JP2002537451A - Polymerization and copolymerization of monoolefins and novel palladium complexes for this. - Google Patents

Abstract

(57) [Summary] In the presence of a palladium complex represented by the formula [L ¹ PdL ² ] ⁺ An ⁻ , a monoolefin having 2 to 12 carbon atoms is added with or without the addition of an alkylaluminum compound. The polymers or copolymers can be obtained alone or in combination with one another or with polar monomers such as methyl acrylate. In the Pd complex, L ¹ represents an uncharged bidentate N, N′-disubstituted diazadiene ligand, preferably a diazabutadiene ligand, and L ² represents an alkoxy having 7 to 8 carbon ring members. Cycloalkene carbanion, preferably 1-methoxycyclooct-4-ene-8σ, 4π ligand L ² {attached to a palladium atom by a σ-bond and bound by a C = C double bond by a complexing π bond} And An ⁻ represents an anion of a non-esterifiable, weakly or uncoordinated acid. New Pd catalyst complexes for polymerization and copolymerization are further disclosed.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a method for polymerizing and copolymerizing a monoolefin in the presence of a specific palladium complex, and to a novel palladium complex suitable for this purpose.

The use of transition metal complexes such as palladium or nickel complexes as catalysts in the polymerization or copolymerization of monoolefins has often been disclosed. Carbon monoxide and monoolefins such as ethylene can be converted to two bidentate N- or P-containing chelating ligands per Pd atom and two non-coordinating acids that are substantially non-esterifiable. It is known from Italian patent application MI91A / 2969 that it is possible to obtain polyketones by copolymerization in the presence of a cationic Pd complex containing the anion of The disadvantage of this method is that relatively high yields of polymer must be achieved using high temperatures and pressures. A similar polyketone is EP-A072
8791, produced by copolymerizing carbon monoxide with olefinically unsaturated compounds such as ethylene and especially styrene in the presence of a cationic Pd complex, in which case the Pd complex is bidentate Compounds having a C ＝ C double bond in addition to the N- or P-containing chelating ligand. The anion forms a σ bond to the Pd atom and the C ＝ C double bond is It contains a bidentate anion of｝ that forms a π bond to an atom. The disadvantage of the latter method of producing polyketone is that Pd
It is based on the combination of a complex with a liquid halogen-containing compound such as dichloroethane or chloroform, ie the presence of a halogenated solvent is required.

In L. Johnson et al. (J. Amer. Chem. Soc. 1995, 117, pp. 6414 to 6415),
Disclosed are cationically activated Pd (II) and Ni (II) catalyst complexes, which are derived from metal dimethyl complexes with diimine ligands, in particular H (OEt ₂ ) ₂ ⁺ B (C ₆ F ₅ ) ₄ ^- is prepared by protonation using. The resulting diethyl ether adduct has diethyl ether and an anion of tetrakis (pentafluorophenyl) borate as ligands in the metal complex cation, and polymerizes a monoolefin such as ethylene, propylene or 1-hexene. To obtain a relatively high molecular weight polymer.

In later literature, L. Johnson et al. (J. Amer. Chem. Soc. 1996, 118, 26
7 to 268) disclose a method of using a cationically activated methyl complex of Pd (II) for copolymerization of ethylene or propylene with an acrylate, and in this copolymerization, as a ligand. Formation of a cationically activated Pd complex containing ethylene or insertion of a chelating acrylate ligand results in the formation of relatively high molecular weight, branched copolymers. International Patent Application WO96 / 2 by Johnson et al.
At 3010, a monoolefin is polymerized in the presence of a transition metal or rare earth metal such as Ti, Zr, Sc, V, Cr, Fe, Co, Ni, Pd to form a highly branched (multi-branched) polymer. Discloses that the metal complex then contains a bidentate N, N'-disubstituted diazadiene ligand. The polymerization results achieved in the presence of the metal complex are strongly dependent on, in particular, the structure of the transition metal complex used. Using a Pd complex containing a diimine ligand and additionally having an ether or ester adduct in the complex, a relatively high molecular weight copolymer of ethylene and methyl acrylate could be produced. A disadvantage of the above method is that the polymerization active catalyst center is formed starting from a metal-dialkyl complex.

[0005] Accordingly, it is an object of the present invention to provide a polymer and copolymer product obtained in the light of the fact that it is known that it depends on the specific detailed structure of the transition metal complex used. The object is to investigate the polymerization and copolymerization of monoolefins and polar comonomers using a very wide variety of transition metal complexes.

