JP6360698B2 - Propylene block copolymer - Google Patents

Description

  The present invention relates to a propylene-based block copolymer. More specifically, the present invention relates to a propylene-based block copolymer that has an excellent balance between rigidity and impact resistance and has excellent appearance characteristics during molding.

  Propylene polymers are used in various fields such as household goods, kitchenware, packaging films, home appliances, machine parts, electrical parts, and automobile parts because of their excellent rigidity, hardness and heat resistance. In particular, automobile parts are often molded by injection molding from the viewpoint of productivity. However, when injection molding is performed using propylene-based polymers known so far, a plurality of periodic striped patterns called flow marks and tiger marks are generated in the direction intersecting the flow direction of the surface of the injection molded product. It is known to stand out. If the flow mark generated on the surface of the molded product is conspicuous, the appearance of the molded product will be damaged. Therefore, painting is performed as necessary to remove the flow mark. As a result, the manufacturing process of automobile parts is complicated. I have to be.

  Several flow mark generation mechanisms have been proposed, and one of them is considered to be related to the destabilization phenomenon of the flow front (melt front) in the mold during injection molding. (Non-Patent Document 1). With this concept, the melt front shape periodically becomes unstable during injection molding, and the mold transfer state of the molten resin periodically fluctuates and solidifies. ).

  Based on this concept, the melt elasticity of the propylene-based polymer is increased, and in particular, assuming transfer to the mold, by increasing the melt elasticity in the low shear rate region, Attempts have been made to stabilize the flow front and improve the flow mark. For example, Patent Document 1 discloses a propylene resin composition comprising a propylene block copolymer containing an ultrahigh molecular weight propylene-ethylene copolymer. In the above invention, an injection-molded product with few flow marks can be obtained, but an appearance defect called a weld line that occurs at the joining point of the molten resin flow may occur. The weld line is a phenomenon in which the traces of the molten resin flow merged to solidify and appear to be streak-like appearance defects. In the above invention, a large amount of ultrahigh molecular weight propylene-ethylene copolymer is contained in the propylene-based block copolymer. Is dispersed as an island structure of sea-island structure, it is presumed that the weld line has become conspicuous as a result of the difficulty of disappearing (relaxing) the merged traces of the molten resin flow. If the weld line is conspicuous, a pre-treatment step for removing the weld line is required at the time of painting, so that there are some restrictions in applying the above technique to automobile parts.

  As mentioned above, although the improvement example of the flow mark was mentioned, the further improvement of the propylene-type polymer is calculated | required in consideration of the elimination of the appearance defect, the improvement of the mechanical property balance, and the like.

JP-A-9-87482

Journal of Japanese Society of Rheology Vol. 35, no. 5,293-299

  An object of the present invention is to provide a propylene-based block copolymer having an excellent balance between molding appearance and impact resistance.

  As a result of intensive studies to solve the above problems, the present inventors have developed a propylene-based block copolymer containing a propylene homopolymer in which a high molecular weight component and a low molecular weight component are controlled within a specific range. In the propylene-based block copolymer, the low molecular weight component is present in a moderate amount so that the dispersibility of the high molecular weight component is improved and the flow mark is improved. Moreover, since the amount of the low molecular weight component is small, the impact strength is excellent. Furthermore, the inventors have found that the propylene-based block copolymer can be obtained by using a specific olefin polymerization catalyst, and have completed the present invention. That is, the present invention relates to the following <1> to <11>.

  <1> It is composed of 5 to 80% by weight of a portion soluble in 23 ° C. n-decane (Dsol) and 20 to 95% by weight of a portion insoluble in 23 ° C. n-decane (Dinsol) (however, Dsol and Dinsol The total amount is 100% by weight), and a propylene-based block copolymer satisfying the following requirements [1] to [6] simultaneously.

[1] Propylene content of Dsol is 30 to 80 mol%
[2] The intrinsic viscosity [η] (dl / g) of Dsol is 1.5 or more and 10.0 or less. [3] Mw / Mn, which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of Dinsol, 7 to 15, Mz / Mw which is a ratio of z average molecular weight (Mz) to weight average molecular weight (Mw) is 4 to 10
[4] LogM in the differential molecular weight distribution curve obtained by GPC measurement of Dinsol has a peak in the range of 2 to 4. [5] The pentad fraction (mmmm) of Dinsol is 93% or more. [6] Propylene-based block copolymer The melt flow rate (MFR) measured at a load of 2.16 kg and a temperature of 230 ° C. in accordance with ASTM D1238E of 25 to 350 g / 10 min.

  <2> The portion soluble in 23 ° C. n-decane (Dsol) is 50 weight of copolymer rubber composed of propylene and one or more olefins selected from ethylene and α-olefins having 4 to 20 carbon atoms. More than 100% by weight and insoluble in 23 ° C. n-decane (Dinsol) is at least one selected from propylene 98.5 to 100 mol%, ethylene and α-olefins having 4 to 20 carbon atoms The propylene-based block copolymer according to <1>, comprising a crystalline propylene-based (co) polymer consisting of 0 to 1.5 mol% of an olefin in an amount of more than 50 wt% and not more than 100 wt%.

  <3> The copolymer rubber is produced by polymerizing propylene and one or more olefins selected from ethylene and an α-olefin having 4 to 20 carbon atoms in one step < 2>. The propylene-based block copolymer according to 2>.

<4> Solid titanium catalyst component (I) containing titanium, magnesium, halogen, a cyclic ester compound (a) specified by the following formula (1) and a cyclic ester compound (b) specified by the following formula (2) When,
An organometallic compound (II) containing a metal atom selected from Group 1, Group 2 and Group 13 of the Periodic Table;
Organosilicon compound (III) represented by the following formula (3)
After adjusting the prepolymerization catalyst [A] in the presence of
<1>-<characteristically produced by polymerizing an olefin containing propylene in the presence of the prepolymerization catalyst [A], the organometallic compound (II) and the organosilicon compound (III) The propylene block copolymer according to any one of 3>.

式（１）において、ｎは５〜１０の整数である。
Ｒ²およびＲ³はそれぞれ独立にＣＯＯＲ¹またはＲであり、Ｒ²およびＲ³のうち少なくとも１つはＣＯＯＲ¹である。環状骨格中の単結合（Ｃ−Ｃ^b結合、Ｒ³がＣＯＯＲ¹である場合のＣ^a−Ｃ^b結合、およびＣ−Ｃ結合（ｎが６〜１０の場合））は、二重結合に置き換えられていてもよい。
Ｒ¹は、それぞれ独立に炭素原子数１〜２０の１価の炭化水素基である。
複数個あるＲは、それぞれ独立に水素原子、炭素原子数１〜２０の炭化水素基、ハロゲン原子、窒素含有基、酸素含有基、リン含有基、ハロゲン含有基およびケイ素含有基から選ばれる原子または基であり、互いに結合して環を形成していてもよいが、少なくとも１つのＲは水素原子ではない。
Ｒが互いに結合して形成される環の骨格中に、二重結合が含まれていてもよく、該環の骨格中に、ＣＯＯＲ¹が結合したＣ^aを２つ以上含む場合は、該環の骨格をなす炭素原子の数は５〜１０である。

In Formula (1), n is an integer of 5-10.
R ² and R ³ are each independently COOR ¹ or R, and at least one of R ² and R ³ is COOR ¹ . A single bond in the cyclic skeleton (C—C ^b bond, C ^a —C ^b bond when R ³ is COOR ¹ , and C—C bond (when n is 6 to 10)) is a double bond. It may be replaced.
R ¹ is each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.
A plurality of Rs are each independently an atom selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, a halogen-containing group and a silicon-containing group. A group which may be bonded to each other to form a ring, but at least one R is not a hydrogen atom.
A double bond may be included in the ring skeleton formed by bonding R to each other, and when the ring skeleton includes two or more C ^a to which COOR ¹ is bonded, The number of carbon atoms constituting the skeleton is 5-10.

式（２）において、ｎは５〜１０の整数である。
Ｒ⁴およびＲ⁵はそれぞれ独立にＣＯＯＲ¹または水素原子であり、Ｒ⁴およびＲ⁵のうち少なくとも１つはＣＯＯＲ¹である。
Ｒ¹は、それぞれ独立に炭素原子数１〜２０の１価の炭化水素基である。
環状骨格中の単結合（Ｃ−Ｃ^b結合、Ｒ⁵がＣＯＯＲ¹である場合のＣ^a−Ｃ^b結合、およびＣ−Ｃ結合（ｎが６〜１０の場合））は、二重結合に置き換えられていてもよい。

In Formula (2), n is an integer of 5-10.
R ⁴ and R ⁵ are each independently COOR ¹ or a hydrogen atom, and at least one of R ⁴ and R ⁵ is COOR ¹ .
R ¹ is each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.
A single bond in the cyclic skeleton (C—C ^b bond, C ^a —C ^b bond when R ⁵ is COOR ¹ , and C—C bond (when n is 6 to 10)) is a double bond. It may be replaced.

Si (OR ¹ ) ₃ (NR ² R ³ ) (3)
In the formula (3), R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, R ² is a hydrocarbon group or hydrogen having 1 to 12 carbon atoms, and R ³ is a hydrocarbon group having 1 to 12 carbon atoms. Indicates.

  <5> The propylene-based block copolymer according to <4>, wherein in the formula (1) and / or (2), all the bonds between carbon atoms in the cyclic skeleton are single bonds.

  <6> The propylene-based block copolymer according to <4>, wherein in the formula (1) and / or (2), n = 6.

  <7> The propylene block copolymer according to <4>, wherein the cyclic ester compound (a) is represented by the following formula (1a) and the cyclic ester compound (b) is represented by the following formula (2a). Coalescence.

式（１ａ）において、ｎは５〜１０の整数である。
環状骨格中の単結合（Ｃ−Ｃ結合（ｎが６〜１０の場合）、Ｃ^a−Ｃ結合およびＣ^b−Ｃ結合）は、二重結合に置き換えられていてもよい。
Ｒ¹は、それぞれ独立に炭素原子数１〜２０の１価の炭化水素基である。
複数個あるＲは、それぞれ独立に水素原子、炭素原子数１〜２０の炭化水素基、ハロゲン原子、窒素含有基、酸素含有基、リン含有基、ハロゲン含有基およびケイ素含有基から選ばれる原子または基であり、互いに結合して環を形成していてもよいが、少なくとも１つのＲは水素原子ではない。
Ｒが互いに結合して形成される環の骨格中に二重結合が含まれていてもよく、該環の骨格中に、ＣＯＯＲ¹が結合したＣ^aを２つ以上含む場合は、該環の骨格をなす炭素原子の数は５〜１０である。

In Formula (1a), n is an integer of 5-10.
Single bonds (C—C bonds (when n is 6 to 10), C ^a —C bonds and C ^b —C bonds) in the cyclic skeleton may be replaced with double bonds.
R ¹ is each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.
A plurality of Rs are each independently an atom selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, a halogen-containing group and a silicon-containing group. A group which may be bonded to each other to form a ring, but at least one R is not a hydrogen atom.
A double bond may be contained in the ring skeleton formed by bonding R to each other, and when the ring skeleton contains two or more C ^a bonded with COOR ¹ , The number of carbon atoms constituting the skeleton is 5 to 10.

式（２ａ）において、ｎは５〜１０の整数である。
Ｒ¹は、それぞれ独立に炭素原子数１〜２０の１価の炭化水素基である。環状骨格中の単結合（Ｃ−Ｃ結合（ｎが６〜１０の場合）、Ｃ^a−Ｃ結合およびＣ^b−Ｃ結合）は、二重結合に置き換えられていてもよい。

In Formula (2a), n is an integer of 5-10.
R ¹ is each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. Single bonds (C—C bonds (when n is 6 to 10), C ^a —C bonds and C ^b —C bonds) in the cyclic skeleton may be replaced with double bonds.

  <8> The propylene-based block copolymer according to <7>, wherein in the formulas (1a) and (2a), all the bonds between carbon atoms in the cyclic skeleton are single bonds.

  <9> The propylene-based block copolymer according to <7>, wherein in the formulas (1a) and (2a), n = 6.

  <10> A propylene resin composition comprising the propylene-based block copolymer according to any one of <1> to <9>, an inorganic filler, and / or an elastomer.

  <11> A molded article comprising the propylene-based block copolymer according to any one of <1> to <9>.

  The propylene-based block copolymer according to the present invention can be suitably used for molded articles such as automobile parts because the flow mark is improved and the impact strength is excellent.

The GPC curve of the part (Dinsol) insoluble in 23 degreeC n-decane in an Example and a comparative example is shown. The GPC curve (magnified part of logM = 2-4) of the part (Dinsol) insoluble in 23 degreeC n-decane in an Example and a comparative example is shown. The flow mark evaluation method of the injection molding obtained from a propylene block copolymer is shown.

  Hereinafter, the propylene-based block copolymer of the present invention will be specifically described.

[Propylene block copolymer]
The propylene block copolymer of the present invention has a portion soluble in 23 ° C. n-decane (Dsol) of 5 to 80% by weight, preferably 10 to 50% by weight, more preferably 10 to 30% by weight and 23 ° C. n. -The decane-insoluble part (Dinsol) is composed of 20 to 95% by weight, preferably 50 to 90% by weight, more preferably 70 to 90% by weight [provided that the total amount of Dsol and Dinsol is 100% by weight ].

