JPH0892317A - Propylene-based polymer and its production - Google Patents

Abstract

PURPOSE: To obtain the subject polymer, having sufficiently large nonlinearity of melt tension and elongational viscosity and excellent in uniform wall thickness properties and shape stability by copolymerizing a propylene with a small amount of a polyvalent ene using a metallocene compound. CONSTITUTION: This propylene-based polymer has 2.0-6.0 value of λ indicating the magnitude of the nonlinearity of elongational viscosity with the proviso that λ=λ1 /λ0 (λ0 is the elongational viscosity at the displacement point; λ1 is the elongational viscosity when the stain attains twice that at the displacement point). Furthermore, this method for producing the polymer comprises polymerizing propylene in the presence of a catalyst system, containing 0.05-2wt.% polyvalent ene and comprising a metallocene compound of formula I or II [M is any transition metal of Ti, Zr and Hf; X<1> and X<2> are each H, a 1-10C hydrocarbon, an alkylsilyl or a halogen; R<1> , R<2> , R<5> and R<6> are each H, a 1-10C hydrocarbon or an alkylsilyl; either of R<1> and R<2> is not H; R<3> and R<4> are each a 1-IOC hydrocarbon or an alkylsilyl or both may mutually be bound to form a ring; Y is C or Si; (n) is 1-3] and an aluminoxane compound or a noncordinating ionic compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene-based polymer having excellent melt tension and a large elongation viscosity non-linearity, and a method for producing the same. More specifically, the present invention relates to a propylene-based polymer in which the melting characteristics of conventional polypropylene are improved, and the molding resin has excellent levelness and shape stability, and a method for producing the same.

[0002]

2. Description of the Related Art Propylene-based polymers are excellent in transparency, rigidity, surface gloss and heat resistance as compared with other polyolefins, and have great utility value. However, since the melt tension is small, it is inferior to blow molding, sheet molding, laminate molding, foam molding and the like. In addition, since the elongational viscosity has a small non-linearity, the molding resin is particularly inferior in wall thickness uniformity and shape stability.

As a method of improving these drawbacks, a method of adding a high-pressure low-density polyethylene is known.
However, with this method, the inherent transparency of polypropylene,
The rigidity and heat resistance are impaired, and it cannot be said to be a sufficient improvement. A method for improving the melt tension by copolymerizing an α-olefin and a diene at both ends is described in JP-A-47-43981 and the like, but the effect is limited to ethylene-based polymers. However, propylene-based polymers have not shown sufficient improvement results.

In addition, there are many reports on examples of copolymers of non-conjugated dienes and propylene and the like. Examples of the branched diene having one vinyl type double bond at the terminal include JP-A-4-173814, JP-A-4-170407 and JP-A-3.
-177402, JP-A-2-281011, JP-A-4-28101
28706, JP-A-4-25510, JP-A-2-145.
611, JP-A-62-115007 and the like. Since these use a Ziegler-Natta type catalyst, the conversion rate of the non-conjugated diene to the polymer is small. In addition, since the non-vinyl type double bond is not introduced into the polymer, an effective crosslinked structure is not formed and the melt tension is not improved. Examples of the non-conjugated diene having vinyl type double bonds at both ends include JP-A-6-80729 and JP-A-3-29.
0416, JP-A-3-290417 and the like,
Since these also use the Ziegler-Natta type catalyst, the conversion rate of the non-conjugated diene to the polymer is small and it cannot be said to be an effective means.

Recently, an example of a copolymer of a non-conjugated diene and propylene using a metallocene catalyst has been reported. For example, JP-A-5-222251 and JP-A-5-22
2121 etc. are mentioned. The metallocene-based catalysts used in these examples are not sufficiently large with mm% of less than 98% in ordinary polymerization, the molecular weight is insufficient, and in addition, the nonlinearity of melt tension and extensional viscosity is insufficient. It cannot be put to practical use.

