JP3279652B2 - Foam molding - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a foam molded article obtained by foaming a specific olefin polymer.

[0002]

BACKGROUND OF THE INVENTION Conventionally, high density polyethylene,
Olefin polymers typified by linear low-density polyethylene and polypropylene are excellent in transparency,
It has excellent mechanical strength such as rigidity and impact strength, and is used as various parts. For example, home appliances such as refrigerator linings are manufactured from polypropylene.

[0003] In order to produce a foam molded article by foaming an olefin polymer such as polypropylene, the olefin polymer cannot be foamed at a high foaming rate because of its low melt tension (MT). ,
There were problems such as the foam cells being coarse and the size of the foam cells being non-uniform.

Therefore, if an olefin polymer having a high melt tension appears, a foam molded article having a high foaming rate, a dense foam cell and a uniform foam cell size can be produced from the olefin polymer. Will be able to

The present inventors have studied on olefin polymers having a high melt tension in order to meet the above requirements. As a result, the α-olefin / polyene copolymer-containing olefin polymer comprising the α-olefin / polyene copolymer and the olefin polymer has a high melt tension, a high foaming rate, and a dense foam cell. The inventors have found that the cells can be uniformly foamed, and thus have excellent bending properties, and have completed the present invention.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a foam molded article which is made of a specific olefin polymer, has a high foaming rate, is dense in foam cells, and is foamed uniformly in foam cell size.

[0007]

According to the present invention, [A] a catalyst component for a transition metal compound and [B] Group I of the periodic table
-Organic metal compound catalyst containing metal selected from group III to group III
With the component, α-olefin and polyene are copolymerized
99. A structural unit derived from an α-olefin.
Derived from the polyene compound in an amount of 999-50 mol%
The structural unit is contained in an amount of 0.001 to 50 mol%.
Α-olefin / polyene copolymer (i)
Polymerization or copolymerization of olefins using a prepolymerization catalyst
Thus, there is provided a foam molded article comprising an α-olefin / polyene copolymer-containing olefin polymer obtained by forming an olefin polymer (ii) .

[0008] Such an α-olefin / polyene copolymer-containing polymer includes, for example, [A] a transition metal compound catalyst component selected from Ti, Zr, Hf, Cr and V, and [B]. In the organometallic compound catalyst component containing a metal selected from Groups I to III of the periodic table, an α-olefin and a polyene compound are added in an amount of 0.01 to 2000 g per 1 g of the [A] transition metal compound catalyst component. It can be produced by polymerizing or copolymerizing an olefin with a prepolymerized catalyst containing an α-olefin / polyene copolymer (i) which has been copolymerized to form an olefin polymer (ii).

[0009]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the foamed molded article comprising the olefin polymer according to the present invention will be specifically described.
First, the α-olefin / polyene copolymer-containing olefin polymer (hereinafter sometimes simply referred to as “olefin polymer”) constituting the foamed molded product will be described in detail.

Such an α-olefin / polyene copolymer-containing polymer comprises (i) an α-olefin / polyene copolymer and (ii) an olefin polymer.

Such an α-olefin / polyene copolymer-containing polymer includes, for example, a copolymer of α-olefin and polyene compound in [A] a transition metal compound catalyst component and [B] an organometallic compound catalyst component. It is obtained by polymerizing or copolymerizing an olefin with a prepolymerized catalyst containing the polymerized α-olefin / polyene copolymer (i) to form an olefin polymer (ii).

The α-olefin and the polyene compound used for forming the above-mentioned α-olefin / polyene copolymer (i) will be described. Examples of the α-olefin used in the present invention include α-olefins having 2 to 20 carbon atoms, and specifically, ethylene, propylene, 1-
Butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, Examples include 1-hexadecene, 1-octadecene, and 1-eicosene. These may be used alone or in combination.

The α-olefin may be the same as or different from the α-olefin forming the olefin polymer (ii) described below. Of these, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 3-methyl
1-butene, 1-eicosene and the like are preferably used.

