JP3301448B2 - 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 is directed to a method for modifying a reactive olefin-based copolymer obtained by polymerization of an α-olefin having 3 to 12 carbon atoms and a cyclic polyene into which a reactive unsaturated compound has been introduced. Adhesion, printability, hydrophilicity, polymer-modifying properties, anti-static properties by introducing functional groups such as hydroxyl group, carboxyl group, epoxy group, halogen group, nitro group, amino group, acyl group and sulfone group into the group Modified copolymers with high heat resistance and flame retardancy
And a method for producing the same.

[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 into 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.
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 copolymerizability with olefins and do not impair the catalytic activity.
A copolymer of a cyclic polyene and an α-olefin capable of introducing a necessary and sufficient amount of an unsaturated group was developed by adding a small amount to an olefin and copolymerizing the same (Japanese Patent Application No. 4-3229).
No. 92, 4-323936.

The present inventors have further studied to develop a modified olefin copolymer having the above-mentioned preferable properties. As a result, the copolymer of cyclic polyene and α-olefin was modified, It has been found that the purpose can be achieved by introducing a suitable functional group into the unsaturated bond.
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 3 to 12 carbon atoms and a compound represented by the general formula (I)

[0014]

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(Wherein R ^{1 to} R ¹⁰ are each a hydrogen atom,
A halogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
They may be the same or different and m is 0
Indicates the above integer. A) a cyclic polyene represented by the general formula (II)

[0016]

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(Wherein, R ^{11 to} R ²⁰ are each a hydrogen atom,
A halogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
They may be the same or different, R represents an alkenyl group or an alkylidene group, and n represents an integer of 0 or more. (A) Obtained by copolymerization with at least one selected from the cyclic polyenes represented by the following formula (a): The content of the polyene units is 10 ^{-6 to} 20 mol%, and the content was measured in decalin at 135 ° C. Intrinsic viscosity 0.01 to 20 deciliters /
g, having a molecular weight distribution of 3.5 or less as measured by gel permeation chromatography (GPC), and (b) no decalin-insoluble matter at 135 ° C., and a cyclic polyene represented by the above general formula (I) The general formula (II
I)

[0018]

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(Wherein R ^{1 to} R ¹⁰ and m are the same as described above), and the above-mentioned general formula (I
General formula (IV) derived from the cyclic polyene represented by I)

[0020]

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(Wherein, R ^{11 to} R ²⁰ , R and n are the same as those described above), and a crystalline olefin random copolymer containing at least one selected from the repeating units represented by the following formulas: It is an object of the present invention to provide a modified copolymer characterized by being modified and having a functional group introduced into at least 5 mol% of unsaturated bonds in the copolymer by a chemical reaction.

The modified copolymer has 3 to 12 carbon atoms.
At least one selected from α-olefins of
After polymerizing at least one selected from the cyclic polyenes represented by the general formulas (I) and (II) in the presence of a catalyst to obtain a crystalline olefin-based random copolymer, The polymer can be produced by modifying a polymer and chemically reacting with its unsaturated bond to introduce a functional group.

In the present invention, the α-olefin having 3 to 12 carbon atoms used as one component of the raw material monomer includes, for example, propylene; butene-1; pentene-1; hexene-1; heptene-1; octene-1; Nonen-
1; decene-1; 4-phenylbutene-1; 6-phenylhexene-1; 3-methylbutene-1; 4-methylpentene-1; 3-methylpentene-1; 3-methylhexene-1; 4-methyl Hexene-1; 5-methylhexene-1; 3,3-dimethylpentene-1; 3,4-dimethylpentene-1; 4,4-dimethylpentene-1; vinylcyclohexane; α- such as vinylcyclohexene;
Olefin, hexafluoropropene; 2-fluoropropene; 3-fluoropropene; and halogen-substituted α-olefins such as 3,4-dichlorobutene-1.

Among these α-olefins, propylene is particularly preferred, and if the obtained olefin copolymer satisfies the conditions described in the claims, the propylene and other α-olefins and styrenes may be used. It may be used in combination with the above. As the other α-olefin, the above α-olefin having 3 to 12 carbon atoms other than propylene,
Examples include ethylene, tetrafluoroethylene, fluoroethylene, 1,1-difluoroethylene, and trifluoroethylene. Further, as styrenes, styrene, p-methylstyrene, o-methylstyrene, m-
Methylstyrene, 2,4-dimethylstyrene, 2,5-
Dimethylstyrene, 3,4-dimethylstyrene, 3,5
-Dimethylstyrene, alkylstyrene such as pt-butylstyrene, p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-
Halogenated styrenes such as bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene and o-methyl-p-fluorostyrene are exemplified.

Similarly, after completion of the copolymerization reaction of propylene and the cyclic polyene, other α-olefins and styrenes (preferably ethylene) are introduced within a range satisfying the conditions described in the claims. Polymerization may be performed. That is, the obtained olefin-based copolymer is composed of a block composed of a propylene unit and a cyclic polyene unit, and a random copolymer block composed of a propylene unit and another unsaturated monomer unit, preferably an ethylene unit. Can be used. On the other hand, as the cyclic polyene used as another component (comonomer) of the raw material monomer, general formula (I)

[0026]

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(Wherein R ^{1 to} R ¹⁰ and m are the same as those described above), and a cyclic polyene having a norbornene skeleton and a cyclopentene skeleton;

[0028]

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(Wherein R ^{11 to} R ²⁰ , R and n are the same as those described above), and at least one selected from cyclic polyenes having a norbornene skeleton and an alkene skeleton.

