Method for controlling the long-chain branching index of olefin polymers

Abstract

To provide a method of separately producing olefin polymers having different long chain branch degrees by a simple method, or to provide a simple method of producing an olefin polymer having a different long chain branch degree.SOLUTION: A method includes: controlling a partial pressure of a gaseous olefin within a range of 0.9-6 MPa (a gauge pressure) in the presence of a catalyst for polymerizing olefin containing a specific transition metal complex. When the partial pressure is increased, an olefin polymer having a low long chain branch degree is easy to be obtained, and when the partial pressure is reduced, an olefin polymer having a high long chain branch degree is easy to be obtained.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a method for efficiently producing olefin polymers with various degrees of branching in their long chains. [Background technology]

[0002] Ethylene polymers are used in a variety of applications. For example, they are used in packaging materials for food and other products such as plastic bags (like shopping bags) and plastic wrap, exterior and interior building materials, automotive parts such as door glass runs, footwear or footwear components, such as the soles (mainly midsoles) of sports shoes, and many other uses.

[0003] It is known that the properties of ethylene polymers change depending on the degree of branching of the long chain. These ethylene polymers are known to have different properties depending on changes in their molecular structure, such as molecular weight and branching structure (e.g., long-chain branching, short-chain). Therefore, ethylene polymers with various structures and properties are used in the market.

[0004] For example, linear ethylene polymers generally have excellent strength but tend to have insufficient moldability. Long-chain branched ethylene polymers have excellent moldability but may lack sufficient strength. Therefore, these polymers are selected and used according to their application.

[0005] The methods for producing ethylene polymers with different degrees of long-chain branching often depend on the type of polymerization catalyst used for ethylene polymerization, the combination of multiple catalysts, and the manufacturing method (such as radical polymerization or anionic polymerization). (For example, Patent Documents 1-3) [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2004-182715 [Patent Document 2] International Publication No. 2004-104055 [Patent Document 3] International Publication No. 2006-080578 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] Transition metal complexes, such as metallocene compounds, are considered suitable catalysts for olefin polymerization used in the polymerization of ethylene. However, producing such a variety of polymers requires methods such as maintaining multiple processes or processes with multiple catalyst supply devices. This can lead to increased costs and risks such as instability in product quality due to catalyst contamination. If a single catalyst could be used to produce ethylene polymers with significantly different degrees of branching, these problems could be avoided.

[0008] Therefore, the present invention aims to provide a method for selectively producing linear ethylene polymers, ethylene polymers with short-chain branching, and ethylene polymers with long-chain branching without changing the type of catalyst. [Means for solving the problem]

[0009] As a result of our investigations, we have found that by using an olefin polymerization catalyst containing a transition metal complex having a specific structure and adjusting the polymerization pressure, it is possible to selectively produce linear ethylene polymers, short-chain branched ethylene polymers, and long-chain branched ethylene polymers. In other words, the present invention is defined by the following requirements.

[0010] [1] When polymerizing ethylene-containing olefins in the presence of transition metal complexes of Groups 3-10 metals from Periods 6 and 7 of the periodic table, By making ethylene essential and adjusting the partial pressure of the olefin gas, which can be any component of an olefin with 3 to 4 carbon atoms, within the range of 0.9 to 6 MPa (gauge pressure), Long chain branching index (I 10A method for producing olefin polymers, wherein the ratio of / I2) is in the range of 4 to 10. (I 10 And I2 is defined as follows: I 10 : Melt flow rate measured at 190°C under a 10 kg load, in accordance with the ASTM D1238 standard. I2: Melt flow rate measured at 190°C under a 2.16 kg load, in accordance with ASTM D1238 standard.

[0011] [2] A method for producing an olefin polymer according to [1], wherein the transition metal complex is a complex containing a transition metal of Group 4 to 5 of the periodic table.

[0012] [3] A method for producing an olefin polymer according to [1], wherein the transition metal complex is a complex containing hafnium.

[0013] [4] A method for producing an olefin polymer according to [1], wherein the polymerization of the olefin is carried out in an environment where the partial pressure is 1.0 to 4.0 MPa.

[0014] [5] A method for producing an olefin polymer according to [1], wherein the polymerization of the olefin is carried out in an environment where the temperature is 90 to 180°C. [Effects of the Invention]

[0015] The present invention makes it possible to produce ethylene polymers with different long-chain branching degrees by using an olefin polymerization catalyst containing a specific transition metal complex and adjusting the polymerization pressure of an ethylene-containing olefin within a specific range. Because polymerization pressure tends to allow for easier control of overall process conditions compared to changing catalysts, it is possible to easily produce ethylene polymers with different degrees of long-chain branching. [Brief explanation of the drawing]

[0016] [Figure 1]This is an example of a configuration of a manufacturing apparatus for carrying out the polymerization method of olefins according to the present invention. [Modes for carrying out the invention]

[0017] The present invention describes a method for producing an olefin polymer. In this specification, "polymer" includes the meaning of copolymer, and "polymerization" includes the meaning of copolymer. Also, the notation "x~y" indicates a range that includes x and y.

[0018] [Transition metal complexes] The transition metal complex used in this invention is a complex of transition metals from groups 3 to 10 of periods 6 and 7 of the periodic table. Preferably, the transition metal is selected from group 4 and group 5 of the periodic table. From the viewpoint of availability, it is preferable to select a metal from period 6. More preferably, it is a transition metal from group 5 of the periodic table, and particularly preferably hafnium. Using such a transition metal-containing complex as a catalyst for olefin polymerization is advantageous for selectively producing ethylene polymers with different degrees of long-chain branching, as will be described later. The reason for this effect will be explained later.

[0019] There are no particular restrictions on the ligands that form such transition metal complexes. Preferably, the ligands have a relatively large structure. A suitable example of such a ligand is one in which a cyclopentadienyl skeleton and a fluorenyl skeleton are linked by carbon or silicon. The cyclopentadienyl skeleton and the fluorenyl skeleton preferably have substituents such as hydrocarbon groups. Examples of transition metal complexes containing ligands like those described above include the following structures.

[0020] [ka]

[0021] 〈R 1 From R 14 〉 In formula [A3], R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 and R 14 are each independently a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, and among the substituents from R 1 to R 4 , any two substituents may be bonded to each other to form a ring, and among the substituents from R 5 to R 12 , any two substituents may be bonded to each other to form a ring, and R 13 and R 14 may be bonded to each other to form a ring.

[0022] Examples of the hydrocarbon group in R 1 to R 14 include, for example, a linear hydrocarbon group, a branched hydrocarbon group, a cyclic saturated hydrocarbon group, a cyclic unsaturated hydrocarbon group, and a group formed by substituting one or more hydrogen atoms of a saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group. The number of carbon atoms of the hydrocarbon group is usually 1 to 20, preferably 1 to 15, more preferably 1 to 10.