  The part soluble in 23 ° C. n-decane (Dsol) is composed mainly of propylene-based copolymer rubber composed of propylene and one or more olefins selected from ethylene and α-olefins having 4 to 20 carbon atoms. Greater than 50% by weight and 100% by weight or less, preferably 80-100% by weight, more preferably 90-100% by weight). One or more olefins selected from ethylene and α-olefins having 4 to 20 carbon atoms contained in the propylene copolymer rubber are higher than the olefins contained in the crystalline propylene (co) polymer described later. Content.

  The portion insoluble in n-decane at 23 ° C. (Dinsol) is mainly composed of a crystalline propylene-based (co) polymer (greater than 50% by weight and less than or equal to 100% by weight, preferably 80 to 100% by weight, more preferably 90 to 90%). 100% by weight). The crystalline propylene-based (co) polymer contains 1.5 mol% or less of a crystalline propylene homopolymer or one or more olefins selected from propylene and ethylene and an α-olefin having 4 to 20 carbon atoms. A crystalline propylene copolymer is shown.

  The propylene-based block copolymer according to the present invention is characterized by satisfying requirements [1] to [6] described later. In the present invention, the “23 ° C. n-decane soluble part (Dsol)” is a propylene block copolymer at 150 ° C. in n-decane, as will be described in detail later in Examples. The part melt | dissolved in the n-decane solution side after temperature-falling to 23 degreeC after heat-dissolving for 2 hours is shown. In the following description, “a portion soluble in 23 ° C. n-decane” is referred to as “n-decane soluble portion”, and “portion insoluble in 23 ° C. n-decane” is referred to as “n-decane insoluble portion”. It may be abbreviated.

  The propylene-based block copolymer of the present invention comprises a skeleton derived from propylene and an skeleton derived from one or more olefins selected from ethylene and an α-olefin having 4 to 20 carbon atoms. Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, -Hexadecene, 1-octadecene, 1-eicosene, etc. are mentioned. As the olefin constituting the skeleton resulting from one or more olefins selected from ethylene and an α-olefin having 4 to 20 carbon atoms in the copolymer, ethylene or an α-olefin having 4 to 10 carbon atoms is preferable. More preferably, they are ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene, and it is more preferable to use one or more.

  Requirements [1] to [6] to be satisfied by the propylene-based block copolymer according to the present invention are as follows.

[1] Propylene content of Dsol is 30 to 80 mol%
[2] The intrinsic viscosity [η] (dl / g) of Dsol is 1.5 or more and 10.0 or less. [3] Mw / Mn, which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of Dinsol, 7 to 15, Mz / Mw which is a ratio of z average molecular weight (Mz) to weight average molecular weight (Mw) is 4 to 10
[4] LogM in the differential molecular weight distribution curve obtained by GPC measurement of Dinsol has a peak in the range of 2 to 4. [5] The pentad fraction (mmmm) of Dinsol is 93% or more. [6] Based on ASTM D1238E of Dinsol The melt flow rate (MFR) measured at a load of 2.16 kg and a temperature of 230 ° C. is 25 to 350 g / 10 min.
Hereinafter, requirements [1] to [6] included in the propylene-based block copolymer of the present invention will be described in detail.

○ Requirement [1]
In the decane-soluble part (Dsol) of the propylene-based block copolymer according to the present invention, the content of monomer units related to propylene in the polymer contained in the component is 30 to 80 mol%, preferably 35 to 75 mol. %, And more preferably 40 to 70 mol%.

  In the propylene block copolymer of the present invention, the content of monomer units related to propylene in the polymer contained in the decane-soluble part (Dsol) is within the above range, so that the decane-soluble part (Dsol) is in the decane-soluble part (Dsol). This polymer has properties as an elastomer. As a result, the propylene-based block copolymer of the present invention can have high impact resistance, which is advantageous in achieving both impact resistance and high melt elasticity. When the melt elasticity of the propylene-based block copolymer is high, it is possible to impart molding processability such as good appearance of the injection-molded product and improved blow moldability and foam moldability.

  In addition, the propylene content concerning this requirement [1] is the supply amount of propylene into the polymerization vessel when copolymerizing propylene and one or more olefins selected from ethylene and an α-olefin having 4 to 20 carbon atoms. It can be adjusted by adjusting.

○ Requirement [2]
The intrinsic viscosity [η] (dl / g) of the decane soluble part (Dsol) of the propylene-based block copolymer of the present invention is usually 1.5 to 10.0, impact resistance, high fluidity, and high melt elasticity. From the viewpoint of optimizing the balance, the range is preferably 2.0 to 7.0, and more preferably 2.5 to 4.0. If the intrinsic viscosity [η] (dl / g) is lower than 1.5 dl / g, the impact resistance of the propylene-based block copolymer may be lowered, which is not preferable. In addition, when the intrinsic viscosity [η] (dl / g) is higher than 10 dl / g, fluidity tends to be lowered and fish eyes are likely to be generated, which makes it difficult to apply to large injection molded products and films. is there.

  By adding a propylene copolymer rubber having a high intrinsic viscosity [η] (dl / g) of the decane soluble part (Dsol), effects such as impact resistance, high fluidity, and high melt elasticity can be obtained. It is common knowledge among those skilled in the art that it can be expressed. However, in this case, there is a problem that fish eyes are easily generated, and it is difficult to industrialize from the viewpoint of deterioration of the appearance of the molded product. On the other hand, the propylene-based block copolymer obtained by continuously polymerizing the decane-soluble part (Dsol) as in the present invention is as described above because the copolymer rubber is finely dispersed throughout the copolymer. In addition to effects such as impact resistance, high fluidity, and high melt elasticity, a molded product in which the generation of fish eyes is suppressed can be obtained.

○ Requirement [3]
The decane-insoluble part (Dinsol) of the propylene-based block copolymer according to the present invention is a ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained from the measured value by gel permeation chromatography (GPC). A certain Mw / Mn value is 7 to 15, and preferably 7 to 12 and more preferably 7 to 10 from the viewpoint of increasing rigidity and maintaining impact resistance.

  Moreover, the decane insoluble part (Dinsol) of the propylene-type block copolymer which concerns on this invention is Mz / Mw value which is a ratio of z average molecular weight (Mz) and weight average molecular weight (Mw) calculated | required from the measured value by GPC. Is 4-10, preferably 5-10, more preferably 6-10.

  Since the decane insoluble part (Dinsol) of the propylene-based block copolymer according to the present invention has a high Mw / Mn value, it exhibits a sufficiently wide molecular weight distribution, and is excellent in moldability and rigidity. Moreover, since the propylene-type block copolymer which concerns on this invention shows high Mz / Mw value as mentioned above, it contains many high molecular weight components, its melt tension (MT) is high and it is excellent in a moldability. Furthermore, a propylene-based block copolymer that satisfies the requirements has improved flow marks and good impact resistance.

  The decane-insoluble part (Dinsol) of the propylene-based block copolymer according to the present invention as described above can be produced by multi-stage polymerization or mixing of plural types of polypropylene, but is obtained by one-stage polymerization. It is preferable. When the decane insoluble part (Dinsol) of the propylene-based block copolymer according to the present invention is obtained by one-stage polymerization, the polymer production apparatus can be made simpler and economical. The high molecular weight component in the system block copolymer is preferable because it does not aggregate and becomes finely dispersed.

  The decane insoluble part (Dinsol) of the propylene-based block copolymer of the present invention has a high Mw / Mn value and a large amount of a high molecular weight component having a high Mz / Mw value, and preferably a high Mz / Mn value described later. Therefore, the high molecular weight component in the propylene-based block copolymer acts as a nucleating agent at the time of molding, and a molded product with a high degree of crystallinity can be obtained without adding a nucleating agent such as filler powder or resin powder. May be obtained. In particular, it is preferable that the high molecular weight material is finely dispersed because the action of a nucleating agent tends to increase.

  In addition, this requirement [3] is one or more olefins 0 to 1 selected from propylene 98.5 to 100 mol%, ethylene and an α-olefin having 4 to 20 carbon atoms in the presence of an olefin polymerization catalyst described later. 0.5 mol% can be obtained by (co) polymerization.

○ Requirement [4]
The decane insoluble part (Dinsol) of the propylene-based block copolymer according to the present invention has a peak in the range of 2 to 4 in LogM in a differential molecular weight distribution curve obtained by measurement by gel permeation chromatography (GPC).

  Here, the peak is a logarithmic display of the molecular weight M (Log M (range: 1 to 8)) on the X axis, and a differential molecular weight distribution (dw / d (Log M) (range: 0 to 1)) on the Y axis. A differential molecular weight distribution curve is created so that the length ratio of the X axis and Y axis of the graph is 5: 3. Here, the peak in the range of 2 to 4 of LogM is the range of 2 to 4 in LogM, the part parallel to the X axis of the graph, or within the range of 30 ° in the first quadrant with respect to the X axis vector, And it is defined as a peak having a line part in the range of 45 ° in the fourth quadrant.

  When the polymer corresponding to the peak is present in the decane insoluble portion (Dinsol) of the propylene-based block copolymer according to the present invention, the flow mark in the injection molded part tends to be improved.

  This requirement [4] is that olefin polymerization catalyst, which will be described later, particularly 98.5 to 100 mol% of propylene, ethylene and α having 4 to 20 carbon atoms in the presence of a catalyst used in combination with the organosilicon compound (III). It can be obtained by (co) polymerizing 0 to 1.5 mol% of one or more olefins selected from olefins.

○ Requirement [5]
The pentad fraction (mmmm) of the decane insoluble part (Dinsol) of the propylene-based block copolymer of the present invention is 93% or more, preferably 94% or more, and more preferably 95% or more. The upper limit of the pentad fraction is 100%, preferably 99.8%, more preferably 99.5%. If the pentad fraction (mmmm) is less than 93%, the rigidity is lowered, and there is a field in which heat resistance cannot ensure the required characteristics in the product field such as a film.

  For example, a propylene polymer polymerized with a titanium trichloride catalyst has an effect of wide molecular weight distribution as described in, for example, JP-A-47-34478, but the pentad fraction in the decane insoluble part is 91. Since it is extremely low, about 92%, it cannot be used for injection molding applications that require high rigidity such as automobile materials.

  The requirement [5] is satisfied because the olefin polymerization catalyst described later includes the cyclic ester compound (a) and the cyclic ester compound (b) as electron donors.

○ Requirement [6]
The melt flow rate (MFR) measured at a load of 2.16 kg and a temperature of 230 ° C. based on ASTM D1238E of the propylene-based block copolymer of the present invention is usually 25 to 350 g / 10 min, preferably 30 to 350 g / 10 min. More preferably, it is 40-300 g / 10min. If the MFR is below the lower limit, fluidity during injection molding may be reduced, making it difficult to apply to large injection molded parts. Moreover, when MFR is higher than the said upper limit, the toughness of a propylene-type block copolymer may fall.

  The propylene-based block copolymer characterized by satisfying the above requirements [1] to [6] is preferably produced using the following olefin polymerization catalyst.

[Olefin polymerization catalyst]
The propylene-based block copolymer according to the present invention comprises a solid titanium catalyst component (I), an organometallic compound (II) containing a metal atom selected from Group 1, Group 2 and Group 13 of the periodic table; After preparing the prepolymerization catalyst [A] in the presence of an olefin polymerization catalyst containing the specific organosilicon compound (III), the prepolymerization catalyst [A], the organometallic compound (II), and the organosilicon It is preferable to be obtained by polymerizing propylene and one or more olefins selected from ethylene and an α-olefin having 4 to 20 carbon atoms in the presence of the compound (III). Hereinafter, each component relating to the olefin polymerization catalyst will be described in detail.

[Solid titanium catalyst component (I)]
The solid titanium catalyst component (I) according to the present invention comprises titanium, magnesium, halogen, a cyclic ester compound (a) specified by the following formula (1), and a cyclic ester compound (b) specified by the following formula (2) )including.

<Cyclic ester compound (a)>
The cyclic ester compound (a) has a plurality of carboxylic acid ester groups and is represented by the following formula (1).

式（１）において、ｎは、５〜１０の整数、好ましくは５〜７の整数であり、特に好ましくは６である。またＣ^aおよびＣ^bは、炭素原子を表わす。

In the formula (1), n is an integer of 5 to 10, preferably an integer of 5 to 7, particularly preferably 6. C ^a and C ^b represent carbon atoms.

R ² and R ³ are each independently COOR ¹ or R, and at least one of R ² and R ³ is COOR ¹ .

The carbon-carbon bonds in the cyclic skeleton are preferably all single bonds, but in the cyclic skeleton, other than the C ^a -C ^a bond and the C ^a -C ^b bond when R ³ is R, Any single bond may be replaced with a double bond. That is, the C—C ^b bond in the cyclic skeleton, the C ^a —C ^b bond when R ³ is COOR ¹ , and the C—C bond (when n is 6 to 10) are replaced with double bonds. It may be done.

A plurality of R ^{1 s} are each independently a monovalent carbon atom having 1 to 20, preferably 1 to 10, more preferably 2 to 8, more preferably 4 to 8, particularly preferably 4 to 6 carbon atoms. It is a hydrogen group. As this hydrocarbon group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, Tetradecyl group, hexadecyl group, octadecyl group, eicosyl group and the like can be mentioned. Among them, n-butyl group, isobutyl group, hexyl group and octyl group are preferable, and n-butyl group and isobutyl group are propylene type having wide molecular weight distribution. The block copolymer is particularly preferable because it can be produced.

  A plurality of R's are each independently an atom selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, a halogen-containing group and a silicon-containing group. Or a group, but at least one R is not a hydrogen atom.

