JP3538508B2 - Crystalline polypropylene - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a crystalline polypropylene polymer and a crystalline polypropylene composition.

[0002]

Since polypropylene is lightweight and has excellent rigidity and heat resistance, it is widely used in various fields such as various containers, daily necessities, automobile parts, electric parts and the like.

In recent years, with the progress of olefin polymerization catalysts,
Using a Ziegler-type catalyst system in which a titanium compound is supported on a halogen-containing magnesium compound, highly active, highly stereoregular polypropylene can be produced.

[0004] However, when polypropylene is produced using the above-mentioned catalyst system, there is a problem that a material having a high melt flow rate (MFR), that is, a material having good moldability, has insufficient rigidity depending on applications.

Accordingly, an object of the present invention is to provide a crystalline polypropylene excellent in balance between moldability and rigidity.

[0006]

Means for Solving the Problems The present inventors have repeatedly studied the physical properties of a homopolypropylene produced by using a Ziegler-type catalyst system. Has a specific relationship. That is, the bending elastic modulus is high on both the low molecular weight side (lower MFR) and the high molecular weight side (higher MFR), and the U-shaped curve shows a minimum bending elastic modulus at a certain intermediate MFR. . Polypropylene MF
When R is increased, the degree of crystallinity is large, so that the flexural modulus is increased. On the other hand, since the fluidity is too high, it is difficult to eliminate burrs generated in the molded product. Also, as the MFR of polypropylene decreases, the bending elastic modulus increases due to the orientation occurring on the surface of the molded product, but on the other hand, the fluidity becomes extremely poor, making molding difficult and causing short shots. Cheap. Then, it has been found that a combination of a material having a high MFR and a material having a low MFR yields a polypropylene having an excellent balance between fluidity and rigidity, and has led to the present invention.

That is, the present invention firstly provides two types of polypropylene components 1 and 2 having different melt flow rates.
(1) a melt flow rate (MFR ₁ ) of component ₁ and a melt flow rate (MFR ₂ ) of component 2;
Is a weight ratio w to the sum of the components 1 and 2,
The following formula (I):

[0008]

(Equation 5) (Where a ₁ = 2460, a ₂ = 4660, a ₃ =
-1.45, β = -0.1143, γ = a is) fulfills the relationship -0.171, an MFR ₁ ≦ MFR _2, and (2) a boiling n the polymer with improved Soxhlet extractor -To provide a crystalline polypropylene polymer characterized in that the weight ratio HI of the residue after extraction with heptane for 6 hours with respect to the whole polymer satisfies HI> 96.2. Preferred embodiments include: (i) MFR ₁ , MFR ₂ and w are represented by the following formula (II):

[0009]

(Equation 6) (Wherein a ₁ , a ₂ , a ₃ , β and γ have the same meanings as above). (Ii) MFR ₁ , MFR ₂ and w are represented by the following formula (II)
I):

[0010]

(Equation 7) (Wherein a ₁ , a ₂ , a ₃ , β and γ have the same meanings as above). (Iii) The above polymer, wherein HI satisfies HI> 97.2. (Iv) The above polymer produced by multi-stage polymerization (particularly two-stage polymerization).

The present invention secondly provides a crystalline polypropylene composition containing two types of polypropylene components 1 'and 2' having different melt flow rates. ( ₁ ) The melt flow rate (MFR _{1 '} ) of component 1' And the melt flow rate (MFR _{2 ′} ) of component 2 ′ and the weight ratio w ′ of component 1 ′ to the sum of components 1 ′ and 2 ′ are represented by the following formula (I ′):

[0012]

(Equation 8) (Where a ₁ = 2460, a ₂ = 4660, a ₃ =
−1.45, β = −0.1143, γ = −0.171) and MFR _{1 ′} ≦ MFR _{2 ′} , and (2) the composition was modified with an improved Soxhlet extractor. A crystalline polypropylene composition is provided, wherein the weight ratio HI of the residue after extraction with boiling n-heptane for 6 hours with respect to the whole composition satisfies HI> 96.2. Preferred embodiments include: (i) 'MFR _1' , MFR _{2 '} and w' are of the following formula (II '):

[0013]

(Equation 9) (Wherein a ₁ , a ₂ , a ₃ , β and γ have the same meanings as above). (Ii) 'MFR _1' , MFR _{2 '} and w' are represented by the following formula (III '):

[0014]

(Equation 10) (Wherein a ₁ , a ₂ , a ₃ , β and γ have the same meanings as above). (Iii) The above composition wherein 'HI satisfies HI> 97.2.

[0015]

DETAILED DESCRIPTION OF THE INVENTION First, the first invention, that is, a propylene polymer will be described. The polymer of the present invention comprises two types of polypropylene components 1 and 2 having different melt flow rates (MFR). The MFR of component 1 (M
That FR _1), the component 2 MFR (referred MFR ₂₎ smaller. It is necessary that the MFR of both components and the content (weight ratio) w of the component 1 satisfy the relationship of the above formula (I). W is the weight ratio of the component 1 to the sum of the components 1 and 2. w is preferably 0.05 to 0.95.