[0023] Examples of the linear hydrocarbon group include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group; and linear alkenyl groups such as allyl group.

[0024] Examples of branched hydrocarbon groups include branched alkyl groups such as isopropyl group, tert-butyl group, tert-amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, and 1-methyl-1-isopropyl-2-methylpropyl group.

[0025] Examples of cyclic saturated hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and methylcyclohexyl groups; and polycyclic groups such as norbornyl, adamantyl, and methyladamantyl groups.

[0026] Examples of cyclic unsaturated hydrocarbon groups include aryl groups such as phenyl, tolyl, naphthyl, biphenyl, phenanthryl, and anthracenyl groups; cycloalkenyl groups such as cyclohexenyl groups; and polycyclic unsaturated alicyclic groups such as 5-bicyclo[2.2.1]hepta-2-enyl groups.

[0027] Examples of groups formed by substituting one or more hydrogen atoms of a saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group include groups formed by substituting one or more hydrogen atoms of an alkyl group such as a benzyl group, cumyl group, 1,1-diphenylethyl group, or triphenylmethyl group with an aryl group.

[0028] R 1 From R 14 Examples of heteroatom-containing hydrocarbon groups include alkoxy groups such as methoxy and ethoxy groups, aryloxy groups such as phenoxy groups, and oxygen-containing hydrocarbon groups such as furyl groups; amino groups such as N-methylamino, N,N-dimethylamino, and N-phenylamino groups, and nitrogen-containing hydrocarbon groups such as pyryl groups; and sulfur-containing hydrocarbon groups such as thienyl groups. The number of carbon atoms in the heteroatom-containing hydrocarbon groups is usually 1 to 20, preferably 2 to 18, and more preferably 2 to 15. However, silicon-containing groups are excluded from the heteroatom-containing hydrocarbon groups.

[0029] R 1 From R 14 Examples of silicon-containing groups in this context include groups represented by the formula -SiR3 (wherein each of the multiple R groups is independently an alkyl group or phenyl group having 1 to 15 carbon atoms), such as trimethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, diphenylmethylsilyl group, and triphenylsilyl group.

[0030] R 1 From R 14 Any two substituents from the substituents up to (e.g., R) can be adjacent substituents. 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 9 and R 10 , R 10 and R 11 , R 11 and R 12 , R 13 and R 14 These elements may be bonded to each other to form a ring. The above ring formation may occur at two or more locations within the molecule.

[0031] In this specification, examples of rings formed by the bonding of two substituents (additional rings) include alicyclic rings, aromatic rings, and heterocyclic rings. Specifically, examples include cyclohexane rings, benzene rings, hydrogenated benzene rings, cyclopentene rings, furan rings, thiophene rings, and other heterocyclic rings and their corresponding hydrogenated heterocyclic rings, with cyclohexane rings, benzene rings, and hydrogenated benzene rings being preferred. Furthermore, such ring structures may have substituents such as alkyl groups on the ring.

[0032] R 5 , R 8 , R 9 and R 12Preferably, it is a hydrogen atom. R 6 , R 7 , R 10 and R 11 R is preferably a hydrogen atom, a hydrocarbon group, an oxygen atom-containing hydrocarbon group, or a nitrogen atom-containing hydrocarbon group, and more preferably a hydrocarbon group. 6 and R 7 They bond to each other to form a ring, and R 10 and R 11 These may be bonded to each other to form a ring. An example of such a fluorenyl group structure is represented by the following formula.

[0033] [ka]

[0034] R 13 and R 14 Preferably, this is a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silicon-containing group, and more preferably an aryl group or a substituted aryl group (an aryl group having a heteroatom-containing hydrocarbon group or a silicon-containing group).

[0035] 〈Y〉 In formula [A3], Y is a carbon atom, a silicon atom, a germanium atom, or a tin atom, preferably a carbon atom.

[0036] <M, Q, j> In formula [A3], M is a transition metal of Group 3 to Group 10 in Periods 6 and 7 of the periodic table, as described above. As described above, a preferred embodiment is a Group 4 metal, and a particularly preferred embodiment is hafnium.

[0037] Q is a halogen atom, and examples of halogen atoms include fluorine, chlorine, bromine, and iodine, with chlorine being particularly preferred. j is an integer between 1 and 4, preferably 2. When j is an integer greater than or equal to 2, Q may be chosen in the same or different combinations.

[0038] Specific examples of the above transition metal complexes include structures similar to those of the compounds listed on pages 29-43 of International Publication No. 2004 / 87775, pages 9-37 of International Publication No. 2006 / 25540, the compounds listed in

[0117] of International Publication No. 2015 / 122414, and the compounds listed in

[0143] of International Publication No. 2015 / 122415.

[0039] Method for producing olefin polymers The present invention provides a method for producing an olefin polymer, characterized by carrying out polymerization of an olefin in the presence of the above-mentioned transition metal complex.

[0040] The method for producing the olefin polymer of the present invention can appropriately employ the same methods as those conventionally known for producing olefin polymers, as long as the above-mentioned transition metal complex is used as a catalytic component for the olefin polymerization reaction.

[0041] The following explains each of the conditions. In the method for producing olefin polymers of the present invention, any of batch polymerization, continuous polymerization, or semi-continuous polymerization can be used as the polymerization method for the olefin polymer. However, the production method of the present invention is particularly effective when a continuous polymerization process with a high production rate is used, and a transition metal complex solution containing the above-mentioned transition metal complex (for example, a hafnium halide type complex compound) (hereinafter also referred to as "transition metal complex (A)"), an organometallic compound (B), and a hydrocarbon compound (C), wherein the molar ratio of the metal elements between component (A) and component (B) [(A) / (B)] is in the range of 1 / 1 to 1 / 500, is considered to function effectively.

[0042] Polymerization reactors include those in which a rotatable stirring shaft with stirring blades is installed in a reaction vessel made of stainless steel or the like. Examples of stirring blades include inclined paddle blades, turbine blades, anchor blades, helical ribbon blades, and large plate blades.

[0043] The size of the reactor and reaction apparatus used in the manufacturing method of the present invention is preferably in the range of 1 liter to 1,000 cubic meters. A more preferable lower limit is 5 liters, and even more preferably 10 liters. On the other hand, a more preferable upper limit is 800 cubic meters, and even more preferably 700 cubic meters. An oversupply of ethylene to the olefin polymerization catalyst, which is considered to be the cause of turbidity, tends to occur more easily when the size of the reactor and reaction apparatus is large, but if the size of the reactor and reaction apparatus is within the above range, an oversupply of olefins such as ethylene to the olefin polymerization catalyst, which is considered to be the cause of turbidity, will be less likely to occur.

