JPH0892321A - Crystalline polypropylene - Google Patents

Abstract

PURPOSE: To obtain a crystalline polypropylene excellent in rigidity, heat resistance and surface hardness. CONSTITUTION: This crystalline polypropylene has 0.1-1000g/10min melt flow rate, >4 to <10 molecular weight distribution, >=94% isotactic pentad fraction, >=40% quantitative ratio of the crystalline phase determined by the pulse NMR method and T2 i and T2 a (μsee) spin-spin relaxation times of the interfacial and amorphous phases in a relationship of T2 a-T2 i<=200.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention provides a crystalline polypropylene excellent in rigidity, heat resistance and surface hardness.

[0002]

2. Description of the Related Art Crystalline polypropylene has relatively excellent rigidity, heat resistance, and surface hardness, so
It is widely used for various purposes such as household and medical parts, but these properties are not sufficiently satisfactory as compared with ABS, polystyrene or engineering plastics. Isotactic polypropylene is a stereoregular polymer whose solid has a partially crystallized structure, but its properties in the solid are known to be closely related to this solid structure. That is, the above-mentioned characteristics generally correspond to the crystallinity, and as the crystallinity increases, the rigidity, heat resistance, and surface hardness improve. From such a viewpoint, many methods for improving these properties have been proposed in the past.

That is, a method of reducing the by-product isotactic component by improving the catalyst, for example, "polymeric Character
"Ization and physical properties" (Kagaku Dojin, 1985, Supplement for Chemistry 43) A method for expanding the molecular weight distribution, for example, JP-A-59-
No. 172507, No. 62-195007, No. 3-12409, No. 2-7070
No. 8, JP-A-3-7703 A method for improving stereoregularity, for example, JP-A-59-
No. 22913, JP-A No. 61-155404 A method of adding a nucleating agent, for example, “polypropylene resin” (Nikkan Kogyo Co., Ltd., Plastic Materials Course, Showa 44)
(Published on November 30, 2013), JP-A-60-139731, and the like.

However, these methods do not sufficiently improve the performance. Further, polypropylene is usually most commonly used after being melted and molded into a desired shape, but it is generally known that the crystallinity also changes depending on the molding processing conditions and the properties change accordingly. It is well known to. Specifically, various properties such as rigidity are improved by a method of lowering the cooling rate during crystallization, a method of annealing a molded product at a temperature equal to or lower than the melting point, and the like.
However, in these methods, the molding processing speed is greatly reduced, equipment and energy for heat treatment are required, and the improved performance is not sufficient.

Therefore, the characteristics of the solid are closely related to the long period, which is an index of the size of the constitutional unit of the solid structure, and the performance is improved by shortening the long period and decreasing the molecular mobility of the amorphous phase. An improved method is proposed in Japanese Patent Laid-Open No. 127406/1990. However, for the solid structure of polypropylene, Saito et al.
As disclosed in 3, 3256 (1990), it has been clarified that it is composed of a three-phase structure of a crystalline phase, an interfacial phase, and an amorphous phase. It cannot be said that the improvement of the performance is sufficient even if only the sex is lowered.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide polypropylene having sufficiently high rigidity, heat resistance and surface hardness. Furthermore, it is intended to improve the rigidity, heat resistance, and surface hardness of a composite material obtained by blending a block copolymer composed of propylene containing the crystalline polypropylene of the present invention as a basic element and another olefin, a filler, or another polymer. is there.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the rigidity, heat resistance, and surface hardness are not limited to the crystallinity of polypropylene but also form a solid structure. The present invention has been completed by finding that it is closely related to the difference in molecular mobility between the interfacial phase and the amorphous phase among the existing phases.

That is, according to the present invention, (A) the MFI: melt flow rate (g / 10 minutes) measured at 230 ° C.
Formula 1 0.1 ≦ MFI ≦ 1000 (1), and (B) the ratio of the weight average molecular weight Mw to the number average molecular weight Mn: Mw / Mn is calculated by Equation 24 <Mw / Mn <10.0 (2) ) And the isotactic pentad fraction (mmmm) (%) measured by (C) ¹³ C-NMR is formula 3 (mmmm) ≧ 94 (3), and (D) at 40 ° C. ¹ H pulse method NMR
The amount ratio Fc (%) of the crystal phase obtained by the formula is Equation 4, Fc ≧ 40 (4), and (E) ¹ H pulse method NMR at 40 ° C.
In obtained in interphase spin - spin relaxation time T ₂ i (microseconds) and amorphous phase of the spin - spin relaxation time T ₂ a (microseconds) is the formula _{5 T 2 a-T 2 i} ≦ 200 (5 ) Is a crystalline polypropylene, and a crystalline polypropylene that satisfies these requirements is
It has been found to have significantly improved elastic modulus, heat resistance, and surface hardness.

