JP2680741B2 - Propylene ethylene copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene ethylene copolymer having excellent flexibility, tensile strength, heat resistance and processability.

[0002]

2. Description of the Related Art In recent years, ethylene propylene rubber (hereinafter referred to as
Flexible olefin resins such as EPR), ethylene propylene terpolymer (hereinafter abbreviated as EPDM) and EPR, a thermoplastic elastomer which is a blend of EPDM and polypropylene, are used in automobile parts and electric wire fields. Widely used in the field of home appliances.

Generally, EPR and EPDM are produced by a solution polymerization method using a vanadium catalyst, and there is a problem that a complicated process is required in addition to low polymerization activity. When it comes to thermoplastic elastomers, these EPRs,
Since it is manufactured by a blending process of EPDM and polypropylene, there is a problem that the process becomes more complicated.

In order to solve the above-mentioned problems, recently, EPR has been performed by using a highly active Ti-based catalyst and by a simplified process.
To a thermoplastic elastomer have been proposed.

[0005]

Among them, JP-A-55-55
No. 118910 discloses that the copolymer has a large molecular weight,
And a propylene ethylene copolymer having a high propylene chain microisotacticity is disclosed, but when the present inventors conducted additional tests, the above propylene ethylene copolymer still has a tensile strength and heat resistance. I was not satisfied.

[0006]

Means for Solving the Problems With respect to the above problems, the present inventors have conducted earnest studies to find out a propylene-ethylene copolymer excellent in flexibility, tensile strength, heat resistance and processability, and as a result, the above problems have been solved. As a result, the present invention has been completed by succeeding in obtaining a propylene-ethylene copolymer having excellent physical properties.

That is, the present invention comprises 15 to 80 mol% of ethylene-based monomer units (hereinafter abbreviated as E) and 8 of propylene-based monomer units (hereinafter abbreviated as P).
In the propylene-ethylene copolymer composed of 5 to 20 mol%, the melt flow rate is 0.01 to 50 g / 10.
And P and E of the propylene ethylene copolymer
The total area of the peaks of the following a), b) and c) in the ¹³ C-nuclear magnetic resonance spectrum of the propylene-ethylene copolymer, of which the stereoregularity of the units consisting of PPEP and EPEP is 4 And [P ^r PEP], [P ^m PEP] and [EPEP], respectively, are propylene-ethylene copolymers having stereoregularity satisfying the following formula (I). a) Peaks derived from a structure in which the stereoregular configuration of the propylene contiguous portion (PP) of the unit consisting of PPEP is racemic. b) A peak derived from a structure in which the stereoregular configuration of the continuous portion of propylene (PP) of the unit consisting of PPEP is meso. c) A peak derived from a unit composed of EPEP.

(Equation 2)

The ropylene-ethylene copolymer of the present invention has an ethylene-based monomer unit (hereinafter abbreviated as E) of 15
˜80 mol%, and the propylene-based monomer unit (hereinafter abbreviated as P) is 85 to 20 mol%.

The propylene-ethylene copolymer of the present invention is
The propylene-ethylene copolymer of the present invention, which will be described later, may contain a monomer unit based on a monomer other than the above-mentioned monomer units within a range not impairing the physical properties. For example,
Α-Olefins other than ethylene and propylene such as 1-butene, 4-methyl-1-pentene, 1-hexene and 3-methyl-1-butene; diene monomers such as 1,4-hexadiene, dicyclopentadiene and ethylidene norbornene It may contain the monomer unit based on 5 mol% or less.

The propylene-ethylene copolymer of the present invention is
It may be a random copolymer or a block copolymer.

The melt flow rate of the propylene ethylene copolymer of the present invention is in the range of 0.01 to 50 g / 10 minutes. Propylene-ethylene copolymers having a melt flow rate of less than 0.01 g / 10 min are difficult to produce, and
A propylene-ethylene copolymer exceeding 0 g / 10 minutes is not preferable because the tensile strength decreases.

The propylene-ethylene copolymer of the present invention is
^{In the} spectrum obtained by ¹³ C-nuclear magnetic resonance measurement, the area of the peak derived from the structure in which the stereoregular configuration of the propylene contiguous portion (PP) of the unit consisting of PPEP is racemic is [P ^r
PEP], the area of the peak derived from the structure in which the stereoregular configuration of the continuous portion of propylene (PP) of the unit made of PPEP is meso is [P
^m PEP] and the area of the peak derived from the unit consisting of EPEP is [EPEP], the stereoregularity of the unit consisting of four consecutive PPEP and EPEP including P and E is represented by the above formula (I). To be satisfied.