[0044] [Polymerization pressure] In the manufacturing method of the present invention, the polymerization pressure (P) when producing the olefin polymer is 0.9 to 20 MPa. The preferred lower limit is 1.0 MPa. On the other hand, the preferred upper limit is 15 MPa, more preferably 10 MPa, and even more preferably 6 MPa. Unless otherwise specified, the pressures in the present invention are gauge pressure values.

[0045] In the present invention, it is crucial to adjust the partial pressure of ethylene and olefins with 3 to 4 carbon atoms, among the olefins described later, to be in the range of 0.9 MPa to 6 MPa. The preferred lower limit of the partial pressure is 1.0 MPa, more preferably 1.2 MPa. On the other hand, the preferred upper limit is 5.0 MPa, more preferably 4.0 MPa, even more preferably 3.5 MPa, and particularly preferably 3.0 MPa.

[0046] When polymerizing an olefin in the presence of the aforementioned specific transition metal complex, the degree of long-chain branching of the resulting olefin polymer can be adjusted by adjusting the partial pressure within the aforementioned range. The index for the degree of long-chain branching in this invention will be described later.

[0047] Under conditions where the partial pressure of the olefin is high, an olefin polymer with a low degree of long-chain branching tends to be obtained. On the other hand, under conditions where the partial pressure of the olefin is low, an olefin polymer with a high degree of long-chain branching tends to be obtained. The reason why the degree of long-chain branching can be adjusted by the partial pressure of the olefin is not yet clear, but the inventors speculate as follows.

[0048] The transition metal complex of the present invention is a complex containing metals from the 6th to 7th periods of the periodic table, with hafnium being a representative example. Since such metals have larger atomic sizes compared to metals used in typical complexes for olefin polymerization catalysts, such as zirconium and titanium, when considering the complex structure, it is possible that the central metal is more easily exposed compared to zirconium complexes, and that the angle between the positional relationships of multiple ligand structures (e.g., cyclopentadienyl skeleton and fluorenyl skeleton) may be somewhat larger.

[0049] In an environment with such a small spread around the central metal, polymerization reactions are dominant when the partial pressure of the highly reactive gaseous olefin is high (i.e., the density of olefin is high). However, when the partial pressure of the olefin is relatively low, chain transfer due to the charging olefin is more likely to occur, potentially leading to the formation of terminal double-bond polymers as by-products. (This tendency may be particularly pronounced with ethylene, the smallest olefin.) When the aforementioned terminal double-bond polymer copolymerizes with an olefin, a long-chain branched polymer is formed. For this reason, in the method for producing olefin polymers of the present invention, the lower the partial pressure of the olefin, the easier it is to form a long-chain branched olefin polymer.

[0050] As shown in the comparative examples of the present invention, a similar trend may be observed with zirconium complexes, but complexes with larger metals, such as hafnium complexes, tend to exhibit a greater change in the degree of long-chain branching due to polymerization pressure.

[0051] This tendency is likely to be more pronounced in complexes with relatively large ligands. In such structures, the influence of the aforementioned environment is expected to be more apparent, and if the ligand is too large or too small, the influence on the long-chain branching degree of the olefin partial pressure may be reduced.

[0052] Therefore, it can be considered that preferred ligands for the transition metal complex used in the present invention are ligands having a basic structure in which the cyclopentadienyl skeleton and the fluorenyl skeleton are linked by carbon, silicon, or the like. Within the aforementioned range of olefin partial pressure, it tends to be possible to produce the desired olefin polymer with relatively high polymerization activity.

[0053] [Polymerization temperature] In the manufacturing method of the present invention, the preferred polymerization temperature for producing olefin polymers is -20 to 200°C. A more preferred lower limit is 20°C, even more preferably 50°C, and particularly preferably 90°C. On the other hand, a more preferred upper limit is 190°C, and even more preferably 180°C. Within this temperature range, a desired olefin polymer can be obtained with high polymerization activity.

[0054] [Regarding the supply of raw materials] In the production method of the present invention, the supply rate of ethylene, olefins such as α-olefins, and hydrogen to the reaction apparatus is determined by considering the amount of transition metal complex (A) (for example, a hafnium halide-type complex compound) contained in the transition metal complex solution and the heat removal capacity of the reaction apparatus. The following explanation will be given as an example of copolymerization between ethylene and α-olefins.

[0055] The supply ratio of ethylene to α-olefin (ethylene / α-olefin) is preferably 0.001 to 1,000, more preferably 0.01 to 100, and even more preferably 0.1 to 10. All of these ratios are molar ratios.

[0056] The molecular weight of the olefin polymer produced can be controlled by the polymerization temperature and other factors described later, but a method of controlling it by a so-called chain transfer reaction involving hydrogen is preferred. The supply ratio of ethylene to hydrogen (hydrogen / ethylene) is preferably 0.001 to 500,000, more preferably 0.01 to 100,000, and even more preferably 0.1 to 10,000. All of these ratios are molar ratios. Of course, when producing low molecular weight olefin polymers for lubricant applications, the above ratio tends to be relatively smaller. The specific preferred range is 0.001 to 100,000, more preferably 0.01 to 10,000, and even more preferably 0.1 to 1,000. All of these ratios are molar ratios.

[0057] The preferred residence time is 1 minute to 10 hours, more preferably 2 minutes to 8 hours, and even more preferably 5 minutes to 5 hours. If the method for producing the ethylene copolymer is continuous polymerization, the residence time can be considered as this polymerization time.

[0058] In the method for producing olefins of the present invention, polymerization of olefins is carried out in the presence of the above-mentioned transition metal complex. In this case, the transition metal complex contained in the above-mentioned transition metal complex solution is typically 1 × 10⁻⁶ as the concentration of transition metal atoms in the polymerization reaction system. -8 ~1 × 10 -2 Gram atoms / liter, preferably 1 × 10⁻⁶ -7 ~1 × 10 -3 It is used for quantities in the range of gram atoms / liter. Furthermore, in the reaction apparatus shown in Figure 1, which will be described later, it is preferable that the olefin polymerization catalyst mentioned above be supplied separately from the ethylene.

[0059] [An embodiment of a reaction apparatus] The production of olefin polymers as described above is carried out, for example, in a reaction apparatus having a liquid phase section and a gas phase section, as shown in Figure 1.

