JPH08109294A - Polypropylene resin composition - Google Patents

Abstract

PURPOSE: To obtain a polypropylene resin composition having a well-balanced combination of impact resistance, rigidity, and heat resistance by compounding a specific mixed PP resin with an olefin rubber or another polyolefin. CONSTITUTION: The composition comprises (A) 50-90 pts.wt. mixed PP consisting of 3-30wt.% PP which is insoluble in hot heptane but soluble in hot octane and has a weight-average mol.wt. of 5,000-1,000,000 and in which the content of pentads each made up of five propylene units bonded through meso bonds only is 70% or higher and the content of pentads each made up of propylene units bonded through racemic bonds only is 5% or higher and 70-95wt.% ultrahighly wstereoregular PP which has a melt flow rate of 0.1-1,000g/10min and in which the meso-average chain length, Nm, calculated from the triad contents using equation I satisfies relationship II, (B) 50-10 pts.wt. at least either an olefin rubber or a polyolefin other than the PPs, and (C) an inorganic filler in an amount of up to 40 pts.wt. per 100 pts.wt. the sum of the components (A) and (B).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to interior and exterior parts for automobiles,
The present invention relates to a polypropylene resin composition having excellent impact resistance and rigidity, which is used for home electric appliance parts and other various industrial parts.

[0002]

2. Description of the Related Art Polypropylene resin is widely used in various fields because it is lightweight and excellent in mechanical strength. However, there is a trade-off relationship between impact resistance and rigidity and heat resistance. For example, when the compounding amount of olefin-based rubber is increased to emphasize impact resistance in automobile bumper materials, flexural elasticity is increased. Rate is about 15 × 10 ³ kg / cm ² , heat distortion temperature is 1
It drops to about 20 ° C. For this reason, there are restrictions on the design and the baking temperature at the time of painting in order to maintain the strength of the parts. On the contrary, if a large amount of inorganic filler is blended in order to emphasize rigidity and heat resistance, there is a problem that impact resistance is significantly lowered.

Therefore, if this problem is solved, it is expected that the range of use of the polypropylene resin material will be expanded, the number of parts that can be covered with one material will be increased, and that it can be advantageously developed in terms of cost.

[0004]

[Means for Solving the Problems] As a result of intensive studies in view of the above problems, a stereoblock polypropylene (hereinafter abbreviated as SBPP) in which an isotactic chain and a syndiotactic chain are alternately connected to form a main chain, It has been found that blending a highly stereoregular polypropylene with an olefin rubber and / or a polyolefin other than the polypropylene and an inorganic filler can improve both impact resistance, rigidity and heat resistance, The present invention has been completed.

That is, the polypropylene resin composition of the present invention is (A) (a) a polypropylene which is insoluble in hot heptane and soluble in hot octane, and in which all five consecutive propylene monomer unit bonds are mesomorphic. Fraction that is a bond ( ¹³ C-N
70% or more, calculated from the pentad fraction by MR,
5 to 30% by weight of polypropylene having a racemic bond content of 5% or more and a weight average molecular weight of 5,000 to 1,000,000, and (b) 0.1 to 1000 g / 10 min of melt flow rate (MFR, 230 ° C). , 2,160 g), ¹³
From the triad fraction obtained by C-NMR, the following formula
(1): Nm = 2 [mm] / [mr] +1 (1) (where [mm]: number of isotactic triads / total number of triads, [mr]: number of heterotactic triads / total number of triads) Composite polypropylene consisting of 70 to 95% by weight of ultra-high stereoregular polypropylene having a meso-average chain length Nm calculated by the following formula (2): Nm> 250 + 29.5log (MFR) (2) 50-90 parts by weight of resin, (B)
An olefin rubber and / or 50 to 10 parts by weight of a polyolefin other than (A), and (C) 0 to 40 parts by weight of an inorganic filler per 100 parts by weight of (A) + (B). To do.

Hereinafter, the present invention will be described in detail. [1] Each component of polypropylene resin composition (A) Composite polypropylene resin (a) Stereoblock polypropylene (SBPP)

(1) Production method SBPP can be obtained by subjecting polypropylene obtained by polymerizing propylene at 60 ° C. or lower in the presence of the following catalyst to extraction treatment with hot heptane and hot octane.

(A) Production catalyst It consists of the following three components. A solid catalyst component containing magnesium, titanium, a halogen and an electron donating compound as essential components. It can be prepared by bringing a magnesium compound, a titanium compound and an electron donating compound into contact with each other, and a halogen-containing compound when each compound does not contain halogen. Organoaluminum compound. General formula: (R ¹ O) _x R ² _2-x Si (OR ³ ) ₂ (where X is 0, 1 or 2, R ¹ is a carbon number 2-10)
R ² is a hydrocarbon group having 1 to 10 carbon atoms, and R ³ is a hydrocarbon group having 2 to 4 carbon atoms, which may be the same or different. ) An organosilicon compound represented by:

Details of the catalyst component and the details thereof are described in JP-A-7-11.
No. 8322 (Japanese Patent Application No. 5-289860).

The amount of the component used relative to the component is 1 to 2,000 gram mol per gram atom of titanium of the component,
It is preferably 20 to 500 gram mol. The amount of the component used is 0.001 to 10 mol, preferably 0.01 to 1.0 mol, per mol of the component.