In the general formulas (I) and (II), R ¹
To R ¹⁰ and R ¹¹ to R ²⁰ are each a hydrogen atom, a hydrocarbon group of a halogen atom, or 1 to 20 carbon atoms, the halogen atom, chlorine atom, fluorine atom, bromine atom and the like. Examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an octyl group,
Examples include a decyl group, a dodecyl group, a tetradecyl group, a pentadecyl group, a heptadecyl group, an octadecyl group, and an alkoxyl group corresponding thereto. The R ^{1 to} R ¹⁰ may be the same or different, and the R ^{11 to} R ²⁰ may be the same or different. M and n are integers of 0 or more. Further, in the general formula (II),
R is - (CH ₂₎ alkenyl represented by _x -CH = CH-D represents an alkylidene group, D is a hydrogen atom or a -
It is a (CH _{2) y} -CH _3. Then, D is the case of the hydrogen atoms x is an integer from 0 to 18, D is - (CH _{2) y} -CH
_In the case of ₃ , x + y is an integer of 0-17.

Specific examples of the cyclic polyene represented by the general formulas (I) and (II) include dicyclopentadiene,
Examples thereof include dimethyldicyclopentadiene, diethyldicyclopentadiene, 5-vinyl-2-norbornene, 5-allyl-2-norbornene, 5-propenyl-2-norbornene, and 5-ethylidene-2-norbornene. These cyclic polyenes may be used alone or in a combination of two or more.

In the present invention, the above-mentioned three to three carbon atoms are first used.
Polymerizing at least one selected from the α-olefins of No. 12 and at least one selected from the cyclic polyenes represented by the general formulas (I) and (II) in the presence of a polymerization catalyst; To produce a crystalline olefin-based random copolymer. As a polymerization catalyst used for producing this crystalline olefin random copolymer, tetramethylsilane was used as a standard in propylene homopolymerization in ¹³ C-NMR measured with a 1,2,4-trichlorobenzene solution. The peak of the propylene methyl group observed between 19.5 and 22.5 ppm was 21.0 to 22.0 pp.
Any polymerization catalyst that gives a peak area of a peak observed in the range of m of 60% or more of the peak area of all methyl groups can be suitably used. Examples of such a polymerization catalyst include, for example, those mainly containing (A) a transition metal compound and (B) a compound capable of forming a cationic species from the transition metal compound of the component (A) or a derivative thereof. be able to.

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.
As the transition metal, specifically, titanium, zirconium, hafnium, chromium, manganese, nickel, palladium or platinum are preferable, and in particular, zirconium,
Hafnium, titanium, nickel and palladium are preferred. Examples of such a transition metal compound include various compounds, and in particular, a compound containing a transition metal of Group 4 or 8 to 10, particularly a transition metal selected from Group 4 of the periodic table, that is, titanium, zirconium or hafnium. Can be suitably used. In particular, the general formula ^{_{CpM 1 R 21 a R 22 b}} R 23 c ··· (VII) Cp 2 M 1 R 21 a R 22 b ··· (VIII) (Cp-A e -Cp) M 1 R 21 a compound or its derivative represented by R ²² _b ··· (IX) or the general formula ^{_{M 1 R 21 a R 22 b}} R 23 c R 24 d ··· (X) are preferred.

In the general formulas (VII) to (X), M¹
Is the periodic table of titanium, zirconium or hafnium
Represents a Group 4 transition metal, wherein 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. R^{twenty one}, R ^{twenty two}, R^{twenty three}And R^{twenty four}Is German
Vertically σ-binding ligand, chelating ligand, Lewis salt
Represents a ligand such as a group.
Physically, hydrogen atom, oxygen atom, halogen atom, carbon number 1
An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms,
Aryl or alkylaryl groups having 6 to 20 carbon atoms
An arylalkyl group, an acyloxy having 1 to 20 carbon atoms
Si, allyl, substituted allyl, substitution containing silicon atom
And chelating ligands.
Acetylacetonate group, substituted acetylacetonate group
And the like. A represents a covalent crosslink.
a, b, c and d are each independently an integer of 0 to 4;
Shows an integer of 0 to 6. R^{twenty one}, R^{twenty two}, R^{twenty three}And R^{twenty four}Is that
Two or more may combine with each other to form a ring. The above Cp
Has a substituent, the substituent has 1 to 20 carbon atoms.
Are preferred. Equations (VIII) and (IX)
And the two Cp may be the same,
It may be different.

The substituted cyclo in formulas (VII) to (IX)
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 (VII)-
R in formula (X) ^{twenty one}~ R^{twenty four}As 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 crosslink by covalent bond of A in the formula (IX)
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 (VII) 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 exemplified.

Examples of the compound represented by the general formula (VIII) 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 Tylcyclopentadienyl) dimethylzirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, bis (pentamethylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) chloromethylzirconium, bis (penta Methylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl)
Examples thereof include (pentamethylcyclopentadienyl) dichlorozirconium, and further, a compound in which zirconium is replaced by titanium or hafnium.

