JP2006002098A - New ethylenic polymer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ethylenic polymer having moldability and mechanical strength improved in well balanced state and suitable for the molding by any of various molding methods. <P>SOLUTION: The ethylenic polymer contains 1-20C short-chain branches and >20C long-chain branches introduced to the polymer main chain and satisfies the conditions (a) to (d). (a) The density of the polymer is 0.880-0.970 g/cm<SP>3</SP>; (b) the melt-flow rate measured at 190°C under a load of 21.18N is 0.01-100 g/10 min; (c) the difference ΔEa [KJ/mol] between the flow activation energy Ea [KJ/mol] and a specifically defined activation energy Ea<SB>L</SB>[KJ/mol] is 1.5-12.5; and (d) the elongation viscosity λmax and ΔEa satisfies the formula λmax≥1.2exp(0.0721×ΔEa). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel ethylene polymer having excellent physical properties and excellent molding processability, and a method for producing the same, and more particularly, a long chain branching in a polymer main chain by polymerization combining two specific metallocene catalysts. And an ethylene polymer that can be optimally designed for various molding methods such as extrusion molding and injection molding, and a specific two metallocene catalyst in combination with a non-conjugated polyene. The present invention relates to a method for producing an ethylene polymer.

  Ethylene polymers such as ethylene polymers and copolymers of ethylene and α-olefin have excellent properties such as physical properties and moldability among resin materials, and are highly economical and compatible with environmental problems. However, due to its versatility and importance, there is a strong demand for further improvement in physical properties in combination with excellent molding processability suitable for any of various molding methods.

In conventional ethylene polymers, HP-LDPE has good moldability but poor mechanical strength, while HDPE and LLDPE have high mechanical strength but generally low moldability. Further, it has not been realized that both physical properties such as moldability and mechanical strength are sufficiently improved. Usually, if one property is improved, the other property is deteriorated.
In terms of moldability, the melt flow characteristics governing moldability are broadly divided into extrudability related to the molten resin pressure under shear stress and molding stability related to melt elasticity during elongation deformation. For example, low viscosity is obtained under high shear stress of extrusion molding, bubbles are stable under high speed molding of inflation molding, neck-in in T-die of extrusion lamination molding is small, and due to the weight of parison in blow molding Molding workability according to various molding methods is required, such as no drooping, but it is very difficult to satisfy all of these.
Rigidity, tensile strength, impact resistance, etc. are important as mechanical strength. However, when long chain branching is introduced, copolymerized or blended into an ethylene polymer in order to improve moldability, these mechanical strengths are generally increased. Will be damaged. For example, when HP-LDPE is blended for improving moldability into an ethylene polymer having high mechanical strength and heat resistance due to a metallocene catalyst, the mechanical strength deteriorates.

Against the background of the above technical situation, many attempts have been made to improve both the moldability and mechanical strength of ethylene-based polymers. For example, high strength and toughness polymerized using constrained geometric catalysts. In addition, although an olefin polymer with improved processability is disclosed (Patent Document 1), it is mainly for the purpose of improving the extrusion characteristics, and since the melt tension value of the examples is relatively low, Improvement in molding stability is insufficient.
Further, as a representative example, an ethylene-α olefin copolymer having an improved molding processability without impairing mechanical properties, specifying flow activation energy, average value of short chain branching, etc. (Patent Document 2) ), An ethylene-based polymer having excellent molding stability and good mechanical properties (Patent Document 3), which defines the melt flow activation energy, molecular weight and die swell ratio, etc. Polyethylene resin (Patent Document 4), which has an inflection point, has a specified HLMFR swell ratio and the number of long-chain branches, is excellent in moldability and strength, polymerized by a catalyst using a plurality of complexes, It defined and activation energy and α- olefin content of the flow, mechanical strength and moldability excellent ethylene copolymer (Patent Document 5), methyl fraction measured by 13 ^C-NMR Identified by the number and the molecular weight ratio of ethylene (co) polymer (Patent Document 6), and the like is disclosed having excellent moldability and mechanical strength.
However, in any of the prior arts, many are defined by specific parameters, and it cannot always be said that the improvement of molding processability or mechanical properties (mainly mechanical strength) is sufficiently achieved. Even if the improvement of molding processability is achieved, the mechanical properties are sacrificed, and no improvement in both properties can be found.

JP-A-6-306121 (Abstract) JP-A-7-62031 (Abstract, paragraph 0003) JP-A-8-319313 (Summary) Japanese Patent Laid-Open No. 11-5814 (Summary) Japanese Patent Laid-Open No. 11-322852 (Abstract, Claim 2) JP 2002-53615 A (summary)

  In view of the prior art in the ethylene polymer described above in paragraphs 0002 to 0004, the present invention improves both the moldability and mechanical strength of the ethylene polymer in a sufficiently balanced manner, and further, as the resin material thereof According to the versatility and importance, it is an object of the present invention to obtain excellent molding processability suitable for any of various molding methods.

  The inventors of the present application have solved the above-described problems of the invention and improved both the moldability and mechanical strength of the ethylene-based polymer in a sufficiently balanced manner, and are excellent in any of various molding methods. Aiming to obtain molding processability, polymerization conditions for ethylene polymers, polymerization catalysts, numerical specifications for various polymers, monomers for copolymers, or branched structures of long and short chains in the molecular skeleton and molecular weight of polymers Regarding the provisions, etc., while considering the prior art, various considerations by multifaceted thinking and various trials by experiments were conducted.

In the process of their consideration and examination, in order to ensure excellent mechanical properties and optical properties such as transparency and heat resistance, which are the main characteristics of ethylene polymers, a metallocene catalyst as a single site catalyst is used as a polymerization catalyst. In order to improve molding processability without impairing mechanical properties, the structure and number of branches of long and short chains in the polymer main chain of the ethylene polymer are related. Recognizing this, the basic requirements for such a novel ethylene polymer could be found.
Continuing with discussion and examination, in moldability, melt flow characteristics are related to extrudability related to molten resin pressure under shear stress, and melt elasticity during elongation deformation is related to molding stability. If the flow activation energy and the elongational viscosity are defined as the characteristics of the ethylene polymer, the molding processability can be further improved without impairing the mechanical properties, and it is unexpected. The required structure of the long and short chains in the polymer main chain and the number of branches are a combination of two specific metallocene catalysts, more preferably a complex with the formation of long chain branches in the presence of a non-conjugated polyene, and substantially long chain branches. It is also possible to find out that it is only necessary to carry out a polymerization reaction using a complex that does not involve the formation of any of the above, as well as the difference in reactivity of the two metallocene catalysts with respect to the nonconjugated polyene and the resulting polymerization. I came to realize until utilize also employed to correlate the provisions of the melt flow rate of between.

Specifically, based on experimental data, short chain branching (SCB) having 1 to 20 carbon atoms and 20 carbon atoms are obtained by using a metallocene catalyst having two (or more than two or more) types of complexes. Excessive long chain branching (LCB) is introduced into the polymer main chain of the ethylene polymer, and the density and melt flow rate required for such polymers are also defined.
And, by giving long and short chain branch structure in the molecular chain and controlling the length and concentration of the long and short chain branch, each of extrusion molding, inflation film molding, laminate molding, blow molding, injection molding, etc. It was possible to embody an ethylene polymer having extremely excellent moldability and a method for producing the ethylene polymer designed to be optimized for the molding method. In addition, excellent molding processability is to have both high extrusion characteristics and high molding stability, in other words, low viscosity under high shear stress and high melt elasticity when subjected to elongation deformation. It is. Of course, depending on the molding method, which one is important is different, and the deformation speed of the resin is also different. What is important is to develop them in a speed range and deformation mode depending on the molding method.
In order to improve the molding processability from this point of view, the flow activation energy and the extensional viscosity as the characteristics of the ethylene polymer and the correlation thereof are specifically defined, and two kinds of metallocene catalysts Controlling the introduction of long and short chains by utilizing the difference in reactivity with non-conjugated polyenes, formulating the correlation of melt flow rate between the polymers produced by the two types of complexes using empirical formulas, and conforming to the present invention Two kinds of possible complexes were experimentally selected in detail, and the overall configuration of the present invention could be set.

By the way, looking at the relationship between the present invention and the prior art, JP-A-6-287228 discloses an ethylene polymer having a long chain branch derived only from an ethylene monomer, and also defines the activation energy of the flow. However, the activation energy of the flow of the example is larger than that of the present invention, and it is intended to improve the balance between the melt flow characteristics and the mechanical properties by introducing long chain branching efficiently as in the present invention. In contrast to the above, there is no description regarding the specific control of the activation energy of the flow.
Further, in Patent Document 5, an ethylene copolymer composition excellent in mechanical strength and moldability produced by a catalyst using two kinds of complexes is disclosed. It is not selected from the viewpoint of introduction of long and short chain branches as in the invention, and it is estimated that the activation energy of the flow is low as long as judged from the examples, and that the long chain branching concentration is generally low, and the difference in activation energy of the flow There is no description.
Further, JP-A-9-227626 discloses polyethylene in which long chain branching is introduced in the presence of a linking hydrocarbon, but the flow characteristics of the polymer are not described, and the complex used for the catalyst is not disclosed. Since it is one type, it is essentially different from the one in which long chain branching is efficiently introduced and the balance between melt flow characteristics and mechanical properties is improved as in the present invention.

  In the above, the background to the creation of the invention of the present application, the features of the configuration of the invention and the differences from the prior art, etc. have been described in general, so the entire configuration of the invention of the present application will be described here. It consists of an invention unit group. The inventions described in [1] and [10] are basic inventions, and other inventions are those in which additional requirements are added to the basic inventions or they are embodied.

ここで、ＳＣＢは主鎖の炭素原子１，０００あたりの炭素数１〜２０の短鎖分岐数［個数／１，０００Ｃ］を表し、Ｂは炭素数１〜２０の短鎖分岐の長さ（炭素数）を表す。
ｄ）伸長粘度λｍａｘとΔＥａとが下記の式（２）を満たす。
λｍａｘ≧１．２ｅｘｐ（０．０７２１×ΔＥａ） 式（２）
［２］炭素数１〜２０の短鎖分岐と炭素数２０を超える長鎖分岐の、高分子主鎖への導入を、二種又は複数種のメタロセン触媒により各々の触媒に応じて行なうことを特徴とする［１］におけるエチレン系重合体。
［３］二種のメタロセン触媒が、エチレンに対し１ｍｏｌ％以下の非共役ポリエンの共存下において非共役ポリエンに対する反応性が異なる遷移金属化合物を触媒成分として含有するものであることを特徴とする、［１］又は［２］におけるエチレン系重合体。
［４］二種のメタロセン触媒が、以下の（ｉ）及び（ｉｉ）に示す遷移金属化合物を含有するものであり、（ｉｉｉ）及び（ｉｖ）の条件を満たすことを特徴とする、［１］〜［３］のいずれかにおけるエチレン系重合体。
（ｉ）助触媒の共存下に、水素及び非共役ポリエンが存在しない条件で重合を行った場合に得られる重合体のメルトフローレート（ＭＦＲ−Ａ）が２ｇ／１０分以下となり、長鎖分岐を有する重合体を生成する遷移金属化合物(錯体Ａ)
（ｉｉ）上記の（ｉ）と同条件で重合を行った場合に得られる重合体のメルトフローレート（ＭＦＲ−Ｂ）がＭＦＲ−Ａの１０倍以上となり、長鎖分岐を有しない重合体を生成する遷移金属化合物（錯体Ｂ）
（ｉｉｉ）錯体Ａ及び助触媒の存在下に、水素が存在せず非共役ポリエンがエチレンに対し０．０１ｍｏｌ％存在した条件で重合を行った場合に得られる重合体のメルトフローレート（ＭＦＲ−Ａ＋）、及び錯体Ａの代わりに錯体Ｂを使用して同条件で重合を行った場合に得られる重合体のメルトフローレート（ＭＦＲ−Ｂ＋）において、下記の式（３）を満たす。
｛（ＭＦＲ−Ａ＋）／（ＭＦＲ−Ａ）｝／｛（ＭＦＲ−Ｂ＋）／（ＭＦＲ−Ｂ）｝＜０．８ 式（３）
（ｉｖ）錯体Ａに由来する重合体成分［Ａ］と錯体Ｂに由来する重合体成分[Ｂ]の量比が、[Ａ]／[Ｂ]＝１０／９０〜９０／１０である。
［５］エチレン系重合体が、エチレン重合体又はエチレンと３〜２０の炭素原子を有するα−オレフィンとの共重合体であり、あるいはそれらに非共役ポリエンが共重合された共重合体であることを特徴とする、［１］〜［４］のいずれかにおけるエチレン系重合体。
［６］錯体Ａが下記の一般式（１）で表される遷移金属化合物であり、錯体Ｂが下記の一般式（２）で表される遷移金属化合物であることを特徴とする、［１］〜［５］のいずれかにおけるエチレン系重合体。
ＭＬ^１ _ｎＲ^１ _ｘ-n 一般式（１）
［式中、Ｍは周期律表４族の遷移金属を表し、Ｌ^１はＭに配位する配位子であり、ジメチルシクロペンタジエニル基、トリメチルシクロペンタジエニル基、下記の化合物［１］で示されるベンゾインデニル基又は置換ベンゾインデニル基、下記の化合物[２]で示されるジベンゾインデニル基又は置換ジベンゾインデニル基のいずれか一種類を２個以上有し、Ｒ^１は炭化水素基、アルコキシル基、ハロゲン原子、水素原子を表す。ｘは遷移金属Ｍの原子価であり、ｎは２≦ｎ≦ｘであり、置換基Ｒ^２〜Ｒ^１５は炭素数１〜３０の炭化水素基、炭素数１〜３０の炭化水素置換基を有するトリアルキル珪素基又は水素原子を表す。］

