JP5155958B2 - Propylene polymer composition - Google Patents

Description

  The present invention relates to a propylene polymer composition having a good balance between rigidity and impact resistance and high elongation.

Polypropylene resins are used in various fields such as daily goods, kitchenware, packaging films, home appliances, machine parts, electrical parts, automobile parts, and the like. In particular, a high impact propylene polymer containing a rubber component is required to have a balance between rigidity and impact resistance, particularly low temperature impact resistance.
In order to improve the low temperature impact resistance, it is effective to use a rubber component having a low glass transition temperature, in other words, a rubber component having a high ethylene content. However, the rubber component having a high ethylene content has a drawback that the elongation is remarkably lowered because of its poor compatibility with the homopolypropylene resin which is a matrix resin.

  Moreover, there is a problem that when polypropylene having a low stereoregularity (atactic polypropylene having a low molecular weight) is added to a high impact propylene polymer, the rigidity is lowered.

Regarding high-impact propylene polymers, it has been reported to improve the elongation of high-impact propylene polymers by combining a high-impact propylene polymer containing a rubber component with a high ethylene content with a rubber component with a low ethylene content. (See Patent Document 1).
There is also an example in which atactic polypropylene having a high molecular weight is used (see Patent Document 2). Patent Document 2 discloses a propylene polymer composition using atactic polypropylene having a high molecular weight.
However, a propylene polymer composition excellent in rigidity, low temperature impact property, heat resistance and elongation has not been obtained yet.

JP-T-2007-538119 JP-A-6-263934

The high-impact propylene polymer composition containing an ethylene-α-olefin copolymer rubber having a high ethylene content and excellent low-temperature impact properties and rigidity has a great disadvantage that its tensile elongation is extremely low.
An object of the present invention is to provide a propylene-based polymer composition having a good balance between rigidity and impact resistance, good heat resistance, and high elongation.

According to the present invention, the following propylene polymer compositions can be provided.
1. A room temperature paraxylene-soluble propylene polymer containing the following components (A) and (B) and having an intrinsic viscosity (135 ° C., tetralin) of 1.5 to 10 dL / g is used as the components (A) and (B The propylene-based polymer composition is contained in an amount of 0.1 to 4% by weight based on the total amount.
(A) 50 to 95% by weight of a crystalline propylene polymer;
5 to 50% by weight of ethylene / α-olefin copolymer rubber composed of ethylene and one or more α-olefins having 3 to 20 carbon atoms;
Propylene polymer comprising: 70 to 98% by weight
(B) Low stereoregular propylene polymer containing 5-90% by weight of a normal temperature para-xylene soluble propylene polymer (B-1) having an intrinsic viscosity (135 ° C., tetralin) of 1.5 to 10 dL / g : 2 to 30% by weight
2. The following components (A) and (B-1) are contained, and (B-1) is contained in an amount of 0.1 to 4% by weight based on the total amount of the components (A) and (B-1). A propylene-based polymer composition.
(A) 50 to 95% by weight of a crystalline propylene polymer;
5 to 50% by weight of ethylene / α-olefin copolymer rubber composed of ethylene and one or more α-olefins having 3 to 20 carbon atoms;
2. A room temperature para-xylene soluble propylene polymer having an intrinsic viscosity (135 ° C., tetralin) of 1.5 to 10 dL / g. The propylene-based polymer composition according to 1 or 2, wherein the melt flow rate (MFR) is 1 to 200 g / 10 minutes.
4). 4. The propylene-based polymer composition according to any one of 1 to 3, wherein the ethylene content of the ethylene / α-olefin copolymer as the component (A) is 45 to 90 mol%.
5. 5. The propylene polymer composition according to any one of 1 to 4, wherein the melt flow rate (MFR) of the component (A) is 5 to 200 g / 10 minutes.
6). The propylene-based polymer composition according to any one of 1 and 3 to 5, wherein the intrinsic viscosity (135 ° C, tetralin) of the component (B) is 1.5 to 5.5 dL / g.
7). The component (A) is a step of polymerizing propylene alone;
Any of 1-6 characterized by being a propylene-based polymer produced by a multistage polymerization method comprising the step of copolymerizing ethylene and one or more types of α-olefin having 3 to 20 carbon atoms. A propylene-based polymer composition according to claim 1.
8). The component (A) is
A crystalline propylene polymer having a mesopentat fraction (mmmm) of 95 mol% or more;
An ethylene / α-olefin copolymer made of vanadium or a metallocene catalyst and composed of one or more α-olefins having 3 to 20 carbon atoms;
The propylene-based polymer composition as described in any one of 1 to 7, wherein
9. The low stereoregular propylene polymer of the component (B) is a homopolymer of propylene, or propylene, and one or more α-olefins selected from ethylene and an α-olefin having 4 to 20 carbon atoms. The propylene-based polymer composition according to any one of 1 and 3 to 8, which is a copolymer.
10. The propylene polymer composition according to any one of 1 and 3 to 9, wherein the component (B) is a low stereoregular propylene polymer produced with a magnesium chloride-supported titanium catalyst.
11. The propylene heavy polymer according to any one of 1, 3 to 10, wherein the component (B) is a low stereoregular propylene polymer produced by bulk polymerization of propylene or a gas phase polymerization method. Combined composition.

