JP2880793B2 - Polypropylene resin composition - Google Patents

Description

The present invention relates to a polypropylene resin composition. More specifically, the present invention relates to a polypropylene resin composition obtained by blending a specific alkylene oxide with polypropylene having high syndiotacticity.

(Prior art)

Polypropylene is a polymer that is inexpensive and has relatively good physical properties.However, it does not contain polar groups, so it has poor adhesion to polymers containing polar groups and it is difficult to apply paint to molded products. In addition, there is a problem that the surface of the molded product is easily charged with static electricity. On the other hand, it is conceivable to mix a compound containing a polar group, but when the compound containing a polar group is a low-molecular compound, there is a problem that the compound emerges on the surface of the molded product, When a compound is used, a polymer containing a polar group is difficult to mix with polypropylene, and the mixture has a problem that the inherent transparency and the like of polypropylene are lost.

[Problems to be solved by the invention]

If a polymer having a polar group can be mixed with polypropylene while maintaining the inherent properties of polypropylene such as transparency, unprecedented characteristics can be imparted to polypropylene, and new utilization can be expected.

[Means for solving the problem]

Means for Solving the Problems The present inventors diligently studied a polypropylene resin composition that solved the above-mentioned problems and completed the present invention.

That is, the present invention is a polypropylene resin composition in which 0.01 to 20 parts by weight of poly (1,2-butylene oxide) is blended with 100 parts by weight of a polypropylene having a syndiotactic structure.

The polypropylene of the syndiotactic structure important in the present invention includes not only propylene homopolymer but also
20% by weight or less of ethylene, or α- having 4 to 20 carbon atoms
Copolymers with olefins can be used and can be produced by using a catalyst consisting of a transition metal compound having two asymmetrically bonded ligands and an aluminoxane. For example, JAEWEN et al. (J. Am. Chem. Soc., 1988, 110, 6255-6256),
Although the compounds described in the literature can be preferably used, when a homopolymer of propylene is produced even if the structure is different, the syndiotactic pentad fraction of the obtained polymer (A. Zambelli et al. Macromolecules vol 6 925 ( 197
3), vol. 8687 (1975)) can be used as long as the catalyst system gives a polymer having a relatively high tacticity of about 0.7 or more. (Where A and B are different aromatic hydrocarbons, R is a hydrocarbon residue having 1 to 20 carbon atoms connecting A and B, or a compound containing silicon or germanium, and X is a halogen atom or a carbon atom having 1 carbon atom. ~ 20 hydrocarbon residues, wherein M is a metal atom selected from titanium, zirconium and hafnium.) A and B have 5 to 30 carbon atoms
And monocyclic or polycyclic aromatic compounds. Specific examples thereof include cyclopetadiene or a compound in which part or all of hydrogen is substituted by an alkyl group having 1 to 10 carbon atoms (where the alkyl group is It may have a structure in which the terminal is again bonded to the cyclopentadiene ring.), A polycyclic aromatic compound such as indene or fluorene, or a compound in which part or all of hydrogen has been substituted with an alkyl group having 1 to 10 carbon atoms. Is exemplified. R is preferably a dialkylmethylene group or a dialkylsilylene group, for example, R ' ₂ C, R' ₂ S
i, R _'2 Ge (wherein R' is may be same or different alkyl radical of hydrogen or carbon number of 1 to 20.) is a compound represented by can be preferably used, further -CR'-CR ' An ethylene group represented by-can also be exemplified (wherein R 'is the same as described above). X can be exemplified by fluorine, chlorine, bromine, iodine, or an aromatic compound such as an alkyl group such as methyl, ethyl, propyl, or butyl, or a cyclopentadienyl group. Particularly, a chlorine or methyl group is preferable. Among them, isopropyl (cyclopentadienyl-1-fluorenyl) hafnium dichloride, isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride described in the above-mentioned document, or a compound in which a part of these hydrogens is substituted by an alkyl residue Is mentioned. The aluminoxane has a general formula: (Wherein R is a hydrocarbon residue having 1 to 3 carbon atoms). Examples thereof include methylaluminoxane wherein R is a methyl group and n is 5 or more. The use ratio of the aluminoxane to the transition metal compound is 1 to 1,000,000 mole times, usually 10 to 5000 mole times.

The polymerization conditions are not particularly limited, and a solvent polymerization method using an inert medium, a bulk polymerization method substantially free of an inert medium, and a gas phase polymerization method can be used. The polymerization temperature is -100 to 200 ° C, and the polymerization pressure is normal pressure to 100 kg /
It is generally performed in cm ² . Preferably -100 to 100
° C, normal pressure ~ 50 kg / cm ² .