化合物［１］

化合物［２］

ＭＬ^２ _ｎＲ^１ _ｘ-n 一般式（２）
［式中、Ｍは周期律表４族の遷移金属を表し、Ｌ^２はＭに配位する配位子であり、シクロペンタジエニル基、置換シクロペンタジエニル基、インデニル基、置換インデニル基を表し、複数個結合している場合は異なっていてもよい。Ｒ^１は炭化水素基、アルコキシル基、ハロゲン原子、水素原子を表す。ｘは遷移金属Ｍの原子価であり、ｎは２≦ｎ≦ｘである。］
［７］錯体Ａが下記の一般式（３）で表される遷移金属化合物であり、錯体Ｂが下記一般式（４）で表される遷移金属化合物であることを特徴とする、［１］〜［５］のいずれかにおけるエチレン系重合体。
ＭＬ^３ _３Ｈ 一般式（３）
［式中、Ｍは周期律表４族の遷移金属を表し、Ｌ^３はＭに配位する配位子であり、ジメチルシクロペンタジエニル基、トリメチルシクロペンタジエニル基、化合物［１］で示されるベンゾインデニル基または置換ベンゾインデニル基、化合物［２］で示されるジベンゾインデニル基又は置換ジベンゾインデニル基のいずれか一種類を２個以上有し、Ｈは水素原子を表す。］
ＭＬ^４ _３Ｈ 一般式（４）
［式中、Ｍは周期律表４族の遷移金属を表し、Ｌ^４はＭに配位する配位子であり、シクロペンタジエニル基、置換シクロペンタジエニル基、インデニル基、置換インデニル基を表し、同一でも異なっていてもよい。Ｈは水素原子を表す。］
［８］錯体Ａが下記の一般式（５）で表される遷移金属化合物であり、錯体Ｂが下記の一般式（６）で表される遷移金属化合物であることを特徴とする、［１］〜［５］のいずれかに記載されたエチレン系重合体。
ＭＬ^３ _３Ｈ-ＡlＲ_３ 一般式（５）
［式中、Ｍは周期律表４族の遷移金属を表し、Ｌ^３はＭに配位する配位子であり、ジメチルシクロペンタジエニル基、トリメチルシクロペンタジエニル基、化合物［１］で示されるベンゾインデニル基又は置換ベンゾインデニル基、化合物［２］で示されるジベンゾインデニル基又は置換ジベンゾインデニル基のいずれか一種類を２個以上有し、Ｈは水素原子、ＡlＲ_３は有機アルミニウム化合物を表す。］
ＭＬ^４ _３Ｈ-ＡlＲ_３ 一般式（６）
［式中、Ｍは周期律表４族の遷移金属を表し、Ｌ^４はＭに配位する配位子であり、シクロペンタジエニル基、置換シクロペンタジエニル基、インデニル基、置換インデニル基を表し、同一でも異なっていてもよい。Ｈは水素原子、ＡｌＲ_３は有機アルミニウム化合物を表す。］
［９］錯体Ａ及び錯体Ｂの遷移金属ＭがＺｒであることを特徴とする、［１］〜［８］のいずれかにおけるエチレン系重合体。
［１０］エチレンに対し１ｍｏｌ％以下の非共役ポリエンの共存下における非共役ポリエンに対する反応性が異なる遷移金属化合物を触媒成分として含有する二種又は複数種のメタロセン触媒を使用して、エチレン又はエチレンと３〜２０の炭素原子を有するα−オレフィンを重合することを特徴とする、［１］におけるエチレン系重合体の製造方法。
［１１］非共役ポリエンの共存下において重合されることを特徴とする、［１０］におけるエチレン系重合体の製造方法。
［１２］非共役ポリエンの濃度を制御することにより、長鎖分岐成分の分岐構造を制御することを特徴とする、［１１］におけるエチレン系重合体の製造方法。
［１３］非共役ポリエンが分子内に２つ以上の末端ビニル構造を持つ化合物であることを特徴とする、［１１］又は［１２］におけるエチレン系重合体の製造方法。
［１４］二種のメタロセン触媒が、以下の（ｉ）及び（ｉｉ）に示す遷移金属化合物を含有するものであることを特徴とする、［１０］〜［１３］のいずれかにおけるエチレン系重合体の製造方法。
（ｉ）助触媒の共存下に、水素及び非共役ポリエンが存在しない条件で重合を行った場合に得られる重合体のメルトフローレート（ＭＦＲ−Ａ）が２ｇ／１０分以下となり、長鎖分岐を有する重合体を生成する遷移金属化合物(錯体Ａ)
（ｉｉ）上記の（ｉ）と同条件で重合を行った場合に得られる重合体のメルトフローレート（ＭＦＲ−Ｂ）がＭＦＲ−Ａの１０倍以上となり、長鎖分岐を有しない重合体を生成する遷移金属化合物（錯体Ｂ）
［１５］遷移金属化合物と助触媒からなる触媒成分を用い、触媒成分を担体に担持させて重合することを特徴とする［１０］〜［１４］のいずれかにおけるエチレン系重合体の製造方法。
［１６］［６］〜［８］のいずれかにおける遷移金属化合物を用いることを特徴とする、［１０］〜［１５］のいずれかにおけるエチレン系重合体の製造方法。 [1] An ethylene-based heavy polymer which satisfies the following conditions a) to d) and has introduced a short chain branch having 1 to 20 carbon atoms and a long chain branch having more than 20 carbon atoms into the polymer main chain: Coalescence.
a) The density measured based on JIS K-7112 is 0.880 to 0.970 g / cm ³ .
b) Based on JIS K-7210 Table 1-Condition 7, the melt flow rate (MFR) measured at a temperature of 190 ° C. under a load of 21.18 N is 0.01 to 100 g / 10 min.
c) The difference ΔEa [KJ / mol] between the activation energy Ea [KJ / mol] of flow and the activation energy Ea _L [KJ / mol] calculated by the following formula (1) is 1.5 to 12.5.

Here, SCB represents the number of short-chain branches having 1 to 20 carbon atoms per 1,000 carbon atoms in the main chain [number / 1,000 C], and B is the length of short-chain branches having 1 to 20 carbon atoms ( Carbon number).
d) The elongational viscosity λmax and ΔEa satisfy the following formula (2).
λmax ≧ 1.2exp (0.0721 × ΔEa) Equation (2)
[2] The introduction of the short chain branch having 1 to 20 carbon atoms and the long chain branch having more than 20 carbon atoms into the polymer main chain is performed according to each catalyst using two or more kinds of metallocene catalysts. The ethylene polymer according to [1], which is characterized.
[3] The two types of metallocene catalysts are characterized in that they contain transition metal compounds having different reactivities with respect to the nonconjugated polyene as a catalyst component in the presence of 1 mol% or less of the nonconjugated polyene with respect to ethylene. Ethylene polymer in [1] or [2].
[4] The two metallocene catalysts contain transition metal compounds shown in the following (i) and (ii), and satisfy the conditions (iii) and (iv): [1 ] The ethylene polymer in any one of [3].
(I) When the polymerization is carried out in the presence of a cocatalyst in the absence of hydrogen and non-conjugated polyene, the melt flow rate (MFR-A) of the polymer obtained is 2 g / 10 min or less, and long chain branching Metal compound (complex A) that produces a polymer having
(Ii) A polymer having a melt flow rate (MFR-B) of 10 or more times that of MFR-A obtained by polymerization under the same conditions as in (i) above, and having no long chain branching Generated transition metal compound (complex B)
(Iii) Polymer melt flow rate (MFR-) obtained when polymerization is carried out in the presence of complex A and a cocatalyst in the presence of 0.01 mol% of non-conjugated polyene with respect to ethylene without hydrogen. A +) and a polymer melt flow rate (MFR-B +) obtained when polymerization is performed under the same conditions using the complex B instead of the complex A, the following formula (3) is satisfied.
{(MFR-A +) / (MFR-A)} / {(MFR-B +) / (MFR-B)} <0.8 Formula (3)
(Iv) The quantity ratio of the polymer component [A] derived from the complex A and the polymer component [B] derived from the complex B is [A] / [B] = 10/90 to 90/10.
[5] The ethylene polymer is an ethylene polymer or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, or a copolymer in which a non-conjugated polyene is copolymerized therewith. The ethylene polymer in any one of [1]-[4] characterized by the above-mentioned.
[6] The complex A is a transition metal compound represented by the following general formula (1), and the complex B is a transition metal compound represented by the following general formula (2), [1 ] The ethylene polymer in any one of [5].
ML ¹ _n R ¹ _x-n general formula (1)
[In the formula, M represents a transition metal of Group 4 of the periodic table, L ¹ is a ligand coordinated to M, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, the following compound [1 Or a dibenzoindenyl group or a substituted dibenzoindenyl group represented by the following compound [2], and R ¹ is carbonized. A hydrogen group, an alkoxyl group, a halogen atom, or a hydrogen atom is represented. x is the valence of the transition metal M, n is 2 ≦ n ≦ x, and the substituents R ^{2 to} R ¹⁵ are hydrocarbon groups having 1 to 30 carbon atoms and hydrocarbon substituents having 1 to 30 carbon atoms. Represents a trialkylsilicon group or a hydrogen atom. ]

Compound [1]

Compound [2]

ML ² _n R ¹ _x-n general formula (2)
[In the formula, M represents a transition metal of Group 4 of the periodic table, L ² is a ligand coordinated to M, cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group. In the case where a plurality of bonds are combined, they may be different. R ¹ represents a hydrocarbon group, an alkoxyl group, a halogen atom, or a hydrogen atom. x is the valence of the transition metal M, and n is 2 ≦ n ≦ x. ]
[7] The complex A is a transition metal compound represented by the following general formula (3), and the complex B is a transition metal compound represented by the following general formula (4), [1] -Ethylene polymer in any one of [5].
ML ³ ₃ H general formula (3)
[Wherein M represents a transition metal of Group 4 of the periodic table, L ³ is a ligand coordinated to M, and dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, compound [1] 2 or more of any one of the indicated benzoindenyl group or substituted benzoindenyl group and the dibenzoindenyl group or substituted dibenzoindenyl group represented by the compound [2], and H represents a hydrogen atom. ]
ML ⁴ ₃ H general formula (4)
[In the formula, M represents a transition metal of Group 4 of the periodic table, L ⁴ is a ligand coordinated to M, cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group Which may be the same or different. H represents a hydrogen atom. ]
[8] The complex A is a transition metal compound represented by the following general formula (5), and the complex B is a transition metal compound represented by the following general formula (6), [1 ] The ethylene polymer as described in any one of [5].
ML ³ ₃ H-AlR ₃ general formula (5)
[Wherein M represents a transition metal of Group 4 of the periodic table, L ³ is a ligand coordinated to M, and dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, compound [1] The benzoindenyl group or the substituted benzoindenyl group shown, or two or more of the dibenzoindenyl group or the substituted dibenzoindenyl group shown by the compound [2], H is a hydrogen atom, and AlR ₃ is Represents an organoaluminum compound. ]
ML ⁴ ₃ H-AlR ₃ general formula (6)
[In the formula, M represents a transition metal of Group 4 of the periodic table, L ⁴ is a ligand coordinated to M, cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group Which may be the same or different. H represents a hydrogen atom, and AlR ₃ represents an organoaluminum compound. ]
[9] The ethylene polymer according to any one of [1] to [8], wherein the transition metal M of the complex A and the complex B is Zr.
[10] Using two or more metallocene catalysts containing, as catalyst components, transition metal compounds having different reactivities to non-conjugated polyenes in the presence of 1 mol% or less of non-conjugated polyene with respect to ethylene, ethylene or ethylene And an α-olefin having 3 to 20 carbon atoms is polymerized. The method for producing an ethylene-based polymer according to [1].
[11] The method for producing an ethylene polymer according to [10], wherein the polymerization is performed in the presence of a non-conjugated polyene.
[12] The method for producing an ethylene polymer according to [11], wherein the branch structure of the long-chain branch component is controlled by controlling the concentration of the non-conjugated polyene.
[13] The method for producing an ethylene polymer according to [11] or [12], wherein the non-conjugated polyene is a compound having two or more terminal vinyl structures in the molecule.
[14] The ethylene-based heavy metal according to any one of [10] to [13], wherein the two metallocene catalysts contain transition metal compounds shown in the following (i) and (ii): Manufacturing method of coalescence.
(I) When the polymerization is carried out in the presence of a cocatalyst in the absence of hydrogen and non-conjugated polyene, the melt flow rate (MFR-A) of the polymer obtained is 2 g / 10 min or less, and long chain branching Metal compound (complex A) that produces a polymer having
(Ii) A polymer having a melt flow rate (MFR-B) of 10 or more times that of MFR-A obtained by polymerization under the same conditions as in (i) above, and having no long chain branching Generated transition metal compound (complex B)
[15] The method for producing an ethylene polymer according to any one of [10] to [14], wherein a catalyst component comprising a transition metal compound and a cocatalyst is used, and the catalyst component is supported on a carrier and polymerized.
[16] The method for producing an ethylene polymer according to any one of [10] to [15], wherein the transition metal compound according to any one of [6] to [8] is used.

  Both moldability and mechanical strength of ethylene polymers are improved in a well-balanced manner, and in addition, excellent molding process suitable for any molding method depending on the versatility and importance of the resin material. Sex can also be obtained.

