JPH0515740B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a highly rigid and highly melt viscoelastic propylene homopolymer composition. More specifically, the present invention relates to a high-rigidity, high-melt viscoelastic propylene homopolymer composition that is extremely superior in rigidity and heat-resistant rigidity. [Prior art] Propylene polymers generally have excellent processability, chemical resistance, electrical properties, and mechanical properties, so they are processed into injection molded products, blow molded products, films, sheets, fibers, etc. It is used for this purpose. However, sheets manufactured by processing propylene polymers tend to sag quickly during heat forming for secondary processing, the range of processing conditions is narrow, the forming efficiency is poor, and wide sheets suffer from the aforementioned sagging. There are various problems such as the large size, the tendency for the thickness of the secondary processed product to become uneven, and the tendency for overlapping wrinkles to occur. For this reason, the current situation is that only small molded products can be manufactured. Further, when a propylene polymer is used for blow molding, there are the following problems. That is, since the parison sags significantly during molding, the thickness of the molded product becomes uneven. For this reason, blow molding can only be applied to small products. If a high molecular weight propylene polymer is used to prevent the above-mentioned sagging, there will be poor fluidity, a large load during molding, a large energy loss, the risk of mechanical troubles, and the roughness of the molded product, resulting in a loss of commercial value, etc. There is a problem with this. On the other hand, depending on the various specific uses of the propylene polymer, the properties of the propylene polymer may not be sufficient, and there is a problem in that the expansion of its specific uses is limited. In particular, in terms of rigidity and heat resistance, it is inferior to polystyrene, ABS resin, polyester, etc., and this has become a serious bottleneck in expanding the use of propylene polymers. Therefore, if it is possible to improve the rigidity, the molded product can be made thinner to that extent, which not only contributes to resource conservation, but also increases the cooling rate of the molded product obtained during molding, so the unit The molding speed per hour can be increased, contributing to improved productivity. For this reason, for the purpose of improving the secondary processability, blow moldability, and rigidity of the above-mentioned sheets related to propylene polymers, Japanese Patent Laid-Open No. 58-219207 filed by the same applicant as the present application has been published. A propylene homopolymer having a specific molecular weight distribution and a specific isotactic pentad fraction is disclosed. Furthermore, in the above publication, an organic nucleating agent consisting of aluminum pt-butylbenzoate or 1,3,2,4-dibenzylidene sorbitol is added to the propylene homopolymer for the purpose of further improving the rigidity. Disclosed. [Problems to be Solved by the Invention] However, the sheet secondary processing of a propylene homopolymer having a specific molecular weight distribution and a specific isotactic pentad fraction disclosed in JP-A-58-219207 is Although the hardness and blow moldability are sufficiently satisfactory for practical purposes, the rigidity, although considerably improved, is still not fully satisfactory. Further, the propylene homopolymer having the above specific molecular weight distribution and specific isotactic pentad fraction is blended with aluminum pt-butylbenzoate or 1,3,2,4-dibenzylidene sorbitol. Although propylene homopolymer compositions have shown considerable improvement in stiffness, they are still not fully satisfactory when used in applications requiring high stiffness and heat-resistant stiffness. The present inventors have conducted extensive research in order to solve the above-mentioned problems regarding propylene-based polymer compositions containing the various nucleating agents described above. As a result, a composition obtained by blending a phosphate compound represented by the following general formula [] (hereinafter referred to as compound A) with a propylene homopolymer having a specific molecular weight distribution and a specific isotactic pentad fraction. However, it was discovered that the problems of the above-mentioned propylene-based polymer compositions could be solved, and the present invention was completed based on this knowledge. (However, in the formula, R ₁ is a direct bond, sulfur, a methylene group, or an alkylidene group having 2 to 4 carbon atoms,
R ₂ and R ₃ are each hydrogen or carbon number 1 to 8
the same or different alkyl groups, M is monovalent to
n represents a trivalent metal atom, and n represents an integer of 1 to 3. ) As is clear from the above description, an object of the present invention is to provide a propylene homopolymer composition which, when formed into a sheet, has outstanding secondary processability, blow moldability, rigidity, and heat-resistant rigidity. It is. [Means for solving the problems] The present invention has the following configuration. Propylene is polymerized in multiple stages, and in the first stage, 35 to 65% by weight of the total polymer is polymerized, and in the second and subsequent stages, 65 to 35% by weight is polymerized. Among the polymer parts produced in the second and subsequent stages, when the intrinsic viscosity of the polymer part with high molecular weight is [η] _H and the intrinsic viscosity of the polymer part with low molecular weight is [η] _L , 3.0≦[η ] _H − [η] _L ≦6.5 ...(1) Each polymer portion has an intrinsic viscosity of Load at 230℃
The relationship between the amount of molten resin discharged in 10 minutes when 2.16Kg is added is 1.00≧P≧0.015logMFR+0.955
To 100 parts by weight of the crystalline propylene homopolymer, 0.01 to 100 parts of a phosphonate compound represented by the following general formula [] (hereinafter referred to as compound A) is added.
