JPH0788450B2 - High rigidity and high melt viscoelastic propylene homopolymer composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a high-rigidity, high-melt viscoelasticity propylene homopolymer composition. More specifically, it relates to a high-rigidity, high-melting viscoelasticity propylene homopolymer composition capable of obtaining a molded article having extremely excellent rigidity and heat resistance.

[Prior Art] Generally, propylene-based polymers have excellent processability, chemical resistance,
Since it has electrical and mechanical properties, it is processed into injection-molded products, blow-molded products, films, sheets, fibers and the like and used for various purposes. However, a sheet produced by processing a propylene-based polymer quickly sags during heat molding for secondary processing, has a narrow range of processing conditions, is inferior in molding efficiency, and has a large sag described above in a wide sheet. In addition, the thickness of the secondary processed product is likely to be non-uniform, and overlapping wrinkles are likely to occur. Therefore, only small molded products can be manufactured. Further, when the propylene polymer is used for blow molding, there are the following problems. That is, the thickness of the molded product becomes non-uniform because the varison droops significantly during molding. Therefore, it can only be applied to the manufacture of small products. If a high-molecular-weight propylene-based polymer is used to prevent the above-mentioned sagging, there is a risk of poor fluidity, a large load during molding, a large energy loss, and mechanical troubles. Is lost.

On the other hand, depending on various specific applications of the propylene-based polymer, the properties of the propylene-based polymer may not be sufficient, and there is a problem that expansion of the specific applications is limited. Especially in terms of rigidity and heat resistance, it is inferior to polystyrene, ABS resin, polyester, etc., and has become a serious bottleneck in expanding applications of propylene-based polymers. Therefore, if it is possible to improve the rigidity (which means rigidity and heat resistance rigidity), it is possible to reduce the thickness of the molded product by that amount, which not only contributes to resource saving, but also increases the cooling rate during molding. Therefore, the molding speed per unit time can be increased, which can contribute to the improvement of productivity.

Therefore, in order to improve the secondary processability, blow moldability, and rigidity of the above-mentioned sheet related to the propylene-based polymer, the Japanese Patent Application Laid-Open No. 58-219207 filed by the same applicant as the present application has been disclosed. Disclosed are crystalline propylene homopolymers having a particular molecular weight distribution and a particular isotactic pentad fraction. Further, in the above publication, an organic nucleating agent such as aluminum p-t-butylbenzoate or 1,3,2,4-dibenzylidene sorbitol is added to the crystalline propylene homopolymer for the purpose of further improving the rigidity. It is disclosed.

[Problems to be Solved by the Invention] However, using the crystalline propylene homopolymer having the specific molecular weight distribution and the specific isotactic pentad fraction disclosed in the above-mentioned JP-A-58-219207. The secondary workability and blow moldability of the obtained sheet are sufficiently satisfactory in practical use, and although the rigidity is considerably improved, they are not yet sufficiently satisfactory. In addition, a crystalline propylene homopolymer having the above-mentioned specific molecular weight distribution and specific isotactic pentad fraction is added to the organic polymer of p-t-butyl aluminum benzoate or 1,3,2,4-dibenzylidene sorbitol at an organic rate. A sheet using a propylene homopolymer composition containing a nucleating agent has a considerable effect of improving the rigidity, but is still sufficiently satisfactory when used in applications requiring high rigidity and heat resistance. Not a thing.

The inventors of the present invention have the above-mentioned problems regarding the propylene-based polymer composition containing the above-mentioned various nucleating agents, that is, the secondary processability of the sheet when formed into a sheet, the blow moldability,
Intensive research was conducted to solve the problems of rigidity and heat resistance. As a result, a crystalline propylene homopolymer having a specific molecular weight distribution and a specific isotactic pentad fraction was compounded with a phosphate compound represented by the following general formula [I] (hereinafter referred to as compound A). It was found that such a composition can solve the above-mentioned problems of the propylene-based polymer composition, and the present invention was completed based on this finding.

(However, in the formula, R represents hydrogen or an alkyl group having 1 to 18 carbon atoms, an alkoxy group, a cycloalkyl group, a phenyl group or a phenoxy group.) As is apparent from the above description, the object of the present invention is a sheet. It is an object of the present invention to provide a propylene homopolymer composition capable of obtaining a molded product which is remarkably excellent in the secondary processability and blow moldability of the sheet and the rigidity and the heat resistance.

[Means for Solving Problems] The present invention has the following configurations.