The present inventors have been conducting long-term research on the relationship between the structure of the molecular chain of propylene-ethylene copolymer and the physical properties. As a result, propylene ethylene having a very small content of the structure in which the stereoregular configuration of the propylene continuous portion (PP) of the unit made of PPEP among the four continuous units of P and E is racemic is extremely small. It has been found that the copolymer is excellent in flexibility, tensile strength, heat resistance and processability.

Considering that the value represented by the above formula of a propylene-ethylene copolymer produced by using a conventional highly active catalyst or a highly stereoregular catalyst is 1.5 to 3.0% at most. The value of the propylene-ethylene copolymer of the present invention represented by the above formula is less than 1.0%, which is significantly small. Therefore, it can be said that the propylene ethylene copolymer of the present invention is excellent in flexibility, tensile strength, heat resistance and processability.

In the structure of the molecular chain of the propylene-ethylene copolymer of the present invention, the area of each peak of the above a) to c) among four continuous units of P and E is "POLYMER" by Hayashi et al. Volume 29, page 2208 (1
1988) and "POLYMER" Vol. 29, p. 138 (1988). That is, from the ¹³ C-nuclear magnetic resonance spectrum (hereinafter, referred to as ¹³ C-NMR spectrum) measured by a nuclear magnetic resonance apparatus having a ¹ H resonance frequency of 270 MHz, P
Of the four consecutive units including and E, a) above
It is possible to obtain each peak of (1) to (c) by calculating the area of each peak by the waveform separation method.

An example of the method for obtaining the areas of the peaks a) to c) is as follows.

FIG. 1 shows a propylene-ethylene copolymer of ¹³
It is a C-NMR spectrum. In FIG. 1, the peak group (1) is derived from the structure in which the stereoregular configuration of the continuous portion of propylene (PP) in the unit made of PPEP is racemic. Also,
The peak group of (2) is derived from the structure in which the stereoregular configuration of the continuous portion (PP) of propylene in the unit composed of PPEP is meso, and the unit composed of EPEP. Therefore, (1)
By calculating the area of each peak group in (2) and (2) by the waveform separation method, the value represented by the above equation can be calculated.

The peaks of the individual peaks belonging to the above-mentioned peak group (1) generally appear at 38.70 to 39.05 ppm represented by chemical shift based on tetramethylsilane. The peaks of the individual peaks belonging to the above peak group (2) generally appear at 37.88 to 38.23 ppm.

The attribution of the individual peaks belonging to the above-mentioned peak groups (1) and (2) is described in the above-mentioned "POL".
YMER, Vol. 29, page 2208 (1988).

The value represented by the above formula of the propylene-ethylene copolymer of the present invention may be less than 1.0%, but in order to obtain a copolymer having more excellent physical properties, it is less than 0.8%. And more preferably less than 0.6%.

The propylene-ethylene copolymer of the present invention is
It may be obtained by any method, and for example, the following method is preferably adopted. The following components A, B A. Titanium compound B. After contacting the iodine compound in an inert hydrocarbon medium, C.I. The above iodine-treated titanium compound D. Organoaluminum compound E. An organic compound represented by the general formula [I] RnSi (OR ') _4-n [I] (wherein R and R'are the same or different hydrocarbon groups, and n is an integer of 1 to 3). After prepolymerization of propylene in the presence of a silicon compound in multiple stages and with different organosilicon compounds in each prepolymerization stage, F. Titanium-containing polypropylene obtained by prepolymerization G. Organoaluminum compound similar to D above. This is a method of copolymerizing propylene and ethylene in the presence of the same organosilicon compound as in E above.

Titanium compound [A] used in the present invention
A compound known to be used for the polymerization of olefins is employed without any limitation. In particular, a titanium compound having high catalytic activity containing titanium, magnesium and halogen as components is preferable. Such a titanium compound having high catalytic activity is obtained by supporting a titanium halide, particularly titanium tetrachloride, on various magnesium compounds. As a method for producing this catalyst, a known method is employed without any limitation.
For example, JP-A-56-155206 and JP-A-56-1
36806, 57-34103, 58-8706,
58-83006, 58-138708, 58-
183709, 59-206408, 59-219.
311, 60-81208, 60-81209, 60-186508, 60-192708, 61-
211309, 61-271304, 62-152
09, 62-1711, 62-72702, 6
The method shown in 2-104810 is adopted.
Specifically, for example, a method in which titanium tetrachloride is co-ground with a magnesium compound such as magnesium chloride, a titanium halide and a magnesium compound in the presence of an electron donor such as alcohol, ether, ester, ketone or aldehyde. Examples thereof include a method of co-milling or a method of bringing a titanium halide, a magnesium compound and an electron donor into contact with each other in a solvent.

The iodine compound [B] used in the present invention is represented by the following general formula. R ″ -I (wherein R ″ is a hydrocarbon group such as an alkyl group, an alkenyl group, an alkynyl group, or an aryl group.)

