JPH03195751A - Polypropylene composition - Google Patents

Abstract

PURPOSE:To obtain a polypropylene composition excellent in balance between easy processability and strength without any problems in bleeding, etc., by adding a nucleating agent to specific polypropylene having relatively low stereoregularity. CONSTITUTION:The objective polypropylene composition obtained by adding (A) 0.005-5 pts.wt. nucleating agent (e.g. a metal salt of an aromatic phosphorus compound) to (B) 100 pts.wt. polypropylene having 0.80-0.91 isotactic pentad fraction (P), 80-95wt.% content of a portion insoluble in boiling n-heptane and the relation between the isotactic pentad fraction (Pr) of the portion insoluble in n-heptane and (P) expressed by the formula 0<(Pr)-(P)<=0.08.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polypropylene composition, more specifically, a polypropylene composition comprising a specific polypropylene having relatively low stereoregularity and a nucleating agent added thereto. This invention relates to a polypropylene composition that has excellent processability and strength balance.

[Prior art and its problems] Conventionally, isotactic polypropylene with well-controlled stereoregularity and a boiling n-heptane insoluble fraction of more than 95% by weight has been produced commercially, and this is also infused with aromatics. Compositions with improved rigidity and transparency by adding various nucleating agents such as aluminum salts of group carboxylic acids and dibenlidene sorbitols are also used in various fields of molded products.

However, polypropylene and its compositions require high energy and high molding pressure during processing due to the high stereoregularity of polypropylene (isotactic pentad fraction (P) of 0.92 to 0.96). The processability may be insufficient, such as when the molded product is hardened, or the resulting molded product may have high rigidity but poor durability. # It had the problem of low impact resistance.

On the other hand, for the above isotactic polypropylene and its composition, the insoluble portion in boiling 11n-heptane is 20Ii
Polypropylene with low stereoregularity of about 80% by weight (Japanese Patent Publication No. 32-10596, Japanese Patent Publication No. 39-121
Publication No. 05, Japanese Patent Publication No. 53-46799, Japanese Patent Application Publication No. 1987
2-102214, etc.) are known. Since the polypropylene requires less energy during processing than isotactic polypropylene, it is expected to be used in the field of film molding, which is different from that of ordinary isotactic polypropylene.

However, these polypropylenes are composed of a boiling point 11n-heptane soluble portion with extremely low stereoregularity and a boiling point 11n-heptane insoluble portion having relatively high stereoregularity. As a result of the extremely low stereoregularity bleeding onto the surface, only a molded article with surface tackiness can be obtained as seen in JP-A-57-47371.

In order to improve this point, a film is produced using a composition in which dibenzylidene sorbitol and zeolite are added to the polypropylene (Japanese Patent Application Laid-open No. 1111727/1983), or a composition in which dibenzylidene sorbitol and the like are added to the polypropylene. Techniques for rapidly cooling and forming a specific crystal structure when
However, the improvement effect is still insufficient because the wood has a large amount of boiling 111n-heptane soluble parts with extremely low stereoregularity. Ta.

In addition, molded articles obtained using the polypropylene or composition are not intended to have low rigidity.

The present inventors have created a polypropylene that combines the advantages of isotactic polypropylene and low stereoregularity polypropylene described above.
We have conducted extensive research into polypropylene compositions that have an excellent balance of ease of workability and strength, and are free from problems such as bleeding.

As a result, when using a composition formed by adding a nucleating agent to a specific polypropylene having relatively low stereoregularity,
The inventors have found that the above problem can be solved, and have completed the present invention based on this knowledge.

As is clear from the above description, an object of the present invention is to provide a polypropylene composition that is easy to process and has an excellent balance of strength.

[L! l! Means to solve g] The present invention has the following configuration.

(1) Isotactic pentad fraction (P) is 0.8
0-0.91. Boiling n-heptane insoluble portion is 80% by weight
~95% by weight, and the isotactic pentad fraction (Pr) of the n-heptane-insoluble portion satisfies the formula O<(Pr)-(P)≦0.08 in relation to the above (P). A polypropylene composition obtained by adding 0.005 parts by weight to 5 parts by weight of a nucleating agent to 10 G parts by weight of polypropylene that satisfies the following.

(2) The composition according to item 1 above, wherein the nucleating agent is a metal salt of an aromatic phosphorus compound.

(3) The composition according to item 1 above, wherein the nucleating agent is dibenzylidene sorbitol.

(4) The composition according to item 1 above, wherein the nucleating agent is a metal salt of an aromatic carboxylic acid.

The configuration of the present invention will be explained in detail below.

The polypropylene that is the main component constituting the composition of the present invention has an isotactic pentad fraction (P) of 0.80 to 0.91, and the polypropylene is boiled using a Soxhlet extractor. 1l
When expressed as the isotactic pentad fraction (Pr) for the insoluble portion when extracted in n-heptane for 6 hours,
Polypropylene has a relationship of 0<(Pr)-(P)≦0.08 with the above (P), and in this case, the boiling 1n-heptane insoluble portion is 80% to 95% by weight of the entire polypropylene. used.

