U.S. patent application number 10/569604 was filed with the patent office on 2006-11-30 for polyolefin functional at one end.
Invention is credited to Terunori Fujita, Haruyuki Makio.
Application Number | 20060270814 10/569604 |
Document ID | / |
Family ID | 34269169 |
Filed Date | 2006-11-30 |
United States Patent
Application |
20060270814 |
Kind Code |
A1 |
Makio; Haruyuki ; et
al. |
November 30, 2006 |
Polyolefin functional at one end
Abstract
A single-chain-end functionalized polyolefin, which is
represented by the following general formula (I): P--X (I) wherein
X is a group containing at least one element selected from oxygen,
sulfur, nitrogen, phosphorus and halogens, P represents a polymer
chain made mainly of an olefin composed only of carbon and hydrogen
atoms, and X is bonded to a terminal of P, wherein the molecular
weight distribution (Mw/Mn) obtained by gel permeation
chromatography (GPC) is from 1.0 to 1.5.
Inventors: |
Makio; Haruyuki; (Chiba,
JP) ; Fujita; Terunori; (Chiba, JP) |
Correspondence
Address: |
BIRCH STEWART KOLASCH & BIRCH
PO BOX 747
FALLS CHURCH
VA
22040-0747
US
|
Family ID: |
34269169 |
Appl. No.: |
10/569604 |
Filed: |
August 27, 2004 |
PCT Filed: |
August 27, 2004 |
PCT NO: |
PCT/JP04/12791 |
371 Date: |
February 24, 2006 |
Current U.S.
Class: |
526/172 |
Current CPC
Class: |
C08F 8/20 20130101; C08F
10/00 20130101; C08F 8/20 20130101; C08F 8/00 20130101; C08F 8/00
20130101; C08F 4/64048 20130101; C08F 110/02 20130101; C08F 110/06
20130101; C08F 10/00 20130101; C08F 8/00 20130101; C08F 110/02
20130101 |
Class at
Publication: |
526/172 |
International
Class: |
C08F 4/06 20060101
C08F004/06 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 27, 2003 |
JP |
2003302240 |
Claims
1. A single-chain-end functionalized polyolefin, which is
represented by the following general formula (I): P--X (I) wherein
X is a group containing at least one element selected from oxygen,
sulfur, nitrogen, phosphorus and halogens, P represents a polymer
chain made mainly of an olefin composed only of carbon and hydrogen
atoms, and X is bonded to a terminal of P, wherein the molecular
weight distribution (Mw/Mn) obtained by gel permeation
chromatography (GPC) is from 1.0 to 1.5.
2. The single-chain-end functionalized polyolefin according to
claim 1, wherein the polymer chain P is made of units of at least
one olefin selected from ethylene and olefins having 3 to 20 carbon
atoms.
3. The single-chain-end functionalized polyolefin according to
claim 1, wherein the polymer chain P comprises the .alpha.-olefin
unit chain which is syndiotactic.
4. The single-chain-end functionalized polyolefin according to any
one of claims 1 to 3, which is obtained by: performing the
following steps 1 and 2 in any order in the presence of an olefin
polymerizing catalyst containing a compound (A) which contains a
transition metal in the groups IV to V; and subsequently performing
the following step 3 if necessary: [step 1] the step of bringing it
into contact with a polar-group-containing olefin (C) represented
by the following general formula (II): CHA=C(R)-Q-Y' (II) wherein
Y' is a group containing at least one element from oxygen, sulfur,
nitrogen, phosphorus and halogens, Q is an alkylene group which may
have a substituent, a carbonyl group, or bivalent oxygen, A and R
each represent a hydrogen atom or a hydrocarbon group which may
have a substituent, and A or R may be bonded together to Q to form
a ring, [step 2] the step of bringing the resultant into contact
with at least one olefin (D) selected from ethylene and olefins
having 3 to 20 carbon atoms n times wherein n is an integer of 1 or
more, so as to mix them (provided that when n is an integer of 2 or
more, the olefins (D) used in the respective contact operations are
different in kind or composition), and [step 3] the step of
chemical conversion.
Description
TECHNICAL FIELD
[0001] The present invention relates to a novel single-chain-end
functionalized polyolefin.
BACKGROUND ART
[0002] Polyolefins such as polyethylene (PE) and polypropylene (PP)
are light and inexpensive and further have characteristics of
having excellent physical properties and workability. On the other
hand, high chemical stability of polyolefins is an obstacle for
giving, thereto, high functionalities, typical examples of which
include printability, paintability, heat resistance and impact
resistance, and a function for improving compatibility thereof with
other polar polymers. There are known methods for making up for
such drawbacks and causing polyolefins to have functionalities.
Examples thereof include a method of polymerizing an olefin with a
polar monomer such as vinyl acetate or a methacrylic acid ester by
radical polymerization; and a method of grafting a polar monomer
such as maleic anhydride to a polyolefin in the presence of a
peroxide. However, according to these methods, it is generally
difficult to control minutely the structure of olefin chain
moieties in the resultant polymers. As a result, excellent,
original physical properties of polyolefin may be damaged.
[0003] In general, it is well known that a process using living
polymerization is useful as a process for producing such a polymer.
In the case of highly-controlled living polymerization, a growing
terminal of the polymer quantitatively keeps reactivity. It is
therefore known that the reactivity is used to cause the terminal
to react directly with a polar-group-containing monomer, whereby a
polymer having a functional group at its terminal position can be
effectively produced.
