JP3378282B2 - Method for producing α-olefin copolymer - Google Patents

Description

Detailed Description of the Invention

[0001] Background of the Invention

FIELD OF THE INVENTION The present invention relates to a method for producing an α-olefin copolymer. More specifically, the present invention comprises a vinyl monomer having a polar group, which is preliminarily subjected to a specific pre-contact treatment, and then copolymerized with an α-olefin in the presence of a specific catalyst, thereby containing a high content of the vinyl monomer having a polar group. , A method for producing an α-olefin copolymer having excellent adhesiveness, printability, hydrophilicity and compatibility with a polymer blend in a high yield.

[0002]

2. Description of the Related Art Homopolymers of α-olefins (including ethylene in the present invention) and their copolymers are inexpensive and have excellent mechanical strength, gloss and transparency. Since it has moldability, moisture resistance and chemical resistance, it is widely used. However, since the olefin polymer has a non-polar molecular structure, it has a poor affinity with other polar substances and has various properties such as adhesiveness, printability, paintability, antistatic property, and compatibility with polymer blends. The property is remarkably inferior. In order to improve it, a method has been proposed in which a polar vinyl monomer is copolymerized with an olefin using a Ziegler-Natta type catalyst to give a polar group to the polyolefin. For example, JP-A-55-9820
No. 9 discloses a copolymer of an α-olefin and a polar vinyl monomer, which has the formula (III) as a polar vinyl monomer.
A method using the monomer shown in is shown.

[0003]

[Chemical 1]

(R ⁵ is a hydrogen atom or a methyl group,
R ⁶ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z ′ is —OH or —COOH. n = 2-1
It is 6. Further, US Pat. No. 3,492,277 discloses a method in which an organoaluminum compound and a polar vinyl monomer are heated at 60 to 150 ° C. and then the product is used for polymerization. However, even if these methods are used, the amount of polar vinyl monomer copolymerized in the polyolefin is generally small, and the activity of the Ziegler-Natta type catalyst may be greatly deteriorated. It is hard to say that the quality effect is still at a practical level in the production of the copolymer.

Further, for the purpose of improving the activity per catalyst and the content of polar vinyl monomer in the copolymer,
It has been proposed to use a catalyst in which a titanium component is supported on a Mg-containing solid product (Japanese Patent Laid-Open Nos. 52-51488, 55-118905, 55-116710). However, these proposals still have low activity per catalyst and are insufficient.

Furthermore, it has been proposed to protect the polar vinyl monomer with a Lewis acid or the like to improve the activity (Japanese Patent Laid-Open Nos. 59-80413 and 59-80414).
And Japanese Patent Laid-Open No. 3-177403). Although these proposals have improved the activity per catalyst to some extent, the proportion of polar vinyl monomers that polymerize is low, and the activity per transition metal is still low, which causes deterioration of the quality of the obtained polymer. Therefore, further improvement is desired.

[0007]

As described above, it was not easy to produce a copolymer obtained by copolymerizing a polar vinyl monomer in a high content, while keeping the activity of the catalyst at a sufficiently satisfactory level.

[0008]

[Summary of the Invention] <Summary> The present invention is intended to solve these problems, and has a sufficiently high catalyst activity and a polar vinyl monomer content. The present invention relates to a production method for providing a high-copolymer. That is, the method for producing an α-olefin copolymer according to the present invention includes the following: an α-olefin having 2 to 20 carbon atoms and a general formula (I), CH ₂ ═CH—C _n H _2n —X (I) (wherein X is OH, SH, COOH, NH ₂ , NHR ¹
Or each group of NR ¹ _2, n is an integer of 1 to 20, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, when R ¹ have more than one may say be identical to In the method for producing an α-olefin copolymer by polymerizing a polar vinyl monomer represented by each of 1) in the presence of a catalyst, a trialkylaluminum is added to the polar vinyl monomer.
And 1.0 to 3.0 moles the amount of um compound, using a polar vinyl monomer into the polymerization mixture was allowed to pre-contact with the trialkyl aluminum compound and the catalyst are the following components (A) and (B ) Is a combination thereof. Ingredient (A) Group IV transition metal compound of the periodic table IV having at least one conjugated five-membered ring, ingredient (B) organoaluminum oxy compound.

[0009] The copolymer of the preparation of concrete The present invention will be described in detail. <Α-Olefin> One of the monomer components constituting the copolymer is α-olefin (including ethylene in the present invention). In the present invention, the number of carbon atoms is about 2 to 20, especially 2 to
No. 12, α-olefins are preferred. Specific examples of such α-olefins include ethylene, propylene, 1
-Butene, 1-hexene, 3-methyl-1-butene, 3
-Methyl-1-pentene, 4-methyl-1-pentene,
3,3-dimethyl-1-butene, 4,4-dimethyl-1
-Pentene, 3-methyl-1-hexene, 4-methyl-
1-hexene, 4,4-dimethyl-1-hexene, 5-
Methyl-1-hexene, allylcyclopentane, vinylcyclopropane, vinylcyclohexane and the like can be mentioned. Of these, preferred is ethylene,
Propylene, 1-butene, 1-hexene, 3-methyl-
1-butene, 3-methyl-1-pentene, 4-methyl-
1-pentene, 5-methyl-1-hexene, etc.,
In particular, ethylene, propylene, 1-butene, 3-methyl-1-butene or 4-methyl-1-pentene is preferable. These α-olefins may be used alone or in combination of two or more.

<Polar Vinyl Monomer> Another monomer component constituting the copolymer of the present invention together with the above-mentioned α-olefin is a polar vinyl monomer. In the present invention, those represented by the general formula (I) can be used. CH in _{2 = CH-C n H 2n} -X (I) formula, X is OH, SH, COOH, each group of NH _2, NHR ¹ or NR ¹ _2, n is an integer of 1 to 20, R ¹ Is a hydrocarbon group having 1 to 20 carbon atoms, and when R ¹ is plural,
Represents the same or different.