  The propylene-based polymer composition according to the present invention has an excellent balance between rigidity such as bending strength and bending elastic modulus and impact resistance, good heat resistance, and good elongation.

The first propylene polymer composition of the present invention contains the following components (A) and (B).
(A) Crystalline propylene-based polymer 50 to 95% by weight, ethylene and ethylene / α-olefin copolymer rubber 5 to 50% by weight composed of one or more α-olefins having 3 to 20 carbon atoms, Propylene polymer comprising: 70 to 98% by weight
(B) Low stereoregular propylene polymer containing 5-90% by weight of a normal temperature para-xylene soluble propylene polymer (B-1) having an intrinsic viscosity (135 ° C., tetralin) of 1.5 to 10 dL / g : 2 to 30% by weight

  And normal temperature paraxylene soluble propylene polymer (B-1) whose intrinsic viscosity (135 degreeC, tetralin) is 1.5-10 dL / g is set to 0.00 with respect to the total amount of a component (A) and (B). It is characterized by containing 1 to 4% by weight. As a result, a polymer composition having an excellent balance between rigidity and impact resistance and excellent elongation is obtained. When the amount of the room temperature para-xylene-soluble propylene polymer is less than 0.1% by weight, the elongation of the composition is insufficient. On the other hand, when it exceeds 4% by weight, the rigidity and the low-temperature impact property become insufficient. The amount of the normal temperature para-xylene-soluble propylene-based polymer is preferably 0.5 to 4% by weight.

  Moreover, the 2nd propylene polymer composition of this invention contains a component (A) and (B-1), and contains 0.1 to 4weight% of (B-1). Thereby, it becomes a polymer composition with favorable elongation.

The crystalline propylene polymer contained in the component (A) is a propylene polymer having a mesopentad fraction [mmmm] of 95 mol% or more measured by ¹³ C-NMR. When [mmmm] is less than 95 mol%, physical properties such as bending elastic modulus and heat deformation temperature may be lowered.
Here, [mmmm] is a pentad unit in a propylene polymer measured by a ¹³ C-NMR spectrum proposed by “Macromolecules, 6, 925 (1973)” by A. Zambelli et al. , Meaning isotactic fraction. The mesopentad fraction [mmmm] of the crystalline propylene polymer can be measured by ¹³ C-NMR by separating the room temperature paraxylene insoluble part.
In addition, the method for determining the assignment of peaks in the measurement of ¹³ C-NMR spectrum was in accordance with the assignment proposed in “Macromolecules, 8, 687 (1975)” by A. Zambelli and the like.

Examples of the crystalline propylene polymer include a propylene homopolymer, a propylene copolymer containing less than 5 mol% of a unit derived from ethylene or an α-olefin having 4 to 20 carbon atoms. Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene and 4-methyl-1-pentene.
The crystalline propylene polymer includes an ethylene copolymer containing less than 5% by weight and 90% by mole or more of ethylene, such as an ethylene homopolymer and an ethylene-α-olefin copolymer. It may be. Here, the α-olefin has 3 to 20 carbon atoms.

  The melt flow rate (MFR: 230 ° C., 2.16 kg) of the crystalline propylene polymer is preferably 20 to 500 g / 10 minutes, and more preferably 30 to 350 g / 10 minutes.

  Examples of the α-olefin having 3 to 20 carbon atoms of the ethylene / α-olefin copolymer rubber contained in the component (A) include propylene, 1-butene, 1-pentene, 1-hexene and 1-octene. .

The ethylene content of the ethylene / α-olefin copolymer rubber measured by ¹³ C-NMR is preferably 45 to 85 mol%, more preferably 50 to 80 mol%. The intrinsic viscosity (135 ° C., tetralin) of the ethylene / α-olefin copolymer rubber is preferably 1.0 to 5.0 dL / g, more preferably 1.5 to 3.0 dL / g.

  Crystalline propylene-based polymer and ethylene / α-olefin copolymer rubber are known methods using ordinary Ziegler-Natta catalysts, specifically, titanium trichloride catalyst, magnesium chloride-supported titanium catalyst, metallocene catalyst, etc. Can be manufactured.