[0004] However, in the case of polymerizing any olefin by living
polymerization, chain transfer reaction of the growing polymer
chain is frequently caused under ordinary conditions; therefore, it
is very difficult to produce an olefin polymer by living
polymerization. Some examples wherein an .alpha.-olefin is
subjected to living polymerization have been reported so far.
However, in any one of the report examples, the polymerization is
conducted at a very low temperature in order to control chain
transfer reaction. The polymerization activity thereof is also a
low value. The molecular weight thereof is also at most several
tens of thousands. Furthermore, monomers that can be polymerized
are restricted in many cases. It is particularly difficult to
produce industrially important ethylene-based (co) polymers or
block copolymers. Concerning stereoregular polymerizations of
.alpha.-olefins, living polymerizations exhibiting a high
regularity are hardly known (see, for example, "Kobunshi", 1988,
47(2), 74-77).
[0005] Under such situations, the Applicant already discloses a
transition metal compound having a salicylaldimine ligand as a
novel catalyst for olefin polymerization (see Japanese Patent
Application Laid-Open No. 11-315109), and further suggests a
process of using the transition metal compound to produce a novel
single-terminal vinyl-group-containing copolymer or a novel
polar-group-containing block copolymer (see Japanese Patent
Application Laid-Open Nos. 2003-73412 and 2003-40953). However, the
two published documents neither disclose any polymer having a polar
functional group only at its single terminal (single-chain-end
functionalized polymer) nor any process for the production thereof.
The present Applicant has eagerly searched a single-chain-end
functionalized polymer which can be used for various purposes and
has overcome the above-mentioned problems, and has then made the
present invention.
DISCLOSURE OF THE INVENTION
[0006] Accordingly, the present invention relates to a polyolefin
which has a polar functional group at its single-terminal position
and is useful for various purposes.
[0007] The single-chain-end functionalized polyolefin (F) of the
present invention is represented by the following general formula
(I): P--X (I) wherein X is a group containing at least one element
selected from oxygen, sulfur, nitrogen, phosphorus and halogens, P
represents a polymer chain made mainly of an olefin composed only
of carbon and hydrogen atoms, and X is bonded to a terminal of P,
wherein the molecular weight distribution (Mw/Mn) obtained by gel
permeation chromatography (GPC) is from 1.0 to 1.5.
[0008] A preferred embodiment of the polymer chain (P) is a polymer
chain made of units of at least one olefin selected from ethylene
and olefins having 3 to 20 carbon atoms.
[0009] The invention also relates to the single-chain-end
functionalized polyolefin (F) produced by a specific production
process. Specifically, the single-chain-end functionalized
polyolefin of the invention comprises a single-chain-end
functionalized polyolefin obtained by: performing the following
steps 1 and 2 in any order in the presence of an olefin
polymerizing catalyst containing a compound (A) which contains a
transition metal in the groups IV to V; and subsequently performing
the following step 3 if necessary:
[step 1] the step of bringing it into contact with a
polar-group-containing olefin (C) represented by the following
general formula (II): CHA=C(R)-Q-Y' (II) wherein Y' is a group
containing at least one element from oxygen, sulfur, nitrogen,
phosphorus and halogens, Q is an alkylene group which may have a
substituent, a carbonyl group, or bivalent oxygen, A and R each
represent a hydrogen atom or a hydrocarbon group which may have a
substituent, and A or R may be bonded together to Q to form a ring,
[step 2] the step of bringing the resultant into contact with at
least one olefin (D) selected from ethylene and olefins having 3 to
20 carbon atoms n times wherein n is an integer of 1 or more, so as
to mix them (provided that when n is an integer of 2 or more, the
olefins (D) used in the respective contact operations are different
in kind or composition), and [step 3] the step of chemical
conversion.
BEST MODES FOR CARRYING OUT THE INVENTION
[0010] The following will describe the single-chain-end
functionalized polyolefin of the present invention, and the
single-chain-end functionalized polyolefin produced by a specific
production process in detail.
Single-Chain-End Functionalized Polyolefin
[0011] The single-chain-end functionalized polyolefin (F) of the
invention is represented by the following general formula (I): P--X
(I)
[0012] In the formula (I), X is a group containing at least one
element selected from oxygen, sulfur, nitrogen, phosphorus and
halogens, that is, a polar functional group. Specific examples
thereof include an oxy group; a peroxy group; a hydroxyl group; a
hydroperoxy group; alkoxy groups such as methoxy, ethoxy, propoxy
and butoxy; aryloxy groups such as phenoxy, methylphenoxy,
dimethylphenoxy, and naphthoxy; arylalkoxy groups such as
phenylmethoxy, and phenylethoxy; an acetoxy group; a carbonyl
group; groups wherein an element in the group XIII or XIV is bonded
to an oxygen, such as silyloxy, boryloxy, and aluminoxy; an amino
group; N-mono-substituted amino groups such as methylamino,
N-benzylamino, and N-cyclohexylamino; N,N-di-substituted alkylamino
groups such as dimethylamino, diethylamino, dipropylamino,
dibutylamino, dicyclohexylamino, dibenzylamino, piperidino, and
morpholino; arylamino or alkylarylamino groups such as phenylamino,
diphenylamino, ditolylamino, dinaphthylamino, and
methylphenylamino; N,N-disilyl-substituted amino groups such as
N,N-bis(trimethylsilyl)amino, N,N-bis(triethylsilyl)amino, and
N,N-bis(t-butyldimethylsilyl)amino; other nitrogen-containing
groups such as imine, amide, imide, ammonium, nitrile and
sulfonamide; sulfonate groups such as methylsulfonate,
trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate,
p-toluenesulfonate, trimethylbenzenesulfonate,
triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, and
pentafluorobenzenesulfonate; sulfinate groups such as
methylsulfinate, phenylsulfinate, benzylsulfinate,
p-toluensulfinate, trimethylbenzenesulfinate, and
pentafluorobenzenesulfinate; alkylthio groups; arylthio groups; a
sulfate group; a sulfide group; a polysufide group; and a thiolate
group. Examples of the phosphorus-containing group include
phosphines such as phenylphosphino, methylphosphino,
ethylphosphino, diphenylphosphino, dimethylphosphino,
diethylphosphino, methylphenylphosphino, and dibenzylphosphino;
phosphine oxides; phosphine sulfides; and phosphinous acids.