In the present invention, among the compounds of general formula (I), those in which X is OH or COOH are preferred. Further, in the present invention, n is 4 among the compounds of the general formula (I).
The above-mentioned hydrocarbon groups, especially 7 or more, are preferable. R ¹ is preferably an alkyl or aryl group having 1 to 8 carbon atoms. Specific examples of the polar vinyl monomer represented by the general formula (I) include 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid,
10-undecenoic acid, 1-hydroxy-4-pentene,
1-hydroxy-5-hexene, 1-hydroxy-6-
Heptene, 1-hydroxy-7-octene, 1-hydroxy-8-nonene, 1-hydroxy-9-decene, 1-
Hydroxy-10-undecene, 1-thiohydro-5-
Hexene, 1-thiohydro-7-octene, 1-thiohydroundecene, 1-amino-6-heptene, 1-amino-7-octene, 1-amino-8-nonene, 1-amino-9-decene, 1 -Amino-10-undecene, 1-
(N-methylamino) -10-undecene, 1- (N-
Examples thereof include ethylamino) -10-undecene, 1- (N-phenylamino) -10-undecene, N, N-diphenylaminoundecene and the like. These polar vinyl monomers can be used alone or in combination of two or more kinds.

<Trialkylaluminum compound> Above
Prior to the copolymerization reaction with the polar vinyl monomer of
The trialkylaluminum compound is represented by the following formula (II)
Is represented by. AlR²R³R^Four            (II) (R², R³And R^FourEach independently, Archi
Group or aryl group. ) R²~ R^FourIndicated by
The alkyl group having 1 to 10 carbon atoms, particularly 1 to
6 is preferable. R², R³And R^FourIs that
These may be the same or different. Such compounds
As a specific example of, Al (CH₃)₃, Al (C
₂H_Five)₃, Al (iC₃H₇)₃, Al (nC
₃H₇)₃, Al (iC_FourH₉) ₃, Al (nC
_FourH₉)₃, Al (iC_FiveH₁₁)₃, Al (nC
_FiveH₁₁)₃, Al (iC₆H₁₃)₃, Al (nC
₆H₁₃)₃, Al (iC₇H₁₅)₃, Al (nC
₇H₁₅)₃, Al (iC₈H₁₇), Al (nC₈H₁₇)
And Al (C_TenH_{twenty one})₃Etc. With these
Preferred aluminum compounds are Al (C
H₃)₃, Al (C₂H_Five)₃, Al (iC
₃H₇)₃, Al (nC₃H₇)₃, Al (iC
_FourH₉)₃, Al (nC_FourH₉)₃, Al (iC
_FiveH₁₁) ₃, Al (nC_FiveH₁₁)₃, Al (iC
₆H₁₃)₃, Al (nC₆H₁₃)₃And more preferable
Some are Al (iC₃H₇)₃, Al (nC₃H₇)
₃, Al (iC_FourH₉)₃, Al (nC_FourH₉)₃, A
l (iC_FiveH₁₁)₃, Al (nC _FiveH₁₁)₃And then
Also preferred is Al (iC_FourH₉)₃Is. this
These organoaluminum compounds can be used alone
Alternatively, two or more kinds may be mixed and used.

<Preliminary contact method> The above-mentioned polar vinyl monomer and the trialkylaluminum compound of the general formula (II) are precontacted with each other in the presence of the above-mentioned polar vinyl monomer and the trialkylaluminum compound, if necessary, with a solvent. It can be performed by contacting with. In this case, the contact amount of the trialkylaluminum compound of the general formula (II) is 1.0 to 3.0 with respect to the polar vinyl monomer.
It is a mole. If this condition is not met, it decreases the activity of the catalyst used in the copolymerization. Also, for the polar vinyl monomers 1 mol having one in the molecule to the group -NH ₂ having two active hydrogen polar vinyl monomers, trialkylaluminum compounds are preferably used 2 moles or more.

The contact temperature is usually about -50 to 150 ° C,
The temperature is preferably 0 to 80 ° C., and the contact product can be heated at the time of contact. The contact time is not particularly limited. The above-mentioned contact product of the polar vinyl monomer and the trialkylaminium compound seems to be immediately produced by the contact between the two, and the upper limit of the contact time is appropriately determined for economic reasons. The solvent used has 5 to 5 carbon atoms.
Suitable are 18 aliphatic, cycloaliphatic and aromatic hydrocarbons, and chlorinated hydrocarbons. Depending on the solubility of the complex compound, it is also possible to use them by appropriately mixing them. For example, in the present invention, pentane, hexane, heptane, octane,
Various solvents such as decane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, benzyl chloride, monochlorobenzene and dichloroethane can be preferably used. Further, the preliminary contact between the polar vinyl monomer and the trialkylaluminum can be carried out under the above-mentioned contact conditions before the initiation of the polymerization in the polymerization tank.

<Production of α-Olefin Copolymer> (Catalyst) In the method for producing an α-olefin copolymer according to the present invention, the above α-olefin and a polar group-containing vinyl monomer are mixed with the following component (A) and It comprises polymerizing using a catalyst in which the component (B) is combined. Here, "combined with" means that a third component other than the component (A) and the component (B) can be used as long as the effect of the present invention is not impaired. <Component (A)> The component (A) is a group IVB transition metal compound of the periodic table having at least one conjugated five-membered ring ligand. Specifically, the following general formula (IV): Q _a (C ₅ H _5-ab R ⁷ _b ) (C ₅ H _5-ac R ⁸ _c ) MeXY (IV) or the following general formula (V): S There is a transition metal compound represented by _a (C ₅ H _5-ad R ⁹ _d ) ZMeXY (V).

Here, Q represents a bonding group bridging the two conjugated five-membered ring ligands, and S represents a bonding group bridging the conjugated five-membered ring ligand and the Z group. Specifically, (i) alkylene groups such as methylene group, ethylene group, isopropylene group, phenylmethylmethylene group, diphenylmethylene group, cyclohexylene group; (b) silylene group, dimethylsilylene group, phenylmethylsilylene group, diphenylsilylene. Group, disilylene group,
A silylene group such as a tetramethyldisilylene group; (c) a hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum [specifically (CH ₃ ) ₂ G
e _{groups, (C 6 H 5) 2} Ge group, (CH ₃₎ P group, (C ₆
H ₅ ) P group, (C ₄ H ₉ ) N group, (C ₆ H ₅ ) N group,
(CH ₃₎ B group, (C ₄ H ₉₎ B group, (C ₆ H ₅₎ B
Group, (C ₆ H ₅ ) Al group, (CH ₃ O) Al group, etc.] and the like. Preferred are alkylene groups and silylene groups. a is 0 or 1. In the above general formula, (C
₅ H _5-ab R ⁷ _b ), (C ₅ H _5-ac R ⁸ _c ), and (C ₅ H _5-ad R ⁹ _d ), the conjugated five-membered ring ligands are defined separately. However, since the definitions themselves of b, c and d, and R ⁷ , R ⁸ and R ⁹ are the same (detailed later), these three conjugated five-membered ring groups may be the same or different. Needless to say.

