JPH0639511B2 - 4-Methylpentene-1-based block copolymer and method for producing the same - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a block copolymer comprising 4-methylpentene-1 and ethylene and a method for producing the same. More specifically, the present invention provides a crystalline 4-methylpentene-1-ethylene block copolymer having excellent thermal properties and impact resistance.

<Technical Background and Problems of Invention> Conventionally, polyethylene has excellent impact resistance but low heat resistance, and poly-4-methylpentene-1 has high heat resistance but low impact resistance. It was

Regarding materials having a good balance of heat resistance and impact resistance, JP-A-56-81326, JP-A-55-137116 and the like describe polyethylene or polypropylene with ethylene-4-methyl-pentene-1 copolymer or It is described that the heat resistance and the impact resistance are improved by introducing the propylene-4-methylpentene-1 copolymer block.

In such a conventional technique, although the impact resistance is improved, the improvement in heat resistance cannot be said to be sufficient. Further, since all of them are random copolymers, the amount of amorphous polymer is increased, which causes a problem such as the reactor fouling.

On the other hand, regarding a 4-methylpentene-1-ethylene block copolymer, a proposal for improving the embrittlement temperature is made in JP-B-45-33903. In this method, addition of Ti (OR) ₄ causes dimerization of ethylene to give butene-1, and a terpolymer of 4-methylpentene-1, ethylene and butene-1 is substantially obtained. ing. Although an improvement in the embrittlement temperature due to the formation of the amorphous polymer can be seen, there is a problem in that the rigidity is low due to the large amount of the polymer, and the reactor's fouling and the like occur.

Further, although blends of homopolymers may be considered, the blends have drawbacks such that it is difficult to uniformly disperse each other and heat deterioration of the polymer is likely to occur during mixing.

<Object of the Invention> The present invention provides a 4-methylpentene-1 system block copolymer having excellent thermal properties as compared with a homopolymer of corresponding monomers or a mixture thereof, and a method thereof. is there.

A polymer mixture with excellent thermal properties can be obtained, but the optimum mixing range is extremely narrow, and since mixing requires shearing force at high temperature, deterioration of the polymer is likely to occur, and uniform dispersion is difficult. Is.

The present invention solves these drawbacks, has high rigidity over a wide composition range, is excellent in heat resistance and impact resistance, and produces less amorphous polymer, and 4-methylpentene-1 polymer and its A manufacturing method is provided.

<Outline of the Invention> The present invention provides a crystalline block copolymer having excellent thermal properties and impact resistance obtained by block copolymerizing 4-methylpentene-1 with ethylene.

Specifically, the first invention is 4-methyl produced using a catalyst comprising (1) a solid substance containing at least magnesium and titanium, (2) an organometallic compound, and (3) an electron donor. A block copolymer of pentene-1 and ethylene, which is a 4-methylpentene-1-ethylene block copolymer having the following characteristics (a) to (f): (a) copolymer 4-methylpentene-1 part is 95 to 5
0% by weight and 5 to 50% by weight of ethylene part, (b) the intrinsic viscosity (135 ° C, in decalin) is 0.5 to 15d.
/ G, (c) at least one of the melting points measured by a differential scanning calorimeter (DSC) is 170 ° C. or higher, and (d) a dynamic elastic modulus E by a dynamic viscoelasticity measurement method. ′ Is 4.5 ×
The temperature for holding 10 ⁸ dyn / cm ² or more is 150 ° C. or more, and (e) the flexural modulus (ASTM D 747-70) is 6,
000-11,000 kg / cm ² , (f) Izod impact strength at -10 ° C (JIS K
7110) is 2.0 kgcm / cm or more.

