WO2006057229A1

WO2006057229A1 - Process for production of low-molecular olefin polymer having a terminal double bond

Info

Publication number: WO2006057229A1
Application number: PCT/JP2005/021415
Authority: WO
Inventors: Junji Saito; Seiichi Ishii; Kenji Michiue; Sadahiko Matsuura; Makoto Mitani; Terunori Fujita
Original assignee: Mitsui Chemicals, Inc.
Priority date: 2004-11-26
Filing date: 2005-11-22
Publication date: 2006-06-01
Also published as: JPWO2006057229A1

Abstract

[PROBLEMS] To provide a process for producing, with high productivity, a low-molecular olefin polymer which is enhanced in the content of unsaturated bonds present at one terminal thereof. [MEANS FOR SOLVING PROBLEMS] A process for the production of a low-molecular olefin polymer having a double bond at the terminal of the backbone chain, characterized by conducting the homopolymerization of ethylene or the copolymerization of ethylene with an α-olefin of 3 to 10 carbon atoms in the presence of a catalyst consisting of (A) a transition metal compound represented by the general formula (I) and (B) at least one member selected from among (B-1) organometallic compounds, (B-2) organoaluminum oxy compounds, and (B-3) compounds capable of reacting with a transition metal compound (A) to form an ion pair: wherein M is a Group 4 transition metal of the periodic table; m is an integer of 1 or 2; R1 is a straight-chain hydrocarbon group of 1 to 5 carbon atoms (Cn'H2n'+1 wherein n' is 1 to 5) or the like; R2 to R5 are each hydrogen, halogeno, hydrocarbyl, or the like; n is a number satisfying the valence of M; and X is hydrogen, halogeno, or the like.

Description

Specification

Method for producing low molecular weight olefin polymer containing double bond at one end

Technical field

The present invention relates to an olefin polymerization method using an olefin polymerization catalyst, and more specifically, an olefin (co) polymer characterized by having a low molecular weight and a double bond at the end of a polymer main chain. And a method for polymerizing olefins using a novel catalyst for olefin polymerization having high polymerization activity. More specifically, the present invention relates to a method for polymerizing olefins in which a specific transition metal compound, an organometallic compound, and a compound that reacts with a transition metal compound to form an ion pair are polymerized or copolymerized.

Background art

[0002] In recent years, as a new olefin polymerization catalyst, JP-A-11-315109 describes a transition metal compound having a salicylaldoimine ligand, and it is described that this complex exhibits high refining and olefin polymerization activity. Has been. Furthermore, in Japanese Patent Application Laid-Open No. 2001-2731, European Patent Application Publication No. 1043341 and Japanese Patent Application Laid-Open No. 2003-073412, a novel compound containing a double bond at one end can be produced by using the transition metal compound. Low molecular weight ethylene polymers, modified end double bonds, and their uses are described. Further, US Pat. No. 6,531,555 discloses a method for producing a low molecular weight ethylene polymer containing a double bond at one end by using the transition metal compound having an electron withdrawing group introduced at a specific position. Yes. Among these, by using the transition metal compound substituted with bromine, a polymer having a high single-end vinyl bond rate (also referred to as single-end unsaturation rate in this specification) is produced. However, in this production method, the vinyl bond ratio at one end is not yet sufficient and the productivity is not sufficient.

[0003] Such low molecular weight ethylene (co) polymers containing a double bond at one end and modified end double bonds are used for their purposes (toner release agents, pigment dispersants, vinyl chloride, etc. In order to achieve higher performance in resin lubricants), a polymer having a higher unsaturated bond group content in the double bond at the end of the polymer chain is required, and high productivity is also required. It was done. Patent Document 1: Japanese Patent Laid-Open No. 11-315109

Patent Document 2: JP 2001-2731 A

Patent Document 3: European Patent Application Publication No. 1043341

Patent Document 4: Japanese Patent Laid-Open No. 2003-073412

Patent Document 5: US Patent No. 6531555

Disclosure of the invention

Problems to be solved by the invention

[0004] In such a situation, the problem to be solved by the present invention, that is, the object of the present invention, is to achieve high productivity, low molecular weight olefins having high single-terminal unsaturated bonds and higher single-terminal unsaturated ratios. It is to provide a method for manufacturing coalescence.

