JP2710797B2 - Method for producing polyolefin resin composition - Google Patents

Description

The present invention relates to a polyolefin resin modified by reacting a copolymer of an alkenylsilane and an olefin with a compound containing a C 又 は C or C ＝ O double bond. It relates to a method for producing the composition.

(Prior art)

Olefin polymers are inexpensive and have a relatively good balance of physical properties, and are therefore used for various purposes. Various improvements have also been made on the random or block copolymerization of olefins for the purpose of improving the balance of physical properties.

[Problems to be solved by the invention]

However, polymers of olefins have characteristics such as polymers containing polar groups by their nature, poor adhesion to metals, etc., and poor adhesion to paints. Attempts have been made to improve the physical properties by introducing a polar group into the polyolefin in order to spread it.

However, in ethylene, it is possible to copolymerize with a monomer containing a polar group by radical polymerization by high-pressure polymerization, but in other polyolefins, when a polar group-containing monomer is radically grafted to the polyolefin, Only the particular method that was said was successful.
The present inventors have previously attempted to modify a polyolefin by treating a copolymer of alkenylsilane and olefin with a compound that reacts with a Si—H bond (Japanese Patent Application No.
-26528, etc.), even if this method reacts under extremely strict conditions, if the obtained composition is used for molding, it may not be able to be molded due to poor flowability or cannot be used by mixing with other olefins. For example, it was difficult to modify polyolefin with good reproducibility.

[Means for solving the problem]

The present inventors have diligently studied a method for producing a modified polyolefin resin composition by solving the above problems, and have reached the present invention.

That is, the present invention provides a copolymer obtained by copolymerizing an olefin and an alkenylsilane using a catalyst comprising a transition metal catalyst and an organometallic compound, and then removing an unreacted monomer. A contact treatment with a compound containing a CＣC or C ＝ O double bond in the presence of a polyolefin resin composition.

In the production of the composition of the present invention, first, a copolymer of alkenylsilane and olefin is produced. The production of the copolymer can be achieved by polymerizing alkenyl silane and olefin in the presence of a known catalyst composed of a transition metal compound and an organometallic compound. The production of alkenylsilane and α-olefin copolymers by polymerization below is disclosed in US Pat. No. 3,223,686.

Here, the alkenyl silane may be vinyl silane, allyl silane, butenyl silane, pentenyl silane, a compound in which one or two Si-H bonds of these monomers are substituted with an alkyl group, or one to three Si-H bonds. And the like.

In the present invention, as the α-olefin, ethylene, propylene, butene-1, pentene-1, hexene-1,
Examples thereof include 2-methylpentene-1 or a mixture thereof, and a mixture thereof with a small amount of an olefin having a larger number of carbon atoms.

As the catalyst comprising a transition metal compound and an organometallic compound used for producing the copolymer according to the present invention, not only those described in the above-mentioned U.S. Patents, but also many α-olefins whose properties have been improved since then disclosed Can be used without any trouble.

The polymerization method is generally a solvent method using an inert solvent, but a bulk polymerization method and a gas phase polymerization method can also be employed. Here, as the catalyst comprising the transition metal compound and the organometallic compound, titanium halide or vanadium halide is preferably used as the transition metal compound, and an organoaluminum compound is preferably used as the organometallic compound.
For example, electron donation of titanium trichloride obtained by reducing titanium tetrachloride with metallic aluminum, hydrogen or organoaluminum, or those obtained by modifying them with an electron donating compound, an organoaluminum compound, and optionally an oxygen-containing organic compound. Catalyst system composed of a volatile compound, a vanadium halide, or a catalyst system composed of vanadium oxyhalide and organoaluminum, or a carrier such as a magnesium halide, or a titanium halide or a halogen treated with an electron-donating compound. A catalyst system composed of a transition metal compound catalyst obtained by carrying vanadium halide and vanadium oxyhalide and an electron donating compound such as an organic aluminum compound and, if necessary, an oxygen-containing organic compound, or a reaction product of magnesium chloride and an alcohol. In hydrogen solvent And then treated with a precipitant such as titanium tetrachloride to make it insoluble in the hydrocarbon solution, treated with an electron-donating compound such as an ester or ether if necessary, and then treated with a titanium halide. Examples include a catalyst system comprising the obtained transition metal compound catalyst, an organic aluminum compound, and, if necessary, an electron donating compound such as an oxygen-containing organic compound (for example, various examples are described in the following literature. Ziegler −Natta Catal
ysts and Polmerization by John Boor Jr (Academic P
ress), Journal of Macromorecular Sience Reviews i
n Macromolecular Chemistry and Physics, C24 (3) 35
5-385 (1984) and C25 (1) 578-597 (1985)).