When polymerizing propylene in multiple stages, 35 to 65 wt% of the total polymer is polymerized in the first stage, and 65 to 35 wt% is polymerized in the second stage and thereafter,
Among the polymer parts produced in the first step and the second step and thereafter, the intrinsic viscosity of the polymer part having a high molecular weight is [η].
_H , where the intrinsic viscosity of a polymer portion having a low molecular weight is [η] _L , 3.0 ≦ [η] _H − [η] _L ≦ 6.5 (1) having an intrinsic viscosity value of each polymer portion, Moreover, the relationship between the isotactic pentad fraction (P) of all polymers and the melt flow rate (MFR; discharge amount of molten resin for 10 minutes when a load of 2.16 kg at 230 ° C. is applied) is 1.00 ≧ P ≧ 0.
Crystalline propylene homopolymer with 015 log MFR + 0.955 10
0.01 to 0 parts by weight of a phosphate compound represented by the following general formula [I] (hereinafter referred to as compound A).
A high-rigidity, high-melting viscoelasticity propylene homopolymer composition containing 1 part by weight.

(In the formula, R represents hydrogen or an alkyl group having 1 to 18 carbon atoms, an alkoxy group, a cycloalkyl group, a phenyl group or a phenoxy group.) The crystalline propylene homopolymer used in the present invention comprises propylene in multiple stages. In the first step, 35-65% by weight of the total amount of the polymer is polymerized, and in the second step and thereafter, 65-35% by weight is similarly polymerized. Of the polymer parts produced in the second and subsequent steps, the intrinsic viscosity of the polymer part having a high molecular weight is [η] _H ,
When the intrinsic viscosity of a polymer portion having a low molecular weight is [η] _L , the intrinsic viscosity value of each polymer portion is 3.0 ≦ [η] _H − [η] _L ≦ 6.5 (1), and The relationship between the isotactic pentad fraction (P) and the melt flow rate (MFR) of all polymers is 1.00 ≧ P ≧ 0.015logMFR + 0.
955 is a crystalline propylene homopolymer. Such a crystalline propylene homopolymer is produced by the production method described in JP-A-58-219207, which is an application of the same applicant as the present application. That is, an organoaluminum compound (i) (eg, triethylaluminum, diethylaluminum monochloride, etc.) or a reaction product (v) of an organoaluminum compound (i) with an electron donor (eg, diisoamyl ether, ethylene glycol monomethyl ether, etc.) Solid product (ii) obtained by reacting benzene with titanium tetrachloride, and a solid product obtained by further reacting an electron donor and an electron acceptor (eg, anhydrous aluminum chloride, titanium tetrachloride, vanadium tetrachloride). The compound (iii) is combined with the organoaluminum compound (i) and the aromatic carboxylic acid ester (iv) (for example, ethyl benzoate, methyl p-toluate, ethyl p-toluate, and 2-ethylhexyl p-toluate). , The aromatic carboxylic acid ester (iv) and the solid Can be obtained by polymerizing the multistage propylene in the presence of a molar ratio iv / iii = 0.1 to 10.0 and the catalyst of the object (iii). In this case, one stage means one section of continuous or temporal supply of these monomers.
The simplest two-step polymerization will be described below. In the present invention, it is desirable that the polymer portion (S1) in the first stage and the portion (S2) in the second stage are in an amount close to an equivalent amount, specifically, (S1) and (S2) Are both 35 to 65% by weight, preferably 40 to 60% by weight, based on the total amount of (S1) + (S2), and the total amount of (S1) + (S2) is 100% by weight. With a crystalline propylene homopolymer in which the amount ratio of (S1) and (S2) is different from the above range, sufficient melt fluidity cannot be obtained, and the kneading effect at the time of granulation becomes insufficient, so that the final Not only is it difficult to obtain a homogeneous molded product, but also the degree of improvement in melt viscoelasticity is small. Further, in the crystalline propylene homopolymer used in the present invention, the difference in molecular weight between both polymer portions must be within a certain range as shown in the following formula (1). Therefore, the polymerization conditions are adjusted by adjusting the gas phase hydrogen concentration. now,
Assuming that the intrinsic viscosity of the high molecular weight portion (135 ° C., tetralin solution) is [η] _H and the intrinsic viscosity of the low molecular weight portion is [η] _L , both are 3.0 ≦ [η] _H − [η] _L ≦ 6.5. (1) must be satisfied. This relationship substantially corresponds to the following expression (2).

