JPH0885714A - Propylene block copolymer, its production, and composition thereof - Google Patents

Abstract

PURPOSE: To obtain a composition excellent in rigidity, impact resistance, heat resistance, and surface hardness by synthesizing a propylene block copolymer having specific material properties. CONSTITUTION: The copolymer comprises 50-97wt.% polypropylene blocks (A) in which (1) the content of xylene-nonextractables as determined at 25 deg.C is 99.0wt.% or higher, (2) the isotactic pentad fraction is 98.0% or higher, (3) the average isotactic-chain length is 500 or longer, and (4) the proportion of the fractions obtained by the column fractionation method and having an average isotactic-chain length of 800 or longer is 10wt.% or larger, and 50-3wt.% blocks (B) of a copolymer of propylene with ethylene and/or a 4-12C α-olefin which blocks satisfy the requirements (1) to (4). It is produced using an improved polymerization catalyst obtained by treating a solid catalyst comprising an Mg compound, a Ti compound, a halogen compound, and an electron-donating compound as essential ingredients with a specific titanium compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is particularly applicable to mechanical parts, electric
The present invention relates to a propylene block copolymer excellent in rigidity, impact resistance, heat resistance and surface hardness, which is preferably used in the field of electronic parts, packaging materials, engineering plastic substitutes, and the like, and a method for producing the same.

[0002]

Polypropylene is generally inexpensive and
In addition, by taking advantage of its characteristics such as lightness, transparency, mechanical strength, heat resistance, and chemical resistance, automobile parts, electricity,
It is widely used for industrial materials such as electronic parts and various packaging materials. In recent years, as the functionality of products has been improved or the cost has been reduced, it has been strongly demanded to improve the characteristics of these materials.

As a method for improving the rigidity, impact resistance and heat resistance of polypropylene, for example, a method of blending ethylene-propylene rubber and a nucleating agent with an ethylene-propylene block copolymer (Japanese Patent Publication No. 60-3420). ) Or a method of blending ethylene-propylene rubber, ethylene copolymer and inorganic filler (JP-A-4-275351, JP-A-5-5051, JP-A-5-98097, JP-A-5-98098). Etc.) are proposed.

[0004]

However, although the above methods all improve some of the properties, the heat resistance and the rigidity are still insufficient.
The present invention has been made in view of such circumstances, and an object of the present invention is to provide a propylene resin composition having excellent rigidity, impact resistance, heat resistance, and surface hardness.

[0005]

As a result of intensive studies, the present inventors have found that the above object can be achieved by a propylene block copolymer having specific physical properties, and the present invention is based on this finding. Has been completed. That is, the present invention provides a polypropylene part (a) having the following physical properties (i) to (iv), and (i) a xylene extraction insoluble part at 25 ° C. of 99.0% by weight or more (ii) isotactic pentad fraction 98.0%
Above (iii) Isotactic average chain length of 500 or more (iv) Total amount of fractions by column fractionation having an isotactic average chain length of 800 or more 10
% By weight or more Copolymer of propylene and ethylene and / or α-olefin having 4 to 12 carbon atoms satisfying all of the following conditions (v) to (viii) (b) (v) Average propylene by two-site model Content (FP)
20 to 80 mol% (vi) 2 sites copolymer produced in the active sites of polymerization preferentially propylene in the model propylene content _(P P) 65 to 90 mol% of _{(P H) (vii) P} H is co Ratio (P _f1 ) in polymer 0.4
0-0.90 (viii) Two-site model blockiness (CSD)
The present invention provides a propylene block copolymer composed of 1.8 to 5.0. Hereinafter, the present invention will be described in detail.

The propylene block copolymer (hereinafter referred to as "BPP") in the present invention comprises a polypropylene part (a) and a copolymer part (b) of propylene with ethylene and / or an α-olefin having 4 to 12 carbon atoms. ) Is a block copolymer. The BPP of the present invention requires that the polypropylene part (a) produced in the first-step reaction has the following physical properties.

That is, (i) the xylene-extractable insoluble portion (hereinafter referred to as "XI") at 25 ° C is 99.0% by weight or more, preferably 99.5% by weight or more, and more preferably 99.7% by weight or more. Is. XI is 99.0% by weight
If it is less than the range, rigidity and heat resistance are poor. The XI was measured by a method in which polypropylene was once dissolved in 135 ° C. orthoxylene and then cooled to 25 ° C. to precipitate the polymer.