In addition, the isotactic pentad fraction in the present invention is defined by Macrora et al.
.

1ecules 6925 (+973), that is, the isotactic fraction in pentad units in a polypropylene molecule measured using C-NMR. In other words, the fraction (P) is It means the fraction of the propylene monomer unit at the center of a chain in which five consecutive propylene monomer units are meso-bonded.However, the above-mentioned method for determining the attribution of the NMR absorption peak is
olecules 8687 (1975).

It is a conventional isotactic polypropylene described as having the above (P) exceeding 0.91 or the 111n-heptane insoluble portion exceeding 95ii mass%, and has excellent processability and resistance to 1.
! (P) is 0.80, resulting in poor El property.
If the content of the 11n-heptane-insoluble portion is less than 80% by weight, the rigidity will be low and the object of the present invention will not be achieved, and bleeding of the 11n-heptane-soluble portion will become a problem. Also, between (Pr) and (P), o<(Prl
- does not satisfy the relationship (P)≦0,08, i.e. (Pr)
-(P) exceeding 0.08 means that the stereoregularity of the boiling point 111n-heptane soluble portion is extremely low, and the bleeding of the boiling point 1ain-heptane soluble portion becomes severe, and the strength balance is also poor. becomes.

Polypropylene that satisfies the above-mentioned physical properties is an essential component in the composition of the present invention, and such polypropylene contains, for example, ■ a titanium-containing solid catalyst component, ■ an organoaluminum compound (A1), and ■ a P=0 bond. It is obtained by polymerizing propylene in the presence of a catalyst in combination with an organosilicon compound (S) having any bond or group selected from , isocyanate group, acryloxy group, and methacryloxy group.

The details are described below.

First, as the titanium-containing solid catalyst component, any known titanium-containing solid catalyst component for producing stereoregular polypropylene can be used, but in industrial production,
Suitably, Japanese Patent Publication No. 59-28,573, Japanese Patent Application Laid-open No. 1983
A titanium catalyst component containing titanium trichloride as a main component obtained by the method described in Publication No. 8-17,104, etc., and JP-A-62
-104.810 Publication, JP-A-62-104,811
titanium in which titanium tetrachloride is supported on a magnesium compound described in JP-A No. 62-104,812, etc.;
A titanium-containing supported catalyst component containing magnesium, halogen, and an electron donor as essential components is used.

In addition, as the organoaluminum compound (A1), -radiation is ^IR', R2p*X3-+p*p+1 (in the formula,
R1 and R2 represent a hydrocarbon group or alkoxy group represented by an alkyl group, cycloalkyl group, or aryl group, X represents a halogen, and p and p″ represent any number in the range O<p+p′≦3. An organoaluminum compound represented by is used.

Specific examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n
-butylaluminum, trinibutylaluminum,
Tri-n-hexylaluminum!・Trialkylaluminum such as soot-hexylaluminum, tri2-methylpentylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, diethylaluminum monochloride, moro-propylaluminum monochloride, di-i-butylaluminum monochloride dialkyl aluminum monohalides such as diethyl aluminum monofluoride, diethyl aluminum monobromide, and diethyl aluminum sonoiodide; dialkyl aluminum hydrides such as diethyl aluminum hydride; alkyl aluminum sesquihalides such as methyl aluminum sesquichloride and ethyl aluminum sesquichloride; Examples include monoalkylaluminum cibarides such as ethylaluminum dichloride and 1-butylaluminum dichloride, and alkoxyalkylaluminums such as monoethoxydiethylaluminium and jetoxymonoethylaluminum can also be used. These organoaluminum compounds can also be used in combination with Z fl or more.

The organosilicon compound (S) used as the third component constituting the catalyst is an organosilicon compound (S) having any bond or group selected from a P=0 bond, an isocyanate group, an acryloxy group, and a methacryloxy group. (
Hereinafter, it may be abbreviated as organosilicon compound (S). ).

Specific examples of the organosilicon compound (S) include tris(
trimethylsilyl) phosphate, tris(ethyldimethylsilyl) phosphate, tris(triethylsilyl) phosphate, bis(trimethylsilyl) methyl phosphate, bis(trimethylsilyl) ethyl phosphate, bis(trimethylsilyl) 1-methylvinyl phosphate, diethyl(trimethylsilylmethyl) phosphate, Organosilicon compounds having a p=o bond such as diethyl(trimethylsilylethyl)phosphonate, diethyl(trimethylsiloxycarbonyl)methylphosphonate, bis(trimethylsilylmethyl)ethylphosphinate, bis(trimethylsilylethyl)ethylphosphinate, trimethylsilyl isocyanate, triethylsilyl Isocyanate, ethyldimethylsilyl isocyanate, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3
-Organosilicate metals having isocyanate groups such as isocyanatepropyldimethylchlorosilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyldimethylmethoxysilane, 3-acryloxypropyltriethoxy Silane, 3-acryloxypropyltris(trimethylsiloxy)silane, 3-acryloxypropylmethylbis(trimethylsiloxy)
Organosilicon compounds having acryloxy groups such as silane,
3-methacryloxypropyltrimethoxysilane, 3-
methacryloxypropylmethyldimethoxysilane, 3-
Methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyljethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 2-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylbis(trimethylsiloxy)methylsilane, 3-methacryloxypropyldimethylethoxysilane Examples include organosilicon compounds having a methacryloxy group such as roxypropyldimethyldichlorosilane, and 121 or more of these are used.