In addition, as a method for producing a propylene-based polymer having an improved melt tension, a. Irradiation of radiation (high energy rays). b. Peroxide crosslinking. And the like, and these are also methods for improving melting characteristics by partially cross-linking after polymerization and introducing long chain branching. However, a requires large-scale equipment, and b
However, since kneading is required, the cost is not desirable.
Further, in both the methods a and b, the resin is deteriorated at the same time, so that the original performance of the resin is easily deteriorated.

[0007]

The object of the present invention is to solve the above-mentioned problems in the prior art and to provide a propylene-based polymer having a sufficiently large melt tension and elongation viscosity upon strain hardening, and an economical method for producing the same. To do.

[0008]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that melt tension can be improved by copolymerizing propylene with a small amount of polyvalent ene using a metallocene compound. The present invention has been accomplished by finding a propylene-based polymer having a sufficiently large elongational viscosity during strain hardening and an effective production method thereof.

The present invention will be described in detail below. The propylene-based polymer in the present invention means homopolypropylene and random polypropylene containing 0 to 10% by weight of ethylene or α-olefin, homopolymer or random polypropylene polymerized in the first stage, and propylene sequentially in the second stage. Ethylene or α-
It means a block polypropylene obtained by polymerizing a rubber component comprising an olefin in an amount of 5 to 70% by weight. The propylene content contained in the random polypropylene is 90% by weight or more, and if it is less than this, the original rigidity is impaired. On the other hand, the propylene content contained in the rubber component is 40 to 70.
Weight percent is preferred. Examples of the α-olefin used above include 1-butene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene and styrene.

The λ value in the present invention is an index of the degree of non-linearity of elongational viscosity developed by the presence of polyvalent ene, and the degree of strain hardening in various moldings is expressed by the elongational viscosity ratio before and after that. It is a representation. Here, λ = λ ₁ / λ ₀ [λ ₀ is the extensional viscosity at the displacement point, and λ ₁ is the extensional viscosity when the strain is twice the strain at the displacement point. The displacement point is a point at which the linear region (extreme deformation region) and the non-linear region (large deformation region) of extensional viscosity are displaced. The range of the λ value is preferably 2.0 or more and less than 6.0, and particularly preferably 3.0 or more and less than 5.0 when importance is attached to thickness uniformity. When the λ value is less than 2.0, sufficient strain hardening does not occur, so that the uniformity and shape stability of the molding resin are poor, and when it is 6.0 or more, the melt fluidity of the polymer decreases and the actual Molding becomes difficult. in addition,
The generation of gel becomes noticeable.

The polyene used in the present invention has a plurality of non-conjugated vinyl groups, has at least two vinyl type double bonds and has 5 to 80 carbon atoms and a molecular weight of 1100.
The following polyvalent enes are valid. A more effective polyvalent ene has 8 to 20 carbon atoms. When the number of vinyl type double bonds is one, it is impossible to effectively increase the melt tension and the extensional viscosity at the time of strain hardening.

As a specific example, 1,4-pentadiene,
1,5-hexadiene, 1,6-heptadiene, 1,7
-Octadiene, 1,8-nonadiene, 1,9-decadiene, 1,13-tetradecadiene, 3-methyl-1,
4-pentadiene, 4-methyl-1,5-hexadiene, 3-methyl-1,5-hexadiene, 1,5,9-
Examples include decatriene.

In the present invention, the content of polyvalent ene introduced into the obtained polyolefin is 0.05 to 2% by weight.
Is. If it is less than 0.05% by weight, the effect of improving the melting property is not remarkable, and if it is 2% by weight or more, the generation of gel or the like is observed, which is a practical problem. The amount is preferably 0.05 to 1% by weight, and more preferably 0.05 to 0.2% by weight in the field of films and the like where appearance is important.

The metallocene compound used in the present invention is
It is represented by the general formula (1) having C ₁ symmetry or the general formula (2) having C ₂ symmetry. The general formula (1) is

[Chemical 3] [M in Formula (1) means a transition metal selected from Ti, Zr, and Hf. X ¹ and X ² may be the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group or a halogen atom. R ¹ , R ² , R ⁵ , and R ⁶ mean a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkylsilyl group, and either one of R ¹ and R ² is not a hydrogen atom.
R ³ and R ⁴ mean a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group, which may be bonded to each other to form a ring. Y means a carbon atom or a silicon atom. In the formula, n is an integer of 1 to 3. ] Is shown. The substituent on the cyclopentadienyl ring is a hydrocarbon group having 1 to 10 carbon atoms (alkyl group, aryl group, alkylaryl group, arylalkyl group, etc.), or
Although it is an alkylsilyl group (trialkylsilyl group, triarylsilyl group, etc.), it is preferably a substituent such as a tert-butyl group having a bulkiness higher than that of a methyl group.