Hereinafter, the best mode for carrying out the invention of the present invention will be described in detail.
1. Ethylene polymer The ethylene polymer according to the present invention is obtained by copolymerizing ethylene alone or ethylene and an α-olefin having 3 to 20 carbon atoms with two or more specific metallocene catalysts. is there. By using the metallocene catalyst, the optical characteristics such as excellent mechanical properties and transparency, which are the main characteristics of the ethylene-based polymer, and heat resistance are ensured.
And in order to improve both moldability and mechanical strength in a well-balanced manner, a metallocene catalyst having two types of complexes enables short chain branching (SCB) having 1 to 20 carbon atoms and long chain branching having more than 20 carbon atoms. (LCB) is introduced into the polymer main chain of the ethylene polymer, and the necessary density and melt flow rate shown in the following a) and b) are also specified as such a polymer. The density of the ethylene-based polymer can be adjusted by adjusting the polymerization conditions or changing the type and amount of the C3-C20 α-olefin copolymerized with ethylene. The MFR of the ethylene polymer according to the present invention can be adjusted by using a general chain transfer agent or hydrogen during polymerization.
a) The density measured based on JIS K-7112 is 0.880 to 0.970 g / cm ³ .
b) Based on JIS K-7210 Table 1-Condition 7, the melt flow rate (MFR) measured at a temperature of 190 ° C. under a load of 21.18 N is 0.01 to 100 g / 10 min.

2. Regulation of activation energy and elongational viscosity In molding processability, the melt flow characteristics are related to the extrudability related to the molten resin pressure under the shear stress, and the melt elasticity at the time of elongational deformation is related to the molding stability. Thus, the flow activation energy and the extensional viscosity are defined as empirical formulas as the characteristics of the ethylene polymer, and the molding processability can be further improved without impairing the mechanical properties.

ここで、ＳＣＢは主鎖の炭素原子１，０００あたりの炭素数１〜２０の短鎖分岐数［個数／１，０００Ｃ］を表し、Ｂは炭素数１〜２０の短鎖分岐の長さ（炭素数）を表す。 (1) Activation energy The difference ΔEa [KJ / mol] between the flow activation energy Ea [KJ / mol] and the activation energy Ea _L [KJ / mol] calculated by the following equation (1) is: 1.5-12.5.

Here, SCB represents the number of short-chain branches having 1 to 20 carbon atoms per 1,000 carbon atoms in the main chain [number / 1,000 C], and B is the length of short-chain branches having 1 to 20 carbon atoms ( Carbon number).

The activation energy of the flow is described in, for example, “Polymer Society, Polymer Experimental Studies Editorial Committee, Polymer Experimental Studies Vol. The viscoelastic frequency dependence is measured, and the activation energy of the flow can be obtained from the shift factor a _T based on the principle of time-temperature superposition.
When the graph of the relationship between the storage elastic modulus (vertical axis) and angular velocity (horizontal axis) measured at a certain reference temperature is fixed, and the data measured at another measurement temperature is moved in parallel to the horizontal axis, Can be overlaid with other data. The shift factor a _T is obtained by changing an amount Log (a _T ) for shifting the data of each measurement temperature so as to overlap the data of the reference temperature according to the Arrhenius equation with respect to the reciprocal 1 / T of the measurement temperature (absolute temperature). The activation energy of flow can be obtained from the slope of the straight line obtained by plotting.

Specifically, the resin used for the test was press-molded into a circular shape having a diameter of 25 mm and a thickness of 1 mm at 180 ° C., and the dynamic viscoelasticity measuring apparatus was a UDS-200 rotary rheometer manufactured by Paar Physica And the dynamic viscoelasticity in temperature (140 degreeC, 170 degreeC, 190 degreeC, 210 degreeC, and 230 degreeC) was measured on condition of the following conditions in nitrogen atmosphere using 25 mm diameter parallel plate.
・ Distortion amount: 10%
Measurement frequency range: 6.22 × 10 ^{−3 to} 6.22 × 10 ² rad / s (210 ° C. and 230 ° C. are 6.22 × 10 ^{−2 to} 6.22 × 10 ² rad / s)
The storage elastic modulus G ′ and the loss elastic modulus G ″ under five temperature conditions were superposed according to the principle of time-temperature superposition with a reference temperature of 190 ° C., and the shift factor a _T was obtained. The activation energy Ea of the flow was calculated from the slope.

The activation energy Ea _L [KJ / mol] calculated by the above formula (1) is the flow activation energy when it is assumed that the ethylene polymer of the present invention has no long chain branching, and “J F. Vega et al, Macromolecules vol.31 No. 11 3639-3647 (1998).

Specifically, the polymer of the present invention was measured for ¹³ C-NMR spectrum under the following conditions using a JNM-GSX400 type NMR apparatus and C10 type probe manufactured by JEOL Ltd., and “Eric T. Hsieh & James” was used. C. Randall, Macromolecules vol. 15, 353-360 (1982) "and" Eric T. Hsieh & James C. Randall, Macromolecules vol. 15, 1402-1406 (1982) ", SBC [number / 1,000C ] And B (the number of carbon atoms) were determined, and the activation energy Ea _{L was} determined by substituting SCB and B into the formula (1).
・ Pulse width: 8.0μs (Flip angle: 40 °)
・ Pulse repetition time: 5 seconds ・ Number of integration: 5,000 times or more ・ Solvent and internal standard: 1,2,4-trichlorobenzene / benzene-d ₆ / hexamethyldisiloxane (mixing ratio: 30/10/1)
・ Measurement temperature: 120 ℃
Sample concentration: 0.3 g / ml

The numerical value specification ΔEa of the present invention is a specification representing the concentration of long chain branching. For example, as shown in “RN Shoff & H. Mavridis, Macromolecules vol. 32 8454 (1999)”, it is good that the flow activation energy Ea is expressed by a linear function with respect to the concentration of the long chain branch. Are known. However, since Ea is also affected by short chain branching, the effect of short chain branching must be eliminated in order to make Ea a parameter only for the concentration of long chain branching.
Therefore, in the present invention, the concentration of the long chain branch is defined as the difference ΔEa from the activation energy Ea _L of the same type and the same number of long chain branches. That is, the difference between the flow activation energy Ea [KJ / mol] obtained above and the activation energy Ea _L [KJ / mol] calculated by the equation (1) is calculated as the flow activation energy difference ΔEa [KJ. / Mol], and ΔEa is 0 when there is no long chain branching, and shows a larger value as the concentration of long chain branching increases.
On the other hand, if the concentration of long-chain branches is simply increased, the melt flow characteristics are improved accordingly, but at the same time, the mechanical strength may be impaired. On the other hand, although it has no or little long chain branching, the flow characteristics are poor. Therefore, ΔEa is preferably in an appropriate range, specifically, 12.5 KJ / mol or less and 1.5 KJ / mol or more. Outside this range, the balance between moldability and mechanical properties is poor, which is inconvenient. This numerical range is set based on the ΔEa data in Table 2 in the examples described later.
In order to set the flow activation energy difference ΔEa within the above range, it can be achieved by adopting the production method of the present invention described later. This is possible by appropriately changing the amount of conjugated polyene used and the polymerization conditions.

ただしω＝１／ｔとする
ここで、Ｇ”（ω）は各速度ωの関数としての損失弾性率、Ｇ”（ω／２）はω／２の関数としての損失弾性率、ｔは時間である。
一方、非定常一軸伸長粘度曲線η_Ｅ（ｔ）において、歪の大きさが２．５以上で伸長粘度が最大となる点における時間をｔ_ｍａｘとし、下記式（６）により伸長粘度パラメータλを求める。λについての概念図を図２に示した。
λ＝η_Ｅ（ｔ_ｍａｘ）／3η⁺ _γ→0（ｔ_ｍａｘ） 式（６）
歪速度（設定値：１．０，０．３，０．１ｓ^−１）におけるλ値を求め、その中の最大値を伸長粘度λｍａｘとする。 (2) Elongation viscosity In the ethylene polymer according to the present invention, the elongation viscosity λmax and ΔEa satisfy the following formula (2).
λmax ≧ 1.2exp (0.0721 × ΔEa) Equation (2)
The elongational viscosity λmax can be obtained as follows.
Based on the method described in “Kunihiro Ozaki, Asao Murai, Nobuo Bessho Kinetsu, Journal of Japanese Society of Rheology Vol. 4 166 (1976)”, the following equation (5)
The viscosity growth function η ⁺ _{γ → 0} (t) shown in FIG.

Where ω = 1 / t
Here, G ″ (ω) is a loss elastic modulus as a function of each speed ω, G ″ (ω / 2) is a loss elastic modulus as a function of ω / 2, and t is time.
On the other hand, in the unsteady uniaxial extensional viscosity curve η _E (t), the time at the point where the magnitude of strain is 2.5 or more and the extensional viscosity becomes maximum is _tmax, and the extensional viscosity parameter λ is expressed by the following equation (6). Ask. A conceptual diagram of λ is shown in FIG.
λ = η _E (t _max ) / 3η ⁺ _{γ → 0} (t _max ) Equation (6)
The λ value at the strain rate (setting values: 1.0, 0.3, 0.1 s ⁻¹ ) is obtained, and the maximum value among them is defined as the extension viscosity λmax.

In the ethylene polymer of the present invention, it is necessary that the elongational viscosity λmax and ΔEa satisfy the formula (2). If the formula (2) is not satisfied, the balance between moldability and mechanical properties is unfavorable. In order to satisfy the formula (2), it can be achieved by adopting the production method of the present invention to be described later. Adjustment within the range of the formula (2) This can be done by appropriately changing the amount used and the polymerization conditions.
The elongational viscosity λmax of the present invention is a rule obtained by measuring the viscosity at a certain strain rate at a specific temperature that maintains the molten state, that is, strain hardening at the elongational viscosity. When the value of λmax is large, strain hardening, which is elastic, is strong, and when the value of λmax is small, strain hardening is weak. Although the optimum value of λmax varies depending on the molding method and molding conditions, it is desirable that the relationship with ΔEa satisfies the formula (7), more preferably the formula (8), and more preferably the formula (9). It is desirable to satisfy | fill, and it is satisfying Formula (10) most desirably.
λmax ≧ 1.2exp (0.0587 × ΔEa) Equation (7)
100 ≧ λmax ≧ 1.2exp (0.0587 × ΔEa) Formula (8)
100 ≧ λmax ≧ 1.2exp (0.0963 × ΔEa) Equation (9)
50 ≧ λmax ≧ 1.2exp (0.0963 × ΔEa) Formula (10)
When λmax is smaller than the lower limit of the above formula, melt elasticity corresponding to the concentration of LCB is not obtained, so that molding stability is low and mechanical strength is inferior. On the other hand, when λmax exceeds 100, excessive residual stress and anisotropy are generated in the molded product, which often causes problems in long-term performance such as impact resistance and stress crack resistance.

3. Metallocene catalyst The catalyst used for obtaining the polymer of the present invention will be described in detail, but the present invention is not limited to the transition metal compounds exemplified below.
In the ethylene polymer of the present invention, in order to improve molding processability without impairing mechanical properties, the structure and the number of branches of long and short chains in the polymer main chain of the ethylene polymer are related. The structure and number of branches required for the long and short chain are determined by combining two or more specific metallocene catalysts, more preferably complex with formation of long chain branch in the presence of non-conjugated polyene and substantially long chain branching. A polymerization reaction may be carried out using a complex that does not involve formation, and a metallocene catalyst having two types of complexes allows a short-chain branch (SCB) having 1 to 20 carbon atoms and a long-chain branch having more than 20 carbon atoms ( LCB) is introduced into the polymer main chain of the ethylene polymer.

(1) Complexes A and B
One complex A employed in the metallocene catalyst having two kinds of complexes of the present invention has a structure in which two or more ligands are coordinated to the central transition metal, and (i) in the presence of a promoter, Transition metal having a melt flow rate MFR-A of a polymer obtained by polymerization in the absence of hydrogen and non-conjugated polyene of preferably 2 g / 10 min or less, more preferably 0.4 g / 10 min or less Any compound may be used.
The other complex B has a structure in which two or more ligands are coordinated to the central transition metal, and (ii) the melt flow of the polymer obtained when polymerization is performed under the same conditions as in (i) above. The rate MFR-B may be a transition metal compound that is preferably 10 times or more that of MFR-A.
(Iii) In the presence of the complex A and the cocatalyst, hydrogen is not present, and the polymer MFR obtained when the polymerization is performed under the condition that 0.01 mol% of the non-conjugated polyene is present with respect to ethylene is expressed as “MFR -A + ", and when MFR of the polymer obtained when polymerization is performed under the same conditions using the complex B instead of the complex A is preferably" MFR-B + ", the following formula (3), Preferably, it is necessary to satisfy the following formula (4).
{(MFR-A +) / (MFR-A)} / {(MFR-B +) / (MFR-B)} <0.8 Formula (3)
{(MFR-A +) / (MFR-A)} / {(MFR-B +) / (MFR-B)} <0.3 Formula (4)
Furthermore, the complex A of the present invention is preferably a transition metal compound that gives a polymer having a long chain branch, and the complex B of the present invention is preferably a transition metal compound that gives a polymer having no long chain branch. . The long chain branching referred to in the present invention is a branch having more than 20 carbon atoms, and the molecular weight of the branched part is 1,100 or more in terms of weight molecular weight.
The amount ratio of the polymer component [A] derived from the complex A and the polymer component [B] derived from the complex B is preferably [A] / [B] = 10/90 to 90/10, more preferably 20 / 80 to 80/20. The ratio of the polymer component [A] to the polymer component [B] can be calculated from the polymerization activity when polymerized with the catalyst comprising the complex A and the cocatalyst, and the complex B and the cocatalyst.
Outside the above range, the balance between the molding processability and mechanical properties of the ethylene polymer is impaired, which is not preferable.

