JP3303888B2 - Modified copolymer and method for producing the same - 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 modified copolymer and a method for producing the same. More specifically, the present invention relates to the addition of a functional group such as a hydroxyl group, a carboxyl group, an epoxy group, a halogen group or an amino group to an unsaturated copolymer obtained by polymerization of an α-olefin and an aromatic compound having an unsaturated group. The present invention relates to a modified copolymer having a high adhesiveness, printability, hydrophilicity, polymer modifying property, antistatic property, flame retardancy and the like, and a method for producing the modified copolymer.

[0002]

2. Description of the Related Art In addition to being inexpensive, homopolymers and copolymers of α-olefins have excellent mechanical strength, gloss, transparency, moldability, moisture resistance, chemical resistance, and the like. Therefore, it is widely used for various applications in many fields. However, since the α-olefin polymer has a non-polar molecular structure, it has poor affinity with other substances, and has a disadvantage that adhesiveness, coating property, printing property, antistatic property and the like are extremely poor. are doing.

In order to make up for such disadvantages, for example, (1) a part of the polymer is oxidized by a chromic acid mixed solution or flame treatment, or (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 method (1) has a severe limitation in industrial practice because the treating agent has a strong acidity or toxicity, or the treating conditions are difficult or the effect is not uniform. In addition, although the method (2) has been partially put to practical use, it is inevitable that the properties of the modified polymer deteriorate and the properties for cross-linking are reduced, and the requirements for increasingly sophisticated use conditions and use forms are met. The fact is that it has not been fully understood. Furthermore, the method (3) has not escaped from the idea, and many problems need to be solved for practical use.

Various techniques have been proposed so far to solve such a problem. For example, JP-A-56-30413 discloses that ethylene and a branched 1,4
A method by copolymerization with a diene is disclosed in
No. 85405 discloses a method based on copolymerization of propylene with 1,4-dienes. These methods make it possible to produce a copolymer having a 1,1-disubstituted olefin in the side chain (that is, having a pendant olefin) by using bifunctional olefins having different reactivities. However, this pendant olefin has the disadvantage that it is susceptible to chemical reaction limitations due to the branched structure. For example, a graft reaction with a polar monomer, an olefin, or the like 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 when producing unsaturated copolymers. Is required to be introduced into the polymerization system in a large amount, so that the production amount of the copolymer relative to the amount of the catalyst used (that is, catalytic activity) is low, and the cost of the catalyst tends to be high.

Further, "Polymer Bretane (Polymer
Bulletin) ", Volume 10, page 109 (1983)
Describes a similar copolymerization method. However, although this method has an advantage that a gelation reaction is relatively unlikely to occur, gelation substantially occurs when an unsaturated group is contained at a high concentration, which is not preferable.

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

In addition, copolymers of α-olefin and non-conjugated diene are disclosed in JP-A-2-269109, JP-A-3-221508, and JP-A-4-469.
No. 09 discloses its contents in detail, but improves copolymerizability with olefins, prevents reduction in catalytic activity during polymerization, and suppresses side reactions such as cyclization reaction and cross-linking reaction on the produced polymer chain. Issues such as suppression remain.

In the case of using ω-alkenylstyrene, an o-allylstyrene system described in “Polymer Chemistry” Vol. 29, No. 328, p. 593 (1972) can be used as a conventional anion polymerization catalyst. It has been reported that when o-allylstyrene is homopolymerized using a cationic polymerization catalyst, structural selectivity is exhibited depending on the type of catalyst. However, it is difficult to produce olefin copolymers with these catalyst systems.

Japanese Patent Application Laid-Open No. Sho 62-95303 discloses a similar copolymer, which is a long-chain branched polyethylene copolymer because of high-pressure radical polymerization. It has the disadvantage of low density and therefore low strength and elastic modulus. Also, the remaining double bond is olefinic, there is only reactivity with olefin,
There is also a disadvantage that the graft modification is limited and cannot react with the polar vinyl monomer. As described above, in reality, satisfactory results cannot be obtained with the conventional improved technology.

On the other hand, a large number of techniques have been known for olefin-based modified copolymers, for example, JP-A-61-85405, JP-A-4-20504, JP-A-4-20505, JP-A-4-20510 discloses a technique relating to an olefin-based modified copolymer. However, they have found patentability mainly in the production of reaction precursors used for the modification reaction,
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 is rich in adhesiveness, printability, hydrophilicity, polymer modification, antistatic properties, flame retardancy and the like. It is an object of the present invention to provide a modified olefin copolymer.

[0012]

Means for Solving the Problems The present inventors have repeated studies on olefin-based copolymers. First, they have excellent copolymers with olefins and do not impair the catalytic activity.
A copolymer of alkenylstyrene and olefin capable of introducing a necessary and sufficient amount of unsaturated group was developed by adding a small amount to olefin and performing copolymerization (Japanese Patent Application No. 4-828).
No. 3, specification No. 4-8284).

The present inventors have further studied to develop a modified olefin copolymer having the above-mentioned preferable properties. As a result, the copolymer of alkenylstyrene and olefin was It has been found that the purpose can be achieved by introducing a suitable functional group for bonding. The present invention has been completed based on such findings. That is, the present invention relates to at least one selected from α-olefins having 2 to 12 carbon atoms and a compound represented by the general formula (I):

[0014]

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Wherein R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, R ² is a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ³ and R ⁴ are a hydrogen atom, a halogen atom or a carbon atom, respectively. And a hydrocarbon group of the formulas 1 to 8, which may be the same or different, and m represents an integer of 0 to 4). The content of the aromatic compound unit obtained by copolymerization with at least one is 10 ^{-6 to} 90 mol%, and the concentration measured in 1,2,4-trichlorobenzene at 135 ° C. is 0.05 g. / Reduced viscosity in deciliters is 0.01 to 3
A modified copolymer characterized by modifying an olefin-based copolymer of 0 deciliter / g and introducing a functional group into at least 5 mol% of unsaturated bonds in the olefin-based copolymer by a chemical reaction. To provide.

The modified copolymer has 2 to 12 carbon atoms.
At least one selected from α-olefins of
An olefin copolymer is obtained by polymerizing at least one selected from the unsaturated group-containing aromatic compounds represented by the general formula (I) in the presence of a catalyst, and then obtaining the olefin copolymer. The compound can be produced by modifying the union and introducing a functional group into the unsaturated bond by a chemical reaction.

In the present invention, the α-olefin having 2 to 12 carbon atoms used as one component of the raw material monomer is, for example, ethylene; propylene; butene-1; pentene-1; hexene-1; heptene-1; 1;
Nonene-1; decene-1; 4-phenylbutene-1; 6
-Phenylhexene-1; 3-methylbutene-1; 4-
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-olefin such as vinylcyclohexene, hexafluoropropene; tetrafluoroethylene; 2-fluoropropene; fluoroethylene; 1,1-difluoroethylene; 3-fluoropropene; trifluoroethylene; and halogen-substituted α-olefins such as 3,4-dichlorobutene-1.

These α-olefins may be used alone or in combination of two or more.
In some cases, it may be used in combination with a cyclic olefin. 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
-Benzylnorbornene; 5-ethylidenenorbornene; 5-vinylnorbornene and the like. These cyclic olefins may be used alone or in a combination of two or more.

On the other hand, the unsaturated group-containing aromatic compound used as another component (comonomer) of the raw material monomer has the general formula (I)

[0020]

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Is a compound represented by the formula: Such a compound is not particularly limited as long as it has an α-olefin residue and a styrene residue in one molecule, and various compounds can be used.

Here, in the general formula (I), R ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, for example, 1 to 20 carbon atoms.
An alkylene group having 6 to 20 carbon atoms, an alkylarylene group having 7 to 20 carbon atoms or an arylalkylene group. Specific examples include a methylene group, an ethylene group, a propylene group, a butylene group, a pentenylene group, a hexylene group, a phenylene group and a tolylene group. R ² is a halogen atom (eg, chlorine, bromine,
Fluorine, iodine) or a monovalent hydrocarbon group having 1 to 8 carbon atoms (for example, methyl, ethyl, propyl, butyl,
A saturated hydrocarbon group represented by an alkyl group such as a pentyl group or an unsaturated hydrocarbon group such as a vinyl group),
m is an integer of 0-4. R ³ and R ⁴ are each a hydrogen atom, a halogen atom (eg, chlorine, bromine, fluorine, iodine) or a monovalent hydrocarbon group having 1 to 8 carbon atoms (eg, methyl, ethyl, propyl, butyl). A saturated hydrocarbon group represented by an alkyl group such as a pentyl group, or an unsaturated hydrocarbon group such as a vinyl group), which may be the same or different.

As the styrene monomer represented by the general formula (I), specifically, R ¹ in the general formula (I) is
When it is an alkylene group, for example, p- (2-propenyl) styrene, m- (2-propenyl) styrene, p-
(3-butenyl) styrene, m- (3-butenyl) styrene, o- (3-butenyl) styrene, p- (4-pentenyl) styrene, m- (4-pentenyl) styrene,
o- (4-pentenyl) styrene, p- (7-octenyl) styrene, p- (1-methyl-3-butenyl) styrene, p- (2-methyl-3-butenyl) styrene, m
-(2-methyl-3-butenyl) styrene, o- (2-
Methyl-3-butenyl) styrene, p- (3-methyl-
3-butenyl) styrene, p- (2-ethyl-3-butenyl) styrene, p- (2-ethyl-4-pentenyl)
Styrene, p- (3-butenyl) -α-methylstyrene, m- (3-butenyl) -α-methylstyrene, o-
(3-butenyl) -α-methylstyrene and the like.