One specific example of this conjugated five-membered ring group is b =
0 (or c = 0, d = 0) cyclopentadienyl group (no substituent other than the bridging group Q or S).
This conjugated five-membered ring group is b ≠ 0 (or c ≠ 0, d ≠ 0)
In the case of having a substituent, one specific example of R ⁷ (or R ⁸ , R ⁹ ) is a hydrocarbon group (C _1- ).
C _20, preferably a C ₁ -C _12), the hydrocarbon group may be bonded to a cyclopentadienyl group as a monovalent group, and two of which are when it is present a plurality May be bonded at the other end to form a ring with a part of the cyclopentadienyl group. A typical example of the latter is R ⁷
(Or R ⁸ and R ⁹ ) share a double bond of the cyclopentadienyl group to form a condensed 6-membered ring,
That is, the conjugated 5-membered ring group is an indenyl group or a fluorenyl group. That is, typical examples of the conjugated 5-membered ring group are a substituted or unsubstituted cyclopentadienyl group, an indenyl group and a fluorenyl group.

R ⁷ , R ⁸ and R ⁹ are, in addition to the above C _{1 to} C ₂₀ , preferably C _{1 to} C ₁₂ hydrocarbon group, a halogen group (for example, fluorine, chlorine, bromine), Alkoxy groups (for example, C _{1 to} C ₁₂ ), silicon-containing hydrocarbon groups (for example, silicon atom to -Si (R))
(R ′) (R ″) in the form of a group having about 1 to 24 carbon atoms, and a phosphorus-containing hydrocarbon group (for example, a phosphorus atom is —P
(A group having about 1 to 18 carbon atoms in the form of (R) (R ')),
A nitrogen-containing hydrocarbon group (for example, a nitrogen atom is -N (R)
(R ') group containing about 1 to 18 carbon atoms or a boron-containing hydrocarbon group (for example, a boron atom containing -B).
A group having about 1 to 18 carbon atoms in the form of (R) (R ') (for example, a group having about 1 to 18 carbon atoms containing a boron atom in the form of -B (R) (R')). b (or c, d)
Is 2 or more and a plurality of R ⁷ (or R ⁸ and R ⁹ ) are present, they may be the same or different. b, c and d are 0 ≦ b ≦ 5, 0 when a is 0
≦ c ≦ 5, 0 ≦ d ≦ 5, when a = 1, 0 ≦ b ≦ 4,
It is an integer that satisfies 0 ≦ c ≦ 4 and 0 ≦ d ≦ 4. Me is a Group IVB transition metal of the Periodic Table, preferably titanium, zirconium and hafnium. Particularly, titanium and zirconium are preferable.

Z is oxygen (-O-), sulfur (-S-),
An alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms,
A thioalkoxy group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, and a nitrogen-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms Group having 1 to 40 carbon atoms, preferably 1 to 1
8 is a phosphorus-containing hydrocarbon group. X and Y are each hydrogen, a halogen group, a carbon number of 1 to 20, preferably 1 to 10
Hydrocarbon group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 10 carbon atoms, an amino group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (specifically, for example, diphenylphosphine group ), Or 1 to 20 carbon atoms,
It is preferably 1 to 12 silicon-containing hydrocarbon groups (specifically, for example, trimethylsilyl group). X and Y may be the same or different. Of these, a halogen group and a hydrocarbon group are preferable.

Specific examples of this transition metal compound when Me is zirconium are as follows. (A) A transition metal having no conjugated cross-linking group and two conjugated five-membered ring ligands, such as (1) bis (cyclopentadienyl) zirconium dichloride, (2) bis (methylcyclopentadienyl) Zirconium dichloride, (3)
Bis (dimethylcyclopentadienyl) zirconium dichloride, (4) bis (trimethylcyclopentadienyl) zirconium dichloride, (5) bis (tetramethylcyclopentadienyl) zirconium dichloride,
(6) Bis (pentamethylcyclopentadienyl) zirconium dichloride, (7) bis (n-butylcyclopentadienyl) zirconium dichloride, (8) bis (indenyl) zirconium dichloride, (9) bis (fluorenyl) zirconium dichloride , (10) bis (cyclopentadienyl) zirconium monochloride monohydride, (11) bis (cyclopentadienyl) methylzirconium monochloride, (12) bis (cyclopentadienyl) ethylzirconium monochloride, (13) Bis (cyclopentadienyl) phenyl zirconium monochloride, (14) bis (cyclopentadienyl) zirconium dimethyl, (15) bis (cyclopentadienyl) zirconium diphenyl, (1)
6) bis (cyclopentadienyl) zirconium dineopentyl, (17) bis (cyclopentadienyl) zirconium dihydride, (18) (cyclopentadienyl) (indenyl) zirconium dichloride, (1
9) (Cyclopentadienyl) (fluorenyl) zirconium dichloride and the like.

(B) a transition metal compound having two five-membered ring ligands bridged by an alkylene group, such as (1) methylenebis (indenyl) zirconium dichloride, (2) ethylenebis (indenyl) zirconium dichloride,
(3) ethylenebis (indenyl) zirconium monohydride monochloride, (4) ethylenebis (indenyl) methylzirconium monochloride, (5) ethylenebis (indenyl) zirconium monomethoxymonochloride, (6) ethylenebis (indenyl) zirconium Diethoxide, (7) ethylenebis (indenyl) zirconium dimethyl, (8) ethylenebis (4,5,5
6,7-Tetrahydroindenyl) zirconium dichloride, (9) ethylenebis (2-methylindenyl) zirconium dichloride, (10) ethylenebis (2-ethylindenyl) zirconium dichloride, (11) ethylenebis (2,4) -Dimethylindenyl) zirconium dichloride, (12) ethylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, (13) ethylene (2-methyl-4) -Tert-butylcyclopentadienyl) (3'-tert-butyl-5'-methylcyclopentadienyl) zirconium dichloride,