MFR ₁ , MFR ₂ and w are preferably represented by the following formula (II):

[0017]

(Equation 11) (Where a ₁ , a ₂ , a ₃ , β and γ have the same meanings as described above). More preferably, the following formula (I
II):

[0018]

(Equation 12) (Where a ₁ , a ₂ , a ₃ , β and γ have the same meanings as described above). If MFR ₁ , MFR ₂ and w do not satisfy the above relationship, a good balance between moldability and rigidity cannot be obtained in the polymer. Preferably, the MFR ₁ is 0.01 to 10 g / 10 min, and the MF is 1.
R ₂ is a 10~300g / 10 minutes. As used herein, the melt flow rate (MFR) is defined as ASTM D1
Measured under the conditions of 230 ° C. and a load of 2.16 kg according to H.238, and the unit is g / 10 minutes (the same applies to the following description).

The polymer of the present invention must further satisfy HI> 96.2. Here, HI is the content of heptane-insoluble matter, and is the weight ratio of the residue (ie, heptane-insoluble matter) after the polymer was extracted with boiling n-heptane for 6 hours using a modified Soxhlet extractor, based on the whole polymer. is there. If the HI is 96.2 or less, a good balance between moldability and rigidity cannot be obtained in the polymer. Preferably HI
> 97.2.

The above formula (I) is satisfied and HI> 96.2
Is satisfied, the polymer of the present invention may contain, in addition to the above components 1 and 2, a polypropylene component having an MFR different from these in an amount of 20% by weight or less. When the polymer of the present invention contains three or more kinds of MFR polypropylene constituent components, it is sufficient that two of them satisfy the above relationship.

The polymer of the present invention can be produced by subjecting polypropylene components 1 and 2 to multi-stage polymerization.
At this time, the order of polymerization of the components does not matter. The number of polymerization stages is not particularly limited as long as it is two or more.
It is a step. The method for producing each of the polypropylene components is not particularly limited. For example, a method described in detail in JP-A-7-133319, that is, using a magnesium chloride-supported stereoregular catalyst and adding an appropriate silane to the prepolymerized It is preferable to produce by a method combining silane addition and main polymerization. In this method, (a) a solid component containing magnesium, titanium, halogen and an electron donating compound as essential components is converted into (d) in the presence of an organoaluminum compound (b) and an organosilicon compound (c). ) Polymerization of propylene (main polymerization) using a catalyst component obtained by contact with olefin (preliminary polymerization).

The solid component (a) is prepared, for example, by contacting a magnesium compound, a titanium compound and an electron donating compound. When none of the above compounds contains a halogen atom, a halogen compound is added thereto and brought into contact. Examples of the magnesium compound include dialkyl magnesium such as Mg (CH ₃ ) ₂ ;
Diarylmagnesium such as (C ₆ H ₅ ) ₂ ; Mg (O
Dialkoxymagnesium such as C ₄ H ₉ ) ₂ ; Mg (O
Diaryloxymagnesium such as C ₆ H ₅ ) ₂ ; C ₂
Alkyl magnesium halides such as H ₅ MgBr; C
Aryl halides such as magnesium ₆ H ₅ MgCl;
(C ₄ H ₉ O) Alkoxy magnesium halide such as MgBr; (C ₆ H ₅ O) aryloxy magnesium halide such as MgCl; magnesium halide such as MgCl ₂ . Magnesium compounds are
(A) When preparing a solid component, it can be prepared from metallic magnesium. As the titanium compound, a divalent, trivalent or tetravalent titanium compound can be used, and specific preferred examples include titanium tetrachloride, trichloroethoxytitanium, dichlorodibutoxytitanium, dichlorodiphenoxytitanium and the like. Examples of the electron donating compound include carboxylic acids and their derivatives (anhydrides, esters, halides, etc.), alcohols, phenols, ethers, ketones, amines, amides, nitriles, aldehydes, alcoholates And the like. Examples of the halogen compound include halogenated hydrocarbons such as methyl chloride; halogenated alcohols such as chloroethanol; halogenated phenols such as bromophenol; HSiCl ₃
And the like; metal halides and the like. The contact of the compound is carried out by mixing and stirring or mechanically co-milling in the presence or absence of an inert medium (e.g., hexane, heptane, cyclohexane, benzene, toluene, etc.). It can be performed under heating at 150 ° C. (A) The solid component is preferably prepared by a method disclosed in detail in JP-A-63-264607, JP-A-58-198503 and JP-A-62-146904. More specifically, (a) metal magnesium, (b) a halogenated hydrocarbon, (c) a compound of the general formula X _n M (OR) _mn (X is a hydrogen atom, a halogen atom or a C ₁ -C ₂₀ hydrocarbon; M is B, C, Al, Si or P; R is a C ₁ -C ₂₀ hydrocarbon; m is the valence of M, m> n ≧ 0), and the magnesium-containing solid obtained by contacting with (d) halogen (E) contact with an electron-donating compound and (f) a titanium compound.
JP-A-264607), (a) contacting a magnesium dialkoxide with a (b) silicon halide compound having a hydrogen-silicon bond, (c) contacting with a titanium halide compound, and then (d) electron donating Contacting with a compound (if necessary, further contacting with a titanium halide compound)
JP-A-62-146904), (a) contacting a magnesium dialkoxide with a silicon halide having a hydrogen-silicon bond, (b) contacting with an electron donating compound, and (d)
This is a method in which a titanium compound is brought into contact (JP-A-58-198503).

Of these, a particular method is most desirable.

