JP3501233B2 - Ethylenically unsaturated copolymer and modified copolymer using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an ethylenically unsaturated copolymer and a modified copolymer obtained by modifying the copolymer. More specifically, the present invention is an ethylene-based unsaturated copolymer obtained by copolymerizing ethylene or ethylene and an α-olefin with a cyclic polyene and having a reactive unsaturated group introduced therein, and a modified product thereof. , The reactive unsaturated group, hydroxyl group, carboxyl group,
Rich in adhesiveness, printability, hydrophilicity, polymer modification, antistatic property, flame retardancy, etc. by introducing functional groups such as epoxy group, halogen group, nitro group, amino group, acyl group, sulfone group. The present invention relates to a modified copolymer.

[0002]

2. Description of the Related Art Conventionally, olefin polymers such as high-density polyethylene, isotactic polypropylene and linear low-density polyethylene have chemical stability, good mechanical properties, and excellent processing characteristics. It is widely used in many fields as a material for various molded products, films, sheets, fibers, synthetic paper, and so on. In order to utilize these olefin-based polymers to a higher degree, attempts have been made for many years to improve the performance by a copolymerization reaction and to improve or impart functionality by a polymer reaction. For example, a method has been disclosed in which an α-olefin such as ethylene or propylene is copolymerized with a branched 1,4-diene (JP-A-56-30413).
JP-A-56-30414). This method enables the production of a copolymer having a 1,1-disubstituted olefin in the side chain (that is, having a pendant olefin) by using a bifunctional olefin having different reactivity. However, the branched 1,4-dienes exemplified here are generally called non-conjugated dienes, and their copolymerizability with olefins is not high, which causes a problem in productivity. Further, in order to obtain an olefin copolymer having a high content of pendant olefins, a high concentration of non-conjugated diene must be added during the polymerization reaction, which causes a decrease in activity due to coordination with the polymerization catalyst and a crosslinking reaction. There was an unavoidable situation. In addition, the pendant olefin has a drawback that it is susceptible to chemical reaction due to its branched structure. For example, the graft reaction with polar monomers and olefins is extremely difficult.

Furthermore, "Polymer Bulletin (Poly
Mer Bulletin) ”, Volume 10, page 109 (1983), describes a similar copolymerization method. However, although this method has an advantage that gelation reaction is relatively unlikely to occur, gelling is substantially generated when a high concentration of unsaturated group is contained, which is not preferable. Further, a method by copolymerization of α-olefin and divinylbenzene is disclosed (JP-A-1-118510, JP-A-1-12381). However, in this method, since the divinylbenzene has a double bond having the same reactivity, a cross-linking reaction occurs concurrently in the copolymerization process with the α-olefin, and there is a drawback that it becomes insoluble and infusible. Since the conversion rate of divinylbenzene to the copolymer is low and many divinylbenzene monomers remain in the copolymer, it is necessary to remove the monomer when carrying out a graft reaction or a polymer reaction subsequently. Have a problem. Further, the pendant olefin becomes a styrenic monomer, and has a drawback that it is restricted in the graft reaction of olefin and the like.

By the way, in general, a ternary copolymer of ethylene and propylene or an α-olefin and a cyclic olefin can be obtained by using a Ziegler type catalyst in which a titanium compound or a vanadium compound and an organic aluminum compound are combined. , A well-known and well-known technique. There are many examples of such a technique, for example, JP-A-61-221206 and JP-A-62-27412.
JP, JP-A-1-156308, JP, JP-A 1-1
No. 97511, Japanese Patent Publication No. 1-501556, Japanese Patent Application Laid-Open No. 2-64111, Japanese Patent Application Laid-Open No. 3-28209, Japanese Patent Application Laid-Open No. 3-188113, Japanese Patent Application Laid-Open No. 3-193.
796, JP-A-4-175630, JP-A-4-503963, etc., for details on copolymerization of α-olefins such as ethylene and propylene with 5-vinylnorbornene, ethylidenenorbornene, dicyclopentadiene and the like. It is described in. However,
The copolymer obtained by these methods has a crystallinity of about 1
It is 2% or less, and it is substantially amorphous without mentioning the melting point and the like, which is not intended by the present inventors. In addition, in Japanese Patent Laid-Open No. 64-54010, 5-
In the copolymerization of alkenyl-2-norbornene and ethylene, the molar ratio of the 5-alkenyl-2-norbornene unit in the copolymer and the residual amount of the alkenyl group derived from this unit is represented by the formula 0.2 ≦ [alkenyl group ] / [5-alkenyl-2-norbornene] ≦ 0.8 has been shown to be satisfied. However, in this case, at least 20% of the alkenyl groups have disappeared, and the possibility that these unsaturated groups induce side reactions such as cross-linking cannot be neglected. However, this is not what the inventors desire.

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

[0006]

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

[0007]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that ethylene or ethylene and an α-olefin and a specific structure are present in the presence of a specific polymerization catalyst. By copolymerizing with a cyclic polyene, an ethylene-based copolymer having specific properties can be efficiently obtained without causing gelation, and the unsaturated bond introduced into the side chain by this copolymerization reaction. It was found that a modified copolymer having the above-mentioned preferable properties can be obtained by introducing an appropriate functional group into the. The present invention has been completed based on such findings. That is, the present invention relates to ethylene or ethylene and an α-olefin and a compound represented by the general formula (I)

[0008]

[Chemical 7]

(In the formula, R ^{1 to} R ¹⁰ are each a hydrogen atom,
Represents 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 cyclic polyene represented by the general formula (II)

[0010]

[Chemical 8]

(In the formula, R ^{11 to} R ²⁰ are each a hydrogen atom,
Represents a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
They may be the same or different, R is an alkenyl group or alkylidene group, and n is an integer of 0 or more. ), Which is obtained by copolymerization with at least one selected from the cyclic polyenes represented by the formula (a), the content of the polyene unit is 0.01 to 3.5 mol%, and (b) the decalin at 135 ° C. Intrinsic viscosity measured in 0.01 to 20 deciliters / g, (c) Molecular weight distribution measured by gel permeation chromatography (GPC) is 1.5-40 and (d) Measurement by differential scanning calorimeter (DSC) Has a crystallization enthalpy (ΔH) of 90 J / g or more and is derived from the general formula (II) derived from the cyclic polyene represented by the general formula (I).
I)

[0012]

[Chemical 9]

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

[0014]

[Chemical 10]

(In the formula, R ^{11 to} R ²⁰ , R and n are the same as above.) A crystalline ethylenically unsaturated copolymer containing at least one selected from the repeating units. And a modified copolymer obtained by modifying the ethylenically unsaturated copolymer and introducing a functional group into at least 5 mol% of the unsaturated bonds in the copolymer by a chemical reaction. Is. There is no particular limitation on the method for producing the ethylenically unsaturated copolymer of the present invention, for example, (a) ethylene or ethylene and α-olefin,
(B) By copolymerizing at least one selected from the cyclic polyene represented by the general formulas (I) and (II) in the presence of a polymerization catalyst described later, a desired specific An ethylene-based copolymer having the above properties can be produced.

