JP2023091322A - Ethylene-non-conjugated polyene copolymer - Google Patents

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 The present invention relates to an ethylene/non-conjugated polyene copolymer which has a high melting point (Tm), good mechanical strength, and is suitable for obtaining a molded article having an excellent balance between workability and mechanical strength.

Polyolefins (olefin polymers) represented by polyethylene and polypropylene require little energy for production, are lightweight, and have excellent recyclability. Reuse, Recycle) is gaining more attention. Polyolefins are used in various fields such as daily necessities, kitchen utensils, packaging films, home electric appliances, machine parts, electric parts, and automobile parts.

It is widely known that the density of polyethylene (ethylene-based polymer) can be adjusted by the amount of α-olefin copolymerized with ethylene (for example, Patent Document 1). Amorphous ethylene/α-olefin copolymer, linear low density polyethylene ( ^LLDPE ), medium density polyethylene (MDPE) and High density polyethylene (HDPE) is manufactured and sold.

JP 2009-197225 A

An object of the present invention is to obtain an ethylene polymer having a high density while having a melting point (Tm) equivalent to that of an ethylene/α-olefin copolymer.

The present invention includes a structural unit (A) derived from ethylene and a structural unit (B) derived from a non-conjugated polyene, and is characterized by satisfying all of the following requirements (1) to (5). It relates to a conjugated polyene copolymer (X).

Ethylene/non-conjugated polyene copolymer (X)
(1) The content of structural units derived from non-conjugated polyene is in the range of 0.01 to 10 mol % [provided that the total of (A) and (B) is 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 in the range of 920-950 kg/m ³ .
(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 5-100.

The ethylene/non-conjugated diene copolymer of the present invention has better processability (moldability) than polyethylene having a similar density, and the resulting molded article has a high melting point (Tm) and mechanical strength. and excellent balance between workability and mechanical strength.

<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 an ethylene-based copolymer that satisfies all of the following requirements (1) to (5).

<Requirement (1)>
The content of structural units derived from non-conjugated polyene is in the range of 0.01 to 10 mol%, preferably 0.05 to 8 mol% [provided that the total of (A) and (B) is 100 mol%]. It is in.

A cyclic or chain non-conjugated polyene is used as the non-conjugated polyene constituting the copolymer (X) of the present invention. Cyclic non-conjugated polyenes include, for example, 5-ethylidene-2-norbornene (ENB), dicyclopentadiene, 5-vinyl-2-norbornene (VNB), norbornadiene, and methyltetrahydroindene. Examples of linear non-conjugated polyene include 1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene, 4-ethylidene-1,7-undecadiene. etc. These non-conjugated polyenes may be used alone or in combination of two or more.

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

The molar amount (mol %) in the copolymer (X) of the present invention was determined by intensity measurement with a ¹ H-NMR spectrometer. Details of the measurement conditions are described in International Publication No. 2015/122415.

<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 the intrinsic viscosity [η] within the above range is excellent in workability.

<Requirement (3)>
The density is in the range of 920-950 kg/m ³ , preferably 930-940 kg/m ³ . A molded article obtained from the copolymer (X) having a density within the above range has excellent mechanical strength.
The density of the copolymer (X) was measured in water at 23°C by the submerged weighing method according to JIS Z8807:2012.

<Requirement (4)>
The melting point (Tm) measured by DSC is in the range of 100 to 130°C, preferably 100 to 125°C. A molded article obtained from the copolymer (X) having a melting point (Tm) within the above range has excellent mechanical strength.

The melting point (Tm) of copolymer (X) was measured by the following method.
Using a differential scanning calorimeter (DSC), seal approximately 5 mg of sample in an aluminum pan, heat from room temperature to 200° C. at 10° C./min, and hold the sample at 200° C. for 3 minutes for complete melting. bottom. It was then cooled to 30°C at 10°C/min and held at 30°C for 3 minutes before heating the sample again to 230°C at 10°C/min. The peak temperature detected in the second heating test was taken as the melting point (Tm).

<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, more preferably 6-30.

The P value is an index of workability, and the copolymer (X) having the P value satisfying the above range can be used for extrusion molding, injection molding, film molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press It has high fluidity in molding processes such as molding, vacuum molding, powder slush molding, calendar molding, and foam molding, and has high shape retention in a molten state.