When R ¹ in the general formula (I) is an arylene group, for example, 4-vinyl-4 ′-(3-butenyl) biphenyl, 4-vinyl-3 ′-(3-butenyl) Biphenyl, 4-vinyl-4 '-(4-pentenyl) biphenyl, 4-vinyl-2'-(4-pentenyl) biphenyl, 4-vinyl-4 '-(2-methyl-3
-Butenyl) biphenyl and the like. In the present invention, these unsaturated group-containing aromatic compounds may be used alone or in a combination of two or more.

In the present invention, first, the above-mentioned carbon number 2
And at least one selected from the unsaturated group-containing aromatic compounds represented by the general formula (I) in the presence of a polymerization catalyst. Thus, an olefin-based copolymer is produced.
This olefin-based copolymer has a content of the aromatic compound unit of from 10 ^{-6 to} 90 mol%, preferably from 10 ^-4 to 70 mol%, more preferably from 10 ^-4 to 50 mol%. The present invention is characterized in that it does not gel even when the content of the aromatic compound unit is relatively large. The reduced viscosity at a concentration of 0.05 g / deciliter measured at 135 ° C. in 1,2,4-trichlorobenzene is 0.01.
To 30 deciliter / g, preferably 0.1 to 20 deciliter / g. If the reduced viscosity is less than 0.01 deciliter / g, the mechanical strength is insufficient, and if it is more than 30 deciliter / g, the moldability is reduced.

Examples of the polymerization catalyst used for producing the olefin-based copolymer include (1) a transition metal compound (A) and (B) a cation-based compound comprising a transition metal compound of the component (A) or a derivative thereof. A catalyst comprising a combination of a compound capable of forming a seed, (2) the component (A) and (B)
A catalyst obtained by combining the component and (C) an organometallic compound,
(3) A catalyst in which the component (A) and the component (C) are combined, and (4) a catalyst in which the component (A) and the (D) halogen-substituted organometallic compound are combined.

As the transition metal compound of the component (A), a transition metal compound containing a metal belonging to Groups 3 to 10 of the periodic table or a lanthanoid-based metal can be used. Specifically, the transition metal is preferably titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, manganese, nickel, palladium, platinum, or the like.

Examples of such transition metal compounds include various compounds. In particular, compounds containing a transition metal selected from Group 4 of the periodic table, ie, titanium, zirconium or hafnium, are preferred. Compounds containing and compounds containing chromium are also suitable. Examples of the transition metal compound, for example, the general formula ^{_{CpM 1 R 5 a R 6 b}} R 7 c ··· (IV) Cp 2 M 1 R 5 a R 6 b ··· (V) (Cp-A e -Cp ) The compounds represented by M ¹ R ⁵ _a R ⁶ _b ... (VI) or the general formulas M ¹ R ⁵ _a R ⁶ _b R ⁷ _c R ⁸ _d .

In the above general formulas (IV) to (VII), M ¹
Represents a transition metal such as titanium, zirconium, hafnium, vanadium, niobium, tantalum, and chromium;
p is a cyclic unsaturated hydrocarbon group such as a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group; Indicates an unsaturated hydrocarbon group. R ⁵ , R ⁶ ,
R ⁷ and R ⁸ each independently represent a σ-binding ligand, a chelating ligand, a ligand such as a Lewis base, etc. Specific examples of the σ-binding ligand include a hydrogen atom An oxygen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group;
Examples thereof include an acyloxy group having 1 to 20 carbon atoms, an allyl group, a substituted allyl group, and a substituent containing a silicon atom. Examples of the chelating ligand include an acetylacetonate group,
Examples thereof include a substituted acetylacetonate group. A represents a covalent crosslink. a, b, c and d each independently represent an integer of 0 to 4; e represents an integer of 0 to 6; R ⁵ ,
Two or more of R ⁶ , R ⁷ and R ⁸ may combine with each other to form a ring. When the Cp has a substituent,
The substituent is preferably an alkyl group having 1 to 20 carbon atoms.
In the formulas (V) and (VI), the two Cp's may be the same or different from each other.

The substituted cyclo in the above formulas (IV) to (VI)
As the pentadienyl group, for example, methylcyclopentane
Dienyl group, ethylcyclopentadienyl group;
Pyrcyclopentadienyl group; 1,2-dimethylcyclo
Pentadienyl group; tetramethylcyclopentadienyl
Group; 1,3-dimethylcyclopentadienyl group;
2,3-trimethylcyclopentadienyl group;
4-trimethylcyclopentadienyl group; pentamethyl
Cyclopentadienyl group; trimethylsilylcyclopen
And a tadienyl group. In addition, the above (IV)-
R in formula (VII) ^Five~ R⁸As a specific example of, for example,
Fluorine, chlorine, bromine,
Methyl as an iodine atom and 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
A methoxy group as an alkoxy group of 1 to 20;
Group, propoxy group, butoxy group, phenoxy group, carbon number
6 to 20 aryl groups, alkylaryl groups or
Phenyl, tolyl, xylyl as alkyl group
A benzyl group, an acyloxy group having 1 to 20 carbon atoms and
Contains a heptadecylcarbonyloxy group and a silicon atom
As a substituent, a trimethylsilyl group, (trimethylsilyl
M) methyl group, Lewis base as dimethyl ether,
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;
Phosphine such as phenyl phosphine, chain unsaturated
Ethylene; butadiene; 1-pentene as a hydrocarbon
Isoprene; pentadiene; 1-hexene and this
Derivatives thereof, as cyclic unsaturated hydrocarbons, benzene;
Ruene; Xylene; Cycloheptatriene; Cyclooctane
Tadiene; cyclooctatriene; cyclooctatetra
And ene and derivatives thereof. Also,
Examples of the covalent cross-linking of A in the formula (VI) include:
For example, methylene bridge, dimethyl methylene bridge, ethylene
Crosslinking, 1,1'-cyclohexylene crosslinking, dimethylsilicone
Crosslinked with len, Crosslinked with dimethylgermylene, Dimethylstannile
Crosslinking and the like.

Examples of the compound represented by the general formula (IV) include (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, and (pentamethylcyclopentadienyl) Tribenzyl zirconium, (pentamethylcyclopentadienyl) trichloro zirconium, (pentamethyl cyclopentadienyl) trimethoxy zirconium, (cyclopentadienyl) trimethyl zirconium, (cyclopentadienyl) triphenyl zirconium, (cyclopentadi (Enyl) tribenzylzirconium, (cyclopentadienyl) trichlorozirconium, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium , (Methylcyclopentadienyl) trimethylzirconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) ) Dimethyl (methoxy) zirconium, (dimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium, and the like, and the like. In these, a compound in which zirconium is replaced with titanium or hafnium is mentioned.

Examples of the compound represented by the general formula (V) include bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) diethyl zirconium, and bis (cyclopentadienyl) diethyl zirconium. Cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium, bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydride Zirconium, bis (methylcyclopentadienyl) dimethyl zirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclopentadienyl) dibenzylzirconium, bis (pentameth Lecyclopentadienyl) dimethyl zirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, bis (pentamethylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) chloromethylzirconium, bis (pentane Methylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl)
Examples thereof include (pentamethylcyclopentadienyl) dichlorozirconium, and further, a compound in which zirconium is replaced by titanium or hafnium.

The compound represented by the general formula (VI) includes, for example, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) dichlorozirconium, ethylenebis (tetrahydroindenyl)
Dimethyl zirconium, 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) dimethylzirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclohexalidene (9-fluorenyl) ) (Cyclopentadienyl) dimethylzirconium, cyclopentylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclobutylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylene (9-fluorenyl) ) (Cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (2,3,5
-Trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dimethylzirconium, dimethylsilylenebis (indenyl) dichlorozirconium, and the like. Alternatively, a compound can be given by substituting hafnium.

Further, as the compound represented by the general formula (VII), for example, tetramethylzirconium, tetrabenzylzirconium, tetramethoxyzirconium,
Tetraethoxyzirconium, tetrabutoxyzirconium, tetrachlorozirconium, tetrabromozirconium, butoxytrichlorozirconium, dibutoxydichlorozirconium, bis (2,5-di-t-butylphenoxy) dimethylzirconium, bis (2,5-di-t -Butylphenoxy) dichlorozirconium, zirconiumbis (acetylacetonate) and the like, and furthermore, compounds in which zirconium is substituted by titanium or hafnium.

Further, as the component (A), in the general formula (VI), two substituted or unsubstituted conjugated cyclopentadienyl groups (at least one of which is a substituted cyclopentadienyl group) ) Can be suitably used a group 4 transition metal compound having a ligand as a multiple coordination compound bonded to each other via an element selected from group 14 of the periodic table. Such compounds include, for example, compounds of the general formula (VII
I)

[0036]

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Or a derivative thereof.

In the general formula (VIII), Y¹Is carbon, kei
Element, germanium or tin atom, R ⁹ _t-C_FiveH_4-tPassing
And R⁹ _u-C_FiveH_4-uAre each substituted cyclopentadie.
The nyl group, t and u represent an integer of 1 to 4. Where R⁹
Represents a hydrogen atom, a silyl group or a hydrocarbon group,
They may be one or different. Also at least one piece
One of the cyclopentadienyl groups has Y¹Bound to
R on at least one carbon next to the carbon⁹Exists.
R^TenIs a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or carbon
An aryl group, an alkylaryl group, or
It represents an arylalkyl group. M^TwoIs titanium, zirconium
Or hafnium atom, X¹Is hydrogen atom, halogen
Atom, alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
An aryl group, an alkylaryl group or an aryl group
It represents an alkyl group or an alkoxy group having 1 to 20 carbon atoms. X
¹May be the same or different from each other, and R^TenAlso
They may be the same or different.