Further, (ii) the isotactic pentad fraction (hereinafter referred to as "IP") must be 98.0% or more, preferably 98.5% or more, and particularly 99.0%.
The above is suitable. If the IP is less than 98.0%, the rigidity and heat resistance are poor, which is not preferable.

The IP is the isotactic fraction in the pentad unit in the polypropylene molecular chain measured by nuclear magnetic resonance ( ¹³ C-NMR) spectroscopy with isotopic carbon. The measurement method is A. Zambelli; Macromol
ecules, 6 , 925 (1973), 8 , 687 (1975) and 13 , 267
The method described in (1980) was followed.

Further, (iii) the isotactic average chain length (hereinafter referred to as "N") is 500 or more, preferably 700.
It is necessary to be 800 or more, particularly preferably 800 or more. N
Is less than 500, the rigidity and heat resistance are poor. In addition, N represents the average length of the isotactic portion of the methyl group in the polypropylene molecule, and the measurement method is JCRandall; Polymer SequenseDistribution, Acade.
mic Press, New York, 1977, Chapter 2). Specifically, polypropylene 1, 2,
In a mixed solvent of 4-trichlorobenzene / deuterated benzene, the temperature was adjusted to 130 ° C. so that the polymer concentration became 10% by weight.
Heat to dissolve. This solution is put into a glass sample tube of 10 mmΦ, and ¹³ C-NMR spectrum is measured by the same method as for IP. An example of this spectrum diagram is shown in FIG.
1A is a spectrum of a methyl group region in polypropylene, and b is an enlarged view of the spectrum.
The spectrum is measured with a pentad unit, that is, five adjacent methyl groups as one unit, and the absorption peak differs depending on the isotacticity of the methyl group (there are 10 types such as mmmm, mmmr structurally). FIG.
Correspondence between the absorption peak and isotacticity is shown in b.

On the other hand, as a polymerization theory, Shan-Nong et al; P
There is a two-site model described in olymer Journal, vol.15, No.12, p859-868 (1983). That is, there are two types of active species at the time of polymerization, that is, the catalyst side and the polymer terminal, the catalyst side is called catalyst-controlled polymerization, and the other is called terminal-controlled polymerization (for details, see Furukawa Junji; Taka Molecular Essence and Topics 2, "Polymer Synthesis", P7
3 (Published by Kagaku Doujin Co., Ltd. (1986)).

According to the above literature, the two-site model is, after all, α: the probability that the D-form and the L-form are added to the polymerization end by the catalyst-controlled polymerization (enantiomorphic process), that is, the degree of disorder in the isotactic chain. Index σ: Probability of meso-form with the addition of the same polymerized end by end-dominated polymerization (Bernoulli process) ω: The ratio of α sites is the theory of 10 types of isotactic strength with different isotacticity in pentad units Can be calculated Then, α, σ, and ω are obtained by the method of least squares so that the intensity measured by NMR and the theoretical intensity match, and each pentad unit is obtained by the following equation.

[0013]

[Table 1]

Next, the average chain length (N) definition formula described in J. C. Randall's reference; N = the number of chains of meso form / the number of units of meso form is applied, and actually determined by the following formula. be able to. N = 1 + (A ₁ + A ₂ + A ₃ ) /0.5 (A ₄ + A ₅ +
A ₆ + A ₇ )

Further, (iv) the total amount of the fractions having an isotactic average chain length (hereinafter referred to as "N _f ") of 800 or more in each fraction by the column fractionation method is 10% by weight of the whole.
It is necessary to be the above, preferably 30% by weight or more, particularly preferably 50% by weight. When _Nf is 800 or more but the total amount is less than 10% by weight, the effect of improving rigidity, surface hardness and heat resistance is poor.

Here, the column fractionation method is to dissolve the xylene-extracted insoluble portion in para-xylene at a temperature of 130 ° C., and then add Celite to lower the temperature to 30 ° C. at a temperature lowering rate of 10 ° C./hour to allow it to adhere to Celite. Then, the method is to fill the column with slurry celite, raise the temperature stepwise every 30 ° C. to 2.5 ° C. with paraxylene as a developing solution, and fractionate polypropylene by fractions. For more information, see MasahiroKakugo et al; Macromolecules, vo
l.21, p314-319 (1988). The N _f of the separated polypropylene is measured by the above N measuring method.