(14) ethylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride,
(15) isopropylidene bis (indenyl) zirconium dichloride, (16) isopropylidene (2,4-
Dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride,
(17) Isopropylidene (2-methyl-4-tert)
Butylcyclopentadienyl) (3′-tertbutyl-5′-methylcyclopentadienyl) zirconium dichloride, (18) methylene (cyclopentadienyl)
(3,4-Dimethylcyclopentadienyl) zirconium dichloride, (19) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium chloride hydride, (20) methylene (cyclopentadienyl) ( 3,4-dimethylcyclopentadienyl) zirconium dimethyl, (21) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium diphenyl, (22) methylene (cyclopentadienyl) (trimethylcyclo) Pentadienyl) zirconium dichloride,

(23) Methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (24) Isopropylidene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (24) 25) isopropylidene (cyclopentadienyl) (2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride, (26) isopropylidene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, (27) isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (2
8) Isopropylidene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, (2
9) isopropylidene (2,5-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride,

(30) isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (31) ethylene (cyclopentadienyl) (3,5-dimethylcyclopentadienyl) zirconium dichloride, ( 32) ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
(33) ethylene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (3
4) ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (3
5) Diphenylmethylene (cyclopentadienyl)
(3,4-diethylcyclopentadienyl) zirconium dichloride, (36) diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, (37) cyclohexylidene (cyclopentadienyl) ) (Fluorenyl) zirconium dichloride, (38) cyclohexylidene (2,
5-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride and the like.

(C) a transition metal compound having a silylene group-bridged five-membered ring ligand, for example, (1) dimethylsilylenebis (indenyl) zirconium dichloride, (2) dimethylsilylenebis (4,5,6,7-tetrahydro) Indenyl) zirconium dichloride, (3) dimethylsilylene bis (2-methylindenyl) zirconium dichloride, (4) dimethylsilylene bis (2,4-dimethylindenyl) zirconium dichloride, (5) dimethylsilylene (2,4- Dimethylcyclopentadienyl)
(3 ', 5'-Dimethylcyclopentadienyl) zirconium dichloride, (6) phenylmethylsilylenebis (indenyl) zirconium dichloride, (7) phenylmethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium Dichloride, (8) phenylmethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, (9) phenylmethylsilylene (2,3,5-trimethylcyclo) Pentadienyl)
(2 ′, 4 ′, 5′-trimethylcyclopentadienyl) zirconium dichloride, (10) phenylmethylsilylenebis (tetramethylcyclopentadienyl) zirconium dichloride, (11) diphenylsilylenebis (indenyl) zirconium dichloride, ( 12) tetramethyldisilylene bis (indenyl) zirconium dichloride,

(13) Tetramethyldisilylenebis (cyclopentadienyl) zirconium dichloride, (1
4) tetramethyldisilylene (3-methylcyclopentadienyl) (indenyl) zirconium dichloride,
(15) Dimethylsilylene (cyclopentadienyl)
(3,4-Dimethylcyclopentadienyl) zirconium dichloride, (16) dimethylsilylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (17) dimethylsilylene (cyclopentadienyl) (tetramethylcyclo Pentadienyl) zirconium dichloride, (18) dimethylsilylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, (19) dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) Zirconium dichloride, (2
0) dimethylsilylene (cyclopentadienyl) (tetraethylcyclopentadienyl) zirconium dichloride, (21) dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,

(22) dimethylsilylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (23) dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) zirconium Dichloride, (24) dimethyl silylene (2
-Methylcyclopentadienyl) (fluorenyl) zirconium dichloride, (25) dimethylsilylene (2,
5-dimethylcyclopentadienyl) (fluorenyl)
Zirconium dichloride, (26) dimethylsilylene (2-ethylcyclopentadienyl) (fluorenyl)
Zirconium dichloride, (27) dimethylsilylene (2,5-diethylcyclopentadienyl) (fluorenyl) Zirconium dichloride, (28) diethylsilylene (2-methylcyclopentadienyl) (2,7-di-t-butylfluor Orenyl) zirconium dichloride,

(29) Dimethylsilylene (2,5-dimethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (30) Dimethylsilylene (2-ethylcyclopentadienyl)
(2,7-di-t-butylfluorenyl) zirconium dichloride, (31) dimethylsilylene (diethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (32) dimethyl Silylene (methylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (33) dimethylsilylene (dimethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (3
4) Dimethylsilylene (ethylcyclopentadienyl)
(Octahydrofluorenyl) zirconium dichloride, (35) dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride and the like.

(D) Transition metal compounds having a five-membered ring ligand bridged by a hydrocarbon group containing germanium, aluminum, boron, phosphorus or nitrogen, such as (1) dimethylgermanium bis (indenyl) zirconium dichloride, ( 2) dimethyl germanium (cyclopentadienyl) (fluorenyl) zirconium dichloride,
(3) methyl aluminum bis (indenyl) zirconium dichloride, (4) phenyl aluminum bis (indenyl) zirconium dichloride, (5) phenylphosphino bis (indenyl) zirconium dichloride,
Examples include (6) ethylboranobis (indenyl) zirconium dichloride, (7) phenylaminobis (indenyl) zirconium dichloride, (8) phenylamino (cyclopentadienyl) (fluorenyl) zirconium dichloride, and the like.

(E) A transition metal compound having one five-membered ring ligand, such as (1) pentamethylcyclopentadienyl- (diphenyl) aminozirconium dichloride,
(2) indenyl- (diphenyl) aminozirconium dichloride, (3) pentamethylcyclopentadienyl-bis (trimethylsilyl) aminozirconium dichloride, (4) pentamethylcyclopentadienylphenoxyzirconium dichloride, (5) dimethylsilylene (tetra) Methylcyclopentadienyl) tert-butylaminozirconium dichloride, (6) dimethylsilylene (tetramethylcyclopentadienyl) phenylaminozirconium dichloride, (7) dimethylsilylene (tetrahydroindenyl) decylaminozirconium dichloride, (8) dimethyl Silylene (tetrahydroindenyl) (bis (trimethylsilyl) amino) zirconium dichloride, (9) dimethylgermane, (10)
Examples thereof include tetramethylcyclopentadienyl (phenyl) aminozirconium dichloride.