The present inventors have determined that the above objects have been achieved by providing a cationically activated P having a chelating diimine ligand L ¹ and a carbanion ligand L ² of an alkoxycycloalkene.
It has been found that this can be achieved by polymerizing ethylene and copolymerizing ethylene with a polar comonomer such as methyl acrylate in the presence of the d complex to obtain a branched polyethylene or copolymer.

[0007] The present invention relates to a method for producing an alkylaluminum compound in the presence or absence of an alkylaluminum compound in the presence of a Pd chelate complex having an N, N'-disubstituted diazadiene ligand.
A method of polymerizing 12 monoolefins or a mixture thereof and a method of copolymerizing these with an olefinically unsaturated polar monomer, wherein the Pd complex has a formula (I):

[0008]

Embedded image

[0009] [However, L ¹ to form a palladium chelate, uncharged bidentate N, represent N'- disubstituted Jiazajien ligand, L ² is bound to the palladium atom with σ- bond, a carbon atom Represents 7 to 8 carbanions of alkoxycycloalkenes, wherein the C = C double bond of the carbanions forms a complexed π-bond with a palladium atom, and An ⁻ is non-esterifiable or substantially non-esterifiable Which represents an anion of a weakly coordinated or non-coordinated acid.] The present invention also provides a polymerization method and a copolymerization method, characterized in that:

[0010] Suitable ligands ^{L 1} cationically activated Pd complexes are described in International Patent Application 96
N, N'-disubstituted diazadiene ligands forming chelate to the corresponding bidentate, Pd atom disclosed in US Pat. These act as bidentate ligands to form metal chelates of formulas (II), (III) and (IV)
Contains diimine represented by

Here, diimines (II), (III) and (IV) are represented by the following formula:

[0012]

Embedded image In the formula (II), R ¹ and R ² may be the same or different and each represents a hydrocarbon group which may be substituted, or a heteroaromatic group which may be substituted; R ³ and R ⁴ may be the same or different and each represent a hydrogen atom or a hydrocarbon group which may be substituted, or R ³ and R ⁴ may be combined to form a divalent group which may be substituted In formula (III), R ⁵ and R ⁶ may be the same or different, and each may be a substituted or unsubstituted hydrocarbon group or a substituted or unsubstituted heteroaromatic group Wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different and each represent a hydrogen atom, a hydrocarbon group which may be substituted, or R ⁹ and R ¹⁰ are combined Has been replaced Forming a may also be a divalent hydrocarbon group; in the formula (IV), ^{R 11} and ^{R 12} may be the same or different, represent a hydrocarbon group which may be substituted respectively, ^{R 13} and ^{R 14} May be the same or different and each represents a hydrogen atom or a hydrocarbon group which may be substituted, or may be combined and substituted 2
Forms a monovalent hydrocarbon group.

Among diazadienes coordinated to a Pd atom in a bidentate fashion, N, N′-disubstituted diazabutadienes of the formula (II) are preferred, among which: On two N atoms, the relatively large and bulky substituents R ¹ and / or R ² ,
For example, those having an aromatic group which may be substituted or a heteroaromatic group which may be substituted are also preferable. Suitable substituents R ¹ and R ² can be the same or different and are substituted phenyl groups, especially phenyl groups substituted at the 2,4- and / or 6-position by a C ₁ -C ₈ alkyl group, for example 2 -Methylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl, 2-tert-butylphenyl,
2,6-diethylphenyl or 2,6-diisopropylphenyl. Other suitable substituents R ¹ and R ² are 2-pyrimidyl and other heteroaromatic groups, in which the heteroatom, in particular the S-, O-, near the C atom bonded to the imino-N atom And / or contains N atoms in the heteroaromatic.

The substituents R ¹ , R ² , R ⁵ and R ⁶ have been found to be very useful, in which the C atom bonded to the imino-N atom has at least two other carbon atoms. Attach to an atom. Particularly preferred substituents R ¹ , R ² , R ⁵ and R ⁶ are 2,6-
Diethylphenyl and 2,6-diisopropylphenyl.

Very useful R ³ and R ⁴ groups are hydrogen atoms, alkyl groups preferably having 1 to 4 carbon atoms (eg methyl groups), alkylene groups such as butylene or 2-ethylbutylene, and also 2 A valently substituted aromatic group, for example, 1,8-naphthylene.

Methods for preparing the uncharged N, N′-disubstituted diazadiene ligand L ¹ are known and can be carried out, for example, by reacting an amine having a suitable structure with glyoxal or 1,2-diketone. . Preparation of preferred ligands L ¹ are disclosed in Examples 1-6.