The "complex viscosity η*" for measuring the P value in the present invention is obtained by using a viscoelasticity measuring device Ares (manufactured by Rheometric Scientific) as a rheometer under the conditions of 190 ° C. and strain of 1.0%, frequency ω = 0 Complex viscosity η*(ω=0.01) at frequency ω=0.01 rad/s Complex viscosity η*(ω=0.1) at frequency ω=0.1 rad/s Complex viscosity η*(ω = 10) and complex viscosity η* (ω = 100) at frequency ω = 100 rad/s (both units are Pa·sec). In addition, from the obtained results, P value (η*(ω=0.1)/η*( ω=100)) is calculated.

When the copolymer (X) of the present invention satisfies all of the above requirements (1) to (5), it is possible to obtain a molded article having good moldability and excellent mechanical strength.
The copolymer (X) of the present invention, in addition to the above requirements (1) to (5),
The copolymer (X) of the present invention has a melt flow rate (MFR) measured at a temperature of 190° C. and a load of 2.16 kg according to JIS K7210, which is usually 0.1 to 1.5 g/10 minutes. , preferably in the range of 0.2 to 1.0 g/10 min.

<Method for producing ethylene/non-conjugated polyene copolymer (X)>
[Bis(4-methylphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -octamethyl octahydrodibenzofluorenyl)]zirconium dichloride (metallocene compound (a)) by copolymerization in the presence of a polymerization catalyst system.

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

Preferably, (a) a metallocene compound, (b) (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) the metallocene compound (a) react to form an ion pair (hereinafter also referred to as "ionized ionic compound") and, if necessary, (c) a particulate carrier. Each component will be specifically described below.

<<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 ionized ionic compound, preferably at least It contains the organometallic compound (b-1).

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

(b-1a) General formula: _{R am} ^Al (OR ^b ) _n H _p X _q [VII]
(In formula [VII], R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is 0<m≦3, n is 0≦n<3, p is 0≦p<3, q is a number satisfying 0≦q<3, and m+n+p+q=3). Compound.

Such compounds include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, tricycloalkylaluminum, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methyl Examples include aluminum dichloride, dimethylaluminum chloride, and diisobutylaluminum hydride.

(b-1b) General formula: M ² AlR ^a ₄ [VIII]
(In the formula [VIII], M ² represents Li, Na or K, and R ^a is a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms.) Complex alkylates of Group 1 metals and aluminum.
Examples of such compounds include LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ .

(b-1c) General formula: R ^a R ^b M ³ [IX]
(In the formula [IX], R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd.).

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

(b-2) Organoaluminumoxy Compound The organoaluminumoxy compound (b-2) may be a conventionally known aluminoxane, or a benzene-insoluble organic compound as exemplified in JP-A-2-78687. It may be an aluminum oxy compound.

Conventionally known aluminoxanes can be produced, for example, by the following method, and are usually obtained as a solution in a hydrocarbon solvent.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerous chloride hydrate, etc. A method of adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension of (1) and reacting the adsorbed water or water of crystallization with the organoaluminum compound. (2) A method in which water, ice or steam is directly acted on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(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.

In addition, the aluminoxane may contain a small amount of organometallic components. Alternatively, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered aluminoxane solution, and then redissolved in the solvent or suspended in a poor solvent for the aluminoxane.

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

Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum and triisobutylaluminum are particularly preferred.
The above organoaluminum compounds may be used singly or in combination of two or more.

In the benzene-insoluble organoaluminumoxy compound, which is one embodiment of the organoaluminumoxy compound (b-2) used in the present invention, the Al component dissolved in benzene at 60° C. is Usually 10% by weight or less, preferably 5% by weight or less, particularly preferably 2% by weight or less, that is, those that are insoluble or sparingly soluble in benzene are preferred.

Examples of the organoaluminumoxy compound (b-2) used in the present invention include an organoaluminumoxy compound containing boron represented by the following general formula [X].

（式［Ｘ］中、Ｒ¹は炭素原子数が１～１０の炭化水素基を示し、Ｒ²～Ｒ⁵は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数が１～１０の炭化水素基を示す。）

(In formula [X], R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms; R ² to R ⁵ may be the same or different; 1 to 10 hydrocarbon groups are shown.)

The organoaluminumoxy compound containing boron represented by the general formula [X] is
General formula: R ¹ -B(OH) ₂ [XI]
(In the formula [XI], R ¹ represents the same group as R ¹ in the general formula [X].) and an organoaluminum compound were placed in an inert solvent in an inert gas atmosphere. It can be produced by reacting at a temperature of −80° C. to room temperature for 1 minute to 24 hours.