Further, in the BPP of the present invention, it is necessary that the propylene-α-olefin copolymer (b) produced in the second stage reaction satisfies all the following conditions. Here, the two-site model of the propylene-α-olefin copolymer will be described by taking the propylene-ethylene copolymer as an example. FIG. 2 shows an example of a nuclear magnetic resonance ( ¹³ C-NMR) spectrum of isotope carbon of a propylene-ethylene copolymer. In the spectrum, 10 peaks shown in (1) to (10) appear due to the difference in chain distribution (arrangement of ethylene and propylene). The name of this chain is Carman, C, J, et a
l; Macromolecules, Vol. 10, p536-544 (1977), and the name is shown in FIG. Such a chain can be expressed as a reaction probability (P) assuming a reaction mechanism of copolymerization, and each (1)-
The relative intensity of the peak in (10) can be expressed as a probability equation based on Bernoulli statistics with P as a parameter.

For example, in the case of (1) Sαα, if the propylene unit is the symbol p and the ethylene unit is the symbol e, the possible chains are [pppp], [ppee], and [epp].
e] and the reaction probability (P)
Express and add. The remaining peaks (2) to (10) can be obtained by formulating equations in the same manner, and optimizing P so that the peak intensity actually measured and those 10 equations are closest to each other. .

The two-site model is a model that assumes this reaction mechanism. HNCHENG; Jounal of Applied Polymer
Sience, Vol.35 p1639-1650 (1988). That is, in the model of copolymerizing propylene and ethylene using a catalyst, propylene content of the copolymer generated at the active sites of polymerization preferentially propylene _{(P H)} (P P)
Assuming two propylene contents (P _P ') of the copolymer produced at the active sites where P and _P preferentially polymerize,
_{When the} ratio of _H in the copolymer (P _f1 ) is used as a parameter, the probability equation shown in Table 2 below is obtained.

[0020]

[Table 2]

P _P , so that the above-mentioned relative intensity of the ¹³ C-NMR spectrum and the probability equation shown in Table 2 match.
It is obtained by optimizing the three parameters P _P 'and P _f1 .

(V) Average propylene content (FP) of the present invention
Is calculated by the following equation using the above three parameters. _{FP = P P × P f1 +} P P '× (1-P f1) FP sought (mol%) The above formula is 20 to 80 mol%, preferably 25 to 75 mol%, more preferably 3
It is 0 to 70 mol%. If the FP is less than 20 mol%, the appearance of the molded product is significantly deteriorated. On the other hand, if it exceeds 80 mol%, the impact resistance decreases, which is not preferable.

Among the above parameters, (vi) _PP
Is 65 to 90 mol%, preferably 68 to 88 mol%, and particularly preferably 70 to 85 mol%. P _P is 6
If it is less than 5 mol%, the rigidity and heat resistance will be reduced. on the other hand,
If it exceeds 90 mol%, impact resistance is impaired, which is not preferable.

Further, (vii) P _f1 is 0.40 to 0.90.
And 0.45 to 0.85 is preferable, and especially 0.
48 to 0.82 is preferable. When P _f1 is less than 0.40, the rigidity and heat resistance decrease. On the other hand, if it exceeds 0.90, impact resistance is impaired, which is not preferable.

Finally, (viii) block property (CSD) is the reactivity ratio of ethylene and propylene. This definition is defined in "Polymerization 1 Reaction Analysis," p5-1.
3. Follow the method published by Baifukan (1975). That is, it is expressed by the following equation using the intensity ratio (Ri) of each peak in the spectrum of FIG. CSD = [(0.5 × R7 + 0.25 × R6 + 0.5 × R3) × R1] /
[0.5 × (R2 + R3)] ^{2 The} CSD obtained by the above formula is 1.8 to 5.0 and 2.0
˜4.5 is preferable, and 2.5 to 4.0 is particularly preferable. If the CSD is less than 1.8, the rigidity and heat resistance will decrease. On the other hand, when it exceeds 5.0, impact resistance at low temperature is impaired, which is not preferable.

