JPH0987343A - Olefin block copolymer, polyolefin material, and preparation of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an olefin block copolymer excellent in impact resistance, etc., by synthesizing polypropylene or polyethylene in the presence of a catalyst and then forming poly(ethylene-co-propylene) at the terminals of it. SOLUTION: An effluent from a container A contg. a metallocene catalyst, an alkylating agent, a cationizing agent and toluene is combined with an effluent from a container B contg. propylene and toluene to synthesize polypropylene at a first stage. A stream coming out of this polymn. zone (a) is combined with a toluene soln. of ethylene from a container C in a polymn. zone (b) to chemically bond poly(propylene-co-ethylene) to the terminals of polypropylene. The resultant stream is then fed into a container D contg. ethanol to deactivate the catalyst to obtain polypropylene-b-poly(ethylene-co-propylene). The resulting olefin block copolymer is useful as a compatibilizer for a crystalline polyolefin and a noncrystalline polyolefin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel block copolymer of polypropylene or polyethylene and poly (ethylene-co-propylene), a polyolefin-based material containing the polymer, and a method for producing them. More specifically, in addition to being excellent in impact resistance, polypropylene or polyethylene and poly (ethylene-co-) useful as a compatibilizing agent for crystalline polyolefin and amorphous polyolefin
Block copolymer with propylene) and a process for producing the same. Further, polypropylene or a polymer in which polyethylene and poly (ethylene-co-propylene) are repeated and polypropylene, or a block copolymer of polyethylene and poly (ethylene-co-propylene) is polypropylene, polyethylene or poly (ethylene-co-propylene). Or a polyolefin-based material mixed in a mixture thereof.

[0002]

2. Description of the Related Art Polyolefins such as polypropylene and polyethylene are excellent in various physical properties (mechanical strength, heat resistance, chemical resistance, electrical insulation, etc.) and processability, and are inexpensive, so they are produced and consumed in large quantities. Has been done. However, for example, polypropylene has relatively high rigidity, but is inferior in impact strength, and for the purpose of improving this point, amorphous poly (ethylene-c
o-Propylene) is blended to improve its properties. In the conventional block-type copolymer, the matrix made of polypropylene and the domain made of poly (ethylene-co-propylene) are phase-separated, which causes whitening due to separation between the matrix and the domain at the time of impact and subsequent deterioration of physical properties. It was desired to improve such problems. The block copolymer in which polypropylene and poly (ethylene-co-propylene) are chemically bonded according to the present invention can solve these problems and provide a material having more excellent properties.

So-called block type copolymers of polypropylene and poly (ethylene-co-propylene) have been known as one grade of polypropylene. However, as a method for producing the block type copolymer, first, polypropylene is used for 30 minutes or more in the first polymerization tank.
It is produced using a two-step polymerization method in which it is synthesized over several hours, and then poly (ethylene-co-propylene) is synthesized over 30 minutes to several hours in the second polymerization tank. Considering the formation time per polymer chain, the so-called block type copolymer obtained by this method does not have polypropylene and poly (ethylene-co-propylene) chemically bonded, and exists in a microblended state. Therefore, it is not a true block copolymer as defined in polymer chemistry, and therefore, the desired properties are not always sufficiently obtained.

[0004]

Therefore, the present inventor has found that a true block copolymer, namely polypropylene or polyethylene, and a poly (ethylene-co-propylene) are chemically bonded to each other to provide a novel true block which has never been present. As a result of various studies to obtain a copolymer, attention was paid to the fact that the olefin polymerization reaction using a transition metal catalyst usually completed in less than 1 second per polymer chain, and a true block was obtained by performing polymerization for a short time using a special device. The present invention has been completed by finding that a copolymer can be obtained, and an object of the present invention is to provide a true block copolymer, a polyolefin-based material in which the true block copolymer is mixed with a polyolefin, and a method for producing the same. That is.

[0005]

The gist of the present invention is to provide an olefin block copolymer in which polypropylene or polyethylene and poly (ethylene-co-propylene) are chemically bonded, and polypropylene or polyethylene and poly (ethylene). -Co-propylene) and a block copolymer chemically bonded to any of polypropylene, polyethylene and poly (ethylene-co-propylene), or a mixture thereof, a polyolefin-based material, That is the manufacturing method.