logHMFR-0.922 logMFR ≧ 1.44 (2) HMFR (high melt flow rate) is the temperature of 230 ℃.
It is the discharge amount of the molten resin for 10 minutes when the load of 10.80 kg is added. [Η] _H − [η] _L <3.0, logHMFR
<0.922logMFR + 1.44, and when the crystalline propylene homopolymer is used, the melt fluidity at the time of melting is insufficient and the degree of improvement in melt viscoelasticity is also insufficient. The sheet thus obtained cannot prevent sagging during secondary processing. On the other hand, when [η] _H − [η] _L > 6.5, the above-mentioned difference in molecular weight between (S1) and (S2) becomes too large, resulting in non-uniformity in molecular weight between the obtained crystalline propylene homopolymer particles. As a result of the increase, the surface roughness of the molded article made of such a crystalline propylene homopolymer becomes remarkable. The melt flow rate (MFR) of the crystalline propylene homopolymer of the present invention obtained as described above is preferably 0.03 to 2.0 g / 10 minutes.
If it is less than 0.03, the fluidity of the melt during granulation or molding will be poor and the granulator or molding machine will require a lot of power, which is not economical and the surface roughness of the resulting molded product will be noticeable. Product value will be lost. On the other hand, when it exceeds 2.0, the produced sheet is largely sagged during the secondary processing, which makes the secondary processing difficult. By the way, the above-mentioned formula (1) has a viscoelasticity which makes it possible to prevent sagging of a molding material during thermoforming of a sheet using a crystalline propylene homopolymer or during blow molding using a crystalline propylene homopolymer. It shows a method for designing a polymer necessary for imparting to a crystalline propylene homopolymer. Similarly, the above-mentioned formula (2) shows the fluidity of the crystalline propylene homopolymer, and the crystalline propylene homopolymer of the present invention having the structure of the polymer of the formula (1) is represented by the formula (2). Satisfies the conditions. Here, the isotactic pentad fraction (P) refers to Macromolecules, Volume 6, Issue 6, November-December,
925-926 (1973) [Macromolecules, Vol.6, No6, Nov
ember-December, 925-926 (1973)], that is, the isotactic fraction in pentad units in the propylene-based polymer molecular chain measured using ₁₃ C-NMR. In other words, the fraction means the fraction of propylene monomer units in which five propylene monomer units are continuously isotactically bonded. ₁₃ C-NMR above
The determination of the attribution of the peak of the spectrum in the measurement using is described in Macromolecules, Volume 8, No. 5, September-10.
Mon, pp. 687-689 (1975) [Macromolecules, Vol.8, No
5, September-October, 687-689 (1975)]. By the way, the measurement by ₁₃ C-NMR in the examples described later was carried out by using an FT-NMR 270 MHz device, and the signal detection limit was improved to 0.001 by the isotactic pentad fraction by the integrated measurement of 27,000 times. went. The requirement of the relational expression between the isotactic pentad fraction (P) and the melt flow rate (MFR) is that the fraction P of a propylene homopolymer having a low MFR generally decreases, so that the propylene homopolymer weight to be used should be reduced. As a unity, the constitutional requirement is to limit the lower limit value of P corresponding to the MFR. Since P is a fraction, 1.00 is the upper limit. 2 above
The intrinsic viscosity in stepwise polymerization is measured at 135 ° C. in a tetralin solution. However, the intrinsic viscosity [η] _{2 at} the second stage is calculated by the following formula. That is, the intrinsic viscosity [η] ₁ of the first step, that is, the intrinsic viscosity [η] _T of the polymer produced through the first step and the second step, the first
The polymerization ratios a and b of the polymer portion generated in the second step and the second step were measured, and [η] _T = a [η] ₁ + b [η] ₂ = a [η] ₁ + (1
-A) Calculate from [η] ₂ . The above MFR complies with JIS K 7210 and has a temperature of 230
Measured at a temperature of 230 ° C and a load of 10.80 kg in accordance with JIS K 7210 according to JIS K 7210.

At this time, the [η] ₁ may be [η] _L or [η] _H. The same applies to the [η] ₂ .

Further, the crystalline propylene homopolymer used in the present invention, in the range not impairing the effects of the present invention, a normal crystalline propylene polymer, that is, a crystalline propylene homopolymer, propylene containing 70 wt% or more propylene component Crystalline random copolymer or crystalline block copolymer with one or more α-olefins such as ethylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1 Polymers, copolymers of propylene and vinyl acetate or acrylic acid ester, or saponified products of the copolymers, copolymers of propylene and unsaturated silane compounds, of propylene and unsaturated carboxylic acids or their anhydrides A copolymer, a reaction product of the copolymer and a metal ion compound, or a crystalline propylene-based polymer is used as an unsaturated carbohydrate. A modified propylene polymer modified with an acid or a derivative thereof, a crystalline propylene polymer can also be used as a mixture of a silane modified propylene polymer modified with an unsaturated silane compound, and the like,
Further, various synthetic rubbers (for example, ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene copolymer rubber, polybutadiene, polyisoprene, polychloroprene, chlorinated polyethylene, chlorinated polypropylene, styrene-butadiene rubber, acrylonitrile). −
Butadiene rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-propylene-butylene-styrene block copolymer) or Thermoplastic synthetic resin (for example, propylene-based polymer such as ultra low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, ultra high molecular weight polyethylene, polybutene, poly-4-methylpentene-1). Polyolefins excluding coalescence, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, polybutylene terephthalate,
(Polycarbonate, polyvinyl chloride, fluororesin, etc.)
It is also possible to use a mixture of the above.

