JP2003147035A - Propylene-based block copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene-based block copolymer having good balance between rigidity and impact resistance, high heat resistance and low gloss. SOLUTION: This block copolymer is obtained through the 1st step of producing a propylene polymer component (PP) using a metallocene catalyst and the 2nd step of producing a propylene-ethylene copolymer component (EP). This block copolymer thus obtained meets the following requirements (1) to (6): (1) melt flow rate is 0.1-150 g/10 min, (2) insoluble to 100 deg.C o- dichlorobenzene, soluble to 140 deg.C o-dichlorobenzene, (3) EP content is 5-50 wt.%, (4) the ethylene content of EP is 10-90 wt.%, (5) meeting the relationship (I): G>=E>=-4.5×10<-3> ×G<2> +1.3×G-7.0 (G is the ethylene content of EP, and E is the ethylene content of the noncrystalline component of EP), and (6) melting point is >=157 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a propylene-based block copolymer containing polypropylene having a specific structure and an ethylene-propylene copolymer. More specifically, the present invention relates to a propylene-based block copolymer that exhibits an extremely good rigidity-impact resistance balance when used as a molding material, has good heat resistance, and exhibits a high-grade appearance due to low gloss. .

[0002]

2. Description of the Related Art Crystalline polypropylene has mechanical properties
It is widely used in various molding fields due to its excellent chemical resistance. However, when a propylene homopolymer is used as the crystalline polypropylene, the rigidity is increased but the impact resistance is insufficient. Therefore, by a method of adding an elastomer such as ethylene-propylene rubber to a propylene homopolymer, or a method of producing a so-called block copolymer by subsequently copolymerizing ethylene and propylene after homopolymerization of propylene, impact resistance is improved. Have been improved. Although the physical properties are considerably improved by these methods, it is desired to further improve the rigidity-impact resistance balance. In addition to these properties, improvement in product differentiation, such as improvement in heat resistance and reduction in gloss peculiar to plastics to give a high-class feeling, is strongly desired.

On the other hand, it is known that isotactic polypropylene can be obtained by polymerizing propylene using a metallocene catalyst different from the conventional Ziegler type catalyst system. Further, after homopolymerization of propylene using the same catalyst, ethylene and propylene are subsequently copolymerized,
It is also known to produce so-called block copolymers. For example, JP-A-4-337308 and JP-A-6-308308
-287257, JP-A-5-202152, JP-A-6-206921 and JP-A-10-
Examples thereof are described in Japanese Patent No. 219047.
In addition, JP-A-11-228648 and JP-A-11-228648
240929, JP-A-11-349649, and JP-A-11-349650 describe examples of propylene-ethylene block copolymers having good rigidity and impact resistance. Although the rigidity and impact resistance are further improved by the above invention, it is necessary to further improve the rigidity and impact resistance as well as the heat resistance, moldability and appearance.

[0004]

That is, regarding the performance of the propylene-ethylene block copolymers exemplified in the above-mentioned prior art, although some improvement in impact resistance was observed, there is still room for improvement in heat resistance. is there. The present inventors have also found that the block copolymer obtained with a metallocene-based catalyst is a new subject in product development in that it has high gloss and gives an appearance lacking in high-class feeling. For this reason, in the propylene block copolymer obtained by the conventional method, further improvement in rigidity-impact resistance balance, moldability, heat resistance and appearance has been a problem.

[0005]

Means for Solving the Problems As a result of intensive investigations by the present inventors to solve the above-mentioned problems in the prior art,
A propylene-based block copolymer containing polypropylene having a specific structure and an ethylene-propylene copolymer having a specific structure in a specific ratio has an extremely good rigidity-impact resistance balance when used as a molding material. The present invention has been completed, and has been found to have high heat resistance, low gloss, and good appearance.

That is, the gist of the present invention is to use a metallocene catalyst to produce a propylene polymer component (PP) by a pre-stage process and a propylene-ethylene copolymer component (EP) by a post-stage process. A block copolymer, which is a propylene-based block copolymer characterized in that the block copolymer satisfies the following requirements (1) to (6). (1) Melt flow rate (MFR) is 0.1 to 15
It is 0 g / 10 minutes. (2) The propylene content of the component which is insoluble in ortho-dichlorobenzene at 100 ° C and soluble in ortho-dichlorobenzene at 140 ° C is 99.5% by weight or more. (3) Propylene in propylene block copolymer
The content of the ethylene copolymer component (EP) is 5 to 50% by weight. (4) The ethylene content (G) of EP is 10 to 90% by weight. (5) The relational expression (I) is established between the ethylene content (G) of EP and the ethylene content (E) of a component having no crystallinity in EP. G ≧ E ≧ −4.5 × 10 ⁻³ × G ² + 1.3 × G − 7.0 (I) (6) The melting point of the block copolymer is 157 ° C. or higher.

Another gist of the present invention is that the above requirements (1)-
A propylene-based block copolymer satisfying (6) and also satisfying the following requirement (7). Requirement (7) [2,1-bond content] and [1,3-bond content] in a component insoluble in orthodichlorobenzene at 100 ° C. and soluble in orthodichlorobenzene at 140 ° C. The sum is 0.06 ~
It is 0.6 mol%. Still another subject matter of the present invention is a propylene block copolymer that satisfies the above requirements (1) to (6) and also satisfies the following requirement (8). Requirement (8)
Insoluble in orthodichlorobenzene at 100 ℃, and 140
[1,3 in the components soluble in ortho-dichlorobenzene at ℃
-Bond content] is 0.06 to 0.6 mol%.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. Requirement (1) Melt flow rate (MFR) The propylene block copolymer of the present invention needs to have an MFR in the range of 0.1 to 150 g / 10 minutes. Generally, the higher the molecular weight, the lower the MFR, and therefore the MFR is a rough standard for representing the magnitude of the molecular weight. If the MFR is less than 0.1 g / 10 minutes, the fluidity during resin molding will be too low and the molding efficiency will be low. Further, the entanglement of the molecular chains is too strong, and the spherulite growth rate is reduced, resulting in a decrease in crystallinity and a decrease in rigidity. On the contrary, if the MFR exceeds 150 g / 10 minutes, the molecular weight becomes too small and the impact strength decreases. Preferred MFR in the present invention
The range is preferably from 4 to 100 g / 10 minutes, particularly preferably from 5 to 50 g, from both aspects of moldability and material properties.
The range is / 10 minutes. Generally, hydrogen gas, which is a chain transfer agent, is used to adjust the MFR, but it can be controlled by the polymerization temperature, the polymerization pressure, the monomer / comonomer raw material composition ratio, and a combination thereof. Is. The control range of these conditions may vary depending on the type of catalyst used.

Requirement (2) Ortho-dichlorobenzene (OD
CB) Insoluble component The propylene-based block copolymer of the present invention is required to have a propylene content of 99.5% by weight or more which is insoluble in ODCB at 100 ° C and soluble in ODCB at 140 ° C. is there. Such a component can be obtained by homopolymerization (homopolymerization) of propylene in the first step or by copolymerizing 0.5% by weight or less of α-olefin in the raw material gas composition. The insoluble component is
It refers to a component that is obtained by using a known temperature rising column fractionation method and is insoluble in ODCB at 100 ° C. but soluble in ODCB at 140 ° C. The heating column fractionation method is, for example, Macromolec
ules, 21, 314-319 (1988).

The ODCB insoluble component at 100 ° C. defined in the present invention is measured as follows. That is, a glass bead carrier (80 to 100 mesh) is packed in a cylindrical column having a diameter of 50 mm and a height of 500 mm, and the temperature is maintained at 140 ° C. Next, the ODC of the sample melted at 140 ° C
200 mL of B solution (10 mg / mL) is introduced into the column. Then, the temperature of the column is increased to 40 ° C at 10 ° C /
Cool at a rate of temperature decrease over time. After holding at 40 ° C for 1 hour, 1
The column temperature is heated to 100 ° C. at a temperature rising rate of 0 ° C./hour and kept for 1 hour. The accuracy of column temperature control through a series of operations is ± 1 ° C.

Then, with the column temperature kept at 100 ° C., ODCB at 100 ° C. was applied at a flow rate of 20 mL / min to 80 ° C.
By flowing 0 mL, the components dissolved in ODCB at 100 ° C. existing in the column are eluted and collected. Then, the column temperature is increased to 140 ° C at a temperature increase rate of 10 ° C / min.
Up to 140 ° C. and left still at 140 ° C. for 1 hour, then 800 mL of a solvent (ODCB) at 140 ° C. is flown at a flow rate of 20 mL / min to make it insoluble in 100 ° C. ODCB and 140 ° C.
A component soluble in ODCB is eluted and collected. 10
The ODCB solution containing components that are insoluble in ODCB at 0 ° C. and soluble in ODCB at 140 ° C. is concentrated to 20 mL using an evaporator and then precipitated in 5 volumes of methanol. The precipitated polymer is collected by filtration and then dried in a vacuum dryer overnight. This is referred to as "100 in the present invention.
ODCB insoluble component at ° C ".

[0012] ODCB is a good solvent for polyolefins and has a high boiling point of 181 ° C. Therefore, it is used for solvent separation in a wide temperature range from low temperature to high temperature. O at 100 ° C
The fact that it is insoluble in DCB means that it is a polypropylene component having high crystallinity among the components constituting the block copolymer, and it is a high component remaining after removing the component having poor crystallinity from the propylene-based block copolymer. It has the meaning of extracting only crystalline components. The propylene content of the component being 99.5% by weight or more means that even if the component is homopolypropylene or a copolymer of propylene and α-olefin, it is extremely less than 0.5% by weight. It is meant to contain only small amounts of α-olefins. Therefore, the ODCB-insoluble component at 100 ° C. has high crystallinity, which means that it has the effect of increasing the rigidity of the propylene block copolymer. At 140 ° C, the polymer is completely dissolved, so a value of 140 ° C is an OD of 100 ° C.
It has the meaning that all the components insoluble in CB can be recovered and used for the analysis of the propylene content. In the present invention, if the propylene content of the above-mentioned ODCB-insoluble component is less than 99.5% by weight, rigidity and heat resistance are deteriorated, which is not preferable. The component is more preferably homopolypropylene in order to maintain high rigidity. Further, such a component is preferably contained in the propylene block copolymer in an amount of 45% by weight or more, particularly 55 to 90% by weight.

Requirement (3) propylene block copolymer
EP content in the propylene-based block copolymer of the present invention, the weight ratio of the propylene-ethylene copolymer component in it,
It is necessary to be 5 to 50% by weight. In order to achieve this range, the weight of PP manufactured in the first step and the weight of EP manufactured in the second step may be set to a predetermined ratio.
Generally, in a propylene-based block copolymer, the propylene-ethylene copolymer is a random copolymer, and a substance having poor crystallinity and exhibiting physical properties such as rubber is a main component, and it is a basic component that develops impact strength. Become a factor. In the present invention, since the propylene-ethylene copolymer has high random copolymerizability, the EP content is 5 to 50% by weight.
It exhibits excellent physical properties in a wide range. If the EP content is less than 5% by weight, the rubber-like portion is too small and the impact strength deteriorates. On the contrary, if the EP content is 50% by weight or more,
There is a problem that the rigidity is lowered due to too few crystalline parts. In the present invention, the preferable EP content is 8 to 4
The range is 0% by weight. The definition and measurement method of the EP content in the propylene block copolymer which is the subject of the present invention will be described in more detail later.