A highly rigid and highly melting viscoelastic propylene homopolymer composition containing 1 part by weight. (However, in the formula, R ₁ is a direct bond, sulfur, a methylene group, or an alkylidene group having 2 to 4 carbon atoms,
R ₂ and R ₃ are each hydrogen or carbon number 1 to 8
the same or different alkyl groups, M is monovalent to
n represents a trivalent metal atom, and n represents an integer of 1 to 3. ) The crystalline propylene homopolymer used in the present invention is obtained by polymerizing propylene in multiple stages, and in the first stage, 35 to 65% by weight of the total polymer is added, and in the second and subsequent stages, the same amount is 65 to 35% by weight. Among the polymer parts produced in the first and second stages, the intrinsic viscosity of the polymer part with higher molecular weight is [η] _H , and the limit viscosity of the polymer part with lower molecular weight is When the viscosity is [η] _L , 3.0≦[η] _H − [η] _L ≦6.5 ...(1) The intrinsic viscosity of each polymer part is as follows, and the isotactic penta of the entire polymer is The relationship between the melt fraction (P) and melt flow rate (MFR) is 1.00≧P
It is a crystalline propylene homopolymer with ≧0.015logMFR+0.955. Such a propylene homopolymer is disclosed in Japanese Patent Application Laid-Open No.
It is manufactured by the manufacturing method described in Japanese Patent No. 58-219207. That is, an organoaluminum compound (), such as triethylaluminum, diethylaluminum monochloride, etc., or a reaction product () of an organoaluminum compound () and an electron donor (A), such as diisoamyl ether, is reacted with titanium tetrachloride (C). The solid product () obtained by reacting an electron donor (A) with an electron acceptor (B) such as titanium tetrachloride is then added to an organoaluminum compound () such as triethylaluminum. , diethylaluminum monochloride, etc., and an aromatic carboxylic acid ester (), for example, methyl p-toluate, in combination with the catalyst, the molar ratio of the aromatic carboxylic acid ester () and the solid product () being from 0.1 to 10.0. It can be obtained by polymerizing propylene in multiple stages in the presence of 1 in this case
A step is a successive or single step of these monomers.
It means a division of temporal supply. The simplest two-step polymerization will be explained below. In the present invention, it is desirable that the polymer portion S1 in the first step and the polymer portion S2 in the second step be in nearly equal amounts, and specifically, S1 and S2 are both S1
+35-65% by weight of the total amount of S2,
Preferably within the range 40-60% by weight, the total amount of S1+S2 is 100% by weight. If the crystalline propylene homopolymer has a different S1+S2 ratio beyond the above range, sufficient melt fluidity will not be obtained, and the kneading effect during granulation will be insufficient, resulting in a homogeneous molded product. Not only is it difficult to obtain, but the degree of improvement in melt viscoelasticity is also small. In addition, the crystalline propylene homopolymer used in the present invention has a molecular weight difference between both polymer parts as shown below.
