JP3485363B2 - Modification method of polyolefin - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention 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 catalyst and a hydrazine compound. 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. Has been done. 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 graft polymerization. In response to this, it is conceivable to introduce a group which easily reacts with polyolefin by polymerization, and then react.However, it is effective to introduce a starting point without deteriorating the original physical properties of polyolefin, and furthermore, to effectively use it. It is extremely difficult to introduce a polar group using the method, and no effective method has been known. [0003] On the other hand, it is desired to develop a method capable of effectively modifying polyolefin. Means for Solving the Problems The present inventors have solved the above-mentioned problems, and have earnestly studied a method for simply modifying and modifying a polyolefin to complete the present invention. That is, the present invention is a method for modifying a polyolefin, comprising subjecting a copolymer of an alkenylsilane and an olefin to a contact treatment with a catalyst and a hydrazine compound. [0006] What As the alkenylsilane in the present invention having at least one Si-H bonds is preferably used, for example, compounds represented by the following general formula (1), [0007] [Formula 1] H ₂ C = _{CH- (CH 2) n -SiH p} R 3-p ( wherein n is 0 to 12, p is 1 to 3, R a hydrocarbon residue of 12 1 carbon atoms.). examples of specific Is 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. [0008] Compounds represented by the following general formula The olefin (Formula 2), [0009] [Chemical Formula 2] H ₂ C = CH-R (wherein R is hydrogen or a hydrocarbon residue having a carbon number of 1 to 12 .)
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 alkenylsilane and olefin can be produced by a bulk polymerization method or a gas phase polymerization method in addition to a solvent method using an inert solvent. In addition, 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 transition metal compound catalyst obtained by supporting a titanium halide on a catalyst system comprising an electron donating compound such as a magnesium halide or a carrier obtained by treating them with an electron donating compound, and an organoaluminum compound. A catalyst system comprising 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 treatment with titanium logenide and an organoaluminum compound, and an electron-donating compound such as an oxygen-containing organic compound, if necessary (for example, the following literature describes various types of catalysts). Examples are described: Ziegler-Natta Ca
talysts and Polymerization by John Boor Jr (Academi
c Press), Journal of Macromolecular 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. In addition, alcohols, aldehydes, water and the like 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 organic aluminum with water or water of crystallization, can also be used. Here, the polymerization ratio of the alkenylsilane to the olefin is usually about 0.001 to 30 mol%, preferably 0.005 to 10 mol%. When used in combination with another olefin polymer, 0.01 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 0.2 to 10
In general, it is generally preferably about 0.5 to 5.0. 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 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 alkenyl silane-olefin copolymer except that alkenyl silane is not used. In the present invention, examples of the hydrazine compound include compounds represented by the following general formula (Formula 3). The amount of the hydrazine compound to be used is generally 0.01 to 1000 equivalent times the alkenylsilane in the copolymer of the olefin and the alkenylsilane. Without, 100
Use beyond 0 equivalents is not particularly effective and not economical. Embedded image (Wherein, R is hydrogen or a hydrocarbon residue having 1 to 12 carbon atoms). In the present invention, as the catalyst, rhodium salts such as rhodium chloride cyclooctadiene complex and triphenylphosphine complex can be preferably used, and further, platinum salts, chloroplatinic acid, platinum chloride benzonitrile complexes, or It is preferable to use an alkoxy compound of a Group IVB metal represented by the following general formula (Chemical Formula 4) alone or in combination with an organometallic compound, such as a titanate ester. 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, M is a metal selected from titanium, zirconium and hafnium.) In the present invention, the method of contacting the alkenylsilane-olefin copolymer with a catalyst and a hydrazine compound includes dissolving the catalyst and the hydrazine compound in a powder, pellet or molded product of the alkenylsilane-olefin copolymer. A method of contacting a hydrazine compound with a premixed alkenylsilane / olefin copolymer and catalyst, and a method of heating and melting a alkenylsilane / olefin copolymer and catalyst in advance. And a method of contacting the hydrazine compound with the molded product. Here, the amount of the catalyst used is 0.0
Generally, it is 1 to 1000 ppm. There is no particular limitation on the method of molding a molded article used in the case of treating with a solution of a catalyst and a hydrazine compound, as long as a copolymer of alkenylsilane and olefin is used. Extrusion molding method by heating and melting the copolymer alone, or other polyolefins of the copolymer, and further fillers and the like, together with a phenolic stabilizer and the like.
