JP2003252930A - Polar group-containing olefin polymer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide one olefin polymer which has a main chain substituted with two polar groups at the ω position and another olefin polymer which has a main chain substituted with polar groups both at the ω position and at one or more (ω-n) positions (n≥1); and a method for producing the same polymers. <P>SOLUTION: The one olefin polymer comprises a main chain substituted with a methylol group and a Y-substituted methyl group (-CH<SB>2</SB>Y, Y is an O or N atom-containing polar group) at the ω position, while another olefin polymer comprises a main chain substituted with a methylol group at the ω position and Y-substituted methyl groups (-CH<SB>2</SB>Y, Y is an O or N atom-containing polar group) at the (ω-n) positions, (n≥1). The method for producing these polymers comprises copolymerizing a 2-20C α-olefin with a polar group-containing olefin: CH<SB>2</SB>=CH-CH<SB>2</SB>-Y (Y is an O or N atom-containing polar group) in the presence of (A) the compound of a transition metal belonging to the 3-10 groups in the periodic table and (B) a catalyst including an organic aluminium compound. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polar group-containing olefin polymer and a method for producing the same, and more specifically, an olefin polymer having two polar groups at the ω-position of the main chain of the olefin polymer and a method for producing the same. The present invention relates to an olefin polymer having polar groups at the ω-position and one or more (ω-n) -positions (n represents an integer of 1 or more) in the olefin polymer main chain, and a method for producing the same.

[0002]

2. Description of the Related Art Generally, an olefin polymer is excellent in moldability, heat resistance, mechanical properties, hygiene compatibility, water vapor permeation resistance, etc., and has a good appearance of a molded product. It is widely used for products, hollow molded products, injection molded products, etc. On the other hand, engineering plastics such as nylon are used in electronic and electrical parts because of their excellent heat resistance and strength, but due to their low impact resistance, olefin-based copolymers are blended. Although it is necessary to improve impact resistance, olefin polymers do not contain polar groups in the molecule and have low compatibility with polar resins such as nylon. Methods for improving compatibility of are widely practiced.

However, in this method, intermolecular cross-linking between olefin polymers and cleavage of the molecular chain occur in parallel with the grafting reaction, so that it is difficult to match the viscosity of the grafted polymer with the polar resin, and the compatibility is poor. Sometimes it wasn't enough. In addition, the appearance of the molded product may be deteriorated due to the gel content generated by intermolecular cross-linking or the eyes and eyes generated by the breakage of the molecular chain.

On the other hand, JP-A 1-259012, 2-51
510, 2-51511, 3-177403, α-
It describes a method of copolymerizing an olefin and a polar group-containing olefin using a titanium catalyst or a vanadium catalyst. According to this method, the above-mentioned crosslinking of molecules and cleavage of molecular chains are less likely to occur, but when these polymerization catalysts are used, the obtained copolymer has a wide molecular weight distribution and inversion. Since the molecular structure is nonuniform, such as when the content is large, the orientation of the polar group at the interface with the polar substance was not sufficient, and the adhesiveness and compatibility with the polar substance were sometimes insufficient. In addition, it is common that polar groups are randomly introduced into the main chain of the olefin polymer,
From the viewpoint of performance, there is an increasing need for a polyolefin having a plurality of polar groups at desired positions and a method for producing the same.

[0005]

SUMMARY OF THE INVENTION In view of the above problems, the present inventors have diligently studied various olefin polymers having a polar group at a desired position of the main chain and a method for producing them, and as a result, have a specific polarity. By adopting the group-containing olefin, the polymerization catalyst component and the polymerization conditions, the polymer main chain has an alkyl group derived from the alkylaluminum molecule, which is one of the constituent components of the polymerization catalyst, at the α-position of the polymer main chain. Narrow molecular weight distribution polar group-containing olefin polymer having two polar groups at the ω position (hereinafter, this polymer may be referred to as polar group-containing olefin polymer (ED)) and a method for producing the same. , And an alkyl group derived from an alkylaluminum molecule, which is one of the constituent components of the catalyst, at the α-position of the polymer main chain, and the ω-position of the polymer main chain and one or more (ω-n) -positions ( However, n represents an integer of 1 or more. A polar group-containing olefin polymer having a narrow molecular weight distribution with a polar group (hereinafter, this polymer may be referred to as a polar group-containing olefin polymer (ID)). The present invention has been completed.

[0006]

The polar group-containing olefin polymer (ED) and the method for producing the same, and the polar group-containing olefin polymer (ID) and the method for producing the same will be sequentially described below. The terms “α-position”, “ω-position” and “(ω-1) -position” used in the present specification are, for example, a polyethylene molecule represented by the following formula (III) and having a carbon number of m. For example, the position of C ¹ is called α position, the position of C ^m is called ω position, the position of C ^(m-1) is the (ω-1) position, and the nth position from the ω position in the formula (III), that is, C [ ^{m- (n-1)} ] is referred to as (ω-n) position.

