JPH107719A - Modifier consisting of olefin / polar monomer copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an application of an olefin / polar monomer copolymer produced using a novel catalyst and having excellent transparency, heat resistance, impact resistance, flexibility and mechanical properties. SOLUTION: The transition metal compound (I) represented by the general formula (i) (M is a transition metal belonging to Groups 8 to 10 of the periodic table, X
¹ and X ² are N or P, R ¹ and R ² are H or a hydrocarbon group, m and n are 1 or 2 and R ³ is a group containing a double bond as shown in the claim). Modifier consisting of an olefin / polar monomer copolymer produced by Embedded image

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an application of an olefin / polar monomer copolymer having excellent transparency and excellent mechanical properties.

[0002]

BACKGROUND OF THE INVENTION Hitherto, olefin polymers such as polyethylene and polypropylene have been widely used as thermoplastic molding materials having excellent rigidity, heat resistance and transparency. Further, olefin polymers have features such as low specific gravity and easy recyclability, and thus have attracted attention in terms of environmental protection, and are desired to be used for a wider range of applications.

Studies have been made on the improvement of physical properties of such olefin polymers according to applications, and a method of modifying olefin polymers by copolymerizing a polar monomer or the like with olefins is also known. For example, copolymers of ethylene and vinyl acetate are known as olefin copolymers having improved impact resistance, flexibility, transparency, strascrack resistance, etc., and are used in various films or sheets, laminates, etc. It's being used. It is also known that when the copolymerization amount of such a polar monomer is increased, the olefin / polar monomer copolymer becomes more rubbery. For example, a copolymer rubber of ethylene and (meth) acrylic acid ester is known. Etc. are known.

Heretofore, the above-mentioned catalysts for producing olefin polymers generally include (i) a solid titanium catalyst component containing magnesium, titanium and a halogen olefin electron donor, and (ii) an organoaluminum compound. Catalysts containing are known.

Also, olefin polymerization catalysts comprising (i) a transition metal compound (metallocene compound) having cyclopentadienyl as a ligand and (ii) an organoaluminum oxy compound as a catalyst component are widely known.

[0006]

An object of the present invention is to provide a use of an olefin / polar monomer copolymer produced using a novel catalyst and having excellent transparency, heat resistance, impact resistance, flexibility and mechanical properties. It is an object.

[0007]

SUMMARY OF THE INVENTION The present invention provides a modifier for an olefin / polar monomer copolymer produced by using a catalyst containing a transition metal compound (I) represented by the following general formula (i).

[0008]

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(Wherein M is a transition metal belonging to Groups 8 to 10 of the periodic table, X ¹ and X ² may be the same or different and each is a nitrogen atom or a phosphorus atom,
¹ and R ² may be the same or different from each other,
A hydrogen atom or a hydrocarbon group, m and n may be the same or different from each other, and are 1 or 2;

[0010]

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(Where R ⁶ , R ⁷ , R ⁶¹ , R ⁶² , R ⁷¹
And R ⁷² may be the same or different and are a hydrogen atom or a hydrocarbon group. And R ⁴ and R ⁵ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, —OR ⁸ , —SR ⁹ ,
-N (R ¹⁰⁾ ₂ or -P (R ¹¹⁾ ₂ (where, R ⁸ ~
R ¹¹ is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an organosilyl group, R ¹⁰ s or R ¹¹ together may also be linked to each other to form a ring. )
R ⁴ and R ⁵ may be linked to each other to form a ring, and R ¹ , R ² , R ⁶ (or R ⁶¹ ,
Two or more of R ⁶² ) and R ⁷ (or R ⁷¹ , R ⁷² ) may be connected to each other to form a ring. ).

The polar monomer is preferably methyl acrylate, ethyl acrylate, methyl methacrylate, vinyl ketone, vinyl acetate, acrylic acid, methacrylic acid. The olefin / polar monomer copolymer as described above is suitable as a hot-melt adhesive, a wax modifier, an asphalt modifier, an ink paint modifier, and the like. Can be.

[0013]

DETAILED DESCRIPTION OF THE INVENTION
The use of the polar monomer copolymer will be specifically described. In the present invention, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" refers to not only homopolymers but also copolymers. May be used with inclusive meaning.

Olefin / Polar Monomer Copolymer In the present invention, the olefin / polar monomer copolymer is obtained by copolymerizing an olefin and a polar monomer in the presence of a specific catalyst as described later.
Specific examples of this olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 3-methyl-1-
Butene, 3-methyl-1-pentene, 3-ethyl-1-pentene,
4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl
-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,
Α-olefins having 2 to 20 carbon atoms such as 1-octadecene and 1-eicosene, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimetano -1,2,3,4,4a, 5,8,
Examples thereof include cyclic olefins having 3 to 20 carbon atoms such as 8a-octahydronaphthalene. Of these, ethylene is particularly preferred. The olefin / polar monomer copolymer may contain two or more units derived from the above olefin.

Specific examples of the polar monomer include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, and bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid. Α, β-unsaturated carboxylic acids such as acids, and metal salts thereof such as sodium, potassium, lithium, zinc, magnesium, calcium, methyl acrylate, ethyl acrylate, n-propyl acrylate;
Isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, Α, β-unsaturated carboxylic acid esters such as isobutyl methacrylate Maleic acid, unsaturated dicarboxylic acids such as itaconic acid, vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, tri Vinyl esters such as vinyl fluoroacetate; unsaturated glycidyl group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate;

Of these, preferred are methyl acrylate, methyl methacrylate, vinyl ketone, vinyl acetate, acrylic acid, methacrylic acid and the like. The olefin / polar monomer copolymer may contain two or more units derived from the above polar monomer.

The olefin / polar monomer copolymer has a unit derived from the olefin in an amount of 99.5 to 0.5 mol%, preferably 99 to 1 mol%, of the unit derived from the olefin. ９９99.5 mol%, preferably 1 to 9
Desirably, it is contained at a ratio of 9 mol%. In the present invention, the content of the unit derived from the polar monomer can be selected according to the use of the olefin / polar monomer copolymer.

In the olefin / polar monomer copolymer,
Other monomers may be copolymerized with the olefin and the polar monomer as described above. Examples of the other copolymerized monomers include styrene, substituted styrenes, allylbenzene, substituted allylbenzenes, vinylnaphthalenes, and substituted vinyls. Naphthalenes, allylnaphthalenes,
Aromatic vinyl compounds such as substituted allyl naphthalenes, vinyl cyclopentanes, substituted vinyl cyclopentanes, vinyl cyclohexane, substituted vinyl cyclohexanes, vinyl cycloheptane, substituted vinyl cycloheptanes, alicyclic vinyl compounds such as allyl norbornane, allyl Trimethylsilane, allyltriethylsilane, 4-trimethylsilyl-1-butene, 6-trimethylsilyl-1-hexene,
8-trimethylsilyl-1-octene, 10-trimethylsilyl
Silane unsaturated compounds such as -1-decene, butadiene,
1,4-hexadiene, 7-methyl-1,6-octadiene, 1,8-
Examples thereof include conjugated and non-conjugated dienes such as nonadiene, 1,9-decadiene, norbornadiene, and dicyclopentadiene.