Examples of the halogens include fluorine, chlorine, bromine, and
iodine. P represents a polymer chain made mainly of an olefin
composed only of carbon and hydrogen atoms. Of such olefin polymer
chains, preferred is a polyolefin polymer chain made of structural
units derived from at least one selected from ethylene and olefins
having 3 to 10 carbon atoms. In the formula (I), X is bonded to a
terminal of P.
[0013] The molecular weight distribution (Mw/Mn) of the
single-chain-end functionalized polyolefin of the invention
represented by the general formula (I), the distribution being
obtained by gel permeation chromatography (GPC), is from 1.0 to
1.5. However, when the single-chain-end functionalized polyolefin
of the invention is produced by adopting a production process (n=1
in the step 2) which will be described later, the molecular weight
distribution (Mw/Mn) is usually 1.2 or less.
[0014] When the polymer chain (P) is a polyethylene chain, that is,
a chain wherein the concentration of a skeleton originating from
ethylene is 80% or more by mol, the weight-average molecular weight
(Mw) of the single-chain-end functionalized polyolefin of the
invention is 5,000 or more, preferably 7,000 or more.
[0015] In the case that the polymer chain P in the single-chain-end
functionalized polyolefin (F) of the invention contains an
.alpha.-olefin chain having 3 to 20 carbon atoms, the
.alpha.-olefin chain has a feature of exhibiting syndiotacticity.
The fact that the .alpha.-olefin chain is syndiotactic can be
identified by various spectral analyses. The following will
describe the fact that the polymer chain (P) of the
single-chain-end functionalized polyolefin in the invention is
syndiotactic on the basis of analytic findings, giving a case in
which the .alpha.-olefin is propylene as an example.
[0016] The .sup.13C NMR spectrum of polypropylene is measured, and
attention is paid to a range of methyl groups of side chains
(19.5-21.7 ppm). The syndiotacticity [rr] of a triad can be
obtained by substituting an integrated value of plural peaks
(19.5-20.2 ppm) corresponding to an rr triad in this range and an
integrated value of peaks (20.2-21.7 ppm) corresponding to a
different mm or mr triad for I(rr)/{I(rr)+I(mr)+I(mm)} wherein I
represents the integrated intensity of each chain in the .sup.13C
NMR. In the case that polypropylene has no regularity, a
statistically-random distribution is generated; therefore, values
close to the following are obtained: I(rr):I(mr):I(mm)=1:2:1 and
[rr]=0.25. In the single-chain-end functionalized polyolefin of the
invention, the [rr] can be controlled into any value from 0.25 to
1.0 by catalytic structure or other polymerizing conditions. In the
case that the regularity is particularly high ([rr]>0.80), a
sharp peak (20.0-20.1 ppm) corresponding to an rrrr pentad makes
its appearance at a higher intensity than peaks resulting from
other chains. Accordingly, the syndiotacticity can be more
precisely evaluated by the [rrrr] In a copolymer made from ethylene
and propylene also, syndiotacticity is kept when chains of
propylene are present therein. In this case, the value of the [rr]
can be obtained from a value obtained by amending overlap of methyl
groups which originates from chains of EPE and EPP wherein E and P
represent an ethylene unit and a propylene unit, respectively, in
each polymer.
[0017] Out of single-chain-end functionalized polyolefins (F),
preferred are polyolefins wherein X is an oxygen-containing group
or nitrogen-containing group or is the two groups from the
viewpoint of exhibiting high reactivity with various chemical
species.
Single-Chain-End Functionalized Polyolefin Produced by a Specific
Production Process
[0018] The single-chain-end functionalized polyolefin of the
invention can be effectively obtained by carrying out steps which
will be detailed below successively in the presence of an olefin
polymerizing catalyst containing a compound (A) which contains a
transition metal in the groups IV to V in the periodic table.
[0019] As the group IV to V transition metal containing compound
(A), transition metal compounds described in the above-mentioned
Japanese Patent Application Laid-Open No. 2003-40953, which was
filed by the Applicant, can be used without any limitation. Of
these transition metal compounds, preferred transition metal
compounds are illustrated below. ##STR1## ##STR2## ##STR3##
##STR4## ##STR5## ##STR6## ##STR7## ##STR8## ##STR9## ##STR10##
[0020] In the production process according to the invention, an
organic aluminum oxy compound (B) can be used together with the
group IV to V transition metal containing compound (A). The organic
aluminum oxy compound (B) may be an aluminoxane known in the prior
art, or an organic aluminum oxy compound insoluble in benzene, as
exemplified in Japanese Patent Application Laid-Open No.
