JP3171709B2 - Modification method of polyolefin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for modifying a polyolefin. More specifically, the present invention relates to a method for modifying a polyolefin, comprising treating a polyolefin obtained by copolymerizing a specific monomer with a mixture of an alkylene oxide and a catalyst.

[0002]

2. Description of the Related Art It is widely practiced to graft-polymerize polyolefins for the purpose of improving solvent resistance, improving adhesion to a polymer containing a polar group, and improving gas permeability. . It is easy to mix a monomer containing a polar group and a radical generator with a polyolefin and heat-melt it for graft polymerization, but the purpose is to cause side reactions such as decomposition of the polyolefin or homopolymerization of the monomer. It is difficult to cause only the graft polymerization of, and no compound other than the unsaturated compound can be introduced. On the other hand, it is conceivable to introduce a group which becomes a polymerization starting point into the polyolefin by polymerization and carry out graft polymerization.However, introducing a starting point without lowering the original physical properties of the polyolefin, and furthermore, It is extremely difficult to carry out the graft polymerization by utilizing it effectively, and no effective method has been known.

[0003]

It is desirable to develop an effective graft polymerization method capable of effectively modifying a polyolefin.

[0004]

Means for Solving the Problems The present inventors have solved the above-mentioned problems and have intensively studied a method for easily graft-polymerizing a polyolefin, and completed the present invention.

That is, according to the present invention, a copolymer of an alkenylsilane and an olefin is preliminarily prepared by adding a rhodium salt, a platinum salt and
General formula (Formula 6)

Embedded image (Wherein R ¹ and R ² are the same or different and have 1 to 12 carbon atoms)
A hydride residue, n is an integer of 0 to 3, M is titanium, zirconium
Metal selected from uranium and hafnium. ) Period
A method for modifying a polyolefin, comprising subjecting a catalyst selected from an alkoxy compound of a Group IVB group metal and an alkylene oxide to a contact treatment with a heated mixture.

In the present invention, alkenyl silanes having at least one Si—H bond are preferably used, for example, a compound represented by the following general formula (Chemical Formula 1):

[0007]

Embedded image H ₂ C = CH— (CH ₂ ) _n —SiH _P R _3-P (where n is 0 to 12, p is 1 to 3, and R is a hydrocarbon residue having 1 to 12 carbon atoms). ) Can be exemplified, specifically, vinyl silane,
Examples thereof include allylsilane, butenylsilane, pentenylsilane, and compounds in which H of Si—H bond in some of these monomers is substituted with chloro.

As the olefin, a compound represented by the following general formula (Formula 2):

[0009]

Embedded image H ₂ C = CH—R (where R is hydrogen or a hydrocarbon residue having 1 to 12 carbon atoms)
Can be exemplified, specifically, ethylene, propylene, butene
In addition to α-olefins such as -1, pentene-1, hexene-1, 2-methylpentene, heptene-1, and octene-1, styrene or a derivative thereof is also exemplified.

In the present invention, the copolymer of olefin and alkenylsilane can be produced by a bulk polymerization method or a gas phase polymerization method in addition to a solvent method using an inert solvent. Further, a catalyst comprising a transition metal compound and an organometallic compound is generally used as a catalyst used in the production. A titanium halide is preferably used as the transition metal compound, and an organoaluminum compound is preferably used as the organometallic compound.

Specifically, titanium tetrachloride obtained by reducing titanium tetrachloride with metallic aluminum, hydrogen or organic aluminum is modified with an electron donating compound, an organic aluminum compound, and if necessary, an oxygen-containing organic compound. A catalyst system comprising an electron donating compound such as, or a carrier such as magnesium halide or a transition metal compound catalyst obtained by supporting them with an electron donating compound and supporting a titanium halide, and an organoaluminum compound. A catalyst system consisting of an electron donating compound such as an oxygen-containing organic compound, or a reaction product of magnesium chloride and an alcohol is dissolved in a hydrocarbon solvent, and then treated with a precipitant such as titanium tetrachloride to form a hydrocarbon solvent. Insolubilize and treat with an electron-donating compound such as an ester or ether if necessary. Examples of the catalyst system include a transition metal compound catalyst obtained by a method of treating with a titanium logenide and an organoaluminum compound, and an electron-donating compound such as an oxygen-containing organic compound as required (for example, various types of compounds described in the following literature). Examples are described: Ziegler-Natta Ca
talysts and Polymerization by John Boor Jr (Academi
c Press), Journal of Macromorecular Science Reviews
in MacromolecularChemistry and Physics, C24 (3) 355
-385 (1984) and C25 (1) 578-597 (1985)).