A second invention relates to a method for producing the copolymer,
In the presence of a catalyst consisting of (1) a solid substance containing at least magnesium and titanium, (2) an organometallic compound, and (3) an electron donor, 4-methylpentene-1 and ethylene are copolymerized to form a block copolymer. In producing the polymer,
The first polymerization step is performed at 50 ° C. or lower, and the second polymerization step is performed at 50 ° C. in the substantially absence of the monomer of the first polymerization step.
There is a method for producing a 4-methylpentene-1-ethylene block copolymer having the following characteristics (a) to (f) by performing the polymerization as described above: (a) 4-methylpentene-in the copolymer One copy is 95-5
0% by weight and 5 to 50% by weight of ethylene part, and (b) the intrinsic viscosity (135 ° C, in decalin) is 0.5 to 15d.
/ G, (c) at least one of the melting points measured by a differential scanning calorimeter (DSC) is 170 ° C or higher, and (d) the dynamic elastic modulus E'by the dynamic viscoelasticity measurement method is 4.5 x
The temperature for holding 10 ⁸ dyn / cm ² or more is 150 ° C. or more, and (e) the flexural modulus (ASTM D 747-70) is 6,
000-11,000 kg / cm ² , and (f) Izod impact strength at -10 ° C (JIS K
7110) is 2.0 kg · cm / cm or more.

<Detailed Description of the Invention> (A) Block Copolymer (a) Composition The block copolymer of the present invention is a crystalline block copolymer composed of 4-methylpentene-1 and ethylene.

The composition of the copolymer of the present invention has a weight ratio of 4-methylpentene-1 / ethylene of 95/5 to 50/50, preferably 95/5 to 60/40, and more preferably 90/1.
It is 0 to 70/30.

When the ethylene content of the copolymer exceeds 50% by weight, the heat resistance of the copolymer deteriorates, while when the ethylene content is less than 5% by weight, there is a problem in impact resistance.

(b) Intrinsic Viscosity The intrinsic viscosity ([η]) of the copolymer of the present invention is 0.5 to 15 d / g as measured in decalin at 135 ° C.

When [η] is less than 0.5, the viscosity at the time of melting is too low and molding is difficult. When [η] exceeds 15, the viscosity at the time of melting is too high and the flowability is extremely deteriorated, which makes molding difficult.

(c) Melting point The melting point represents the position of the melting peak obtained by measurement with a differential scanning calorimeter (DSC).

If at least one of these melting points does not exist at 170 ° C. or higher, the heat resistance of the copolymer deteriorates.

(d) Dynamic Modulus E ′ The copolymer of the present invention is characterized by high mechanical strength over a wide temperature range.

As a method for evaluating thermal properties, a dynamic viscoelasticity measurement method is used,
The dynamic elastic modulus E'obtained in the same measurement was evaluated, and E'was 4.
It is necessary that the temperature for holding 5 × 10 ⁸ dyn / cm ² or more is 150 ° C. or more.

When E'is 4.5 × 10 ⁸ dyn / cm ² or less, the mechanical strength of the polymer is insufficient.

More specifically, for example, the temperature at which E'of poly-4-methylpentene-1 holds 4.5 × 10 ⁸ dyn / cm ² is as high as 229 ° C., and the heat resistance is good. Since it is 138 ° C., it cannot be said that the thermal property is good.

(e) Flexural rigidity The flexural rigidity of the copolymer of the present invention is ASTM-D-747.
The value measured according to −70 is 6,000 to 11,000.
It is 0 kg / cm ² . Bending rigidity less than 6,000 kg / cm ² is soft, and bending rigidity is 11,000 kg / c.
If it exceeds m ² , the rigidity is high but it becomes brittle, which is not preferable.

(f) Izod impact strength The copolymer of the present invention has an Izod impact strength (JIS K7110) measured at -10 ° C of 2.0 kg · cm / cm or more.

Those having an Izod impact strength of less than 2.0 kg · cm / cm are not preferable because the impact strength is weak.

