Ethylene-non-conjugated polyene copolymer

Abstract

To obtain an ethylene-based polymer having a higher density while having a melting point (Tm) similar to that of an ethylene-α-olefin copolymer.SOLUTION: There is provided an ethylene-non-conjugated polyene copolymer (X) which contains a constituent unit (A) derived from ethylene and a constituent unit (B) derived from a non-conjugated polyene and satisfies all of the following requirements (1) to (5). (1) The content of the constituent unit derived from a non-conjugated polyene is in the range of 0.01 to 10 mol% [provided that the total of (A) and (B) is defined as 100 mol%]. (2) The intrinsic viscosity [η] measured in decalin at 135°C is in the range of 1.0 to 2.0 dl / g. (3) The density is in the range of 920 to 950 kg / m3. (4) The melting point (Tm) measured by DSC is in the range of 100 to 130°C. (5) P value [η*(ω=0.1) / η*(ω=100)] determined by melt viscoelasticity measurement is in the range of 5 to 100.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an ethylene-non-conjugated polyene copolymer that has a high melting point (Tm) and good mechanical strength, and is suitable for obtaining a molded article that is well-balanced between processability and mechanical strength. [Background technology]

[0002] Polyolefins (olefin polymers), such as polyethylene and polypropylene, require little energy to produce, are lightweight, and are highly recyclable, so they are attracting increasing attention in various industries as they work toward the 3Rs (Reduce, Reuse, Recycle) to create a recycling-oriented society. Polyolefins are used in a variety of fields, including daily necessities, kitchen utensils, packaging films, home appliances, machine parts, electrical parts, and automotive parts.

[0003] It is widely known that the density of polyethylene (ethylene polymer) can be adjusted by the amount of α-olefin copolymerized with ethylene (for example, Patent Document 1). By appropriately adjusting the amount of α-olefin copolymerized, the density of polyethylene can be adjusted to 875 to 970 kg / m 3 Amorphous ethylene-α-olefin copolymers with a wide range of densities, linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), and high-density polyethylene (HDPE), are manufactured and sold. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-197225 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to obtain an ethylene-based polymer having a melting point (Tm) equivalent to that of an ethylene-α-olefin copolymer and a high density. [Means for solving the problem]

[0006] The present invention relates to an ethylene-non-conjugated polyene copolymer (X) that contains a structural unit (A) derived from ethylene and a structural unit (B) derived from a non-conjugated polyene, and that satisfies all of the following requirements (1) to (5):

[0007] Ethylene-non-conjugated polyene copolymer (X) (1) The content of structural units derived from non-conjugated polyenes is in the range of 0.01 to 10 mol % (where the total of (A) and (B) is taken as 100 mol %). (2) The intrinsic viscosity [η] measured in decalin at 135°C is in the range of 1.0 to 2.0 dl / g. (3) Density: 920 to 950 kg / m 3 is in the range. (4) The melting point (Tm) measured by DSC is in the range of 100 to 130°C. (5) The P value [η*(ω=0.1) / η*(ω=100)] determined by melt viscoelasticity measurement is in the range of 5 to 100. [Effects of the Invention]

[0008] The ethylene-non-conjugated diene copolymer of the present invention has better processability (moldability) than polyethylene having a similar density, and the obtained molded articles have a high melting point (Tm) and good mechanical strength, resulting in an excellent balance between processability and mechanical strength. DETAILED DESCRIPTION OF THE INVENTION

[0009] <Ethylene-non-conjugated polyene copolymer (X)> The ethylene-non-conjugated polyene copolymer (X) of the present invention (hereinafter sometimes referred to as "copolymer (X)") is a copolymer mainly composed of ethylene that satisfies all of the following requirements (1) to (5):

[0010] Requirement (1) The content of structural units derived from non-conjugated polyenes is in the range of 0.01 to 10 mol %, preferably 0.05 to 8 mol % (where the total of (A) and (B) is taken as 100 mol %).