  Among these, R other than a hydrogen atom is preferably a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso group. Aliphatic hydrocarbon groups such as -propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, vinyl group, phenyl group, octyl group , An alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Among them, an aliphatic hydrocarbon group is preferable, and specifically, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, and a sec-butyl group are preferable.

R may be bonded to each other to form a ring, and the ring skeleton formed by bonding R to each other may contain a double bond, and the ring skeleton In the case where two or more C ^a bonded with COOR ¹ are contained, the number of carbon atoms constituting the skeleton of the ring is 5 to 10.

  Examples of such a ring skeleton include a norbornane skeleton and a tetracyclododecene skeleton.

  A plurality of Rs may be a carbonyl structure-containing group such as a carboxylic acid ester group, an alkoxy group, a siloxy group, an aldehyde group or an acetyl group, and these substituents include carbon atoms having 1 to 20 carbon atoms. It preferably contains one or more hydrogen groups.

Such a cyclic ester compound (a) is described in International Publication No. 2006/077945 pamphlet. In particular,
Diethyl 3-methylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3-methylcyclohexane-1,2-dicarboxylate,
Diisopropyl 3-methylcyclohexane-1,2-dicarboxylate,
Di-n-butyl 3-methylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3-methylcyclohexane-1,2-dicarboxylate,
Dihexyl 3-methylcyclohexane-1,2-dicarboxylate,
3-methylcyclohexane-1,2-dicarboxylate diheptyl,
Dioctyl 3-methylcyclohexane-1,2-dicarboxylate,
Di-2-ethylhexyl 3-methylcyclohexane-1,2-dicarboxylate,
Didecyl 3-methylcyclohexane-1,2-dicarboxylate,
4-methylcyclohexane-1,3-dicarboxylate diethyl,
4-methylcyclohexane-1,3-dicarboxylate diisobutyl,
4-methylcyclohexane-1,2-dicarboxylate diethyl,
Di-n-propyl 4-methylcyclohexane-1,2-dicarboxylate,
4-methylcyclohexane-1,2-dicarboxylate diisopropyl,
Di-n-butyl 4-methylcyclohexane-1,2-dicarboxylate,
4-methylcyclohexane-1,2-dicarboxylate diisobutyl,
4-methylcyclohexane-1,2-dicarboxylic acid dihexyl,
4-methylcyclohexane-1,2-dicarboxylate diheptyl,
Dioctyl 4-methylcyclohexane-1,2-dicarboxylate,
Didecyl 4-methylcyclohexane-1,2-dicarboxylate 4-methylcyclohexane-1,2-dicarboxylate,
Diethyl 5-methylcyclohexane-1,3-dicarboxylate,
Diisobutyl 5-methylcyclohexane-1,3-dicarboxylate,
Diethyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Diisopropyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-butyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
3,4-dimethylcyclohexane-1,2-dicarboxylic acid dihexyl,
Diheptyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Dioctyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Didecyl 3,4-dimethylcyclohexane-1,2-dicarboxylate 3,2-dimethylcyclohexane-1,2-dicarboxylate,
Diethyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
3,6-dimethylcyclohexane-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
3,6-dimethylcyclohexane-1,2-dicarboxylic acid dihexyl;
Diheptyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Dioctyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Di-2-ethylhexyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Didecyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Diethyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
Diisopropyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
Di-n-butyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
3,6-diphenylcyclohexane-1,2-dicarboxylic acid dihexyl;
Dioctyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
Didecyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
Diethyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
3-methyl-6-ethylcyclohexane-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
3-hexyl-6-ethylcyclohexane-1,2-dicarboxylic acid dihexyl;
3-methyl-6-ethylcyclohexane-1,2-dicarboxylic acid diheptyl,
Dioctyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Dimethyl 2-ethylhexyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Didecyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Diethyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
3-methyl-6-ethylcyclohexane-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
3-hexyl-6-ethylcyclohexane-1,2-dicarboxylic acid dihexyl;
3-methyl-6-ethylcyclohexane-1,2-dicarboxylic acid diheptyl,
Dioctyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Dimethyl 2-ethylhexyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Didecyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Diethyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
3-hexyl-6-n-propylcyclohexane-1,2-dicarboxylate dihexyl;
3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate diheptyl,
Dioctyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Di-2-ethylhexyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Didecyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Diethyl 3-hexylcyclohexane-1,2-dicarboxylate,
3-hexylcyclohexane-1,2-dicarboxylate diisobutyl,
Diethyl 3,6-dihexylcyclohexane-1,2-dicarboxylate,
3-hexyl-6-pentylcyclohexane-1,2-dicarboxylate diisobutyl,
Diethyl 3-methylcyclopentane-1,2-dicarboxylate,
Diisobutyl 3-methylcyclopentane-1,2-dicarboxylate,
3-methylcyclopentane-1,2-dicarboxylic acid diheptyl,
Didecyl 3-methylcyclopentane-1,2-dicarboxylate,
4-methylcyclopentane-1,3-dicarboxylate diethyl,
4-methylcyclopentane-1,3-dicarboxylate diisobutyl,
4-methylcyclopentane-1,2-dicarboxylate diethyl,
4-methylcyclopentane-1,2-dicarboxylate diisobutyl,
4-methylcyclopentane-1,2-dicarboxylic acid diheptyl,
Didecyl 4-methylcyclopentane-1,2-dicarboxylate,
Diethyl 5-methylcyclopentane-1,3-dicarboxylate,
Diisobutyl 5-methylcyclopentane-1,3-dicarboxylate,
Diethyl 3,4-dimethylcyclopentane-1,2-dicarboxylate,
Diisobutyl 3,4-dimethylcyclopentane-1,2-dicarboxylate,
3,4-dimethylcyclopentane-1,2-dicarboxylic acid diheptyl,
Didecyl 3,4-dimethylcyclopentane-1,2-dicarboxylate,
Diethyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Diisobutyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Diheptyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Didecyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Diethyl 3-hexylcyclopentane-1,2-dicarboxylate,
Diethyl 3,5-dihexylcyclopentane-1,2-dicarboxylate,
3-hexyl-5-pentylcyclopentane-1,2-dicarboxylate diisobutyl,
Diethyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,
Di-n-propyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,
3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,
3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate diisobutyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate dihexyl;
Dimethyl of 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,
Didecyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,
Diethyl 3-methylcycloheptane-1,2-dicarboxylate,
Diisobutyl 3-methylcycloheptane-1,2-dicarboxylate,
3-methylcycloheptane-1,2-dicarboxylic acid diheptyl,
Didecyl 3-methylcycloheptane-1,2-dicarboxylate,
4-methylcycloheptane-1,3-dicarboxylate diethyl,
4-methylcycloheptane-1,3-dicarboxylate diisobutyl,
4-methylcycloheptane-1,2-dicarboxylate diethyl,
4-methylcycloheptane-1,2-dicarboxylate diisobutyl,
4-methylcycloheptane-1,2-dicarboxylic acid diheptyl,
Didecyl 4-methylcycloheptane-1,2-dicarboxylate,
Diethyl 5-methylcycloheptane-1,3-dicarboxylate,
Diisobutyl 5-methylcycloheptane-1,3-dicarboxylate,
Diethyl 3,4-dimethylcycloheptane-1,2-dicarboxylate,
Diisobutyl 3,4-dimethylcycloheptane-1,2-dicarboxylate,
Diheptyl 3,4-dimethylcycloheptane-1,2-dicarboxylate,
Didecyl 3,4-dimethylcycloheptane-1,2-dicarboxylate,
Diethyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Diisobutyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Diheptyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Didecyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Diethyl 3-hexylcycloheptane-1,2-dicarboxylate,
Diethyl 3,7-dihexylcycloheptane-1,2-dicarboxylate,
3-hexyl-7-pentylcycloheptane-1,2-dicarboxylate diisobutyl,
Diethyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,
Di-n-propyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,
3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,
Diisobutyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,
3-methyl-7-n-propylcycloheptane-1,2-dicarboxylic acid dihexyl;
Dioctyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,
Didecyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,
Diethyl 3-methylcyclooctane-1,2-dicarboxylate,
Diethyl 3-methylcyclodecane-1,2-dicarboxylate,
Diisobutyl 3-vinylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
Diethyl 3,6-dicyclohexylcyclohexane-1,2-dicarboxylate,
Norbornane-2,3-dicarboxylate diisobutyl,
Tetracyclododecane-2,3-dicarboxylate diisobutyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
Di-n-propyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
Diisobutyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
3,6-dimethyl-4-cyclohexene-1,2-dicarboxylic acid dihexyl;
Diheptyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
Dioctyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
Di-2-ethylhexyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
Didecyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
Diethyl 3,6-dihexyl-4-cyclohexene-1,2-dicarboxylate,
3-hexyl-6-pentyl-4-cyclohexene-1,2-dicarboxylate diisobutyl,
Etc.

In addition, the following compounds:
3,6-dimethylcyclohexane-1,2-diacetate,
3,6-dimethylcyclohexane-1,2-dibutanate,
3-methyl-6-propylcyclohexane-1,2-diol acetate,
3-methyl-6-propylcyclohexane-1,2-dibutanate,
3,6-dimethylcyclohexane-1,2-dibenzoate,
3,6-dimethylcyclohexane-1,2-ditoluate,
3-methyl-6-propylcyclohexane-1,2-dibenzoate,
3-methyl-6-propylcyclohexane-1,2-ditoluate,
Etc. can also be mentioned as a preferable example.

The compound having a diester structure as described above has isomers such as cis and trans derived from a plurality of COOR ¹ groups in the formula (1), and any structure meets the object of the present invention. Although it has an effect, it is preferable that the trans isomer content is higher. The higher the content of the trans isomer, the higher the activity and the stereoregularity of the resulting polymer, as well as the effect of broadening the molecular weight distribution.

  As the cyclic ester compound (a), compounds represented by the following formulas (1-1) to (1-6) are preferable.

上記式（１−１）〜（１−６）中の、Ｒ¹およびＲは式（１）での定義と同様である。

In the above formulas (1-1) to (1-6), R ¹ and R are the same as defined in formula (1).

In the above formulas (1-1) to (1-3), the single bond in the cyclic skeleton (except for the C ^a -C ^a bond and the C ^a -C ^b bond) is replaced with a double bond. Also good.

In the above formulas (1-4) to (1-6), the single bond in the cyclic skeleton (excluding the C ^a -C ^a bond) may be replaced with a double bond.

  Moreover, in said formula (1-3) and (1-6), n is an integer of 7-10.

  As the cyclic ester compound (a), a compound represented by the following formula (1a) is particularly preferable.

式（１ａ）中の、ｎ、Ｒ¹およびＲは式（１）での定義と同様であり、環状骨格中の単結合（ただしＣ^a−Ｃ^a結合およびＣ^a−Ｃ^b結合を除く。）は、二重結合に置き換えられていてもよい。すなわち、環状骨格中のＣ−Ｃ結合（ｎが６〜１０の場合）、Ｃ^a−Ｃ結合およびＣ^b−Ｃ結合は、二重結合に置き換えられていてもよい。

In the formula (1a), n, R ¹ and R are the same as defined in the formula (1), and exclude ^a single bond in the cyclic skeleton (however, a C ^a -C ^a bond and a C ^a -C ^b bond). ) May be replaced by a double bond. That is, the C—C bond (when n is 6 to 10), the C ^a —C bond, and the C ^b —C bond in the cyclic skeleton may be replaced with a double bond.

Specifically, as the compound represented by the above formula (1a),
Diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-hexyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-octyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Di-n-hexyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Di-n-octyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Di-n-hexyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Di-n-octyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3,6-diethylcyclohexane-1,2-dicarboxylate,
Di-n-hexyl 3,6-diethylcyclohexane-1,2-dicarboxylate,
Di-n-octyl 3,6-diethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Di-n-hexyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Di-n-octyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Diisobutyl 3-methyl-5-ethylcyclopentane-1,2-dicarboxylate,
Di-n-hexyl 3-methyl-5-ethylcyclopentane-1,2-dicarboxylate,
Di-n-octyl 3-methyl-5-ethylcyclopentane-1,2-dicarboxylate,
Di-n-hexyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,
Di-n-octyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,
Diisobutyl 3,5-diethylcyclopentane-1,2-dicarboxylate,
Di-n-hexyl 3,5-diethylcyclopentane-1,2-dicarboxylate,
Di-n-octyl 3,5-diethylcyclopentane-1,2-dicarboxylate,
Diisobutyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Di-n-hexyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Di-n-octyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Diisobutyl 3-methyl-7-ethylcycloheptane-1,2-dicarboxylate,
Di-n-hexyl 3-methyl-7-ethylcycloheptane-1,2-dicarboxylate,
Di-n-octyl 3-methyl-7-ethylcycloheptane-1,2-dicarboxylate,
Di-n-hexyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,
Di-n-octyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,
Diisobutyl 3,7-diethylcycloheptane-1,2-dicarboxylate,
Di-n-hexyl 3,7-diethylcycloheptane-1,2-dicarboxylate,
Di-n-octyl 3,7-diethylcycloheptane-1,2-dicarboxylate,
Etc.

Among the above compounds,
Diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-hexyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-octyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Di-n-hexyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Di-n-octyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Di-n-hexyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Di-n-octyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3,6-diethylcyclohexane-1,2-dicarboxylate,
Di-n-hexyl 3,6-diethylcyclohexane-1,2-dicarboxylate,
More preferred is di-n-octyl 3,6-diethylcyclohexane-1,2-dicarboxylate. These compounds can be produced using the Diels Alder reaction.