  As a general method for introducing long-chain branching, there is a method using a complex that easily causes macromonomer formation and reinsertion due to β-hydrogen elimination during polymerization. As an example of a catalyst complex, a bridged indene is coordinated. Examples of the complex are children. However, when such a complex (particularly a complex that produces a long-chain branched structure that is considered to be effective for improving processability) is used alone, the MFR of the resulting polymer inevitably decreases from the polymer structure, It will be far below the practical range. As a countermeasure, a method using a chain transfer agent (hydrogen) at the time of polymerization is used to lower the molecular weight, but the effect of improving workability is diminished because the molecular weight of the long-chain branching component required is also reduced. It is not preferable to use a complex that forms a long-chain branched polymer alone. In the present invention, in order to obtain a practical MFR polymer while maintaining a long-chain branched structure effective for improving processability, a specific complex that produces a low-MFR long-chain branched polymer and a relatively MFR A well-balanced ethylene polymer can be obtained by combining a specific complex that produces a high-molecular-weight polymer and polymerizing under specific conditions to introduce long-chain branching preferentially into a high-molecular-weight component (low MFR component). can get. Such new findings are groundbreaking in the metallocene catalyst field.

In the present invention, the object of the present invention can also be achieved by producing two types of polymers using specific complexes separately, and mixing the two types of polymers. By using a metal compound as one catalyst and producing an ethylene polymer using the catalyst, it becomes possible to uniformly mix two types of polymers with significantly different physical properties as a result of polymerization, and has excellent homogeneity Can be manufactured.
Furthermore, in order to achieve the object of the invention, the inventors of the present application have studied the coexistence of a non-conjugated polyene at the time of polymerization with respect to a catalyst using two kinds of the above-mentioned complexes (may be three or more kinds). It has also been newly discovered that the presence of a small amount of non-conjugated polyene significantly improves the physical property values that are indicative of processability. This is largely due to the difference in reactivity of the complex used with respect to the non-conjugated polyene. It was found that the effect is further increased by “combining the complex under a predetermined condition”, and when the catalyst of such a combination is used, the characteristics of the ethylene polymer can be controlled by the non-conjugated polyene concentration.

化合物［１］

化合物［２］

ここで置換基Ｒ^２〜Ｒ^1５は炭素数１〜３０の炭化水素基、炭素数１〜３０の炭化水素置換基を有するトリアルキル珪素基又は水素原子である。炭化水素基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、シクロヘキシル基などのアルキル基；ビニル基、アリル基などのアルケニル基；フェニル基、ジメチルフェニル基、ジエチルフェニル基、ジプロピルフェニル基、ジブチルフェニル基、トリメチルフェニル基、トリエチルフェニル基、トリプロピルフェニル基、トリブチルフェニル基、ビフェニル基、ナフチル基、アントリル基などのアリール基；トリチル基、フェネチル基、ベンズヒドリル基、フェニルプロピル基、フェニルブチル基、ネオフィル基などのアリールアルキル基、スチリル基などのアリールアルケニル基が挙げられる。これらは分岐があってもよい。
さらに、２つのシクロペンタジエニル骨格の有する配位子が、炭化水素基、シリレン基、置換シリレン基で架橋された、エチレンビス（インデニル）基、エチレンビス(４，５，６，７−テトラヒドロインデニル)基、ジメチルシリレンビス（インデニル）基なども有効である。中心遷移金属に結合したこれ以外の基は炭化水素基、アルコキシル基、ハロゲン原子又は水素原子である。 (2) Exemplification of Complex A Complex A used in the present invention is a complex that accompanies the generation of LCB when used in a polymerization reaction. Examples of such transition metal compounds include the following as a transition metal compound: It has a structure in which two or more ligands are coordinated. 1,3-dimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadienyl group, benzoindenyl group or substituted benzoindenyl group shown in compound [1] below, compound [2] And a dibenzoindenyl group or a substituted dibenzoindenyl group.

Compound [1]

Compound [2]

Here, the substituents R ^{2 to} R ¹⁵ are a hydrocarbon group having 1 to 30 carbon atoms, a trialkyl silicon group having a hydrocarbon substituent having 1 to 30 carbon atoms, or a hydrogen atom. Specific examples of the hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl group; an alkenyl group such as a vinyl group and an allyl group; a phenyl group and a dimethylphenyl group Aryl groups such as diethylphenyl group, dipropylphenyl group, dibutylphenyl group, trimethylphenyl group, triethylphenyl group, tripropylphenyl group, tributylphenyl group, biphenyl group, naphthyl group, anthryl group; trityl group, phenethyl group, Examples thereof include arylalkyl groups such as benzhydryl group, phenylpropyl group, phenylbutyl group and neophyll group, and arylalkenyl groups such as styryl group. These may be branched.
Furthermore, an ethylene bis (indenyl) group, an ethylene bis (4,5,6,7-tetrahydrol) in which a ligand having two cyclopentadienyl skeletons is crosslinked with a hydrocarbon group, a silylene group, or a substituted silylene group. Indenyl) groups, dimethylsilylenebis (indenyl) groups, and the like are also effective. The other group bonded to the central transition metal is a hydrocarbon group, an alkoxyl group, a halogen atom or a hydrogen atom.

Some specific examples of these complexes A are (1,3-Me ₂ Cpd) ₂ ZrCl ₂ , (1,3-Me ₂ Cpd) ₂ ZrBr ₂ , (1,3-Me ₂ Cpd) ₂ ZrMe _2. , (1,3-Me ₂ Cpd) ₂ Zr (OEt) ₂ , (1,3-Me ₂ Cpd) ₂ ZrBz ₂ , (1,2,4-Me ₃ Cpd) ₂ ZrCl ₂ , (1,2, 4-Me ₃ Cpd) ₂ ZrBr ₂ , (1,2,4-Me ₃ Cpd) ₂ ZrMe ₂ , (1,2,4-Me ₃ Cpd) ₂ Zr (OEt) ₂ , (1,2,4- _{Me 3 Cpd) 2 ZrBz 2,} (BzIND) 2 ZrCl 2, (BzIND) 2 ZrBr 2, (BzIND) 2 ZrMe 2, (BzIND) 2 Zr (OEt) 2, (BzIND) 2 ZrBz 2, (DBI) 2 _{ZrCl 2, (DBI) 2 ZrBr} 2, (DBI) _{ZrMe 2, (DBI) 2 Zr} (OEt) 2, (DBI) 2 ZrBz 2, Et (IND) 2 ZrCl 2, Et (IND) 2 ZrBr 2, Et (IND) 2 ZrMe 2, Et (IND) 2 Zr (OEt) ₂ , Et (IND) ₂ ZrBz ₂ , Et (4,5,6,7-H ₄ -IND) ₂ ZrCl ₂ , Et (4,5,6,7-H ₄ -IND) ₂ ZrBr ₂ Et (4,5,6,7-H ₄ -IND) ₂ ZrMe ₂ , Et (4,5,6,7-H ₄ -IND) ₂ Zr (OEt) ₂ , Et (4, 5, 6, 7-H ₄ -IND) ₂ ZrBz ₂ , Me ₂ Si (IND) ₂ ZrCl ₂ , Me ₂ Si (IND) ₂ ZrBr ₂ , Me ₂ Si (IND) ₂ ZrMe ₂ , Me ₂ Si (IND) ₂ Zr ( _{OEt) 2, Me 2 Si (} IND) 2 ZrBz 2, (1, _{-Me 2 Cpd) 3 ZrH, (} 1,2,4-Me 3 Cpd) 3 ZrH, (BzIND) 3 ZrH, (DBI) 3 ZrH, (1,3-Me 2 Cpd) 2 (IND) ZrH, ( 1,2,4-Me ₃ Cpd) ₂ (IND) ZrH, (BzIND) ₂ (IND) ZrH, (DBI) ₂ (IND) ZrH, and the like.
Here, Cpd represents a cyclopentadienyl group, Bz represents a benzyl group, IND represents an indenyl group, BzIND represents a benzoindenyl group, and DBI represents a dibenzoindenyl group.

(3) Exemplification of Complex B Complex B used in the present invention is a complex that is substantially not accompanied by generation of LCB when used for polymerization. As a ligand of such a transition metal compound, complex A described above is used. Examples include cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, and substituted indenyl group other than the ligand used in the above. It is a trialkyl silicon group having a hydrocarbon substituent having 1 to 30 carbon atoms, which may be the same or different.
Specific examples of the hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl group; an alkenyl group such as a vinyl group and an allyl group; a phenyl group and a dimethylphenyl group Aryl groups such as diethylphenyl group, dipropylphenyl group, dibutylphenyl group, trimethylphenyl group, triethylphenyl group, tripropylphenyl group, tributylphenyl group, biphenyl group, naphthyl group, anthryl group; trityl group, phenethyl group, Examples thereof include arylalkyl groups such as benzhydryl group, phenylpropyl group, phenylbutyl group and neophyll group, and arylalkenyl groups such as styryl group. These may be branched.

Some specific examples of the complex B are (Cpd) ₂ ZrCl ₂ , (Cpd) ₂ ZrBr ₂ , (Cpd) ₂ ZrMe ₂ , (Cpd) ₂ Zr (OEt) ₂ , (Cpd) ₂ ZrBz ₂ , _{(MeCpd) 2 ZrCl 2, (} MeCpd) 2 ZrBr 2, (MeCpd) 2 ZrMe 2, (MeCpd) 2 Zr (OEt) 2, (MeCpd) 2 ZrBz 2, (PrCpd) 2 ZrCl 2, (PrCpd) 2 ZrBr _{2, (PrCpd) 2 ZrMe 2} , (PrCpd) 2 Zr (OEt) 2, (PrCpd) 2 ZrBz 2, (BuCpd) 2 ZrCl 2, (BuCpd) 2 ZrBr 2, (BuCpd) 2 ZrMe 2, (BuCpd) ₂ Zr (OEt) ₂ , (BuCpd) ₂ ZrBz ₂ , (MePrCpd) ₂ ZrCl ₂ , (MePrCpd) ₂ ZrBr ₂ , (Me _{PrCpd) 2 ZrMe 2, (MePrCpd} ) 2 Zr (OEt) 2, (MePrCpd) 2 ZrBz 2, (MeBuCpd) 2 ZrCl 2, (MeBuCpd) 2 ZrBr 2, (MeBuCpd) 2 ZrMe 2, (MeBuCpd) 2 Zr ( (OEt) ₂ , (MeBuCpd) ₂ ZrBz ₂ , (IND) ₂ ZrCl ₂ , (IND) ₂ ZrBr ₂ , (IND) ₂ ZrMe ₂ , (IND) ₂ Zr (OEt) ₂ , (IND) ₂ ZrBz ₂ , (MeIND) ₂ ZrCl ₂ , (MeIND) ₂ ZrBr ₂ , (MeIND) ₂ ZrMe ₂ , (MeIND) ₂ Zr (OEt) ₂ , (MeIND) ₂ ZrBz ₂ , (4, 5, 6, 7-H ₄ -IND _{) 2 ZrCl 2, (4,5,6,7-} H 4 -IND) 2 ZrBr 2, (4,5,6,7-H 4 -IND) 2 Zr _{e 2, (4,5,6,7-H 4} -IND) 2 Zr (OEt) 2, (4,5,6,7-H 4 -IND) 2 ZrBz 2, (IND) (MeCpd) ZrCl 2 , (IND) (MeCpd) ZrBr 2, (Cpd) 3 ZrH, (MeCpd) 3 ZrH, (PrCpd) 3 ZrH, (BuCpd) 3 ZrH, (MePrCpd) 3 ZrH, (MeBuCpd) 3 ZrH, (IND) 3 ZrH, (MeIND) ₃ ZrH, (4, 5, 6, 7-H ₄ -IND) ₃ ZrH, (Cpd) ₂ (IND) ZrH, (MeCpd) ₂ (IND) ZrH, (PrCpd) ₂ (IND) ZrH, (BuCpd) ₂ (IND) ZrH, (MePrCpd) ₂ (IND) ZrH, (MeBuCpd) ₂ (IND) ZrH, (MeIND) ₂ (IND) ZrH, (4,5,6,7-H ₄ − IND) ₂ (IND) ZrH _{(IND) 2 (BzIND) ZrH} , (IND) 2 (DBI) ZrH, and the like _{(IND) 2 (Me 2 Cpd} ) ZrH.

(4) Example of combination of complex A and complex B In the present invention, two kinds of transition metal compounds (complex A and complex B) are used as a catalyst in a combination that satisfies a predetermined condition. Specific combinations are exemplified below.
(1,3-Me ₂ Cpd) ₂ ZrCl ₂ and (IND) ₂ ZrCl ₂ , (1,3-Me ₂ Cpd) ₂ ZrMe ₂ and (IND) ₂ ZrMe ₂ , (1,2,4-Me ₃ Cpd ) ₂ ZrCl ₂ and (IND) ₂ ZrCl ₂ , (BzIND) ₂ ZrCl ₂ and (IND) ₂ ZrCl ₂ , (BzIND) ₂ ZrMe ₂ and (IND) ₂ ZrMe ₂ , (DBI) ₂ ZrCl ₂ and (BuCpd) ₂ ZrCl ₂ , (DBI) ₂ ZrMe ₂ and (IND) ₂ ZrMe ₂ , Et (IND) ₂ ZrCl ₂ and (BuCpd) ₂ ZrCl ₂ , Et (IND) ₂ ZrMe ₂ and (IND) ₂ ZrMe ₂ , Et ( 4,5,6,7-H ₄ -IND) ₂ ZrCl ₂ and (BuCpd) ₂ ZrCl ₂ , Et (4,5,6,7-H ₄ -IND) ₂ ZrMe ₂ and (IND) ₂ ZrMe ₂ , Me ₂ Si (IND) ₂ ZrCl ₂ and (BuCpd) ₂ ZrCl ₂ , Me ₂ Si (IND) ₂ ZrMe ₂ and (IND) ₂ ZrMe ₂ , (1,3-Me ₂ Cpd) ₃ ZrH and (IND) ₃ ZrH, (1,2,4-Me ₃ Cpd) ₃ ZrH and (IND) ₃ ZrH, (BzIND) ₃ ZrH and (IND) ₃ ZrH, (DBI) ₃ ZrH and (IND) ₃ ZrH, Combinations of (BzIND) ₂ (IND) ZrH and (IND) ₃ ZrH, (DBI) ₂ (IND) ZrH and (MePrCpd) ₃ ZrH, and the like can be given.