Regarding the usage amounts of the above titanium-containing solid catalyst component, organoaluminum compound (^1) and organosilicon compound (S), the amount of organoaluminum compound (At) is 0.1 per mol of Tj in the titanium-containing solid catalyst component. ~2000
mol, and organosilicon compound (S) from 0.01 to 10
Use 0 mol.

If the amount of the organosilicon compound (S) used is outside the above range, polypropylene having the stereoregularity described above cannot be obtained, and isotactic polypropylene is produced in large quantities.
Problems arise in polymerization operation and quality.

The above-mentioned catalysts combined in the prescribed amounts can be used as they are for propylene polymerization, but from the viewpoint of operability during propylene polymerization, titanium-containing solid catalyst components and organic It is more desirable to use a catalyst component that is preactivated by combining it with an aluminum compound (^2) and reacting this with an olefin.

Pre-activation is performed by adding 0.005g to 500g of organoaluminum compound (^,) per 1g of titanium-containing solid catalyst component.
, solvent O~50j2, hydrogen 0~1,000mj2, and olefin 0.01g~5. Using QQOg, preferably 0.05g to 3.000g, at 0℃ to 100℃
It is desirable to react the olefins for a period of minutes to 20 hours to react 0.01 g to 200 g of olefin per gram of the titanium-containing solid catalyst component.

The reaction of olefins for preactivation can be carried out in aliphatic or aromatic hydrocarbon solvents or in liquefied olefins such as liquefied propylene and liquefied butene-1 without using a solvent. It is also possible to react in phases. Furthermore, it can also be carried out in the presence of an olefin polymer or hydrogen in advance.

The olefins used for preactivation include ethylene, propylene, butene-1, pentene-1, hexene-1,
Straight chain olefins such as heptene-1, octene-1, etc.
-Methyl-pentene-1,2-methylpentene-1,3
Examples include branched chain olefins such as -methylbutene-1, styrene, and the like. Further, as the organoaluminum compound (^,), the same compounds as mentioned above (8) can be mentioned.

After preactivation, the solvent, organoaluminum compound (
^2) Unreacted olefin can be removed by vacuum distillation, etc., and it can be used in the polymerization as a dry powder, or it can be used in a suspended state in a solvent that does not exceed aOj2 per gram of the titanium-containing solid catalyst component. Alternatively, after removing the solvent, unreacted olefin, and organoaluminum compound (^2) by filtration or decantation, it can be used as a dried powder.

Polymerization of propylene is carried out using the catalyst thus combined or preactivated. The polymerization format for propylene is n-hexane, n-hexane,
- Slurry polymerization carried out in a hydrocarbon solvent such as heptane, low octane, benzene or toluene; bulk polymerization carried out in liquefied propylene; and gas phase polymerization carried out in the gas phase.

Polymerization temperature is 20°C to 100°C, preferably 30°C to 90°C
℃ 0 polymerization pressure is normal pressure (Okgf/c+a2G)
Polymerization is carried out at ~50 kgf/cm'G and usually for a polymerization time of about 30 minutes to 15 hours. During polymerization, adding an appropriate amount of hydrogen to adjust the molecular weight is the same as in conventional propylene polymerization methods. Note that polymerization can be carried out by either batch polymerization or continuous polymerization.

It should be noted that polypropylene that can be used in the present invention as described above cannot necessarily be obtained within the range of the above polymerization conditions, and may vary depending on the individual catalyst and polymerization conditions (in particular, the specific type of (S) used). It is necessary to check the molar ratio of Ti to Ti, polymerization temperature, etc.) and select it so as to satisfy the necessary physical property requirements described above.

As described above, the polypropylene constituting the polypropylene composition of the present invention is obtained. However, there are no restrictions on the manufacturing method for the polypropylene used in the present invention, and any polypropylene that satisfies the physical property requirements described above may be used. For example, it can also be manufactured by the following method.

The method consists of: ■ a titanium trichloride composition; ■ a dialkylaluminum monohalide (^); ■ a reaction product of an organoaluminum compound and water (^4); and, if necessary, an electron donor (B1). It is obtained by polymerizing propylene in the presence of a combined catalyst.

As the titanium trichloride composition and dialkyl aluminum monohalide, the titanium trichloride composition and dialkyl aluminum monohalide in the examples given above as the titanium-containing solid catalyst component and organoaluminum compound (^1) are used. It will be done.