Means for solving the problem

[0005] The applicant has reached the present invention as a result of intensive studies in order to achieve the above object. That is, the method for producing a low molecular weight olefin-containing polymer having a single-end double bond according to the present invention includes:

(A) a transition metal compound represented by the following general formula (I), (BXB-1) an organometallic compound, (B-2) an organoaluminum compound, and (B-3) a transition metal compound In the presence of a catalyst comprising at least one compound selected from compounds that react with (A) to form ion pairs, ethylene is homopolymerized or ethylene is copolymerized with 3 to 10 carbon olefins. It is characterized by that.

[0006] [Chemical 1]

(In the formula, M represents a transition metal atom of Group 4 of the periodic table,

m represents an integer of 1 to 2, R ¹ represents a linear hydrocarbon group having 1 to 5 carbon atoms (CH 2, n = 1 to 5) or a hydrogen atom η ′ 2η ′ + 1

, R ^{2 to} R ⁵ may be the same or different from each other, hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, X-containing group , A phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of R ^{2 to} R ⁵ may be connected to each other to form a ring.

When m is 2, two R ^{2 to} R ⁵ may be connected to each other.

n is a number that satisfies the valence of M;

X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a X-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a key Represents a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X You can combine with Le to form a ring. )

In the above transition metal compound, it is preferable that R ¹ is hydrogen or a methyl group, R ⁵ is a phenylethyl group, a diphenylmethyl group, a cuminole group, a diphenylethyl group, or a triphenylmethyl group, and M is Zr.

[0008] The low molecular weight olefin polymer containing a single terminal double bond obtained in the present invention contains a vinyl, vinylene, or vinylidene type double bond at one terminal, and in the presence of the above olefin polymerization catalyst, Can be produced by homopolymerization or copolymerization of ethylene and hyolein having 3 to 10 carbon atoms. Examples of the olefin having 3 to 10 carbon atoms used in the present invention include propylene, 1-butene, 3_methyl-1-butene, 1-pentene, 3-methyl-1-butene, and 1-to. Xene, 4-methyl-1-pentene, 4-methinole_1_pentene, 3-methyl-1-pentene, 1-octene, 1-decene, etc., and one or more of these are used . Of these, propylene and 1-butene are particularly preferred.

[0009] The low molecular weight (co) polymer obtained in the present invention contains 95 to 100 mol% of structural units derived from ethylene, preferably 96 to 100 mol%, particularly preferably 97 to 100 mol%. On the other hand, the structural unit derived from α-olefin having 3 to 10 carbon atoms is 0 to 5 mol%, preferably 0 to 4 mol%, more preferably 0 to 3 mol%.

The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the low molecular weight (co) polymer obtained in the present invention is 500 or more and 2000 or less, preferably 800 or more and 1800 or less. Further, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn, also referred to as molecular weight distribution in the present specification) is 1.:! To 2.5. 1. 2 to 2.3, more preferably ί 1. It is in the range of 3 to 2.2.

[0010] Mw and Mw / Mn are measured as follows using GPC-150 manufactured by Millipore.

The separation column is TSK GNH HT, the column size is 7.5 mm in diameter and 300 mm in length, and the column temperature is 140 ° C. Use 0-dichlorobenzene (Wako Pure Chemicals) as the mobile phase and 0.025% by weight BHT (Takeda Pharmaceutical) as the antioxidant, and move at 1. Oml / min. The sample concentration is 0.1% by weight, the sample injection volume is 500 microliters, and a differential refractometer is used as the detector. Standard polystyrene is manufactured by Tosoh Corporation.

[0011] The low molecular weight (co) polymer obtained in the present invention has a vinyl, vinylene, or vinylidene group at the end of the polymer main chain, and the content of these groups as measured by _NMR or ¹³ C-NMR The ratio of the saturated bonds) is 95% or more of all terminal ends, more preferably 96% or more, and particularly preferably 97% or more. Here, one end means a terminal having an unsaturated bond in the polymer main chain in the case of a polymer having an unsaturated bond, and a polymer main chain in the case of a polymer having no unsaturated bond. Check the other end.