Further, specific examples of the polyene compound include the following compounds. 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,
6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 6-methyl-1,6-nonadiene, 7-
Methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-
Ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7-
Methyl-1,6-decadiene, 6-methyl-1,6-undecadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-octadiene, 1,6-heptadiene, 1,7-octadiene, 1, 8-nonadiene, 1,9-decadiene, 1,13-tetradecadiene,
1,5,9-decatriene, butadiene, aliphatic polyene compounds such as isoprene, vinylcyclohexene, vinylnorbornene, ethylidene norbornene, dicyclopentadiene, cyclooctadiene, 2,5-norbornadiene,
1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,3-divinylcyclopentane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,4-
Diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5-diallylcyclooctane, 1-allyl-4-isopropenylcyclohexane, 1-isopropenyl-4-vinylcyclohexane, 1-isopropenyl-3-vinylcyclo Alicyclic polyene compounds such as pentane, and aromatic polyene compounds such as divinylbenzene and vinylisopropenylbenzene;

These may be used alone or in combination. In the present invention, among the polyene compounds as described above, a polyene compound having 7 or more carbon atoms and having an olefinic double bond at both terminals is preferable, and further an aliphatic having an olefinic double bond at both terminals. Or an alicyclic polyene compound is more preferable.

Specifically, 1,6-heptadiene, 1,7-octadiene, 1,9-decadiene, 1,13-tetradecadiene,
1,5,9-decatriene, 1,4-divinylcyclohexane, 1,
Preferred examples include 3-divinylcyclopentane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, and 1,3,4-trivinylcyclohexane.

Of these, aliphatic polyene compounds having 8 or more carbon atoms, preferably 10 or more carbon atoms, are preferred, and linear aliphatic polyene compounds having 10 or more carbon atoms are particularly preferred.

In forming the α-olefin / polyene copolymer (i), among the above α-olefin and polyene compounds, ethylene / 1,7-octadiene, ethylene / 1,9-decadiene, ethylene / 1 / 1,13-tetradecadiene, ethylene / 1,5,9-decatriene, propylene /
1,7-octadiene, propylene / 1,9-decadiene, propylene / 1,13-tetradecadiene, propylene / 1,5,9-
Decatriene, butene / 1,9-decadiene, butene / 1,5,
9-decatriene, 4-methyl-1-pentene / 1,9-decadiene, 3-methyl-1-butene / 1,9-decadiene, 1-eicosene / 1,9-decadiene, propylene / 1,4-divinylcyclohexane , Butene / 1,4-divinylcyclohexane.

In such an α-olefin / polyene copolymer (i), the constitutional unit derived from the α-olefin is usually 99.999 to 50 mol%, preferably 99.999 mol%.
999 to 70 mol%, more preferably 99.995 to 7
5 mol%, more preferably 99.99-80 mol%,
Particularly preferably, the amount of the structural unit derived from the polyene compound is 0.001 to 50 mol%, preferably 0.001 to 30 mol%, more preferably 0.005 to 25 mol, in an amount of 99.95 to 85 mol%. %, More preferably 0.01%
-20 mol%, particularly preferably 0.05 to 15 mol%.

Also, α-olefin / polyene copolymer
(i) may contain a unit derived from another olefin described below as long as the object of the present invention is not impaired. In this case, the constituent unit derived from the olefin is usually contained in an amount of less than 30 mol%, preferably 20 mol% or less, particularly preferably 15 mol% or less.

The composition ratio of the α-olefin / polyene copolymer (i) as described above can be calculated by measuring the amounts of the α-olefin and the polyene compound consumed during the polymerization. Specifically, the structural unit [P mol%] derived from polyene is calculated as follows.

[0022]

(Equation 1)

(Where, [P ₀ ]: the number of moles of the polyene compound supplied at the time of polymerization [P _r ]: the number of moles of the unreacted polyene compound [α ₀ ]: the number of moles of the α-olefin supplied at the time of polymerization [Α _r ]: Number of moles of unreacted α-olefin) [α _r ] and [P _r ] are determined by measuring unreacted α-olefin and polyene compound remaining in the polymerization vessel by gas chromatography or the like. Is determined by

The olefin used for forming the olefin polymer (ii) forming the α-olefin / polyene copolymer-containing polymer is the aforementioned olefin having 2 carbon atoms.
To 20 α-olefins.

Further, substituted styrenes such as styrene and dimethylstyrene, substituted allylbenzenes such as allylbenzene and allyltoluene, aromatic vinyl compounds such as vinylnaphthalene, substituted vinylnaphthalene, allylnaphthalene and substituted allylnaphthalene, vinylcyclohexane , Substituted vinylcyclohexanes, vinylcyclopentane, substituted vinylcyclopentanes, vinylcycloheptane, substituted vinylcycloheptanes, alicyclic vinyl compounds such as allylnorbornane, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, Tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,
Cyclic olefins such as 3,4,4a, 5,8,8a-octahydronaphthalene, allyltrimethylsilane, allyltriethylsilane, 4-trimethylsilyl-1-butene, 6-trimethylsilyl-1-hexene, 8-trimethylsilyl-1- Octen, 10
-Silane-based unsaturated compounds such as trimethylsilyl-1-decene and the above-mentioned polyene compounds.