The general formula (2) is

[Chemical 4] [M in Formula (2) means a transition metal selected from Ti, Zr, and Hf. X ¹ and X ² may be the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group or a halogen atom. R ¹ means a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group, and R ⁴ or R ⁵ means a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group. R ² and R ³ represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkylsilyl group, which may be bonded to each other to form a ring. Y means a carbon atom or a silicon atom. Where n is 1 to 3
Is an integer. ] Is shown.

Specific examples of the metallocene compounds represented by the general formulas (1) and (2) in which M is Zr and X ¹ and X ² are chlorine atoms are shown below. As an example of the general formula (1), ethylene (4-methyl-cyclopentadienyl)
(3-methyl-indenyl) zirconium dichloride,
Ethylene (4-t-butyl-cyclopentadienyl) (3
-Methyl-indenyl) zirconium dichloride, ethylene (4-t butyl-cyclopentadienyl) (3-t
Butyl-indenyl) zirconium dichloride, ethylene (4-methyl-cyclopentadienyl) (3-tbutyl-indenyl) zirconium dichloride, ethylene (4-tbutyl-cyclopentadienyl) (3-trimethylsilyl-indenyl) zirconium dichloride , Ethylene (4-tbutyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (4-methyl-cyclopentadienyl) (3-methyl-
Indenyl) zirconium dichloride, isopropylidene (4-tbutyl-cyclopentadienyl) (3-methyl-indenyl) zirconium dichloride, isopropylidene (4-tbutyl-cyclopentadienyl) (3-
t-butyl-indenyl) zirconium dichloride, isopropylidene (4-t-butyl-cyclopentadienyl)
(Fluorenyl) zirconium dichloride, dimethylsilylene (4-tbutyl-cyclopentadienyl) (3-
Methyl-indenyl) zirconium dichloride, dimethylsilylene (4-tbutyl-cyclopentadienyl)
(3-t-Butyl-indenyl) zirconium dichloride, dimethylsilylene (4-tbutyl-cyclopentadienyl) (3-trimethylsilyl-indenyl) zirconium dichloride, dimethylsilylene (4-tbutyl-)
Cyclopentadienyl) (fluorenyl) zirconium dichloride and the like.

As an example of the general formula (2), ethylenebis (2-methyl-indenyl) zirconium dichloride,
Ethylenebis (2-ethyl-indenyl) zirconium dichloride, ethylenebis (2,4-dimethyl-indenyl) zirconium dichloride, ethylenebis (2-methyl-4-tbutyl-indenyl) zirconium dichloride, ethylenebis (2-methyl-) 4-trimethylsilyl-indenyl) zirconium dichloride, ethylenebis (2-methyl-benzindenyl) zirconium dichloride, isopropylidenebis (2-methyl-indenyl) zirconium dichloride, isopropylidenebis (2-ethyl-indenyl) zirconium dichloride,
Isopropylidene bis (2,4-dimethyl-indenyl) zirconium dichloride, isopropylidene bis (2-methyl-4-tbutyl-indenyl) zirconium dichloride, isopropylidene bis (2-methyl-4)
-Trimethylsilyl-indenyl) zirconium dichloride, isopropylidenebis (2-methyl-4-phenyl-indenyl) zirconium dichloride, isopropylidenebis (2-methyl-benzindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-)
Indenyl) zirconium dichloride, dimethylsilylenebis (2-ethyl-indenyl) zirconium dichloride, dimethylsilylenebis (2,4-dimethyl-indenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-tbutyl-indenyl) zirconium dichloride , Dimethylsilylene bis (2-methyl-
Examples thereof include 4-trimethylsilyl-indenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-benzindenyl) zirconium dichloride and the like.

