JPH03750A - Polyolefin resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyolefin resin compsn. with an excellent balance of physical properties between rigidity and impact resistance by irradiating a compsn. comprising an alkenylsilane and an olefin and a specified compd. with a radiation. CONSTITUTION:A compsn. comprising a copolymer of an alkenylsilane (e.g. vinylsilane) and an olefin (e.g. propylene), an OH-contg. compd. (pref. a compd. contg. two or more OH groups) and a C=C-contg. compd. (pref. a compd. contg. two or more C=C groups) and if necessary, a polyolefin contg. no alkenylsilane (e.g. propylene or pentene-1) is irradiated with a radiation. The title compsn. with an excellent balance of physical properties between rigidity and impact resistance is obtd. thereby.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a polyolefin composition obtained by irradiating a composition comprising a copolymer of alkenylsilane and olefin and a specific compound with radiation.

[Prior art]

Olefin polymers are used in a variety of applications because they are inexpensive and have relatively well-balanced physical properties.

Furthermore, various improvements have been made in random or block copolymerization of olefins with the aim of improving the balance of physical properties.

[Problem to be solved by the invention]

However, even if copolymerization is performed with other olefins, if the impact resistance is essentially improved, the stiffness will be correspondingly inferior. It is extremely difficult to improve impact resistance while maintaining the same properties, and it has not been possible to obtain a product that is excellent in both properties.

[Means to solve the problem]

The present inventors have completed the present invention by earnestly searching for a polyolefin resin composition that solves the above problems and has an excellent balance of physical properties.

That is, the present invention provides a polyolefin resin obtained by irradiating a composition consisting of a copolymer of alkenylsilane and olefin, a compound selected from OH-containing compounds and C═C-containing compounds, and optionally a polyolefin that does not contain alkenylsilane. It is a composition.

The copolymer of alkenylsilane and olefin used in the production of the composition of the present invention can usually be obtained by polymerizing olefin and alkenylsilane using a so-called Ziegler-Natsuta catalyst consisting of a transition metal catalyst and an organometallic compound. For example, An example is disclosed in US Pat. No. 3,223,686. Furthermore, a graft copolymer obtained by graft polymerizing a polyolefin by heat-treating it with alkenylsilane in the presence of a radical polymerization initiator such as peroxide may also be used. As the alkenylsilane, those having at least one 5i-H bond are preferably used, such as -ShiC=CI-(CHt).

-5i) IJs-p (where n is θ~12, p is 1~3
, R is a hydrocarbon residue having 1 to 12 carbon atoms), and specific examples include vinylsilane, allylsilane, butenylsilane, pentenylsilane, or 5t-H of 1 to 3 of these monomers. Examples include compounds in which H in the bond is replaced with chlorine. In addition, as an olefin, the general formula 〇zC-CI-R (in the formula, P has 1 to 1 carbon atoms)
12 hydrocarbon residues. ) can be exemplified,
Specifically, ethylene, propylene, butene-1, pentene-1, hexene-1,2 methylpentene, heptene-1
In addition to α-olefins such as 1 and octene-1, styrene or derivatives thereof are also exemplified.

In the present invention, for the copolymer of olefin and alkenylsilane, a catalyst consisting of TiCl3 and triethylaluminum described in the above-mentioned U.S. patent can be used, but it is more preferable to use various highly active catalysts that have been developed since then and give polyolefins. used.

As the polymerization method, in addition to a solvent method using an inert solvent, a bulk polymerization method and a gas phase polymerization method can also be employed. Here, as the catalyst consisting of a transition metal compound and an organometallic compound, a titanium halide is preferably used as the transition metal compound, and an organoaluminum compound is preferably used as the organometallic compound. titanium trichloride obtained by reduction with an electron-donating compound and an organoaluminum compound,
Furthermore, if necessary, a catalyst system consisting of an electron-donating compound such as an oxygen-containing organic compound, or a transition metal compound obtained by supporting titanium halide on a carrier such as magnesium halide, or a carrier treated with an electron-donating compound. A catalyst system consisting of a catalyst and an organoaluminum compound, and if necessary an electron-donating compound such as an oxygen-containing organic compound, or a reaction product of magnesium chloride and alcohol is dissolved in a hydrocarbon solvent, and then a precipitant such as titanium tetrachloride is used. By treatment, it becomes insolubilized in hydrocarbon solvents, and if necessary, esters,
Catalyst system consisting of a transition metal compound catalyst obtained by treatment with an electron-donating compound such as ether and then treatment with titanium halide, an organoaluminium compound, and if necessary an electron-donating compound such as an oxygen-containing organic compound. (For example, various examples are described in the following documents. Ziegler-Natta Cat
alysts and polymerization
n by John Boor Jr.
demic Press)+Journal of
Jlacros+oricular 5ience R
views in acrosolecula
r Chemistry and Physics
s, C24(3) 355-385 (1984), same C
25(1) 578-597 (1985)) or a catalyst consisting of a transition metal catalyst and aluminoxane soluble in a hydrocarbon solvent.