Here, as the electron donating compound, oxygen-containing compounds such as ether, ester, orthoester and alkoxysilicon compound can be preferably exemplified, and alcohol, aldehyde, water and the like can also be used.

Examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, and alkylaluminum dihalide.Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Examples of the halide include chlorine, bromine and iodine.

Here, the polymerization ratio of the alkenyl silane and the α-olefin is not particularly limited, but is usually alkenyl silane.
It is preferably about 30 mol% to 0.01 mol% for the catalytic activity during polymerization, or for the reaction between the copolymer and the unsaturated compound and its utilization, particularly about 10 mol% to 0.05 mol%. Is preferred.

The molecular weight of the polymer is not particularly limited, but is preferably extremely high, for example, not more than 10 as the intrinsic viscosity measured with a tetralin solution at 135 ° C., and usually about 0.1 to 5 as the intrinsic viscosity.

In the present invention, after the polymerization reaction, unreacted monomers (olefin and alkenylsilane) are removed and then subjected to a contact treatment with a compound containing a C ＝ C or C ＝ O double bond in the presence of a catalyst. . As the compound containing a C 化合物 C or C ＝ O double bond, the group bonded to C 基 C or C ＝ O is not particularly limited, and examples thereof include various compounds known as vinyl compounds and vinylidene compounds, and aldehydes. And various compounds known as ketones.

Vinyl compounds, as the vinylidene compound, directly to the double bond, or - (CH ₂₎ n _- carboxylic acid across the group,
Carboxylic acid ester, nitro, those containing a polar group such as sulfonic acid, or a general polar group-containing vinyl compound in which the above-mentioned various polar groups are bonded to a phenyl group, polymethylene oxide, So-called macromers in which polyalkylene oxides such as polyethylene oxide and polyprolene oxide, and silicones having a -SiO- bond are directly or indirectly bonded to a vinyl group can also be used.

Examples of the C-O-containing compound include aldehydes and ketones. Specific examples include aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, and benzaldehyde, acetone, methyl ethyl ketone, and methyl propyl. Ketone, diethyl ketone, 2-hexanone, 3-hexanone, cyclohexanone, biacetyl,
Examples include acetophenone, benzophenone, and the like, and those in which some of the hydrogens are substituted with the above polar groups.

In contacting with the above compound, a known hydrosilylation catalyst, for example, a metal catalyst of Group VIII of the periodic table such as a triphenylphosphine complex of rhodium, chloroplatinic acid or a salt thereof (organic silicon compound chemistry, Makoto Kumada et al. It is necessary to have a radical initiator such as an azo compound and an amine such as triethylamine. Since the hydrosilylation reaction is relatively fast, the reaction proceeds sufficiently at a temperature around room temperature, but the reaction rate or side reaction can be controlled by cooling or heating as necessary, for example, by avoiding a crosslinking reaction.

In the reaction, when the polymerization of olefin and alkenylsilane is performed by a solvent polymerization method, the polymerization solvent may be used as it is as a solvent for the reaction, but when the polymerization is performed by a bulk polymerization method or a gas phase polymerization method, C When the compound containing a ＣC or C ＝ O double bond is in a liquid state, the compound having C そ の ま ま C or C
The method is carried out by dispersing a copolymer of alkenylsilane and olefin (hereinafter simply referred to as a copolymer) in a compound containing a ＯO double bond, or by further using a hydrocarbon as a diluting solvent. Is common, but when the compound containing a C ＝ C or C ＝ O double bond is a solid, it is dissolved in a solvent that dissolves the compound containing a C ＝ C or C ＝ O double bond, The contact treatment with the copolymer is performed in the solution.

The unreacted compound containing a C ＝ C or C ＝ O double bond after the contact treatment is usually removed by filtration, evaporation removal, washing or the like, but depending on the use of the composition, the unreacted compound may be removed. It is not necessary to completely remove the compound, and in some cases, some unreacted compounds may be left as they are to form a composition.