(B) Polymerization conditions The polymerization reaction of propylene may be in a gas phase or a liquid phase. When the polymerization is carried out in a liquid phase, normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, It can be carried out in an inert hydrocarbon solvent such as benzene, toluene, xylene or in a liquid monomer.

The polymerization temperature is 60 ° C. or lower, preferably 0 to 60 ° C.
And the polymerization pressure may be, for example, 1 to 60 atm. The molecular weight of the resulting polymer can also be controlled by the presence of hydrogen or other known molecular weight regulators. Polymerization reaction is carried out in a continuous or batch reaction,
The conditions may be normal. Further, the polymerization reaction may be carried out in one stage or in multiple stages.

(C) Extraction treatment The obtained polypropylene is extracted with hot heptane to recover the insoluble matter. Then, the hot heptane-insoluble matter is extracted with hot octane to recover the polypropylene component soluble in hot octane. The polypropylene component thus obtained is SB
It is PP.

The hot heptane and hot octane are boiling heptane and octane, respectively. Further, a component soluble in hot heptane has insufficient crystallinity, and a component insoluble in hot heptane and also insoluble in hot octane has insufficient impact resistance improving performance.

(2) Physical properties The stereoregularity of SBPP is Macromolecules, 6 , 925 (19)
73), that is, ¹³ C-NMR method. ^{By the 13} C-NMR method, a pentad fraction showing the bonded state of five consecutive propylene monomer units was obtained, and the propylene monomer unit at the center of the chain had a meso bond and a racemic bond fractions. Desired. However, the peaks are assigned by the method described in Macromolecules, 6 , 687 (1975), and specifically, the intensity distributions of mmmm peaks and rrrr peaks in all absorption peaks in the methyl hydrocarbon region of the ¹³ C-NMR spectrum. It is measured as a rate. Below, the respective fractions are [mmmm] (meso bond), [r
rrr] (racemic bond).

The SBPP of the present invention has a meso bond fraction of 70% or more and a racemic bond fraction of 5% or more. When the meso bond is less than 70%, the crystallinity is insufficient, and when the racemic bond is less than 5%, the impact resistance improving performance is insufficient. The preferred meso bond fraction is 70-80.
%, And the preferable fraction of racemic bonds is 5 to 10%.

The SBPP used in the present invention is also characterized by a weight average molecular weight of 5,000 to 1,000,000. When the weight average molecular weight is less than 5,000, impact resistance improving performance is insufficient, and when it exceeds 1,000,000, fluidity is insufficient. The preferred weight average molecular weight is 100,000 to 50.
In many cases.

(B) Ultra-high stereoregular polypropylene (1) Production method Ultra-high stereoregular polypropylene (HSPP) is obtained by polymerizing propylene at 60 ° C. or lower in the presence of the following catalyst to obtain polypropylene obtained by heating with hot heptane. It is obtained by extraction processing with.

(A) Production catalyst It consists of the following three components. A component produced by contacting a solid catalyst component containing magnesium, titanium, a halogen and an electron donating compound as essential components with propylene in the presence of a trialkylaluminum and an organosilicon compound. Organoaluminum compound. General formula: (R ¹ O) R ² Si (OCH ₃ ) ₂ (wherein R ¹ is a hydrocarbon group having 1 to 10 carbon atoms,
R ² is a hydrocarbon group (including a cyclic hydrocarbon group) having a secondary or tertiary carbon atom having 2 to 10 carbon atoms. ) An organosilicon compound represented by:

Details of the catalyst component and the details thereof are described in JP-A-7-11.
No. 8323 (Japanese Patent Application No. 5-289861).

The amount of the component used relative to the component is 1 to 2,000 gram mol per 1 gram atom of titanium of the component,
It is preferably 20 to 500 gram mol. The amount of the component used is 0.001 to 10 mol, preferably 0.01 to 1.0 mol, per mol of the component.

(B) Polymerization conditions The polymerization reaction of propylene may be either gas phase or liquid phase. When the polymerization is carried out in liquid phase, normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, It can be carried out in an inert hydrocarbon solvent such as benzene, toluene, xylene or in a liquid monomer. The polymerization temperature is 60 ° C or lower, preferably in the range of 0 to 60 ° C, and the polymerization pressure is, for example, 1 to
60 atmospheres is sufficient. The molecular weight of the resulting polymer can also be controlled by the presence of hydrogen or other known molecular weight regulators. The polymerization reaction is carried out by a continuous or batch reaction, and the conditions therefor may be ordinary ones. Further, the polymerization reaction may be carried out in one stage or in multiple stages.

(C) Extraction treatment The obtained polypropylene powder is treated with hot heptane (boiling heptane) in an extractor for 5 minutes to 1 day, preferably 30 minutes.
Extraction treatment is performed for 10 minutes to 10 minutes to remove hot heptane-soluble components.

(2) Physical properties (a) Melt flow rate (MFR, 230 ° C., 2.16 kg load) The ultrahigh stereoregular polypropylene obtained as described above has an MFR of 0.1 to 1000 g / 10 min. MFR is
If it is less than 0.1 g / 10 minutes, fluidity is insufficient, and
If it exceeds 1000 g / 10 minutes, the impact resistance becomes insufficient. The preferred MFR is 10 to 1000 g / 10 min, and particularly preferred is 30 to 500 g / 10 min.

