JP3352524B2 - Method for modifying polyolefin molded article - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for modifying a polyolefin molded product. More specifically, the present invention relates to a method for modifying a polyolefin molded product, which comprises treating a molded product composed of a polyolefin copolymerized with a specific monomer with an acetylene derivative.

[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.

[0005] Rhodium or platinum salts or the general formula
Titanium, zirconium, hafnium represented by (Chem. 4)
A method for modifying a polyolefin molded article, comprising subjecting an acetylene derivative to contact with a molded article comprising an alkenylsilane-olefin copolymer containing a catalyst selected from the above-mentioned alkoxy compounds .

## STR4 ## R ¹ _n M (OR ^Two ) _4-n (Where R ¹ , R ^Two Is the same
Different hydrocarbon residues having 1 to 12 carbon atoms, n is an integer of 0 to 3
The number and M are selected from titanium, zirconium and hafnium
Metal)

In the present invention, alkenyl silanes containing at least one Si—H bond are preferably used, for example, a compound represented by the following general formula (Formula 5 ):

[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)

The olefin is represented by the following general formula (formula
6 ) a compound represented by the formula:

[0009]

Embedded image H ₂ C ＝ CH—R (wherein R is hydrogen or a hydrocarbon residue having 1 to 12 carbon atoms), and specific examples thereof include ethylene, propylene, butene-1, pentene-1, and In addition to α-olefins such as 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 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 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 and the olefin is usually about 0.001 to 30 mol%, preferably 0.01 to 10 mol%, of the alkenyl silane. When used in combination with another olefin polymer, 0.1 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
In general, it is generally preferably about 1.0 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 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 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.

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 The following general formulas (such as titanates)
It is preferable to use an alkoxy compound of a Group IVB metal of the periodic table shown in 7 ) alone or in combination with an organometallic compound.

[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, metal selected from hafnium)

In the present invention, examples of the acetylene derivative include acetylene, methylacetylene, ethylacetylene, butylacetylene and the like, as well as phenylacetylene and a part or all of hydrogen of the phenyl group are other monovalent groups such as hydrocarbon residues. Examples thereof include compounds substituted with groups such as a group, a hydroxyl group, a nitrile group, a nitro group, and a halogen.

The molded article comprising a catalyst containing an alkenylsilane and an olefin used in the present invention can be produced by various methods.
A copolymer of alkenylsilane and olefin and a catalyst, and if necessary, other polyolefins and the like are mixed and heated and molded, or a copolymer of alkenylsilane and olefin and other olefins and the like are mixed if necessary. It is obtained by impregnating the molded product with the catalyst by immersing it in a solution containing the catalyst.

The method of heat-melting the alkenylsilane-olefin copolymer and the catalyst is not particularly limited, and examples thereof include injection molding, extrusion molding, press molding, and blow molding. After mixing the polymer and the catalyst at a low temperature, the mixture is heated and melted by press molding, or the catalyst is heated and melted and mixed with a polyolefin containing no alkenylsilane to form a master pellet of the catalyst; It is also possible to perform injection molding by mixing pellets obtained by heating and melting and mixing a copolymer of olefin and olefin with an additive other than the catalyst. The molding temperature is a temperature at which the polymer can be melt-molded, and is about 150 to 300 ° C.

In the molding, various fillers can be mixed, such as metal hydroxides, oxides, nitrides, carbides, and the like, needle-like, scale-like, fibrous, etc. Those having a shape having a large reinforcing effect such as those having a reinforcing effect are preferably used. Specifically, talc, kaolin, mica, calcium carbonate, calcium silicate, calcium sulfate, calcium sulfite, barium titanate and the like can be used.

The acetylene derivative can be grafted at a high concentration when mixed so that the alkenylsilane concentration in the molded product becomes 0.01 to 20 mol%, preferably 0.1 to 10 mol%.

The method of molding a molded article made of a copolymer of an alkenylsilane and an olefin with a solution containing a catalyst is not particularly limited as long as a copolymer of an alkenylsilane and an olefin is used. It can be molded by the usual molding method, and the alkenyl silane and olefin copolymer alone, or the other polyolefin of the copolymer, and the filler etc. are heated and melt-mixed with a phenolic stabilizer and extrusion molded. It can be obtained by molding by an injection molding method, an injection molding method, a press molding method, a blow molding method or the like. As the filler, the same one as described above can be used.

The acetylene derivative 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%.

The molding is then treated with a solution of the catalyst.
The catalyst is contacted in a state of being dissolved in a solvent, and the contact temperature is from room temperature to 150 ° C., but it is effective to carry out the treatment at as high a temperature as possible unless the molded product is deformed. The contact time is several minutes to several hours. As the solvent used here,
Hydrocarbon compounds having 1 to 20 carbon atoms and halogenated hydrocarbon compounds can be used, and halogenated hydrocarbon compounds and aromatic hydrocarbon compounds are particularly preferably used. Specifically, benzene, toluene, xylene, ethylbenzene,
Examples thereof include dichloromethane, chloroform, dichloroethane, trichloroethane, and perchloroethane, which are usually used after being dissolved so that the concentration of the catalyst becomes 0.01 to 1000 ppm. The amount of the catalyst solution used is sufficient if the molded product can be immersed.