Two or more other monomers may be copolymerized. The olefin / polar monomer copolymer may contain a unit derived from such another monomer in an amount of 80 mol% or less, preferably 70 mol% or less.

Specific examples of such an olefin / polar monomer copolymer include α-olefin / acrylic acid copolymer, α-olefin / methyl acrylate copolymer,
α-olefin / ethyl acrylate copolymer, α-olefin / isopropyl acrylate copolymer, α-olefin / n-butyl acrylate copolymer, α-olefin ・
Isobutyl acrylate copolymer, α-olefin / 2-ethylhexyl acrylate copolymer, α-olefin / methacrylic acid copolymer, α-olefin / methyl methacrylate copolymer, α-olefin / ethyl methacrylate copolymer Copolymer, α-olefin / isopropyl methacrylate copolymer, α-olefin / n-butyl methacrylate copolymer, α-olefin / isobutyl methacrylate copolymer, α-olefin / 2-ethylhexyl methacrylate copolymer, α-olefin / vinyl acetate copolymer, α-olefin / vinyl propionate copolymer, α-olefin / ethyl acrylate / maleic anhydride copolymer, α-olefin
Examples include olefin / ethyl acrylate / glycidyl methacrylate copolymer, α-olefin / vinyl acetate / glycidyl methacrylate copolymer, α-olefin / glycidyl methacrylate copolymer, and the like. Among these, those in which the α-olefin is ethylene are preferred.

The olefin / polar monomer copolymer is produced by using a catalyst containing a transition metal compound (I) represented by the following general formula (i). As the cocatalyst component (II), selected from (II-a) organoaluminumoxy compounds, (II-b) alkylboronic acid derivatives and (II-c) compounds which react with transition metal compounds to form ion pairs Formed using at least one compound. (I) Transition metal compound

[0022]

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In the formula, M is a transition metal atom belonging to Groups 8 to 10 of the periodic table, and is preferably nickel, palladium or platinum. X ¹ and X ² may be the same or different and are a nitrogen atom or a phosphorus atom.

R ¹ and R ² may be the same or different and are a hydrogen atom or a hydrocarbon group. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group,
a linear or branched alkyl group having 1 to 20 carbon atoms such as sec-butyl group, tert-butyl group, pentyl group, and hexyl group; an aryl group having 6 to 20 carbon atoms such as phenyl group and naphthyl group Group; a substituted aryl group in which 1 to 5 substituents such as the alkyl group having 1 to 20 carbon atoms are substituted on these aryl groups.

M and n are each independently R ¹ bonded to X ¹
The number of ^one group and the number of R ² groups bonded to X ² , which may be the same or different, and are 1 or 2.

[0026]

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## EQU1 ## Where R ⁶ , R ⁷ , R ⁶¹ ,
R ⁶² , R ⁷¹ and R ⁷² may be the same or different and are each a hydrogen atom or a hydrocarbon group similar to R ¹ and R ² .

The above R ¹ , R ² , R ⁶ (or R ⁶¹ ,
R ⁶² ) and R ⁷ (or R ⁷¹ , R ⁷² ) may form a ring by connecting two or more of them, preferably adjacent groups, to each other.

R ⁴ and R ⁵ may be the same or different and are a hydrogen atom, a halogen atom or a hydrocarbon group. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Specific examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms, such as R ¹ and R ^2, and 7 to 20 carbon atoms such as a benzyl group. And an aralkyl group. One or more substituents such as the alkyl group having 1 to 20 carbon atoms may be substituted on the aryl group and the aralkyl group. Also, as R ⁴ and R ⁵ ,
^{-OR 8, -SR 9, -N (} R 10) 2 or -P
The group represented by (R ¹¹ ) ₂ is also shown.

R ^{8 to} R ¹¹ are the same as the above-mentioned R ¹ and R ² , an alkyl group having 1 to 20 carbon atoms and 6 to
C6-C20 cycloalkyl groups such as 20 aryl groups and cyclohexyl groups; C7-C20 aralkyl groups such as benzyl groups; methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group And an organic silyl group such as a triethylsilyl group. The aryl group and the aralkyl group may have one or more substituents such as the alkyl group having 1 to 20 carbon atoms. R ^{10 and} R ¹¹ may be connected to each other to form a ring.

Such R ⁴ and R ⁵ may be linked to each other to form a ring. In the present invention, the above transition metal compound (I) is preferably represented by the following general formula (ii).

[0032]

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(Where M, X ¹ , X ² , R ¹ , R ² , R
⁴ , R ⁵ , R ⁶ and R ⁷ are the same as those in the general formula (i). Specific examples of the transition metal compound represented by the general formula (ii) are shown below. In the following formula, iPr is an isopropyl group.

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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Examples of the transition metal compound represented by the general formula (ii) include compounds in which palladium or nickel in the compounds exemplified above is replaced by platinum. Examples of the transition metal compound (I) represented by the general formula (i) include the following compounds in addition to the compound represented by the above formula (ii). In the following formula, iPr represents an isopropyl group.

[0045]

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[0046]

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Further, there may be mentioned, for example, compounds in which palladium or nickel in the compounds exemplified above is replaced by platinum.

The above transition metal compounds (I) may be used in combination of two or more. The catalyst used for producing the ethylene-based polymer in the present invention includes, together with the above-mentioned (I) transition metal compound, a cocatalyst component (I
(II-a) organoaluminum oxy compounds as (I), (I-a)
At least one compound selected from Ib) an alkylboronic acid derivative and (II-c) a compound which reacts with the transition metal compound to form an ion pair is used.

(II-a) Organoaluminum Oxy Compound The (II-a) organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, and is exemplified in JP-A-2-78687. May be a benzene-insoluble organic aluminum oxy compound.

The conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent. (1) Compounds containing water of adsorption or salts containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerium chloride A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of the above, and reacting the water of adsorption or water of crystallization with the organoaluminum compound. (2) A method in which water, ice or steam is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organic metal component. The solvent or unreacted organoaluminum compound may be removed from the recovered solution of the aluminoxane by distillation, and then redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

The organoaluminum compound used in preparing the aluminoxane includes an organometallic compound (II)
Trialkylaluminum as described below as I),
Tricycloalkyl aluminum, dialkyl aluminum halide, dialkyl aluminum hydride,
Organic aluminum compounds such as dialkylaluminum alkoxides and dialkylaluminum aryloxides can be used.

Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred. In preparing the aluminoxane, two or more organoaluminum compounds can be used in combination.

At the time of preparing aluminoxane, solvents such as aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; cyclopentane; Alicyclic hydrocarbons such as cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene and light oil; and halogens (chlorine and bromine) of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons A hydrocarbon solvent such as a compound is used. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

In the benzene-insoluble organoaluminum oxy compound used in the present invention, the Al component soluble in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. Yes, insoluble or poorly soluble in benzene.

(II-b) Alkyl Boronic Acid Derivative The alkyl boronic acid derivative (B-2) used in the present invention is
For example, it is represented by the following general formula (iii).

[0057]

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In the formula, R ¹² is a hydrocarbon group having 1 to 10 carbon atoms. R ¹³ may be the same or different and are a hydrogen atom, a halogen atom, a siloxy group optionally having a lower alkyl group, or a hydrocarbon group having 1 to 10 carbon atoms.

The above-mentioned alkylboronic acid derivative (B-2) represented by the general formula (iii) is obtained by reacting an alkylboronic acid represented by the following general formula (iv) with an organoaluminum compound. In an inert solvent under a gas atmosphere,
It can be produced by reacting at room temperature for 1 minute to 24 hours.

R ¹² -B- (OH) ₂ (iv) (wherein R ¹² is the same group as described above). As the alkylboronic acid represented by the above formula (iv), specifically, methylboron Acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboron Acid and 3,5-bis (trifluoromethyl) phenylboronic acid.

Of these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid and pentafluorophenylboronic acid are preferred. These can be used in combination of two or more.

The organoaluminum compound to be reacted with such an alkylboronic acid can be represented by, for example, the following general formulas (v), (vi) and (vii). _{^{(R 13) 3-p -Al}} -Y p ... (v) (R 13) 3-p -Al- [OSi (R 14) 3] p ... (vi) (R 13) 2 -Al-O-Al _{^{- (R 13) 2 ... (}} vii) ( wherein, Y is a hydrogen atom or a halogen atom, R ¹⁴
Is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms, p is 0 ≦ p <3, and R ¹³ is the same group as described above. Specific examples of the organoaluminum compound represented by the general formulas (v), (vi), and (vii) include trialkylaluminum, tricycloalkylaluminum, which will be described later as the organometallic compound (III), Examples thereof include dialkyl aluminum halide, dialkyl aluminum hydride, dialkyl aluminum alkoxide, and dialkyl aluminum aryloxide.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These can be used in combination of two or more.

(II-c) Reaction with Transition Metal Compound and Ion
Compounds that form pairs The compounds that form an ion pair by reacting with the transition metal compound used in the present invention (hereinafter referred to as ionic compounds) are described in JP-A-1-501950 and JP-A-1-502.
No. 036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, U.S. Pat.
No. 8 publication, Lewis acids, ionic compounds,
Examples thereof include borane compounds and carborane compounds.

Examples of the Lewis acid include a compound represented by BR ₃ (R is a phenyl group which may have a substituent such as a fluorine group, a methyl group or a trifluoromethyl group or a fluorine group), For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p -Tolyl) boron, tris (o-tolyl) boron, tris (3,5-
Dimethylphenyl) boron and the like.

Further, examples of the ionic compound include a compound represented by the following general formula (viii).

[0067]

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In the formula, R ¹⁵ includes H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal and the like.

R ^{16 to} R ¹⁹ may be the same or different and are an organic group, preferably an aryl group or a substituted aryl group. Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; N, N-diethylanili Nium cation, N,
N, N- such as N-2,4,6-pentamethylanilinium cation
Dialkylanilinium cation; di (isopropyl)
Examples thereof include an ammonium cation and a dialkylammonium cation such as a dicyclohexylammonium cation.

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

R ¹⁵ is preferably a carbonium cation, an ammonium cation, or the like, and particularly preferably a triphenylcarbonium cation or an N, N-diethylanilinium cation.

The ionic compound is represented by the following formula (i)
The boron compound represented by x) can be preferably exemplified.

[0074]

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Further, examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p -Tolyl) boron, trimethylammoniumtetra (o-tolyl) boron, tri (n-butyl) ammoniumtetra (pentafluorophenyl) boron, tripropylammoniumtetra (o, p-dimethylphenyl) boron,
Tri (n-butyl) ammonium tetra (m, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditri Fluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron and the like.

Specific examples of the N, N-dialkylanilinium salt include, for example, N, N-dimethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra (phenyl) boron, N, N-2, 4,6-pentamethylanilinium tetra (phenyl) boron and the like.

Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Further, as an ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl)
Borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenylcyclopentadienyl complex,
An N, N-diethylanilinium pentaphenylcyclopentadienyl complex, a boron compound represented by the following formula (x), and the like can also be mentioned.

[0080]

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Specific examples of the borane compound include decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, and bis [tri (n-butyl) ammonium ] Undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-
Salts of anions such as butyl) ammonium] dodecachlorododecaborate; tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) Borate) salts of metal borane anions such as nickelate (III).

Specific examples of the carborane compound include, for example, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl- 1,3-dicarbanonaborane,
Dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarboundecaborane (13), 2,
7-dicarboundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri (n-butyl ) Ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carboundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadeca Borate, tri (n-butyl) ammonium bromo-1-carbadecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (1
2), tri (n-butyl) ammonium 7-carboundecaborate (13), tri (n-butyl) ammonium 7,8-
Dicarboundecaborate (12), tri (n-butyl)
Ammonium 2,9-dicarboundecaborate (12),
Tri (n-butyl) ammonium dodecahydride-8-
Methyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-
Dicarbaune decaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaune Decaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carboundecaborate Salts of anions such as tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8 -Dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) co Belt salt (III), tri (n- butyl) ammonium bis (undecapeptide 7,8-dicarbaundecaborate deca borate)
Nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-Dicarboundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) ferrate (III) (N-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8 -Dicarboundecaborate) cobaltate (II
I), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium]
Bis (undecahydride-7-carboundecaborate) manganate (iv), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (III), Bis [tri (n-butyl) ammonium] bis (undecahydride-7-
(Carboundecaborate) nickelate (iv) and the like, and salts of metal carborane anions.

The above (II-a) organoaluminum oxy compound, (II-b) alkylboronic acid derivative, (II-a)
c) Any one of the ionic compounds may be used alone, or two or more of them may be used in combination.