Examples of the compound A used in the present invention include aluminum hydroxy-di-phenyl phosphate, aluminum hydroxy-bis (p-methylphenyl) phosphate, aluminum hydroxy-bis (p-ethylphenyl) phosphate, aluminum hydroxy. −
Bis (pn-propylphenyl) phosphate, aluminum hydroxy-bis (pi-propylphenyl) phosphate, aluminum hydroxy-bis (pn-butylphenyl) phosphate, aluminum hydroxy-bis ( p-i-butylphenyl)
Phosphate, aluminum hydroxy-bis (p
-S-butylphenyl) phosphate, aluminum hydroxy-bis (pt-butylphenyl) phosphate, aluminum hydroxy-bis (pn-)
Amylphenyl) phosphate, aluminum hydroxy-bis (p-i-amylphenyl) phosphate, aluminum hydroxy-bis (ps-amylphenyl) phosphate, aluminum hydroxy-bis (pt-amylphenyl) ) Phosphate, aluminum hydroxy-bis (p-hexylphenyl) phosphate, aluminum hydroxy-bis (pn-octylphenyl) phosphate, aluminum hydroxy-bis (p-2-ethylhexylphenyl) phosphate, Aluminum hydroxy-
Bis (pt-octylphenyl) phosphate, aluminum hydroxy-bis (p-nonylphenyl)
Phosphate, aluminum hydroxy-bis (p
-Dodecylphenyl) phosphate, aluminum hydroxy-bis (p-tridecylphenyl) phosphate, aluminum hydroxy-bis (p-hexadecylphenyl) phosphate, aluminum hydroxy-bis (p-octadecylphenyl) phosphate , Aluminum hydroxy-bis (p-methoxyphenyl) phosphate, aluminum hydroxy-bis (p-ethoxyphenyl) phosphate, aluminum hydroxy-bis (p-propoxyphenyl) phosphate, aluminum hydroxy-bis (p -Butoxyphenyl) phosphate, aluminum hydroxy-bis (p-butoxyphenyl) phosphate, aluminum hydroxy-bis (p-octoxyphenyl) phosphate Examples thereof include sulfate, aluminum hydroxy-bis (p-cyclohexylphenyl) phosphate, aluminum hydroxy-bis (p-biphenylyl) phosphate, aluminum hydroxy-bis (p-phenoxyphenyl) phosphate, and the like. Oxy-bis (pt-butylphenyl) phosphate is preferred. These phosphate compounds can be used alone or in combination of two or more. The compounding ratio of the compound A is 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the above-mentioned crystalline propylene homopolymer. If the amount is less than 0.01 parts by weight, the effect of improving rigidity and heat resistance will not be sufficiently exerted, and if it exceeds 1 part by weight, further improvement of the above effects cannot be expected and is not practical. It is uneconomical again.

In the composition of the present invention, various additives usually added to propylene-based polymers such as phenol-based, thioether-based, phosphorus-based antioxidants, light stabilizers, clarifying agents, nucleating agents, Lubricants, antistatic agents, anti-fog agents, anti-blocking agents, anti-drop agents, pigments, heavy metal deactivators (copper damage inhibitors), radical generators such as peroxides, dispersants such as metal soaps or medium Additives, inorganic fillers (eg talc, mica, clay, wollastonite, zeolite,
Asbestos, calcium carbonate, aluminum hydroxide, magnesium hydroxide, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, zinc sulfide, barium sulfate, calcium silicate, glass fiber, carbon fiber, carbon black, potassium titanate, metal fiber Etc.) or a coupling agent (for example, silane-based, titanate-based, boron-based, aluminate-based, zircoaluminate-based, etc.) surface-treated inorganic filler or organic filler (for example, wood powder, (Pulp, waste paper, synthetic fiber, natural fiber, etc.) can be used together as long as the object of the present invention is not impaired. Particularly, when an inorganic filler is used in combination, the rigidity and the heat resistance rigidity are further improved, and therefore it is preferable to use them together.

