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WO2006057229A1 - Procédé de synthèse d’un polymère oléfinique de faible masse molaire comportant une double liaison terminale - Google Patents

Procédé de synthèse d’un polymère oléfinique de faible masse molaire comportant une double liaison terminale Download PDF

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Publication number
WO2006057229A1
WO2006057229A1 PCT/JP2005/021415 JP2005021415W WO2006057229A1 WO 2006057229 A1 WO2006057229 A1 WO 2006057229A1 JP 2005021415 W JP2005021415 W JP 2005021415W WO 2006057229 A1 WO2006057229 A1 WO 2006057229A1
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group
containing group
transition metal
molecular weight
compound
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PCT/JP2005/021415
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English (en)
Japanese (ja)
Inventor
Junji Saito
Seiichi Ishii
Kenji Michiue
Sadahiko Matsuura
Makoto Mitani
Terunori Fujita
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Mitsui Chemicals, Inc.
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Priority to JP2006547775A priority Critical patent/JPWO2006057229A1/ja
Publication of WO2006057229A1 publication Critical patent/WO2006057229A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • the problem to be solved by 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.
  • the method for producing a low molecular weight olefin-containing polymer having a single-end double bond includes:
  • 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.
  • M represents a transition metal atom of Group 4 of the periodic table
  • 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.
  • 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. )
  • 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
  • M is Zr.
  • 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 .
  • propylene and 1-butene are particularly preferred.
  • 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%.
  • the structural unit derived from ⁇ -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 ⁇ 1. It is in the range of 3 to 2.2.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ m, and a bull group peak of 4 ⁇ 85 to 5.0 ⁇ m (B), 5.5 to 5.8ppm.
  • Single-terminal unsaturation (U%) is the peak area of (A), (B), and (C).
  • the numerator indicates the peak area based on terminal bulle, vinylene, and vinylidene
  • 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
  • V (%) ⁇ S / (S + S) ⁇ X 200 (%)
  • the numerator indicates the area of the peak based on all unsaturated terminals
  • the denominator indicates the area of all terminals.
  • 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.
  • the method for producing a low molecular weight olefin polymer containing a single-end double bond in the present invention will be specifically described.
  • 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:
  • (B-2) an organoaluminum compound
  • Transition metal compound A compound that reacts with (A) to form an ion pair Force At least one compound selected
  • the (A) transition metal compound used in the present invention is a compound represented by the following general formula (I).
  • N ⁇ M is generally a force indicating coordination, and may or may not be coordinated in the present invention.
  • M represents a transition metal belonging to Group 4 of the periodic table, specifically titanium, dinolecodium, and hafnium, and preferably dinoleconium.
  • n represents an integer of 1 to 2, and is preferably 2.
  • a methyl group or a hydrogen atom 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.
  • transition metal compound (A) is represented by the following formula (II).
  • each of R 2 to R 5 may be connected to each other.
  • ⁇ is a number satisfying the valence of ⁇ , 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.
  • halogen atom examples include fluorine, chlorine, bromine and iodine.
  • hydrocarbon group examples 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.
  • transition metal compound ( ⁇ ) represented by the general formula (I) are shown below, but are not limited thereto.
  • 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.
  • 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
  • both starting compounds are dissolved in a solvent.
  • 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.
  • an acid catalyst such as formic acid, acetic acid, or paratoluenesulfonic acid may be used as the catalyst.
  • 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.
  • 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.
  • 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.
  • 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.
  • transition metal compound (A) can be used in the polymerization as it is without isolating the transition metal compound (A).
  • 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.
  • 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.
  • 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.
  • the organoaluminum compound is used singly or in combination of two or more.
  • 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.
  • the ionized ionic compounds (B-3) as described above are used singly or in combination of two or more.
  • transition metal compound (A) used in the present invention is used as a catalyst
  • an organoaluminum compound (B-2) such as methylaluminoxane as a promoter component is used in combination
  • an olefinic compound is obtained.
  • it exhibits very high polymerization activity.
  • component (A) and component (B) are added to the polymerization vessel in any order.
  • At least two or more of the catalyst components may be contacted in advance.
  • an olefin polymer is obtained by polymerizing or copolymerizing olefins in the presence of the catalyst for olefin polymerization as described above.
  • 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.
  • 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.
  • 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.
  • the polymerization temperature of olefins using such olefin polymerization catalysts is usually -50 to
  • 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.
  • 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 ⁇ -olefins introduced. Furthermore, it can be adjusted according to the amount of ingredient ( ⁇ ) used.
  • Ligand L-2 was synthesized based on the production method described in US Pat. No. 6,531,555.
  • 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).
  • 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.
  • 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.
  • 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.
  • a hexane solution (1.00m mol / mL in terms of aluminum atom) was injected with 0.20mL (0.20mmol)
  • 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.
  • 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
  • hexane aluminum atom equivalent 1.00 mm ol / mL 0.20 mL (0.20 mmol
  • the solution of compound (3) in toluene 0.0002 mmol / ml
  • lmL 0.0002mmol
  • 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.
  • 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.
  • hexane solution aluminum atom equivalent 1.00mmol / mL
  • 0.25mL 0.25mmol
  • compound (1) in toluene solution 0.0003mmol / mL
  • 1.0mL 0.0 003mmol
  • 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.
  • 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.
  • 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.

