JP3422426B2 - Olefin-based unsaturated copolymer, method for producing the same, and modified copolymer using the unsaturated copolymer - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel olefinic unsaturated copolymer, a method for producing the same, and a modified copolymer using the unsaturated copolymer. More specifically, the present invention provides an olefin copolymer having a reactive unsaturated group obtained by copolymerizing an α-olefin having 2 to 12 carbon atoms and a non-conjugated diene, and an efficient production of the same. And a method of modifying the olefin-based copolymer so that the reactive unsaturated group has a hydroxyl group, a carboxyl group,
It has excellent adhesiveness, printability, hydrophilicity, polymer modification, antistatic property, and flame retardancy obtained by introducing functional groups such as epoxy group, halogen group, nitro group, amino group, acyl group, and sulfone group. It relates to a modified copolymer.

[0002]

2. Description of the Related Art A homopolymer of α-olefin and its copolymer are inexpensive and have excellent mechanical strength, luster, transparency, moldability, moisture resistance, chemical resistance and the like. Therefore, it is widely used for various applications in many fields. However, since this α-olefin polymer has a non-polar molecular structure, it has a poor affinity with other substances, and has the drawback of being extremely inferior in adhesiveness, paintability, printability, antistatic properties, and the like. is doing.

In order to make up for such drawbacks, for example, (1) a part of the polymer is oxidized by a chromic acid mixture or flame treatment, and (2) a polar group-containing compound such as maleic anhydride by a radical generator. , Methyl methacrylate,
Methods such as graft modification with acrylonitrile or (3) copolymerization with a polar group-containing comonomer have been proposed. However, the above method (1) is greatly limited in industrial practice because the treatment agent has strong acidity or toxicity, or the treatment conditions are difficult and the effect is not uniform. In addition, although the method of (2) has been partially put into practical use, it is inevitable that the properties of the modified polymer will deteriorate due to deterioration and cross-linking, and it will meet increasingly sophisticated requirements for use conditions and usage forms. The reality is that they are not fully used. Furthermore, the method of (3) is still in the realm of ideas,
Many problems need to be solved for practical use.

Various techniques have been proposed so far for the purpose of solving these problems. For example, in JP-A-56-30413, ethylene and branched 1,4
-A method by copolymerization with a diene is also disclosed in JP-A-61-
Japanese Patent No. 85405 discloses a method by copolymerization of propylene and 1,4-dienes. These methods make it possible to produce a copolymer having a 1,1-disubstituted olefin in a side chain (that is, having a pendant olefin) by using a bifunctional olefin having different reactivity. However, this pendant olefin has the drawback of being susceptible to chemical reaction constraints due to the branched structure. For example, the graft reaction with polar monomers and olefins is extremely difficult. Also, originally,
Since the copolymerizability of olefins and 1,4-dienes is low, it is necessary to use a large amount of expensive 1,4-diene compounds in the production of unsaturated copolymers. Therefore, there is a problem that the copolymer production amount (that is, the catalyst activity) with respect to the amount of the catalyst used is low and the catalyst cost tends to be high because it is necessary to introduce a large amount of the above into the polymerization system.

Furthermore, "Polymer Bulletin (Polymer
Bulletin) ", Volume 10, Page 109 (1983)
Also describes a similar copolymerization method. However, although this method has an advantage that gelation reaction is relatively unlikely to occur, gelling is substantially generated when a high concentration of unsaturated group is contained, which is not preferable.

Further, a method by copolymerization of α-olefin and divinylbenzene has been disclosed (Japanese Patent Laid-Open No. 1-11).
18510 and Japanese Patent Laid-Open No. 1-123811).
However, in this method, since the divinylbenzene has a double bond having the same reactivity, a cross-linking reaction occurs in the copolymerization process with the α-olefin, and the divinylbenzene tends to be insoluble and infusible. Further, since the conversion rate of divinylbenzene to the copolymer is low and many divinylbenzene monomers remain in the copolymer, it is necessary to remove the monomer when carrying out a graft reaction or a polymer reaction subsequently. Have a problem. Further, the pendant olefin becomes a styrenic monomer, and has a drawback that it is restricted in the graft reaction of olefin and the like.

Regarding other copolymers of α-olefin and non-conjugated diene, JP-A-2-269109, JP-A-3-221508 and JP-A-4-469.
The contents are disclosed in detail in Japanese Patent Publication No. 09. However, in recent years, among the linear non-conjugated dienes, 2 of 2-substituted form
-Methyl-1,5-hexadiene is a catalyst system comprising a combination of a homogeneous transition metal compound and an aluminoxane or a compound capable of reacting with the transition metal compound to form an ionic complex. It has been reported to be carried out [Journal of the American Chemical Society (J. Am. Chem. Soc.)] Volume 114, 356.
5 to 3567 (1992)], problems such as improvement of copolymerizability with olefins, prevention of deterioration of catalytic activity during polymerization, and suppression of side reactions such as cyclization reaction and cross-linking reaction on the produced polymer chain continue. Remaining.

When ω-alkenyl styrene is used, a conventional anionic polymerization catalyst is used in the o-allyl styrene system described in "Polymer Chemistry", Vol. 29, No. 328, page 593 (1972). It has been reported that, when homopolymerization of o-allylstyrene is carried out using a cationic polymerization catalyst, structure selectivity is exhibited depending on the catalyst species. However, it is difficult to produce an olefin copolymer with these catalyst systems.

A similar copolymer is disclosed in JP-A-62-95303, but this is a long-chain branched polyethylene copolymer because it is a high-pressure radical polymerization. It has a low density and therefore has a drawback of low strength and low elastic modulus. In addition, the residual double bond is olefinic and has only reactivity with olefins,
There is also a drawback that the graft modification is limited and the reaction with the polar vinyl monomer cannot be performed. As described above, it is the actual situation that the conventional improved techniques cannot provide satisfactory results.

On the other hand, a number of techniques have been known so far for olefin-based modified copolymers. Japanese Patent Laid-Open No. 4-20510 discloses a technique relating to an olefin-based modified copolymer. However, these have been found to be patentable in the production of reaction precursors mainly used for modification reactions,
The denaturation reaction itself is a combination of known techniques.

[0011]

SUMMARY OF THE INVENTION The present invention overcomes the drawbacks of the prior art and provides an unsaturated group-containing olefin-based copolymer with less gel formation, and adhesiveness, printability and hydrophilicity. The purpose of the present invention is to provide a modified olefin-based copolymer rich in polymer modifying property, antistatic property, flame retardancy and the like.

[0012]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies on unsaturated group-containing olefin copolymers. It was found that the cyclization polymerization did not proceed in the polymerization with the transition metal catalyst system, and the good copolymerization reaction proceeded in the copolymerization with olefins without the crosslinking reaction or the cyclization polymerization. It was also found that a modified copolymer suitable for the above purpose can be obtained by introducing an appropriate functional group into the unsaturated bond introduced into the side chain by this copolymerization reaction. The present invention has been completed based on such findings. That is, the present invention is an α- having 2 to 12 carbon atoms.
At least one selected from olefins and the general formula (I)

[0013]

[Chemical 2]

(In the formula, R ^{1 to} R ⁷ each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, which may be the same or different, and R ⁸ is an alkyl group having 1 to ⁸ carbon atoms. A group, Q is a divalent organic group having 1 to 20 carbon atoms), and is a unit derived from the non-conjugated diene and obtained by copolymerization with at least one selected from the non-conjugated dienes. Is 10 ^{−6 to} 20 mol%, and the reduced viscosity measured at a concentration in decalin at 135 ° C. of 0.05 g / deciliter is 0.01 to 30 deciliter / g. The present invention provides a copolymer and a modified copolymer having a functional group introduced into at least 5 mol% of unsaturated bonds of the olefinic unsaturated copolymer by a chemical reaction. In addition, the olefinic unsaturated copolymer has an α of 2 to 12 carbon atoms.
At least one selected from olefins and at least one selected from non-conjugated dienes represented by general formula (I), (A) transition metal compound and (B) the transition metal compound or It can be produced by copolymerizing the derivative thereof in the presence of a catalyst containing a compound capable of forming an ionic complex as a main component.