(III) Organometallic Compound In the present invention, (III) an organometallic compound can be used, if necessary, as a catalyst component for producing an ethylene-based polymer. Specific examples of the (III) organometallic compound include organometallic compounds of Groups 1 and 2 and Groups 12 and 13 of the periodic table as described below.

[0085] (III-a) general formula R ^a _m Al (OR ^b) an organic aluminum compound represented by _n H _p X _q. (Wherein, R ^a and R ^b may be the same or different from each other and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms,
X represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n
<3, p is a number satisfying 0 ≦ p <3, q is a number satisfying 0 ≦ q <3, and m + n + p + q = 3. ) (III-b) 1-group metal and alkylated complex of aluminum represented by the general formula M ¹ AlR ^a _4. (In the formula, M ¹ represents Li, Na, or K, and ^Ra is a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms.) (III-c) Formula R ^a R ^b M group 2 or group 12 dialkyl compound of a metal represented by ^2.
(In the formula, R ^a and R ^b may be the same or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ² is Mg, Zn or Cd.) Examples of the organoaluminum compound belonging to the above (III-a) include the following compounds.

[0086] formula R ^a _m Al (OR ^b) an organoaluminum compound represented by the _3-m. (Wherein R ^a and R ^b
May be the same or different, and have 1 carbon atom
Represents preferably 15 to 15 hydrocarbon groups, and m is preferably a number satisfying 1.5 ≦ m ≦ 3. ) General formula organoaluminum compound represented by R ^a _m AlX _3-m. (Wherein, R ^a represents a hydrocarbon group having from 1 to 15 preferably 1 to 4 carbon atoms, X is a halogen atom, m is preferably 0 <m <3.) The general formula R ^a _m An organoaluminum compound represented by AlH _3-m . (Wherein, ^Ra represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 2 ≦ m
<3. ) General formula R ^a _m Al (organic aluminum compound represented by OR ^b) _n X _q. (Wherein, R ^a and R ^b may be the same or different and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0 <m ≦ 3, n is 0 ≦ n <3, q is 0 ≦ q <
3 and m + n + q = 3. More specifically, aluminum compounds belonging to (III-a) include, for example, trimethylaluminum, triethylaluminum, tripropylaluminum, trin-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and the like. Tri-n-alkylaluminum, triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3- Methylpentyl aluminum, tri-4-methylpentyl aluminum, tri-2-methylhexyl aluminum, tri-3-methylhexyl aluminum, tri-2-ethylhexyl aluminum, etc. Tri branched-chain alkyl _{aluminum, (i-C 4 H 9} ) x Al y (C 5 H 10) z ( wherein, x, y
And z are positive numbers and z ≧ 2x. ), Tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminums such as triphenylaluminum and tritolylaluminum; dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; Trialkenyl aluminum such as isoprenyl aluminum, isobutyl aluminum methoxide, isobutyl aluminum ethoxide,
Alkali aluminum alkoxides such as isobutylaluminum isopropoxide, dimethylaluminum methoxide, dimethylaluminum ethoxide, diethylaluminum ethoxide, dialkylaluminum alkoxides such as dibutylaluminum butoxide, ethylaluminum sesquietoxide, alkylaluminum sesquibutoxide and the like Alkoxide, partially alkoxylated alkyl aluminum having an average composition represented by ^Ra _2.5 Al (OR ^b ) _0.5 , dialkyl aluminum aryloxide such as diethyl aluminum phenoxide, dimethyl aluminum chloride, diethyl aluminum chloride, dibutyl Aluminum chloride, diisobutyl aluminum chloride, di Such as alkylaluminum dihalides such as dialkylaluminum halides such as butylaluminum bromide, ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide; Other partially hydrogenated alkylaluminums such as partially halogenated alkylaluminums, dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride, alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride , Ethyl aluminum ethoxycyclolide, Partially alkoxylated and halogenated alkylaluminums such as butylaluminum butoxycyclolide and ethylaluminum ethoxybromide can be mentioned.

Further, a compound similar to (III-a) can also be used, and examples thereof include an organic aluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Examples of the compound belonging to the above (III-b) include LiAl (C ₂ H ₅ ) ₄ LiAl (C ₇ H ₁₅ ) _{4 and the} like.

The compounds belonging to the above (III-c) include dimethylmagnesium, diethylmagnesium, dibutylmagnesium, butylethylmagnesium and the like.

Further, as the organometallic compound (III), methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium chloride, butyl magnesium Magnesium bromide, butylmagnesium chloride and the like can also be used.

Further, a compound which forms the above-mentioned organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium can also be used.

As the organometallic compound (III), among the above, a metal compound having a branched alkyl group is preferable, a metal compound having an isobutyl group is particularly preferable, and a triisobutyl metal compound is particularly preferable, and triisobutylaluminum is particularly preferable. preferable.

The organometallic compound (III) can be used in combination of two or more kinds. As described above, the organometallic compound (III) having an alkyl group is selected from the group consisting of R ⁴ and / or R ⁴ bonded to the transition metal (M) in the transition metal compound (I) represented by the general formula (I). ^{When 5} is an atom or group other than an alkyl group (for example, a halogen atom such as chlorine or bromine or a group such as an alkoxy group such as a methoxy group, an ethoxy group or a butoxy group), an alkylating agent which substitutes these for an alkyl group Act as

The organometallic compound (III) also acts as a scavenger and removes water and other impurities from the system to keep the reaction system clean, so that the catalyst can exhibit a high activity stably. The effect is obtained. Such an effect is exhibited regardless of whether R ⁴ and / or R ⁵ bonded to the transition metal (M) in the transition metal compound (I) is an alkyl group.

In the present invention, the catalyst component as described above can be used by being supported on a fine particle carrier. The fine particle carrier has a particle size of 10 to 300 μm, preferably 20 to 2 μm.
A 00 μm granular or particulate solid is used, and the solid may be an inorganic compound or an organic compound.

As the inorganic compound, a porous oxide is preferable. Specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO,
TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO
₂ or a mixture thereof, for example, SiO ₂ —Mg
O, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V
Examples include ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , and SiO ₂ —TiO ₂ —MgO. Among them, those containing SiO ₂ and / or Al ₂ O ₃ as a main component are preferable.

The above-mentioned inorganic oxides include Na ₂ CO ₃ , K
₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , A
l ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ )
₂ , a small amount of carbonate, sulfate, nitrate and oxide components such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O and Li ₂ O may be contained.

The nature of the inorganic carrier used in the present invention varies depending on the type and the production method, but the specific surface area is 50 to 10%.
00 m ² / g, preferably 100 to 700 m ² / g, and the pore volume is desirably 0.3 to 2.5 cm ³ / g. The inorganic carrier is used by firing at 100 to 1000 ° C, preferably 150 to 700 ° C, if necessary.