[0012] NMR is measured at 120 ° C after completely dissolving the polymer in orthodichlorobenzene containing a small amount of deuterated benzene as a lock solvent in a sample tube. The amount of terminal unsaturated bonds and the degree of unsaturation in one terminal in a low molecular weight polymer consisting only of ethylene are determined by ifi-NMR. Each hydrogen peak of the polymer has a terminal saturated methyl group (A) of 0 · 65 to 0 · 85 卯 m, and a bull group peak of 4 · 85 to 5.0 卯 m (B), 5.5 to 5.8ppm. Observed at (C). Single-terminal unsaturation (U%) is the peak area of (A), (B), and (C).

A

, S, and S, the following formula is used.

B C

[0013] U (%) = [(S + S) / 3] / {S / 3} X 200 (%)

B C A

In the above formula, the numerator indicates the peak area based on terminal bulle, vinylene, and vinylidene, and the denominator indicates the area of the terminal methyl group. The single-terminal olefination rate (single-terminal unsaturation rate (V%)) of a copolymer of ethylene and eleven-year-old lefin is the sum of the peak areas derived from all unsaturated terminals in ¹³ C_NMR and the total S

X

If the sum of the peak areas derived from the saturated ends is s, it is calculated by the following formula.

γ

[0014] V (%) = {S / (S + S)} X 200 (%)

X X Y

In the above formula, the numerator indicates the area of the peak based on all unsaturated terminals, and the denominator indicates the area of all terminals.

The invention's effect

[0015] The production method of the present invention efficiently provides a low molecular weight olefin polymer containing a single-end double bond useful in various applications.

BEST MODE FOR CARRYING OUT THE INVENTION

[0016] Hereinafter, the method for producing a low molecular weight olefin polymer containing a single-end double bond in the present invention will be specifically described. In the present specification, the term “polymerization” is sometimes used in the meaning including not only homopolymerization but also copolymerization, and the term “polymer” refers to a copolymer that is not only a homopolymer. Is sometimes used in a meaning that also includes. The olefin polymerization catalyst used in the present invention is:

(A) —a transition metal compound represented by the general formula (I);

(B) (B-1) an organometallic compound,

(B-2) an organoaluminum compound, and

(B-3) Transition metal compound A compound that reacts with (A) to form an ion pair Force At least one compound selected

It is characterized by the following.

[Transition metal compounds (A)]

The (A) transition metal compound used in the present invention is a compound represented by the following general formula (I).

[0017] [Chemical 2]

[0018] (Here, N ····· M is generally a force indicating coordination, and may or may not be coordinated in the present invention.)

In the general formula (I), M represents a transition metal belonging to Group 4 of the periodic table, specifically titanium, dinolecodium, and hafnium, and preferably dinoleconium.

m represents an integer of 1 to 2, and is preferably 2.

[0019] R ¹ represents a straight-chain hydrocarbon group having 1 to 5 carbon atoms (CH 2, n = 1 to 5) or a hydrogen atom η '2η' + 1

Preferably a methyl group or a hydrogen atom.

R ^{2 to} R ⁵ may be the same as or different from each other, a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a thio-containing group, phosphorus-containing groups, Kei-containing group, a germanium-containing group or a tin-containing group, Yo also form a ring more than is bonded to each other of R ² to R ⁵ les, but, R ⁵ Is preferably a hydrocarbon group, particularly preferably a phenylethyl group, a diphenylmethyl group, a tamyl group, a diphenylethyl group, or a triphenylmethyl group.

[0020] When m is 2, the transition metal compound (A) is represented by the following formula (II).

[0021] [Chemical 3]

(

X, has the same meaning as n, '~ 1 ^5' are each synonymous with 1 ^ to 1 ⁵ in the formula (I). )

When m is 2, each of R ^{2 to} R ⁵ may be connected to each other. In the above formula (Π), R ¹ and R ¹ ′, R ² and R ² ′, R ³ and R ³ ′, R ⁴ and R ⁴ ′, R ⁵ and R ⁵ 'Means that they may be concatenated.