Examples of the compound represented by the general formula (IX) include ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) dichlorozirconium, and ethylene bis (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, examples of the compound represented by the general formula (X) include tetramethyl zirconium, tetrabenzyl zirconium, tetramethoxy zirconium,
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 (IX), 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, those represented by the general formula (XI)

[0041]

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The compounds represented by the following or derivatives thereof
be able to. Y in the general formula (XI)¹Is carbon, kei
Element, germanium or tin atom, R^{twenty five} _t -C_FiveH_4-tPassing
And R^{twenty five} _u-C_FiveH_4-uAre each substituted cyclopentadie.
The nyl group, t and u represent an integer of 1 to 4. Where R^{twenty five}
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 carbon^{twenty five}Exists.
R²⁶Is 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 R²⁶Also
They may be the same or different.

The substituted cyclopentadienyl group in the above formula (XI) includes, for example, methylcyclopentadienyl group; ethylcyclopentadienyl group; isopropylcyclopentadienyl group; 1,2-dimethylcyclopentadienyl 1,3-dimethylcyclopentadienyl group; 1,2,3-trimethylcyclopentadienyl group;
1,2,4-trimethylcyclopentadienyl group and the like. 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. A 2-ethylhexyl group, a 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 and arylalkyl group include phenyl group, tolyl group, xylyl group, and benzyl group. Methyl group Specific examples of R ^26, an ethyl group, a phenyl group, a tolyl group, a xylyl group, and a benzyl group. Examples of the compound of the general formula (XI) 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 (XII)

[0044]

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The compounds represented by the following formulas are also included. In the compound of the general formula (XII), Cp represents 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, etc. A cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group. M ³ represents a titanium, zirconium or hafnium atom; X ² represents a hydrogen atom, a halogen 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, or 1 carbon atom. ~ 20 alkoxy groups. Z is SiR ^{27
_{2, CR 27 2, SiR 27}} 2 SiR 27 2, CR 27 2 CR 27 2
_{^{, CR 27 2 CR 27 2 CR}} 27 2, CR 27 = CR 27, CR
²⁷ ₂ SiR ²⁷ ₂ or GeR ²⁷ ₂ indicates, Y ² is -N (R
^{28) -, - O -,} - S- , or -P (R ²⁸⁾ - shows the. R ²⁷ is a hydrogen atom or a group selected from alkyl, aryl, silyl, alkyl halide, aryl halide groups having up to 20 non-hydrogen atoms and combinations thereof, and R ²⁸ has 1 to 10 carbon atoms. Or an aryl group having 6 to 10 carbon atoms, or a condensed ring system of one or more R ²⁷ and up to 30 non-hydrogen atoms. w represents 1 or 2.

A transition containing a transition metal belonging to Group 5 to Group 10
There is no particular limitation on the metal compound.
Examples of the body include tetramethylchromium, tetra (t-butane)
Xy) chromium, bis (cyclopentadienyl) chromium,
Hydride tricarbonyl (cyclopentadienyl) chloro
Hexacarbonyl (cyclopentadienyl)
, Bis (benzene) chromium, tricarbonyltris
(Triphenylphosphonate) chromium, tris (allyl)
Chromium, triphenyl tris (tetrahydrofuran)
ROM, chrome tris (acetylacetonate)
I can do it. Specific examples of manganese compounds include trical
Bonyl (cyclopentadienyl) manganese, pentacal
Bonylmethylmanganese, bis (cyclopentadienyl)
Manganese, manganese bis (acetylacetonate), etc.
Is mentioned. Specific examples of nickel compounds include Zika
Rubonyl bis (triphenylphosphine) nickel, di
Bromobis (triphenylphosphine) nickel, dinitrogen
Bis [bis (tricyclohexylphosphine) nickel
), Chlorohydridobis (tricyclohexylphosph
In) nickel, chloro (phenyl) bis (triphenyl)
Ruphosphine) nickel, dimethyl bis (trimethylpho
Sphine) nickel, diethyl (2,2'-bipyridi)
Le) nickel, bis (allyl) nickel, bis (cyclo
Pentadienyl) nickel, bis (methylcyclopenta
Dienyl) nickel, bis (pentamethylcyclopenta)
Dienyl) nickel, allyl (cyclopentadienyl)
Nickel, (cyclopentadienyl) (cyclooctadi
En) nickel tetrafluoroborate, bis (cyclo
Kutadiene) nickel, nickel bisacetylacetona
, Allyl nickel chloride, tetrakis (triphe
Nylphosphine) 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, 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-
(Cyclooctadiene) palladium tetrafluoroborate, tetrakis (acetonitrile) palladium nitetrafluoroborate, and the like. In the polymerization catalyst used in the present invention, the transition metal compound of the component (A) may be used alone or in combination of two or more.

On the other hand, in the polymerization catalyst, 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), includes (B-1) A compound which reacts with the transition metal compound as the component (A) to form an ionic complex;
2) Aluminoxane can be exemplified. The (B-
As the compound of the component (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. And a coordination complex compound composed of a cation and an anion having a plurality of groups bonded to an element. As a compound comprising such a cation and an anion in which a plurality of groups are bonded to an element, a compound represented by the general formula ([L ¹ -R ²⁹ ] ^{k +} ) _p ([M ⁴ Z ¹ Z ² · Z ⁿ ] ^{(hg) -)} _q ··· (XIII) or ([L ^{2] k} +) _p ^{([M 5 Z 1 Z 2 ·· Z} n ] _{^{(hg) -) q ··· (}} XIV) ( where, L ² is M ^{6, R 30 R 31 M 7} , R 32 3 C or R ³³
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 ²⁹ is a hydrogen atom, carbon number 1
20 represents an alkyl group, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R ³⁰ and R ³¹ are each a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group,
R ³² represents an alkyl group, an aryl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms. R ³³ represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine. g is a valence of M ⁴ or M ⁵ and is an integer of 1 to 7, h is an integer of 2 to 8, k is [L ¹ -R ²⁹ ],
[L ² ] is an ionic valence of 1 to 7 and p is an integer of 1 or more, and q = (p × k) / (h−g). ] It is a compound represented by these.

