JP2002003455A - Transition metal complex, catalyst for polymerization containing the same, and method for producing olefinic copolymer by using the catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transition metal complex capable of efficiently providing a polymer, especially capable of introducing a polar monomer into an olefin in high content, and further to provide a catalyst containing the complex, and a method for producing an olefinic copolymer obtained by using the catalyst. SOLUTION: Ethanol is reacted with N,N-dimethylethylenediamine and salicylaldehyde, and the residue obtained by concentrating the reaction liquid is purified to provide salicylideneamine derivative. The salicylideneamine derivative is reacted with methanol and sodium borohydride, and a diamine compound is separated from the concentrate obtained by concentrating the reaction liquid. The resultant diamine compound is reacted with chloro(methyl) (1,5- cyclooctadiene)palladium (II), potassium carbonate and dried dichloromethane, and the objective transition metal complex is obtained as a precipitate formed by adding n-pentane to the concentrate of the obtained reaction liquid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a transition metal complex, a catalyst for polymerization, and a method for producing an olein-based copolymer using the catalyst. More specifically, a polymerization catalyst capable of efficiently obtaining an olefin-based copolymer having a high content of structural units derived from a monomer having a polar functional group, and a novel transition metal used in the polymerization catalyst The present invention relates to a complex and a method for producing an olefin-based copolymer from which the above-mentioned copolymer can be efficiently obtained by using the polymerization catalyst. The transition metal complex of the present invention is suitably used as a polymerization catalyst. Further, the polymerization catalyst of the present invention may be a copolymer of an olefin and a polar monomer, a homopolymerization of an olefin or a polar monomer, a copolymer of two or more different olefins, a copolymer of two or more different polar monomers, and a Michael addition. It can be suitably used as a catalyst when performing a reaction or the like.

[0002]

2. Description of the Related Art Polyolefins have many excellent characteristics but do not have sufficient adhesiveness, printability and dyeability. Therefore, these problems have been improved by introducing a monomer having a polar functional group (hereinafter, also simply referred to as “polar monomer”). A method of copolymerizing an olefin with a polar monomer using a large amount of a Lewis acid compound has been known (Japanese Patent Application Laid-Open No. S59-5959).
43003, JP-A-60-262807,
JP-A-61-278508 and the like. However, this method has a problem that the obtained copolymer contains many impurities.

A method using a chromium compound is also known (Japanese Patent Application Laid-Open No. 61-278508, Japanese Patent Application Laid-Open
-282204). However, there are problems that the content of the structural unit derived from the polar monomer cannot be sufficiently increased and that a toxic chromium compound is contained.

[0004] In addition, Periodic Table Group 8 or 9 or 10
Catalyst comprising a transition metal compound of group III and a Lewis acid and / or ionized ionic compound (JP-A-9-302018)
JP-A-10-298231), and a catalyst comprising a rhodium compound and an arylboron compound (JP-A-10-298231). Further, cationic metal complexes are also known as catalysts. For example, a compound of a transition metal selected from Group 4 of the periodic table, a coordination complex such as triethylammonium tetraphenylborate (JP-A-4-309508), a bulky diimine ligand, and a tetraarylborate as a counter anion Palladium complex {J. Am. Chem. Soc. , 118, p267
(1996). Recently, a nickel complex having a salicylaldimine ligand {Organometallics, 17, p31
Neutral metal complexes such as 49 (1998)} are also known as catalysts. However, even when these catalysts are used, the content of the structural unit derived from the polar monomer cannot be sufficiently increased, and it is required that the polar monomer can be introduced at a higher content.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and enables efficient copolymerization of an olefin and a polar monomer. A polymerization catalyst capable of obtaining a high olefin-based copolymer, a novel transition metal complex used therein, and an olefin-based copolymer capable of efficiently obtaining the above-described copolymer using the polymerization catalyst. An object of the present invention is to provide a method for producing a polymer.

[0006]

According to the first aspect of the present invention, there is provided a transition metal complex having a transition metal belonging to Group 10 of the periodic table as a central atom, and two coordination sites at the cis position occupied by a neutral ligand. The organic metal compound thus obtained is reacted with the diamine compound represented by the above formula (1). Further, the polymerization catalyst of the second invention has an organometallic compound having a transition metal belonging to Group 10 of the periodic table as a central atom and two coordination sites at the cis position occupied by a neutral ligand; It contains a transition metal complex formed by the reaction with the diamine compound represented by the general formula (1). Further, the method for producing an olefin copolymer of the third invention is characterized in that an olefin and a polar monomer are copolymerized using the polymerization catalyst according to the second invention.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The transition metal complex of the first invention has the following general formula (2)
Is a complex represented by

Embedded image However, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹
Is a hydrogen atom or an organic group, which may be the same or different, and may be mutually connected to form a ring.

