JP2710806B2 - Method for producing polyolefin resin composition - Google Patents

Description

The present invention relates to a method for producing a modified polyolefin resin composition by reacting a copolymer of alkenylsilane and olefin with a compound having an alcohol or silanol group. .

[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, olefin polymers are characterized by poor adhesion to polymers containing polar groups, metals, etc. due to their essence, and poor adhesion to paints, further expanding the applications of polyolefins. Therefore, attempts have been made to improve physical properties by introducing a polar group into polyolefin.

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), in this method, if an attempt is made to increase the amount of a compound that reacts with a Si-H bond,
When trying to mold the resulting composition, it was difficult to modify the polyolefin with good reproducibility, for example, it could not be molded due to poor flowability or could not be used by mixing with other olefins.

[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 dissolves a copolymer obtained by copolymerizing an olefin and an alkenylsilane using a catalyst comprising a transition metal catalyst component and an organometallic compound under heating in a solvent that dissolves the copolymer, Next, a method for producing a polyolefin resin composition, comprising subjecting the copolymer to a compound having an alcohol or a silanol group at a low temperature at which the copolymer is dissolved, in the presence of a base, in a contact treatment.

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.

In addition to the solvent method using an inert solvent as the polymerization method,
A bulk polymerization method and a gas phase polymerization method can also be adopted. 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 metal aluminum, hydrogen, or organic aluminum, or those obtained by modifying them with an electron donating compound, an organic aluminum compound, and, if necessary, an oxygen-containing organic compound. Catalyst system consisting of a volatile compound, vanadium halide, or a catalyst system consisting of vanadium oxyhalide and organoaluminum, or a carrier such as magnesium halide, or a titanium halide, Transition metal compound obtained by carrying vanadium halide and vanadium oxyhalide Catalyst system consisting of catalyst component and electron donating compound such as organoaluminum compound, oxygen-containing organic compound if necessary, or reaction product of magnesium chloride and alcohol In a hydrocarbon solvent By dissolving and then insoluble in a hydrocarbon solvent by treating with a precipitant such as titanium tetrachloride, treating with an electron-donating compound such as an ester or ether if necessary, and then treating with a titanium halide. Examples of the catalyst system include an obtained transition metal compound catalyst component, 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 Catalysts and Pol
ymerization by John Boor Jr (Academic Press), Jou
rnal of Macromorecular Sience Reviews in Macromole
cular Chemistry and Physics, C24 (3) 355-385 (19
84), 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.
About 30 mol% to about 0.01 mol% is preferable for the catalytic activity at the time of polymerization, or for the reaction of the copolymer with a compound having an alcohol or a silanol group and its utilization,
In particular, it is preferably about 10 mol% to 0.05 mol%.

The molecular weight of the polymer is not particularly limited, but it is preferable that the molecular weight be extremely high, for example, the intrinsic viscosity measured with a tetralin solution at 135 ° C. does not become 3 or more, and more preferably the intrinsic viscosity is about 0.1 to 2.

In the present invention, the copolymer obtained by the above reaction is
First dissolved in a solvent, as the solvent used here,
Preferably, a hydrocarbon compound having 6 to 12 carbon atoms, or a halogenated hydrocarbon compound in which a part to all of the hydrogen atoms are substituted with a halogen atom is preferably used.
It is dissolved by heating to 200C to 200C.

The solution is cooled after or prior to the addition of a compound having an alcohol or a silanol group described below. The temperature after cooling is usually preferably 100 ° C. or lower from the viewpoint of preventing the cross-linking reaction from proceeding by a side reaction. Next, after the addition of the compound containing an OH group, the reaction is carried out by adding a base in a cooled state.
Hereinafter, the reaction is carried out by keeping the temperature usually at -70 ° C or higher, generally at 0 ° C to 80 ° C. Here, as the compound having an alcohol or a silanol group, polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin, polyethylene glycol, and polypropylene are used in addition to ordinary monohydric alcohols such as methanol and ethanol from the viewpoint of improving the physical properties of polyolefin. Polymers such as glycols,
Further, a compound in which an OH group is bonded to polybutadiene or a compound in which an OH group is bonded to silicone can be used.

In contacting with the above compound, known bases used for reacting a compound having an alcohol or silanol group with a compound having a Si—H group are used. As the base, preferably a metal alcoholate, particularly an alkali metal alcoholate, is used.
Organic bases such as alkylamines can also be used. Where OH
Since the reaction between the group and the Si-H group is relatively fast, the reaction proceeds sufficiently at a temperature near normal temperature, but the reaction rate or side reaction can be controlled by cooling or heating as necessary.