In the olefinic unsaturated copolymer of the present invention, the number of carbon atoms used as one component of the raw material monomer is 2
Examples of the α-olefin of to 12 include ethylene; propylene; butene-1; pentene-1; hexene-1;
Heptene-1; Octene-1; Nonene-1; Decene-
1; 4-phenylbutene-1; 6-phenylhexene-
1; 3-methylbutene-1; 4-methylpentene-1;
3-methylpentene-1; 3-methylhexene-1; 4
-Methylhexene-1; 5-methylhexene-1; 3,
3-dimethylpentene-1; 3,4-dimethylpentene-1; 4,4-dimethylpentene-1; vinylcyclohexane; α-olefins such as vinylcyclohexene,
Hexafluoropropene; Tetrafluoroethylene; 2
-Fluoropropene; fluoroethylene; 1,1-difluoroethylene; 3-fluoropropene; trifluoroethylene; halogen-substituted α-olefins such as 3,4-dichlorobutene-1.

These α-olefins may be used alone or in combination of two or more kinds,
Moreover, you may use it in combination with a cyclic olefin depending on the case. Examples of the cyclic olefin include cyclopentene; cyclohexene; norbornene; 5-methylnorbornene; 5-ethylnorbornene; 5-propylnorbornene; 5,6-dimethylnorbornene; 1-methylnorbornene; 7-methylnorbornene; -Trimethylnorbornene; 5-phenylnorbornene; 5
-Benzyl norbornene; 5-ethylidene norbornene; 5-vinyl norbornene and the like. These cyclic olefins may be used alone or in combination of two or more.

On the other hand, the non-conjugated diene used as the other component (comonomer) of the raw material monomer is represented by the general formula (I)

[0018]

[Chemical 3]

At least one selected from the compounds represented by the formulas (wherein R ^{1 to} R ⁸ and Q are the same as above). In the general formula (I), R ^{1 to} R ⁷
Each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, which may be the same or different. R
⁸ represents an alkyl group having 1 to ⁸ carbon atoms. The carbon number 1 to
The alkyl group of 8 may be linear, branched or cyclic, and specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group and a heptyl group. , Octyl group and the like. Q is a divalent organic group having 1 to 20 carbon atoms, and specific examples thereof include an alkylene group having 1 to 20 carbon atoms,
Examples thereof include an alkenylene group, a cycloalkylene group, a cycloalkenylene group, a divalent substituted aromatic group and a divalent polycyclic hydrocarbon group.

Specific examples of the non-conjugated diene represented by the above general formula (I) include 3-methyl-1,5-hexadiene; 3-ethyl-1,5-hexadiene; 3,4-dimethyl-1, 5-hexadiene; 3-methyl-1,7-octadiene; 3-ethyl-1,7-octadiene; 3,
4-dimethyl-1,7-octadiene; 3,5-dimethyl-1,7-octadiene and the like can be mentioned.
These non-conjugated dienes may be used alone or in combination of two or more. The olefinic unsaturated copolymer of the present invention is selected from at least one selected from α-olefins having 2 to 12 carbon atoms and a non-conjugated diene represented by the general formula (I). By copolymerizing at least one kind with (A) a transition metal compound and (B) a transition metal compound or a compound containing an ionic complex-forming compound as a main component, which is capable of forming an ionic complex,
can get. As the transition metal compound of the component (A) in the catalyst, a transition metal compound containing a metal belonging to Group 3 to 10 of the periodic table or a lanthanoid series metal can be used. Specific examples of the transition metal include titanium, zirconium, hafnium, vanadium, chromium,
Manganese, nickel, palladium, platinum or the like is preferable, and zirconium, hafnium, titanium, vanadium or chromium is particularly preferable. Examples of such a transition metal compound include various compounds, particularly Group 4 and 8 to 1
A compound containing a Group 0 transition metal, especially a compound containing a transition metal selected from Group 4 of the periodic table, that is, a compound containing titanium, zirconium, or hafnium can be preferably used. In particular, the general formula ^{_{CpM 1 R 9 a R 10 b}} R 11 c ··· (II) Cp 2 M 1 R 9 a R 10 b ··· (III) (Cp-A e -Cp) M 1 R 9 a compound or its derivative represented by R ¹⁰ _b ··· (IV) or formula ^{_{M 1 R 9 a R 10 b}} R 11 c R 12 d ··· (V) are preferred.

In the above general formulas (II) to (V), M¹
Is the periodic table of titanium, zirconium or hafnium
Indicates a Group 4 transition metal, Cp is cyclopentadienyl
Group, substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, tetrahydroindenyl group, substituted tetra
Hydroindenyl group, fluorenyl group or substituted fluorescein
Cyclic unsaturated hydrocarbon group such as nyl group or chain unsaturated carbonization
Indicates a hydrogen group. R⁹, R ^Ten, R¹¹And R¹²Each is German
Vertical σ-bonding ligand, chelating ligand, Lewis salt
A ligand such as a group is shown, and as a σ-bonding ligand,
Physically, hydrogen atom, oxygen atom, halogen atom, carbon number 1
~ 20 alkyl groups, C1-20 alkoxy groups,
C6-C20 aryl group, alkylaryl group
Or arylalkyl group, acyloxy group having 1 to 20 carbon atoms
Si group, allyl group, substituted allyl group, substitution containing silicon atom
Groups and the like, and as the chelating ligand,
Acetylacetonate group, Substituted acetylacetonate group
Can be exemplified. A indicates crosslinking by covalent bond.
a, b, c and d are each independently an integer of 0 to 4, and e is
Indicates an integer of 0 to 6. R⁹, R^Ten, R¹¹And R¹²Is that
Two or more may combine with each other to form a ring. Cp above
Has a substituent, the substituent has 1 to 20 carbon atoms.
Alkyl groups of are preferred. Smell of formula (III) and formula (IV)
Therefore, two Cp's may be the same or different from each other.
It may be

Substituted cyclohexyl in the above formulas (II) to (IV)
Examples of the pentadienyl group include methylcyclopenta
Dienyl group, ethylcyclopentadienyl group; isopro
Pyrcyclopentadienyl group; 1,2-dimethylcyclo
Pentadienyl group; tetramethylcyclopentadienyl
Group; 1,3-dimethylcyclopentadienyl group; 1,
2,3-trimethylcyclopentadienyl group; 1,2,
4-trimethylcyclopentadienyl group; pentamethyl
Cyclopentadienyl group; trimethylsilylcyclopen
Examples thereof include a tadienyl group. In addition, (II) ~
R in formula (V) ⁹~ R¹²For example,
Fluorine atom, chlorine atom, bromine atom as halogen atom,
Iodine atom, methyl as an alkyl group having 1 to 20 carbon atoms
Group, ethyl group, n-propyl group, isopropyl group, n-
Butyl group, octyl group, 2-ethylhexyl group, carbon number
Methoxy group and ethoxy as the alkoxy group of 1 to 20
Group, propoxy group, butoxy group, phenoxy group, carbon number
6 to 20 aryl groups, alkylaryl groups or
Phenyl group, tolyl group, xylyl as reel alkyl group
Group, benzyl group, and acyloxy group having 1 to 20 carbon atoms
The heptadecylcarbonyloxy group and silicon atom.
Trimethylsilyl group as a substituent, (trimethylsilyl group
) Methyl group, dimethyl ether as a Lewis base, di-
Ethers such as ethyl ether and tetrahydrofuran
, Thioethers such as tetrahydrothiophene,
Esters such as tylbenzoate, acetonitrile;
Nitriles such as benzonitrile, trimethylamine;
Triethylamine; tributylamine; N, N-dimethyl
Luaniline; pyridine; 2,2'-bipyridine; phena
Amines such as nitroline, triethylphosphine;
Phosphines such as Liphenylphosphine, chain unsaturated
As hydrocarbons, ethylene; butadiene; 1-pente
Isoprene; Pentadiene; 1-Hexene and this
As a derivative thereof, as a cyclic unsaturated hydrocarbon, benzene;
Ruene; Xylene; Cycloheptatriene; Cyclooctane
Tadiene; Cyclooctatriene; Cyclooctatetra
Examples thereof include ene and derivatives thereof. Also, above
Examples of the covalent cross-linking of A in the formula (IV) include
For example, methylene bridge, dimethylmethylene bridge, ethylene
Cross-linked, 1,1'-cyclohexylene cross-linked, dimethylsilyl
Lene cross-link, dimethyl germylene cross-link, dimethyl stannile
And cross-linking.