  By the production method combining a plurality of complexes of the present invention, it is possible to produce a homogeneous ethylene polymer with very few microgels, and it is possible to remarkably improve those listed in the prior art.

(5) Method for synthesizing complexes In the above examples of complexes, transition metal compounds having three ligands have been shown, but most of these are novel compounds that have not been known so far. Two examples of compound synthesis methods are shown below as [Synthesis Method 1] and [Synthesis Method 2]. However, the synthesis method of these transition metal compounds is not limited to these methods.

[Synthesis Method 1]
The following compounds a), b) and c) are produced by bringing them into contact with each other.
a) L ¹ L ² M ¹ X ¹ ₂
b) L ³ H
c) LiR
Here, L ¹ , L ² and L ³ represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a benzoindenyl group and a substituted benzoindenyl group, respectively. The substituent is a hydrocarbon group having 1 to 30 carbon atoms or an organosilicon group having a hydrocarbon group having 1 to 30 carbon atoms as a substituent, and may be the same or different. Of these, substituents bonded to the same cyclopentadienyl ring may be bonded to each other to form a cyclic hydrocarbon group (including a polycyclic structure). M ¹ represents a transition metal of Group 4 of the periodic table, and is preferably zirconium. X ¹ represents fluorine, chlorine, bromine or iodine, and the two X ¹ may be the same or different. Chlorine or bromine is preferable, and chlorine is particularly preferable. R represents an alkyl group such as an ethyl group, a propyl group, a butyl group, or a hexyl group. These may be branched. An n-butyl group is preferable.

When contacting compounds a), b) and c), usually in an inert atmosphere such as nitrogen or argon, generally aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, heptane, hexane, decane, dodecane, The reaction is carried out with stirring or non-stirring in the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon such as cyclohexane, or an oxygen-containing hydrocarbon solvent such as diethyl ether or tetrahydrofuran. Although there is no restriction | limiting in particular in a contact order, Specifically, it is desirable to carry out in the following orders.
After contacting compounds a) and c), b) is contacted. In contacting, each component may be added at once, may be added over a certain period of time, or may be added in divided portions. Moreover, you may perform contact of each component in multiple times.
The contact between the compounds a) and c) is usually carried out at a temperature of −100 to 0 ° C., preferably −80 to −40 ° C., preferably 5 minutes to 24 hours, more preferably 30 minutes to 3 hours. Thereafter, the temperature is preferably raised to −30 ° C. to 30 ° C., more preferably near 0 ° C. to 10 ° C., and then the generated alkali metal halide such as LiCl is removed by filtration. Further, after contacting compound b), the mixture is preferably stirred at a temperature of 0 ° C. to 150 ° C., more preferably 20 ° C. to 80 ° C., preferably 5 minutes to 3 days, more preferably 1 hour to 24 hours. After removing the solvent in the reaction solution, the transition metal compound of the present invention can be obtained after washing with an aliphatic hydrocarbon such as pentane or hexane.
After contacting compounds a), b) and c) with heating and stirring, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, aliphatic or alicyclic hydrocarbons such as heptane, hexane, decane, dodecane and cyclohexane LiCl can also be removed from the reaction solution by filtration from a liquid inert hydrocarbon solution such as Alternatively, after removing the solvent from the reaction solution, LiCl can be removed by washing with an oxygen-containing hydrocarbon solvent such as tetrahydrofuran.
Compound a) to c) are used in a proportion of preferably 1 to 50 mol, more preferably 2 to 8 mol of compound b) and 1 mol of compound c) to 1 mol of compound a). Can be used.

[Synthesis Method 2]
The following compounds d) and e) can be produced by contacting each other.
d) Ind ₃ ZrH
e) L ⁴ -H
Here, L ⁴ represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a benzoindenyl group, or a substituted benzoindenyl group. The substituent is a hydrocarbon group having 1 to 30 carbon atoms or an organosilicon group having a hydrocarbon group having 1 to 30 carbon atoms as a substituent, and may be the same or different. Of these, substituents bonded to the same cyclopentadienyl ring may be bonded to each other to form a cyclic hydrocarbon group (including a polycyclic structure).

When contacting compounds d) and e), usually in an inert atmosphere such as nitrogen or argon, generally aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, heptane, hexane, decane, dodecane, cyclohexane, etc. The reaction is carried out with or without stirring in the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon, or an oxygen-containing hydrocarbon solvent such as diethyl ether or tetrahydrofuran.
The contact between compounds d) and e) is usually carried out at a temperature of -80 to 150 ° C, preferably 0 to 50 ° C, preferably 1 minute to 3 hours, more preferably 10 minutes to 1 hour. Thereafter, the temperature is preferably raised to 0 ° C. to 150 ° C., more preferably near 20 ° C. to 110 ° C., and preferably stirred for 5 minutes to 3 days, more preferably 1 hour to 24 hours. After removing the solvent from the reaction solution, a novel transition metal compound can be obtained after washing with an aliphatic hydrocarbon such as pentane or hexane.
The compound d) and e) can be used at a ratio of preferably 1 to 50 mol, more preferably 2 to 8 mol, of compound e) with respect to 1 mol of compound d).
Ind ₃ ZrH of the compound d) can be obtained by the synthesis method 1 described above.

Furthermore, in the present invention, the following compounds in which alkylaluminum is bonded to a transition metal having three ligands are used, and these are also novel compounds that have been hardly known so far.
L ⁵ ₃ M ² -H-M ³ R ₃
Here, L ⁵ is a ligand having a cyclopentadienyl skeleton, and represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a benzoindenyl group, or a substituted benzoindenyl group. M ² represents a transition metal of Group 4 of the periodic table, and is preferably zirconium. M ³ is a group 13 compound of the periodic table, preferably aluminum or boron. R represents an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, or a hexyl group. These may be branched. An i-butyl group is preferable.
Although the example of the synthesis | combining method of the said compound is shown as [the synthesis method 3] below, the synthesis method is not restricted to this.

[Synthesis Method 3]
The following compounds f), g) and h) are produced by bringing them into contact with each other.
f) Ind ₃ ZrH
g) L ⁶ -H
h) AlR ₃
Here, L ⁶ represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a benzoindenyl group, or a substituted benzoindenyl group. The substituent is a hydrocarbon group having 1 to 30 carbon atoms or an organosilicon group having a hydrocarbon group having 1 to 30 carbon atoms as a substituent, and may be the same or different. Of these, substituents bonded to the same cyclopentadienyl ring may be bonded to each other to form a cyclic hydrocarbon group (including a polycyclic structure). R represents an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, or a hexyl group, and these may be branched. An i-butyl group is preferable.

When contacting compounds f), g), h), usually in an inert atmosphere such as nitrogen or argon, generally aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, heptane, hexane, decane, dodecane In the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon such as cyclohexane, or an oxygen-containing hydrocarbon solvent such as diethyl ether or tetrahydrofuran, the reaction is performed with stirring or without stirring.
The contacting of compounds f), g) and h) is usually carried out at a temperature of −80 to 150 ° C., preferably 10 to 100 ° C., preferably 1 minute to 48 hours, more preferably 10 minutes to 6 hours. . After removing the solvent in the reaction solution (concentration under reduced pressure if necessary), a novel transition metal compound can be obtained by washing with an aliphatic hydrocarbon such as pentane or hexane.
The compound f), g), h) are used in a proportion of preferably 0 to 50 mol, more preferably 0 to 8 mol, and h) 1 to 3 mol of compound g) with respect to 1 mol of compound f). Can be used.
Ind ₃ ZrH of the compound f) can be obtained by the synthesis method described above.

(6) Other components of metallocene catalyst The ethylene polymer of the present invention reacts with two types of transition metal compounds as described above to form ion pairs by reacting with the following organoaluminum oxy compounds or transition metal compounds. In combination with a compound to be used, or a mixture thereof, it is used for a polymerization reaction as a catalyst for olefin polymerization.

The organoaluminum oxy compound has an Al—O—Al bond in the molecule, and the number of bonds is usually in the range of 1 to 100, preferably 1 to 50. Such an organoaluminum oxy compound is a product usually obtained by reacting an organoaluminum compound with water. The reaction between organoaluminum and water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene and xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used. It is preferred to use group hydrocarbons.
As the organoaluminum compound used for the preparation of the organoaluminum oxy compound, any of the compounds represented by the following general formula can be used, but trialkylaluminum is preferably used.
R _t AlX _3-t
In the formula, R represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group or aralkyl group having 1 to 18 carbon atoms, preferably 1 to 12, X represents a hydrogen atom or a halogen atom, and t represents 1 ≦ t ≦ An integer of 3 is shown.
The alkyl group of the trialkylaluminum may be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, etc. It is particularly preferred that
Two or more of the above organoaluminum compounds can be used in combination. The reaction ratio of water to the organoaluminum compound (water / Al molar ratio) is preferably 0.25 / 1 to 1.2 / 1, particularly 0.5 / 1 to 1/1, and the reaction temperature is Usually, it is in the range of −70 to 100 ° C., preferably −20 to 20 ° C. The reaction time is usually selected in the range of 5 minutes to 24 hours, preferably 10 minutes to 5 hours. As water required for the reaction, not only mere water but also crystal water contained in copper sulfate hydrate, aluminum sulfate hydrate and the like and components capable of generating water in the reaction system can be used.
Of the above organoaluminum oxy compounds, those obtained by reacting alkylaluminum with water are usually called aluminoxanes, and in particular methylaluminoxane (including those substantially consisting of methylaluminoxane (MAO)) Suitable as an organoaluminum oxy compound.
As the organoaluminum oxy compound, two or more of the above organoaluminum oxy compounds can be used in combination, or a solution obtained by dispersing or dispersing the organoaluminum oxy compound in an inert hydrocarbon solvent is used. Also good.

Specific examples of compounds that react with transition metal compounds to form ion pairs include borane compounds and borate compounds.
More specifically, the borane compound is represented by triphenylborane, tri (o-tolyl) borane, tri (p-tolyl) borane, tri (m-tolyl) borane, tri (o-fluorophenyl) borane, tris (p -Fluorophenyl) borane, tris (m-fluorophenyl) borane, tris (2,5-difluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-trifluoromethylphenyl) borane, tris ( 3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluorobiphenyl) borane, tris ( Perfluoroanthryl) borane, tris (perfluoro) Naphthyl) borane.
Among these, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluoro) Biphenyl) borane, tris (perfluoroanthryl) borane, and tris (perfluorobinaphthyl) borane are more preferred, and tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris ( Examples are perfluoronaphthyl) borane and tris (perfluorobiphenyl) borane.

A specific example of the borate compound is a compound represented by the following general formula.
[L-H] ⁺ [BR ₄ ] ⁻
In the formula, L is a neutral Lewis base, H is a hydrogen atom, and [L-H] is a Bronsted acid such as ammonium, anilinium, or phosphonium. Examples of ammonium include trialkyl-substituted ammonium such as trimethylammonium, triethylammonium, tripropylammonium, and tri (n-butyl) ammonium, and dialkylammonium such as di (n-propyl) ammonium and dicyclohexylammonium.
Examples of anilium include N, N-dialkylanilinium such as N, N-dimethylanilinium, N, N-diethylanilinium, and N, N-2,4,6-pentamethylanilinium. Examples of the phosphonium include triarylphosphonium, tributylphosphonium, triarylphosphonium such as tri (methylphenyl) phosphonium, tri (dimethylphenyl) phosphonium, and trialkylphosphonium.
R is the same or different aromatic or substituted aromatic hydrocarbon group containing 6 to 20, preferably 6 to 16 carbon atoms, which may be linked to each other by a bridging group, of the substituted aromatic hydrocarbon group As the substituent, an alkyl group represented by a methyl group, an ethyl group, a propyl group, an isopropyl group or the like, or a halogen such as fluorine, chlorine, bromine or iodine is preferable.

Specific examples of the compound represented by the above general formula include tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5-ditrifluoro). Methylphenyl) borate, tributylammonium tetra (2,6-difluorophenyl) borate, tributylammonium tetra (perfluoronaphthyl) borate, dimethylaniliniumtetra (pentafluorophenyl) borate, dimethylaniliniumtetra (2,6-ditrifluoro) Methylphenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (2,6-difluorophenyl) Rate, dimethylanilinium tetra (perfluoronaphthyl) borate, triphenylphosphonium tetra (pentafluorophenyl) borate, triphenylphosphonium tetra (2,6-ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (3,5-ditri Fluoromethylphenyl) borate, triphenylphosphonium tetra (2,6-difluorophenyl) borate, triphenylphosphonium tetra (perfluoronaphthyl) borate, trimethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethylammonium tetra ( Examples include pentafluorophenyl) borate.
Among these, tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5-ditrifluoromethylphenyl) borate, tributylammonium tetra (perfluoro) Naphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2,6-ditrifluoromethylphenyl) borate and the like are more preferable.

A second example of the borate compound is represented by the following general formula.
[L ′] ⁺ [BR ₄ ] ⁻
In the formula, L ′ is a carbocation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, t-butyl cation, pentyl cation, tropinium cation, benzyl cation, trityl cation, sodium cation, proton, etc. Is mentioned. R has the same definition as R in the general formula in paragraph 0045.