It must be within a certain range as in (1). Therefore, the polymerization conditions are controlled by adjusting the gas phase hydrogen concentration. Now, if the intrinsic viscosity of the high molecular weight part (135℃, tetralin solution) is [η] _H and the intrinsic viscosity of the low molecular weight part is [η] _L , then both are 3.0≦[η] _H − [η] _L ≦6.5 ...(1) must be satisfied. This relationship is expressed by the following formula (2)
substantially corresponds to logHMFR−0.922logMFR≧1.44 ……(2) Here, HMFR is load 10.80 at temperature 230℃
This is the amount of molten resin discharged in 10 minutes when kg is added. That is, for [η] _H − [η] _L < 3.0, logHMFR
<0.922logMFR + 1.44, and the use of such a crystalline propylene homopolymer results in insufficient melt flow characteristics during melting and an insufficient degree of improvement in melt viscoelasticity. In the case of a sheet that has been folded, it is impossible to prevent the sheet from sagging during secondary processing. On the contrary, [η] _H − [η] _L ＞6.5
In this case, the molecular weight difference between the S1 and S2 portions described above becomes too large, and as a result, the non-uniformity of the molecular weight between the obtained propylene homopolymer particles becomes large, and as a result, molded products made from such propylene homopolymer have rough surfaces. becomes noticeable. 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, requiring a lot of power for the granulator or molding machine, making it uneconomical, and the surface of the resulting molded product will be extremely rough, making it difficult to manufacture products. lose value. Moreover, if it exceeds 2.0, the produced sheet will sag during secondary processing, making it difficult to perform the secondary processing. Incidentally, the above-mentioned equation (1) represents the viscoelasticity that makes it possible to prevent the molding material from sagging during thermoforming of sheets using crystalline propylene homopolymer or blow molding using crystalline propylene homopolymer. This shows a method for designing a polymer necessary for adding it to a crystalline propylene homopolymer. Similarly, the above formula (2) indicates the fluidity of the crystalline propylene homopolymer, and the crystalline propylene homopolymer of the present invention having the structure of the polymer of formula (1) has the formula
Satisfies condition (2). Here, the isotactic pentad fraction is macromolecules, 6
Volume, No. 6, November-December, pp. 925-926 (1973)
[Macromolecules, Vol.6, No., November−
December, 925-926 (1973)], that is, the isotactic fraction in pentad units in a propylene 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 isotactically bonded consecutively. The method for determining the attribution of spectral peaks in measurements using ¹³ C-NMR described above is described in Macromolecules, Vol. 8, No. 5, 9.
Mon-October, pp. 687-689 (1975)
[Macromolecules, Vol.8, No.5, September-
October, 687-689 (1975)]. By the way, for ^{the 13C} -NMR measurement in the examples described later, a 270MHz FT-NMR device was used, and the 27000MHz
Through multiple integrated measurements, the signal detection limit was improved to 0.001 in isotactic pentad fraction. The requirements for the above relational expression between isotactic pentad fraction (P) and melt flow rate (MFR) are that propylene homopolymers with low MFR generally have a lower fraction P, so the propylene homopolymer to be used is As a combination, the configuration requirement is to limit the lower limit value of P corresponding to the MFR. Since P is a fraction, the upper limit is 1.00. The intrinsic viscosity in the two-step polymerization described above is
Measured in tetralin solution at 135°C. However, the second stage intrinsic viscosity [η] ₂ was determined by the following formula. That is, the intrinsic viscosity of the first stage [η] ₁ , the intrinsic viscosity of the entire polymer produced through the first and second stages [η] _T , the polymerization of the polymer portion produced in the first and second stages Measure the ratios a and b, [η] _T = a [η] ₁ + b [η] ₂ = a [η] ₁ + (1-
a) [η] Determined from ₂ . The MFR mentioned above complies with JIS K7210,
230℃, load 2.16Kg, and HMFR is JIS K7210
Measured at 230℃ and a load of 10.80Kg. In this case, the [η] ₁ may be [η] _L or [η] _H. In addition, in the case of the crystalline propylene homopolymer used in the present invention, the homopolymer contains propylene and ethylene, butene-1, pentene-1,4-methyl-
Crystalline random copolymers or crystalline block copolymers with one or more α-olefins such as pentene-1, hexene-1, octene-1, vinyl acetate with propylene, acrylic esters, etc. Copolymers or saponified products of the copolymers, copolymers of propylene and unsaturated carboxylic acids or their anhydrides, reaction products of the copolymers with metal ion compounds, etc. Mixtures of modified propylene polymers modified with saturated carboxylic acids or derivatives thereof can also be used, and various synthetic rubbers (e.g. ethylene-propylene copolymer rubber,