(B) Meso Mean Chain Length Nm Meso Mean Chain Length Nm of Ultra High Stereoregular Polypropylene
Is the triad fraction determined by ¹³ C-NMR,
Formula (1): Nm = 2 [mm] / [mr] +1 (1) (where [mm]: number of isotactic triads / total number of triads [mr]: number of heterotactic triads / total) It can be calculated by the number of triads).

Meso-average chain length Nm calculated by the above formula (1)
Must satisfy the following formula (2): Nm> 250 + 29.5log (MFR) (2). If the formula (2) is not satisfied, high rigidity and high impact resistance will not be sufficiently exhibited.

(B) Olefin-based rubber and / or polyolefin other than (A) (a) Olefin-based rubber Olefin-based rubber is a copolymer of ethylene and α-olefin other than ethylene, for example, ethylene-propylene rubber. (EPR), ethylene-propylene-diene rubber (EPDM) obtained by copolymerizing a diene compound with (EPR), and ethylene-butene rubber (EBR).

(1) Ethylene-Propylene Rubber (EPR) The ethylene-propylene rubber (EPR) preferably has an ethylene content of 50 to 90 mol% and a propylene content of 50 to 10 mol%. A more preferable range is ethylene
70-80 mol% and propylene 30-30 mol%. Melt flow rate of ethylene-propylene rubber (MFR, 230
(° C, 2.16 kg load) is preferably 0.5 to 20 g / 10 minutes, more preferably 0.5 to 10 g / 10 minutes.

(2) Ethylene-propylene-diene rubber (EPDM) Examples of the diene compound in the ethylene-propylene-diene rubber (EPDM) include ethylidene norbornene, dicyclopentadiene and 1,4-hexadiene. Similarly, the melt flow rate of the ethylene-propylene-diene rubber is preferably 0.5 to 20 g / 10 minutes, more preferably 0.5 to 10 g / 10 minutes.

(3) Ethylene-butene rubber (EBR) The ethylene-butene rubber (EBR) has an ethylene content of 70.
˜85 mol%, butene-1 content is preferably 15-30 mol%. A more preferable range is 75 to 85 for ethylene.
Mol% and butene-1 are 15 to 25 mol%. Melt index of ethylene-butene rubber (EBR) (MI, 190 ° C, 2.1
The load (6 kg load) is preferably 1 to 30 g / 10 minutes, more preferably 1 to 20 g / 10 minutes.

The number average molecular weight of such an olefin rubber is preferably 2 × 10 ⁴ to 8 × 10 ⁴ , and particularly 3 × 10 ⁴ to
6 × 10 ⁴ is preferable. The weight average molecular weight is 7 × 10 ^4.
˜20 × 10 ⁴ is preferable, and 10 × 10 ^{4 to} 20 × 10 ⁴ is particularly preferable.

The above-mentioned olefin rubbers may be used alone or in admixture of two or more kinds.

(B) Polyolefin other than (A) For the purpose of improving the ductility of the polypropylene resin composition, it is preferable to add a polyolefin such as linear low density polyethylene, low density polyethylene, or ordinary polypropylene. The polyolefin can be blended with the olefin rubber or alone in the ultrahigh stereoregular polypropylene. When compounded with olefin rubber,
The weight ratio of olefin rubber / polyolefin is 1:10.
It is preferably set to 10: 1.

(1) Linear low-density polyethylene Among them, preferable linear low-density polyethylene is a linear copolymer of ethylene and an α-olefin having 4 to 8 carbon atoms. Examples of the α-olefin include 4-methylpentene, 1-butene, 1-hexene and the like. The content of ethylene in linear low density polyethylene is 90 mol%
Or more, preferably 95 mol% or more. Such linear low-density polyethylene has a density of usually 0.910 to 0.940 g / cm ³ , preferably 0.910 to 0.930 g / cm ³ , and 0.7 to 60 g / 1.
It has a melt index (MI, 190 ° C., 2.16 kg load) of 0 minutes, preferably 3 to 20 g / 10 minutes.

(2) Normal polypropylene (a) Homopolypropylene Homopolypropylene has a melt flow rate of 1
It is preferably about 100 g / 10 min.

(B) Block polypropylene Block polypropylene having an ethylene content of 1
-7 wt%, preferably 2-6 wt% propylene-ethylene block copolymer is preferred. The propylene-ethylene block copolymer is mainly composed of a propylene homopolymer part and a propylene-ethylene random copolymer part.

(I) Propylene Homopolymer Part The propylene homopolymer part is a propylene homopolymer or a copolymer part with a trace amount of ethylene that does not impair the crystallinity. In order to maintain high rigidity, the residue after extraction with boiling n-hexane for 6 hours is 90% by weight.
As described above, high crystallinity polypropylene of 95% by weight or more is desirable. Especially melt flow rate (230 ℃, 2,
It is desirable that the amount of 160 g) is 50 to 200 g / 10 minutes. The ratio of the propylene homopolymer part to the whole copolymer is 8
It is preferably from 8 to 98% by weight, more preferably 90%
~ 96 wt%.

(Ii) Propylene-Ethylene Random Copolymer Portion The ethylene content in the propylene-ethylene random copolymer portion is preferably 25-75% by weight, 30-
More preferably, it is 60% by weight. The proportion of the propylene-ethylene random copolymer portion with respect to the entire copolymer is preferably 2 to 12% by weight, more preferably 4 to
10% by weight.