The crystal form of polypropylene is usually a single injection crystal (α crystal), and as described above, three phases having an amorphous phase between the crystal phases and an interface phase having an intermediate property between the crystal phase and the amorphous phase. It is known to have a structure. The crystalline polypropylene proposed in the present invention has a solid structure in which the amount ratio of the crystal phase is high and the spin-spin relaxation times obtained by pulse method NMR of the interface phase and the amorphous phase are close. Since the spin-spin relaxation time of each phase obtained by pulse method NMR is a measure of the molecular mobility of each phase, the crystalline polypropylene proposed in the present invention has a high degree of crystallinity and a high degree of crystallinity in the interfacial phase and the amorphous phase. It is a crystalline polypropylene having a solid structure in which the molecular mobility of the phases is close, that is, a solid structure close to a two-phase structure. Hereinafter, the present invention will be specifically described.

The crystalline polypropylene in the present invention is
Melt flow rate MFI at 230 ° C (g / 10
Min) is 0.1 g / 10 min or more and 1000 g / 10 min or less, preferably 0.5 g / 10
Min or more, 500 g / 10 min or less, most preferably 1.0
It is g / 10 minutes or more and 100 g / 10 minutes or less. MFI
Is less than 0.1 g / 10 minutes, the fluidity is poor and 100
If it exceeds 0 g / 10 minutes, the fluidity is too high and many molding defects occur, which is not preferable.

The molecular weight distribution Mw / Mn, which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the crystalline polypropylene in the present invention, must be more than 4 and less than 10, preferably. It is 5 or more and 7 or less. M
When w / Mn is 4 or less, fluidity is poor and Mw /
When Mn is 10 or more, the molded product tends to have anisotropy, and sufficient properties cannot be obtained as the molded product.

The isotactic pentad fraction (mmmm) (%) of the crystalline polypropylene in the present invention is 9
It is necessary to be 4 (%) or more, preferably 95.
% Or more. Isotactic pentad fraction 94
If it is less than%, sufficient characteristics cannot be obtained. Isotactic pentat fraction (mmmm) means A. Zabel
li et al., Macromolecules, 6, 9
25 (1973), that is, ¹³ C-
It is an isotactic fraction in a pentad unit in a polypropylene molecular chain measured by a method using NMR. The isotactic pentad fraction is the fraction of propylene monomer units at the center of a chain in which five propylene monomer units are continuously meso-bonded. However, regarding the attribution of the peaks, Macromolecules, 8,
687 (1975). Specifically, the isotactic pentad unit is measured as the intensity fraction of the (mmmm) peak in all absorption peaks in the methyl carbon region of the ¹³ C-NMR spectrum.

The quantity ratio Fc (%) of the crystalline phase of the crystalline polypropylene in the present invention is 40% or more, preferably 41.
%, Most preferably 42% or more, the effect of improving various properties is high. Spin-spin relaxation time T ₂ i (microsecond) of the interfacial phase of the crystalline polypropylene in the present invention
And the spin-spin relaxation time T ₂ a (microsecond) of the amorphous phase have a relationship of T ₂ a−T ₂ i ≦ 200, preferably T
By satisfying the relation _{2 a-T 2 i ≦ 190} , the effect of improving the properties is very high.

The measurement of spin-spin relaxation by the pulse method NMR can be carried out according to the method described in J. Nishi et al. Chem. Phys. 8
2.9 (1985), the solid-echo method and the CPMG method are combined to obtain a decay curve of spin-spin relaxation, which is separated into three components by least square using a computer, and the relaxation curve is obtained. The crystal phase, the interfacial phase, and the amorphous phase were assigned from the shorter side, and the quantitative ratio of each phase and the relaxation time were derived.