The iodine compounds that can be preferably used in the present invention are as follows. For example, iodine, methyl iodide, ethyl iodide, propyl iodide, butyl iodide, iodobenzene, p-iodinated toluene and the like.

The above titanium compound [A] and iodine compound [B] are contacted in an inert hydrocarbon medium.

As the inert hydrocarbon medium, saturated aliphatic hydrocarbons or aromatic hydrocarbons such as propane, butane, pentane, hexane, octane, decane, cyclohexane, benzene and toluene are preferably used, and these are used alone. Alternatively, they can be mixed and used.

The contact temperature is -100 ° C to 100 ° C.
It is possible to select from the range of, and a temperature of 0 ° C to 40 ° C is particularly preferable. The contact time is not particularly limited, but is preferably in the range of 1 hour to 24 hours.

The amount of each component used is 0.1 to 100 (I / Ti (molar ratio)) based on the titanium atom in the titanium compound.
It is 0, preferably 0.5 to 50. After the contact, the titanium compound is preferably washed with the above-mentioned inert hydrocarbon medium.

Next, prepolymerization is carried out in the presence of the above-mentioned iodine-treated titanium compound [C], organoaluminum compound [D] and organosilicon compound [E].

As the organoaluminum compound [D], compounds known to be used for the polymerization of olefins can be adopted without any limitation. For example, trialkyl aluminums such as trimethyl aluminum, triethyl aluminum, tri-n propyl aluminum, tri-n butyl aluminum, tri-i butyl aluminum, tri-n hexyl aluminum, tri-n octyl aluminum, and tri-n decyl aluminum; Examples include diethyl aluminum monohalides such as diethyl aluminum monochloride; alkyl aluminum halides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride and the like. Other alkoxy aluminums such as monoethoxydiethylaluminum and diethoxymonoethylaluminum can be used. Among them, triethylaluminum is most preferred. The amount of the organoaluminum compound used in each prepolymerization step is 1 to Al / Ti (molar ratio) with respect to Ti atoms in the iodine-treated titanium compound.
It is 100, preferably 2 to 20.

Further, as the organosilicon compound [E], the compound represented by the general formula [I] can be used without any limitation. R and R'in the general formula [I] are hydrocarbon groups such as an alkyl group, an alkenyl group, an alkynyl group and an aryl group. Examples of the organosilicon compound suitably used in the present invention are as follows. For example, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, ethyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane. Methoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, 6-triethoxysilyl2-
Norbornene and the like.

The amount of the organosilicon compound used in each prepolymerization step is 0.1 to 100, preferably 0.5 to 10 in terms of Si / Ti (molar ratio) with respect to Ti atoms in the titanium compound subjected to iodine treatment. is there.

In the prepolymerization of the present invention, the above iodine compound [B] is used in addition to the above iodine-treated titanium compound [C], organoaluminum compound [D] and organosilicon compound [E]. Improves the isotacticity of the obtained copolymer, and further,
It is preferable for improving the tensile strength and heat resistance.

The amount of the iodine compound used in each prepolymerization step is 0.1 to 100, preferably 0.5 to 50, in terms of I / Ti (molar ratio) with respect to the iodine-treated titanium atom in the titanium compound. Is.

In the present invention, the term "preliminary polymerization carried out in multiple stages" means that propylene is prepolymerized in the presence of the above-mentioned components [C], [D], [E] and optionally [B]. Preliminary polymerization of propylene is further repeated in the presence of the obtained titanium-containing polypropylene and the components [D], [E] and optionally [B]. The prepolymerization is preferably performed in a range of 2 to 5 times. Each of the above-mentioned components used in each prepolymerization may be added sequentially or may be used as a mixture. The amount of propylene polymerized in each prepolymerization step is 0.1 to 100 g per 1 g of the iodine-treated titanium compound,
It is preferably in the range of 1 to 100 g, and industrially 2 to 100 g.
A range of 50 g is preferred.

Different types of organosilicon compounds are used in each prepolymerization stage. As the organosilicon compound, it is preferable to use a compound in which at least one of R and R'in the general formula [I] is a bulky hydrocarbon group such as a phenyl group, a cyclohexyl group or a norbornyl group. The order of use of the organosilicon compounds used in each prepolymerization step is not particularly limited.

In each preliminary polymerization, it is preferable to polymerize propylene alone, but 5 mol% of α-olefin other than propylene such as ethylene, 1-butene, 1-pentene, 1-hexene and 4-methylpentene-1. The following may be copolymerized with propylene. It is also possible to make hydrogen coexist at each prepolymerization stage.