Preferred examples of electron-donating compounds in Uni include oxygen-containing compounds such as ethers, esters, orthoesters, and alkoxy silicon compounds, and alcohols, aldehydes, water, and the like can also be used.

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.

Further, the aluminoxane is an oligomer polymer obtained by reacting the above organoaluminium with water or water of crystallization.

There is no particular restriction on the polymerization ratio of alkenylsilane and olefin, but from the standpoint of mixing with polyolefin, alkenylsilane is usually about 0.001 to 30 mol χ, preferably 0.1 to 10 mol χ. . In addition, when using the copolymer alone without mixing, preferably 0
．． 001 to 5 mol χ.

There is no particular restriction on the molecular weight of the polymer, but it is preferably the same or lower than the molecular weight of the polyolefin used in the mixture. In some cases, polymerization similar to polyolefins (&[
composition, molecular weight, etc.) may be used. The molecular weight is about 10,000 to 1,000,000. There are no particular restrictions on the method of grafting alkenylsilane to polyolefin, and the methods and conditions used for ordinary graft copolymerization can be used. Usually, the method and conditions used for graft copolymerization are heated to a temperature higher than the decomposition temperature of the radical initiator in the presence of the polyolefin and alkenylsilane used. This allows easy graft copolymerization.

The polyolefins used in the present invention include the above-mentioned general olefins represented by IC=CH-R (in the formula, R is a hydrocarbon residue having 1 to 12 carbon atoms), specifically ethylene, propylene, butene-1, pentene 11hexene
1,2-methylpentene, heptene-1, octene-1
In addition to α-olefins such as styrene or its derivatives, not only homopolymers but also random copolymers of each other, or the initial olefin alone or copolymerized with a small amount of other olefins, and then two or more olefins are copolymerized. Examples include so-called block copolymers produced by copolymerizing olefins.

Examples of compounds selected from OH-containing compounds and C═C-containing compounds used in the present invention include alcohols, and polyhydric alcohols can be used in addition to monohydric alcohols. Other examples include glycol oligomers. Specifically, water, methanol, ethanol, propatool, butanol, pentanol, hexanol, heptatool, octatool,
Monohydric alcohols having 1 to 12 carbon atoms such as phenol and cresol, polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin, diethylene glycol, triethylene glycol, polyethylene glycol, dipro, pyrene glycol, tripropylene glycol, and polypropylene glycol. Polysiloxanes having an OH group at the end, in addition to glycols such as etherified or esterified glycols such as
Alternatively, polybutadiene and the like are also exemplified. In particular, those having two or more OH groups are preferably used. The C=C compound has 2 to 20 carbon atoms, usually 5 to 20 carbon atoms.
Examples include unsaturated aliphatic hydrocarbons or alicyclic hydrocarbons, such as olefins such as pentene, hexene, heptene, octene, and cyclohexene; Examples include those having two =C bonds, or those in which one or more of the hydrogen atoms of these compounds are substituted with a polar group such as carboxylic acid, carboxylic acid ester, nitro, or sulfonic acid; Those having at least 1 C═C groups are preferably used.

There is no particular limit to the amount of the above compound used, but it is common to use 0.1 to 204 tX per composition, and if it is less than 0.1 wt%, there is no effect of improving physical properties, and 20 w!
If it is 2 or more, the original physical properties of polyolefin cannot be obtained, which is not preferable.

The polyolefins used as necessary in the present invention include the above-mentioned general 2 〇IC=CH-R (wherein P is carbon number
to 12 hydrocarbon residues, specifically ethylene, propylene, butene-1, pentene-1
, hexene-1,2-methylpentene, heptene-1,
In addition to α-olefins such as octene-1, styrene or its derivatives are not only homopolymers but also random copolymers of each other, or the starting olefin alone or copolymerized with a small amount of other olefins, and then 2 Examples include so-called block copolymers produced by copolymerizing more than one type of olefin. Methods for producing these polyolefins are already known, and various brands are available on the market. Further, it can be produced in the same manner as the above-mentioned method for producing a polymer of olefin and alkenylsilane except that alkenylsilane is not used.

In the present invention, there are no particular restrictions on the method of mixing the copolymer of alkenylsilane and olefin, a compound selected from OH-containing compounds and C═C-containing compounds, and optionally with polyolefin that does not contain alkenylsilane. Usual mixing methods can be used, such as mixing with a Henschel mixer or the like and then melt-mixing with an extruder, or melt-mixing with a roll. The ratio of the copolymer of alkenylsilane and olefin used in a mixture depends on the alkenylsilane content in the copolymer, but usually the ratio of the copolymer in the mixture is 0.1w.
It is preferable that the amount of alkenylsilane is 0.005wt% or more in the polyolefin when irradiated with radiation.
From the viewpoint of improving physical properties, it is preferable to have a certain degree of presence.
It is possible to use various known additives during mixing, and there are no particular limitations.