The organic compounds forming the particulate carrier include ethylene, propylene, 1-butene, 4-methyl-1
A (co) polymer formed mainly of an α-olefin having 2 to 14 carbon atoms such as pentene or a (co) polymer formed mainly of vinylcyclohexane or styrene.

The catalyst used in the present invention may contain other components useful for polymerization in addition to the above components. In the catalyst used in the present invention, when the transition metal compound (I) is brought into contact with the catalyst component (II), it is presumed that an ionic coordination compound represented by the following general formula (xi) is formed.

[0101]

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(Wherein, M ¹ , X ¹ , X ² , R ¹ , R ² ,
m and n are the same as those in the general formula (I), R ²¹ is a hydrocarbon group, and Z is an ion formed from the catalyst component (II). In the general formula (xi), R ²¹ is a hydrocarbon group such as an alkyl group of R ⁴ or R ^{5 in} the general formula (I) or an alkyl group introduced by the (III) organometallic compound. is there.

The ionic coordination compound represented by the general formula (xi) includes an ether compound formed from the catalyst component (II) upon contact of the transition metal compound (I) with the catalyst component (II). (Ether molecule) or the like may coordinate to the transition metal represented by M. Such an ionic coordination compound is represented by the following general formula (xii).

[0104]

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(Wherein, M ¹ , X ¹ , X ² , R ¹ , R ² ,
m and n are the same as those in the general formula (I), R ²¹ and Z are the same as those in the general formula (xi), and R ²² is the same as the transition metal compound (I) and the catalyst component (II). Is an ether compound (ether molecule) formed from the catalyst component (II) upon contact with the catalyst. Specific examples of the ether compound (ether molecule) represented by R ²² in the general formula (xii) include dimethyl ether, diethyl ether, dipropyl ether,
Dibutyl ether and the like.

In the present invention, when the transition metal compound (I) and the catalyst component (II) as described above come into contact, (meth)
When an acrylate ester is present, the following general formula (xi
It is presumed that the ionic coordination compound shown in ii) is formed.

[0107]

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(Wherein, M ¹ , X ¹ , X ² , R ¹ , R ² ,
m and n are the same as those in the general formula (I), R ²³ and Z are the same as those in the general formula (xi), and R ²⁴ and R ²⁵
Is a part of the residue of the (meth) acrylate. As the (meth) acrylic ester, those exemplified above as the polar monomer can be mentioned.

In producing an olefin / polar monomer copolymer using a catalyst from the above catalyst components,
The transition metal compound (I) is desirably used at a concentration of about 10 ^-5 to 1 mmol / L (polymerization volume), preferably 10 ^-4 to 1 mmol / L.

When an organoaluminum oxy compound (II-a) or an alkylboronic acid derivative (II-b) is used as the catalyst component (II), the compound (II-a) or (II-a)
b) is the molar ratio of the aluminum atom to the transition metal compound (I) [(II-a) or (II-b) /
(I)], but usually 10 to 1000, preferably 20 to 50
When the ionic compound (II-c) is used as the catalyst component (II), the molar ratio to the transition metal compound (I) [(B-3) / (I)] is 0. 1 to
It is desirable that it be used in an amount such that it becomes 10 preferably 1-5.

The organometallic compound (C) has a molar ratio [(C) / (I)] to the transition metal compound component (I) of 0.0.
It is used as needed in an amount of 1 to 100, preferably 0.05 to 50.

The order of contact of the catalyst components as described above is not particularly limited. It may be used for polymerization after being brought into contact in advance, and it is preferably about -100 to 150 ° C, and more preferably about -80 to 12 ° C.
The contact can be made in advance at a temperature of about 0 ° C. At the time of contact, an inert hydrocarbon solvent can be used.

Further, the catalyst component may be used by preliminarily polymerizing an olefin. The olefin / polar monomer copolymer according to the present invention, in the presence of the catalyst as described above,
It is obtained by copolymerizing an olefin and a polar monomer as described above.

The polymerization can be carried out by any of a gas phase polymerization method, a slurry polymerization method and a liquid phase polymerization method such as a solution polymerization method. Inert hydrocarbons can be used as the polymerization medium, for example, propane, butane, isobutane,
Aliphatic hydrocarbons such as pentane, hexane, octane, decane, dodecane, hexadecane and octadecane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane and cyclooctane; and aromatics such as benzene, toluene and xylene Petroleum fractions such as hydrocarbons, gasoline, kerosene, and light oil can be used. Of these, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum fractions and the like are preferred.

In the liquid phase polymerization, a monomer which is liquid at the time of polymerization may be used as a solvent. The polymerization temperature is usually -100 to 10 when performing slurry polymerization.
0 ° C., and usually -5 when performing solution polymerization.
The temperature is in the range of 0 to 250 ° C., and is generally in the range of 0 to 300 ° C., preferably 20 to 100 ° C. when performing gas phase polymerization.

The polymerization pressure is from normal pressure to 120 kg / cm ^2, preferably from normal pressure to 50 kg / cm ² . The polymerization may be performed in any of a batch system, a semi-continuous system, and a continuous system, and the polymerization may be performed in two or more stages under different reaction conditions. At the time of polymerization, the molecular weight of the obtained olefin / polar monomer copolymer can be adjusted using hydrogen or the like.

[0117] Applications olefin-polar monomer copolymer as described above can be different depending on the composition will be used in various known applications as an olefin-polar monomer copolymer applications. Depending on the content of the polar monomer component, vulcanization with a peroxide is also possible. Specifically, olefin-polar monomer copolymers having a high polar monomer component content and being rubbery are excellent in flexibility, transparency, impact resistance, and strascrack resistance. It can be widely used for rubber products such as chemicals, heat-resistant gaskets, various industrial products, hoses, tubes, seals, rubber boots, electric wire coating, electric parts, anti-vibration rubber, adhesives, etc.

A resin having a low content of polar monomer components is excellent in ozone resistance and weather resistance, and is used as an agricultural sheet material, a blending agent for various polymers, and various modifiers, adhesives, coating agents, and the like. It can be used as a material for heat molding.

As the above modifier, it can be used as a wax modifier, an asphalt modifier, an ink paint modifier and the like. The olefin / polar monomer copolymer is suitable as a pressure-sensitive adhesive, a hot-melt adhesive, and the like, and is also suitable as a hot-melt adhesive such as a PP film laminated heat sealant.

The olefin / polar monomer copolymer is suitable as a thermoforming material. For example, the olefin / polar monomer copolymer is heat-molded into a sheet, an undrawn or drawn film, a filament, or other various shaped articles. Can be used.