The ligand L ² is a carbanion of an alkoxycycloalkene that forms a chelate with Pd, has 7 or 8 carbon atoms in the ring, and is bonded to the Pd atom by a σ bond,
The C = C double bond of the carbanion is complexed with the Pd atom by a π bond (complexing).
π bond). Alkoxy derivatives of cycloalkene carbanions can contain in particular 1 to 8 carbon atoms in their alkoxy groups, but are preferably not methoxy, and are preferably cyclooctadiene-by the molecular addition of alcohols in the presence of alkali. Alternatively, it can be produced from a norbornadiene-Pd complex by a method known per se. A preferred synthesis of di (1-methoxycyclooct-4-ene-8σ, 4π) -μ, μ′-dichloropalladium (formula (VI)) starting from cyclooctadiene-Pd complex (V) is as follows: The following formula:

[0018]

Embedded image And disclosed in Example 7.

The obtained L ² -dichloro-Pd complex (V) is reacted with an uncharged diazadiene ligand L ¹ as shown in Examples 8 to 11, and these are [L ¹ PdL ² ]. ⁺ An ^- catalyst complex, for example converted into the catalyst complex of formula (VII) used according to the invention:

[0020]

Embedded image

In this synthesis, a high yield of a suitable Pd catalyst complex is obtained since the sensitive R-Pd-R intermediate is avoided.

Possible anions An ⁻ are non-esterifiable or substantially non-esterifiable anions of weakly or non-coordinating acids, which have in particular a pKa value of less than 3, preferably less than 2. But not a hydrogen halide. Suitable anions are known to those skilled in the art and often have a bulky structure. Examples of suitable anions An ⁻ are tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, p-toluenesulfonate, trifluoromethanesulfonate,
Tetraphenylborate, tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and tetrakis (pentafluorophenyl) borate,
Of these, hexafluorophosphate, hexafluoroantimonate, tetrafluoroborate, tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and tetrakis (pentafluorophenyl) borate are preferred. Regarding coordination abilities, see literature such as W. Beck et al. Chem. Rev. 88 (1988) 1405.
〜1421 and SH Strauss, Chem. Rev. 93 (1993) 927-942.

The present invention further provides a novel and predetermined palladium complex represented by the formula (I), wherein a) L ¹ is represented by the formula (II) The uncharged N, N'-disubstituted diazabutadiene ligands {R ¹ and R ² may be the same or different and each have at least 1
Represents a phenyl group substituted with a C ₁ -C ₈ hydrocarbon group, and R ³ and R ⁴ may be the same or different, and are each a hydrogen atom or a C ₁ -C ₁₈ hydrocarbon group, preferably Represents an alkyl group, or R ³ and R ⁴ are taken together to form 18
Up pieces, in particular to form a 2-12 divalent hydrocarbon group having carbon atoms}, b) ^{L 2} is, _{1-C 1} ~C ₈ alkoxy cyclooctadiene-4-ene -8Shiguma, 4 [pi]
C) An ⁻ is an anion of a weakly or preferably non-coordinating acid, as described above, which is non-esterifiable or substantially non-esterifiable, tetrafluoroborate, tetrakis It is preferred to represent [3,5-bis (trifluoromethyl) phenyl] borate, tetrakis (pentafluorophenyl) borate, hexafluorophosphate or hexafluoroantimonate.

Suitable olefins as monomers or comonomers are aliphatic and cycloaliphatic monoolefins having 2 to 12 carbon atoms and having an olefinic C ＝ C double bond which is not part of an aromatic system. . Monoolefins that are hydrocarbons are preferred. Preferred monoolefins for homopolymerization are monoolefins having 2 to 6 carbon atoms, especially ethylene, propylene and cyclopentene.

Olefinically unsaturated polar monomers as comonomers are specific monoolefinic monomers having a C ＝ O group, which, due to their structure, are capable of complexing with a cationically activated Pd atom. . Particularly noteworthy by way of example are acrylic acid, methacrylic acid, their esters and also vinyl ketones, with methacrylic acid and especially alkyl esters of acrylic acid being particularly preferred. Among these,
Methyl acrylate is particularly preferred.