The transition metal complex can be obtained from an organometallic compound having a specific structure and a diamine compound having a specific structure. Of these, "organic metal compounds"
Is N, which is a transition metal of Group 10 of the periodic table as a central atom.
i, any of Pd and Pt. Usually, the organometallic compound is a planar four-coordinate compound. The above “cis position” indicates that two coordination sites are adjacent to each other.

The above-mentioned "neutral ligand" is a compound which can exist independently and stably. This neutral ligand may be a ligand that coordinates one of two ligands with one neutral ligand (hereinafter, simply referred to as “bidentate neutral ligand”). Also, 1
A ligand coordinated to one coordination site by one neutral ligand (hereinafter, simply referred to as “monodentate neutral ligand”) may be used.
When the monodentate neutral ligand is coordinated to the two adjacent coordination sites, one type of monodentate ligand may be coordinated with two types of monodentate ligand. You may coordinate to each coordination site.

[0010] Such neutral ligands include, for example,
Aromatic compounds, olefin compounds, carbon monoxide, ether compounds, acetonitrile, benzonitrile, phosphine compounds (such as triphenylphosphine), phosphite compounds, cyclic diene compounds (norbornadiene, 1,5
-Cyclooctadiene, etc.) and diamine compounds (ethylenediamine, etc.). When the neutral ligand is acetonitrile, at least one of benzonitrile and a phosphine compound, the stability of the obtained transition metal complex is high, and when this transition metal complex is used as a polymerization catalyst, It is preferable because of its good catalytic activity. In addition, the inner cyclic diene compound and the diamine compound of the neutral ligand are compounds that can be a monodentate neutral ligand or a bidentate neutral ligand.

The organometallic compound, in addition to having a neutral ligand, occupies one coordination site by an atom or a substituent which is eliminated by being subjected to a nucleophilic attack capable of forming a complex. Is preferred. Examples of such an atom or a substituent that is eliminated by receiving a nucleophilic attack capable of forming a complex include an atom or a substituent that can be eliminated as an anion when the central atom is subjected to a nucleophilic attack. Among such atoms or substituents, when a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom) or an alkoxy group (such as a methoxy group, an ethoxy group, or a propoxy group), the transition metal of the present invention is used. It is preferable because a complex formation reaction is facilitated in obtaining a complex. In particular, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom is preferable, and a chlorine atom or a bromine atom is particularly preferable.

Further, a group occupying the remaining one of the four coordination sites of the organometallic compound {normally represented by the general formula (2)
In it is not particularly limited remains} after the reaction of the organometallic compound and the diamine compound as the R ^9, a hydrogen atom, a hydrocarbon group, is preferably any one of an oxygen-containing hydrocarbon group and a sulfur-containing hydrocarbon group. When the groups binding to the organometallic compound are these groups, high activity is exhibited when the obtained transition metal complex is used as a catalyst for copolymerizing an olefin and a polar monomer.

Examples of such a group include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a t-butyl group, a cyclopentyl group, a cyclohexyl group. A cycloalkyl group such as a group, an aryl group such as a phenyl group, an o-tolyl group, a p-tolyl group, a mesityl group, an alkylaryl group such as a 2,4,6-tri-t-butylphenyl group, a benzyl group, etc. Arylalkyl group, methoxyethyl group, p
Oxygen-containing hydrocarbon groups such as -methoxyphenyl group; sulfur-containing hydrocarbon groups such as methylthioethyl group and methylthiophenyl group.

Examples of the organometallic compound having the above-mentioned neutral ligand, atom, substituent, compound and the like include, for example, chloro (methyl) (norbornadiene) palladium (II), chloro (methyl) (1, 5-cyclooctadiene) palladium (II), chloro (methyl) (ethylenediamine) palladium (II), cis-chloro (methyl) bis (benzonitrile) palladium (II), c
and is-chloro (methyl) bis (triphenylphosphine) palladium (II).