Requirement (4) EP ethylene content (G) The propylene block copolymer of the present invention must have an ethylene content (G) in the EP of 10 to 90% by weight. It is preferably 20 to 60% by weight, more preferably 25 to 50% by weight. The method of measuring G will be described later. G is a factor that affects the crystallinity and rubber properties of the propylene-ethylene copolymer. In particular, it has a great influence on impact resistance at low temperatures below room temperature, especially at extremely low temperatures such as -10 to -30 ° C. When G is less than 10% by weight,
As a result of the increase in the glass transition temperature of EP, there is the disadvantage that the impact strength at low temperatures decreases. Further, a phenomenon occurs in which a part of EP is solubilized in PP serving as a matrix, which causes a problem that rigidity and heat resistance are lowered. On the other hand, when G exceeds 90% by weight, EP is not uniformly dispersed in PP and impact strength is reduced. The ethylene content (G) of EP can be controlled to a desired value within the range defined by the present invention by adjusting the composition ratio of the raw material gas in the propylene-ethylene block copolymer production step in the latter step. it can.

Requirement (5) Relationship between G and E In the propylene block copolymer of the present invention, the ethylene content (G) of EP and the ethylene content (E) of the non-crystalline component of EP are In between, the following relational expression (I)
It is necessary that G ≧ E ≧ −4.5 × 10 ⁻³ × G ² + 1.3 × G −7.0 (I)

EP is a propylene-ethylene random copolymer, whose main component is a rubber-like molecule having no crystallinity, but has a crystallinity part based on a relatively long ethylene chain and / or propylene chain. Molecules may also be present. The impact absorption characteristics of the propylene-based block copolymer strongly depend on the glass transition temperature of the rubber portion, and the E value is an index showing the high glass transition temperature. Further, the E value also serves as an index showing the affinity between the PP phase and the EP phase, and the dispersed particle size of EP is strongly influenced by the E value. On the other hand, the G value is an index of the average ethylene content of all EPs including molecules having crystallinity and molecules having no crystallinity. The G value and the E value generally show a positive correlation, and the higher the G value, the higher the E.

That is, the higher the average ethylene content of all EPs, the higher the ethylene content of the rubber component having no crystallinity. The G value is always larger than the E value. The magnitude relationship does not reverse, and the theoretical limit is G = E. The propylene block copolymer has a form in which the EP component is spherically dispersed in the polypropylene continuous phase, and when the inside of the spherical EP dispersed phase is observed more microscopically, the rubber part (rubber component )
It is general that lamellae derived from a crystalline component are mixed.

As a result of repeated examinations of various physical properties of EP, the inventors of the present invention should not increase the difference between the G value and the E value. It has been found that bringing them closer to each other leads to improvement in physical properties, which is the subject of the present invention. The propylene-based block copolymer disclosed in the present invention has a very high randomness of EP, so that the physical property correlation between the G value and the E value has a theoretical upper limit line as compared with conventionally known block copolymers. The physical properties are closer to E = G shown. Further, in the present invention, 10 ≦ G ≦ 90, preferably 20
Since ≦ G ≦ 60, and more preferably 25 ≦ G ≦ 50, the propylene-based block copolymer of the present subject matter has E
-G belongs to a region that satisfies a certain condition. In other words, the difference between the G value and the E value is usually within 5% by weight, preferably within 3% by weight, and particularly 2% by weight.
Within. Especially when the G value is in the range of 20 to 50% by weight,
The difference between the E value and the E value is 0 to 2% by weight, more preferably 0 to 1% by weight.

When the G value and the E value do not satisfy the relational expression (I), the strength of the affinity between the amorphous component and the crystalline component in EP does not reach the critical point, so that the impact resistance is high. It is speculated that the balance between flexibility and rigidity will not be improved to a satisfactory level. Further, when the relationship between the G value and the E value does not satisfy the above relational expression (I), PP which is a crystal part and E which is a rubber part.
As a result of the higher affinity of P, the particle size of EP particles dispersed in the PP phase becomes smaller, the gloss increases, and a good appearance cannot be obtained. The reason for the deterioration of the physical properties, particularly the balance between rigidity and impact resistance, is that the same EP is caused by the fact that the size of lamellae present in rubber increases or agglomerates.
It is considered that the impact absorption capacity changes even when the content is increased. Further, the size of the dispersed EP particles also changes at the same time, resulting in an inconvenience that the gloss value increases. On the contrary, as the G value and the E value approach, the lamella dispersed in the rubber becomes smaller, and the degree of cohesion decreases, so it is possible to maintain a good rigidity / impact resistance balance with a low gloss value. It is believed that
The G value can be set to a desired value by changing the ethylene / propylene raw material composition ratio in the latter step. Further, the E value can satisfy the relational expression (I) of the requirement (5) of the present invention by appropriately selecting the catalyst and the polymerization condition as described later.

< Determination of Parameters of Requirements (3) to (5)
Method> In the present invention, the EP content in the propylene-based block copolymer, the ethylene content in the EP (G), and the ethylene content in the EP having no crystallinity (E)
Is calculated by the following method.

1. Analyzing equipment used Cross sorting equipment Dia Instruments Co., Ltd. CFC T-100 (CF
Abbreviated as C) Fourier transform infrared absorption spectrum analysis FT-IR, fixed wavelength infrared spectrophotometer attached as a detector of Perkin Elmer 1760X CFC is removed and FT-IR is connected instead, This FT-IR is used as a detector. The transfer line from the outlet of the solution eluted from the CFC to the FT-IR has a length of 1 m, and is 1 throughout the measurement.
Hold temperature at 40 ° C. The flow cell attached to the FT-IR has an optical path length of 1 mm and an optical path width of 5 mmφ and is maintained at 140 ° C. throughout the measurement. Gel permeation chromatography (GPC) The GPC column after CFC is AD806M manufactured by Showa Denko.
Three S are connected in series and used.

2. CFC measurement conditions Solvent: Orthodichlorobenzene (ODCB) Sample concentration: 4 mg / mL Injection volume: 0.4 mL Crystallization: The temperature is lowered from 140 ° C to 40 ° C over about 40 minutes. Fractionation method: Fractionation temperature at elevated temperature elution fractionation is set to 40, 100 and 140 ° C., and fractionation is performed into three fractions in total. 40
Ingredients (fraction 1) that elute below 40 ° C, 40 to 10
Component eluting at 0 ° C. (fraction 2), 100-14
The elution ratios (unit: weight%) of the components (fraction 3) eluted at 0 ° C. are defined as W ₄₀ , W ₁₀₀ , and W ₁₄₀ , respectively. W
₄₀ + W ₁₀₀ + W ₁₄₀ = 100. The separated fractions are automatically transported to the FT-IR analyzer as they are. Solvent flow rate during elution: 1 mL / min

3. FT-IR measurement conditions After starting the elution of the sample solution from GPC in the latter stage of CFC,
FT-IR measurement is performed under the following conditions, and GPC-IR data is collected for each of the above fractions 1 to 3. A conceptual diagram of CFC-FT-IR is shown in FIG. Detector: MCT Resolution: 8 cm ^-1 Measurement interval: 0.2 minutes (12 seconds) Accumulation count per measurement: 15 times

4. Post-treatment and analysis of measurement results The elution amount and molecular weight distribution of the components eluted at each temperature are FT-
The absorbance at 2945 cm ^-1 obtained by IR is used as a chromatogram and determined. The elution amount is standardized so that the total elution amount of each elution component is 100%. The conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance using standard polystyrene. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F2
0, F10, F4, F1, A5000, A2500, A
1000. ODCB (0.5
0.4m of solution dissolved in BHT (mg / mL)
Make L injections to create a calibration curve. For the calibration curve, a cubic expression obtained by approximation by the least square method is used. For the conversion to the molecular weight, a general-purpose calibration curve is used with reference to “Size Exclusion Chromatography” by Sadao Mori (Kyoritsu Shuppan). The following numerical values are used for the viscosity formula ([η] = K × Mα) used at that time. When preparing a calibration curve using standard polystyrene K = 0.000138, α = 0.70 When measuring a sample of a propylene-based block copolymer K = 0.00103, α = 0.78 Ethylene content distribution of each eluted component ( The distribution of ethylene content along the molecular weight axis) was determined by using the ratio of the absorbance at 2956 cm ^-1 and the absorbance at 2927 cm ^-1 obtained by GPC-IR, using polyethylene, polypropylene or ¹³ C-N
Converted to ethylene content (% by weight) using a calibration curve prepared in advance using ethylene-propylene-rubber (EPR) whose ethylene content is known by MR measurement and the like and mixtures thereof. Ask.

<EP content> Propylene in the present invention
The EP content of the block copolymer is determined by the following formula (II).
And is required by the following procedure.         EP content (wt%) =   W₄₀× A₄₀/ B₄₀+ W₁₀₀× A₁₀₀/ B₁₀₀+ W₁₄₀× A₁₄₀/ B₁₄₀  (II) (W₄₀, W₁₀₀, W₁₄₀In each fraction mentioned above
Elution rate (unit: weight%), A₄₀, A₁₀₀, A₁₄₀
Is W₄₀, W₁₀₀, W₁₄₀For each fraction corresponding to
Actual average ethylene content (% by weight)
Yes, B₄₀, B ₁₀₀, B₁₄₀Contained in each fraction
It is the ethylene content (unit weight%) of EP. A
₄₀, A₁₀₀, A₁₄₀, B₄₀, B₁₀₀, B₁₄₀How to find
To do. The meaning of the formula (II) is as follows. (II) Expression right
The first term on the side is in fraction 1 (portion soluble at 40 ° C)
This is a term for calculating the amount of EP contained. Fraction 1
W contains EP only and not PP, W₄₀Gazo
Fraction 1-derived EP contained in the whole as it is
Fraction 1, which contributes to the amount of
In addition, a small amount of PP-derived components (components with extremely low molecular weight
And atactic polypropylene).
Need to be corrected. So W₄₀To A₄₀/ B₄₀
By multiplying by, the EP component of fraction 1
Calculate the amount of origin. For example, the average et of fraction 1
Ren content (A₄₀) Is 30% by weight and the fraction
Ethylene content of EP contained in 1 (B₄₀) Is 40 weight
%, 30/40 of fraction 1 = 3/4
(Ie 75% by weight) is derived from EP and the remaining 1/4 is from PP
It will be coming. Thus, in the first term on the right side, A₄₀/ B
₄₀The operation to multiply by is the weight% of fraction 1 (W₄₀) From
Means to calculate the EP contribution. After the second term on the right side
The same is true for each fraction, and for each fraction
The EP content is the sum of the calculated and added values.

(1) As described above, the average ethylene contents corresponding to the fractions 1 to 3 obtained by CFC measurement are A ₄₀ , A ₁₀₀ , and A ₁₄₀ , respectively (units are% by weight). The method for obtaining the average ethylene content will be described later. (2) Determine the ethylene content corresponding to the peak position in the differential molecular weight distribution curve of fraction 1 (see FIG. 2) as B
₄₀ (unit is weight%). With respect to the fractions 2 and 3, it is considered that the rubber part is completely eluted at 40 ° C., and the same definition cannot be defined. Therefore, in the present invention, B ₁₀₀ = B ₁₄₀ = 100 is defined. B
₄₀ , B ₁₀₀ and B ₁₄₀ are the ethylene content of EP contained in each fraction, but it is practically impossible to analytically determine this value. The reason is that there is no means for completely separating and separating PP and EP mixed in the fraction. As a result of an examination using various model samples, B ₄₀ can successfully explain the effect of improving the physical properties of materials by using the ethylene content corresponding to the peak position of the differential molecular weight distribution curve of fraction 1. all right. Also, B _100, B _{1 40} is to have a crystallinity of ethylene-derived chain, and two points that relatively small compared to the amount of EP amount of EP contained in these fractions is contained in fraction 1 100 for both reasons
It is closer to the actual situation and there is almost no error in calculation. Therefore, B ₁₀₀ = B ₁₄₀ = 100 is set for analysis.