[0007]

[Chemical 1]

In the present specification, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" is not limited to homopolymers. However, it may be used in the sense of including a copolymer.

(1) Polar group-containing olefin polymer (E
D) and method for producing the same The polar group-containing olefin polymer (ED) has an alkyl group derived from alkylaluminum, which is one of the catalyst constituents, at the α position of the polymer main chain, and the ω position of the polymer main chain. Is a polar group-containing olefin polymer having a methylol group and a methyl group substituted with Y represented by the following general formula (I).

--CH ₂ Y (I) In the formula, Y represents a polar group containing an oxygen atom or a nitrogen atom, and specifically, a hydroxyl group; a carboxyl group; an amino group,
N-methylamino group, N-ethylamino group, N-n-propylamino group, N, N-dimethylamino group, N, N-diethylamino group, and other amino groups; methoxycarbonyl group, ethoxycarbonyl group, and other ester groups Examples thereof include amide groups such as aminocarbonyl group, N-methylaminocarbonyl group and N-ethylaminocarbonyl group.
Of these, a hydroxyl group, an amino group and an amide group are preferable in terms of performance and production, and a hydroxyl group and an amino group are particularly preferable.

This polar group-containing olefin polymer (ED)
Can be manufactured by sequentially performing the following three steps, that is, step 1, step 2 and step 3.

(Step 1) (A) A compound of a transition metal selected from Groups 3 to 10 of the periodic table (group 3 also includes lanthanoids and actinides), and (B) (B-1) organoaluminumoxy. compound (B-2) an organoaluminum compound represented by R ^a ₃ Al (wherein, R ^a represents a linear alkyl group having 1 to 10 carbon atoms.) and (B-3) the compound (a) In the presence of a catalyst consisting of at least one compound selected from compounds that form an ion pair by reacting with an α-olefin having 2 to 20 carbon atoms and a polar represented by the following general formula (II) Process of copolymerizing with group-containing olefin

[0013] _{CH 2 = CH-CH 2 -Y} (II) ( wherein, Y represents a polar group containing an oxygen atom or a nitrogen atom.)

(Step 2) Step of oxidizing the product obtained in Step 1 (Step 3) Step of hydrolyzing the product obtained in Step 2

Hereinafter, each step will be described in order. Step 1 In the step 1, in the presence of the following polymerization catalyst, under an anhydrous condition in which an oxidizing agent does not exist, an α-olefin having 2 to 20 carbon atoms and a polar group represented by the following general formula (II) are contained. This is a step of polymerizing with an olefin. _{CH 2 = CH-CH 2 -Y} (II)

(A) a compound of a transition metal selected from Groups 3 to 10 of the periodic table (group 3 also includes lanthanoids and actinides); and (B) (B-1) an organoaluminum oxy compound, and ( B-2) an organoaluminum compound represented by R ^a ₃ Al (wherein, R ^a represents a linear alkyl group having 1 to 10 carbon atoms.) (B-3) to react with the compound (a) A catalyst for polymerization formed from at least one compound selected from compounds forming an ion pair.

The transition metal compound selected from the groups (3) to (10) of the periodic table (A) used in the production of the polar group-containing olefin polymer (ED) (lanthanoids and actinides are included in the group 3) is as follows. It is represented by formula (IV).

[0018]

[Chemical 2]

In the formula, M ¹ represents a transition metal atom selected from Group 4 of the periodic table, R ^{1 to} R ¹⁴ may be the same or different from each other, and are a hydrocarbon group having 1 to 40 carbon atoms, A halogenated hydrocarbon group having 1 to 40 carbon atoms, an oxygen-containing group,
R ¹³ and R ¹⁴ , which represent a sulfur-containing group, a silicon-containing group, a halogen atom or a hydrogen atom and are adjacent to each other, may be linked to each other to form a ring together with the carbon atom to which those groups are bonded, X ¹ and X ² may be the same or different from each other, and are a hydrocarbon group having 1 to 20 carbon atoms, or 1 carbon atom.
To 20 halogenated hydrocarbon groups, oxygen-containing groups, sulfur-containing groups, silicon-containing groups, hydrogen atoms or halogen atoms, Y ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, or 1 carbon atom. To 20 divalent halogenated hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, divalent tin-containing groups, -O-, -CO-, -S-, -SO-,- SO2-,-
Ge -, - Sn -, - NR 20 -, - P (R 20) -, - PO (O)
^{(R 20) -, - BR} 20 - or -AlR ²⁰ - (provided that, R ²⁰ may be the same or different, carbon atoms 1-2
A hydrocarbon group of 0, a halogenated hydrocarbon group of 1 to 20 carbon atoms is a hydrogen atom or a halogen atom.

M ¹ in the general formula (IV) is titanium,
Zirconium and hafnium are preferable, and zirconium is particularly preferable. X ¹ and X ² in the general formula (IV) are
A halogen atom is preferable, and a chlorine atom is particularly preferable. Y ¹ in the general formula (IV) is preferably a divalent silicon-containing group, and particularly preferably a dimethylsilylene group.