[0060] In this reactor, as shown in Figure 1, ethylene and gases such as hydrogen are supplied into the reactor in the ratio specified in (I) above. When producing ethylene copolymers using the reactor shown in Figure 1, it is preferable to set the ratio (EM1 / EM2) of the molar concentration of ethylene in the gas supplied to the liquid phase of the reactor (EM1) to the molar concentration of ethylene in the gas phase of the reactor (EM2) to a range of, for example, 1 to 50. By controlling the composition of both gases within this range, it is possible to suppress the spread of the composition distribution, such as the occurrence of turbidity.

[0061] In the reaction apparatus shown in Figure 1, ethylene copolymers are produced by a continuous polymerization process. In the continuous polymerization process, unreacted gas is circulated and reused (hereinafter, this reused unreacted gas is also referred to as circulating gas). Specifically, as shown in Figure 1, it is preferable to add an appropriate amount of raw material gases such as ethylene and hydrogen to the circulating gas, whose pressure has been adjusted by a compressor, and supply it to the liquid phase of the reaction system. By adopting this method, the composition of the supplied gas can be easily controlled within a desirable range, and turbidity can be efficiently prevented.

[0062] The method for producing olefin polymers according to the present invention is often carried out by continuous solution polymerization using a transition metal complex solution, as shown in Figure 1. In this case, it is important to select conditions that allow for long-term continuous operation. Considering these factors, in addition to the above conditions, it is preferable to carry out the reaction system with a polymer concentration in the range of 1 to 90% by mass, more preferably 5 to 85% by mass, and even more preferably 10 to 80% by mass. Within this range of polymer concentration, problems such as fouling are less likely to occur, which is advantageous for stable operation over a long period of time.

[0063] In the method for producing olefin polymers of the present invention, the transition metal complex described above can be used in combination with organometallic compounds as shown below. Some of these compounds serve as co-catalysts for olefin polymerization catalysts. Specific compounds are described below.

[0064] [Organometallic compound (B)] The organometallic compound (B) that may be used in the method for producing olefin polymerization of the present invention is a known organometallic compound having reducing ability. Specific examples are described below.

[0065] Examples of the organometallic compound according to the present invention include organometallic compounds containing Groups 1 and 2 of the periodic table. Other preferred examples include organometallic compounds containing Group 13 metals of the periodic table. Among them, the following organoaluminum compounds described in JP-A-2010-248526 are preferred.

[0066] 〔Organoaluminum compound〕 For the olefin polymerization catalyst used in the present invention, it is preferable to use an organoaluminum compound in combination. Examples of such compounds include, for example, an organoaluminum compound represented by the following general formula (6), a complex alkylated product of a Group 1 metal and aluminum represented by the following general formula (7), or an organoaluminum oxy compound.

[0067] R a m Al(OR b ) n H p X q …(6) (In the formula, R a and R b may be the same or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. X represents a halogen atom. m is a number where 0 < m ≦ 3, n is a number where 0 ≦ n < 3, p is a number where 0 ≦ p < 3, q is a number where 0 ≦ q < 3, and m + n + p + q = 3.)

[0068] M 2 AlR a 4…(7) (In the formula, M 2 represents Li, Na or K, and R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.)

[0069] Examples of the organoaluminum compound represented by the general formula (6) include compounds represented by the following general formulas (8), (9), (10), or (11).

[0070] R a m Al(OR b ) 3-m …(8) (In the formula, R a and R b may be the same or different from each other and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably a number of 1.5 ≦ m ≦ 3.)

[0071] R a m AlX 3-m …(9) (In the formula, R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is preferably 0 < m < 3.)

[0072] R a m AlH 3-m …(10) (In the formula, R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 2 ≦ m < 3.)

[0073] R a m Al(OR b ) n X q …(11) (In the formula, R a and R b may be the same or different from each other and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is 0 < m ≦ 3, n is 0 ≦ n < 3, q is 0 ≦ q < 3, and m + n + q = 3.)

[0074] More specifically, the aluminum compounds represented by the above general formulas (8), (9), (10), or (11) include tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum; Tri-branched alkylaluminum compounds such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, and tri-2-ethylhexylaluminum; Tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; Triarylaluminum, such as triphenylaluminum and tritrilaluminum; Dialkylaluminum hydrides such as diisopropylaluminum hydride and diisobutylaluminum hydride; General formula (i-C4H9) x Al y (C5H 10 ) z Alkenyl aluminum such as isoprenyl aluminum, represented by the formula (wherein x, y, and z are positive numbers and z ≥ 2x); Alkylaluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide, and isobutylaluminum isopropoxide; Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, and dibutylaluminum butoxide; Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; General formula R a2.5 Al(OR b ) 0.5 Partially alkoxylated alkylaluminum having an average composition represented by, for example; Alkyl aluminum allyloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis(2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), and isobutylaluminum bis(2,6-di-t-butyl-4-methylphenoxide); Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride; Alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide; Partially halogenated alkylaluminum such as alkylaluminum dihalides like ethylaluminum dichloride, propylaluminum dichloride, and butylaluminum dibromide; Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; Alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride, and other partially hydrogenated alkylaluminums; Partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide. Examples include:

[0075] Furthermore, compounds similar to the compound represented by the general formula (6) above can also be used. For example, organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom can be cited. Specific examples of such compounds include (C2H5)2AlN(C2H5)Al(C2H5)2, etc.

[0076] Examples of compounds represented by the above general formula (7) include LiAl(C2H5)4 and LiAl(C7H 15 ) Fourth place can be mentioned. Furthermore, compounds that form the above-mentioned organoaluminum compounds within the polymerization system, such as a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium, can also be used.

[0077] Of these, organoaluminum compounds are preferred. The organoaluminum compounds represented by the above general formula (6), or the complex alkylates of a Group 1 metal and aluminum represented by the above general formula (7), can be used individually or in combination of two or more.

[0078] Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferred. These can be used individually or in combination of two or more.

[0079] It is also preferable to combine it with components known as co-catalysts for olefin polymerization, as described below. Examples of the above compounds include compounds that react with transition metal complexes (A) (for example, hafnium halide-type complex compounds) to form the following ion pairs, and organoaluminum oxy compounds. (In this invention, boron may also be considered a metal element.) Such components are sometimes referred to as co-catalysts for olefin polymerization catalysts.

[0080] [Compounds that react with transition metal complexes (A) to form ion pairs] Examples of compounds that react with transition metal complexes (A) (for example, hafnium halide-type complex compounds) to form ion pairs include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Japanese Patent Publication No. 1-501950, Japanese Patent Publication No. 1-502036, Japanese Patent Application Publication No. 3-179005, Japanese Patent Application Publication No. 3-179006, Japanese Patent Application Publication No. 3-207703, Japanese Patent Application Publication No. 3-207704, and U.S. Patent No. 5321106, etc.