In many cases, the Pd complex used according to the invention is used with the addition of an alkylaluminum compound (at least one alkyl group having from 1 to 25 carbon atoms attached to the aluminum atom). Was found to be effective. In the alkylaluminum compound, a halogen or oxygen atom or, for example, an alkoxy group can be bonded to the aluminum atom. Examples of suitable aluminum compounds are triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride, methylaluminoxane {an oligomer represented by the formula [MeAlO] _n (Me is methyl, n preferably represents 5 to 30) ”or A modified methylaluminoxane in which about 20 to 30 mol% of methyl groups have been replaced by isobutyl groups. Advantageously, the amount of alkylaluminum compound added is about 5 to 15 moles per mole of Pd complex catalyst used.

The monomers and comonomers are used in large excess for the polymerization with organometallic catalysts, based on the amount of Pd complex used. For example, the amount of catalyst ranges from ^10-7 to ^10-3 gram atoms of palladium per mole of ethylenically / olefinically unsaturated compound (monomer or monomer + comonomer).

The polymerization method of the present invention comprises the steps of:
It is carried out by contact with the monomer, preferably in the presence of an organic diluent or solvent. Organic diluents which have been found to be very useful are organic hydrocarbons, especially aromatic hydrocarbons such as benzene or toluene.

[0029] The polymerization temperature is generally in the range of -20 to 300 ° C, especially 10 to 150 ° C. The polymerization temperature is particularly preferably in the range of 20 to 120 ° C. The method may be performed at a pressure slightly below atmospheric, from atmospheric to high. In general, the pressure during the polymerization ranges from 0.1 to 3000 bar (1 × 10 ^{4 to} 3 × 10 ⁸ Pa), in particular from 1 to 150 bar (1 × 10 ^{5 to} 1.5 × 10 ⁷ Pa). Is within. Suitable polymerization reactors are, for example, autoclaves and stirrers that can use suitable pressurization. The method can be performed batchwise or continuously. The polymerization time is determined in part by the polymerization temperature, and can be up to 10 hours to achieve a satisfactory yield. The polymerization is satisfactorily stopped by adding hydrogen chloride in an alcohol such as methanol. After washing the diluent or solvent layer with water and filtering, for example using an aluminum oxide column, it is advantageous to separate the polymer or polymer mixture by evaporation of the solvent or diluent and to dry the polymer.

The results obtained by the method of the present invention are shown in Table 1 and some of the results are surprising. Therefore, a relatively low molecular weight polymer having a multi-branched structure is obtained by homopolymerization of ethylene. By the copolymerization of ethylene and 1-hexene, the molecular weight of the obtained copolymer can be significantly increased from the molecular weight of the ethylene homopolymer. Copolymerization of ethylene and methyl acrylate gives a low molecular weight polymer with a relatively broad molecular weight distribution.

The copolymers obtainable with polar monomers are used, for example, as a viscosity index improves in mineral oil, a dispersed flow improves in diesel fuel, as a plasticizer for polymers or as a lubricant. be able to. It is also advantageous that olefin polymers and copolymers can be processed with other elastomers or thermoplastic polymers to produce polymer blends having good toughness and tackiness, depending on the choice of polymer.

The following examples illustrate the invention but do not limit it. Unless indicated otherwise, parts and percentages are by weight. The number and weight average molecular weights reported for the polymers were determined by gel permeation chromatography (GPC) using HDPE standards. The structure (branch) of the obtained polymer was measured by NMR spectroscopy. In this regard, DE Axelson et al.,
Macromolecules 12 (1979) 41-52; T. Usami et al., Macromolecules 17 (1
984) 1757-1761 and JV Prasad et al., Eur.Polym.J. 27 (1991) 251-
See the article on page 254.

[0033]

EXAMPLES Example 1 Synthesis of Ligand 1-1: 1,4-Di (2,6-diisopropylphenyl) diazabutadiene 62.86 ml of 2,6-diisopropylaniline (300 mmol, 90%
Concentration solution) was mixed with 300 ml of methanol and treated with 1 ml of formic acid. Then 21.76 g of a 40% strength glyoxal (as a 150 mmole 40% strength aqueous solution) were added dropwise. Stir for 8 hours to obtain a pale yellow suspension, which is filtered,
The solid was washed with 200 ml of cold methanol. The resulting product was dried under reduced pressure. The yield was 32.8% of the theoretical value (18.5 g). ¹ H-NMR analysis (in CDCl ₃ ): δ 1.2 (24 H, CH ₃ in isopropyl), 2.9 (4 H, isopropyl), 7.2 (6 H aromat. (Aromatic)), 8
. 1 (2H, = CH-CH =).