(F) Further, it is also possible to use the compounds (a) to (e) in which chlorine is replaced by bromine, iodine, hydride, methyl, phenyl or the like. Furthermore, in the present invention can also be used compounds changing the central metal of the exemplified zirconium compounds above as component (A) (a) to (f) of zirconium titanium and Hafuniu arm.
Among these, zirconium compounds, hafnium compounds and titanium compounds are preferable. More preferred are zirconium compounds, hafnium compounds and titanium compounds crosslinked with an alkylene group or a silylene group.

<Component (B)> The component (B) is an organoaluminum oxy compound. A typical example is alumoxane. Alumoxane is a product obtained by reacting one type of trialkylaluminum or two or more types of trialkylaluminum with water. Specifically, methylalumoxane, ethylalumoxane, butylalumoxane, isobutylalumoxane, etc. obtained from one type of trialkylaluminum, and methylethylalumoxane, methylbutylalumoxane obtained from two types of trialkylaluminum and water. Examples include xane and methylisobutylalumoxane. In the present invention, it is possible to use a plurality of these alumoxanes in combination, and it is also possible to use alumoxane in combination with other alkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride.

It is also possible to use modified alumoxane by reacting two kinds of alumoxane or one kind of alumoxane with another organoaluminum compound. Preferred among these are methylalumoxane, isobutylalumoxane, methylisobutylalumoxane and mixtures of these alumoxanes and trialkylaluminums. Particularly preferred are methylalumoxane and methylisobutylalumoxane. Among them, for the polymerization of propylene, the chemical shift in the measurement of ²⁷ Al-NMR is 160-160.
Methylisobutylalumoxane, which is characterized by being located between 250 ppm and having a line width of 3000 Hz or more, is preferable.

These alumoxanes can be prepared under various known conditions. Specifically, the following methods can be exemplified. (A) a method in which a trialkylaluminum is directly reacted with water using a suitable organic solvent such as toluene, benzene or ether; and (b) a salt hydrate containing trialkylaluminum and water of crystallization, such as copper sulfate or aluminum sulfate. A method of reacting with a hydrate, (c) a method of reacting trialkylaluminum with water impregnated in silica gel, etc., (d) a mixture of trimethylaluminum and triisobutylaluminum, and mixing with toluene, benzene, ether or the like. A method of directly reacting with water using an organic solvent,
(E) A method in which trimethylaluminum and triisobutylaluminum are mixed and heated to react with a salt hydrate having water of crystallization, for example, copper sulfate, aluminum sulfate hydrate,
(F) A method in which silica gel or the like is impregnated with water, treated with triisobutylaluminum, and then additionally treated with trimethylaluminum, and (to) methylalumoxane and isobutylalumoxane are synthesized by a known method. A method of quantitatively mixing and reacting by heating.

Another example is an organoaluminum oxy compound represented by the following formula (VI).

[Chemical 2] (However, R ¹⁰ is a hydrocarbon residue having 1 to ¹⁰ carbon atoms,
R ¹¹ is hydrogen, halogen, siloxy group or 1 to 10 carbon atoms.
The hydrocarbon residue, four R ¹¹ may be the same or different. )

Component (A) is a reaction product of the following components (i) and (ii). Component (i): General formula R ¹⁰ -B (OH) ₂ (where hydrocarbon residue R ¹⁰ is 1 to 10 carbon atoms) component (ii): an organoaluminum compound the general formula R ¹⁰ -B (OH) _The component (i) represented by ₂ is an alkylboronic acid (R ¹⁰ has 1 carbon atom).
-10, preferably 1-6 hydrocarbon residues). Specific examples of such an alkylboronic acid include:
Methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, is
o-butylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid and 3,5-bis (trifluoromethyl) phenylboronic acid, etc. It is illustrated. Of these, preferred are methylboronic acid, iso-butylboronic acid, 3,5
-Difluorophenylboronic acid and pentafluorophenylboronic acid. More preferred is methylboronic acid.

Specific examples of the organoaluminum of the component (ii)
Then the general formula R¹¹ _3-qAlX_qOr R¹¹ _3-qA
l [OSi (R¹²)₃]_qOr (R¹¹)₂AlOAl
(R ¹¹)₂Some are represented by. (However, R¹¹Is charcoal
A hydrocarbon residue having a prime number of 1 to 10, X is hydrogen or halogen
R group¹²Is hydrogen, halogen or C1-10
Represents a hydrocarbon residue, q represents 0 ≦ q <3, respectively.
You ) Specifically, (a) trimethylaluminum,
Liethyl aluminum, triisobutyl aluminum,
Trihexyl aluminum, trioctyl aluminum
Aluminum, tridecyl aluminum, tri-n-butyl aluminum
Um, tri-n-propylaluminum, triisopreni
Trialkylaluminum such as aluminum
(B) Dimethyl aluminum chloride, diethyl aluminum
Monochromate, diisobutylaluminum mono
Chloride, methylaluminum sesquichloride, ethi
Lualuminum sesquichloride, ethylaluminum
Alkyl aluminum halide such as dichloride,
(C) Dimethyl aluminum hydride, diethyl
Luminium hydride, diisobutylaluminum
Alkyl aluminum hydride such as idride,
(D) Dimethyl aluminum (trimethylsiloxy
De), dimethyl aluminum (trimethylsiloxy)
), Diethyl aluminum (trimethylsiloxide)
Alkyl aluminum siloxide, such as (e) tetra
Isobutyl alumoxane, tetraethyl alumoxane, etc.
The tetraalkyl alumoxane of and the like are exemplified. this
It is also possible to use a mixture of a plurality of these. these
Among the organoaluminum compounds, preferred ones are tri
Methyl aluminum, triisobutyl aluminum, di
Methyl aluminum chloride, diisobutyl aluminium
Muchloride, diisobutylaluminum hydride, etc.
Induction of methyl aluminum and isobutyl aluminum
It is a conductor. More preferred is trimethylaluminum
Aluminum, triisobutylaluminum, and mixtures thereof
Is.