Examples of the heat molded article include extrusion molding,
Examples include molded articles obtained by a known heat molding method such as injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, calender molding, and foam molding. Hereinafter, the heat molded product will be described with reference to several examples.

When the heat-formed body is, for example, an extruded body, its shape and product type are not particularly limited, but for example, sheets, films (unstretched), pipes, hoses,
Wire coating, filaments and the like, especially sheets,
Films and filaments are preferred.

When extruding the olefin / polar monomer copolymer, a conventionally known extruder and molding conditions can be employed. For example, a single screw extruder,
Using a kneading extruder, ram extruder, gear extruder, etc., extrude the molten olefin / polar monomer copolymer from a T-die or the like to form a sheet or film (unstretched)
Etc.

The stretched film is prepared by subjecting the above-mentioned extruded sheet or extruded film (unstretched) to a known stretching method such as a tenter method (longitudinal and transverse stretching, transverse and longitudinal stretching), a simultaneous biaxial stretching method and a uniaxial stretching method. It can be obtained by stretching.

The stretching ratio when stretching a sheet or an unstretched film is usually about 20 to 70 times for biaxial stretching and about 2 to 10 times for uniaxial stretching. It is desirable to obtain a stretched film having a thickness of about 5 to 200 μm by stretching.

An inflation film can also be produced as a film-shaped molded product. Sheets and film molded articles made of the olefin / polar monomer copolymer according to the present invention as described above have heat sealability, heat resistance, impact resistance, flexibility, stress crack resistance, weather resistance, aging resistance, It has excellent transparency, transparency, gloss, mechanical properties, moisture-proof properties and gas barrier properties, and can be widely used as packaging films. Particularly, it is suitably used for press through packs used for packaging heavy packaging films (bags, laminates), agricultural films, injection molded films, pharmaceutical tablets, capsules and the like.

The filament molded article can be produced, for example, by extruding a molten olefin / polar monomer copolymer through a spinneret. The filament thus obtained may be further drawn. This stretching may be carried out to such an extent that at least one axis of the filament is molecularly oriented, and it is usually desirable to carry out the stretching at a magnification of about 5 to 10 times. The filament comprising the olefin / polar monomer copolymer according to the present invention is excellent in rigidity, heat resistance and impact resistance.

An injection molded article can be produced by injection molding an olefin / polar monomer copolymer into various shapes using a conventionally known injection molding apparatus under known conditions. The injection molded article comprising the olefin / polar monomer copolymer according to the present invention has excellent rigidity, heat resistance, impact resistance, surface gloss, chemical resistance, abrasion resistance, etc. It can be widely used for exterior materials for automobiles, housings for electric home appliances, containers and the like.

The blow molded article can be manufactured by blow molding an olefin / polar monomer copolymer using a conventionally known blow molding apparatus under known conditions.

For example, in extrusion blow molding, the olefin / polar monomer copolymer is used at a resin temperature of 100.degree.
It is extruded from a die in a molten state at 0 ° C. to form a tubular parison. Then, the parison is held in a mold having a desired shape, air is blown into the parison, and the parison is mounted on the mold at a resin temperature of 130 ° C. to 300 ° C. to form a hollow. A molded article can be manufactured. The stretching (blow) magnification is preferably about 1.5 to 5 times in the lateral direction.

In the injection blow molding, the olefin / polar monomer copolymer is heated at a resin temperature of 100 ° C. to 300 ° C.
A parison mold is formed by molding the parison, then the parison is held in a mold having a desired shape, air is blown into the parison, and a hollow molded body is manufactured by mounting the mold at a resin temperature of 120 ° C to 300 ° C. can do. Then, a hollow molded product is obtained. The stretching (blow) magnification is 1.1 to 1.1 in the longitudinal direction.
It is preferably 1.8 times and 1.3 to 2.5 times in the horizontal direction.

The blow molded article comprising the olefin / polar monomer copolymer according to the present invention is excellent in rigidity, heat resistance and impact resistance, and also excellent in moisture resistance. Examples of the press-formed body include a mold stamping-formed body. For example, the base material and the skin material are simultaneously press-formed, and the base material when the two are integrally combined (mold stamping) is used. It can be formed of a monomer copolymer.

Specific examples of such a molded stamping molded body include automotive interior materials such as door trim, rear package trim, seat back garnish, and instrument panel.

The press-formed product comprising the olefin / polar monomer copolymer according to the present invention is hardly charged, and has improved rigidity, heat resistance, impact resistance, aging resistance, surface gloss, chemical resistance, abrasion resistance and the like. Are better.

In the present invention, when the olefin / polar monomer copolymer is used, various additives, other polymers, and the like may be used as needed as long as the object of the present invention is not impaired.
Other rubber components and the like may be appropriately contained. Additives include nucleating agents, antioxidants, hydrochloric acid absorbers, heat stabilizers, weather stabilizers, light stabilizers, ultraviolet absorbers, slip agents, antiblocking agents, antifogging agents, lubricants, antistatic agents, Flame retardants, pigments, dyes, dispersants, copper damage inhibitors, neutralizing agents, foaming agents, plasticizers, foam inhibitors, crosslinking agents, flow improvers such as peroxides, weld strength improvers, natural oils, synthetics Oil, wax and the like can be mentioned. In particular, it is preferable to add a heat stabilizer as described below at the time of heat molding. When forming into a film, it is preferable to add an antistatic agent.

For example, if the olefin / polar monomer copolymer contains a nucleating agent, the crystal grains can be refined, the crystallization speed can be improved, and high-speed molding can be performed.
As the nucleating agent, various conventionally known nucleating agents are used without any particular limitation, and among them, the following nucleating agents can be preferably used.

[0137]