[0081] Specifically, examples of Lewis acids include compounds represented by BR3 (where R is a phenyl group or fluorine, which may have substituents such as fluorine, a methyl group, or a trifluoromethyl group), such as trifluoroborone, triphenylborone, tris(4-fluorophenyl)borone, tris(3,5-difluorophenyl)borone, tris(4-fluoromethylphenyl)borone, tris(pentafluorophenyl)borone, tris(p-tolyl)borone, tris(o-tolyl)borone, tris(3,5-dimethylphenyl)borone, trimethylborone, and triisobutylborone.

[0082] Examples of ionic compounds include those represented by the following general formula (1).

[0083] [ka]

[0084] In the formula, R e+ H + Examples include carbenium cations, oxonium cations, ammonium cations, phosphonium cations, cycloheptyltrienyl cations, and ferrocenium cations containing transition metals. f ~R i These may be the same or different from each other, and are organic groups, preferably aryl groups or substituted aryl groups.

[0085] Specific examples of the above-mentioned carbenium cations include trisubstituted carbenium cations such as triphenylcarbenium cation, tris(methylphenyl)carbenium cation, and tris(dimethylphenyl)carbenium cation.

[0086] Specifically, examples of the above-mentioned ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri(n-propyl)ammonium cation, triisopropylammonium cation, tri(n-butyl)ammonium cation, and triisobutylammonium cation; N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and N,N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation.

[0087] Specific examples of the phosphonium cations mentioned above include triarylphosphonium cations such as triphenylphosphonium cation, tris(methylphenyl)phosphonium cation, and tris(dimethylphenyl)phosphonium cation.

[0088] Of the above, R e+ Preferred cations include carbenium cations and ammonium cations, with triphenylcarbenium cations, N,N-dimethylanilinium cations, and N,N-diethylanilinium cations being particularly preferred.

[0089] Specific examples of carbenium salts include triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(3,5-ditrifluoromethylphenyl)borate, tris(4-methylphenyl)carbenium tetrakis(pentafluorophenyl)borate, and tris(3,5-dimethylphenyl)carbenium tetrakis(pentafluorophenyl)borate.

[0090] Examples of ammonium salts include trialkylsubstituted ammonium salts, N,N-dialkylanilinium salts, and dialkylammonium salts. Specifically, trialkyl-substituted ammonium salts include triethylammonium tetraphenyl borate, tripropylammonium tetraphenyl borate, tri(n-butyl)ammonium tetraphenyl borate, trimethylammonium tetrakis(p-tolyl) borate, trimethylammonium tetrakis(o-tolyl) borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl) borate, triethylammonium tetrakis(pentafluorophenyl) borate, tripropylammonium tetrakis(pentafluorophenyl) borate, tripropylammonium tetrakis(2,4-dimethylphenyl) borate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl) borate, tri(n-butyl)ammonium tetrakis(4-trifluoromethylphenyl) borate, and tri(n-butyl)ammonium Examples include niumtetrakis(3,5-ditrifluoromethylphenyl)borate, tri(n-butyl)ammoniumtetrakis(o-tolyl)borate, dioctadecylmethylammoniumtetraphenylborate, dioctadecylmethylammoniumtetrakis(p-tolyl)borate, dioctadecylmethylammoniumtetrakis(o-tolyl)borate, dioctadecylmethylammoniumtetrakis(pentafluorophenyl)borate, dioctadecylmethylammoniumtetrakis(2,4-dimethylphenyl)borate, dioctadecylmethylammoniumtetrakis(3,5-dimethylphenyl)borate, dioctadecylmethylammoniumtetrakis(4-trifluoromethylphenyl)borate, dioctadecylmethylammoniumtetrakis(3,5-ditrifluoromethylphenyl)borate, and dioctadecylmethylammonium.

[0091] Specific examples of N,N-dialkylanilinium salts include N,N-dimethylanilinium tetraphenyl borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium tetrakis(3,5-ditrifluoromethylphenyl) borate, N,N-diethylanilinium tetraphenyl borate, N,N-diethylanilinium tetrakis(pentafluorophenyl) borate, N,N-diethylanilinium tetrakis(3,5-ditrifluoromethylphenyl) borate, N,N-2,4,6-pentamethylanilinium tetraphenyl borate, and N,N-2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl) borate.

[0092] Examples of dialkylammonium salts include di(1-propyl)ammonium tetrakis(pentafluorophenyl)borate and dicyclohexylammonium tetraphenylborate.

[0093] Furthermore, other examples include ferrocenium tetrakis(pentafluorophenyl) borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N,N-diethylanilinium pentaphenylcyclopentadienyl complex, or borate compounds represented by the following formula (2) or (3), or borate compounds containing active hydrogen represented by the following formula (4), or borate compounds containing a silyl group represented by the following formula (5).

[0094] [ka] (In the formula, Et represents an ethyl group.)

[0095] [ka]

[0096] Borate compounds containing active hydrogen: [B-Qn(Gq(TH)r)z] - A+ …(4) Here, B represents boron. G represents a polybonded hydrocarbon radical, and preferred polybonded hydrocarbons are alkylene, allylene, ethylene, and alkylene radicals containing 1 to 20 carbon atoms. Preferred examples of G include phenylene, bisphenylene, naphthalene, methylene, ethylene, propylene, 1,4-butadiene, and p-phenylenemethylene. The polybonded radical G has an r+1 bond, meaning one bond is bonded to a borate anion, and the other r bond of G is bonded to a (TH) group. A + It is a cation.

[0097] In the above general formula, T is O, S, NR j , or PR j Represents R j represents a hydrocarbanyl radical, a trihydrocarbanylsilyl radical, a trihydrocarbanylgermanium radical, or a hydride. q is an integer of 1 or more, preferably 1. The TH group can be -OH, -SH, -NRH, or PR j H is mentioned, and here R j is a hydrocarbinyl radical or hydrogen having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. Preferred R j These are alkyl, cycloalkyl, allyl, allylalkyl, or alkylallyls having 1 to 18 carbon atoms. -OH, -SH, -NR j H or PR j H can be found in, for example, -C(O)-OH, -C(S)-SH-C(O)-NR j H and C(O)-PR j H is also acceptable. The most preferred group having an active hydrogen is the -OH group. Q is a hydride, dihydrocarbylamide, preferably a dialkylamide, halide, hydrocarbyl oxide, alkoxide, allyl oxide, hydrocarbyl, substituted hydrocarbyl radical, etc. Here, n+z is 4.