The propylene-ethylene block copolymer can be produced by separately polymerizing propylene and ethylene in advance to prepare the respective parts and mixing them, or by mixing propylene and ethylene in one polymerization reaction system. A method of multistage polymerization and the like can be mentioned.

(C) Inorganic Filler The inorganic filler is generally used as a filler or a reinforcing material for resins and the like, and examples thereof include talc, mica, short glass fibers, fiber crystalline calcium silicate, calcium carbonate and the like. Can be mentioned. Of these, talc and short glass fibers are particularly preferable. The average particle diameter of the inorganic filler is preferably 15 μm or less. In the case of needles or fibrous materials, the fiber diameter is 1 to 100 μm and the aspect ratio is 3 to
30 is preferable.

(D) Other Additive Components The polypropylene resin composition of the present invention has other additives such as a heat stabilizer, a weather resistance agent, a copper resistance agent, an antioxidant and a light stabilizer for the purpose of modifying the polypropylene resin composition. Stabilizer, flame retardant, plasticizer,
An antistatic agent, a nucleating agent, a release agent, a foaming agent, a pigment and the like can be added.

[2] Mixing ratio The mixing ratio of each component is (A) 50% composite polypropylene resin.
To 90 parts by weight, preferably 60 to 80 parts by weight, (B)
The olefin rubber and / or the polyolefin other than (A) is 50 to 10 parts by weight, preferably 20 to 40 parts by weight,
The amount of the inorganic filler (C) is 40 parts by weight or less, preferably 0 to 10 parts by weight, per 100 parts by weight of (A) + (B).

If the amount of the composite polypropylene resin is less than 50 parts by weight, the flexural modulus, hardness, etc. of the resulting polypropylene resin composition are likely to decrease, and if it exceeds 90 parts by weight, the tensile elongation at break and the impact resistance decrease. On the other hand, if the olefin rubber of (B) and / or the polyolefin other than (A) is less than 10 parts by weight, tensile elongation at break, impact resistance, etc. are low, and if it exceeds 50 parts by weight, mechanical properties such as flexural modulus are increased. Strength is reduced.

SB in composite polypropylene resin
The proportion of PP is 3 to 30% by weight and the proportion of ultrahigh stereoregular polypropylene is 70 to 97% by weight. If the proportion of SBPP is less than 3% by weight (the proportion of ultrahigh stereoregular polypropylene exceeds 97% by weight), the impact resistance is insufficient, and if the proportion of SBPP exceeds 30% by weight ( If the ratio of ultra-high stereoregular polypropylene is less than 70)
Insufficient rigidity. The preferred SBPP ratio is 5 to 1
0% by weight and the preferred proportion of ultrahigh stereoregular polypropylene is 90 to 95% by weight.

Further, if the amount of the inorganic filler (C) exceeds 40 parts by weight per 100 parts by weight of the resin component ((A) + (B)), the impact resistance and the tensile elongation decrease. The content of the preferable inorganic filler is 0 to 10 parts by weight.

[3] Method for producing polypropylene resin composition Obtained by melt-kneading the above components at 190 to 250 ° C., preferably 200 to 230 ° C., using an extruder such as a single screw extruder or a twin screw extruder. be able to.

[0047]

EXAMPLES The present invention will be described in detail with reference to the following examples, but the present invention is not limited thereto.

Reference Example 1 Production of SBPP Preparation of catalyst components In a 1 liter reaction vessel equipped with a reflux condenser, under a nitrogen gas atmosphere, chip-shaped metallic magnesium (purity: 99.5
%, Average particle size 1.6 mm) 8.3 g and n-hexane 250 ml
Was charged, and after stirring for 1 hour at 68 ° C., the metallic magnesium was taken out and dried under reduced pressure at 65 ° C. to obtain pre-activated metallic magnesium.

Next, a suspension of 140 ml of n-butyl ether and 0.5 ml of a solution of n-butylmagnesium chloride in n-butyl ether (1.75 mol / liter) added to the pre-activated metallic magnesium was kept at 55.degree. , And n-butyl chloride 38.5 in 50 ml of n-butyl ether
The solution in which ml was dissolved was added dropwise over 50 minutes. 4 at 70 ℃ under stirring
After performing the reaction for a time, the reaction solution was kept at 25 ° C.

Next, HC (OC ₂ H ₅ ) ₃ was added to this reaction solution.
55.7 ml was added dropwise over 1 hour. After the dropping, 15 at 60 ℃
After reacting for 3 minutes, the reaction product solids are n-hexane 300 ml each
Washed 6 times with water, dried under reduced pressure at room temperature for 1 hour, and magnesium.
Solid magnesium-containing 31.6 containing 19.0% and 28.9% chlorine
g was recovered.

In a 300 ml reaction vessel equipped with a reflux condenser, a stirrer and a dropping funnel, 6.3 g of magnesium-containing solid and 50 ml of n-heptane were put into a suspension under a nitrogen gas atmosphere to prepare a suspension, which was stirred at room temperature. A mixed solution of 20 ml (0.02 mmol) of 2,2,2-trichloroethanol and 11 ml of n-heptane was added dropwise from the dropping funnel over 30 minutes, and then at 80 ° C.
It was stirred for 1 hour. The solid obtained is filtered off and n-
Wash 4 times with 100 ml of hexane each time, and add 100 each of toluene.
It was washed twice with ml to obtain a solid component.