The substituted cyclopentadienyl group in the above formula (VIII) includes, for example, methylcyclopentadienyl group; ethylcyclopentadienyl group; isopropylcyclopentadienyl group; 1,2-dimethylcyclopentadienyl A 1,3-dimethylcyclopentadienyl group; a 1,2,3-trimethylcyclopentadienyl group; a 1,2,4-trimethylcyclopentadienyl group. Specific examples of X ¹ include F, Cl, Br, I as a halogen atom, and methyl, ethyl, n-propyl, isopropyl, n-butyl, octyl, and the like as an alkyl group having 1 to 20 carbon atoms. 2-ethylhexyl group, methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group as C1-C20 alkoxy group, phenyl group, tolyl as C6-C20 aryl group, alkylaryl group or arylalkyl group Group, xylyl group, benzyl group and the like. R ¹⁰
Specific examples include a methyl group, an ethyl group, a phenyl group, a tolyl group, a xylyl group, and a benzyl group. Examples of the compound of the general formula (VIII) include, for example, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, and a compound obtained by substituting zirconium with titanium or hafnium. . Furthermore, the general formula (IX)

[0040]

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The compounds represented by the following formulas are also included. The general formula
In the compound of (IX), Cp is cyclopentadienyl
Group, substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, tetrahydroindenyl group, substituted tetra
Hydroindenyl, fluorenyl or substituted fluor
Cyclic unsaturated hydrocarbon group such as an n-yl group or chain unsaturated carbon
Shows a hydrogen group. M^ThreeIs titanium, zirconium or hafni
X^TwoIs hydrogen atom, halogen atom, carbon
An alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms
Group, alkylaryl group or arylalkyl group or
Represents an alkoxy group having 1 to 20 carbon atoms. Z is SiR¹¹
_Two, CR¹¹ _Two , SiR¹¹ _Two SiR¹¹ _Two , CR¹¹ _Two CR¹¹
_Two , CR¹¹ _Two CR¹¹ _Two CR¹¹ _Two , CR¹¹= CR¹¹, CR
¹¹ _Two SiR¹¹ _TwoOr GeR¹¹ _Two And Y^TwoIs -N (R
¹²)-, -O-, -S- or -P (R¹²) Indicates-. Up
Note R¹¹Is an atom with hydrogen atoms or up to 20 non-hydrogen atoms
Alkyl, aryl, silyl, alkyl halide, halo
A group selected from gallified aryl groups and their combinations
Yes, R¹²Is alkyl having 1 to 10 carbons or carbon number
6 to 10 aryl groups, or one or more aryl groups
R above¹¹Forms a fused ring system of up to 30 non-hydrogen atoms with
May be. w represents 1 or 2.

The transition metal compound containing a transition metal belonging to Group 5 to Group 10 is not particularly limited, and specific examples of the vanadium compound include vanadium trichloride, vanadyl trichloride, vanadium triacetylacetonate, and the like.
Vanadium tetrachloride, vanadium tributoxide, vanadyl dichloride, vanadyl bisacetylacetonate, vanadyl triacetylacetonate, dibenzene vanadium, dicyclopentadienyl vanadium, dicyclopentadienyl vanadium dichloride, cyclopentadienyl vanadium trichloride, Dicyclopentadienylmethyl vanadium and the like.

Specific examples of the niobium compound include niobium pentachloride, tetrachloromethyl niobium, dichlorotrimethyl niobium, dicyclopentadienyl niobium dichloride, dicyclopentadienyl niobium trichloride, pentabutoxy niobium, and tantalum. Specific examples of the compound include tantalum pentachloride, dichlorotrimethyl tantalum,
Dicyclopentadienyl tantalum trihydride, pentabutoxy tantalum and the like.

Specific examples of the chromium compound include tetrame
Butyl chromium; tetra (t-butoxy) chromium;
Clopentadienyl) chromium; hydride tricarbonyl
(Cyclopentadienyl) chromium; hexacarbonyl
(Cyclopentadienyl) chromium; bis (benzene) c
Rom; tricarbonyl tris (triphenyl phosphonate
Le) chromium; tris (allyl) chromium; triphenylt
Lith (tetrahydrofuran) chromium; chrome tris (A
Cetyl acetonate) and the like. Manganese compound
Specific examples of the product include tricarbonyl (cyclopentadiene).
Enyl) manganese; pentacarbonylmethylmanganese;
Bis (cyclopentadienyl) manganese; manganese bis
(Acetylacetonate) and the like. nickel
Specific examples of the compound include dicarbonylbis (triphenyl
Nylphosphine) nickel; dibromobis (triphenyl)
Ruphosphine) nickel; dinitrogen bis [bis (trisic)
Rohexylphosphine) nickel]; chlorohydrido
(Tricyclohexylphosphine) nickel; chloro
(Phenyl) bis (triphenylphosphine) nicke
Dimethyl bis (trimethylphosphine) nickel;
Diethyl (2,2'-bipyridyl) nickel; bis (A
Ril) nickel; bis (cyclopentadienyl) nickel
Bis (methylcyclopentadienyl) nickel;
(Pentamethylcyclopentadienyl) nickel;
Ryl (cyclopentadienyl) nickel; (cyclopen
Tadienyl) (cyclooctadiene) nickeltetraf
Fluoroboronate; bis (cyclooctadiene) nickel;
Nickel bisacetylacetonate; allyl nickel
Loride; tetrakis (triphenylphosphine) nickel
Nickel chloride; formula (C₆H_Five) Ni [OC (C₆H_Five) CH = P (C
₆H_Five)_Two] [P (C₆H_Five)_Three], (C₆H_Five) Ni [OC
(C₆H_Five) C (SO_ThreeNa) = P (C₆H_Five)_Two] [P
(C ₆H_Five)_ThreeAnd the like.

Specific examples of the palladium compound include dichlorobis (benzonitrile) palladium; carbonyltris (triphenylphosphine) palladium; dichlorobis (triethylphosphine) palladium; bis (t-butyl isocyanate) palladium; Dichloro (tetraphenylcyclobutadiene) palladium; dichloro (1,5-cyclooctadiene) palladium; allyl (cyclopentadienyl) palladium; bis (allyl) palladium; allyl (1,5-cyclooctadiene) palladium Tetrafluoroborate; (acetylacetonate) (1,5-
Cyclooctadiene) palladium tetrafluoroborate; tetrakis (acetonitrile) palladium tetrafluoroborate;

The transition metal compound of the component (A) may be used alone or in combination of two or more.
Further, those modified with an electron donating compound can also be used. In the polymerization catalyst, as the compound capable of forming a kaotin species from the transition metal compound of the component (A) or a derivative thereof, which is used as the component (B), (B-1) the component (A) A compound which reacts with a transition metal compound to form an ionic complex and (B-2) aluminoxane 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 comprising an anion bonded to an element, particularly a coordination complex compound comprising a cation and an anion having a plurality of groups bonded to the element can be suitably used. Examples of the compound such cations and a plurality of groups consisting of bound anions to elemental general formula ([L ¹ -R ^{13] k +)} _p ^{([M 4 Z 1 Z 2 ·· Z} n ] ^{(ih) -} ) _Q・ ・ ・ (X) or ([L ² ] ^{k +} ) _p ([M ⁵ Z ¹ Z ² · Z ⁿ ] ^(ih)- ) _q・ ・ ・ (XI) (where L ² is M ^{6, R 14 R 15 M 7} , R 16 3 C or R ¹⁷
M ⁷ is a) wherein, L ¹ is a Lewis base, M ⁴ and M ⁵
Are the 5th, 6th, 7th, 8th to 10th groups of the periodic table,
Elements selected from Groups 11, 12, 13, 14, and 15, preferably elements selected from Groups 13, 14, and 15, M ⁶ and M ⁷ are groups 3 and 4, respectively, of the periodic table.
Group 5, group 5, group 6, group 7, group 8 to group 10, group 1, group 11, group 2
Group, an element selected from group 12 and group 17, Z ¹ to Z ⁿ are each a hydrogen atom, a dialkylamino group, a carbon number 1-2
0 alkoxy group, C6-C20 aryloxy group, C1-C20 alkyl group, C6-C20 aryl group, alkylaryl group, arylalkyl group,
A halogen-substituted hydrocarbon group having 1 to 20 carbon atoms,
20 acyloxy group, an organic metalloid group or a halogen atom, Z ¹ to Z ⁿ may form a ring of two or more thereof with each other. R ¹³ is a hydrogen atom, carbon number 1 to
R ¹⁴ and R ¹⁵ each represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group;
R ¹⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ¹⁷ represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine. h is a valence of M ⁴ or M ⁵ and is an integer of 1 to 7, i is an integer of 2 to 8, k is [L ¹ -R ¹³ ],
[L ² ] is an integer of 1 to 7 in ionic valence, p is an integer of 1 or more, and q = (p × k) / (i−h). ] It is a compound represented by these.

[0047] Here, specific examples of the Lewis base represented by L ^1, 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 and dioxane; thioethers such as diethylthioether and tetrahydrothiophene; ethylbenzoate And the like.