On the other hand, the “diamine compound” of the two kinds of raw material compounds for obtaining the transition metal complex is a compound represented by the general formula (1). As R ^{1 to} R ⁸ in the general formula (1), a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Alkyl groups such as isobutyl group and t-butyl group, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, aryl groups such as phenyl group, o-tolyl group, p-tolyl group, mesityl group, 2,4,6-trialkyl group Alkylaryl groups such as -t-butylphenyl group; arylalkyl groups such as benzyl group; methoxyethyl group; oxygen-containing hydrocarbon groups such as p-methoxyphenyl group; methylthioethyl group;
Sulfur-containing hydrocarbon groups such as methylthiophenyl group, dialkylamino groups such as dimethylamino group and diethylamino group, silyl groups such as trimethylsilyl group and tributylsilyl group, alkoxy groups such as methoxy group, ethoxy group and butoxy group, phenoxy group etc. And arylaryloxy groups such as o-tolyloxy group and p-tolyloxy group, arylalkyloxy groups such as benzyloxy group, and nitro group.

Among them, at least one (more preferably two, more preferably three) of R ¹ , R ² and R ⁸
Is preferably any one of an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group, and an arylalkyl group. When a transition metal complex obtained using such a diamine compound is used as a polymerization catalyst, a polymer having a large molecular weight is easily obtained.

Preferred specific examples of the diamine compound include, for example, the following chemical formulas (1) to (9).

Embedded image In the chemical formula, Me represents a methyl group, i-Pr represents an isopropyl group, and t-Bu represents a tert-butyl group.

The method for obtaining the diamine compound represented by the general formula (1) is not particularly limited. For example, as shown in the following reaction formula (1), an ethylenediamine-based compound is reacted with a salicylaldehyde-based compound. To obtain a salicylideneamine derivative, and then the following reaction formula (2)
As described above, the compound of the above general formula (1) can be obtained by reducing the imine portion of the obtained salicylideneamine derivative. The above reaction formulas (1) and (2)
R1 to R8 in are the same as those in the general formula (1).

[0019]

Embedded image

[0020]

Embedded image

The transition metal complex of the first invention is obtained by reacting the above-mentioned organometallic compound with a diamine compound. This reaction method is not particularly limited. For example, there is a method in which a diamine compound represented by the general formula (1) is reacted with sodium hydride in a reaction medium to form phenoxide, and then reacted with an organometallic compound. Also,
There is also a method in which a diamine compound and an organometallic compound are reacted in a reaction medium containing a base.

In each case, the reaction temperature is -4.
The temperature is preferably 0 to 120 ° C (more preferably -20 to 80 ° C). The reaction time is preferably 5 minutes to 100 hours (more preferably, 30 minutes to 10 hours). Further, as the reaction medium, hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene, inert hydrocarbons such as xylene, chloroform, methylene chloride, dichloroethane, halogenated hydrocarbons such as chlorobenzene, and the like can be used. . These may be used alone or in combination of two or more.

The transition metal complex according to the first aspect of the present invention includes copolymerization of an olefin with a polar monomer, homopolymerization of an olefin, copolymerization of two or more different olefins, homopolymerization of a polar monomer, and two or more different polar monomers. It can be suitably used as a polymerization catalyst used for copolymerization of, a catalyst used for Michael addition reaction, and the like. When this transition metal complex is used, after the organic metal compound and the diamine compound are reacted, the obtained transition metal complex can be isolated and used as a catalyst. Moreover, you may use together with another compound produced | generated by reaction of an organometallic compound and a diamine compound.

The polymerization catalyst of the second invention contains the transition metal complex of the first invention. This polymerization catalyst can be suitably used for the same polymerization and copolymerization catalyst as described above. The polymerization catalyst preferably contains 50 to 100% by mass (more preferably 70 to 100% by mass) of the transition metal complex of the first invention when the whole is 100% by mass. When the content is less than 50% by mass, the effect of containing the transition metal complex is not sufficiently obtained, which is not preferable. This catalyst can contain, for example, a Lewis acid, an ion-pair type compound having a non-coordinating anion, an organic aluminum oxy compound, an alkylboronic acid derivative, and the like, in addition to the transition metal complex of the first invention.

The polymerization catalyst of the second invention may be added to a reaction system containing a monomer for obtaining a desired polymer in a state where the transition metal complex of the first invention is already contained. it can. Further, before the reaction between the organometallic compound and the diamine compound, that is, without containing the transition metal complex of the first invention, the organometallic compound and the diamine compound are separately added to the reaction system. As the transition metal complex of the first invention is generated, it can be used so that the polymerization reaction proceeds.

The monomer that can be polymerized by the transition metal complex of the first invention and the monomer that can be homopolymerized or copolymerized by the polymerization catalyst of the second invention are not particularly limited. As the olefin among the monomers, ethylene, propylene, 1-
Butene, 1-pentene, 1-hexene, 1-heptene,
1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 4
Α-olefins such as -methyl-1-pentene.