The method for producing the crystalline polypropylene having a solid structure proposed in the present invention will be exemplified below. The present invention is not limited to this. As a method for obtaining the crystalline polypropylene having a solid structure of the present invention, a catalyst system comprising a solid catalyst component containing at least Mg, Cl, an aromatic carboxylic acid ester, and Ti as its components, an organoaluminum compound, and an alkoxysilane is used. In the two-stage polymerization using, a methoxysilane compound having at least one aromatic hydrocarbon group is added at the time of the polymerization in the previous step to perform polymerization, and a specific hydrocarbon group other than the aromatic hydrocarbon group is further added in the subsequent step. The method of polymerizing by adding a methoxysilane compound having

The solid catalyst component (A) containing at least Mg, Cl, an aromatic carboxylic acid ester, and Ti as its components is, for example, a magnesium compound, a titanium compound,
It can be produced by reacting a halogenating agent and an aromatic carboxylic acid ester in any order. As a specific method, a method of co-milling the activated magnesium halide, the titanium compound and the aromatic carboxylic acid ester at the same time or stepwise, the aromatic compound or the other electron to the magnesium compound in a homogeneous state. A method of bringing a titanium compound into contact with a precipitate obtained by reacting a halogenating agent or a reducing agent with or without a donor in the presence of an aromatic carboxylic acid ester, etc. Can be used, and more specifically, JP-B-60-11924 and JP-A-1-213.
311, JP-A 1-259003, JP-A-2-28201, JP-A-2-138312, JP-A-2-138313, and JP-A-4-238.
The methods described in JP-A No. 11 and JP-A No. 4-216804 can be referred to.

As the organoaluminum component (B),
It is good to use the compound represented by the general formula AlRmXa-m.
Yes. Here, X is OR, Cl, Br or H, and R is C₁
~ C ₁₈A hydrocarbon residue of, preferably alkyl
Group and annealed group. Further, m is an arbitrary value of 0 <m ≦ 3.
Is a number. Specifically, triethylaluminum, die
Chill aluminum chloride and the like.

Further, as the methoxysilane compound (C) added in the previous polymerization, the general formula R ¹ _t R ² _s Si is used.
_{(OCH 3) 4 - t -} s ( wherein R ¹ represents an aromatic hydrocarbon group, R ² represents a linear hydrocarbon group having 1 to 3 carbon atoms, s is 0 ≦ s <2, t Is a number satisfying the relation of 1 ≦ s + t ≦ 2, and is, for example, phenyltrimethoxysilane, toluyltrimethoxysilane, diphenyldimethoxysilane,
Phenylmethyldimethoxysilane, phenylethyldimethoxysilane, phenyl n-propyldimethoxysilane, p-toluylmethyldimethoxysilane and the like can be used.

The methoxysilane compound (D) to be added in the subsequent polymerization is represented by the general formula R ³ _X R ⁴ _Y Si (OCH
₃ ) _4-X-Y (In the formula, R ³ represents a branched hydrocarbon group or an alicyclic hydrocarbon group, R ⁴ represents a linear hydrocarbon group having 1 to 3 carbon atoms, and x represents 0). ≦ x <2, y is a number in the range of 0 <y ≦ 2, and 1 ≦ x + y ≦ 2.), And examples thereof include diisopropyldimethoxysilane, diisobutyldimethoxysilane, and isobutylisopropyl. Dimethoxysilane, disec-butyldimethoxysilane, ditert-butyldimethoxysilane,
tert-butylmethyldimethoxysilane, tert-
Butylethyldimethoxysilane, tert-butyl n-
Propyldimethoxysilane, tert-butylisopropyldimethoxysilane, tert-butyltrimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, dicyclohexyldimethoxysilane, dicyclopentylmethoxysilane and the like can be used.

The use ratio of the catalyst components (A), (B), (C), and (D) is 1 (g) of the solid catalyst component (A), and (B) is the aluminum atom in (B). Converted to 1
˜3000 mmol, preferably 5˜1000 mmol, and as the use ratio of (C) and (D),
0.01-1000 mmol, preferably 0.05-1000 mmol, calculated as the total of silicon atoms in (C) and (D).
It is preferably used in the range of 100 mmol. (C)
As the mixing ratio of (D) and (D), the molar ratio of the amount of (C) used to the amount of (D) used is 1.0: 0.1 to 0.
A range of 1: 1 is preferred.

All of these catalyst components (A), (B), and (C) may be used by bringing them into contact with each other during the polymerization.
In addition, after the polymerization, it may be used by contacting with any one of the three in advance and then contacting with the other one, and the contact may be carried out in an inert gas atmosphere or an olefin atmosphere. In addition, hydrogen or the like can be added to control the molecular weight of the polymerization.