The composition of the present invention is prepared by adding a predetermined amount of the compound A and the various additives usually added to the propylene-based polymer to the above-mentioned crystalline propylene homopolymer according to the present invention in a conventional mixing device such as Henschel. Mixer (trade name),
Mix using a super mixer, ribbon blender, Banbury mixer, etc., and use a normal single-screw extruder, twin-screw extruder, Brabender or roll to melt and knead temperature 17
It can be obtained by melt-kneading and pelletizing at 0 ° C to 300 ° C, preferably 200 ° C to 250 ° C. The obtained composition is used for producing a desired molded article by various molding methods such as an injection molding method, an extrusion molding method and a blow molding method.

[Operation] In the present invention, the phosphate compound represented by the compound A has rigidity and heat resistance as a nucleating agent like the phosphate compound disclosed in JP-B-41-16303 and JP-A-53-105550. It is generally known to act to improve rigidity. However, said Japanese Patent Publication No. 41-16303
Compound A, which is a monobasic aluminum salt of a phosphate compound (aluminum normal salt) disclosed in JP-A-53-105550 and JP-A-53-105550, has a specific molecular weight distribution and a specific isotacticity according to the present invention. By blending with a crystalline propylene homopolymer having a pentad fraction, a surprising synergistic effect that cannot be predicted from the blending of conventionally known nucleating agents is exerted, and a composition having extremely excellent rigidity and heat resistance is obtained. I found that I could get it.

[Effects of the Invention] The composition of the present invention is significantly superior in (1) rigidity and heat resistance as compared with a conventionally known propylene homopolymer composition containing various nucleating agents. (2) Not only can it contribute to resource saving by reducing the thickness of molded products,
Since the cooling rate at the time of molding is also increased, the molding rate per unit time can be increased, which can contribute to the improvement of productivity.
(3) Polypropylene resin can be used in applications where polyesters such as polystyrene, ABS resin, polyethylene terephthalate and polybutylene terephthalate have been conventionally used, and the applications of polypropylene resin can be expanded. (4) Since the sheet has excellent secondary processability and blow moldability, it can be suitably used for producing a secondary processing sheet and a blow molded product.

[Examples] Hereinafter, the present invention will be specifically described with reference to Examples, Comparative Examples, and Production Examples, but the present invention is not limited thereto.

The evaluation methods used in Examples and Comparative Examples were as follows.

1) Secondary workability of sheet (heated vacuum formability): A sheet having a width of 60 cm and a thickness of 0.4 mm was prepared by extrusion molding using the obtained pellets, and the heat vacuum formability of the sheet was evaluated as a model. Cut the sheet into 40 cm x 40 cm,
Fix it tightly in a frame of cm x 40 cm and put it in a thermostatic chamber at 200 ° C. Eventually, the sheet fixed to the frame is heated and the central part of the frame starts to hang down, and at some point, it begins to return to the original position due to heat contraction. After that, it begins to hang down again. At this time, (a) the sag amount immediately before the sheet starts to return is measured as the maximum sag amount (mm).

(B) The amount of deformation (mm) at which the sheet droops to the maximum and returns to the original position in the direction of the original position is measured, and (the amount of deformation /
Record the maximum amount of droop) x 100 as the maximum amount of return (%).

(C) Measure the time (seconds) from the point where the sheet returns to the maximum until it hangs down again 10 mm, and use it as the holding time.

The material having good secondary workability (vacuum formability) of the sheet by the above evaluation method means a material having minimum sag, maximum return, and long holding time.

2) Rigidity: width 60 cm, thickness 0.4 m using the obtained pellets
A sheet of m was prepared by an extrusion molding method, and Young's modulus (based on ASTM D 882) and tensile yield strength (based on ASTM D 882) were measured using the sheet to evaluate rigidity. A material having high rigidity means a material having a large Young's modulus and tensile yield strength.

In the examples and comparative examples, two types of test pieces, MD (vertical; extrusion direction) and TD (horizontal; direction perpendicular to the extrusion direction) of the sheet were prepared, and Young's modulus and tensile yield strength were used using the test pieces. Was measured and shown as the average value.

3) Heat resistance rigidity: length of 130mm using the obtained pellets,
A test piece having a width of 13 mm and a thickness of 6.5 mm was prepared by an injection molding method, and the heat distortion temperature was evaluated by measuring the heat distortion temperature using the test piece (according to JIS K 7207; 4.6 kgf / cm ² load). . A material having high heat resistance and rigidity means a material having a high heat distortion temperature.