In the present invention, ethylene or ethylene and an α-olefin are used as the monomer component (a). Examples of the α-olefin include propylene, 1-butene, 1-pentene and 1-pentene. 3 to 20 carbon atoms such as hexene, 1-octene and 4-methylpentene-1
The α-olefin may be used. These α-olefins may be used alone or in combination of two or more kinds. When ethylene and α-olefin are used in combination, the α-olefin is α-olefin based on the total amount of ethylene units and α-olefin units in the resulting copolymer.
It is desirable to use it in such a ratio that the amount of the olefin unit becomes 25% by weight or less. On the other hand, the cyclic polyene used as the (b) monomer component is represented by the general formula (I)

[0017]

[Chemical 11]

A cyclic polyene having a norbornene skeleton and a cyclopentene skeleton represented by the formula (wherein R ^{1 to} R ¹⁰ and m are the same as above), and the general formula (II)

[0019]

[Chemical 12]

At least one selected from the cyclic polyenes having a norbornene skeleton and an alkene skeleton represented by the formula (wherein R ^{11 to} R ²⁰ , R and n are the same as above).

In the general formulas (I) and (II), R ¹
To R ¹⁰ and R ^{11 to} R ²⁰ are each a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and examples of the halogen atom include a chlorine atom, a fluorine atom and a bromine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, octyl group,
Examples thereof 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 from each other, and the R ^{11 to} R ²⁰ may be the same or different from each other. Further, m and n are integers of 0 or more. Furthermore, 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 above 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 combination of two or more.

The crystalline ethylenically unsaturated copolymer of the present invention mainly comprises (A) a transition metal compound and (B) a compound capable of reacting with the transition metal compound or a derivative thereof to form an ionic complex. It can be obtained by copolymerizing the above-mentioned monomer components in the presence of a polymerization catalyst as a component.

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 series metal can be used.
As the above transition metal, specifically, titanium, zirconium, hafnium, chromium, manganese, nickel, palladium or platinum is preferable, and zirconium,
Hafnium, titanium, nickel and palladium are preferred. Examples of such a transition metal compound include various compounds, particularly compounds containing a transition metal of Groups 4 and 8 to 10, particularly a transition metal selected from Group 4 of the periodic table, that is, titanium, zirconium or hafnium. A compound containing is preferably 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 above general formulas (VII) to (X), M¹
Is the periodic table of titanium, zirconium or hafnium
Indicates a Group 4 transition metal, Cp is cyclopentadienyl
Group, substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, tetrahydroindenyl group, substituted tetra
Hydroindenyl group, fluorenyl group or substituted fluorescein
Cyclic unsaturated hydrocarbon group such as nyl group or chain unsaturated carbonization
Indicates a hydrogen group. R^{twenty one}, R ^{twenty two}, R^{twenty three}And R^{twenty four}Each is German
Vertical σ-bonding ligand, chelating ligand, Lewis salt
A ligand such as a group is shown, and as a σ-bonding ligand,
Physically, hydrogen atom, oxygen atom, halogen atom, carbon number 1
~ 20 alkyl groups, C1-20 alkoxy groups,
C6-C20 aryl group, alkylaryl group
Or arylalkyl group, acyloxy group having 1 to 20 carbon atoms
Si group, allyl group, substituted allyl group, substitution containing silicon atom
Groups and the like, and as the chelating ligand,
Acetylacetonate group, Substituted acetylacetonate group
Can be exemplified. A indicates crosslinking by covalent bond.
a, b, c and d are each independently an integer of 0 to 4, and e is
Indicates an integer of 0 to 6. 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. Cp above
Has a substituent, the substituent has 1 to 20 carbon atoms.
Alkyl groups of are preferred. Smell of formula (VIII) and formula (IX)
Therefore, two Cp's may be the same or different from each other.
It may be

Substituted cyclohexyl in the above formulas (VII) to (IX)
Examples of the pentadienyl group include methylcyclopenta
Dienyl group, ethylcyclopentadienyl group; isopro
Pyrcyclopentadienyl group; 1,2-dimethylcyclo
Pentadienyl group; tetramethylcyclopentadienyl
Group; 1,3-dimethylcyclopentadienyl group; 1,
2,3-trimethylcyclopentadienyl group; 1,2,
4-trimethylcyclopentadienyl group; pentamethyl
Cyclopentadienyl group; trimethylsilylcyclopen
Examples thereof include a tadienyl group. In addition, (VII) ~
R in formula (X) ^{twenty one}~ R^{twenty four}For example,
Fluorine atom, chlorine atom, bromine atom as halogen atom,
Iodine atom, methyl as an alkyl group having 1 to 20 carbon atoms
Group, ethyl group, n-propyl group, isopropyl group, n-
Butyl group, octyl group, 2-ethylhexyl group, carbon number
Methoxy group and ethoxy as the alkoxy group of 1 to 20
Group, propoxy group, butoxy group, phenoxy group, carbon number
6 to 20 aryl groups, alkylaryl groups or
Phenyl group, tolyl group, xylyl as reel alkyl group
Group, benzyl group, and acyloxy group having 1 to 20 carbon atoms
The heptadecylcarbonyloxy group and silicon atom.
Trimethylsilyl group as a substituent, (trimethylsilyl group
) Methyl group, dimethyl ether as a Lewis base, di-
Ethers such as ethyl ether and tetrahydrofuran
, Thioethers such as tetrahydrothiophene,
Esters such as tylbenzoate, acetonitrile;
Nitriles such as benzonitrile, trimethylamine;
Triethylamine; tributylamine; N, N-dimethyl
Luaniline; pyridine; 2,2'-bipyridine; phena
Amines such as nitroline, triethylphosphine;
Phosphines such as Liphenylphosphine, ethylene;
Butadiene; 1-Pentene; Isoprene; Pentadie
Chain-unsaturated such as 1-hexene and their derivatives
Hydrocarbons, Benzene; Toluene; Xylene; Cyclohep
Tatriene; Cyclooctadiene; Cyclooctatriene
Such as cyclooctatetraene and derivatives thereof
Examples include cyclic unsaturated hydrocarbons. Also, the above (I
For example, the covalent cross-linking of A in the formula (X) is
For example, methylene bridge, dimethylmethylene bridge, ethylene bridge
Bridge, 1,1'-cyclohexylene bridge, dimethylsilyle
Crosslinking, dimethylgermylene crosslinking, dimethylstannylene
Examples include crosslinking.

Examples of the compound represented by the general formula (VII) include (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl). Tribenzylzirconium, (pentamethylcyclopentadienyl) trichlorozirconium, (pentamethylcyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadiene (Enyl) tribenzyl zirconium, (cyclopentadienyl) trichloro zirconium, (cyclopentadienyl) trimethoxy zirconium, (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, Among these, compounds in which zirconium is replaced with titanium or hafnium are mentioned.

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

The compound represented by the general formula (IX) is, for example, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) dichlorozirconium, ethylenebis (tetrahydroindenyl).
Dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium, dimethylsilylenebis (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) Dimethylzirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dichlorozirconium, [phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, diphenylmethylene (cyclopentadienyl) (9 -Fluorenyl) dimethyl zirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexalidene (9-fluorenyl ) (Cyclopentadienyl) dimethylzirconium, cyclopentylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclobutylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylene (9-fluorenyl) ) (Cyclopentadienyl) dimethyl zirconium, dimethylsilylene bis (2,3,5
-Trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dimethylzirconium, dimethylsilylenebis (indenyl) dichlorozirconium, etc. Alternatively, a compound in which hafnium is substituted is included.