[0011] The non-conjugated polyene constituting the copolymer (X) of the present invention may be a cyclic or linear non-conjugated polyene. Examples of cyclic non-conjugated polyenes include 5-ethylidene-2-norbornene (ENB), dicyclopentadiene, 5-vinyl-2-norbornene (VNB), norbornadiene, and methyltetrahydroindene. Examples of linear non-conjugated polyenes include 1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene, and 4-ethylidene-1,7-undecadiene. These non-conjugated polyenes may be used alone or in combination.

[0012] Among these non-conjugated polyenes, ENB and VNB are preferred. Specific examples of the copolymer (X) of the present invention include ethylene-ENB copolymer, ethylene-VNB copolymer, ethylene-ENB-VNB copolymer, and the like.

[0013] The molar amount (mol %) of the copolymer (X) of the present invention is 1 The intensity was determined by measuring the intensity using a H-NMR spectrometer. Details of the measurement conditions are described in WO 2015 / 122415.

[0014] <Requirement (2)> The intrinsic viscosity [η] measured in decalin at 135° C. is in the range of 1.0 to 2.0 dl / g, preferably 1.4 to 1.7 dl / g. The copolymer (X) having an intrinsic viscosity [η] in the above range has excellent processability.

[0015] <Requirement (3)> Density: 920-950 kg / m 3 , preferably 930 to 940 kg / m3 The molded article obtained from the copolymer (X) having a density in the above range has excellent mechanical strength. The density of the copolymer (X) was measured in water at 23°C by a liquid weighing method in accordance with JIS Z8807:2012.

[0016] <Requirement (4)> The melting point (Tm) measured by DSC is in the range of 100 to 130° C., preferably 100 to 125° C. Molded articles obtained from the copolymer (X) having a melting point (Tm) in the above range have excellent mechanical strength.

[0017] The melting point (Tm) of the copolymer (X) was measured by the following method. Using a differential scanning calorimeter (DSC), approximately 5 mg of sample was sealed in an aluminum pan and heated from room temperature to 200°C at 10°C / min. The sample was then held at 200°C for 3 minutes to completely melt it. The sample was then cooled to 30°C at 10°C / min and held at 30°C for 3 minutes. The sample was then heated again to 230°C at 10°C / min. The peak temperature detected in the second heating test was taken as the melting point (Tm).

[0018] Requirement (5) The P value [η*(ω=0.1) / η*(ω=100)] determined by melt viscoelasticity measurement is in the range of 5-100, preferably 6-50, and more preferably 6-30.

[0019] The P value is an index of processability, and a copolymer (X) having a P value that satisfies the above range has high fluidity and high shape retention in a molten state in molding processes such as extrusion molding, injection molding, film molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendar molding, and foam molding.

[0020] The "complex viscosity η*" used to measure the P value in this invention was measured using an Ares viscoelasticity measuring device (manufactured by Rheometric Scientific) at 190°C and 1.0% strain, measuring the complex viscosity η*(ω=0.01) at a frequency of ω=0.1 rad / s, the complex viscosity η*(ω=0.1) at a frequency of ω=10 rad / s, and the complex viscosity η*(ω=100) at a frequency of ω=100 rad / s (all in units of Pa·sec). From the results obtained, the P value (η*(ω=0.1) / η*(ω=100)), which is the ratio (η* ratio) of the complex viscosities η*(ω=0.1) and η*(ω=100), was calculated.

[0021] The copolymer (X) of the present invention satisfies all of the above requirements (1) to (5), and therefore has good moldability and can give molded articles with excellent mechanical strength. The copolymer (X) of the present invention satisfies the above requirements (1) to (5) and also: The copolymer (X) of the present invention has a melt flow rate (MFR) measured in accordance with JIS K7210 at a temperature of 190°C and a load of 2.16 kg, which is usually in the range of 0.1 to 1.5 g / 10 min, preferably 0.2 to 1.0 g / 10 min.