As specific examples of M ⁴ and M ⁵ ,
Specific examples of B, Al, Si, P, As, Sb and the like, preferably B or P, M ⁶ include Li, Na, Ag, C
Specific examples of M ⁷ such as u, Br, I include Mn, F
e, Co, Ni, Zn and the like. Specific examples of Z ¹ to Z ⁿ may, for example, as a dialkylamino group dimethylamino group; diethylamino group, a methoxy group as an alkoxy group having 1 to 20 carbon atoms, an ethoxy group, n- butoxy group, having 6 to 20 carbon atoms A phenoxy group as an aryloxy group; a 2,6-dimethylphenoxy group; a naphthyloxy group, a 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 alkylaryl group or arylalkyl group; Benzyl group; 4-tert-butylphenyl group; 2,6-dimethylphenyl group; 3,5-dimethylphenyl group;
Dimethylphenyl group; 2,3-dimethylphenyl group; p-fluorophenyl group as a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms; 3,5-difluorophenyl group; pentachlorophenyl group; 3,4,5-trifluoro Phenyl group; pentafluorophenyl group; 3,5-di (trifluoromethyl) phenyl group; F and C as halogen atoms
l, Br, I, pentamethylantimony group, trimethylsilyl group, trimethylgermyl group as organic metalloid groups,
Examples include a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group. Specific examples of R ¹³ and R ¹⁶ include the same as those described above.
Specific examples of the substituted cyclopentadienyl group for R ¹⁴ and R ¹⁵ include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. It is. 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 (X) and (XI),
Preferably, M ⁴ and M ⁵ are boron. General formula (X),
Among the compounds of (XI), specifically, the following compounds can be particularly preferably used. For example, the compounds of the general formula (X) include triethylammonium tetraphenylborate; tri (n-butyl) ammonium tetraphenylborate; trimethylammonium tetraphenylborate; tetraethylammonium tetraphenylborate; methyltri (n-butyl) tetraphenylborate Ammonium; benzyltriphenyl (n-butyl) ammonium tetraphenylborate; dimethyldiphenylammonium tetraphenylborate; methyltriphenylammonium tetraphenylborate; trimethylanilinium tetraphenylborate; methylpyridinium tetraphenylborate; benzylpyridinium tetraphenylborate; tetraphenylborate Methyl (2-cyanopyridinium); trimethylsulfonium tetraphenylborate; benzyl tetraphenylborate Methylsulfonium; triethylammonium tetrakis (pentafluorophenyl) borate; tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate; triphenylammonium tetrakis (pentafluorophenyl) borate; tetrabutylammonium tetrakis (pentafluorophenyl) borate; Tetraethylammonium tetrakis (pentafluorophenyl) borate; tetramethyl (tetrafluorophenyl) borate [methyltri (n-butyl) ammonium]; tetrakis (pentafluorophenyl) borate [benzyltri (n-butyl) ammonium]; tetrakis (pentafluorophenyl) Methyl diphenyl ammonium borate; Methyl triphenyl ammonium tetrakis (pentafluorophenyl) borate; Teto Dimethyl ammonium dikis (pentafluorophenyl) borate; Anilinium tetrakis (pentafluorophenyl) borate; Methylanilinium tetrakis (pentafluorophenyl) borate; Dimethylanilinium tetrakis (pentafluorophenyl) borate; Trimethyl tetrakis (pentafluorophenyl) borate Anilinium; dimethyl tetrakis (pentafluorophenyl) borate (m-nitroanilinium); dimethyl tetrakis (pentafluorophenylmethyl) borate (p-bromoanilinium); pyridinium tetrakis (pentafluorophenyl) borate; tetrakis (pentafluorophenyl) ) Boric acid (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); trimethylsulfonium tetrakis (pentafluorophenyl) borate; benzyldimethylsulfonium tetrakis (pentafluorophenyl) borate; tetrafelphonium tetrakis (pentafluorophenyl) borate; tetrakis ( Dimethyl 3,5-ditrifluoromethylphenyl) borate; dimethyl tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) borate Anilinium; tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) triethylammonium borate; tris (pentafluorophenyl) (p-
Pyridinium trifluoromethyltetrafluorophenyl) borate; Tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) borate (N-
Methyl pyridinium); tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) borate (O-cyano-N-methylpyridinium); tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) borate ( p-cyano-N-
Benzylpyridinium); triphenylphosphonium tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) borate; dimethylanilinium tris (pentafluorophenyl) (2,3,5,6-tetrafluoropyridinyl) borate Triethylammonium tris (pentafluorophenyl) (2,3,5,6-tetrafluoropyridinyl) borate; pyridinium tris (pentafluorophenyl) (2,3,5,6-tetrafluoropyridinyl) borate; Tris (pentafluorophenyl) (2,3,5,6-tetrafluoropyridinyl) borate (N-methylpyridinium); Tris (pentafluorophenyl) (2,3,5,6-tetrafluoropyridinyl) Boric acid (O-cyano-N-methylpyridinium); (Pentafluorophenyl)
(2,3,5,6-tetrafluoropyridinyl) boric acid (p-cyano-N-benzylpyridinium); tris (pentafluorophenyl) (2,3,5,6-tetrafluoropyridinyl) borate Phenylphosphonium;
Tris (pentafluorophenyl) (phenyl) dimethylanilinium borate; tris (pentafluorophenyl) [3,5-di (trifluoromethyl) phenyl] dimethylanilinium borate; tris (pentafluorophenyl) (4-trifluoromethyl Dimethylanilinium phenyl) borate; dimethylanilinium triphenyl (pentafluorophenyl) borate; triethylammonium hexafluoroarsenate;

On the other hand, compounds of the general formula (XI) include ferrocenium tetraphenylborate; silver tetraphenylborate; trityl tetraphenylborate; tetraphenylborate (tetraphenylporphyrin manganese); ferrocenium tetrakis (pentafluorophenyl) borate; (Pentafluorophenyl) boric acid (1,1'-dimethylferrocenium); decamethylferrocenium tetrakis (pentafluorophenyl) borate; acetylferrocenium tetrakis (pentafluorophenyl) borate; tetrakis (pentafluorophenyl) borate Formyl ferrocenium; cyanoferrocenium tetrakis (pentafluorophenyl) borate; silver tetrakis (pentafluorophenyl) borate; triti tetrakis (pentafluorophenyl) borate Lithium tetrakis (pentafluorophenyl) borate; sodium tetrakis (pentafluorophenyl) borate; tetrakis (pentafluorophenyl) borate (manganese tetraphenylporphyrin); tetrakis (pentafluorophenyl) borate (tetraphenylporphyrin iron chloride); tetrakis ( Pentafluorophenyl) boric acid (zinc tetraphenylporphyrin); silver tetrafluoroborate; silver hexafluoroarsenate; silver hexafluoroantimonate; Compounds other than the general formulas (X) and (XI) include, for example, tris (pentafluorophenyl)
Boric acid; tris [3,5-di (trifluoromethyl) phenyl] boric acid; triphenyl boric acid and the like can also be used.

As the component (B-1), a compound 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. Is also good. On the other hand, as the aluminoxane of the component (B-2), the general formula (XII)

[0052]

Embedded image

(Wherein R ¹⁸ is an alkyl group, alkenyl group, aryl group having 1 to 20, preferably 1 to 12 carbon atoms,
A hydrocarbon group such as an arylalkyl group, s indicates the degree of polymerization and is usually an integer of 3 to 50, preferably 7 to 40. Aluminoxane represented by the general formula (XI)
II)

[0054]

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(Wherein R ¹⁸ and s are the same as described above). Preferred among the compounds of the general formulas (XII) and (XIII) are aluminoxanes having a degree of polymerization of 7 or more. When an 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 obtained by modifying an aluminoxane represented by the general formulas (XII) and (XIII) with a compound having active hydrogen such as water and which is insoluble in an ordinary solvent can also be suitably used.

Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water. The method is not particularly limited, and the reaction may be carried out according to a known method. For example, a method of dissolving an organoaluminum compound in an organic solvent and bringing it into contact with water, a method of adding an organoaluminum compound at the beginning during polymerization and adding water later, water of crystallization contained in a metal salt or the like, There are a method of reacting water adsorbed on an inorganic or organic substance with an organoaluminum compound, a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane, and further reacting water. These aluminoxanes may be used alone or in a combination of two or more. In the present invention,
As the catalyst component (B), only the component (B-1) may be used, only the component (B-2) may be used, and the components (B-1) and (B-2) may be used. May be used in combination. On the other hand, as the organometallic compound as the catalyst component (C) in the polymerization catalyst, a compound represented by the general formula (XIV) M ⁸ R ¹⁹ _r (XIV) is used. R in the general formula (XIV)
¹⁹ represents 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 an aralkyl group having 7 to 20 carbon atoms. Specific examples of R ¹⁹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Examples include an isobutyl group, a hexyl group, a 2-ethylhexyl group, and a phenyl group. M ⁸ is the periodic table 1
It is a metal belonging to Group 4 or 11 to 14, and specific examples include lithium, sodium, potassium, magnesium, zinc, cadmium, aluminum, boron, gallium, silicon, tin and the like. r represents the valence of M ^8.

There are various compounds represented by the general formula (XIV). Specifically, methyl lithium,
Alkyllithium compounds such as ethyllithium, propyllithium, butyllithium, diethylmagnesium,
Alkylmagnesium compounds such as ethylbutylmagnesium and dinormalbutylmagnesium; dialkylzinc compounds such as dimethylzinc, diethylzinc, dipropylzinc and dibutylzinc; alkylgallium compounds such as trimethylgallium, triethylgallium and tripropylgallium; triethylboron; Examples thereof include alkyl boron compounds such as propyl boron and tributyl boron, and alkyl tin compounds such as tetraethyl tin and tetraphenyl tin. When M ⁸ is aluminum, there are various compounds. Specific examples include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trin-hexylaluminum, and trioctylaluminum. These organometallic compounds may be used alone or in a combination of two or more.