Embedded image

(Wherein R ¹ is oxygen, sulfur or a group having 1 carbon atom)
A 10 hydrocarbon group, R ^2, R ³ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, R ^2, R ³ may be heterologous be homologous, R ² to each other , R ^{3 and} R ²
And R ³ may be bonded to form a ring, and M is 1 to 3
Is a valent metal atom, and n is an integer of 1 to 3. ) Specifically, sodium-2,2'-methylene-bis (4,6-di-
(t-butylphenyl) phosphate, sodium-2,2'-
Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis- (4,6-di-t-butylphenyl) phosphate, lithium-2,2 ' -Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-i-propyl-
6-t-butylphenyl) phosphate, lithium-2,2'-
Methylene-bis (4-methyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-ethyl-6-
t-butylphenyl) phosphate, calcium-bis [2,2'-thiobis (4-methyl-6-t-butylphenyl) phosphate], calcium-bis [2,2'-thiobis (4-ethyl-6 -t-butylphenyl) phosphate], calcium-bis [2,2'-thiobis- (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2'-thiobis (4, 6-di-t-butylphenyl) phosphate],
Magnesium-bis [2,2'-thiobis- (4-t-octylphenyl) phosphate], sodium-2,2'-butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2, 2'-butylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2 , 2'-t-octylmethylene-bis (4,6-
Di-t-butylphenyl) phosphate, calcium
Bis- (2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate), magnesium-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) ) Phosphate], barium-bis [2,2'-methylene-bis (4,6-di-t-
Butylphenyl) phosphate], sodium-2,2'-
Methylene-bis (4-methyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4-ethyl-
6-t-butylphenyl) phosphate, sodium (4,
4'-dimethyl-5,6'-di-t-butyl-2,2'-biphenyl) phosphate, calcium-bis [(4,4'-dimethyl-6,6'-
Di-t-butyl-2,2'-biphenyl) phosphate], sodium-2,2'-ethylidene-bis (4-m-butyl-6-t-butylphenyl) phosphate, sodium-2,2 ' -Methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-ethylphenyl) phosphate, potassium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, calcium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2 ' -
Ethylidene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-ethylidene-bis (4,6
-Di-t-butylphenyl) phosphate], aluminum-tris [2,2'-methylene-bis (4,6-di-t-butylfell) phosphate] and aluminum-tris [2,
2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate] and mixtures of two or more thereof.

Of these, sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate is particularly preferred.

[0140]

Embedded image

(Wherein R ⁴ is hydrogen or C 1-10)
Wherein M is a monovalent to trivalent metal atom,
n is an integer of 1 to 3. ) Specifically, sodium-bis (4-t-butylphenyl)
Phosphate, sodium-bis (4-methylphenyl) phosphate, sodium-bis (4-ethylphenyl) phosphate, sodium-bis (4-i-propylphenyl) phosphate, sodium-bis (4-t-
Octylphenyl) phosphate, potassium-bis (4
-t-butylphenyl) phosphate, calcium-bis (4-t-butylphenyl) phosphate, magnesium
-Bis (4-t-butylphenyl) phosphate, lithium-bis (4-t-butylphenyl) phosphate, aluminum-bis (4-t-butylphenyl) phosphate and mixtures of two or more thereof can do.

Among them, sodium-bis (4-t
-Butylphenyl) phosphate is preferred.

[0143]

Embedded image (In the formula, R ⁵ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.) Specifically, 1,3,2,4-dibenzylidene sorbitol,
3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1,3- p-ethylbenzylidene-2,4-benzylidenesorbitol, 1,3-p-methylbenzylidene-2,4
-p-ethylbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol,
1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,
3,2,4-di (p-ethylbenzylidene) sorbitol, 1,3,
2,4-di (pn-propylbenzylidene) sorbitol, 1,
3,2,4-di (pi-propylbenzylidene) sorbitol,
1,3,2,4-di (pn-butylbenzylidene) sorbitol,
1,3,2,4-di (ps-butylbenzylidene) sorbitol,
1,3,2,4-di (pt-butylbenzylidene) sorbitol,
1,3,2,4-di (2 ', 4'-dimethylbenzylidene) sorbitol, 1,3,2,4-di (p-methoxybenzylidene) sorbitol, 1,3,2,4-di (p- Ethoxybenzylidene) sorbitol, 1,3-benzylidene-2-4-p-chlorobenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-benzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4- p-methylbenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-
Methylbenzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol and 1,3,2,4-di (p-chlorobenzylidene) sorbitol and these And a mixture of two or more of the above.

Among these, 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene)
Sorbitol, 1,3,2,4-di (p-ethylbenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p- (Chlorbenzylidene) sorbitol and mixtures of two or more thereof are preferred.

Examples of the nucleating agent include metal salts of aromatic carboxylic acids and aliphatic carboxylic acids, such as aluminum benzoate, aluminum pt-butylbenzoate, sodium adipate, sodium thiophenecarboxylate, and pillow. And sodium recarboxylate. In addition, an inorganic compound such as talc described below can also be used as a nucleating agent.

The nucleating agent is added in an amount of 0.001 to 1 based on 100 parts by weight of the olefin / polar monomer copolymer.
It is desirably 0 parts by weight, preferably 0.01 to 5 parts by weight, more preferably about 0.1 to 3 parts by weight.

As the antioxidant, a phenolic antioxidant, a sulfuric antioxidant, a phosphorus antioxidant and the like can be used. Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, stearyl (3,3-dimethyl-4-hydroxybenzyl) thioglycolate, and stearyl-β- (4-hydroxy-3 , 5-di-te
rt-butylphenol) propionate, distearyl-
3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,4,6-tris (3 ', 5'-di-tert-butyl-4'-hydroxybenzylthio) -1,3,5- Triazine, distearyl (4
-Hydroxy-3-methyl-5-tert-butylbenzyl) malonate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol) ), 2,2′-methylenebis [6- (1-methylcyclohexyl) p-cresol], bis [3,5-bis [4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4'-butylidenebis (6-tert-butyl-m-cresol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-
Butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-
Methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butyl) benzylisocyanurate, 1,3,5-tris (3,5-di-tert -
Butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, tetrakis [methylene-3- (3,5-di-tert-butyl-
4-hydroxyphenyl) propionate] methane, 1,3,
5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris [(3,5-di-tert-
Butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 2-octylthio-4,6-di (4-
Phenols such as hydroxy-3,5-di-tert-butyl) phenoxy-1,3,5-triazine, 4,4′-thiobis (6-tert-butyl-m-cresol) and 4,4′-butylidenebis (2
-tert-butyl-5-methylphenol), and polyhydric phenol carbonate oligoesters such as oligoester carbonate (for example, having a degree of polymerization of 2 to 10).

Examples of the sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl-, dimyristyl- and distearyl- and polyhydric alcohols such as alkylthiopropionic acid such as butyl-, octyl-, lauryl- and stearyl- ( Examples include esters of glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) (for example, pentaerythritol tetralauryl thiopropionate).

Examples of the phosphorus-based antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-diphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, Triphenyl phosphite, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-
5-tert-butyl-4-hydroxyphenyl) butane diphosphite, tetra (C ₁₂ -C ₁₅ mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, tetra (tridecyl) -4,4'-butylidene bis (3-methyl-6-tert-butylphenol) diphosphite, tris (3,5-di-tert-
Butyl-4-hydroxyphenyl) phosphite, tris (mono / di mixed nonylphenyl) phosphite, hydrogenated
-4,4'-isopropylidene diphenol polyphosphite, bis (octylphenyl) bis [4,4'-butylidenebis (3-methyl-6-tert-butylphenol)]-1,6-
Hexanediol diphosphite, phenyl-4,4'-isopropylidene diphenol pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di -ter
t-butyl-4-methylphenyl) pentaerythritol diphosphite, tris [4,4′-isopropylidenebis (2
-tert-butylphenol)] phosphite, phenyl
Diisodecyl phosphite, di (nonylphenyl) pentaerythritol diphosphite), tris (1,3-di-
Stearoyloxyisopropyl) phosphite, 4,4 '
-Isopropylidenebis (2-tert-butylphenol)
Di (nonylphenyl) phosphite, 9,10-di-hydro-9
-Oxa-9-oxa-10-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-tert-butylphenyl)-
4,4'-biphenylenediphosphonite and the like.