The polar monomers among the monomers include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid and metal salts of these acids such as sodium, potassium, lithium, zinc, magnesium and calcium. , Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, methacryl Α, β-unsaturated carboxylic acid esters such as ethyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, maleic acid, itaconic acid, fumaric acid,
Maleic anhydride, itaconic anhydride, bicyclo [2,2,
1] -5-heptene-2,3-dicarboxylic acid and other unsaturated dicarboxylic acids and anhydrides thereof, vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, trifluoroacetate Examples include vinyl esters such as vinyl acetate, and glycidyl group-containing radically polymerizable monomers such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate.

In the manufacturing method of the third invention, the olefin
For polymerization used when copolymerizing a monomer with a polar monomer
The amount of the transition metal complex contained in the medium depends on the total amount used in the copolymerization.
When the molar amount of the monomer is 1, the model of the transition metal complex is
The molar amount is 10^-6-10 ^-1(More preferably 10^-Five
-10^-2) Is preferable. When this molar ratio is 10 ^-6
If it is less than 3, the polymerization catalyst is deactivated and a polymer is not sufficiently obtained.
The molecular weight of the obtained polymer is too high
There is a tendency and it is not preferable. On the other hand, 10^-1With the above, I got
The molecular weight of the resulting polymer is too small
It is not preferable because physical properties tend to decrease.

Further, the polymerization method in this production method is not particularly limited, and it can be carried out by liquid phase polymerization such as suspension polymerization or solution polymerization, gas phase polymerization or the like. Among them, solvents that can be used in liquid phase polymerization include inert hydrocarbons such as hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene, and xylene, and halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, and chlorobenzene. Can be mentioned.
Further, the polymerization temperature is preferably -50 to 250 ° C, and the polymerization pressure is preferably normal pressure to 19.6 MPa (more preferably normal pressure to 200 kgf / cm ² ).
The polymerization system may be any of a batch system, a semi-continuous system, and a continuous system.

In the olefin copolymer obtained by copolymerizing an olefin and a polar monomer in this production method, the structural unit derived from the polar monomer contained in the copolymer is from 1 to 99 mol% (further, Can be 1 to 95 mol%, especially 1 to 90 mol%). still,
The proportion of the structural unit derived from the olefin can be adjusted between 1 and 99 mol% (further 5 to 99 mol%, especially 10 to 99 mol%).

In the copolymerization of an olefin and a polar monomer, besides these monomers, for example, butadiene, 1,4-hexadiene, 7-methyl-1,6-octadiene, 1,8-nonadiene, One or two or more of conjugated or non-conjugated dienes such as 1,9-decadiene, and cyclic unsaturated hydrocarbons such as cyclopropene, cyclobutene, cyclopentene, norbornadiene and dicyclopentadiene can be copolymerized. . However, it is preferable that the proportion of other monomers in the total monomers be 80 mol% or less (more preferably 70 mol% or less).
If it exceeds 80 mol%, the characteristics of the olefin and the polar monomer are hardly developed, which is not preferable.

[0032]

The present invention will now be described more specifically with reference to examples and comparative examples. In the following, all operations were performed in a nitrogen atmosphere unless otherwise specified. The molecular weight of the obtained polymer means a molecular weight in terms of polystyrene determined by gel permeation chromatography. This molecular weight is measured under the following measurement conditions. Column: T
SKgel (G4000HXL and G2500HX
L), solvent: tetrahydrofuran, detector: RI, flow rate: 1 ml / min.

[1] Example 1 (1) Synthesis of salicylideneamine derivative A-1 50 ml of ethanol was placed in a 100 ml eggplant-shaped flask.
And 2.64 g of N, N-dimethylethylenediamine (3
0 mmol) and 3.66 g of salicylaldehyde (30
mmol) and stirred at room temperature for 1 hour. Thereafter, the reaction solution was concentrated under reduced pressure, and the obtained residue was purified by a silica gel column to give 5.26 g of yellow-brown oil A-1.
Was obtained (90.0% yield).

The obtained yellow oil A-1 was dissolved in chloroform and identified by ¹ H-NMR.
(CDCl ₃ , 270 MHz): δ = 2.32 (s, 6
H); δ = 2.66 (t, 2H); δ = 3.73
(T, 2H); δ = 6.87 (t, 1H); δ = 6.
95 (d, 1H); δ = 7.23-7.24
(M, 2H); δ = 8.37 (s, 1H); δ = 1
3.41 (s, 1H). This indicates that the obtained yellow oil A-1 is a salicylideneamine derivative represented by the following chemical formula (10).