[0022] <Method for producing ethylene-non-conjugated polyene copolymer (X)> The copolymer (X) of the present invention is a copolymer of ethylene and a non-conjugated polyene, which is a kind of metallocene compound, [bis(4-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride (metallocene compound (a)) in the presence of a polymerization catalyst system containing the compound (a).

[0023] <Polymerization catalyst containing metallocene compound (a)> Polymerization catalysts that can be suitably used in producing the copolymer (X) of the present invention include those that contain the above metallocene compound (a) and are capable of copolymerizing monomers.

[0024] Preferably, a polymerization catalyst composed of (a) a metallocene compound, (b) at least one compound selected from (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) a compound that reacts with the metallocene compound (a) to form an ion pair (hereinafter also referred to as an "ionizing ionic compound"), and further, if necessary, (c) a particulate carrier is exemplified. Hereinafter, each component will be specifically described.

[0025] <<Compound (b)>> The compound (b) is at least one compound selected from (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) an ionizing ionic compound, and preferably contains at least the organometallic compound (b-1).

[0026] (b-1) Organometallic compound As the organometallic compound (b-1), for example, organometallic compounds of Groups 1, 2, 12, and 13 of the periodic table represented by the following general formulas [VII] to [IX] are used.

[0027] (b-1a) General formula: R a m Al(OR b ) n H p X q ···[VII] (In formula [VII], 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.) An organoaluminum compound represented by.

[0028] Examples of such compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and tri-n-octylaluminum, tricycloalkylaluminums, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methylaluminum dichloride, dimethylaluminum chloride, and diisobutylaluminum hydride.

[0029] (b-1b) General formula: M 2 AlR a 4. [VIII] (In formula [VIII], M 2 indicates Li, Na, or K, and R a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4. A complex alkylation product of aluminum and a metal of Group 1 of the periodic table, represented by: Such compounds include LiAl(C2H5)4, LiAl(C7H 15 ) 4 can be exemplified.

[0030] (b-1c) General formula: R a R b M 3 [IX] (In formula [IX], R a and R b may be the same or different and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms; M 3 is Mg, Zn or Cd. Dialkyl compounds containing a metal of Group 2 or 12 of the periodic table represented by

[0031] Among the above organometallic compounds (b-1), organoaluminum compounds such as triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, etc. are preferred. These organometallic compounds (b-1) may be used singly or in combination of two or more.

[0032] (b-2) Organoaluminum oxy compounds The organoaluminum oxy compound (b-2) may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminum oxy compound such as those exemplified in JP-A No. 2-78687.

[0033] Conventionally known aluminoxanes can be produced, for example, by the following method, and are usually obtained as a solution in a hydrocarbon solvent. (1) A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of a compound containing adsorbed water or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, or cerous chloride hydrate, to react the adsorbed water or water of crystallization with the organoaluminum compound. (2) A method in which water, ice, or water vapor is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran. (3) A method in which an organoaluminum compound such as trialkylaluminum is reacted with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene, or toluene.

[0034] The aluminoxane may contain a small amount of an organometallic component. After the solvent or unreacted organoaluminum compound is removed by distillation from the recovered aluminoxane solution, the aluminoxane may be redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

[0035] Examples of organoaluminum compounds used in preparing aluminoxane include the same organoaluminum compounds as those exemplified as organoaluminum compounds belonging to the above (b-1a).

[0036] Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and among these, trimethylaluminum and triisobutylaluminum are particularly preferred. The organoaluminum compounds as described above may be used singly or in combination of two or more.

[0037] The benzene-insoluble organoaluminum oxy-compound (b-2) used in the present invention is preferably one in which the Al component dissolved in benzene at 60°C is usually 10% by weight or less, preferably 5% by weight or less, and particularly preferably 2% by weight or less, calculated as Al atoms, relative to 100% by weight of benzene. In other words, the benzene-insoluble organoaluminum oxy-compound is preferably one which is insoluble or poorly soluble in benzene.

[0038] The organoaluminum oxy compound (b-2) used in the present invention may also include boron-containing organoaluminum oxy compounds represented by the following general formula [X].