In the prepolymerization, the above-mentioned solid component (a) is
(D) In the presence of an organoaluminum compound and (c) an organosilicon compound, (d) is contacted with an olefin (for example, an α-olefin such as ethylene, propylene or butene). Examples of the organic aluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, and the like. Examples of the organosilicon compound include bis (oxacyclopent-3-yl) dimethoxysilane, dimethoxymethyl-2-oxacyclohexylsilane, and 2,3,4-trimethyl-3-azacyclopentyltrimethoxysilane. . It is preferable to add an electron donating compound at the time of preliminary polymerization, if necessary. As such an electron donating compound, for example, an organosilicon compound such as tetramethoxysilane, tetraphenoxysilane, and vinyltriethoxysilane is preferable.

The prepolymerization is preferably carried out in the presence of an inert medium, usually at a temperature of 100 ° C. or lower. The polymerization system may be a batch system or a continuous system, and may be performed in one stage or in two or more stages. Preferably, the concentration of (b) organoaluminum compound in the prepolymerized system is 10
Used to be ~ 500 mmol / l,
(A) It is used in an amount of 1 to 50,000 mol per 1 g of titanium in the solid component. (C) The organosilicon compound is used so that the concentration in the prepolymerization system is 5 to 1000 mmol / L. The olefin polymer is incorporated into the (a) solid component by the prepolymerization, and the amount of the polymer is preferably 0.1 to 200 g per 1 g of the (a) solid component.

[0026] The catalyst component thus prepared can be diluted or washed with an inert medium. After washing, it may be dried.

Alternatively, the solid component (a) of the above catalyst
In the above, a catalyst further containing a metal oxide can also be used. The metal oxide is an oxide of an element selected from the group of elements of Groups II to IV of the Periodic Table of the Elements,
For example, B ₂ O ₃ , MgO, Al ₂ O ₃ ,
SiO ₂ , CaO, TiO ₂ , ZnO, ZrO ₂ , Sn
O ₂ , BaO, ThO _{2 and the} like can be mentioned. Among them, B ₂ O ₃ , MgO, Al ₂ O ₃ , SiO ₂ , Ti
O ₂ and ZrO ₂ are preferred, and SiO ₂ is particularly preferred.
Further, composite oxides containing these metal oxides, for example, S
_{iO 2 -MgO, SiO 2 -Al 2} O 3, SiO 2 -T
iO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ ,
SiO ₂ —TiO ₂ —MgO or the like can also be used.

These metal oxides are usually used in powder form. Since the form such as the size and shape of the powder often affects the form of the obtained olefin polymer, it is desirable to appropriately adjust the form. It is desirable that the metal oxide be fired at as high a temperature as possible for the purpose of removing poisonous substances when used, and that the metal oxide be handled so as not to come into direct contact with the atmosphere.

When a metal oxide is contained, a preferred method for preparing the component (a) is described in JP-A-58-162607 and JP-A-55-9
No. 4909, No. 55-115405, No. 57-108107, No. 61-21109, No. 61-174204, No. 61-174
Methods disclosed in JP-A-205, JP-A-61-174206, and JP-A-62-7706 are exemplified. More specifically, a method in which a reaction product of a metal oxide and a magnesium dialkoxide is brought into contact with an electron-donating compound and a tetravalent titanium halide (JP-A-58-162607); A method in which a reaction product of a hydrocarbyl halide compound is contacted with a Lewis base compound and titanium tetrachloride (JP-A-55-94909). A reaction product of a porous carrier such as silica and an alkylmagnesium compound is treated with titanium. A method of bringing into contact with an electron-donating compound and a silicon halide compound before contacting with a compound (JP-A-55-115405 and JP-A-57-108107), metal oxides, alkoxy-containing magnesium compounds,
A method of contacting an aromatic polycarboxylic acid having a carboxyl group at the ortho position or a derivative thereof and a titanium compound (JP-A-61-174204), a metal oxide, an alkoxy group-containing magnesium compound,
A method of contacting a silicon compound having a hydrogen-silicon bond, an electron donating compound and a titanium compound (JP-A-61-1)
No. 74205) Metal oxides, alkoxy-containing magnesium compounds,
A method of contacting a halogen element or a halogen-containing compound, an electron-donating compound and a titanium compound (JP-A-61
-174206), a method of contacting a reaction product obtained by contacting a metal oxide, dihydrocarbylmagnesium and a halogen-containing alcohol with an electron-donating compound and a titanium compound (JP-A-61-21109). A method in which a solid obtained by contacting a metal oxide, hydrocarbylmagnesium, and a compound containing a hydrocarbyloxy group (corresponding to the above-mentioned alkoxy group-containing compound) is contacted with a halogen-containing alcohol, and further contacted with an electron-donating compound and a titanium compound ( JP
62-7706). Of these, methods (1) and (2) are particularly desirable.

Using the catalyst component thus obtained, if necessary, in combination with an organometallic compound and / or an electron-donating compound, the polypropylene components 1 and 2
Multistage polymerization is performed in an arbitrary order (main polymerization reaction). As the organometallic compound, an organic compound of Li, Mg, Ca, Zn, and Al can be used. Of these, organoaluminum compounds are particularly preferred, for example, trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum; dialkylaluminum monohalides such as diethylaluminum chloride; monoalkylaluminum dihalides such as ethylaluminum dibromide; Alkyl aluminum sesquihalides such as chloride; dialkyl aluminum monoalkoxides such as dimethyl aluminum methoxide; dialkyl aluminum hydrides such as diisobutyl aluminum hydride; Examples of the electron donating compound include dimethoxymethyl-2-oxacyclohexylsilane, 2,3,4-trimethyl-3-azacyclopentyltrimethoxysilane, bis (oxacyclopent-3-yl) dimethoxysilane, and isopropoxycyclopentane. Organic silicon compounds such as dienyldimethoxysilane and t-butoxycyclopentadienyldimethoxysilane are exemplified.

