阅读说明：本技术 丙烯系嵌段共聚物及其制造方法以及烯烃聚合用固体状钛催化剂成分 (Propylene block copolymer, process for producing the same, and solid titanium catalyst component for olefin polymerization ) 是由 佐久间笃 津留和孝 冈村健一郎 于 2019-03-07 设计创作，主要内容包括：本发明的目的在于提供能充分抑制向聚合器内壁附着的丙烯系嵌段共聚物。为达到上述目的的本发明的丙烯系嵌段共聚物,其根据下式由掉落秒数X(秒)和掉落秒数Y(秒)计算出的流动性评价值为40％以下,所述掉落秒数X(秒)是使用内径11.9mm的不锈钢制漏斗,使常温的100g共聚物掉落时的掉落秒数,所述掉落秒数Y(秒)是使用内径11.9mm的漏斗,使在10kg载荷下、于80℃保持24小时后的100g共聚物掉落时的掉落秒数。流动性评价值(％)＝{(Y/X)-1}×100。(The purpose of the present invention is to provide a propylene block copolymer which can sufficiently suppress adhesion to the inner wall of a polymerization vessel. The propylene-based block copolymer of the present invention for achieving the above object has a flowability evaluation value of 40% or less calculated from the number of seconds X (seconds) of falling when 100g of the copolymer at room temperature is dropped using a stainless steel funnel having an inner diameter of 11.9mm and the number of seconds Y (seconds) of falling when 100g of the copolymer is dropped using a funnel having an inner diameter of 11.9mm under a load of 10kg and held at 80 ℃ for 24 hours, according to the following formula. The flowability evaluation value (%) { (Y/X) -1} × 100.)

1. A propylene block copolymer having a flowability evaluation value of 40% or less as calculated from the number of seconds of falling X (seconds) and the number of seconds of falling Y (seconds) according to the following formula,

x (second) is the number of seconds of dropping 100g of the copolymer at room temperature using a funnel made of stainless steel having an inner diameter of 11.9mm, Y (second) is the number of seconds of dropping 100g of the copolymer after holding the copolymer at 80 ℃ for 24 hours under a load of 10kg using a funnel having an inner diameter of 11.9mm,

the flowability evaluation value (%) { (Y/X) -1} × 100.

2. The propylene-based block copolymer according to claim 1, wherein the Dsol content is 30 to 40% by mass based on 100% by mass of the total of Dsol, which is a component soluble in n-decane at 23 ℃ and Dinsol, which is a component hardly soluble in n-decane at 23 ℃.

3. The propylene-based block copolymer according to claim 2, wherein the content of ethylene units in the Dsol is 36.0 mol% or more.

4. A method for producing a propylene-based block copolymer, comprising:

in the presence of the solid titanium catalyst component (i),

a 1 st polymerization step of polymerizing propylene and optionally another alpha-olefin to produce a crystalline propylene-based (co) polymer, and

a 2 nd polymerization step of polymerizing the crystalline propylene-based (co) polymer produced in the 1 st polymerization step with 1 polymer material selected from the group consisting of a rubber component, an amorphous or low-crystalline ethylene-propylene copolymer (EPR) and an amorphous ethylene- α -olefin copolymer,

the solid titanium catalyst component (i) is produced by contacting a solid compound (S), a titanium compound represented by the formula (IV) and an electron donor,

the solid compound (S) has a 1 st pore distribution index represented by the formula (I) of 2 or more and contains a magnesium compound (II-0),

pore distribution index No. 1 x/y … (I)

In the formula (I), x is the cumulative pore volume of pore diameter 0.001-0.1 μm measured by mercury porosimeter; y is the cumulative pore volume of 0.1 to 1.0 μm measured by a mercury porosimeter;

Ti(OR)_gX_4-g…(IV)

in the formula (IV), R is a hydrocarbon group; x is a halogen atom; g is an integer satisfying 0 ≦ g ≦ 4.

5. The method for producing a propylene-based block copolymer according to claim 4, wherein the 1 st polymerization step and the 2 nd polymerization step are both polymerization steps performed in the presence of hydrogen.

6. The method for producing a propylene-based block copolymer according to claim 4 or 5, wherein the magnesium compound (II-0) is a solid complex compound defined by the following formula (II), wherein when a in formula (II) is 0, g in formula (IV) is not 4;

MgX_aRs_b·(RtOH)_m…(II)

in the formula (II), X is a halogen atom, Rs is a hydrocarbon group containing a heteroatom, Rt is a hydrocarbon group which may contain a heteroatom, m is a real number satisfying 2.0. ltoreq. m.ltoreq.3.3, a is an integer satisfying 0. ltoreq. a.ltoreq.2, b is an integer satisfying 0. ltoreq. b.ltoreq.2, and the sum of a and b is 2.

7. A solid titanium catalyst component produced by contacting a solid compound (S), a titanium compound represented by the formula (IV) and an electron donor,

the solid compound (S) has a 1 st pore distribution index represented by the formula (I) of 2 or more and contains a magnesium compound (II-0),

pore distribution index No. 1 x/y … (I)

In the formula (I), x is the cumulative pore volume of pore diameter 0.001-0.1 μm measured by mercury porosimeter, y is the cumulative pore volume of pore diameter 0.1-1.0 μm measured by mercury porosimeter;

Ti(OR)_gX_4-g…(IV)

in the formula (IV), R is a hydrocarbon group, X is a halogen atom, and g is an integer satisfying 0g 4.