(B) Copolymerization (a) catalyst The catalyst used in the present invention is a combination of (1) a solid substance containing at least magnesium and titanium, (2) an organometallic compound, and (3) an electron donor,
Examples of the solid substance include metal magnesium, magnesium hydroxide, magnesium carbonate, magnesium oxide,
Magnesium chloride and the like, and double salts, double oxides, carbonates, chlorides containing a magnesium atom and a metal selected from magnesium, silicon, aluminum and calcium,
Inorganic solids such as hydroxides and those obtained by treating or reacting these inorganic solid carriers with oxygen-containing compounds, sulfur-containing compounds, hydrocarbons, halogen-containing substances, silicon-containing compounds, nitrogen-containing compounds, phosphorus-containing compounds, etc. An example is a carrier in which a titanium compound is supported by a known method.

Examples of the oxygen-containing compound include alcohols, aldehydes, ketones, ethers, carboxylic acids and their derivatives. Thiouene as a sulfur-containing compound,
Thiol and the like are preferable. Aromatic hydrocarbons are preferable as the hydrocarbon, and specific examples thereof include deurene, anthracene, and naphthalene. The halogen-containing substance is preferably a halogenated hydrocarbon, specifically 1,2
-Dichloroethane, n-butyl chloride, t-butyl chloride, p-dichlorobenzene and the like can be mentioned. As the silicon-containing compound, tetraethoxysilane, vinyltriethoxysilane, and allyltriethoxysilane are preferable. Examples of the nitrogen-containing compound include acid amides, amines and nitriles, particularly benzoic acid amides, pyridine,
Benzonitrile is preferred. Examples of the phosphorus-containing compound include phosphites and phosphites, with triphenyl phosphite, triphenyl phosphite, tri-n-butyl phosphite, and tri-n-butyl phosphite being particularly preferable.

Examples of other solid substances that can be preferably used in the present invention include reaction products of organomagnesium compounds such as so-called Grignard compounds and titanium compounds. As the organic magnesium compound, for example,
Organomagnesium compounds such as those represented by the general formulas RMgX, R ₂ Mg, and RMg (OR) (wherein R is an organic residue,
X represents halogen) and their ether complexes,
Further, these organomagnesium compounds are further added with other organometallic compounds such as organosodium, organolithium,
Those modified by adding various compounds such as organic potassium, organic boron, organic calcium, and organic zinc can be used.

Examples of the titanium compound used in the present invention include titanium halides, alkoxy halides, oxides, and halogenated oxides. Specific examples of these are titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium,
4 such as monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium and tetraisopropoxytitanium
Examples include various titanium trihalides obtained by reducing a tetravalent titanium compound and titanium tetrahalide with hydrogen, aluminum, titanium or an organometallic compound, and various tetravalent halogenated alkoxytitaniums with an organometallic compound. Examples thereof include trivalent titanium compounds such as compounds obtained by reduction.

Of these titanium compounds, tetravalent titanium compounds are particularly preferable.

Specific examples of these solid substances include Mg
O-RX-TiCl ₄ system (Japanese Patent Publication No. 51-3514),
MgO-AlCl ₃ -TiCl ₄ system (JP-A-54-134
789 _{No.), Mg-SiCl 4 -ROH-} TiCl 4 type (JP-B-50-23864), MgCl ₂ -Al (O
R) ₃ -TiCl ₄ system (Japanese Patent Publication Nos. 51-152 and 5)
2-15111 Patent), Mg-Cl ₂ - aromatic hydrocarbons -
TiCl ₄ system (Japanese Patent Publication No. 52-48915), MgCl ₂
-SiCl ₂ -ROH-TiCl ₄ system (JP-A-49-10
6581), Mg (OOCR) _2- Al (OR) _3- TiC
l ₄ system (JP-B-52-11710), MgCl ₂ -RX
-TiCl ₄ system (JP-A-52-42584), Mg-
POCl ₃ -TiCl ₄ system (Japanese Patent Publication No. 51-153), M
gCl ₂ -AlOCl-TiCl ₄ system (Japanese Patent Publication No. 54-15)
316), RMgX-TiCl ₄ system (Japanese Patent Publication No. 50-3)
9470 _{No.), MgCl 2 -CH 2 = CHSi} (OR) 3 -
P (OR) ₃ -ROR-TiCl ₄ system (Japanese Patent Application No. 58-178
No. 272), MgCl ₂ —CH ₂ ═CHSi (OR) ₃ —P
Typical examples are solid catalyst components such as (OR) ₃ -TiCl ₄ system (Japanese Patent Application No. 58-3558).