R ² and R ⁷ in the general formula (IV) are preferably sterically bulky, and such groups include isopropyl group, t-butyl group, α, α-dimethylpropyl group and α- Examples thereof include a phenethyl group and an α, α-dimethylbenzyl group. Further, R ⁹ in the general formula (IV) is preferably an alkyl group having 1 to 5 carbon atoms. Particularly preferably, both R ² and R ⁷ in the general formula (IV) are t-butyl groups, and R ⁹ is a methyl group.

Transition metal compounds (A) having preferable requirements for M ¹ , R ^{1 to} R ¹⁴ , X ¹ , X ² and Y ^1.
Has a structural formula represented by the following formula (V).

[0023]

[Chemical 3]

The polar group-containing olefin used in the method for producing the polar group-containing olefin polymer (ED) is represented by the following general formula (II). _{CH 2 = CH-CH 2 -Y} (II)

In the formula, Y represents a polar group containing an oxygen atom or a nitrogen atom, and specifically, allyl alcohol in which Y in the general formula (II) is —OH; Y in the general formula (II) is —COOH. Acrylic acid which is; acrylic acid ester in which Y in the general formula (II) is -COOR ^g (R ^g represents a hydrocarbon group having 1 to 20 carbon atoms); and Y in the general formula (II) is -CONR ^s R ^t (in the formula, R ^s and R ^t represent a hydrocarbon group having 1 to 20 carbon atoms and may be the same or different from each other); the general formula (II)
Y is —NR ^u R ^v (wherein R ^u and R ^v represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms and may be the same or different from each other), Examples thereof include N-substituted allylamines such as N-methylallylamine, N-ethylallylamine, N, N-dimethylallylamine, and N-phenylallylamine, or N, N-disubstituted allylamines. Among these, Y is —OH, —NH ₂ , —NHMe, —NH
Et and -CONH ₂ are preferable in terms of physical properties and performance.

Next, each compound of the component (B) will be described. (B-1) Organoaluminum Oxy Compound The (B-1) organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, or as exemplified in JP-A-2-78687. It may be a benzene-insoluble organoaluminum 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 adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. The method of adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension of, and reacting the adsorbed water or crystal water with the organoaluminum compound. (2) A method in which water, ice or water vapor 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 organometallic component. Further, the solvent or unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane, and then redissolved in the solvent or suspended in a poor solvent for the aluminoxane.

Specific examples of the organoaluminum compound used for preparing the aluminoxane will be described later (B
The same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to -2) can be mentioned. Among these, trialkyl aluminum and tricycloalkyl aluminum are preferable, and trimethyl aluminum is particularly preferable. The above organoaluminum compounds may be used alone or in combination of two or more.

As the solvent used for preparing the aluminoxane, aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. , Cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene, and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbon halides Among these, hydrocarbon solvents such as chlorinated compounds and brominated compounds are mentioned. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

In the benzene-insoluble organoaluminum oxy compound used in the present invention, the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. Some are preferred, that is, those that are insoluble or sparingly soluble in benzene.

The polar group-containing olefin polymer (E
As the organoaluminum oxy compound used in the production of D), an organoaluminum oxy compound containing boron is also preferably used.

The above-mentioned (B-1) organoaluminum oxy compounds may be used alone or in combination of two or more. (B-2) Organoaluminum Compound The (B-2) organoaluminum compound used in the production of the polar group-containing olefin polymer (ED) has the general formula R ^a ₃
It is an organoaluminum compound represented by Al. In the formula,
Ra represents ^a linear alkyl group having 1 to 10 carbon atoms. Specific examples of such an organoaluminum compound include trimethylaluminum, triethylaluminum, and triethylaluminum.
Examples thereof include n-butylaluminum, tri-n-propylaluminum, tri-n-pentylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and tri-n-decylaluminum. Preferably, three types of triethylaluminum, trimethylaluminum, or tri-n-octylaluminum are preferable because a polar group is regioselectively introduced at the ω-position of the olefin polymer. Furthermore, triethylaluminum or trimethylaluminum is 100%. It is particularly preferable because it exhibits ω-position selectivity.

As the organoaluminum compound (B-2), dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, dimethyl aluminum bromide; methyl aluminum sesquichloride, ethyl aluminum sesquichloride, n
-Alkyl aluminum sesquichlorides such as butyl aluminum sesquichloride and ethyl aluminum sesquibromide; Alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride and ethyl aluminum dibromide; Alkyl aluminum hydrides such as diethyl aluminum hydride: R ^a _n AlY _{3 -n} (In the formula, R ^a has 1 to 10 carbon atoms.
Represents a straight chain alkyl group of Y is —OR ^c group, —OSiR ^d ₃
Group, -OAlR ^e ₂ group, -NR ^f ₂ group, -SiR ^g ₃ group or -N
(R ^h ) AlR ⁱ ₂ group, n is 1 to 2, R ^c ,
R ^d , R ^e and R ⁱ represent a methyl group, an ethyl group or the like,
R ^f represents hydrogen, a methyl group, an ethyl group, etc., and R ^g and R ^h represent a methyl group, an ethyl group, etc. It is also possible to use a compound represented by).