Also, a reaction product of an organoaluminum compound and water (A4
) is a reaction product of an organoaluminum compound and water similar to the above-mentioned (A1), and is mainly an alkylaluminoxane represented by the following general formula [1] and general formula [11] or a general formula [1F or General formula [I! ] In,
A halogenated aluminoxane in which R is partially substituted with a halogen atom such as chlorine or bromine, and the halogen content is 40% by weight or less, preferably 30% by weight or less. Among these, methylaluminoxane, which is a reaction product of trimethylaluminum and water, is most preferred.

R7 formula 14 (l Al→70-^IR2E I ](
OA11n [+1] (In the formula; R is an alkyl group having 1 to 8 carbon atoms, and n is an integer of 1 to about 20.) There are various methods for reacting the organoaluminum compound and water at this time. For example, the following method can be exemplified.

(1) Adding an organic aluminum compound to a hydrocarbon medium suspension of a compound containing adsorbed water or a salt having water of crystallization, such as copper sulfate hydrate, aluminum sulfate hydrate, magnesium chloride hydrate, etc. How to react.

(2) A method in which water is directly applied to an organoaluminum compound in a medium such as benzene, toluene, or ethyl ether.

In the production of polypropylene used in the present invention, the reaction product (A4) of the above-mentioned organoaluminum compound and water is
Not only can it be used alone, but it is also possible to use a mixture of this product [A4] and unreacted organoaluminum compound (A2).

The electron donor (B1) used as necessary with each of the above catalyst components is an organic compound having an atom of oxygen, nitrogen, sulfur, or phosphorus, i.e., ethers, alcohols, esters, aldehydes, fatty acids, ketones,
Nitriles, amines, amides, ureas or thioureas, incyanates, azo compounds, phosphines, phosphites, phosphinites, hydrogen sulfide or thioethers, thioalcohols, silanols and 5i-0-
These include organosilicon compounds having C bonds.

The usage amount of each of the above catalyst components is from o,oos mol to 2 mol per mol of titanium atom in the titanium trichloride composition.
00 moles of dialkyl aluminum monohalide (A,
), an electron donor (at)O ~ 100 mol, and the reaction product (A4) of an organoaluminum compound and water was adjusted to the molar ratio of aluminum to dialkylaluminum monohalide (^, ) ((A4)/ (A3)) is 0.00
It is used within the range of 5 to 30. Especially (A4)/(^,
) is important; if the molar ratio is outside the above range, the desired polypropylene with relatively low stereoregularity cannot be obtained.

The catalysts combined in the above-mentioned predetermined amounts can be used as they are for propylene polymerization, but from the viewpoint of stable operation during propylene polymerization, titanium trichloride compositions are used instead of the titanium trichloride composition.
It is more preferable to use a catalyst component that is preactivated by combining a titanium trichloride composition and diethylaluminium monochloride (^,) and reacting this with an olefin.

The conditions for preactivation are the same as those for preactivation of the titanium-containing solid catalyst component described above. The polypropylene used in the present invention is obtained by polymerizing the olefin in the presence of the catalyst thus obtained or the preactivated catalyst. The same polymerization conditions as in the case of obtaining polypropylene described above are also used for the polymerization.

Another component of the composition of the invention is a nucleating agent. As the nucleating agent, any known nucleating agent that is generally used as a nucleating agent for polypropylene can be used. Specific examples include sodium bis-(p-t-butylphenyl) phosphate, potassium-bis-(p-t-butylphenyl) phosphate, and sodium-bis-(p-t-butylphenyl) phosphate.
-cyclohexylphenyl) phosphate, sodium pt-butylphenyl phosphate, sodium-2
, 2°-methylene-bis-(4,6-di-butylphenyl) phosphate, sodium-2,2°-ethylidene-bis-(4,6-di-butylphenyl) phosphate, lithium-2,2 -methylene-bis-(4,
Aromatic phosphorus compounds such as 6-di-t-butylphenyl) phosphate, sodium-2,2°-ethylidene-bis-(4-i-propyl-6-t-butylphenyl) phosphate, 13.2.4- Dibenzylidene sorbitol, 1,3,
2,4-di(p-methylhenzylidene) sorbitol,
1,32.4-di(p-ethylbenzylidene) sorbitol, 132.4-di(p-propylbenzylidene) sorbitol, 1,3,2.4-di(2°, 4゛-
dimethylbenzylidene) sorbitol, 1.3-p-
Chlorbenzylidene-2,4-p-methylbensylidene sorbitol, 1,2,3°4-di(p-chlorobenzylidene) sorbitol, l.

2.3.Benzylidene sorbitols such as 4-di (p-methoxybenzylidene) sorbitol, 1,3,2,4-di (p-ethoxybenzylidene) sorbitol,
Sodium benzoate, potassium benzoate, aluminum benzoate, pt-butyl aluminum benzoate, di-
Examples include metal salts of aromatic carboxylic acids such as aluminum pt-butylbenzoate, as well as talc and kaolin.