[0035]

Embedded image

(2) Synthesis of diamine compound A-2 In a 200 ml eggplant-shaped flask, 100 ml of methanol was placed.
And the salicylideneamine derivative (A-
1) Charge 3.85 g (20 mmol) and 1.53 g of sodium borohydride while stirring at room temperature
(40 mmol) was added little by little, and stirring was continued for 2 hours. Thereafter, the reaction solution was concentrated under reduced pressure. Next, chloroform was added to the obtained concentrated liquid to perform extraction, and then water was added for washing, and an organic phase containing chloroform was separated by a separating funnel. After the organic phase was dried over anhydrous magnesium sulfate, it was further concentrated under reduced pressure, and the obtained concentrate was purified by passing through a silica gel column to obtain 3.27 g of yellow oil A-2 (yield 84). .1%).

The obtained yellow oily substance A-2 was dissolved in chloroform and identified by ¹ H-NMR.
(CDCl ₃ , 270 MHz): δ = 2.23 (s,
6H); δ = 2.44 (t, 2H); δ = 2.72
(T, 2H); δ = 3.99 (s, 2H); δ = 5.9
0 (bs, 2H); δ = 6.73-6.83 (m,
2H); δ = 6.98 (d, 1H); δ = 7.15
(T, 1H). It can be seen that the obtained yellow oil is a diamine compound represented by the following chemical formula (11).

[0038]

Embedded image

(3) Synthesis of transition metal complex A-3 0.531 g (2.0 mmol) of chloro (methyl) (1,5-cyclooctadiene) palladium (II) was placed in a Schlenk reaction tube which had been sufficiently dried and purged with nitrogen. ), 0.427 g (2.2 mmol) of diamine compound A-2 and 1.106 g (8.0 mmol) of potassium carbonate were added, 20 ml of dry dichloromethane was added, and the mixture was stirred at room temperature for 14 hours. After filtering off the insoluble matter, the solvent amount was reduced to about 2 ml under reduced pressure.
And concentrated. After 15 ml of dry n-pentane was added to the concentrate to form a precipitate, the precipitate was separated by filtration and washed twice with 5 ml of dry n-pentane. Then, it dried under vacuum and 0.524g of yellow-white solid A-3 was obtained (83.3% of yield).

The obtained yellowish white solid was dissolved in chloroform and identified by ¹ H-NMR (CDCl ₃ , 270 MHz). As a result, δ = 0.48 (s, 3H);
2.31 (d, 1H); δ = 2.45 (m, 1
H); δ = 2.54-2.84 (m, 8H); δ = 2.
92 (m, 1H); δ = 3.15 (d, 1H); δ
= 4.18 (t, 1H); δ = 6.34 (t, 2
H); δ = 6.48 (d, 1H); δ = 6.71
(D, 1H); δ = 6.95-6.98 (m, 2H)
Met. From this result, it can be seen that the obtained yellow-white solid A-3 is a transition metal complex A-3 represented by the following chemical formula (12).

[0041]

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(4-1) Copolymerization Using Transition Metal Complex A-3 (Experimental Example 1-1) In a sufficiently dried 100 ml autoclave, 20 ml of dichloroethane and the transition metal complex A-3 obtained in (3) were added.
And cooled to −78 ° C., and then methyl acrylate 8.69 was added.
g (100 mmol) was added, and the internal atmosphere was replaced so that the charging pressure of ethylene became 0.2 MPa (2 atm). This autoclave was heated to 70 ° C. and polymerized for 10 hours while stirring. After 10 hours, the mixture was cooled to -78 ° C, and the polymerization was stopped by adding 5 ml of methanol and 20 ml of hexane. The solvent was distilled off from the obtained reaction solution under reduced pressure, and then dried under reduced pressure with a vacuum pump to obtain 4.36 g of an ethylene / methyl acrylate copolymer. Table 1 shows the results of analyzing the obtained ethylene-methyl acrylate copolymer.

[0043]

[Table 1]

(4-2) Copolymerization Using Transition Metal Complex A-3 (Experimental Example 1-2) Except that the charging pressure of ethylene was adjusted to be 0.1 MPa (1 atm), (4-1) The copolymerization was carried out in the same manner as in the above) to obtain an ethylene / methyl acrylate copolymer 4.0
8 g were obtained. The results of analyzing the obtained ethylene-methyl acrylate copolymer are also shown in Table 1.