Propylene-α in BPP of the present invention
The proportion of the olefin copolymer (b) is 3 to 50% by weight, preferably 5 to 45% by weight, and especially 10 to 40%.
Weight percent is preferred. If the proportion of (b) is less than 3% by weight, the impact resistance strength will decrease. On the other hand, if it exceeds 50% by weight, rigidity and heat resistance are impaired, which is not preferable.

The BPP polymerization of the present invention is carried out in the presence of an inert hydrocarbon such as hexane, heptane, kerosene or a liquefied α-olefin solvent such as propylene in a slurry method,
The temperature condition is room temperature to 130 ° C., preferably 50 to 90 ° C., pressure 2 to 50, by a gas phase polymerization method in the absence of a solvent.
It is carried out under the condition of kg / cm ² . As the reactor in the polymerization step, those usually used in the technical field can be appropriately used, and examples thereof include a stirred tank reactor, a fluidized bed reactor, a circulation reactor, and a continuous type, a semi-batch type, or a batch type. Either method may be used. Specifically, it can be obtained using a known multistage polymerization method. That is, it is a method in which propylene is polymerized in the first step reaction and then propylene and α-olefin are copolymerized in the second step reaction. For example, JP-B-36-15284 and JP-B-38-14834 are disclosed. JP-A-53-35788, JP-A-53-35789, and JP-A-56-55416.

The BPP of the present invention cannot be obtained by a known Ziegler-Natta type catalyst such as a titanium trichloride-based catalyst or a magnesium chloride-supported titanium catalyst. Examples of the catalyst for obtaining the BPP of the present invention include magnesium compounds,
A solid catalyst containing a titanium compound, a halogen-containing compound, and an electron-donating compound as essential components is further prepared by a general formula: TiXa
Yb (In the formula, X is a halogen atom of Cl, Br, I,
Is an electron-donating compound, a is 3 or 4, and b is an integer of 3 or less), and is then washed with a halogen-containing compound and further washed with a hydrocarbon. A polymerization catalyst may be used.

Ti Xa in the above formula is, for example, RPSCo.
utts, et al, Advan.Organometal.Chem., 9 , 135 (1970), 4th Edition New Experimental Chemistry Lecture 17 Inorganic and chelate complexes Maruzen of the Chemical Society of Japan (1991) p.35, HKKakkoen, et al, J. Organ
As described in Omet. Chem., 453 , 175 (1993), etc., it is generally known that an electron-donating compound easily forms a complex.

X is a halogen atom of Cl, Br, I, of which Cl is preferred. a is 3 or 4, but is preferably 4. Examples of Y generally include oxygen-containing compounds, nitrogen-containing compounds, phosphorus-containing compounds and sulfur-containing compounds. Examples of the oxygen-containing compound include alcohols, ethers, esters, acid halides, acid anhydrides and the like. These electron donating compounds may be used alone or in combination of two or more. Among these, esters are preferable, and phthalates are particularly preferable. B of Y is the a
When b is 3, b is 1 to 3, when a is 4, 1 or 2 is preferable, and particularly preferably, a is 4 and b is 1.

The BPP of the present invention is further improved in rigidity, heat resistance and impact strength by blending a nucleating agent. In the field of synthetic resins, the nucleating agent refers to a substance that has an effect of growing a crystal by becoming a nucleus when added to a crystalline resin, and there are various substances. Specific examples include metal salts of carboxylic acids, dibenzylidene sorbitol derivatives, metal phosphate salts, talc and inorganic fillers such as calcium carbonate. These nucleating agents are 1
One kind may be used, or two or more kinds may be used in combination.

The amount of the nucleating agent added is generally 0.05 to 0.5% by weight, excluding the inorganic filler, and preferably 0.
08-0.4% by weight, especially 0.1-0.35% by weight
Is preferred. On the other hand, inorganic fillers such as talc are 5
30% by weight, preferably 7 to 28% by weight, particularly 9
-25% by weight is preferred. The combination of these nucleating agents is
A known mixing method, for example, a ribbon blender, a tumbler, or a Henschel mixer is used to mix the components,
Further, it is obtained by melt mixing using a kneader, mixing roll, Banbury mixer, extruder or the like. The temperature at the time of melt mixing is usually 170 to 280 ° C, preferably 190 to 260 ° C. The composition obtained is
By a known melt molding method and compression molding method, a film,
It can be formed into a sheet, a tube, a bottle or the like and used alone, or can be used as a laminated body by laminating other materials.