Specific examples of such an organoaluminum compound include the following compounds. (I) Compounds represented by R ^a _n Al (OR ^c ) _3-n , such as dimethyl aluminum methoxide and diethyl aluminum ethoxide. (Ii) ^a compound represented by R ^a _n Al (OSiR ^d ₃ ) _3-n ,
For example, (C ₂ H ₅ ) ₂ Al (OSi (CH ₃ ) ₃ ) and the like. (Iii) ^a compound represented by R ^a _n Al (OAlR ^e ₂ ) _3-n ,
Such as _{(C 2 H 5) 2 Al} (OAl (C 2 H 5) 2). (Iv) ^a compound represented by R ^a _n Al (NR ^f ₂ ) _3-n , for example
_{(CH 3) 2 Al (N} (C 2 H 5) 2), (C 2 H 5) 2 Al (NH (C
_{H 3)), (CH 3} ) 2 Al (NH (C 2 H 5)), (C 2 H 5) 2 Al [N
_{(Si (CH 3) 3)} 2] and the like. _{^{(V) R a n Al (}} SiR g 3) a compound represented by _3-n, such as _{Me 2 Al (Si (CH 3} ) 3).

The above (B-2) organoaluminum compounds may be used alone or in combination of two or more.

(B-3) Ionized Ionic Compound Compound (B-3) which reacts with the transition metal compound (A) used in the present invention to form an ion pair (hereinafter referred to as "ionized ionic compound"). As Japanese Patent Laid-Open No. 1-50
No. 1950, No. 1-502036, No. 3-179005, No. 3-179006, No. 3-207703, No. 3-20
Examples thereof include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in 7704, USP-5321106 and the like. further,
Heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as the Lewis acid, BR ₃ (R
Is a phenyl group which may have a substituent such as fluorine, a methyl group and a trifluoromethyl group, or fluorine. ), 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 can be mentioned.

Examples of the ionic compound include compounds represented by the following general formula (VI).

[0040]

[Chemical 4]

In the formula, examples of R ¹⁵ include H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal. R ^{16 to} R ^{19, which} may be the same or different, are organic groups, preferably aryl groups or substituted aryl groups.

Specific examples of the carbonium cation include triphenylcarbonium cation, tri (methylphenyl) carbonium cation, tri (dimethylphenyl) carbonium cation, and other trisubstituted carbonium cations.

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-dimethylaniline. Cation, N, N-diethylanilinium cation, N, N-
Examples include N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as di (i-propyl) ammonium cation and 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 or an ammonium cation, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation. As the ionic compound, a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt,
A dialkyl ammonium salt, a triaryl phosphonium salt, etc. can also be mentioned.

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, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (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 (3,3
5-ditrifluoromethylphenyl) 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-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2, 4,6-pentamethylanilinium tetra (phenyl) boron and the like can be mentioned.

Specific examples of the dialkyl ammonium 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, N, N-diethylanilinium pentaphenylcyclo Pentadienyl complex, the following formula (VII) or (VII
The boron compound represented by I) may also be mentioned.

[0050]

[Chemical 5]

[0051]

[Chemical 6]

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, anion salts such as bis [tri (n-butyl) ammonium] dodecachlorododecaborate; tri (n-butyl) ammonium bis (dodecahydride dodecaborate)
Examples thereof include salts of metal borane anions such as cobalt salt (III) and bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickelate (III).

Specific examples of the carborane compound include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), and 6,9-dicarbadecaborane (1).
4), dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-
1,3-Dicarbano Naborane, Undeca Hydride-
1,3-dimethyl-1,3-dicarbanonaborane, 7,
8-dicarbaundecaborane (13), 2,7-dicarbaundecaborane (13), undeca hydride-
7,8-dimethyl-7,8-dicarbaundecaborane,
Dodecahydride-11-methyl-2,7-dicarbaundecaborane, tri (n-butyl) ammonium 1-
Carbadecaborate, tri (n-butyl) ammonium 1-carbaundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri ( n-butyl) ammonium bromo-
1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (12),
Tri (n-butyl) ammonium 7-carbaundecaborate (13), tri (n-butyl) ammonium 7,
8-dicarbaundecaborate (12), tri (n-butyl) ammonium 2,9-dicarbaundecaborate (12), tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaundeca Borate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, Tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride n-Butyl) ammonium undeca hydride-4,6 Salts of anions such as dibromo-7-Cal bounce deca borate;

Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaun) Decaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undeca) Hydride-7,8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cuprate (III), tri (n) -Butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) gold Salt (III), tri (n- butyl)
Ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) ferrate (II
I), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride) -7,8-Dicarbaundecaborate) cobaltate (III), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III), bis [tri] (N-Butyl) ammonium] bis (undecahydride-7
-Carbaundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ) Ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV) and other salts of metal carborane anions.