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

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

[0032]

[Chemical 13]

The compound represented by
be able to. Y in the general formula (XI)¹Is carbon, Kei
Element, germanium or tin atom, R^{twenty five} _t -C_FiveH_4-tOver
And R^{twenty five} _u-C_FiveH_4-uAre each substituted cyclopentadiene
The nyl group, t and u represent an integer of 1 to 4. Where R^{twenty five}
Are hydrogen atoms, silyl groups or hydrocarbon groups,
It may be one or different. Also, at least one piece
The other cyclopentadienyl group is Y¹Is bound to
R on at least one carbon next to the carbon^{twenty five}Exists.
R²⁶Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or carbon
An aryl group of 6-20, an alkylaryl group, or
Indicates an arylalkyl group. M²Is titanium, zirconium
Or a hafnium atom, X¹Is a hydrogen atom, halogen
Atom, alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Aryl group, alkylaryl group or aryl group of
It shows a alkyl group or an alkoxy group having 1 to 20 carbon atoms. X
¹R may be the same or different from each other, and R²⁶Also
They may be the same or different from each other.

Examples of the substituted cyclopentadienyl group in the above general formula (XI) include methylcyclopentadienyl group; ethylcyclopentadienyl group; isopropylcyclopentadienyl group; 1,2-dimethylcyclopentadienyl group. Group; 1,3-dimethylcyclopentadienyl group; 1,2,3-trimethylcyclopentadienyl group;
Examples include 1,2,4-trimethylcyclopentadienyl group. Specific examples of X ¹ include F, Cl, Br, I as a halogen atom, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an octyl group as an alkyl group having 1 to 20 carbon atoms, 2-ethylhexyl group, methoxy group as an alkoxy group having 1 to 20 carbon atoms,
Examples of the ethoxy group, propoxy group, butoxy group, phenoxy group, aryl group having 6 to 20 carbon atoms, alkylaryl group or arylalkyl group include phenyl group, tolyl group, xylyl group and benzyl group. Specific examples of R ²⁶ include a methyl group, an ethyl group, a phenyl group, a tolyl group, a xylyl group, and a benzyl group. Examples of the compound represented by the general formula (XI) include dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, and compounds obtained by substituting zirconium with titanium or hafnium. . Furthermore, the general formula (XII)

[0035]

[Chemical 14]

It also includes compounds represented by: The general formula
In the compound of (XII), Cp is cyclopentadienyl
Group, substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, tetrahydroindenyl group, substituted tetra
Hydroindenyl group, fluorenyl group or substituted fluorescein
Cyclic unsaturated hydrocarbon group such as nyl group or chain unsaturated carbonization
Indicates a hydrogen group. M³Is titanium, zirconium or hafni
X represents a um atom²Is hydrogen atom, halogen atom, carbon
C1-C20 alkyl group, C6-C20 aryl
Group, alkylaryl group or arylalkyl group, or
Represents an alkoxy group having 1 to 20 carbon atoms. Z is SiR²⁷
₂, CR²⁷ ₂ , SiR²⁷ ₂SiR²⁷ ₂ , CR²⁷ ₂CR²⁷
₂ , CR²⁷ ₂CR²⁷ ₂CR²⁷ ₂ , CR²⁷= CR²⁷, CR
²⁷ ₂SiR²⁷ ₂Or GeR²⁷ ₂ Indicates Y²Is -N (R
²⁸)-, -O-, -S- or -P (R²⁸) -Indicates. Up
Note R²⁷Is a hydrogen atom or an atom having up to 20 non-hydrogen atoms
Rualkyl, aryl, silyl, alkyl halide, halo
A group selected from aryl gen groups and combinations thereof
Yes, R²⁸Is alkyl having 1 to 10 carbons or the number of carbons
6-10 aryl groups, or one or more
R above²⁷To form a fused ring system of up to 30 non-hydrogen atoms
You may. w represents 1 or 2.

Transitions containing transition metals of groups 5 to 10
There is no particular limitation on the metal compound, and chromium compound
Examples of the body include tetramethyl chrome and tetra (t-but
Xy) chromium, bis (cyclopentadienyl) chromium,
Hydride tricarbonyl (cyclopentadienyl) chloride
Hexacarbonyl (cyclopentadienyl) chloride
Mu, bis (benzene) chromium, tricarbonyl tris
(Triphenylphosphonate) Chromium, Tris (allyl)
Chromium, triphenyltris (tetrahydrofuran)
ROM, chrome tris (acetylacetonate), etc.
You can 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 dica
Rubonyl bis (triphenylphosphine) nickel, di
Bromobis (triphenylphosphine) nickel, dinitride
Elementary bis [bis (tricyclohexylphosphine) nicke
], Chlorohydridobis (tricyclohexylphosphine
In) nickel, chloro (phenyl) bis (triphenyl)
Ruphosphine) nickel, dimethylbis (trimethylphosphine)
Sphine) nickel, diethyl (2,2'-bipyridy
Nickel), bis (allyl) nickel, bis (cyclo)
Pentadienyl) nickel, bis (methylcyclopenta)
Dienyl) nickel, bis (pentamethylcyclopenta)
Dienyl) nickel, allyl (cyclopentadienyl)
Nickel, (Cyclopentadienyl) (Cyclooctadiene
Ene) nickel tetrafluoroborate, bis (cyclo)
Ktadiene) nickel, nickel bisacetylacetona
, Allyl nickel chloride, tetrakis (trif
Phenylphosphine) nickel, nickel chloride, formula (C₆H_Five) Ni [OC (C₆H_Five) CH = P (C
₆H_Five)₂] [P (C₆H_Five)₃], (C₆H_Five) Ni [OC
(C₆H_Five) C (SO₃Na) = P (C₆H_Five)₂] [P
(C ₆H_Five)₃] And the like.

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

In the polymerization catalyst, a compound capable of reacting with the transition metal compound or its derivative to form an ionic complex is used as the component (B). As the component (B), an ionic compound which reacts with the transition metal compound of the component (B-1) (A) to form an ionic complex,
Examples thereof include (B-2) aluminoxane and (B-3) Lewis acid.

As the component (B-1), the above-mentioned component (A) is used.
Reacts with transition metal compounds to form ionic complexes
Any ionic compound can be used
However, the following general formula (XIII), (XIV)       ([L¹-R²⁹]^{k +})_p([Z]^-)_q              ... (XIII)       ([L²]^{k +})_p([Z]^-)_q                    ... (XIV) (However, L²Is M^Five, R³⁰R³¹M⁶, R³² ₃C or R
³³M⁶Is. ) [(XIII), (XIV) In the formula, L¹Is Lewis
Base, [Z]^-Is a non-coordinating anion [Z ¹]^-as well as
[Z²]^-, Where [Z¹]^-Has multiple groups bound to an element
Anion, that is, [M^FourA¹A²... Aⁿ]
^-(Where M^FourIs an element of Groups 5 to 15 of the Periodic Table, preferably
Or elements of Groups 13 to 15 of the Periodic Table. A¹~ AⁿIs
Hydrogen atom, halogen atom, carbon atom of 1 to 20
Alkyl group, dialkylamino group having 2 to 40 carbon atoms, carbon
C1-20 alkoxy group, C6-20 aryl
Group, aryloxy group having 6 to 20 carbon atoms, 7 to 4 carbon atoms
0 alkylaryl group, C7-40 aryla group
Alkyl group, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms,
An acyloxy group having 1 to 20 carbon atoms, an organic metalloid group,
Or a hydrocarbon group containing a hetero atom having 2 to 20 carbon atoms
You A¹~ AⁿTwo or more of them may form a ring
Yes. n is [(central metal M^FourValence of +1)
You ), [Z²] ^-Is the logarithm of the reciprocal of the acid dissociation constant (pK
a) Bronsted acid having -10 or less alone or Bronsted acid
A conjugate base of a combination of Ted acid and Lewis acid, or
A conjugate base generally defined as a superacid is shown. Also,
The chair base may be coordinated. Also, R²⁹Is hydrogen
Child, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 6 to 20 carbon atoms
Reel group, alkylaryl group or arylalkyl group
Indicates R³⁰And R³¹Are each cyclopentadienyl
Group, substituted cyclopentadienyl group, indenyl group or phenyl group
Ruorenyl group, R³²Is an alkyl group having 1 to 20 carbon atoms,
Reel group, alkylaryl group or arylalkyl group
Indicates. R³³Is tetraphenylporphyrin, phthalocyanine
A macrocyclic ligand such as anine is shown. k is [L¹-R²⁹],
[L²] Is an integer of 1 to 3 in ion valence, and p is an integer of 1 or more.
The number, q = (k × p). M^FiveIs the first to the periodic table
M, which contains elements of groups 3, 11 to 13 and 17
⁶Indicates an element belonging to groups 7 to 12 of the periodic table. ]
Those can be suitably used.

Specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine , Phosphines such as triphenylphosphine and diphenylphosphine, thioethers such as tetrahydrothiophene, esters such as ethyl benzoate, and nitriles such as acetonitrile and benzonitrile. Specific examples of R ²⁹ include hydrogen, methyl group, ethyl group, benzyl group and trityl group, and specific examples of R ³⁰ and R ³¹ include cyclopentadienyl group and methylcyclopentadienyl group. , Ethylcyclopentadienyl group,
Examples thereof include a pentamethylcyclopentadienyl group. Specific examples of R ³² include phenyl group, p-tolyl group, p-methoxyphenyl group and the like, and specific examples of R ³³ include tetraphenylporphine,
Examples thereof include phthalocyanine, allyl and methallyl. Further, specific examples of M ⁵ include Li, Na,
K, Ag, Cu, Br, I, I _{3 and the} like can be mentioned, and specific examples of M ⁶ include Mn, Fe, Co, Ni,
Zn etc. can be mentioned.

[Z ¹ ] ^- , that is, [M ⁴ A ¹ A
² ... A ⁿ ], specific examples of M ⁴ include B, A
1, Si, P, As, Sb, etc., preferably B and Al
Is mentioned. As specific examples of A ¹ and A ^{2 to} A ⁿ , dimethylamino group, diethylamino group and the like as dialkylamino group, methoxy group, ethoxy group, n-butoxy group as alkoxy group or aryloxy group,
As a hydrocarbon group such as phenoxy group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group,
Fluorine, chlorine, bromine, etc. as halogen atoms such as isobutyl group, n-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group, 3,5-dimethylphenyl group. As a hydrocarbon group containing iodine or a hetero atom, a p-fluorophenyl group, 3,
5-difluorophenyl group, pentachlorophenyl group,
Pentamethylantimony group, trimethylsilyl group, trimethyl as organic metalloid group such as 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group, bis (trimethylsilyl) methyl group Examples thereof include germyl group, diphenylarsine group, dicyclohexylantimony group and diphenylboron.

Further, a non-coordinating anion, that is, pKa
There -10 or less Bronsted acid alone or Bronsted the slashed.nsted acid and Lewis acid combination conjugate base [Z ^{2] -} trifluoromethanesulfonic acid anion Specific examples of (CF ₃ SO ₃₎ ^-, bis (trifluoromethanesulfonyl ) Methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (Cl
O ₄ ) ^- , trifluoroacetic acid anion (CF ₃ CO ₂ )
^- , Hexafluoroantimony anion (Sb
F ₆ ) ^- , Fluorosulfonate anion (FS
O ₃ ) ^- , Chlorosulfonate anion (ClS
O ₃ ) ⁻ , fluorosulfonate anion / 5-antimony fluoride (FSO ₃ / SbF ₅ ) ⁻ , fluorosulfonate anion / 5-arsenic fluoride (FSO ₃ / As
F ₅ ) ⁻ , trifluoromethanesulfonic acid / 5-antimony fluoride (CF ₃ SO ₃ / SbF ₅ ) ^{—, and the} like.

Specific examples of the ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, that is, the compound of the component (B-1) are as follows.
Triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl tetraphenylborate (tri-n- Butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl tetraphenylborate (2-cyanopyridinium) , Tetrakis (pentafluorophenyl) borate triethylammonium, tetrakis (pentafluorophenyl) ) Tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) tetra-n-butylammonium borate, tetrakis (pentafluorophenyl) tetraethylammonium borate, tetrakis (pentafluorophenyl) Benzyl (tri-n-butyl) ammonium borate, Methyldiphenylammonium tetrakis (pentafluorophenyl) borate, Triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, Methylanilinium tetrakis (pentafluorophenyl) borate, Tetrakis (penta) Fluorophenyl) borate dimethylanilinium, tetrakis (pentafluorophenyl) borate trimethylanilinium, tetrakis Methylpyridinium pentafluorophenyl) borate, Benzylpyridinium tetrakis (pentafluorophenyl) borate, Methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), Benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), Tetrakis ( Methyl (4-cyanopyridinium) pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate, ferrocenium tetraphenylborate, tetraphenyl Silver borate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, tetrakis (pentafluorophenyl) borate fe Rothenium, tetrakis (pentafluorophenyl)
Boric acid (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) borate decamethylferrocenium, tetrakis (pentafluorophenyl) silver borate, tetrakis (pentafluorophenyl) trityl borate, tetrakis (pentafluorophenyl) Lithium borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate theoraphenylporphyrin manganese, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate,
Examples thereof include silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate.

As the component (B-1), one type of ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex may be used, or two or more types may be used in combination. You may use. On the other hand, the aluminoxane as the component (B-2) is represented by the general formula (XV)

[0046]

[Chemical 15]

(In the formula, each R ³⁴ independently has 1 to 20 carbon atoms,
It is preferably a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group or an arylalkyl group having 1 to 12 or a halogen atom, which may be the same or different. s represents the degree of polymerization and is usually 3 to 50, preferably 7
A chain aluminoxane represented by the formula:
And general formula (XVI)

[0048]

[Chemical 16]

(In the formula, R ³⁴ and s are the same as the above.), And the cyclic aluminoxane shown can be mentioned. Examples of the method for producing the aluminoxane include a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other, but the means therefor is not particularly limited, and the reaction may be performed according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and then brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization and then water is added, water of crystallization contained in a metal salt, etc. , A method of reacting water adsorbed to an inorganic substance or an organic substance with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting with water. The aluminoxane may be insoluble in toluene. These aluminoxanes may be used alone or in combination of two or more.

Further, the Lewis acid as the component (B-3) is not particularly limited and may be an organic compound or a solid inorganic compound. A boron compound or an aluminum compound is preferably used as the organic compound, and a magnesium compound or an aluminum compound is preferably used as the inorganic compound.
Examples of the aluminum compound include bis (2,6-
Di-t-butyl-4-methylphenoxy) aluminum methyl, (1,1-bi-2-naphthoxy) aluminum methyl and the like, magnesium compounds such as magnesium chloride and diethoxy magnesium, and aluminum compounds such as aluminum oxide. , Aluminum chloride, and the like, as the boron compound, for example, triphenylboron, tris (pentafluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, tris [(4-fluoromethyl) phenyl] boron. ，
Trimethylboron, triethylboron, tri-n-butylboron, tris (fluoromethyl) boron, tris (pentafluoroethyl) boron, tris (nonafluorobutyl) boron, tris (2,4,6-trifluorophenyl) boron, Tris (3,5-difluoro) boron, Tris [3,3
5-bis (trifluoromethyl) phenyl) boron, bis (pentafluorophenyl) fluoroboron, diphenylfluoroboron, bis (pentafluorophenyl) chloroboron, dimethylfluoroboron, diethylfluoroboron,
Examples thereof include di-n-butylfluoroboron, pentafluorophenyldifluoroboron, phenyldifluoroboron, pentafluorophenyldichloroboron, methyldifluoroboron, ethyldifluoroboron and n-butyldifluoroboron. These Lewis acids may be used alone or in combination of two or more.