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, and cyclohexylboronic acid. , phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, 3,5-bis(trifluoromethyl)phenylboronic acid and the like.

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

Examples of the organoaluminum compound to be reacted with such an alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to (b-1a) above. Among these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable.
The organoaluminumoxy compound (b-2) as described above may be used alone or in combination of two or more.

(b-3) Ionized ionic compound As the ionized ionic compound (b-3), JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-H9 3-179006, JP-A-3-207703, JP-A-3-207704, USP5321106, Lewis acids, ionic compounds, borane compounds and carborane compounds. In addition, heteropolycompounds and isopolycompounds may also be mentioned. Such ionized ionic compounds (b-3) may be used singly or in combination of two or more.

Specific examples of Lewis acids include compounds represented by BR ₃ (R is a phenyl group or fluorine optionally having a substituent such as fluorine, a methyl group and a trifluoromethyl group). , for example 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, tris(3,5-dimethylphenyl)boron and the like.

Examples of the ionic compound include compounds represented by the following general formula [XII].

（式［ＸＩＩ］中、Ｒ¹⁺としては、Ｈ⁺、カルボニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオン、遷移金属を有するフェロセニウムカチオンなどが挙げられる。Ｒ²～Ｒ⁵は、互いに同一でも異なっていてもよく、有機基、好ましくはアリール基または置換アリール基である。）

(In formula [XII], R ¹⁺ includes H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, and the like. ² to R ⁵ may be the same or different and are organic groups, preferably aryl groups or substituted aryl groups.)

Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

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 cations, N,N-diethylanilinium cations, N,N,2,4,6-pentamethylanilinium cations;
di(isopropyl)ammonium cations, dialkylammonium cations such as dicyclohexylammonium cations, and the like.

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

As R ¹⁺ , carbonium cations, ammonium cations, etc. are preferred, and triphenylcarbonium cations, N,N-dimethylanilinium cations, and N,N-diethylanilinium cations are particularly preferred.

Examples of ionic compounds include trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

Specific examples of trialkyl-substituted ammonium salts include triethylammoniumtetra(phenyl)boron, tripropylammoniumtetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammoniumtetra(p-tolyl) Boron, trimethylammoniumtetra(o-tolyl)boron, tri(n-butyl)ammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammoniumtetra( N,N-dimethylphenyl)boron, tri(n-butyl)ammoniumtetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammoniumtetra(3,5-ditrifluoromethylphenyl)boron, tri(n -butyl)ammoniumtetra(o-tolyl)boron and the like.

Specific examples of N,N-dialkylanilinium salts include N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron, N,N,2,4,6 -pentamethylanilinium tetra(phenyl)boron and the like.

Specific examples of dialkylammonium salts include di(1-propyl)ammoniumtetra(pentafluorophenyl)boron, dicyclohexylammoniumtetra(phenyl)boron and the like.

Furthermore, as ionic compounds, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, ferroceniumtetra(pentafluorophenyl)borate, triphenylcarbeniumpentaphenyl Cyclopentadienyl complexes, N,N-diethylanilinium pentaphenylcyclopentadienyl complexes, boron compounds represented by the following formula [XIII] or [XIV], and the like can also be mentioned. In addition, in the following formula, Et represents an ethyl group.

Specific examples of borane compounds include decaborane; bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, salts of anions such as [tri(n-butyl)ammonium] dodecaborate, bis[tri(n-butyl)ammonium]decachlorodecaborate, bis[tri(n-butyl)ammonium]dodecachlorododecaborate; -Butyl) ammonium bis(dodecahydride dodecaborate) cobaltate (III), bis[tri(n-butyl)ammonium] bis(dodecahydride dodecaborate) nickelate (III) and the like, metal borane anion salts, etc. mentioned.