  The cyclic ester compound (a) having a diester structure as described above has isomers such as cis and trans, and any structure has an effect meeting the object of the present invention. Higher rates are particularly preferred because they tend to have higher activity and stereoregularity of the resulting polymer, as well as the effect of broadening the molecular weight distribution. The ratio of the trans form of the cis form and the trans form is preferably 51% or more. A more preferred lower limit is 55%, even more preferred is 60%, and particularly preferred is 65%. On the other hand, the preferable upper limit is 100%, more preferably 90%, still more preferably 85%, and particularly preferably 79%.

<Cyclic ester compound (b)>
The cyclic ester compound (b) has a plurality of carboxylic acid ester groups and is represented by the following formula (2).

式（２）において、ｎは、５〜１０の整数、好ましくは５〜７の整数であり、特に好ましくは６である。またＣ^aおよびＣ^bは、炭素原子を表わす。

In the formula (2), n is an integer of 5 to 10, preferably an integer of 5 to 7, particularly preferably 6. C ^a and C ^b represent carbon atoms.

The carbon-carbon bonds in the cyclic skeleton are preferably all single bonds, but other than the C ^a -C ^a bond and the C ^a -C ^b bond in the case where R ⁵ is a hydrogen atom in the cyclic skeleton. Any single bond may be replaced with a double bond. That is, in the cyclic skeleton, the C—C ^b bond, the C ^a —C ^b bond when R ⁵ is COOR ¹ , and the C—C bond (when n is 6 to 10) are replaced with double bonds. It may be done.

R ⁴ and R ⁵ are each independently COOR ¹ or a hydrogen atom, at least one of R ⁴ and R ⁵ is COOR ¹ , and R ¹ is independently 1 to 1 of 1 to 20 carbon atoms. Valent hydrocarbon group.

A plurality of R ^{1 s} are each independently a monovalent carbon atom having 1 to 20, preferably 1 to 10, more preferably 2 to 8, more preferably 4 to 8, particularly preferably 4 to 6 carbon atoms. It is a hydrogen group. As this hydrocarbon group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, Tetradecyl group, hexadecyl group, octadecyl group, eicosyl group and the like can be mentioned. Among them, n-butyl group, isobutyl group, hexyl group and octyl group are preferable, and n-butyl group and isobutyl group are propylene type having wide molecular weight distribution. The block copolymer is particularly preferable because it can be produced.

As such a cyclic ester compound (b),
Cyclohexane-1,2-dicarboxylate diethyl,
Di-n-propyl cyclohexane-1,2-dicarboxylate,
Diisopropylcyclohexane-1,2-dicarboxylate,
Cyclohexane-1,2-dicarboxylate di-n-butyl,
Cyclohexane-1,2-dicarboxylate diisobutyl,
Cyclohexan-1,2-dicarboxylate dihexyl,
Diheptyl cyclohexane-1,2-dicarboxylate,
Dioctyl cyclohexane-1,2-dicarboxylate,
Cyclohexane-1,2-dicarboxylate di-2-ethylhexylcyclohexane-1,2-dicarboxylate didecyl,
Cyclohexane-1,3-dicarboxylate diethyl,
Cyclohexane-1,3-dicarboxylate diisobutyl,
Diethyl cyclopentane-1,2-dicarboxylate,
Diisopropyl cyclopentane-1,2-dicarboxylate,
Diisobutyl cyclopentane-1,2-dicarboxylate,
Cycloheptane-1,2-dicarboxylate diheptyl,
Didecyl cyclopentane-1,2-dicarboxylate,
Diethyl cyclopentane-1,3-dicarboxylate,
Cyclopentane-1,3-dicarboxylate diisobutyl,
Diethyl cycloheptane-1,2-dicarboxylate,
Diisopropyl cycloheptane-1,2-dicarboxylate,
Diisobutyl cycloheptane-1,2-dicarboxylate,
Diheptyl cycloheptane-1,2-dicarboxylate,
Didecyl cycloheptane-1,2-dicarboxylate,
Diethyl cycloheptane-1,3-dicarboxylate,
Diisobutyl cycloheptane-1,3-dicarboxylate,
Diethyl cyclooctane-1,2-dicarboxylate,
Diethyl cyclodecane-1,2-dicarboxylate,
4-cyclohexene-1,2-dicarboxylate diethyl,
Di-n-propyl 4-cyclohexene-1,2-dicarboxylate,
Diisopropyl 4-cyclohexene-1,2-dicarboxylate,
Di-n-butyl 4-cyclohexene-1,2-dicarboxylate,
Diisobutyl 4-cyclohexene-1,2-dicarboxylate,
4-cyclohexene-1,2-dicarboxylic acid dihexyl;
4-cyclohexene-1,2-dicarboxylate diheptyl,
Dioctyl 4-cyclohexene-1,2-dicarboxylate,
Didecyl 4-cyclohexene-1,2-dicarboxylate,
4-cyclohexene-1,3-dicarboxylate diethyl,
Diisobutyl 4-cyclohexene-1,3-dicarboxylate,
Diethyl 3-cyclopentene-1,2-dicarboxylate,
Diisopropyl 3-cyclopentene-1,2-dicarboxylate,
Diisobutyl 3-cyclopentene-1,2-dicarboxylate,
Diheptyl 3-cyclopentene-1,2-dicarboxylate,
Didecyl 3-cyclopentene-1,2-dicarboxylate,
Diethyl 3-cyclopentene-1,3-dicarboxylate,
Diisobutyl 3-cyclopentene-1,3-dicarboxylate,
4-cycloheptene-1,2-dicarboxylate diethyl,
4-cycloheptene-1,2-dicarboxylate diisopropyl,
4-cycloheptene-1,2-dicarboxylate diisobutyl,
4-cycloheptene-1,2-dicarboxylic acid diheptyl,
Didecyl 4-cycloheptene-1,2-dicarboxylate,
4-cycloheptene-1,3-dicarboxylate diethyl,
Diisobutyl 4-cycloheptene-1,3-dicarboxylate,
Diethyl 5-cyclooctene-1,2-dicarboxylate,
Examples include diethyl 6-cyclodecene-1,2-dicarboxylate.

In addition, the following compounds:
Cyclohexane-1,2-diacetate,
Cyclohexane-1,2-dibutanate,
Cyclohexane-1,2-dibenzoate,
Cyclohexane-1,2-ditoluate,
Etc. can also be mentioned as preferable examples.

  The compound having a diester structure as described above has isomers such as cis and trans, and any structure has an effect that meets the object of the present invention. The ratio of the trans form of the cis form and the trans form is preferably 51% or more. A more preferred lower limit is 55%, even more preferred is 60%, and particularly preferred is 65%. On the other hand, the preferable upper limit is 100%, more preferably 90%, still more preferably 85%, and particularly preferably 79%. The reason for this is unknown, but it is presumed that the variation of the stereoisomer described later is in a region suitable for wide molecular weight distribution.

  In particular, the trans purity of cyclohexane-1,2-dicarboxylic acid diester in which n = 6 in the above formula (2) is in the above range.

  If the trans purity is less than 51%, the effect of wide molecular weight distribution, activity, stereospecificity and the like may be insufficient. On the other hand, if the trans purity exceeds 79%, the effect of wide molecular weight distribution may be insufficient. That is, if the trans purity is within the above range, it is advantageous to achieve both a high level of both the effect of broadening the molecular weight distribution of the polymer obtained and the activity of the catalyst and the high stereoregularity of the polymer obtained. There are many.

  The cyclic ester compound (b) is particularly preferably a compound having a cycloalkane-1,2-dicarboxylic acid diester structure or a cycloalkene-1,2-dicarboxylic acid diester structure represented by the following formula (2a).

式（２ａ）中の、ｎ、Ｒ¹は前記同様（すなわち、式（２）での定義と同様）であり、環状骨格中の単結合（ただしＣ^a−Ｃ^a結合およびＣ^a−Ｃ^b結合を除く。すなわち、Ｃ−Ｃ^a結合、Ｃ−Ｃ^b結合およびＣ−Ｃ結合（ｎが６〜１０の場合））は、二重結合に置き換えられていてもよい。

In the formula (2a), n and R ¹ are the same as described above (that is, as defined in the formula (2)), and a single bond in the cyclic skeleton (however, a C ^a -C ^a bond and a C ^a -C ^b In other words, the C—C ^a bond, the C—C ^b bond, and the C—C bond (when n is 6 to 10)) may be replaced with a double bond.

Specifically, as the compound represented by the above formula (2a),
Cyclohexane-1,2-dicarboxylate di-n-butyl,
Cyclohexane-1,2-dicarboxylate diisobutyl,
Cyclohexan-1,2-dicarboxylate dihexyl,
Diheptyl cyclohexane-1,2-dicarboxylate,
Dioctyl cyclohexane-1,2-dicarboxylate,
Cyclohexane-1,2-dicarboxylate di-2-ethylhexyl,
Diisobutyl cyclopentane-1,2-dicarboxylate,
Diheptyl cyclopentane-1,2-dicarboxylate,
Diisobutyl cycloheptane-1,2-dicarboxylate,
And cycloheptane-1,2-dicarboxylic acid diheptyl.

Among the above compounds,
Cyclohexane-1,2-dicarboxylate diisobutyl,
Cyclohexan-1,2-dicarboxylate dihexyl,
Diheptyl cyclohexane-1,2-dicarboxylate,
Dioctyl cyclohexane-1,2-dicarboxylate,
Cyclohexane-1,2-dicarboxylate di-2-ethylhexyl,
Is more preferable. The reason is not only the catalyst performance, but also that these compounds can be produced relatively inexpensively using the Diels Alder reaction.

  The cyclic ester compounds (a) and (b) may be used alone or in combination of two or more.

  The combined molar ratio of the cyclic ester compound (a) and the cyclic ester compound (b) (cyclic ester compound (a) / (cyclic ester compound (a) + cyclic ester compound (b)) × 100 (mol%)) is 10 mol. % Or more is preferable. More preferably, it is 30 mol% or more, particularly preferably 40 mol% or more, and particularly preferably 50 mol%. A preferred upper limit is 99 mol%, preferably 90 mol%. More preferably, it is 85 mol%, Most preferably, it is 80 mol%.

  The solid titanium catalyst component (I) of the present invention has a low content of the cyclic ester compound (a) of the solid titanium catalyst component (I) under conditions of a wide range of combined molar ratios of the cyclic ester compound (a). However, an olefin polymer having a very wide molecular weight distribution can be provided. The cause of this effect is unknown, but the present inventors presume as follows.

  It is self-evident that the cyclic ester compound (a) has a large number of steric structural variations that can be formed compared to the cyclic ester compound (b) due to the presence of the substituent R. For this reason, the influence of the cyclic ester compound (a) is dominant on the molecular weight distribution, and it is considered that an olefin polymer having an extremely wide molecular weight distribution can be provided even if the combination molar ratio is low.

  On the other hand, since the cyclic ester compound (a) and the cyclic ester compound (b) are relatively similar in structure, the basic performance such as activity and stereoregularity hardly affects the effect of each other compound (the structure is When different compounds are used, there are many examples in which the activity, stereoregularity, etc. change drastically, and the effect of one compound becomes dominant.

  Therefore, the solid titanium catalyst component (I) used in the present invention gives an olefin polymer having a very wide molecular weight distribution and high stereoregularity with high activity even if the content of the cyclic ester compound (a) is low. be able to.

  The propylene-based block copolymer of the present invention is a polymer having a wide molecular weight distribution. The reason for this is currently unknown, but the following causes are presumed.

It is known that the cyclic hydrocarbon structure forms various three-dimensional structures such as a chair type and a boat type. Furthermore, if the cyclic structure has a substituent, the possible three-dimensional structure variations are further increased. Further, of the carbon atoms forming the cyclic skeleton of the cyclic ester compounds, the bond between the ester group (COOR ¹ group) carbon atom is bonded with an ester group (COOR ¹ group) other carbon atoms bound If it is a single bond, the variation of the three-dimensional structure which can be taken spreads. The ability to take such a variety of three-dimensional structures leads to the formation of a variety of active species on the solid titanium catalyst component (I). As a result, when olefin polymerization is performed using the solid titanium catalyst component (I), olefin polymers having various molecular weights can be produced at the same time, that is, a propylene block copolymer having a wide molecular weight distribution is produced. can do.

  In the present invention, the cyclic ester compounds (a) and (b) may be formed in the process of preparing the solid titanium catalyst component (I). For example, when preparing the solid titanium catalyst component (I), a step in which the carboxylic anhydride or carboxylic acid dihalide corresponding to the cyclic ester compounds (a) and (b) substantially contacts with the corresponding alcohol. By providing, the cyclic ester compounds (a) and (b) can be contained in the solid titanium catalyst component.

  For the preparation of the solid titanium catalyst component (I) used in the present invention, a magnesium compound and a titanium compound are used in addition to the cyclic ester compounds (a) and (b). Moreover, unless the objective of this invention is impaired, you may use the catalyst component (c) and catalyst component (d) which are mentioned later in combination.

<Magnesium compound>
Specifically, as the magnesium compound used for the preparation of the solid titanium catalyst component (I) according to the present invention,
Magnesium halides such as magnesium chloride and magnesium bromide;
Alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, phenoxy magnesium chloride;
Alkoxy magnesium such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, 2-ethylhexoxy magnesium;
Aryloxymagnesium such as phenoxymagnesium;
Known magnesium compounds such as magnesium carboxylates such as magnesium stearate can be mentioned.

  These magnesium compounds may be used alone or in combination of two or more. These magnesium compounds may be complex compounds with other metals, double compounds, or mixtures with other metal compounds.