The present invention will be described in detail. The polypropylene or polyethylene of the present invention and poly (ethylene-
The block copolymer with (co-propylene) has excellent impact resistance, and also exhibits properties useful as a compatibilizing agent between the crystalline polyolefin and the amorphous polyolefin. In the case of polypropylene, a crystalline one having a high isotacticity is preferable, but it is not necessarily limited to this.
Also, when synthesizing the block copolymer according to the present invention,
It is also possible to make polypropylene or polyethylene or poly (ethylene-co-propylene) coexist by controlling the polymerization method and conditions.

In this method for producing a polymer, for example, a catalyst in which titanium tetrachloride is supported on magnesium chloride and a cocatalyst such as triethylaluminum, or a metallocene compound such as hafnium or zirconium and a methylaluminoxane or boron compound are combined. To use. First, polypropylene or polyethylene is synthesized in a narrow tube for 0.01 to 10 seconds, and then poly (ethylene-co-propylene) is continuously synthesized in the same time. On this occasion,
The block chain length can be changed by changing the respective times. Further, it is possible to repeat this step twice or more, and further, it is also possible to make the polymerization time when repeating it longer (about 1 minute to 2 hours).

As the catalyst, in addition to the type in which titanium tetrachloride is supported on magnesium chloride, various types of high activity catalysts such as titanium trichloride catalyst or metallocene catalyst are used. Further, these catalysts are previously treated with a promoter such as alkylaluminum, an activator such as methylaluminoxane, a cationizing agent such as a boron compound, or an electron-donating compound such as an aromatic ester or a silicon compound. It is also possible to coexist. As the cocatalyst used in the present invention, various alkylaluminums can be used, for example, trialkylaluminums such as triethylaluminum and triisobutylaluminum, alkylaluminum halides such as diethylaluminum chloride and ethylaluminum sesquichloride, diethylaluminum. Alkyl aluminum halides such as halides, diisobutyl aluminum halides and the like can be mentioned. The polymerization temperature is not particularly limited, but it is usually carried out in the temperature range of 0 ° C to 200 ° C.
The solvent used in the reaction is not particularly limited, but usually toluene, xylene, hexane, heptane or the like is used.

An example of the polymerization method of the present invention will be described with reference to the drawings. FIG. 1 is an explanatory diagram of a method for polymerizing an olefin block copolymer in which polypropylene and poly (ethylene-co-propylene) are chemically bonded using a metallocene catalyst. A metallocene catalyst, an alkylating agent, and a cationizing agent are dispersed in toluene in container A, propylene is dissolved in toluene in container B, and toluene in which ethylene is dissolved is charged in container C. Outflow through a Teflon tube attached to the bottom of each container. First
At the stage, the effluent of the container A and the effluent of the container B are combined to synthesize polypropylene. The overlapping area is a
Indicated by Polypropylene, unreacted propylene and a catalyst are present in the flow exiting the polymerization zone a, and a toluene solution of ethylene is merged into the stream from the container C to form poly (propylene-co-ethylene) at the end of the polypropylene in the polymerization zone b. Are chemically bound. Then, it was introduced into a container D containing ethanol, the catalyst was deactivated and the reaction stopped, and polypropylene-b-poly (ethylene-co-propylene)
Is obtained. Then, the target block copolymer is obtained by washing and drying under reduced pressure. Here, the composition of the produced polymer can be controlled by changing the lengths of the polymerization region a and the polymerization region b and the amounts of propylene and ethylene present in the container A, the container B and the container C.

In FIG. 2, as in FIG. 1, a toluene slurry of the catalyst is put in the container A, and a toluene solution of the cocatalyst is put in the container B, and propylene is dissolved in each. Furthermore, container C
Is filled with toluene in which ethylene is dissolved. As in the case of FIG. 1, polypropylene-b-poly (ethylene-co
-Propylene), propylene, ethylene or a mixed gas of propylene and ethylene alone in the container D,
Or it is introduced sequentially and polymerized as necessary, and as a result,
Polypropylene-b-poly (ethylene-) in which these monomers are polymerized and previously polymerized in polypropylene, polyethylene and / or poly (ethylene-co-propylene).
It is possible to obtain a polyolefin-based material in which co-propylene) is mixed.