The aluminoxane compound and the non-coordinating ionic compound used in the polymerization will be described below.
The aluminoxane compound used in the present invention is an organoaluminum compound represented by the general formula (3) or the general formula (4). General formula (3)

[Chemical 5] General formula (4)

[Chemical 6] R ⁷ is a methyl group, an ethyl group, a propyl group, a butyl group,
It is a hydrocarbon group such as an isobutyl group, preferably a methyl group. m is an integer of 4 to 100, preferably 6 or more and particularly 10 or more. A method for producing a compound of this kind is known, and for example, a method obtained by adding a trialkylaluminum to a hydrocarbon solvent suspension of salts having crystal water (copper sulfate hydrate, aluminum sulfate hydrate) is exemplified. You can The aluminoxane compound can be used by supporting it on a carrier such as silica, alumina or magnesium chloride. It is also possible to modify it so as to be suitable for each process. For example, when used in a non-liquid phase polymerization method, it can be modified with water or an electron donating compound.

The non-coordinating ionic compound is represented by the following formula. (MX ¹ X ² X ³ X ⁴ ) ^(nm)-. C ^{(nm) +} (In the above formula, M is a metal selected from Groups 5 to 15 in the periodic table, X ¹ , X ² and X ³ , X ⁴ are each a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a substituted alkyl group, A halogen-substituted aryl group, an organic metalloid group or a halogen atom is shown, and C is a counter cation such as carbonium or ammonium.
m is an valence of M and is an integer of 1 to 7, and n is an integer of 2 to 8. )

Specific examples of these compounds include triethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, tri (n-butylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) boron, tributylammonium tetrakis ( Pentafluorophenyl) borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (3,5trifluoromethylphenyl) borate And the like, preferably triphenylcarbonium tetrakis (pentafluorophenyl) borate or dimethylanilinium tetrakis. Pentafluorophenyl) borate - a preparative.

The polymerization method used in the present invention includes liquid phase polymerization (solvent-based solution polymerization, such as high temperature solution polymerization, and solvent-free melt polymerization, such as high-pressure polymerization), slurry polymerization (solvent-based system and solvent-free system). Both systems (eg bulk slurry polymerization) and gas phase polymerization are possible. Further, multistage polymerization in which a plurality of the same or different processes are continuously performed is also possible.

When an aluminoxane compound is used in the polymerization, a mixture of both components of the metallocene compound and the aluminoxane compound may be supplied in advance to the reaction system, or both components may be supplied to the reaction system. In any case, the concentration molar ratio of both components in the polymerization system is not particularly limited, but preferably, the complex concentration is 10 ⁻³ to 10 ⁻¹⁰ mol / l, and the molar ratio of Al / complex is A ratio of 10 or more, particularly 100 or more is preferably used.

When a non-coordinating ionic compound is used in the polymerization, a mixture of the metallocene compound, the trialkylaluminum, and the non-coordinating ionic compound may be supplied to the reaction system. Each component may be supplied individually. In any case, the molar concentration of each component in the polymerization system is not particularly limited, but preferably, the complex concentration is 10 ⁻³ to 10 ⁻¹⁰ m 2.
The molar ratio of trialkylaluminum / complex is preferably in the range of 50 to 1000, and the molar ratio of non-coordinating ionic compound / complex is in the range of 0.5 to 10, particularly preferably in the range of 1 to 5. To be

The olefin pressure in the reaction system is not particularly limited, but is preferably in the range of normal pressure to 50 kg / cm ² G. The amount of polyvalent ene supplied is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the olefin in the reaction system.
Is. The polymerization temperature is not limited, but preferably -30.
C. to 200.degree. C., particularly preferably 0.degree. C. to 80.degree. The molecular weight control during polymerization is
It can be carried out by a known means such as selection of temperature or introduction of hydrogen.