[2] Example 2 (1) Synthesis of salicylideneamine derivative B-1 50 ml of ethanol was placed in a 100 ml eggplant-shaped flask.
3.49 g of N, N-diethylethylenediamine (30 m
mol) and 3.66 g of salicylaldehyde (30 mm
ol) and stirred at room temperature for 1 hour. Thereafter, the reaction solution was concentrated under reduced pressure, and the obtained residue was purified by a silica gel column to obtain 6.24 g of yellow-brown oil B-1 (yield 93.8%).

The obtained yellow oily substance B-1 was dissolved in chloroform and identified by ¹ H-NMR.
(CDCl ₃ , 270 MHz): δ = 1.03 (t,
6H); δ = 2.58 (q, 4H); δ = 2.75
(T, 2H); δ = 3.66 (t, 2H); δ = 6.
85 (t, 1H); δ = 6.94 (d, 1H);
δ = 7.21-7.27 (m, 2H); δ = 8.32
(S, 1H); δ = 13.53 (bs, 1H). The yellow oil thus obtained was represented by the following chemical formula (13)
It can be seen that this is a salicylideneamine derivative B-1 represented by

[0047]

Embedded image

(2) Synthesis of diamine compound B-2 The procedure of Example 1 (2) was repeated except that salicylideneamine derivative B-1 was used in place of 4.41 g instead of salicylideneamine derivative A-1. As a result, 4.23 g of a yellow oil B-2 was obtained (yield: 95.1%).

The obtained yellow oily substance B-2 was dissolved in chloroform and identified by ¹ H-NMR.
(CDCl ₃ , 270 MHz): δ = 1.02 (t,
6H); δ = 2.50-2.71 (m, 6H); δ =
3.99 (s, 2H); δ = 6.20 (bs, 2
H); δ = 6.73-6.83 (m, 2H); δ =
6.98 (d, 1H); δ = 7.15 (t, 1H)
Met. This indicates that the obtained yellow oil B-2 is a diamine compound B-2 represented by the following chemical formula (14).

[0050]

Embedded image

(3) Synthesis of transition metal complex B-3 Diamine compound B-2 was used instead of diamine compound A-2.
Was used in the same manner as in Example 1 (3) except that 0.489 g of yellow solid B-3 was obtained (yield: 82).
%).

The obtained yellowish white solid B-3 was dissolved in chloroform and identified by ¹ H-NMR.
(CDCl ₃ , 270 MHz): δ = 0.38 (s,
3H); δ = 1.38 (t, 3H); δ = 1.55
(T, 3H); δ = 2.42-3.05 (m, 7
H); δ = 3.12 (m, 1H); δ = 3.40
(Dd, 1H); δ = 4.31 (t, 1H); δ =
6.38 (t, 1H); δ = 6.75 (d, 1
H); δ = 7.02 (m, 2H). This indicates that the obtained yellow-white solid is a transition metal complex B-3 represented by the following general formula (15).

[0053]

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(4) Copolymerization Using Transition Metal Complex B-3 (Experimental Example 2-1) The transition metal complex B-3 was replaced with 3 instead of the transition metal complex A-3.
Ethylene and methyl acrylate were copolymerized in the same manner as in Example 1 (4-1) except that 4 mg was used. as a result,
4.59 g of an ethylene / methyl acrylate copolymer was obtained. The results of analyzing the obtained ethylene-methyl acrylate copolymer are also shown in Table 1.

(5) Copolymerization Using Transition Metal Complex B-3 (Experimental Example 2-2) 20 ml of dichloroethane and a transition metal complex B were placed in a 50 ml eggplant-shaped flask which had been sufficiently dried and purged with nitrogen.
-3 (34 mmol (0.1 mmol in terms of Pd atom)), and 8.69 g of methyl acrylate (100 m
mol), 8.42 g (100 mmol) of 1-hexene
Was added. This was heated to 70 ° C and polymerized while stirring for 10 hours, then cooled to -78 ° C, and the polymerization was stopped by adding 5 ml of methanol and 20 ml of hexane. The solvent was distilled off from the obtained reaction solution under reduced pressure, and then dried under reduced pressure with a vacuum pump to obtain 6.31 g of 1-hexene-methyl acrylate copolymer. The results of analyzing the obtained 1-hexene-methyl acrylate copolymer are also shown in Table 1.