The polypropylene composition of the present invention is made by adding the above-described nucleating agent to polypropylene that satisfies the physical property requirements described above. The amount of the nucleating agent added is 5 parts by weight of o, oos based on 100 parts by weight of polypropylene. If the amount of the nucleating agent added is less than 0.005 parts by weight, the rigidity of molded products manufactured using the resulting composition will be low, and if the amount exceeds 5 parts by weight, the effects of the present invention cannot be expected to improve. It is not economical.

In producing the composition of the present invention, predetermined amounts of the above-mentioned polypropylene and nucleating agent may be mixed and then kneaded. As a mixing device, a high-speed stirring device such as a Hensel mixer (trade name) or a super mixer is used. As the kneading device, a Pan Bali mixer, a roll, a conider, an axle-shaft or a twin-shaft extruder, etc. may be used.

Mixing conditions are not limited, but are from room temperature to 100°C, preferably from room temperature to 60°C, for 30 seconds to 1 hour, preferably 1 minute to 30 minutes. The mixing conditions are also not limited, but the kneading time is 10 seconds to IO minutes, preferably 20 seconds to 5 minutes, as residence time in the extruder.

The kneading temperature is 150°C to 300°C, preferably 16°C.
It is 0°C to 260°C. After kneading, it is desirable to cool and cut the mixture and use it as a granular composition.

In addition to the above-mentioned polypropylene and nucleating agent, the composition of the present invention may contain various stabilizers and additives that are normally added to polypropylene as necessary, ultraviolet absorbers, light stabilizers, antistatic agents, A neutralizing agent, a lubricant, an anti-blocking agent, a copper damage inhibitor, a flame retardant, a pigment, etc. can be used in combination as appropriate.

Furthermore, the composition of the present invention may contain polymers such as polyethylene, polybutene, ethylene-propylene rubber, etc., and arbitrary fillers within a range that does not significantly impair the object of the present invention. Examples of the filler include inorganic fillers such as mica, zeolite, calcium carbonate, glass fiber, and carbon fiber, the above-mentioned inorganic fillers treated with coupling agents such as silane compounds, titanium compounds, and aluminum compounds, or wood powder. , valves, waste paper, synthetic fibers, natural fibers, and other organic fillers.

The thus obtained polypropylene composition of the present invention can be used to form molded products such as injection molded products, unstretched films, stretched films, and sheets by known molding techniques such as injection molding, vacuum forming, extrusion molding, blow molding, and stretching. provided for use.

[Example] The present invention will be explained below with reference to Examples. Definitions of terms used in Examples and Comparative Examples and measurement methods are as follows.

(1) MFR: Melt flow rate according to JIS 721O condition 14 in Table 1. (Unit: 8710 minutes) (2) Isotactic pentad fraction: Measured using JEOL GX-270 manufactured by JEOL based on the method described above.

(3) Boiling H111n-heptane insoluble portion: represents the solid residue after polypropylene is extracted with boiling H1n-heptane based on the method described above.

(4) Spiral flow: The polypropylene composition is molded by an injection molding machine at a melt resin temperature of 220°C, with a radius of 3
mm semicircular shape, ^rchimedes in the length direction
The length of the resin inside the mold was measured when the resin was injected for 15 seconds at an injection pressure of 600 kgf/cm'' into a spiral mold at 50°C.The longer the resin length, the better the melt fluidity of the resin. It shows good workability.

(5) Flexural modulus: JI of the polypropylene composition using an injection molding machine at a molten resin temperature of 220°C and a mold temperature of 50°C.
An S-shaped test piece was prepared. The test piece was left in a room with a humidity of 50% and a room temperature of 23°C for 96 hours, and then the flexural modulus was measured at 23°C in accordance with JIS 7230. (unit'
kgf/c+n2) (6) Izotsu impact strength: (5)
A test piece was prepared in the same manner as above, and the Izod impact strength was measured at 23°C in accordance with JIS K 7203.

(Unit: kgLcm/cm) (7) Internal haze: For a 1 mm test piece obtained in the same manner as in (5), after applying liquid paraffin to both sides of the test piece, haze was removed in accordance with JIS K 7105. The transparency inside the test piece was evaluated excluding the influence of the surface.

(JIL rank: %) (8) Blocking force: The polypropylene composition was extruded using a T-die type film forming machine at a molten resin temperature of 230°C, and then rolled to a thickness of 1 m using a cooling roll at 20°C.
After forming an a+ sheet, the sheet was heated with hot air at 140°C for 6 days.
The film was heated for 0 seconds, and then stretched 7 times in both length and width directions using a biaxial stretching machine to obtain a biaxially stretched film with a thickness of 20 μm. 2c
++(width) The force required for shearing the sample was measured using a machine at a speed of 300 mm/min. The lower the numerical value is, the less the bleed of 111n-heptane solubles and other components is, and the better the blocking resistance is.