(3) Determine the EP content according to the following formula
It     EP content (wt%) =     W₄₀× A₄₀/ B₄₀+ W₁₀₀× A₁₀₀/ 100 + W₁₄₀× A₁₄₀/ 100 (III ) That is, W, which is the first term on the right side of equation (III)₄₀× A₄₀/ B
₄₀Indicates the EP content (% by weight) having no crystallinity,
W which is the sum of the second and third terms₁₀₀× A₁₀₀/ 100 + W ₁₄₀
× A₁₄₀/ 100 is the EP content (% by weight) with crystallinity
Indicates. Where B₄₀And obtained by CFC measurement
Average ethylene content A of each of fractions 1 to 3₄₀, A
₁₀₀, A₁₄₀Is calculated as follows. Figure 2 shows the crystal content
Fraction 1 separated according to the difference in cloth
Measure the molecular weight distribution with a GPC column that forms part of the analyzer.
Fixed curve and connected behind the GPC column
The corresponding FT-IR was used to measure the molecular weight distribution curve.
It is an example showing a distribution curve of the determined ethylene content.
The ethylene content corresponding to the peak position of the differential molecular weight distribution curve
The amount is B₄₀Becomes Also, in FIG.
Data points, which are captured as data points
Of the product of the weight percentage and the ethylene content for each data point
The sum is the average ethylene content A₄₀Becomes

The significance of setting the above three types of separation temperatures is as follows. In the CFC analysis of the present invention,
40 ° C. is a temperature condition necessary and sufficient to separate only polymers having no crystallinity (for example, most of EP, or extremely low molecular weight components and atactic components among propylene polymer components (PP)). It has a certain meaning. 100 ° C. means only a component that is insoluble at 40 ° C. but soluble at 100 ° C. (for example, a component having crystallinity in EP due to the chain of ethylene and / or propylene, and PP having low crystallinity) Is a temperature necessary and sufficient for the elution. 140 ° C. means only components that are insoluble at 100 ° C. but soluble at 140 ° C. (for example, a component having particularly high crystallinity in PP and a component having extremely high molecular weight and ethylene crystallinity in EP). The temperature is necessary and sufficient to elute and recover the total amount of the propylene block copolymer used for analysis. Note that the EP component contained in W ₁₄₀ is extremely small and can be practically ignored.

<G and E> Ethylene content in EP (G) (% by weight) = (W ₄₀ × A
_{40 + W 100 × A 100 +} W 140 × A 140) / [EP] However, [EP] is the EP content determined previously (wt%). Of the EP, the ethylene content (E) (% by weight) of the part having no crystallinity was almost 40% in the elution of the rubber part.
Since it is completed at a temperature of not more than 0 ° C, the value of B ₄₀ is approximated.

Requirement (6) Propylene block copolymer
Melting point of the propylene-based block copolymer of the present invention needs to have a melting point of 157 ° C. or higher. Melting point 157 ° C
If it is less than this, heat resistance and rigidity are insufficient. Such high melting point P
To obtain P, a metallocene complex, a cocatalyst, a polymerization condition and the like are appropriately combined and used. Generally, this can often be achieved by increasing the polymerization pressure and / or decreasing the polymerization temperature. It can also be achieved by using the catalyst components (A) to (C) disclosed in the present invention in combination. In the case of a propylene-based block copolymer, the melting point of the product is controlled by the propylene polymer component (PP). Therefore, the melting point of the block copolymer is approximately PP
It can also be said that the melting point is, and the polymerization reaction in the first step is dominant. Further, the heat resistance of the propylene-based block copolymer strongly depends on the melting point of PP, and the higher the melting point, the higher the improvement. However, on the other hand, even with the same melting point, 8
The larger the loss tangent due to crystal relaxation occurring around 0 ° C., the worse the heat resistance and the high temperature creep resistance. This is because the relaxation of stress against deformation becomes large. Therefore, PP
Is the tan δ at 80 ° C. and the ta at a lower temperature of 50 ° C.
It is preferable that the ratio of nδ is small. Specifically, in order to exhibit good heat resistance, tan δ at 80 ° C. is preferably 4/3 times or less of tan δ at 50 ° C.
Here, tan δ at 50 ° C. and 80 ° C. uses a dynamic viscoelasticity measuring device RDA-II manufactured by Rheometrics, and the temperature is 50 ° C. and 80 ° C. in a geometry of width 12 mm, thickness 3 mm, and length 30 mm. After being stabilized for 5 minutes respectively, the loss elastic modulus E '' and the storage elastic modulus are measured by applying torsional vibration strain with the longitudinal axis as the rotation axis and an angular frequency of 6.28 rad / s and strain of 0.1%. Ratio of E'E "/ E '
That is.

Requirement (7) Content of Different Bonds ODC of the propylene block copolymer in the present invention
The B-insoluble component preferably contains a specific amount of different types of bonds (positional irregular units based on 2,1-insertion and 1,3-insertion of propylene). In the present invention, [2,1-
The sum of [bond content] and [1,3-bond content] is 0.06
It is preferably about 0.6 mol%. The content of the above bond is measured by ¹³ C-NMR.

<Details of ¹³ C-NMR Measurement Method> 1
350 to 500 m in a 0 mmφ sample tube for NMR
The sample of g was added to about 2.0 mL of ODCB and about 0.5 mL of deuterated benzene as a lock solvent in a solvent at 130 ° C.
After completely dissolving with, the measurement is carried out at 130 ° C. by the complete proton decoupling method. As the measurement conditions, a flip angle of 65 ° and a pulse interval of 5T1 or more (T1 is the longest value of the spin lattice relaxation time of the methyl group) are selected. In the propylene polymer, T1 of the methylene group and the methine group is shorter than that of the methyl group, so that the recovery of the magnetization of all carbons is 99% or more under this measurement condition. From the spectrum measured under the above conditions, according to the following formula, [2,1-bond content]
And [1,3-bond content].

[0033]

[Equation 1]

In this equation, A, A, A, A
, A, A, A, A and A are respectively
42.3 ppm, 35.9 ppm, 38.6 ppm, 3
0.6 ppm, 36.0 ppm, 31.5 ppm, 3
The areas are 1.0 ppm, 37.2 ppm, and 27.4 ppm, and the carbon abundance ratios shown in the following partial structures (I) and (II) are shown.

[0035]

[Chemical 1]

It is not clear why the degree of improvement in impact strength is reduced unless the amount of different bonds is 0.06 mol% or more.
A polymer segment containing a heterogeneous bond has higher mobility than a segment without a heterogeneous bond. Therefore, when a shock is applied, a local plastic deformation can be caused to absorb a larger impact energy. 0.06 mol%
In the following, it is estimated that the impact strength is reduced because the effect of generating such a segment having high mobility is small. On the other hand, the heterogeneous bond becomes a defect when the polypropylene forms crystals, and also has the effect of lowering the rigidity. In particular, when it exceeds 0.6 mol%, the crystallinity decreases sharply,
At the same time, the thickness of the crystalline lamella becomes thin, resulting in a decrease in rigidity and heat resistance. The content of these different kinds of bonds can be kept within the range defined by the present invention by selecting an appropriate metallocene complex and combining an appropriate metallocene complex and a cocatalyst. Further, it is possible to keep the polymerization temperature within the range defined by the present invention by carrying out the polymerization at an appropriate polymerization temperature and / or by selecting an appropriate polymerization pressure. As a general fluctuation tendency, [1,3-bond content] increases as the polymerization temperature increases, and [2,1-bond content] increases as the polymerization pressure increases.

Requirement (8) [1,3-bond content] In the propylene block copolymer of the present invention, the [1,3 bond content] is 0.06 to 0.6 mol%. preferable. When the content exceeds 0.06 mol%, the mobility of the amorphous component is improved, and as a result, the impact strength improving effect becomes more remarkable. However, when the content exceeds 0.6 mol%, the degree of crystallinity is greatly reduced, resulting in deterioration of rigidity and heat resistance. Among the heterogeneous bonds, the segment containing the 1,3-bond has a higher molecular mobility than the segment containing the 2,1-bond, and thus is excellent in the effect of improving the impact resistance. This [1,3-bond content]
Can be within the scope of the present invention by selecting an appropriate metallocene complex and combining an appropriate metallocene complex and a cocatalyst. Further, it is possible to keep the polymerization temperature within the range defined by the present invention by carrying out the polymerization at an appropriate polymerization temperature and / or by selecting an appropriate polymerization pressure.

<Production of Propylene Block Copolymer>
The method for producing a propylene-based block copolymer according to the present invention is not particularly limited as long as it gives a propylene-based block copolymer satisfying the above physical properties,
Among them, a catalyst system suitable for producing the copolymer of the present invention is a specific metallocene catalyst, and an olefin polymerization catalyst obtained by contacting the following components A, B and C as shown below. Can be used

<Component (A)> Transition metal compound component (A)
Is represented by the following general formula (Ia).

[0040]

[Chemical 2]

In the general formula (Ia), R ¹ , R ² , R ⁴ and R
^5's each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group having 1 to 12 carbon atoms, or a halogenated hydrocarbon group having 1 to 12 carbon atoms. R
³ and R ⁶ each independently represent a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms which forms a condensed ring with the five-membered ring to which it is bonded. R ⁷ and R ⁸ are each independently an aryl group having 6 to 20 carbon atoms and 6 carbon atoms.
~ 20 halogen or halogenated hydrocarbon substituted aryl groups. Q represents a bonding group bridging two conjugated five-membered ring ligands at arbitrary positions, M represents a metal atom selected from Groups 4 to 6 of the periodic table, and X and Y represent a hydrogen atom or a halogen atom. , A hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group. m and n each represent the number of substituents R ⁷ and R ⁸ substituted on the sub ring, and each independently represent an integer of 0 to 20. The transition metal compound of the present invention is preferably racemic.

The above R ¹ , R ² , R ⁴ , and R ⁵ have 1 to 10 carbon atoms.
Specific examples of the hydrocarbon group of are methyl, ethyl, n-
Propyl, i-propyl, n-butyl, i-butyl, s
-Butyl, t-butyl, n-pentyl, n-hexyl,
Examples thereof include an alkyl group such as cyclopropyl, cyclopentyl and cyclohexyl, an alkenyl group such as vinyl, propenyl and cyclohexenyl, as well as a phenyl group and a naphthyl group. Specific examples of the silicon-containing hydrocarbon group having 1 to 12 carbon atoms represented by R ¹ , R ² , R ⁴ and R ⁵ include trialkylsilyl groups such as trimethylsilyl, triethylsilyl and t-butyldimethylsilyl, bis (trimethylsilyl). ) Examples include alkylsilylalkyl groups such as methyl.

In the above halogenated hydrocarbon group having 1 to 12 carbon atoms, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. And
When the halogen atom is, for example, a fluorine atom, the above halogenated hydrocarbon group is a compound in which a fluorine atom is substituted at any position of the above hydrocarbon group. Specific examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl,
2,2,1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, o-,
m-, p-fluorophenyl, o-, m-, p-chlorophenyl, o-, m-, p-bromophenyl, 2,4
-, 3,5-, 2,6-, 2,5-difluorophenyl, 2,4-, 3,5-, 2,6-, 2,5-dichlorophenyl, 2,4,6-trifluorophenyl, Two
4,6-trichlorophenyl, pentafluorophenyl, pentachlorophenyl and the like can be mentioned.

Of these, R ¹ and R ⁴ are preferably hydrocarbon groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl and phenyl, and R ² and R ⁵ are preferably hydrogen atoms. . As R ³ and R ⁶ , it is preferable that the sub ring formed from the shared portion of the adjacent conjugated five-membered ring is a 7 to 10-membered ring, particularly a pentamethylene group, 1,
A 3-pentadienylene group and a 1,4-pentadienylene group are preferred. Preferable specific examples of the aryl group having 6 to 20 carbon atoms for R ⁷ and R ⁸ include phenyl group, methylphenyl group, dimethylphenyl group, mesityl group, ethylphenyl group, diethylphenyl group, triethylphenyl group,
i-propylphenyl group, di-propylphenyl group,
Tri i-propylphenyl group, n-butylphenyl group,
Di-n-butylphenyl group, tri-n-butylphenyl group,
An aryl group such as a t-butylphenyl group, a di-t-butylphenyl group, a tri-t-butylphenyl group, a biphenylyl group, a p-terphenyl group, a m-terphenyl group, a naphthyl group, an anthryl group and a phenanthryl group can be mentioned. Among these, a t-butylphenyl group, a biphenylyl group, a p-terphenyl group, a naphthyl group, an anthryl group and a phenanthryl group are particularly preferable.