Examples of the compound represented by the general formula (II) include (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl). Tribenzylzirconium, (pentamethylcyclopentadienyl) trichlorozirconium, (pentamethylcyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadiene (Enyl) tribenzyl zirconium, (cyclopentadienyl) trichlorozirconium, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconi (Methylcyclopentadienyl) trimethylzirconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) ) Dimethyl (methoxy) zirconium, (dimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium, and the like, Among these, compounds in which zirconium is replaced with titanium or hafnium are mentioned.

Examples of the compound represented by the general formula (III) include bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) diethylzirconium, bis ( Cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium, bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydride Zirconium, bis (methylcyclopentadienyl) dimethylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclopentadienyl) dibenzylzirconium, bis (pentamethyi) Rucyclopentadienyl) dimethyl zirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, bis (pentamethylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) chloromethylzirconium, bis (penta Methylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl)
(Pentamethylcyclopentadienyl) dichlorozirconium and the like, as well as compounds in which zirconium is replaced with titanium or hafnium.

Examples of the compound represented by the general formula (IV) include ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) dichlorozirconium, ethylenebis (tetrahydroindenyl).
Dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium, dimethylsilylenebis (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) Dimethylzirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dichlorozirconium, [phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, diphenylmethylene (cyclopentadienyl) (9 -Fluorenyl) dimethyl zirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexalidene (9-fluorenyl ) (Cyclopentadienyl) dimethylzirconium, cyclopentylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclobutylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylene (9-fluorenyl) ) (Cyclopentadienyl) dimethyl zirconium, dimethylsilylene bis (2,3,5
-Trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dimethylzirconium, dimethylsilylenebis (indenyl) dichlorozirconium, etc. Alternatively, a compound can be given by substituting with hafnium.

Further, examples of the compound represented by the general formula (V) include tetramethylzirconium, tetrabenzylzirconium, tetramethoxyzirconium,
Tetraethoxyzirconium, tetrabutoxyzirconium, tetrachlorozirconium, tetrabromozirconium, butoxytrichlorozirconium, dibutoxydichlorozirconium, bis (2,5-di-t-butylphenoxy) dimethylzirconium, bis (2,5-di-t -Butylphenoxy) dichlorozirconium, zirconium bis (acetylacetonate), and the like, and compounds in which zirconium is replaced with titanium or hafnium.

Further, as the component (A), in the general formula (IV), two substituted or unsubstituted conjugated cyclopentadienyl groups (provided that at least one is a substituted cyclopentadienyl group). A group 4 transition metal compound having a multicoordinating compound as a ligand, which is bonded to each other via an element selected from group 14 of the periodic table, can be preferably used. Examples of such a compound include general formula (VI)

[0028]

[Chemical 4]

Examples of the compound represented by
be able to. Y in the general formula (VI)¹Is carbon, Kei
Element, germanium or tin atom, R¹³ _t-C_FiveH_4-tOver
And R¹³ _u-C_FiveH_4-uAre each substituted cyclopentadiene
The nyl group, t and u represent an integer of 1 to 4. Where R¹³
Are hydrogen atoms, silyl groups or hydrocarbon groups,
It may be one or different. Also, at least one piece
The other cyclopentadienyl group is Y¹Is bound to
R on at least one carbon next to the carbon¹³Exists.
R¹⁴Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or carbon
An aryl group of formula 6 to 20, an alkylaryl group or
Indicates an arylalkyl group. M²Is titanium, zirconium
Or a hafnium atom, X¹Is a hydrogen atom, halogen
Atom, alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Aryl group, alkylaryl group or aryl group of
It shows a alkyl group or an alkoxy group having 1 to 20 carbon atoms. X
¹R may be the same or different from each other, and R¹⁴Also
They may be the same or different from each other.

Examples of the substituted cyclopentadienyl group in the above general formula (VI) include methylcyclopentadienyl group; ethylcyclopentadienyl group; isopropylcyclopentadienyl group; 1,2-dimethylcyclopentadienyl group. Group; 1,3-dimethylcyclopentadienyl group; 1,2,3-trimethylcyclopentadienyl group;
Examples include 1,2,4-trimethylcyclopentadienyl group. Specific examples of X ¹ include F, Cl, Br, I as a halogen atom, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an octyl group as an alkyl group having 1 to 20 carbon atoms, 2-ethylhexyl group, methoxy group as an alkoxy group having 1 to 20 carbon atoms,
Examples of the ethoxy group, propoxy group, butoxy group, phenoxy group, aryl group having 6 to 20 carbon atoms, alkylaryl group or arylalkyl group include phenyl group, tolyl group, xylyl group and benzyl group. Specific examples of R ¹⁴ include a methyl group, an ethyl group, a phenyl group, a tolyl group, a xylyl group, and a benzyl group. Examples of the compound represented by the general formula (VI) include dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, and compounds obtained by substituting zirconium with titanium or hafnium. . Furthermore, the general formula (VII)

[0031]

[Chemical 5]

It also includes compounds represented by: The general formula
In the compound of (VII), Cp is cyclopentadienyl
Group, substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, tetrahydroindenyl group, substituted tetra
Hydroindenyl group, fluorenyl group or substituted fluorescein
Cyclic unsaturated hydrocarbon group such as nyl group or chain unsaturated carbonization
Indicates a hydrogen group. M³Is titanium, zirconium or hafni
X represents a um atom²Is hydrogen atom, halogen atom, carbon
C1-C20 alkyl group, C6-C20 aryl
Group, alkylaryl group or arylalkyl group, or
Represents an alkoxy group having 1 to 20 carbon atoms. Z is SiR¹⁵
₂, CR¹⁵ ₂ , SiR¹⁵ ₂SiR¹⁵ ₂ , CR¹⁵ ₂CR¹⁵
₂ , CR¹⁵ ₂CR¹⁵ ₂CR¹⁵ ₂ , CR¹⁵= CR¹⁵, CR
¹⁵ ₂SiR¹⁵ ₂Or GeR¹⁵ ₂ Indicates Y²Is -N (R
¹⁶)-, -O-, -S- or -P (R¹⁶) -Indicates. Up
Note R¹⁵Is a hydrogen atom or an atom having up to 20 non-hydrogen atoms
Rualkyl, aryl, silyl, alkyl halide, halo
A group selected from aryl gen groups and combinations thereof
Yes, R¹⁶Is alkyl having 1 to 10 carbons or the number of carbons
6-10 aryl groups, or one or more
R above¹⁵To form a fused ring system of up to 30 non-hydrogen atoms
You may. w represents 1 or 2.

Transitions containing transition metals of groups 5 to 10
The metal compound is not particularly limited, and a vanadium compound
As specific examples of, vanadium trichloride, vanadyl
Trichloride, vanadium triacetylacetonate,
Vanadium tetrachloride, vanadium tributoxy
De, vanadyl dichloride, vanadyl bisacetylacetate
Nato, vanadyl triacetylacetonate, dibenze
Nvanadium, dicyclopentadienyl vanadium, di
Cyclopentadienyl vanadium dichloride, cyclope
Interdienyl vanadium trichloride, dicyclopenta
Dienyl methyl vanadium etc. are mentioned. Chromation
Specific examples of the compound include tetramethyl chromium, tetra
(T-Butoxy) chromium, bis (cyclopentadiene)
) Chromium, hydridotricarbonyl (cyclopentadiene
(Phenyl) chromium, hexacarbonyl (cyclopentadiene)
Nyl) chromium, bis (benzene) chromium, tricarboni
Lutris (triphenylphosphonate) chromium, Tris
(Allyl) chromium, triphenyl tris (tetrahydro
Furan) chrome, chrome tris (acetylacetoner)
G) etc. Specific examples of manganese compounds
Is a tricarbonyl (cyclopentadienyl) manga
, Pentacarbonylmethylmanganese, bis (cyclope
N-dienyl) manganese, manganese bis (acetylacetate)
Tonato) and the like. Specific examples of nickel compounds
As dicarbonylbis (triphenylphosphine
Nickel), dibromobis (triphenylphosphine)
Nickel), dinitrogen bis [bis (tricyclohexyl)
Phosphine) nickel], chlorohydridobis (tris
Chlorohexylphosphine) Nickel, Chloro (phenyl)
Ru) bis (triphenylphosphine) nickel, dimethyl
Rubis (trimethylphosphine) nickel, diethyl
(2,2'-bipyridyl) nickel, bis (allyl) di
Nickel, bis (cyclopentadienyl) nickel, bis
(Methylcyclopentadienyl) nickel, bis (pen
Tamethylcyclopentadienyl) nickel, allyl
Chlopentadienyl) nickel, (cyclopentadienyl)
) (Cyclooctadiene) nickel tetrafluoroboro
Acid salt, bis (cyclooctadiene) nickel, nickel
Bisacetylacetonate, allyl nickel chloride,
Tetrakis (triphenylphosphine) nickel, chloride
Nickel, formula (C₆H_Five) Ni [OC (C₆H_Five) CH = P (C
₆H_Five)₂] [P (C₆H_Five)₃], (C₆H_Five) Ni [OC (C₆H_Five) C (SO₃Na) = P
(C₆H_Five)₂] [P (C ₆H_Five)₃] And the like.