Example 2 Synthesis of ligand 1-2: 1,4-di (2,6-diisopropylphenyl) -2,3-dimethyldiazabutadiene 20 ml of 2,6-diisopropylphenylamine (95 .44 mmol, 9
(0% strength solution) was mixed with 100 ml of methanol and then treated with 1 ml of formic acid. Then, 4.2 ml (45.14 mmol, 99% strength solution) of biacetyl (dimethylglyoxal) was added dropwise. Stirring for 8 hours gave a pale suspension which was filtered and the solid was washed with 200 ml of methanol. The resulting product was dried under reduced pressure. The yield was 82.4% of theory. ¹ H-NMR analysis (in CDCl ₃ ): δ 1.2 (24H, CH ₃ in isopropyl)
, 2.06 (6H, 2,3-dimethyl), 2.7 (4H, CH in isopropyl)
7.2 (6H aromatic).

Example 3 Synthesis of Ligand 1-3: 1,4-Di (2,6-dimethylphenyl) diazabutadiene The procedure was substantially the same as that of Example 1, but , 6-Dimethylphenylamine was used as the amine. The yield was 10.3% of theory.

Example 4 Synthesis of Ligand 1-4: 1,4-Di (2,6-dimethylphenyl) -2,3-dimethyldiazabutadiene The procedure is substantially the same as that of Example 2. However, 2,6-dimethylphenylamine was used as the amine. The yield was 51.7% of theory. ¹ H-N
MR analysis (in _{CDCl 3): δ2.06 (18H)} , 6.93 (2H, para - aromatic), 7.08 (4H, meta - aromatic).

Example 5 Synthesis of Ligand 1-5: 1,4-di (2,6-diethylphenyl) diazabutadiene The procedure was substantially the same as that of Example 1, but , 6-Diethylphenylamine was used as the amine. The yield was 23.0% of theory.

Example 6 Synthesis of Ligand 1-6: 1,4-di (2,6-diethylphenyl) -2,3-dimethyldiazabutadiene The procedure is substantially the same as that of Example 2. However, 2,6-diethylphenylamine was used as the amine. The yield was 42.3% of theory.

Example 7 Synthesis of di (1-methoxycyclooct-4-ene-8σ-4π) -μ, μ′-dichloropalladium intermediate: 0.8 g of dry sodium carbonate (7.5 mmol) Is added to a yellow suspension of [Pd (COD) Cl ₂ ] (7 mmol) (COD = cyclooctadiene) in methanol, and the resulting mixture is stirred at room temperature for 50 minutes. The suspension turned white. The product was filtered off and washed with cold methanol and diethyl ether. The product was dried under reduced pressure to give a yield of 84% of theory. Elemental analysis gave the following values: C: 38%; H: 5.3%; Cl: 13.0% (theory: C: 37.7%;
H: 4.7%; Cl: 12.8%).

Example 8 Catalyst 2P1-2: [1,4-di (2,6-diisopropylphenyl) -2,3
-Dimethyldiazabutadienyl] [1-methoxycyclooct-4-ene-8σ
Synthesis of [4,4π] palladium hexafluorophosphate 0.75 of solid [Pd (COD-OCH ₃ ) Cl] ₂ prepared in Example 7
g (1.33 mmol) were suspended in 70 ml of methanol. To this suspension was added 1,4-di (2,6-diisopropylphenyl) -2,2 prepared in Example 2.
1.29 g (3.2 mmol) of 3-dimethyldiazabutadiene were added. The molar ratio of palladium to the diazabutadiene compound was 1: 1.2. After stirring for about 3 hours, a yellow solution formed. 0.52 g (3.
A solution of 2 mmol) of ammonium hexafluorophosphate in 5 ml of methanol was added dropwise. A crystalline precipitate formed immediately and was filtered off after 30 minutes, washed with diethyl ether and dried under reduced pressure. The yield is 73.0 of theoretical.
7%. ¹ H-NMR analysis (in CDCl ₃ ) was as follows: 1.1 ppm methyl of 3H d isopropyl, 1.21 ppm methyl of 3H d isopropyl, 1.39 ppm methyl of 3H d isopropyl, 1.37 ppm 3H d-isopropyl methyl, 1.45 ppm 12H d-isopropyl methyl, 1.30 ppm 8H dd COD ′ ligand CH ₂ , 2.39 ppm 8H s methyl backbone, 2.43 ppm 3H s COD ′ methoxy, 2.50 ppm 3H s methyl backbone, 4.81 ppm 1H m COD 'double bond, 5.30 ppm 1H m COD' double bond, 3.02 ppm 4H isopropyl CH, 1.83 ppm 1H COD '( ^* HC -Pd), 2.10 ppm 1H COD '( ^* HC-methoxy).