(A) in the polymerization catalyst used in the present invention
When the compound (B-1) is used as the component (B), the catalyst component and the component (B) are preferably used in a molar ratio of 10: 1 to 1: 100, more preferably 2 : 1 to 1:10, more preferably 1: 1 to 1: 5, and when the compound (B-2) is used, the molar ratio is preferably 1:20 to 1: 10000. The range of 1: 100 to 1: 2000 is desirable. Furthermore, when the compound (B-3) is used, the molar ratio is preferably 10: 1 to 1: 2000, more preferably 5: 1 to 1: 1000, and further preferably 2: 1 to 1: 5.
A range of 00 is desirable. The polymerization catalyst is the above-mentioned (A)
The component and the component (B) may be contained as the main components, and the component (A), the component (B) and the component (C) may be contained.
It may contain an organoaluminum compound as a main component. Here, the organoaluminum compound as the component (C) is represented by the general formula (XVII) R ³⁵ _r AlQ _3-r (XVII) (wherein, R ³⁵ is an alkyl group having 1 to 10 carbon atoms, and Q is Hydrogen atom, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Is an aryl group or a halogen atom, and r is an integer of 1 to 3).

Specific examples of the compound represented by the general formula (XVII) include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl. Aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum sesquichloride and the like can be mentioned. These organoaluminum compounds may be used alone or in combination of two or more. The (A) catalyst component and (C) catalyst component are preferably used in a molar ratio of 1: 1 to 1: 200.
The range of 0, more preferably 1: 5 to 1: 1000, and further preferably 1:10 to 1: 500 is desirable. By using the (C) catalyst component, the polymerization activity per transition metal can be improved, but if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.

Next, in the present invention, the above (A),
At least one of (B) and the (C) catalyst component used as desired can be used by supporting it on a suitable carrier. The type of the carrier is not particularly limited, and any of an inorganic oxide carrier, other inorganic carriers and organic carriers can be used, but an inorganic oxide carrier or another inorganic carrier is particularly preferable. As the inorganic oxide carrier,
Specifically, SiO ₂ , Al ₂ O ₃ , MgO, Zr
O ₂ , TiO ₂ , Fe ₂ O ₃ , B ₂ O ₃ , CaO, Zn
Examples include O, BaO, ThO ₂ and mixtures thereof, such as silica alumina, zeolite, ferrite, and glass fiber. Among these, especially SiO ₂ , A
1 ₂ O ₃ is preferred. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate and the like. On the other hand, as inorganic carriers other than the above, MgCl ₂ , Mg (O
Examples thereof include magnesium compounds such as C ₂ H ₅ ) ₂ and complex salts thereof, and organomagnesium compounds represented by MgR ³⁶ _i X ³ _j . Here, R ³⁶ has 1 carbon atom
20 alkyl group, an alkoxy group or an aryl group having 6 to 20 carbon atoms having 1 to 20 carbon atoms, X ³ represents a halogen atom or an alkyl group having a carbon number of 1 to 20, i is 0 to 2, j
Is 0 to 2.

As the organic carrier, polystyrene,
Styrene-divinylbenzene copolymer, polyethylene,
Examples thereof include polymers such as polypropylene, substituted polystyrene and polyarylate, starch, carbon and the like. Here, the properties of the carrier used vary depending on the type and production method, but the average particle size is usually 1 to 300 μm,
Preferably 10 to 200 μm, more preferably 20 to 1
It is 00 μm. When the particle size is small, fine powder in the polymer increases, and when the particle size is large, coarse particles in the polymer increase, which causes decrease in bulk density and clogging of the hopper. The specific surface area of the carrier is usually 1 to 1000 m ² / g, preferably 5
0-500 m ² / g, pore volume is usually 0.1-5 cm ³ /
g, preferably 0.3 to ³ cm ³ / g. If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and the pore volume can be obtained from the volume of nitrogen gas adsorbed according to, for example, the BET method (see Journal of American Chemical Society, Volume 60, page 309 (1983)). . Further, the carrier is usually 1
It is desirable to use it after firing at 50 to 1000 ° C, preferably 200 to 800 ° C. The method of loading on a carrier is not particularly limited, and a conventionally used method can be used. In this polymerization reaction, the cyclic polyene may be charged at the start of the polymerization, or may be added during the polymerization, and the addition method is not particularly limited, and any one of batch addition, divided addition or continuous addition may be used. But it's okay.

Further, the polymerization method is not particularly limited, and a solvent polymerization method (suspension polymerization, solution polymerization) using an inert hydrocarbon or the like, or a bulk polymerization method in which the polymerization is carried out under the substantially absence of an inert hydrocarbon solvent. The gas phase polymerization method can also be used. Examples of the hydrocarbon solvent used in the copolymerization include butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane and other saturated hydrocarbons, benzene, toluene, xylene and other aromatic hydrocarbons, Chlorine-containing solvents such as chloroform, dichloromethane, ethylene dichloride and chlorobenzene can be used. The polymerization temperature is -100 to 2
The polymerization is generally carried out at a temperature of 00 ° C. and a polymerization pressure of atmospheric pressure to 100 kg / cm ² , preferably -50 to 100.
C, normal pressure to 50 kg / cm ² , more preferably 0 to 1
It is in the range of 00 ° C. and 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 or a third component and polymerization temperature.

The crystalline ethylenically unsaturated copolymer of the present invention contains 0.01 to 3.5 mol% of units derived from the cyclic polyene represented by the general formula (I) and / or (II). It is necessary to contain it in a ratio. Also, the intrinsic viscosity measured in decalin at a temperature of 135 ° C. is 0.01 to 20 deciliters /
g, preferably 0.05 to 10 deciliter / g.
The molecular weight of this ethylene-based copolymer is not particularly limited, but the molecular weight determined by gel permeation chromatography (GPC) at a temperature of 135 ° C. using 1,2,4-trichlorobenzene as a solvent (polyethylene conversion). Is 1,000 to about the weight average molecular weight (Mw).
2,000,000, preferably 5,000 to 1,000,000
And the number average molecular weight (Mn) is 500 to 1,
It is preferably in the range of 00000, and further, the molecular weight distribution is 1.5 to 40, preferably 10 or less, more preferably 5 or less. Further, the ethylene-based copolymer is
The crystallization enthalpy (ΔH) measured by a differential scanning calorimeter (DSC) is 90 J / g or more, preferably 95 to 250.
J / g. Here, regarding the measurement conditions of DSC,
Using a Perkin-Elmer DSC-7 type device, under a nitrogen gas atmosphere of the whole system, the temperature was raised from room temperature to 190 ° C. at a rate of 20 ° C./minute and maintained for 3 minutes, and then at room temperature at a rate of 20 ° C./minute. Decrease temperature to 5 minutes and hold, then 2
The temperature was raised at a rate of 0 ° C./minute, and ΔH was measured in this process. Further, the ethylene-based copolymer of the present invention has, as a unit having an unsaturated bond, a general formula (III) derived from the cyclic polyene represented by the general formula (I).