The polymerization method for obtaining the crystalline polypropylene of the present invention is not particularly limited, but it is preferable to use polymerization in a liquid monomer and gas phase polymerization,
In particular, when the gas phase polymerization method is adopted, the effect is particularly large, and a polymer is produced by a two-step polymerization method by combining these two arbitrary polymerization methods. Preferred combinations include a method in which polymerization in liquid propylene is followed by gas phase polymerization and a method in which gas phase polymerization is followed by gas phase polymerization.

In the polymerization in a liquid monomer, the olefin can be polymerized by using the liquid olefin as a polymerization solvent for the catalyst under the condition that the olefin such as propylene is a liquid. For example, in the case of propylene, the polymerization can be carried out in liquid propylene at a temperature of room temperature to 90 ° C. and a pressure of 10 to 45 kg / cm ² . On the other hand, the gas phase polymerization is carried out at room temperature to 1 at a pressure of 1 to 50 kg / cm ^{2 in} the absence of a solvent under the condition that an olefin such as propylene is a gas.
Polymerization can be carried out at a temperature of 20 ° C. by taking measures such that the catalyst and the olefin such as propylene are brought into good contact with each other, for example, by mixing with a fluidized bed, a moving bed or a stirrer.

For example, when using a gas phase polymerization apparatus having a stirring fluidized bed, various types can be used, but particularly preferably, a helical stirring blade is used,
It has a stirring bed composed of a finely divided polymer whose Froude number at its center is operated under the conditions of 1 to 3, and propylene alone or propylene and hydrogen are continuously or intermittently fed to the polymerization zone, It is possible to use a gas phase polymerization apparatus having a basic constitution that polymerization is started by supplying each component to the polymerization zone, and the obtained polymer is continuously or intermittently taken out from the polymerization zone.

The polymerization conditions are, for example, 40 to 9
Temperature of 5 ° C, and 10-35 kg / cm ² (gauge pressure)
Under the pressure of propylene, propylene alone or propylene and hydrogen are continuously or intermittently supplied to the polymerization zone to remove the heat of polymerization generated by the polymerization and to replenish the propylene consumed by the polymerization, and the unreacted propylene. Is taken out from the polymerization zone, liquefied and fed again to the polymerization zone in a liquid state, and further, the obtained polymer is continuously or intermittently taken out from the polymerization zone. .

In the present invention, a propylene polymer can be produced by connecting two or more gas phase polymerization devices described above. For example, in the first-stage polymerization, the polymerization temperature is 50 to 95 ° C., and the polymerization pressure is 17 to 35 kg / c.
A propylene polymer is produced under the condition of m ^{2 under} the condition that the average residence time of the polymer is 1.5 to 4 hours, and the obtained polymer is continuously transferred to the latter-stage polymerization tank and the polymerization is further continued. At this time, for example, a method of producing a polymer at a pressure lower than that of the former stage by at least 7 kg / cm ² and a polymerization temperature of 50 to 90 ° C. can be used. Further, at that time, a step of removing the gas accompanying the fine powdery polymer, a step of pressurizing the fine powdery polymer from which the accompanying gas has been removed, and a step of introducing the pressurized fine powdery polymer into the latter-stage polymerization tank. It may be provided. More specifically, the Japanese Patent Application No. 5 filed previously by the present inventors.
The method described in JP-A-261999 can be used. Regarding the relationship between the molar ratio of hydrogen to propylene in the gas phase and the molar ratio of hydrogen to propylene in the gas phase in the latter step in the polymerization in the former step in the present invention, it is possible to supply hydrogen in the latter step without newly feeding hydrogen. It is preferable to continue the polymerization or to carry out the polymerization under the condition that the molar ratio in the latter step is smaller than the molar ratio in the former step.

The weight ratio of the amount produced in each polymerization stage in the present invention is such that the ratio of the amount produced in the first stage to the amount produced in the second stage is 65 to 5.
95 to 35 to 5 range, preferably 71 to 90 to 29 to
It is preferably in the range of 10, more preferably 80 to 90 to 20 to 10. When the production ratio in the latter-stage polymerization tank exceeds the above range, the appearance becomes poor, and when it is less than the above range, the moldability is deteriorated and the rigidity of the molded product is not improved. Regarding this continuous gas phase multi-stage polymerization method, US Pat. Nos. 4,012,073, 4,330,645 and 4,442 are referred to.
271 and British Patent No. 1032945, the methods and examples thereof can be referred to.