Contact ratio between the component (i) and the component (ii) When the component (i) and the component (ii) are reacted, the use ratio is arbitrary, but in order to efficiently produce the desired reaction product. Has a molar ratio of component (i) to component (ii) of 1:
It is preferable to set it to 2. Also, the component (i)
And the reaction of the component (ii) is usually carried out in an inert solvent under an inert gas atmosphere. Various contact methods can be used. For example, (a) component (i) in a toluene solvent
And then the reaction mixture is added dropwise with a diluted solution of component (ii) in toluene, (b) component (ii) diluted with hexane.
Method of supplying component (i) as a solid in a solution and reacting, (c) Method of diluting component (i) and component (ii) in toluene and dropping each at a constant rate into another container to react , Etc. are exemplified. The reaction temperature and the reaction time of the component (i) and the component (ii) are arbitrary, but generally, since a side reaction is likely to occur due to a rapid reaction, both components are kept at a low temperature, for example, -78 to.
After mixing at 30 ° C., preferably −78 to 10 ° C., it is preferable to gradually raise the temperature, for example, to -10 to 70 ° C.
The reaction time is arbitrary as long as the desired product is obtained, but it is generally carried out in the range of 1 minute to 24 hours.

The present invention relates to a process for producing an α-olefin copolymer using a catalyst in which the components (A) and (B) are combined, and in addition to the components (A) and (B), The third component can be optionally used as long as the effects of the invention are not impaired. Examples of the third component that can be added include active hydrogen-containing compounds such as H ₂ O, methanol, ethanol and butanol, ether,
Electron-donating compounds such as esters and amines, phenyl borate, dimethylmethoxyaluminum, phenyl phosphite, tetraethoxysilane, alkoxy-containing compounds such as diphenyldimethoxysilane, triethylborane, triphenylborane, tris (pentafluorophenyl) borane Examples thereof include organoboron compounds such as triphenylcarbyltetrakis (pentafluorophenyl) borane.

<Catalyst formation> The catalyst used in the method of the present invention comprises the above-mentioned components (A) and (B) in a polymerization tank or in a polymerization tank in the presence or absence of a monomer to be polymerized. It can be obtained by contacting the bottom. The amounts of the component (A) and the component (B) used in the present invention are arbitrary, but generally, the atomic ratio of the aluminum atom in the component (A) to the transition metal of the component (B) (Al / M
e) 0.01 to 100,000, preferably 0.1 to
It is 30,000. Any contacting method may be used, and they may be introduced separately at the time of polymerization and contacted, or those contacted in advance may be used.

<Copolymerization of α-Olefin> Needless to say, the method of the present invention is applied to solvent polymerization using a solvent, but substantially no solvent is used in liquid phase solventless polymerization, gas phase polymerization, It also applies to melt polymerization. It is also applied to continuous polymerization and batch polymerization. As a solvent in the case of solvent polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, or toluene is used alone or in a mixture. Polymerization temperature is -78 to 2
The temperature is about 00 ° C, preferably -20 to 100 ° C. The olefin pressure of the reaction system is not particularly limited, but is preferably in the range of normal pressure to 50 kg / cm ² · G. In the polymerization, the molecular weight can be controlled by known means such as selection of temperature and pressure or introduction of hydrogen.

In the method of the present invention, the catalyst component (A) and the component (B), the components to be added if necessary, and the addition method of the contact product of the α-olefin and the polar vinyl monomer and the trialkylaluminum compound. Can adopt various aspects. For example, a method of preliminarily mixing the contact product and the organoaluminum oxy compound and then copolymerizing with an olefin, and the catalyst components (A) and (B) and the polymerization component are simultaneously supplied to the polymerization system without premixing. The method etc. can be adopted. Of course,
The copolymerization is not limited to random copolymerization, but may be a sequential polymerization mode in which the polymerization components and proportions are changed midway. The polymerization can be appropriately carried out by a continuous system, a batch system, a semi-continuous system or the like. After polymerization, the resulting polymer can be treated with butanol or the like to decompose any trihydrocarbylaluminum that may be present in complexed form with the copolymerized polar vinyl monomer. <Production Polymer> The α-olefin-polar vinyl monomer copolymer produced is not limited by the monomer composition of the copolymer, but usually the polar vinyl monomer is 0.01
~ 30 mol%, preferably 0.03-10 mol%
It contains a certain amount. The copolymer itself is not only useful as a polar polymer due to the polarity resulting from the group X present therein, but also can be modified into a derivative by focusing on the reactivity of the polar group X.

[0043]

【Example】

<Example-1> Production of catalyst component (A) Dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride was prepared according to the method described in J. Orgmet. Chem.
(342) 21-29 1988 and J. Orgme
t. Chem. (369) 359-370 1989 . Specifically, 300 ml with nitrogen substitution
In the flask, bis (indenyl) dimethylsilane 5.4
g was diluted with 150 ml of tetrahydrofuran and then -50 ° C.
After cooling to below, n-butyllithium (1.6M /
23.6 ml of L) was added dropwise over 30 minutes. After the dropping was completed, the temperature was raised to room temperature over 1 hour, and the reaction was performed at room temperature for 4 hours to synthesize a reaction solution A. Introduce 200 ml of tetrahydrofuran into a 500 ml flask purged with nitrogen and at -50 ° C.
After cooling to below, 4.38 g of zirconium tetrachloride was slowly introduced. Then, after introducing the entire amount of reaction formula A, 3
The temperature was slowly raised to room temperature over time. After reacting for 2 hours at room temperature, the temperature was further raised to 60 ° C. and reacted for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and then toluene 10
3.86 g of dimethylsilylene bis (indenyl) zirconium dichloride crude crystal was dissolved in 0 ml and redistilled.
Obtained. Then, the crude crystals were added to 150 ml of dichloromethane.
It was dissolved in and introduced into a 500 ml autoclave.
After introducing 5 g of carbon (0.5 wt% platinum supported) catalyst, H
_The hydrogenation reaction was carried out for 5 hours under the conditions of ₂ = 50 kg / cm ² · G and 50 ° C. After completion of the reaction, the catalyst was filtered off, the solvent was distilled off under reduced pressure, the residue was extracted with toluene and recrystallized to obtain 1.26 g of the objective dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride.