The radiation used in the present invention includes α rays, β rays, and γ rays.
rays, X-rays, neutron beams, etc., and gamma rays and electron beams are particularly preferably used.The irradiation amount is generally about several tens of rad to several tens of Mrad, and the degree of physical property improvement is The dose is irradiated to provide suitable conditions. There are no particular restrictions on the temperature and environment during irradiation, and the irradiation can be carried out at a temperature below the deformation temperature of the polyolefin, which is usually room temperature. It may also be carried out in air or in an inert gas atmosphere such as nitrogen. Radiation irradiation can be performed either before or after molding, but especially after molding in order to increase the irradiation dose and improve physical properties. It is preferable to do so.

〔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 42 and containing 9) cg of steel balls having a diameter of 12a* is prepared. 300 g of magnesium chloride, 60-tetraethoxysilane and 45+d of α, α, α-trichlorotoluene were placed in each pot under a nitrogen atmosphere and ground for 40 hours. 300 g of the thus obtained co-pulverized product was placed in a flask of 52, and titanium tetrachloride 1.52 and 1.5i of toluene were added and heated at 100°C.
The mixture was stirred for 0 minutes, and then the supernatant liquid was removed. 1.51 titanium tetrachloride and 1.51 toluene were added again, and 100
The mixture was stirred at ℃ for 30 minutes, and then the supernatant was removed. Thereafter, the solid content was repeatedly washed with n-hexane to obtain a transition metal catalyst slurry. When a part of the sample was sampled and the titanium content was analyzed, the titanium content was 1.9 wt%.

In a pressure-resistant glass autoclave with an internal volume of 20 lbs., too much toluene was added under a nitrogen atmosphere, and the above transition metal catalyst was placed at 50 g.
Diethylaluminium chloride 0.128d, p-)
Add 0.06 m of methyl ruylate and 0.20 m of triethylaluminum, then add 4.0 m of vinylsilane. After pressurizing Og, propylene was charged to the reactor until the concentration reached 5 kg/cd, 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 38 g of powder.

Intrinsic viscosity (hereinafter referred to as η) measured in a tetralin solution at 135°C
When the melting point and crystallization temperature were measured using a differential thermal analyzer as the maximum peak temperature by raising or lowering the temperature at 10°C/win, the obtained powder had an η of 1.60. , melting point 15β℃, crystallization temperature 119℃
It was a crystalline polypropylene. According to elemental analysis, it contained 1.7 wt% of vinylsilane units.

Silicone oil "5F-8" containing 5 parts of this copolymer, 93 parts of a block copolymer of propylene and ethylene with an ethylene content of 7.5 wtχ, and OB manufactured by Toshi Silicone Co., Ltd.
427' 2 parts, phenolic stabilizer 10/10000
After adding the weight ratio (to polypropylene copolymer) and the weight ratio of calcium stearate to 15/10000 and melt-mixing, it was made into a 1 cm x 5 cm sheet with thicknesses of 2 m- and 1+ mm. Apply an electron beam (750kV) to this sheet for 5 Mrad.
After irradiation, the following physical properties were measured.

Bending rigidity: kg/cd ASTM D747
(23℃) Tensile yield strength: kg/cd AST
M 0638 (23°C) A, Izoft (with notch) Impact strength: kg - cm/cwhASTM D2
56 (23°C, -iooC) The results are shown in Table 1.

Comparative Example 1 The physical properties of a polypropylene block copolymer alone were measured. The results are shown in Table 1.

Comparative Example 2 Same as Example 1 except that the physical properties were measured without irradiating with electron beam.
The results obtained in the same manner as above are shown in Table 1. This result shows that the physical properties are inferior to those irradiated with electron beams.

Comparative example 3 The same procedure as in Example 1 was carried out except that silicone oil was not used.

The results are shown in Table 1.

Example 2 The same procedure as in Example 1 was carried out except that polybutadiene having OHg at the end (B011-1000-2.5, manufactured by Nisseki Kagaku ■) was used instead of silicone oil. The results are shown in Table 1.

Example 3 The same procedure as Example 1 was carried out except that divinylbenzene was used instead of silicone oil. The results are shown in Table 1.

Example 4 Liquid polybutadiene (Nisseki Chemical Co., Ltd.) instead of silicone oil
5 parts of Nippon Polybutadiene) and 9 parts of polypropylene
The same procedure as in Example 1 was carried out except that a copolymer (allylsilane content: 1.8 wtχ) copolymerized with allylsilane instead of vinylsilane was used. The results are shown in Table 1.

Table 1 [Effects of the Invention] The composition of the present invention has an excellent balance of physical properties between rigidity and impact resistance, and is extremely valuable industrially.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. Copolymer of alkenylsilane and olefin and OH-containing
A polyolefin resin composition obtained by irradiating a composition comprising a compound selected from C═C-containing compounds and, if necessary, a polyolefin that does not contain alkenylsilane.