[0049] 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 ²⁹ and R ³² include the same as those described above.
Specific examples of the substituted cyclopentadienyl group for R ³⁰ and R ³¹ include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Can 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 general formulas (XIII) and (XIV), those in which M ⁴ and M ⁵ are boron are preferred. Among the compounds of the general formulas (XIII) and (XIV), specifically, the following can be particularly preferably used. For example, compounds of the general formula (XIII) include triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate,
Tetraethylammonium 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 Tri (n-butyl) ammonium phenyl) borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetrabutylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate [Methyltri (n-butyl) ammonium], tetrakis (pentafluorophenyl) ) Boric acid [benzyltri (n-butyl) ammonium], methyldiphenylammonium tetrakis (pentafluorophenyl) borate, methyltriphenylammonium tetrakis (pentafluorophenyl) borate, dimethyldiphenylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluoro) Anilinium phenyl) borate, methylanilinium tetrakis (pentafluorophenyl) borate,
Dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, dimethyl (m-nitroanilinium) tetrakis (pentafluorophenyl) borate, dimethyltetrakis (pentafluorophenylmethyl) borate (p- Bromoanilinium), pyridinium tetrakis (pentafluorophenyl) borate, p-cyanopyridinium tetrakis (pentafluorophenyl) borate, N-methylpyridinium tetrakis (pentafluorophenyl) borate, 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, tetraferphosphonium tetrakis (pentafluorophenyl) borate, dimethylanitetrakis (3,5-ditrifluoromethylphenyl) borate Lium, 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) triphenylphosphonium borate, tris (pentafluorophenyl) ( 2,3,5
Dimethylanilinium 6-tetrafluoropyridinyl) borate, tris (pentafluorophenyl) (2,3
5,6-tetrafluoropyridinyl) triethylammonium borate, tris (pentafluorophenyl) (2
3,5,6-tetrafluoropyridinyl) pyridinium borate, tris (pentafluorophenyl) (2,3
5,6-tetrafluoropyridinyl) borate (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) triphenylphosphonium borate, tris (pentafluorophenyl)
Dimethylanilinium (phenyl) borate, dimethylanilinium tris (pentafluorophenyl) [3,5-di (trifluoromethyl) phenyl] borate, dimethylanilinium tris (pentafluorophenyl) (4-trifluoromethylphenyl) borate Dimethylanilinium triphenyl (pentafluorophenyl) borate, triethylammonium hexafluoroarsenate, and the like.

On the other hand, compounds of the general formula (XIV) include ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, manganese tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate and tetrakis (Pentafluorophenyl) borate (1,1'-dimethylferrocenium), decamethylferrocenium tetrakis (pentafluorophenyl) borate, acetylferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate Formylferrocenium, cyanoferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, trikis (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, and the like. Compounds other than the general formulas (XIII) and (XIV) 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.

The compound (B-1), which reacts with the transition metal compound of the component (A) to form an ionic complex, may be used singly 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 (XV)

[0054]

Embedded image

(Wherein R ³⁴ represents an alkyl group, alkenyl group, aryl group having 1 to 20 carbon atoms, 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 (XV)
I)

[0056]

Embedded image

(Wherein R ³⁴ and s are the same as described above).

Among the compounds represented by formulas (XV) and (XVI), aluminoxane having a degree of polymerization of 7 or more is preferred. When an aluminoxane having a degree of polymerization of 7 or more or a mixture thereof is used, high activity can be obtained. Further, modified aluminoxanes which are obtained by modifying the aluminoxanes represented by the general formulas (XV) and (XVI) with a compound having active hydrogen such as water and which are insoluble in ordinary solvents 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 means 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.

In the polymerization catalyst used in the present invention,
If desired, as the component (C), an organometallic compound, preferably a compound represented by the general formula (XVII) R ³⁴ _r AlQ _3-r (XVII) wherein R ³⁴ is the same as described above, and Q is a hydrogen atom Represents an alkoxy group having 1 to 20 carbon atoms or a halogen atom,
Is a number from 1 to 3. ] Can be used. In particular, when a compound which reacts with the transition metal compound of the component (A) shown as the component (B-1) to form an ionic complex is used as the component (B), the organic aluminum compound (C) is used in combination. High activity can be obtained. The general formula (XVII)
Specific examples of the compound represented by are trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride,
Examples include methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, and ethylaluminum sesquichloride.

Next, in the present invention, (A)
At least one of the catalyst component (B) and the catalyst component (C) used as required can be 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 , MgO, Zr
O ₂ , TiO ₂ , Fe ₂ O ₃ , B ₂ O ₃ , CaO, Zn
O, BaO, ThO ₂ and mixtures thereof, for example, silica alumina, zeolite, ferrite, glass fiber and the like can be mentioned. Among these, SiO ₂ , A
l ₂ O ₃ is 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 , Mg (O
Examples thereof include magnesium compounds such as C ₂ H ₅ ) ₂ and complex salts thereof, and organomagnesium compounds represented by MgR ³⁵ _i X ³ _j . Here, R ³⁵ has 1 carbon atom.
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 ³ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, i is 0 to 2, j
Is 0-2.