Ethylene-propylene-nonconjugated diene copolymer rubber, polybutadiene, polyisoprene, chlorinated polyethylene, chlorinated polypropylene, styrene-
Butadiene rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-
styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-propylene-butylene-styrene block copolymer, etc.) or thermoplastic synthetic resins (such as polyethylene, polybutene, poly-4-methylpentene-1 Polyolefins, polystyrene, styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene copolymers, polyamides, polyethylene terephthalate, polybutylene terephthalate, excluding propylene-based polymers such as
It is also possible to use a mixture of polyvinyl chloride, etc.). At this time, the mixture satisfies the above formula (1) and the above 1.00≧P≧0.015logMFR+
It is sufficient as long as it satisfies 0.955. Compound A used in the present invention is sodium-
2,2'-methylene-bis-(4,6-di-t-butylphenyl) phosphate, sodium-
2,2'-ethylidene-bis-(4,6-di-t-
butyl phenyl) phosphate, lithium
2,2'-methylene-bis-(4,6-di-t-butylphenyl)phosphate, lithium-2,
2'-ethylidene-bis-(4,6-di-t-butylphenyl) phosphate, sodium-2,
2'-ethylidene-bis-(4-i-propyl-6
-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis-(4-methyl-6
-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis-(4-ethyl-6
-t-butylphenyl) phosphate, calcium-bis-[2,2'-thiobis-(4-methyl-
6-t-butylphenyl) phosphate], calcium-bis-[2,2'-thiobis-(4-ethyl-6-t-butylphenyl) phosphate],
Calcium-bis-[2,2'-thiobis-(4,6
-di-t-butylphenyl) phosphate],
Magnesium-bis-[2,2'-thiobis-(4,
6-di-t-butylphenyl) phosphate],
Magnesium-bis-[2,2'-thiobis-(4-
t-octylphenyl) phosphate], sodium-2,2'-butylidene-bis-(4,6-
di-methylphenyl) phosphate, sodium-2,2'-butylidene-bis-(4,6-di-
t-butylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis-(4,
6-dimethylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis-
(4,6-di-t-butylphenyl)phosphate, calcium-bis-[2,2'-methylene-
Bis-(4,6-di-t-butylphenyl) phosphate], Magnesium-bis-[2,2'-methylene-bis-(4,6-di-t-butylphenyl) phosphate], Barium-bis-[2 ，
2'-methylene-bis-(4,6-di-t-butylphenyl) phosphate], sodium-2,
2'-methylene-bis-(4-methyl-6-t-butylphenyl) phosphate, sodium-
2,2'-methylene-bis-(4-ethyl-6-t
-butylphenyl) phosphate, sodium (4,4'-dimethyl-6,6'-di-t-butyl-
2,2'-biphenyl) phosphate, calcium bis-[(4,4'-dimethyl-6,6'-di-t
-butyl-2,2'-biphenyl) phosphate], sodium-2,2'-ethylidene-bis-
(4-s-butyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-
Bis-(4,6-di-methylphenyl)phosphate, sodium-2,2'-methylene-bis-
(4,6-di-ethylphenyl) phosphate,
Potassium-2,2'-ethylidene-bis-(4,6
-di-t-butylphenyl) phosphate, calcium-bis-[2,2'-ethylidene-bis-
(4,6-di-t-butylphenyl) phosphate], magnesium-bis-[2,2'-ethylidene-bis-(4,6-di-t-butylphenyl)
phosphate], barium-bis-[2,2'-ethylidene-bis-(4,6-di-t-butylphenyl) phosphate], aluminum-tris-
[2,2'-methylene-bis-(4,6-di-t-butylphenyl) phosphate], aluminum-tris-[2,2'-ethylidene-bis-(4,6
-di-t-butylphenyl) phosphate] or a mixture of two or more thereof. Especially sodium-2,2'-methylene-bis-
(4,6-di-t-butylphenyl) phosphate is preferred. The blending 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 part by weight, the effect of improving stiffness and heat resistance stiffness will not be sufficiently exhibited, and if it is more than 1 part by weight, no further improvement can be expected and it is not only impractical but also It is uneconomical. In the composition of the present invention, various additives that are usually added to propylene polymers, such as phenol-based, thioether-based, phosphorus-based antioxidants, light stabilizers, clarifying agents, nucleating agents, Lubricants, antistatic agents, antifogging agents, antiblocking agents, non-drop agents,
Pigments, heavy metal deactivators (copper inhibitors), radical generators such as peroxides, dispersants or neutralizing agents such as metal soaps, inorganic fillers (e.g. 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 fibers, etc.) or coupling agents (for example, silane-based, titanate-based, boron-based, aluminate-based, zircoaluminate-based, etc.). Alternatively, organic fillers (for example, wood flour, pulp, waste paper, synthetic fibers, natural fibers, etc.) may be used in combination without impairing the purpose of the present invention. In particular, when an inorganic filler is used in combination, the rigidity and heat-resistant rigidity are further improved, so it is preferable to use the inorganic filler in combination. The composition of the present invention is prepared by adding predetermined amounts of the compound A and the various additives usually added to propylene polymers to the crystalline propylene homopolymer according to the present invention using a conventional mixing device, such as a mixing device. Cell Mixer (product name), Super Mixer,
Mix using a ribbon blender, Banbury mixer, etc., and melt and knead with a normal single screw extruder, twin screw extruder, Brabender or roll, etc. at a melt kneading temperature of 170°C.