[0023] η is a number satisfying the valence of Μ, specifically 2, 3, preferably 2.

X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a X-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a key Represents a silicon-containing group, a germanium-containing group, or a tin-containing group, and among them, a halogen atom and a hydrocarbon group are particularly preferable. A plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.

[0024] Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Specific examples of the hydrocarbon group include alkyl groups such as methinole, ethyl, propyl, and butyl; alkenyl groups such as vinyl, propenyl, and cyclohexenyl; and benzyl, phenyl, phenylpropyl, and other alkenyl groups. Reel alkyl groups; forces including, but not limited to phenyl, tolyl, dimethylphenylol, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, phenanthryl, and the like.

[0025] Specific examples of the transition metal compound (Α) represented by the general formula (I) are shown below, but are not limited thereto.

[0026] [Chemical 4]

[0027] In the present invention, in the compound as described above, zirconium metal is titanium, Hough. A transition metal compound replaced with can also be used.

The method for producing such a transition metal compound (A) is not particularly limited and can be produced, for example, as follows.

First, the ligand constituting the transition metal compound (A) is a salicylaldehyde compound and a primary amin compound represented by the formula Ri-NH (R ¹ is as defined above), for example, A

2

It can be obtained by reacting with a rualkylamine compound. Specifically, both starting compounds are dissolved in a solvent. Among solvents that can be used commonly used for such a reaction, alcohol solvents such as methanol and ethanol, hydrocarbon solvents such as tonolene, and the like are preferable. Subsequent stirring from room temperature to reflux conditions for about :! to 48 hours gives the corresponding ligand in good yield. When synthesizing the ligand compound, an acid catalyst such as formic acid, acetic acid, or paratoluenesulfonic acid may be used as the catalyst. In addition, when molecular sieves, anhydrous magnesium sulfate or anhydrous sodium sulfate is used as a dehydrating agent, or the reaction is performed while dehydrating with Dean Stark, the reaction proceeds effectively.

[0028] Next, the corresponding transition metal compound (A) can be synthesized by reacting the ligand thus obtained with the transition metal M-containing compound. Specifically, the synthesized ligand is dissolved in a solvent and brought into contact with a base as necessary to prepare a phenoxide salt, and then mixed with a metal compound such as a metal halide or metal alkylate at a low temperature. Stir for about 1 to 48 hours at ° C to room temperature or under reflux conditions. Among solvents that can be used commonly used for such reactions, polar solvents such as ether and tetrahydrofuran (THF), hydrocarbon solvents such as toluene, and the like are preferably used. Examples of the base used in preparing the phenoxide salt include lithium salts such as n-butyllithium, metal salts such as sodium salts such as sodium hydride; strengths that can exemplify triethylamine, pyridine and the like. Not as long.

[0029] Depending on the properties of the compound, the corresponding transition metal compound (A) can be synthesized by directly reacting the ligand with the metal compound without going through the preparation of the phenoxide salt. Further, the transition metal M in the synthesized transition metal compound (A) can be exchanged with another transition metal by a conventional method. Also, for example! When one or more of ^ ~ ⁵ is hydrogen, substituents other than hydrogen can be introduced at any stage of the synthesis. The

[0030] In addition, the transition metal compound (A) can be used in the polymerization as it is without isolating the transition metal compound (A).

Specific examples of organometallic compounds (B_l) used in the present invention include the following organometallic compounds of Groups 1, 2 and 12, 13 of the periodic table, but are not limited thereto.

[0031] Specifically, tri-n-alkyl aluminums such as trimethylaluminum, triethylaluminum, trioctylaluminum, and tridecylaluminum; tri-branched alkylaluminums such as triisopropylaluminum and triisobutylaluminum; Tricycloalkylaluminum such as hexanolamine and tricyclooctylaluminum; Dialkylaluminum hydride such as diisobutylaluminum hydride; Organic such as dialkylaluminum alkoxide such as dimethylaluminum methoxide, jetylaluminum ethoxide, and dibutylaluminum butoxide Examples include aluminum compounds.