Further, as the halogen-substituted organometallic compound (D) of the catalyst component in the polymerization catalyst, a compound represented by the general formula (XV) (R ²⁰ ) _n M ⁹ (X ³ ) _jn (XV) Is used. R in the general formula (XV)
²⁰ represents 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 an aralkyl group having 7 to 20 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a hexyl group, a 2-ethylhexyl group, and a phenyl group. M ⁹ is in the periodic table 2 to 4 or 12
It is a metal belonging to Groups 14 to 14, and specific examples include magnesium, zinc, cadmium, aluminum, boron, gallium, silicon, and tin. X ³ represents a halogen atom, that is, a chlorine atom, a bromine atom, an iodine atom, or the like. j is the valence of M ⁹ , usually a real number of 2 to 5, and n is a real number of 0 <n <j, which indicates various real numbers.

As the compound represented by the general formula (XV),
There are various things. Specifically, alkyl halogeno magnesium compounds such as ethylchloromagnesium and ethylbromomagnesium, alkyl halogenogallium compounds such as diethylchlorogallium and ethyldichlorogallium, alkylhalogenoboron compounds such as diethylchloroboron, tributylchlorotin, triphenylchloro An alkylhalogenotin compound such as tin is exemplified. When M ⁹ is aluminum, there are various compounds. Specifically, dialkylaluminum monohalides such as diethylaluminum monochloride, diethylaluminum monobromide, diethylaluminum monoiodide, diisopropylaluminum monochloride, diisobutylaluminum monochloride, dioctylaluminum monochloride or methylaluminum sesquichloride, ethylaluminum sesquichloride And alkylaluminum sesquihalides such as chloride, ethylaluminum sesquibromide and butylaluminum sesquichloride. These halogen-substituted organometallic compounds may be used alone,
Two or more kinds may be used in combination.

In the present invention, at least one of the catalyst components can be used as a polymerization catalyst supported on a suitable carrier. The type of the carrier is not particularly limited, and any of an inorganic oxide carrier, another inorganic carrier, and an organic carrier can be used. In particular, an inorganic oxide carrier or another inorganic carrier is preferable. As the inorganic oxide carrier, specifically, SiO ₂ , Al ₂ O ₃ , Mg
O, ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , B ₂ O ₃ , Ca
O, ZnO, BaO, ThO ₂ and mixtures thereof, for example, silica alumina, zeolite, ferrite, glass fiber and the like can be mentioned. Among these, in particular, Si
O ₂ and Al ₂ O ₃ are preferred. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate, or the like. On the other hand, as inorganic carriers other than the above, MgCl ₂ ,
Examples thereof include magnesium compounds such as Mg (OC ₂ H ₅ ) ₂ and complex salts thereof, and organomagnesium compounds represented by MgR ²¹ _x X ⁴ _y . Here, R ²¹ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, X ⁴ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0
And y is 0 to 2.

As the organic carrier, polystyrene,
Examples 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 the production method, but the average particle size is usually 1 to 300 µm, preferably 10 to 200 µm, more preferably 20 to 100 µm. If the particle size is small, fine powder in the polymer increases, and if the particle size is large, coarse particles in the polymer increase, which causes a decrease in bulk density and clogging of a hopper. The specific surface area of the support is usually 1 to 1000 m ² /
g, preferably 50 to 500 m ² / g, and 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 determined from the volume of nitrogen gas adsorbed according to, for example, the BET method (Journal of American Chemical Society, No. 60).
Vol., P. 309 (1983)). Further, the carrier is usually at 150 to 1000 ° C, preferably at 200 ° C.
It is desirable to use by firing at ~ 800 ° C. There is no particular limitation on the method of being supported on the carrier, and a conventionally used method can be used.

In the present invention, as described above, as the polymerization catalyst, a cationic species is formed from (1) the transition metal compound (A) and (B) the transition metal compound of the component (A) or a derivative thereof. A catalyst in combination with a compound capable of
(2) a catalyst obtained by combining the components (A), (B) and (C) with an organometallic compound; (3) the component (A) with (C)
A catalyst in which the component is combined and a catalyst in which (4) the component (A) is combined with the (D) halogen-substituted organometallic compound are usually used. When the catalyst component (B) is further divided into (B-1) a compound which reacts with the transition metal compound of the component (A) to form an ionic complex, and (B-2) aluminoxane, The combination of components is generally
(A) a combination of the components (A) and (B-1), (B)
A combination of the component (A), the component (B-1), and the component (C),
(C) a combination of the component (A) and the component (B-2);
A combination of the component (A), the component (B-2), and the component (C),
(E) a combination of the components (A) and (C), and (f)
It is a combination of the components (A) and (D).

Next, the use ratio of each catalyst component will be described. When (A) component (A) and component (B-1) are used as the polymerization catalyst, the molar ratio of component (A) / component (B-1) is 1 / 0.01 to 1/100, preferably 1/1 to 1
It is desirable to use both components so as to be in the range of / 10. (B) When the component (A), the component (B-1) and the component (C) are used, the molar ratio of the component (A) / the component (B-1) is the same as in the case of the above (A). Is the component (A) /
(C) The component molar ratio is 1/0 to 1/500, preferably 1
It is preferably in the range of / 1/1/100. Also,
(C) When the component (A) and the component (B-2) are used, the molar ratio of the component (A) / the component (B-2) is 1/20 to 1
It is desirable to use both components so as to be in the range of / 10,000, preferably 1/100 to 1/2000. (D)
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 in the case of the above (c). The molar ratio of component (A) / component (C) is 1/10 to 1/500, preferably 1/1 to 1
/ 100 is desirable.

On the other hand, when the component (A) and the component (C) are used, the molar ratio of the component (A) / the component (C) is 1
/ 1-1 / 5000, preferably 1 / 1-1 / 2000
It is desirable to use both components as in the range. (F) When the component (A) and the component (D) are used, the molar ratio of the component (A) / the component (D) is 1 / 0.5 to 1/1.
It is desirable to use both components in a range of 000, preferably 1/10 to 1/500. In the polymerization catalyst comprising the combination, no particular limitation is imposed on the addition order of the catalyst components, The amount of the polymerization catalyst, the monomer / transition metal molar ratio is 10 / 1-10 ^9/1, preferably 10 ^{2/10 7/1} to become so chooses is desirable range. Using the polymerization catalyst, α having 2 to 12 carbon atoms
-An olefin copolymer obtained by polymerizing at least one selected from olefins and at least one selected from unsaturated group-containing aromatic compounds represented by the general formula (I) is As a unit derived from the aromatic compound, (a) a compound represented by the general formula (XVI):

[0065]

Embedded image

And (b) the general formula (XVII)

Embedded image

(Wherein, R ¹ , R ² , R ³ , R ⁴ and m are the same as those described above). By using (B-1) a compound capable of reacting with a transition metal compound to form an ionic complex or (B-2) aluminoxane as the catalyst component, the selectivity of the unit (b) can be significantly increased. . When an organometallic compound is used as a catalyst component, the use of (a)
The selectivity of the unit is improved. On the other hand, by using the alkyl aluminum halide, the selectivity of the unit (b) can be significantly increased. Therefore, in order to obtain a structure having both the units (a) and (b), the following method can be used. That is, (1) an organoaluminum compound is added to a compound capable of forming an ionic complex by reacting with an aluminoxane-based catalyst or a transition metal compound, and (2) changing the type of an organometallic compound or a halogen-containing organometallic compound. Alternatively, a desired structure can be controlled by performing a method such as a mixed system or (3) changing the molar ratio of copolymer charged. However, when the content of the unit derived from the comonomer represented by the general formula (I) is increased, the crosslinking reaction becomes apparent.

The method of copolymerizing the α-olefin and the unsaturated group-containing aromatic compound includes slurry polymerization, solution polymerization,
Any method such as bulk polymerization and gas phase polymerization may be used, and any of continuous polymerization and discontinuous polymerization may be used. In the case of solution polymerization, examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, pentane, hexane, heptane and octane. Fatty hydrocarbons can be used. In this case, the monomer / solvent (volume ratio) can be arbitrarily selected. The molecular weight or composition of the obtained 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 monomer charge ratio, the type of catalyst, and the like. Further, with regard to control of random and block structures, when copolymerization is performed in the presence of a monomer, a copolymer having high randomness is generated. In addition, when the homopolymerization is performed in advance and the copolymerization is advanced by adding a comonomer component, a copolymer having a high blocking property can be obtained. As the stereoregularity, those having an isotactic structure, a syndiotactic structure, and an atactic structure can be obtained.

In the present invention, the unsaturated olefin-based copolymer obtained in this manner is modified, and a functional group,
For example, a hydroxyl group, a carboxyl group, an epoxy group, a halogen group, a nitro group, an amino group, an acyl group and a sulfone group are introduced. The olefinically unsaturated bond refers to a vinyl group and an alkenyl group having 3 or more carbon atoms. Thus, the general formula (II)

[0070]

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(Wherein, E ¹ and V ¹ each represent a halogen atom, a monovalent metal atom or a substituent containing at least one of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and a tin atom. And these may be the same or different, and R ¹ , R ² , R ³ , R ⁴ and m are the same as those described above), and the general formula (III)

[0072]

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(Wherein E ² and V ² each represent a halogen atom, a monovalent metal atom or a substituent containing at least one of carbon, oxygen, nitrogen, sulfur, silicon and tin atoms) And they may be the same or different, and R ¹ , R ² , R ³ , R ⁴ and m are the same as defined above.) A modified copolymer containing the following chemically modified units is obtained.