The present polymerization reaction is carried out in a gas phase or a liquid phase (for example, in an inert hydrocarbon such as butane, isobutane, cyclohexane, benzene, and toluene and in a liquid monomer).
The polymerization can be carried out at a polymerization temperature of -80 to + 150 ° C and a polymerization pressure of 1 to 60 atm. The polymerization reaction may be a batch type or a continuous type,
Further, it may be performed in one stage or in two or more stages.
In order to adjust the molecular weight of the produced polymer, a known molecular weight controlling agent such as hydrogen can be present in the polymerization reaction system. By changing the type and amount of the molecular weight controlling agent for each polymerization reaction of each component, a desired MF can be obtained.
A polypropylene component having R can be obtained. The weight ratio of the propylene components 1 and 2 is adjusted by adjusting the polymerization reaction time of each component. Control of these conditions is known to those skilled in the art.

The polymer of the present invention can be used as a composition containing conventional additives. Conventional additives include antioxidants, heat stabilizers, light stabilizers, flame retardants, plasticizers, antistatic agents, lubricants, release agents, nucleating agents, fillers, and the like.

Next, the composition of the second invention will be described. The composition of the present invention comprises two polypropylene components 1 'and 2' with different melt flow rates. The MFR of the component 1 ′ (MFR _{1 ′} ) is the MFR of the component 2 ′ (MFR _{1 ′} ).
FR _{2 ′} ). MFR of both components, and component 1 '
Is required to satisfy the relationship of the above formula (I ′). W 'is the weight ratio of component 1' to the sum of components 1 'and 2', preferably 0.05
0.95.

MFR _{1 ′} , MFR _{2 ′} and w ′ preferably have the following formula (II ′):

[0035]

(Equation 13) (Wherein a ₁ , a ₂ , a ₃ , β and γ have the same meanings as above), and more preferably the following formula (II)
I '):

[0036]

[Equation 14] (Where a ₁ , a ₂ , a ₃ , β and γ have the same meanings as described above). If MFR _{1 ′} , MFR _{2 ′} and w ′ do not satisfy the above relationship, a good balance between moldability and rigidity cannot be obtained in the composition. Preferably, the MFR _{1 ′} is 0.01 to 10 g / 10 minutes,
And MFR _{2 '} is 10-300 g / 10min.

The composition of the present invention needs to satisfy HI> 96.2. When the HI is 96.2 or less, a good balance between moldability and rigidity cannot be obtained in the composition. Preferably, HI> 97.2.

The composition of the present invention can be produced by separately producing the polypropylene component 1 'and the polypropylene component 2', and then blending (and optional components) at a predetermined ratio, followed by melt-kneading. . The equipment, conditions, and the like used for melt-kneading are known to those skilled in the art.
Polypropylene component 1 'and polypropylene component 2'
Can be produced by using the production method described in the production of the polymer of the present invention described above. Instead of multi-stage polymerization of components 1 and 2, each component is separately polymerized. At that time, the polymerization reaction of each component may be performed in one stage or in multiple stages. Alternatively, commercially available polypropylene can be used as the component 1 'and / or the component 2'.

The composition of the present invention can be used as long as it satisfies the above-mentioned requirements, that is, it satisfies the above formula (I ') and
If I> 96.2 is satisfied, in addition to components 1 and 2,
A polypropylene component having a different MFR from these may be contained in an amount of 20% by weight or less of the entire resin component. When three or more kinds of MFR polypropylene components are contained in the composition of the present invention, it is sufficient that two of them satisfy the above relationship.

In the composition of the present invention, in addition to the above-mentioned components, other resins such as polyethylene can be blended as long as the object of the present invention is not impaired, and an antioxidant, a heat stabilizer, Various additives such as a light stabilizer, a flame retardant, a plasticizer, an antistatic agent, a lubricant, a release agent, a nucleating agent, and a filler can be blended.

[0041]

The present invention will be described in more detail with reference to the following examples. The percentages are by weight unless otherwise specified.

The MFR was measured at 230 ° C. under a load of 2.16 kg in accordance with ASTM D1238. HI
The (heptane-insoluble content) was determined as the weight ratio of the residue after extracting the sample with boiling n-heptane for 6 hours using a modified Soxhlet extractor with respect to the whole sample. The flexural modulus is
It was measured according to JIS K-6758.

Example 1 (Composition) (1) Preparation of Component A for Production of Polypropylene Component 2 A chip-shaped metallic magnesium (purity 99.5%) was placed in a 1-liter reaction vessel equipped with a reflux condenser under a nitrogen gas atmosphere. ,
8.3 g of an average particle size (1.6 mm) and 250 ml of n-hexane were added, and the mixture was stirred at 68 ° C. for 1 hour. The metallic magnesium was taken out and dried at 65 ° C. under reduced pressure to obtain preactivated metallic magnesium.