Production Examples 1 to 3 (Production Example of Crystalline Propylene Homopolymer Used in Examples and Comparative Examples) (1) Preparation of Catalyst n-Hexane 600 ml, diethyl aluminum monochloride (DEAC) 0.50 mol, diisoamyl ether 1.20 mol
Reaction mixture (v) (diisoamyl ether / DEAC molar ratio 2.4) by mixing at 25 ° C for 1 minute and reacting at the same temperature for 5 minutes.
Got 4.0 mol of titanium tetrachloride was placed in a reactor purged with nitrogen, heated to 35 ° C., and the whole amount of the reaction product solution (v) was added dropwise thereto for 180 minutes, and then kept at the same temperature for 30 minutes.
The temperature was raised to 5 ° C and the reaction was continued for another 1 hour, the mixture was cooled to room temperature (20 ° C), the supernatant was removed, 4000 ml of n-hexane was added, and the operation of removing the supernatant by decantation was repeated 4 times.
190 g of solid product (ii) was obtained. With the total amount of the solid product (ii) suspended in 3000 ml of n-hexane, 20 ° C
Then, 160 g of diisoamyl ether and 350 g of titanium tetrachloride were added at room temperature for about 1 minute and reacted at 65 ° C. for 1 hour. After completion of the reaction, the mixture was cooled to room temperature, the supernatant was removed by decantation, 4000 ml of n-hexane was added, and the mixture was stirred for 10 minutes, allowed to stand, and the supernatant was removed. This procedure was repeated 5 times, and the pressure was reduced. It was dried under to obtain a solid product (iii).

(2) Preparation of pre-activated catalyst After replacing the stainless reactor with an inclined blade with an internal volume of 20 liters with nitrogen gas, add 15 liters of n-hexane, 42 g of diethylaluminum monochloride, 30 g of solid product (iii) at room temperature. After that, put 15Nl of hydrogen, propylene partial pressure 5kg / cm
^The mixture was reacted at ² G for 5 minutes, unreacted propylene, hydrogen and n-hexane were removed under reduced pressure to obtain a pre-activated catalyst (vi) in the form of powder (solid product (iii) 1 g of propylene 82.
0g reaction).

(3) Polymerization of propylene n was dried in a polymerization vessel having an internal volume of 50 l, which was replaced with nitrogen gas.
-Hexane 20 l, diethyl aluminum monochloride 8
g, 2 g of the pre-activated catalyst (vi) and 2.2 g of methyl p-toluate were charged and hydrogen was added to maintain the inside of the vessel at 70 ° C.
Then, supply propylene into the vessel and increase the pressure in the vessel to 10 kg.
/ cm ² G, the hydrogen concentration in the gas phase was 11 mol% in Preparation Example 1, 5 mol% in Preparation Example 2 and 14 mol% in Preparation Example 3, and the temperature was
The first stage polymerization was carried out at 70 ° C. Polymer amount 3kg
At that point, the supply of propylene was stopped, the temperature inside the vessel was cooled to room temperature, and hydrogen and unreacted propylene were discharged. Then, a part of the polymerized slurry was extracted, and the intrinsic viscosity [η] ₁ was measured and the titanium content in the polymer was analyzed by the fluorescent X-ray method, and the polymer yield per unit weight of the catalyst was determined.

Then, the temperature inside the polymerization vessel was raised again to 70 ° C and the polymerization pressure was 10 kg / cm.
² G, gas phase hydrogen concentration was 0.4 mol% in Production Example 1, and in Production Example 2
While maintaining 0.07 mol% and Production Example 3 at 0.08 mol%,
The second stage polymerization was carried out. 2k polymer amount is 3k
When the amount reached g, the supply of propylene was stopped, the temperature inside the vessel was cooled to room temperature, and hydrogen and unreacted propylene were discharged. Then, a part of the polymerization slurry was extracted, the intrinsic viscosity [η] _T was measured, and the titanium content in the polymer was analyzed by a fluorescent X-ray method to obtain the polymer yield per catalyst unit polymerization, and the above-mentioned first step was conducted. The yield value of was used to determine the ratio of the amounts of the polymer in the first and second stages, and the intrinsic viscosity [η] ₂ of the polymer obtained only by the second stage polymerization was calculated. . To the polymerized slurry after the extraction, 5 l of methanol was added and stirred at 90 ° C. for 30 minutes, then 40 ml of a 20 wt% sodium hydroxide aqueous solution was added, and further stirred for 20 minutes.
Next, the mixture was cooled to room temperature, 5 liters of water was added, washing with water and separation of water were carried out 3 times, the slurry obtained was filtered, and the filtered product was dried to obtain a white polymer powder. The analysis results of the polymer are shown in Table 1. Here, [η] _L = [η] ₁ and [η] _H = [η] ₂ .