The content of the crystalline propylene polymer in the propylene polymer of component (A) is 50 to 95% by weight, preferably 60 to 90% by weight, and particularly preferably 65 to 85% by weight. .
On the other hand, the content of the ethylene / α-olefin copolymer is 5 to 50% by weight, preferably 10 to 40% by weight, and particularly preferably 15 to 35% by weight. When the weight ratio of the ethylene / α-olefin copolymer is less than 5% by weight, the impact resistance is lowered, whereas when it exceeds 50% by weight, the rigidity and the heat distortion temperature are lowered.
The component (A) may contain two or more crystalline propylene polymers and ethylene / α-olefin copolymers.

  MFR of (A) component becomes like this. Preferably it is 5-200 g / 10min, More preferably, it is 20-100 g / 10min. The MFR can be adjusted by controlling the molecular weight of each component.

  The production method of the component (A) is not particularly limited, but the crystalline propylene polymer and the ethylene / α-olefin copolymer rubber are melt blended, or the crystalline propylene polymer is produced by a multistage polymerization process. It can be obtained by continuously performing the process and the process for producing the ethylene / α-olefin copolymer rubber.

  When each component is produced separately and melt blended, the process is not particularly limited, but the crystalline propylene polymer is economically preferred to be produced by bulk or gas phase polymerization, and an ethylene / α-olefin copolymer. It is preferable in terms of quality that the rubber is produced by solution polymerization or bulk polymerization. In consideration of economy and quality stability, it is preferable to use a twin screw extruder.

  In the case of melt blending, the ethylene / α-olefin copolymer rubber can be produced by a known method using a vanadium or metallocene catalyst. Moreover, you may use what is marketed for industrial uses, for example, Tafmer P0480, Tafmer P0280, Engage 8200 (all are Mitsui Chemicals, Inc.), etc.

  When producing the same component at once in a multistage process, bulk polymerization, bulk (production of crystalline propylene polymer) -gas phase (production of ethylene / α-olefin copolymer rubber), or gas phase polymerization Is economically preferable.

  For example, using a reactor in which two or more polymerization tanks are connected, and a bulk polymerization method using propylene itself as a liquid medium, it comprises a transition metal catalyst component containing magnesium and titanium, an organoaluminum compound, and an electron donating compound. First, propylene is polymerized using a catalyst to produce a propylene homopolymer so as to be 50 to 95% by weight of the total polymer, and then copolymerized with ethylene and an α-olefin. An ethylene / α-olefin copolymer rubber can also be produced so as to be ˜50% by weight.

The low stereoregular propylene polymer of component (B) is a normal temperature paraxylene-soluble propylene polymer having an intrinsic viscosity [η] measured in tetralin of 135 ° C. of 1.5 to 10 dL / g. Contains by weight.
When the intrinsic viscosity of the normal temperature para-xylene soluble propylene polymer is 1.5 to 10 dL / g, the effect of improving the elongation is exhibited and the impact resistance strength is also improved. If the intrinsic viscosity is less than 1.5 dL / g, the effect of improving the elongation is insufficient, and if it exceeds 10 dL / g, the fluidity deteriorates. The intrinsic viscosity is preferably 1.5 to 6 dL / g, and particularly preferably 1.8 to 4 dL / g.

Moreover, (B) component contains 5-90 weight% of normal temperature paraxylene soluble propylene polymers. If it is less than 5% by weight, the effect of improving the elongation is insufficient, and if it exceeds 90% by weight, the rigidity may be greatly reduced. The amount of the soluble propylene polymer is preferably 20 to 80% by weight, and particularly preferably 50 to 70% by weight.
The room temperature para-xylene-soluble propylene polymer is obtained as a room temperature para-xylene-soluble part of a low-order propylene-based polymer.

(B) As a propylene polymer of a component, the propylene homopolymer or the propylene copolymer containing the unit derived from less than 6 mol% ethylene or a C4-C20 alpha olefin is mentioned. In addition, about a propylene copolymer, when the content rate of ethylene or a C4-C20 alpha olefin exceeds 6 mol%, there exists a possibility that rigidity and a heat deformation temperature may fall.
The intrinsic viscosity (135 ° C., tetralin) of the component (B) is usually preferably 1.5 to 5.5 dL / g.