Specific examples of the above compounds include trityl tetraphenyl borate, trityl tetra (o-tolyl) borate, trityl tetra (p-tolyl) borate, trityl tetra (m-tolyl) borate, trityl tetra (o-fluorophenyl) borate. , Trityltetra (p-fluorophenyl) borate, trityltetra (m-fluorophenyl) borate, trityltetra (3,5-difluorophenyl) borate, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditri Fluoromethylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, tropiniumtetraphenylborate, tropiniumtetra (o-tolyl) Borate, tropinium tetra (p-tolyl) borate, tropinium tetra (m-tolyl) borate, tropinium tetra (o-fluorophenyl) borate, tropinium tetra (p-fluorophenyl) borate, tropinium tetra (m- Fluorophenyl) borate, tropinium tetra (3,5-difluorophenyl) borate, tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (3,5 -Ditrifluoromethylphenyl) borate, tropinium tetra (perfluoronaphthyl) borate and the like can be exemplified.
Among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, tropy Nitrotetra (pentafluorophenyl) borate, tropiniumtetra (2,6-ditrifluoromethylphenyl) borate, tropiniumtetra (3,5-ditrifluoromethylphenyl) borate, tropiniumtetra (perfluoronaphthyl) borate is preferred .

An olefin polymerization catalyst comprising two or more transition metal compounds used in the present invention, an organoaluminum oxy compound, a compound that reacts with these transition metal compounds to form an ion pair, or a mixture thereof is supported on a carrier. Can be used as a solid catalyst.
As the carrier, an inorganic carrier, a particulate polymer carrier, or a mixture thereof is used. As the inorganic carrier, a metal, a metal oxide, a metal chloride, a metal carbonate, a carbon substance, or a mixture thereof can be used.
Suitable metals that can be used for the inorganic carrier include, for example, iron, aluminum, nickel and the like.
Further, alone oxide or composite oxide of the Periodic Table 1-8 Group elements as the metal oxide and the like, for example _{SiO 2, Al 2 O 3,} MgO, CaO, B 2 O 3, TiO 2, ZrO ₂ , Fe ₂ O ₃ , Al ₂ O ₃ · MgO, Al ₂ O ₃ · CaO, Al ₂ O ₃ · SiO ₂ , Al ₂ O ₃ · MgO · CaO, Al ₂ O ₃ · MgO · SiO ₂ , Al ₂ Examples include natural or synthetic various single or composite oxides such as O ₃ .CuO, Al ₂ O ₃ .Fe ₂ O ₃ , Al ₂ O ₃ .NiO, and SiO ₂ .MgO. Here, the above formula is not a molecular formula but represents only the composition, and the structure and component ratio of the composite oxide used in the present invention are not particularly limited. In addition, the metal oxide used in the present invention may absorb a small amount of moisture or may contain a small amount of impurities.
As the metal chloride, for example, chloride of alkali metal or alkaline earth metal is preferable, and specifically, MgCl ₂ , CaCl _{2 and the} like are preferable.
The metal carbonate is preferably an alkali metal or alkaline earth metal carbonate, and specific examples include magnesium carbonate, calcium carbonate, and barium carbonate.
Examples of the carbonaceous material include carbon black and activated carbon. Any of the above inorganic carriers can be suitably used in the present invention, but the use of metal oxides, silica, alumina and the like is particularly preferable.

These inorganic carriers are usually baked in air or an inert gas such as nitrogen or argon at 200 to 800 ° C., preferably 400 to 600 ° C., to adjust the amount of surface hydroxyl groups to 0.8 to 1.5 mmol / g. It is preferable to use.
The properties of these inorganic carriers are not particularly limited, but usually the average particle size is preferably 5 to 200 μm, more preferably 10 to 150 μm, and the specific surface area is preferably 150 to 1,000 m ² / g, more preferably 200. ˜500 m ² / g, pore volume is preferably 0.3 to 2.5 cm ³ / g, more preferably 0.5 to 2.0 cm ³ / g, and apparent specific gravity is preferably 0.20 to 0.50 g. It is preferable to use an inorganic carrier having a / cm ³ , more preferably 0.25 to 0.45 g / cm ³ .
Although the above-mentioned inorganic carriers can be used as they are, as a pretreatment, these carriers are trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, diisobutylaluminum. It can be used after contacting an organoaluminum compound such as hydride or an organoaluminum oxy compound containing an Al—O—Al bond.

Each of the components used when obtaining a catalyst for olefin polymerization from a carrier, which comprises two or more transition metal compounds used in the present invention, an organoaluminum oxy compound, a compound which reacts with a transition metal compound to form an ion pair, or a mixture thereof. A contact method is not specifically limited, For example, the following methods are arbitrarily employable.
(I) Two transition metal compounds are mixed and then contacted with a cocatalyst and then contacted with a support.
(II) A transition metal compound and a cocatalyst are contacted, then contacted with another transition metal compound, and then contacted with a support.
(III) One kind of transition metal compound is brought into contact with the cocatalyst, then brought into contact with the support, and then another transition metal compound is brought into contact.
(IV) The two transition metal compounds are brought into contact with the support, and then the promoter is brought into contact.
(V) The cocatalyst and the support are contacted, and then contacted with the two transition metal compounds.
Among these contact methods, (I), (II), (III) and (V) are preferable. In any contact method, usually in an inert atmosphere such as nitrogen or argon, generally an aromatic hydrocarbon such as benzene, toluene, xylene or ethylbenzene, an aliphatic or alicyclic such as heptane, hexane, decane, dodecane or cyclohexane. In the presence of a liquid inert hydrocarbon such as a group hydrocarbon, a method of bringing each component into contact with stirring or non-stirring is employed. This contact is usually performed at a temperature of −100 ° C. to 200 ° C., preferably −50 ° C. to 100 ° C., preferably 10 minutes to 50 hours, and more preferably 1 hour to 24 hours.
In addition, when contacting the carrier with a transition metal compound, an organoaluminum oxy compound, a compound that reacts with the transition metal compound to form an ion pair, there is an aromatic hydrocarbon solvent in which certain components are soluble or hardly soluble Any aliphatic or alicyclic hydrocarbon solvent in which the seed component is insoluble or hardly soluble can be used.
In the case where the contact reaction between the components is performed stepwise, this may be used as it is as the solvent for the subsequent contact reaction without removing the solvent used in the previous step. In addition, after the previous contact reaction using a soluble solvent, after adding a liquid inert hydrocarbon in which a certain component is insoluble or hardly soluble, and recovering a desired product as a solid, or once the soluble solvent is used. After removing part or all by means such as concentration and drying to remove the desired product as a solid, the subsequent catalytic reaction of the desired product is carried out using any of the inert hydrocarbon solvents described above. It can also be implemented. In this invention, it does not prevent performing contact reaction of each component in multiple times.

The ratio of the compound that forms two or more transition metal compounds used in the present invention, an organoaluminum oxy compound, and a transition metal compound to form an ion pair and the carrier are not particularly limited, but the following ranges are preferable.
When using an organoaluminum oxy compound, the atomic ratio (Al / M) of the aluminum of the organoaluminum oxy compound to the transition metal (M) in the transition metal compound is usually 1 to 100,000, preferably 5 to 1,000, More preferably, the range of 50 to 200 is desirable, and when a compound that reacts with a transition metal compound to form an ion pair is used, the atomic ratio (B / M) of boron to the transition metal of the transition metal compound is usually 0. It is desirable to select in the range of 01 to 100 mol, preferably 0.1 to 50 mol, more preferably 0.2 to 10 mol.
The amount of the support used is 1 g per 0.0001 to 5 mmol of the transition metal in the transition metal compound, preferably 0.001 to 0.5 mmol, and more preferably 0.01 to 0.1 mmol.
A transition metal compound, an organoaluminum oxy compound, a compound that reacts with a transition metal compound to form an ion pair and a support are brought into contact with each other by any one of the contact methods (I) to (V), and then the solvent is removed. By doing so, the catalyst for olefin polymerization can be obtained as a solid catalyst. It is desirable to remove the solvent under normal pressure or reduced pressure, preferably 0 to 200 ° C., more preferably 20 to 150 ° C., preferably 1 minute to 50 hours, more preferably 10 minutes to 10 hours.
The olefin polymerization catalyst can also be obtained by the following method.
(VI) The transition metal compound and the carrier are contacted to remove the solvent, and this is used as a solid catalyst component, which is contacted with an organoaluminum oxy compound and a compound that forms an ion pair by reacting with the transition metal compound under polymerization conditions.
(VII) A compound that reacts with an organoaluminum oxy compound and a transition metal compound to form an ion pair and a carrier are brought into contact with each other to remove the solvent, which is used as a solid catalyst component and brought into contact with the transition metal compound under polymerization conditions.
In these contact methods, the same conditions as described above can be used for the component ratio, contact conditions, and solvent removal conditions.

Two or more transition metal compounds used in the present invention can be used as a catalyst by being supported on a layered silicate.
The layered silicate is a silicate compound having a crystal structure in which planes formed by ionic bonds or the like are stacked in parallel with each other with a weak binding force.
Most layered silicates are naturally produced mainly as a main component of clay minerals, but these layered silicates are not limited to natural ones, and may be artificial synthetics. Among these, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, teniolite, and other smectites, vermiculites, and mica are preferred.
In general, natural products are often non-ion-exchangeable (non-swellable). In that case, in order to have a preferable ion-exchange (or swellable), the ion-exchangeability (or swellable) is improved. It is preferable to perform the process for providing. Among such treatments, particularly preferred are the following chemical treatments. Here, the chemical treatment may be any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure and chemical composition of the layered silicate. Specifically, (a) acid treatment using hydrochloric acid, sulfuric acid, etc., (b) alkali treatment using NaOH, KOH, NH _3, etc. Salt treatment with a salt comprising at least one anion selected from the group consisting of a cation containing at least one selected atom and a halogen atom or an anion derived from an inorganic acid, (d) alcohol, carbonization Examples of the organic treatment include hydrogen compounds, formamide, and aniline. These processes may be performed independently or two or more processes may be combined.
The layered silicate can be controlled in particle properties by pulverization, granulation, sizing, fractionation, etc. at any time before or after all steps.
Layered silicates can be used as they are, but these layered silicates are trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, diisobutylaluminum hydride, etc. And an organoaluminum oxy compound containing an Al—O—Al bond.

In order to support two or more transition metal compounds used in the present invention on the layered silicate, the transition metal compound and the layered silicate are brought into contact with each other, or the transition metal compound, the organoaluminum compound, and the layered silicate are brought into contact with each other. You may let them. The contact method of each component is not specifically limited, For example, the following methods are arbitrarily employable.
(VIII) Two transition metal compounds and an organoaluminum compound are brought into contact with each other, and then brought into contact with a carrier (layered silicate).
(IX) Two kinds of transition metal compounds and a carrier are brought into contact with each other and then brought into contact with an organoaluminum compound.
(X) One kind of transition metal compound and a carrier are brought into contact, then the carrier and organoaluminum are brought into contact, and then another transition metal compound is brought into contact.
(XI) After contacting the organoaluminum oxy compound and the carrier, the two transition metal compounds are contacted.
Of these contact methods, (VIII) and (XI) are particularly preferred. In any contact method, usually in an inert atmosphere such as nitrogen or argon, generally an aromatic hydrocarbon such as benzene, toluene, xylene or ethylbenzene, an aliphatic or alicyclic such as heptane, hexane, decane, dodecane or cyclohexane. In the presence of a liquid inert hydrocarbon such as a group hydrocarbon, a method of bringing each component into contact with stirring or non-stirring is employed.
The use ratio of the transition metal compound, the organoaluminum compound, and the carrier is not particularly limited, but the following ranges are preferable. The amount of transition metal compound supported is 0.0 per gram of layered silicate.
001 to 5 mmol, preferably 0.001 to 0.5 mmol, more preferably 0.01 to 0.1 mmol. When the organoaluminum compound is used, the amount of Al supported is in the range of 0.01 to 100 mol, preferably 0.1 to 50 mol, more preferably 0.2 to 10 mol.
For the method of supporting and removing the solvent, the same conditions as those for the inorganic carrier can be used. The olefin polymerization catalyst thus obtained may be used after prepolymerization of the monomer as necessary for adjusting the particle shape and the like.

4). Polymerization in the presence of non-conjugated polyene In the present invention, in the use of the above-mentioned two specific metallocene catalysts, ethylene is homopolymerized in the presence of a small amount of non-conjugated polyene such as α, ω-non-conjugated diene or the like. By copolymerizing with other olefins, a polyethylene composition having excellent processability can be produced without impairing mechanical strength.
The olefins referred to here include α-olefins, cyclic olefins, styrene analogs and polar group-containing olefins.

In the present invention, in the polymerization in the presence of non-conjugated polyene, a method for controlling the structure of the long-chain branching component by controlling the non-conjugated polyene concentration was found, and the processability of the polyethylene composition was greatly improved. did. The usable non-conjugated polyene has 5 to 24 carbon atoms, and preferably is a 6 to 18 carbon non-conjugated diene or non-conjugated triene having two or more terminal double bonds. Preferred examples include 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,13-tetradecadiene, Examples include 3-methyl-1,4-pentadiene, 1,5,9-decatriene, 1,2,4-trivinylcyclohexane, and more preferably 1,7-octadiene.
The amount of the non-conjugated polyene used in the present invention is 0 to 1 mol%, preferably 0 to 0.5 mol%, more preferably 0.0001 to 0.05 mol%, relative to ethylene in the polymerization system. If the amount of non-conjugated polyene used exceeds 1 mol%, the balance between the molding processability and mechanical properties of the ethylene polymer is impaired, which is not preferable.
In addition, the concept which shows the difference of the MFR of the polymer polymerized using the complex A and B of this invention in FIG. 1 and the difference in the reactivity when a polyene is made to coexist is shown in figure by FIG. There is a difference in MFR of 10 times or more when polyene is not present, and it is shown that the decrease in MFR due to complex A is greater than that due to complex B when polyene is present.