  Among these, a magnesium compound containing a halogen is preferable, and a magnesium halide, particularly magnesium chloride is preferably used. In addition, alkoxymagnesium such as ethoxymagnesium is also preferably used. The magnesium compound may be derived from other substances, for example, obtained by contacting an organic magnesium compound such as a Grignard reagent with a halogenated titanium, a halogenated silicon, a halogenated alcohol, or the like. Good. For example, when alkoxymagnesium and tetraalkoxytitanium are combined, it is preferable to react with silicon tetrachloride as a halogenating agent to form magnesium halide.

<Titanium compound>
Examples of titanium compounds include general formulas;
Ti (OR) _g X _4-g
(R is a hydrocarbon group, X is a halogen atom, and g is 0 ≦ g ≦ 4.)
The tetravalent titanium compound shown by these can be mentioned. More specifically,
Titanium tetrahalides such as TiCl ₄ and TiBr ₄ ;
_{Ti (OCH 3) Cl 3,} Ti (OC 2 H 5) Cl 3, Ti (O-n-C 4 H 9) Cl 3, Ti (OC 2 H 5) Br 3, Ti (O-isoC 4 H 9 ) Trihalogenated alkoxytitanium such as Br ₃ ;
Dihalogenated alkoxytitanium such as Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ ;
Monohalogenated alkoxytitanium such as Ti (OCH ₃ ) ₃ Cl, Ti (On-C ₄ H ₉ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Br;
Examples thereof include tetraalkoxytitanium such as Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₄ H ₉ ) ₄ , and Ti (O-2-ethylhexyl) ₄ .

  Among these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used alone or in combination of two or more.

  Examples of the magnesium compound and the titanium compound as described above may include compounds described in detail in Patent Document 1, Patent Document 2, and the like.

  For the preparation of the solid titanium catalyst component (I) of the present invention, any known method can be used without limitation, except that the cyclic ester compounds (a) and (b) are used. Specific preferred methods include, for example, the following methods (P-1) to (P-4).

  (P-1) A solid adduct comprising a magnesium compound and a catalyst component (c), a cyclic ester compound (a) and (b), and a liquid titanium compound are suspended in the presence of an inert hydrocarbon solvent. Method to contact in turbid state.

  (P-2) A method in which a solid adduct comprising a magnesium compound and a catalyst component (c), cyclic ester compounds (a) and (b), and a titanium compound in a liquid state are contacted in a plurality of times.

  (P-3) A solid adduct comprising a magnesium compound and a catalyst component (c), a cyclic ester compound (a) and (b), and a liquid titanium compound are suspended in the presence of an inert hydrocarbon solvent. The method of making it contact in a cloudy state, and making it contact in several steps.

  (P-4) A method of contacting a magnesium compound in a liquid state comprising a magnesium compound and a catalyst component (c), a titanium compound in a liquid state, and the cyclic ester compounds (a) and (b).

  A preferable reaction temperature in the preparation of the solid titanium catalyst component (I) is -30 ° C to 150 ° C, more preferably -25 ° C to 140 ° C, and further preferably -25 ° C to 130 ° C.

  The production of the solid titanium catalyst component can also be carried out in the presence of a known medium, if necessary. Examples of this medium include aromatic hydrocarbons such as slightly polar toluene and known aliphatic hydrocarbons such as heptane, hexane, octane, decane, and cyclohexane, and alicyclic hydrocarbon compounds. Aliphatic hydrocarbons are preferred examples.

  When the olefin polymerization reaction is carried out using the solid titanium catalyst component (I) produced in the above range, the effect of obtaining a polymer having a wide molecular weight distribution, the activity of the catalyst and the high stereoregulation of the obtained polymer Sex at a higher level.

<Catalyst component (c)>
As the catalyst component (c) used for forming the solid adduct or the liquid magnesium compound, a known compound capable of solubilizing the magnesium compound in a temperature range of about room temperature to about 300 ° C. is preferable. Aldehydes, amines, carboxylic acids and mixtures thereof are preferred. Examples of these compounds include compounds described in detail in Patent Document 1 and Patent Document 2.

More specifically, as an alcohol having the above-mentioned solubilizing ability of magnesium compound,
Aliphatic alcohols such as methanol, ethanol, propanol, butanol, isobutanol, ethylene glycol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, decanol, dodecanol;
Cycloaliphatic alcohols such as cyclohexanol and methylcyclohexanol;
Aromatic alcohols such as benzyl alcohol and methylbenzyl alcohol;
Examples thereof include aliphatic alcohols having an alkoxy group such as n-butyl cellosolve.

  Examples of the carboxylic acid include organic carboxylic acids having 7 or more carbon atoms such as caprylic acid and 2-ethylhexanoic acid.

  Examples of the aldehyde include aldehydes having 7 or more carbon atoms such as capric aldehyde and 2-ethylhexyl aldehyde.

  Examples of the amine include amines having 6 or more carbon atoms such as heptylamine, octylamine, nonylamine, laurylamine, 2-ethylhexylamine.

  As said catalyst component (c), said alcohol is preferable, and especially ethanol, propanol, butanol, isobutanol, hexanol, 2-ethylhexanol, decanol, etc. are preferable.

  The amount of the magnesium compound and catalyst component (c) used in preparing the solid adduct or liquid magnesium compound varies depending on the type, contact conditions, and the like. It is used in an amount of 0.1 to 20 mol / liter, preferably 0.5 to 5 mol / liter per unit volume of c). Further, if necessary, a medium inert to the solid adduct can be used in combination. As said medium, well-known hydrocarbon compounds, such as heptane, hexane, octane, decane, are mentioned as a preferable example.

  The composition ratio of magnesium to the catalyst component (c) in the solid adduct or liquid magnesium compound obtained varies depending on the type of compound used, but cannot be specified unconditionally, but with respect to 1 mol of magnesium in the magnesium compound. The catalyst component (c) is preferably in the range of 2.0 mol or more, more preferably 2.2 mol or more, further preferably 2.3 mol or more, particularly preferably 2.4 mol or more and 5 mol or less. .

<Aromatic carboxylic acid ester and / or compound having two or more ether bonds via a plurality of carbon atoms>
The solid titanium catalyst component (I) of the present invention further includes an aromatic carboxylic acid ester and / or a compound having two or more ether bonds via a plurality of carbon atoms (hereinafter also referred to as “catalyst component (d)”). .) May be included. When the solid titanium catalyst component (I) of the present invention contains the catalyst component (d), the catalyst activity may be improved, the stereoregularity may be increased, or the molecular weight distribution may be further broadened.

  As the catalyst component (d), known aromatic carboxylic acid esters and polyether compounds that are preferably used in conventional olefin polymerization catalysts, such as those described in Patent Document 1 and Japanese Patent Application Laid-Open No. 2001-354714, are listed. The compound can be used without limitation.

  Specific examples of the aromatic carboxylic acid ester include aromatic carboxylic acid monoesters such as benzoic acid esters (such as ethyl benzoate) and toluic acid esters, and aromatic polyvalent carboxylic acid esters such as phthalic acid esters. Can be mentioned. Among these, aromatic polycarboxylic acid esters are preferable, and phthalic acid esters are more preferable. As the phthalic acid esters, phthalic acid alkyl esters such as ethyl phthalate, n-butyl phthalate, isobutyl phthalate, hexyl phthalate, and heptyl phthalate are preferable, and diisobutyl phthalate is particularly preferable.

  More specifically, examples of the polyether compound include compounds represented by the following formula (4).

なお、上記式（４）において、ｍは１〜１０の整数、より好ましくは３〜１０の整数であり、特に好ましくは３〜５である。Ｒ¹¹、Ｒ¹²、Ｒ³¹〜Ｒ³⁶は、それぞれ独立に、水素原子、あるいは炭素、水素、酸素、フッ素、塩素、臭素、ヨウ素、窒素、硫黄、リン、ホウ素およびケイ素から選択される少なくとも１種の元素を有する置換基である。

In the above formula (4), m is an integer of 1 to 10, more preferably an integer of 3 to 10, and particularly preferably 3 to 5. R ¹¹ , R ¹² , R ^{31 to} R ³⁶ are each independently at least one selected from a hydrogen atom or carbon, hydrogen, oxygen, fluorine, chlorine, bromine, iodine, nitrogen, sulfur, phosphorus, boron and silicon. A substituent having a seed element.

R ¹¹ and R ¹² are preferably a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 2 to 6 carbon atoms, and R ^{31 to} R ³⁶ are preferably a hydrogen atom or a carbon atom. It is a hydrocarbon group of number 1-6.

Specific examples of R ¹¹ and R ¹² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, 2 -An ethylhexyl group, a decyl group, a cyclopentyl group, and a cyclohexyl group are mentioned, Preferably they are an ethyl group, n-propyl group, isopropyl group, n-butyl group, and isobutyl group.

Specific examples of R ^{31 to} R ³⁶ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group, preferably a hydrogen atom and a methyl group.

Arbitrary R ¹¹ , R ¹² , R ^{31 to} R ³⁶ , preferably R ¹¹ and R ¹² may jointly form a ring other than a benzene ring, and an atom other than carbon is contained in the main chain. May be.

As specific compounds having two or more ether bonds as described above,
2-isopropyl-1,3-dimethoxypropane,
2-s-butyl-1,3-dimethoxypropane,
Monosubstituted dialkoxypropanes such as 2-cumyl-1,3-dimethoxypropane;
2-isopropyl-2-isobutyl-1,3-dimethoxypropane,
2,2-dicyclohexyl-1,3-dimethoxypropane,
2-methyl-2-isopropyl-1,3-dimethoxypropane,
2-methyl-2-cyclohexyl-1,3-dimethoxypropane,
2-methyl-2-isobutyl-1,3-dimethoxypropane,
2,2-diisobutyl-1,3-dimethoxypropane,
2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane,
2,2-diisobutyl-1,3-diethoxypropane,
2,2-diisobutyl-1,3-dibutoxypropane,
2,2-di-s-butyl-1,3-dimethoxypropane,
2,2-dineopentyl-1,3-dimethoxypropane,
2-isopropyl-2-isopentyl-1,3-dimethoxypropane,
2-substituted dialkoxypropanes such as 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane 2,3-dicyclohexyl-1,4-dimethoxybutane,
2,3-dicyclohexyl-1,4-diethoxybutane,
2,3-diisopropyl-1,4-diethoxybutane 2,4-diphenyl-1,5-dimethoxypentane,
2,5-diphenyl-1,5-dimethoxyhexane,
2,4-diisopropyl-1,5-dimethoxypentane,
2,4-diisobutyl-1,5-dimethoxypentane,
Dialkoxyalkanes such as 2,4-diisoamyl-1,5-dimethoxypentane,
2-methyl-2-methoxymethyl-1,3-dimethoxypropane,
2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane,
Trialkoxyalkanes such as 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane,
2,2-diisobutyl-1,3-dimethoxy-4-cyclohexene,
2-isopropyl-2-isoamyl-1,3-dimethoxy-4-cyclohexene,
2-cyclohexyl-2-methoxymethyl-1,3-dimethoxy-4-cyclohexene,
2-isopropyl-2-methoxymethyl-1,3-dimethoxy-4-cyclohexene,
2-isobutyl-2-methoxymethyl-1,3-dimethoxy-4-cyclohexene,
2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxy-4-cyclohexene,
2-isopropyl-2-ethoxymethyl-1,3-dimethoxy-4-cyclohexene,
Examples thereof include dialkoxycycloalkanes such as 2-isobutyl-2-ethoxymethyl-1,3-dimethoxy-4-cyclohexene.

  Of these, 1,3-diethers are preferable, and in particular, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl. -1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, and 2,2-bis (cyclohexylmethyl) 1,3-dimethoxypropane are preferred.

  These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  The above cyclic ester compounds (a) and (b), the catalyst component (c), and the catalyst component (d) may be considered to belong to a component called an electron donor among those skilled in the art. The above-mentioned electron donor component has the effect of increasing the stereoregularity of the resulting polymer while maintaining the high activity of the catalyst, the effect of controlling the composition distribution of the resulting copolymer, the particle shape of the catalyst particles, It is known to show an aggregating agent effect for controlling the particle size.

  The above-mentioned cyclic ester compounds (a) and (b) are considered to have an effect of further controlling the molecular weight distribution by themselves being electron donors.

In the solid titanium catalyst component (I) of the present invention, the halogen / titanium (atomic ratio) (that is, the number of moles of halogen atom / number of moles of titanium atom) is 2 to 100, preferably 4 to 90. Desirable,
Cyclic ester compound (a) / titanium (molar ratio) (that is, number of moles of cyclic ester compound (a) / number of moles of titanium atom) and cyclic ester compound (b) / titanium (molar ratio) (that is, cyclic ester compound) The number of moles of (b) / number of moles of titanium atoms) is 0.01-100, preferably 0.2-10,
The catalyst component (c) should have a catalyst component (c) / titanium atom (molar ratio) of 0 to 100, preferably 0 to 10.

  Here, as a preferable ratio of the cyclic ester compound (a) and the cyclic ester compound (b), the value (moles) of 100 × cyclic ester compound (a) / (cyclic ester compound (a) + cyclic ester compound (b)) %) Is 5 mol%, preferably 25 mol%, more preferably 40 mol%, and particularly preferably 50 mol%. The upper limit is 99 mol%, preferably 90 mol%, more preferably 85 mol%, particularly preferably 80 mol%.

  Magnesium / titanium (atomic ratio) (that is, the number of moles of magnesium atoms / the number of moles of titanium atoms) is 2 to 100, preferably 4 to 50.