(6) Homopolymerization of Polar Monomer Using Transition Metal Complex B-3 (Experimental Example 2-3) 20 ml of dichloroethane and a transition metal complex were placed in a 50-ml eggplant-shaped flask which had been sufficiently dried and purged with nitrogen. B
-3 (34 mmol (0.1 mmol in terms of Pd atom)), and 8.69 g of methyl acrylate (100 m
mol) was added. This was heated to 70 ° C. and polymerized while stirring for 10 hours. After 10 hours, the mixture was cooled to -78 ° C, and the polymerization was stopped by adding 5 ml of methanol and 20 ml of hexane. The solvent was distilled off from the obtained reaction solution under reduced pressure, and then dried under reduced pressure with a vacuum pump to obtain 8.23 g of a methyl acrylate polymer. The results of analyzing the obtained methyl acrylate polymer are also shown in Table 1.

[3] Example 3 (1) Synthesis of Salicylideneamine Derivative C-1 50 ml of ethanol was placed in a 100 ml eggplant-shaped flask.
4.33 g of N, N-diisopropylethylenediamine
(30 mmol) and 3.66 g of salicylaldehyde
(30 mmol) and stirred at room temperature for 1 hour.
Thereafter, the reaction solution was concentrated under reduced pressure, and the obtained residue was purified by a silica gel column to give a yellow-brown oil C-1 (6.8).
6 g was obtained (92.1% yield).

As a result of dissolving the obtained yellow-brown oil C-1 in chloroform and identifying it by ¹ H-NMR, (CDC
l ₃ , 270 MHz): δ = 0.98 (s, 6H)
Δ = 1.00 (s, 6H); δ = 2.72 (t, 2
H); δ = 2.98-3.03 (m, 2H); δ = 3.
56 (t, 2H); δ = 6.84 (t, 1H); δ
= 6.94 (d, 1H); δ = 7.21-7.27.
(M, 2H); δ = 8.26 (s, 1H); δ = 1
3.69 (bs, 1H). This shows that the obtained yellow-brown oil C-1 is a salicylideneamine derivative C-1 represented by the following chemical formula (16).

[0059]

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(2) Synthesis of Diamine Compound C-2 Example 1 was repeated except that 4.97 g of salicylideneamine derivative C-1 was used instead of salicylideneamine derivative A-1.
In the same manner as in (2), 4.88 g of yellow oil C-2 was obtained (yield 97.4%). The obtained yellow oil C-2 was dissolved in chloroform and identified by ¹ H-NMR. As a result, (CDCl ₃ , 270 MHz): δ = 1.02
(D, 12H); δ = 2.63 (s, 4H); δ =
3.00 (m, 2H); δ = 3.99 (s, 2
H); δ = 6.12 (bs, 2 H); δ = 6.73
−6.83 (m, 2H); δ = 6.98 (d, 1
H); δ = 7.15 (t, 1H). This indicates that the obtained yellow oil C-2 is a diamine compound C-2 represented by the following chemical formula (17).

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(3) Synthesis of transition metal complex C-3 Diamine compound C-2 was used instead of diamine compound A-2.
Was used in the same manner as in Example 1 (3), except that 0.554 g of yellowish white solid C-3 was obtained (yield: 82).
%). The obtained yellow-white solid C-3 was dissolved in chloroform and identified by ¹ H-NMR. As a result, (CDC
l ₃ , 270 MHz): δ = 0.40 (s, 3H);
δ = 1.43 (d, 6H); δ = 1.62 (d, 6H)
H); δ = 2.43-3.20 (m, 7H); δ =
3.12 (m, 1H); δ = 3.50 (dd, 1
H); δ = 4.35 (t, 1H); δ = 6.42
(T, 1H); δ = 6.83 (d, 1H); δ = 7.
09 (m, 2H). Thus, the obtained yellow-white solid was converted to a transition metal complex C represented by the following general formula (18).
It turns out that it is -3.

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(4) Copolymerization using transition metal complex C-3 (Experimental Example 3) 20 ml of dichloroethane and transition metal complex C-
3, and 37 mg (0.1 mmol in terms of Pd atom) were added thereto, and 8.69 g (100 mm
ol) and 8.42 g (100 mmol) of 1-hexene
And added. While keeping the flask at 50 ° C, 10
Polymerization was carried out by stirring for a period of time, followed by cooling to −78 ° C., and adding 5 ml of methanol and 20 ml of hexane to terminate the polymerization. After washing the obtained reaction solution with water and drying,
The solvent was distilled off under reduced pressure, and then dried under reduced pressure with a vacuum pump.
4.09 g of 1-hexene-methyl acrylate copolymer
Obtained. Table 1 also shows the results of analyzing the analysis results of the obtained 1-hexene-methyl acrylate copolymer.