Next, 140 ml of n-butyl ether and an n-butyl ether solution of n-butylmagnesium chloride (1.75 mol / l) were added to 0.5 g of the metallic magnesium.
The resulting suspension was maintained at 55 ° C., and a solution of 38.5 ml of n-butyl chloride dissolved in 50 ml of n-butyl ether was added dropwise over 50 minutes. After performing the reaction at 70 ° C. for 4 hours with stirring, the reaction solution was kept at 25 ° C.

Next, HC (OC) was added to the reaction solution.
It was added dropwise ₂ H _{5) 3 55.7ml} over one hour. After the completion of the dropwise addition, the reaction was carried out at 60 ° C. for 15 minutes, and the solid produced by the reaction was washed six times with 300 ml each of n-hexane and dried under reduced pressure at room temperature for 1 hour. Was recovered.

Under a nitrogen gas atmosphere, 6.3 g of a magnesium-containing solid and 50 ml of n-heptane were put into a 300 ml reaction vessel equipped with a reflux condenser, a stirrer and a dropping funnel to form a suspension. , 2,2,2-trichloroethanol 20ml (0.02mmol) and n-heptane 11m
of mixed solution was added dropwise from a dropping funnel over 30 minutes, and further stirred at 80 ° C. for 1 hour. The obtained solid was separated by filtration, washed four times with 100 ml each of n-hexane at room temperature, and twice with 100 ml each of toluene to obtain a solid component.

To the above solid component was added 40 ml of toluene,
Further, titanium tetrachloride was added so that the volume ratio of titanium tetrachloride / toluene became 3/2, and the temperature was raised to 90 ° C. Under stirring, a mixed solution of 2 ml of di-n-butyl phthalate and 5 ml of toluene was added dropwise over 5 minutes, followed by stirring at 120 ° C. for 2 hours.
The obtained solid substance was separated by filtration at 90 ° C., and toluene 100 m each.
2 times at 90 ° C. Further, titanium tetrachloride was added so that the volume ratio of titanium tetrachloride / toluene became 3/2, and the mixture was stirred at 120 ° C. for 2 hours. The obtained solid substance was separated by filtration at 110 ° C. and washed seven times with 100 ml of n-hexane at room temperature seven times to obtain 5.5 g of a component A. Main polymerization In a 1.5-liter autoclave sufficiently purged with nitrogen, the polymerization catalyst component A obtained above was placed under a nitrogen atmosphere.
8.1 mg, 2 ml of n-heptane solution of triethylaluminum (0.2 mol / l) and 2 ml of n-heptane solution of isopropoxycyclopentadienyldimethoxysilane (0.04 mol / l) were mixed, and the mixture was kept for 5 minutes. . Next, 11 liters of hydrogen gas and 1 liter of liquid propylene as a molecular weight regulator were injected under pressure, and then the polymerization was carried out at an internal temperature of 70 ° C. for 1 hour. After completion of the polymerization, hydrogen and unreacted propylene were purged, and the polymer in the autoclave was taken out.
285.3 g of the polymer (component 2 ') were obtained and the MFR _2' was 15
5.2 g / 10 min. The measured HI of this polymer was 97.0. (2) Production of polypropylene component 1 'Polymerization was carried out in the same manner as in the above-mentioned component (1), except that the amount of hydrogen (molecular weight controlling agent) was changed from 11 liters to 0.3 liters. Polymer (component 1 ')
187.3 g were obtained, and the MFR _{1 '} was 0.13 g / 10 minutes. The measured HI of this polymer was 98.6. (3) Preparation of composition The polypropylene component 2 'obtained in the above (1) and (2)
And 1 'were blended in the proportions shown in Table 1, and 2,6-
Ditertiary butyl-4-methylphenol (BHT)
0.18% by weight, distearyl thiodipropionate (DS
TDP) 0.08% by weight, tetrakis- {methylene- (3,5-ditert-butyl-4-hydroxyhydrocinnamate)
Methane (IRGANOX1010: trade name, manufactured by Ciba Geigy) 0.04% by weight and calcium stearate 0.06% by weight were added. After dry blending, the mixture was melt-kneaded using a Brabender (Lab Blast Mill, manufactured by Toyo Seiki Co., Ltd.) at a kneading temperature of 190 ° C. and a rotation speed of 100 rpm, and pelletized. Next, a test piece was injection-molded from the pellet, and using this, the MFR was measured.
Was determined, and the flexural modulus was measured. Table 1 shows the results.

Example 2 (Composition) (1) Preparation of Polypropylene Component 2 'Preparation of Component A' A 200-ml flask equipped with a dropping funnel and a stirrer was purged with nitrogen. In this flask, silicon oxide (D
AVISON, trade name: G-952) was calcined in a nitrogen stream at 200 ° C. for 2 hours and further at 700 ° C. for 5 hours, and 5 g and n-heptane 40 ml were added. further,
n-butylethylmagnesium (hereinafter referred to as BEM)
20 ml of a 20% n-heptane solution (manufactured by Texas Alkyls, trade name: MAGARA BEM) was added, and the mixture was stirred at 90 ° C. for 1 hour.