As the laminating method, a so-called dry laminate molding method, a coextrusion lamination method, a coextrusion method, a coextrusion method, a coextrusion method or a coextrusion method is used in which other thermoplastic resins are laminated by using an adhesive such as polyurethane, polyester or polyacrylic. An injection molding method, a co-extrusion pipe molding method, etc. are mentioned. The multilayer laminate thus obtained can be formed into a molded body by a method of reheating and stretching using a molding method such as vacuum molding, pressure molding, stretch blow molding or the like.

Further, the BPP of the present invention contains additives commonly used by those skilled in the art, such as an antioxidant, a weather resistance stabilizer, an antistatic agent, a lubricant, an antiblocking agent and an antifogging agent.
A pigment, a plasticizer, a softening agent and the like may be appropriately added within a range that does not impair the object of the present invention.

[0035]

EXAMPLES The present invention will now be described in more detail with reference to examples. In addition, the measuring method of each physical property is shown below. [MFR] In accordance with JIS K7210, a melt indexer manufactured by Takara Co. was used. [Ethylene content] CJ Carman et al; Macromolecule
s, 10, 537 was based on ¹³ C-NMR method described in (1977). [Flexural Modulus] Based on JIS K7203. [Izod impact strength] In accordance with JIS K7110,
It was measured with a notch. [Drop weight impact strength] According to ASTM D3029-78, the weight is dropped from a height of 1 m, and the weight load is 100%.
The load when 50% of the 20 test pieces was broken was calculated while changing every g. The temperature was measured under the condition of -20 ° C. [Deflection temperature under load] In accordance with JIS K7207B method,
The load was measured at 4.6 kg.

[Rockwell hardness] JIS K7202
The scale R was used for the measurement. Also used BPP
A production example of is shown below. (A) Preparation of solid catalyst 56.8 g of anhydrous magnesium chloride was added to anhydrous ethanol 1
00g, Idemitsu Kosan Vaseline oil (CP15N) 5
00 ml and Shin-Etsu Silicone Silicone Oil (KF
96) In a 500 ml mixed solution, under a nitrogen atmosphere,
Completely dissolved at 0 ° C. This mixture is made by T.
The mixture was stirred for 3 minutes at 120 ° C. and 3000 revolutions / minute using a K homomixer. Then, the mixture was transferred into 2 liters of anhydrous heptane while maintaining stirring and cooling so as to maintain 0 ° C or lower. The obtained white solid was thoroughly washed with anhydrous heptane and vacuum dried at room temperature. White solid 3 obtained
0 g was suspended in 200 ml of anhydrous heptane, and 500 ml of titanium tetrachloride was added dropwise over 1 hour while stirring at 0 ° C. Next, when heating started to 40 ° C, 4.96 g of diisobutyl phthalate was added, and the temperature was raised to about 100 ° C by about 1
Raised in time. After reacting at 100 ° C. for 2 hours, a solid portion was collected by hot filtration. Titanium tetrachloride (500 ml) was added to the obtained solid portion, and the mixture was reacted at 120 ° C. for 1 hour under stirring, and then the solid portion was collected by hot filtration again, and 60 ° C.
1 liter of hexane 7 times, then hexane 1 at room temperature
Wash 3 times with liters.

(B) TiCl ₄ [C ₆ H ₄ (COO ⁱ C
Preparation of ₄ H ₉ ) ₂ ] To a solution of 1 liter of hexane containing 19 g of titanium tetrachloride, 27.8 g of diisobutyl phthalate was added dropwise over about 30 minutes while maintaining 0 ° C. After the dropping was completed, the temperature was raised to 40 ° C. and the reaction was performed for 30 minutes. After the reaction was completed, the solid portion was collected and washed with 500 ml of hexane 5 times to obtain the desired product.