Examples of the halogen having 6 to 20 carbon atoms or the halogenated hydrocarbon-substituted aryl group represented by R ⁷ and R ⁸ include the case where the halogen is fluorine, chlorine or bromine. Specific examples thereof include a halogen atom. For example, in the case of a fluorine atom, a compound in which a fluorine atom is substituted at any position of the above hydrocarbon group can be exemplified. Explaining preferred specific examples by taking fluorine as an example, a fluorophenyl group, a (trifluoromethyl) phenyl group, a methylfluorophenyl group,
Fluorodimethylphenyl group, (fluoromethyl) methylphenyl group, ethylfluorophenyl group, diethylfluorophenyl group, triethylfluorophenyl group, fluoro i-propylphenyl group, fluorodi i-propylphenyl group, (fluoro i-propyl) i- Propylphenyl group, fluorotri i-propylphenyl group, n
-Butylfluorophenyl group, di-n-butylfluorophenyl group, (fluorobutyl) butylphenyl group, tri-n-butylfluorophenyl group, t-butylfluorophenyl group, di-t-butylfluorophenyl group, tri-t-
Butyl fluorophenyl group, fluorobiphenylyl group,
Examples thereof include a fluoro p-terphenyl group, a fluoro m-terphenyl group, a fluoronaphthyl group, a fluoroanthryl group, and a fluorophenanthryl group. The halogenated hydrocarbon group is preferably a fluorinated hydrocarbon-substituted aryl group as the fluorinated compound, and the chlorinated hydrocarbon-substituted aryl group as the chlorinated compound, and is preferably a t-butylfluorophenyl group, a fluorobiphenylyl group, a fluoro p-terphenyl group. , Fluoronaphthyl group, fluoroanthryl group, fluorophenanthryl group, t-butylchlorophenyl group, chlorobiphenylyl group, chloro p-terphenyl group, chloronaphthyl group, chloroanthryl group, chlorophenanthryl group are particularly preferable. preferable.

M and n are preferably each independently 1 to
It is an integer of 5. When m and / or n are integers of 2 or more, the plurality of groups R ⁷ (or R ⁸ ) may be the same or different from each other. When m and / or n is 2 or more, R ^{7 s} or R ^{8 s} may be linked to each other to form a new ring structure. The bonding position of R ⁷ and R ⁸ with respect to R ³ and R ⁶ is not particularly limited, but is preferably a carbon adjacent to each 5-membered ring (carbon at α position).

Q is preferably a methylene group, an ethylene group, a silylene group, an oligosilylene group, or a germylene group. Preferable examples include ethylene, isopropylidene, dimethylsilylene, methylphenylsilylene, diphenylsilylene, dimethylgermylene, methylphenylgermylene, diphenylgermylene and the like.
M is preferably titanium, zirconium, or hafnium, and particularly preferably hafnium. X and Y are preferably halogen, more preferably chlorine atom. A specific example of the preferable complex in the component (A) is dimethylsilylenebis (2-ethyl-4-t).
-Butylphenyl-indenyl) zirconium chloride, dimethylsilylenebis (7- (1-methyl-3-phenylindenyl)) zirconium dichloride, dimethylsilylenebis (2-isopropyl-4-naphthyl-indenyl) zirconium dichloride, dimethylsilylenebis (2-Methyl-4-tert-butylcyclopentadienyl) hafnium dichloride, dimethylsilylene bis (2
-Ethyl-4- (4-tert-butyl-3-chlorophenyl)
-4H-azurenyl) zirconium dichloride, dimethylsilylenebis (2-ethyl-4-phenyl-4H-azulenyl) hafnium dichloride, dimethylsilylenebis (2-ethyl-4-naphthyl-4H-azulenyl) hafnium dichloride, dimethylsilylenebis ( 2-Ethyl-4-biphenyl-4H-azurenyl) hafnium dichloride, dimethylsilylenebis (2-ethyl-4-)
(2-Fluoro-4-biphenyl) -4H-azurenyl) hafnium dichloride, dimethylsilylenebis (2
-Ethyl-4- (4-chloro-2-naphthyl-4H-azurenyl)) hafnium dichloride, dimethylsilylenebis (2-ethyl-4- (4-chloro-2-tetrahydronaphthyl-4H-tetrahydroazulenyl)) hafnium Dichloride, dimethylsilylene bis (2-ethyl-
4- (3-chloro-4-t-butyl-phenyl-4H-
Azulenyl)) hafnium dichloride, methylsilylene bis (2-ethyl-4- (3-chloro-4-trimethylsilyl-phenyl-4H-azulenyl)) hafnium dichloride and the like. Among these, dimethylsilylene bis (2-ethyl-4- (2-fluoro-4) is particularly preferable.
-Biphenyl) -4H-azurenyl) hafnium dichloride, dimethylsilylene bis (2-ethyl-4- (4-
Chloro-2-naphthyl-4H-azurenyl)) hafnium dichloride, dimethylsilylene bis (2-ethyl-4)
-(3-Chloro-4-t-butyl-phenyl-4H-azurenyl)) hafnium dichloride, methylsilylene bis (2-ethyl-4- (3-chloro-4-trimethylsilyl-phenyl-4H-azurenyl)) hafnium dichloride Etc. are preferred.

<Component (B)> In the present invention, as the component (B), a component selected from the group consisting of the following (b-1) to (b-4) is used. (B-1) Particulate carrier carrying aluminum oxy compound, (b-2) Component (A) reacting with component (A)
Particulate carrier carrying an ionic compound or Lewis acid capable of converting cations to cations, (b-3) solid acid particles, (b-4) ion-exchange layered silicate. Among these, it is desirable to use (b-4) an ion-exchange layered silicate. In the present invention, the ion-exchange layered silicate used as a raw material (hereinafter simply referred to as silicate) has a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other by a binding force, and , Refers to a silicate compound in which the contained ions are exchangeable.
Since most silicates are naturally produced mainly as the main component of clay minerals, impurities other than ion-exchange layered silicates (quartz, cristobalite, etc.) are often contained, but they are also included. But it's okay. Specific examples of silicate include
For example, Haruo Shiramizu, "Clay Mineralogy," Asakura Shoten (1995
The following layered silicates are listed in (1).

That is, smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, vermiculites such as vermiculite, mica, illite, sericite, mica such as glauconite, attapulgite, Sepiolite, palygorskite, bentonite,
Examples include pyrophyllite, talc, and chlorite groups. In the silicate used as a raw material in the present invention, the main component silicate is 2:
A silicate having a type 1 structure is preferable, a smectite group is more preferable, and montmorillonite is particularly preferable. The type of the interlayer cation is not particularly limited, but a silicate containing an alkali metal or an alkaline earth metal as a main component of the interlayer cation is preferable from the viewpoint of being relatively easily and inexpensively available as an industrial raw material.

(Chemical Treatment) The silicate used in the present invention is
It can be used as it is without any particular treatment, but it is preferably subjected to chemical treatment. Here, as the chemical treatment, both surface treatment for removing impurities adhering to the surface and treatment for affecting the structure of clay can be used. Specifically, JP-A-5-301917,
JP-A-7-224106, JP-A-8-12761
Known acid treatments, alkali treatments, salt treatments, organic substance treatments and the like disclosed in Japanese Patent Publication No. 3 can be used. Among these treatments, a solid catalyst component having a higher melting point and a higher activity can be obtained by using a metal oxide such as lithium oxide and a treatment of sulfuric acid at the same time.

<Component (C)> The component (C) is an organoaluminum compound, and a compound represented by the general formula AlR ⁹ _p X _3-p is suitable. In this formula, R ⁹ represents a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen, hydrogen, an alkoxy group or an amino group. p is a number greater than 0 and up to 3. R ⁹ is preferably a trialkylaluminum having 1 to 8 carbon atoms.

(Catalyst Formation / Preliminary Polymerization) The catalyst according to the present invention is formed by bringing the above-mentioned components into contact with each other in a (preliminary) polymerization tank at the same time or continuously, or at once or plural times. be able to.
As these contact methods, various known methods can be used.
Further, the amounts of the components (A), (B) and (C) used in the present invention are arbitrary, and various known methods can be used. The catalyst of the present invention is preferably subjected to a prepolymerization treatment, which comprises contacting it with an olefin and polymerizing it in a small amount. The olefin used is not particularly limited, but ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene and the like are used. It can be illustrated. The olefin feed method may be any method such as a feed method of maintaining the olefin in the reaction tank at a constant rate or in a constant pressure state, a combination thereof, or a stepwise change. The temperature and time for prepolymerization are not particularly limited, but each is -20 ° C.
It is preferably in the range of -100 ° C and 5 minutes to 24 hours. The amount of the prepolymerized polymer is preferably 0.01 to 100 g, more preferably 0.1 to 50 g, based on 1 g of the component (B). Further, the component (C) can be added or added during the prepolymerization. A method in which a polymer such as polyethylene or polypropylene or a solid of an inorganic oxide such as silica or titania is allowed to coexist during or after the contact of each of the above components is also possible.

[Polymerization / Production of Propylene-Based Block Copolymer] As a method for producing the block copolymer of the present invention, the preceding step of producing the propylene polymer component (PP) is followed by the propylene-ethylene copolymer component. (E
It is composed of the latter step of producing P), and in each step, either the bulk polymerization method or the gas phase polymerization method can be adopted. However, in the latter step, since EP to be produced is a rubber component and it is desirable that it is not eluted in a solvent,
A gas phase polymerization method is preferably adopted. Further, as the polymerization method, either a batch method or a continuous method can be adopted for both the first step and the second step. In the present invention, a two-stage polymerization consisting of a former stage and a latter stage is usually carried out, but in some cases, each stage can be further divided. In particular, a method of making various kinds of rubber components by dividing the latter step into two or more steps is also one of the physical property improving methods.

Method for Producing Propylene Polymer Component (PP) PP is produced in the preceding polymerization step. Homopolymerization of propylene using a metallocene catalyst, preferably a catalyst comprising components (A) to (C) described above, or propylene /
Copolymerization of α-olefin. That is, a propylene homopolymer or a copolymer of propylene and an α-olefin is provided in a single stage or multiple stages in an amount of 50 to 95% by weight, preferably 60 to 92% by weight, based on the total polymerization amount (whole propylene block copolymer). This is a step of forming so as to correspond to. The amount of α-olefin used is 0.5% by weight or less based on all monomers (the total of propylene and α-olefin). In the present invention, the α-olefin is
It is a concept of olefin including ethylene and other than propylene. As PP, a propylene homopolymer is preferable, but in the case of producing a copolymer with α-olefin, α
-Ethylene is most preferred as the olefin.

One of the characteristics of the block copolymer of the present invention is that PP has a high melting point as shown in the requirement (6). In order to produce such a high melting point PP, the metallocene complex is selected, or the polymerization conditions capable of producing the high melting point PP, such as the polymerization temperature, the polymerization pressure, the selection of the cocatalyst, etc., are selected depending on the individual properties of the metallocene complex. Condition selection is required. The conditions to be taken differ depending on the individual complex, but generally higher polymerization pressure is preferred. Generally, the polymerization temperature is preferably lower. In such a case, the preferable conditions are, for example, a polymerization temperature of 30 to 120 ° C, preferably about 50 to 80 ° C. Polymerization pressure is 0.1-5M
Pa, preferably 0.1 to 3 MPa. Further, it is preferable to use a molecular weight adjusting agent so that the fluidity (MFR) of the final polymer becomes appropriate, and hydrogen is preferable as the molecular weight adjusting agent.