  In addition, the content of components other than the cyclic ester compounds (a) and (b) described above, for example, the catalyst component (c) and the catalyst component (d) is preferably cyclic ester compounds (a) and ( b) It is 20 weight% or less with respect to 100 weight%, More preferably, it is 10 weight% or less.

  Except for using the cyclic ester compounds (a) and (b) as more detailed preparation conditions for the solid titanium catalyst component (I), for example, EP585869A1 (European Patent Application Publication No. 0585869) and the aforementioned Patent Document 2 Etc. can be preferably used.

[Organometallic Compound (II)]
Examples of the organometallic compound (II) according to the present invention include organometallic compounds containing a metal atom selected from Group 1, Group 2 and Group 13 of the periodic table. Specifically, a compound containing a Group 13 metal, for example, an organoaluminum compound, a complex alkylated product of a Group 1 metal and aluminum, an organometallic compound of a Group 2 metal, or the like can be used. Among these, an organoaluminum compound is preferable.

  Specific examples of the organometallic compound (II) include organometallic compound catalyst components described in known documents such as the above-mentioned EP585869A1.

[Organic silicon compound (III)]
Examples of the organosilicon compound (III) according to the present invention include an organosilicon compound represented by the following formula (3).

Si (OR ¹ ) ₃ (NR ² R ³ ) (3)
In the above formula (3), R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, preferably an unsaturated or saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms, particularly preferably. A saturated aliphatic hydrocarbon group having 2 to 6 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, ter-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, A cyclopentyl group, n-hexyl group, cyclohexyl group, etc. are mentioned. Particularly preferred is an ethyl group.

In said formula (3), R < ² > is a C1-C12 hydrocarbon group or hydrogen, Preferably, a C1-C12 unsaturated or saturated aliphatic hydrocarbon group or hydrogen is mentioned. . Specific examples include hydrogen, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, ter-butyl group, sec-butyl group, n-pentyl group, iso-pentyl. Group, cyclopentyl group, n-hexyl group, cyclohexyl group, octyl group and the like. Particularly preferred is an ethyl group.

In said formula (3), R < ³ > is a C1-C12 hydrocarbon group, Preferably, a C1-C12 unsaturated or saturated aliphatic hydrocarbon group etc. are mentioned. Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, ter-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, Examples include a cyclopentyl group, an n-hexyl group, a cyclohexyl group, and an octyl group. Particularly preferred is an ethyl group.

  Specific examples of the organosilicon compound (III) according to the present invention include dimethylaminotriethoxysilane, diethylaminotriethoxysilane, diethylaminotrimethoxysilane, diethylaminotrin-propoxysilane, di-n-propylaminotriethoxysilane, methyln -Propylaminotriethoxysilane, t-butylaminotriethoxysilane, ethyl n-propylaminotriethoxysilane, ethylisopropylaminotriethoxysilane and methylethylaminotriethoxysilane. These organosilicon compounds may be used alone or in combination of two or more.

[Propylene block copolymer production method]
The production method of the propylene-based block copolymer according to the present invention is not limited as long as the requirements [1] to [6] are satisfied.

  In the method for producing a propylene-based block copolymer of the present invention, after preparing a prepolymerization catalyst [A] obtained by prepolymerizing an olefin in the presence of the above-mentioned olefin polymerization catalyst, the main polymerization (polymerization) is performed. ) Is preferable.

<Preliminary polymerization catalyst [A]>
The propylene-based block copolymer according to the present invention is controlled to have a molecular weight distribution in a specific range, and for the purpose of obtaining a product satisfying the requirement [4] of the propylene-based block copolymer, the prepolymerization catalyst [A] It is preferable to carry out polymerization of propylene in the presence of the prepolymerization catalyst [A], the organometallic compound [B], and the organosilicon compound (III) (defined as main polymerization).

  The prepolymerization catalyst [A] is formed by prepolymerizing olefins and the like in the presence of the solid titanium catalyst component (I), the organometallic compound (II), and the organosilicon compound (III).

  This prepolymerization is usually 0.1 to 1000 g, preferably 0.3 to 500 g, particularly preferably, per 1 g of the total amount of the solid titanium catalyst component (I), the organometallic compound (II) and the organosilicon compound (III). Is carried out by prepolymerizing olefins in an amount of 1 to 200 g.

  In the prepolymerization, a catalyst having a higher concentration than the catalyst concentration in the system in the main polymerization can be used.

  Propylene is preferably used as the olefin used in the prepolymerization.

  The concentration of the solid titanium catalyst component (I) in the prepolymerization is usually about 0.001 to 200 mmol, preferably about 0.01 to 50 mmol, particularly preferably 0, in terms of titanium atom per liter of the liquid medium. Desirably, the range is from 1 to 20 mmol.

  The amount of the organometallic compound (II) in the prepolymerization is an amount that usually produces 0.1 to 1000 g, preferably 0.3 to 500 g of polymer per 1 g of the solid titanium catalyst component (I). The amount is usually about 0.1 to 300 mol, preferably about 0.5 to 100 mol, particularly preferably 1 to 50 mol per mol of titanium atom in the solid titanium catalyst component (I). desirable.

  The amount of the organosilicon compound (III) in the prepolymerization is usually 0.1 to 50 mol, preferably 0.5 to 30 mol, more preferably per mol of titanium atom in the solid titanium catalyst component (I). Is used in an amount of 1 to 10 mol.

  The prepolymerization is carried out under mild conditions by adding olefins and the above-mentioned solid titanium catalyst component (I), organometallic compound (II), and organosilicon compound (III) to an inert hydrocarbon medium. be able to.

In this case, specifically as the inert hydrocarbon medium used,
Aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene;
Cycloaliphatic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, cycloheptane, methylcycloheptane, cyclooctane;
Aromatic hydrocarbons such as benzene, toluene, xylene;
Halogenated hydrocarbons such as ethylene chloride and chlorobenzene;
Alternatively, a mixture thereof can be used.

  Of these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. Thus, when using an inert hydrocarbon medium, it is preferable to perform prepolymerization by a batch type.

  On the other hand, the prepolymerization can be carried out using the olefin itself used for the prepolymerization as a solvent, or the prepolymerization can be carried out in a substantially solvent-free state. In this case, it is preferable to perform preliminary polymerization continuously.

  The temperature during the prepolymerization is usually -20 to + 100 ° C, preferably -20 to + 80 ° C, more preferably 0 to + 40 ° C.

<Main polymerization>
As the main polymerization method in the present invention, a solvent polymerization method using an inert medium, a bulk polymerization method using the monomer itself as a liquid solvent, a gas phase polymerization method in which the monomer is polymerized in a gas state, or a combination thereof may be used. Is possible. In the main polymerization in the present invention, propylene, ethylene, and an α-olefin having 4 to 20 carbon atoms are present in the presence of the above-mentioned prepolymerization catalyst [A], organometallic compound (II), and organosilicon compound (III). A propylene-based block copolymer can be obtained by polymerizing one or more olefins selected from the group consisting of:

In the main polymerization in the method for producing a propylene-based block copolymer of the present invention, the prepolymerized catalyst [A] is a solid titanium catalyst component (I) present in the prepolymerized catalyst [A] per 1 liter of polymerization volume. The amount is usually about 0.0001 to 0.5 mmol, preferably about 0.005 to 0.1 mmol in terms of titanium atoms derived from the above. The organometallic compound (II) is usually used in an amount of about 1 to 2000 mol, preferably about 5 to 500 mol, per 1 mol of titanium atom in the prepolymerization catalyst [A] in the polymerization system. Used. The organosilicon compound (III) is used in an amount of 0.001 to 50 mol, preferably 0.01 to 30 mol, particularly preferably 0.05 to 20 mol, relative to 1 mol of the organometallic compound (II). It is done.

  If the main polymerization is carried out in the presence of hydrogen, the molecular weight of the resulting polymer can be adjusted (lowered), and a polymer having a high melt flow rate can be obtained. Since the amount of hydrogen necessary for adjusting the molecular weight varies depending on the type of production process used, the pressure, and the temperature, the range cannot be determined unconditionally. Therefore, in the process of producing the propylene polymer component, it is desirable to determine the amount of hydrogen in consideration of pressure and temperature so that the target MFR is obtained in the range of 25 to 400 g / 10 minutes.

In the main polymerization in the present invention, the polymerization temperature is usually about 20 to 200 ° C, preferably about 30 to 100 ° C, more preferably 50 to 90 ° C. The pressure (gauge pressure) is usually set to normal pressure to 100 kgf / cm ² (9.8 MPa), preferably about ^{2 to} 50 kgf / cm ² (0.20 to 4.9 MPa). In the method for producing a propylene block copolymer of the present invention, the polymerization can be carried out by any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions.

  The method for producing a propylene-based block copolymer according to the present invention will be described in more detail.

  According to another knowledge of the present inventors, the n-decane insoluble part (Dinsol) constituting the propylene-based block copolymer of the present invention is a propylene homopolymer, a propylene random polymer (ethylene and having 4 or more carbon atoms). a propylene-based polymer containing a skeleton derived from one or more olefins selected from α-olefins in an amount not exceeding 1.5 mol%), or a mixture of two or more of these.

  On the other hand, the n-decane soluble part (Dsol) is substantially the same as propylene / ethylene copolymer, propylene / α-olefin copolymer, propylene / ethylene / α-olefin copolymer or a mixture of two or more of these. (The “copolymer” includes a random polymer).

  Therefore, the propylene-based block copolymer of the present invention can be produced by one of the following production methods.

Method A;
A method for producing a propylene-based block copolymer satisfying the requirements [1] to [6] by continuously performing the following two polymerization steps (polymerization step 1 and polymerization step 2) (hereinafter, this method) Is referred to as “straight weight method”, and the propylene block copolymer obtained by this method may be referred to as a propylene block copolymer (A)).

  (Polymerization step 1) A step of producing a (co) polymer of propylene and, if necessary, one or more olefins selected from ethylene and an α-olefin having 4 to 20 carbon atoms in the presence of a solid titanium catalyst component. (Crystalline propylene (co) polymer production process).

  (Polymerization step 2) A step of producing a copolymer of propylene and one or more olefins selected from ethylene and an α-olefin having 4 to 20 carbon atoms in the presence of a solid titanium catalyst component (copolymer rubber production) Process).

Method B;
After the (co) polymer produced in the polymerization step 1 of the method A and the copolymer produced in the polymerization step 2 of the method A are individually produced in the presence of a solid titanium catalyst component, they are physically treated. (Hereinafter referred to as this method “blending method”, and the propylene-based block copolymer obtained by this method may be referred to as a propylene-based copolymer (B)).

  In the presence of the olefin polymerization catalyst described above, the propylene-based block copolymer according to the present invention is, as described in Method A, homopolymerization of propylene in a propylene medium in the polymerization step 1 or ethylene and carbon atoms of 4 to 4 Propylene-based copolymer containing a skeleton derived from one or more olefins selected from 20 α-olefins in an amount not exceeding 1.5 mol% is produced, and in the polymerization step 2, propylene, ethylene and the number of carbon atoms are Copolymerization with one or more olefins selected from 4 to 20 α-olefins, and the finally obtained propylene block copolymer is soluble in room temperature n-decane (Dsol) 5 to 80 It is characterized in that it is composed of 20% to 95% by weight and a portion insoluble in room temperature n-decane (Dinsol).

  When propylene is homopolymerized using the above olefin polymerization catalyst, the decane-insoluble component content is not less than 70% by weight, preferably not less than 85% by weight, particularly preferably not less than 90% by weight. A propylene-based block copolymer having a high content, that is, a high content of the crystalline component is obtained.

  Furthermore, according to the method for producing a propylene-based block copolymer of the present invention, the molecular weight distribution can be reduced by the action of the catalyst for olefin polymerization of the present invention without performing multi-stage polymerization, for example, polymerization with a small number of stages, for example, single-stage polymerization. A wide propylene polymer can be obtained.

[Propylene-based resin composition]
The propylene-based block copolymer according to the present invention can take the form of a propylene-based resin composition blended with an auxiliary material as long as the characteristics of the present invention are not impaired. Hereinafter, an elastomer, an inorganic filler, and an additive are demonstrated as an example of a typical submaterial.

<Elastomer>
Examples of elastomers include ethylene / α-olefin random copolymer rubber, ethylene / α-olefin / non-conjugated polyene random copolymer rubber, hydrogenated block copolymer rubber, other elastic polymer rubber, and mixtures thereof. Can be mentioned.

  The ethylene / α-olefin random copolymer is a random copolymer rubber of ethylene and an α-olefin having 3 to 20 carbon atoms. Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-octene, Examples include decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicocene. These α-olefins can be used alone or in combination. Of these, propylene, 1-butene, 1-hexene and 1-octene are particularly preferably used.

  The ethylene / α-olefin random copolymer has a molar ratio of ethylene to α-olefin (ethylene / α-olefin) of 95/5 to 70/30, preferably 90/10 to 75/25. The ethylene / α-olefin random copolymer has an MFR of 0.1 g / 10 min or more, preferably 0.5 to 5 g / 10 min at 230 ° C. and a load of 2.16 kg.

  When the α-olefin of the ethylene / α-olefin random copolymer is ethylene, the propylene-based resin composition according to the present invention may be produced in the form of a propylene-based block copolymer. The propylene-based block copolymer can be produced by continuously performing the following two polymerization steps (polymerization step 1 and polymerization step 2).

  (Polymerization step 1) A step of producing a propylene polymer component by polymerizing propylene and, if necessary, another α-olefin in the presence of a solid titanium catalyst component (a propylene polymer production step).