When a molded product is produced using the powdery polymer of crystalline polypropylene obtained as described above, a proper amount of a heat stabilizer, an antioxidant, an ultraviolet absorber, an antiblocking agent is added if necessary. , A lubricant, a nucleating agent, a coloring agent and other additives can be added. Further, polymers such as low density polyethylene, high density polyethylene, polybutene, ethylene-propylene rubber and inorganic fillers such as mica, talc and glass fiber can be mixed and used.

[0029]

EXAMPLES The present invention will be described below with reference to examples. Each measured value used in the examples is measured according to the method described below. The polymer powder obtained was added with P as an additive.
-EPQ (manufactured by Sand Co.) was added at 0.05% by weight and calcium stearate at 0.1% by weight, and the mixture was granulated at a temperature of 230 ° C using a twin-screw extruder and used for the following measurements. 1. Compliant with MFI ASTM D1238 (230 ° C, 2.16k
g, condition L). 2. Molecular weight distribution Mw / Mn As the molecular weight distribution Mw / Mn, for example, 150C manufactured by Waters Co., Ltd. is used as gel permeation chromatography (GPC) according to the definition described on page 151 of “Polymer Experimental Studies” published by Kyoritsu Publishing. The column is TOSOH TSK-GEL GMH6- manufactured by Tosoh Corporation.
HT and SHODEX AT-80 manufactured by Showa Denko KK
7 / S was used, 1,2,4-trichlorobenzene was used as the solvent, and calculation was performed based on the measurement results at a measurement temperature of 140 ° C. The calibration curve was prepared using standard monodisperse polystyrene. 3. Isotactic pentat fraction (mmmm) The device is JNM-GX400 manufactured by JEOL Ltd.
The measurement was performed at 0 ° C. with a waiting time of 3.181 seconds and an integration count of 5000 times. Ortho-dichlorobenzene was used as the solvent.

The following physical property measurements were carried out by molding the pellets obtained by granulation into an intended test piece using an injection molding machine (IS-150EN manufactured by Toshiba Corp.). 4. Pulse Method NMR Measurement by pulse NMR was performed at 40 ° C. using PC-20 manufactured by Bruker. The obtained decay curve of spin-spin relaxation was converted by a connected Transier Recorder manufactured by Autonics Co., Ltd., taken out into a computer, and then separated by the least-squares method to obtain the quantitative ratio of each phase and the relaxation time. 5. Flexural modulus It was performed according to ASTM D790. 6. Heat distortion temperature According to ASTM D648 (4.16 kgf / cm ² ).
I went. 7. Surface hardness It was performed according to ASTM D785.

[0031]

Example 1 (I) Synthesis of Organomagnesium Component Containing Alkoxy Group It was previously prepared from triethylaluminum and dibutylmagnesium.
Composition formula Al synthesized ₆(C₂H_Five)₃(N-C
_FourH₉)_{1 2}An organomagnesium complex component 25 represented by
N-heptane containing 0 mmol (based on magnesium)
Place the solution in a 1 liter flask that has been thoroughly purged with nitrogen.
Then, while cooling and stirring in an ice bath, n-
Add 27.4 cc (300 mmol) of butyl alcohol.
It was slowly added dropwise over 1 hour to react, and further stirred at room temperature.
The reaction was carried out for 1 hour under stirring. A relatively viscous colorless transparent solution
Obtained and analyzed, it was found that the solution contained n per mol of Mg.
-Contains 1.20 mol of butoxy group, magnesium
Was 1.0 mol / liter.

(II) Synthesis of Magnesium-Containing Solid by Reaction with Chlorosilane Compound To a 1 liter flask sufficiently replaced with nitrogen, 500 mmol of trichlorosilane as a 1 mol / liter n-heptane solution was charged, and stirred to 65 Kept at 0 ° C. and n- of the alkoxy group-containing organomagnesium component
The total amount of the heptane solution was added over 1 hour, and the mixture was further reacted at 65 ° C for 1 hour with stirring. The white solid produced was filtered off,
By sufficiently washing with n-heptane and drying, 29.5 g of a white solid (a) was obtained. As a result of analyzing this solid component, in 1 g of the solid, 7.45 mmol of Mg and Cl1
It contained 4.2 mmol and butoxy group 2.82 mmol, and the specific surface area measured by the BET method was 123 m ² / g.
Met.