[0032] The organometallic compound (B-1) is used singly or in combination of two or more.

The organoaluminum compound (B-2) used in the present invention may be a conventionally known aluminoxane, or may be insoluble in benzene as exemplified in JP-A-2-78687. It may be an organoaluminum compound.

[0033] The organoaluminum compound is used singly or in combination of two or more.

Compounds that react with transition metal compounds (A) to form ion pairs (B-3)>

As the compound (B-3) (also referred to as “ionized ionic compound (B-3)” in the present specification) that forms an ion pair by reacting with the transition metal compound (A) used in the present invention, JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Examples include Lewis acids, ionic compounds, borane compounds and carborane compounds described in Japanese Patent No. 5321106. In addition, heteropoly compounds and An isopoly compound can also be mentioned.

[0034] Specifically, tris (pentafluorophenyl) boron, triphenylcarbtetrakis (pentafluorophenyl) borate, N, N_dimethylaniliniumtetrakis (pentafluorophenyl) borate, etc. This is not the case.

The ionized ionic compounds (B-3) as described above are used singly or in combination of two or more.

[0035] When the transition metal compound (A) used in the present invention is used as a catalyst, when an organoaluminum compound (B-2) such as methylaluminoxane as a promoter component is used in combination, an olefinic compound is obtained. On the other hand, it exhibits very high polymerization activity.

In the polymerization, the method of using each component and the order of addition are arbitrarily selected, and the following methods are exemplified.

(1) A method in which component (A) is added alone to the polymerization vessel.

(2) A method in which component (A) and component (B) are added to the polymerization vessel in any order.

[0036] In the method (2), at least two or more of the catalyst components may be contacted in advance.

In the method for polymerizing olefins according to the present invention, an olefin polymer is obtained by polymerizing or copolymerizing olefins in the presence of the catalyst for olefin polymerization as described above.

In the present invention, the polymerization can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization, and gas phase polymerization methods. 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 And alicyclic hydrocarbons such as xane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof. Olefin itself can also be used as a solvent.

[0037] Using the Orefin polymerization catalyst as described above, when performing polymerization of Orefin, Ingredient (A) is, per liter of the reaction volume, usually 10- ¹² ~ 10- ² mol, preferably 10- ^1Q ~: used in an amount such that ^10-3 molar. Component (Bl) is a molar ratio of component (Bl) to all transition metal atoms (M) in component (A) [(B-1) / M] force usually from 0.01 to 100000, preferably 0. Can be used in an amount of between 05 and 50000. Component (B-2) is a mono-it [(B-2) / M] of aluminum atoms in component (B-2) and all transition metals (M) in component (A), usually 10 to 500,000. The amount is preferably 20 to 100000. Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) to transition metal atom (M) in component (A) usually:! To 10, preferably Is used in an amount of 1-5.

[0038] The polymerization temperature of olefins using such olefin polymerization catalysts is usually -50 to

+ 200 ° C, preferably in the range of 0 to 170 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ² , and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. it can. Furthermore, the polymerization can be carried out in two or more stages having different reaction conditions.

[0039] The molecular weight of the obtained olefin polymer can be adjusted by the presence of hydrogen in the polymerization system, the force for changing the polymerization temperature, or the amount of α-olefins introduced. Furthermore, it can be adjusted according to the amount of ingredient (成分) used.

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[0040] [Example]

[Synthesis Example 1] (Synthesis of Ligand L-1)

A fully dry, nitrogen-substituted lOOmL reactor is charged with 15.4 g (56.1 mmol) of 5-chloro-3-tamylsalicylide, 60 mL of toluene and 4.42 g of methylamine (40% methanol solution, 56.9 mmol) at room temperature. For 5 hours. The reaction solution was concentrated under reduced pressure to obtain 16.0 g (yield 99%) of a reddish brown oil represented by the following formula L-1.