As the organometallic compound (2) used in the present invention, organometallic compounds of groups I to IV of the periodic table, which are known as a component of Ziegler catalyst, can be used, but organoaluminum compounds and organozinc compounds are particularly preferred. Specific examples include the general formulas R ₃ Al, R ₂ AlX, RAlX ₂ , and R ₂ Al.
Organoaluminum compounds of OR, RAl (OR) X and R ₃ Al ₂ X ₃ (wherein R represents an alkyl group or aryl group having 1 to 20 carbon atoms, X represents a halogen atom, and R may be the same or different) ) Or a general formula R ₂ Zn (wherein R is an alkyl group having 1 to 20 carbon atoms, which may be the same as or different from each other), specifically, triethylaluminum. , Triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride, diethyl aluminum ethoxide, ethyl aluminum sesquichloride,
Examples include diethylzinc and mixtures thereof.

In the present invention, the amount of the organometallic compound used is not particularly limited, but is usually 0.1 to 1000 relative to the titanium compound.
It can be used in molar times.

Examples of the electron donor (3) used in the present invention include carboxylic acid esters, ethers, ketones, alcohols, silicic acid esters and the like.
Among them, silicic acid esters, particularly tetraethoxysilane, monophenyltriethoxysilane, and monophenyltrimethoxysilane are preferable.

In the present invention, the amount of the electron donor used is not particularly limited, but is usually 0.01 to 1 with respect to the organometallic compound.
It can be used 0 times by mole, preferably 0.1 to 5 times by mole.

(b) Block Copolymerization The process for producing the block copolymer of the present invention comprises at least two steps: a step (A) of producing a block part consisting of 4-methylpentene-1 and a step (B) of producing an ethylene block part. Consists of.

The order of step (A) and step (B) is not particularly limited. The preferred block copolymerization method is described below.

In step (A), 4-methylpentene-1 is polymerized in the presence or absence of a solvent. Examples of the solvent used include saturated aliphatic hydrocarbons such as butane, pentane, hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, and inert solvents such as alicyclic hydrocarbons such as cyclopentane and cyclohexane. However, bulk polymerization using 4-methylpentene-1 as a solvent is preferable.

The polymerization temperature is 50 ° C or lower, and particularly preferably 20 to 50 ° C. If the polymerization temperature is out of the above range, the heat resistance of the resulting copolymer will not be improved.

The polymerization time is not particularly limited and is usually 1 to 1000 minutes, preferably 5 to 300 minutes.

The molecular weight can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but it is effectively performed by adding hydrogen to the polymerization system.

Then, after removing 4-methylpentene-1 remaining in the step (A) by an appropriate method such as purging or distillation, the step
Polymerization of ethylene is carried out in (B).

Polymerization of ethylene is carried out in the gas phase or in the presence of an inert solvent.

As the inert solvent, the same one as in step (A) can be used.

The polymerization condition in step (B) is a temperature of 50 ° C. or higher, preferably 50
The polymerization time is usually from 1 to 1000 minutes, preferably from 5 to 300 minutes, although the polymerization time is not particularly limited.

When the polymerization temperature is out of the above range, the polymerization rate becomes slow, and the thermal properties of the obtained copolymer deteriorate.

The molecular weight can be controlled effectively by adding hydrogen. If necessary, prior to the polymerization in step (B), ethylene may be used for prepolymerization. The prepolymerization conditions are 20 to 50 ° C. and 5 to 120 minutes. Such treatment improves the polymer particle properties of the resulting copolymer.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples.