Technical Field

The present invention relates to a propylene block copolymer, a method for producing the same, and a solid titanium catalyst component for olefin polymerization.

Background

Propylene-based resins are used in various fields such as daily sundries, kitchen supplies, packaging films, household electric appliances, machine parts, electric parts, and automobile parts.

In addition, depending on the application, a propylene block copolymer having improved impact resistance and the like by directly polymerizing a propylene polymer with a rubber component, an amorphous or low crystalline ethylene-propylene copolymer (EPR), an amorphous ethylene- α -olefin copolymer and the like may be used. However, it is known that the propylene-based block copolymer is liable to adhere to the inner wall of the polymerization vessel or to adhere to each other during storage.

Therefore, for example, patent document 1 and the like report a method of improving the flowability of a propylene block copolymer by supplying a flow modifier and the like when polymerizing a propylene polymer with the rubber component.

Patent document 2 suggests a method of introducing a large amount of a rubber component by controlling the shape of a solid titanium catalyst component for producing a propylene block polymer.

Disclosure of Invention

Technical problem to be solved by the invention

However, even when a propylene-based block copolymer is produced by the method described in patent document 1, adhesion to the inner wall of a polymerization vessel cannot be sufficiently suppressed.

Further, patent document 2 discloses that a propylene block copolymer having a high rubber content and excellent flowability can be obtained, but the results of experimental data calculation suggest that the rubber component of the propylene block copolymer having a high rubber content disclosed in the examples is a rubber component having a low ethylene unit content (relatively hard and hardly flowable).

The present invention has been made in view of the above-described problems of the conventional art, and an object of the present invention is to provide: a propylene block copolymer which can sufficiently suppress adhesion to the inner wall of a polymerization vessel, a method for producing the propylene block copolymer, and a solid titanium catalyst component for producing the propylene block copolymer. The propylene block copolymer is preferably: even if the rubber component has a high ethylene unit content and is easy to flow, the adhesion of the propylene block copolymer to the inner wall of the polymerization vessel can be sufficiently suppressed.

Means for solving the problems

[1] A propylene block copolymer having a flowability evaluation value of 40% or less as calculated from the number of seconds of falling X (seconds) and the number of seconds of falling Y (seconds) according to the following formula,

x (second) is the number of seconds of dropping 100g of the copolymer at room temperature using a funnel made of stainless steel having an inner diameter of 11.9mm, Y (second) is the number of seconds of dropping 100g of the copolymer after holding the copolymer at 80 ℃ for 24 hours under a load of 10kg using a funnel having an inner diameter of 11.9mm,

the flowability evaluation value (%) { (Y/X) -1} × 100.

[2] The propylene block copolymer according to [1], wherein the content of Dsol is 30 to 40 mass% based on 100 mass% of the total of the component soluble in n-decane at 23 ℃ (Dsol) and the component hardly soluble in n-decane at 23 ℃ (Dinsol).

[3] The propylene-based block copolymer according to [2], wherein the content of the ethylene unit in the Dsol is 36.0 mol% or more.

[4] A method for producing a propylene-based block copolymer, comprising:

in the presence of the solid titanium catalyst component (i),

a 1 st polymerization step of polymerizing propylene and optionally another alpha-olefin to produce a crystalline propylene-based (co) polymer, and

a 2 nd polymerization step of polymerizing the crystalline propylene-based (co) polymer produced in the 1 st polymerization step with 1 polymer material selected from the group consisting of a rubber component, an amorphous or low-crystalline ethylene-propylene copolymer (EPR) and an amorphous ethylene- α -olefin copolymer,

the solid titanium catalyst component (i) is produced by contacting a solid compound (S), a titanium compound represented by the formula (IV) and an electron donor,

the solid compound (S) has a 1 st pore distribution index represented by the formula (I) of 2 or more and contains a magnesium compound (II-0),

pore distribution index No. 1 x/y … (I)

(in the formula (I), x is the cumulative pore volume of pore diameter 0.001-0.1 μm measured by mercury porosimeter, y is the cumulative pore volume of pore diameter 0.1-1.0 μm measured by mercury porosimeter),

Ti(OR)_gX_4-g…(IV)

(in the formula (IV), R is a hydrocarbon group; X is a halogen atom; g is an integer satisfying 0. ltoreq. g.ltoreq.4).

[5] The method for producing a propylene-based block copolymer according to [4], wherein the 1 st polymerization step and the 2 nd polymerization step are both polymerization steps carried out in the presence of hydrogen.

[6] The method for producing a propylene-based block copolymer according to [4] or [5], wherein the magnesium compound (II-0) is a solid complex compound defined by the following formula (II), and when a in the formula (II) is 0, g in the formula (IV) is not 4.

MgX_aRs_b·(RtOH)_m…(II)

(in the formula (II), X is a halogen atom, Rs is a heteroatom-containing hydrocarbon group, Rt is a heteroatom-optionally containing hydrocarbon group, m is a real number satisfying 2.0. ltoreq. m.ltoreq.3.3, a is an integer satisfying 0. ltoreq. a.ltoreq.2, b is an integer satisfying 0. ltoreq. b.ltoreq.2, and the sum of a and b is 2).