Specific examples of carborane compounds include 4-carbanonabolane, 1,3-dicarbanonabolane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonabolane, and dodecahydride. -1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarboundecaborane, 2,7-dicarboundecaborane , undecahydride-7,8-dimethyl-7,8-dicarbaundecaborate, dodecahydride-11-methyl-2,7-dicarbaundecaborate, 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-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, tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri(n-butyl) ) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri(n-butyl)ammonium salts of anions such as 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-dicarbaundecaborate) Ferrate (III), Tri(n-butyl)ammonium bis(undecahydride-7,8-dicarboundecaborate) cobaltate(III), Tri(n-butyl)ammonium bis(undecahydride-7) ,8-dicarbaundecaborate)nickelate (III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate)cuprate(III), tri(n-butyl) Ammonium bis(undecahydride-7,8-dicarbaundecaborate)aurate (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) Ferrate (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) chromate (III), tri(n-butyl)ammonium bis( Tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris[tri(n-butyl)ammonium] bis(undecahydride-7-carbaundecaborate) chromate (III) , bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboundecaborate) manganate (IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbohydrate) boundecaborate) cobaltate (III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboundecaborate)nickelate (IV) and the like, and salts of metal carborane anions. be done.

The heteropoly compound consists of atoms selected from silicon, phosphorus, titanium, germanium, arsenic and tin and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus tungstic acid, germanotungstic acid, stannotungstic acid, phosphomolybdovanadate, phosphotungstovanadate, germanotungstovanadate, phosphomolybdotungstovanadate, germanomolybdotungstovanadate, phosphomolybdotungstic acid , phosphomolybdoniobic acid, and salts of these acids, such as metals of Groups 1 and 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and organic salts such as triphenylethyl salts can be used, but are not limited to these.

Among the ionizable ionic compounds (b-3), the above-described ionic compounds are preferred, among which triphenylcarbenium tetrakis(pentafluorophenyl)borate and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate. more preferred.

In the present invention, the above metallocene compound (a), an organometallic compound (b-1) such as triisobutylaluminum, an organoaluminumoxy compound (b-2) such as methylaluminoxane, and triphenylcarbenium tetrakis are used as the polymerization catalyst. When using a metallocene catalyst containing an ionized ionic compound (b-3) such as (pentafluorophenyl)borate, extremely high polymerization activity can be exhibited in the production of the copolymer (X).

(c) Particulate Carrier The particulate carrier (c) used as necessary in the present invention is an inorganic compound or an organic compound, and is a solid in the form of granules or fine particles.

As the inorganic compound, porous oxides, inorganic halides, clays, clay minerals or ion-exchange layered compounds are preferred. Specific examples thereof include those described in WO2015/122495.

The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as they are, or may be used after being subjected to treatments such as ball milling and sieving. Alternatively, water may be newly added and adsorbed, or may be used after heat dehydration treatment. Furthermore, it may be used alone or in combination of two or more.

Among these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, hectorite, taeniolite and synthetic mica.
Examples of organic compounds include granular or particulate solids with particle sizes in the range of 10 to 300 μm. Specifically, (co)polymers produced mainly from α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, and styrene can be exemplified as a (co)polymer produced as a main component, and a modified product thereof.

The polymerization catalyst used in the present invention is a metallocene compound (a), and at least one selected from an organometallic compound (b-1), an organoaluminumoxy compound (b-2) and an ionized ionic compound (b-3). In addition to the seed compound (b) and the optionally used carrier (c), a specific organic compound component (d) can also be included, if desired.

(d) Organic compound component In the present invention, the organic compound component (d) is used for the purpose of improving the polymerization performance and the physical properties of the resulting polymer, if necessary. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds and sulfonates.

<<Method and conditions for producing copolymer (X)>>
The copolymer (X) of the present invention is produced by copolymerizing ethylene and non-conjugated polyene.
When such monomers are copolymerized, the method of use and order of addition of each component constituting the polymerization catalyst described above can be arbitrarily selected, and the following methods (1) to (5) are exemplified.
(1) A method of adding the metallocene compound (a) alone to a polymerization vessel.
(2) A method in which the metallocene compound (a) and the compound (b) are added in any order to the polymerization vessel.
(3) A method in which the catalyst component in which the metallocene compound (a) is supported on the carrier (c) and the compound (b) are added in any order to the polymerization vessel.
(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 in any order to the polymerization reactor.
(5) A method of adding a catalyst component comprising a metallocene compound (a) and a compound (b) supported on a carrier (c) to a polymerization vessel.

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

Further, the solid catalyst component in which the metallocene compound (a) is supported on the carrier (c) and the solid catalyst component in which the metallocene compound (a) and the compound (b) are supported on the carrier (c) are prepolymerized with olefin. Alternatively, a catalyst component may be further supported on the prepolymerized solid catalyst component.