After the obtained suspension was cooled to 0 ° C., a solution in which 11.2 g of tetraethoxysilane was dissolved in 20 ml of n-heptane was added dropwise from a dropping funnel over 30 minutes. After completion of dropping, the temperature was raised to 50 ° C over 2 hours.
Stirring was continued for hours. After the completion of the reaction, the supernatant was removed by decantation, and the resulting solid was washed at room temperature with 60 ml of n-heptane, and the supernatant was removed by decantation. This washing treatment with n-heptane was further performed four times.

To the obtained solid, 50 ml of n-heptane was added to form a suspension, and 2,2,2-trichloroethanol was added to the suspension.
A solution of 0 g dissolved in 10 ml of n-heptane was added dropwise from a dropping funnel at 25 ° C. over 15 minutes. After completion of the dropwise addition, stirring was continued at 25 ° C. for 30 minutes. After completion of the reaction, washing was performed twice at room temperature with 60 ml of n-heptane and three times with 60 ml of toluene. When the obtained solid (solid component I) was analyzed, SiO ₂ 36.6%, Mg 5.1
% And Cl 38.5%.

The solid component I obtained above was added to n-heptane
10 ml and 40 ml of titanium tetrachloride were added, the temperature was raised to 90 ° C., and di-n-butyl phthalate dissolved in 5 ml of n-heptane was added.
6 g was added over 5 minutes. Thereafter, the temperature was raised to 115 ° C., and the reaction was carried out for 2 hours. After the temperature was lowered to 90 ° C., the supernatant was removed by decantation, and the mixture was washed twice with 70 ml of n-heptane. Furthermore, n-heptane 15 ml and titanium tetrachloride 40
Then, the mixture was reacted at 115 ° C. for 2 hours. After the reaction,
The obtained solid component was washed eight times at room temperature with 60 ml of n-hexane. Then, drying was performed at room temperature under reduced pressure for 1 hour to obtain 8.3 g of a catalyst component (component A '). Component A 'contained, in addition to 3.1% Ti, silicon oxide, Cl and di-n-butyl phthalate. Main polymerization In a 1.5-liter autoclave sufficiently purged with nitrogen, the polymerization catalyst component A ′ obtained above was placed under a nitrogen atmosphere.
21.1 mg, 2 ml of a solution of triethylaluminum in n-heptane (0.2 mol / l) and a solution of t-butoxycyclopentadienyldimethoxysilane in n-heptane (0.
(04 mol / l) and mixed for 2 minutes. Next, hydrogen gas 8 as a molecular weight regulator was used.
After pressurizing 1 liter and 1 liter of liquid propylene, polymerization was carried out for 1 hour at an internal temperature of the autoclave of 70 ° C. After completion of the polymerization, hydrogen and unreacted propylene were purged, and the polymer in the autoclave was taken out. 252.8 g of the polymer (component 2 ') were obtained and the MFR _2' was 147.
3 g / 10 min. The measured HI of this polymer was 96.7. (2) Production of polypropylene component 1 'Polymerization was carried out in the same manner as in component (2') except that the amount of hydrogen gas was changed to 0.1 liter. 173.2 g of polymer (component 1 ') were obtained, and MFR _1'
Was 0.16 g / 10 minutes. The HI of this polymer measured 98.3. (3) Preparation of composition The polypropylene component 2 'obtained in the above (1) and (2)
A composition was prepared in the same manner as in Example 1, (3) except that (1) and (1) were used, followed by injection molding to prepare test pieces. Table 1 shows the results of the physical property measurements.

Example 3 (Composition) (1) Preliminary polymerization of polypropylene component 2 'The polymerization catalyst component A prepared in (1) of Example 1 was prepolymerized as follows: A stirrer was attached. Under a nitrogen gas atmosphere, 5.3 g of the polymerization catalyst component A and 200 ml of n-heptane were put into a 500 ml reactor and cooled to 0 ° C. with stirring. Next, triethylaluminum (hereinafter, T
A solution of n-heptane (abbr.
It was added so as to be mmol / liter, and stirred for 5 minutes. Next, propylene was supplied and polymerization was performed for 1 hour.
After completion of the polymerization, the solid phase was washed with 150 ml of n-hexane three times at room temperature. The solid phase was further dried under reduced pressure at room temperature for 1 hour to prepare a catalyst component B. As a result of measuring the amount of magnesium contained in the catalyst component B, the prepolymerized amount was 2.3 g per 1 g of the component A. Main polymerization In place of catalyst component A, catalyst component B 25.2 m obtained above
g) and the polymerization reaction was carried out in the same manner as in the main polymerization in (1) of Example 1 except that the amount of hydrogen gas was changed to 11 liters, thereby producing a polypropylene component 2 '. The obtained polymer weighed 263.2 g. MFR of this polymer
_{2 '} was 161.3 g / 10 min and HI was 97.1. (2) Production of polypropylene component 1 'Polymerization was carried out in the same manner as in the production of component 2' of (1) except that the amount of hydrogen gas was changed to 0.8 liter. 165.3 g of a polymer (component 1 ') were obtained. The MFR _{1 'of} this polymer is 1.2 g / 10 min and the HI is 98.3
Met. (3) Preparation of composition The polypropylene component 2 'obtained in the above (1) and (2)
A composition was prepared in the same manner as in Example 1, (3) except that (1) and (1) were used, followed by injection molding to prepare test pieces. Table 1 shows the results of the physical property measurements.