40 ml of toluene was added to the above solid component, titanium tetrachloride was further added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the temperature was raised to 90 ° C. With stirring, a mixed solution of 2 ml of di-n-butyl phthalate and 5 ml of toluene was added dropwise, and then the mixture was stirred at 120 ° C. for 2 hours. The solid substance obtained was filtered off at 90 ° C and washed twice with 100 ml of toluene each time.
Washed at ° C. Furthermore, titanium tetrachloride was added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and 120
The mixture was stirred at 0 ° C for 2 hours and washed with 100 ml of n-hexane at room temperature seven times to obtain 5.5 g of a catalyst component.

In a 100-liter stainless steel autoclave equipped with a polymerization stirrer, under a nitrogen gas atmosphere, a solution of triisobutylaluminum (TIBAL) in n-heptane (0.2 mol / mol) was added.
120 ml of t-butyl t-butoxydi-n-propoxysilane (0.04 mol / liter) were mixed and held for 5 minutes. Then, 36 liters of hydrogen gas as a molecular weight controlling agent and 60 liters of liquid propylene were injected under pressure, and then the temperature of the reaction system was raised to 80 ° C. After 600 mg of the catalyst component obtained above was charged into the reaction system, propylene was polymerized for 1 hour. After the completion of polymerization, unreacted propylene was purged to obtain 14.2 kg of white polypropylene powder. The polypropylene production amount (CE) per 1 g of the component was 23.7 kg.

200 g of the obtained polypropylene powder was put into a cylindrical filter paper and extracted with heptane by a Soxhlet extractor for 5 hours to remove hot heptane-insoluble components. The hot heptane-insoluble component remaining on the cylindrical filter paper was further extracted with octane for 10 hours, and the hot-octane-soluble component was recovered, and then octane was removed with an evaporator, and 97.0 g of the hot heptane-insoluble component was removed.
Thermal octane soluble stereoblock polypropylene (S
BPP) was obtained. The production amount (CEsb) of this SBPP per 1 g of the component was 11.5 kg. [Mmmm] and [rrrr] of SBPP measured by ¹³ C-NMR were 75.0% and 5.4%, respectively, and the weight average molecular weight Mw measured by GPC was 1.50 × 10 ⁵ .

Further, 0.1% BHT was added to this SBPP, and the mixture was kneaded at 170 ° C. for 3 minutes in a nitrogen atmosphere, and then measured by DSC at a scanning speed of 10 ° C./minute. Endothermic peaks were observed at 119 ° C. and 162 ° C. did. These are Macromol.Chem., 193
, 1765 as reported in (1992), each corresponding to the melting of the crystal by syndiotactic chain and isotactic chain, together with the results of ¹³ C-NMR indicated above, the polypropylene stereo block It has a structure.

Reference Example 2 Production of Ultra High Stereoregular Polypropylene (HSPP-1) Preparation of Catalyst Components In a 1 liter reaction vessel equipped with a reflux condenser, under a nitrogen gas atmosphere, chip-shaped metallic magnesium (purity: 99.5
%, Average particle size 1.6 mm) 8.3 g and n-hexane 250
After adding 1 ml and stirring at 68 ° C. for 1 hour, metallic magnesium was taken out and pre-activated metallic magnesium was obtained by a method of drying under reduced pressure at 65 ° C.

Then, a suspension of 140 ml of n-butyl ether and 0.5 ml of a solution of n-butyl magnesium chloride in n-butyl ether (1.75 mol / l) added to the pre-activated metallic magnesium was kept at 55 ° C. , And n-butyl chloride 38.5 in 50 ml of n-butyl ether
The solution in which ml was dissolved was added dropwise over 50 minutes. 4 at 70 ℃ under stirring
After performing the reaction for a time, the reaction solution was kept at 25 ° C.

Next, HC (OC ₂ H ₅ ) ₃ was added to this reaction solution.
55.7 ml was added dropwise over 1 hour. After the dropping, 15 at 60 ℃
After reacting for 3 minutes, the reaction product solids are n-hexane 300 ml each
Washed 6 times with water, dried under reduced pressure at room temperature for 1 hour, and magnesium.
Solid magnesium-containing 31.6 containing 19.0% and 28.9% chlorine
g was recovered.

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

40 ml of toluene was added to the above solid component, titanium tetrachloride was further added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the temperature was raised to 90 ° C. With stirring, a mixed solution of 2 ml of di-n-butyl phthalate and 5 ml of toluene was added dropwise, and the mixture was stirred at 120 ° C. for 2 hours. The solid substance obtained was filtered off at 90 ° C and washed twice with 100 ml of toluene each time at 90 ° C. Titanium tetrachloride was added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the volume was adjusted to 2 at 120 ℃.
The mixture was stirred for an hour and washed with 100 ml of n-hexane at room temperature seven times to obtain 5.5 g of a catalyst component.