Specific examples of the palladium compound include dichlorobis (benzonitrile) palladium, carbonyltris (triphenylphosphine) palladium, dichlorobis (triethylphosphine) palladium, bis (isocyanated-t-butyl) palladium, and palladium bis (acetylacetate). Nato), dichloro (tetraphenylcyclobutadiene) palladium, dichloro (1,5-cyclooctadiene) palladium, allyl (cyclopentadienyl) palladium, bis (allyl) palladium, allyl (1,5-cyclooctadiene) palladium Tetrafluoroborate, (acetylacetonate) (1,5-
Examples thereof include cyclooctadiene) palladium tetrafluoroborate and tetrakis (acetonitrile) palladium ditetrafluoroborate. In the polymerization catalyst used in the present invention, the transition metal compound as the component (A) may be used alone or in combination of two or more, and those modified with an electron donating compound should be used. You can

On the other hand, as the compound capable of forming an ionic complex from the transition metal compound of the component (A) or its derivative used as the component (B) in the polymerization catalyst, (B-1) The ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, and the aluminoxane (B-2) can be exemplified. As the compound of the component (B-1), any compound can be used as long as it can react with the transition metal compound of the component (A) to form an ionic complex. A compound composed of an anion bonded to an element, particularly a coordination complex compound composed of a cation and an anion having a plurality of groups bonded to the element can be preferably used. As a compound composed of such a cation and an anion in which a plurality of groups are bound to an element, a compound represented by the general formula ([L ¹ -R ¹⁷ ] ^{k +} ) _p ([M ⁴ Z ¹ Z ² ·· Z ⁿ ] ^{(hg) -} ) _Q・ ・ ・ (VIII) or ([L ² ] ^{k +} ) _p ([M ⁵ Z ¹ Z ² ·· Z ⁿ ] ^(hg)- ) _q・ ・ ・ (IX) (where L ² is M ⁶ , R ¹⁸ R ¹⁹ M ⁷ , R ²⁰ ₃ C or R ^21
7 is a) wherein M, L ¹ Group 5 Lewis base, M ⁴ and M ^5, respectively Periodic Table, Group 6, Group 7, 8-10, 11, Group 12
An element selected from Group 13, 13, 14 and 15 groups, preferably an element selected from Group 13, 14 and 15 groups, M
⁶ and M ⁷ are the 3rd, 4th, 5th, and 6th groups of the periodic table, respectively.
An element selected from Group 7, Group 7, 8-10, Group 1, 11, Group 2, 12 and Group 17, Z ^{1 to} Z ⁿ are a hydrogen atom, a dialkylamino group, and an alkoxy group having 1 to 20 carbon atoms, respectively. Group, aryloxy group having 6 to 20 carbon atoms, 1 to carbon atoms
20 alkyl group, C 6-20 aryl group, alkylaryl group, arylalkyl group, C 1-20
Represents a halogen-substituted hydrocarbon group, an acyloxy group having 1 to 20 carbon atoms, an organic metalloid group or a halogen atom,
¹ to Z ⁿ may form a ring of two or more thereof with each other. R ¹⁷ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R ¹⁸ and R ¹⁹ each represent a cyclopentadienyl group or a substituted cyclopenta group. Dienyl group, indenyl group or fluorenyl group, R ²⁰ has 1 carbon atom
To 20 alkyl groups, aryl groups, alkylaryl groups or arylalkyl groups. R ²¹ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. g is an valence of M ⁴ and M ⁵ and is an integer of 1 to 7, and h is 2
8 is an integer, k is an ionic valence of [L ¹ -R ¹⁷ ] and [L ² ] and is an integer of 1 to 7, p is an integer of 1 or more, q = (p × k) /
(H-g). ] It is a compound represented by these.

Specific examples of the Lewis base represented by L ¹ are ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, tri-n-butylamine, N. , N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N
-Amines such as dimethylaniline, phosphines such as triethylphosphine, triphenylphosphine and diphenylphosphine, ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, dioxane, thioethers such as diethylthioether and tetrahydrothiophene, ethylbenzoate And the like.

As specific examples of M ⁴ and M ⁵ ,
B, Al, Si, P, As, Sb, etc., preferably B or P, M ⁶ are exemplified by Li, Na, Ag, C.
Specific examples of M ⁷ , such as u, Br, and I, include Mn and F.
e, Co, Ni, Zn, etc. may be mentioned. Specific examples of Z ^{1 to} Z ⁿ include, for example, a dimethylamino group as a dialkylamino group; a diethylamino group, a methoxy group, an ethoxy group, an n-butoxy group, and a carbon number of 6 to 20 as an alkoxy group having 1 to 20 carbon atoms. Phenoxy group as an aryloxy group; 2,6-dimethylphenoxy group; naphthyloxy group, methyl group as an alkyl group having 1 to 20 carbon atoms;
Ethyl group; n-propyl group; isopropyl group; n-butyl group; n-octyl group; 2-ethylhexyl group, aryl group having 6 to 20 carbon atoms; phenyl group as an alkylaryl group or arylalkyl group; p-tolyl group Benzyl group; 4-t-butylphenyl group; 2,6-dimethylphenyl group; 3,5-dimethylphenyl group; 2,4-
Dimethylphenyl group; 2,3-dimethylphenyl group; p-fluorophenyl group as halogen-substituted hydrocarbon group having 1 to 20 carbon atoms; 3,5-difluorophenyl group; pentachlorophenyl group; 3,4,5-trifluoro group Phenyl group; pentafluorophenyl group; 3,5-di (trifluoromethyl) phenyl group, F, C as halogen atom
1, Br, I, pentamethylantimony group as organic metalloid group, trimethylsilyl group, trimethylgermyl group,
Examples thereof include diphenylarsine group, dicyclohexylantimony group, and diphenylboron group. Specific examples of R ¹⁷ and R ²⁰ are the same as those mentioned above.
Specific examples of the substituted cyclopentadienyl group for R ¹⁸ and R ¹⁹ include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. To be Here, the alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups is an integer of 1 to 5.