[0044]Production of component (B) 1 with a stirrer and a reflux condenser with sufficient nitrogen substitution
Dehydrated and deoxygenated toluene 1 in a 000 ml flask
00 ml was introduced. Then one of the two dropping funnels
And 0.72 g of trimethylaluminum (10 mm
,) Triisobutylaluminum 1.96 g (10 m
Limol) is diluted with 50 ml of toluene and saturated with the other
Introduce water-containing toluene and mix under 30 ° C.
Minium solution and toluene containing saturated water were added to Al and H₂O
Was fed in equimolar amounts over 3 hours. End of feed
Then, the temperature was raised to 50 ° C. and the reaction was performed for 2 hours. After the reaction is complete, melt
The medium was distilled off under reduced pressure to obtain 1.9 g of a white solid. Got
Dilute the white solid in toluene ²⁷Al-NMR measurement results
Fruit, chemical shift 174ppm, half width 5844Hz
The spectrum ofContact of polar vinyl monomer with trialkylaluminum
Production of products Toluene is added to a 1000 ml flask with nitrogen substitution 160
ml, 10-undecen-1-ol 40 ml (195
Mmol), and cooling to 0 ° C. with ice water, 300 m
Triisobutylaluminum diluted in 1 of toluene
(TiBA) 38.6 g (195 mmol) for 30 minutes
It was dropped. After completion of dropping, react at room temperature for 3 hours.
It was Almost no gas is generated in about 1 hour
It was

Preparation of α-Olefin Copolymer A fully dehydrated and deoxygenated n-heptane was placed in a stainless steel autoclave having an internal volume of 1.5 liter, which was sufficiently replaced with propylene gas and equipped with a stirring and temperature control device. 400 ml, 0.05 mol of 10 -undecen-1-ol / TiBA contact product obtained above, 12 mmol of methylisobutylalumoxane of component (B), dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride of component (A) 4 μmol (μmo
1) Introduced, and polymerized at 50 ° C. under a propylene (α-olefin) pressure of 7 kg / cm ² · G for 2 hours. After completion of polymerization
The obtained slurry was extracted into 2 liters of methanol, and the precipitated polymer was filtered and dried to obtain the desired propylene /
49.8 g of an undecenol copolymer was obtained. The catalytic activity is 27,200 g · polymer / g · component (A), ¹³
As a result of C-NMR measurement, the undecenol content was 2.25.
It was mol%.

Example-2 Toluene was used as a polymerization solvent in the copolymerization of Example-1.
Using 00 ml, 10 -undecen-1-ol / TiB
A contact product of 0.1 mol, component (B) methylisobutylalumoxane 10 mmol, component (A) dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride 2 μmol, 40 ° C., 7 kg / cm ²
-Polymerized with G for 2 hours. The results are shown in Table-1.

Example 3 Contact between polar vinyl monomer and trialkylaluminum
Preparation of catalytic product Instead of using 160 ml of toluene, 40 ml of 10-undecen-1-ol, 20 ml (170 mmol) of 5-hexen-1-ol and 80 ml of toluene, instead of TiBA diluted in 300 ml of toluene. 33.7 g of TiBA diluted with 200 ml of toluene
A contact product was prepared according to Example-1, except that (170 mmol) was added dropwise. Production of α-Olefin Copolymer All the polymerizations were carried out according to Example-2 except that the 5-hexen-1-ol contact product obtained above was used. Table of results
Shown in 1.

Example 4 Contact between polar vinyl monomer and trialkylaluminum
Preparation of catalytic product After mixing 40 ml (197 mmol) of 10-undecenoic acid and 160 ml of toluene, 58.5 g (296 mmol) of triisobutylaluminum was added to 300 ml of toluene.
The solution diluted to ml was added dropwise over 1 hour. After completion of the dropping, the temperature was heated to 70 ° C. and the reaction was further performed for 3 hours to obtain a contact product. Production of α-Olefin Copolymer All the polymerizations were carried out under the same conditions as in Example-2 except that the contact product obtained above was used as 10-undecenoic acid in a molar ratio of 0.03 with respect to propylene. The results are shown in Table-1
Shown in.

Example-5, Comparative Example-1 , Production of Contact Product of 1,2 Polar Vinyl Monomer In the production of the contact product of Example-1, instead of triisobutylaluminum, trimethylaluminum (Example 5 ), Polyisobutylalumoxane (manufactured by Tosoh Akzo Co., Ltd.) (Comparative Example 1), or diethylaluminum chloride (Comparative Example 2) in an amount of 234 mmol, respectively, and all were produced under the same conditions as in Example-1. Production of α-Olefin Copolymer All were polymerized under the same conditions as in Example-2 except that the contact product obtained above was used as a polar vinyl monomer in a molar ratio of 0.03 to propylene. . The results are shown in Table-1.

[0050]

[Table 1]

Example 6 Preparation of Component (A) Isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride was synthesized by the following method. Add THF to a 500 ml flask with sufficient nitrogen substitution.
After introducing 200 ml and 5 g of fluorene and cooling to −50 ° C. or lower, 67 ml of a dilute solution of methyllithium diethyl ether (1.4 M) was added dropwise over 30 minutes, and then gradually warmed to room temperature and reacted for 3 hours. . Then again -5
After cooling to 0 ° C. or below, 6,6-dimethylfulvene 10
g was added dropwise over 30 minutes. After completion of the dropping, the temperature was slowly raised to room temperature and the reaction was performed for 2 days and nights. After the reaction was completed, H ₂ O was added to 6
The reaction was stopped by adding 0 ml, the ether layer was separated, dried over anhydrous MgSO ₄ , and the ether was evaporated to dryness to give 2-cyclopentadienyl 2
17.6 g of crude fluorenylpropane crystals were obtained. Then, 10 g of the above-mentioned crude crystal was diluted with 100 ml of THF, and -5
Cooled to below 0 ° C., n-butyllithium 46.0 ml
(0.0736 mol) was added dropwise over 10 minutes. The mixture was returned to room temperature over 1 hour and reacted at room temperature for 2 hours. Next, the solvent was evaporated and dried under a nitrogen stream, 100 ml of dichloromethane was added, and the mixture was cooled to -50 ° C or lower. Next, a solution prepared by previously mixing 8.16 g of zirconium tetrachloride in 50 ml of dichloromethane at low temperature was fed all at once. After mixing, the temperature was slowly raised over 3 hours, and the reaction was carried out at room temperature for one day. After the reaction was completed, the solid matter was filtered off, and the filtrate was concentrated and recrystallized to give 4.68.
g of red isopropylidene (cyclopentadienyl)
A (fluorenyl) zirconium dichloride component (A) was obtained. Production of α-Olefin Copolymer All components were polymerized under the same conditions as in Example-2 except that the component (A) obtained above was used in an amount of 2 μm. The results are shown in Table-2.