The low stereoregular propylene polymer of component (B) can be produced, for example, according to the method described in JP-A-6-263934. More specifically, it can be produced by a gas phase one-stage polymerization method, a slurry one-stage polymerization method, or bulk polymerization. In bulk polymerization or gas phase one-stage polymerization, for example, (a) a solid catalyst component containing magnesium, titanium, a halogen atom, and an electron donor as essential components, and (b) an organoaluminum compound are used as necessary. (I) a solid component obtained by prepolymerizing an olefin in the presence of a combination with an electron donor, or a crystalline polyolefin powder such as crystalline polypropylene or polyethylene having a uniform particle size; A solid component obtained by dispersing the component, (b) an organoaluminum compound, and (d) an electron donor (melting point of 100 ° C. or higher) used as necessary, or a solid catalyst component obtained by combining these methods; A combination of an organoaluminum compound, an alkoxy group-containing aromatic compound, and an electron donor used as desired. In the presence of a catalyst, alone propylene, or propylene and obtained by polymerizing ethylene or α- olefins.
The production process is not particularly limited, but bulk polymerization or gas phase polymerization is preferable in consideration of economy and production stability.

The intrinsic viscosity of the room temperature paraxylene soluble propylene polymer (room temperature paraxylene soluble part) in the component (B) can be adjusted by, for example, the polymerization temperature and the type and concentration of organic aluminum.
Further, the amount of the normal temperature para-xylene soluble part can be adjusted by, for example, the polymerization temperature, the amount of electron donor added, or the like.

There is no restriction | limiting in particular in the manufacturing method of the propylene polymer composition of this invention, For example, it can manufacture by melt-kneading the component (A) and (B) mentioned above. It is preferable to use an extruder from the viewpoint of economy.
The MFR of the propylene polymer composition of the present invention is usually 1 to 200 g / 10 minutes, preferably 5 to 150 g / 10 minutes.
The composition of the present invention can be molded into a desired shape by a known method such as extrusion molding or injection molding.

  In addition to the components (A) and (B), known additives such as antioxidants, ultraviolet absorbers and lubricants can be added to the composition of the present invention. These components can be used as long as the effects of the present invention are not impaired. The composition of the present invention may consist only of components (A) and (B), or may consist only of components (A) and (B) and the additives described above.

First, components (A) and (B) constituting the propylene polymer composition of the present invention were produced in Production Examples. Each component was evaluated by the following methods.
(1) Measurement of melt flow rate (MFR) Based on JISK7210-1999, it measured on condition of temperature 230 degreeC and load 2.16kg.
(2) Content of ethylene-propylene copolymer rubber 5 g of propylene polymer, 0.5 g of BHT (2,6-di-t-butyl-p-cresol), 500 ml of paraxylene in a 1 liter round bottom flask And stirred at 130 ° C. for 3 hours. The obtained paraxylene solution was transferred to a 1 liter beaker and gradually cooled with stirring. After reaching room temperature, the mixture was allowed to stand for 6 hours. Next, the precipitated polymer insoluble in room temperature paraxylene was filtered through a 400 mesh stainless steel wire mesh, the wire mesh was dried at 90 ° C. for 6 hours, and weighed to determine the amount of room temperature paraxylene insoluble part (Xinsol). Further, the filtrate (rubber paraxylene solution) was added to 3 liters of methanol to precipitate and recover the rubber component. The obtained rubber-like polymer was dried at 90 ° C. for 6 hours, weighed to obtain a normal temperature para-xylene soluble part amount (Xsol), and the rubber amount was calculated by the following formula.
Rubber amount (wt%) = 100 × Xsol / (Xinsol + Xsol)
(3) Ethylene unit content
^It calculated | required by < ¹³ > C-NMR measurement.
(4) Intrinsic viscosity [η]
The sample was dissolved in tetralin and measured at 135 ° C.

(5) Room temperature para-xylene soluble part of low stereoregular propylene polymer The room temperature para-xylene insoluble part amount (Xinsol) was determined in the same manner as (2) above. Further, the filtrate was poured into 3 liters of methanol to precipitate and collect the polymer. The obtained polymer was dried at 90 ° C. for 6 hours to obtain a normal temperature paraxylene-soluble propylene-based polymer. Subsequently, it weighed and calculated | required normal temperature paraxylene soluble part amount (Xsol), and calculated normal temperature paraxylene soluble propylene polymer amount with the following formula | equation.
Amount of soluble part (wt%) = 100 × Xsol / (Xinsol + Xsol)

(6) Mesopentad fraction [mmmm]
Macromolecules, 6,925 (1973).