In the present invention, the introduction of the functional group into the olefinically unsaturated bond means that the functional group is derived by utilizing the olefinically unsaturated bond. A desired functional group can be introduced by a method such as modification to form a functional group or binding of a compound having a functional group to an olefinically unsaturated bond. 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 20 mol% or more of the olefinically unsaturated bond in the unsaturated olefin-based copolymer. is there. If the introduction amount 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 of introducing a hydroxyl group into the unsaturated olefin-based copolymer is not particularly limited, but may be a method of oxidizing an olefinically unsaturated bond, or a method of oxidizing an olefinically unsaturated bond. It is roughly classified into a method by an addition reaction to an olefinically unsaturated bond, and others. Examples of the method by oxidation of olefinically unsaturated bonds include (a) oxidation of aqueous hydrogen peroxide and an organic acid such as formic acid via peracid, and (ii) a phase transfer catalyst such as a quaternary ammonium salt. Or oxidation in the absence of permanganate, (c) oxidation with hydrogen peroxide water, permanganate, etc. catalyzed by oxides such as osmium, ruthenylum, tungsten, selenium, (d) bromine, etc. Hydrolysis of an adduct of a halogen or hydrogen halide or a sulfuric acid adduct, and (e) hydrolysis of an epoxy group introduced by various reactions. On the other hand, a compound containing one or more hydroxyl groups in a molecule is one having an active hydrogen capable of performing an addition reaction to an olefinically unsaturated bond, in particular, a Michael type addition reaction (having two or more hydroxyl groups. And one of them is used for the addition reaction), and specific examples include thiol compounds such as thioglycerol and thioglycol. In addition, a hydroxyl group can be introduced by an addition reaction of an aldehyde known as a Prince reaction, an oxidation reaction following hydroboration, or a demercuration reaction following oxymercuration of mercuric acetate or the like.

(Ii) Introduction of Carboxyl Group There is no particular limitation on the method of introducing a carboxyl group. It is roughly classified into a method based on an addition reaction to a saturated bond, and others. Specific examples include (a) oxidation with a hydroxylating reagent (such as potassium permanganate),
(B) Hydrolysis after reaction with a radical reaction reagent (such as maleic anhydride), (c) Derivation of a carboxyl group through acylation in a demetalation reaction after reaction with a metalation reagent (eg, alkyl lithium), etc. Is mentioned.

(Iii) Introduction of Epoxy Group There is no particular limitation on the method of introducing an epoxy group into the unsaturated olefin-based copolymer, but a method of oxidizing an olefinically unsaturated bond, one or more epoxy groups in the molecule, The method is based on an addition reaction of a compound containing a group to an olefinically unsaturated bond, and other methods. Examples of the method by oxidation of olefinically unsaturated bonds include (a) oxidation with peracids such as formic acid, peracetic acid, and perbenzoic acid;
Oxidation with sodium hypochlorite or the like in the presence or absence of a metal porphyrin complex such as a manganese porphyrin complex, and (c) hydrogen peroxide in the presence or absence of a catalyst such as a vanadium, tungsten, or molybdenum compound And (d) oxidation with alkaline hydrogen peroxide, and (e) neutralization of an adduct in an acetic acid / t-butyl hypochlorite system with an alkali. On the other hand, a compound containing one or more epoxy groups in a molecule has an active hydrogen capable of performing an addition reaction to an olefinically unsaturated bond, in particular, a Michael type addition reaction, and specific examples thereof include thioglycidol, And thiol compounds such as glycidyl thioglycolate.

(Iv) Introduction of Nitro Group and Amino Group There is no particular limitation on the method of introducing a nitro group into the unsaturated olefin-based copolymer. ), The desired product can be obtained easily and in good yield. Further reduction of the nitro compound enables introduction of 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 with high yield by reacting a reaction reagent comprising aluminum chloride, acetyl chloride and carbon disulfide.

(Vi) Introduction of a sulfone group The method of introducing a sulfone group is not particularly limited. For example, the sulfone group can be easily and efficiently introduced by using sulfuric anhydride, fuming sulfuric acid, concentrated sulfuric acid, chlorosulfonic acid or the like as a sulfonating reagent. can do. The reaction is carried out in a state where the unsaturated olefin-based copolymer is swollen or dissolved by a solvent or in a molten state, but the reaction in a dissolved or molten state is preferred. When a solvent is used, the solvent is appropriately selected depending on the type of the reaction. Examples thereof include aliphatic, alicyclic, aromatic hydrocarbons and halides thereof, esters, ketones, ethers having 6 or more carbon atoms, and carbon disulfide. Is used. These may be used alone or as a mixture of two or more. The selectivity of the reaction is not necessarily 10
It is not necessary to be 0%, and if a sulfone group is substantially introduced, a product by a side reaction may be mixed.

(Vii) Introduction of Halogen There is no particular limitation on the method of introducing a halogen into the unsaturated olefin-based copolymer. Can introduce halogen. Examples of the hydrogen halide include hydrogen chloride, hydrogen bromide, hydrogen iodide, and the like, preferably hydrogen bromide and hydrogen iodide. Examples of the halogen include chlorine, bromine, iodine, bromine monochloride, iodine monochloride,
Among them are iodine monobromide, among which bromine,
Bromine monochloride and iodine monochloride are preferred. The amount of halogen introduced is such that the halogen content in the unsaturated olefin-based copolymer is at least 0.05% by weight, preferably at least 0.5% by weight, more preferably at least 1% by weight. 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 is not necessarily required to be 100%, and a product by a side reaction may be mixed as long as halogen is substantially introduced.

[0081]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. Glass container Preparation Example 1 methylaluminoxane prepared purged with argon inner volume 500 ml, 200 ml of toluene, copper sulfate pentahydrate _{(CuSO 4 · 5H 2 O)} 17.8g (71 mmol) and trimethyl aluminum 24 ml ( 250
Mmol) and reacted at 40 ° C. for 8 hours. Thereafter, toluene was further distilled off under reduced pressure from the solution obtained by removing the solid components, thereby obtaining 6.7 g of a catalyst product (methylaluminoxane). Its molecular weight measured by freezing point depression method was 610. Also, JP-A-62-32
When a high magnetic field component based on ¹ H-NMR measurement based on No. 5391, that is, 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 based on tetramethylsilane. 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 2.35 ppm
Is measured with reference to the high magnetic field component (that is, -0.1 to -0.0.
5 ppm) and other magnetic field components (ie, 1.0 to -0.1 ppm)
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) was mixed with 45 mmol of boron trichloride. Reaction in hexane provided tris (pentafluorophenyl) boron as a white solid. By reacting 41 mmol of this tris (pentafluorophenyl) boron with 41 mmol of lithium pentafluorophenyl, lithium tetrakis (pentafluorophenyl) borate was obtained as a white solid. Then, 16 mmol of lithium tetrakis (pentafluorophenyl) borate and 16 mmol of tri-n-butylammonium hydrochloride were reacted in water to obtain 12.8 mmol of tri-n-butylammonium tetrakis (pentafluorophenyl) borate as a white solid. I got it.

Preparation Example 3 Preparation of Solid Catalyst Component (Solid A) 200 ml of dehydrated and purified n-heptane was placed in a well-dried four-neck flask having a capacity of 500 ml.
Mmol), 1.06 g (17.5 mmol) of isopropyl alcohol was added with stirring, and the mixture was treated at 80 ° C. for 1 hour. Subsequently, the temperature was lowered to room temperature, the supernatant was extracted, 150 ml of n-heptane was added, and the mixture was stirred.
The extraction was repeated twice to wash, and then n-heptane 1
50 ml, 2.63 g (17.5 mmol) of ethyl benzoate and 83 g (440 mmol) of titanium tetrachloride were introduced, the temperature was raised to the boiling point, and the mixture was reacted for 2 hours. After the reaction,
The temperature was lowered to 80 ° C., the mixture was allowed to stand, and the supernatant was extracted.
Washing was performed by repeating draining twice. Thereafter, 83 g of titanium tetrachloride was added again, and the reaction was carried out for 1 hour up to the boiling point.
After standing, the liquid was drained, n-heptane was further added, and the mixture was washed repeatedly by stirring, standing, and draining until no chlorine ion was detected. Thus, a solid catalyst component (solid A) was obtained. When the Ti in the obtained solid catalyst component was measured by a colorimetric method, the supported amount was 48 mg-Ti / g-carrier.

Preparation Example 4 Preparation of Solid Catalyst Component (Solid B) 150 ml of dehydrated and purified hexane was placed in a well-dried 500 ml four-necked flask.
Then 10.0 g (88 mmol) of magnesium diethoxide were introduced, followed by 22 mmol of silicon tetrachloride. While stirring, 33 mmol of isopropyl alcohol was added dropwise at room temperature over 1 hour. Further, after reacting the reaction system at the boiling point for 2 hours, 220 mmol of titanium tetrachloride was added dropwise over 1 hour. Then, after reacting for 3 hours, it was cooled to room temperature. After standing still
The supernatant was taken out, 150 ml of hexane was newly added, and washing, washing, standing, and draining were repeated twice. When Ti in the obtained solid catalyst component (solid B) was measured by a colorimetric method, the supported amount was 42 mg-Ti /
g-carrier.