'Η NMR (CDCl): 1.71 (s, 6H), 3.33 (s, 3H), 7.10-7.44 (m, 7H), 8.16 (s, lH), 13.8 (s, lH)

[0041] [Chemical 5]

L-1

[0042] [Synthesis Example 2] (Synthesis of Ligand L-2)

Ligand L-2 was synthesized based on the production method described in US Pat. No. 6,531,555.

[0043] [Chemical 6]

L-2

[0044] [Synthesis Example 3] (Synthesis of transition metal compound (1))

In a 500 mL reactor thoroughly dried and purged with argon, 12.1 g (42.0 mmol) of ligand L-l and 150 mL of jetyl ether were charged, cooled to -78 ° C, and stirred. To this, 27.8 mL (n-hexane solution, 1.57M, 43.7 mmol) of n_butyllithium was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, then slowly warmed to room temperature, and further stirred at room temperature for 3 hours to prepare a lithium salt. This solution was added to 4.84 g of ZrCl (THF) complex cooled to -78 ° C.

4 2

The solution was added dropwise to 150 mL of a tetrahydrofuran solution containing (20.8 mol). After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring for 12 hours at room temperature, the solvent of the reaction solution was distilled off. Dissolve the resulting solid in 200 mL of methylene chloride and filter the insoluble matter with a glass filter. Removed. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with 80 mL of jetyl ether and 150 mL of n_hexane, and dried under reduced pressure to obtain 11.4 g of a yellow powder compound represented by the following formula (1) (yield 75%) was obtained.

'Η NMR (CDCl): 1.67 (s, 6H), 1.92 (s, 6H), 2.30 (s, 6H), 7.00-7.60 (m, 12H), 7.70 (s, 2H), 7.7

9 (s, 2H)

FD-mass spectrometry: 734

[0045] [Chemical 7]

Compound (1)

[Synthesis Example 4] (Synthesis of transition metal compound (2))

Ligand L-2 1.94 g (7.18 mmol) was dissolved in tetrahydrofuran 20 mL in a 200 mL reactor thoroughly dried and purged with argon. This solution was added dropwise over 30 minutes to a suspension of 1 OmL of tetrahydrofuran and 268 mg (7.18 mmol) of sodium hydride cooled to _30 ° C, stirred at that temperature for 2 hours, and then slowly warmed to room temperature. The mixture was further stirred at room temperature for 3 hours to prepare a sodium salt. The solution thus prepared was added dropwise to 50 mL of a tetrahydrofuran solution containing 1.38 g (20.8 mol) of a ZrCl (THF) complex cooled to -78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring for 12 hours at room temperature, the solvent of the reaction solution was distilled off. The obtained solid was dissolved in 70 mL of methylene chloride, and insoluble matters were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was suspended in 40 mL of n-hexane, filtered and dried under reduced pressure to obtain 372 mg (yield 14.8%) of a yellow powder compound represented by the following formula (2).

FD-mass spectrometry: 699 [0047] [Chemical 8]

Compound (2)

[0048] [Example 1]

A stainless steel autoclave with an internal volume of lOOOOmL that was sufficiently purged with nitrogen was charged with 500 mL of heptane, and ethylene was allowed to flow at 100 liter / hr for 15 minutes at room temperature to saturate the liquid phase and gas phase. Subsequently, the temperature was raised to 80 ° C., and then the pressure of ethylene was increased to 8 kg / m³ to maintain the temperature. MMAO (manufactured by Tosohichi Finechem Co., Ltd.) in a hexane solution (aluminum atom equivalent 1.00 mmol / mL) 0.20 mL (0.20 mmol) is injected, and the toluene solution (0.0002 mmol / mL) of compound (1) 0.15 mL (0.00003 mmol) was injected to initiate the polymerization. The pressure was maintained while continuously supplying ethylene gas, and the polymerization was carried out at 80 ° C for 15 minutes, and then the polymerization was stopped by injecting 5 mL of methanol. The product was obtained by distilling off the solvent from the resulting polymer slurry. By drying under reduced pressure at 80 ° C. for 10 hours, 48.22 g of a polymer was obtained. The polymerization activity was 6429 kg / mmo 卜 Zr'h, and the product was Mw = 1550, Mw / Mn = 2.32 in terms of polyethylene, and the one-terminal unsaturation rate measured by H-NMR = 99.0 mol%. .