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.

Next, the use ratio of each catalyst component in the present invention will be described. When the component (1) (A) and the component (B-1) are used as the catalyst components, the component (A) /
(B-1) Component molar ratio is from 1 / 0.1 to 1/100, preferably from 1 / 0.5 to 1/10, and more preferably from 1/1 to 1/1.
It is desirable to use both components in a range of 5.
(2) 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 (1). However, the molar ratio of component (A) / component (C) is 1/2000 to 1/1, preferably 1/10.
It is desirable to be in the range of 00 to 1/5, more preferably 1/500 to 1/10.

When (3) component (A) and component (B-2) are used, the molar ratio of component (A) / component (B-2) is 1/20 to 1/10000, preferably 1/100
It is desirable to use both components so as to be in the range of １／1/2000. (4) Component (A), component (B-2), and (C)
When the component is used, the molar ratio of the component (A) / the component (B-2) is the same as in the case of the above (3), but the molar ratio of the component (A) / the component (C) is 1/2000 to 2000. 1/1, preferably 1/1000 to 1/5, more preferably 1/500 to
It is desirable to be in the range of 1/10. In this polymerization reaction, the cyclic polyene may be charged at the start of the polymerization, or may be added during the polymerization.The method of addition is not particularly limited, and any of batch addition, divisional addition, or continuous addition may be used. May be.

The polymerization method is not particularly limited, and a solvent polymerization method using an inert hydrocarbon or the like (suspension polymerization or solution polymerization) or a bulk polymerization method in which polymerization is performed under the condition that substantially no inert hydrocarbon solvent is present. Alternatively, a gas phase polymerization method can be used. Examples of the hydrocarbon solvent used in the copolymerization include saturated hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; Chlorine-containing solvents such as chloroform, dichloromethane, ethylene dichloride, and chlorobenzene are exemplified. The polymerization temperature is -100 to 2
The polymerization is generally carried out at a temperature of 00 ° C. and a polymerization pressure of normal pressure to 100 kg / cm ² , preferably -50 to 100
° C, normal pressure-50 kg / cm ² , more preferably 0-1
It is in the range of 00 ° C., normal pressure to 20 kg / cm ² . The copolymer of the present invention can be adjusted by a combination of known techniques such as addition of hydrogen and a third component and polymerization temperature.

The crystalline olefin random copolymer thus obtained has a cyclic polyene unit of 10 ^-6 to 2
It must be contained at a ratio of 0 mol%, preferably 0.001 to 15 mol%, more preferably 0.001 to 12 mol%. The intrinsic viscosity [η] measured in a decalin solution at 135 ° C. is 0.01 to 20 deciliters / liter.
g, preferably 0.05 to 10 deciliter / g.
The molecular weight of this crystalline olefin random copolymer is not particularly limited, but the molecular weight (polyethylene) determined by gel permeation chromatography (GPC) at 135 ° C using 1,2,4-trichlorobenzene as a solvent. Conversion) is the weight average molecular weight (Mw)
2,000 to 20,000, preferably 5,000 to 1,
Number average molecular weight (Mn) in the range of 00000
Is preferably in the range of 500 to 100,000.
Further, the molecular weight distribution (Mw / Mn) needs to be 3.5 or less, preferably 3.2 or less. When the molecular weight distribution exceeds 3.5, the content of the low molecular weight substance increases, and when a molded article is formed, it may cause stickiness.

Further, the olefin random copolymer has no decalin-insoluble components at 135 ° C.
General formula (III) derived from the cyclic polyene represented by

[0068]

Embedded image

(Wherein R ^{1 to} R ¹⁰ and m are the same as described above), and the above-mentioned general formula (II)
General formula (IV) derived from a cyclic polyene represented by

[0070]

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(In the formula, R ^{11 to} R ²⁰ and n are the same as described above.) This is because IR and
It is clear from the measurement of ¹ H-NMR [“Industrial Chemistry Magazine”
Vol. 67, No. 11, 256 pages (1964),
And Vol. 69, No. 4, pp. 120 (1966)
Year). ]. Also, this copolymer is
Since no insoluble matter was found in 135 ° C decalin,
It is clear that there is no gel component.

The crystalline olefin random copolymer has a crystallinity of 5% or more, preferably 10 to 65%, more preferably 1 to 5% as measured by an X-ray diffraction method (powder method).
It is in the range of 5-65%. The degree of crystallinity is determined by X-ray diffractometer (manufactured by Rigaku Denki Co., Ltd.) to obtain an X-ray diffraction diagram of 2θ: 4 to 30 °, separate a crystal part from an amorphous part by a drawing method, and obtain a total X-ray. It is a value obtained from the ratio between the intensity and the X-ray intensity of the crystal part.

The crystalline olefin random copolymer has the following characteristics when propylene is used as the α-olefin. That is, (a) ¹³ C-N
In the MR measurement, in the 1,2,4-trichlorobenzene solution, the peak of the propylene methyl group between 19.5 and 22.5 ppm based on tetramethylsilane is 21.0-22. The peak area of the peak observed between 0 ppm is 60% or more of the entire peak area derived from the methyl group, and (b) the melting point (Tm) measured by a differential scanning calorimeter (DSC) is 100 ° C or more. so,
The crystallization enthalpy (ΔH) is 25 J / g or more.
When the Tm is lower than 100 ° C., the copolymer is substantially equivalent to an amorphous copolymer and is not intended by the present invention. Here, as for the measurement conditions of DSC, the temperature was increased from room temperature to 190 ° C. at a rate of 20 ° C./min from the room temperature and maintained for 3 minutes in a whole system nitrogen gas atmosphere using a DSC-7 apparatus manufactured by Perkin Elmer. Thereafter, the temperature was lowered to room temperature at a rate of 20 ° C./min and maintained for 5 minutes, and then the temperature was raised at a rate of 20 ° C./min, and Tm and ΔH were measured in the process.