It can be obtained by molding by injection molding, press molding, blow molding, or the like. As the filler, a metal hydroxide, oxide, nitride, carbide, or the like, which has a large reinforcing effect, such as an acicular, scaly, or fibrous material, is preferably used. Specifically, talc,
Kaolin, mica, calcium carbonate, calcium silicate,
Calcium sulfate, calcium sulfite, barium titanate and the like can be used. There is no particular limitation on the method of molding the alkenylsilane / olefin copolymer and the catalyst by heating and melting and mixing them, and examples thereof include injection molding, extrusion molding, press molding, and blow molding. After mixing the olefin copolymer and the catalyst well at a low temperature, heat-melt it by press molding to mold it, or heat-melt the catalyst to a polyolefin containing no alkenylsilane and mix it to make a master pellet of the catalyst. It is also possible to perform injection molding by mixing pellets obtained by heating and melting and mixing an alkenylsilane-olefin copolymer and a polyolefin or an additive other than a catalyst, such as an antioxidant. In molding, various fillers can be mixed, and the same ones as described above can be used. Here, the alkenylsilane in the molded product is generally mixed so as to have a concentration of 0.001 to 20 mol%, preferably 0.01 to 10 mol%. The molding temperature is a temperature at which the polymer can be melt-molded, and is about 150 to 300 ° C. The contact temperature when contacting the hydrazine compound or the mixture of the hydrazine compound and the catalyst is from room temperature to 150 ° C. When contacting the molded article, it is effective to perform as high temperature as possible unless the molded article is deformed. The same applies to contact in the powder state, but in this case, even if the powder is deformed, there is no problem depending on the case, and the preferable range of the contact temperature is widened. The contact time is several minutes to several hours. The hydrazine compound is used in a solution state,
As the solvent used here, a hydrocarbon compound having 1 to 20 carbon atoms is generally used, but a hydrazine compound can be used as the solvent. Specifically, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatic hydrocarbon compounds such as benzene, toluene, xylene, ethylbenzene, and cumene can be used, and the hydrazine compound usually has a concentration of 100 to 1%. It is generally used by dissolving in water. The present invention will be further described with reference to examples. Example 1 A vibrating mill equipped with four 4-liter inner crushing pots containing 9 kg of steel balls having a diameter of 12 mm was prepared. 300 g of magnesium chloride, 60 ml of tetraethoxysilane and α, α, α-trichlorotoluene 45
ml was added and crushed for 40 hours. Co-ground product 300 thus obtained
g in a 5 liter flask, and add 1.5 liters of titanium tetrachloride and 1.5 liters of toluene.
Stirring was carried out for a minute 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 the titanium content was analyzed, 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 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 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 using a tetralin solution at 135 ° C., and the temperature was measured at 10 ° C. /
When the melting point and crystallization temperature were measured as the maximum peak temperature by raising or lowering the temperature at min, the obtained powder had η of 2.35, a melting point of 156 ° C, and a crystallization temperature of 120 ° C.
Is a crystalline propylene copolymer. According to elemental analysis, it contained 1.3 wt% of a vinylsilane unit. 10 g of the obtained copolymer was dispersed in a solution of 100 mg of dimethyl titanocene and 20 g of methyl hydrazine in 50 ml of toluene, and subjected to a contact treatment at 30 ° C. for 2 hours. After the reaction, the mixture was filtered, and the copolymer powder was repeatedly washed with toluene and then dried. After heating the obtained powder at 260 ° C., it was pressed to form a sheet having a thickness of 0.1 mm, and the infrared absorption spectrum was measured.The absorption attributed to the Si-H bond of about 2160 cm ⁻¹ disappeared, and the The absorption of NH 3 bond was observed at ^-1 and it was confirmed that it was modified with hydrazine. The weight increase was 0.15%. 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 18 g of allylsilane was used instead of vinylsilane. The η of the copolymer was 1.85, the melting point was 158 ° C., the crystallization temperature was 115 ° C., and the ratio of extraction residue when extracted with boiling n-heptane for 6 hours was 96.8%.
A sheet was prepared in the same manner as in Example 1 except that 10 g of this powder was used, and the infrared absorption spectrum was measured.
The absorption attributed to the Si-H bond of cm ^-1 disappears, and about 3150 cm ^-1
The absorption of an NH 2 bond was observed, and it was confirmed that the compound was modified with hydrazine. Example 3 Example 3 was repeated except that hydrazine was used as the hydrazine compound.
1 and was measured infrared absorption spectrum into a sheet in the same manner, the absorption disappeared attributed to Si-H bonds of about 2160 cm ^-1, are observed absorption of NH bond at about 3150 cm ^-1,
It was confirmed that it was modified with hydrazine. The weight increase was 0.18%. According to the present invention, the polyolefin can be efficiently modified by carrying out the method of the present invention, which is extremely valuable industrially.

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Claims (1)

(57) [Claims 1] A <br/> Rukenirushiran and copolymers of olefins having at least one Si-H bond the contact treatment with the catalyst and hydrazine compounds, olefin copolymer of
Reacting a hydrazine compound with a Si-H group to form a hydrazine
A method for modifying a polyolefin, which comprises introducing a group .