The heteropoly compound includes an atom selected from silicon, phosphorus, titanium, germanium, arsenic and tin,
It is composed of one or more atoms selected from vanadium, niobium, molybdenum and tungsten.
Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorous Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdo Tungstic acid, phosphomolybdo niobate, and salts of these acids, such as metals of Group 1 or 2 of the Periodic Table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium. ,barium Salts with organic salts of triphenyl ethyl salts, and the like can be used but not limited thereto.

The above-mentioned (B-3) ionized ionic compounds may be used alone or in combination of two or more.

The polar group-containing olefin copolymer (E
In the production of O), the transition metal compounds (A), (B
-1) Organoaluminum oxy compound, (B-2) Organoaluminum compound, and (B-3) Ionized ionic compound and at least one compound (B), and, if necessary, a carrier (C) Can be used. The carrier (C) is an inorganic or organic compound, and is a granular or fine particle solid. Of these, the inorganic compound is preferably an oxide, an inorganic chloride, clay, a clay mineral, or an ion-exchange layered compound. As the oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, Ti
O ₂ , B ₂ O ₃ , CaO, ZnO, BaO and ThO ₂ can be exemplified. As the inorganic chloride, MgCl ₂ ,
MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used. The clay used as a carrier in the present invention includes kaolin,
Bentonite, kibushi clay, gyrome clay, allophane,
Hisingelite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite, halloysite, etc. are mentioned, and as the ion-exchange layered compound, α-Zr (HAsO ₄ ) ₂・ H ₂ O, α-
_{Zr (HPO 4) 2, α} -Zr (KPO 4) 2 · 3H 2 O,
α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ · H ₂
O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ-Zr (HP
O ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti (NH ₄ P
Examples thereof include crystalline acid salts of polyvalent metals such as O ₄ ) ₂ · H ₂ O.

At the time of polymerization, the usage and order of addition of each component are arbitrarily selected, and the following methods are exemplified. (i) A method of adding the component (A) and the component (B) to the polymerization vessel in any order. (ii) A method of adding the catalyst component in which the component (A) is supported on the carrier (C) and the component (B) to the polymerization vessel in any order. (iii) A method of adding the catalyst component in which the component (B) is supported on the carrier (C) and the component (A) to the polymerization vessel in any order. (iv) A method of adding the catalyst component in which the component (A) is supported on the carrier (C) and the catalyst component in which the component (B) is supported on the carrier (C) to the polymerization vessel in any order. (v) A method of adding a catalyst component in which a component (A) and a component (B) are supported on a carrier (C) to a polymerization vessel. In each of the above methods (i) to (v), at least two or more of the catalyst components may be contacted in advance.

The solid catalyst component in which the component (A) and the component (B) are supported on the above component (C) may be prepolymerized with an olefin, and on the prepolymerized solid catalyst component, Furthermore, a catalyst component may be supported.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane. Alicyclic hydrocarbons such as; benzene, toluene, xylene, and other aromatic hydrocarbons; ethylene chloride, chlorobenzene, dichloromethane, and other halogenated hydrocarbons, or mixtures thereof. The olefin itself is used as a solvent. You can also

When the olefin is polymerized using the above-mentioned olefin polymerization catalyst, the component (A) is
Usually 10 ^-12 to 10 ^-1 mol per liter of polymerization volume,
It is preferably used in an amount such that it is 10 ⁻¹⁰ to 10 ⁻² mol. The component (B-1) is a molar ratio [(B-1) / M] of the component (B-1) and all transition metal atoms (M) in the component (A).
Is usually 1 to 500000, preferably 20 to 1000
It is used in an amount such that it becomes 00. In the component (B-2), the molar ratio [(B-2) / M] of the aluminum atom in the component (B-2) and the transition metal atom (M) in the component (A) is usually 0. 01 to 100,000, preferably 0.05 to 500
It is used in an amount such that it becomes 00. The component (B-3) has a molar ratio [(B-3) / M] of the component (B-3) to the transition metal atom (M) in the component (A) of usually 1 to 500, preferably It is used in an amount of 1 to 200.

The polar group-containing olefin has 2 to 20 carbon atoms.
Is charged into the polymerization reactor together with the α-olefin.
As such an α-olefin having 2 to 20 carbon atoms,
Linear or branched α-olefins such as ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-
Methyl-1-butene, 1-hexene, 4-methyl-1-pentene,
3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene; cyclic olefins such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene,
Mention may be made of tetracyclododecene. In addition to olefins, chain or cyclic dienes such as butadiene, isoprene, 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene and 7-methyl-1,6-octadiene, 6,10-dimethyl-1 , 5,9-Undecatriene,
Chain or cyclic triene such as 5,9-dimethyl-1,4,8-decatriene, 6,10,14-trimethyl-1,5,9,13-pentadecateethraene, 5,9,13-trimethyl Various polyenes such as chain or cyclic tetraenes such as -1,4,8,12-tetradecatetraene can also be copolymerized.