In a 500 ml reactor equipped with a prepolymerization stirrer, under a nitrogen gas atmosphere, 3.5 g of the component obtained above and 300 n-heptane were added.
ml was added and cooled to -5 ° C with stirring. Next, a solution of triethylaluminum (TEAL) in n-heptane (2.
(0 mol / liter) and cyclohexyl i-propoxydimethoxysilane were added so that the concentrations of TEAL and cyclohexyl i-propoxydimethoxysilane in the reaction system were 60 mmol / liter and 10 mmol / liter, respectively, and the mixture was stirred for 5 minutes.

Next, after depressurizing the system, propylene gas was continuously introduced to polymerize propylene for 4 hours.
After completion of the polymerization, purge propylene in the gas phase with nitrogen gas,
The solid phase was washed with 100 ml of n-hexane three times at room temperature. Further, the solid phase portion was dried under reduced pressure at room temperature for 1 hour to prepare a catalyst component. As a result of measuring the amount of magnesium contained in the catalyst component, the amount of preliminary polymerization was 1.8 g per 1 g of the component.
Met.

In a 100-liter stainless steel autoclave equipped with the main polymerization stirrer, 120 ml of n-heptane solution of TEAL (0.2 mol / l) and n-heptane of i-propyl t-amyloxydimethoxysilane were placed in a nitrogen gas atmosphere. 120 ml of the solution (0.04 mol / liter) was mixed and held for 5 minutes.

Next, as a molecular weight control agent, hydrogen gas 17.0
After pressurizing liter and 60 liter of liquid propylene,
The reaction system was heated to 50 ° C. Catalyst component 600 obtained above
After charging mg to the reaction system, propylene was polymerized for 1 hour. After completion of the polymerization, purge unreacted propylene,
16.2 kg of white polypropylene powder was obtained. Polypropylene production amount (CE) per 1 g of catalyst component is 27.0 kg
Met. The polymerization conditions and results are shown in Tables 1 and 2.

100 g of the obtained polypropylene powder was put in a cylindrical filter paper and extracted with heptane for 5 hours using a Soxhlet extractor to remove hot heptane-soluble components. As a result
96.0 g of hot heptane-insoluble polypropylene (HSPP)
I got Amount of HSPP produced per 1 g of catalyst component (CE
sb) was 25.3 kg. The MFR of this polypropylene was 150 g / 10 minutes. [Mm] and [mr] measured by ¹³ C-NMR are 99.6% and 0.3%, respectively.
And the meso-average chain length Nm calculated from these is 665.
Met. The N'calculated from N '= 250 +29.5 log (MFR) was 323.4.

Reference Example 3 Production of Ultra High Stereoregular Polypropylene (HSPP-2) The same conditions as in Reference Example 1 except that the catalyst component, the catalyst component, the amount of hydrogen gas and the polymerization temperature were as shown in Table 1. Was used to polymerize propylene. The polypropylene production amount (CE) per 1 g of the component is 14.2 kg, and the hot heptane-insoluble polypropylene production amount (CEhs) is 13.6 kg,
The MFR was 15.0 g / 10 min, the [mm] and [mr] measured by ¹³ C-NMR were 99.4% and 0.4%, respectively, and the meso-average chain length Nm calculated from these was 49.
It was 8.0 and N'was 281.1.

Reference Examples 4 and 5 Reference Example 2 except that the production of ordinary polypropylene (PP-1, PP-2), catalyst component, catalyst component, amount of hydrogen gas and polymerization temperature were as shown in Table 1. Polymerization of propylene was carried out under the same conditions as above. Polypropylene production amount (CE) per 1 g of catalyst component, thermal heptane-insoluble polypropylene production amount (CEhs), MFR, [mm] and [mr] of the polypropylene measured by ¹³ C-NMR, and meso-average chain calculated by these The length is shown in Table 2.

[0068] Table 1 Polymerization conditions hydrogen gas amount polymerization temperature Ingredient (l) (℃) HSPP-1 TIBAL C1 2.5 60 PP-1 TEAL C2 5.5 50 PP-2 TEAL C2 1.5 70 Note: TIBAL: triisobutylaluminum. TEAL: Triethyl aluminum. C1: Cyclohexyl i-propoxydimethoxysilane. C2: cyclohexylmethyldimethoxysilane.

Table 2 Polymerization results CE CEhs MFR [mm] [mr] Nm N ′ PP-1 15.8 14.7 150 98.2 1.1 179.5 316.7 PP-2 29.0 28.3 15.0 98.0 1.3 151.8 267.8

Note: The unit is as follows. CE: kg-pp / g-cat ・ hr. CEh: kg-pp / g-cat ・ hr. MFR: g / 10 minutes. [Mm]:%. [Mr]:%. N ′ = 250 + 29.5 log (MFR).

Examples 1 to 8 1. Raw material SBPP Mw = 1.50 × 10 ⁵ [mmmm]: 75.0% [rrrr]: 5.4%

HSPP-1: Ultrahigh stereoregular polypropylene produced in Reference Example 2. MFR = 150 g / 10 min (230 ° C., 2,160 g) [mm]: 99.6% [mr]: 0.3% Meso average chain length: 665 Flexural modulus: 27 × 10 ³ kg / cm ²

HSPP-2: Ultrahigh stereoregular polypropylene produced in Reference Example 3. MFR = 15 g / 10 min (230 ° C, 2,160 g) [mm]: 99.4% [mr]: 0.4% Meso average chain length: 498 Bending elastic modulus: 25 × 10 ³ kg / cm ²