[0057]

[Chemical 17]

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

[0059]

[Chemical 18]

(In the formula, R ^{11 to} R ²⁰ , R and n are the same as the above), and at least one selected from the repeating units. In the ethylene-based copolymer, the molar ratio of the double bond based on the cyclic polyene component in the copolymer and the double bond not based on the norbornene ring in the cyclic polyene component [cyclic in the copolymer [Double bond based on polyene component] / [double bond not based on norbornene ring in cyclic polyene component] is usually
It is in the range of 0.85-1.0, preferably 0.86-1.0, and more preferably 0.88-1.0. Here, the amount of double bonds not depending on the norbornene ring in the cyclic polyene component was calculated from the amount of the consumed cyclic polyene, and the amount of double bonds based on the cyclic polyene component in the copolymer was calculated from NMR. Value was used. That is, in the present invention, it is found that the cyclic polyene is substantially involved in the reaction only by the unsaturated group of the norbornene skeleton during the copolymerization with ethylene or ethylene and the α-olefin. In addition, since the ethylene copolymer has substantially no insoluble matter in 135 ° C. decalin, it has substantially no gel component.

In the present invention, the ethylenically unsaturated copolymer is modified so that at least 5 mol% of the unsaturated bonds of the copolymer are chemically reacted with a functional group such as a hydroxyl group.
Carboxyl group, epoxy group, halogen group, nitro group,
An amino group, an acyl group and a sulfone group are introduced. In this way, a general formula (V) obtained by introducing a functional group into the unsaturated bond of the unit represented by the general formula (III)

[0062]

[Chemical 19]

(In the formula, W ¹ and V ¹ are each a substituent containing at least one of a halogen atom, a monovalent metal atom or 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 R ^{1 to} R ¹⁰ and m are the same as the above), and the unsaturated group of the unit represented by the general formula (IV). A general formula (V
I)

[0064]

[Chemical 20]

(In the formula, W ² and V ² are each a substituent containing at least one of a halogen atom, a monovalent metal atom or a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and a tin atom. , They may be the same or different, and D is a hydrogen atom or-(CH) _y -C.
H ₃ is shown, and 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. The modified copolymer of the present invention containing a chemically modified unit consisting of at least one selected from the repeating units represented by In the unit represented by the general formula (IV),
If R is an alkenyl group, D in the chemical modification unit represented by the general formula (VI) is a hydrogen atom, and if R is an alkylidene group, D is - a (CH _{2) y} -CH _3.

In the present invention, introducing the functional group into the unsaturated bond means deriving the functional group by utilizing the unsaturated bond, and modifying the unsaturated bond to change the functional group. A desired functional group can be introduced by a method such as generation or binding of a compound having a functional group to an unsaturated bond. The introduced amount of the functional group is 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, most preferably 20 mol% or more of the unsaturated bonds in the ethylenically unsaturated copolymer. When the amount introduced is less than 5 mol%, the content of the functional group is small and the modifying effect is not sufficiently exhibited. Next, a method for introducing each functional group will be described. (I) Introduction of hydroxyl group The method for introducing a hydroxyl group into the ethylenically unsaturated copolymer is not particularly limited, but it is a method by oxidation of an unsaturated bond, unsaturated compound having one or more hydroxyl groups in the molecule. It is roughly classified into a method by an addition reaction to a bond, and others. As an example of the method by oxidation of the unsaturated bond, (a)
Oxidation by hydrogen peroxide and organic acids such as formic acid via peracid, (b) Oxidation by permanganate in the presence or absence of a phase transfer catalyst such as quaternary ammonium salt, (c) Oxidation with hydrogen peroxide solution, permanganate, etc. using oxides of osmium, ruthenium, tungsten, selenium, etc., and hydrolysis of (d) halogen or hydrogen halide adducts such as bromine, or sulfuric acid adducts. (E) Hydrolysis of the epoxy group introduced by various reactions. On the other hand, a compound having one or more hydroxyl groups in the molecule has active hydrogen capable of undergoing an addition reaction to an unsaturated bond, particularly a Michael type addition reaction (having two or more hydroxyl groups , Including the case where one of them is used for an addition reaction), and specific examples thereof include thiol compounds such as thioglycerol and thioglycol. In addition, the hydroxyl group can also be introduced by an aldehyde addition reaction known as the Prince reaction, an oxidation reaction subsequent to hydroboration, a demercuration reaction subsequent to oxymercuration of mercuric acetate or the like.

(Ii) Introduction of Carboxyl Group The method of introducing the carboxyl group is not particularly limited, but it is a method by oxidation of an unsaturated bond, or a method of introducing a carboxyl group into an unsaturated bond of a compound containing one or more carboxyl groups. It is roughly classified into methods by addition reaction and others. Specific examples include (a) oxidation with a hydroxylating agent (potassium permanganate, etc.), hydrolysis after (b) reaction with a radical reaction agent (maleic anhydride, etc.), (c) metallizing agent (eg alkyl Lithium), a method of leading a carboxyl group through acylation in a demetallation reaction after the reaction, and the like.

(Iii) Introduction of Epoxy Group The method for introducing the epoxy group into the ethylenically unsaturated copolymer is not particularly limited, but the method by oxidation of the unsaturated bond, the introduction of one or more epoxy groups in the molecule The method is broadly classified into a method by an addition reaction of a contained compound to an unsaturated bond, and others. As an example of the method by oxidation of unsaturated bond,
(A) Oxidation with peracids such as formic acid, peracetic acid, and perbenzoic acid; (b) Oxidation with sodium hypochlorite in the presence or absence of metalloporphyrin complexes such as manganeseporphyrin complexes; ) Oxidation with hydrogen peroxide, hydroperoxide or the like in the presence or absence of a catalyst such as vanadium, tungsten or molybdenum compound,
(D) Oxidation with alkaline hydrogen peroxide, (e) acetic acid /
There is a method such as neutralization of an adduct with a t-butyl hypochlorite system with an alkali. On the other hand, a compound containing one or more epoxy groups in the molecule has active hydrogen capable of undergoing an addition reaction to an unsaturated bond, particularly a Michael type addition reaction, and specific examples thereof include thioglycidol and thioglycol. Examples thereof include thiol compounds such as glycidyl acid.

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

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

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

(Vii) Introduction of Halogen The method of introducing halogen into the ethylenically unsaturated copolymer is not particularly limited. Halogen can be introduced. Examples of the hydrogen halide include hydrogen chloride, hydrogen bromide, hydrogen iodide and the like, preferably hydrogen bromide and hydrogen iodide. Examples of halogen include chlorine, bromine,
Examples thereof include iodine, bromine monochloride, iodine monochloride, iodine monobromide, and among these, bromine, bromine monochloride and iodine monochloride are preferable. Regarding the amount of halogen introduced, the halogen content in the ethylenically unsaturated copolymer is 0.
It is desirable to introduce the compound in an amount of 05% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more. When the halogen content is less than 0.05% by weight, the halogen content is too small and the halogen modification effect is not sufficiently exhibited. The selectivity of the reaction does not necessarily have to be 100%, and the product of the side reaction may be mixed if halogen is substantially introduced.