(JI-position: kgf/cm') Example 1 (1) Production of polypropylene ■ Preparation of titanium-containing solid catalyst component In a stainless steel reactor equipped with a stirrer, decane 31
, anhydrous magnesium chloride 480g, orthotitanic acid n-
1.7 grams of butyl and 1.95 grams of 2-ethyl-1-hexanol were mixed and heated to 130° C. for 1 hour with stirring to dissolve and form a homogeneous solution. The homogeneous solution was
180 g of diisobutyl phthalate at 0°C and without stirring.
After 1 hour had passed, 5.2 kg of silicon tetrachloride was added dropwise over 25 hours to precipitate a solid, and the mixture was further heated to 70°C for 1 hour. The solid was separated from the solution and washed with hexane to give a solid product.

The total amount of the solid product was mixed with 15 IL of titanium tetrachloride dissolved in 1,2-dichloroethane + 5j2, and then 360 g of diisobutyl phthalate was added and the mixture was heated to 100 g with stirring.
After reacting at 100°C for 2 hours, decantation was performed at the same temperature to remove the liquid phase, 1,2-dichloroethane Ii and titanium tetrachloride 151 were added again, the mixture was stirred at 100°C for 2 hours, and washed with hexane. After drying, a titanium-containing supported catalyst component was obtained.

The TI content of the titanium-containing supported catalyst component is 3.0% by weight.
Met.

■ Preparation of preactivated catalyst components After purging a stainless steel reactor with a stirrer with an internal volume of 301 kg with nitrogen gas, 20 It of n-hexane, 15 Ig of triethylaluminum, 4 g of diphenyldimethoxysilane,
5g and titanium-containing supported catalyst component 10 obtained in step ① above
After adding 0g, feed 150g of propylene and heat at 30°C.
After 0 reaction time, the solid part was washed with 0-hexane and further dried for preactivation. A catalyst component was obtained.

■ Propylene polymerization L/D with nitrogen displacement and internal volume of 80°C and a stirrer =
After charging 20 kg of polypropylene powder obtained by a known method with an MFR of 3.0 into the horizontal polymerization vessel of step 3, n-hexane was added to the preactivated catalyst component obtained in step (2) above, and a polymerization vessel of 4.0
After making a suspension in n-hexane of 30% by weight, the suspension was converted to 0.423 milligram atoms/hr in terms of T1 atoms, and a 30% by weight n-hexane solution of triethylaluminum and 3-isocyanatepropyltriethoxysilane was converted to TI atoms. were continuously supplied so that the molar ratio was 200 and 50, respectively.

In addition, hydrogen was supplied to the polymerization vessel so that the concentration in the gas phase in the polymerization vessel was kept at 0.2% by volume, and propylene was supplied to the polymerization vessel so that the total pressure was maintained at 23kg/cm'G to carry out gas phase polymerization of propylene. The test was carried out continuously for 72 hours at 70°C. During the polymerization period, the polymer retention level in the polymerization vessel is 60% by volume.
Continuously feed 10 kg/h of polymer from the polymerization vessel so that
I extracted it with r.

The extracted polymer was then treated with 0.0% propylene oxide.
After contact treatment with nitrogen gas containing 2% by volume at 85° C. for 30 minutes, a polypropylene powder was obtained. Isotactic pentad fraction (P) of Zhai polypropylene
is 0.840, boiling n-heptane insoluble portion 87.61i
%, and the isotactic pentad fraction (Pr) of the boiling rheobutane-insoluble portion was 0.872.

(2) Production details of polypropylene composition In a 1N toojL Hensel mixer (trade name), 20 g of the polypropylene obtained in (1) was added to tetrakis[methylene-3-(3°, 5°-di-t-butyl- 10 g of 4°-hydroxyphenyl)propionate comethane, log calcium stearate, and 10 g of sodium 22°-methylenebis-(4,6-di-t-butylphenyl)phosphate as a nucleating agent were added and mixed with stirring for 3 minutes.

Subsequently, using a single screw extruder with an inner diameter of 40 mm, 230
The mixture was melt-kneaded and extruded at 0.degree. C., cooled with water, and then cut to obtain a granular polypropylene composition.

Comparative Example 1 A polypropylene composition was obtained in the same manner as in Example 1 (2) except that sodium-2,2°-methylene-bis-(4,6-di-t-butylphenyl) phosphate was not added.

Comparative Example 2 (1) In (1) (■) of Example 1, except that 3-isocyanatepropyltriethoxysilane was not used and the hydrogen concentration in the gas phase in the polymerization vessel was 0.1% by volume. conducted polymerization of propylene in the same manner,
The polymerization of propylene was stopped 24 hours after the start of polymerization because the fluidity of the produced polymer deteriorated, resulting in failure in removing the polymerization heat and failure in extracting the polymer from the polymerization vessel.

(2) A polypropylene composition was obtained in the same manner as in (2) of Example 1 except that the polypropylene obtained in (1) above was used as the polypropylene.

Polypropylene was obtained by polymerizing propylene in the same manner as above.

(2) A polypropylene composition was obtained in the same manner as in (2) of Comparative Example 1, except that the polypropylene obtained in (1) above was used as the polypropylene.