In the present invention, the olefin random copolymer is modified, and a functional group such as a hydroxyl group, a carboxyl group, an epoxy group is added to at least 5 mol% of the olefinically unsaturated bonds of the copolymer by a chemical reaction. , A halogen group, a nitro group, an amino group, an acyl group and a sulfone group. Thus, the general formula (V) obtained by introducing a functional group into the olefinically unsaturated bond of the unit represented by the general formula (III)

[0075]

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(Wherein Z 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 R ^{1 to} R ¹⁰ and m are the same as above, and the unsaturated unit of the unit represented by the general formula (IV) General formula (V
I)

[0077]

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(Wherein Z ² and V ² 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 they may be the same or different, and D is a hydrogen atom or-(CH) _y -C
H ₃ represents, when D is a hydrogen atom, x is an integer of 0 to 18,
D is - (CH) if x + y of the _y -CH ₃ is an integer of 0~17, R ¹¹ ~R ²⁰ and n are as defined above. A modified copolymer containing at least one chemically modified unit selected from the repeating units represented by the formula (1) is obtained. In the unit represented by the general formula (IV), when R is an alkenyl group, D in the chemically modified unit represented by the general formula (VI) is a hydrogen atom, and when R is an alkylidene group, There - is (CH _{2) y} -CH _3.

In the present invention, the introduction of the functional group into the olefinically unsaturated bond means that the functional group is derived using 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 introduction amount of the functional group is 5 mol% of the olefinic unsaturated bond in the olefin random copolymer.
Or more, preferably 10 mol% or more, more preferably 15 mol% or more.
Mol% or more, most preferably 20 mol% or more. 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 olefin random copolymer is not particularly limited, but a method of oxidizing an olefinically unsaturated bond, an olefin of a compound containing one or more hydroxyl groups in the molecule. And a method based on an addition reaction to a sexually unsaturated bond, and others. Examples of the method based on the oxidation of olefinically unsaturated bonds include (a) oxidation via hydrogen peroxide and an organic acid such as formic acid via peracid, and (b)
Oxidation with permanganate or the like in the presence or absence of a phase transfer catalyst such as a quaternary ammonium salt, (c) aqueous hydrogen peroxide catalyzed by an oxide such as osmium, ruthenylum, tungsten, or selenium; Oxidation with manganate, etc., (d) hydrolysis of adducts of halogen or hydrogen halide such as bromine or sulfuric acid adducts, and (e) hydrolysis of epoxy groups introduced by various reactions. . On the other hand, a compound containing one or more hydroxyl groups in the molecule is an addition reaction to an olefinically unsaturated bond,
Particularly, it has an active hydrogen capable of performing a Michael type addition reaction (including a case where two or more hydroxyl groups are used and one of them is used for the addition reaction), and specific examples thereof include thioglycerol. And thiol compounds such as 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 The method of introducing a carboxyl group is not particularly limited. However, the method of oxidizing an olefinically unsaturated bond, the method of olefinic unreacting 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 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 olefin random copolymer, but a method of oxidizing an olefinically unsaturated bond, one or more epoxy groups in the molecule. And a method based on an addition reaction of a compound containing an olefinic unsaturated bond. 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 The method for introducing a nitro group into the olefin random copolymer is not particularly limited, but ordinary nitrating agents (eg, fuming nitric acid, mixed acid, acetyl nitrate, etc.) , A desired product can be easily obtained with high yield. Further reduction of the nitro compound enables introduction of an amino group.

(V) Introduction of acyl group The method of 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 Sulfone Group The method for introducing the 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 in which the olefin random 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 olefin random copolymer. , 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 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. Regarding the introduction amount of the halogen, it is preferable to introduce the halogen so that the halogen content in the olefin random copolymer is 0.05% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more. 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. Reaction selectivity is not necessarily 100%
It is not necessary that the product of the side reaction be mixed if the halogen is substantially introduced.

[0086]

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 transition metal compound Prepared according to a conventional method, and confirmed to be the target compound by ¹ H-NMR. Bis (indenyl) bis (dimethylsilyl) zirconium dichloride (catalyst 1) indenyl (cyclopentadienyl) (dimethylsilyl) zirconium dichloride (catalyst 2) dimethylsilylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride (catalyst) 3)