The propylene-based polymer obtained in the present invention can be applied to fields in which it can be used conventionally. For example, injection molded products,
Examples include fields such as films, sheets, blows, laminae, foams and fibers. Further, it can be molded by a usual molding method. As the additives such as the stabilizer, those used in the relevant industry can be applied. In addition, other commonly known resins such as polypropylene, EPR, EBR, EPD
It can be used by mixing with rubber such as M. Further, it can be used in combination with a nucleating agent, an inorganic filler, a fiber and the like.
Further, it is also possible to carry out modification such as grafting reaction, maleic anhydride, etc., crosslinking, bisbreak, etc., as in conventional polyolefins.

[0026]

EXAMPLES Next, the present invention will be specifically described by way of examples. The analytical instruments used for measuring the physical properties are shown below. The content and mm% of polyvalent ene are EX-40 manufactured by JEOL.
It was determined by ¹³ C-NMR measurement using 0. MFR is J
According to IS K6760, temperature 230 ° C, load 2.16
It is a value measured under the condition of kg. The melt tension (MT) value is the melt tension tester II manufactured by Toyo Seiki Co., Ltd.
Using a mold, the diameter of the orifice is 2.095 ± 0.005 mm,
Olephis length 8.000 ± 0.025 mm, resin temperature 230 ° C., take-up speed 6.5 m / min, extrusion speed 1
It is a value measured at 5 m / min. The elongational viscosity was measured using a Toyo Seiki capillary rheometer at a molding temperature of 230 ° C.
Using a uniform strand having a diameter of 3 mm obtained in 1. as a sample, using an extensional viscosity measuring device manufactured by Toyo Seiki Co., Ltd., a measuring temperature of 180
It was measured at a temperature of 0.1 ° C. and a strain rate of 0.1 s ⁻¹ . Further, the presence or absence of the gel component was confirmed by a film having a thickness of about 20 μm formed by a biaxial stretching device manufactured by Toyo Seiki.

Example 1 Isopropylidene (4-tbutyl-cyclopentadienyl) (3-tbutyl-indenyl) zirconium dichloride was synthesized according to JP-A-5-2090013. [Polymerization] S with an internal volume of 1.2 liter which has been sufficiently replaced with nitrogen
In a US autoclave, 1.5 ml of a 0.5 mmol / ml hexane solution of triisobutylaluminum and 1,7
-Added 0.5 g of octadiene, propylene 6mo
After the addition of 1 liter, the temperature was maintained at 25 ° C. Next, 1m of a 0.5 mmol / ml hexane solution of triisobutylaluminum
1, isopropylidene (4-tbutyl-cyclopentadienyl) (3-tbutyl-indenyl) zirconium dichloride 1 μmol / ml toluene solution 1 ml and triphenylcarbonium tetrakis (pentafluorophenyl) borate 2 μmol / ml Polymerization was started by press-fitting a solution prepared by mixing 0.75 ml of a toluene solution in a flask previously replaced with nitrogen with nitrogen from an addition device. Polymerization was carried out for 60 minutes to obtain 85 g of a polymer. The results are shown in Table 1.

(Example 2) Polymerization was carried out according to Example 1 except that 1,9-decadiene was used instead of 1,7-octadiene to obtain 93 g of a polymer.

(Example 3) Polymerization was carried out according to Example 2 except that the amount of 1,9-decadiene used was 2.6 g.
87 g of polymer was obtained.

Example 4 Polymerization was carried out in the same manner as in Example 1 except that 1.3 g of 1,13-tetradecadiene was used instead of 1,7-octadiene to obtain 48 g of a polymer.

Example 5 Tosoh Akzo's methylaluminoxane (2.7mo in terms of aluminum) was placed in an SUS autoclave having an internal volume of 1.2 liters, which was sufficiently replaced with nitrogen.
1 / l of toluene solution) and 0.5 g of 1,9-decadiene are added, followed by isopropylidene (4-t).
1 ml of a 1 μmol / ml toluene solution of butyl-cyclopentadienyl) (3-tbutyl-indenyl) zirconium dichloride was added. Then propylene 6mo
1 was charged and polymerization was carried out at 25 ° C. for 60 minutes. 79 g
A polymer of The results are shown in Table 1.