[0039] [ka] (In formula [X], R 1 represents a hydrocarbon group having 1 to 10 carbon atoms, and R 2 ~R 5 may be the same or different and represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.)

[0040] The boron-containing organoaluminum oxy compound represented by the general formula [X] is General formula: R 1 -B(OH)2 [XI] (In formula [XI], R 1 is R in the general formula [X] 1 The alkylboronic acid represented by the formula (I) is the same group as that represented by the formula (I). The alkylboronic acid can be produced by reacting an alkylboronic acid represented by the formula (I) 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.

[0041] Examples of the alkylboronic acid represented by the general formula [XI] 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.

[0042] Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred, and these may be used singly or in combination of two or more.

[0043] Examples of organoaluminum compounds to be reacted with such alkylboronic acids include the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the above (b-1a). Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferred. The organoaluminum oxy compounds (b-2) as described above may be used singly or in combination of two or more.

[0044] (b-3) Ionized ionic compounds Examples of the ionizable ionic compound (b-3) include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-T-1-501950, JP-T-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and US Pat. No. 5,321,106. Further examples include heteropoly compounds and isopoly compounds. Such ionizable ionic compounds (b-3) can be used singly or in combination of two or more.

[0045] Specific examples of Lewis acids include compounds represented by BR3 (R is fluorine or a phenyl group which may have a substituent such as fluorine, a methyl group, or a trifluoromethyl group), such as trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron, and tris(3,5-dimethylphenyl)boron.

[0046] The ionic compound may, for example, be a compound represented by the following general formula [XII].

[0047] [ka] (In formula [XII], R 1+ As for H + , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation containing a transition metal, etc. 2 ~R 5 may be the same or different and are organic groups, preferably aryl groups or substituted aryl groups.

[0048] Specific examples of the carbonium cation include tri-substituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

[0049] Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri(n-butyl)ammonium cation; N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and N,N,2,4,6-pentamethylanilinium cation; Examples include dialkylammonium cations such as di(isopropyl)ammonium cation and dicyclohexylammonium cation.

[0050] Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.

[0051] R 1+ As the cation, a carbonium cation, an ammonium cation, etc. are preferred, and a triphenylcarbonium cation, an N,N-dimethylanilinium cation, and an N,N-diethylanilinium cation are particularly preferred.

[0052] Examples of the ionic compound include trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

[0053] Specific examples of trialkyl-substituted ammonium salts include triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tri(n-butyl)ammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(N,N-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammonium tetra(3,5-ditrifluoromethylphenyl)boron, and tri(n-butyl)ammonium tetra(o-tolyl)boron.

[0054] Specific examples of N,N-dialkylanilinium salts include N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, and N,N,2,4,6-pentamethylanilinium tetra(phenyl)boron.

[0055] Specific examples of dialkylammonium salts include di(1-propyl)ammonium tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron, and the like.

[0056] Further examples of ionic compounds include triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, ferrocenium tetra(pentafluorophenyl)borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N,N-diethylanilinium pentaphenylcyclopentadienyl complex, and boron compounds represented by the following formula [XIII] or [XIV]: In the following formulas, Et represents an ethyl group.

[0057] [ka]

[0058] [ka]

[0059] Specific examples of the borane compound include decaborane; salts of anions such as 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; and 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).

[0060] Specific examples of the carborane compound include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane, and undecahydride-7,8-dimethyl-7,8 -Dicarbaundecaborane, Dodecahydride-11-methyl-2,7-dicarbaundecaborane, Tri(n-butyl)ammonium 1-carbadecaborate, Tri(n-butyl)ammonium-1-carbaundecaborate, 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 ) ammonium-6-carbadecaborate, tri(n-butyl)ammonium-7-carbaundecaborate, tri(n-butyl)ammonium-7,8-dicarbaundecaborate, tri(n-butyl)ammonium-2,9-dicarbaundecaborate, tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate salts of anions such as tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarboxundecaborate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicarboxundecaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarboxundecaborate, and tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carbaundecaborate; Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)ferrate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)nickelate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cuprate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)aurate(III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbandecaborate)ferrate salts of metal carborane anions such as salt (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarboxundecaborate)chromate(III), tri(n-butyl)ammonium bis(tribromooctahydride-7,8-dicarboxundecaborate)cobaltate(III), tris[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)chromate(III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)manganate(IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)cobaltate(III), and bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)nickelate(IV).