Propylene-ethylene copolymer component (E
P) Manufacturing Method In the latter polymerization step of the present invention, an ethylene / propylene copolymer having a content weight ratio of propylene and ethylene of 10/90 to 90/10 is produced. In this step, an amount corresponding to 5 to 50% by weight, preferably 8 to 40% by weight of the total amount of polymerization (whole propylene block copolymer) is formed. In this step, an active hydrogen-containing compound or an electron-donating compound such as a nitrogen-containing compound or an oxygen-containing compound may be present. The feature of the block copolymer of the present invention is that EP is
It means that the polymer is uniformly and randomly polymerized (the composition distribution is uniform), but in order to produce such a polymer, the following means can be used.

(1) In the process of producing a propylene-ethylene copolymer, the fluctuation of the composition of the polymerization gas over time should be made as small as possible, and the supply gas composition (monomer / comonomer ratio) should be kept constant. Generally, when an EP is to be produced, it is necessary to supplement the raw material monomer or comonomer corresponding to the amount of propylene and ethylene consumed with the progress of polymerization to maintain the same composition as the initial raw material composition. is there. When manufacturing an EP having a uniform composition distribution, it is important to maintain the composition of the raw material gas to be fed with high accuracy. The raw material composition can be maintained by monitoring using a gas chromatograph (GC).

In particular, when a metallocene catalyst capable of producing PP having a high melting point is used, the propylene monomer has high polymerizability, so that when propylene-ethylene copolymerization is carried out, propylene is more preferable than ethylene in the mixed gas composition. However, if the result of monitoring is not fed back to the operation of replenishing the raw material promptly, the polymerization is carried out while the raw material composition deviates from the desired value. For example, when the composition ratio of ethylene becomes temporarily excessive, a polymer having a high ethylene content is produced. In such cases,
This time, the polymer production will be continued with the raw material composition such that the ethylene content will be reduced, and the desired ethylene content will be adjusted in the final product. By suppressing such fluctuations as much as possible, conventional metallocene catalysts and Ziegler
It is possible to secure physical properties better than those of the block copolymer obtained with the Natta (ZN) catalyst system. Further, according to the conventional technical common sense, the raw materials are replenished at the same value as the initial raw material composition on the assumption that the consumption balance due to the polymerization of propylene and ethylene is constant without strictly monitoring by GC or the like.

However, in the present invention, when the polymerization enters a steady state, the initial raw material composition which is generally regarded as the conventional technique is not maintained but the raw material having the same value as the propylene / ethylene content ratio of the EP to be produced is used. By maintaining the composition, the consumption and supply of the raw materials by the catalyst can be well balanced, and the consumption and replenishment of ethylene and propylene can be performed without excess or deficiency, resulting in extremely small fluctuations in the composition distribution, which cannot be achieved with conventional products. It is possible to obtain a block copolymer having physical properties not found. The inventors of the present invention were affected by the history of fluctuations in the raw material composition, and as a result, the composition distribution became non-uniform, resulting in a decrease in the effect of adding rubber that improves impact resistance, and the material physical properties such as rigidity, impact resistance, and luster. It is the fact that it was causing a loss. Another method is to monitor the raw material composition on a feed basis without returning the unreacted raw material used for the polymerization to the reactor again. For example, it is also effective to eliminate the fluctuation of the composition of the polymerization gas by flowing a polymerization gas of a monomer mixture gas of a constant composition in an amount of 10 to 1000 times the production amount of EP, that is, the amount of the consumed monomer.

(2) Use of a metallocene catalyst having a high copolymerizability. By using a specific metallocene catalyst in addition to keeping the raw material composition constant, the randomness of EP can be further enhanced, and the block copolymer of the present subject matter can be produced. What is a specific metallocene catalyst?
A specific metallocene complex described as preferable in the above is combined with an ion-exchange layered salt.

The propylene block copolymer of the present invention thus obtained is, if necessary, an antioxidant, an ultraviolet absorber, an antistatic agent, a nucleating agent, a lubricant, a flame retardant, an antiblocking agent, a coloring agent, After blending various additives such as inorganic or organic fillers, and further various synthetic resins, it is possible to heat-melt and knead using a melt-kneading machine, and then use it as pellets cut into granules as a molding material. is there. These pellet-shaped molding materials are molded by various known polypropylene molding methods, for example, injection molding, extrusion molding, foam molding, blow molding and other techniques, and various industrial injection molded parts, various containers, unstretched films. It is possible to produce various molded products such as uniaxially stretched film, biaxially stretched film, sheet, pipe and fiber. As the physical properties of the molded product, the flexural modulus is 920 MPa or more, preferably 940.
It is possible to easily manufacture a product having a MPa or more and a deflection temperature under load of 109 ° C. or more, preferably 110 ° C. or more.

[0062]

EXAMPLES The following examples serve to explain the present invention more specifically. The present invention is not limited by these examples without departing from the gist thereof. The following catalyst synthesis step and polymerization step were all performed under a purified nitrogen atmosphere. The solvent used was dehydrated with Molecular Sieve MS-4A. Below, the measuring method and apparatus of each physical-property value in this invention are shown.

(1) MFR device Melt indexer measuring method manufactured by Takara Co., Ltd. JIS-K7210 (230 ° C., 2.16 k)
g load). (2) Content of propylene in the portion insoluble in ODCB at 100 ° C It was determined from the infrared absorption spectrum of the component insoluble in ODCB at 100 ° C, which was recovered according to the method described above. (3) The ethylene content (G) of EP, the ethylene content (E) of the amorphous portion in EP, and the EP content of the whole propylene-based block copolymer were measured according to the methods described above.

(4) Melting point Using a DSC7 type differential scanning calorimeter manufactured by Perkin-Elmer Co., the sample was heated from room temperature to 80 ° C./min at 230 ° C.
Up to 50 ° C. at −10 ° C./min and held at the same temperature for 3 min.
The peak temperature at the time of melting under the temperature rising condition of 10 ° C./min was defined as the melting point. (5) Flexural Modulus (FM) (Unit: MPa) Measured at 23 ° C. according to JIS-K7203. The dimensions of the molded product used were 90 × 10 × 4 mm. (6) IZOD impact strength (Unit: kJ
/ M < ² >) It measured at -30 degreeC based on JIS-K7110.

(7) Deflection temperature under load (unit: ° C) According to JIS-K7207, 4.6 kgf / cm ²
It was measured under the conditions. However, in order to adjust the condition of the test piece before measurement, after molding, an operation of annealing at 100 ° C. for 30 minutes and cooling to room temperature is performed. (8) Gloss (unit:%) Measured at 23 ° C. according to JIS-K7105.

<Example 1> [Complex synthesis] Synthesis of dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (2-fluoro-4-biphenyl) -4H-azulenyl]} hafnium: (a ) Synthesis of racemic / meso mixture; 2-fluoro-4-
Bromobiphenyl (4.63 g, 18.5 mmol) was added to diethyl ether (40 mL) and hexane (40 mL).
Was dissolved in the mixed solvent of, and a pentane solution of t-butyllithium (22.8 mL, 36.9 mmol, 1.62 N) was added dropwise at -78 ° C, and the mixture was stirred at -5 ° C for 2 hours. 2-Ethylazulene (2.36 g, 16.6 mmo) was added to this solution.
1) was added and the mixture was stirred at room temperature for 1.5 hours. After cooling to 0 ° C., tetrahydrofuran (40 mL) was added. N-Methylimidazole (40 μL) and dimethyldichlorosilane (1.0 mL, 8.30 mmol) were added, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 1 hour. After this, add dilute hydrochloric acid,
After liquid separation, the organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to give dimethylsilylenebis (2-ethyl-4- (2-fluoro-4-biphenylyl) -1,4-
A crude product of dihydroazulene (6.3 g) was obtained.

Next, the crude product obtained above was dissolved in diethyl ether (23 mL), and a solution of n-butyllithium in hexane was prepared at -78 ° C. (10.3 mL, 16.6 mm).
ol, 1.56 mol / L) was added dropwise, the temperature was gradually raised, and the mixture was stirred at room temperature for 2 hours. In addition, toluene (185m
L) was added, the mixture was cooled to −78 ° C., hafnium tetrachloride (2.65 g, 8.3 mmol) was added, the temperature was gradually raised, and the mixture was stirred overnight at room temperature. Most of the solvent was distilled off from the obtained slurry solution under reduced pressure, and after filtration, toluene (4 m
L), hexane (9 mL), ethanol (20 mL),
Wash with hexane (10 mL) and dichloro {1,
1'-Dimethylsilylenebis [2-ethyl-4- (2-
Fluoro-4-biphenylyl) -4H-azulenyl]}
Racemic meso mixture of hafnium (1.22 g, yield 1
6%) was obtained.

(B) Purification of racemic body: The crudely purified product (1.1 g) of the racemic / meso mixture obtained above was suspended in dichloromethane (30 mL) and irradiated with 30 spectra using a high pressure mercury lamp (100 W). . The solvent of this solution was distilled off under reduced pressure. Dichloromethane (40 mL) was added to the obtained solid to suspend it, and the suspension was filtered. Wash with hexane (3 mL),
When dried under reduced pressure, the racemic purified product (577 mg, 52
%)was gotten. 1 H-NMR (300 MHz, CDCl ₃ ) δ1.02
(S, 6H, SiMe ₂ ), 1.08 (t, J = 8H
z, 6H, CH ₃ CH ₂ ), 2.54 (sept, J = 8)
Hz, 2H, CH ₃ CH ₂ ), 2.70 (sept, J =
_{8Hz, 2H, CH 3 CH 2} ), 5.07 (brs, 2
H, 4-H), 5.85-6.10 (m, 8H), 6.
83 (d, J = 12 Hz, 2H), 7.30-7.6.
(M, 16H, arom).

[Chemical treatment of ion-exchange layered silicate] 500 g of ion-exchanged water was put into a 5 L separable flask equipped with a stirring blade and a reflux device, and further 249 g (5.93 mol) of lithium hydroxide monohydrate. Was charged and stirred. Separately, 581 g (5.93 mol) of sulfuric acid was diluted with 500 g of ion-exchanged water and added dropwise to the lithium hydroxide aqueous solution using a dropping funnel. Next, 350 g of commercially available granulated montmorillonite (Ben clay SL, manufactured by Mizusawa Chemical Co., Ltd., average particle size: 28.0 μm) is added, and the mixture is stirred. Then, the temperature is raised to 108 ° C. over 30 minutes and heat treatment is performed for 150 minutes. After the treatment, it was cooled to 50 ° C. over 1 hour. This slurry was subjected to vacuum filtration with a device in which an aspirator was connected to a nutsche and a suction bottle. The cake was recovered, 5.0 L of pure water was added to re-slurry, and filtration was performed. This operation was repeated 4 more times. The filtration was completed within a few minutes. P of the final washing solution (filtrate)
H was 5. Collected cake under nitrogen atmosphere 11
Dry overnight at 0 ° C. As a result, 275 g of a chemically treated product was obtained. When the compositional analysis was performed by fluorescent X-ray, the molar ratio of the constituent elements to the main component, silicon, was found to be Al / S.
i = 0.21, Mg / Si = 0.046, Fe / Si =
It was 0.022.