Example 9 Catalyst 2P1-1: [1,4-di (2,6-diisopropylphenyl) -2,3
-Dimethyldiazabutadienyl] [1-methoxycyclooct-4-ene-8σ
[4π] palladium tetrakis (pentafluorophenyl) borate The procedure was substantially the same as in Example 8, except that dimethylanilinium tetrakis (
(Pentafluorophenyl) borate was used as an activator instead of ammonium hexafluorophosphate. The yield was 93.6% of theory.

Example 10 Catalyst 1P1-1: [1,4-di (2,6-diisopropylphenyl) diazabutadienyl] [1-methoxycyclooct-4-ene-8σ, 4π] palladium tetrakis ( The procedure for the synthesis of pentafluorophenyl) borate was essentially the same as in Example 9, except that the 1,4-di (
2,6-diisopropylphenyl) diaza butadiene was used as the ligand ^{L 1.} The yield was 88.0% of theory.

Example 11 Catalyst 6P1-1: [1,4-di (2,6-diethylphenyl) -2,3-dimethyldiazabutadienyl] [1-methoxycyclooct-4-ene-8σ , 4π
The procedure for the synthesis of palladium tetrakis (pentafluorophenyl) borate was essentially the same as in Example 9, except that the 1,4-di (
2,6-diethyl-phenyl) -2,3-dimethyl-diaza-butadiene was used as the ligand ^{L 1.} The yield was 97.5% of theory.

Example 12 (Polymerization experiment P1) 300 ml of dry toluene are introduced into a 500 ml four-necked flask and 20 mmol of triisobutylaluminum and 2.83 mmol of Example 1
Catalyst 1P1-1 prepared at 0 was added. To this solution is added ethylene at atmospheric pressure for 1 hour.
It was passed at a flow rate of 40 liters per hour and the polymerization temperature was set at 55 ° C. After 7 hours, the polymerization was stopped by adding hydrogen chloride in methanol,
The mixture was separated on a separatory funnel. The toluene layer was washed with water and then dried. After filtration through a neutral aluminum oxide column, the polymer was filtered off by evaporation of toluene (7 ° C., 1 mbar (1 × 10 ³ ), 3 hours) and analyzed. Table 1 shows the results.

Example 13 (Polymerization Experiment P2) The procedure was substantially the same as Example 12, but the catalyst 6P1-1 prepared in Example 11 was used as the catalyst. Table 1 shows the results.

Example 14 (Polymerization Experiment P3) The procedure was substantially the same as in Example 12 (polymerization experiment P1), except that catalyst 2P1-2 was used as the palladium catalyst complex. Table 1 shows the experimental results. It's a normal way of saying

Example 15 (Polymerization Experiment P4) The procedure was substantially the same as in Example 12, but the catalyst 2P1-1 prepared in Example 9 was used as the catalyst. Table 1 shows the experimental results.

Example 16 (Polymerization experiment P5) 150 ml of dry toluene and 150 ml of dry 1-hexene were added to 500 ml of
Into a four-necked flask. After the addition of 20 mmol of triisobutylaluminum and 2.83 mmol of catalyst 2P1-1, ethylene was passed through the solution at atmospheric pressure at a flow rate of 40 l / h and the polymerization temperature was reduced to 55 ° C.
Set to. After a further 7 hours, the polymerization was stopped by adding hydrogen chloride in methanol. The resulting mixture was separated in a separatory funnel, the toluene layer was washed with water and dried. After filtration through a neutral aluminum oxide column, the polymer was filtered off by evaporating the toluene (75 ° C., 0.1 mbar, 3 hours). Table 1 shows the experimental results.

Example 17 (Polymerization Experiment P6) (Ethylene / 1-Decene) 150 ml of dry toluene and 150 ml of dry 1-decene were introduced into a 500 ml four-necked flask. 20 mmol of triisobutylaluminum and 2
. After the addition of 83 mmol of catalyst 2P1-1, ethylene was passed through the solution at atmospheric pressure at a flow rate of 40 liters per hour. Thereafter, the polymerization temperature is set to 55
C. and polymerized for 7 hours. The polymerization was stopped by adding hydrogen chloride in methanol. After separating the mixture in a separatory funnel, the toluene layer was washed with water and dried. After filtration through a neutral aluminum oxide column, the polymer was filtered off by evaporating the toluene (75 ° C., 0.1 mbar, 3 hours).
Table 1 shows the experimental results.