  (Polymerization step 2) A step of copolymerizing propylene and ethylene in the presence of a solid titanium catalyst component to produce a propylene-ethylene copolymer rubber component (copolymer rubber production step).

  In producing the propylene-ethylene copolymer rubber, the ethylene / (ethylene + propylene) gas ratio is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and still more preferably 15 to Polymerization is carried out while controlling at 60 mol%.

  The propylene-based block copolymer (A) according to the present invention is preferably produced by the production method described above, and it is more preferred that the polymerization step 1 is performed in the previous stage and the polymerization step 2 is performed in the subsequent stage. Each polymerization step (polymerization step 1, polymerization step 2) can also be performed using two or more polymerization vessels.

  Here, when the step of producing the propylene polymer component (polymerization step 1 of the above production method) is performed in two or more tanks, the intrinsic viscosity [η] of the propylene polymer produced in each tank is 4 dl. / G or less is preferable.

  Moreover, it is preferable to superpose | polymerize in 1 step in the process (polymerization process 2 of the said manufacturing method) which manufactures the said propylene-ethylene copolymer rubber component.

<Inorganic filler>
As an inorganic filler which is an essential constituent of the propylene-based resin-modified material, talc, magnesium sulfate fiber, glass fiber, carbon fiber, mica, calcium carbonate, magnesium hydroxide, ammonium phosphate salt, silicates, It is roughly classified into inorganic fillers such as carbonates and carbon black, and organic fillers such as wood powder, cellulose, polyester fiber, nylon fiber, kenaf fiber, bamboo fiber, jude fiber, rice flour, starch, and corn starch.

  As the inorganic filler, talc, magnesium sulfate fiber, glass fiber, and carbon fiber are preferably used.

<Additives>
Stabilizers used in the present invention include heat stabilizers, weather stabilizers, light stabilizers, chloride absorbers, fillers, crystal nucleating agents, softeners, antistatic agents, slip agents, antiblocking agents, antifogging agents, Known stabilizers such as lubricants, dyes, pigments, natural oils, synthetic oils and waxes can be used without limitation. For example, known phenol stabilizers, organic phosphite stabilizers, thioether stabilizers, hindered amine stabilizers, higher fatty acid metal salts such as calcium stearate, inorganic oxides and the like.

  The propylene block copolymer (A) used in the present invention is characterized by containing a relatively large amount of high molecular weight components as described above. It is known that high molecular weight components tend to be relatively easily cut by energy such as heat, light, and shear. When molecular cutting occurs, the molecular weight distribution becomes narrow, which may cause problems such as a reduction in high-speed molding performance and difficulty in manufacturing a large molded product. Therefore, it is preferable to select an additive having a higher effect than the conventional additive and increase the amount of the additive.

[Injection molded body]
The propylene-based block copolymer and the propylene-based resin composition containing the propylene-based block copolymer according to the present invention are free from defects in the appearance of flow marks in injection-molded products and have good impact strength.

  Therefore, the use of the injection-molded body is not limited, but in particular, automotive exterior parts such as bumpers, side moldings, fenders, undercovers, automotive interior parts such as instrument panels, door trims, pillars, and engine room peripheral parts. In addition, it can be suitably used for automobile parts, home appliance parts, food containers, beverage containers, medical containers, containers and the like. Conventionally known conditions can be adopted without limitation for the molding conditions of the injection-molded article of the present invention.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

  In the following examples, the physical properties of the propylene block copolymer and the propylene resin composition were measured by the following methods.

(1) Molecular weight distribution Liquid chromatograph: Waters ALC / GPC 150-C plus type (Suggested refractometer detector integrated type)
Column: Tosoh Corporation GMH6-HTx2 and GMH6-HTLx2 were connected in series.

Mobile phase medium: o-dichlorobenzene Flow rate: 1.0 ml / min Measurement temperature: 140 ° C.
Calibration curve creation method: Standard polystyrene sample used Sample concentration: 0.10% (w / w)
Sample solution volume: 500 μl
Mw / Mn value and Mz / Mw value were calculated by analyzing the obtained chromatogram by a known method. The measurement time per sample was 60 minutes.

(2) Presence / absence of GPC log M = 2 to 4 peaks The chromatogram obtained by measurement according to the method described in (1) above, the X-axis represents the logarithm of molecular weight M (Log M (range: 1 to 8)). The differential molecular weight distribution curve is created so that the Y axis is the differential molecular weight distribution (dw / d (LogM) (range: 0 to 1)) and the length ratio of the X axis and the Y axis of the graph is 5: 3. .

  The presence or absence of a peak in the range where LogM is 2 to 4 is within the range of 2 to 4 in LogM, within the range of 30 ° in the first quadrant with respect to the portion parallel to the X axis of the graph or the X axis vector. Judgment is made by whether or not the four quadrants have a line portion within a range of 45 °.

(3) Isotactic pendant fraction (mmmm: [%])
It is one of the indexes of the stereoregularity of the polymer, and the pentad fraction (mmmm,%) for which the microtacticity was examined was assigned to ¹³ C-- which was assigned in the propylene polymer based on Macromolecules 8,687 (1975). It was calculated from the peak intensity ratio of the NMR spectrum. ^{The 13} C-NMR spectrum was measured using an EX-400 device manufactured by JEOL, based on TMS, using a temperature of 130 ° C. and an o-dichlorobenzene solvent.

(4) 23 ° C. n-decane soluble (insoluble) component amount ([wt%])
About 3 g of a propylene-based block copolymer (measured to a unit of 10 ^-4 g. In addition, this weight was expressed as b (g) in the following formula), 500 ml of decane, and decane. A small amount of a heat-resistant stabilizer was charged, and the mixture was heated to 150 ° C. in 2 hours while stirring with a stirrer in a nitrogen atmosphere to dissolve the propylene-based block copolymer, and kept at 150 ° C. for 2 hours. It was gradually cooled to 23 ° C. over 8 hours. The liquid containing the obtained propylene-based block copolymer precipitate was filtered under reduced pressure using a 25G-4 standard glass filter manufactured by Iwata Glass Co., Ltd. 100 ml of the filtrate was collected and dried under reduced pressure to obtain a part of the decane-soluble component, and this weight was measured to the unit of 10 ⁻⁴ g (this weight is expressed as a (g) in the following equation). did). After this operation, the amount of decane soluble component was determined by the following formula.

23 ° C. n-decane soluble component (Dsol) content = 100 × (500 × a) / (100 × b)
23 ° C. n-decane insoluble component (Dinsol) content = 100−100 × (500 × a) / (100 × b)
(5) Content of skeleton derived from propylene (amount of C3)
In order to measure the skeleton concentration derived from propylene in Dsol, 20-30 mg of sample was dissolved in 0.6 ml of 1,2,4-trichlorobenzene / heavy benzene (2: 1) solution, and then carbon nuclear magnetic resonance analysis ( ¹³ C-NMR). The quantity of propylene was determined from the dyad chain distribution. In the case of a propylene-ethylene copolymer, PP = Sαα, EP = Sαγ + Sαβ, and EE = 1/2 (Sβδ + Sδδ) + 1 / 4Sγδ were used, and the following formula was used.

Propylene (mol%) = (PP + 1 / 2EP) × 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE)
Ethylene (mol%) = (1 / 2EP + EE) × 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE)
(6) Intrinsic viscosity ([η]: [dl / g])
It measured at 135 degreeC using the tetralin solvent.

(7) Melt flow rate (MFR: [g / 10 min])
Based on ASTM D1238E, it was measured with a 2.16 kg load. The measurement temperature was 230 ° C.

(8) Flexural modulus The flexural modulus (FM: [MPa]) was measured in accordance with ISO178 under the following conditions.
<Measurement conditions>
Test piece: 10 mm (width) x 4 mm (thickness) x 80 mm (length)
Bending speed: 2 mm / min Bending span: 64 mm
(9) Charpy impact test The Charpy impact test ([kJ / m ² ]) was measured according to ISO 179 under the following conditions.
<Test conditions>
Temperature: 23 ° C, -10 ° C
Test piece: 10 mm (width) x 4 mm (thickness) x 80 mm (length)
The notch is machined.

(10) Appearance of injection-molded product (flow mark generation start distance)
As the flow mark of the injection molded product, an injection mold having a length of 420 mm, a width of 100 mm, and a thickness of 2 mm and capable of forming a flat plate and having a gate at the center (50 mm) was used. Here, the area where the flow mark was generated from the gate was visually evaluated. In this test, in order to make it easy to determine the flow mark, 2 parts by weight of a black colored master batch was dry blended with 100 parts by weight of the propylene-based resin composition, and injection molding was performed.

<Test piece injection molding conditions>
Injection molding machine: Part number IS150E Toshiba Machine Co., Ltd. cylinder temperature: 220 ° C
Mold temperature: 40 ℃
Injection time (primary filling time): 4 seconds Holding pressure time: 10 seconds Shape of molded product and flow mark evaluation method: as shown in FIG.

[Example 1]
(1) Preparation of solid titanium catalyst component (1) A high-speed stirring device (made by Tokushu Kika Kogyo Co., Ltd. (TK homomixer type M)) with an internal volume of 2 liters was sufficiently purged with nitrogen. 10 g of magnesium, 24.2 g of ethanol, and 3 g of trade name Leodol SP-S20 (sorbite distearate manufactured by Kao Corporation) were added, and the temperature of the system was increased while stirring the suspension. And stirred at 800 rpm for 30 minutes. Next, 1 liter of purified decane that had been cooled to −10 ° C. in advance was put into this suspension using a Teflon (registered trademark) tube having an inner diameter of 5 mm while stirring at a high speed so as not to cause precipitation. Transferred to a 2 liter glass flask (with a stirrer). The solid produced by the transfer was filtered and washed thoroughly with purified n-heptane to obtain a solid adduct in which 2.8 mol of ethanol was coordinated with respect to 1 mol of magnesium chloride.

  This solid adduct was suspended in decane, and 23 mmol of the above solid adduct in terms of magnesium atom was introduced into 100 ml of titanium tetrachloride maintained at −20 ° C. with stirring and mixed. A liquid was obtained. The mixture was heated to 80 ° C. over 5 hours, and when it reached 80 ° C., diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate (cis isomer, trans isomer mixture) was converted into a solid adduct. Was added in an amount of 0.085 mol per 1 mol of magnesium atom, and the temperature was raised to 110 ° C. in 40 minutes. When the temperature reached 110 ° C., cyclohexane 1,2-dicarboxylate diisobutyl (cis isomer, trans isomer mixture) was further added in an amount of 0.0625 mol with respect to 1 mol of magnesium atom in the solid adduct, and the temperature was adjusted. These were reacted by holding at 110 ° C. with stirring for 90 minutes.

  After completion of the reaction for 90 minutes, the solid part was collected by hot filtration, and the solid part was resuspended in 100 ml of titanium tetrachloride, and then heated to 110 ° C. and stirred for 45 minutes. These were allowed to react by holding. After completion of the reaction for 45 minutes, the solid part was again collected by hot filtration, and washed sufficiently with decane and heptane at 100 ° C. until no free titanium compound was detected in the washing solution.

  The solid titanium catalyst component (1) prepared by the above operation was stored as a decane suspension, and a part of this was dried for the purpose of examining the catalyst composition.

  The composition of the solid titanium catalyst component (α-1) thus obtained was 3.2 mass% titanium, 17 mass% magnesium, 57 mass% chlorine, diisobutyl 3,6-dimethylcyclohexane 1,2-dicarboxylate. They were 10.6% by mass, 8.9% by mass of diisobutyl cyclohexane 1,2-dicarboxylate, and 0.6% by mass of an ethyl alcohol residue.

(2) Preparation of prepolymerization catalyst (1) 70 g of solid titanium catalyst component (1), 128 mL of triethylaluminum, 36.3 ml of diethylaminotriethoxysilane, 10.0 L of heptane were inserted into an autoclave with a stirrer having an internal volume of 20 L, While maintaining the temperature at 15 to 20 ° C., 700 g of propylene was inserted, and the reaction was carried out with stirring for 60 minutes. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst (1) was resuspended in purified heptane and adjusted with heptane to a concentration of 1.0 g / L.

(3) Main polymerization An internal volume 58 L jacketed circulation type tubular polymerizer was charged with propylene at 40 kg / hour, hydrogen at 188 NL / hour, and a heptane slurry of the prepolymerized catalyst (1) as a prepolymerized catalyst (1) at 0.55 g / Polymerization was carried out continuously in a state where 4.0 ml / hour of triethylaluminum and 2.9 ml / hour of diethylaminotriethoxysilane were continuously fed, and no gas phase was present. The temperature of the tubular polymerizer was 70 ° C., and the pressure was 3.5 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. To the polymerization reactor, propylene was supplied at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 8.9 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 3.4 MPa / G.

  The obtained slurry was transferred to a transfer pipe having an internal volume of 2.4 L, gasified and gas-solid separated, and then the polypropylene homopolymer powder was sent to a gas phase polymerizer having an internal volume of 480 L. / Propylene block copolymerization was performed. Propylene, ethylene, and hydrogen are continuously added so that the gas composition in the gas phase polymerization vessel is ethylene / (ethylene + propylene) = 0.18 (molar ratio) and hydrogen / ethylene = 0.13 (molar ratio). Supplied. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 1.90 MPa / G.

  The resulting propylene block copolymer was vacuum dried at 80 ° C.

