JPH01263138A - Polypropylene resin composition - Google Patents

Abstract

PURPOSE:To obtain a crystalline polypropylene resin composition, containing a reaction product of a specific crystalline propylene copolymer with cyclohexyl alcohol (derivative) and capable of providing molded products excellent in physical properties. CONSTITUTION:A polypropylene resin composition containing (A) a reaction product prepared by reacting a crystalline polypropylene copolymer obtained by polymerizing an alkenylsilane (e.g., vinylsilane) with propylene in the presence of a stereoregular catalyst (preferably a catalyst system consisting of a titanium halide and an organometallic compound) with cyclohexyl alcohol (derivative) in an equimolar amount or more based on Si units in the above-mentioned copolymer preferably in the presence of an alkaline (earth) metal (oxide) and (B) crystalline polypropylene (random or block copolymer, etc., of propylene with other olefins).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a crystalline polypropylene resin composition containing a specific compound.

[Conventional technology]

Although polypropylene is a polymer with excellent rigidity, there is a problem in that the degree of crystallinity of molded products is relatively low, and the physical properties of ordinary molded products are inferior to the originally expected physical properties. To solve this problem, a method of adding various nucleating agents is usually used, and a molded product with excellent rigidity or transparency is obtained.

[Problems to be solved by the invention]

The method of adding a nucleating agent is simple and effective, but it requires the addition of a relatively large amount of nucleating agents, which may cause variations in the physical properties of the molded product due to poor dispersion of the nucleating agent, or bleeding of the added nucleating agent. There was a problem. For this purpose, it is known to add a specific polymer compound, but a more effective compound is desired.

[Means for solving problems]

The present inventors have diligently searched for more effective compounds and have arrived at the present invention.

That is, the present invention is a crystalline polypropylene resin composition containing a reaction product of a crystalline propylene copolymer obtained from alkenylsilane and propylene using a stereoregular catalyst and cyclohexyl alcohol or a derivative thereof.

In the present invention, as a method for producing a crystalline propylene copolymer obtained by using alkenylsilane and propylene using a stereoregular catalyst, for example, the method disclosed in U.S. Pat. No. 3,223,686 can be used as is. As the monomer, those having at least one 5i-H bond are used, and in addition to vinylsilane, allylsilane, butenylsilane, and pentenylsilane, the 5i-
1 (one or two of the bonds are substituted with an alkyl group can also be exemplified.As stereoregular catalysts, many catalysts with improved performance have since been disclosed, and these can be used. Even if it is legal, in addition to the solvent method using an inert solvent, bulk polymerization method and gas phase polymerization method can also be adopted.Here, as the stereoregular catalyst, a catalyst system consisting of a transition metal catalyst and an organometallic compound can be preferably exemplified. As the transition metal catalyst, titanium halides are preferably used, such as titanium trichloride obtained by reducing titanium tetrachloride with metallic aluminum, hydrogen, or organoaluminum, or titanium trichloride obtained by modifying these with an electron-donating compound, and organoaluminum compounds. Furthermore, if necessary, a catalyst system consisting of a stereoregularity improver such as an oxygen-containing organic compound, or a transition metal catalyst obtained by supporting titanium halide on a carrier such as magnesium halide, or a carrier treated with an electron-donating compound. An example is a catalyst system consisting of a stereoregularity improver such as an organoaluminum compound and, if necessary, an oxygen-containing organic compound. (For example, various examples are described in the following literature.
er-Natta Catalysts and Po
lymerization by JohnBoor
Jr<Academrc Press>+Journa
I of Macromorecular Science
e-Reviews in Macromolecules
ar Chemistry and Physics
C24, (3) 355-385 (1984), C2, where the stereoregularity improver or electron-donating compound is usually preferably exemplified by oxygen-containing compounds such as ethers, esters, orthoesters, and alkoxy silicon compounds;
Further, alcohols, aldehydes, water, etc. can also be used as electron-donating compounds.

As the organoaluminum compound, trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkyl aluminum civalide can be used, and examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, hexyl group, etc. Examples of halides include chlorine, bromine, and iodine.

Here, the polymerization ratio of alkenylsilane and propylene is not particularly limited as long as the resulting polymer maintains crystallinity, but usually alkenylsilane is 30 mol χ to 0.0 mol.
It is preferable to set the amount to 1 mol χ for the catalytic activity during polymerization, for mixing with the crystalline polypropylene to be mixed, and for the effect of improving physical properties to be sufficient. There is no particular limit to the molecular weight of the polymer, but extremely high molecular weights, such as 13
The intrinsic viscosity measured with a 5°C tetralin solution should not exceed 10.

In the present invention, the copolymer of propylene and alkenylsilane is cyclohexyl alcohol or a derivative thereof, specifically, one in which one or more hydrogen atoms of the cyclohexyl group are substituted with an alkyl group, a halogen alkoxy group, etc. reacts. Here, the amount of cyclohexyl alcohol or its derivative used is generally at least equimolar to the Si unit in the copolymer of propylene and alkenylsilane. The presence of hydroxide is effective, and room temperature is sufficient for the reaction temperature, but
May be heated. In some cases, the mixture may be mixed with polypropylene, which will be described later, and then reacted with cyclohexyl alcohol.