These α-olefins can be used alone or in combination of two or more. The polymerization temperature of olefins using such an olefin polymerization catalyst is usually -50 to + 200 ° C, preferably 0 to 17
It is in the range of 0 ° C. Polymerization pressure is usually normal pressure to 100 kg
/ Cm ² , preferably under atmospheric pressure to 50 kg / cm ² , and the polymerization reaction can be carried out by any of batch method, semi-continuous method and continuous method. It is also possible to carry out the polymerization in two or more stages under different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by allowing at least one compound such as hydrogen, an organosilicon compound and a dialkylzinc compound to be present in the polymerization system, or by changing the polymerization temperature. Further, it can be adjusted depending on the difference in the component (B) used.

The polymerization reaction is carried out in a completely anhydrous state without any oxidizing agent such as oxygen molecules.

Step 2 Step 2 is a step of oxidizing the polymerization reaction product obtained in Step 1. The reaction conditions will be described in detail below. First, the types of oxidizers are oxygen, chlorine, bromine,
Examples thereof include iodine, hypochlorous acid, and peroxides,
From the viewpoint of handling, oxygen, chlorine, air, hydrogen peroxide, peracetic acid, and m-chloroperbenzoic acid are preferable. The reaction temperature is 200 ° C. or lower, preferably 100 ° C. or lower. Also,
The reaction time is 50 hours or less, and usually the reaction is completed within 20 hours.

Step 3 Step 3 is a step of hydrolyzing the oxidation reaction product obtained in Step 2. The reaction conditions will be described in detail below. Hydrolysis can be carried out by contacting with water or an organic solvent containing water under acidic conditions. Among the commonly used acids, inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid can be used.
To 1,000,000 times by mole, preferably 10 to
It is preferable to use 1000 times mol for hydrolysis. As the organic solvent, those having an affinity for water are preferable, and examples thereof include methanol and acetone. The reaction temperature is 200 ° C or lower, preferably 100 ° C or lower. The time required for hydrolysis is 50 hours or less, and usually 5 hours or less.

(2) Polar group-containing olefin polymer (I
D) and its production method The polar group-containing olefin polymer (ID) has an alkyl group derived from alkylaluminum, which is one of the catalyst constituents, at the α-position of the polymer main chain, and has an ω-position of the polymer main chain. Has a methylol group at one or more (ω-n) positions (n is 1
Indicates the above integer. ) Is a polar group-containing olefin polymer having a methyl group substituted with Y represented by the following general formula (I). -CH ₂ Y (I)

In the formula, Y represents a polar group containing an oxygen atom or a nitrogen atom, specifically, hydroxyl group; carboxyl group; amino group, N-methylamino group, N-ethylamino group, N
-N-propylamino group, N, N-dimethylamino group, N, N
Examples thereof include amino groups such as diethylamino group; ester groups such as methoxycarbonyl group and ethoxycarbonyl group, amide groups such as aminocarbonyl group, N-methylaminocarbonyl group and N-ethylaminocarbonyl group. Of these, a hydroxyl group, an amino group and an amide group are preferable in terms of performance and production, and a hydroxyl group and an amino group are particularly preferable.

This polar group-containing olefin polymer (ID)
Can be manufactured by sequentially performing the following three steps, that is, step 1, step 2 and step 3. (Step 1) (A) A compound of a transition metal selected from Groups 3 to 10 of the periodic table (group 3 also includes lanthanoids and actinides), and (B) (B-1) an organoaluminum oxy compound (B -2) an organoaluminum compound represented by R ^b ₃ Al (in the formula, R ^b represents an alkyl group having a branched structure having 3 to 10 carbon atoms), and (B-3) the compound (A) In the presence of a catalyst consisting of at least one compound selected from compounds that form an ion pair by reacting with an α-olefin having 2 to 20 carbon atoms and a polar represented by the following general formula (II) step characterized by copolymerizing a radical-containing monomer _{CH 2 = CH-CH 2 -Y} (II) ( wherein, Y represents a polar group containing an oxygen atom or a nitrogen atom.)

(Step 2) Step of oxidizing the product obtained in Step 1 (Step 3) Step of hydrolyzing the product obtained in Step 2

When the polar group-containing olefin polymer (ID) is produced, the same conditions as those for producing the polar group-containing olefin polymer (ED) described above can be preferably used in Step 2 and Step 3. Therefore, the explanation is omitted. Therefore,
In the following description, manufacturing conditions will be described only for step 1.