[Catalyst Preparation / Preliminary Polymerization]
It was carried out using a solvent and a monomer that had been deoxidized and dehydrated under an inert gas. The chemically treated ion-exchange layered silicate granules produced above were dried under reduced pressure at 200 ° C. for 4 hours. 200 g of the chemically treated montmorillonite obtained above was introduced into an autoclave having an internal volume of 10 L, 1160 mL of heptane, and 840 mL (0.5 m) of a heptane solution of triethylaluminum (0.6 mmol / mL).
was added over 30 minutes, and the mixture was stirred at 25 ° C. for 1 hour. The slurry is then allowed to settle and the supernatant 1300
After extracting mL, the mixture was washed twice with 2600 mL of heptane, and heptane was added so that the total amount of heptane finally became 1200 mL. Next, in a 2 L flask, 5.93 g (6 mol) of dimethylsilylene bis (2-ethyl-4- (2-fluoro-4-biphenyl) -4H-azulenyl) hafnium dichloride and 516 m of heptane were added.
After adding L and stirring well, 84 mL of a heptane solution of triisobutylaluminum (140 mg / mL)
(11.8 g) was added at room temperature, and the mixture was stirred for 60 minutes. Then, the above solution was introduced into the montmorillonite slurry prepared in the autoclave previously, stirred for 60 minutes, and heptane was further introduced until the total volume became 5 L, and kept at 30 ° C. Propylene there at a constant speed of 100 g / hr, 4
It was introduced at 0 ° C for 4 hours and then maintained at 50 ° C for 2 hours. The prepolymerized catalyst slurry was collected with a siphon, the supernatant was removed, and then dried at 40 ° C. under reduced pressure. By this operation, a prepolymerized catalyst containing 2.0 g of polypropylene per 1 g of the catalyst was obtained.

[Polymerization / Production of propylene block copolymer] 400 mg of triisobutylaluminum and 150 Nm of hydrogen were placed in a well-dried autoclave equipped with a 3 L stirring blade.
After introducing L and 750 g of propylene, the temperature in the polymerization tank was maintained at 65 ° C., and 55 mg of the prepolymerized catalyst obtained above in terms of a solid catalyst component was press-fitted to start bulk polymerization of propylene (first stage polymerization). During the polymerization, the temperature was kept at 65 ° C., and hydrogen was continuously introduced at a rate of 250 NmL / hr so that the hydrogen concentration in the gas phase part in the polymerization system became constant. After 1 hour, unreacted monomer was purged and then replaced with nitrogen gas. Furthermore, propylene and ethylene were continuously introduced so that the mole fraction of ethylene was 60 mol% and the mixed gas was introduced until the total pressure of the polymerization tank was 1.8 MPa, and the gas phase of the propylene-ethylene copolymer component (EP) was increased. Polymerization was started (second-stage polymerization). During the polymerization, by introducing a propylene / ethylene mixed gas having a composition of 35 mol% of ethylene so as to be equal to the composition of ethylene in the EP produced, the composition of the mixed gas in the polymerization tank was 60 mol in terms of the mole fraction of ethylene. Kept%. During the polymerization, the temperature inside the tank was maintained at 65 ° C., and the mixed gas was introduced so that the total pressure was maintained at 1.8 MPa. After 45 minutes, the unreacted monomer was purged, the autoclave was opened, and the reacted polymer was recovered.

IRGANOX was added as a compounding component to the obtained powdery propylene block copolymer.
1010 (manufactured by Ciba Specialty Chemicals)
0.10% by weight, IRGAFOS 168 (manufactured by Ciba Specialty Chemicals) 0.10% by weight, and 0.05% by weight of calcium stearate are mixed, kneaded and granulated by a single-screw extruder, and pelletized propylene. A system block copolymer was obtained. The obtained block copolymer pellet was introduced into an injection molding machine heated at a mold temperature of 40 ° C. and a cylinder temperature of 220 ° C., and a test piece was molded by injection molding.
The bending modulus, IZOD impact strength, gloss and deflection temperature under load of the obtained injection-molded piece were measured by the methods described above. The powders obtained in the following examples were also treated in the same manner, and the physical properties were measured in the same manner.

Example 2 In the post-stage polymerization for producing the EP of Example 1, the composition of the mixed gas introduced at the start of the polymerization was 70 mol% of ethylene, and ethylene was 50 mo during the polymerization.
Polymerization was performed in the same manner as in Example 1 except that 1% of a mixed gas was introduced.

<Comparative Example 1> In a 3 L-round bottom four-necked flask equipped with a vacuum stirrer and a thermometer, Mg (OE
t) ₂ : 2.0 mol was charged, and then Ti (OBu) ₄
Was charged so that Ti (OBu) ₄ /Mg=0.6 (molar ratio) to magnesium in the charged Mg (OEt) ₂ , and the temperature was raised while stirring at 200 rpm.
After reacting at 150 ° C. for 2.0 hours, the temperature was lowered to 120 ° C., and a toluene solution of Si (OPh) ₄ was charged into Mg.
For magnesium in (OEt) ₂ , Si (OP
h) It was added so that _{4 /} Mg = 0.5 (molar ratio). After the addition was completed, the reaction was carried out at the same temperature for 1.0 hour. After the reaction was completed, the temperature was lowered to room temperature, and Si (OEt) ₄ was added to Mg in the charged Mg (OEt) _{2 to} obtain Si.
(OEt) ₄ / Mg was added in an amount of 0.2 (molar ratio) to obtain a slurry of Ti / Mg contact product.

The entire amount of the slurry obtained here is cooled and cooled.
Induction stirring type 10L-autoc with heating jacket
[Mg] = 0.486 mol / L after transfer to the reeve
Diluted with toluene to give toluene. This
Cool the rally to -10 ° C with stirring at 300 rpm.
However, Mg (OEt) charged with diethyl phthalate ₂
Diethyl phthalate / Mg =
0.1 (molar ratio) was added. Continue to T
iCl_FourWas charged with Mg (OEt)₂Magnesium inside
Against TiCl_Four/Mg=4.0 (molar ratio)
Thus, the solution was added dropwise over 1.0 hour to obtain a uniform solution. This
At the time of, the phenomenon that the viscosity of the liquid rises and becomes a gel,
It didn't happen.

The obtained homogeneous solution was heated at 15 ° C. at 0.5 ° C./minute.
The temperature was raised to and held at the same temperature for 1 hour. Then, the temperature was again raised to 50 ° C. at 0.5 ° C./minute, and the temperature was maintained at 50 ° C. for 1 hour. Furthermore, the temperature was raised to 117 ° C. at 1.0 ° C./minute, and the treatment was performed at the same temperature for 1 hour. After completion of the treatment, heating / stirring was stopped, the supernatant liquid was removed, and the residual liquid ratio =
It was washed so as to be 1/50 to obtain a solid slurry. Next, the amount of toluene in the obtained solid slurry is changed to TiCl ₄
The concentration was adjusted to 2.0 mol / L · toluene, and Mg (OE) was initially charged with TiCl ₄ at room temperature.
t) ₂ with respect to magnesium in TiCl ₄ / Mg =
It was added so as to be 5.0 (molar ratio). The temperature of this slurry was raised with stirring at 300 rpm, and at 117 ° C.,
The reaction was carried out for 1 hour.

After completion of the reaction, heating / stirring was stopped, the supernatant liquid was removed, and the residue was washed with toluene so that the residual liquid ratio was 1/150 to obtain a toluene slurry of a solid catalyst component. The total amount of the solid slurry obtained here was adjusted to an inner diameter of 66
It was transferred to a reaction tank having a three-way receding blade of 0 mm and a straight body portion of 770 mm, and diluted with n-hexane so that the concentration of the solid catalyst component became 3 g / L. 3 of this slurry
Triethylaluminum was mixed with triethylaluminum / solid catalyst component = 25 ° C. while stirring at 00 rpm.
3.44 mmol / g, and then t
-Butylethyldimethoxysilane, t-butylethyldimethoxysilane / solid catalyst component = 1.44 mmol
/ G. After the addition was completed, the mixture was kept at 25 ° C. for 30 minutes while being continuously stirred.

Then, propylene gas was fed into the liquid phase at a constant rate over 72 minutes. After stopping the feed of propylene gas, washing with n-hexane was performed by a sedimentation washing method to obtain a prepolymerized catalyst slurry with the residual liquid ratio = 1/12. The obtained prepolymerized catalyst contained 2.7 g of propylene polymer per 1 g of the solid catalyst component. After introducing 550 mg of triethylaluminum, 3000 NmL of hydrogen and 750 g of propylene into a well-dried autoclave with a 3 L stirring blade, the temperature in the polymerization tank was kept at 70 ° C,
The prepolymerized catalyst obtained above was converted into a solid catalyst component in an amount of 10
mg was injected under pressure to start bulk polymerization of propylene. The temperature was kept at 70 ° C. during the polymerization. After 1 hour, unreacted monomer was purged and subsequently replaced with nitrogen gas. Further, subsequently, a mixed gas of propylene and ethylene was introduced so that the mole fraction of ethylene was 20 mol% and the total pressure of the polymerization tank was 1.8 MPa, and the gas phase polymerization of EP was started. During the polymerization, by introducing a propylene / ethylene mixed gas having a composition of 30 mol% of ethylene so as to be equal to the composition of ethylene in the EP produced, the mixed gas composition in the polymerization tank becomes 2 in terms of ethylene mole fraction.
0 mol% was kept. The temperature in the tank during polymerization is 75 ° C.
And the mixed gas was introduced so that the total pressure was maintained at 1.8 MPa. After 45 minutes, unreacted monomers were purged, the autoclave was opened, and the reacted polymer was recovered. IRGANOX 1010 (manufactured by Ciba Specialty Chemicals) 0.10 wt% IRGAFOS containing these propylene block copolymers and blending components
168 (manufactured by Ciba Specialty Chemicals) 0.
10 wt% and calcium stearate of 0.05 wt% were blended, and kneaded and granulated by a single-screw extruder to obtain a pellet-shaped resin block copolymer. The block copolymer pellets obtained were introduced into an injection molding machine heated at a mold temperature of 40 ° C. and a cylinder temperature of 220 ° C.,
A test piece was molded by injection molding. The bending modulus, IZOD impact strength, gloss and deflection temperature under load of the obtained injection-molded piece were measured by the methods described above.

<Comparative Example 2> 550 mg of triethylaluminum was added to a well-dried autoclave equipped with a 3 L stirring blade.
After introducing 3000 NmL of hydrogen and 750 g of propylene, the internal temperature of the polymerization tank was kept at 70 ° C., and 10 mg of the prepolymerized catalyst obtained in Comparative Example 1 was converted into a solid catalyst component, and bulk polymerization of propylene was started. The temperature was kept at 70 ° C. during the polymerization. After 1 hour, unreacted monomer was purged and subsequently replaced with nitrogen gas. Furthermore, propylene and ethylene are continuously added so that the ethylene mole fraction is 2
5 mol% and the total pressure of the polymerization tank is 1.8MP
The mixed gas was introduced so as to be a, and the gas phase polymerization of EP was started. During the polymerization, by introducing a propylene / ethylene mixed gas having a composition of 45 mol% of ethylene so as to be equal to the composition of ethylene in the EP produced, the composition of the mixed gas in the polymerization tank is 25 mol% in terms of the mole fraction of ethylene.
Kept. Further, the temperature in the tank during the polymerization was kept at 75 ° C., and the mixed gas was introduced so that the total pressure was kept at 1.8 MPa. After 45 minutes, the unreacted monomer was purged, the autoclave was opened, and the reacted polymer was recovered.

Comparative Example 3 [Synthesis of Complex] (r) -Dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride was synthesized according to the method described in the document of Organometallics 13,964 (1994). did. [Synthesis of catalyst] A glass reactor equipped with a stirring blade having an internal volume of 0.5 L was charged with MAOON SiO ₂ manufactured by WITCO.
2.4 g (20.7 mmol-Al) was added, 50 mL of n-heptane was introduced, and (r) -dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride solution was diluted with toluene in advance.
0 mL (0.0637 mmol) was added, and then 4.14 mL (3.03 mmol) of triisobutylaluminum (TIBA) / n-heptane solution was added. After reacting at room temperature for 2 hours, propylene was allowed to flow and prepolymerization was carried out. By this operation, a prepolymerized catalyst containing 1.3 g of polypropylene per 1 g of the catalyst was obtained. [Polymerization] Instead of the catalyst used in Example 1, the prepolymerized catalyst synthesized above was converted to 100 in terms of solid catalyst component.
Polymerization was performed in the same manner as in Example 1 except that the amount of the mixed gas introduced was 3 mg and the composition of the mixed gas introduced at the start of the polymerization in EP polymerization was 30 mol% of ethylene, and the mixed gas of 30 mol% of ethylene was also introduced during the polymerization.