[0098] As [B-Qn(Gq(TH)r)z] in the above general formula (4), for example, triphenyl(hydroxyphenyl)borate, diphenyl-di(hydroxyphenyl)borate, triphenyl(2,4-dihydroxyphenyl)borate, tri(p-tolyl)(hydroxyphenyl)borate, tris(pentafluorophenyl)(hydroxyphenyl)borate, tris(2,4-dimethylphenyl)(hydroxyphenyl)borate, tris(3,5-dimethylphenyl)(hydroxyphenyl)borate, tris[3,5-di(trifluoromethyl)phenyl Examples include [nyl](hydroxyphenyl)borate, tris(pentafluorophenyl)(2-hydroxyethyl)borate, tris(pentafluorophenyl)(4-hydroxybutyl)borate, tris(pentafluorophenyl)(4-hydroxycyclohexyl)borate, tris(pentafluorophenyl)[4-(4-hydroxyphenyl)phenyl]borate, tris(pentafluorophenyl)(6-hydroxy-2-naphthyl)borate, and the most preferred is tris(pentafluorophenyl)(4-hydroxyphenyl)borate. Furthermore, the -OH group of the above borate compound is changed to -NHR j (Here, R j Substitutions with methyl, ethyl, or t-butyl are also preferred.

[0099] A is the countercation of the borate compound. +Examples include carbonium cations, tropyllium cations, ammonium cations, oxonium cations, sulfonium cations, and phosphonium cations. Also included are cations of metals and organometallic compounds that are easily reduced themselves. Specific examples of these cations include triphenylcarbonium ions, diphenylcarbonium ions, cycloheptatrinium, indenium, triethylammonium, tripropylammonium, tributylammonium, dimethylammonium, dipropylammonium, dicyclohexylammonium, trioctylammonium, N,N-dimethylammonium, diethylammonium, 2,4,6-pentamethylammonium, N,N-dimethylphenylammonium, di-(i-propyl)ammonium, dicyclohexylammonium, triphenylphosphonium, triphosphonium, tridimethylphenylphosphonium, tri(methylphenyl)phosphonium, triphenylphosphonium ions, triphenyloxonium ions, triethyloxonium ions, pyrinium, silver ions, gold ions, platinum ions, copper ions, palladium ions, mercury ions, and ferrocenium ions. Among these, ammonium ions are particularly preferred.

[0100] Borate compounds containing silyl groups: [B-Qn(Gq(SiR k R l R m )r)z] - A + …(5) Here, B represents boron. G represents a polybonded hydrocarbon radical, and preferred polybonded hydrocarbon radicals include alkylene, allylene, ethylene, and alkylene radicals containing 1 to 20 carbon atoms. Preferred examples of G include phenylene, bisphenylene, naphthalene, methylene, ethylene, propylene, 1,4-butadiene, and p-phenylenemethylene. The polybonded radical G has an r+1 bond, meaning one bond is bonded to a borate anion, and the other bond r of G is (SiR k R l R m ) Bonds with the group. A+ It is a cation.

[0101] R in the above general formula k , R l , R m R represents a hydrocarbanyl radical, trihydrocarbanylsilyl radical, trihydrocarbanylgermanium radical, hydrogen radical, alkoxy radical, hydroxyl radical, or halogen compound radical. k , R l , R m These groups are independent of each other and may be the same or different groups. Q is a hydride, dihydrocarbylamide, preferably a dialkylamide, halide, hydrocarbyl oxide, alkoxide, allyl oxide, hydrocarbyl, substituted hydrocarbyl radical, etc., and more preferably a pentafluorobenzyl radical. Here, n+z is 4.

[0102] In the above general formula (5), [B-Qn(Gq(SiR k R l R m )r)z] - Examples include triphenyl(4-dimethylchlorosilylphenyl) borate, diphenyl-di(4-dimethylchlorosilylphenyl) borate, triphenyl(4-dimethylmethoxysilylphenyl) borate, tri(p-tolyl)(4-triethoxysilylphenyl) borate, tris(pentafluorophenyl)(4-dimethylchlorosilylphenyl) borate, tris(pentafluorophenyl)(4-dimethylmethoxysilylphenyl) borate, tris(pentafluorophenyl)(4-trimethoxysilylphenyl) borate, and tris(pentafluorophenyl)(6-dimethylchlorosilyl-2-naphthyl) borate. The countercation of the borate compound is A. + A in equation (4) above is + The same things can be cited.

[0103] Examples of borane compounds include salts of anions such as decaborane (14), bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, bis[tri(n-butyl)ammonium]dodecaborate, bis[tri(n-butyl)ammonium]decachlorodecaborate, and bis[tri(n-butyl)ammonium]dodecachlorododecaborate, as well as salts of metal borane anions such as tri(n-butyl)ammonium bis(dodecahydridedodecaborate)cobaltate (III) and bis[tri(n-butyl)ammonium]bis(dodecahydridedodecaborate)nickelate (III).

[0104] Specifically, the carborane compounds include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbowndecaborane (13), 2,7-dicarbowndecaborane (13), and undecahydride-7,8-dimethyl-7 ,8-Dicarboundecaporane, Dodecahydride-11-methyl-2,7-Dicarboundecaporane, Tri(n-butyl)ammonium 1-carbadecaborate, Tri(n-butyl)ammonium 1-carboundecaporate, Tri(n-butyl)ammonium 1-carbadodecaborate, Tri(n-butyl)ammonium 1-trimethylsilyl-1-carbadecaborate, Tri(n-butyl)ammonium bromo-1-carbadodecaborate, Tri(n-butyl)ammonium 6-carbadecabo Rate (14), tri(n-butyl)ammonium 6-carbadecaborate (12), tri(n-butyl)ammonium 7-carbadecaborate (13), tri(n-butyl)ammonium 7,8-dicalbounddecaborate (12), tri(n-butyl)ammonium 2,9-dicalbounddecaborate (12), tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicalbounddecaborate, tri(n-butyl)ammonium undecahydride-8-ethyl-7 Salts of anions such as ,9-dicarboxylate, tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarboxylate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicarboxylate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarboxylate, tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carboxylate;Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)ferrate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)cobaltate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)nickelate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)copperate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)goldate (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbowndecaborate)iron Examples include salts of metal carborane anions such as salts (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarboundecaborate)chromate (III), tri(n-butyl)ammonium bis(tribromooctahydride-7,8-dicarboundecaborate)cobaltate (III), tris[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)chromate (III), bis[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)manganate (IV), bis[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)cobaltate (III), and bis[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)nickelate (IV). Furthermore, two or more compounds that react with transition metal complexes (A) (for example, hafnium halide-type complex compounds) to form ion pairs can be used in combination.