Example 2.3 In (2) of Example 1, the amount of sodium-2,2-methylene-bis-(4,6-di-butylphenyl)phosphate added was 2 g (Example 2) and 60 g (Example 2). A polypropylene composition was obtained in the same manner as in Example 3) except for making the following changes.

Comparative Example 3 (1) In (1) (1) of Example 1, diphenyldimethoxysilane was used instead of 3-isocyanatepropyltriethoxysilane so that the molar ratio to Ti was 20, and each catalyst component was added to the polymerization vessel. The total pressure inside is 23k
Example 4 (1) In (1) (■) of Example 1, the molar ratio of 3-acryloxypropyltrimethoxysilane to TI was changed in place of 3-isocyanatepropyltriethoxysilane. Polypropylene was obtained by polymerizing propylene in the same manner except that the catalyst components were used in such a manner that the total pressure in the polymerization vessel was maintained at 23 kg/ci'G.

(2) In (2) of Example 1, 20 kg of the polypropylene obtained in (1) above was used as the polypropylene, and sodium-2,2-methylene-bis-(4°6-di-butylphenyl) was used as the nucleating agent. 1 instead of phosphate
．． A polypropylene composition was obtained in the same manner except that 20 g of 3,2,4-di(p-methylbenzylidene) sorbitol was used.

Comparative Example 4 In (2) of Example 4, IJ, 2.4-G (p-
A polypropylene composition was obtained in the same manner except that methylbenzylidene) sorbitol was not added.

Example 5 (1) Production of polypropylene ■ Preparation of titanium-containing solid catalyst component n-hexane 61, diethylaluminum monochloride (DEAC) 5.0 mol, diisoamyl ether 1
2.0 mol was mixed at 25°C for 1 minute and reacted at the same temperature for 5 minutes to form reaction product liquid (I) (diisoamyl ether/
A DEAC molar ratio of 2.4) was obtained. 40 mol of titanium tetrachloride was placed in a reactor purged with nitrogen, heated to 35°C, and the entire amount of the reaction product liquid (1) was added dropwise over 30 minutes, kept at the same temperature for 30 minutes, and heated to 75°C. The temperature was raised and the reaction was further carried out for 1 hour, cooled to room temperature, the supernatant liquid was removed, n-hexane was added 20 times, and the supernatant liquid was removed by decantation, which was repeated 4 times to obtain a solid product (+1). I got it.

Suspend the entire amount of this (1■) in n-hexane 31,
Add 200g of diethylaluminum monochloride,
Propylene 1. at 30°C. Add okg and react for 1 hour.
A polymerized solid product (II-A) was obtained (
Propylene reaction amount aoog). After the reaction, after removing the supernatant liquid, adding 300 mJZ of n-hexane and removing by decantation was repeated twice, and 2.5 kg of the solid product (o-A) subjected to the above polymerization treatment was transferred to n- Suspended in xane 6j2, 3.5 kg of titanium tetrachloride was added at room temperature for about 10 minutes, and after reacting at 80°C for 30 minutes, 1.6 kg of diisoamyl ether was added.
After the reaction was completed at 0°C for 1 hour, the supernatant was removed by decantation, and n-hexane at 40°C was added.
After repeating the operation of stirring for 10 minutes, standing still, and removing the supernatant liquid five times, the mixture was dried under reduced pressure to obtain a titanium trichloride composition. Titanium content in 1g of titanium trichloride composition is 192mg
Met.

■ Preparation of preactivated catalyst component After purging a stainless steel reactor with inclined blades with an internal volume of 1502 cm with nitrogen gas, using n-hexane at 100°C, 114 g of diethylaluminium monochlorite, and titanium trichloride composition 1 obtained in ■. After adding .8 kg at room temperature, 1.8N+113 ethylene was supplied at 30°C for 2 hours to cause a reaction (1.0 kg of ethylene was added per 1 g of titanium trichloride composition).
8), unreacted ethylene was removed, washed with n-hexane, filtered and dried to obtain a preactivated catalyst component.

■ Polymerization of propylene In (1) of Example 1, as the preactivated catalyst component, the preactivated catalyst component obtained in the above
．． 8 milligram atoms/hr, and diethylaluminum monochloride and tris(trimethylsilyl) phosphate in place of triethylaluminum and 3-isocyanatepropyltriethoxysilane in molar ratios to Ti atoms of 7.0 and 2.0, respectively. Furthermore, the hydrogen concentration in the gas phase in the polymerization vessel can be reduced to 0.
．． Polypropylene was obtained in the same manner except that the content was 7% by volume. The isotactic pentad fraction (P) of the polypropylene is 0.820, boiling! The tin-heptane insoluble portion is 85.51% by weight, and the isotactic pentad fraction (Pr) of the boiling raw butane insoluble portion is 0.86.
It was 5.

(2) Production of polypropylene composition In (2) of Example 1, the polypropylene obtained in (1) above was used as the polypropylene, and the sodium-2,2°-methylene-bis-(4,6- G1
A polypropylene composition was obtained in the same manner except that 20 g of aluminum pt-butylbenzoate was used in place of (-butylphenyl) phosphate.