Comparative Example 1 (Composition) (1) Production of Polypropylene Component 2 'In the main polymerization, tetrapropanol was used in place of 2 ml of a solution of isopropoxycyclopentadienyldimethoxysilane in n-heptane (0.04 mol / l). Example 3 except that 2 ml of an ethoxysilane n-heptane solution (0.04 mol / l) was used and the amount of hydrogen gas was changed to 1.8 liters.
A polymerization reaction was performed in the same manner as in (1). The weight of the obtained polymer (component 2 ') was 202.5 g. M of this polymer
FR _{2 '} was 147.3 g / 10 min and HI was 95.4. (2) Production of polypropylene component 1 'Polymerization was carried out in the same manner as in the production conditions of component 2' in (1) except that the amount of hydrogen gas was changed to 0.01 liter. 150.2 g of a polymer (component 1 ') was obtained. The MFR _{1 'of} this polymer is 0.16 g / 10 min and the HI is 95.8
Met. (3) Preparation of composition The polypropylene component 2 'obtained in the above (1) and (2)
A composition was prepared in the same manner as in Example 1, (3) except that (1) and (1) were used, followed by injection molding to prepare test pieces. Table 1 shows the results of the physical property measurements.

[0054]

[Table 1] Example 4 (two-stage polymerization) (1) First-stage polymerization (production of component 1) Obtained in (1) of Example 3 in a 1.5-liter autoclave sufficiently purged with nitrogen under a nitrogen atmosphere. 16.4 mg of polymerization catalyst component B, 2 ml of n-heptane solution of triethylaluminum (0.2 mol / l) and 2 ml of n-heptane solution of t-butoxycyclopentadienyldimethoxysilane (0.04 mol / l)
Were mixed and kept for 5 minutes. Next, 500 ml of hydrogen gas as a molecular weight regulator and 1 liter of liquid propylene were injected under pressure, and then the polymerization was carried out at an internal temperature of 70 ° C. for 40 minutes.

A sample was partially collected from the liquid phase in the autoclave. The weight of the polymer in the sample was 7.2 g, its MFR ₁ was 1.1 g / 10 min, and HI was 98.3. (2) Second Stage Polymerization (Production of Component 2) Subsequently, while maintaining the internal temperature of the autoclave at 70 ° C., 11 liters of hydrogen was added to start the second stage polymerization,
Polymerization was performed for 40 minutes. After completion of the polymerization, hydrogen and unreacted propylene were purged, and the polymer in the autoclave was taken out. 280.8 g of polymer were obtained. (3) Analysis Next, chemical analysis of the polymer was performed by induction plasma emission analysis, and the polymer yield per catalyst unit in the first and second stages was determined. From this value, the polymer yield in the first and second stages was determined. The polymerization amount ratio of the polymer component was determined. The MFR _{2 of} the polymer component formed in the second stage is the MFR _{1 of} the polymer obtained in the first stage, the MFR of the polymer finally obtained, and the polymerization amount of the polymer components in the first and second stages. It was calculated from the ratio. The HI of the polymer component obtained in the second stage is
HI of polymer separately polymerized under the same conditions as the second stage polymerization
Guessed from. Table 2 shows the results. (4) Measurement of physical properties of polymer 2,6-
Ditertiary butyl-4-methylphenol (BHT)
0.18% by weight, distearyl thiodipropionate (DS
0.08% by weight of TDP), 0.04% by weight of tetrakis- {methylene- (3,5-ditert-butylhydroxyhydrocinnamate) methane (IRGANOX1010, trade name, manufactured by Ciba-Geigy) and 0.06% by weight of calcium stearate were added. After dry blending, the mixture was melt-kneaded using a Brabender (Lab Blast Mill, manufactured by Toyo Seiki Co., Ltd.) at a kneading temperature of 190 ° C. and a rotation speed of 100 rpm, and pelletized. Next, a test piece was injection-molded from the pellet, and using this, the MFR was measured, the HI was determined, and the flexural modulus was measured. Table 2 shows the results.

Example 5 (Two-stage polymerization) (1) The same procedure as in (4) of Example 4 except that 10.3 mg of the catalyst component A 'prepared in Example 2 was used instead of the catalyst component B for the two-stage polymerization reaction. (2)
In the same manner as in the above, the component 1 polymer was polymerized in the first stage using 300 ml of hydrogen, and the component 2 polymer was polymerized in the second stage using 8 liters of hydrogen. (2) Analysis The polymer was analyzed in the same manner as in (3) of Example 4.
Table 2 shows the results. (3) Measurement of physical properties of polymer Melt-kneading was carried out in the same manner as in (4) of Example 4 except that the polymer (component 1 + component 2) finally obtained in (1) above was used, followed by injection molding. To prepare a test piece. Table 2 shows the results of the respective physical property measurements.

COMPARATIVE EXAMPLE 2 (Two-stage polymerization) (1) Two-stage polymerization In the polymerization, 2-m solution of t-butoxycyclopentadienyldimethoxysilane in n-heptane (0.04 mol / l) was used.
Example 2 was repeated except that 2 ml of an n-heptane solution of tetraethoxysilane (0.04 mol / l) was used instead of 1 and the amount of hydrogen gas was changed to 50 ml in the first stage and 200 ml in the second stage. In the same manner as in (1) and (2) of No. 4, component 1 polymer was polymerized in the first stage, and component 2 polymer was polymerized in the second stage. (2) Analysis The polymer was analyzed in the same manner as in (3) of Example 4.
Table 2 shows the results. (3) Measurement of physical properties of polymer Melt-kneading was carried out in the same manner as in (4) of Example 4 except that the polymer (component 1 + component 2) finally obtained in (1) above was used, followed by injection molding. To prepare a test piece. Table 2 shows the results of the respective physical property measurements.