Step 1 Step 1 is represented by an α-olefin having 2 to 20 carbon atoms and the following general formula (II) in the presence of the following polymerization catalyst under anhydrous conditions in which no oxidizing agent is present. It is a step of polymerizing with a polar group-containing monomer. _{CH 2 = CH-CH 2 -Y} (II)

(A) a compound of a transition metal selected from Groups 3 to 10 of the periodic table (group 3 also includes lanthanoids and actinides), (B) an organoaluminum oxy compound, and (B-1) B-2) Organoaluminum compound represented by R ^b ₃ Al (In the formula, R ^b represents an alkyl group having a branched structure having 3 to 10 carbon atoms.) (B-3) The compound (A) It is formed from at least one compound selected from compounds that react with each other to form an ion pair.

Regarding the polymerization catalyst relating to the polar group-containing olefin polymer (ID), the polymerization conditions, and the applicable polar group-containing olefin and α-olefin, one component (B-2) R ^b constituting the polymerization catalyst is used. _The polar group-containing olefin polymer described above (with the exception of using an organoaluminum compound represented by ₃ Al (in the formula, R ^b represents an alkyl group having a branched structure of 3 to 10 carbon atoms)). This is the same as in the case of manufacturing ED). Therefore, only the component (B-2) will be described here.

(B-2) Organoaluminum Compound The (B-2) organoaluminum compound used in the production of the polar group-containing olefin polymer (ID) is an organoaluminum compound represented by R ^b ₃ Al. Where R
^b represents an alkyl group having a branched structure having 3 to 10 carbon atoms. Such organoaluminum compounds include triisopropylaluminum, triiso-butylaluminum, trisec-butylaluminum, tri (1,3-dimethylpropyl) aluminum, tri (1,3-dimethylbutyl).
Aluminum and the like can be exemplified. The organoaluminum compound (B-2) has a dialkylaluminum halide, an alkylaluminum sesquihalide, an alkylaluminum dihalide, and an alkylaluminum hydride skeleton described in the method for producing a polar group-containing olefin polymer (ED), and is bonded to aluminum. The alkyl group having 3 to 10 carbon atoms has a branched structure (R
It is also possible to use the compounds which are ^b ). These (B-2)
The organoaluminum compounds may be used alone or in combination of two or more.

[0077]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto.

The identification of the polymers obtained in the examples is ¹ H-
NMR (JEOL JNM GSX-400), ¹³ C-NM
R (JEOL JNM GSX-270), GPC (Wa
ter150-C, dichlorobenzene solvent, 140 ° C)
Went by.

Example 1 Step 1 900 ml of toluene was charged into a glass polymerization vessel having a capacity of 1000 ml, which had been sufficiently replaced with nitrogen, and nitrogen was passed at a rate of 20 liters / hour and kept at 50 ° C. for 10 minutes. It was. To this, triethyl aluminum (48mmo
l) and allyl alcohol (40 mmol) were added and stirred for 5 minutes, then the nitrogen flow was stopped and ethylene was flowed at a rate of 2 liters / hour. Then, 0.0008 mmol of dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-ditert-butylfluorenyl) zirconium dichloride represented by the following formula (V) and methylaluminoxane 0: Toluene slurry solution, which was brought into contact with 4300 mmol for 10 minutes at room temperature, was added to start polymerization, and after polymerization was carried out at 50 ° C. for 100 minutes under normal pressure, a small amount of isobutyl alcohol was added to stop the polymerization.

[0080]

[Chemical 7]

Step 2 Air was passed through the polymerization liquid obtained in Step 1 at a rate of 100 liters / hour to carry out an oxidation reaction at 80 ° C. for 10 hours, and then a small amount of isobutyl alcohol was added to stop the reaction. Step 3 Then, the reaction product obtained in Step 2 is added with a concentrated hydrochloric acid aqueous solution 5
50 ml of isobutyl alcohol solution containing ml was added and heated at 75 ° C. under nitrogen. Add the polymer solution to a large excess of methanol to precipitate the polymer and
The desired polymer was obtained by drying under reduced pressure for a period of time.

Example 2 900 ml of toluene was charged into a glass-made polymerization vessel having a capacity of 1000 ml which had been sufficiently replaced with nitrogen, and nitrogen was passed at a rate of 20 liters / hour and kept at 50 ° C. for 10 minutes. To this, triethyl aluminum (48mmo
l) and allylamine (40 mmol) were added and stirred for 5 minutes, then nitrogen flow was stopped and ethylene was added at 2 liter /
Circulated in the amount of time. Dimethylsilylene (2-methyl-
Polymerization was performed by adding a toluene slurry solution in which 0.25 mmol of 4,5-benzo-1-indenyl) (2,7-ditert-butylfluorenyl) zirconium dichloride and 7.90 mmol of methylaluminoxane were contacted at room temperature for 10 minutes. Was started and the polymerization was carried out at 100 ° C. for 180 minutes under normal pressure, and then a small amount of isobutyl alcohol was added to stop the polymerization. Further, 50 ml of isobutyl alcohol solution containing 5 ml of concentrated hydrochloric acid aqueous solution was added, and the mixture was heated at 75 ° C. under nitrogen. The polymer solution was added to a large excess of methanol to precipitate the polymer, and the polymer was dried under reduced pressure at 80 ° C. for 12 hours to obtain a polymer having a polar group introduced only at the main chain terminal. Oxygen was passed through this polymerization liquid at a rate of 100 liters / hour, an oxidation reaction was carried out at 80 ° C. for 10 hours, and then a small amount of isobutyl alcohol was added to terminate the polymerization. Furthermore, concentrated hydrochloric acid aqueous solution 5
50 ml of isobutyl alcohol solution containing ml was added and heated at 75 ° C. under nitrogen. Add the polymer solution to a large excess of methanol to precipitate the polymer and
The desired polymer was obtained by drying under reduced pressure for a period of time.
When the obtained polymer was measured by ¹³ CNMR, it was confirmed that the polymer was a polar group-containing olefin polymer having a methylol group and a methylamino group at the ω-position of the polymer main chain (-CH ₂ OH: 64.2ppm,-). CH ₂ NH ₃ ⁺ : 43.5 ppm, -CH-: 3
8.7 ppm).