[Production of propylene polymer (A-1 to A-5) as component (A)]
Production Example 1 (Production of A-1)
(1) Preparation of magnesium compound Into a glass reactor equipped with a stirrer with an internal volume of 6 liters substituted with nitrogen, 2430 g of ethanol, 16 g of iodine and 160 g of metallic magnesium were added and hydrogen gas was added from the system under reflux conditions while stirring. The reaction was carried out under heating until the occurrence of was eliminated to obtain a solid reaction product. The reaction liquid containing the solid product was dried under reduced pressure to obtain a magnesium compound (diethoxymagnesium).

(2) Preparation of solid catalyst component A three-necked flask with a stirrer having an internal volume of 0.5 liter was replaced with nitrogen gas, and then 60 ml of dehydrated octane and 16 g of diethoxymagnesium were added. After heating to 40 ° C. and adding 2.4 ml of silicon tetrachloride and stirring for 20 minutes, 1.6 ml of dibutyl phthalate was added. This solution was heated to 80 ° C., and subsequently 77 ml of titanium tetrachloride was added dropwise, followed by stirring at an internal temperature of 125 ° C. for 2 hours. Then, stirring was stopped, the solid part was settled, and the supernatant was extracted. 100 ml of dehydrated octane was added, and the temperature was raised to 125 ° C. while stirring and held for 1 minute. Then, stirring was stopped, the solid part was allowed to settle, and the supernatant was extracted. After repeating this washing operation seven times, 122 ml of titanium tetrachloride was added to the solid part, and the mixture was stirred at an internal temperature of 125 ° C. for 2 hours. Thereafter, the washing operation with dehydrated octane was repeated 6 times to obtain a solid catalyst component (C-1).

(3) Preparation of prepolymerization catalyst component A three-necked flask with a stirrer with an internal volume of 0.5 liter was replaced with nitrogen gas, and then dehydrated heptane 400 ml, triethylaluminum 28.4 mmol, diethylaminotriethoxysilane 7.1 mmol and 4 g of the solid catalyst component (C-1) prepared in (2) above were added. Propylene was introduced with stirring at room temperature. After 1 hour, stirring was stopped, and as a result, a prepolymerized catalyst component (C-2) in which 4 g of propylene was polymerized per 1 g of the solid catalyst was obtained.

(4) Production of Propylene Polymer (A-1) 1.5 kg of liquid propylene and 1.2 MPa-G of hydrogen were charged into an autoclave equipped with a stirrer with an internal volume of 5 liters purged with nitrogen. Subsequently, 6 mmol of triethylaluminum and 0.75 mmol of diethylaminotriethoxysilane were added. The internal temperature was raised to 65 ° C., and 0.01 mmol of the prepolymerized catalyst component (C-2) was added as titanium atoms. Subsequently, the internal temperature was raised to 70 ° C., and propylene polymerization was performed for 60 minutes. After completion of the polymerization, the internal temperature was lowered to 60 ° C., and the hydrogen concentration in the gas phase was adjusted to 8.0 mol%.
Subsequently, ethylene was added at 0.5 MPa-G, and propylene and ethylene were copolymerized at an internal temperature of 60 ° C. for 120 minutes. After completion of the reaction, unreacted gas was removed to obtain 769 g of a propylene polymer. This polymerization operation was repeated to obtain a required amount of propylene polymer (A-1).

Production Example 2 (Production of A-2)
The copolymerization of propylene and ethylene in Production Example 1 (4) was carried out in the same manner as in Production Example 1 except that the copolymerization time was 15 minutes, to obtain 640 g of a propylene polymer (A-2).

Production Example 3 (Production of A-3)
The propylene / ethylene copolymer of Production Example 1 was carried out in the same manner as in Production Example 1 except that the copolymerization time was 180 minutes, to obtain 854 g of a propylene-based polymer (A-3).

Production Example 4 (Production of A-4)
Propylene / ethylene copolymerization in Production Example 1 was carried out in the same manner as in Production Example 1 except that ethylene was charged at 0.6 MPa-G to obtain 787 g of a propylene-based polymer (A-4).

Production Example 5 (Production of A-5)
Propylene homopolymer (manufactured by Prime Polymer Co., Ltd .: J13B, MFR = 220 g / 10 min (230 ° C., load 2.16 kg), mesopentat fraction [mmmm] = 97.2 mol%, melting point (Tm) = 162.4 ° C. ) 1420 g, ethylene-propylene copolymer rubber (manufactured by Mitsui Chemicals, Inc .: Toughmer P0480, ethylene content: 81 mol%, intrinsic viscosity: 1.7 dL / g) to 580 g, 2,6-di-t-butyl-p -2.0 g of cresol (BHT), 2.0 g of Irganox 1010 (phenolic antioxidant, manufactured by Ciba Specialty Chemicals), and 2 of Irgaphos 168 (produced by phosphorus antioxidant, manufactured by Ciba Specialty Chemicals) 0.0 g and 2.0 g of calcium stearate were added and thoroughly blended.
The blend was melt-kneaded at 190 ° C. using a twin screw extruder (manufactured by Technobel) with a screw diameter of 15 mm to obtain a propylene polymer (A-5).