[0049] [Comparative Example 1]

A stainless steel autoclave with an internal volume of lOOOOmL that was sufficiently purged with nitrogen was charged with 500 mL of heptane, and ethylene was allowed to flow at 100 liter / hr for 15 minutes at room temperature to saturate the liquid phase and gas phase. Subsequently, the temperature was raised to 80 ° C, and then the pressure of ethylene was increased to 8 kgm ² G to maintain the temperature. MMAO (manufactured by Tosohichi Finechem Co., Ltd.) in a hexane solution (1.00m mol / mL in terms of aluminum atom) was injected with 0.20mL (0.20mmol), and the toluene solution of compound (2) (0.0002mmol / mL) 1.0 mL (0.0002 mmol) was injected to initiate the polymerization. Continuous supply of ethylene gas While maintaining the pressure, polymerization was carried out at 80 ° C. for 15 minutes, and then the polymerization was terminated by press-fitting 5 mL of methanol. The product was obtained by distilling off the solvent from the resulting polymer slurry. By drying under reduced pressure at 80 ° C. for 10 hours, 20.1 g of a polymer was obtained. The polymerization activity was 402 kg / mmo 卜 Zr'h, and the product was Mw = 1490, Mw / Mn = 2.70 in terms of polyethylene, and the single-terminal unsaturation measured by Η NMR was 95.5 mol%.

[0050] [Comparative Example 2]

A stainless steel autoclave with an internal volume of lOOOOmL that was sufficiently purged with nitrogen was charged with 500 mL of heptane, and ethylene was allowed to flow at 100 liter / hr for 15 minutes at room temperature to saturate the liquid phase and gas phase. Subsequently, after raising the temperature to 80 ° C, the pressure was increased to 8 kg m ² G of ethylene to maintain the temperature. MMAO (manufactured by Tosoichi Finechem) in hexane (aluminum atom equivalent 1.00 mm ol / mL) 0.20 mL (0.20 mmol) was injected, and the solution of compound (3) in toluene (0.0002 mmol / ml) lmL (0.0002mmol) was injected to initiate the polymerization. Polymerization was carried out at 80 ° C for 15 minutes while maintaining a constant pressure by supplying ethylene gas continuously, and then the polymerization was stopped by injecting 5 mL of methanol. The resulting polymer solution was added to 3 L of methanol containing a small amount of hydrochloric acid to precipitate the polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours to obtain 24.36 g of an ethylene polymer. The polymerization activity is 487 kg / mmo 卜 Zr 'h, and the product is Mw = 2220 in terms of polyethylene, Mw / Mn = 2.4 One-end bullation rate (one-end unsaturation rate) = 94 • OmoP / o It was.

[0051] [Chemical 9]

Compound (3)

[0052] [Example 2] 450 mL of heptane was charged into a stainless steel autoclave with an internal volume of lOOOOmL that had been sufficiently purged with nitrogen, and propylene was allowed to flow at room temperature for 15 minutes at 100 liter / hr to saturate the liquid phase and gas phase. Subsequently, the temperature was raised to 80 ° C, and then propylene was increased to 4 kg · m ² G to maintain the temperature. In addition, ethylene was introduced to 8 kgm and the temperature was maintained. MMAO (Tosoh Finechem Co., Ltd.) in hexane solution (aluminum atom equivalent 1.00mmol / mL) 0.25mL (0.25mmol) was injected, then compound (1) in toluene solution (0.0003mmol / mL) 1.0mL (0.0 003mmol) ) Was injected to initiate polymerization. The pressure was maintained while continuously supplying ethylene gas, and the polymerization was carried out at 80 ° C for 15 minutes, and then the polymerization was stopped by injecting 5 mL of methanol. The product was obtained by distilling off the solvent from the resulting polymer slurry. By drying under reduced pressure at 80 ° C. for 10 hours, 38.86 g of a copolymer was obtained. The polymerization activity was 518 kg / m mo 卜 Zr 'h, the product was Mw = 1380 and Mw / Mn = 2.20 in terms of polyethylene, and the one-terminal unsaturation measured by ¹³ C_NMR was 99.5 mol%. .