Various measuring methods in the examples will be shown below.

(1) Melting point Differential scanning calorimeter (Seiko Electronics Co., Ltd., SSC /
Set the sample (about 10 mg) in 580 DSC 30),
After being kept at 260 ° C. for 5 minutes, the temperature is lowered to 40 ° C. at 10 ° C./minute and kept at the same temperature for 5 minutes. Then, the temperature was raised at 10 ° C./min, and the peak position at the time of temperature rise was taken as the melting point.

(2) Izod impact strength Using an impact tester with a refrigerator manufactured by Toyo Seiki Co., Ltd., JIS
It measured at -10 degreeC based on -K-7110.

(3) Bending Rigidity Using an Orzen type rigidity measuring instrument manufactured by Toyo Tester Industry Co., Ltd., the bending rigidity was measured according to ASTM D-747-70.

(4) 4-Methylpentene-1 Content A calibration curve was prepared in advance using infrared spectroscopy and ¹³ C-NMR, and the content was measured using infrared spectroscopy. A ₇₂₀
/ A ₉₂₀ ratio (where A is the wavenumber expressed as a decimal number (cm ^-1 ).
Represents the absorbance ratio at. ) And the calibration curve, 4-methyl-1
-The pentene content was determined.

(5) Measurement of Dynamic Elastic Modulus E'It was measured under the following conditions using a viscoelasticity spectrometer VES-F type manufactured by Iwamoto Seisakusho.

Measurement conditions: temperature range −150 ° C. to melting point Temperature rising rate 1 ° C./min Frequency 5 Hz Test piece Length 30 mm, width 4 mm, thickness 1 mm Example 1 (a) Production of solid catalyst component Anhydrous magnesium chloride 10 g (105 mmol) And vinyltriethoxysilane 1.84m (8.8mmol)
And 1.2 m (4.6 mmol) of triphenyl phosphite were placed in a stainless steel pot with an internal volume of 400 m containing 25 stainless steel balls each having a diameter of 1/2 inch, and the balls were kept under a nitrogen atmosphere at room temperature for 6 hours. After milling, diphenyl ether 0.3
4 g (2 mmol) was added and further 16 under nitrogen atmosphere.
Time ball milling was performed. 5 g of the obtained solid powder
Then, 20 m of titanium tetrachloride was placed in a 200 m round bottom flask and stirred at 100 ° C. for 2 hours under a nitrogen atmosphere. Then, in order to remove the excess titanium tetrachloride, the washing liquid was washed with hexane until titanium tetrachloride was not observed. Then, it was dried under reduced pressure to obtain a solid catalyst component. 1 g of the obtained solid catalyst component contained 26 m of titanium.

(b) Polymerization 3 The stainless steel autoclave with an induction stirrer of 3 was replaced with nitrogen, and 4-methylpentene-1 was 750 m.
Then, 2.5 mmol of triethylaluminum, 1.4 mmol of phenyltriethoxysilane and 100 mg of the above solid catalyst component were added, and the temperature was raised to 50 ° C. with stirring to polymerize 4-matylpentene-1 for 60 minutes. Natsuta.

After that, 4-methylpentene-1 was purged to the outside of the system, 1500 m of hexane was added, 1 mmol of diethylene glycol mono-n-butyl ether was added, and further hydrogen was charged so that the partial pressure of vapor phase was 1.3 kg / cm ^2. Then, the system was heated to 70 ° C. Ethylene was continuously introduced so that the total pressure was 4.3 kg / cm ² · G, and polymerization was carried out for 6 minutes.

After completion of the polymerization, excess ethylene was discharged and methanol was added to terminate the polymerization. The content was taken out and immersed in hydrochloric acid-acidified methanol for a day and dried to obtain 82 g of a white polymer. This is the total amount of the product including the amorphous polymer. The catalytic activity is 31,500 g copolymer / gTi,
The amount of amorphous polymer soluble in hexane was 4.3 wt%.