[7] A solid titanium catalyst component produced by contacting a solid compound (S), a titanium compound represented by the formula (IV) and an electron donor,

the solid compound (S) has a 1 st pore distribution index represented by the formula (I) of 2 or more and contains a magnesium compound (II-0),

pore distribution index No. 1 x/y … (I)

(in the formula (I), x is the cumulative pore volume of pore diameter 0.001-0.1 μm measured by mercury porosimeter, y is the cumulative pore volume of pore diameter 0.1-1.0 μm measured by mercury porosimeter);

Ti(OR)_gX_4-g…(IV)

(in the formula (IV), R is a hydrocarbon group, X is a halogen atom, and g is an integer satisfying 0. ltoreq. g.ltoreq.4).

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a propylene block copolymer which can sufficiently suppress adhesion to the inner wall of a polymerization vessel and a method for producing the propylene block copolymer can be provided.

Drawings

FIG. 1 is a schematic view of a funnel used for obtaining a flowability evaluation value for the propylene block copolymer of the present invention.

Detailed Description

The propylene block copolymer of the present invention has a flowability evaluation value of 40% or less, which is calculated from the number of seconds of dropping X (seconds) when 100g of the copolymer at room temperature is dropped using a stainless steel funnel having an inner diameter of 11.9mm and the number of seconds of dropping Y (seconds) when 100g of the copolymer is dropped using a stainless steel funnel having an inner diameter of 11.9mm after being held at 80 ℃ for 24 hours under a load of 10kg, according to the following formula.

Fluidity evaluation value (%) { (Y/X) -1} × 100

Specifically, the funnel has a shape shown in fig. 1. This funnel has the same shape as the "volumetric specific gravity measuring apparatus" described in FIG. 2 in the appendix of JIS K6720 (1998), and is a truncated cone-shaped funnel in which the uppermost diameter (the length of a shown in FIG. 1) is 94.9mm, the height of the truncated cone (the length of b shown in FIG. 1) is 114mm, and the inner diameter of the particle falling portion (the length of c shown in FIG. 1) is 11.9 mm. The inclination of the truncated cone-shaped slope (the angle d shown in fig. 1) is 20 °.

The propylene block copolymer has a characteristic that it is less likely to adhere to the inner wall of a polymerization vessel, a flow path wall, or the like when it flows through a polymerization vessel, a flow path, or the like made of metal, particularly stainless steel.

1. Propylene block copolymer

The propylene block copolymer is a copolymer obtained by directly polymerizing a propylene polymer with a rubber component, an amorphous or low-crystalline ethylene-propylene copolymer (EPR), an amorphous ethylene- α -olefin copolymer, or the like. The propylene block copolymer of the present invention is preferably in the form of particles, and more preferably propylene block copolymer particles formed in the polymerization described later.

The propylene-based block copolymer is not particularly limited as long as it contains a propylene-derived structural unit, and is preferably a copolymer containing a rubber component, more preferably a copolymer having a component soluble in n-decane at 23 ℃ (hereinafter also referred to as "Dsol component") and a component poorly soluble in n-decane at 23 ℃ (hereinafter also referred to as "Dinsol"), from the viewpoints of excellent balance among rigidity, impact resistance and molding processability, and the ease with which a molded article having a good appearance can be obtained.

The Dsol component is a component obtained by dissolving a propylene block copolymer in n-decane at 150 ℃ for 2 hours under heating, and then cooling to 23 ℃ to dissolve the propylene block copolymer in the n-decane solution, and the other components of the propylene block copolymer are Dinsol components.

The Dsol component may be a component mainly composed of the rubber component, and is preferably a component mainly composed of a copolymer rubber component of propylene and 1 or more α -olefins selected from ethylene and α -olefins having 4 to 20 carbon atoms. More specifically, the amount of the rubber component in the Dsol component is more than 50% by mass, preferably 80% by mass or more and 100% by mass or less, and more preferably 90% by mass or more and 100% by mass or less.

Examples of the above 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, 1-hexadecene, 1-octadecene, 1-eicosene and the like. The α -olefin to be copolymerized is preferably ethylene or an α -olefin selected from α -olefins having 4 to 10 carbon atoms, and more preferably an α -olefin selected from ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene.

The amount of the structural unit derived from ethylene and 1 or more α -olefins selected from α -olefins having 4 to 20 carbon atoms contained in the Dsol component is usually 25 mol% or more of the copolymer rubber, more than the amount of the structural unit derived from ethylene or α -olefins having 4 to 20 carbon atoms contained in the crystalline propylene-based (co) polymer component and the decane-insoluble component (Dinsol component) described later.

In particular, the Dsol component containing ethylene units tends to have a low glass transition temperature, and therefore, the Dsol component preferably contains a large amount of ethylene units. The lower limit of the ethylene unit content in the Dsol component is preferably 30 mol%, more preferably 36.0 mol%, and still more preferably 40 mol%. On the other hand, the upper limit is preferably 70 mol%, more preferably 65 mol%, and still more preferably 60 mol%.