[0105] (Organoaluminum oxy compounds) The organoaluminum oxy compound may be a conventionally known aluminoxane, or it may be a benzene-insoluble organoaluminum oxy compound as exemplified in Japanese Patent Publication No. 2-78687. Conventionally known aluminoxanes can be produced by methods such as those described below, and are usually obtained as solutions in a hydrocarbon solvent.

[0106] (1) A method of reacting the adsorbed water or crystal water with the organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to a suspension of a hydrocarbon medium containing a compound or salt containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, or cerium chloride hydrate.

[0107] (2) A method of directly reacting an organoaluminum compound such as trialkylaluminum with water, ice, or water vapor in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran.

[0108] (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene, or toluene.

[0109] The aluminoxane may contain small amounts of organometallic components. Alternatively, the recovered aluminoxane solution may be distilled to remove the solvent or unreacted organoaluminum compounds, and then redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

[0110] Specific examples of organoaluminum compounds used in the preparation of aluminoxanes include those similar to those exemplified as organoaluminum compounds represented by the general formula (8) above.

[0111] Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred. The organoaluminum compounds described above can be used individually or in combination of two or more. Aluminoxanes prepared from trimethylaluminum are called methylaluminoxanes or MAOs and are particularly commonly used compounds.

[0112] Solvents used in the preparation of aluminoxanes include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene, and diesel fuel; or halogenated compounds of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, particularly chlorinated and brominated hydrocarbon solvents. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferred.

[0113] Furthermore, the benzene-insoluble organoaluminum oxy compounds used in the present invention have an Al component that dissolves in benzene at 60°C, typically 10% or less, preferably 5% or less, and particularly preferably 2% or less in terms of Al atoms, and are insoluble or sparingly soluble in benzene. Examples of organoaluminum oxy compounds used in the present invention include organoaluminum oxy compounds containing boron represented by the following general formula (12).

[0114] [ka] (In the formula, R c R represents a hydrocarbon group with 1 to 10 carbon atoms. d These may be the same or different atoms, and represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.

[0115] The boron-containing organoaluminum oxy compound represented by the above general formula (12) can be produced by reacting an alkylboronic acid represented by the following general formula (13) with an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of -80°C to room temperature for 1 minute to 24 hours.

[0116] R c B(OH)2…(13) (In the formula, R c (This indicates the same base as above.)

[0117] Specific examples of alkylboronic acids represented by the general formula (13) above include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, and 3,5-bis(trifluoromethyl)phenylboronic acid. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These can be used individually or in combination of two or more.

[0118] Specific examples of organoaluminum compounds to be reacted with such alkylboronic acids include organoaluminum compounds similar to those exemplified as organoaluminum compounds represented by general formula (6) or (7) above.

[0119] The organoaluminum oxy compounds used in this invention can be used individually or in combination of two or more. Among the organoaluminum compounds described above, organoaluminum oxy compounds can be cited as suitable compounds.

[0120] In addition to the boron compounds and organoaluminum oxy compounds mentioned above, the organometallic compound (B) can also be mentioned. This organometallic compound (B) may be used in combination with the boron compounds and organoaluminum oxy compounds mentioned above.

[0121] [Other components used in the reaction] In the present invention, the polymerization reaction can usually be carried out in a hydrocarbon medium. Specific examples of such hydrocarbon mediums include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane; and petroleum fractions such as gasoline, kerosene, and diesel fuel. Furthermore, olefins can also be used for polymerization. In addition, known components useful in polymerization reactions may be used in combination. For example, fluorine-containing compounds (such as alcohol-based compounds) can be used.

[0122] [Olefin] The olefin used in the olefin polymerization of the present invention is essential for ethylene. Other examples of α-olefins include linear or branched α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and vinylcyclohexane. Linear or branched α-olefins having 3 to 10 carbon atoms are preferred as α-olefins, with propylene, 1-butene, 1-hexene, and 1-octene being more preferred. When the resulting polymer is used for applications such as lubricants, olefins with a small number of carbon atoms, such as ethylene and propylene, are preferred from the viewpoint of shear stability. On the other hand, for applications such as modifiers to improve the impact resistance of resins, olefins with a relatively large number of carbon atoms, such as 1-butene, 1-hexene, 1-octene, and 1-decene, are preferred. These olefins can be used individually or in combination of two or more.

[0123] In the present invention, copolymerization may be carried out using other copolymerizable olefinic monomers in addition to ethylene and α-olefins. Examples of such olefinic monomers include polyenes, vinyl aromatic compounds, vinyl alicyclic compounds, and cyclic olefins.

[0124] Examples of polyenes include 1,4-hexadiene, 1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,7-nonadien, 1,8-nonadien, 1,8-decadien, 1,9-decadien, 1,12-tetradecadien, 1,13-tetradecadien, 3-methyl-1,4-hexadiene, and 3-methyl-1,5 -Hexadiene, 3-ethyl-1,4-hexadiene, 3-ethyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,3-dimethyl-1,5-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 2,5-norbornadiene, 7-methyl-2,5-norbornadiene, 7-ethyl-2,5-norbornadiene Bornadiene, 7-propyl-2,5-norbornadiene, 7-butyl-2,5-norbornadiene, 7-pentyl-2,5-norbornadiene, 7-hexyl-2,5-norbornadiene, 7,7-dimethyl-2,5-norbornadiene, 7,7-methylethyl-2,5-norbornadiene, 7-chloro-2,5-norbornadiene, 7-bromo-2,5-norbornadiene Examples include 7-fluoro-2,5-norbornadiene, 7,7-dichloro-2,5-norbornadiene, 1-methyl-2,5-norbornadiene, 1-ethyl-2,5-norbornadiene, 1-propyl-2,5-norbornadiene, 1-butyl-2,5-norbornadiene, 1-chloro-2,5-norbornadiene, and 1-bromo-2,5-norbornadiene. Furthermore, the following compounds with the following structures can also be cited as polyenes.

[0125] [ka]

[0126] One or more polyenes are used, preferably 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinylnorbornene, and norbornadiene. Examples of vinyl aromatic compounds include styrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene. Examples of vinyl alicyclic compounds include vinylcyclohexane, vinylcycloheptane, and vinylcyclooctane. Examples of cyclic olefins include cyclohexene and 2-norbornene.

[0127] In this invention, hydrogen is typically used as a molecular weight modifier to adjust the molecular weight of the resulting polymer. Hydrogen is supplied to the reaction apparatus together with ethylene.

[0128] [Olefin polymer] The olefin polymer produced by the manufacturing method of the present invention can also be used as a main component or modifier for molded articles that can be produced by known methods such as injection molding, extrusion molding, inflation molding, and calendering.