EPR: ethylene-propylene rubber EPO2P Mooney viscosity M _{1 + 4} (100 ° C.) = 24 MFR = 3.2 g / 10 minutes (230 ° C., 2,160 g) manufactured by Nippon Synthetic Rubber Co., Ltd. Propylene content: 26% by weight

EBR: Ethylene-butene rubber EBM2041P MI = 3.5 g / 10 minutes (190 ° C., 2,160 g) manufactured by Nippon Synthetic Rubber Co., Ltd. Specific gravity: 0.88 Butene content: 12% by weight

LLDPE: Linear low-density polyethylene manufactured by Nippon Unicar Co., Ltd., NUCG-5361 MI = 4.0 g / 10 minutes (190 ° C., 2,160 g) Specific gravity: 0.934

C-1: Talc Fuji Talc Co., Ltd., LMR-100 Average particle size: 1.8 to 2.0 μm

C-2: Short glass fiber MAFT120 manufactured by Asahi Fiber Glass Co., Ltd. Average fiber diameter: 13 μm Average fiber length: 3 mm

2. Kneading method The raw materials were weighed in a predetermined weight ratio shown in Table 3, dry-blended with a high-speed mixer, and then melt-kneaded with a twin-screw extruder. Kneading temperature is 190-250 ℃, screw rotation speed is 20
It was 0 rpm. The kneaded product extruded in a strand form from the die was cooled with water and continuously cut with a cutter to obtain pellets.

3. Molding method The pellets obtained were molded by an injection molding machine at 210 ° C and 600
A test piece was prepared by injection molding at kg / cm ² .

4. Physical property measurement Physical property measurement of each test piece was performed by the following methods. The measurement results are shown in Table 3. (1) MFR (g / 10min): 230 ° C, 2, 1 according to ASTM D1238
Measured at 60g. (2) MI (g / 10 min): 190 ° C, 2,160 according to ASTM D1238
Measured in g. (3) Tensile elongation (%): measured by ASTM D638. (4) Flexural modulus (× 10 ³ kg / cm ² ): Measured by ASTM D790. (5) Izod test (kg / cm / cm): According to ASTM D256 3.
Measured with a notch using a 2 mm thick test piece. (6) Heat distortion temperature (℃): Measured by ASTM D648. (7) Rockwell hardness: measured by ASTM D785. (8) Brittleness temperature (° C): Measured by ASTM D746.

Table 3 Example No. 1 2 2 3 4 Blending ratio (wt%) SBPP 5 5 55 HSPP-1 50 50 50-HSPP-2--45 EPR 35 20 20 20 EBR-15-10 LLDPE- − 15 − Talc 10 10 10 20 Short glass fiber − − − − Physical properties of composition MFR 24 25 25 8 Tensile elongation at break>500>500>500> 500 Flexural modulus 19.5 20 21 27.5 Izod at 23 ℃ 60 61 60 48 Impact strength -30 ℃ 10 9 9 6 Thermal deformation at 4.6 kg / cm ² 132 135 135 144 Temperature 18.5 kg / cm ² − − − 90 Rockwell hardness 67 69 70 90 Embrittlement temperature (℃) -45 -43- 42 -10

Table 3 (continued) Example No. 5 6 7 8 Compounding ratio (wt%) SBPP 55 55 HSPP-1 65-75 65 HSPP-2-45-EPR 20 20 10-EBR-10- − LLDPE − − 10 20 Talc 10 − − 10 Short glass fiber − 20 − − Physical properties of composition MFR 30 5 28 33 Tensile elongation at break> 500 250> 500 350 Flexural modulus 29 53 24 31 Izod at 23 ° C 13 31 40 8 Impact strength -30 ℃ 5 5 12 4 Thermal deformation at 4.6 kg / cm ² 141 148 115 140 Temperature 18.5 kg / cm ² 79 100 − 82 Rockwell hardness 94 97 87 95 Embrittlement temperature (℃) -5 5- 50 5

Comparative Examples 1 and 2 Pellets were prepared under the same conditions as in Examples except that the composition was changed, and the physical properties were measured. The results are shown in Table 4.

[0085]

Comparative Examples 3 to 8 The following conventional polypropylenes (prepared in Reference Examples 4 and 5) having substantially the same MFR were used in place of the ultrahigh stereoregular polypropylene used in the Examples, and pellets were prepared under the same conditions as in the Examples. Was prepared and the physical properties were measured. The results are shown in Table 5.

PP-1 MFR = 150 g / 10 min (230 ° C., 2,160 g) [mm]: 98.2% [mr]: 1.1% [mmmm]: 94.3% [rrrr]: 0.3% Meso Mean Chain Length: 315 Flexural modulus: 20 × 10 ³ kg / cm ²

PP-2 MFR = 15 g / 10 min (230 ° C., 2,160 g) [mm]: 98.0% [mr]: 1.3% [mmmm]: 94.2% [rrrr]: 0.3% Meso Mean Chain Length ^* : 265 Flexural modulus: 19 × 10 ³ kg / cm ²