Alternatively, the polymerization can be carried out using a catalyst comprising a transition metal catalyst soluble in a hydrocarbon solvent and an aluminoxane.

As the electron-donating compound, oxygen-containing compounds such as ethers, esters, orthoesters and alkoxysilicon compounds can be preferably exemplified, and alcohols, aldehydes and water can also be used.

As the organoaluminum compound, trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, and alkylaluminum dihalide can be used. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Illustrative examples of the halide include chlorine, bromine and iodine. Aluminoxane, which is an oligomer to a polymer obtained by reacting the above-mentioned organoaluminum with water or water of crystallization, can also be used.

Here, the polymerization ratio of the alkenylsilane to the olefin is usually about 0.01 to 30 mol%, preferably 0.1 to 10 mol%. When it is used in a mixture with another olefin polymer, the content is 1 to 20 mol%.

The molecular weight of the polymer is not particularly limited, and the molecular weight is determined according to the purpose. In terms of physical properties, it is better to have a relatively high molecular weight, but in terms of moldability, if the molecular weight is too high, moldability deteriorates.
Intrinsic viscosity measured in tetralin solution at 135 ° C is 0.5 to 10
It is generally about dl / g , particularly preferably about 1.0 to 5.0 dl / g .

A graft copolymer obtained by graft-polymerizing an alkenylsilane onto a polyolefin (for example, a polyolefin used as a mixture as described below) can also be used for the purpose of the present invention. There is no particular limitation on the method of grafting the alkenyl silane to the method, and the method and conditions used for ordinary graft copolymerization can be used, and the usually used polyolefin and alkenyl silane are radical initiators in the presence of a radical initiator such as peroxide. The graft copolymerization can be easily performed by heating to a temperature equal to or higher than the decomposition temperature.

In the present invention, the above-mentioned copolymer and polyolefin can be mixed and used, if necessary. As the polyolefin to be used, an olefin represented by the above general formula (Formula 2), specifically, ethylene, propylene, butene
-1, pentene-1, hexene-1, 2-methylpentene, heptene-1, octene-1, and other α-olefins, homopolymers of styrene or its derivatives, random copolymers of each other, or first A so-called block copolymer produced by copolymerizing an olefin alone or a small amount of another olefin and then copolymerizing two or more olefins is exemplified.

The methods for producing these polyolefins are already known, and various brands are available on the market. Alternatively, the alkenyl silane can be produced by using the same method as that for producing the copolymer of olefin and alkenyl silane except that alkenyl silane is not used.

The catalyst used in the present invention includes:
Rhodium salts such as rhodium chloride cyclooctadiene complex and triphenyl phosphine complex, platinum iodide, bromoplatinic acid, platinum chloride benzonitrile complex, and titanate ester are represented by the following general formula (Formula 3). alkoxy compound of periodic table group IVB metals indicated are found using.

[0021]

R ¹ _n M (OR ² ) _4-n (wherein R ¹ and R ² are the same or different hydrocarbon residues having 1 to 12 carbon atoms, n is an integer of 0 to 3, and M is titanium , Zirconium, hafnium.)

In the present invention, examples of the alkylene oxide include compounds represented by the following general formula (4) having a three-membered ring ether group in which oxygen is added to a carbon-carbon unsaturated bond.

[0023]

Embedded image (In the formula, R ₁ is hydrogen or a hydrocarbon residue having 1 to 20 carbon atoms.) Specific examples include ethylene oxide, propylene oxide, pentene oxide, hexene oxide, octene oxide, cyclohexene oxide, and styrene oxide.

The present invention is characterized in that the above-mentioned alkylene oxide and the catalyst are mixed in advance by heating. There is no particular limitation on the mixing method, but it is used by dissolving the catalyst in the alkylene oxide and heating, or by dissolving the catalyst in a solvent that dissolves the catalyst, adding the alkylene oxide and heating. The heating temperature is 30 to 150 ° C, preferably 40 to 100 ° C. As the solvent, carbon number 1 ~
Twenty hydrocarbon compounds and halogenated hydrocarbon compounds can be used, and in particular, halogenated hydrocarbon compounds and aromatic hydrocarbon compounds are preferably used. Specifically, benzene, toluene, xylene, ethylbenzene, dichloromethane, chloroform, dichloroethane, trichloroethane, perchloroethane and the like are exemplified. Usually, the alkylene oxide is used so as to have a concentration of 1 to 100%, preferably 5 to 100%. You. Further, the catalyst is mixed so that the concentration of the catalyst in the solution is 0.1 to 10,000 ppm.