Example 18 (Polymerization experiment P7) 300 ml of dry toluene are introduced into a 500 ml four-necked flask and 20 mmol of triisobutylaluminum and 2.83 mmol of catalyst 2P1
-1 was added. With the solution temperature set at 55 ° C., propylene was passed through the solution at atmospheric pressure at a flow rate of 40 liters per hour. After 7 hours, the polymerization was stopped by adding hydrogen chloride in methanol, and the resulting mixture was separated in a separatory funnel. The toluene layer was washed with water and dried. After filtration through a neutral aluminum oxide column, the toluene was evaporated (75 ° C,
0.1 mbar, 3 hours), the polymer was filtered off. Table 1 shows the experimental results.

Example 19 (Polymerization experiment P8) (1-butene) 300 ml of dry toluene are introduced into a 500 ml four-necked flask and 20 mmol of triisobutylaluminum and 2.83 mmol of catalyst 2P1
-1 was added to this. To this solution is added 1-butene at atmospheric pressure at 40 per hour.
Passed at a flow rate of 1 liter and the polymerization temperature was set at 55 ° C. Seven hours later,
The polymerization was stopped by adding hydrogen chloride in methanol. The resulting mixture was separated in a separatory funnel, the toluene layer was washed with water, dried and filtered through a neutral aluminum oxide column. By evaporating the toluene (7
The polymer was filtered off at 5 ° C., 0.1 mbar, 3 hours). Table 1 shows the experimental results.

Example 20 (Polymerization experiment P9) 120 ml of dry toluene and 3 g of methyl acrylate are introduced into a 500 ml four-necked flask, and 0.27 mmol of catalyst 2P1-1 are added to this mixture did. Thereafter, ethylene was passed through the mixture at atmospheric pressure at a flow rate of 40 liters per hour, and the polymerization temperature was set at 54 to 56 ° C. After 7 hours, the polymerization was stopped by adding hydrogen chloride in methanol. After filtration through a neutral aluminum oxide column, the toluene was evaporated (75 ° C, 0 ° C).
. (1 mbar, 3 hours), the polymer was filtered off. Table 1 shows the experimental results.

Example 21 (Polymerization Experiment P10) 350 ml of dry cyclopentene was introduced into a 500 ml four-necked flask,
Then 4.9 mmol of triisobutylaluminum and 0.49 mmol of catalyst 2P1-1 were added. Polymerization occurred at 55 ° C., and the polymer precipitated as a white powder. After 7 hours, the polymerization was stopped by adding hydrogen chloride in methanol. The polymer was filtered off, washed with water and dried under reduced pressure. The melting point of the polymer is 25
It was 0 ° C (DSC analysis).

[0054]

[Table 1]

[Procedural Amendment] Submission of translation of Article 34 Amendment

[Submission date] January 27, 2001 (2001.1.27)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Contents of correction]

[Claims]

Embedded image [Where L ¹ is a group of formulas II to IV:

Embedded image In the formula, R ¹ , R ² , R ⁵ and R ⁶ may be the same or different and each represents an optionally substituted hydrocarbon group or a heteroaromatic group, and R ³ and R ⁴ are the same or different. R ⁹ and R ¹⁰ may be different, each represent a hydrogen atom or an optionally substituted hydrocarbon group, or combine to form an optionally substituted divalent hydrocarbon group, They may be the same or different and each represent a hydrogen atom or a hydrocarbon group which may be substituted, or
R ¹¹ and R ¹² may be the same or different, each represents a hydrocarbon group which may be substituted, and R ¹³ and R ¹⁴ may be the same or different, L represents a hydrogen atom or an optionally substituted hydrocarbon group, or is selected from ligands represented by｝ which combine to form an optionally substituted divalent hydrocarbon group; ² represents a carbanion of an alkoxycycloalkene of 7 or 8 carbon atoms, wherein the alkoxy group contains 1 to 8 carbon atoms, which is bonded to the palladium atom by a σ-bond, and the C = C double of the carbanion bond forms a palladium ion and π- bonded, an ^- is tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, p- toluenesulfonyl , Trifluoromethanesulfonate, tetraphenylborate, tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and tetrakis (pentafluorophenyl) borate]. And copolymerization methods.