[4] Comparative Example 1 (Comparative Polymerization) In place of the transition metal complex A-3, 26 mg of untreated chloro (methyl) (1,5-cyclooctadiene) palladium (II) (0.2 mg) was used. Polymerization was carried out in the same manner as in Example 1 (4-1) except that 1 mmol) was used. As a result, only 0.05 g of the copolymer was obtained.

[5] Comparative Example 2 (Comparative Polymerization) Instead of the transition metal complex A-3, a diamine compound A-2
Was added as is (22 mg, 0.1 mmol),
Polymerization was carried out in the same manner as in Example 1 (4-1). As a result, only 0.08 g of the copolymer was obtained.

[6] Comparative Example 3 (Comparative Polymerization) Instead of the transition metal complex A-3, 28 mg (0.05 mmol) of a palladium complex represented by the following chemical formula (19)
And a boron compound 44m represented by the following chemical formula (20)
g (0.05 mmol), the partial pressure of ethylene charged was set to 0.12 MPa (1.2 atm), the input amount of methyl acrylate was set to 2.583 g (30 mmol),
Polymerization was carried out in the same manner as in Example 1 (4-1), except that dichloromethane was used as a solvent and the polymerization temperature was set at 40 ° C. As a result, the obtained polymer was a copolymer containing only a small amount of structural units derived from the polar monomer methyl acrylate. The results of analyzing the obtained ethylene-methyl acrylate copolymer are also shown in Table 1.

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[7] Effects of Examples 1 to 3 and Comparative Examples 1 to 3 In Table 1, the catalytic activity in terms of the molar amount of Pd was 0.5 to 28.2 g / mmol in Comparative Examples 1 to 3. On the other hand, in Examples 1-1 to 1-3, 40.8 to 82.
It is as large as 3 g / mmol. As described above, it can be seen that when the transition metal complex of the present invention is used as a catalyst, a copolymer is efficiently obtained. Further, in the copolymers obtained in Examples 1-1 to 1-3, the constitutional unit derived from the polar monomer in the molar ratio was 4.8 of the constitutional unit derived from the olefin.
１10.8 times, indicating that a large amount of polar monomer was introduced. In addition, the copolymer obtained in Examples 1-1 to 3 has a molecular weight of 33,000 to 96,000 and is a practical polymer. Furthermore, the molecular weight distribution is relatively narrow, 2.2 to 2.6, and the polymer obtained in this sense is practical.

The transition metal complex according to the first aspect of the present invention is a novel compound, which is used as a catalyst during the copolymerization of an olefin and a polar monomer to provide an olefin having a high content of structural units derived from the polar monomer. A system copolymer can be obtained efficiently. According to the polymerization catalyst of the second invention, it is possible to efficiently obtain an olefin copolymer having a high content of structural units derived from a polar monomer. Further, according to the method for producing an olefin copolymer of the third invention, an olefin copolymer having a high content of a structural unit derived from a polar monomer can be efficiently obtained.

Continued on the front page (72) Inventor Kaoru Kimura 1-1, Funami-cho, Minato-ku, Nagoya-shi Toagosei Co., Ltd. Nagoya Research Laboratory F-term (reference) 4H006 AA01 AB40 BJ50 BN30 BU38 4H050 AA01 AA03 AB40 WB11 WB13 WB14 WB21 4J015 DA09 DA23 4J100 AA02P AA03P AA04P AA07P AA15P AA16P AA17P AA18P AA19P AA21P AG02Q AG04Q AG05Q AG08Q AJ02Q AJ08Q AJ09Q AK07Q AK08Q AK18Q AK31Q AK32Q AL03Q AL10Q BA08Q08

Claims (3)

[Claims] 1. An organometallic compound having a transition metal belonging to Group 10 of the periodic table as a central atom and two ligands at the cis position occupied by a neutral ligand, and a compound represented by the following general formula (1): A transition metal complex produced by reacting with the diamine compound shown below. Embedded image However, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are a hydrogen atom or an organic group, which may be the same or different, and To form a ring. 2. An organometallic compound having a transition metal belonging to Group 10 of the periodic table as a central atom and two coordination sites at cis positions occupied by neutral ligands, and a compound represented by the following general formula (1): A polymerization catalyst comprising a transition metal complex formed by a reaction with the diamine compound shown below. Embedded image However, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are a hydrogen atom or an organic group, which may be the same or different, and To form a ring. 3. A process for producing an olefin copolymer, comprising copolymerizing an olefin with a monomer having a polar functional group using the polymerization catalyst according to claim 2.