(C) Preparation of polymerization catalyst component 20 g of the solid catalyst obtained in (a) above was added to 300 parts of toluene.
TiC obtained in (b) above at 25 ° C.
I ₄ [C ₆ H ₄ (COO ⁱ C ₄ H ₉ ) ₂ ] 5.2 g was treated for 1 hour to be supported. After the completion of loading, the solid portion was collected by hot filtration and 300 ml of toluene and 10 m of titanium tetrachloride.
re-suspended in 1 l, washed with stirring at 90 ° C. for 1 hour, and the solid portion was collected by hot filtration, and then the reaction product was mixed with 500 ml of 90 ° C. toluene 5 times and 500 ml of hexane at room temperature.
And washed three times.

[0039] Under prepolymerization nitrogen atmosphere, in a content volume of 3-liter autoclave, n- heptane 500 ml, triethyl aluminum 6.0 g, dicyclopentyldimethoxysilane 3.9
g, and 10 g of the polymerization catalyst component obtained in (c) above were added and stirred at a temperature range of 0 to 5 ° C for 5 minutes. next,
Propylene was fed into the autoclave so that 10 g of propylene was polymerized per 1 g of the polymerization catalyst component, and 0 to 5 was added.
Prepolymerization was carried out in the temperature range of ° C for 1 hour. The resulting prepolymerized solid catalyst component was washed with 500 ml of n-heptane three times and used for the following main polymerization.

Main Polymerization (1) First-stage polymerization: 2.0 g of prepolymerized solid catalyst prepared by the above method in an autoclave equipped with a stirrer and having an internal volume of 60 liters under a nitrogen atmosphere, and triethylaluminum 1
1.4 g, dicyclopentyldimethoxysilane 6.84
g, then 18 kg of propylene, and hydrogen were charged so that the concentration would be 13000 mol ppm with respect to propylene.
The temperature was raised to 75 ° C. and polymerization was carried out for 1 hour. Then, unreacted propylene was removed to terminate the polymerization. After the reaction,
The reaction product was sampled.

(2) Second-stage polymerization: After completion of the first-stage polymerization, liquid propylene was removed, and a mixed gas of ethylene / propylene = 40/60 (molar ratio) at a temperature of 75 ° C. was 2.2 Nm ³ / hour, and hydrogen was used. Copolymerization was carried out for 40 minutes at a feed rate of 20 Nl / hr. After the polymerization was completed, the unreacted gas was removed to terminate the polymerization. As a result, a propylene-ethylene block copolymer having an ethylene content of 9.5% by weight and an MFR of 16.9 g / 10 minutes (hereinafter referred to as "BPP1") 8.6.
I got kg.

Similarly, the amount of hydrogen charged during the first stage polymerization,
The polymerization time during the second stage polymerization and the amount of ethylene were adjusted so that the ethylene content was 10.8% by weight and the MFR was 7.3 g / 1.
A propylene-ethylene block copolymer (hereinafter referred to as "BPP2") having 0 minutes and an ethylene content of 6.
Propylene-ethylene block copolymer having 1 wt% and MFR of 26.8 g / 10 minutes (hereinafter referred to as "BPP3").
I got). In addition, during the second-stage polymerization, the ethylene content was 7.8% by weight, the butene-1 content was 0.7% by weight, and the MFR was 15. A propylene-ethylene block copolymer (hereinafter referred to as "BPP4") having a weight of 3 g / 10 minutes was obtained.

Furthermore, the following two types of BP are used for comparison.
P was used. Tosoh Akzo AA type titanium trichloride 6.0g, diethyl aluminum chloride 23.5g
Was used as a catalyst component, 18 kg of propylene and hydrogen were charged so that the concentration would be 8000 mol ppm based on propylene, the temperature was raised to 70 ° C., and the polymerization was carried out in the same manner as in BPP1. As a result, ethylene content was 9.8. Wt% and MFR
Of 18.2 g / 10 minutes (hereinafter referred to as "BPP5"), except that the catalyst prepared in (a) above was used and the amount of hydrogen at the first stage polymerization was 9300 mol ppm. Polymerization was carried out in the same manner as above, with an ethylene content of 10.1% by weight and an MFR of 18.4 g / 1.
What was 0 minutes (hereinafter referred to as "BPP6") was obtained.