In the present invention, an alkenylsilane / olefin copolymer is brought into contact with a solution obtained by heating and mixing the catalyst and the alkylene oxide. At this time, the copolymer of the alkenylsilane and the olefin is usually brought into contact with a catalyst because the crosslinking reaction often proceeds by contact with the catalyst. The amount of the solution obtained by heating and mixing the catalyst and the alkylene oxide may be an amount capable of immersing a copolymer of alkenylsilane and olefin or a molded product. The contact temperature is from room temperature to 150 ° C., but since the catalyst and the alkylene oxide have been heat-treated in advance, it can be carried out at a relatively low temperature of 100 ° C. or less, especially 80 ° C. or less. Examples of the molding method include injection molding, extrusion molding, and press molding. Here, alkylene oxide can be grafted at a high concentration when mixed so that the alkenylsilane concentration in the molded product is 0.01 to 20 mol%, preferably 0.1 to 10 mol%.

[0026]

The present invention will be further described with reference to examples.

Example 1 A vibrating mill equipped with four 4-liter crushing pots containing 9 kg of steel balls having a diameter of 12 mm and having a capacity of 4 liters is 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.
ml was added and crushed for 40 hours. Co-ground product 300 thus obtained
g in a 5 liter flask, 1.5 liters of titanium tetrachloride and 1.5 liters of toluene are added.
The mixture was stirred for minutes, and then the supernatant was removed. Add 1.5 liters of titanium tetrachloride and 1.5 liters of toluene again,
The mixture was stirred at 100 ° C. 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 was sampled and analyzed for titanium content, the titanium content was 1.9 wt%.

In a 5 liter autoclave, under a nitrogen atmosphere, 40 ml of toluene, 100 mg of the above-mentioned transition metal catalyst, 0.128 ml of diethylaluminum chloride, 0.06 ml of methyl p-toluate and 0.20 ml of triethylaluminum were placed, and 1.5 kg of propylene and 80 g of vinylsilane were added. Plus hydrogen
After injection of 0.5N liter, polymerization was carried out at 75 ° C for 2 hours. After the polymerization, unreacted propylene was purged, the powder was taken out, and dried by filtration to obtain 480 g of powder.

The intrinsic viscosity (hereinafter abbreviated as η) was measured with a tetralin solution at 135 ° C., and the temperature was measured at 10 ° C. /
The melting point and crystallization temperature were measured as the maximum peak temperature by raising or lowering the temperature by min. The obtained powder was a crystal having η of 2.35 dl / g , melting point of 156 ° C, and crystallization temperature of 120 ° C. Propylene copolymer.
According to elemental analysis, it contained 1.3 wt% of a vinylsilane unit.

A sheet having a thickness of about 800 μm was prepared by press-molding 100 g of the obtained copolymer at 240 ° C., and stretched 5 × 5 times at 158 ° C. to obtain a stretched film of about 30 μm. On the other hand, 100 mg of cyclooctadiene complex of rhodium chloride
A film of the above copolymer was put into a solution which was dissolved in 1 l of cyclohexene oxide and treated at 80 ° C for 1 hour, and contacted at 30 ° C for 2 hours. Next, the surface of the film was washed with toluene, and the infrared absorption spectrum was measured. As a result, an absorption was observed at about 1100 cm ^-1 and a weight increase of about 3.5 was observed.

Example 2 A propylene copolymer having an allylsilane content of 0.25 wt% was produced by polymerization in the same manner as in Example 1 except that 1 g of allylsilane was used instead of vinylsilane. Η of the copolymer is 1.85 dl
/ G , melting point: 158 ° C., crystallization temperature: 115 ° C., extraction ratio with boiling n-heptane for 6 hours was 96.8%. A molded product was prepared in the same manner as in Example 1 except that 100 g of this powder was used, and the same procedure as in Example 1 was carried out except that a solution obtained by dissolving 30 ml of propylene oxide in 70 ml of toluene was used instead of cyclohexene oxide. It was a weight increase, and absorption was similarly observed at 1100 cm ^-1 in the infrared absorption spectrum.

[0032]

According to the present invention, a graft polymer can be efficiently obtained by carrying out the method of the present invention, which is extremely valuable industrially.

Claims (1)

(57) [Claims] 1. A alkenylsilane advance rhodium salt of a copolymer of an olefin, salts of platinum and the following general formula (Formula 5) embedded image (Wherein R ¹ and R ² are the same or different and have 1 to 12 carbon atoms)
A hydride residue, n is an integer of 0 to 3, M is titanium, zirconium
Metal selected from uranium and hafnium. ) Period
A method for modifying a polyolefin, comprising subjecting a catalyst selected from an alkoxy compound of a Group IVB group metal to a solution obtained by heating and mixing an alkylene oxide with a catalyst.