Table 1 shows the physical properties of the obtained copolymer. The measurement results of the IR spectrum and the dynamic elastic modulus E'of the copolymer are shown in FIGS. 1 and 2, respectively.

Example 2 In Example 1, the solid catalyst component was changed to 50 mg, hydrogen was charged so that the partial pressure was 0.025 kg / cm ^2, and the first stage polymerization was carried out for 90 minutes. Pressure 0.9kg / c
Polymerization was performed at m ² and a total pressure of 3.0 kg / cm ² . Polymerization conditions other than the above are the same as in Example 1. The results are shown in Table 1.

Example 3 The procedure of Example 1 was repeated except that the polymerization conditions of Example 1 were changed as shown in Table 1. The results are shown in Table 1.

The stainless steel autoclave with an induction stirrer of Examples 4 to 63 was replaced with nitrogen, and 1500 m of n-hexane was added,
2.5 mmol of triethylaluminum and 100 mg of the solid catalyst component of Example 1 were added, and the first stage ethylene polymerization was carried out under the polymerization conditions shown in Table 1. After that, unreacted ethylene and n-hexane as a polymerization solvent were purged out of the system, and then 4-methylpentene- was used as a second stage polymerization.
750 m and phenyltriethoxysilane 1.
4 mmol was added and the second reaction was carried out under the polymerization conditions shown in Table 1.
A staged polymerization was carried out. The results are shown in Table 1.

Example 7 Using the solid catalyst component of Example 1 (50 mg), the first stage polymerization was carried out under the polymerization conditions shown in Table 1, followed by the second step.
Before carrying out the step, ethylene was injected under pressure so that the internal pressure was 2 kg / cm ^2, and prepolymerization was carried out at 20 ° C. for 10 minutes without newly supplying ethylene. Then, a second stage ethylene polymerization was carried out under the polymerization conditions shown in Table 1.

The results are shown in Table 1.

Comparative Examples 1 and 2 Using the catalyst of Example 1, ethylene (solid catalyst component 10 m
g) and 4-methylpentene-1 (solid catalyst component 50 m
The homopolymerization of g) was carried out. Table 2 shows the polymerization conditions and results.
It was shown to.

Comparative Examples 3 and 4 Using the catalyst of Example 1, copolymers having 4-methylpentene-1 contents of 2 wt% and 97 wt% were synthesized. The polymerization conditions and the properties of the copolymer are shown in Table 2.

Comparative Example 5 Using the catalyst of Example 1, the polymerization temperature in the first polymerization stage was adjusted to 80
Polymerization was carried out in the same manner as in Example 1 except that the temperature was 40 ° C, the hydrogen partial pressure was 0.05 kg / cm ² , the polymerization time was 60 minutes, the polymerization temperature was 40 ° C in the second polymerization step, and the polymerization time was 10 minutes. as a result,
The amount of the amorphous polymer soluble in hexane was 13.0 wt%, which was larger than that in Example 2. Other properties are shown in Table 2.

Comparative Example 6 40 g of polyethylene (obtained in Comparative Example 1) and 10 g of poly-4-methylpentene-1 (obtained in Comparative Example 2) were used 260 in a nitrogen atmosphere using a Toyo Seiki KK Plastograph. The mixture was kneaded at 5 ° C for 5 minutes to obtain a blended product. The properties of the blend are shown in Table 2.

Example 8 (a) Preparation of solid catalyst component Stainless steel pot with an internal volume of 400 m containing 10 g of anhydrous magnesium chloride and 0.5 m of 1,2-dichloroethane containing 25 stainless steel balls having a diameter of 1/2 inch. In a nitrogen atmosphere at room temperature for 1
Ball milling was done for 6 hours. Obtained solid powder 5
g and 20 m of titanium tetrachloride were placed in a 200 m round bottom flask and stirred at 100 ° C. for 2 hours under a nitrogen atmosphere. Then, in order to remove the excess titanium tetrachloride, the washing liquid was washed with hexane until titanium tetrachloride was not observed. Then, it was dried under reduced pressure to obtain a solid catalyst component. 13.2 g of the obtained solid catalyst component contained 23.2 mg of titanium.