Examples 1 to 3, Comparative Examples 1 to 9 Each intrinsic viscosity ([η]), each melt flow rate (MFR), each high melt flow rate (produced in Production Examples 1 to 3 shown in Table 2 below) HMFR) and 100 parts by weight of a powdery crystalline propylene homopolymer having each isotactic pentad fraction (P), aluminum hydroxide-bis (pt-butylphenyl) phosphate as compound A and other Henschel mixer (trade name) with a prescribed amount of each additive in the blending ratio shown in Table 2 below.
After being stirred and mixed for 3 minutes, the mixture was melt-kneaded at 200 ° C. with a single screw extruder having a diameter of 40 mm to form pellets. Further, as Comparative Examples 1 to 9, Production Examples 1 to 1 shown in Table 2 below.
Powdery crystalline propylene homopolymer having intrinsic viscosity, melt flow rate, high melt flow rate and isotactic pentad fraction prepared in 3
A predetermined amount of each of the additives described in Table 2 below was mixed with 0 parts by weight, and melt-kneaded according to Examples 1 to 3 to obtain pellets.

The sheet used for the secondary workability and rigidity test of the sheet is
The resulting pellets were prepared by extrusion at a resin temperature of 250 ° C. The test pieces used for the heat resistance rigidity test were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C.

Using the obtained sheet and test piece, the secondary workability, rigidity and heat resistance rigidity of the sheet were evaluated by the above-mentioned test method. The results are shown in Table 2.

Examples 4 to 6 and Comparative Examples 10 to 18 Each intrinsic viscosity ([η]), each melt flow rate (MFR), each high melt flow rate (produced in Production Examples 1 to 3 shown in Table 3 below) HMFR) and 100 parts by weight of powdery crystalline propylene homopolymer having each isotactic pentad fraction (P), aluminum hydroxy-bis (pt-butylphenyl) phosphate as compound A, inorganic filling Predetermined amounts of fine particle talc having an average particle size of 2 to 3 μm and other additives are used as agents.
The mixture was placed in a Henschel mixer (trade name) at the compounding ratio shown in the table, stirred and mixed for 3 minutes, and then melt-kneaded at 200 ° C. in a single screw extruder having a diameter of 40 mm to form pellets. Further, as Comparative Examples 10 to 18, powdery powders having the intrinsic viscosities, the melt flow rates, the high melt flow rates and the isotactic pentad fractions produced in Production Examples 1 to 3 shown in Table 3 below. The crystalline propylene homopolymer (100 parts by weight) was mixed with a predetermined amount of each of the additives shown in Table 3 below, and melt-kneaded according to Examples 4 to 6 to obtain pellets.

The sheet used for the secondary workability and rigidity test of the sheet is
The resulting pellets were prepared by extrusion at a resin temperature of 250 ° C. The test pieces used for the heat resistance rigidity test were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C.

Using the obtained sheet and test piece, the secondary workability, rigidity and heat resistance rigidity of the sheet were evaluated by the above-mentioned test method. The results are shown in Table 3.

The compounds and additives relating to the present invention shown in Tables 2 to 3 are as follows.

Compound A: Aluminum hydroxy-bis (pt-butylphenyl) phosphate Nucleating agent 1: p-t-Butyl aluminum benzoate Nucleating agent 2: 1,3,2,4-dibenzylidene sorbitol Nucleating agent 3: Sodium-bis (pt-butylphenyl)
Phosphate [manufactured by Adeka Argus Chemical Co., Ltd .; MARK
NA-10UF] Nucleating agent 4: Aluminum-bis (pt-butylphenyl) phosphate Nucleating agent 5: Aluminum-2,2'-methylene-bis (4,6-
Di-t-butylphenyl) phosphate nucleating agent 6: aluminum hydroxy-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate phenolic antioxidant 1: 2,6 -Di-t-butyl-p-
Cresol phenolic antioxidant 2: tetrakis [methylene-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methanephosphorus antioxidant 1: tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene- Di-phosphonite Phosphorus antioxidant 2: Bis (2,4-di-t-butylphenyl) -pentaerythritol-diphosphite Ca-St: Calcium stearate Inorganic filler: Talc (average particle size 2-3μ ) The examples and comparative examples described in Table 2 are crystalline propylene homopolymers each having an intrinsic viscosity, a melt flow rate, a high melt flow rate and an isotactic pentad fraction as a propylene polymer. This is the case when used. As can be seen from Table 2, Examples 1 to 3 are prepared by compounding Compound A with a crystalline propylene homopolymer having a molecular weight distribution and an isotactic pentad fraction within the scope of the present invention. Compared to Examples 1 to 3 and Comparative Examples 1 to 3 (a crystalline propylene homopolymer having a molecular weight distribution and an isotactic pentad fraction within the scope of the present invention, without an organic nucleating agent). As a result, although Examples 1 to 3 and Comparative Examples 1 to 3 have similar secondary workability of the sheet, Comparative Examples 1 to 3 are still insufficient in the effect of improving rigidity and heat resistance rigidity. Further, in order to improve the rigidity and heat resistance of Comparative Examples 1 to 3, a crystalline propylene homopolymer having a molecular weight distribution and an isotactic pentad fraction within the scope of the present invention comprises a compound other than compound A. Comparing Comparative Examples 4 to 9 and Examples 1 to 3 in which the organic nucleating agent is mixed, Comparative Example 4
Nos. 9 to 9 have a considerable effect of improving rigidity and heat resistance, but they are not yet sufficient, and Examples 1 to 3 have extremely excellent rigidity and heat resistance, and when compound A is added, a remarkable synergistic effect is recognized. I understand. In particular, it is clear that the effect of the present invention is not exhibited in Comparative Example 7 in which the aluminum normal salt of the compound A (monobasic aluminum salt) according to the present invention is blended, and this is described in JP-B-41-16303. Nothing is described in Japanese Patent Laid-Open Publication No. Sho 53-105550. That is, the rigidity and the heat resistance obtained by the present invention are unique to the first time when the compound A is blended with the crystalline propylene homopolymer having the isotactic pentad fraction within the range limited in the present invention. Can be said to be the effect of.