For each prepolymerization, it is usually preferable to apply slurry polymerization. As a solvent, hexane, heptane,
Saturated aliphatic hydrocarbons or aromatic hydrocarbons such as cyclohexane, benzene, and toluene may be used alone, or a mixed solvent thereof may be used. Each prepolymerization temperature is
The temperature of −20 to 100 ° C., particularly 0 to 60 ° C. is preferable, and each stage of the prepolymerization may be carried out under the condition of different temperature. The pre-polymerization time may be appropriately determined according to the pre-polymerization temperature and the polymerization amount in the pre-polymerization, and the pressure in the pre-polymerization is not limited, but in the case of slurry polymerization, it is generally from atmospheric pressure to 5 kg / cm. It is about ² G. Each prepolymerization may be carried out by any of batch, semi-batch and continuous methods. After the completion of each prepolymerization, hexane, heptane,
Saturated aliphatic hydrocarbons or aromatic hydrocarbons such as cyclohexane, benzene, and toluene are preferably washed alone or with a mixed solvent thereof, and the number of washings is usually preferably 5 to 6 times.

After the preliminary polymerization, main polymerization is carried out.
The main polymerization is carried out in the presence of the titanium-containing polypropylene, organoaluminum compound and organosilicon compound obtained by the above-mentioned prepolymerization.

As the organoaluminum compound used in the main polymerization, those used in the above-mentioned prepolymerization can be used, most preferably triethylaluminum. The amount of the organoaluminum compound used is Al / Ti based on the titanium atom in the titanium-containing polypropylene obtained by prepolymerization.
(Molar ratio), 10 to 1000, preferably 50 to 50
0.

Further, as the organosilicon compound, the compound represented by the above general formula [I] can be adopted without any limitation. The amount of the organosilicon compound used in the main polymerization is Si / Ti (molar ratio) with respect to Ti atoms in the titanium-containing polypropylene.
And is 0.1 to 1000, preferably 0.5 to 500.

Other polymerization conditions are not particularly limited as long as the effects of the present invention are observed, but the following conditions are generally preferred. The polymerization temperature is, for example, 80 ° C. or lower, and 20
It is preferable to adopt from the range of up to 70 ° C. Hydrogen may be allowed to coexist as a molecular weight regulator. Further, the polymerization may be carried out by any method such as slurry polymerization using propylene and ethylene itself as a solvent, gas phase polymerization, solution polymerization and the like.
The polymerization system may be a batch system, a semi-batch system, or a continuous system.

In the main polymerization, propylene and ethylene are copolymerized, but the copolymerization may be conducted in two or more stages under different conditions. For example, in the first stage propylene or other α-olefins such as ethylene, 1-
Butene, 4-methyl-1-pentene, 1-hexene, 3
-Methyl-1-butene homopolymerization or random copolymerization of propylene and less than 5 mol% of α-olefins other than propylene, followed by a second stage of random copolymerization of propylene and ethylene, Propylene, ethylene and other α-olefin 5 as the second stage of
Random copolymerization of less than mol%, or copolymerization of propylene and ethylene in both the first and second stages
A method in which the ratio of propylene and ethylene is changed in the second stage and the second stage to carry out copolymerization is possible. Homopolymerization of propylene or other α-olefin in the first stage,
Alternatively, the amount of polymer produced by random copolymerization of propylene and an α-olefin other than propylene can be arbitrarily adjusted by the ratio in the total polymer, but is preferably 90% by weight or less.

In the main polymerization, in order to control the stereoregularity of propylene, an electron donor such as ether, amine, amide, sulfur-containing compound, nitrile, carboxylic acid, acid amide, acid anhydride or acid ester may coexist. it can.

After completion of the main polymerization, the monomer can be evaporated from the polymerization system to obtain a polymer. This polymer may be subjected to known washing or countercurrent washing with a hydrocarbon having 7 or less carbon atoms.

In the present invention, in order to improve the processability of the copolymer obtained by the above method, the molecular weight can be adjusted appropriately.

For example, the copolymer of the present invention may be melt-kneaded in the presence of an organic peroxide. By this melt-kneading, a copolymer having excellent processability and an arbitrarily adjusted molecular weight can be obtained. In carrying out melt-kneading, the copolymer and the organic peroxide are mixed, but the mixing method is not particularly limited. For example, a method of mechanically mixing with a blender such as a blender or a mixer, a method of dissolving an organic peroxide in a suitable solvent and attaching it to a copolymer, and a method of mixing by drying the solvent, etc. is there.

As the melt-kneading temperature, a temperature not lower than the melting temperature of the copolymer and not lower than the decomposition temperature of the organic peroxide is adopted. However, if the heating temperature is too high, the polymer is thermally deteriorated. Generally, the melting temperature is preferably set in the range of 170 to 300 ° C, particularly 180 to 250 ° C.