[0083]

Industrial Applicability According to the present invention, an olefin copolymer having a narrow molecular weight distribution and having a polar group at a specific position can be produced by combining specific production steps.

[Brief description of drawings]

1 shows the ¹³ C-NMR spectrum of the polymer obtained in Example 1. FIG.

Continued front page    F-term (reference) 4J028 AA01 AB01 AC01 AC03 AC09                       AC27 AC31 AC41 AC45 AC49                       AC50 BA01B BA02B BB01B                       BC12B BC13B BC14B BC15B                       BC25B EA01 EB02 EB03                       EB04 EB05 EB06 EB07 EB08                       EB09 EB10 EB13 EB14 EB15                       EB16 EB17 EB18 EB25 EB26                       EC01 EC02 FA02 GA06                 4J100 AA02P AA03P AA04P AA05P                       AA06P AA07P AA09P AA15P                       AA16P AA17P AA18P AA19P                       AD02Q AD03Q AM14Q AM15Q                       AN02Q AN04Q AN05Q AN06Q                       AR01P AR04P AR05P AR11P                       AR15P AR17P CA03 CA04                       CA27 DA04 FA00 FA03 FA09                       FA19 HA01 HA08

Claims (4)

[Claims] 1. A polar group-containing olefin polymer having a methylol group and a methyl group substituted by Y represented by the following general formula (I) at the ω-position of the polymer main chain. —CH ₂ Y (I) (In the formula, Y represents a polar group containing an oxygen atom or a nitrogen atom.) 2. A polymer having a methylol group at the ω-position of the main chain and at one or more (ω-n) -positions (n represents an integer of 1 or more) represented by the following general formula (I). A polar group-containing olefin polymer having a methyl group substituted with Y represented. —CH ₂ Y (I) (In the formula, Y represents a polar group containing an oxygen atom or a nitrogen atom.) 3. The method for producing a polar group-containing olefin polymer according to claim 1, wherein the following Step 1, Step 2 and Step 3 are sequentially carried out. (Step 1) (A) A compound of a transition metal selected from Groups 3 to 10 of the periodic table (group 3 also includes lanthanoids and actinides), and (B) (B-1) an organoaluminum oxy compound (B). -2) organoaluminum compounds represented by R ^a ₃ Al (wherein, R ^a represents a linear alkyl group having 1 to 10 carbon atoms.) and reacted with (B-3) the compound (a) In the presence of a catalyst consisting of at least one compound selected from the group consisting of compounds forming an ion pair, an α-olefin having 2 to 20 carbon atoms and a polar group-containing olefin represented by the following general formula (II): step _{CH 2 = CH-CH 2 -Y} (II) ( wherein, Y represents a polar group containing an oxygen atom or a nitrogen atom.), which comprises copolymerizing the door obtained above (step 2) step 1 Step of oxidizing the obtained product (Step 3) Hydrolyze the product obtained in Step 2. Disassembling process 4. The method for producing a polar group-containing olefin polymer according to claim 2, wherein the following Step 1, Step 2 and Step 3 are sequentially carried out. (Step 1) (A) A compound of a transition metal selected from Groups 3 to 10 of the periodic table (group 3 also includes lanthanoids and actinides), and (B) (B-1) an organoaluminum oxy compound (B -2) an organoaluminum compound represented by R ^b ₃ Al (in the formula, R ^b represents an alkyl group having a branched structure having 3 to 10 carbon atoms), and (B-3) the compound (A) In the presence of a catalyst consisting of at least one compound selected from compounds that form an ion pair by reacting with an α-olefin having 2 to 20 carbon atoms and a polar represented by the following general formula (II) step CH ₂ = (wherein, Y represents a polar group containing an oxygen atom or a nitrogen _{atom.) CH-CH 2 -Y (} II) , which comprises copolymerizing an group-containing olefin (step 2) step The step of oxidizing the product obtained in step 1 (step 3) The product hydrolyzing