It can be obtained by melt-kneading and pelletizing at a temperature of .degree. C. to 300.degree. C., preferably 200.degree. C. to 250.degree. The obtained composition is used to produce a desired molded article by various molding methods such as injection molding, extrusion molding, and blow molding. In particular, the composition of the invention has 2
When used in the production of sheets for subsequent processing and blow-molded products, the effects of the present invention will be significant, which is preferable. [Function] In the present invention, the phosphate compound represented by Compound A is generally known to act as a nucleating agent to improve stiffness and heat-resistant stiffness, as disclosed in JP-A-58-1736. However, by blending the compound A with the propylene homopolymer having a specific molecular weight distribution and a specific isotactic pentad fraction according to the present invention, an unexpected surprise that cannot be predicted from the blending of conventionally known nucleating agents can be obtained. A synergistic effect is exhibited, and a composition with extremely excellent stiffness and heat-resistant stiffness is obtained. [Effects] The composition of the present invention is significantly superior in (1) rigidity and heat-resistant rigidity compared to conventionally known compositions of propylene homopolymer compositions containing various nucleating agents. (2) Not only can the molded product be made thinner, contributing to resource conservation, but also the cooling rate during molding is faster, which increases the molding speed per unit time, contributing to improved productivity. can. (3) Polypropylene resin can now be used in applications where polystyrene, ABS resin, polyester, etc. have traditionally been used, and the applications of polypropylene resin can be expanded. [Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, Comparative Examples, and Production Examples, but the present invention is not limited by the present invention. The evaluation method used in Examples and Comparative Examples was as follows. () Secondary processability of sheet (heat vacuum formability);
Using the obtained pellets, width 60cm, thickness 0.4mm
In order to create a sheet by extrusion molding method and evaluate the heat vacuum formability of the sheet using a model,
The sheet is cut to 40 cm x 40 cm, fixed tightly in a 40 cm x 40 cm frame, and placed in a constant temperature room at 200°C. Eventually, the sheet fixed to the frame will heat up and the center of the frame will begin to sag, and at a certain point, due to heat contraction, it will begin to return to its original position. After that, it starts to droop again and behaves as if it were sagging. At this time, (a) measure the amount of sagging just before the sheet starts to return as the maximum amount of sagging (mm). (b) Measure the amount of deformation (mm) at which the sheet returned to its original position from the point where it sank to the maximum, and calculate the amount of deformation returned to the maximum / maximum amount of droop x 100 as the maximum amount of return (%) Record as. (c) Measure the time (seconds) from when the sheet returns to its maximum position until it hangs down 10mm again and use this as the holding time. A material with good secondary processability (vacuum formability) of a sheet according to the above evaluation method refers to a material with minimum droop, maximum return, and long holding time. () Rigidity: Using the obtained pellets, width 60cm,
A sheet with a thickness of 0.4 mm was created by extrusion molding,
Predetermined test pieces were prepared using the sheet, and rigidity was evaluated by measuring Young's modulus (based on ASTM D882) and measuring tensile yield strength (based on ASTM D882). A highly rigid material is one that has a high Young's modulus and a high tensile yield strength. In addition, the examples and comparative examples are sheet MD
Young's modulus and tensile yield strength were measured using two types of test specimens: (vertical; extrusion direction) and TD (horizontal; direction perpendicular to the extrusion direction), and the average values are shown. () Heat resistance rigidity;
A test piece of 130 mm, width 13 mm, and thickness 6.5 mm was created by injection molding, and the heat distortion temperature was measured using the test piece (based on JIS K7207; 4.6 Kgf/cm ² load).
The heat resistance rigidity was evaluated by: A material with high heat resistance and rigidity is one that has a high heat deformation temperature. Production Examples 1 to 3 (Production Examples of Crystalline Propylene Homopolymers Used in Examples and Comparative Examples) (1) Preparation of Catalyst 600 ml of n-hexane, 0.50 mol of diethylaluminum monochloride (DEAC), and 1.20 mol of diisoamyl ether. Mix for 1 minute at 25°C.