[0129] The degree of long-chain branching of the olefin polymer obtained by the method for producing olefin polymers of the present invention is as follows: 10 The ratio of I² to I² (I 10 The indicator is (I2). I 10 : Melt flow rate measured at 190°C under a 10 kg load, in accordance with the ASTM D1238 standard. I2: Melt flow rate measured at 190°C under a 2.16 kg load, in accordance with ASTM D1238 standard. The above I2 is an indicator similar to the value generally referred to as the melt flow rate of olefin polymers.

[0130] Polymers with a high degree of long-chain branching tend to have higher molten resin flowability under high load conditions because their long-chain branches intertwine with adjacent polymer chains, but this effect is relatively smaller under low load conditions. For this reason, the above I 10 / I2 is useful as an indicator of the degree of branching in long chains. (I 10 A higher I2 value indicates a greater number of long-chain branches.

[0131] In the method for producing olefin polymers of the present invention, I 10 The present invention is characterized by producing an olefin polymer with an I2 value of 4 to 10. As described above, in the method of the present invention, by adjusting the polymerization pressure, the above I 10 It is possible to selectively produce olefin polymers over a wide range of I2 values. 10 Polymers with a high / I2 value have a high degree of long-chain branching and excellent moldability, making films such as food packaging materials a suitable example of an application. On the other hand, the above I 10 Polymers with a low / I2 value are highly linear polymers with excellent strength, making them suitable for applications requiring high strength, such as packaging materials for heavy items like rice bags.

[0132] The present invention's method for producing olefin polymers enables the production of polymers with a wide range of long-chain branching degrees by adjusting the polymerization pressure, thus eliminating the need to change catalysts and allowing for efficient implementation.

[0133] When the polymer obtained by the olefin polymer production method of the present invention is used as a modifier or the like, the melt flow rate (MFR) of the polymer is not particularly limited, but is preferably in the range of 0.01 to 1000 g / 10 min, more preferably 0.1 to 500 g / 10 min, even more preferably 0.1 to 200 g / 10 min, even more preferably 0.1 to 100 g / 10 min, and particularly preferably 0.1 to 50 g / 10 min. It is also preferable that the MFR of the olefin polymer be 2.0 or higher.

[0134] In this invention, the above-mentioned MFR is measured at 190°C and under a 2.16 kg load, according to the ASTM D1238 standard method as described above. The polymer described above is an ethylene-based copolymer obtained by copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms as needed, and preferably contains 60 or more, more preferably 65 mol%, and even more preferably 70 or more structural units derived from ethylene. The upper limit for structural units derived from ethylene is, of course, 100 mol%. When copolymerization with an α-olefin having 3 to 20 carbon atoms is essential, the upper limit is preferably 98 mol%, more preferably 95 mol%, even more preferably 90 mol%, and particularly preferably 85 mol%. With such a composition, it can be suitably used in various applications such as a modifier. [Examples]

[0135] The present invention will be described in more detail below based on examples, but the present invention is not limited in any way to these examples.

[0136] [Examples 1-8, Comparative Examples 1-4] The copolymerization of ethylene and 1-butene was carried out using the method described below. Two transition metal complex solutions were used, prepared at 10 hours and 48 hours after preparation. There was no change in operating performance, and polymers with the physical properties described later were obtained with stable activity.

[0137] (Continuous polymerization method) Polymerization of ethylene and 1-octene was carried out using a 100L pressure reactor with a stirring blade and a temperature-controllable jacket, equipped with a compressor and valve line for circulating unreacted gas (sometimes called a circulation line), an n-hexane feed line, a feed line for source gases (ethylene and hydrogen), a 1-octene feed line, a catalyst feed line (transition metal complex, triphenylcarbeniumtetrakis(pentafluorophenyl)borate (sometimes called a boron co-catalyst in this specification)), and a content (product) extraction line. In this setup, the ethylene and hydrogen feed line was connected to the circulation line mentioned above.

[0138] The continuous polymerization conditions at the steady state stage and the properties of the resulting polymer are shown in Table 1. The common conditions for continuous polymerization are as follows: Polymerization temperature: 125℃ n-hexane: 16 L / hour Maintain reaction liquid volume of 28L. Production speed: 8 kg / hour

[0139] Hafnium complex: A compound with the following structural formula.

[0140] [ka] Zirconium complex: di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride

[0141] [Table 1-1]

[0142] [Table 1-2]

[0143] As shown in the above results, the results of the examples show that in ethylene / 1-octene copolymerization using a hafnium complex, the ethylene partial pressure is greater than in the comparative example. 10 The variation in / I2 is large, and the I of the polymer obtained depends on the polymerization pressure. 10 It is clear that / I2 is easy to control.

Claims

1. Long-chain branching index of olefin polymers (I 10 / I 2 ) is a method for adjusting, When polymerizing ethylene-containing olefins in the presence of transition metal complexes of Groups 3 to 10 of Periods 6 and 7 of the Periodic Table, as represented by the following formula [A3], By adjusting the partial pressure of the olefin gas, which is made of ethylene as an essential component and any olefin having 3 to 4 carbon atoms, within the range of 0.9 to 6 MPa (gauge pressure), The aforementioned long chain branching index (I 10 / I 2 Adjust the value between 4 and 10. A method for adjusting the long-chain branching index of olefin gases by adjusting their partial pressure. (I 10 and the I 2 It is defined as follows: I 10 : Melt flow rate measured at 190°C under a 10 kg load, in accordance with the ASTM D1238 standard. I 2 (Melt flow rate measured at 190°C under a 2.16 kg load, in accordance with ASTM D1238 standard.) 【Chemistry 1】 [R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, and R14 are each independently a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silicon-containing group, and any two substituents from R1 to R4 may be bonded to each other to form a ring, any two substituents from R5 to R12 may be bonded to each other to form a ring, and R13 and R14 may be bonded to each other to form a ring. Y is a carbon atom, a silicon atom, a germanium atom, or a tin atom. M represents the transition metals of Groups 3 through 10 in Periods 6 and 7 of the periodic table. Q is a halogen atom. j is an integer between 1 and 4.

2. The preparation method according to claim 1, wherein the transition metal complex is a complex containing a transition metal of Group 4 to 5 of the periodic table.

3. The preparation method according to claim 1, wherein the transition metal complex is a complex containing hafnium.

4. The preparation method according to claim 1, wherein the polymerization of the olefin is carried out in an environment where the partial pressure is 1.0 to 4.0 MPa.

5. The preparation method according to claim 1, wherein the polymerization of the olefin is carried out in an environment with a temperature of 90 to 180°C.

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