Table 5 Comparative Example No. 3 4 5 6 7 8 Compounding ratio (wt%) SBPP 5 5 5 5 5 5 PP-1 50 50 50-65-PP-2--45-75 EPR 35 20 20 20 20 − EBR − 15 − 10 − − LLDPE − − 15 − − − Talc 10 10 10 20 10 − Short glass fiber − − − − − 20 Physical properties of composition MFR 24 25 25 8 30 8 Tensile elongation at break> 500 >500>500>500>500> 500 Flexural modulus 16 16.2 16.8 24 24.5 51 Izod at 23 ℃ 61 62 60 47 13 17 Impact strength -30 ℃ 10 9 9 6 5 8 Thermal deformation at 4.6 kg / cm ² 120 120 121 119 128 − Temperature 18.5 kg / cm ² − − − 80 77 154 Rockwell hardness 58 60 61 80 89 108 Embrittlement temperature (℃) -45 -43 -42 -10 -5 −

Comparative Examples 9 to 14 A polypropylene resin composition having the same composition as that of the example except that SBPP was not added was prepared under the same conditions as those of the example, and the physical properties were measured. The results are shown in Table 6.

Table 6 Comparative Example No. 9 10 11 12 13 14 Blending ratio (wt%) HSPP-1 55 55 55-70-HSPP-2 --- 50-50 EPR 35 20 20 20 20-EBR-15- 10 − − LLDPE − − 15 − − − Talc 10 10 10 20 10 − Short glass fiber − − − − − 20 Physical property of composition MFR 24 25 25 8 30 8 Tensile elongation at break 400> 500 450> 500 200 4 Bending Elastic modulus 20 20.5 21 28 30 56 Izod at 23 ℃ 42 40 40 30 7 7 Impact strength -30 ℃ 9 8 8 4 3 6 Thermal deformation at 4.6 kg / cm ² 133 135 136 145 140 − Temperature 18.5 kg / cm ² − − − 90 80 160 Rockwell hardness 68 70 70 90 95 115 Embrittlement temperature (℃) -42 -40 -40 0 10 −

Comparative Examples 15 to 20 Polypropylene resin compositions were prepared under the same conditions as in Examples except that SBPP was not compounded and ordinary polypropylene was compounded instead of ultrahigh stereoregular polypropylene, and the physical properties were measured. It was The results are shown in Table 7.

Table 7 Comparative Example No. 15 16 17 18 19 20 Blending ratio (% by weight) PP-1 55 55 55-70-PP-2 --- 50-80 EPR 35 20 20 20 20-EBR-15- 10 − − LLDPE − − 15 − − − Talc 10 10 10 20 10 − Short glass fiber − − − − − 20 Physical property of composition MFR 24 25 25 8 30 8 Tensile elongation at break 400> 500 450> 500 200 4 Bending Elastic modulus 16 16.5 17 24 25 51 Izod at 23 ℃ 43 40 40 31 7 7 Impact strength -30 ℃ 9 8 8 4 3 6 Thermal deformation at 4.6 kg / cm ² 121 122 122 120 130 − Temperature 18.5 kg / cm ² − − − 81 79 155 Rockwell hardness 60 61 62 82 90 110 Embrittlement temperature (℃) -43 -40 -40 0 10-

As is clear from the above results, the polypropylene resin composition of the present invention has a good balance of elongation, impact resistance, rigidity and heat resistance, but in the case of the polypropylene resin composition of Comparative Example. At least one of the above properties is inferior.

[0095]

The polypropylene resin composition of the present invention is
It has a good balance of impact resistance, which was conventionally in a trade-off relationship, and rigidity and heat resistance, and can be widely used for various purposes.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Satoshi Ueki 4-1-1 Tsukiji, Chuo-ku, Tokyo Tonen Kagaku Co., Ltd. (72) Inventor Shigeyuki Toki 4-1-1 Tsukiji, Chuo-ku, Tokyo Tonen Kagaku Co., Ltd. (72) Inventor Takesumi Nishio 1 Toyota-cho, Toyota City, Aichi Prefecture Toyota Motor Co., Ltd. (72) Inventor Takao Nomura 1-cho, Toyota City, Aichi Prefecture Toyota Motor Co., Ltd.

Claims (3)

[Claims] 1. (A) (a) A polypropylene which is insoluble in hot heptane and soluble in hot octane, and in which all the bonds of five consecutive propylene monomer units are meso bonds ( ¹³
70% or more, and the proportion of all racemic bonds is 5% or more.
It also has 3 to 30% by weight of polypropylene having a weight average molecular weight of 5,000 to 1,000,000 and (b) 0.1 to 1000 g / 10 min of melt flow rate (MFR, 230 ° C, 2,160 g) and is determined by ¹³ C-NMR. From the triad fraction, the following formula (1): Nm = 2 [mm] / [mr] +1 ... (1) (where [mm]: isotactic triad number / total triad number, [mr]: hetero Ultra high stereoregular polypropylene 70 to 97 in which the meso average chain length Nm calculated by the number of tactic triads / total number of triads satisfies the following formula (2): Nm> 250 + 29.5log (MFR) (2) 50 to 90 parts by weight of a composite polypropylene resin composed of 100% by weight, and (B)
A polypropylene resin composition comprising 50 to 10 parts by weight of an olefin rubber and / or a polyolefin other than (A). 2. The polypropylene resin composition according to claim 1, wherein 4 parts per 100 parts by weight of (C) the (A) + (B).
A polypropylene resin composition comprising 0 part by weight or less of an inorganic filler. 3. The polypropylene resin composition according to claim 1 or 2, wherein the polyolefin other than (A) is linear low density polyethylene.