The mixture was allowed to react at the same temperature for minutes to obtain a reaction product solution (2.4 molar ratio of diisoamyl ether/DEAC). Titanium tetrachloride in a reactor purged with nitrogen.
4.0 mol was added, heated to 35°C, and the entire amount of the reaction product solution () was added dropwise over 180 minutes.
Keep at the same temperature for 30 minutes, then raise the temperature to 75℃ and continue for 1 hour.
The reaction was allowed to proceed for an hour, cooled to room temperature (20°C), the supernatant liquid was removed, 4000 ml of n-hexane was added, and the supernatant liquid was removed by decantation. This operation was repeated four times to obtain 190 g of a solid product (). . The entire amount of this solid product () was suspended in 3000 ml of n-hexane, and 160 g of diisoamyl ether and 350 g of titanium tetrachloride were added at 20°C over about 1 minute at room temperature and reacted at 65°C for 1 hour. Ta. After the reaction was completed, the mixture was cooled to room temperature, the supernatant liquid was removed by decantation, 4000 ml of n-hexane was added, the mixture was stirred for 10 minutes, and the operation of standing still and removing the supernatant liquid was repeated 5 times. After that, it was dried under reduced pressure to obtain a solid product (). (2) Preparation of preactivated catalyst After purging a stainless steel reactor with internal volume 20 with inclined blades with nitrogen gas, 15
, 42g of diethylaluminum monochloride,
After adding 30 g of solid product () at room temperature, hydrogen
Add 15N, propylene partial pressure 5Kg/cm ² G to 5
After reacting for 1 minute, unreacted propylene, hydrogen and n-hexane were removed under reduced pressure to obtain a preactivated catalyst () in the form of powder (1 g of solid product ()).
82.0g of propylene per reaction). (3) Polymerization of propylene 20 g of dried n-hexane, 8 g of diethylaluminum monochloride, 2 g of the preactivated catalyst (2), and 2.2 g of methyl p-toluate were placed in a polymerization vessel with an internal volume of 50 g purged with nitrogen gas. Hydrogen was added to maintain the inside of the vessel at 70°C. Next, propylene is supplied into the vessel to reduce the pressure inside the vessel.
The first stage polymerization was carried out at 10 Kg/cm ² G, hydrogen concentration in the gas phase of 11% as in Production Example 1, 5% as Production Example 2 and 14% as Production Example 3, and a temperature of 70°C. When the amount of polymer reached 3 kg, the supply of propylene was stopped, the temperature inside the vessel was cooled to room temperature, and unreacted propylene with hydrogen was discharged. Then, a part of the polymerization slurry is extracted,
Measurement of [η] ₁ and analysis of the titanium content in the polymer were carried out by fluorescent X-ray method to determine the polymer yield per unit weight of catalyst. Then, the temperature inside the polymerization vessel was raised to 70℃ again and the polymerization pressure was increased.
10Kg/cm ² G, gas phase hydrogen concentration as Production Example 1
0.4%, 0.07% as Production Example 2 and Production Example 3
The second stage of polymerization was carried out while maintaining the concentration at 0.08%. When the amount of polymer in the second stage reached 3 kg, the supply of propylene was stopped, the temperature inside the vessel was cooled to room temperature, and unreacted propylene with hydrogen was discharged. Next, a part of the polymerization slurry is extracted, and [η] _T is measured and the titanium content in the polymer is analyzed by fluorescent X-ray method to determine the polymer yield per unit weight of catalyst. Using the yield value, the ratio of the amount of polymer in the first stage and the second stage was determined, and the intrinsic viscosity [η] ₂ of the polymer obtained only in the second stage polymerization was determined by calculation. After adding methanol from step 5 to the polymerization slurry after the extraction, stirring at 90°C for 30 minutes,
Add 40ml of sodium hydroxide aqueous solution of wt%,
Stirred for an additional 20 minutes. Next, the mixture was cooled to room temperature, water 5 was added thereto, water washing and water separation were performed three times, and the resulting slurry was filtered, and the filtrate was dried to obtain a white polymer powder. The analysis results of the polymer are shown in Table 1. Here, [η] _L = [η] ₁ , [η] _H = [η]
It is ₂ . Examples 1 to 3, Comparative Examples 1 to 6 Each intrinsic viscosity, each melt flow rate (MFR), each high melt flow rate (HMFR), and each isoproduced in Production Examples 1 to 3 shown in Table 2 below. Sodium-2,2'-methylene-bis-(4,6-di-t-butylphenyl) phosphate as compound A was added to 100 parts by weight of a powdered crystalline propylene homopolymer having a tactical pentad fraction (P). and other additives in the proportions listed in Table 2 below in a Hensel mixer (trade name), stirred and mixed for 3 minutes, and then
The mixture was melt-kneaded at 200°C using a single-screw extruder (mm) to form pellets. In addition, as Comparative Examples 1 to 6, powders having each intrinsic viscosity, each melt flow rate, each high melt flow rate, and each isotactic pentad fraction manufactured in Production Examples 1 to 3 shown in Table 2 below. Crystalline propylene homopolymer 100
Predetermined amounts of additives listed in Table 2 below were added to the parts by weight, and the mixture was melt-kneaded in accordance with Examples 1 to 3 to obtain pellets. The sheet used for the sheet secondary processability and rigidity tests was prepared by extrusion molding the obtained pellets at a resin temperature of 250°C. In addition, the test piece used for the heat resistance stiffness test was obtained by heating the pellets at a resin temperature of 250.
