JP2710804B2 - Method for producing polyolefin resin molded article - 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 molded article 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 alkenyl silane using a catalyst comprising a transition metal catalyst component and an organometallic compound, and then treating the copolymer under conditions in which a silanol bond is generated after molding or at the time of molding. The molded product
After heat contact treatment with a hydrocarbon compound having 5 to 20 carbon atoms,
Either the molded article subjected to the heat contact treatment is contact-treated with a compound having an alcohol or a silanol group in the presence of a base, or the molded article which has been treated and crosslinked under the conditions where the silanol bond is generated, has 5 carbon atoms in the presence of the base. ~ 20 hydrocarbon compounds,
And heating and contacting with a compound having an alcohol or a silanol group.

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, electrons 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 and an organoaluminum compound, and optionally an oxygen-containing organic compound A catalyst system comprising a donating compound, a vanadium halide, or a catalyst system comprising vanadium oxyhalide and organoaluminum, or a carrier such as magnesium halide, or a titanium halide obtained by treating them with an electron donating compound, or 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 The hydrocarbon solvent Dissolved in, then insolubilized in a hydrocarbon solvent by treatment with precipitants such as titanium tetrachloride, optionally ester,
A catalyst comprising a transition metal compound catalyst component obtained by a treatment with an electron-donating compound such as ether and then a titanium halide, and an electron-donating compound such as an organic aluminum compound and, if necessary, an oxygen-containing organic compound. (For example, various examples are described in the following literature. Ziegler-Natta Catalysts and P
olymerization by John Boor Jr (Academic Press), J
ournal of Macromorecular Sience Reviews in Macromo
lecular Chemistry and Physics, C24 (3) 355-385
(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.
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 10 or more, more preferably the intrinsic viscosity is about 0.1 to 4.

In the present invention, the copolymer obtained by the above reaction is
It is heated and melted together with a usual additive such as an antioxidant and, if necessary, a polyolefin containing no alkenylsilane, and molded. The molding method is not particularly limited, and a molded product having a desired shape is obtained by ordinary extrusion molding, injection molding, or the like. At this time, it is possible to crosslink at the same time as molding in the presence of water, alcohol, oxygen and the like. In addition, a known catalyst such as an inorganic or organic base or an organic acid salt used for forming a silanol bond may be mixed and molded, followed by heat treatment with water, alcohol, or the like, for crosslinking. Here, the degree of crosslinking is not particularly limited, and may be determined according to the purpose of use of the molded product.
H-bonding should not be lost. Usually, the degree of crosslinking is about 20 to 100% of the extraction residue when extracted with boiling xylene for 6 hours.

In the present invention, the molded product obtained by the above operation is then subjected to heat contact treatment with a hydrocarbon compound having 5 to 20 carbon atoms. The degree of heating is preferably such that the surface slightly swells without deformation of the molded product. When the degree of crosslinking is relatively high, it is preferable to perform the reaction at a relatively high temperature, and when the degree of crosslinking is not so high, it is preferable to perform the reaction at a relatively low temperature.
Processed by heating to ~ 180 ° C.

As the hydrocarbon compound having 5 to 20 carbon atoms, aliphatic, alicyclic, or aromatic hydrocarbons can be used, and halogenated hydrocarbons in which some to all of these hydrogens are substituted with halogen atoms can be used. Hydrogen compounds are also preferably used.

In the heat contact treatment, a compound having an alcohol or a silanol group and a base are allowed to coexist, or after the heat contact treatment, the mixture is cooled and then contacted with a compound having an alcohol or a silanol group and a base. It is general that the temperature at the time of cooling is usually about 100 ° C to 0 ° C. The amount ratio of the compound having an alcohol or silanol group and the base to be used may be determined according to the purpose and is not particularly limited. 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. It is also possible to use a polymer such as glycol, a compound in which an OH group is bonded to polybutadiene, or a compound in which an OH group is bonded to silicone.

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-milled material thus obtained was placed in a flask of 5 and toluene 2.0 was added thereto, and the mixture was treated at 115 ° C. for 2 hours. Then, toluene was extracted at 90 ° C. and further washed 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.
Add 50 ml, then add 30 g of vinylsilane to 1200 g of propylene
g of hydrogen and 1N of hydrogen, and polymerized 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 1.95, the vinylsilane content was 1.1 wt%, and strong absorption was observed at 2150 cm ^-1 in the infrared absorption spectrum. After mixing 10 g of this polymer and 0.01 g of a phenolic antioxidant, the mixture was heated to 230 ° C. and pressurized in an oxygen atmosphere to form a sheet having a thickness of 1 mm. A part of this sheet is made with boiling xylene 6
Extraction for a time revealed an insoluble content of 85%. Also, a part of the sheet (2 g) was placed in a 200 ml flask, 100 ml of toluene was added, and the mixture was heated at 100 ° C. under a nitrogen atmosphere for 10 minutes.
Polyethylene glycol (molecular weight 600) after cooling to ℃
Was added and stirred, then 0.1 g of potassium t-butoxide was added, and the mixture was stirred at 30 ° C for 8 hours. After the reaction, the sheet was taken out, washed well with toluene, and dried to obtain a sheet-shaped composition. Absorption of ethylene glycol according to the infrared absorption spectrum was observed at 1100 cm ^-1, of 2150 cm ^-1 Si-
H absorption was reduced. The added amount of polyethylene glycol estimated from the change in weight was 1: 0.02.

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 0.2 g of sodium methoxide was used instead of 0.1 g of butoxide. The added amount calculated from the weight increase was 1: 0.01.

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. The addition amount determined from the weight increase was 1: 0.02. Was.

〔The invention's effect〕

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

Claims (1)

(57) [Claims] 1. A copolymer obtained by copolymerizing an olefin and an alkenyl silane using a catalyst comprising a transition metal catalyst component and an organometallic compound, is treated and crosslinked after molding or under conditions in which a silanol bond is generated during molding. After the molded article is subjected to heat contact treatment with a hydrocarbon compound having 5 to 20 carbon atoms, the molded article subjected to the heat contact treatment is contacted with a compound having an alcohol or a silanol group in the presence of a base, or the silanol bond is formed. A polyolefin resin molded article characterized in that it is subjected to heat contact treatment with a hydrocarbon compound having 5 to 20 carbon atoms and a compound having an alcohol or a silanol group in the presence of a base and a cross-linked molded article treated under the resulting conditions. Production method.