2-78687.
[0021] The known aluminoxane can be produced by, for example, a
process as described below, and is usually obtained as a solution
containing a solvent of a hydrocarbon.
[0022] (1) A process of adding an organic aluminum compound, such
as trialkylaluminum, to a suspension of a compound containing
absorbed water or a salt containing crystal water, such as
magnesium chloride hydrate, copper sulfate hydrate, aluminum
sulfate hydrate, nickel sulfate hydrate or cerium (I) chloride
hydrate, in a hydrocarbon medium, so as to cause the absorbed water
or crystal water to react with the organic aluminum compound.
(2) A process of causing water, ice or water vapor to act directly
on an organic aluminum compound, such as trialkylaluminum, in a
solvent such as benzene, toluene, ethyl ether or
tetrahydrofuran.
(3) A process of causing an organic tin oxide such as dimethyltin
oxide or dibutyltin oxide to react with an organic aluminum
compound, such as trialkylaluminum, in a solvent such as decane,
benzene or toluene.
[0023] Specific examples of the organic aluminum compound used when
the aluminoxane is prepared include tri-n-alkylaluminums such as
trimethylaluminum, triethylaluminum, tri-n-butylaluminum,
tripropylaluminum, tripentylaluminum, trihexylaluminum, and
trioctylaluminum; branched-trialkyl aluminums such as
triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum,
and tri-2-ethylhexylaluminum; tricycloalkylaluminums such as
tricyclohexylaluminum, and tricyclooctylaluminum; triarylaluminums
such as triphenylaluminum, and tritolylaluminum; and
trialkenylaluminums such as triisoprenylaluminum represented by
(i-C.sub.4H.sub.9).sub.xAl.sub.y(C.sub.5H.sub.10).sub.z wherein x,
y and z are each a positive number and z.gtoreq.2x. Of these,
trialkylaluminums and tricycloalkylaluminums are preferred and
trimethylaluminum is particularly preferred. The above-mentioned
organic aluminum compounds may be used alone or in combination of
two or more thereof.
[0024] In the production process according to the invention, at
least one selected from the following can be caused to be present
together with the group IV to V transition metal containing
compound (A) and the organic aluminum oxy compound (B): an organic
metal compound, a compound which can react with the transition
metal compound (A) to form an ion pair, a carrier, and an organic
compound. About the four components used if necessary, ones
described in the Japanese Patent Application Laid-Open No.
2003-40953 can be used without any limitation.
[0025] The single-chain-end functionalized polyolefin (F) of the
invention is obtained by performing the following steps 1 and 2 in
any order in the presence of an olefin polymerizing catalyst
containing a compound (A) which contains a transition metal in the
groups IV to V, and subsequently performing the following step 3 if
necessary; that is, the single-chain-end functionalized polyolefin
(F) of the invention is obtained [i] by carrying out the steps 1
and 2 in this order, and carrying out the step 3 if necessary; or
[ii] by carrying out the step 2 and step 1 in this order, and
carrying out the step 3 if necessary:
[step 1] the step of bringing it into contact with a
polar-group-containing olefin (C) represented by the following
general formula (II): CHA=C(R)-Q-Y' (II) wherein Y' is a group
containing at least one element from oxygen, sulfur, nitrogen,
phosphorus and halogens, Q is an alkylene group which may have a
substituent, a carbonyl group, or bivalent oxygen, A and R each
represent a hydrogen atom or a hydrocarbon group which may have a
substituent, and A or R may be bonded together to Q to form a ring,
[step 2] the step of bringing the resultant into contact with at
least one olefin (D) selected from ethylene and olefins having 3 to
20 carbon atoms n times wherein n is an integer of 1 or more, so as
to mix them (provided that when n is an integer of 2 or more, the
olefins (D) used in the respective contact operations are different
in kind or composition), and [step 3] the step of chemical
conversion
[0026] Y' in the general formula (II) used in the step 1 is a group
containing at least one element from oxygen, sulfur, nitrogen,
phosphorus and halogens. Examples of such a group include an oxy
group; a peroxy group; a hydroxyl group; a hydroperoxy group;
alkoxy groups such as methoxy, ethoxy, propoxy and butoxy; aryloxy
groups such as phenoxy, methylphenoxy, dimethylphenoxy, and
naphthoxy; arylalkoxy groups such as phenylmethoxy, and
phenylethoxy; an acetoxy group; a carbonyl group; groups wherein an
element in the group XIII or XIV is bonded to an oxygen, such as
silyloxy, boryloxy, and aluminoxy; an amino group;
N-mono-substituted amino groups such as methylamino, N-benzylamino,
and N-cyclohexylamino; N,N-di-substituted alkylamino groups such as
dimethylamino, diethylamino, dipropylamino, dibutylamino,
dicyclohexylamino, dibenzylamino, piperidino, and morpholino;
arylamino or alkylarylamino groups such as phenylamino,
diphenylamino, ditolylamino, dinaphthylamino, and
methylphenylamino; N,N-disilyl-substituted amino groups such as
N,N-bis(trimethylsilyl)amino, N,N-bis(triethylsilyl)amino, and
N,N-bis(t-butyldimethylsilyl)amino; nitrogen-containing groups such
as imine, amide, imide, ammonium, nitrile and sulfonamide;
sulfonate groups such as methylsulfonate,
trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate,
p-toluenesulfonate, trimethylbenzenesulfonate,
triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, and
pentafluorobenzenesulfonate; sulfinate groups such as
methylsulfinate, phenylsulfinate, benzylsulfinate,
p-toluensulfinate, trimethylbenzenesulfinate, and
pentafluorobenzenesulfinate; alkylthio groups; arylthio groups; a
sulfate group; a sulfide group; a polysufide group; and a thiolate
group. Examples of the phosphorus-containing group include
phosphines such as phenylphosphino, methylphosphino,
ethylphosphino, diphenylphosphino, dimethylphosphino,
diethylphosphino, methylphenylphosphino, and dibenzylphosphino;
phosphine oxides; phosphine sulfides; and phosphinous acids.