The unreacted alcohol or compound having a silanol group after the contact treatment is usually removed by filtration, evaporation removal, washing, or the like, but it is not necessary to completely remove the unreacted compound depending on the use of the composition. 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, 200 g of magnesium chloride, 75 ml of di-n-butyl phthalate, and 40 ml of titanium tetrachloride were added to each pot and pulverized for 40 hours. 100 g of the co-ground product thus obtained was placed in a flask of 5 and treated with toluene 2.0 at 115 ° C. for 2 hours, followed by extracting toluene at 90 ° C. and further washing once with 4 heptane seven times to obtain a titanium catalyst component. Analysis showed that it contained 1.9 wt% titanium.

Toluene in an autoclave with an internal volume of 5 under a nitrogen atmosphere
40 ml, the transition metal catalyst component 50 mg, methylcyclohexyldimethoxysilane 0.05 ml, triethylaluminum 0.
50 ml was added, then 30 g of vinylsilane and 120 g of propylene
0 g and 4N of hydrogen were charged, and polymerization was carried out at 70 ° C. for 4 hours. Then
After unreacted propylene and vinylsilane were purged, the powder was taken out, dried, weighed and measured for physical properties. As a result, 480 g of the powder was obtained. Do)
Was 1.35, the vinylsilane content was 1.1 wt%, and strong absorption was observed at 2150 cm ^-1 in the infrared absorption spectrum. 10 g of this polymer was placed in a 200 ml flask, 100 ml of toluene was added, and the mixture was heated and dissolved at 115 ° C. under a nitrogen atmosphere. Then 30 ° C
After cooling to 50m polyethylene glycol (molecular weight 600)
l and stirred, and then potassium-t-butoxide was added.
0.1 g was added and the mixture was stirred at 30 ° C. for 6 hours. After the reaction, the slurry was taken out and filtered, and the polymer was thoroughly washed with toluene. According to the infrared absorption spectrum, the absorption of ethylene glycol was 11
It was observed at 00 cm ^-1 and the absorption of Si-H at 2150 cm ^-1 was reduced. The ratio of polypropylene and polyethylene glycol calculated from the increase in weight was 1: 0.09. This polymer can be thermoformed by hot pressing at 230 ° C., and η obtained by polymerizing propylene with the above catalyst separately.
1.62, polypropylene 10% having an extraction residue ratio of 96.8% extracted with boiling n-heptane for 6 hours using a Soxhlet extractor.
When the mixture was mixed at a ratio of 0 to 10 and heated and formed, a uniform sheet was formed. This sheet did not show unevenness even when stretched at 150 ° C.

Comparative Example 1 Using the copolymer obtained in Example 1, 10 g of the polymer was added without dissolving in advance to 100 ml of toluene, 50 ml of polyethylene glycol and 0.1 g of potassium-t-butoxide, and the mixture was stirred at 100 ° C. for 3 hours. When analyzed similarly, the ratio of polypropylene and polyethylene glycol was 1: 0.05,
Hot pressing at 230 ° C. did not yield a uniform sheet. When the reaction was carried out at 30 ° C. for 6 hours, the weight did not increase at all, and the Si—H group hardly decreased.

Example 2 Potassium-t- was used by using allylsilane instead of vinylsilane and using an OH-containing compound of polybutadiene (BOH-100-2.5 manufactured by Nisseki Chemical Co., Ltd.) instead of polyethylene glycol.
Example 1 was repeated except that 0.1 g of sodium methoxide was used instead of 0.1 g of butoxide. The ratio of polypropylene to polybutadiene calculated from the weight increase was 1: 0.07, and the obtained composition was moldable in the same manner as in Example 1.

Example 3 The procedure of Example 1 was repeated, except that OH-containing silicone (Silicone Oil SF-8427, manufactured by Toray Silicone Co., Ltd.) was used instead of polyethylene glycol. 0.06, and the composition obtained was moldable.

[Effects of the Invention] By carrying out the method of the present invention, a composition containing a polar group is easily obtained, which is extremely valuable industrially.

Claims (1)

(57) [Claims] 1. A copolymer obtained by copolymerizing an olefin and an alkenylsilane using a catalyst comprising a transition metal catalyst component and an organometallic compound is dissolved in a solvent which dissolves the copolymer under heating, and then dissolved. A method for producing a polyolefin resin composition, comprising contacting the copolymer with a compound having an alcohol or silanol group at a temperature lower than the temperature at which the copolymer is dissolved in the presence of a base.