Table 3 shows the propylene-based polymer used in Table 2,
Furthermore, it is a combination of talc as an inorganic filler,
Regarding this, the same effect as described above was confirmed.

From this, the composition of the present invention is superior in the secondary processability of the sheet, the rigidity and the heat resistance as compared with the composition of the conventionally known crystalline propylene homopolymer blended with a nucleating agent. It was found that it was remarkably excellent, and the remarkable effect of the composition of the present invention was confirmed.

Claims (7)

[Claims] 1. When polymerizing propylene in multiple stages,
In the first stage, 35 to 65% by weight of the total amount of the polymer is polymerized, in the second stage and thereafter, 65 to 35% by weight is similarly polymerized, and in the first stage and the second and later stages. When the intrinsic viscosity of the polymer portion having a high molecular weight is [η] _H and the intrinsic viscosity of the polymer portion having a low molecular weight is [η] _L among the produced polymer portions, 3.0 ≦ [η] _H − [η ] _L ≤ 6.5 (1) has an intrinsic viscosity value of each polymer part, and has isotactic pentad fraction (P) and melt flow rate (MFR; load at 230 ° C of 2.16) of all polymers. The relationship with the amount of molten resin discharged in 10 minutes when kg is added is 1.00 ≥ P ≥ 0.
Crystalline propylene homopolymer with 015 log MFR + 0.955 10
0.01 to 0 parts by weight of a phosphate compound represented by the following general formula [I] (hereinafter referred to as compound A).
A high-rigidity, high-melting viscoelasticity propylene homopolymer composition containing 1 part by weight. (In the formula, R represents hydrogen or an alkyl group having 1 to 18 carbon atoms, an alkoxy group, a cycloalkyl group, a phenyl group or a phenoxy group.) 2. A high-rigidity, high-melting viscoelastic propylene homopolymer according to claim 1, wherein the crystalline propylene homopolymer has a melt flow rate (MFR) of 0.03 to 2.0 g / 10 minutes. Composition. 3. A crystalline propylene homopolymer between a high melt flow rate (HMFR; discharge amount of molten resin for 10 minutes when a load of 10.80 kg at 230 ° C. is applied) and a melt flow rate (MFR). logHMFR-0.922logMFR ≧ 1.44 (2) The high-rigidity and high-melting viscoelastic propylene homopolymer composition according to claim (1), which has HMFR and MFR satisfying (2). 4. In the general formula [I], R has 1 to 9 carbon atoms.
The high-rigidity, high-melt viscoelastic propylene homopolymer composition according to any one of claims (1) to (3), wherein the propylene homopolymer composition is an alkyl group. 5. The compound according to any one of claims (1) to (3), wherein aluminum hydroxy-bis (pt-butylphenyl) phosphate is compounded as the compound A. A high-rigidity, high-melting viscoelastic propylene homopolymer composition. 6. The high-rigidity and high-melting viscoelastic propylene homopolymer composition according to any one of claims (1) to (3), which comprises an inorganic filler. 7. As an inorganic filler, talc, mica, clay, wollastonite, zeolite, asbestos, calcium carbonate, aluminum hydroxide, magnesium hydroxide, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, zinc sulfide, sulfuric acid. Use of one or more selected from barium, calcium silicate, glass fiber, carbon fiber, carbon black, potassium titanate and metal fiber. High rigidity and high rigidity according to claim (6). Melt viscoelastic propylene homopolymer composition.