Known organic peroxides are generally used in the present invention. As a typical organic peroxide,
For example, ketone peroxides such as methyl ethyl ketone peroxide and methyl isobutyl ketone peroxide; diacyl peroxides such as isobutyryl peroxide and acetyl peroxide; diisopropylbenzene hydroperoxide and other hydroperoxides; 2,5-dimethyl 2,5 Dialkyl peroxides such as di- (t-butylperoxy) hexane and 1,3-bis- (t-butylperoxyisopropyl) benzene; 1,1-di-t-butylperoxy-cyclohexane and other peroxy compounds. Oxyketals; alkyl peresters such as t-butylperoxyacetate and t-butylperoxybenzoate; t-butylperoxyisopropyl carbonate and other percarbonates. The amount of the organic peroxide used is different depending on the melt index setting value of the copolymer to be obtained and is not unconditionally determined, but 0.001 to 1.0 part by weight relative to 100 parts by weight of the copolymer, Preferably 0.01-
0.5 parts by weight is common.

Various antioxidants, heat stabilizers, chlorine scavengers, molding aids and the like can be optionally added to the copolymer of the present invention.

[0051]

[Effect] The propylene-ethylene copolymer of the present invention has a novel molecular structure, is excellent in flexibility, and is excellent in tensile strength, heat resistance and processability. The copolymer obtained by the present invention can be suitably used in various fields in which conventional thermoplastic elastomers are used.

For example, in the field of injection molding, bumpers, mudguards, lamp packings for automobile parts, and various packings for home electric appliances, ski shoes, grips, roller skates, etc. can be mentioned.
On the other hand, in the extrusion molding field, it can be suitably used as various automobile interior materials, various insulating sheets as home electric appliances and electric wire materials, coating materials for cords and cables, and waterproof sheets, waterproof materials, joint materials, etc. in the field of civil engineering and construction materials. .

[0053]

EXAMPLES The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

The measuring method used in the following examples will be described. 1) the content of ethylene-based monomer units, and The content of ethylene-based monomer units can be determined according to G.I. J. R
by Ay et al., Macromolecules No. 1
Volume 0, page 773 (1977),
That is, it was determined from the intensity ratio of the peak based on the resonance of the methylene carbon present in the main chain of the propylene-ethylene copolymer. [P ^r PEP] Also, the value of ──────────────── × 100 (%) is calculated by Hayashi et al. As [P ^m PEP] + [EPEP], which is “POLYMER” 29. Volume 2208 pages (1988
Year) and "POLYMER" 29 volumes 138 pages (198)
I asked for it according to the method published in (8 years). 2) Melt flow rate According to ASTM D-790. 3) Shore A hardness A test piece was prepared according to JIS K6301, and the test piece was tested using an A type tester. 4) Tensile strength A test piece was prepared using a No. 3 dumbbell according to JIS K6301 and measured at a speed of 200 mm / min. 5) Softening temperature Using TMA manufactured by Seiko Denshi Co., a temperature rising rate of 20 ° C./min.
The temperature was measured with a 49 g load and a 0.1 mm needle.

Example 1 [Preparation of Titanium Compound] The titanium component was prepared according to the method of Example 1 in JP-A-58-83006. That is, anhydrous magnesium chloride 0.95 g (10 mmol). Decane 10 ml, and 2
-Ethylhexyl alcohol 4.7 ml (30 mmol) 1
After heating and stirring at 25 ° C. for 2 hours, 0.55 g (3.75 mmol) of phthalic anhydride was added to this solution, and the mixture was further stirred and mixed at 125 ° C. for 1 hour to obtain a uniform solution. Titanium tetrachloride 4 kept at 120 ° C after cooling to room temperature
The entire amount was added dropwise into 0 ml (0.36 mol) over 1 hour. After the charging is completed, the temperature of this mixed solution is kept at 1
The temperature was raised to 10 ° C., and when it reached 110 ° C., 0.54 ml (2.5 mmol) of diisophthalate was added, and the mixture was maintained at the same temperature for 2 hours with stirring. After completion of the reaction for 2 hours, a solid portion was collected by hot filtration, and this solid portion was mixed with 200 ml of TiC.
After resuspension in l _4, 2 hours, it was heated reaction again 110 ° C.. After the completion of the reaction, the solid part was collected again by hot filtration and sufficiently washed with Delon and hexane until no free titanium compound was detected during the washing.

The solid Ti catalyst component prepared by the above manufacturing method was stored as a heptane slurry. The composition of the solid Ti catalyst component is 2.1% by weight titanium, 57% by weight chlorine,
It was 18.0% by weight of magnesium and 21.9% by weight of diisobutyl phthalate.