Among the compounds of the above general formulas (VIII) and (IX), those in which M ⁴ and M ⁵ are boron are preferable. Among the compounds of the general formulas (VIII) and (IX), the following compounds can be used particularly preferably. For example, as the compound of the general formula (VIII), triphenylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate,
Tetraphenylammonium tetraphenylborate, methyltri (n-butyl) ammonium tetraphenylborate,
Benzyltri (n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate,
Methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl tetraphenylborate (2-cyanopyridinium), trimethylsulfonium tetraphenylborate, benzylmethylsulfonium tetraphenylborate, triethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluoro (Phenyl) borate tri (n-butyl) ammonium, tetrakis (pentafluorophenyl) borate triphenylammonium, tetrakis (pentafluorophenyl) borate tetrabutylammonium, tetrakis (pentafluorophenyl) borate tetraethylammonium, tetrakis (pentafluorophenyl) borate [Methyltri (n-butyl) ammonium], tetrakis (pentafluorophenyl) ) Borate [benzyltri (n-butyl) ammonium], tetrakis (pentafluorophenyl) borate methyldiphenylammonium, tetrakis (pentafluorophenyl) borate methyltriphenylammonium, tetrakis (pentafluorophenyl) borate dimethyldiphenylammonium, tetrakis (pentafluoro) Phenyl) anilinium borate, tetrakis (pentafluorophenyl) methylanilinium borate,
Dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, dimethyl (m-nitroanilinium) tetrakis (pentafluorophenyl) borate, dimethyl tetrakis (pentafluorophenylmethyl) borate (p- Bromoanilinium), pyridinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (p-cyanopyridinium), tetrakis (pentafluorophenyl) borate (N-methylpyridinium), tetrakis (pentafluorophenyl) borate ( N-benzylpyridinium),
Tetrakis (pentafluorophenyl) borate (O-cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate (p-cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate (p-cyano-N-) Benzylpyridinium), tetrakis (pentafluorophenyl) borate trimethylsulfonium, tetrakis (pentafluorophenyl) borate benzyldimethylsulfonium, tetrakis (pentafluorophenyl) borate tetrafelphosphonium, tetrakis (3,5-ditrifluoromethylphenyl) borate dimethylani Lithium, tris (pentafluorophenyl)
Dimethylanilinium (p-trifluoromethyltetrafluorophenyl) borate, triethylammonium tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) borate, tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) ) Pyridinium borate, tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) borate (N-methylpyridinium), tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) borate (O-cyano- N-methylpyridinium), tris (pentafluorophenyl)
(P-Trifluoromethyltetrafluorophenyl) borate (p-cyano-N-benzylpyridinium), tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) borate triphenylphosphonium, tris (pentafluorophenyl) ( 2, 3, 5,
Dimethylanilinium 6-tetrafluoropyridinyl) borate, tris (pentafluorophenyl) (2,3,3
5,6-Tetrafluoropyridinyl) borate triethylammonium, tris (pentafluorophenyl) (2,
3,5,6-Tetrafluoropyridinyl) pyridinium borate, tris (pentafluorophenyl) (2,3,3
5,6-Tetrafluoropyridinyl) boric acid (N-methylpyridinium), tris (pentafluorophenyl)
(2,3,5,6-tetrafluoropyridinyl) boric acid (O-cyano-N-methylpyridinium), tris (pentafluorophenyl) (2,3,5,6-tetrafluoropyridinyl) boric acid ( p-cyano-N-benzylpyridinium), tris (pentafluorophenyl) (2,
3,5,6-Tetrafluoropyridinyl) borate triphenylphosphonium, tris (pentafluorophenyl)
Dimethylanilinium (phenyl) borate, Tris (pentafluorophenyl) [3,5-di (trifluoromethyl) phenyl] dimethylanilinium borate, Tris (pentafluorophenyl) (4-trifluoromethylphenyl) dimethylanilinium borate , Dimethylanilinium triphenyl (pentafluorophenyl) borate, triethylammonium hexafluoroarsenate, and the like.

On the other hand, examples of the compound of the general formula (IX) include ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylborate (tetraphenylporphyrin-manganese), tetrakis (pentafluorophenyl) ferrocenium borate and tetrakis. (Pentafluorophenyl) borate (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) decamethylferrocenium borate, acetylferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate Formylferrocenium, tetrakis (pentafluorophenyl) borate cyanoferrocenium, tetrakis (pentafluorophenyl) silver borate, tetrakis (pentafluorophenyl) borate tri Lithium, tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (tetraphenylporphyrin manganese), tetrakis (pentafluorophenyl) borate (tetraphenylporphyrin iron chloride), tetrakis (Pentafluorophenyl) boric acid (tetraphenylporphyrin zinc), silver tetrafluoroborate, silver hexafluoroarsenate, silver hexafluoroantimonate, etc. may be mentioned. Examples of compounds other than the general formulas (VIII) and (IX) include tris (pentafluorophenyl)
Boric acid, tris [3,5-di (trifluoromethyl) phenyl] boric acid, triphenylboric acid and the like can also be used.

The component (B-1), which reacts with the transition metal compound of the component (A) to form an ionic complex, may be used alone or in combination of two or more. Good. On the other hand, the aluminoxane as the component (B-2) is represented by the general formula (X)

[0041]

[Chemical 6]

(Wherein R ²² is an alkyl group, an alkenyl group, an aryl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms,
A hydrocarbon group such as an arylalkyl group, s represents the degree of polymerization, and is generally an integer of 3 to 50, preferably 7 to 40. ) A chain aluminoxane represented by the general formula (X)
I)

[0043]

[Chemical 7]

The cyclic aluminoxane represented by the formula (wherein R ²² and s are the same as above) can be mentioned.

Among the compounds represented by the general formulas (X) and (XI), aluminoxane having a degree of polymerization of 7 or more is preferable. When the aluminoxane having a degree of polymerization of 7 or more or a mixture thereof is used, high activity can be obtained. Further, a modified aluminoxane which is insoluble in a general solvent obtained by modifying the aluminoxane represented by the general formulas (X) and (XV) with a compound having active hydrogen such as water can also be preferably used. Examples of the method for producing the aluminoxane include a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other, but the means therefor is not particularly limited, and the reaction may be performed according to a known method. For example, an organoaluminum compound is dissolved in an organic solvent, a method of bringing it into contact with water, a method of initially adding an organoaluminum compound during polymerization, and a method of adding water later, water of crystallization contained in a metal salt, There are a method of reacting water adsorbed on an inorganic substance or an organic substance with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting with water. These aluminoxanes may be used alone or in combination of two or more. In the present invention, as the catalyst component (B), only the component (B-1) may be used, or only the component (B-2) may be used.
You may use together (1) component and (B-2) component. In the polymerization catalyst used in the present invention, if desired, (C)
Components as may be an organic metal compound represented by the general formula _{^{(XII) M 8 R 23 r}} ··· (XII). R ²³ in the general formula (XII) is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a carbon number. 7
~ 20 aralkyl groups are shown. Specific examples of R ²³ include
Examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, hexyl group, 2-ethylhexyl group and phenyl group. Also,
M ⁸ is a metal belonging to Groups 1 to 4 or 11 to 14 of the Periodic Table, and specific examples thereof include lithium, sodium, potassium, magnesium, zinc, cadmium, aluminum, boron, gallium, silicon and tin. To be r represents the valence of M ⁸ .

Among the compounds represented by the above general formula (XII), a compound in which M ⁸ is aluminum is preferable,
Examples of such compounds include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride. And ethyl aluminum sesquichloride. The organometallic compounds may be used alone or in combination of two or more.

Next, in the present invention, the above (A),
At least one of (B) and the (C) catalyst component used as desired can be used by supporting it on a suitable carrier. The type of the carrier is not particularly limited, and any of an inorganic oxide carrier, other inorganic carriers and organic carriers can be used, but an inorganic oxide carrier or another inorganic carrier is particularly preferable. As the inorganic oxide carrier,
Specifically, SiO ₂ , Al ₂ O ₃ , MgO, Zr
O ₂ , TiO ₂ , Fe ₂ O ₃ , B ₂ O ₃ , CaO, Zn
Examples include O, BaO, ThO ₂ and mixtures thereof, such as silica alumina, zeolite, ferrite, and glass fiber. Among these, especially SiO ₂ , A
1 ₂ O ₃ is preferred. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate and the like. On the other hand, as inorganic carriers other than the above, MgCl ₂ , Mg (O
Examples thereof include magnesium compounds such as C ₂ H ₅ ) ₂ and complex salts thereof, and organomagnesium compounds represented by MgR ²⁴ _i X ³ _j . Where R ²⁴ is 1 carbon
20 alkyl group, an alkoxy group or an aryl group having 6 to 20 carbon atoms having 1 to 20 carbon atoms, X ³ represents a halogen atom or an alkyl group having a carbon number of 1 to 20, i is 0 to 2, j
Is 0 to 2.

As the organic carrier, polystyrene,
Examples thereof include polymers such as polyethylene, polypropylene, substituted polystyrene and polyarylate, starch and carbon. Here, the properties of the carrier used vary depending on the type and production method, but the average particle size is usually 1 to 300 μm, preferably 10 to 200 μm, and more preferably 20 to 100 μm. When the particle size is small, fine powder in the polymer increases, and when the particle size is large, coarse particles in the polymer increase, which causes decrease in bulk density and clogging of the hopper. The specific surface area of the carrier is usually 1 to 1000 m ² /
g, preferably 50 to 500 m ² / g, the pore volume is usually
It is 0.1 to ⁵ cm ³ / g, preferably 0.3 to ³ cm ³ / g. If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and the pore volume can be obtained from the volume of nitrogen gas adsorbed according to the BET method (Journal of American Chemical Society, No. 60).
Vol., Page 309 (1983)). Further, the carrier is usually 150 to 1000 ° C., preferably 200.
It is desirable to use by firing at ~ 800 ° C. The method of loading on a carrier is not particularly limited, and a conventionally used method can be used.