[0061] The heteropoly compound is composed of an atom selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten. Specifically, usable examples include phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanomolybdic acid, germanomolybdic acid, arsenic molybdic acid, tinmolybdic acid, phosphotungstic acid, germanotungstic acid, tintungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdotungstic acid, phosphomolybdoniobic acid, and salts of these acids, such as salts with metals of Group 1 or 2 of the periodic table, specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., and organic salts such as triphenylethyl salts.

[0062] Among the ionizing ionic compounds (b-3), the above-mentioned ionic compounds are preferred, and among them, triphenylcarbenium tetrakis(pentafluorophenyl)borate and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate are more preferred.

[0063] In the present invention, when a metallocene catalyst containing the above metallocene compound (a), an organometallic compound (b-1) such as triisobutylaluminum, an organoaluminum oxy compound (b-2) such as methylaluminoxane, and an ionizing ionic compound (b-3) such as triphenylcarbenium tetrakis(pentafluorophenyl)borate is used as the polymerization catalyst, extremely high polymerization activity can be exhibited in the production of the copolymer (X).

[0064] (c) Particulate carrier In the present invention, the particulate carrier (c) used as needed is an inorganic or organic compound, and is a granular or fine particle solid.

[0065] The inorganic compound is preferably a porous oxide, an inorganic halide, a clay, a clay mineral, or an ion-exchangeable layered compound, specific examples of which include those described in WO2015 / 122495.

[0066] The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as is, or may be used after treatment such as ball milling or sieving. They may also be used after newly adding and adsorbing water or after heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more.

[0067] Of these, clay or clay minerals are preferred, and montmorillonite, vermiculite, hectorite, taeniolite and synthetic mica are particularly preferred. Examples of organic compounds include granular or particulate solids with particle sizes in the range of 10 to 300 μm. Specific examples include (co)polymers mainly composed of α-olefins having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, and (co)polymers mainly composed of vinylcyclohexane and styrene, and modified products thereof.

[0068] The polymerization catalyst used in the present invention comprises a metallocene compound (a), at least one compound (b) selected from an organometallic compound (b-1), an organoaluminum oxy compound (b-2), and an ionizing ionic compound (b-3), a carrier (c) used as needed, and may further contain a specific organic compound component (d) as needed.

[0069] (d) Organic compound component In the present invention, the organic compound component (d) is used as needed to improve the polymerization performance and the physical properties of the resulting polymer. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

[0070] <Production method and conditions for copolymer (X)> The copolymer (X) of the present invention is produced by copolymerizing ethylene and a non-conjugated polyene. When copolymerizing such monomers, the method of use and order of addition of the components constituting the polymerization catalyst described above can be selected arbitrarily, and examples thereof include the following methods (1) to (5). (1) A method in which the metallocene compound (a) is added alone to a polymerization reactor. (2) A method in which the metallocene compound (a) and the compound (b) are added to a polymerization reactor in any order. (3) A method in which a catalyst component in which a metallocene compound (a) is supported on a carrier (c) and a compound (b) are added to a polymerization reactor in any order. (4) A method in which the catalyst component in which the compound (b) is supported on the carrier (c) and the metallocene compound (a) are added to a polymerization reactor in any order. (5) A method in which a catalyst component in which a metallocene compound (a) and a compound (b) are supported on a carrier (c) is added to a polymerization reactor.

[0071] In each of the above methods (2) to (5), at least two of the metallocene compound (a), the compound (b) and the support (c) may be contacted in advance. In the above methods (4) and (5) in which the compound (b) is supported, an unsupported compound (b) may be added in any order, if necessary. In this case, the compound (b) may be the same as or different from the compound (b) supported on the support (c).