[Contact with Iodine Compound] Purified heptane (500 ml) was added to a 1 l-autoclave subjected to N ₂ substitution.
Add 10 mmol of solid Ti catalyst component and 50 mmol of iodine, and add 2.
The mixture was stirred at 0 ° C for 8 hours. The solid portion of the obtained slurry was thoroughly washed with purified heptane until no free iodine was detected in the washing liquid.

[Preliminary Polymerization] Purified heptane (200 ml), triethylaluminum (50 mmol) and diphenyldimethoxysilane (5) were placed in an N ₂ -substituted 1-autoclave.
After loading 0 mmol, 50 mmol of iodine, and 5 mmol of the above-mentioned iodine-treated solid Ti catalyst component in terms of Ti atom, 5 g per 1 g of propylene solid Ti catalyst component was added.
It was continuously introduced into the reactor for an hour and the first prepolymerization was performed. The temperature during this period was kept at 15 ° C. One hour later, the introduction of propylene was stopped, and the inside of the reactor was sufficiently replaced with N ₂ . The solid portion of the resulting slurry was washed six times with purified heptane.

Furthermore, 1 l of this solid component was subjected to N ₂ substitution.
-Charge into an autoclave, 200 ml of purified heptane,
After adding 50 mmol of triethylaluminum, 50 mmol of phenyltriethoxysilane, and 10 mmol of iodine, propylene was continuously introduced into the reactor for 1 hour so that the amount became 5 g with respect to 1 g of the solid Ti catalyst component, and the second preliminary polymerization was performed. Was applied. The temperature during this period was kept at 15 ° C.
The solid part of the obtained slurry was washed six times with purified heptane to obtain a titanium-containing polypropylene.

[Polymerization] Content of 400 l with N ₂ substitution
200 liters of propylene were charged into the autoclave, and 274 mmol of triethylaluminum, 274 mmol of phenyltriethoxysilane and 14 mol% of ethylene gas were added.
Ethylene was supplied so that the internal temperature of the autoclave was raised to 45 ° C., and 1.1 mmol of titanium-containing polypropylene was charged as titanium atoms. Then, the internal temperature of the autoclave was raised to 50 ° C., and propylene and ethylene were copolymerized for 1 hour. The polymerization pressure was 24 kg / cm ² , and the temperature during this period was kept at 50 ° C. and was kept at 14 mol% while confirming the ethylene concentration by gas chromatography. After 1 hour, unreacted propylene was purged to obtain a white granular polymer. The yield was 33 kg. The results are shown in Table 1.

As shown in the ¹³ C-NMR spectrum of the obtained copolymer, no peak based on P ^r PEP was detected,

To the obtained white granular polymer, 1,3-
Bis- (t-butylperoxyisopropyl) -benzene was mixed as shown in Table 1, an antioxidant, a heat stabilizer, and a chlorine scavenger were further added thereto, and mixed with a Henschel mixer.

Then, a 40 mmφ extruder was extruded so that the resin temperature at the die outlet was 220 ° C. to obtain pellets.
The results are shown in Table 1. The value of the above formula was 0 even after decomposition with the organic peroxide, and did not change.

Examples 2 to 5 In the polymerization of Example 1, the ethylene gas concentration was 18 mol.
% (Example 2) 25 mol% (Example 3), 35 mol%
(Example 4) The same operation as in Example 1 was performed except that the amount was changed to 45 mol% (Example 5). The results are shown in Table 1.

Examples 6 to 8 Example 2 was repeated except that hydrogen was added so as to obtain the melt flow rate shown in Table 1 in the polymerization of Example 2.
The same operation as described above was performed. The results are shown in Table 1.

Example 9 [Preparation of Titanium Compound] The titanium compound was prepared according to the method of Example 1 in JP-A-62-104810. That is, 100 g of aluminum trichloride (anhydrous) and 29 g of magnesium hydroxide
Was reacted while being pulverized with a vibration mill at 250 ° C. for 3 hours. After completion of heating, the mixture was cooled in a nitrogen stream to obtain a solid product (I).

Purified decane 1 in a glass flask
5 ml, solid product (I) 2.5 g, orthotitanic acid n-
Butyl 8.5 g, 2-ethyl-1-hexanol 9.8
g were mixed and heated to 130 ° C. for 1.5 hours with stirring to dissolve them to obtain a uniform solution. Bring the solution to 70 ° C.,
After adding 1.8 g of ethyl p-toluate and reacting for 1 hour, 26 g of silicon tetrachloride was added dropwise over 2 hours with stirring to precipitate a solid, and the mixture was further stirred at 70 ° C. for 1 hour. The solid was separated from the solution and washed with purified hexane to obtain a solid product (II).