<Comparative Example 4> In the former step (propylene bulk polymerization) of Example 2, 4.75 g of ethylene (corresponding to 0.63% by weight in the raw material composition) was introduced, except that the copolymerization was performed. Was polymerized in the same manner as in Example 2.

Comparative Example 5 A PP block copolymer (trade name: Novatec PP BC7) manufactured by Nippon Polychem Co., Ltd., which is a commercial product and manufactured by a Ziegler-Natta catalyst, was used.

Comparative Example 6 550 mg of triethylaluminum was added to a well-dried autoclave equipped with a 3 L stirring blade.
After introducing 3000 NmL of hydrogen and 750 g of propylene, the internal temperature of the polymerization tank was kept at 70 ° C., and 10 mg of the prepolymerized catalyst obtained in Comparative Example 1 was converted into a solid catalyst component, and bulk polymerization of propylene was started. The temperature was kept at 70 ° C. during the polymerization. After 1 hour, unreacted monomer was purged and subsequently replaced with nitrogen gas. Further, propylene and ethylene are continuously added, and the ethylene mole fraction is 3
0 mol% and the total pressure of the polymerization tank is 1.8MP
The mixed gas was introduced so as to be a, and the gas phase polymerization of EP was started. During the polymerization, by introducing a propylene / ethylene mixed gas having a composition of 55 mol% of ethylene so as to be equal to the composition of ethylene in the EP produced, the composition of the mixed gas in the polymerization tank is 30 mol% in terms of ethylene mole fraction.
Kept. Further, the temperature in the tank during the polymerization was kept at 75 ° C., and the mixed gas was introduced so that the total pressure was kept at 1.8 MPa. After 30 minutes, the unreacted monomer was purged, the autoclave was opened, and the reacted polymer was recovered.

<Example 3> 400 ml of triisobutylaluminum was placed in a well-dried autoclave equipped with a 3 L stirring blade.
After introducing 50 g of hydrogen, 60 NmL of hydrogen and 750 g of propylene, the temperature in the polymerization tank was maintained at 65 ° C., and 55 mg of the prepolymerization catalyst obtained in Example 1 in terms of a solid catalyst component was injected under pressure to start bulk polymerization of propylene. During the polymerization, the temperature is 65
C., and hydrogen was continuously introduced at a rate of 100 NmL / hr so that the hydrogen concentration in the gas phase part in the polymerization system was constant. After 1 hour, unreacted monomer was purged,
Then, the atmosphere was replaced with nitrogen gas. Further, subsequently, a mixed gas of propylene and ethylene was introduced so that the mole fraction of ethylene was 85 mol% and the total pressure of the polymerization tank was 1.8 MPa to start the gas phase polymerization of EP. During the polymerization, by introducing a mixed gas having a composition of 70 mol% of ethylene so as to be equal to the composition of ethylene in the EP produced, the composition of the mixed gas in the polymerization tank becomes 85 mol% in terms of the ethylene mole fraction. I kept it. During the polymerization, the temperature in the tank was 6
The mixed gas was introduced so as to maintain the temperature at 5 ° C. and the total pressure at 1.8 MPa. After 45 minutes, the unreacted monomer was purged, the autoclave was opened, and the reacted polymer was recovered.

<Example 4> 400 ml of triisobutylaluminum was placed in a well-dried autoclave equipped with a 3 L stirring blade.
After introducing g, 300 NmL of hydrogen and 750 g of propylene, the internal temperature of the polymerization tank was maintained at 65 ° C., and 55 mg of the prepolymerization catalyst obtained in Example 1 in terms of solid catalyst component was injected under pressure to start bulk polymerization of propylene. During the polymerization, the temperature is 65
C., and hydrogen was continuously introduced at a rate of 300 NmL / hr so that the hydrogen concentration in the gas phase part in the polymerization system was constant. After 1 hour, unreacted monomer was purged,
Then, the atmosphere was replaced with nitrogen gas. Further, subsequently, a mixed gas of propylene and ethylene was introduced so that the mole fraction of ethylene was 95 mol% and the total pressure of the polymerization tank was 1.8 MPa, and the gas phase polymerization of EP was started. During the polymerization, by introducing a mixed gas having a composition of 90 mol% of ethylene so as to be equal to the composition of ethylene in the produced EP, the mixed gas composition in the polymerization tank was adjusted to 95 mol% in terms of the ethylene mole fraction. I kept it. During the polymerization, the temperature in the tank was 6
The mixed gas was introduced so as to maintain the temperature at 5 ° C. and the total pressure at 1.8 MPa. After 45 minutes, the unreacted monomer was purged, the autoclave was opened, and the reacted polymer was recovered.

Example 5 A well-dried autoclave with a 3 L stirring blade was charged with 400 m of triisobutylaluminum.
After introducing 90 g of hydrogen, 90 NmL of hydrogen, and 750 g of propylene, the internal temperature of the polymerization tank was maintained at 65 ° C., and 55 mg of the prepolymerization catalyst obtained in Example 1 in terms of a solid catalyst component was injected under pressure to start bulk polymerization of propylene. During the polymerization, the temperature is 65
C., and hydrogen was continuously introduced at a rate of 100 NmL / hr so that the hydrogen concentration in the gas phase part in the polymerization system was constant. After 1 hour, unreacted monomer was purged,
Then, the atmosphere was replaced with nitrogen gas. Further, subsequently, a mixed gas of propylene and ethylene was introduced so that the mole fraction of ethylene was 45 mol% and the total pressure of the polymerization tank was 1.8 MPa, and the gas phase polymerization of EP was started. During the polymerization, by introducing a mixed gas having a composition of 20 mol% of ethylene so as to be equal to the composition of ethylene in the EP produced, the composition of the mixed gas in the polymerization tank becomes 45 mol% in terms of the ethylene mole fraction. I kept it. During the polymerization, the temperature in the tank was 6
The mixed gas was introduced so as to maintain the temperature at 5 ° C. and the total pressure at 1.8 MPa. After 20 minutes, the unreacted monomer was purged, the autoclave was opened, and the reacted polymer was recovered.

<Example 6> 400 ml of triisobutylaluminum was placed in a well-dried autoclave equipped with a 3 L stirring blade.
After introducing g, 100 NmL of hydrogen, and 750 g of propylene, the temperature in the polymerization tank was kept at 65 ° C., and 55 mg of the prepolymerization catalyst obtained in Example 1 in terms of a solid catalyst component was injected under pressure to start bulk polymerization of propylene. During the polymerization, the temperature is 65
C., and hydrogen was continuously introduced at a rate of 100 NmL / hr so that the hydrogen concentration in the gas phase part in the polymerization system was constant. After 1 hour, unreacted monomer was purged,
Then, the atmosphere was replaced with nitrogen gas. Further, subsequently, a mixed gas of propylene and ethylene was introduced so that the mole fraction of ethylene was 55 mol% and the total pressure of the polymerization tank was 1.8 MPa, and the gas phase polymerization of EP was started. During the polymerization, by introducing a mixed gas having a composition of 30 mol% of ethylene so as to be equal to the composition of ethylene in the produced EP, the composition of the mixed gas in the polymerization tank has a molar fraction of ethylene of 55 mol%. I kept it. During the polymerization, the temperature in the tank was 6
The mixed gas was introduced so as to maintain the temperature at 5 ° C. and the total pressure at 1.8 MPa. After 80 minutes, the unreacted monomer was purged, the autoclave was opened, and the reacted polymer was recovered.

[0088] As shown in <Embodiment 7> FIG. 3, during the stirred gas-phase polymerization vessel 11 of a stirring device with liquid phase polymerization vessel 1,0.5M ³ having an inner volume of 0.4 m ^3, sedimentation liquid By a process incorporating a classification system consisting of a power classifier 3, a concentrator 4 (hydrocyclone), and a countercurrent pump 5 and a degassing system consisting of a double-tube heat exchanger 8 and a fluidized-flush tank 7, propylene is produced. -Continuous production of ethylene block copolymer was carried out. In the liquid phase polymerization tank 1, liquefied propylene,
Hydrogen and triisobutylaluminum (TIBA) were continuously fed. The feed amounts of liquefied propylene and TIBA were 90 kg / hr and 21.2 g, respectively.
/ Hr, and hydrogen was fed so that the molar concentration was 300 ppm. Further, the prepolymerized catalyst obtained in Example 1 was fed so as to have a solid catalyst component conversion of 2.21 g / hr. Further, the polymerization tank 1 was cooled so that the polymerization temperature was 65 ° C.

The slurry polymerized in the polymerization tank 1 is supplied to the liquid force classifier 3 by using the slurry pump 2 at about 12 m ³ / hr.
Was fed at a volume flow rate of. From the lower part of the hydraulic classifier 3, a slurry containing a relatively large amount of large-sized particles is extracted,
The remaining slurry is transferred from the upper part of the hydraulic classifier 3 to the concentrator 4
Supplied to. From the upper part of the concentrator 4, a supernatant liquid containing almost no solid particles was taken out, and this was supplied to the lower part of the liquid force classifier as a countercurrent by using a pump 5. On the other hand, the slurry containing a relatively large amount of small-sized particles extracted from the lower portion of the concentrator 4 was circulated in the liquid phase polymerization tank 1. Liquid classifier 3
The extraction rate of the slurry extracted from the lower part of the slurry is about 1 as polypropylene particles contained in the slurry.
It was 7.4 kg / hr. The average residence time of the polypropylene particles in the liquid phase polymerization tank 1 and the circulation line was 1.25 hours.

The polypropylene particles have an average particle diameter (Dp ₅₀ ) of 564 μm and an average catalyst efficiency (CE) of 79.
00 g / g and MFR were 59.5 g / 10 minutes. CE is defined as the polypropylene yield (g) per 1 g of the solid component contained in the solid catalyst component (A). The slurry withdrawn from the lower part of the liquid force classifier 3 was fed to the fluidized flash tank 7 via the double-tube heat exchanger 8 in the wake. In the fluidized flash tank 7, the temperature inside the tank was maintained at 65 ° C. while feeding the propylene gas heated from the lower part. The solid polypropylene particles obtained here are sent to the gas phase polymerization tank 11,
Copolymerization of propylene and ethylene (EP polymerization) was performed.

In order to enhance the mixing effect, a mixed gas of ethylene, propylene and hydrogen was circulated by the gas blower 9 in the gas phase polymerization tank 11 additionally provided with a stirring blade. Ethylene and propylene were fed such that the sum of the partial pressures of ethylene and propylene was 1.4 MPaG and the mole fraction of ethylene was constant at 60 mol%. Replacement system 1 for the solid polypropylene particles obtained here
Sent to 0. In the substitution system 10, after receiving a certain amount of polymer and monomer gas, the gas was purged to 0 MPaG, and after further increasing to 1.9 MPaG with nitrogen,
The polymer was sent to the gas phase polymerization tank 11. In addition, the hydrogen concentration in the gas phase is 30 pp, including hydrogen generated by polymerization.
A purge gas amount was set so as to maintain m, and propylene and ethylene were fed so that the above-mentioned polymerization pressure gas composition was obtained. Further, ethanol was fed as an active hydrogen compound. The feed amount of ethanol was adjusted to a molar ratio of 0.46 with respect to aluminum in TIBA supplied together with the polymer particles supplied to the gas phase polymerization tank 11.