Regarding the polypropylene portion sampled at the end of the first-stage polymerization of the above copolymer, XI, IP,
N and N _f were measured. The results are shown in Table 2. The IP measurement conditions are as follows. Measuring device JNM-GSX400 manufactured by JEOL Ltd. Measurement mode: Proton decoupling method Pulse width: 8.0 μs Pulse repetition time: 3.0 s Accumulation frequency: 20000 times Solvent: 1,2,4-Trichlorobenzene / heavy benzene Mixed solvent (75/25 wt%) Internal circulation: Hexamethyldisiloxane Sample concentration: 300 mg / 3.0 ml Solvent measurement temperature: 120 ° C

[0045]

[Table 3]

For each ethylene-propylene copolymer part obtained in the second step, FP, P _P , P _f1 and CSD were analyzed by NMR spectrum and two-site model analysis.
I asked. The results are shown in Table 4.

[0047]

[Table 4]

Further, as a nucleating agent, pt-butyl benzoic acid aluminum salt was used.

Examples 1 to 7 and Comparative Examples 1 to 4 BPP and nucleating agent whose types and amounts are shown in Table 5 and di-t-butyl-p-cresol 0.05% by weight as a stabilizer, 0.10% by weight of pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and 0.10% by weight of calcium stearate are mixed, and a super mixer manufactured by Kawata Manufacturing Co., Ltd. (SMV20 type) were mixed and pelletized using a twin-screw extruder (AS30 type) manufactured by Nakatani Machinery Co., Ltd. The obtained pellets were heated at a temperature of 22 using an injection molding machine (IS-170FII) manufactured by Toshiba Machine Co., Ltd.
Each test piece was prepared at 0 ° C. and a mold cooling temperature of 50 ° C. 2 Place the obtained test piece in a thermostatic chamber at a relative humidity of 50% and a temperature of 23 ° C.
After standing for a day, the flexural modulus, Izod impact strength (with notch), falling weight impact strength, deflection temperature under load and Rockwell hardness were measured. The results obtained are shown in Table 5.

[0050]

[Table 5]

[0051]

Since the resin composition of the present invention is excellent in rigidity, impact resistance, heat resistance and surface hardness, it is particularly useful for automobile parts, electric / electronic parts, packaging materials and the like.

[Brief description of drawings]

FIG. 1 is an example of a nuclear magnetic resonance spectrum in the methyl region of polypropylene.

FIG. 2 is an example of a nuclear magnetic resonance spectrum of an ethylene-propylene copolymer.

FIG. 3 is a diagram showing names of carbons derived from a chain distribution in polyolefin.

[Explanation of symbols]

 a ・ ・ ・ Spectral diagram b ・ ・ ・ Enlarged view of a

Claims (3)

[Claims] 1. A polypropylene part (a) having the following physical properties (i) to (iv): 50 to 97% by weight, and (i) a xylene extraction insoluble part at 25 ° C .: 99.0% by weight or more (ii) isotactic Chick pentad fraction 98.0%
Above (iii) Isotactic average chain length of 500 or more (iv) Total amount of fractions by column fractionation having an isotactic average chain length of 800 or more 10
% By weight or more Copolymer part of propylene and ethylene and / or α-olefin having 4 to 12 carbon atoms (b) 50 to 3% by weight (v) 2 satisfying all of the following conditions (v) to (viii) Average propylene content by site model (FP)
20 to 80 mol% (vi) 2 sites copolymer produced in the active sites of polymerization preferentially propylene in the model propylene content _(P P) 65 to 90 mol% of _{(P H) (vii) P} H is co Ratio (P _f1 ) in polymer 0.4
0-0.90 (viii) Two-site model blockiness (CSD)
A propylene block copolymer consisting of 1.8 to 5.0. 2. A solid catalyst containing a magnesium compound, a titanium compound, a halogen-containing compound, and an electron-donating compound as essential components, further comprising a compound represented by the general formula: Ti Xa .Yb (wherein
X is a halogen atom of Cl, Br, I, Y is an electron-donating compound, a is 3 or 4, and b is an integer of 3 or less. The method for producing a propylene block copolymer according to claim 1, which is obtained by polymerizing using an improved polymerization catalyst obtained by washing and further washing with a hydrocarbon. 3. A propylene block copolymer resin composition comprising the propylene block copolymer according to claim 1 and at least 0.05 to 30% by weight of a nucleating agent.