtained.
[0109] The poly(n-butyl acrylate) obtained was evaluated by GPC in
the same manner as in Example 1. Tetrahydrofuran was used as the
solvent for GPC. The polystyrene-equivalent weight average
molecular weight and number average molecular weight were 170,500
and 101,500, respectively, and the ratio of weight average
molecular weight to number average molecular weight (Mw/Mn), an
index indicating the molecular weight distribution, was 1.68.
EXAMPLE 13
[0110] (1) Synthesis of Copper Compounds
[0111] In the following, unless otherwise specified, dried and
distilled reagents were used.
Synthesis of diimine copper(II) compound
[0112] To a argon-substituted 250-ml Schlenk flask having Dimroth
condenser, 2.5 g of acenaphthenequinone, 1.85 g of anhydrous
copper(II) chloride, and 150 ml of gracial acetic acid were added.
After stirring the mixture for 30 minutes, 5.20 ml of
2,6-diisopropylaniline in a syringe was added dropwise to the
mixture.
[0113] Then, the mixture was heated in an oil bath (the temperature
of the bath was 120.degree. C.) and refluxed. After two hours, the
temperature of the system was returned to ordinary temperature. The
resulting dark green crystals were filtered and recrystallized with
toluene-methanol, and 6.96 g of the desired product, which is the
diimine copper(II) compound represented by the formula (4) given
below, was obtained. Identification was preformed by IR and
elemental analysis. 4
[0114] (2) Synthesis of Polyethylene
[0115] A 300-ml glass pressure vessel was purged with argon, and
then followed by addition of 26 mg of the diimine copper(II)
compound prepared as described in above (1), 2 ml of 20% solution
of triisobutylaluminum (product of Tosoh-akzo) in toluene, 328 mg
of N,N-dimethylanilinium tetra(pentafluorophenyl)borate, 120 mg of
2,6-di-t-butyl-4-methylphenol and 58 ml of dried toluene. Then,
while introducing gaseous ethylene into the vessel and maintaining
the system inside at 1.1 kg/cm.sup.2 G, the polymerization was
carried out at 0.degree. C. for 4 hours. Thereafter, the reaction
was terminated by adding 150 ml of methanol to the reaction
solution, and the precipitated polymer was recovered, whereupon 0.9
g of polyethylene was obtained.
[0116] The polyethylene obtained was subjected to polymer analysis
by gel permeation chromatography (GPC) and differential scanning
calorimetry (DSC) o-Dichlorobenzene was used as the solvent for
GPC. The weight average molecular weight was 490,000 and the number
average molecular weight was 196,000, and the ratio of weight
average molecular weight to number average molecular weight
(Mw/Mn), an index indicating the molecular weight distribution, was
thus 2.50. The melting curve obtained by DSC showed a peak, namely
melting temperature, at 139.degree. C. No melting peak was observed
at 60.degree. C. or below.
EXAMPLE 14
[0117] 1.5 g of Polyethylene was obtained under the same conditions
as in Example 13 except that a stainless pressure vessel was used
and initial polymerization pressure was 10.0 kg/cm.sup.2.
[0118] The polyethylene obtained was evaluated in the same manner
as in Example 13. The weight average molecular weight was 320, 000
and the number average molecular weight was 140,000, and the ratio
of weight average molecular weight to number average molecular
weight (Mw/Mn), an index indicating the molecular weight
distribution, was 2.29.
[0119] The melting curve obtained by DSC showed a peak, namely
melting temperature, at 138.degree. C. Like Example 13, no melting
peak was observed at 60.degree. C. or below.
EXAMPLE 15
[0120] (1) Synthesis of Polyethylene
[0121] A 300-ml glass pressure vessel was purged with argon, and
then charged with 100 ml of toluene, followed by addition of 26 mg
of the diimine copper (II) compound prepared as described in above
(1) of Example 13, and 926 mg of methylaluminum di(tris
2,4,6-t-butylphenoxide), 2 ml of 20% solution of
triisobutylaluminum (product of Tosoh-akzo) in toluene, 32.8 mg of
N,N-dimethylanilinium tetra(pentafluorophenyl)borate, and 58 ml of
dried toluene. Then, while introducing gaseous ethylene into the
vessel and maintaining the system inside at 1.1 kg/cm.sup.2 G, the
polymerization was carried out at 0.degree. C. for 4 hours.
Thereafter, the reaction was terminated by adding 150 ml of
methanol to the reaction solution, and the precipitated polymer was
recovered, whereupon 0.9 g of polyethylene was obtained
[0122] The polyethylene obtained was subjected to polymer analysis
by gel permeation chromatography (GPC) and differential scanning
calorimetry (DSC) o-Dichlorobenzene was used as the solvent for
GPC. The weight average molecular weight was 540,000 and the number
average molecular weight was 183,000, and the ratio of weight
average molecular weight to number average molecular weight
(Mw/Mn), an index indicating the molecular weight distribution, was
thus 2 95. The melting curve obtained by DSC showed a peak, namely
melting temperature, at 139.degree. C. No melting peak was observed
at 60.degree. C. or below.
EXAMPLE 16
[0123] 1.2 g of Polyethylene was obtained under the same conditions
as in Example 15 except that a stainless pressure vessel was used
and initial polymerization pressure was 10.0 kg/cm.sup.2.
[0124] The polyethylene obtained was evaluated in the same manner
as in Example 15. The weight average molecular weight was 610,000
and the number average molecular weight was 230,000, and the ratio
of weight average molecular weight to number average molecular
weight (Mw/Mn), an index indicating the molecular weight
distribution, was 2.65.
[0125] The melting curve obtained by DSC showed a peak, namely
melting temperature, at 138.degree. C. Like Example 15, no melting
peak was observed at 60.degree. C. or below.
Industrial Applicability
[0126] The method of producing a polymer using a copper compound in
accordance with the present invention, which has the constitution
mentioned above, uses a copper catalyst, which is excellent in
stability, easy to handle and inexpensive, as a polymerization
catalyst and thus provides a polymer narrow in molecular weight
distribution with ease and at low cost.
* * * * *