(b) Polymerization Polymerization was carried out in the same manner as in Example 1 except that the above solid catalyst component was used. The properties of the obtained copolymer are shown in Table 1.

Example 9 (a) Production of solid catalyst component 40 g of magnesium oxide and 133 g of aluminum trichloride
A stainless steel pot having an internal volume of 400 m containing 25 stainless steel balls each having a diameter of 1/2 inch and 9.5 g of a reaction product obtained by heating and reacting with and heated at 300 ° C. for 4 hours and 1.7 g of titanium tetrachloride. put in,
Ball milling was performed for 16 hours at room temperature under a nitrogen atmosphere. 39 mg per 1 g of solid powder obtained after ball milling
It contained titanium.

(b) Polymerization Polymerization was carried out in the same manner as in Example 1 except that the solid catalyst component obtained above was used. The properties of the obtained copolymer are shown in Table 1.

[Brief description of drawings]

FIG. 1 shows 4-methylpentene-1-obtained in Example 1.
FIG. 3 is a diagram showing an IR spectrum of an ethylene block copolymer. The horizontal axis represents the wave number (cm ^-1 ). FIG. 2 is a diagram showing the measurement results of the temperature dependence of the dynamic elastic modulus E '. The vertical axis represents E '(dyn / cm ² , logarithmic scale), and the horizontal axis represents temperature (° C).

Claims (2)

[Claims] 1. A solid substance containing (1) at least magnesium and titanium, (2) an organometallic compound, and (3) the following (a) produced using a catalyst comprising an electron donor:
A 4-methylpentene-1-ethylene block copolymer having the characteristics of (f) to (f). (a) 4-methylpentene-1 part in the copolymer is 95 to 5
0% by weight and 5 to 50% by weight of ethylene part, (b) the intrinsic viscosity (135 ° C, in decalin) is 0.5 to 15d.
/ G, (c) at least one of the melting points measured by a differential scanning calorimeter (DSC) is 170 ° C. or higher, and (d) a dynamic elastic modulus E by a dynamic viscoelasticity measurement method. ′ Is 4.5 ×
The temperature for holding 10 ⁸ dyn / cm ² or more is 150 ° C. or more, and (e) the flexural modulus (ASTM D 747-70) is 60.
0 to 11,000 kg / cm ² , (f) Izod impact strength at -10 ° C (JIS K
7110) is 2.0 kgcm / cm or more. 2. Coexisting 4-methylpentene-1 and ethylene in the presence of a catalyst comprising (1) a solid substance containing at least magnesium and titanium, (2) an organometallic compound, and (3) an electron donor. In producing the block copolymer by polymerization, the first polymerization step is performed at 50 ° C. or lower, and the second polymerization step is performed at 50 ° C. or higher substantially in the absence of the monomer of the first polymerization step. (A) 4-methylpentene-1 part in the copolymer was 95 to 5
0% by weight and 5 to 50% by weight of ethylene part, and (b) the intrinsic viscosity (135 ° C, in decalin) is 0.5 to 15d.
/ G, (c) at least one of the melting points measured by a differential scanning calorimeter (DSC) is 170 ° C or higher, and (d) the dynamic elastic modulus E'by the dynamic viscoelasticity measurement method is 4.5 x
The temperature for holding 10 ⁸ dyn / cm ² or more is 150 ° C. or more, and (e) the flexural modulus (ASTM D 747-70) is 6,
000-11,000 kg / cm ² , and (f) Izod impact strength at -10 ° C (JIS K
7110) is 2.0 kg · cm / cm or more, a 4-methylpentene-1-ethylene block copolymer is produced.