Production Example 1 400 ml of toluene and triisobutylaluminum were placed in a reactor equipped with a stirrer having an internal volume of 1000 ml.
1.0 mmol, and then 5 mmol of methylaluminoxane (MAO) of Preparation Example 1 and heating to 50 ° C.
Stirring was started. In addition, bis (indenyl) bis (dimethylsilyl) zirconium dichloride (catalyst 1) 0.0
1 mmol and 100 mmol of dicyclopentadiene
Each was added as a toluene solution, and propylene was added to 6.0 k
The polymerization was performed at g / cm ² · G for 2 hours. After the reaction, the unreacted gas was removed, and the polymer was washed with methanol to obtain 68.6 g of a white polymer. GPC (Equipment; Waters AL
C / GPC 150C, column; TSKHM + manufactured by Toso-
GMH 6 × 2, flow rate 1.0 ml / min, converted to polyethylene) The measurement results are Mw 105800, Mn 3640
0, Mw / Mn 2.91, intrinsic viscosity [η] is 1.05
It was deciliter / g. The melting point of the copolymer was measured to be 132 ° C., and the crystallization enthalpy was 55.8.
J / g, and the crystallinity determined by X-ray diffraction was 22.7%. In addition, according to IR measurement, 1610 cm ⁻¹ , 940
A characteristic peak derived from the comonomer component was confirmed at cm ⁻¹ . Of all peak areas derived from the methyl group of propylene determined from the measurement of ¹³ C-NMR, 21.0 to 22.0 pp
The peak area ratio existing in m was 68.7%. further
The content of dicyclopentadiene units determined by ¹ H-NMR was 7.63 mol%. (Resin A)

Production Examples 4 to 7 Copolymers were produced according to Production Example 1 under the polymerization conditions shown in Table 1. The yield and properties of this product are shown in Table 1.

[0091]

[Table 1]

[0092]

[Table 2]

(Note) Catalyst 1; bis (indenyl) bis (dimethylsilyl) zirconium dichloride Catalyst 2; indenyl (cyclopentadienyl) (dimethylsilyl) zirconium dichloride catalyst 3; dimethylsilylbis (2,4-dimethylcyclopenta Dienyl) zirconium dichloride MAO; methylaluminoxane of Preparation Example 1, except that 1
/ 5 mol times triisobutylaluminum in combination. Anilinium; dimethylanilinium tetrakis (pentafluorophenyl) boron of Preparation Example 2, but with 0.3 mmol of triisobutylaluminum in combination. Propylene pressure, 6.0 kg / cm ² G

Example 1 (Introduction of Hydroxyl Group) 5.0 g of the resin A obtained in Production Example 1 was mixed with 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. By infrared spectroscopy (IR method), the initially observed peak at 1610 cm ^-1 almost disappeared, and a new broad peak appeared around 3300 cm ^-1 . The conversion of olefinically unsaturated bonds into hydroxyl groups in Resin A measured by NMR was 92 mol%.

Example 2 A reaction was carried out in the same manner as in Example 1 except that the resin C obtained in Production Example 3 was used instead of the resin A. By the IR method, disappearance of the peak at 1640 cm ⁻¹ and 33
A broad peak near 00 cm ^-1 was observed. The conversion of olefinically unsaturated bonds into hydroxyl groups in resin C is approximately 10
It was 0%.

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 1610 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 almost 100%.

Example 4 A reaction was carried out in the same manner as in Example 3, except that the resin D obtained in Production Example 4 was used instead of the resin B. By the IR method, disappearance of a peak at 1640 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 D was almost 100%.

Example 5 (Introduction of Epoxy Group) 5.0 g of the resin A obtained in Production Example 1 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, 161
0cm peak around ^-1 disappeared, since the epoxy group-specific peaks were observed 3040Cm ^-1, introduction of epoxy groups was confirmed. The conversion of the olefinically unsaturated bond into an epoxy group in the resin A was 86 mol%.

Example 6 A reaction was carried out in the same manner as in Example 5, except that the resin C obtained in Production Example 3 was used instead of the resin A. The disappearance of the peak at 1640 cm ^{-1 and} the peak near 3040 cm ^{-1 due} to the introduction of the epoxy group were confirmed by the IR method. The conversion of olefinically unsaturated bonds in resin C is about 9
It was 0 mol%.

Example 7 (Introduction of Nitro Group) 10.0 g of the resin B obtained in Production Example 2, 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 mixed at 80 ° C. for 10 minutes. The reaction was performed 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, 1610c
The characteristic peak at m ^-1 disappeared, and around 1560 cm ^-1 and 13
A sharp peak due to the presence of the nitro group was observed around 50 cm ^-1 . The conversion of olefinically unsaturated bonds into nitro groups in Resin B was almost 100%.

Example 8 (Introduction of Amino Group) 5.0 g of the nitrated 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 mixed at 80 ° C. 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 D obtained in Production Example 4 was used instead of the resin B. By the IR method, disappearance of the peak at 1640 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 Resin D 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 A obtained in Production 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 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 10 cm ^-1, confirming the peak around 1070 cm ^-1 and 650 cm ^-1 due to the new sulfone groups introduced. The conversion of olefinically unsaturated bonds into sulfone groups in the resin A was 95 mol%.

Example 12 A reaction was carried out in the same manner as in Example 11, except that the resin C obtained in Production Example 3 was used instead of the resin A. In IR method, to confirm the disappearance and 1070cm peak around ^-1 and 650 cm ^-1 peak of 1640 cm ^-1. The conversion of olefinically unsaturated bonds in Resin C was almost 100%.

Example 13 (Acylation) 5.0 g of the resin B obtained in Production 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, 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 1610 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 B was almost 100%.

Example 14 A reaction was carried out in the same manner as in Example 13 except that the resin D obtained in Production Example 4 was used instead of the resin B. The IR method was confirmed and disappearance of the peak of 1640 cm ^-1, a peak around 1800 cm ^-1 and 1100 cm ^-1. The conversion of the olefinically unsaturated bonds in the resin D was almost 100%.