〔Example〕

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

Example 1 A vibration mill equipped with four crushing pots having an internal volume of 4 and containing 9 kg of steel balls having a diameter of 12 mm was prepared. Under a nitrogen atmosphere, 300 g of magnesium chloride, 60 ml of tetraethoxysilane, and 45 ml of α, α, α-trichlorotoluene were added to each pot, followed by addition of 40 ml.
Crushed for hours. 300 g of the co-ground product thus obtained was placed in a flask of 5, and after 1.5 parts of titanium tetrachloride and 1.5 parts of toluene were added, the mixture was stirred at 100 ° C. for 30 minutes, and then the supernatant was removed. Add 1.5,
The mixture was stirred at 100 ° C. for 30 minutes, the supernatant was again removed, and the obtained solid was repeatedly washed with n-hexane to obtain a transition metal catalyst slurry. When a part was sampled and the titanium content was analyzed, it was 1.9 wt%.

In a pressure-resistant glass autoclave having an internal volume of 200 ml, under a nitrogen atmosphere, 40 ml of toluene, 20 mg of the above transition metal catalyst, 0.128 ml of diethylaluminum chloride, and methyl p-toluate
0.06 ml and 0.20 ml of triethylaluminum were added, then 0.5 g of vinylsilane was injected, followed by propylene.
g and polymerized at 70 ° C. for 2 hours. Next, unreacted propylene and vinylsilane were purged, and nitrogen was further introduced to completely purge unreacted monomers. When a part of the powder was taken out and the physical properties were measured, the powder 135
The intrinsic viscosity (hereinafter abbreviated as η) measured with a tetralin solution at ℃ is 1.75, the vinylsilane content is 0.3 wt%,
Strong absorption was observed at 2150 cm ^-1 in the infrared absorption spectrum. Then, 5 ml of polyethylene glycol monomethacrylate (Blenmer PEG300, manufactured by NOF Corporation) and 0.05 g of triphenylphosphine complex of rhodium chloride were added to the mixture.
Stirred at C for 2 hours. After the reaction, the slurry was taken out and filtered, and the polymer was thoroughly washed with toluene. According to infrared absorption spectrum absorption of ethylene glycol was observed at 1100 cm ^-1, absorption of Si-H of 2150 cm ^-1 was reduced. The ratio of polypropylene and polyethylene glycol monomethacrylate calculated by elemental analysis was 1: 0.18. This polymer can be thermoformed by hot pressing at 230 ° C., η1.62 separately obtained by polymerizing propylene with the above-mentioned catalyst, and boiling with n-heptane using a Soxhlet extractor.
Proportion of extraction residue 96.8% polypropylene extracted for time
When mixed at a ratio of 10 to 100 and heated and formed, a uniform sheet was formed. This sheet did not show unevenness even when stretched at 150 ° C.

Comparative Example 1 A copolymer of propylene and vinylsilane was taken out and dried, and 10 g of a polymer containing 0.3 wt% of vinylsilane was added to 10 g of the copolymer.
To the mixture were added 5 ml of toluene, 5 ml of polyethylene glycol monomethacrylate, and 0.05 g of a triphenylphosphine complex of rhodium chloride, followed by stirring at 50 ° C. for 2 hours. When analyzed at the same time, the ratio of polypropylene to polyethylene glycol monomethacrylate was 1: 0.14, but a uniform sheet could not be obtained by hot pressing at 230 ° C. When the sheet was stretched, the sheet was cut.

Example 2 Using allyl silane instead of vinyl silane and methacrylate of polysilicon (AK-5 manufactured by Toa Gosei Chemical Co., Ltd.) instead of polyethylene glycol monomethacrylate, a tetrahydrofuran solution of chloroplatinic acid (0.05 g as chloroplatinic acid) was used. Other than that used, it carried out similarly to Example 1, the ratio of the macromer of polysilicon was 0.12, and the obtained composition was shapeable like Example 1.

Example 3 An acetophenone was used in place of polyethylene glycol monomethacrylate, and the reaction temperature was changed to 50 ° C., except that the addition amount of acetophenone was 0.05.
And the resulting composition was moldable.

Comparative Example 2 The procedure of Example 3 was repeated except that the copolymer once taken out of the system was used in the same manner as in Comparative Example 1, but the resulting composition could not be thermoformed.

〔The invention's effect〕

By carrying out the method of the present invention, a composition containing a polar group is easily obtained and is extremely valuable industrially.

Claims (1)

(57) [Claims] An olefin and an alkenylsilane are copolymerized using a catalyst comprising a transition metal catalyst and an organometallic compound,
Then, a copolymer obtained by removing unreacted monomers is subjected to a contact treatment with a compound containing a C ＝ C or C ＝ O double bond in the presence of a hydrosilylation catalyst. A method for producing a resin composition.