When the content of the ethylene unit is high, the glass transition temperature of the rubber component is lowered and the crystallinity is also lowered, so that the rubber component becomes soft and tends to flow easily particularly at high temperatures. In the present invention, it can be considered that: even a propylene block copolymer containing a large amount of such a rubber component that flows easily is excellent in productivity because adhesion of the polymer is not likely to occur in a polymerization vessel or a storage chamber described later.

From the viewpoint of easily obtaining a molded article excellent in balance between rigidity and impact resistance, the content of the Dsol component in the propylene-based block copolymer is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 50% by mass or less, further preferably 25% by mass or more and 50% by mass or less, and particularly preferably 30% by mass or more and 40% by mass or less, with respect to 100% by mass of the total of the Dsol component and the Dinsol component.

The intrinsic viscosity [ η ] of the Dsol component is preferably 1.5dl/g to 10.0dl/g, more preferably 2.0dl/g to 7.0dl/g, from the viewpoint that a composition excellent in balance among impact resistance, high fluidity, and high melt elasticity can be easily obtained, and a molded article having good appearance can be easily obtained.

The above [. eta. ] is a value of [. eta.sp/C obtained by dissolving 20mg of a propylene-based block copolymer in 15ml of decalin, measuring the specific viscosity [. eta.sp ] in an oil bath at 135 ℃, adding 5ml of a decalin solvent to the decalin solution, diluting the solution, measuring the specific viscosity [. eta.sp ] in the same manner, and repeating the operation 3 times, wherein the concentration (C) is extrapolated to 0 in the relational expression showing the relationship between the concentration and the specific viscosity.

The Dinsol component is a component mainly composed of a crystalline propylene-based (co) polymer component. More specifically, the amount of the crystalline propylene-based (co) polymer component in the Dinsol component is more than 50% by mass, preferably 80% by mass or more and 100% by mass or less, and more preferably 90% by mass or more and 100% by mass or less.

The crystalline propylene-based (co) polymer component is a crystalline propylene homopolymer or a copolymer of propylene and 1 or more kinds of α -olefins, among α -olefins composed of ethylene and α -olefins having 4 to 20 carbon atoms. Wherein the amount of the structural unit derived from the α -olefin is 1.5 mol% or less of the crystalline propylene-based (co) polymer component.

From the viewpoint of easily obtaining a molded article excellent in balance between rigidity and impact resistance, the content of the Dinsol component in the propylene-based block copolymer is preferably 50% by mass or more and 95% by mass or less, more preferably 50% by mass or more and 90% by mass or less, further preferably 50% by mass or more and 75% by mass or less, and particularly preferably 60% by mass or more and 70% by mass or less, with respect to 100% by mass of the total of the Dsol component and the Dinsol component.

Examples of the above 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, 1-hexadecene, 1-octadecene, 1-eicosene and the like. The α -olefin to be copolymerized is preferably ethylene or an α -olefin selected from α -olefins having 4 to 10 carbon atoms, and more preferably an α -olefin selected from ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene.

The Melt Flow Rate (MFR) of the propylene-based block copolymer as measured at 230 ℃ under a load of 2.16kg may be 5g/10 min or more and 300g/10 min or less, and preferably 5g/10 min or more and 200g/10 min or less.

When the MFR is within the above range, the propylene block copolymer has excellent flowability, and therefore a composition which can be easily injection-molded can be obtained from the propylene block copolymer. Further, a molded article having more excellent impact resistance and suitable for use in automobile parts and the like can be easily obtained from the composition.

From the viewpoint of easily obtaining a molded article having a more excellent balance between rigidity and impact resistance, the content of the propylene-based block copolymer is preferably 58 mass% or more and 90 mass% or less, and more preferably 60 mass% or more and 90 mass% or less, based on the total mass of the composition.

The composition may contain other components such as a resin other than the propylene block copolymer, a light-resistant stabilizer, a heat-resistant stabilizer, a weather-resistant stabilizer, an anti-aging agent, an antioxidant, a fatty acid metal salt, a softening agent, a dispersing agent, a filler, a colorant, a pigment, an antistatic agent, a slip agent, an anti-blocking agent, an antifogging agent, a lubricant, a natural oil, a synthetic oil, and a wax.

2. Production of propylene-based Block copolymer

The above propylene block polymer was obtained as follows: first, the components constituting the Dinsol component, particularly the crystalline propylene-based (co) polymer, are synthesized, and then the components constituting the Dsol component, particularly the rubber component, are polymerized with the components constituting the Dinsol component. In this case, the fluidity evaluation value can be reduced to 40 or less by using a solid titanium catalyst component (i) produced using the following solid compound (S) as a starting material as a catalyst, and synthesizing the components constituting the Dinsol component and polymerizing the components constituting the Dsol component. The solid compound is preferably a solid compound as described later.

2-1 production of solid titanium catalyst component (i)

The solid titanium catalyst component (I) can be produced by contacting a titanium compound with a solid compound (S) having a 1 st pore distribution index of 2 or more, which is represented by the following formula (I). In this case, from the viewpoint of increasing the molecular weight of the obtained polymer or easily controlling the molecular weight distribution, the electron donor may be further contacted so that the electron donor is contained in the solid titanium catalyst component (i).