As other antioxidants, 6-hydroxychroman derivatives such as α, β, γ and δ various tocopherols or mixtures thereof, 2- (4-methyl-penta-3-enyl) -6-hydroxychroman 2,5-dimethyl substituted, 2,5,8-trimethyl substituted, 2,5,7,8-tetramethyl substituted, 2,2,7-trimethyl-5-tert-butyl-6-hydroxychroman , 2,2,5-trimethyl-7-tert-butyl-6-hydroxychroman, 2,2,5-trimethyl-6-tert-butyl-6-hydroxychroman, 2,2-dimethyl-5-tert-butyl -6-Hydroxychroman can also be used.

The general formula M _x Al _y (OH) _{2x + 3y-2z}
(A) _z · aH ₂ O (M is Mg, Ca or Zn,
A is an anion other than a hydroxyl group, x, y, and z are positive numbers,
a is 0 or a positive number), for example, Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O, Mg ₅ Al
_{2 (OH) 14 CO 3 ·} 4H 2 O, Mg 10 Al 2 (OH)
₂₂ (CO ₃ ) ₂ .4H ₂ O, Mg ₆ Al ₂ (OH) ₁₆ HPO ₄
・ 4H ₂ O, Ca ₆ Al ₂ (OH) ₁₆ CO ₃・ 4H ₂ O, Z
n ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O, Zn ₆ Al ₂ (O
H) ₁₆ SO ₄ .4H ₂ O, Mg ₆ Al ₂ (OH) ₁₆ SO _3.
For example, 4H ₂ O can be used as a hydrochloric acid absorbent.

As the light stabilizer, for example, 2-hydroxy
Hydroxybenzophenones such as -4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone-2,2'-di-hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone, 2- (2'- Hydroxy-3'-t
ert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-Hydroxy-5'-methylphenyl) benzotriazole, 2- (2 '
Benzotriazoles such as -hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole, phenyl salicylate, p-tert-butylphenyl salicylate, 2,4-
Di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-
Benzoates such as 4-hydroxybenzoate, 2,2 '
-Thiobis (4-tert-octylphenol) Ni salt, [2,
Nickel compounds such as 2'-thiobis (4-tert-octylphenolate)]-n-butylamine Ni, (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonic acid monoethyl ester Ni salt, α Acrylonitriles such as methyl-cyano-β-methyl-β- (p-methoxyphenyl) acrylate and N'-2-ethylphenyl-N-ethoxy-5-ter
Oxalic acid dianilides such as t-butylphenyloxalic acid diamide and N-2-ethylphenyl-N'-2-ethoxyphenyloxalic acid diamide, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate , Poly [{(6- (1,1,3,3-tetramethylbutyl) imino} -1,3,5-triazine-2,4-diyl} 4- (2,2,6,6-tetramethyl Hindered amine compounds such as [piperidyl) imino {hexamethylene], and condensates of 2- (4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl) ethanol and dimethyl succinate.

Examples of the lubricant include higher hydrocarbons such as aliphatic hydrocarbons such as paraffin wax, polyethylene wax and polypropylene wax, capric acids, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid and behenic acid. Fatty acids or metal salts thereof (eg, lithium salt, calcium salt, sodium salt, magnesium salt, potassium salt), aliphatic alcohols such as palmityl alcohol, cetyl alcohol, stearyl alcohol, amides of caprones, amides of caprylic acid and caprin Aliphatic amides such as acid amides, lauric amides, myristic amides, palmitic amides, stearic amides, esters of aliphatic and alcohols, fluoroalkylcarboxylic acids or metal salts thereof, Fluorine compounds such as Russia alkylsulfonic acid metal salts.

The above additives are contained in the olefin / polar monomer copolymer in an amount of 0.0001% by weight to 10% by weight.
May be contained. The olefin resin composition composition according to the present invention includes silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, and calcium sulfate. , Potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber ,
A filler such as a polyethylene fiber, a polypropylene fiber, a polyester fiber, and a polyamide fiber may be contained.

The olefin / polar monomer copolymer contains the above-mentioned additives, whereby the balance of physical properties, durability, paintability, printability, scratch resistance, moldability and the like are further improved. A shaped body can be formed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location // (C08F 210/00 220: 18 216: 36 218: 08 220: 06)

Claims (6)

[Claims] An olefin produced by using a catalyst containing a transition metal compound (I) represented by the following general formula (i):
Modifier consisting of polar monomer copolymer. Embedded image (Wherein, M is a transition metal belonging to Groups 8 to 10 of the periodic table, X ¹ and X ² may be the same or different from each other and are a nitrogen atom or a phosphorus atom, and R ¹ and R ² are May be the same or different from each other, and are a hydrogen atom or a hydrocarbon group; m and n may be the same or different from each other;
Or 2, and (Where R ⁶ , R ⁷ , R ⁶¹ , R ⁶² , R ⁷¹ and R
⁷² may be the same or different and are each a hydrogen atom or a hydrocarbon group. R ⁴ and R ⁵ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, —OR ⁸ ,
^{-SR 9, -N (R 10)} 2 or -P (R ¹¹⁾ ₂ (where, R ⁸ to R ¹¹ is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an organic silyl group, R ¹⁰
Or between R ¹¹ each other may be bonded to form a ring. And R ⁴ and R ⁵ may be linked to each other to form a ring, and R ¹ , R ² , R ⁶ (or R ⁶¹ , R ⁶² ) and R ⁷ (or R ⁷¹ , R ⁷²⁾ ) May be linked to each other to form a ring. ). 2. The olefin / polar monomer copolymer according to claim 1, wherein the polar monomer is methyl acrylate, ethyl acrylate, methyl methacrylate, vinyl ketone, vinyl acetate, acrylic acid, or methacrylic acid. Modifier consisting of coalescence. 3. A hot melt adhesive comprising the olefin / polar monomer copolymer according to claim 1. 4. A wax modifier comprising the olefin / polar monomer copolymer according to claim 1 or 2. 5. An asphalt modifier comprising the olefin / polar monomer copolymer according to claim 1 or 2. 6. An ink paint modifier comprising the olefin / polar monomer copolymer according to claim 1 or 2.