Production Example 1 Production of Copolymer (Resin A) 100 ml of toluene and 20 mmol of p- (3-butenyl) styrene were placed in a reaction vessel having an internal volume of 500 ml and equipped with a stirrer. Two millimoles of aminoxan was added, immersed in a thermostat at 50 ° C., and stirring was started. To this was added 0.01 mmol of dicyclopentadienyltitanium dichloride, and ethylene was copolymerized at 1.0 kg / cmG for 2 hours. After the reaction,
The unreacted gas was removed, and the polymer was washed with methanol to obtain 3.93 g of a white polymer. FIG. 1 shows the IR absorption spectrum of the obtained polymer. Only the stretching vibration of the carbon-carbon double bond of the olefin unit at 1,640 cm ^{-1 due to} the p- (3-butenyl) styrene residue was observed. further,
^{When 1} H-NMR was measured, the unreacted olefin was
4.8-5.1, 5.7-6.0 ppm. This clearly indicates an olefin derived from the p- (3-butenyl) group. The melting point of the copolymer was measured and found to be 122 ° C. This indicates that the methylene chain is disturbed, that is, the copolymer is randomly copolymerized. Further, the reduced viscosity (in 1,2,4-trichlorobenzene,
Measurement at 135 ° C., concentration 0.05 g / deciliter: The same applies hereinafter. ) Is 0.19 deciliter / g, p-
The content of (3-butenyl) styrene unit was 17.0 mol% based on ¹ H-NMR. (Resin A)

Production Example 2 Production of Copolymer (Resin B) In Production Example 1, ethylene bisindenyl zirconium dichloride was used in place of dicyclopentadienyltitanium dichloride, and propylene was 3.0 kg / kg.
cm ² · G, and polymerized at 30 ° C. for 2 hours.
A copolymer was produced in the same manner as in Production Example 1. as a result,
The yield of the copolymer was 5.94 g, and a symmetric bending vibration of a methyl group due to propylene was observed at 1380 cm ^-1 in the IR absorption spectrum. Further, as in Production Example 1, an absorption based on a carbon-carbon double bond was present at 1640 cm ^-1 . The p- (3-butenyl) styrene unit content in the copolymer was 12.8 mol%, the reduced viscosity was 0.24 deciliter / g, and the melting point was 137.7 ° C. (Resin B)

Production Example 3 Production of Copolymer (Resin C) As in Production Example 1, 100 ml of toluene and p-
8 mmol of (3-butenyl) styrene, 0.5 mmol of triisobutylaluminum, and 0.02 mmol of the boron compound prepared in Preparation Example 2 were added. To this was added 0.01 mmol of dicyclopentadienyl zirconium chloride,
Ethylene was copolymerized at 1.0 kg / cm ² G for 2 hours. After the reaction, the unreacted gas was removed, and the polymer was washed with methanol to obtain 3.9 g of a white polymer. The IR absorption spectrum shows that 1-attributable to p- (3-butenyl) styrene residue.
Only the stretching vibration of the carbon-carbon double bond of the olefin unit at 640 cm ^-1 was observed. Further, when the melting point was measured, it was 108.9 ° C., which indicated that the ethylene chain was disturbed, that is, random copolymerization was performed. Also,
The reduced viscosity was 0.29 deciliter / g. As a result of ¹ H-NMR analysis, the copolymer composition was found to be p- (3-butenyl)
The content of styrene units was 28.4 mol%. (Resin C)

Production Example 4 Production of Copolymer (Resin D) The procedure of Production Example 3 was repeated, except that propylene was saturated with 0.5 kg / g · G before introducing ethylene. Copolymerization was performed. As a result, the yield of the copolymer was 6.20 g, and the IR absorption spectrum contained the same absorption as in Production Example 3. The copolymer composition was 84.8 mol% of ethylene units, 9.2 mol% of propylene units, and p- (3
-Butenyl) 6.0 mol% of styrene units and melting point 112
° C, reduced viscosity 0.21 deciliter / g. (Resin D)

Production Example 5 Production of Copolymer (Resin E) 100 ml of degassed and purified toluene, 2 mmol of triisobutylaluminum, 8 mmol of p- (3-butenyl) styrene were placed in a dried 500 ml pressure-resistant glass reaction tube. Was immersed in a thermostat at 50 ° C., and stirring was started. To this, propylene was added at 0.5 kg / cm ² ·
After saturation at the pressure of G, the total pressure is 1.0 kg / c with ethylene.
m ² · G. Next, 0.01 mmol of the solid catalyst (solid A) prepared in Preparation Example 3 was added as a titanium atom, and copolymerization was performed for 1 hour. During this time, the total pressure is 1 kg with ethylene
/ Cm ² · G was adjusted to the reaction pressure. After completion of the reaction, unreacted gas was removed, and the polymer was washed with methanol to obtain 10.8 g of a white powder. The infrared absorption spectrum (IR) of the obtained polymer was measured. The result is shown in FIG. 1,630c is added to p- (3-butenyl) styrene.
Stretching vibration of the unsaturated carbon-carbon double bond (vinyl group) of the m- ¹ styrene unit and stretching vibration of the carbon-carbon double bond of the olefin unit of 1,640 cm- ¹ existed. Only absorption at 1,630 cm ^-1 was observed for the polymer. ¹ H-NMR also showed the same results as IR.
That is, 5.05 to 5.15 ppm, 5.55 to 5.65 pp
Only unreacted olefins specific to styrene units were found in m. Further, the melting point was measured by a differential scanning calorimeter, and it was 104 ° C. And the reduced viscosity (1, 2,
135 g in 4-trichlorobenzene, concentration 0.05 g /
Measured in deciliters: The same applies hereinafter. ) Was 2.4 deciliters / g, and the copolymer composition was 2.3 mol% of p- (3-butenyl) styrene unit, 70.5 mol% of ethylene unit, and 27.2 mol% of propylene unit. . (Resin E)

Production Example 6 Production of Copolymer (Resin F) Except that in Production Example 5, triethylaluminum was used instead of triisobutylaluminum, and propylene pressure was 2.0 kg / cm ² · G without using ethylene. Is
Copolymerization was carried out in the same manner as in Production Example 5. As a result, the yield of the copolymer was 5.9 g. To remove the amorphous polymer from the copolymer, Soxhlet extraction was performed for 6 hours using heptane as a solvent. IR of this heptane insoluble part
In the absorption spectrum, as in Production Example 5, 1,630 cm
^{At -1} , stretching vibration of the carbon-carbon double bond of the styrene unit was observed. In addition, absorptions specific to isotactic polypropylene were present at 1168 cm ⁻¹ and 998 cm ⁻¹ . The melting point of the copolymer was 148 ° C., which was lower than that of isotactic polypropylene. Further, the content of p- (3-butenyl) styrene unit in the heptane-insoluble portion was 6.0 mol%. (Resin F)

Production Example 8 Production of Copolymer (Resin G) In a stainless steel pressure-resistant autoclave, 400 ml of toluene, 3 mmol of triisobutylaluminum,
20 mmol of p- (3-butenyl) styrene are charged,
The temperature was raised to 80 ° C. 7 kg / cm ² G of hydrogen
, And then 3 kg / cm ² G of ethylene was introduced. To this reaction system, 0.02 mmol of the solid catalyst component (solid B) prepared in Preparation Example 4 was added as titanium atoms. After the start of the copolymerization, ethylene was continuously supplied so as to keep the total pressure constant. After copolymerization for one hour, the copolymer was recovered. As a result, the yield of the copolymer was 29.7 g.
In the IR absorption spectrum, absorption of a carbon-carbon double bond of a styrene unit was observed at 1,630 cm ^-1 . When the melting point was measured, it was 132 ° C., which was lower than the melting point of the linear high-density polyethylene, indicating that a random copolymer was formed. Also,
The content of p- (3-butenyl) styrene unit was 1.8 mol%, and the reduced viscosity was 0.65 dl / g. (Resin G)

Example 1 (Introduction of Hydroxyl Group) 5.0 g of the resin A obtained in Production Example 1 was dissolved in toluene 2 at 120 ° C.
Dissolve in 100 ml and add 90% by weight
A reagent in which 10 g of formic acid and 1.5 g of 30% by weight of hydrogen peroxide were mixed and stirred in advance was added dropwise over 1 hour, and the mixture was further heated at 110 ° C. for 1 hour. Next, after a neutralization treatment with methanol dissolved in sodium hydroxide, the polymer was poured into a large amount of acetone to precipitate the polymer, washed sufficiently, and dried under reduced pressure to obtain a modified copolymer. According to infrared spectroscopy (IR method), the peak at 1640 cm ^-1 which was initially observed almost disappeared, and a new broad peak appeared around 3300 cm ^-1 . The conversion of the olefinically unsaturated bond into a hydroxyl group in the resin A measured by NMR was 78 mol%.

Example 2 A reaction was carried out in the same manner as in Example 1 except that the resin E obtained in Production Example 5 was used instead of the resin A. According to the IR method, disappearance of the peak at 1630 cm ^-1 and 33
A broad peak near 00 cm ^-1 was observed. The conversion of olefinically unsaturated bonds into hydroxyl groups in Resin E was 87 mol%.

Example 3 (Introduction of Carboxyl Group) 5.0 g of the resin B obtained in Production Example 2 was mixed with toluene 2 at 120 ° C.
Of acetic acid.
g, paraformaldehyde 1.8 g, 98% by weight concentrated sulfuric acid 1
Add 3 ml of the mixture and, with vigorous stirring, 3
Refluxed 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 a polymer, washed sufficiently, and dried under reduced pressure to obtain a modified copolymer. By the IR method, the peak at 1640 cm ^-1 disappeared, and a sharp peak was newly observed around 1700 cm ^-1 . The conversion of olefinically unsaturated bonds into carboxyl groups in resin B was 82 mol%.

Example 4 A reaction was carried out in the same manner as in Example 3 except that the resin F obtained in Production Example 6 was used instead of the resin B. By the IR method, disappearance of a peak at 1630 cm ^{-1 and} a peak near 1700 cm ^-1 corresponding to a carboxyl group were confirmed. The conversion of olefinically unsaturated bonds into carboxyl groups in Resin F was almost 100%.