[0073]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Example 1 (1) Preparation of dimethylanilinium tetrakis (pentafluorophenyl) borate Pentafluorophenyllithium prepared from 152 mmol of bromopentafluorobenzene and 152 mmol of butyllithium was reacted with 45 mmol of boron trichloride in hexane. , Tris (pentafluorophenyl) boron was obtained as a white solid. 41 mmol of the obtained tris (pentafluorophenyl) boron was reacted with 41 mmol of pentafluorophenyllithium to isolate lithium tetrakis (pentafluorophenyl) boron as a white solid. Next, by reacting 16 mmol of lithium tetrakis (pentafluorophenyl) boron with 16 mmol of dimethylaniline hydrochloride in water, dimethylanilinium tetrakis (pentafluorophenyl) borate as a white solid 11.4.
Obtained mmol. The fact that the product is the target is ¹ H-N
It was confirmed by MR and ¹³ C-NMR. (2) Copolymerization of ethylene and dicyclopentadiene Under a nitrogen atmosphere, 400 ml of toluene, 0.6 mmol of triisobutylaluminum (TIBA), 2 mmol of ethylenebis (indenyl) zirconium dichloride in an autoclave of 1 liter at room temperature, 4 micromoles of dimethylanilinium tetrakis (pentafluorophenyl) borate prepared in (1) was added in this order, 0.08 mol of dicyclopentadiene was subsequently added, and the temperature was raised to 80 ° C., then the ethylene partial pressure was 8 kg. / C
30 while continuously introducing ethylene so as to obtain m ² G
Reaction was carried out for a minute. After completion of the reaction, the polymer solution was poured into 2 liters of methanol to precipitate a copolymer, and the copolymer was filtered and dried. The yield and properties of the copolymer are shown in Table 1.

Examples 2 to 4 Using the catalysts shown in Table 1 and monomers other than ethylene,
A copolymer was produced in the same manner as in Example 1. The yield and physical properties of each copolymer are shown in Table 1.

Comparative Example 1 In Example 1, a combination of 0.016 mmol of magnesium-supported titanium trichloride and 10 mmol of triethylaluminum was used as the catalyst system, and the polymerization temperature was 7%.
By the same procedure except that the temperature was 0 ° C, 58.2 g of the polymer was obtained.
Got This polymer has an intrinsic viscosity of 3.10 deciliters /
g, Tm137.2 ° C., ΔH204.0 J / g. Further, IR measurements, 940 cm ^-1, which seems from dicyclopentadiene units, the peak of 1610 cm ^-1 was not confirmed.

Comparative Example 2 In Comparative Example 1, 5 was used instead of dicyclopentadiene.
Polymerization was carried out by the same procedure except that 0.10 mol of vinyl-2-norbornene was used. As a result, polymer 57.
1 g was obtained. This polymer has a Tm of 136.2 ° C and a ΔH20 of
0.1 J / g, and from the results of IR measurement, 1640c showing the presence of a 5-vinyl-2-norbornene unit.
No peaks at m ⁻¹ and 900 cm ⁻¹ could be confirmed.

Example 5 Copolymerization of ethylene and 5-vinyl-2-norbornene Under a nitrogen atmosphere, 400 ml of toluene, 1.5 mmol of triisobutylaluminum (TIBA), tetra (n-butoxy) were added to a 1 liter autoclave at room temperature. ) 20 micromoles of zirconium and 40 micromoles of dimethylanilinium tetrakis (pentafluorophenyl) borate prepared in (1) were added in this order, followed by addition of 0.10 mols of 5-vinyl-2-norbornene,
After heating to 80 ° C, the ethylene partial pressure is 8 kg / cm ²
The reaction was carried out for 30 minutes while continuously introducing ethylene so as to attain G. After completion of the reaction, the polymer solution was poured into 2 liters of methanol to precipitate a copolymer, and the copolymer was filtered and dried. The yield and properties of the copolymer are shown in Table 1.

Examples 6 to 8 Using the catalysts shown in Table 1 and monomers other than ethylene,
A copolymer was produced in the same manner as in Example 5. The yield and physical properties of each copolymer are shown in Table 1.

[0079]

[Table 1]

[0080]

[Table 2]

[Note] Ind: ethylenebis (indenyl) zirconium dichloride TBZ: tetra (n-butoxy) zirconium DCPD: dicyclopentadiene 5VNB: 5-vinyl-2-norbornene 5ENB: 5-ethylidene-2-norbornene US: [ Double bond based on cyclic polyene component in copolymer] / [double bond not based on norbornene ring in cyclic polyene component] (molar ratio) In Examples 2 to 4, the promoter and the organoaluminum compound were used. , And the polymerization conditions are the same as in Example 1, and Examples 6 to 8 are the same as in Example 5.

Example 9 (Introduction of hydroxyl group) 5.0 g of the resin obtained in Example 1 was added to toluene 20 at 120 ° C.
The solution was dissolved in 0 ml, and 10 g of 90% by weight formic acid and 1.5 g of 30% by weight hydrogen peroxide solution were mixed in advance with stirring and added dropwise over 1 hour.
It heat-processed at 10 degreeC for 1 hour. Next, after neutralization treatment with sodium hydroxide-dissolved methanol, the polymer was precipitated by pouring it into a large amount of acetone, thoroughly washed and dried under reduced pressure to obtain a modified copolymer. By the infrared spectroscopy (IR method), the initially observed peak at 1610 cm ^-1 almost disappeared, and a broad peak newly appeared near 3300 cm ^-1 . The conversion rate of unsaturated bonds in the resin to hydroxyl groups measured by the NMR method was almost 100%.

Example 10 (Introduction of Carboxyl Group) 5.0 g of the resin obtained in Example 2 was mixed with toluene 20 at 120 ° C.
Dissolve in 0 ml and add 10 g of acetic acid to this solution,
A mixture of 1.8 g of paraformaldehyde and 1 ml of 98% by weight concentrated sulfuric acid was added, and the mixture was refluxed for 3 hours with vigorous stirring. After completion of the reaction, the mixture was neutralized with methanol dissolved in sodium hydroxide, poured into a large amount of acetone to precipitate the polymer, thoroughly washed, and dried under reduced pressure to obtain a modified copolymer. By the IR method, the peak at 1640 cm ^-1 disappeared,
A sharp peak was newly observed near 1700 cm ^-1 .
The conversion rate of the unsaturated bond in the resin to the carboxyl group was almost 100%.

Example 11 (Introduction of Epoxy Group) 5.0 g of the resin obtained in Example 3 was added to toluene 20 at 120 ° C.
It was dissolved in 0 ml, 0.2 g of t-butyl hydroperoxide and 15 mg of hexacarbonyl molybdenum were added to this solution, and the mixture was refluxed for 2 hours. This was poured into a large amount of cold methanol to precipitate a polymer, which was washed and then dried under reduced pressure to obtain a modified copolymer. 1610 by the IR method
cm ^-1 peak around disappears, since the epoxy group-specific peaks were observed at 3040cm ^-1, introduction of epoxy groups was confirmed. The conversion rate of unsaturated bonds in the resin to epoxy groups was almost 100%.

Example 12 (Introduction of Nitro Group) 10.0 g of the resin obtained in Example 5, 200 ml of toluene, 98% by weight, 10 ml of concentrated sulfuric acid, and 67% by weight.
10 ml of nitric acid was mixed and reacted at 80 ° C. for 10 minutes while stirring. After completion of the reaction, the mixture was neutralized with sodium hydroxide-dissolved methanol, washed thoroughly, and dried under reduced pressure to obtain a modified copolymer. 1640c by IR method
The characteristic peak at m ^-1 disappeared, and around 1560 cm ^-1 and 13
A sharp peak due to the presence of a nitro group was observed near 50 cm ^-1 . The conversion of unsaturated bonds in the resin to nitro groups was almost 100%.