Of the propylene polymers (A-1 to A-5) produced in Production Examples 1 to 5, the MFR, the content of the crystalline propylene polymer, the crystalline propylene homopolymer in the crystalline propylene polymer, Table 1 shows the content, [mmmm] of the crystalline propylene polymer, the content of the ethylene-propylene copolymer rubber, the ethylene unit content in the copolymer rubber, and the intrinsic viscosity of the copolymer.
In addition, the content rate of the crystalline propylene-type polymer in A-1 to A-4 was calculated | required from the normal temperature paraxylene insoluble part. Further, the [mmmm] of the crystalline propylene polymer and the content of the crystalline propylene homopolymer were determined from ¹³ C-NMR of the room temperature paraxylene insoluble part.

[Production of Low Stereoregular Propylene Polymer (B-1, B-3 to B-8) as Component (B)]
Production Example 6 (Production of B-1)
(1) Preparation of solid catalyst component 160 g of diethoxymagnesium prepared in the same manner as in Production Example 1 and 800 ml of dehydrated heptane were added to a 5-neck flask equipped with a stirrer and replaced with nitrogen. After heating to 40 ° C. and adding 24 ml of silicon tetrachloride and stirring for 20 minutes, 23 ml of diethyl phthalate was added. The temperature of the solution was raised to 90 ° C., and 770 ml of titanium tetrachloride was subsequently added dropwise using a dropping funnel. After completion of dropping, the internal temperature was raised to 110 ° C. and stirred for 2 hours. After completion of the reaction, the solid part was allowed to settle, the supernatant was removed, and then washed 7 times with 80 ° C. dehydrated heptane. Furthermore, 1220 ml of titanium tetrachloride was added, the internal temperature was set to 110 ° C., and the mixture was stirred for 2 hours. After completion of the reaction, the solid part was allowed to settle and the supernatant liquid was removed, followed by washing 6 times with dehydrated heptane at 80 ° C. to obtain a solid catalyst component (C-3).

(2) Preparation of prepolymerization catalyst component 48 g of the solid catalyst component (C-3) and 400 ml of dehydrated heptane were added to a three-necked flask equipped with a stirrer with an internal volume of 1 liter purged with nitrogen. The mixture was heated to 40 ° C., and 2.7 ml of triethylaluminum and 2.0 ml of cyclohexylmethyldimethoxysilane were added. While stirring, propylene gas was continuously supplied for 2 hours. After stopping the supply of propylene, the temperature was kept at 40 ° C. for 30 minutes. Thereafter, the solid component was sufficiently washed with dehydrated heptane to obtain a prepolymerized catalyst (C-4).

(3) Production of propylene polymer (B-1) 1.5 kg of liquid propylene was charged into an autoclave with a stirrer having an internal volume of 5 liters purged with nitrogen, followed by 2 mmol of triethylaluminum and 0.4 mmol of cyclohexylmethyldimethoxysilane. 1-allyl-3,4-dimethoxybenzene (0.05 mmol) was added. The internal temperature was raised to 65 ° C., and 0.04 mmol of the prepolymerized catalyst (C-4) was added as titanium atoms. Subsequently, the internal temperature was raised to 70 ° C., and polymerization was carried out for 90 minutes. After completion of the polymerization, unreacted propylene gas was removed to obtain 428 g of a propylene polymer (B-1).

Production Example 7 (Production of B-3)
The polymerization in Production Example 6 was carried out in the same manner as in Production Example 6 except that the amount of 1-allyl-3,4-dimethoxybenzene added was 0.03 mmol, to obtain 516 g of a propylene polymer (B-3). .

Production Example 8 (Production of B-4)
The polymerization in Production Example 6 was carried out in the same manner as in Production Example 6 except that the amount of cyclohexylmethyldimethoxysilane added was 0.07 mmol, to obtain 500 g of a propylene polymer (B-4).

Production Example 9 (Production of B-5)
Into an autoclave equipped with a stirrer with an internal volume of 5 liters substituted with nitrogen, 1.5 kg of liquid propylene was charged, followed by 2 mmol of triethylaluminum, 0.4 mmol of cyclohexylmethyldimethoxysilane, 1-allyl-3,4-dimethoxybenzene. 11 mmol was charged. Thereafter, 3.4 L of ethylene gas was charged. The internal temperature was raised to 65 ° C., and 0.04 mmol of the prepolymerized catalyst obtained in Production Example 6 was added as titanium atoms. Subsequently, the internal temperature was raised to 70 ° C., and polymerization was carried out for 90 minutes. After the polymerization was completed, unreacted propylene gas was removed to obtain 496 g of a propylene polymer (B-5).