[0053] [Example 3]

440 mL of heptane was charged into a stainless steel autoclave with an internal volume of lOOOOmL that had been sufficiently purged with nitrogen, and propylene was allowed to flow at 100 liter / hr for 15 minutes at room temperature to saturate the liquid phase and gas phase. Subsequently, the temperature was raised to 80 ° C, and then propylene was increased to 0.6 MPaG to maintain the temperature. Further, ethylene was introduced until the pressure became 0.8 MPaG, and the temperature was maintained. MMAO (manufactured by Tosoichi Finechem) hexane solution (1.00 mmol / mL in terms of aluminum atom) was injected with 0.25 mL (0.25 mmol), and then compound (1) in toluene solution (0.0005 mmol / mL) 2.0 mL ( 0.0005 mmol) was injected to initiate the polymerization. The pressure was maintained while continuously supplying ethylene gas, and the polymerization was carried out at 80 ° C for 15 minutes, and then the polymerization was stopped by injecting 5 mL of methanol. The product was obtained by distilling off the solvent from the resulting polymer slurry. By drying under reduced pressure at 80 ° C. for 10 hours, 19.16 g of a copolymer was obtained. The product had a polyethylene conversion of Mw = 1050, Mw / Mn = 2.34, a propylene content of 3.7 mol%, and a single-terminal unsaturation rate of 99.5 mol%.

Industrial applicability

[0054] The low molecular weight olefin polymer containing a single-end double bond efficiently provided by the production method of the present invention may be used as it is or after further modification. In a blended form of resin and additives, it exhibits useful performance in various industrial fields.

Claims

Claims (A) A transition metal compound represented by the following general formula (I): (B) (B-1) an organometallic compound, (B-2) an organoaluminum compound, and (B-3) In the presence of a catalyst comprising at least one compound selected from compounds that react with transition metal compounds (A) to form ion pairs, ethylene is homopolymerized or ethylene and α-olefin having 3 to 10 carbon atoms A process for producing a low molecular weight olefin polymer having a double bond at the end of a polymer main chain, wherein the polymer is copolymerized.

[Chemical 1]

(Where Μ represents a transition metal atom of group 4 of the periodic table,

m represents an integer of 1 to 2,

R ¹ represents a straight hydrocarbon group having 1 to 5 carbon atoms (CH 2, n = 1 to 5) or a hydrogen atom.

n '2n' + l

R ^{2 to} R ⁵ may be the same as or different from each other, a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a thio-containing group, Indicates a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of R ^{2 to} R ⁵ may be connected to each other to form a ring.

When m is 2, two R ^{2 to} R ⁵ may be connected to each other.

n is a number that satisfies the valence of M;

X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a X-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic group A compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. When n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and are represented by X A plurality of groups may be bonded to each other to form a ring. )

[2] The method for producing a low molecular weight olefin polymer according to claim 1, wherein, in the general formula (I), R ¹ is hydrogen or a methyl group.

[3] The general formula (I), wherein R ⁵ is a phenylethyl group, a diphenylmethyl group, a Tamyl group, a diphenylethyl group, or a triphenylmethyl group. A method for producing a low molecular weight olefin polymer.

[4] The method for producing a low molecular weight olefin polymer according to any one of [1] to [3], wherein in the general formula (I), M is Zr.

[5] The polymer having the double bond at the end of the polymer main chain,

(1) structural units structural units derived from ethylene is 95 to 100 mole ^_0/0, derived from alpha _ Orefin is in the range of 0 to 5 mol%,

(2) The weight average molecular weight (Mw) measured by GPC is 500 or more and 2000 or less,

(3) The molecular weight distribution (Mw / Mn) is 1 · l≤Mw / Mn≤2.5

(4) It has a vinyl, vinylene, or vinylidene group at the end of the polymer main chain, and the content of these groups measured by _NMR or ¹³ C-NMR is 95% or more of all the ends. The method for producing a low molecular weight olefin polymer according to any one of claims 1 to 4.