(Embodiment 6) 300 m fully replaced with nitrogen
5 ml of methylaluminoxane (1.3 mol / l of toluene solution in terms of aluminum) manufactured by Tosoh Akzo Co., Ltd.
0 ml and 50 ml of toluene were added, and then triethyl phosphate 1.16 g was added, and the mixture was heated with stirring at 80 ° C. for 4 hours. Washing with toluene gave a solid modified methylaluminoxane. [Polymerization] S with an internal volume of 1.2 liter which has been sufficiently replaced with nitrogen
In a US autoclave, 2.5 ml of a 0.5 mmol / ml hexane solution of triisobutylaluminum, 50 mg of the triethyl phosphate modified methylaluminoxane prepared above, isopropylidene (4-t butyl-cyclopentadienyl) (3-t Butyl-indenyl) zirconium dichloride 1 μmol / ml toluene solution 1 ml
Was thrown in. Next, 0.5 g of 1,9-decadiene was added together with 6 mol of propylene, and polymerization was carried out at 25 ° C. for 60 minutes. 83 g of polymer was obtained. The results are shown in Table 1.

Example 7 To a 1.2 liter autoclave made of SUS, which had been sufficiently purged with nitrogen, 1.5 ml of a 0.5 mmol / ml hexane solution of triisobutylaluminum and 0.5 g of 1,9-decadiene were added. did. After adding 1.0 mmol of hydrogen and 6 mol of propylene, the temperature was maintained at 25 ° C. Then, 1 ml of a 0.5 mmol / ml hexane solution of triisobutylaluminum, dimethylsilylene (4-tbutyl-cyclopentadienyl)
1 μmol of (fluorenyl) zirconium dichloride
/ Ml toluene solution 1 ml and triphenylcarbonium tetrakis (pentafluorophenyl) borate 2 μmol / ml toluene solution 0.75 ml were mixed in a flask previously purged with nitrogen, and then a suspension was added with nitrogen from an addition device. This started the polymerization. Polymerization was carried out for 60 minutes to obtain 12 g of polymer. The results are shown in Table 1.

(Example 8) Polymerization was carried out in the same manner as in Example 7 except that dimethylsilylenebis (2-methyl-indenyl) zirconium dichloride was used as the metallocene compound to obtain 14 g of a polymer.

(Example 9) Polymerization was carried out according to Example 7 except that dimethylsilylenebis (2-methyl-benzindenyl) zirconium dichloride was used as the metallocene compound to obtain 88 g of a polymer.

(Example 10) Into an autoclave made of SUS having an internal volume of 1.2 liter which had been sufficiently purged with nitrogen, 1.5 ml of a 0.5 mmol / ml hexane solution of triisobutylaluminum and 2.6 g and 1 of 1,9-decadiene were added. −
5.0 g of hexene was added. After adding 1.0 mmol of hydrogen and 6 mol of propylene, the temperature was maintained at 25 ° C. Then 0.5 mmol / m of triisobutylaluminum
1 hexane solution 1 ml, dimethylsilylene bis (2-methyl-benzindenyl) zirconium dichloride 1
A suspension prepared by mixing 1 ml of a μmol / ml toluene solution and 0.75 ml of a 2 μmol / ml toluene solution of triphenylcarbonium tetrakis (pentafluorophenyl) borate in a flask previously replaced with nitrogen was pressurized with nitrogen from an addition device. By doing so, the polymerization was started. Polymerization 6
The operation was performed for 0 minutes to obtain 86 g of a polymer.

(Comparative Example 1) Polymerization was carried out in the same manner as in Example 1 except that 1,7-octadiene was not used. As a result, 70
g of polymer was obtained. MFR = 53 and small molecular weight,
Poor melting characteristics. The results are shown in Table 1.

Comparative Example 2 Polymerization was carried out in the same manner as in Example 2 except that the amount of 1,9-decadiene used was 0,017 g. As a result, 74 g of polymer was obtained. MFR = 16, the molecular weight is small and the melting property is poor.

(Comparative Example 3) Polymerization was carried out in the same manner as in Example 2 except that the amount of 1,9-decadiene used was 17 g and the amount of propylene supplied was 3 mol. As a result, 45 g of polymer was obtained. Gel was observed in the appearance of the biaxially stretched film.