The polymerization temperature was 65 ° C., and the withdrawal rate of the propylene / ethylene block copolymer withdrawn from the gas phase polymerization tank 11 was adjusted to be about 20 kg / hr. The average residence time in the gas phase polymerization tank 11 is 1.5 hours.
It was r. When the polymer particles extracted from the gas-phase polymerization tank 11 were analyzed, the MFR was 32.0 g / 10 minutes, the bulk density (BD) was 0.488 g / cc, and the EP content was 1
It was 5.7% by weight. The average CE of the propylene / ethylene block copolymer was 9000 g / g. With respect to the obtained propylene-based block copolymer,
As a compounding ingredient, IRGANOX1010 (manufactured by Ciba Specialty Chemicals) 0.10% by weight, IRG
AFOS168 (Ciba Specialty Chemicals) 0.10% by weight, calcium stearate 0.05
The propylene-based block copolymer in pellet form was obtained by blending the mixture in an amount of wt% and kneading and granulating with a single-screw extruder. The obtained block copolymer pellet was introduced into an injection molding machine heated at a mold temperature of 40 ° C. and a cylinder temperature of 220 ° C., and a test piece was molded by injection molding. With respect to the obtained injection-molded piece, the flexural modulus, IZOD impact strength, and
The gloss and deflection temperature under load were measured.

<Example 8> In Example 7, ethylene was fed so that the mole fraction of ethylene in the gas phase polymerization tank 11 was constant at 70 mol%, and the feed amount of ethanol as an active hydrogen compound was changed to the gas phase. The molar ratio was set to 0.10 with respect to aluminum in TIBA supplied together with the polymer particles supplied to the polymerization tank 11. When the withdrawal rate of the propylene / ethylene block copolymer withdrawn from the gas phase polymerization tank 11 was adjusted to be about 20 kg / hr, the average residence time in the gas phase polymerization tank 11 was 2.3 hours. When the polymer particles extracted from the gas phase polymerization tank 11 were analyzed, the MFR was 25.
0g / 10 minutes, bulk density (BD) is 0.483g / c
The c and EP contents were 17.5% by weight. The average CE of the propylene / ethylene block copolymer is 95
It was 00 g / g.

Example 9 [Synthesis Synthesis] Synthesis of dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (3-chloro-4-tertbutyl-phenyl) -4H-azulenyl]} hafnium : (A) Synthesis of racemic / meso mixture; 3-chloro-4-t
ert butyl bromobenzene (4.58g, 18.5m
mol) was dissolved in a mixed solvent of diethyl ether (40 mL) and hexane (40 mL), and a solution of t-butyllithium in pentane (22.8 mL, 36.9 mmol,
1.62N) was added dropwise at -78 ° C, and the mixture was stirred at -5 ° C for 2 hours. 2-Ethylazulene (2.36 g, 1
6.6 mmol) was added and the mixture was stirred at room temperature for 1.5 hours. 0
After cooling to ℃, tetrahydrofuran (40 mL) was added.
N-Methylimidazole (40 μL) and dimethyldichlorosilane (1.0 mL, 8.30 mmol) were added, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 1 hour. After this, dilute hydrochloric acid was added, and after liquid separation, the organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to give dimethylsilylenebis (2-ethyl-4- (3-chloro-4-tertbutylphenyl)-. A crudely purified product of 1,4-dihydroazulene (6.1 g) was obtained.

Next, the crude product obtained above was dissolved in diethyl ether (23 mL), and a solution of n-butyllithium in hexane was prepared at -78 ° C. (10.3 mL, 16.6 mm).
ol, 1.56 mol / L) was added dropwise, the temperature was gradually raised, and the mixture was stirred at room temperature for 2 hours. In addition, toluene (185m
L) was added, the mixture was cooled to −78 ° C., hafnium tetrachloride (2.65 g, 8.3 mmol) was added, the temperature was gradually raised, and the mixture was stirred overnight at room temperature. Most of the solvent was distilled off from the obtained slurry solution under reduced pressure, and after filtration, toluene (4 m
L), hexane (9 mL), ethanol (20 mL),
Wash with hexane (10 mL) and dichloro {1,
1'-Dimethylsilylenebis [2-ethyl-4- (3-
Chloro-4-tertbutylphenyl) -4H-azurenyl]} hafnium racemic meso mixture (1.70)
g, yield 20%) was obtained.

(B) Purification of racemate: 1.5 g of the obtained mixture was dissolved in 75 mL of dichloromethane and irradiated with 30 spectra by using a high pressure mercury lamp (100 w). The solvent was distilled off from this solution under reduced pressure, washing with hexane was repeated, washing with ether was performed, and drying was performed.
(4-tert-butyl-3-chlorophenylyl) -4H
0.27 g of racemic form of -azulenyl]} hafnium was obtained. ¹ H-NMR (CDCl ₃ ) δ 1.00 (s, 6H, Si
Me ₂ ), 1.05 (t, J = 5.6 Hz, 6H, 2-
CH ₂ CH ₃ ), 1.47 (s, 18H, tBu), 2.
4-2.5 (m, 2H, 2- CH 2 CH 3), 2.6-
2.7 (m, 2H, 2- CH 2 CH 3), 4.99 (d,
J = 3.0 Hz, 2H, 4-H), 5.8-6.1.
(M, 6H), 6.78 (d, J = 11.7Hz, 2
H), 7.2-7.6 (m, 12H)

[Chemical treatment of ion-exchange layered silicate] 500 g of ion-exchanged water was put into a 5 L separable flask equipped with a stirring blade and a reflux device, and further 249 g (5.93 mol) of lithium hydroxide monohydrate. Was charged and stirred. Separately, 581 g (5.93 mol) of sulfuric acid was diluted with 500 g of ion-exchanged water and added dropwise to the lithium hydroxide aqueous solution using a dropping funnel. Next, 350 g of commercially available granulated montmorillonite (Ben clay SL, manufactured by Mizusawa Chemical Co., Ltd., average particle size: 28.0 μm) is added, and the mixture is stirred. Then, the temperature is raised to 108 ° C. over 30 minutes and heat treatment is performed for 150 minutes. After the treatment, it was cooled to 50 ° C. over 1 hour. This slurry was subjected to vacuum filtration with a device in which an aspirator was connected to a nutsche and a suction bottle. The cake was recovered, 5.0 L of pure water was added to re-slurry, and filtration was performed. This operation was repeated 4 more times. The filtration was completed within a few minutes. P of the final washing solution (filtrate)
H was 5. Collected cake under nitrogen atmosphere 11
Dry overnight at 0 ° C. As a result, 275 g of a chemically treated product was obtained. When the compositional analysis was performed by fluorescent X-ray, the molar ratio of the constituent elements to the main component, silicon, was found to be Al / S.
i = 0.21, Mg / Si = 0.046, Fe / Si =
It was 0.022.

[Catalyst Preparation / Preliminary Polymerization]
It was carried out using a solvent and a monomer that had been deoxidized and dehydrated under an inert gas. The chemically treated ion-exchange layered silicate granules produced above were dried under reduced pressure at 200 ° C. for 4 hours. 10 g of the chemically treated montmorillonite obtained above was introduced into a round-bottomed flask having an internal volume of 1 L, and heptane 450 was added.
mL, and further heptane solution of triethylaluminum (0.6 mmol / mL) 42 mL (0.025 mo
1) was added over 30 minutes, and the mixture was stirred at 25 ° C for 1 hour.
Then, the slurry was allowed to stand still, 400 mL of the supernatant was withdrawn, then washed twice with 500 mL of heptane, and finally heptane was extracted and adjusted so that the total amount of heptane was 100 mL. Next, dichloro {1,1'-methylsilylene bis [2-ethyl-4- (3-chloro-4-
tert-Butylphenyl) -4H-azurenyl]} hafnium 0.25 g (0.3 mmol) and heptane 516
After adding mL and stirring well, 84 m of a heptane solution of triisobutylaluminum (140 mg / mL) was added.
L (11.8 g) was added at room temperature, and the mixture was stirred for 60 minutes. Then, the above solution was introduced into the montmorillonite slurry prepared in the autoclave previously, stirred for 60 minutes, and heptane was further introduced until the total volume became 5 L, and kept at 30 ° C. Propylene there at a constant speed of 100 g / hr,
It was introduced at 40 ° C for 4 hours and then maintained at 50 ° C for 2 hours. The prepolymerized catalyst slurry was collected with a siphon, the supernatant was removed, and then dried at 40 ° C. under reduced pressure. By this operation, a prepolymerized catalyst containing 2.0 g of polypropylene per 1 g of the catalyst was obtained.

[Polymerization] Polymerization was carried out in the same manner as in Example 1 except that 55 mg of the above prepolymerized catalyst was used as the solid catalyst component.

As described above, the results of each example are shown in Table 1 (No. 1),
The results of each comparative example are shown in Table 1 (No. 2).
Further, the relationship between the G value and the E value in each example and comparative example is shown in FIG.

[0101]

[Table 1] Table 1 (1)

[0102]

[Table 2] Table 1 (Part 2)

[0103]

[Table 3] Table 2

[0104]

When the propylene block copolymer of the present invention is used as a molding material, it exhibits a very good balance of rigidity and impact resistance, has good heat resistance, and has a low gloss, resulting in a high-class feeling. Has a certain appearance.

[Brief description of drawings]

FIG. 1 is a conceptual flow chart of CFC-FT-IR.

FIG. 2 is a GPC-FT-IR analysis result diagram of fraction 1.

[Fig. 3] Manufacturing process flow chart of continuous two-stage polymerization method

FIG. 4 is a relational diagram of G value and E value in Examples and Comparative Examples.

[Explanation of symbols]

1. Liquid phase polymerization tank 2. Slurry circulation pump 3. Liquid classifier 4. Concentrator 5. Countercurrent pump 6. Double tube heat exchanger 7. Fluidized flash tank 8. Heat exchanger 9. Gas blower 10. Replacement system 11. Gas phase polymerization tank 12. Cyclone 13. Circulating gas cooler 14. Gas blower 15. Cyclone 16. hopper 17. Screw feeder 18. Dryer 19. hopper 20. Gas blower

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masaaki Ito             No. 1 Toho-cho, Yokkaichi-shi, Mie Japan Polyke             Mu Co., Ltd. Catalyst Development Center (72) Inventor Yu Hayakawa             No. 1 Toho-cho, Yokkaichi-shi, Mie Japan Polyke             Mu Material Development Center F-term (reference) 4J026 HA04 HA27 HA38 HA43 HB03                       HB04 HB27 HB38 HB45 HB48                       HE01

Claims (4)

[Claims] 1. A propylene-based block copolymer obtained by a first step of producing a propylene polymer component (PP) and a second step of producing a propylene-ethylene copolymer component (EP) using a metallocene catalyst. And the said block copolymer satisfies the following requirements (1)-(6), The propylene type block copolymer characterized by the above-mentioned. (1) Melt flow rate (MFR) is 0.1 to 15
It is 0 g / 10 minutes. (2) The propylene content of the component which is insoluble in ortho-dichlorobenzene at 100 ° C and soluble in ortho-dichlorobenzene at 140 ° C is 99.5% by weight or more. (3) Propylene in propylene block copolymer
The content of the ethylene copolymer component (EP) is 5 to 50% by weight. (4) The ethylene content (G) of EP is 10 to 90% by weight. (5) The relational expression (I) is established between the ethylene content (G) of EP and the ethylene content (E) of a component having no crystallinity in EP. G ≧ E ≧ −4.5 × 10 ⁻³ × G ² + 1.3 × G − 7.0 (I) (6) The melting point of the block copolymer is 157 ° C. or higher. 2. A [2,1-bond content] and a [1,3-bond content] in a component which is insoluble in ortho-dichlorobenzene at 100 ° C. and soluble in ortho-dichlorobenzene at 140 ° C. The propylene-based block copolymer according to claim 1, wherein the sum of the above is 0.06 to 0.6 mol%. 3. The [1,3-bond content] in the component which is insoluble in orthodichlorobenzene at 100 ° C. and soluble in orthodichlorobenzene at 140 ° C. is 0.06 to 0.6 mol%. The propylene-based block copolymer according to claim 1. 4. The propylene block copolymer according to claim 1, wherein the content of the component having no crystallinity in EP is 95% by weight or more.