[0072] In addition, the solid catalyst component in which the metallocene compound (a) is supported on the support (c) and the solid catalyst component in which the metallocene compound (a) and the compound (b) are supported on the support (c) may be prepolymerized with an olefin, or the prepolymerized solid catalyst component may further have a catalyst component supported thereon.

[0073] The copolymer (X) of the present invention can be suitably obtained by copolymerizing ethylene and a non-conjugated polyene in the presence of the above-mentioned polymerization catalyst. When polymerizing ethylene and a non-conjugated polyene using the above polymerization catalyst, the metallocene compound (a) is usually used in an amount of 10 -12 ~10 -2 moles, preferably 10 -10 ~10 -8 It is used in molar amounts.

[0074] Compound (b-1) is used in an amount such that the molar ratio of compound (b-1) to the total transition metal atoms (M) in metallocene compound (a) [(b-1) / M] is usually 0.01 to 50,000, preferably 0.05 to 10,000. Compound (b-2) is used in an amount such that the molar ratio of aluminum atoms in compound (b-2) to the total transition metal atoms (M) in metallocene compound (a) [(b-2) / M] is usually 10 to 50,000, preferably 20 to 10,000. Compound (b-3) is used in an amount such that the molar ratio of compound (b-3) to the transition metal atoms (M) in metallocene compound (a) [(b-3) / M] is usually 1 to 20, preferably 1 to 15.

[0075] In the present invention, the method for producing the copolymer (X) can be carried out by any of a liquid phase polymerization method such as solution (dissolution) polymerization or suspension polymerization, or a gas phase polymerization method, and is not particularly limited, but preferably includes a step of obtaining the following polymerization reaction liquid.

[0076] The step of obtaining a polymerization reaction liquid is a step of copolymerizing ethylene and a non-conjugated polyene in the presence of the metallocene compound (a) using an aliphatic hydrocarbon as a polymerization solvent to obtain a polymerization reaction liquid of copolymer (X).

[0077] Examples of polymerization solvents include aliphatic hydrocarbons and aromatic hydrocarbons. Specific examples 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; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. These solvents can be used alone or in combination of two or more. Olefins themselves can also be used as solvents. Among these, hexane is preferred from the viewpoint of separation and purification from the resulting copolymer (A).

[0078] The polymerization temperature is usually −50 to +200° C., preferably in the range of 0 to +150° C., and more preferably in the range of +70 to +110° C. Although it depends on the attained molecular weight and polymerization activity of the metallocene catalyst system used, a higher temperature (+70° C. or higher) is desirable from the viewpoints of catalytic activity, copolymerizability, and productivity.

[0079] The polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably 1.1 to 5 MPa gauge pressure, more preferably 1.2 to 2.0 MPa gauge pressure, and the polymerization reaction can be carried out by any of batch, semi-continuous, and continuous methods. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions. Among these, in the present invention, it is preferable to adopt a method in which ethylene and a non-conjugated polyene are continuously supplied to a reactor to carry out copolymerization.

[0080] The reaction time (average residence time when copolymerization is carried out by a continuous method) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours, and more preferably 10 minutes to 2 hours.

[0081] The molecular weight of the resulting copolymer (X) can be adjusted by adding hydrogen to the polymerization system or by changing the polymerization temperature. Furthermore, it can also be adjusted by the amount of compound (b) used. Specific examples include triisobutylaluminum, methylaluminoxane, and diethylzinc. When hydrogen is added, the amount is preferably about 0.001 to 100 nL per kg of olefin.

[0082] The present invention preferably comprises, after the step (1) of copolymerizing in the presence of the polymerization catalyst, a step (2) of deactivating the polymerization catalyst by adding a catalyst deactivator. As the catalyst deactivator, alcohols can be used, and methanol or ethanol is preferred, with ethanol being particularly preferred.