(Comparative Example 4) Polymerization was conducted in the same manner as in Example 1 except that 2.6 g of 1,3-butadiene was used instead of 1,7-octadiene to obtain 11 g of a polymer.

Comparative Example 5 Polymerization was performed in the same manner as in Example 1 except that 5.0 g of 1-hexene was used instead of 1,7-octadiene to obtain 82 g of a polymer. MFR =
The molecular weight is 60 and the molecular weight is small, resulting in poor melting characteristics.

(Comparative Example 6) Polymerization was carried out in the same manner as in Example 7 except that 1,9-decadiene was not used, and 13 g of a polymer was obtained. The results are shown in Table 1.

(Comparative Example 7) Polymerization was conducted in the same manner as in Example 8 except that 1,9-decadiene was not used, and 13 g of a polymer was obtained. The results are shown in Table 1.

(Comparative Example 8) Polymerization was conducted in the same manner as in Example 9 except that 1,9-decadiene was not used, to obtain 88 g of a polymer. The results are shown in Table 1.

Comparative Example 9 Polymerization was carried out according to Example 2 except that ethylenebis (indenyl) zirconium dichloride was used as the metallocene compound to obtain 41 g of a polymer. MFR = 15, which is small in molecular weight and inferior in melting property.

[0046]

[Table 1]

[0047]

Industrial Applicability According to the present invention, it is possible to provide a propylene-based polymer having a sufficiently large non-linearity of melt tension and elongational viscosity and excellent in thickness uniformity and shape stability of a molding resin.

Claims (3)

[Claims] 1. A propylene-based polymer characterized by having a λ value showing a degree of nonlinearity of extensional viscosity of 2.0 or more and less than 6.0. Here, λ = λ ₁ / λ ₀ [λ ₀ is the extensional viscosity at the displacement point, and λ ₁ is the extensional viscosity when the strain is twice the strain at the displacement point. The displacement point is a point at which the linear region (extreme deformation region) and the non-linear region (large deformation region) of extensional viscosity are displaced. ] 2. The propylene-based polymer according to claim 1, which contains 0.05 to 2% by weight of polyvalent ene. 3. A method represented by the general formula (1) or (2):
Talocene compounds and aluminoxane compounds or non-
Polymerization using a catalyst system composed of coordinating ionic compounds
The propylene-based heavy according to claim 1 or 2, characterized in that
Manufacturing method of coalescence. [Chemical 1][M in Formula (1) is a transition of Ti, Zr, or Hf.
Means metal. X¹And X² Are the same or different
May be hydrogen atom, carbonization of 1 to 10 carbon atoms
Hydrogen group, alkylsilyl group, halogen atom
To taste. R¹ , R² , R^Five , R⁶ Is hydrogen atom, carbon atom
Means a hydrocarbon group having 1 to 10 children and an alkylsilyl group
Then R¹ , R² One of them is not a hydrogen atom.
Also, R ³ , R^Four Is a hydrocarbon having 1 to 10 carbon atoms
Group or alkylsilyl group, which are bonded to each other
May form a ring. Y is a carbon atom or a silicon atom
Means In the formula, n is an integer of 1 to 3. ] [Chemical 2][M in Formula (2) is a transition of Ti, Zr, or Hf.
Means metal. X¹And X² Are the same or different
May be hydrogen atom, carbonization of 1 to 10 carbon atoms
Hydrogen group, alkylsilyl group, halogen atom
To taste. R¹ Is a hydrocarbon group having 1 to 10 carbon atoms,
R is a silyl group, R^Four , R^Five Is a hydrogen atom, charcoal
Hydrocarbon group having 1 to 10 elementary atoms, alkylsilyl group
means. Also, R² , R³ Is the number of hydrogen atoms and carbon atoms
1 to 10 hydrocarbon groups or alkylsilyl groups
Meaning, they may combine with each other to form a ring. Y is carbon
Means an atom or a silicon atom. Where n is 1 to 3
Is an integer. ]