To the total amount of the solid product (II), 1.5 ml of diisobutyl phthalate was added together with 30 ml of 1,2-dichloroethane and 30 ml of titanium tetrachloride, and the mixture was stirred at 10
After reacting at 0 ° C. for 2 hours, the liquid phase portion was removed by decantation at the same temperature, 1,2-dichloroethane (30 ml), titanium tetrachloride (30 ml) and diisobutyl phthalate (1.5 g) were added again, and the mixture was stirred at 100 ° C. After reacting at ℃ for 2 hours, the solid part was collected by hot filtration, washed with purified hexane, and dried under reduced pressure at 25 ℃ for 1 hour to obtain a solid product (III
) Got.

The solid product (III) was spherical and had an average particle size of 15 μm, and its particle size distribution was extremely narrow. This solid product (III) was used as a solid Ti catalyst component.

The compositional analysis result of the solid Ti catalyst component was as follows: Ti 3.0% by weight (hereinafter referred to as%), Cl 56.2.
%, Mg 17.6%, Al 1.7%, diisobutyl phthalate 20.1%, butoxy group 1.1%, 2-ethylhexyloxy group 0.2%, p-toluate ethyl 0.1%.
Met. Hereinafter, contact with an iodine compound, prepolymerization, and polymerization were performed in the same manner as in Example 2. The results are shown in Table 1.

Example 10 [Preparation of titanium compound] The titanium compound was prepared according to the method of Example 1 in JP-A-62-111706. That is, a glass three-necked flask (thermometer,
50 ml of purified heptane, 50 ml of titanium tetrabutoxide, 7.0 g of anhydrous magnesium chloride are added to a stirrer). After that, the temperature of the flask was raised to 90 ° C., and magnesium chloride was completely dissolved over 2 hours. Next, the flask was cooled to 40 ° C., and 10 ml of methyl hydrogen polysiloxane was added to precipitate magnesium chloride-titanium tetrabutoxide complex. This was washed with purified heptane to give an off-white solid.

50 ml of a heptane slurry containing 10 g of the precipitated solid obtained above was introduced into a glass three-necked flask (equipped with a thermometer and a stirrer) having an inner volume of 300 ml which was replaced with nitrogen. Then, 20 ml of a heptane solution containing 5.8 ml of silicon tetrachloride was added at room temperature over 30 minutes, and the mixture was further added at 30 ° C. for 4 minutes.
The reaction was performed for 5 minutes. Furthermore, the reaction was carried out at 90 ° C. for 1.5 hours, and after completion of the reaction, the product was washed with purified heptane. Then, 50 ml of a heptane solution containing 1.5 ml of diheptyl phthalate was added and reacted at 50 ° C. for 2 hours, then washed with purified heptane, further 25 ml of titanium tetrachloride was added and reacted at 90 ° C. for 2 hours. This was washed with purified heptane to obtain a solid Ti catalyst component. The titanium content in the solid Ti catalyst component was 3.04% by weight.

Hereinafter, contact with an iodine compound, prepolymerization,
The main polymerization was performed in the same manner as in Example 2. The results are shown in Table 1.

Examples 11 to 12 Using the titanium-containing polypropylene obtained by the prepolymerization of Example 1, propylene was polymerized prior to the copolymerization of propylene ethylene, and the polypropylene portion and the propylene ethylene copolymer portion were separated. Was polymerized.

That is, 1000 ml of propylene, 1.10 mmol of triethylaluminum, and 1.10 of diphenyldimethoxysilane were placed in a ₂ l-autoclave which had been subjected to N ₂ substitution.
After charging mmol, it heated up to 70 degreeC. Next, the titanium-containing polypropylene obtained by the preliminary polymerization was added in an amount of 4.38 × 10 ⁻³ mmol in terms of titanium atom to start the polymerization. 30
Polymerization was carried out for minutes (Example 11) and 60 minutes (Example 12). During this period, the temperature was kept at 70 ° C.

Then, the autoclave was rapidly cooled to 55 ° C., and ethylene was added so that the concentration became 30 mol%.
Polymerization was carried out for 0 minutes. During this period, ethylene is 30 mol%
Was intermittently fed so that the temperature was maintained at 55 ° C. Unreacted monomers were purged to obtain white granular propylene ethylene copolymer. Then, it was decomposed with an organic peroxide in the same manner as in Example 1. The results are shown in Table 1. There was no change compared to before the solution.

Comparative Example 1 The same operation as in Example 1 was carried out except that the contact with the iodine compound of Example 1 and the prepolymerization were not carried out. The results are shown in Table 1. ^{As shown in the 13} C-NMR spectrum,
A peak based on P ^r PEP is clearly observed.