The copolymer (X) of the present invention can be suitably obtained by copolymerizing ethylene and non-conjugated polyene in the presence of the above polymerization catalyst.
When ethylene and non-conjugated polyene are polymerized using the polymerization catalyst as described above, the metallocene compound (a) is generally 10 ^-12 to 10 ^-2 mol, preferably 10 ^-10 mol, per liter of reaction volume. It is used in an amount such that it is ˜10 ⁻⁸ mol.

In the compound (b-1), the molar ratio [(b-1)/M] between the compound (b-1) and all the transition metal atoms (M) in the metallocene compound (a) is usually 0.01 to It is used in an amount of 50,000, preferably 0.05 to 10,000. In the compound (b-2), the molar ratio [(b-2)/M] of aluminum atoms in the compound (b-2) and all transition metals (M) in the metallocene compound (a) is usually 10. -50,000, preferably 20-10,000. In the compound (b-3), the molar ratio [(b-3)/M] between the compound (b-3) and the transition metal atom (M) in the metallocene compound (a) is usually 1 to 20, preferably is used in an amount of 1 to 15.

In the present invention, the method for producing the copolymer (X) can be carried out by either liquid phase polymerization such as solution (dissolution) polymerization or suspension polymerization, or gas phase polymerization, and is not particularly limited. It is preferable to have a step of obtaining the following polymerization reaction solution.

The step of obtaining a polymerization reaction solution includes 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 solution of the copolymer (X). is the process of obtaining

Examples of the polymerization solvent include aliphatic hydrocarbons and aromatic hydrocarbons. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; and benzene, toluene, and xylene. and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, which may be used singly or in combination of two or more. Also, the olefin itself can be used as a solvent. Of these, hexane is preferred from the viewpoint of separation and purification from the resulting copolymer (A).

The polymerization temperature is usually -50 to +200°C, preferably 0 to +150°C, more preferably +70 to +110°C. (+70°C or higher) is desirable from the viewpoint of catalytic activity, copolymerizability and productivity.

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 is a batch system or a semi-continuous system. , continuous method. Furthermore, it is also possible to carry out the polymerization in two or more stages with different reaction conditions. In the present invention, among these methods, it is preferable to employ a method in which ethylene and non-conjugated polyene are continuously supplied to a reactor for copolymerization.

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. , more preferably 10 minutes to 2 hours.

The molecular weight of the obtained copolymer (X) can also be adjusted by allowing hydrogen to exist in the polymerization system or by changing the polymerization temperature. Furthermore, it can also be adjusted by the amount of the compound (b) used. Specific examples include triisobutylaluminum, methylaluminoxane, and diethylzinc. When hydrogen is added, the appropriate amount is about 0.001 to 100 NL per 1 kg of olefin.

The present invention preferably includes a step (2) of deactivating the polymerization catalyst by adding a catalyst deactivator after the step (1) of carrying out copolymerization in the presence of the polymerization catalyst.
Alcohols can be used as the catalyst deactivator, and methanol or ethanol is preferable, and ethanol is particularly preferable.

In the step (2), the catalyst deactivator is preferably 0.05 to 3.0 mol times, more preferably 0.06 to 2.5 mol times, the organometallic compound (b-1), More preferably, by adding in an amount of 0.08 to 2.0 mol times, the catalyst degenerated by the catalyst deactivator such as ethanol is slightly generated, and as a result of moderately polymerizing the low molecular weight component, the molecular weight distribution is moderate. A wide copolymer (X) can be obtained. On the other hand, when the amount of the catalyst deactivator added is too large, almost no degraded catalyst is produced and the low-molecular-weight components are hardly polymerized, so that the obtained copolymer (X) tends to have a narrow molecular weight distribution. be. In addition, if the catalyst deactivator is not added or if the amount added is too small, a large amount of alteration catalyst is generated and a large amount of low-molecular-weight components is polymerized. tend to be too many.

<Application of ethylene/non-conjugated polyene copolymer (X)>
The copolymer (X) of the present invention can be used for various known molded articles.
The copolymer (X) of the present invention may optionally contain inorganic fillers such as heat stabilizers, weather stabilizers, ultraviolet absorbers, light stabilizers, 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, compatibilizers, etc. Various additives may be added as long as the objects of the present invention are not impaired.

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

Molded articles made of the copolymer (X) of the present invention are also excellent in mechanical properties.
Specific examples of molded articles are used in a wide range of applications ranging from household goods such as daily necessities and recreational uses to general industrial uses and industrial goods. For example, home appliance material parts, communication equipment parts, electric parts, electronic parts, automobile parts, other vehicle parts, ships, aircraft materials, machine mechanism parts, building materials, civil engineering materials, agricultural materials, electric tool parts, food containers , films, sheets, and fibers.