In the present invention, the catalyst-containing molded product obtained by the above-mentioned method is then subjected to a contact treatment with an acetylene derivative. At the time of contact, the acetylene derivative may be used alone or in a gaseous or liquid state, or may be mixed with another inert compound to be used as a mixed gas or a mixed solution. As the gas used here, nitrogen, helium, argon, oxygen, air, especially nitrogen, helium,
An inert gas such as argon can be preferably used. As the solvent, a hydrocarbon compound having 1 to 20 carbon atoms and a halogenated hydrocarbon compound can be used, and particularly, a halogenated hydrocarbon compound and an aromatic hydrocarbon compound are preferably used. Is done. Specifically, those exemplified as the solvent used for dissolving the catalyst described above can be used. The concentration of the acetylene derivative at the time of the contact is generally 100 to 1%. The contact treatment temperature is generally from room temperature to 250 ° C., but it is effective to carry out the treatment at as high a temperature as possible unless the molded product is deformed. The contact time is generally several minutes to several hours.

[0031]

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

Example 1 A vibrating mill equipped with four crushing pots having a capacity of 4 liters and 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, 1.5 liters of titanium tetrachloride and 1.5 liters of toluene are added.
After stirring for minutes, 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 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. /
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.

[0035] 100 g of the obtained copolymer and 10 mg of a cyclooctadiene complex of rhodium chloride were mixed well and pressed to obtain a molded product having a thickness of 2 mm. This molded product was placed in a 200-ml flask, and a 1: 1 mixed solution of phenylacetylene and toluene was added thereto so that the molded product was immersed, and the mixture was treated at 100 ° C. for 3 hours. Then, when the infrared absorption spectrum of the sheet was measured, absorption of a phenyl group was observed at about 1620 cm ^-1 and a weight increase of about 0.2% 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. 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 residues when extracted with boiling n-heptane for 6 hours was 96.8%.
A molded article was prepared in the same manner as in Example 1 except that 100 g of this powder was used, and the reaction time with phenylacetylene was changed to 24 hours.
% Increase in weight, and also 1620 in the infrared absorption spectrum.
Absorption was seen at cm ^-1 .

Example 3 100 g of the copolymer obtained in Example 1 was press-molded to a thickness of 2 mm.
Was obtained. This molded product was placed in a 200-ml flask, and the molded product was immersed in a solution of rhodium chloride cyclooctadiene complex (500 mg) in toluene (100 ml) and treated at 80 ° C. for 3 hours. Then, the molded product was taken out and washed with toluene, then put into a 1: 1 mixed solution of phenylacetylene and toluene and treated at 110 ° C. for 4 hours.
Next, the infrared absorption spectrum of the sheet was measured.
At 1620 cm ^-1 phenyl group absorption was observed, and a weight gain of about 0.7% was observed.

Example 4 A molded article was prepared in the same manner as in Example 3 except that 100 g of the copolymer obtained in Example 2 was used, and the reaction time with phenylacetylene was changed to 24 hours. As a result, the weight was increased by about 0.7%, and absorption was similarly observed at 1620 cm ^-1 in the infrared absorption spectrum.

[0039]

According to the present invention, a polyolefin molded product can be efficiently modified by implementing the method of the present invention, which is extremely valuable industrially.

Claims (3)

(57) [Claims] 1. A salt of rhodium or platinum, or a compound of the general formula
Titanium, zirconium, hafnium represented by (Chemical Formula 1)
A method for modifying a polyolefin molded article, comprising subjecting an acetylene derivative to a molded article comprising an alkenylsilane-olefin copolymer containing a catalyst selected from the above-mentioned alkoxy compounds . [Image Omitted] R ¹ _n M (OR ² ) _4-n (where R ¹ and R ² are the same?
Different hydrocarbon residues having 1 to 12 carbon atoms, n is an integer of 0 to 3
The number and M are selected from titanium, zirconium and hafnium
Metal) 2. A salt of rhodium or platinum, or a compound of the general formula
Titanium, zirconium, hafnium represented by (Chemical Formula 2)
The molded article comprising a copolymer of an alkenylsilane and an olefin containing a catalyst selected from the above-mentioned alkoxy compounds is a molded article obtained by heat-melting molding of a polymer of an alkenylsilane and an olefin and a catalyst. the method of. Embedded image R ¹ _n M (OR ² ) _4-n (wherein R ¹ and R ² are the same
Different hydrocarbon residues having 1 to 12 carbon atoms, n is an integer of 0 to 3
The number and M are selected from titanium, zirconium and hafnium
Metal) 3. A salt of rhodium or platinum, or a compound of the general formula
Titanium, zirconium, hafnium represented by (Chemical Formula 3)
The molded product comprising an alkenylsilane / olefin copolymer containing a catalyst selected from the alkoxy compounds of the above, wherein the molded product comprising an alkenylsilane / olefin copolymer is treated with a solution containing a catalyst. 2. The method according to 1. Embedded image R ¹ _n M (OR ² ) _4-n (where R ¹ and R ² are the same?
Different hydrocarbon residues having 1 to 12 carbon atoms, n is an integer of 0 to 3
The number and M are selected from titanium, zirconium and hafnium
Metal)