Comparative Example 5 A polypropylene composition was obtained in the same manner as in Example 5 (2) except that aluminum pt-butylbenzoate was not added.

Comparative Example 6 (1) In (1) (■) of Example 1, tris(trimethylsilyl) phosphate was not used and other catalyst components were used to maintain the total pressure in the polymerization vessel at 23 kg/cm"G. Propylene was polymerized in the same manner except that it was supplied to obtain polypropylene.

(2) A polypropylene composition was obtained in the same manner as in (2) of Example 5, except that the polypropylene obtained in (1) above was used as the polypropylene.

Example 6 (1) Production of polypropylene (1) Preparation of titanium-containing solid catalyst component A titanium trichloride composition was obtained in the same manner as in (11) of Example 5.

■ Preparation of preactivated catalyst components After purging a stainless steel reactor with inclined blades with an internal volume of 801 cm with nitrogen gas, 40 J2 of n-hexane, 43 g of diethylaluminium monochloride, and 450 g of the titanium trichloride composition obtained in (2) were added. After the addition at room temperature, the temperature inside the reactor was raised to 40°C, 300g of propylene was added, and preactivation treatment was performed at 40°C for 1 hour. (0.5 g of propylene reacted per 1 g of titanium trichloride composition) After the reaction, n
- After washing with hexane, filtration and drying were performed to obtain a preactivated catalyst component.

■Reaction product between organoaluminum compound and water (^4)
After purging a stainless steel reactor equipped with a stirrer with an internal volume of 300 ρ with nitrogen, 37 kg of copper sulfate pentahydrate and 50 ρ of dehydrated toluene were charged, and after cooling to 10°C, the internal temperature reached 1.
500 mol of trimethylaluminum diluted with 50 J2 of toluene was added over 4 hours while stirring to maintain the temperature at 5°C.

After the addition, the reaction was continued at 15° C. for 48 hours, and then the solids were removed, and a portion of the toluene was distilled off under reduced pressure at room temperature to obtain 40 volumes of a toluene solution containing methylaluminoxane.

■Polymerization of propylene In Example 5 (1) (■), toluene was added to the preactivated catalyst component obtained in (■) above to prepare a 4.0% by weight toluene suspension. Using an activated catalyst component, in addition to diethylaluminium monochloride, feed a toluene suspension of methylaluminoxane obtained in step ① above so that the ratio of aluminum atoms IAI to diethylaluminum monochloride is 0.13. In addition, instead of tris(trimethylsilyl)phosphate, methyl methacrylate is supplied at a molar ratio to titanium atoms of 0.05, and the hydrogen concentration in the gas phase of the polymerization vessel is set to 0.8% by volume, Polypropylene was obtained by polymerizing propylene in the same manner except that each catalyst component was supplied so that the total pressure within the polymerization vessel was maintained at 23 kg/cm2G.

The isotactic pentad fraction (P) of the obtained polypropylene was o, aao, the boiling n-heptane insoluble portion was 91.0% by weight, and the isotactic pentad fraction (P) of the boiling n-heptane insoluble portion was 91.0% by weight. ) was 0.905.

(2) Production of polypropylene composition A polypropylene composition was obtained in the same manner as in Example 1 (2) except that the polypropylene obtained in (1) above was used as the polypropylene.

Comparative Example 7 A polypropylene composition was obtained in the same manner as in Example 6 (2) except that sodium-2,2°-methylene-bis-(4,6-di-t-butylphenyl) phosphate was not added. Ta.

Regarding the above Examples and Comparative Examples, the composition of the polypropylene composition (regarding the polypropylene and the nucleating agent) and the evaluation results are shown in the table.

[Effect of the invention] As is clear from the examples already described, when the polypropylene composition of the present invention (see Examples 1 to 6) is processed into a molded article, it has excellent fluidity when melted. , contributing to energy conservation and productivity improvement.

Moreover, the obtained molded product has the same rigidity and blocking resistance as a molded product obtained using ordinary polypropylene (see Comparative Example 3), but has excellent impact resistance and transparency, so it can be used for various purposes. It can be widely used in various fields.

that's all Procedural amendment (spontaneous) 1991 (Monday)

Claims (4)

[Claims] (1) Isotactic pentad fraction (P) is 0.8
0-0.91, boiling n-heptane insoluble portion is 80% by weight
~95% by weight, and the isotactic pentad fraction (Pr) of the n-heptane insoluble portion satisfies the formula 0<(Pr)-(P)≦0.08 in relation to the above (P). A polypropylene composition obtained by adding 0.005 parts by weight to 5 parts by weight of a nucleating agent to 100 parts by weight of polypropylene that satisfies the following. (2) The composition according to claim 1, wherein the nucleating agent is a metal salt of an aromatic phosphorus compound. (3) The composition according to claim 1, wherein the nucleating agent is dibenzylidene sorbitol. (4) The composition according to claim 1, wherein the nucleating agent is a metal salt of an aromatic carboxylic acid.