Example 15 (Introduction of Halogen) 5.0 g of the resin A obtained in Production Example 1 and 300 ml of carbon tetrachloride were heated to 50 ° C. and stirred in a nitrogen atmosphere to form a suspension. 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. By IR method, 1610 cm ^-1
The disappearance of the peak was confirmed, and the bromine content was measured by ion chromatography to be 9.4% by weight.

Example 16 A reaction was performed in the same manner as in Example 15 except that the resin C obtained in Production Example 3 was used instead of the resin A. The bromine content measured by ion chromatography was 2.4% by weight.

Test Example 1 Resin A, which is a precursor of the modified copolymer obtained in Examples 1, 3, 5, 7, 8, 12, and 14 and the modified copolymer obtained in Production Example 1, was used. Melt press, 40mm × 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 2 shows the results of visual observation.

[0111]

[Table 3]

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,
The modified copolymers obtained in 9, 10, 11 and 13 and the resin D obtained in Production Example 4 were pasted together 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 3.

[0113]

[Table 4]

[0114]

The modified copolymer of the present invention is characterized in that a hydroxyl group, a carboxyl group, an epoxy group, a halogen group, an amino group are added to the olefinically unsaturated bond of the copolymer obtained by polymerization of an α-olefin and a cyclic polyene. It has a functional group such as a group and is excellent in adhesiveness, printability, hydrophilicity, polymer modifying property, antistatic property, flame retardancy, etc., and is suitably used for various applications.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 8/00-8/50 C08F 232/08

Claims (4)

(57) [Claims] 1. An at least one selected from α-olefins having 3 to 12 carbon atoms and a compound represented by the general formula (I): (Wherein, R ^{1 to} R ¹⁰ each represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and m represents an integer of 0 or more. A) a cyclic polyene represented by the general formula (II): (Wherein, R ^{11 to} R ²⁰ each represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and R represents an alkenyl group or an alkylidene group, n represents an integer of 0 or more. obtained by copolymerization of at least one selected from the cyclic polyene represented by), with 10 ^-6 to 20 mol% content of (a) the polyene units The intrinsic viscosity measured in decalin at 135 ° C. is 0.01 to 20 deciliters / g, and gel permeation chromatography (GP
The molecular weight distribution measured in C) is 3.5 or less, and (b) there is no decalin-insoluble matter at 135 ° C., and the general formula (II) derived from the cyclic polyene represented by the above general formula (I)
I) (Wherein, R ^{1 to} R ¹⁰ and m are the same as described above), and a general formula (IV) derived from the cyclic polyene represented by the general formula (II). ] Wherein, in the formula, R ^{11 to} R ²⁰ , R and n are the same as described above, a crystalline olefin random copolymer containing at least one selected from the repeating units represented by the following formula: At least 5 mol% of unsaturated bonds in the copolymer
Hydroxyl, carboxyl, epoxy by chemical reaction
Group, halogen group, nitro group, amino group, acyl group and
A modified copolymer having at least one functional group selected from rufone groups . 2. A crystalline olefin random copolymer, a one using propylene as α- olefins, in (i) ¹³ C-NMR measurement, 1,2,4
In the trichlorobenzene solution, the peak of the methyl group of propylene was 19.5 to 2 based on tetramethylsilane.
Of those observed between 2.5 ppm, 21.0-
The peak area observed between 22.0 ppm is 60% or more of the entire peak area derived from the methyl group,
(B) Melting point (T) measured by differential scanning calorimeter (DSC)
m) is 100 ° C. or more and the crystallization enthalpy (ΔH) is 2
The modified copolymer according to claim 1, which satisfies a condition of 5 J / g or more. 3. A compound represented by the general formula (V) obtained by introducing a functional group into an unsaturated bond of a unit represented by the general formula (III) as a chemically modified unit. (Wherein, Z ¹ and V ¹ are a hydrogen atom, a hydroxyl group,
Boxyl group, halogen group, nitro group, amino group, acyl
Or Z ¹ and V ¹ together
Form an epoxy group. However, if Z ¹ and V ¹ are simultaneously water
They cannot be elementary atoms. R ^{1 to} R ¹⁰ and m are the same as described above. ) And a general formula (VI) obtained by introducing a functional group into the unsaturated bond of the unit represented by the general formula (IV). (Wherein, Z ² and V ² each represent a hydrogen atom, a hydroxyl group,
Boxyl group, halogen group, nitro group, amino group, acyl
Or Z ² and V ² together
Form an epoxy group. However, if Z ² and V ² are simultaneously water
They cannot be elementary atoms. D is a hydrogen atom or-(CH ₂ )
_{Y represents} —CH _3, and when D is a hydrogen atom, x is an integer of 0 to 18, and when D is — (CH ₂ ) _y —CH ₃ , x + y is an integer of 0 to 17, and R ^{11 to} R ²⁰ and n is the same as above. 2. The modified copolymer according to claim 1, which contains at least one selected from the repeating units represented by the formula: 4. At least one selected from the group consisting of α-olefins having 3 to 12 carbon atoms and at least one selected from the cyclic polyenes represented by the general formulas (I) and (II) and after the by presence polymerization catalyst to obtain a crystalline olefin random copolymer, the copolymer by modifying a hydroxyl group by a chemical reaction to the unsaturated bond, a carboxyl
Sil group, epoxy group, halogen group, nitro group, amino
At least one selected from a group, an acyl group and a sulfone group
The method for producing a modified copolymer according to any one of claims 1 to 3, wherein a kind of functional group is also introduced.