Next, the use ratio of each catalyst component in the present invention will be described. When (1) (A) component and (B-1) component are used as the catalyst component, (A) component /
It is desirable to use both components so that the molar ratio of component (B-1) is in the range of 1 / 0.01 to 1/100, preferably 1/1 to 1/10. (2) When using the components (A), (B-1) and (C), the components (A) / (B-
1) The component molar ratio is the same as in the case of (1) above,
The component (A) component / (C) component molar ratio is 1/0 to 1/500,
It is preferably in the range of 1/1 to 1/100. Further, when the component (3) (A) and the component (B-2) are used, the molar ratio of the component (A) / the component (B-2) is 1 /.
20 to 1/10000, preferably 1/100 to 1/2
It is desirable to use both components so that they are in the range of 000. (4) When the component (A), the component (B-2) and the component (C) are used, the molar ratio of the component (A) / the component (B-2) is the same as the case (3). But component (A) /
The molar ratio of the component (C) is 1/0 to 1/500, preferably 1
It is preferably in the range of / 1 to 1/100. The ratio of particular limitation is not also the monomer and the catalyst for the addition order of the catalyst components, the monomer / transition metal molar ratio is generally 10/10 ^9/1, preferably from 10 ^2/1
It is chosen to be in the range of 10 ^7/1. As the copolymerization method of the α-olefin and the non-conjugated diene, any method such as slurry polymerization, solution polymerization, bulk polymerization, gas phase polymerization may be used, and any of continuous polymerization and discontinuous polymerization may be used. Good. Here, in the solution polymerization, as the solvent, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, pentane, hexane, heptane, octane, etc. Can be used. In this case, monomer /
The solvent (volume ratio) can be arbitrarily selected. The molecular weight or composition of the resulting copolymer may be controlled by a commonly used method. The molecular weight can be controlled by, for example, hydrogen, temperature, monomer concentration and the like. The composition can be controlled by, for example, changing the charging ratio of the monomer or the catalyst species. Further, regarding the control of random and block structures, when copolymerization is carried out in the coexistence of a monomer, a copolymer having high randomness is produced.
In addition, when homopolymerization is performed in advance and then copolymerization is advanced by adding a comonomer component, a copolymer having a high block property can be obtained. And as for stereoregularity, isotactic structure, syndiotactic structure,
An atactic structure can be obtained. The polymerization temperature, -100 to 200 ° C., but as the polymerization pressure is generally carried out at normal pressure to 100 kg / cm ^2, preferably -50 to 100 ° C., under normal pressure to 50 kg / cm ^2, more preferably Is in the range of 0 to 100 ° C. and normal pressure to 20 kg / cm ² .

The olefinically unsaturated copolymer of the present invention thus obtained has a unit derived from the non-conjugated diene represented by the general formula (I) of 10 ^{−6 to} 20 mol%, preferably 0.001 to 15 mol%, more preferably 0.001
It is necessary to contain it in the ratio of ~ 12 mol%. The present invention is characterized in that it does not gel even when the content of the non-conjugated diene unit is relatively large. Then, the reduced viscosity at a concentration of 0.05 g / deciliter measured at 135 ° C. in decalin is 0.01 to 30 deciliter / g, preferably 0.1 to 20 deciliter / g. If this reduced viscosity is less than 0.01 deciliter / g, the mechanical strength will be insufficient, and if it exceeds 30 deciliter / g, the moldability will be reduced.

In the present invention, the olefinic unsaturated copolymer is modified so that at least 5 mol% of the olefinic unsaturated bonds of the copolymer are functionally reacted with a functional group such as a hydroxyl group, a carboxyl group or an epoxy group. , A halogen group, a nitro group, an amino group, an acyl group, a sulfone group and the like are introduced.

In the present invention, the introduction of the functional group into the olefinic unsaturated bond means that the functional group is derived by utilizing the olefinic unsaturated bond. A desired functional group can be introduced by a method such as modification to generate a functional group or bonding a compound having a functional group to an olefinic unsaturated bond. This introducing method is not particularly limited and may be performed not only in a solution state but also in a molten state. The amount of the functional group introduced is 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, most preferably 2 mol% of the olefinic unsaturated bond in the olefinic unsaturated copolymer.
It is 0 mol% or more. When the amount introduced is less than 5 mol%, the content of the functional group is small and the modifying effect is not sufficiently exhibited. Next, a method for introducing each functional group will be described. (I) Introduction of Hydroxyl Group The method for introducing a hydroxyl group into an olefinic unsaturated copolymer is not particularly limited, but a method by oxidation of an olefinic unsaturated bond, a compound containing one or more hydroxyl groups in the molecule It is roughly classified into a method by an addition reaction to an olefinically unsaturated bond, and others. Examples of the method of oxidizing an olefinic unsaturated bond include (a) oxidation via hydrogen peroxide solution and an organic acid such as formic acid via a peracid, and (b) presence of a phase transfer catalyst such as a quaternary ammonium salt. Or, oxidation in the absence of permanganate, etc., (c) hydrogen peroxide solution using oxides of osmium, ruthenium, tungsten, selenium, etc. as a catalyst, oxidation by permanganate, etc., (d) bromine, etc. Of the halogen or hydrogen halide adduct, or sulfuric acid adduct, and (e) hydrolysis of the epoxy group introduced by various reactions. On the other hand, a compound having one or more hydroxyl groups in the molecule has active hydrogen capable of undergoing an addition reaction to an olefinic unsaturated bond, particularly a Michael type addition reaction (having two or more hydroxyl groups However, a case where one of them is used for an addition reaction is also included), and specific examples thereof include thiol compounds such as thioglycerol and thioglycol. In addition, the hydroxyl group can also be introduced by an aldehyde addition reaction known as the Prince reaction, an oxidation reaction subsequent to hydroboration, a demercuration reaction subsequent to oxymercuration of mercuric acetate or the like.

(Ii) Introduction of Carboxyl Group The method for introducing a carboxyl group is not particularly limited, but it is a method by oxidation of an olefinic unsaturated bond, or an olefinic compound of a compound containing one or more carboxyl groups in the molecule. It is roughly classified into a method by an addition reaction to a saturated bond, and others. Specific examples include (a) oxidation with a hydroxylating agent (potassium permanganate, etc.),
(B) Hydrolysis after reaction with radical reaction reagent (maleic anhydride, etc.), (c) Method for leading carboxyl group through acylation by demetalation reaction after reaction with metalation reagent (eg, alkyllithium), etc. Is mentioned.

(Iii) Introduction of Epoxy Group The method of introducing an epoxy group into an olefinic unsaturated copolymer is not particularly limited, but it is a method of oxidizing an olefinic unsaturated bond, one or more epoxy groups in a molecule. It is roughly classified into a method by an addition reaction of a compound containing a group to an olefinic unsaturated bond, and others. Examples of the method by oxidation of olefinic unsaturated bond include (a) oxidation by peracids such as performic acid, peracetic acid, and perbenzoic acid, (b)
Oxidation with sodium hypochlorite or the like in the presence or absence of a metalloporphyrin complex such as a manganese porphyrin complex, hydrogen peroxide in the presence or absence of a catalyst such as (c) vanadium, tungsten or molybdenum compound Methods such as oxidation with hydroperoxide, (d) oxidation with alkaline hydrogen peroxide, and (e) neutralization of the adduct of acetic acid / t-butyl hypochlorite system with alkali. On the other hand, a compound containing one or more epoxy groups in the molecule has active hydrogen capable of undergoing an addition reaction to an olefinic unsaturated bond, particularly a Michael type addition reaction, and specific examples include thioglycidol. Examples thereof include thiol compounds such as glycidyl thioglycolate.

(Iv) Introduction of nitro group and amino group The method for introducing the nitro group into the olefinic unsaturated copolymer is not particularly limited, but a usual nitration agent (eg fuming nitric acid, mixed acid, acetyl nitrate, etc.) is used. The desired product can be easily obtained in high yield by treating with (1). Further reduction of the nitro compound makes it possible to introduce an amino group.

(V) Introduction of acyl group The method for introducing an acyl group is not particularly limited,
For example, an acyl group can be introduced in good yield by allowing a reaction reagent composed of aluminum chloride, acetyl chloride and carbon disulfide to act.