Examples of the halogens include fluorine, chlorine, bromine, and
iodine. Of these, preferred are silyloxy, aluminoxy, boryloxy, and
N,N-disiyl-substituted amino groups, which do not poison the
catalyst easily and which generate active hydrogen in the case that
hydrolysis is performed after the end of the step 2.
[0027] In the general formula (II), Q is an alkylene group which
may have a substituent, a carbonyl group, or bivalent oxygen. Q is
usually an alkylene group which may have a substituent wherein the
total number of carbon atoms is from 1 to 20. Of alkylene groups
having such a requirement, an unsubstituted linear alkylene group
represented by the following formula (III) is preferably used:
--[CH.sub.2]n- (III) wherein n is a positive integer of 1 to
15.
[0028] In the general formula (II), A and R each represent a
hydrogen atom or a hydrocarbon group which may have a substituent,
and A or R may be bonded together to Q to form a ring. Of
structures satisfying such requirements, a cycloolefin represented
by the following formula (IV) or (IV') is preferably used:
##STR11## wherein p represents an integer of 1 to 10, and is bonded
to Y at any position, q is an integer of 0 to 10, and when q is 0,
the cycloolefin is a monocycloolefin.
[0029] Examples of the olefin having 3 to 20 carbon atoms, used in
the step 2, include linear or branched .alpha.-olefins having 3 to
20 carbon atoms, such as propylene, 1-butene, 2-butene, 1-pentene,
3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene,
3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene, 1-octadecene, and 1-eicocene; and cyclic olefins
having 3 to 20 carbon atoms, such as cyclopentene, cycloheptene,
norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl
1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene. Other
examples of the olefin having 3 to 20 carbon atoms include
vinylcyclohexane, dienes and polyenes. Additional examples of the
olefin include such as aromatic vinyl compounds styrene,
o-methylstyrene, m-methylstyrene, p-methylstyrene,
o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, and
p-ethylstyrene, and other mono- or poly-alkylstyrenes; and
3-phenylpropylene, 4-phenylbutene, and .alpha.-methylstyrene. These
olefins may each contain in the molecule thereof a heteroatom such
as an oxygen, nitrogen, or silicon atom. The olefins may be used
alone or in combination of two or more thereof.
[0030] In the case that n is set to 2 in the [step 2] in the
production of the single-chain-end functionalized polyolefin (F)
and then olefins (D) used in the first and second contacts in this
production are made different from each other in kind or
composition, the polymer chain (P) in the single-chain-end
functionalized polyolefin (F) represented by the general formula
(I) can be rendered a block type chain composed of two kinds of
olefin chains each having a controlled molecular weight (the
wording "different in kind or composition" in the step 2 related to
the invention means the following: "different in kind"; "different
in composition"; and further "different in kind and composition").
For example, in the case that after the step 1 is carried out the
olefin (D) used in the first olefin-contact in the step 2 is
ethylene and the olefin (D) used in the second step 2 is propylene,
the resultant single-chain-end functionalized polyolefin is a
single-chain-end functionalized block polymer represented by the
following general formula (V): X-PE-PP (V) wherein X has the same
meanings as in the formula (I), and PE and PP represent a
polyethylene chain and a polypropylene chain, respectively.
[0031] In the case that after the step 1 is carried out the olefin
(D) used in the first olefin-contact in the step 2 is ethylene and
the olefin (D) used in the second step 2 is ethylene and propylene,
the resultant single-chain-end functionalized polyolefin is a
single-chain-end functionalized block polymer represented by the
following formula (VI): X-PE-EPR (VI) wherein X has the same
meanings as in the formula (I), and PE and EPR represent a
polyethylene chain and an ethylene/polypropylene copolymer chain,
respectively.
[0032] The step 3, which may be performed if necessary, is a step
for converting the group (Y') in the general formula (II) to a
different group by a reaction such as hydrolysis, oxidization,
reduction, or nucleophilic substitution. For example, in Example 1
in the present specification, hydrolysis reaction is used to
convert a Y' group: Me.sub.2Al--O-- to a different group (hydroxyl
group). However, the conversion is not limited to this chemical
conversion.
[0033] In the invention, the polymerization can be carried out by
any one of liquid-phase polymerizations, such as dissolution
polymerization, suspension polymerization, and gas-phase
polymerizations.