In the present invention, a syndiotactic structure means
Of the absorption measured by ¹³ C-NMR, the peak intensity observed at about 20.2 ppm is the peak intensity of all methyl groups attributed to propylene units, whereas the peak intensity of propylene homopolymer is 0.7%.
As described above, a copolymer having a ratio of 0.3 or more is used for the copolymer. If this ratio is less than 0.7 for a propylene homopolymer or less than 0.3 for a copolymer, there is a problem that the surface of the molded product becomes sticky when the composition is formed. As a preferable molecular weight, an intrinsic viscosity measured with a tetralin solution at 135 ° C. is preferably about 0.1 to 10 dl / g in terms of physical properties and moldability.

One component used in the present invention, poly (1,2-
As butylene oxide, a method of polymerizing 1,2-butylene oxide using an oxide catalyst (for example, R. Nomur)
a. J. Polym. Sci. Polym. Chem. Ed., Vol. 26, 627 (198
8))) or a method using an aluminum compound (DABansleben et al., J. Polym. Sci. Polym. Chem. Ed., Vol. 2)
2,2489 (1984))
About 0000 can be used. If the molecular weight is too small, there is a problem that the molded product is raised on the surface, and if the molecular weight is too large, there is a problem that mixing is difficult. The mixing ratio was 100 for polypropylene with a syndiotactic structure.
The amount is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight with respect to parts by weight. If the amount is too small, there is no effect of improving the physical properties.

The method of mixing is not particularly limited, and a method of dry-mixing with an ordinary Henschel mixer and then melt-granulating is sufficient. At that time, it is of course possible to mix various stabilizers and nucleating agents.

〔Example〕

 Hereinafter, the present invention will be described with reference to Examples.

Example 1 0.2 g of isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride obtained by lithiation of isopropylcyclopentadienyl-1-fluorene synthesized according to a conventional method, reaction with zirconium tetrachloride and recrystallization. And 30 g of methylaluminoxane (polymerization degree 16.1) manufactured by Tosoh Akzo Co., Ltd., and toluene was added in an autoclave having an internal volume of 200, and the polymerization pressure was 3 kg / cm ^2.
-G, polymerized at 20 ° C for 2 hours, then decalcified with methanol and methyl acetoacetate, washed with aqueous hydrochloric acid, and filtered to obtain 5.6 kg of syndiotactic polypropylene. This polypropylene has a syndiotactic pentad fraction of 0.935 according to ¹³ C-NMR, η measured at 135 ° C. tetralin solution is 1.45 dl / g, MW / MN measured at 1,2,4-trichlorobenzene. Was 2.2. A known stabilizer was added to the polypropylene, and the mixture was granulated with an extruder.
It was melt pressed at 0 ° C. to form a 1 mm sheet. The following physical properties of this sheet were measured.

Flexural rigidity: kg / cm ² ASTM D-747 (23 ° C) Tensile yield strength: kg / cm ² ASTM D-638 (23 ° C) Elongation at break:% ASTM D-638 (23 ° C) Izod (notched ) Impact strength: kg · cm / cm ASTM D-638 (23 ° C, -10 ° C) Haze:% According to ASTM D1003.

The flexural rigidity was 5300 kg / cm ² , the tensile yield strength was 240 kg / cm ² , the elongation at break was 520%, the Izod impact strength was 14.2 and 3.6 (23 ° C. and −10 ° C., respectively), and the haze was 28%. on the other hand
Poly (1,2-butylene oxide) was synthesized according to J. Polym. Sci. Polym. Chem. Ed., Vol. 26, 627 (1988). However, phenylantimony oxide was used as a catalyst in an amount of 1 g per 100 ml of 1,2-butylene oxide, and polymerized at 25 ° C for 100 hours to obtain 45 g of a polymer having a molecular weight of 12,000. The same procedure was followed except that this poly (1,2-butylene oxide) was used in an amount of 5 parts by weight per 100 parts by weight of polypropylene.
5100kg / cm ^2, the tensile yield strength of 220kg / cm ^2, an elongation at break of 620
%, Izod impact strength 12.5, 3.4 (23 ℃, -1 respectively)
0 ° C.), the haze was 31%, and almost no decrease in physical properties was observed. An aqueous paint (Aqua Color R-16S, manufactured by Toyo Ink Co., Ltd.) was applied to the sheet with a brush, and the sheet was baked and dried at 60 ° C. for 30 minutes in an air oven. When the adhesion strength of the coating film of this test piece was measured by the method of JIS K-5400 (cross-cut cellophane tape test method), the number of cross-cut coating films remained was as good as 80. On the other hand, 0 was obtained without using poly (1,2-butylene oxide). The wetting index of this sheet (measured with a wetting standard solution)
Was 38 to 40 dyn / cm ² , whereas that without poly (1,2-butylene oxide) was 30 dyn / cm ² or less.

〔The invention's effect〕

The composition of the present invention can be expected for various uses as a functional polypropylene and is extremely valuable.

Claims (1)

(57) [Claims] 1. A polypropylene resin composition comprising 0.01 to 20 parts by weight of poly (1,2-butylene oxide) per 100 parts by weight of polypropylene having a syndiotactic structure.