Production Example 10 (Production of B-6)
In Production Example 9, the same procedure as in Production Example 9 was carried out except that the amount of ethylene gas input was 15.4 L and the amount of prepolymerization catalyst was 0.02 mmol as titanium atoms, and 487 g of a propylene polymer (B-6) was added. Obtained. Thus, B-6 having the following characteristics was obtained.

Production Example 11 (Production of B-7)
At the same time as the internal temperature was raised to 80 ° C., a dehydrated heptane: 400 milliliters, triethylaluminum 2 millimoles and 0.005 millimoles of the solid catalyst component shown in Production Example 1 as titanium atoms were added to a stainless steel autoclave with an internal volume of 1 liter. Propylene was increased to 0.8 MPa and polymerization was carried out for 3 hours. After the completion of the polymerization, the product was put into 2 liters of methanol and suction filtered to take out the polymer. Furthermore, the obtained polymer was vacuum-dried at 80 degreeC for 6 hours, and the propylene polymer (B-7) 80g was obtained.

Production Example 12 (Production of B-8)
In a 1 liter stainless steel autoclave, dehydrated heptane: 400 milliliters, triisobutylaluminum 2 millimoles, 1-allyl-3,4-methoxybenzene 0.2 millimoles, and the solid catalyst component shown in Production Example 1 as titanium atoms 0.005 mmol was added, the internal temperature was raised to 80 ° C., and at the same time, propylene was increased to 0.8 MPa, and polymerization was carried out for 3 hours. After the polymerization was completed, the produced polymer was precipitated in 2 liters of methanol and filtered to take out the solid part. The obtained polymer was vacuum-dried at 80 ° C. for 6 hours to obtain 55 g of a propylene polymer (B-8).

  Intrinsic viscosity, normal paraxylene-soluble part amount, and soluble part of the low stereoregular propylene-based polymers (B-1, B-3 to B-8) and B-2 produced in Production Examples 6 to 12 Table 2 shows the intrinsic viscosity and the ethylene unit content in the soluble part. B-2 is manufactured by Prime Polymer Co., Ltd .: E2900.

Example 1
475 g of A-1 obtained in Production Example 1, 25 g of B-1 obtained in Production Example 6, 0.5 g of 2,6-di-t-butyl-p-cresol (BHT), Irganox 1010 (phenol) System antioxidant (Ciba Specialty Chemicals) 0.5g, Irgaphos 168 (Phosphorus antioxidant, Ciba Specialty Chemicals) 0.5g, and calcium stearate 0.5g, fully blended . This blend was melt kneaded at 190 ° C. with a twin screw extruder (manufactured by Technobell) having a screw diameter of 15 mm to prepare a propylene polymer composition.

The following physical properties were evaluated for the propylene polymer composition. The results are shown in Table 3.
(1) MFR
Based on JIS K 7210-1999, the measurement was performed at a temperature of 230 ° C. and a load of 2.16 kg.
(2) Elongation It measured according to JISK7162 using the ISO 1/2 test piece.
(3) Flexural strength and flexural modulus Measured according to JIS K 7171 using an ISO t = 4 mm bar.
(4) Charpy impact strength Measured according to JIS K 7111 using an ISO t = 4 mm bar.
(5) Thermal deformation temperature It measured with a load of 0.45 MPa according to JIS K 7191 using an ISO t = 4 mm bar.

Examples 2-4
A propylene polymer composition was prepared and evaluated in the same manner as in Example 1 except that the amounts of A-1 and B-1 in Example 1 were changed as shown in Table 1. The results are shown in Table 3.

Examples 5-9
A propylene polymer composition was prepared and evaluated in the same manner as in Example 1 except that the type of the component (B) was changed in Example 1. The results are shown in Table 3.

Comparative Example 1
A propylene-based polymer composition was prepared and evaluated in the same manner as in Example 1 except that B-7, which has a low intrinsic viscosity of the room temperature paraxylene soluble portion, was used instead of B-1 in Example 1. The results are shown in Table 3.

Comparative Example 2
A propylene polymer composition was prepared and evaluated in the same manner as in Example 1 except that the component (B) was not used in Example 1. The results are shown in Table 3.

Comparative Example 3
A propylene polymer composition was prepared and evaluated in the same manner as in Example 1 except that the amounts of A-1 and B-1 in Example 1 were changed as shown in Table 1. The results are shown in Table 3.