[0034] Specific examples of an inert hydrocarbon medium used in the
liquid-phase polymerization include aliphatic hydrocarbons such as
propane, butane, pentane, hexane, heptane, octane, decane,
dodecane, and kerosene; alicyclic hydrocarbons such as
cyclopentane, cyclohexane, and methylcyclopentane; aromatic
hydrocarbons such as benzene, toluene, and xylene; halogenated
hydrocarbons such as ethylene chloride, chlorobenzene, and
dichloromethane; and mixtures thereof. The olefin itself can be
used as the solvent.
[0035] When the single-chain-end functionalized polyolefin
according to the invention is produced in the presence of the
above-mentioned catalyst, the operations composed of the steps 1
and 2 are usually carried out without isolating any product in each
of the steps. Usually, the catalyst is once charged when the
initial step 1 is started. The group IV to V transition metal
compound (A) is used in an amount ranging usually from 10.sup.-12
to 1 mole, preferably from 10.sup.-10 to 10.sup.-1 mole per liter
of the reaction volume. The organic aluminum oxy compound (B) is
used in such an amount that the mole ratio of aluminum atoms in the
component (B) to transition metal atoms (M) in the transition metal
compound (A) (Al/M) will be a value ranging usually from 10 to
500,000, preferably from 50 to 100,000.
[0036] When an organic metal compound, a compound which can react
with the transition metal compound (A) to form an ion pair, a
carrier and an organic compound, as other optional components, are
used together, the used amounts thereof are amounts described in
Japanese Patent Application Laid-Open No. 11-315109.
[0037] The step 1 can be finished by the contact usually at -20 to
50.degree. C., preferably at -10 to 25.degree. C. for 1 to 300
minutes, preferably for 20 to 200 minutes.
[0038] In the step 2, the polymerization reaction is advanced by
the contact usually at -20 to 75.degree. C., preferably at 0 to
50.degree. C. for 1 to 600 minutes, preferably for 5 to 180
minutes. The pressure in the step 2 is usually from a normal
pressure to 100 kg/cm.sup.2, preferably from a normal pressure to
50 kg/cm.sup.2. The polymerization reaction can be conducted by any
one of batch type, semi-continuous type, and continuous type
processes. The polymerization can be conducted at two or more
separated stages wherein reaction conditions are different.
[0039] The single-chain-end functionalized polyolefin of the
invention can be developed into various applications. The
polyolefin can be applied to, for example, a high molecular weight
additive; a compatibility accelerator; a diblock copolymer useful
as a compatibility accelerator or modifier for polymer; a precursor
of a triblock copolymer useful as thermoplastic elastomer or the
above-mentioned articles; or a surface modifier for improving
paintability, adhesive property and other properties of resin. The
polyolefin can be used, in the form of a macromonomer, as raw
material of a polymer having a specific structure such as a
comb-shaped or star-shaped structure, and applied to a viscosity
adjustor for oil, or some other agents.
[0040] In the hydrolysis step of the step 3, which is an optional
constituting requirement of the production process according to the
invention, water or alcohol is usually used as a hydrolyzing agent,
and the hydrolysis is conducted under an acidic or basic condition.
The hydrolysis may be conducted in the presence of an organic
solvent in a two-phase system, or conducted in a gas phase using
steam. Usually, the following conditions are adopted: a temperature
of 0 to 800.degree. C. and a time of 1 minute to 24 hours.
[0041] The invention will be specifically described on the basis of
examples hereinafter. However, the invention is not limited to
these examples. The structures of polymers obtained in the examples
were each decided by use of NMR (FT; 270 MHz: .sup.1H; and 67.5
MHz: .sup.13C), DSC, high-temperature GPC, and so on.
EXAMPLE 1
[0042] Into a glass reactor having an internal volume of 500 mL and
purged sufficiently with nitrogen were charged 250 mL of toluene
and 15.2 mmol of methylaluminoxane, the amount being an amount in
terms of aluminum atoms therein. Thereto was added a solution of
21.3 mg (0.136 mmol) of
Me.sub.2AlO--(CH.sub.2).sub.4CH.dbd.CH.sub.2 in toluene. Thereto
was added a solution of 88.9 mg (containing diethyl ether, 0.101
mmol) of a titanium complex,
bis[N-(3-t-butylsalicylidene)-2,3,4,5,6-pentafluoroanilinate]titanium
dichloride intoluene, and then the components were caused to react
at 27.degree. C. for 15 minutes. Thereafter, the reaction solution
was cooled to 0.degree. C. Thereafter, a mixed gas of ethylene and
nitrogen (gas flow rate: ethylene, 5 L/h; and nitrogen, 50 L/h),
the pressure of which was a normal pressure, was blown from the
bottom of the reactor to the inside thereof so as to cause the
components to react at 0.degree. C. for 5 minutes. Thereafter, the
supply of ethylene was stopped and methanol was added thereto,
thereby terminating the polymerization. After the termination of
the polymerization, the reactant was poured into 600 mL of methanol
containing a small amount of hydrochloric acid to precipitate the
entire amount of a polymer. The polymer was collected by
filtration. The polymer was dried at 80.degree. C. under a reduced
pressure for 10 hours so as to be yielded in an amount of 0.266 g.