(Vi) Introduction of Sulfone Group The introduction method of the sulfone group is not particularly limited, but it can be introduced easily and efficiently by using, for example, sulfuric anhydride, fuming sulfuric acid, concentrated sulfuric acid or chlorosulfonic acid as a sulfonation agent. can do. The reaction is carried out in a state where the olefinic unsaturated copolymer is swollen or dissolved in a solvent, or in a molten state, and the reaction in a dissolved or molten state is preferable. When a solvent is used, the solvent is appropriately selected depending on the type of reaction, and examples thereof include aliphatic, alicyclic, aromatic hydrocarbons and their halides, esters having 6 or more carbon atoms, ketones, ethers and carbon disulfide. Is used. These solvents may be used alone or in combination of two or more. The selectivity of the reaction is not always 10
It does not have to be 0%, and a product of a side reaction may be mixed in as long as a sulfo group is substantially introduced.

(Vii) Introduction of Halogen The method of introducing halogen into the olefinic unsaturated copolymer is not particularly limited, but for example, hydrogen halide or halogen is added to the olefinic unsaturated bond by a conventional method. By this, halogen can be introduced. Examples of the hydrogen halide include hydrogen chloride, hydrogen bromide, hydrogen iodide and the like, preferably hydrogen bromide and hydrogen iodide. Examples of halogen include chlorine, bromine, iodine, bromine monochloride, iodine monochloride,
Iodine monobromide and the like can be mentioned. Among them, bromine,
Bromine monochloride and iodine monochloride are preferred. Regarding the amount of halogen introduced, the halogen content in the olefinic unsaturated copolymer should be 0.05% by weight or more, preferably 0.5% by weight or more, and more preferably 1% by weight or more. Is desirable. When the halogen content is less than 0.05% by weight, the halogen content is too small and the halogen modification effect is not sufficiently exhibited. The selectivity of the reaction does not necessarily have to be 100%, and the product of the side reaction may be mixed if halogen is substantially introduced.

[0059]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Preparation Example 1 Preparation of Methylaluminoxane In a glass container having an inner volume of 500 ml replaced with argon, 200 ml of toluene, 17.8 g (71 mmol) of copper sulfate pentahydrate (CuSO ₄ .5H ₂ O) and 24 ml of trimethylaluminum ( 250
(Mmol) and added, and reacted at 40 ° C. for 8 hours. Then, toluene was distilled off under reduced pressure from the solution obtained by removing the solid component to obtain 6.7 g of a catalyst product (methylaluminoxane). The molecular weight of this product measured by the freezing point depression method was 610. Also, JP-A-62-32
A high magnetic field component measured by ¹ H-NMR measurement based on Japanese Patent No. 5391, that is, when its proton nuclear magnetic resonance spectrum is observed in a toluene solution at room temperature, a methyl proton signal based on an “Al—CH ₃ ” bond is a tetramethylsilane standard. It is found in the range of 1.0 to -0.5 ppm.
Since the proton signal of tetramethylsilane (0 ppm) is in the observation area of the methyl proton based on the "Al-CH _3" bonds, the "Al-CH _3" methyl proton signal based on the binding of toluene in tetramethylsilane reference Methyl proton signal 2.35ppm
The high magnetic field component (i.e., -0.1 to -0.
5 ppm) and other magnetic field components (ie 1.0 to -0.1 ppm)
When divided into and, the high magnetic field component was 43% of the whole.

Preparation Example 2 Preparation of tri-n-butylammonium tetrakis (pentafluorophenyl) borate Pentafluorophenyllithium prepared from bromopentafluorobenzene (152 mmol) and butyllithium (152 mmol) and 45 mmol of boron trichloride were prepared. Reaction with hexane gave tris (pentafluorophenyl) boron as a white solid. 41 mmol of this tris (pentafluorophenyl) boron was reacted with 41 mmol of pentafluorophenyllithium to obtain lithium tetrakis (pentafluorophenyl) boric acid as a white solid. Next, 16 mmol of lithium tetrakis (pentafluorophenyl) boric acid and 16 mmol of tri-n-butylammonium hydrochloride were reacted in water to give trin-butylammonium tetrakis (pentafluorophenyl) borate as a white solid (12.8 mmol). I was able to get it.

Example 1 Preparation of Copolymer (Resin A) 200 ml of toluene and 20 mmol of 3-methyl-1,5-hexadiene were placed in a reaction vessel with stirring having an inner volume of 500 ml, and prepared in Preparation Example 1. 2 mmol of methylaminoxane was added, and the mixture was immersed in a constant temperature bath at 50 ° C. and stirring was started. To this, 0.01 mmol of dicyclopentadienyl titanium dichloride was added, and ethylene was copolymerized at 2.0 kg / cmG for 2 hours. After the reaction,
Unreacted gas was removed, and the polymer was washed with methanol to obtain 13.0 g of a white polymer.

By IR measurement, 3-methyl-1,5-
Only stretching vibrations of the carbon-carbon double bond of the 1,640 cm ^-1 olefin unit due to the hexadiene residue were observed. Further, when ¹ H-NMR was measured, unreacted olefin was found at 4.8 to 5.1 and 5.7 to 6.0 ppm.
This clearly indicates an olefin derived from the 3-methyl-1,5-hexadiene group. The melting point of the copolymer was measured and found to be 128 ° C. This indicates that the methylene chains are disturbed, that is, they are randomly copolymerized. Furthermore, the reduced viscosity (in Decalin, 13
(Measurement at 5 ° C, concentration of 0.05 g / deciliter, the same applies hereinafter)
Is 0.19 deciliter / g, 3-methyl- in the copolymer
The content of 1,5-hexadiene units was 7.5 mol% by ¹ H-NMR. (Resin A)

Example 2 Preparation of Copolymer (Resin B) In Example 1, ethylenebisindenylzirconium dichloride was used in place of dicyclopentadienyltitanium dichloride, and propylene was 3.0 kg / c.
A copolymer was produced in the same manner as in Example 1 except that the polymerization was carried out at m ² · G and the polymerization was carried out at 30 ° C for 2 hours. As a result, the yield of the copolymer was 9.50 g, and the symmetric bending vibration of the methyl group due to propylene at 1380 cm ^-1 was observed in the IR absorption spectrum. Further, as in Example 1, there was absorption based on the carbon-carbon double bond at 1640 cm ^-1 . The content of 3-methyl-1,5-hexadiene unit in the copolymer was 2.7 mol%, the reduced viscosity was 0.31 deciliter / g, and the melting point was 137.7 ° C. (Resin B)

Example 3 Production of Copolymer (Resin C) As in Example 1, 100 ml of toluene, 3-
20 mmol of ethyl-1,5-hexadiene, 0.5 mmol of triisobutylaluminum and 0.02 mmol of the boron compound prepared in Preparation Example 2 were added. To this, 0.01 mmol of dicyclopentadienyl titanium dichloride was added, and ethylene was copolymerized at 2.0 kg / cm ² G for 2 hours. After the reaction was completed, unreacted gas was removed and the polymer was washed with methanol to obtain 16.0 g of a white polymer.

IR absorption spectrum shows 3-ethyl-
Only stretching vibrations of the carbon-carbon double bond of the olefin unit at 1640 cm ^{-1 due} to the 1,5-hexadiene residue were observed. further The melting point was measured to be 124 ° C., showing that the ethylene chain was disturbed, that is, random copolymerization was performed. The reduced viscosity was 0.27 deciliter / g. Copolymer composition is ¹ H-NMR
As a result of analysis, the content of 3-ethyl-1,5-hexadiene units was 9.2 mol%. (Resin C)

Example 4 Preparation of Copolymer (Resin D) In Example 3, propylene was saturated with 1.0 kg / cm ² · G before introducing ethylene, and 3-methyl-
Other than using 20 mmol of 1,5-hexadiene,
Terpolymerization was carried out in the same manner as in Example 3. As a result, the copolymer yield was 11.4 g, and the IR absorption spectrum showed absorption similar to that in Example 3. The copolymer composition was 84.8 mol% ethylene units and 9. propylene units.
2 mol%, 3-methyl-1,5-hexadiene unit 6.0
The melting point was 119 ° C and the reduced viscosity was 0.24 deciliter / g. (Resin D)

Example 5 (Introduction of Hydroxyl Group) 5.0 g of the resin A obtained in Example 1 was mixed with toluene 2 at 120 ° C.
90% by weight in this solution
10 g of formic acid and 1.5 g of 30 wt% hydrogen peroxide solution were mixed in advance and added dropwise over 1 hour, and the mixture was heated at 110 ° C. for 1 hour. Next, after neutralization treatment with sodium hydroxide-dissolved methanol, the polymer was precipitated by pouring it into a large amount of acetone, thoroughly washed and dried under reduced pressure to obtain a modified copolymer. By the infrared spectroscopy (IR method), the initially observed peak at 1640 cm ⁻¹ almost disappeared, and a broad peak newly appeared at around 3300 cm ⁻¹ . The conversion rate of the olefinic unsaturated bond in the resin A to the hydroxyl group measured by the NMR method was 90 mol%.