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Abstract

La présente invention a pour objet un procédé de synthèse à haut rendement d’un polymère oléfinique de faible masse molaire, dont la teneur en liaisons insaturées en bout de chaîne est supérieure à la moyenne. La présente invention a notamment pour objet le procédé de synthèse d’un polymère oléfinique de faible masse molaire, possédant une double liaison terminale au bout de la chaîne principale. Ledit procédé est caractérisé en ce que l’homopolymérisation de l’éthylène ou la copolymérisation de l’éthylène avec une α-oléfine en C3-C10 est menée en présence d'un catalyseur constitué de (A) un dérivé de métal de transition de formule générale (I) et (B) au moins un membre du groupe constitué par (B-1) les composés organométalliques, (B-2) les composés de type organooxoaluminium, et (B-3) les composés capables de réagir avec un dérivé de métal de transition de type (A) afin de former une paire d'ions : (I) où M est un métal de transition du Groupe 4 du tableau périodique ; m est un entier égal à 1 ou à 2 ; R1 est un groupement hydrocarbure linéaire en C1-C5 (Cn'H2n'+1 où n’ est compris entre 1 et 5) ou un groupement similaire ; les groupements R2 à R5 représentent chacun un atome d’hydrogène, d’halogène, un groupement hydrocarbure, ou un groupement similaire ; n est un nombre correspondant à la valence de M ; et X est un atome d’hydrogène, d’halogène, ou un groupement similaire.
PCT/JP2005/021415 2004-11-26 2005-11-22 Procédé de synthèse d’un polymère oléfinique de faible masse molaire comportant une double liaison terminale WO2006057229A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008013085A1 (fr) 2006-07-25 2008-01-31 Nippon Paper Chemicals Co., Ltd. Résine de polyoléfine modifiée et ses utilisations
US9670346B2 (en) 2014-12-09 2017-06-06 Mitsui Chemicals, Inc. Propylene-based resin composition
US9714306B2 (en) 2014-03-28 2017-07-25 Mitsui Chemicals, Inc. Olefin resin and method for producing same

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JPH11315109A (ja) * 1997-04-25 1999-11-16 Mitsui Chem Inc オレフィン重合用触媒、遷移金属化合物、オレフィンの重合方法およびα−オレフィン・共役ジエン共重合体
WO2004052980A1 (fr) * 2002-12-11 2004-06-24 Johnson Matthey Plc Reaction de polymerisation et catalyseur associe
JP2004523503A (ja) * 2000-12-19 2004-08-05 ユニベーション・テクノロジーズ・エルエルシー オレフィンオリゴマー化用触媒、それらの製造及び使用
CN1524836A (zh) * 2003-09-17 2004-09-01 大连理工大学 一类西佛碱配位锆络合物乙烯齐聚催化剂的制备和应用

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JPH11315109A (ja) * 1997-04-25 1999-11-16 Mitsui Chem Inc オレフィン重合用触媒、遷移金属化合物、オレフィンの重合方法およびα−オレフィン・共役ジエン共重合体
JP2004523503A (ja) * 2000-12-19 2004-08-05 ユニベーション・テクノロジーズ・エルエルシー オレフィンオリゴマー化用触媒、それらの製造及び使用
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CN1524836A (zh) * 2003-09-17 2004-09-01 大连理工大学 一类西佛碱配位锆络合物乙烯齐聚催化剂的制备和应用

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008013085A1 (fr) 2006-07-25 2008-01-31 Nippon Paper Chemicals Co., Ltd. Résine de polyoléfine modifiée et ses utilisations
US8236900B2 (en) 2006-07-25 2012-08-07 Nippon Paper Chemicals Co., Ltd. Modified polyolefin resin and uses thereof
US9714306B2 (en) 2014-03-28 2017-07-25 Mitsui Chemicals, Inc. Olefin resin and method for producing same
US9670346B2 (en) 2014-12-09 2017-06-06 Mitsui Chemicals, Inc. Propylene-based resin composition

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