(III) Synthesis of solid catalyst component Titanium tetrachloride (20) was placed in a 500 cc flask containing 10 g of the solid component obtained in (II) and sufficiently replaced with nitrogen.
cc and toluene 200 cc were added, and phthalic acid di-
2.0 cc (7.5 mmol) of n-butyl was added, and the mixture was stirred at room temperature for 1 hour. After the contact, the supernatant was removed, 80 cc of titanium tetrachloride was further added, the temperature was raised, and contact was continued at a temperature of 120 ° C. for 3 hours. After completion of the reaction, the solid was separated by hot filtration, and 200 cc of toluene heated to 100 ° C. and 3
The solid component (b-1) was made into n-hexane slurry after being contacted twice and washed with n-hexane. When a part of this was collected and analyzed, the Ti content in the solid component was 1.7% by weight.

[Polymerization] 50 kg of finely powdered polypropylene
Polymerization was carried out using a process in which two reactors with a stirrer having an internal volume of 200 liters and having a stirring bed consisting of were connected. First, the reactor in the first stage was stirred under the conditions of Froude number of 2.2, the polymerization temperature was 85 ° C, and the polymerization pressure was 27 kg / cm ^2.
Polymerization was initiated by continuously feeding the solid catalyst component, triethylaluminum, and diphenyldimethoxysilane while continuously feeding propylene and hydrogen so as to maintain the above conditions. At that time, the polymer production rate in the first stage was 20 kg / hr, and the MFI of the produced polymer was 15
The catalyst feed amount and hydrogen feed amount were controlled so as to be g / 10 minutes. Regarding the feed ratio of each catalyst component, the molar ratio of triethylaluminum to the amount of Ti in the solid catalyst component is 1: 400, and the molar ratio of diphenyldimethoxysilane and triethylaluminum is 1: 1.
Polymerization was carried out under the condition of 0.

A part of the polymerized product in the first stage is intermittently sent to the second stage reactor together with propylene gas, and dicyclopentyldimethoxysilane is further fed in the first stage without adding new hydrogen. 1.5 times the feed amount of
Polymerization was continued under the conditions of 18 ° C. and 18 kg / cm ² . The final polymer production was 24 kg / hr. The molar concentration of hydrogen in the gas phase was 1/2 that of the former stage. The polymer production ratio of the first and second stages was 5: 1.

The amount of the propylene polymer obtained per 1 g of the solid catalyst component was 45.2 kg. The polymer was granulated with an extruder to obtain pellets. The MFI of the obtained pellets was 10.3 g / 10 minutes, the molecular weight distribution was Mw / M.
n is 4.5, and the isotactic pentad fraction (m
mmm) was 96.8%. After molding the pellets at 230 ° C with an injection molding machine, cut out the test pieces and
Measurement of 0 ° C. pulsed NMR was performed. As a result, the crystal phase amount ratio Fa was 42.1%, and the interfacial phase relaxation time T ₂ i was 95.
The microsecond and the relaxation time T ₂ a of the amorphous phase were 285 (microseconds). The measurement results of other physical properties are shown in Table 1.

[0037]

Comparative Example 1 Polymerization was carried out using only one reactor equipped with a stirrer and having an inner volume of 200 liters, which had a stir bed composed of 50 kg of finely powdered polypropylene. The reactor was stirred under the condition of Froude number of 2.2, the polymerization temperature was 85 ° C, and the polymerization pressure was 2
Polymerization was initiated by continuously feeding the solid catalyst component, triethylaluminum, and dicyclopentylmethoxysilane while continuously feeding propylene and hydrogen so as to maintain the condition of 7 kg / cm ² . At that time, the catalyst feed amount and the hydrogen feed amount were controlled so that the polymer production rate in the former stage was 20 kg / hr and the MFI of the produced polymer was 10 g / 10 min. As the feed ratio of each catalyst component, the molar ratio of triethylaluminum to the amount of Ti in the solid catalyst component is 1: 400,
Polymerization was carried out under the condition that the molar ratio of dicyclopentylmethoxysilane and triethylaluminum was 1:10. The produced amount of the propylene polymer was 2 per 1 g of the solid catalyst component.
It was 2.5 kg. The evaluation results are shown in Table 1.

[0038]

Comparative Example 2 Example 1 except that no additional dicyclopentyldimethoxysilane was added in the latter stage of Example 1.
Polymerized in the same manner as. The amount of the propylene polymer obtained per 1 g of the solid catalyst component was 39.8 kg. The evaluation results are shown in Table 1.