Example 5 (Introduction of Epoxy Group) 5.0 g of the resin C obtained in Production Example 3 was mixed with toluene 2 at 120 ° C.
Then, 0.2 g of t-butyl hydroperoxide and 15 mg of hexacarbonylmolybdenum were added to the solution, and the mixture was refluxed for 2 hours. This was poured into a large amount of cold methanol to precipitate a polymer, washed, and dried under reduced pressure to obtain a modified copolymer. According to the IR method, 164
The peak derived from the 3-butenyl group around 0 cm ^-1 disappeared, and the peak specific to the epoxy group was observed at 3040 cm ^-1 , confirming the introduction of the epoxy group. Resin C
The conversion of olefinically unsaturated bonds into epoxy groups therein was 72 mol%.

Example 6 A reaction was carried out in the same manner as in Example 5, except that the resin G obtained in Production Example 7 was used instead of the resin C. The disappearance of the peak at 1630 cm ^{-1 and} the peak near 3040 cm ^{-1 due} to the introduction of the epoxy group were confirmed by IR. The conversion of olefinically unsaturated bonds in Resin G was almost 100%.

Example 7 (Introduction of Nitro Group) 10.0 g of the resin D obtained in Production Example 4, 200 ml of toluene and 10 ml of 67% by weight sulfuric acid were mixed.
The reaction was carried out at 0 ° C. with stirring. After the completion of the reaction, the mixture was neutralized with methanol dissolved in sodium hydroxide, sufficiently washed, and dried under reduced pressure to obtain a modified copolymer. By IR method,
Characteristic peaks by a 3-butenyl group 1640 cm ^-1 disappeared, sharp peaks due to the presence of the nitro group was observed at around 1560 cm ^-1 and near 1350 cm ^-1. The conversion of olefinically unsaturated bonds into nitro groups in Resin D is approximately 1
00%.

Example 8 (Introduction of Amino Group) 5.0 g of the nitration-modified copolymer obtained in Example 7, 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. with 3 g. The reaction was carried out with stirring for hours. After completion of the reaction, the mixture was neutralized with methanol dissolved in sodium hydroxide, sufficiently washed, and dried under reduced pressure to obtain a modified copolymer. 1560cm specific to nitro group by IR method
^-1 and 1350 cm ^-1 disappear, and 3400-35
A broad peak due to the amino group appeared at 00 cm ^-1 .

Example 9 A reaction was carried out in the same manner as in Example 7, except that the resin E obtained in Production Example 5 was used instead of the resin D. By the IR method, disappearance of the peak at 1630 cm ^-1 and 156
0cm ^-1, confirmed the appearance of the peak of 1350cm ^-1.
The conversion of olefinically unsaturated bonds into nitro groups in this resin E was almost 100%.

Example 10 Using the modified copolymer obtained in Example 9, a reaction was carried out in the same manner as in Example 8. By IR method, 1560c
m ^-1 , disappearance of peak at 1350 cm ^-1 and 3400 to 35
The appearance of a broad peak at 00 cm ^-1 was observed.

Example 11 (Introduction of a Sulfone Group) 10 g of the resin B obtained in Production Example 2 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 40 g of chlorosulfonic acid was added over 6 hours while stirring. Then
Glacial acetic acid was added until no more hydrogen chloride evolved, the reaction was poured into a large volume of water, decanted and re-poured into water. This operation was repeated several times, washed sufficiently, washed with acetone to wash tetrachloroethane, and dried under reduced pressure to obtain a desired modified copolymer. According to the IR method, 16
And disappearance of the peak of 40 cm ^-1, confirmed the peak around 1070 cm ^-1 and 650 cm ^-1 due to the new sulfone groups introduced. The conversion of the olefinically unsaturated bond into the sulfone group in the resin B was 77 mol%.

Example 12 A reaction was carried out in the same manner as in Example 11, except that the resin G obtained in Production Example 7 was used instead of the resin B. In IR method, to confirm the disappearance and 1070cm peak around ^-1 and 650 cm ^-1 peak of 1630 cm ^-1. The conversion of olefinically unsaturated bonds in Resin G was almost 100%.

Example 13 (Acylation) 5.0 g of the resin A obtained in Production Example 1 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, the mixture was further stirred for 15 minutes, and the content was poured into methanol to which hydrochloric acid was added. The aluminum chloride was removed, and the residue was thoroughly washed with dilute hydrochloric acid and water. I 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 of the olefinically unsaturated bond in the resin A was 89 mol%.

Example 14 A reaction was carried out in the same manner as in Example 13, except that the resin F obtained in Production Example 6 was used instead of the resin A. The IR method was confirmed and disappearance of the peak of 1630 cm ^-1, a peak around 1800 cm ^-1 and 1100 cm ^-1. The conversion of the olefinically unsaturated bond in the resin F was almost 100%.

Example 15 (Introduction of Halogen) 5.0 g of the resin C obtained in Production Example 3 and 300 ml of carbon tetrachloride were heated to 50 ° C. and stirred in a nitrogen atmosphere to form a suspension, and then bromine was added. 20 g was charged, and the reaction was continued for 30 minutes. After the completion of the reaction, the content was poured into a large amount of methanol for precipitation. After sufficient washing, the resultant was dried under reduced pressure to obtain a modified copolymer. According to the IR method, 1640 cm ^-1
The disappearance of the peak was confirmed, and the bromine content was determined by ion chromatography to be 39.7% by weight.

Example 16 A reaction was carried out in the same manner as in Example 15 except that the resin F obtained in Production Example 6 was used instead of the resin C. The bromine content determined by ion chromatography was 10.7% by weight.

Test Example 1 Each of the modified copolymers obtained in Examples 1, 3, 5, 7, 8, 12, and 14 and the resin A which is a precursor of the modified copolymer obtained in Production Example 1 was used. Melt press, 40mm x 40mm,
A press sheet having a thickness of 0.1 mm was prepared. Distilled water was dropped at the center of each press sheet, and the shape of the droplet was measured using a droplet shape method. Table 1 shows the results of visual observation.

[0109]

[Table 1]

Test Example 2 0.05 mm thick and 100.0 m long from which dirt was sufficiently removed
m, between two copper plates 20 mm wide,
Each of the modified copolymers obtained in 9, 10, 11, and 13 and the resin E obtained in Production Example 5 were laminated and melt-pressed so as to have a margin of 20 mm. The actual load at the start of peeling was determined by the same method as defined in “Test Method”. The results are shown in Table 2.

[0111]

[Table 2]

[0112]

The modified copolymer of the present invention is characterized in that a hydroxyl group, a carboxyl group, an epoxy group is added to an olefinically unsaturated bond of a copolymer obtained by polymerization of an α-olefin and an unsaturated group-containing aromatic compound. , Halogen group, amino group and other functional groups are introduced to improve adhesiveness, printability, hydrophilicity,
It has excellent polymer modifying properties, antistatic properties, flame retardancy, etc., and is suitably used for various applications.

[Brief description of the drawings]

FIG. 1 is an IR absorption spectrum of the copolymer obtained in Production Example 1.

FIG. 2 is an IR absorption spectrum of the copolymer obtained in Production Example 5.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-194666 (JP, A) JP-A-5-194665 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 8/00-8/50

Claims (5)

(57) [Claims] 1. An 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 is a hydrocarbon group having 1 to 20 carbon atoms, R ² is a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ³ and R ⁴ are a hydrogen atom, a halogen atom or a carbon atom having 1 to 1 carbon atoms, respectively) At least one selected from the unsaturated group-containing aromatic compounds represented by the following formulas: Having a content of the aromatic compound unit of 10 ^{-6 to} 90 mol% obtained by copolymerization with
The reduced viscosity at a concentration of 0.05 g / deciliter measured at 135 ° C. in 2,4-trichlorobenzene is 0.01 to 3
An olefin copolymer of 0 deciliters / g is modified, and a hydroxyl group, a carboxyl group, and a hydroxyl group are chemically reacted to at least 5 mol% of unsaturated bonds in the olefin copolymer .
Epoxy group, halogen group, nitro group, amino group, acyl
At least one member selected from the group consisting of
Modified copolymer, characterized in that the introduction of functional groups. 2. The modified copolymer according to claim 1, wherein the unsaturated bond in the olefin-based copolymer is mainly a vinyl group, and the vinyl group is modified. 3. The modified copolymer according to claim 1, wherein the unsaturated bond in the olefin-based copolymer is mainly an alkenyl group having 3 or more carbon atoms, and the alkenyl group is modified. 4. A unit derived from the modified general formula (I), which is represented by the general formula (II): (Wherein, E ¹ and V ¹ are a hydrogen atom, a hydroxyl group,
Boxyl group, halogen group, nitro group, amino group, acyl
Or E ¹ and V ¹ together
Form an epoxy group. However, E ¹ and V ¹ at the same time water
They cannot be elementary atoms. R ¹ , R ² , R ³ , R ⁴ and m
Is the same as above. And a repeating unit represented by the general formula (III): (Wherein, E ² and V ² represent a hydrogen atom, a hydroxyl group,
Boxyl group, halogen group, nitro group, amino group, acyl
Or E ² and V ² together
Form an epoxy group. However, if E ² and V ² are
They cannot be elementary atoms. R ¹ , R ² , R ³ , R ⁴ and m
Is the same as above. 2. The modified copolymer according to claim 1, which contains at least one chemically modified unit selected from the repeating units represented by the formula: 5. At least one selected from α-olefins having 2 to 12 carbon atoms and at least one selected from unsaturated group-containing aromatic compounds represented by the general formula (I) After the polymerization in the presence of a catalyst to obtain an olefin-based copolymer, the olefin-based copolymer is modified, and a hydroxyl group, a carboxyl group,
Epoxy group, halogen group, nitro group, amino group, acyl
At least one member selected from the group consisting of
The method for producing a modified copolymer according to any one of claims 1 to 4 , wherein a functional group is introduced.