Pore distribution index No. 1 x/y … (I)

In the formula (I), x is the cumulative pore volume of pore diameter 0.001-0.1 μm measured by mercury porosimeter, and y is the cumulative pore volume of pore diameter 0.1-1.0 μm measured by mercury porosimeter.

The lower limit of the 1 st pore distribution index is preferably 2.0, more preferably 2.1, and still more preferably 2.2. On the other hand, the upper limit is not particularly limited, but is preferably 12, more preferably 10, still more preferably 8, and particularly preferably 7.

The above formula (I) suggests that the number of pores having a relatively small pore diameter of 0.001 to 0.1 μm is far larger than that of pores having a relatively large pore diameter of 0.1 to 1.0. mu.m. Alternatively, it is considered to be a parameter suggesting a tendency that relatively small and deep pores tend to be large.

In the solid compound (S), the 2 nd pore distribution index represented by the following formula (I') is preferably a value greater than 0.5. The 2 nd pore distribution index is more preferably 0.56 or more, still more preferably 0.58 or more, particularly preferably 0.60 or more, and particularly preferably 0.62 or more. The upper limit value is of course 1. More preferably 0.745.

Pore distribution index No. 2 x α/x β … (I')

In the formula (I'), x alpha is the cumulative pore volume of pore diameter 0.01-0.1 μm measured by mercury porosimeter, and x beta is the cumulative pore volume of 0.001-1.0 μm measured by mercury porosimeter.

The 2 nd pore distribution index indicates that the catalyst of the present invention mainly has 0.01 to 0.1 μm pores on a volume basis. It can be easily estimated that: the presence of such a pore diameter greatly affects the excellent particle flowability which is a feature of the present invention.

The pore volume of the solid compound of the present invention having a pore diameter of 0.001 to 1.0 μm is not particularly limited as long as it is within the range of the object of the present invention. Preferably 50mm³More than g and 1500mm³The ratio of the carbon atoms to the carbon atoms is less than g. A more preferred lower limit is 80mm³Per g, more preferably 100mm³Per g, particularly preferably 120mm³(ii) in terms of/g. On the other hand, the more preferable upper limit value is 1000mm³Per g, more preferably 800mm³Per g, particularly preferably 500mm³/g。

Within such a pore volume range, the preferable effects such as blocking resistance tend to be easily exhibited.

The propylene block copolymer of the present invention has a feature that it is not easily melt-adhered to, for example, the inner wall of a polymerizer or a storage chamber, and the present inventors consider that the above-mentioned definition of formula (I) is important in order to realize such a feature. Although the mechanism is not yet determined, it is presumed as follows.

The shape of the solid compound as the raw material is said to tend to be maintained in the solid titanium catalyst component (i). Therefore, the present inventors considered that the solid compound (S) satisfying such a predetermined shape has a relatively small specific pore diameter ratio and thus has a large surface friction resistance due to a large surface area, and thus the rubber component is less likely to bleed out on the surface.

On the other hand, it can be considered that: if the pore diameter is too small, the rubber component may be easily diffused on the surface, for example, by volcanic explosion. In addition, it is also conceivable that: if the pore diameter is too large, the pores may penetrate into the inside of the rubber composition and the rubber composition may be likely to be leaked out on the surface.

Therefore, the inventors considered that: the high proportion of pores in the range of the specific pore diameter is an important element for exhibiting the effect of the present invention.

2-1-1 solid Compound (S)

The solid compound (S) is characterized by containing a magnesium compound (II-0). The preferred magnesium compound is a magnesium compound used in the raw material complex described later.

The solid compound (S) preferably has a structure containing a solid compound having a composition represented by the formula (II).

MgX_aRs_b·(RtOH)_m…(II)

In the formula (II), X is a halogen atom, Rs is a hydrocarbon group containing a heteroatom, Rt is a hydrocarbon group which may contain a heteroatom, m is a real number satisfying 2.0. ltoreq. m.ltoreq.3.3, a is an integer satisfying 0. ltoreq. a.ltoreq.2, b is an integer satisfying 0. ltoreq. b.ltoreq.2, and the sum of a and b is 2.

In the formula (II), Rs may be an alkoxy group, an aryloxy group, a carboxylate group, or the like.

The structure represented by RtOH in formula (II) is derived from an alcohol represented by RtOH. Examples of the above alcohols include: aliphatic alcohols including methanol, ethanol, propanol, butanol, isobutanol, ethylene glycol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, decanol, dodecanol and the like; alicyclic alcohols including cyclohexanol, methylcyclohexanol, and the like; aromatic alcohols including benzyl alcohol and methylbenzyl alcohol; and alkoxy group-containing aliphatic alcohols including n-butyl cellosolve and the like.

The solid compound (S) represented by the formula (II) can be produced, for example, as follows: a slurry liquid containing a complex represented by the formula (III) (which may be referred to as a "raw material complex") and a hydrocarbon solvent is continuously brought into contact with an inert gas at a liquid temperature of 25 ℃ to 80 ℃.

MgX_aRs_b·(RtOH)_n…(III)

In the formula (III), X, Rs and Rt are the same as X, Rs and Rt in the formula (II), and n is a real number satisfying 0.45 m/n 0.99.