Example 13 (Introduction of amino group) 5.0 g of the nitrated modified copolymer obtained in Example 12, 200 ml of toluene, 6 g of stannous chloride and 30 g of concentrated sulfuric acid were mixed, and the mixture was mixed at 80 ° C. for 3 days. The reaction was carried out with stirring for a time. After completion of the reaction, the mixture was neutralized with sodium hydroxide-dissolved methanol, washed thoroughly, and then dried under reduced pressure to obtain a modified copolymer. 1560c peculiar to nitro group by IR method
The peaks at m ^-1 and 1350 cm ^-1 disappeared, and 3400-3
A broad peak due to an amino group appeared at 500 cm ^-1 .

Example 14 (Introduction of Sulfone Group) 10 g of the resin obtained in Example 6 and 20 g of tetrachloroethane
And 100 ml of toluene are mixed and the mixture is mixed at 60 ° C for 3 times.
After heating for 0 minutes, the system was cooled and 40 g of chlorosulfonic acid was added over 6 hours with stirring. Then, glacial acetic acid was added until hydrogen chloride was not generated, the reaction product was put into a large amount of water, and the mixture was decanted and then put into water again.
This operation was repeated several times, and after sufficient washing, it was washed with acetone to wash tetrachloroethane and dried under reduced pressure to obtain the desired modified copolymer. 161 by the IR method
And disappearance of the peak of the 0 cm ^-1, confirming the peak around 1070 cm ^-1 and 650 cm ^-1 due to the new sulfone groups introduced. The conversion rate of the unsaturated bond to the sulfone group in this resin was almost 100%.

Example 15 (Acylation) 5.0 g of the resin obtained in Example 7 was gradually added to a well-stirred mixed solution of 10 g of anhydrous aluminum chloride, 8 g of acetyl chloride and 200 ml of carbon disulfide. . After the addition, stirring is continued for further 15 minutes, the content is poured into methanol to which hydrochloric acid is added, aluminum chloride is removed, and the mixture is thoroughly washed with dilute hydrochloric acid and water, then washed with alcohol and dried under reduced pressure to obtain a modified copolymer. Got The IR method, a peak of 1640 cm ^-1 disappeared and the peak around 1800 cm ^-1 and near 1100 cm ^-1 due to the newly acetyl group introduced was observed. The conversion rate of olefinic unsaturated bonds in the resin was almost 100%.

Example 16 (Introduction of Halogen) 5.0 g of the resin obtained in Example 5 and 300 ml of carbon tetrachloride were heated to 50 ° C. under a nitrogen atmosphere and stirred to make a suspension, and then bromine was added. 20 g was added and the reaction was continued for 30 minutes. After completion of the reaction, the content was put into a large amount of methanol to cause precipitation, which was thoroughly washed and then dried under reduced pressure to obtain a modified copolymer. The disappearance of the peak at 1640 cm ^-1 was confirmed by the IR method, and the bromine content was measured by ion chromatography to find that it was 9.4% by weight.

Test Example 1 Each modified copolymer obtained in Examples 9, 10, 11, 12, 13, 14, 15 and a resin which is a precursor of the modified copolymer obtained in Example 1 (comparative) Example 3) is melt pressed and 4
A press sheet having a thickness of 0 mm × 40 mm and a thickness of 0.1 mm was prepared. Distilled water was dropped on the center of each press sheet, and the shape of the droplet was measured using the droplet shape method. The results of visual observation are shown in Table 2.

[0091]

[Table 3]

[0092]

The ethylenically unsaturated copolymer of the present invention is
A crystalline ethylenically unsaturated copolymer having a reactive unsaturated group obtained by copolymerizing ethylene or ethylene and an α-olefin with a cyclic polyene, and modifying the same to give the reactive unsaturated group. The modified copolymer of the present invention can be easily obtained by introducing a functional group such as a hydroxyl group, a carboxyl group, an epoxy group, a halogen group or an amino group.
The modified copolymer of the present invention is excellent in adhesiveness, printability, hydrophilicity, polymer modification property, antistatic property, flame retardancy and the like, and is suitably used for various applications.

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08F 210/00-210/18 C08F 8/00-8/50

Claims (6)

(57) [Claims] 1. Ethylene or ethylene and an α-olefin and a compound represented by the general formula (I): (In the formula, 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. ) And a general formula (II) (In the formula, 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 is an alkenyl group or an alkylidene group; Represents an integer of 0 or more.), Which is obtained by copolymerization with at least one selected from the cyclic polyenes represented by (a) the content of the polyene unit is 0.01 to 3.5 mol. %, (B) the intrinsic viscosity measured in 135 ° C. decalin is 0.01 to 20 deciliter / g,
(C) Gel permeation chromatography (GP
The molecular weight distribution measured in C) is 1.5 to 40, and the crystallization enthalpy (ΔH) measured by a differential scanning calorimeter (DSC) is 90 J / g or more, and the molecular weight distribution is represented by the general formula (I). Formula (III) derived from cyclic polyene (Wherein R ^{1 to} R ¹⁰ and m are the same as above), and a general formula (IV) derived from the cyclic polyene represented by the above general formula (II): ] (In the formula, R ^{11 to} R ²⁰ , R and n are the same as above.)
A crystalline ethylenically unsaturated copolymer containing at least one selected from the repeating units represented by: 2. The molar ratio of the double bond based on the cyclic polyene component in the copolymer to the double bond not based on the norbornene ring in the cyclic polyene component is represented by the formula 0.85 ≦ (in the copolymer: The crystalline ethylenically unsaturated copolymer according to claim 1, which satisfies the relationship of (double bond based on cyclic polyene component) / (double bond not based on norbornene ring in cyclic polyene component) ≦ 1.00. 3. The crystalline ethylenically unsaturated copolymer according to claim 1, which does not substantially contain a 135 ° C. decalin insoluble matter. 4. The ethylenically unsaturated copolymer according to any one of claims 1 to 3 is modified, and a functional group is introduced into at least 5 mol% of unsaturated bonds in the copolymer by a chemical reaction. A modified copolymer characterized by the following. 5. A compound represented by the general formula (V) wherein a functional group is introduced into an unsaturated bond of a unit represented by the general formula (III) as a chemically modified unit. (In the formula, W ¹ and V ¹ each represent a substituent containing at least one of a halogen atom, a monovalent metal atom or 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 R ^{1 to} R ¹⁰ and m are the same as those described above.) And a functional unit for the unsaturated bond of the unit represented by the general formula (IV). General formula (VI) having a group introduced (In the formula, W ² and V ² each represent a substituent containing at least one of a halogen atom, a monovalent metal atom or a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and a tin atom, and may be the same as or different from each other, D is a hydrogen atom or - indicates (CH _{2) y} -CH _3, when D is hydrogen atom x is an integer from 0 to 18, D is -
(CH ₂₎ if x + y of the _y -CH ₃ is an integer of 0~17, R ¹¹ ~R ²⁰ and n are as defined above. The modified copolymer according to claim 4, containing at least one selected from the repeating units represented by the formula (4). 6. The functional group introduced by modification is a hydroxyl group,
Carboxyl group, epoxy group, halogen group, nitro group,
The modified copolymer according to claim 4, which is at least one selected from an amino group, an acyl group, and a sulfone group.