5. Copolymerized monomer In the present invention, it can be copolymerized with α-olefins, cyclic olefins, styrene analogs and polar group-containing olefins.
The α-olefins include those having 3 to 20 carbon atoms, preferably 3 to 8 carbon atoms, specifically, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene. And vinylcyclohexane. Two or more kinds of α-olefins can be copolymerized, and the amount of α-olefin is selected in the range of 40 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less of the total monomers. .
As the cyclic olefin, those having 3 to 24 carbon atoms, preferably 3 to 18 carbon atoms can be used in the present invention, and examples thereof include cyclopropene, cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene, cyclooctene, and cyclodecene. , Cyclododecene, tetracyclodecene, octacyclodecene, dicyclopentadiene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene 5,5,6-trimethyl-2-norbornene, ethylidene norbornene and the like. The amount of the cyclic olefin is 50 mol% or less, usually 1 to 50 mol%, preferably 2 to 50 mol% of the copolymer.
Styrene analogs that can be used in the present invention are styrene and styrene derivatives, which include t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N , N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene, and the like.

6). Polymerization method The polymerization reaction can be carried out by slurry polymerization, solution polymerization, or gas phase polymerization in the presence of the metallocene catalyst. Slurry polymerization or gas phase polymerization is preferred, with substantially no oxygen and moisture, aliphatic hydrocarbons such as isobutane, hexane, heptane, aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, methylcyclohexane, etc. The olefin is polymerized in the presence or absence of an inert hydrocarbon solvent selected from alicyclic hydrocarbons. As for the polymerization conditions at this time, the temperature is preferably 20 to 200 ° C., more preferably 50 to 100 ° C., the pressure is preferably in the range of normal pressure to 7 MPa, more preferably normal pressure to 3 MPa, and the polymerization time is preferable. Is 5 minutes to 10 hours, more preferably 5 minutes to 5 hours.
The molecular weight of the produced polymer can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but the molecular weight can be adjusted more effectively by adding hydrogen to the polymerization reaction system. it can.
Further, the polymerization can be carried out without any trouble even if a component for removing water, a so-called scavenger, is added to the polymerization system. Such scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum and triisobutylaluminum, organoaluminum oxy compounds, modified organoaluminum compounds containing branched alkyl, organozinc compounds such as diethylzinc and dibutylzinc, diethylmagnesium. Organic magnesium compounds such as dibutylmagnesium and ethylbutylmagnesium, and Grignard compounds such as ethylmagnesium chloride and butylmagnesium chloride are used. Of these, triethylaluminum, triisobutylaluminum, and ethylbutylmagnesium are preferable, and triethylaluminum is particularly preferable.
The present invention can also be applied to a multistage polymerization system having two or more stages having different polymerization conditions such as hydrogen concentration, monomer and comonomer concentration, nonconjugated diene concentration, polymerization pressure, and polymerization temperature.

  In the following, the present invention will be described in more detail and specifically by comparing each comparative example with each example, the configuration and effects of the present invention will be clarified, and each requirement of the configuration of the present invention will be rationalized. Establish gender and significance.

[Measurement of polymer properties]
The physical properties of the polymers obtained in each Example and each Comparative Example were measured by the method described below. The resin used for the test was prepared by adding 0.1 parts by weight of B-225 (Ciba Specialty Chemicals, Inc., Irganox (registered trademark)) as an antioxidant, and kneading at 150 ° C. for 10 minutes. Was used.
1) Melt flow rate MFR and DSR
MFR was measured under the conditions of a temperature of 190 ° C. and a load of 21.18 N according to Table 1-Condition 7 of JIS K-7210.
At this time to measure the diameter D _S of the extruded strands from the die, to determine the specific D _{S /} Do of the diameter Do of the orifice, and a DSR.
2) Density Measured according to JIS K-7112.
3) High load melt flow rate HLMFR and HL / MFR
HLMFR was measured under the conditions of a temperature of 190 ° C. and a load of 21.18 N according to Table 1-Condition 7 of JIS K-7210.
Further, the ratio HLMFR / MFR between HLMFR and MFR was defined as HL / MFR.
4) Flow ratio FR
FR is a value obtained by calculation from MFR ₁₀ / MFR ₂ of the melt flow rate. Here, MFR ₂ is a value measured under conditions of a temperature of 190 ° C. and a load of 21.18 N according to JIS K-7210-1999. MFR ₁₀ is a temperature of 190 ° C. and a load of 98.98 according to JIS K-7210-1999. It is a value measured under the condition of 06N.
5) Memory effect ME
It measured as follows using the melt indexer used by JISK-7210. Under the condition of a cylinder temperature of 240 ° C., after the sample is filled in the apparatus, only the piston is mounted, and after 6 minutes, the molten sample is pushed out at a constant rate of 3 g / min. Cut at the outlet just below, and then place a graduated cylinder containing ethyl alcohol directly below the orifice so that the liquid level is 20 mm from the bottom of the orifice, take a straight extrudate, and set its diameter to 0. Measure in units of 01 mm. The value is divided by the orifice inner diameter of 2.095 mm to obtain the ME value.
6) Measurement of molecular weight and molecular weight distribution by GPC Using an Alliance GPC2000 model manufactured by Waters Co., Ltd., measurement was performed under the following conditions to obtain molecular weight and molecular weight distribution.
Column: Showdex HT-G and HT-806M × 2 columns Solvent: 1,2,4-trichlorobenzene Temperature: 140 ° C.
-Flow rate: 1.0 ml / min The column was calibrated by a monodisperse polystyrene (S-7300 S-3900 S-1950 S-1460 S-1010 S-565 S-152 S-66.0 S-28. 5 S-5.05 each 0.2 mg / ml solution)
n-eicosane and n-tetracontane were measured, and the logarithmic values of elution time and molecular weight were approximated by a quartic equation. In addition, the following formula was used for conversion of the molecular weight of polystyrene and polyethylene.
M _PE = 0.468 × M _PS
7) Number of short chain branches per 1,000 C of main chain (SCB)
A ¹³ C-NMR spectrum was measured under the following conditions using a JNM-GSX 400 type NMR apparatus manufactured by JEOL Ltd. and a C10 type probe.
・ Pulse width: 8.0μs (Flip angle = 40 °)
・ Pulse repetition time: 5 seconds ・ Number of integration: 5,000 times or more ・ Solvent and internal standard: 1,2,4-trichlorobenzene / benzene-d ₆ / hexamethyldisiloxane (mixing ratio: 30/10/1)
・ Measurement temperature: 120 ℃
Sample concentration: 0.3 g / ml
Analysis of the obtained spectrum is, for example, “Eric T. Hsieh & James C. Randall, Macromolecules vol. 15, 353-360 (1982)” for ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer. About the polymer, it carried out according to the literature of "Eric T. Hsieh & James C. Randall, Macromolecules vol. 15, 1402-1406 (1982)", and calculated | required SCB.
8) Flow activation energy Ea
According to the method described in paragraph 0018.
9) Elongation viscosity λmax
A resin used for the test was hot-pressed at 190 ° C. to prepare a 150 mm × 70 mm × 2 mm sheet, and a sheet punched out from this sheet to 7 mm × 70 mm × 2 mm was used as a sample. An unsteady uniaxial extensional viscosity curve at 140 ° C. and strain rate (setting values: 1.0, 0.3, 0.1 s ⁻¹ ) was measured using an RME type uniaxial extensional viscosity measuring device manufactured by Rheometric.
Next, from the dynamic viscoelasticity measurement data at 140 ° C. measured under the same conditions as the activation energy of flow, λmax is calculated using equations (5) and (6) described in paragraph 0022 and the calculation method. did.
10) Melting point measurement by differential thermal scanning calorimeter (DSC) Using a DSC6200R melting point measuring device manufactured by Seiko Electronics, 5 mg of sample was held at 180 ° C. for 3 minutes, then cooled to 0 ° C. at 10 ° C./min The melting point was measured by holding at 10 ° C. for 10 minutes and then raising the temperature at 10 ° C./min.

[Preparation of polymerization catalyst]
Toluene and hexane used for complex preparation and catalyst preparation were degassed and dehydrated with molecular sieve 3A. As the methylaluminoxane MAO, Albemarle 20 wt% toluene solution product (Al concentration is about 2.9 mol / L) was used. The silica used as the carrier for the solid catalyst was a material having a surface area of 290 m ² , a pore volume of 1 ml / g, and an average particle size of 45 μm and calcined at 650 ° C. for 7 hours. Benzoindene was a mixture of 4,5-benzoindene and 6,7-benzoindene, and was synthesized based on “Bulletin de la Society Chimique de Frace (1967) 3 987-992”. Dibenzoindene is 1H-cyclopenta [1] phenanthrene, and one synthesized based on “Organanometallics (1997) 16 3413-3420” was used.

[Synthesis of transition metal complexes]
(Preparation of trisindenylzirconium hydride (complex 1))
Under a nitrogen atmosphere, 1 mmol (0.39 g) of bisindenylzirconium dichloride (Ind ₂ ZrCl ₂ ) was suspended in 30 ml of toluene in a 100 ml eggplant-shaped flask and cooled to −78 ° C. with a cryogen (dry ice-ethanol). -Add 2 mmol of butyl lithium (n-BuLi). The mixed solution is taken out of the cryogen and the temperature is raised slowly, and 4 mmol of indene is added at around 0 ° C. The temperature is further raised to room temperature and the reaction is carried out for 30 minutes. Lithium chloride (LiCl) precipitated after the reaction is filtered off. The filtrate was further reacted at 50 ° C. for 12 hours, and the deposited precipitate was washed with n-hexane to obtain Complex 1 with a yield of 64%.
(Preparation of trisbenzoindenylzirconium hydride (complex 2))
Under a nitrogen atmosphere, 0.31 mmol (0.14 g) of trisindenylzirconium hydride was suspended in 5 ml of hexane in a 50 ml eggplant-shaped flask, and 1.2 mmol of benzoindene (BenzInd) was added and reacted at 50 ° C. for 2 hours. After removing the solvent, the precipitated solid was washed with n-hexane to obtain Complex 2 in a yield of 83%.
(Preparation of tris (dibenzoindenyl) zirconium hydride (complex 3))
Under a nitrogen atmosphere, 0.64 mmol (0.28 g) of trisindenylzirconium hydride was taken in a 50 ml eggplant-shaped flask, and 21 ml of a 0.1 mol / L toluene solution of dibenzoindene was added and suspended at 80 ° C. for 30 minutes. Reacted. After removing the solvent, the precipitated solid was washed with n-hexane to obtain 0.38 g of Complex 3 in a yield of 80%.

[Preparation of solid catalyst]
(Preparation of solid catalyst I)
46 mg (0.1 mmol) of complex 1 and 59 mg (0.1 mmol) of complex 2 were placed in a 100 ml eggplant flask, 20 ml of toluene and 14 ml of methylaluminoxane toluene solution (40 mmol of Al) were added thereto, and then 300 ml of magnetic The above mixed solution was added to a flask equipped with an induction stirrer and degassed by adding 10 g of silica. Thereafter, the solvent was removed under reduced pressure to obtain a solid catalyst having good fluidity.
(Preparation of solid catalyst II)
It was prepared in the same manner as the solid catalyst I except that 46 mg (0.1 mmol) of complex 1 and 118 mg (0.2 mmol) of complex 2 were used.
(Preparation of solid catalyst III)
It was prepared in the same manner as the solid catalyst I except that 46 mg (0.1 mmol) of complex 1 and 177 mg (0.3 mmol) of complex 2 were used.
(Preparation of solid catalyst IV)
Prepared in the same manner as Solid catalyst I except that 58 mg (0.1 mmol) of complex 2 was used.
(Preparation of solid catalyst V)
Based on JP 2000-154196 A (Example 8), it was prepared as follows.
In a 50 ml flask, 5.7 ml of toluene, 1.4 g (3 mmol) of an n-butanol (1: 1) mixture of zirconium tetra n-butoxide, 2.1 g (18 mmol) of indene, 1.1 g of 1-methyl-3-propylcyclopentadiene (9 mmol) was added, heated to 90 ° C., and 21 ml of a toluene solution of triisobutylaluminum (1.2 mol / L) was added dropwise to the solution over 2 hours to prepare a transition metal complex solution. A solution prepared by mixing 4.4 ml of this solution (0.09 mol / L), 14 ml of a toluene solution of methylaluminoxane, and 20 ml of toluene was degassed by adding 10 g of silica to a flask equipped with a 300 ml magnetic induction stirrer in advance. Added to the soup. Thereafter, the solvent was removed under reduced pressure to obtain a solid catalyst having good fluidity.
(Preparation of solid catalyst VI)
Prepared in the same manner as Solid catalyst I except that 46 mg (0.1 mmol) of complex 1 was used.
(Preparation of solid catalyst VII)
A solid catalyst I was prepared in the same manner except that 74 mg (0.1 mmol) of the complex 3 was used.

[Polymerization reaction]
Example 1
In a gas phase continuous polymerization apparatus (internal volume 100 L, fluidized bed diameter 10 cm) prepared at a predetermined temperature, comonomer / ethylene molar ratio, hydrogen / ethylene molar ratio, gas composition of nitrogen concentration 30 mol%, and pressure 0.8 MPa shown in Table 1. Polymerization was carried out at a constant gas composition and temperature while intermittently supplying a solid catalyst. As the comonomer, 1,7-octadiene mixed with 1-hexene at a ratio of 2 ml / L was used. The physical properties of the obtained polymer are shown in Table 2.
(Example 2)
Polymerization was carried out in the same manner as in Example 1 except that the solid catalyst and polymerization conditions shown in Table 1 were changed. The results are shown in Table 2.
Example 3
Polymerization was carried out in the same manner as in Example 1 except that the solid catalyst and polymerization conditions shown in Table 1 were changed. The results are shown in Table 2.
Example 4
Polymerization was carried out in the same manner as in Example 3 except that 1,7-octadiene diluted to 1-hexene at a concentration of 5 ml / L was used. The results are shown in Table 2.
(Examples 5-6)
Polymerization was carried out in the same manner as in Example 1 using the solid catalysts and polymerization conditions shown in Table 1. The results are shown in Table 2.
(Comparative Example 1)
It carried out similarly to Example 8 of Unexamined-Japanese-Patent No. 2000-154196.
(Comparative Examples 2-3)
Polymerization was carried out in the same manner as in Example 1 except that the solid catalyst and polymerization conditions shown in Table 1 were changed. 1,7-octadiene was not used. The results are shown in Table 2.
(Comparative Example 4)
30 parts by weight of high pressure method low density polyethylene LS601 manufactured by Nippon Polyethylene Co., Ltd. was melt-kneaded with 70 parts by weight of the polymer obtained in Comparative Example 1.