Example 6 (Introduction of Carboxyl Group) 3.0 g of the resin B obtained in Example 2 was mixed with toluene 2 at 120 ° C.
Dissolve it in 00 ml and add 10 parts of acetic acid to this solution.
g, paraformaldehyde 1.8 g, 98% by weight concentrated sulfuric acid 1
Add 3 ml of the mixture and stir vigorously for 3
Reflux for hours. After completion of the reaction, the mixture was neutralized with methanol dissolved in sodium hydroxide, poured into a large amount of acetone to precipitate the polymer, thoroughly washed, and dried under reduced pressure to obtain a modified copolymer. By the IR method, the peak at 1640 cm ^-1 disappeared, and a new sharp peak was newly observed around 1700 cm ^-1 . The conversion rate of the olefinic unsaturated bond in the resin B to the carboxyl group was almost 100%.

Example 7 (Introduction of Epoxy Group) 5.0 g of the resin C obtained in Example 3 was added to toluene 2 at 120 ° C.
The solution was dissolved in 00 ml, 0.2 g of t-butyl hydroperoxide and 15 mg of hexacarbonyl molybdenum were added to this solution, and the mixture was refluxed for 2 hours. This was poured into a large amount of cold methanol to precipitate a polymer, which was washed and then dried under reduced pressure to obtain a modified copolymer. IR method: 164
0cm peak around ^-1 disappeared, since the epoxy group-specific peaks were observed 3040Cm ^-1, introduction of epoxy groups was confirmed. The conversion rate of the olefinic unsaturated bond in the resin C to the epoxy group was 85 mol%.

Example 8 (Introduction of Nitro Group) Resin D (10.0 g) obtained in Example 4, 200 ml of toluene, 10 ml of 98% by weight concentrated sulfuric acid and 10 ml of 67% by weight nitric acid were mixed, and the mixture was kept at 80 ° C. for 10 minutes. The reaction was carried out with stirring. After completion of the reaction, the mixture was neutralized with sodium hydroxide-dissolved methanol, washed thoroughly, and dried under reduced pressure to obtain a modified copolymer. 1640c by IR method
The characteristic peak at m ^-1 disappeared, and around 1560 cm ^-1 and 13
A sharp peak due to the presence of a nitro group was observed near 50 cm ^-1 . The conversion rate of the olefinically unsaturated bond in Resin D to the nitro group was almost 100%.

Example 9 (Introduction of amino group) 5.0 g of the nitrated modified copolymer obtained in Example 8, 200 ml of toluene, 6 g of stannous chloride and 30 g of concentrated sulfuric acid were mixed and the mixture was mixed at 80 ° C. for 3 hours. The reaction was carried out with stirring for a time. After completion of the reaction, the mixture was neutralized with sodium hydroxide-dissolved methanol, washed thoroughly, and then dried under reduced pressure to obtain a modified copolymer. 1560 cm peculiar to nitro group by IR method
^-1 and 1350 cm ^-1 peaks disappeared, 3400-35
A broad peak due to an amino group appeared at 00 cm ^-1 .

Example 10 (Introduction of Sulfonyl Group) 5.0 g of Resin A obtained in Example 1 and tetrachloroethane 20
g and 100 ml of toluene were mixed and heated at 60 ° C. for 30 minutes, then the system was cooled and 4.0 g of chlorosulfonic acid was added over 6 hours while stirring. Then
Glacial acetic acid was added until hydrogen chloride was not generated, the reaction product was poured into a large amount of water, the mixture was decanted, and then poured into water again. This operation was repeated several times, and after sufficient washing, it was washed with acetone to wash tetrachloroethane and dried under reduced pressure to obtain the desired modified copolymer. 16 by the IR method
And disappearance of the peak of 40 cm ^-1, confirming the peak around 1070 cm ^-1 and 650 cm ^-1 due to the new sulfone groups introduced. The conversion rate of the olefinic unsaturated bond in the resin A to the sulfone group was almost 100%.

Example 11 (Acylation) 5.0 g of the resin B obtained in Example 2 was gradually added to a well-stirred mixed solution consisting of 10 g of anhydrous aluminum chloride, 8 g of acetyl chloride and 200 ml of carbon disulfide. . After the addition, stirring is continued for further 15 minutes, the content is poured into methanol to which hydrochloric acid is added, aluminum chloride is removed, and the mixture is thoroughly washed with dilute hydrochloric acid and water, then washed with alcohol and dried under reduced pressure to obtain a modified copolymer. Got The IR method, a peak of 1640 cm ^-1 disappeared and the peak around 1800 cm ^-1 and near 1100 cm ^-1 due to the newly acetyl group introduced was observed. The conversion rate of the olefinic unsaturated bond in the resin B was almost 100%.

Example 12 (Introduction of Halogen) The resin C (5.0 g) obtained in Example 3 and 300 ml of carbon tetrachloride were heated to 50 ° C. under a nitrogen atmosphere and stirred to make a suspension, and then bromine was added. 20 g was added and the reaction was continued for 30 minutes. After completion of the reaction, the content was put into a large amount of methanol to cause precipitation, which was thoroughly washed and then dried under reduced pressure to obtain a modified copolymer. 1640 cm ^-1 by IR method
The disappearance of the peak was confirmed and the bromine content was measured by ion chromatography to find that it was 29.6% by weight.

Test Example 1 The modified copolymers obtained in Examples 5, 6, 7, 8, 9, 10, and 11 and the resin A as a precursor of the modified copolymer obtained in Example 1 were used. Melt pressed, 40 mm x 40 mm,
A press sheet having a thickness of 0.1 mm was prepared. Distilled water was dropped on the center of each press sheet, and the shape of the droplet was measured using the droplet shape method. The results of visual observation are shown in Table 1.

[0076]

[Table 1]

[0077]

The olefinic unsaturated copolymer of the present invention is obtained by copolymerizing an α-olefin with a non-conjugated diene, produces less gel, and is an olefin of the copolymer. The modified copolymer in which functional groups such as hydroxyl group, carboxyl group, epoxy group, halogen group, amino group, etc. are introduced into the unsaturated bond, the combination is adhesiveness, printability, hydrophilicity, polymer modification, antistatic It has excellent properties and flame retardancy and is suitable for various applications.

Continuation of front page (56) Reference JP-A-3-177402 (JP, A) JP-A-4-173815 (JP, A) JP-A-2-123114 (JP, A) JP-A-2-51512 (JP , A) JP-A-1-135810 (JP, A) JP-A-5-59112 (JP, A) JP-A-5-501729 (JP, A) JP-A-1-503788 (JP, A) International Publication 92 / 001723 (WO, A1) Patent 3217416 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 210/00-210/18 C08F 4/64-4/69 C08F 8/00 -8/50

Claims (3)

(57) [Claims] 1. At least one selected from α-olefins having 2 to 12 carbon atoms and a compound represented by the general formula (I): ^(Wherein, R 1 to R ⁷ each represent a hydrogen atom, ^{R 8} is an alkyl group having 1 to 8 carbon atoms, Q is. Showing a divalent organic group having 1 to 20 carbon atoms) represented by Obtained by copolymerization with at least one selected from non-conjugated dienes, and the content of units derived from the non-conjugated dienes is 10 ^{−6 to} 20.
Mol% and concentration in decalin at 135 ° C. 0.05 g /
An olefinic unsaturated copolymer having a reduced viscosity of 0.01 to 30 deciliters / g measured in deciliters. 2. At least one selected from α-olefins having 2 to 12 carbon atoms and at least one selected from non-conjugated dienes represented by the general formula (I),
The copolymerization according to claim 1, wherein (A) the transition metal compound and (B) the transition metal compound or a derivative thereof is used in the presence of a catalyst containing a compound capable of forming an ionic complex as a main component. Process for producing olefinically unsaturated copolymer. 3. The olefinic unsaturated copolymer according to claim 1, wherein at least 5 mol% of the unsaturated bonds have hydroxyl groups and calcium groups.
Boxyl group, epoxy group, halogen group, nitro group, amine
A modified copolymer having a functional group selected from the group consisting of a vinyl group, an acyl group and a sulfone group .