Comparative Example 3 (Two-stage polymerization) (1) Two-stage polymerization reaction In the polymerization, 2-m solution of t-butoxycyclopentadienyldimethoxysilane in n-heptane (0.04 mol / l) was used.
Example 4 was repeated except that 2 ml of a solution of tetraethoxysilane in n-heptane (0.04 mol / l) was used and the amount of hydrogen gas was changed to 200 ml in the first stage and to 1.8 liter in the second stage. As in (1) and (2) above,
The first stage polymerized the component 1 polymer and the second stage polymerized the component 2 polymer. (2) Analysis The polymer was analyzed in the same manner as in (3) of Example 4.
Table 2 shows the results. (3) Measurement of physical properties of polymer Melt-kneading was carried out in the same manner as in (4) of Example 4 except that the polymer (component 1 + component 2) finally obtained in (1) above was used, followed by injection molding. To prepare a test piece. Table 2 shows the results of the respective physical property measurements.

[0059]

[Table 2]

[0060]

The crystalline polypropylene polymer and the composition of the present invention have excellent balance between moldability and rigidity, and can be used for a wide range of applications. In particular, it is suitable for injection molding applications.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 10/00-10/14 C08F 110/00-110/14 C08F 210/00-210/18 C08L 23 / 00-23/36

Claims (5)

(57) [Claims] 1. A polymer comprising two types of polypropylene components 1 and 2 having different melt flow rates,
(1) Melt flow rate (MFR) of component 1
₁ ) and the melt flow rate (M
FR ₂ ), and components 1 and 2 of component 1
Is a weight ratio w to the total of the following formula (I): (Where a ₁ = 2460, a ₂ = 4660, a ₃ =
-1.45, β = -0.1143, γ = a is) fulfills the relationship -0.171, an MFR ₁ ≦ MFR _2, and (2) a boiling n the polymer with improved Soxhlet extractor -A crystalline polypropylene polymer characterized in that the weight ratio HI of the residue after extraction with heptane for 6 hours with respect to the whole polymer satisfies HI> 96.2. 2. Two kinds of poly having different melt flow rates.
In a polymer containing propylene components 1 and 2,
(1) Melt flow rate (MFR) of component 1
₁ ) and the melt flow rate (M
FR ₂ ), and components 1 and 2 of component 1
Weight ratio w to the sum of the following formula (II): [number 2] ( Where a ₁ = 2460, a ₂ = 4660, a ₃ =
−1.45, β = −0.1143, γ = −0.171
Is satisfied) and MFR ₁ ≦ MFR ₂
And (2) boiling the polymer in a modified Soxhlet extractor.
Polymerization of the residue after 6 hours of extraction with n-heptane
The weight ratio HI to the whole body satisfies HI> 97.2.
A crystalline polypropylene polymer, characterized in that: 3. A propylene polymerized by a multistage polymerization method.
Two types of polypropylene with different melt flow rates
In a polymer containing component components 1 and 2, MFR ₁
= 0.01 to 10 g / 10 min, MFR ₂ = 10 to 300
g / 10 minutes, MFR ₁ ≦ MFR ₂ , and the polymer
In a modified Soxhlet extractor with boiling n-heptane.
Weight ratio of residue after time extraction to total polymer
A crystal characterized in that HI satisfies HI> 97.2.
Polypropylene polymer. 4. A crystalline polypropylene composition comprising two types of polypropylene components 1 ′ and 2 ′ having different melt flow rates, wherein (1) a melt flow rate (MFR _{1 ′} ) of component _{1 ′} and a melt flow rate of component 2 ′ Having a melt flow rate (MFR _{2 ′} ), and component 1 ′
The weight ratio w ′ to the sum of the components 1 ′ and 2 ′ is represented by the following formula (I ′): (Where a ₁ = 2460, a ₂ = 4660, a ₃ =
−1.45, β = −0.1143, γ = −0.171) and MFR _{1 ′} ≦ MFR _{2 ′} , and (2) the composition was treated with an improved Soxhlet extractor. Of the residue after 6 hours of extraction with boiling n-heptane,
A crystalline polypropylene composition, wherein a weight ratio HI to the whole composition satisfies HI> 96.2. 5. Two kinds of poly having different melt flow rates.
Crystalline polypropylene containing propylene components 1 'and 2'
In the lenticular composition, (1) melt 1
Mel having low rate (MFR _{1 ′} ) and component 2 ′
Flow rate (MFR _{2 ′} ), as well as component 1 ′
The weight ratio w ′ to the sum of components 1 ′ and 2 ′ is
Formula (II '): [number 4] ( Where a ₁ = 2460, a ₂ = 4660, a ₃ =
−1.45, β = −0.1143, γ = −0.171
Is satisfied) and MFR _{1 ′} ≦ MFR _{2 ′}
And (2) the polymer is an improved Soxhlet extractor
Of the residue after extraction with boiling n-heptane for 6 hours at
The weight ratio HI to the whole polymer is HI> 97.2.
A crystalline polypropylene polymer characterized by satisfying.