[0011]

EXAMPLES AND COMPARATIVE EXAMPLES Next, the present invention will be specifically described with reference to Examples. Example 1 Polypropylene-b-poly (ethylene-co-propylene) is produced using the apparatus of FIG. In the container A, as a metallocene catalyst, 0.26 g of dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride and 18 mm of triisobutylaluminum were used.
and N, N-dimethylanilinium tetra (pentafluorophenyl) borate as a cationizing agent 0.6
100 ml of a toluene solution containing 6 mmol of a polymerization catalyst for olefin was charged and left at 30 ° C. for 2 minutes with stirring. Propylene in the container B and ethylene in the container C were dissolved in 100 ml of toluene at a pressure of 8 kgf / cm ² G, and the polymerization regions a and b were each added to 0.5
Polymerization of propylene and polymerization of ethylene and propylene were carried out at 30 ° C. for 2 seconds to obtain 1.33 g of a polymer.

Example 2 A polyolefin-based material containing polypropylene-b-poly (ethylene-co-propylene) is produced using the apparatus shown in FIG. 100 ml of a toluene slurry containing 1 g of the catalyst was charged into the container A, and propylene contained 0.68 in it.
It was added so as to be mol / l. The catalyst used was prepared by the following method. That is, magnesium chloride and ethyl benzoate were co-ground with a vibration mill for 30 hours, wet treated with titanium tetrachloride at 90 ° C. for 2 hours, washed with heptane, and finally replaced with toluene. In a container B, a toluene solution containing 14 mmol of triethylaluminum and 0.7 mmol of cyclohexylmethyldimethoxysilane as an external donor was used, and 0.68 mol of propylene was added to the toluene solution.
/ L was added. In the container C, ethylene 0.
It was dissolved in 100 ml of toluene so as to be 21 mol / l. As a first step at a temperature of 30 ° C., polypropylene is polymerized in the polymerization zone a for 0.1 seconds, and poly (ethylene-c bonded to the polypropylene in the polymerization zone b).
o-propylene) synthesis for 0.1 seconds, then in container D, first polypropylene for 10 minutes,
Then, poly (ethylene-co-propylene) was synthesized for 15 minutes at 80 ° C. to give polypropylene-b-poly (ethylene-co-propylene) 0.37.
42.6 g of a polyolefin-based material containing g was obtained.

[0013]

As described above, the present invention succeeded in synthesizing a polyolefin block copolymer which could not be synthesized by the conventional polymerization method or polymerization technique.
This is different from the conventional so-called block-type copolymer, and has different characteristics from the conventional so-called block-type copolymer due to the chemical bonding of polypropylene or polyethylene and poly (ethylene-co-propylene). And is also extremely useful as a compatibilizer for crystalline polyolefin and amorphous polyolefin.

[Brief description of drawings]

FIG. 1 is an explanatory view of an example of a polymerization method of the present invention.

FIG. 2 is an explanatory diagram of a method for producing a polyolefin-based material of the present invention.

[Explanation of symbols]

 A, B, C, D container a, b, superposition area

Claims (7)

[Claims] 1. An olefin-based block copolymer in which polypropylene or polyethylene and poly (ethylene-co-propylene) are chemically bonded. 2. A block copolymer in which polypropylene or polyethylene and poly (ethylene-co-propylene) are chemically bonded is present in any one of polypropylene, polyethylene and poly (ethylene-co-propylene) or a mixture thereof. A polyolefin-based material characterized in that 3. A method for producing an olefin-based block copolymer, which comprises synthesizing polypropylene or polyethylene in the presence of a catalyst and then producing poly (ethylene-co-propylene) at the terminal of the polypropylene or polyethylene. 4. The method for producing an olefinic block copolymer according to claim 3, in the presence of a Ziegler catalyst. 5. The method for producing an olefin block copolymer according to claim 3, in the presence of a metallocene catalyst. 6. A method for producing a polyolefin-based material, which comprises repeating the steps of synthesizing polypropylene or polyethylene in the presence of a catalyst, and then synthesizing poly (ethylene-co-propylene). 7. After synthesizing polypropylene or polyethylene in the presence of a catalyst, poly (ethylene-co-propylene) is formed at the terminal of the polymer, and then polypropylene and / or polyethylene and / or poly (ethylene-co-) are formed. A method for producing a polyolefin-based material, which comprises synthesizing propylene).