The above-mentioned raw material complex can be produced as follows: reacting a magnesium halide comprising magnesium chloride and magnesium bromide; alkoxy magnesium halides including methoxy magnesium chloride, ethoxy magnesium chloride, and phenoxy magnesium chloride; alkoxy magnesium including ethoxy magnesium, isopropoxy magnesium, butoxy magnesium and 2-ethylhexoxy magnesium; aryloxy magnesium including phenoxy magnesium and the like; and a magnesium compound such as a carboxylate of magnesium including magnesium stearate, and the alcohol represented by the above RtOH, particularly an alcohol capable of dissolving the above magnesium compound, are contacted in a known manner.

The solid compound (S) is produced by bringing a slurry liquid containing the raw material complex and a hydrocarbon solvent into contact with an inert gas continuously at a liquid temperature of 25 ℃ to 80 ℃ to smoothly remove the alcohol component (RtOH) from the raw material complex.

The inert gas may be: rare gases including helium, neon, argon, and the like; hydrocarbon gases including methane, ethane, propane, and the like; and nitrogen and the like which do not substantially react with the titanium compound and the organometallic compound.

The slurry concentration of the slurry liquid is not particularly limited, but is preferably 10g/L to 200g/L, more preferably 30g/L to 150g/L, in view of fluidity and the protective function of the solid compound (S).

The liquid temperature of the slurry liquid at the time of the contact is preferably 25 ℃ or higher from the viewpoint of improving the efficiency of removing the alcohol by the inert gas, and is preferably 80 ℃ from the viewpoint of suppressing the deterioration of the solid compound (S). From the above viewpoint, the liquid temperature at the time of the contact is preferably 25 ℃ or higher and 80 ℃ or lower, and more preferably 40 ℃ or higher and 70 ℃ or lower.

The supply rate of the inert gas is preferably 5NL/hr or more and 300NL/hr or less, more preferably 5NL/hr or more and 40NL/hr or less, still more preferably 5NL/hr or more and 30NL/hr or less, particularly preferably 5NL/hr or more and 25NL/hr or less, and particularly preferably 7NL/hr or more and 20NL/hr or less, per 1L of the slurry liquid. When the supply rate is 5NL/hr or more, the efficiency of alcohol removal by the inert gas can be sufficiently improved.

The supply time of the inert gas is preferably 1 hour or more and 60 hours or less, more preferably 3 hours or more and 40 hours or less, further preferably 3 hours or more and 36 hours or less, particularly preferably 3 hours or more and 20 hours or less, and particularly preferably 5 hours or more and 15 hours or less. If the supply rate is 1 hour or more, the efficiency of alcohol removal by the inert gas can be sufficiently improved.

When the inert gas is supplied, the inside of the system can be homogenized by a method such as stirring by a stirring blade or the like in the system. By planning the supply method and the supply position of the inert gas, a homogeneous state similar to stirring may be formed in the system by the inert gas. Examples thereof include: a method of providing an inert gas ejection port in the lower part of the system, and disposing a plurality of inert gas ejection ports in the system.

By appropriately adjusting the slurry concentration, the liquid temperature at the time of contact, the inert gas supply rate, and the inert gas supply time, the solid compound (S) having the 1 st pore distribution index of 2 or more represented by the formula (I) can be produced.

Since the above method is a reaction in a liquid phase environment using a hydrocarbon compound, the temperature, the amount of an inert gas which is considered to be responsible for removing an alcohol, and the like can be controlled relatively accurately, and therefore, the above method is effective in forming a solid compound (S) having a highly controlled structure such as that of the above formula (I).

In addition to the above-described methods, a method of removing an alcohol in a gas phase can also be employed. The above-mentioned production method in a liquid phase environment is preferable from the viewpoint of ease of shape control.

2-1-2. titanium compound

The titanium compound used for producing the solid titanium catalyst component (i) by contacting with the solid compound (S) has a composition represented by the formula (IV).

Ti(OR)_gX_4-g…(IV)

In the formula (IV), R is a hydrocarbon group, X is a halogen atom, and g is an integer satisfying 0 ≦ g ≦ 4 [ when a in the formula (II) is 0, g is not 4 ].

Examples of R in the formula (IV) include methyl, ethyl, propyl, butyl and the like.

Examples of the titanium compound represented by the formula (IV) include: comprising TiCl₄And TiBr₄And the like titanium tetrahalides; including Ti (OCH)₃)Cl₃、Ti(OC₂H₅)Cl₃、Ti(O-n-C₄H₉)Cl₃、Ti(OC₂H₅)Br₃And Ti (O-isoC)₄H₉)Br₃Etc. of titanium trihalide alkoxides; including Ti (OCH)₃)₂Cl₂And Ti (OC)₂H₅)₂Cl₂Titanium alkoxides dihalides, etc.; including Ti (OCH)₃)₃Cl、Ti(O-n-C₄H₉)₃Cl and Ti (OC)₂H₅)₃Alkoxy titanium monohalides such as Br; and comprises Ti (OCH)₃)₄、Ti(OC₂H₅)₄、Ti(OC₄H₉)₄And Ti (O-2-ethylhexyl)₄And the like titanium tetraalkoxide. Of these, preferred is a titanium tetrahalide, and more preferred is titanium tetrachloride (TiCl)₄)。

2-1-3. Electron donors

The electron donor may be an aromatic carboxylic acid ester, an alicyclic carboxylic acid ester, a polyether compound, or the like.