It was prepared by injection molding at a temperature of 50°C and a mold temperature of 50°C. Using the obtained sheet and test piece, the sheet's secondary processability, rigidity, and heat-resistant rigidity were evaluated by the test method described above. These results are shown in Table 2. Examples 4 to 6, Comparative Examples 7 to 12 Each intrinsic viscosity, each melt flow rate (MFR), each Heil melt flow rate (HMFR) and each isoproduced in Production Examples 1 to 3 shown in Table 3 below. Sodium-2,2'-methylene-bis-(4,6-di-t-butylphenyl) phosphate as compound A was added to 100 parts by weight of a powdered crystalline propylene homopolymer having a tactical pentad fraction (P). , predetermined amounts of particulate talc with an average particle size of 2 to 3 μm as an inorganic filler and other additives were placed in a Hensel mixer (trade name) at the mixing ratios listed in Table 3 below, and mixed by stirring for 3 minutes. The mixture was melt-kneaded at 200°C using a single-screw extruder with a rear diameter of 40 mm to form pellets. In addition, as Comparative Examples 7 to 2, powders having each intrinsic viscosity, each melt flow rate, each high melt flow rate, and each isotactic pentad fraction manufactured in Production Examples 1 to 3 shown in Table 3 below. Crystalline propylene homopolymer
Predetermined amounts of the additives listed in Table 3 below were added to 100 parts by weight, and the mixture was melt-kneaded in accordance with Examples 4 to 6 to obtain pellets. The sheet used for the sheet secondary processability and rigidity tests was prepared by extrusion molding the obtained pellets at a resin temperature of 250°C. In addition, the test piece used for the heat resistance stiffness test was obtained by heating the pellets at a resin temperature of 250.
It was prepared by injection molding at a temperature of 50°C and a mold temperature of 50°C. Using the obtained sheet and test piece, the sheet's secondary processability, rigidity, and heat-resistant rigidity were evaluated by the test method described above. These results are shown in Table 3. The compounds and additives according to the present invention shown in Tables 2 and 3 are as follows. Compound A: Sodium-2,2'-methylene-bis-(4,6-di-t-butylphenyl) phosphate [manufactured by Adeka Argus Chemical Co., Ltd.;
MARK NA-11] Nucleating agent 1; Aluminum pt-butylbenzoate Nucleating agent 2; 1,3,2,4-dibenzylidene sorbitol Nucleating agent 3; Sodium-bis-(4-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] Methaneline antioxidant 1; Tetrakis(2,4-di-
t-butylphenyl)-4,4'-biphenylene-di-phosphonitophosphorous antioxidant 2; bis(2,4-di-t-butylphenyl)-pentaerythritol-diphosphite Ca-St; calcium stearate inorganic filler ; Talc (average particle size 2-3μ)

【table】

【table】

【table】

[Table] The Examples and Comparative Examples listed in Table 2 are crystalline propylene alone having various intrinsic viscosities, various melt flow rates, various high melt flow rates, and various isotactic pentad fractions as propylene polymers. This is the case when a polymer is used. As can be seen from Table 2, in Examples 1 to 3 Compound A was blended with a crystalline propylene homopolymer having a molecular weight distribution and an isotactic pentad fraction within the range of the present invention. Comparison of Examples 1 to 3 and Comparative Examples 1 to 3 (crystalline propylene homopolymer having a molecular weight distribution and isotactic pentad fraction within the range of the present invention without using an organic nucleating agent) As can be seen, although the secondary processability of the sheets in Examples 1 to 3 and Comparative Examples 1 to 3 is comparable, Comparative Examples 1 to 3 still have insufficient effects of improving rigidity and heat-resistant rigidity. Furthermore, in order to improve the rigidity and heat-resistant rigidity of Comparative Examples 1 to 3, a compound other than Compound A was added to a crystalline propylene homopolymer having a molecular weight distribution and an isotactic pentad fraction within the range of the present invention. Comparative Examples 4 to 6 and Examples 1 to 3 using organic nucleating agents