[0083] In step (2), the catalyst deactivator is preferably added in an amount of 0.05 to 3.0 mol times, more preferably 0.06 to 2.5 mol times, and even more preferably 0.08 to 2.0 mol times the amount of the organometallic compound (b-1). This allows for the generation of a small amount of catalyst denatured by the catalyst deactivator, such as ethanol, and moderate polymerization of low molecular weight components, resulting in a copolymer (X) with a moderately broad molecular weight distribution. On the other hand, if too much catalyst deactivator is added, almost no denatured catalyst is generated, and almost no polymerization of low molecular weight components occurs, resulting in a narrow molecular weight distribution of the resulting copolymer (X). Furthermore, if no catalyst deactivator is added, or if too little is added, a large amount of denatured catalyst is generated, resulting in the polymerization of a large amount of low molecular weight components, resulting in a copolymer (X) with an excessively high content of low molecular weight components.

[0084] <Applications of ethylene-non-conjugated polyene copolymer (X)> The copolymer (X) of the present invention can be used for various known molded articles. If necessary, the copolymer (X) of the present invention may contain various additives commonly used in polyolefins, such as heat stabilizers, weather stabilizers, ultraviolet absorbers, light stabilizers, inorganic fillers such as talc, calcium carbonate, metal powder, titanium oxide and zinc oxide, waxes, lubricants, slip agents, nucleating agents, antiblocking agents, antistatic agents, antifogging agents, pigments, dyes, dispersants, flame retardants, flame retardant aids, plasticizers and compatibilizers, within the range that does not impair the object of the present invention.

[0085] <Molded body> The molded article of the present invention contains the copolymer (X) of the present invention. Specific examples of the method for producing the molded article (molding method) include conventionally known polyolefin molding methods, such as known thermoforming methods such as extrusion molding, injection molding, film molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendar molding, and foam molding.

[0086] The molded article made of the copolymer (X) of the present invention also has excellent mechanical properties. Specific examples of molded articles include a wide range of applications, from household goods for daily necessities and recreational use to general industrial and industrial products, including home appliance parts, communication device parts, electrical parts, electronic parts, automobile parts, other vehicle parts, ship and aircraft materials, machine mechanism parts, building materials, civil engineering materials, agricultural materials, power tool parts, food containers, films, sheets, and fibers. [Example]

[0087] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. The symbols (a) to (w) shown in Examples 1 to 3 represent the amounts of each unit shown in Table 1 below.

[0088] Examples 1 to 3 Dehydrated and purified n-hexane (C6) was fed into one feed port of a 136 L continuous polymerization reactor at a rate of (a) L / h, and [bis(4-methylphenyl)methylene (η 5-cyclopentadienyl)(η 5 A hexane solution of (b) mmol / L (4 mmol / L) of [(2-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride (ZD) was continuously fed at a rate of (c) L / h, a hexane solution of triisobutylaluminum (4 mmol / L) was continuously fed at a rate of (d) L / h, a hexane slurry of triphenylcarbenium tetrakis(pentafluorophenyl)borate (CB-3) was continuously fed at a rate of (e) mmol / L (f) L / h, VNB was continuously fed at a rate of (g) g / h, and ENB was continuously fed at a rate of (h) g / h [total hexane (T-C6): (i) L / h]. Simultaneously, ethylene (C2") was continuously fed at a rate of (j) kg / h and hydrogen was continuously fed at a rate of (k) NL / h to another feed inlet of the polymerization reactor. Continuous solution polymerization was carried out under the conditions of a polymerization temperature of 1°C, a total pressure of (m) MPaG, and a residence time of (n) min.