The polymerization activity per mmol of titanium was 30.9 g, the
number-average molecular weight (Mn) of the polymer was 13,000, the
ratio of the weight-average molecular weight (Mn) to the
number-average molecular weight (Mn), (Mw/Mn), was 1.08, and the
melting peak temperature based on DSC was 133.8.degree. C. In the
.sup.1H NMR spectrum (FT, 270 MHz, in C.sub.2D.sub.2Cl.sub.4, at
120.degree. C.) of this polymer, a triplet corresponding to a
methylene group adjacent to an OH group made its appearance near
3.64 ppm, and an overlap of methyl groups of two types at terminals
made its appearance near 0.95 ppm. The integration ratio
therebetween was 2:6. In the .sup.13C NMR spectrum (FT, 67.5 MHz,
in C.sub.2D.sub.2Cl.sub.4, at 120.degree. C.), the methyl groups
made their appearance at 13.9 ppm and 19.7 ppm, and a signal
corresponding to the methylene group adjacent to the OH group made
its appearance at 62.9 ppm. From the above, a structure of a
polymer of the following formula was identified: ##STR12##
EXAMPLE 2
[0043] Into a glass reactor having an internal volume of 500 mL and
purged sufficiently with nitrogen were charged 250 mL of toluene
and 10.0 mmol of methylaluminoxane, the amount being an amount in
terms of aluminum atoms therein. The reaction solution was cooled
to 0.degree. C., and then thereto was added a solution of 10.7 mg
(0.0685 mmol) of Me.sub.2AlO--(CH.sub.2).sub.4CH.dbd.CH.sub.2 in
toluene. Thereto was added a solution of 58.4 mg (containing the
weight of diethyl ether, 0.0666 mmol) of a titanium complex,
bis[N-(3-t-butylsalicylidene)-2,3,4,5,6-pentafluoroanilinate]
titanium dichloride in toluene, and then the components were caused
to react at 0.degree. C. for 30 minutes. Thereafter, propylene (gas
flow rate: 100 L/h), the pressure of which was a normal pressure,
was blown from the bottom of the reactor to the inside thereof so
as to cause the components to react at 0.degree. C. for 105
minutes. Thereafter, the supply of propylene was stopped, and
methanol was added thereto, thereby terminating the polymerization.
After the termination of the polymerization, the reactant was
poured into 600 mL of methanol containing a small amount of
hydrochloric acid to precipitate the entire amount of a polymer.
The polymer was collected by filtration. The polymer was dried at
80.degree. C. under a reduced pressure for 10 hours so as to be
yielded in an amount of 0.354 g. The polymerization activity per
mmol of titanium was 3.04 g, the number-average molecular weight
(Mn) of the polymer was 8, 820, the ratio of the weight-average
molecular weight (Mw) to the number-average molecular weight (Mn),
(Mw/Mn), was 1.05, and the melting peak temperature based on DSC
was 144.4.degree. C. In the .sup.1H NMR spectrum (FT, 270 MHz, in
C.sub.2D.sub.2Cl.sub.4, at 120.degree. C.) of this polymer, a
triplet corresponding to a methylene group adjacent to an OH group
made its appearance near 3.64 ppm. In the .sup.13C NMR spectrum
(FT, 67.5 MHz, in C.sub.2D.sub.2Cl.sub.4, at 120.degree. C.), a
signal corresponding to the methylene group adjacent to the OH
group made its appearance at 62.9 ppm. Peaks at 22.5-24.0 ppm
corresponding to isopentyl and isobutyl groups, which were
unreacted initiating ends, hardly made their appearance.
##STR13##
EXAMPLE 3
[0044] Propylene was polymerized under the same conditions as in
Example 2 except that Me.sub.2AlO--(CH.sub.2).sub.9CH.dbd.CH.sub.2
was used instead of Me.sub.2AlO--(CH.sub.2).sub.4CH.dbd.CH.sub.2.
The polymerization activity per mmol of titanium was 3.03 g, the
number-average molecular weight (Mn) of the polymer was 8,200, and
the ratio of the weight-average molecular weight (Mw) to the
number-average molecular weight (Mn), (Mw/Mn), was 1.09. In the
.sup.1H NMR spectrum (FT, 270 MHz in C.sub.2D.sub.2Cl.sub.4, at
120.degree. C.) of this polymer, a triplet corresponding to a
methylene group adjacent to an OH group made its appearance near
3.64 ppm. ##STR14##
EXAMPLE 4
[0045] Propylene was polymerized under the same conditions as in
Example 2 except that Me.sub.3SiO--(CH.sub.2).sub.9CH.dbd.CH.sub.2
was used instead of Me.sub.2AlO--(CH.sub.2).sub.4CH.dbd.CH.sub.2.
The polymerization activity per mmol of titanium was 2.88 g, the
number-average molecular weight (Mn) of the polymer was 7,700, the
ratio of the weight-average molecular weight (Mw) to the
number-average molecular weight (Mn), (Mw/Mn), was 1.06, the
weight-average molecular weight (Mw) of the polymer was 9,250, the
ratio of the weight-average molecular weight to the number-average
molecular weight (Mn) was 1.06, and the melting peak temperature
based on DSC was 142.0.degree. C. In the .sup.1H NMR spectrum (FT,
270 MHz, in C.sub.2D.sub.2Cl.sub.4, at 120.degree. C.) of this
polymer, a triplet corresponding to a methylene group adjacent to
an OH group made its appearance near 3.64 ppm.