EXAMPLES Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
Symbols such as (a) to (w) shown in Examples 1 to 3 are quantities in units shown in Table 1 below.

[Examples 1 to 3]
Dehydrated and purified n-hexane (C6) is supplied at a rate of (a) L/h to one feed port of a continuous polymerization reactor with a volume of 136 L, and [bis (4-methylphenyl) methylene ( η ⁵ -cyclopentadienyl)(η ⁵ -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride (ZD) in hexane solution (b) at a ratio of (b) mmol/L to (c) L/h, triisobutylaluminum Hexane solution (4 mmol / L) (d) L / h, hexane slurry of triphenylcarbenium tetrakis (pentafluorophenyl) borate (CB-3) (e) mmol - B / L) (f) L / h, VNB was continuously fed at a rate of (g) g/h and ENB (h) g/h [total hexane (T-C6): (i) L/h]. At the same time, ethylene (C2") was continuously supplied to another supply port of the polymerization vessel at a rate of (j) kg/h and hydrogen (k) NL/h, and the polymerization temperature was 1°C and the total pressure (m) MPaG. , and a residence time of (n) minutes.

The hexane solution of ethylene/non-conjugated polyene copolymer (X) produced in the polymerization vessel is continuously discharged through the outlet provided on the side wall of the polymerization vessel, and the jacket section is heated with 8 kg/cm ² steam. connected to the connected pipe. A hexane solution of ethylene/non-conjugated polyene copolymer (X) heated to about 170°C in a connecting pipe with a steam jacket was provided at the end of the connecting pipe so as to maintain a solution volume of about 28 L in the polymerization tank. By adjusting the degree of opening of the liquid level control valve, the liquid was continuously sent to the flash tank through the double pipe inner pipe heated with 10 kg/cm ² steam. Immediately after the liquid level control valve, a supply port for injecting methanol, which is a catalyst deactivator, is attached, and it is injected at a rate of 12 L / h as a 1.0 vol% hexane diluted solution and joins the hexane solution. let me During the transfer into the flash tank, the solution temperature and pressure control valve opening were set so that the pressure in the flash tank was 0.05 MPaG and the temperature of the steam part in the flash tank was maintained at 180°C.

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

The physical properties of the polymers obtained in Examples and Reference Examples were measured by the following measuring methods.
(1) Tensile properties A sheet with a thickness of 4 mm was formed by press molding, a type 1B test piece was punched, and the tensile yield stress, tensile fracture strain, and tensile fracture stress were measured in accordance with JIS K7161 and JIS K7162. bottom.
(2) Durometer hardness (D hardness)
A sheet having a thickness of 4 mm was produced by press molding, a type 1B test piece was punched out, and the D hardness was measured according to JIS K7215.

[Reference Example 1]
As the linear low-density polyethylene (LLDPE), an ethylene/1-hexene copolymer [trade name ULTZEX 2022F manufactured by Prime Polymer Co., Ltd.] (UZ2022F) was used.
Table 1 shows the results.

As is clear from Table 1, the ethylene/non-conjugated polyene copolymer (X) shown in Examples 1 to 3 has a larger P value than the LLDPE shown in Reference Example, has high fluidity in molding, and can be melted. It retains its shape well under certain conditions. In addition, the ethylene/non-conjugated polyene copolymer (X) shown in Examples 1 to 3 has a large P value, regardless of whether the melting point (Tm) is equal to or lower than that of LLDPE shown in Reference Example. High tensile breaking stress.

Claims (3)

An ethylene/non-conjugated polyene copolymer comprising a structural unit (A) derived from ethylene and a structural unit (B) derived from a non-conjugated polyene and satisfying all of the following requirements (1) to (5): Union (X).
Ethylene/non-conjugated polyene copolymer (X)
(1) The content of structural units derived from non-conjugated polyene is in the range of 0.01 to 10 mol % [provided that the total of (A) and (B) is 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 in the range of 920-950 kg/m ³ .
(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 5-100. The copolymer according to claim 1, wherein the non-conjugated polyene of the ethylene/non-conjugated polyene copolymer (X) is selected from 5-vinyl-2-norbornene and 5-ethylidene-2-norbornene. (X). 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. The copolymer (X) according to .