（ａ）１，７−オクタジエン／エチレンフィードモル比［ｐｐｍ］
（ｂ）水素／エチレン重合系内モル比×１０，０００
（ｃ）重合系内モル比

(A) 1,7-octadiene / ethylene feed molar ratio [ppm]
(B) Hydrogen / ethylene polymerization internal molar ratio × 10,000
(C) Intrapolymer molar ratio

[Evaluation of extrusion lamination molding]
In order to demonstrate the high moldability of the ethylene-based polymer of the present invention, Example 1, Example 2 and Comparative Example 1 were performed under the following conditions using a laminate molding machine having a width of 1,100 mm equipped with a 90 mmφ extruder. Then, extrusion lamination molding of the polymer obtained in Comparative Example 4 was performed.
The results are shown in Table 3. The neck-in is the difference between the T die width and the film forming width when the laminate thickness is 20 μm, the line speed is 100, 150, and 200 m / min, and the drawdown is stably formed at a constant rotation speed of 30 rpm of the extruder. Is the highest possible speed.
・ Air gap: 120mm
-Resin temperature at molding: 290 ° C
・ Line speed: Listed in the table ・ Laminate thickness: 20 μm
・ T die width: 800mm
-Base material: Unitika biaxially stretched polyethylene terephthalate having a thickness of 12 μm Examples 1 and 2 are 30 high-pressure low-density polyethylenes for imparting moldability to a resin having no long chain branching as in Comparative Example 4. Both extrusion load and neck-in are excellent compared with the case where parts by weight are added. Since Comparative Example 1 did not have long-chain branching, melt elasticity was insufficient, the line speed could not be increased to 40 mm / min or more, and extrusion laminate molding was practically impossible.
In addition, when Example 1 and Example 2 were compared, the neck-in was more excellent in Example 2 where the ratio of the complex capable of introducing long chain branching was higher, that is, in Example 2 where both ΔEa and λmax values were higher.

[Consideration of results of Examples and Comparative Examples]
The ethylene-based polymers obtained in Examples 1 to 6 all have a ΔEa value condition (a condition satisfying the range of 1.5 to 12.5) and ΔEa and λmax shown in the following formula (2). Both the relations are satisfied, and the strain hardening, which is elastic, is strong despite the relatively low long-chain branching concentration. In other words, mechanical strength and molding stability can be achieved at a high level. Furthermore, since these polymers also have a relatively high FR value, high extrusion characteristics can be expected.
λmax ≧ 1.2exp (0.0721 × ΔEa) Equation (2)
Comparing Example 1 and Example 2, Example 2 with a higher ratio of complexes capable of introducing long chain branching has higher ΔEa and λmax values. This shows that the long chain branching concentration can be controlled without changing the long chain branching structure depending on the complex composition.
When Example 1 is compared with Example 6, when the diene is copolymerized (Example 1), the ΔEa value increases and the λmax value becomes very high as compared with the case where the diene is not copolymerized (Example 6). ing. Copolymerization of the diene increases the overall long chain branching concentration and also shows that long chain branching is selectively introduced by the high molecular weight component. Similarly, when Example 3 and Example 4 are compared, Example 4 with a large amount of diene used increases λmax as the ΔEa value increases.
Thus, in the present invention, it is shown that the long chain branched structure can be controlled by the presence or concentration of diene, and the balance between molding processability and mechanical properties can be controlled by combining with two complex compositions. .
In addition, Examples 1 and 2 are superior in both extrusion load and neck-in as compared with the case of adding high-pressure low-density polyethylene for imparting molding processability to a resin having no long chain branching as in Comparative Example 4. Since Comparative Example 1 does not have long-chain branching, it has insufficient melt elasticity and does not have extrusion laminate formability.
Furthermore, as shown in Comparative Example 1 and Comparative Example 2, when a complex that cannot introduce long chain branching is used as a catalyst, both the condition of ΔEa value and the above formula (2) are not satisfied. Since the stability is low and the FR value is also low, the extrusion characteristics are inferior. As shown in Comparative Example 3, when a complex capable of introducing a long chain branch is used as a catalyst, the ΔEa value is high, but the λmax value is low, and the above formula (2) is not satisfied. Since such a polymer has a high FR, high extrusion characteristics can be expected, but the molding stability and mechanical strength are poor.
As described above, according to the present invention, the long chain branch structure and the concentration thereof can be controlled, and as a result, a high moldability can be imparted at a relatively low long chain branch concentration without impairing the mechanical strength. This not only leads to reduction of product loss at the time of molding, but also contributes to resource saving measures such as volume reduction and thinning, and the effect is extremely great both industrially and socially.
From the above results, the superiority of the ethylene polymer of the present invention and the production method thereof is clear with respect to the prior art seen in each comparative example, and the significance and rationality of the configuration of the present invention are proved. Has been.

It is a graph which shows the concept of the difference of the MFR of the polymer polymerized using the complexes A and B of this invention, and the difference of the reactivity of both complexes when coexisting polyene. It is a graph showing the unsteady uniaxial extensional viscosity curve for calculating | requiring the extensional viscosity prescription | regulation (lambda) max of this invention.

Claims (16)

An ethylene polymer satisfying the following conditions a) to d), wherein a short chain branch having 1 to 20 carbon atoms and a long chain branch having more than 20 carbon atoms are introduced into the polymer main chain.
a) The density measured based on JIS K-7112 is 0.880 to 0.970 g / cm ³ .
b) Based on JIS K-7210 Table 1-Condition 7, the melt flow rate (MFR) measured at a temperature of 190 ° C. under a load of 21.18 N is 0.01 to 100 g / 10 min.
c) The difference ΔEa [KJ / mol] between the activation energy Ea [KJ / mol] of flow and the activation energy Ea _L [KJ / mol] calculated by the following formula (1) is 1.5 to 12.5.

Here, SCB represents the number of short-chain branches having 1 to 20 carbon atoms per 1,000 carbon atoms in the main chain [number / 1,000 C], and B is the length of short-chain branches having 1 to 20 carbon atoms ( Carbon number).
d) The elongational viscosity λmax and ΔEa satisfy the following formula (2).
λmax ≧ 1.2exp (0.0721 × ΔEa) Equation (2) The introduction of a short chain branch having 1 to 20 carbon atoms and a long chain branch having more than 20 carbon atoms into a polymer main chain is performed according to each catalyst using two or more kinds of metallocene catalysts. The ethylene polymer according to claim 1. The two kinds of metallocene catalysts contain transition metal compounds having different reactivities to non-conjugated polyene as catalyst components in the presence of 1 mol% or less of non-conjugated polyene with respect to ethylene. The ethylene polymer according to claim 1 or 2. The two metallocene catalysts contain the transition metal compounds shown in the following (i) and (ii), and satisfy the conditions (iii) and (iv): Item 4. The ethylene polymer according to any one of Items 3.
(I) When the polymerization is carried out in the presence of a cocatalyst in the absence of hydrogen and non-conjugated polyene, the melt flow rate (MFR-A) of the polymer obtained is 2 g / 10 min or less, and long chain branching Metal compound (complex A) that produces a polymer having
(Ii) A polymer having a melt flow rate (MFR-B) of 10 or more times that of MFR-A obtained by polymerization under the same conditions as in (i) above, and having no long chain branching Generated transition metal compound (complex B)
(Iii) Polymer melt flow rate (MFR-) obtained when polymerization is carried out in the presence of complex A and a cocatalyst in the presence of 0.01 mol% of non-conjugated polyene with respect to ethylene without hydrogen. A +) and a polymer melt flow rate (MFR-B +) obtained when polymerization is performed under the same conditions using the complex B instead of the complex A, the following formula (3) is satisfied.
{(MFR-A +) / (MFR-A)} / {(MFR-B +) / (MFR-B)} <0.8 Formula (3)
(Iv) The quantity ratio of the polymer component [A] derived from the complex A and the polymer component [B] derived from the complex B is [A] / [B] = 10/90 to 90/10. The ethylene polymer is an ethylene polymer or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, or a copolymer obtained by copolymerizing a non-conjugated polyene with them. The ethylene polymer according to any one of claims 1 to 4. The complex A is a transition metal compound represented by the following general formula (1), and the complex B is a transition metal compound represented by the following general formula (2). Item 6. The ethylene polymer according to any one of Items 5 to 6.
ML ¹ _n R ¹ _xn general formula (1)
[In the formula, M represents a transition metal of Group 4 of the periodic table, L ¹ is a ligand coordinated to M, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, the following compound [1 Or a dibenzoindenyl group or a substituted dibenzoindenyl group represented by the following compound [2], and R ¹ is carbonized. A hydrogen group, an alkoxyl group, a halogen atom, or a hydrogen atom is represented. x is the valence of the transition metal M, n is 2 ≦ n ≦ x, and the substituents R ^{2 to} R ¹⁵ are hydrocarbon groups having 1 to 30 carbon atoms and hydrocarbon substituents having 1 to 30 carbon atoms. Represents a trialkylsilicon group or a hydrogen atom. ]

Compound [1]

Compound [2]

ML ² _n R ¹ _x-n general formula (2)
[In the formula, M represents a transition metal of Group 4 of the periodic table, L ² is a ligand coordinated to M, cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group. In the case where a plurality of bonds are combined, they may be different. R ¹ represents a hydrocarbon group, an alkoxyl group, a halogen atom, or a hydrogen atom. x is the valence of the transition metal M, and n is 2 ≦ n ≦ x. ] The complex A is a transition metal compound represented by the following general formula (3), and the complex B is a transition metal compound represented by the following general formula (4). 5. The ethylene-based polymer described in any one of 5 above.
ML ³ ₃ H general formula (3)
[Wherein M represents a transition metal of Group 4 of the periodic table, L ³ is a ligand coordinated to M, and dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, compound [1] 2 or more of any one of the indicated benzoindenyl group or substituted benzoindenyl group and the dibenzoindenyl group or substituted dibenzoindenyl group represented by the compound [2], and H represents a hydrogen atom. ]
ML ⁴ ₃ H general formula (4)
[In the formula, M represents a transition metal of Group 4 of the periodic table, L ⁴ is a ligand coordinated to M, cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group Which may be the same or different. H represents a hydrogen atom. ] The complex A is a transition metal compound represented by the following general formula (5), and the complex B is a transition metal compound represented by the following general formula (6). Item 6. The ethylene polymer according to any one of Items 5 to 6.
ML ³ ₃ H-AlR ₃ general formula (5)
[Wherein M represents a transition metal of Group 4 of the periodic table, L ³ is a ligand coordinated to M, and dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, compound [1] The benzoindenyl group or the substituted benzoindenyl group shown, or two or more of the dibenzoindenyl group or the substituted dibenzoindenyl group shown by the compound [2], H is a hydrogen atom, and AlR ₃ is Represents an organoaluminum compound. ]
ML ⁴ ₃ H-AlR ₃ general formula (6)
[In the formula, M represents a transition metal of Group 4 of the periodic table, L ⁴ is a ligand coordinated to M, cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group Which may be the same or different. H represents a hydrogen atom, and AlR ₃ represents an organoaluminum compound. ] The ethylene-based polymer according to any one of claims 1 to 8, wherein the transition metal M of the complex A and the complex B is Zr. Using two or more metallocene catalysts containing, as a catalyst component, transition metal compounds having different reactivities to non-conjugated polyenes in the presence of 1 mol% or less of non-conjugated polyene with respect to ethylene, The method for producing an ethylene-based polymer according to claim 1, wherein an α-olefin having 20 carbon atoms is polymerized. The method for producing an ethylene polymer according to claim 10, wherein the polymerization is performed in the presence of a non-conjugated polyene. 12. The method for producing an ethylene polymer according to claim 11, wherein the branch structure of the long-chain branch component is controlled by controlling the concentration of the non-conjugated polyene. The method for producing an ethylene polymer according to claim 11 or 12, wherein the non-conjugated polyene is a compound having two or more terminal vinyl structures in the molecule. The two types of metallocene catalysts contain the transition metal compounds shown in the following (i) and (ii): The ethylene-based heavy metal according to any one of claims 10 to 13, Manufacturing method of coalescence.
(I) When the polymerization is carried out in the presence of a cocatalyst in the absence of hydrogen and non-conjugated polyene, the melt flow rate (MFR-A) of the polymer obtained is 2 g / 10 min or less, and long chain branching Metal compound (complex A) that produces a polymer having
(Ii) A polymer having a melt flow rate (MFR-B) of 10 or more times that of MFR-A obtained by polymerization under the same conditions as in (i) above, and having no long chain branching Generated transition metal compound (complex B) The method for producing an ethylene polymer according to any one of claims 10 to 14, wherein a catalyst component comprising a transition metal compound and a cocatalyst is used, and the catalyst component is supported on a carrier for polymerization. The method for producing an ethylene polymer according to any one of claims 10 to 15, wherein the transition metal compound according to any one of claims 6 to 8 is used.

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