Comparing Comparative Examples 4 to 6, although the improvement effect on stiffness and heat resistance stiffness is considerably recognized, it is still not sufficient. It can be seen that a synergistic effect is observed. That is, the rigidity and heat-resistant rigidity obtained by the present invention are as follows:
This can be said to be a unique effect observed when Compound A is used in a crystalline propylene homopolymer having an isotactic pentad fraction within a limited range in the present invention. Table 3 shows the results in which the propylene polymer used in Table 2 was further combined with talc as an inorganic filler, and the same effect as described above was confirmed with this as well. This shows that the composition of the present invention has better sheet fabrication properties, stiffness, and heat-resistant stiffness than conventionally known compositions made by simply blending a nucleating agent with a crystalline propylene homopolymer. It was found that the composition of the present invention had a remarkable effect on the composition of the present invention.

Claims (1)

[Scope of Claims] 1. Polymerizing propylene in multiple stages, in which 35 to 65% by weight of the total polymer is polymerized in the first stage, and 65 to 35% by weight in the second and subsequent stages, Among the polymer parts produced in the first stage and the second stage, the intrinsic viscosity of the polymer part with a high molecular weight is [η] _H , and the intrinsic viscosity of the polymer part with a low molecular weight is [η] _L. When 3.0≦[η] _H − [η] _L ≦6.5 ...(1) Each polymer portion has an intrinsic viscosity of and melt flow rate (MFR; load at 230℃)
The relationship between the amount of molten resin discharged in 10 minutes when 2.16Kg is added is 1.00≧P≧0.015logMFR+0.955
To 100 parts by weight of crystalline propylene homopolymer, 0.01 parts of a phosphonate compound represented by the following general formula [] (hereinafter referred to as compound A) was added.
A highly rigid and highly melting viscoelastic propylene homopolymer composition containing ~1 part by weight. (However, in the formula, R ₁ is a direct bond, sulfur, a methylene group, or an alkylidene group having 2 to 4 carbon atoms,
R ₂ and R ₃ are each hydrogen or carbon number 1 to 8
the same or different alkyl groups, M is monovalent to
n represents a trivalent metal atom, and n represents an integer of 1 to 3. 2. The high-rigidity, high-melt viscoelastic propylene homopolymer composition according to claim 1, wherein the crystalline propylene homopolymer has a melt flow rate (MFR) of 0.03 to 2.0 g/10 minutes. 3 High melt flow rate (HMFR; load 10.80 at 230℃ of crystalline propylene homopolymer)
Crystallinity with (HMFR) and (MFR) that satisfy the relationship between melt flow rate (MFR) and melt flow rate (MFR) (discharge amount of molten resin in 10 minutes when Kg is added) The high rigidity and high melt viscoelastic propylene homopolymer composition according to claim 1, which uses a propylene homopolymer. 4 In the general formula [], R ₁ is a methylene group,
The highly rigid and highly melting viscoelastic propylene homopolymer composition according to any one of claims 1 to 3, wherein the alkyl groups represented by R ₂ and R ₃ are t-butyl groups. 5 Sodium-2,2'-methylene-bis-(4,6-di-t-butylphenyl) as compound A
A highly rigid and highly melting viscoelastic propylene homopolymer composition according to any one of claims 1 to 3, which contains a phosphate. 6. The highly rigid and highly melting viscoelastic propylene homopolymer composition according to any one of claims 1 to 3, which contains an inorganic filler. 7 Talc, mica, clay, as inorganic fillers
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,
7. The highly rigid and highly melting viscoelastic propylene homopolymer composition according to claim 6, which uses one or more selected from carbon black, potassium titanate, and metal fibers.