[0089] The hexane solution of ethylene-non-conjugated polyene copolymer (X) produced in the polymerization reactor was continuously discharged through an outlet provided on the side wall of the polymerization reactor, and the pressure in the jacket was 8 kg / cm 2 The hexane solution of ethylene-non-conjugated polyene copolymer (X) heated to about 170°C in the steam-jacketed connecting pipe was maintained at a liquid level of 10 kg / cm by adjusting the opening of the liquid level control valve installed at the end of the connecting pipe so as to maintain the solution volume in the polymerization vessel at about 28 L. 2 The liquid was continuously fed to the flash tank through the inner pipe of a double pipe heated with steam. A supply port for injecting methanol, a catalyst deactivator, was attached immediately after the liquid level control valve, and methanol was injected as a 1.0 vol% diluted hexane solution at a rate of 12 L / h to join the hexane solution. During transfer to the flash tank, the solution temperature and the pressure control valve opening were set so that the pressure inside the flash tank was maintained at 0.05 MPaG and the temperature of the vapor in the flash tank was maintained at 180°C.

[0090] As a result, ethylene-non-conjugated polyene copolymer (X) was obtained at a production rate of (p) kg / h. The polymerization mileage of ethylene-non-conjugated polyene copolymer (X) was (q) kg / mmol-Zr, the [η] of ethylene-non-conjugated polyene copolymer (X) was (r) dl / g, the MFR was (s) g / 10 min, the melting point (Tm) was (t) °C, and the density was (u) kg / m 3 The content of VNB was (v) mol% (mol %), and the content of ENB was (w) mol% (mol %).

[0091] The physical properties of the polymers obtained in the examples and reference examples were measured by the following methods. (1) Tensile properties The sheet was press-molded to prepare a 4 mm thick sheet, and a type 1B test piece was punched out from the sheet, and the tensile yield stress, tensile breaking strain, and tensile breaking stress were measured in accordance with JIS K7161 and JIS K7162. (2) Durometer hardness (D hardness) A 4 mm thick sheet was prepared by press molding, and a Type 1B test piece was punched out, and the D hardness was measured in accordance with JIS K7215.

[0092] [Reference example 1] The linear low-density polyethylene (LLDPE) used was an ethylene-1-hexene copolymer (UltZex 2022F, manufactured by Prime Polymer Co., Ltd.) (UZ2022F). The results are shown in Table 1.

[0093] [Table 1]

[0094] As is clear from Table 1, the ethylene-non-conjugated polyene copolymers (X) shown in Examples 1 to 3 have larger P values, higher fluidity during molding, and better shape retention in a molten state than the LLDPE shown in Reference Example. Furthermore, the ethylene-non-conjugated polyene copolymers (X) shown in Examples 1 to 3 have larger P values ​​and therefore higher tensile stress at break than the LLDPE shown in Reference Example, despite having melting points (Tm) equal to or lower than those of the LLDPE shown in Reference Example.

Claims

1. A method for producing an ethylene-non-conjugated polyene copolymer (X), comprising: copolymerizing ethylene and a non-conjugated polyene in the presence of a polymerization catalyst system comprising [bis(4-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride; The ethylene / non-conjugated polyene copolymer (X) comprises a structural unit (A) derived from ethylene and a structural unit (B) derived from a non-conjugated polyene, and is characterized in that it satisfies all of the following requirements (1) to (5): A method for producing an ethylene-non-conjugated polyene copolymer (X). (1) The content of structural units derived from non-conjugated polyenes is in the range of 0.01 to 10 mol % (where the total of (A) and (B) is taken as 100 mol %). (2) The intrinsic viscosity [η] measured in decalin at 135°C is in the range of 1.0 to 2.0 dl / g. (3) Density is 920 to 950 kg / m 3 is in the range. (4) The melting point (Tm) measured by DSC is in the range of 100 to 130°C. (5) The P value [η*(ω=0.1) / η*(ω=100)] determined by melt viscoelasticity measurement at 190°C is in the range of 5 to 100.

2. 2. The method for producing copolymer (X) according to claim 1, wherein the non-conjugated polyene of the ethylene-non-conjugated polyene copolymer (X) is selected from the group consisting of 5-vinyl-2-norbornene and 5-ethylidene-2-norbornene.

3. 3. The method for producing copolymer (X) according to claim 1 or 2, wherein the ethylene-non-conjugated polyene copolymer (X) has a content of structural units derived from an α-olefin having 3 or more carbon atoms of 1.0 mol % or less.

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