  With respect to 100 parts by weight of the obtained propylene-based block copolymer, 0.1 parts by weight of heat stabilizer IRGANOX 1010 (Ciba Geigy Co., Ltd.), 0.1 parts by weight of heat stabilizer IRGAFOS168 (Ciba Geigy Co., Ltd.), A heat-resistant stabilizer IRGANOX 1076 (trade name of Ciba Geigy Co., Ltd.) 0.1 parts by weight and calcium stearate 0.1 parts by weight are mixed with a tumbler, and then melt-kneaded in a twin screw extruder under the following conditions to form a pellet-shaped polypropylene resin. A composition was prepared, and a molded product was further produced with an injection molding machine.

<Melting and kneading conditions>
Same-direction biaxial kneader: Product number NR2-36, manufactured by Nakatani Machinery Co., Ltd. Kneading temperature: 190 ° C
Screw rotation speed: 200rpm
Feeder rotation speed: 400rpm
Nitrogen flow in hopper <Molded product for measuring mechanical properties / Injection molding conditions>
Injection molding machine: Part number NEX110-12E, manufactured by Nissei Plastic Injection Molding Machine Co., Ltd. Cylinder temperature: 195 ° C
Mold temperature: 40 ℃
Injection time-pressure holding time: 42 seconds (primary filling time: 2 seconds)
Cooling time: 10 seconds.

[Comparative Example 1]
(1) Preparation of solid titanium catalyst component (2) An anhydrous magnesium chloride 95.2 g, decane 442 ml and 2-ethylhexyl alcohol 390.6 g were heated at 130 ° C. for 2 hours to obtain a homogeneous solution, 21.3 g of phthalic anhydride was added thereto, and further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.

  After cooling the homogeneous solution thus obtained to 23 ° C., 75 ml of this homogeneous solution was dropped into 200 ml of titanium tetrachloride maintained at −20 ° C. over 1 hour. After charging, the temperature of the mixture was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.22 g of diisobutyl phthalate (DIBP) was added and stirred at the same temperature for 2 hours. Retained.

  After completion of the reaction for 2 hours, the solid part was collected by hot filtration, and the solid part was resuspended in 275 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours. After completion of the reaction, the solid part was again collected by hot filtration, and washed thoroughly with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution.

Here, the detection of this free titanium compound was confirmed by the following method. 10 ml of the supernatant of the above solid catalyst component was collected with a syringe into a 100 ml branched Schlenk previously purged with nitrogen and charged. Next, the solvent hexane was dried in a nitrogen stream, and further vacuum-dried for 30 minutes. To this, 40 ml of ion-exchanged water and 10 ml of (1 + 1) sulfuric acid were charged and stirred for 30 minutes. This aqueous solution was transferred to a 100 ml volumetric flask through a filter paper, followed by conc. As a masking agent for iron (II) ions. Add 1 ml of H ₃ PO ₄ and 5 ml of 3% H ₂ O ₂ as a coloring reagent for titanium, shake the volume up to 100 ml with ion-exchanged water, and after 20 minutes, observe the absorbance at 420 nm using UV. Free titanium was washed away until this absorption was not observed.

  The solid titanium catalyst component (2) prepared as described above was stored as a decane slurry, and a part thereof was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component (2) thus obtained was 2.3% by weight of titanium, 61% by weight of chlorine, 19% by weight of magnesium and 12.5% by weight of DIBP.

(2) Preparation of prepolymerized catalyst (2) 70 g of solid titanium catalyst component (2), 91.8 mL of triethylaluminum, 26.1 mL of diethylaminotriethoxysilane, and 10.0 L of heptane were inserted into an autoclave equipped with a stirrer with an internal volume of 20 L. The inner temperature was kept at 15 to 20 ° C., 700 g of propylene was inserted, and the reaction was allowed to proceed with stirring for 60 minutes. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst (2) was resuspended in purified heptane and adjusted with heptane to a concentration of 1.0 g / L.

(3) Main polymerization A circulating tubular polymerizer with a capacity of 58 L in a jacketed circulation type tubular polymerizer is 40 kg / hour of propylene, 188 NL / hour of hydrogen, and 0.32 g / h as a prepolymerization catalyst (2) of heptane slurry of the prepolymerization catalyst (2). Polymerization was carried out in the state of full liquid in the absence of a gas phase by continuously supplying triethylaluminum 2.9 ml / hour and diethylaminotriethoxysilane 1.2 ml / hour. The temperature of the tubular polymerizer was 70 ° C., and the pressure was 3.5 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. To the polymerization reactor, propylene was supplied at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 9.0 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 3.4 MPa / G.

  The obtained slurry was transferred to a transfer pipe having an internal volume of 2.4 L, gasified and gas-solid separated, and then the polypropylene homopolymer powder was sent to a gas phase polymerizer having an internal volume of 480 L. / Propylene block copolymerization was performed. Propylene, ethylene, and hydrogen are continuously added so that the gas composition in the gas phase polymerization reactor is ethylene / (ethylene + propylene) = 0.20 (molar ratio) and hydrogen / ethylene = 0.13 (molar ratio). Supplied. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 1.4 MPa / G.

  The resulting propylene block copolymer was vacuum dried at 80 ° C.

  In the same manner as in Example 1, it was melt-kneaded with a twin screw extruder to prepare a pellet-shaped polypropylene resin composition, and a molded product was prepared with an injection molding machine.

[Comparative Example 2]
(2) Production of prepolymerized catalyst (3) 70 g of solid titanium catalyst component (1), 38.3 mL of triethylaluminum, and 10.0 L of heptane were inserted into an autoclave equipped with a stirrer with an internal volume of 20 L, and the internal temperature was adjusted to 15 to 20 ° C. While maintaining, 700 g of propylene was inserted and reacted while stirring for 60 minutes. The resulting prepolymerized catalyst (3) was resuspended in purified heptane and adjusted with heptane to a concentration of 1.0 g / L.

(3) Main polymerization A circulating tubular polymerizer with a capacity of 58 L in a jacket is 0.34 g / 40 with 40 kg / hour of propylene, 175 NL / hour of hydrogen, and a heptane slurry of prepolymerized catalyst (3) as prepolymerized catalyst (3). Time, 2.5 ml / hour of triethylaluminum, and 1.8 ml / hour of diethylaminotriethoxysilane were continuously fed, and polymerization was carried out in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70 ° C., and the pressure was 3.5 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied to the polymerization vessel at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 7.7 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 3.4 MPa / G.

  The obtained slurry was transferred to a transfer pipe having an internal volume of 2.4 L, gasified and gas-solid separated, and then the polypropylene homopolymer powder was sent to a gas phase polymerizer having an internal volume of 480 L. / Propylene block copolymerization was performed. Propylene, ethylene, and hydrogen are continuously added so that the gas composition in the gas phase polymerization reactor is ethylene / (ethylene + propylene) = 0.20 (molar ratio) and hydrogen / ethylene = 0.076 (molar ratio). Supplied. Polymerization was carried out at a polymerization temperature of 70 ° C. and a pressure of 1.6 MPa / G.

  The resulting propylene block copolymer was vacuum dried at 80 ° C.

  In the same manner as in Example 1, it was melt-kneaded with a twin screw extruder to prepare a pellet-shaped polypropylene resin composition, and a molded product was prepared with an injection molding machine.

  The propylene-based block copolymer according to the present invention is less likely to generate a flow mark and has a good impact strength, and thus can be suitably used for various injection molded articles such as automobile parts.

Claims (9)

It is composed of 5 to 80% by weight of a portion soluble in 23 ° C. n-decane (Dsol) and 20 to 95% by weight of a portion insoluble in 23 ° C. n-decane (Dinsol) (however, the total amount of Dsol and Dinsol is 100% by weight)
Following requirements [1] to [6] A simultaneously satisfied to flop propylene-based process for producing the block copolymer,
A solid titanium catalyst component (I) containing titanium, magnesium, halogen, a cyclic ester compound (a) specified by the following formula (1) and a cyclic ester compound (b) specified by the following formula (2);
An organometallic compound (II) containing a metal atom selected from Group 1, Group 2 and Group 13 of the Periodic Table;
Organosilicon compound (III) represented by the following formula (3)
After adjusting the prepolymerization catalyst [A] in the presence of
A process for producing a propylene-based block copolymer, wherein an olefin containing propylene is polymerized in the presence of the prepolymerization catalyst [A], the organometallic compound (II) and the organosilicon compound (III) .
[1] Propylene content of Dsol is 30 to 80 mol%
[2] The intrinsic viscosity [η] (dl / g) of Dsol is 1.5 or more and 10.0 or less. [3] Mw / Mn, which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of Dinsol, 7 to 15, Mz / Mw which is a ratio of z average molecular weight (Mz) to weight average molecular weight (Mw) is 4 to 10
[4] LogM in the differential molecular weight distribution curve obtained by GPC measurement of Dinsol has a peak in the range of 2 to 4. [5] The pentad fraction (mmmm) of Dinsol is 93% or more. [6] Propylene-based block copolymer The melt flow rate (MFR) measured at a load of 2.16 kg and a temperature of 230 ° C. in accordance with ASTM D1238E of 25 to 350 g / 10 min

(In Formula (1), n is an integer of 5-10.
R ² and R ³ are each independently COOR ¹ or R, and at least one of R ² and R ³ is COOR ¹ .
A single bond in the cyclic skeleton (C—C ^b bond, C ^a —C ^b bond when R ³ is COOR ¹ , and C—C bond (when n is 6 to 10)) is a double bond. It may be replaced.
R ¹ is each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.
A plurality of Rs are each independently an atom selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, a halogen-containing group and a silicon-containing group. A group which may be bonded to each other to form a ring, but at least one R is not a hydrogen atom.
A double bond may be included in the ring skeleton formed by bonding R to each other, and when the ring skeleton includes two or more C ^a to which COOR ¹ is bonded , The number of carbon atoms constituting the skeleton is 5-10. )

(In Formula (2), n is an integer of 5-10.
R ⁴ and R ⁵ are each independently COOR ¹ or a hydrogen atom, and at least one of R ⁴ and R ⁵ is COOR ¹ .
R ¹ is each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.
A single bond in the cyclic skeleton (C—C ^b bond, C ^a —C ^b bond when R ⁵ is COOR ¹ , and C—C bond (when n is 6 to 10)) is a double bond. It may be replaced. )
Si (OR ¹ ) ₃ (NR ² R ³ ) (3)
(In the formula (3), R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, R ² is a hydrocarbon group or hydrogen having 1 to 12 carbon atoms , and R ³ is a hydrocarbon having 1 to 12 carbon atoms. Group.) In the propylene-based block copolymer,
The part (Dsol) soluble in n-decane at 23 ° C. is more than 50% by weight of a copolymer rubber composed of propylene and one or more olefins selected from ethylene and α-olefins having 4 to 20 carbon atoms. Up to 100% by weight,
The portion insoluble in 23 ° C. n-decane (Dinsol) is composed of 98.5 to 100 mol% of propylene and 0 to 1.5 mol% of one or more olefins selected from ethylene and an α-olefin having 4 to 20 carbon atoms. The method for producing a propylene-based block copolymer according to claim 1, wherein the crystalline propylene-based (co) polymer is contained in an amount of more than 50% by weight and 100% by weight or less. 3. The production of a propylene-based block copolymer according to claim 1, wherein in the formula (1) and / or (2), all of the bonds between carbon atoms in the cyclic skeleton are single bonds. Method. In the said Formula (1) and / or (2), it is n = 6, The manufacturing method of the propylene-type block copolymer of any one of Claims 1-3 characterized by the above-mentioned. The said cyclic ester compound (a) is following formula (1a), and the said cyclic ester compound (b) is following formula (2a), The propylene of any one of Claims 1-4 characterized by the above-mentioned. A method for producing a block copolymer.

(In Formula (1a), n is an integer of 5-10.
Single bonds (C—C bonds (when n is 6 to 10), C ^a —C bonds and C ^b —C bonds) in the cyclic skeleton may be replaced with double bonds.
R ¹ is each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.
A plurality of Rs are each independently an atom selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, a halogen-containing group and a silicon-containing group. A group which may be bonded to each other to form a ring, but at least one R is not a hydrogen atom.
A double bond may be contained in the ring skeleton formed by bonding R to each other, and when the ring skeleton contains two or more C ^a bonded with COOR ¹ , The number of carbon atoms constituting the skeleton is 5 to 10. )

(In Formula (2a), n is an integer of 5-10.
R ¹ is each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.
Single bonds (C—C bonds (when n is 6 to 10), C ^a —C bonds and C ^b —C bonds) in the cyclic skeleton may be replaced with double bonds. ) 6. The method for producing a propylene-based block copolymer according to claim 5 , wherein in the formulas (1a) and (2a), all the bonds between carbon atoms in the cyclic skeleton are single bonds. In the said Formula (1a) and (2a), it is n = 6, The manufacturing method of the propylene-type block copolymer of Claim 5 or 6 characterized by the above-mentioned. A polymerization step 1 in which the polymerization (co) polymerizes propylene and, if necessary, one or more olefins selected from ethylene and an α-olefin having 4 to 20 carbon atoms;
Propylene and, claim characterized in that it is performed by continuously carrying out the polymerization step 2 of copolymerizing one or more olefins selected from ethylene and having 4 to 20 carbon atoms α- olefin 1-7 The manufacturing method of the propylene-type block copolymer of any one of these. The propylene according to claim 8 , wherein the polymerization step 2 is a step of polymerizing propylene and one or more olefins selected from ethylene and an α-olefin having 4 to 20 carbon atoms in one step. A method for producing a block copolymer.

Images