In the present invention, the crystalline polypropylene to be mixed with the reaction product of the crystalline propylene copolymer obtained by using the above-mentioned alkenylsilane and propylene using a stereoregular catalyst and cyclohexyl alcohol is not particularly limited, and various molecular weights may be used as necessary. or random or block copolymers with other olefins such as ethylene, butene, hexene, etc. can be used. The object of the present invention is to improve the physical properties of crystalline polypropylene in which alkenylsilane and propylene are mixed with a crystalline propylene copolymer obtained using a stereoregular catalyst, and the composition thereof is wide-ranging.

To obtain the crystalline polypropylene, it is sufficient to use the above-mentioned catalyst and polymerization method during polymerization.Many methods have already been proposed for producing copolymers, and if necessary, random copolymers with other olefins may be used. Copolymerization, or so-called block copolymerization, in which only propylene is first polymerized and then other olefins and propylene are polymerized, and the polymerization reaction can also be carried out in an inert medium, in liquid monomers, or in the gas phase. .

In the present invention, there is no particular restriction on the method of mixing the two components, and they can be sufficiently mixed by a general method such as pre-mixing with a Henschel mixer, followed by melt-mixing with an extruder and granulation. At this time, it is of course possible to mix various known additives such as stabilizers.

〔Example〕

The present invention will be further explained with reference to Examples below.

Example 1 A vibratory mill equipped with four grinding pots each having an internal volume of 41 and containing 9 kg of steel balls each having a diameter of 12 m was prepared. 300 g of magnesium chloride and 60 ml of tetraethoxysilane were placed in each pot under a nitrogen atmosphere. α, α, α-Trichlorotoluene 4
5ml was added and pulverized for 40 hours. 300 g of the co-pulverized material obtained in this way was put into a 51 flask and titanium tetrachloride 1,51
, 1.51% of toluene was added, stirred at 100 @C for 30 minutes, the supernatant was removed, and 1.51% of titanium tetrachloride was added in the same manner.
, 1.51 g of toluene was added, and the mixture was stirred at 100"C for 30 minutes. The supernatant liquid was removed, and the solid content was washed repeatedly with n-hexane to obtain a transition metal catalyst slurry. A portion was sampled to remove the titanium content. According to the analysis, it was 1.9wtχ
Met.

In a pressure-resistant glass autoclave with an internal volume of 200 m1, 40 m1 of toluene and 20 mg of the above transition metal catalyst were placed in a nitrogen atmosphere.
, diethylaluminum chloride 0.128ml,
Methyl p-toluate 0.06 ml,) Diethylaluminium 0. b) Next, propylene was charged to a concentration of 5 kg/cm" and polymerization was carried out at 70"C for 2 hours at a constant pressure. Thereafter, the slurry was taken out, filtered and dried to obtain 29 g of powder.

Intrinsic viscosity (hereinafter abbreviated as η) measured with a tetralin solution at 135°C using a differential thermal analyzer at 10°C/+*
When the melting point and crystallization temperature were measured as the maximum peak temperature by increasing or decreasing the temperature in increments, η was 1°39, melting point was 152°C, crystallization temperature was 108°C, and it was found to be crystalline polypropylene. According to elemental analysis, it contained 1.6wtχ of vinylsilane units.

Next, 10 g of this copolymer was dispersed in 100 ml of cyclohexyl alcohol, metal sodium O and Ig were added, and the mixture was reacted at room temperature for 10 hours. The slurry was filtered, and the powder was thoroughly washed with toluene and then dried. According to the infrared absorption spectrum of this polymer, the absorption attributed to 5i-H (2150cn+-') disappeared, and the absorption attributed to ether bonds (near 1100cm'') was observed.

Separately, propylene was polymerized and η was 1.65, and the extraction residual rate when extracted with a Soxhlet extractor (hereinafter abbreviated as II),
Polypropylene with a ratio of powder weight after extraction/powder weight before extraction (expressed as a 100 fraction) of 97.1χ was obtained, and the above reactant Log and 1000 g of polypropylene, a phenolic stabilizer at a weight ratio of 10/10000 (to polypropylene), and a steer. Calcium phosphate was added in a weight ratio of 15/10000 and granulated to obtain a composition.

Next, the melt flow index was measured using this composition, and an injection sheet with a thickness of II was made.
Bending stiffness was measured.

Melt flow index (Ml) AST
M 01238 (230' C) Bending rigidity
657M D747-63 (20''c> Comparative Example 1 The physical properties were measured in the same manner as in Example 1 except that the reaction product of the copolymer of vinylsilane and propylene and cyclohexyl alcohol was not used. The results are shown in the table. .

Example 2 Example 1 except that allylsilane was used instead of vinylsilane
The copolymer was allyl sila 72.9w.
t%, η was 1.34, and the melting point was 146°ct'.

The results are shown in the table.

〔effect〕

The composition of the present invention has extremely excellent physical properties and is extremely valuable industrially.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] (1) A crystalline polypropylene resin composition containing a reaction product of a crystalline propylene copolymer obtained from alkenylsilane and propylene using a stereoregular catalyst and cyclohexyl alcohol or a derivative thereof.