The electron donor is particularly preferably an alicyclic polycarboxylic acid ester represented by the formula (V) or (VI), a polyether compound, or the like.

R^d(COOR^e)_p…(V)

R^d(OCOR^e)_p…(VI)

In the formulae (V) and (VI), R^dIs an alicyclic hydrocarbon having 5 to 20 carbon atoms, R^eIs a hydrocarbon group having 6 to 15 carbon atoms, and p is an integer of 2 or 3.

Examples of the alicyclic polycarboxylic acid ester represented by the formula (V) include: cyclohexyl-1, 2-dihexanoate, cyclohexyl-1, 2-dioctanoate, cyclohexyl-1, 2-didecanoate, cyclohexyl-1, 2-di (dodecanoate), cyclohexyl-1, 2-diheptanoate, 3, 6-dimethylcyclohexyl-1, 2-dioctanoate, 3, 6-dimethylcyclohexyl-1, 2-decenoate, 3, 6-dimethylcyclohexyl-1, 2-dodecenoate, 3-methyl-6-propylcyclohexyl-1, 2-dioctanoate, 3-methyl-6-propylcyclohexyl-1, 2-didecanoate and 3-methyl-6-propylcyclohexyl-1, 2-di (dodecenoate), and the like.

Examples of the alicyclic polycarboxylic acid ester represented by the formula (VI) include: including dioctyl 3, 6-dimethylcyclohexane-1, 2-dicarboxylate, didecyl 3, 6-dimethylcyclohexane-1, 2-dicarboxylate, dioctyl 3-methyl-6-ethylcyclohexane-1, 2-dicarboxylate, didecyl 3-methyl-6-ethylcyclohexane-1, 2-dicarboxylate, alicyclic polycarboxylic acid esters in which the cyclic skeleton of 3-methyl-6-n-propylcyclohexane-1, 2-dicarboxylic acid dioctyl ester, 3-methyl-6-n-propylcyclohexane-1, 2-dicarboxylic acid didecyl ester, 3, 6-diethylcyclohexane-1, 2-dicarboxylic acid dioctyl ester, 3, 6-diethylcyclohexane-1, 2-dicarboxylic acid didodecyl ester, and the like is substituted with a hydrocarbon group or the like; and alicyclic polycarboxylic acid esters having no substituent other than a carboxylic acid ester in the cyclic skeleton, including cyclohexane-1, 2-dicarboxylic acid di-n-hexyl ester, cyclohexane-1, 2-dicarboxylic acid di-heptyl ester, cyclohexane-1, 2-dicarboxylic acid dioctyl ester, cyclohexane-1, 2-dicarboxylic acid didecyl ester, cyclohexane-1, 2-dicarboxylic acid didodecyl ester, and the like.

The polyether compound is a compound having 2 or more ether bonds disposed on both sides with an aromatic carboxylic acid ester or a plurality of carbon atoms interposed therebetween. Examples of the above polyether compounds include: and 1, 3-diethers such as 2-isopropyl-2-isobutyl-1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-dicyclohexyl-1, 3-dimethoxypropane, and 2, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane.

2-1-4. contact of solid Compound (S), titanium Compound and Electron Donor

The solid titanium catalyst component (i) can be produced by contacting the solid compound (S), the titanium compound represented by the formula (IV), and the optional electron donor.

When these components are brought into contact with each other, an aliphatic carboxylic acid ester, an aromatic carboxylic acid ester, an alcohol, an aldehyde, a ketone, an ether, an amine, a silane compound, a phosphate ester, or another electron donor is brought into contact with each other, whereby the stereoregularity of the obtained propylene-based block copolymer can be improved while maintaining the high catalytic activity of the solid titanium catalyst component (i).

The contact can be carried out by a known method such as the following (P-1) to (P-3).

(P-1) A slurry of the solid compound (S), the liquid titanium compound and preferably 1 or more electron donors are contacted in a suspended state in the presence of an inert hydrocarbon solvent.

(P-2) contacting a slurry of the solid compound (S), the liquid titanium compound, and preferably 1 or more electron donors, in a plurality of times.

(P-3) the slurry of the solid compound (S), the liquid titanium compound and preferably 1 or more electron donors are contacted in a suspension state in the presence of an inert hydrocarbon solvent in a plurality of times.

2-2. production of propylene-based Block copolymer

The propylene-based block copolymer can be produced by the following steps: a first polymerization step of polymerizing propylene and optionally another α -olefin in the presence of the solid titanium catalyst component (i), preferably the olefin polymerization catalyst, to produce a crystalline propylene-based (co) polymer; and a 2 nd polymerization step of polymerizing the crystalline propylene-based (co) polymer produced in the 1 st polymerization step, the rubber component, the amorphous or low-crystalline ethylene-propylene copolymer (EPR), and the amorphous ethylene- α -olefin copolymer raw material.

The 1 st polymerization step and the 2 nd polymerization step can be carried out by any of liquid phase polymerization methods such as bulk polymerization, solution polymerization and suspension polymerization, and gas phase polymerization.