EXAMPLE 5
[0046] Into a glass reactor having an internal volume of 500 mL and
purged sufficiently with nitrogen were charged 250 mL of toluene
and 4.82 mmol of methylaluminoxane, the amount being an amount in
terms of aluminum atoms therein. Thereto was added a solution of
15.5 mg (0.0532 mmol) of
(Me.sub.3Si).sub.2N-m-C.sub.6H.sub.4--(CH.sub.2).sub.2CH.dbd.CH.-
sub.2 in toluene. Thereto was added a solution of 42.3 mg
(containing diethyl ether, 0.0482 mmol) of a titanium complex,
bis[N-(3-t-butylsalicylidene)-2,3,4,5,6-pentafluoroanilinate]titanium
dichloride in toluene, and then the components were caused to react
at 0.degree. C. for 120 minutes. Thereafter, a mixed gas of
ethylene and nitrogen (gas flow rate: ethylene, 5 L/h; and
nitrogen, 50 L/h), the pressure of which was a normal pressure, was
blown from the bottom of the reactor to the inside thereof so as to
cause the components to react at 0.degree. C. for 3.5 minutes.
Thereafter, the supply of ethylene was stopped and methanol was
added thereto, thereby terminating the polymerization. After the
termination of the polymerization, the reactant was poured into 600
mL of methanol containing a small amount of hydrochloric acid to
precipitate the entire amount of a polymer. The polymer was
collected by filtration. The polymer was dried at 80.degree. C.
under a reduced pressure for 10 hours so as to be yielded in an
amount of 0.148 g. The polymerization activity per mmol of titanium
was 52.5 g, the number-average molecular weight (Mn) of the polymer
was 13,700, and the ratio of the weight-average molecular weight
(Mw) to the number-average molecular weight (Mn), (Mw/Mn), was
1.15. In the .sup.1H NMR spectrum (FT, 270 MHz, in
C.sub.2D.sub.2Cl.sub.4, at 120.degree. C.) of this polymer, a
triplet corresponding to a methylene group adjacent to a phenyl
group, aromatic protons, and an overlap of methyl groups of two
types at terminals made their appearance near 2.53 ppm, 6.45-6.65
ppm and 7-7.13 ppm, at an integration ratio of 2:4:6. From the
above, a structure of a polymer of the following formula was
identified: ##STR15##
EXAMPLE 6
[0047] Into a glass reactor having an internal volume of 500 mL and
purged sufficiently with nitrogen were charged 250 mL of toluene
and 6.48 mmol of methylaluminoxane, the amount being an amount in
terms of aluminum atoms therein. Thereto was added a solution of
21.0 mg (0.0669 mmol) of
(Me.sub.3Si).sub.2N--(CH.sub.2).sub.9CH.dbd.CH.sub.2 in toluene.
Thereto was added a solution of 56.8 mg (containing diethyl ether,
0.0647 mmol) of a titanium complex,
bis[N-(3-t-butylsalicylidene)-2,3,4,5,6-pentafluoroanilinate]titanium
dichloride intoluene, and then the components were caused to react
at 0.degree. C. for 150 minutes. Thereafter, a mixed gas of
ethylene and nitrogen (gas flow rate: ethylene, 5 L/h; and
nitrogen, 50 L/h), the pressure of which was a normal pressure, was
blown from the bottom of the reactor to the inside thereof so as to
cause the components to react at 0.degree. C. for 3 minutes.
Thereafter, the supply of ethylene was stopped and methanol was
added thereto, thereby terminating the polymerization. After the
termination of the polymerization, the reactant was poured into 600
mL of methanol containing a small amount of hydrochloric acid to
precipitate the entire amount of a polymer. The polymer was
collected by filtration. The polymer was dried at 80.degree. C.
under a reduced pressure for 10 hours so as to be yielded in an
amount of 0.143 g. The polymerization activity per mmol of titanium
was 44.1 g, the number-average molecular weight (Mn) of the polymer
was 15,500, and the ratio of the weight-average molecular weight
(Mw) to the number-average molecular weight (Mn), (Mw/Mn), was
1.10. In the .sup.1H NMR spectrum (FT, 270 MHz, in
C.sub.2D.sub.2Cl.sub.4, at 120.degree. C.) of this polymer, a
triplet corresponding to a methylene group adjacent to a NH.sub.3Cl
group, a multiplet corresponding to a methylene group adjacent
thereto, and an overlap of methyl groups of two types at terminals
made their appearance near 3 ppm, 1.80 ppm and 0.95 ppm, at an
integration ratio of 2:2:6. From the above, a structure of a
polymer of the following formula was identified: ##STR16##
COMPARATIVE EXAMPLE 1
[0048] Propylene was polymerized under the same conditions as in
Example 2 except that
Me.sub.2AlO--(454644CH.sub.2).sub.4CH.dbd.CH.sub.2 was not added.
The polymerization activity per mmol of titanium was 3.16 g, and
the melting peak temperature based on DSC was 146.0.degree. C. In
the .sup.1H NMR spectrum (FT, 270 MHz, in C.sub.2D.sub.2Cl.sub.4,
at 120.degree. C.) of this polymer, no peak made its appearance
near 3.64 ppm. In the .sup.13CNMR spectrum (FT, 67.5 MHz, in
C.sub.2D.sub.2Cl.sub.4, at 120.degree. C.), peaks at 22.5-24.0 ppm
corresponding to isopentyl and isobutyl groups at the terminals
made their appearance.
INDUSTRIAL APPLICABILITY
[0049] The polyolefin having a polar functional group at its single
terminal position itself, or the polyolefin subjected to a further
modifying treatment is useful for various purposes.
* * * * *