Embedded image [However, R ¹ and R ² may be the same or different and each may be an optionally substituted aromatic group having 6 to 18 carbon atoms, or at least one S, O
Or an optionally substituted heteroaromatic group having an N atom and having at least 3 carbon atoms, wherein R ³ and R ⁴ may be the same or different, and each is a hydrogen atom or C ₁ -C ₁₈ represent a hydrocarbon group, or coalesce, claim 1, represented by] forming a 2-18 amino optionally substituted divalent hydrocarbon group having carbon atoms The method described in.

Embedded image Wherein L ¹ is a compound of formula II:

Embedded image ｛R ¹ and R ² may be the same or different, each represents a phenyl group substituted with at least one C ₁ -C ₈ hydrocarbon group, and R ³ and R ⁴ are the same or different And each represents a hydrogen atom or a C ₁ -C ₁₈ hydrocarbon group, or combines to form a divalent hydrocarbon group having up to a total of 18 carbon atoms. L ² is a 1-C ₁ -C ₈ alkoxycyclooct-4-ene-8σ, 4π ligand, and An ⁻ is tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, p-toluene Sulfonate, trifluoromethanesulfonate, tetraphenylborate, tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and tetrakis (Pentafluorophenyl) borate].

──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J015 EA08 4J028 AA01A AB00A AC45A BA00A BA01B BB00A BB01B BC15B BC16B BC17B BC25B EA01 EB01 EB02 EB04 EB05 EB06 EB07 GA06

Claims (8)

[Claims] 1. A method for polymerizing a monoolefin having 2 to 12 carbon atoms or a mixture thereof in the presence or absence of an alkylaluminum compound in the presence of a palladium complex, and a method for polymerizing a monoolefin having 2 to 12 carbon atoms with an olefinically unsaturated polar monomer. Wherein the palladium complex has the formula (I): [However, L ¹ to form a palladium chelate, uncharged bidentate N, represent N'- disubstituted Jiazajien ligand, L ² is bound to the palladium atom with σ- bond, a carbon atom 7-8 And wherein the C = C double bond of the carbanion forms a complexed π-bond with a palladium atom, and An ⁻ is non-esterifiable or substantially non-esterifiable. And represents a coordinated or non-coordinated acid anion]. 2. The method according to claim 1, wherein the mixture of ethylene is polymerized with an ester of acrylic acid and / or methacrylic acid. 3. The method according to claim 1, wherein the polymerization is carried out in the presence of an aromatic hydrocarbon. 4. A as a ligand L ² in the palladium complex, the method according to any one of claims 1 to 3 using 1-alkoxyalkyl cyclooctadiene-4-ene -8Shiguma, a carbanion of 4 [pi]. 5. A ligand L ¹ palladium complexes to be used, formula (II): 2] [However, R ¹ and R ² may be the same or different and each has a carbon atom of 6 to 1
Represents an optionally substituted aromatic group or an optionally substituted heteroaromatic group having 3 to 18 carbon atoms having at least one S-, O- or N-hetero atom. may be R ³ and ^{R 4} are the same or different, each a hydrogen _atom, or represents a C 1 _{-C 1 8} hydrocarbon group, or ^{R 3} and ^{R 4} are united, having 2 to 18 carbon atoms Forming a divalent hydrocarbon group which may be substituted]. The method according to any one of claims 1 to 4, wherein the diazabutadiene is represented by the following formula: 6. The anion An ⁻ is tetrafluoroborate, tetrakis [
The method according to any one of claims 1 to 5, which is an anion of 3,5-bis (trifluoromethyl) phenyl] borate, tetrakis (pentafluorophenyl) borate, pentafluorophosphate or hexafluoroantimonate. 7. A compound of formula (I): Wherein L ¹ is a group represented by the formula (II): Wherein R ¹ and R ² may be the same or different, each represents a phenyl group substituted with at least one C ₁ -C ₈ hydrocarbon group, and R ³ and R ⁴ are the same or different May be different and each represent a hydrogen atom or a C ₁ -C ₁₈ hydrocarbon group, or R ³ and R ⁴ combine to form a divalent hydrocarbon group having up to a total of 18 carbon atoms A N, N′-disubstituted diazabutadiene ligand represented by the formula: wherein L ² is a 1-C ₁ -C ₈ alkoxycyclooct-4-ene-8σ, 4π ligand; and An ⁻ represents a weakly or non-coordinating acid anion that cannot be esterified or is substantially not esterifiable]. 8. The method according to claim 1, wherein the anion An ⁻ of the formula (I) is tetrafluoroborate, tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, tetrakis (pentafluorophenyl) borate, hexafluorophosphate or hexafluoroantimony. The palladium complex according to claim 7, which is an anion of a nate.