Example 7 Preparation of Component (A) Dimethylsilylenebis (2-methylindenyl) zirconium dichloride was prepared by the following method. 500 ml
In a glass reaction vessel, 4.3 g of 2-methylindene
(33 mmol) was dissolved in 80 ml of tetrahydrofuran, and 21 ml of a 1.6 M hexane solution of n-butyllithium was slowly added dropwise to the reaction vessel while cooling. After stirring at room temperature for 1 hour, cooling again, 2.1 g of dimethyldichlorosilane was slowly added dropwise, and after stirring at room temperature for 12 hours,
50 ml of water was added, the organic phase was separated and dried to obtain 3.5 g of dimethylbis (2-methylindenyl) silane.
Dimethylbis (2-methylindenyl) obtained by the above method
3.5 g of silane was dissolved in 7.0 ml of tetrahydrofuran, and 13.9 ml of a 1.6 M hexane solution of n-butyllithium was slowly added dropwise under cooling. After stirring at room temperature for 3 hours, 2.6 g (11 mmol) of zirconium tetrachloride /
Slowly add dropwise to a solution of 60 ml of tetrahydrofuran,
After stirring for 5 hours, hydrogen chloride gas was blown in and then dried. Subsequently, methylene chloride was added to separate the soluble matter and crystallize at low temperature to obtain 0.45 g of orange powder. Production of α-Olefin Copolymer All components were polymerized under the same conditions as in Example-2 except that the component (A) obtained above was used in an amount of 2 μm. The results are shown in Table-2.

Comparative Example-3 0.2 g of titanium trichloride manufactured by Marubeni Solvay Co. as the component (A) and diethyl as the component (B) instead of the components (A) and (B) for producing the α-olefin copolymer. 1.0 g of aluminum chloride
Polymerization was carried out under the same conditions as in Example-2 except that the polymerization was carried out. The results are shown in Table-2.

Example-8Production of α-olefin copolymer Stirring and temperature control equipment fully replaced with propylene gas
Stainless steel auto with an internal volume of 1.5 liter
Add 3 times of deaerated and deoxygenated toluene to the clave.
00 ml, 10-undecen-1-ol 20 ml (9
8 mmol) and then triisobutylaluminium
29.0 g (146 mmol) of n-heptane
Introduce 200 ml diluent and stir for 30 minutes at 30 ° C.
It was Then, the component (B) was synthesized in Example-1 and
10 mmol tylisobutylalumoxane, ingredient
As (A) dimethylsilylene bis (tetrahydroin
2 μmol of phenyl) zirconium dichloride was added
After that, the propylene pressure is 7 kg / cm ²・ Pressurize to G, 4
Polymerization was carried out at 0 ° C. for 2 hours. The results are shown in Table-2.

[0055]

[Table 2]

Example 9 Production of α-Olefin Copolymer A fully degassed and deoxygenated toluene was placed in a stainless steel autoclave with an internal volume of 1.5 liter equipped with a stirring and temperature control device, which was sufficiently substituted with ethylene gas. 400
ml, 0.1 mol of a contact product of 10-undecen-1-ol and TiBA obtained in Example-1, and methylisobutylalumoxane 10 obtained in Example-1 as the component (B).
2 μm of dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride as component (A)
mol introduced, ethylene pressure at 65 ° C 2 kg / cm ² ·
Polymerization with G for 2 hours. As a result, 27.8 g of a desired copolymer was obtained. As a result of IR spectrum measurement, undecenol was contained at 1.87 mol%, the melting point of the polymer was 122.5 ° C., and MI (190 ° C.) was 0.5 g /
It was 10 minutes.

[0057]

INDUSTRIAL APPLICABILITY According to the present invention, an α-olefin copolymer having a high content of a polar vinyl monomer and having excellent adhesiveness, printability, hydrophilicity and compatibility in a polymer blend can be obtained in a high yield. It becomes possible to manufacture.

[Brief description of drawings]

FIG. 1 is for helping understanding of the technical content of the present invention.

Front page continuation (72) Inventor Toshio Asada 1 Toho-cho, Yokkaichi, Mie Prefecture Yokkaichi Research Institute, Mitsubishi Yuka Co., Ltd. (56) Reference JP-A-3-177403 (JP, A) JP-A-4-218514 (JP, A) JP 59-80413 (JP, A) JP 59-80414 (JP, A) JP 5-320256 (JP, A) JP 4-306208 (JP, A) JP-A-55-118905 (JP, A) JP-A-52-51488 (JP, A) JP-A-55-98209 (JP, A) JP-A-3-207707 (JP, A) JP-A-4-309507 ( JP, A) JP-A-4-45108 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (5)

(57) [Claims] 1. An α-olefin having 2 to 20 carbon atoms and a general formula (I), CH ₂ ═CH—C _n H _2n —X (I) (wherein, X is OH, SH, COOH, NH ₂ , NHR ¹
Or each group of NR ¹ _2, n is an integer of 1 to 20, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, when R ¹ there are a plurality, may be the same or different, each Represent)
In the method for producing an α-olefin copolymer by polymerizing a polar vinyl monomer represented by the formula (3) in the presence of a catalyst, a trialkylaluminum is added to the polar vinyl monomer.
And 1.0 to 3.0 moles the amount of um compound, using a polar vinyl monomer into the polymerization mixture was allowed to pre-contact with the trialkyl aluminum compound and the catalyst are the following components (A) and (B ) Is a combination of these, and the manufacturing method of the alpha olefin copolymer characterized by the above-mentioned. Component (A) of the periodic table having at least one five-membered ring conjugated IV B group Qian <br/> transfer metal compound, component (B) an organoaluminum oxy-compound. 2. that the α-olefin is propylene
The α-olefin copolymer according to claim 1, characterized in that
Manufacturing method. 3. X is OH.
Alternatively, the method for producing an α-olefin copolymer according to item 2. 4. Claims characterized in that X is COOH
Item 1. Production of α-olefin copolymer according to item 1 or 2
Law. 5. Trialkyl aluminum compound
It is sobutylaluminum.
To the production of the α-olefin copolymer according to any one of
Law.