In the 1 st polymerization step and the 2 nd polymerization step, the solid titanium catalyst component (i) may be further brought into contact with an organometallic compound (ii) containing at least one element selected from the group consisting of group 1 elements, group 2 elements and group 13 elements to prepare an olefin polymerization catalyst. At this time, the electron donor (iii) may be further contacted.

Examples of the above organometallic compound (ii) include: a group 13 element-containing compound such as an organoaluminum compound; a complex alkylate of a group 1 element with aluminum, a group 2 element-containing organometallic compound, and the like.

Examples of the electron donor (iii) include: an organosilicon compound represented by the formula (VII), a silane compound represented by the formula (VIII), a compound represented by the formula (IX), and the like.

R_nSi(OR')_4-n…(VII)

Si(OR^a)₃(NR^bR^c)…(VIII)

RNSi(OR^a)₃…(IX)

In formula (VII), R and R' are hydrocarbon groups, and n is an integer of 0< n < 4.

In the formula (VIII), R^aIs a hydrocarbon group having 1 to 6 carbon atoms, R^bIs a hydrocarbon group of 1 to 12 carbon atoms or hydrogen, R^cIs a hydrocarbon group having 1 to 12 carbon atoms.

In the formula (IX), R^aIs a hydrocarbon group having 1 to 6 carbon atoms, and RN is a cyclic amine group such as a perhydroquinolinyl group, a perhydroisoquinolinyl group, a 1,2,3, 4-tetrahydroquinolinyl group, a 1,2,3, 4-tetrahydroisoquinolinyl group, or an octamethyleneimino group.

Examples of the organosilicon compounds represented by the formula (VII) include: diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-pentylmethyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, phenyltriethoxysilane, cyclohexyltrimethoxysilane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, tricyclopentylmethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, cyclopentyldimethylethoxysilane, and the like.

Examples of the silane compound represented by the formula (VIII) include: dimethylamino triethoxysilane, diethylamino trimethoxysilane, diethylamino triethoxysilane, diethylamino tri-n-propoxysilane, di-n-propylaminotriethoxysilane, methyl-n-propylaminotriethoxysilane, tert-butylaminotriethoxysilane, ethyl-n-propylaminotriethoxysilane, ethyl-isopropylaminotriethoxysilane, and methyl-ethylaminotriethoxysilane, etc.

Examples of the compound represented by the formula (IX) include: (perhydroquinoline) triethoxysilane, (perhydroisoquinoline) triethoxysilane, (1,2,3, 4-tetrahydroquinoline) triethoxysilane, (1,2,3, 4-tetrahydroisoquinoline) triethoxysilane, octamethyleneiminotriethoxysilane, and the like.

The reaction temperature at the time of the above-mentioned contact is preferably-30 ℃ or higher and 150 ℃ or lower, more preferably-25 ℃ or higher and 130 ℃ or lower, and still more preferably-25 ℃ or higher and 120 ℃ or lower.

The amount of the solid titanium catalyst component (i) used in the 1 st polymerization step and the 2 nd polymerization step is 0.0001 mmol to 0.5 mmol, preferably 0.005 mmol to 0.1 mmol, in terms of titanium atom, per 1 liter of the polymerization volume.

The amount of the organometallic compound (ii) used in the 1 st polymerization step and the 2 nd polymerization step may be 1 mol or more and 2000 mol or less, preferably 5mol or more and 500 mol or less, based on 1 mol of titanium atoms in the polymerization system.

The amount of the electron donor (iii) used in the 1 st polymerization step and the 2 nd polymerization step may be 0.001 mol or more and 50 mol or less, preferably 0.01 mol or more and 30 mol or less, and more preferably 0.05 mol or more and 20 mol or less, based on 1 mol of the organometallic compound (ii) in the polymerization system.

The polymerization temperature in the 1 st polymerization step and the 2 nd polymerization step can be 20 ℃ to 200 ℃, preferably 30 ℃ to 100 ℃, and more preferably 50 ℃ to 90 ℃.

The pressure (gauge pressure) in the 1 st polymerization step and the 2 nd polymerization step can be set to a range from normal pressure to 9.8MPa or less, preferably from 0.20MPa to 4.9 MPa.

In the above-mentioned 1 st polymerization step and 2 nd polymerization step, the Melt Flow Rate (MFR) and the intrinsic viscosity [ η ] of Dsol may be adjusted to a desired range in order to reduce the molecular weight of the obtained polymer, or the polymerization may be carried out in the presence of hydrogen.

In the 2 nd polymerization step, for example, propylene and 1 or more α -olefins selected from ethylene and α -olefins having 4 to 20 carbon atoms may be polymerized with the crystalline propylene (co) polymer obtained in the 1 st polymerization step. For example, when the rubber component is a propylene-ethylene copolymer rubber, the ethylene/(ethylene + propylene) gas ratio is preferably 5 mol% or more and 80 mol% or less, more preferably 10 mol% or more and 70 mol% or less, and still more preferably 15 mol% or more and 60 mol% or less.

Further, it is also possible to carry out prepolymerization at a higher catalyst concentration before the 1 st polymerization step and the 2 nd polymerization step.