[0039]

Comparative Example 3 Polymerization was carried out in the same manner as in Example 1 except that dicyclopentyldimethoxysilane was not additionally added in the latter stage of Example 1 but dicyclopentyldimethoxysilane was simultaneously added together with diphenyldimethoxysilane in the former stage. The production amount of the propylene polymer obtained per 1 g of the solid catalyst component was 41.8 Kg. The evaluation results are shown in Table 1.

[0040]

Examples 2 to 6 The types of methoxysilane used in the first and second stages were changed to the combinations and the molar ratios used in Table 1, and the ratio of the polymer production amount in the first stage and the polymer production amount in the second stage was changed to those in Examples. 5: 2 for Example 2, 4: 1 for Example 3, 3: 1 for Example 4, 7: 1 for Example 5, Example 6
Then, the same procedure as in Example 1 is performed except that the ratio is changed to 4: 1,
The evaluation results are shown in Table 1.

[0041]

Example 7 Polymerization was carried out by using a process in which two reactors each having a stirrer and having an inner volume of 200 liters, each having a stirring bed made of 50 kg of finely powdered polypropylene, were connected. First, while the propylene and hydrogen were continuously fed so that the reactor in the first stage was stirred under the conditions of Froude number of 2.2 and the polymerization temperature was 85 ° C. and the polymerization pressure was 27 kg / cm 2, the solid catalyst component, Triethylaluminum and diphenyldimethoxysilane were continuously fed to start the polymerization. At that time, the polymer production rate in the former stage was 20 kg / hr, and the MFI of the produced polymer was 20 g / hr.
The catalyst feed amount and hydrogen feed amount were controlled so as to be 10 minutes. Regarding the feed ratio of each catalyst component, the polymerization was carried out under the conditions that the molar ratio of triethylaluminum to the amount of Ti in the solid catalyst component was 1: 400 and the molar ratio of diphenyldimethoxysilane and triethylaluminum was 1:10.

A part of the polymerized product polymerized in the first stage is intermittently sent to the reactor in the subsequent stage through a step of removing entrained gas and a step of pressurizing with nitrogen gas, and hydrogen is newly added. Without addition, dicyclopentyldimethoxysilane was further added in an amount 1.5 times the feed amount of diphenyldimethoxysilane fed in the previous stage, and the temperature was 80 ° C. and 18 kg.
The polymerization was continued under the condition of / cm ₂ . The final polymer production was 24 kg / hr. The hydrogen molar concentration in the gas phase was 1/50 of that in the first step. The polymer production ratio of the first and second stages was 5: 1.

The production amount of the propylene polymer obtained per 1 g of the solid catalyst component was 44.8 kg. The evaluation results are shown in Table 1.

[0044]

[Table 1]

[0045]

As described above, the crystalline polypropylene of the present invention has sufficiently high rigidity, heat resistance and surface hardness. Furthermore, it is possible to improve the rigidity, heat resistance, and surface hardness of a composite material obtained by blending a block copolymer or a filler or another polymer composed of propylene containing the crystalline polypropylene of the present invention as a basic element and another olefin. it can. Therefore, if the crystalline polypropylene of the present invention is used for various industrial, household or medical parts that require rigidity, heat resistance and surface hardness, product thinning, recycling, etc. are facilitated and resource saving is achieved. Can greatly contribute to the point.

Claims (1)

[Claims] 1. (A) MFI measured at 230 ° C .: melt flow rate (g / 10 minutes) is 0.1 ≦ MFI ≦ 1000 (1), and (B) weight average molecular weight Mw and number average. Ratio with molecular weight Mn: Mw / Mn is 4 <Mw / Mn <10.0 (2), and (C) ¹³ C-NMR measured isotactic pentad fraction (mmmm) (%) Is (mmmm) ≧ 94 (3), and (D) ¹ H pulse method NMR at 40 ° C.
Amount ratio Fc (%) of the crystal phase obtained in step S1 is Fc ≧ 40 (4), and (E) ¹ H pulse method NMR at 40 ° C.
In obtained in interphase spin - spin relaxation time T ₂ i (microseconds) and amorphous phase of the spin - spin relaxation time T ₂ a (microseconds) _{is, T 2 a-T 2 i} ≦ 200 (5) A crystalline polypropylene characterized by having a relationship.