Example 10
A propylene polymer composition was prepared and evaluated in the same manner as in Example 1 except that A-2 was used instead of A-1 in Example 1. The results are shown in Table 4.

Comparative Example 4
A propylene polymer composition was prepared and evaluated in the same manner as in Example 1 except that A-2 was used in place of A-1 in Example 1 and the component (B) was not used. The results are shown in Table 4.

Example 11
A propylene polymer composition was prepared and evaluated in the same manner as in Example 1 except that A-3 was used instead of A-1 in Example 1. The results are shown in Table 4.

Comparative Example 5
A propylene polymer composition was prepared and evaluated in the same manner as in Example 1 except that A-3 was used in place of A-1 in Example 1 and the component (B) was not used. The results are shown in Table 4.

Example 12
A propylene polymer composition was prepared and evaluated in the same manner as in Example 1 except that A-4 was used instead of A-1 in Example 1 and B-8 was used instead of B-1. The results are shown in Table 4.

Comparative Example 6
A propylene-based polymer composition was prepared and evaluated in the same manner as in Example 1 except that A-4 was used in place of A-1 in Example 1 and B-7 was used in place of B-1. The results are shown in Table 4.

Comparative Example 7
A propylene-based polymer composition was prepared and evaluated in the same manner as in Example 1 except that A-4 was used in place of A-1 in Example 1 and the component (B) was not used. The results are shown in Table 4.

Example 13
A-5 is used in place of A-1 in Example 1, B-3 is used in place of B-1, the amount is changed, and BHT, Irganox 1010, Irgafos 168, and calcium stearate are not added. A propylene-based polymer composition was prepared and evaluated in the same manner as in Example 1 except that. The results are shown in Table 4.

Examples 14 and 15
A-5 was used instead of A-1 in Example 1, and the type and amount of component (B) were changed as shown in Table 4, and BHT, Irganox 1010, Irgaphos 168, and calcium stearate were not added. A propylene-based polymer composition was prepared and evaluated in the same manner as in Example 1 except that. The results are shown in Table 4.

Comparative Example 8
In Example 15, a propylene polymer composition was prepared and evaluated in the same manner as in Example 15 except that the component (B) was not used. The results are shown in Table 4.

The propylene-based polymer composition of the present invention can be suitably used in the fields of home appliances, mechanical parts, electrical parts, automobile parts and the like.

Claims (7)

Obtained by melt-kneading the following components (A) and (B),
The room temperature para-xylene soluble part (B-1) contained in a component (B) is contained 0.1 to 4 weight% with respect to the total amount of the said component (A) and (B), It is characterized by the above-mentioned. A method for producing a propylene-based polymer composition.
(A) 50 to 95% by weight of a crystalline propylene polymer having a mesopentat fraction (mmmm) measured by ¹³ C-NMR of 95 mol% or more ,
An ethylene content of 45 to 90 mol%, ethylene and an ethylene / α-olefin copolymer rubber composed of one or more α-olefins having 3 to 20 carbon atoms,
Propylene polymer comprising: 70 to 98% by weight
(B) a propylene homopolymer containing 5 to 90% by weight of a normal temperature paraxylene soluble part (B-1) having an intrinsic viscosity (135 ° C, tetralin) of 1.5 to 10 dL / g , and less than 6 mol% Propylene-based polymer selected from propylene copolymers containing units derived from ethylene or an α-olefin having 4 to 20 carbon atoms : 2 to 30% by weight The method for producing a propylene-based polymer composition according to claim 1 , wherein the melt flow rate (MFR) is 1 to 200 g / 10 minutes. The method for producing a propylene-based polymer composition according to claim 1 or 2 , wherein the melt flow rate (MFR) of the component (A) is 5 to 200 g / 10 minutes. The intrinsic viscosity (135 ° C, tetralin) of the component (B) is 1.5 to 5.5 dL / g, The production of the propylene-based polymer composition according to any one of claims 1 to 3 Way . The component (A) is a step of polymerizing propylene alone;
Claim to ethylene, characterized in that one or more of the α- olefin having 3 to 20 carbon atoms, a propylene-based polymer produced in a multistage polymerization process having the steps of copolymerizing 1-4 The manufacturing method of the propylene-type polymer composition in any one of. The component (B), the production of propylene-based polymer composition according to any one of claims 1 to 5, characterized in that a low-stereoregular propylene-based polymer produced by the magnesium chloride-supported titanium catalyst Way . The propylene heavy polymer according to any one of claims 1 to 6 , wherein the component (B) is a low stereoregular propylene polymer produced by bulk polymerization of propylene or a gas phase polymerization method. A method for producing a combined composition.