Comparative Example 2 In an autoclave having an internal capacity of 400 liters, which had been subjected to N ₂ substitution, 200 liters of propylene, 3.6 g of δ-TiCl ₃ (manufactured by Marubeni Solvay Co., Ltd.), and Et ₂ AlCl were added in a molar ratio of 10 times relative to δ-TiCl _3. Addition, and the ethylene gas concentration is 13 mol
Polymerization was carried out at 55 ° C. for 60 minutes while supplying so that the amount became 100%. The results are shown in Table 1. ^As shown in the ¹³ C-NMR spectrum, a peak based on P ^r PEP is clearly observed.

Comparative Example 3 500 ml of water-free hexane was charged as a solvent into a glass autoclave having an internal capacity of 1 liter which had been subjected to N ₂ substitution, and vanadium oxytrichloride (VOCl ₃ ) and ethylaluminum sesquichloride (Et) were added. _1.5 AlC
l _1.5) and 0.1mmol respectively, and 1mmol addition, a mixed gas of ethylene and propylene (molar ratio 2: 3) at a rate of 200 l / Hr in a solvent, was supplied for 60 minutes, the polymerization was carried out. During this period, the temperature was kept at 55 ° C. The results are shown in Table 1. ^As shown in the ¹³ C-NMR spectrum, P ^r P
The EP peak is large and clearly observed.

Comparative Examples 4 to 6 Examples 1 and 4 of JP-A-55-118910.
And the same operation as in Example 8 was carried out to obtain a propylene-ethylene copolymer (Comparative Examples 4, 5 and 6 respectively). The propylene-ethylene copolymer obtained in Comparative Example 4 was further decomposed using an organic peroxide. The results are shown in Table 1. As shown in the ¹³ C-NMR spectrum of the propylene-ethylene copolymer obtained in Comparative Example 4, P
^A peak based on rPEP is clearly observed. Comparative Example 7 A propylene-ethylene copolymer was obtained in the same manner as in Example 1, except that prepolymerization was not performed. The results are shown in Table 1.

[Table 1]

[Brief description of the drawings]

FIG. 1 shows ¹³ C-of a propylene ethylene copolymer.
It is a schematic diagram of an NMR spectrum.

FIG. 2 is a ¹³ C-NMR spectrum of the propylene-ethylene copolymer of the present invention obtained in Example 1.

FIG. 3 is an enlarged view of a ¹³ C-NMR spectrum of the propylene-ethylene copolymer of the present invention obtained in Example 1.

FIG. 4 is a ¹³ C-NMR spectrum of the propylene-ethylene copolymer of the present invention obtained in Example 2.

FIG. 5 is an enlarged view of ¹³ C-NMR spectrum of the propylene-ethylene copolymer of the present invention obtained in Example 2.

FIG. 6 is an enlarged view of a ¹³ C-NMR spectrum of the propylene-ethylene copolymer of the present invention obtained in Example 3.

FIG. 7 is a ¹³ C-NMR spectrum of the propylene-ethylene copolymer of the present invention obtained in Example 4.

FIG. 8 is an enlarged view of a ¹³ C-NMR spectrum of the propylene-ethylene copolymer of the present invention obtained in Example 4.

FIG. 9 is a ¹³ C-NMR spectrum of the propylene-ethylene copolymer of the present invention obtained in Example 5.

FIG. 10 is a graph of ^{13 of the} copolymer obtained in Comparative Example 1.
It is a C-NMR spectrum.

FIG. 11 is a graph of ^{13 of the} copolymer obtained in Comparative Example 1.
It is an enlarged view of a C-NMR spectrum.

FIG. 12 is a graph of ^{13 of the} copolymer obtained in Comparative Example 4.
It is a C-NMR spectrum.

Figure 13 is a copolymer obtained in Comparative Example 4 ¹³
It is an enlarged view of a C-NMR spectrum.

Claims (1)

(57) [Claims] 1. A monomer unit based on ethylene (hereinafter referred to as E
Abbreviated) is 15 to 80 mol%, and a propylene-based monomer unit (hereinafter abbreviated as P) is 85 to 20 mol%.
A propylene-ethylene copolymer having a melt flow rate of 0.01 to 50 g / 10 minutes and having 4 consecutive units of P and E of the propylene-ethylene copolymer, PPEP and EPEP The stereoregularity of the unit consisting of the following a) in the ¹³ C-nuclear magnetic resonance spectrum of the propylene ethylene copolymer:
The areas of the peaks in b) and c) are calculated as [P ^r PE
P], [P ^m PEP] and [EPEP],
A propylene-ethylene copolymer having stereoregularity satisfying the following formula (I). a) Peaks derived from a structure in which the stereoregular configuration of the propylene contiguous portion (PP) of the unit consisting of PPEP is racemic. b) A peak derived from a structure in which the stereoregular configuration of the continuous portion of propylene (PP) of the unit consisting of PPEP is meso. c) A peak derived from a unit composed of EPEP. (Equation 1)