These may be used alone or in combination. Of these, ethylene, propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, vinylcyclohexane, dimethylstyrene, allyltrimethylsilane, allylnaphthalene, etc. It is preferably used.

In the polymer [I] containing the α-olefin / polyene copolymer, the α-olefin / polyene copolymer (i) is used in an amount of usually 0.001 to 99% by weight, preferably 0.005 to 90% by weight. % By weight, particularly preferably 0.01 to
In an amount of 88% by weight, the olefin polymer (ii) is 99.9%
It is contained in an amount of 99 to 1% by weight, preferably 99.995 to 10% by weight, particularly preferably 99.99 to 12% by weight.

Among the α-olefin / polyene copolymer-containing polymer [I] used in the present invention,
α-olefin-polyene copolymer (i)
In an amount of 15% by weight, preferably 0.008 to 10% by weight,
Those containing the olefin polymer (ii) in an amount of 99.999 to 85% by weight, preferably 99.992 to 90% by weight, are particularly preferred.

The α-olefin / polyene copolymer-containing polymer [I] used in the present invention is ASTM D123
Melt flow rate (MF
R) is 5000 or less, preferably 0.01 to 3000 g
/ 10 minutes, more preferably 0.02 to 2000 g / 10 minutes,
Particularly preferred is 0.05 to 1000 g / 10 min.

The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.05 to 20 dl / g, preferably 0.1 to 20 dl / g.
It is 1 to 15 dl / g, particularly preferably 0.2 to 13 dl / g.

Such an α-olefin / polyene copolymer-containing polymer has a high melt tension (melt tension,
MT). In the α-olefin / polyene copolymer-containing polymer used in the present invention, the melt tension (MT) expressed in relation to the melt flow rate (MFR) is specifically as follows.

For example, the α-olefin / polyene copolymer (i) forming the α-olefin / polyene copolymer-containing polymer is an ethylene / polyene copolymer, and the olefin polymer (ii) is polypropylene. In this case, the α-olefin / polyene copolymer-containing polymer has a log [MT] ≧ −0.8 log [MFR] +0.3, preferably a log [MT] ≧ −0.8 log [MFR] + 0.5 More preferably, log [MT] ≧ −0.8 log [MFR] +0.7 Particularly preferably, the relational expression of log [MT] ≧ −0.8 log [MFR] +0.8 is satisfied. .

The α-olefin / polyene copolymer (i) forming the α-olefin / polyene copolymer-containing polymer is a copolymer of an α-olefin having 3 or more carbon atoms and a polyene, When the olefin polymer (ii) is polypropylene, the α-olefin / polyene copolymer-containing polymer has a log [MT] ≧ −0.8 log [MFR] +0.30, preferably a log [MT ] ≧ −0.8 log [MFR] +0.35 More preferably, the expression of log [MT] ≧ −0.8 log [MFR] +0.40 is satisfied.

Further, for example, the α-olefin / polyene copolymer-containing polymer comprises the above-mentioned ethylene / polyene copolymer (i) and polyethylene (ii), and the density of the olefin polymer is about 0.92 g. / Cm ³ , MFR 1g
/ 10 minutes, the melt tension of the olefin polymer is at least 2.5 g, preferably at least 3.5 g, more preferably at least 4.0 g, even more preferably at least 4.5 g, particularly preferably at least 5.0 g. It is.

The melt tension (M) of the polymer [I] containing the α-olefin / polyene copolymer used in the present invention
T) satisfies the above-mentioned relational expression with the melt flow rate (MFR) and also satisfies the following expression with the intrinsic viscosity ([η]).

For example, the α-olefin / polyene copolymer (i) forming the α-olefin / polyene copolymer-containing polymer [I] is an ethylene / polyene copolymer,
When the olefin polymer (ii) is polypropylene, the α-olefin / polyene copolymer-containing polymer [I] has a log [MT] ≧ 3.7 log [[η]]-1.5, preferably Log [MT] ≧ 3.7 log [[η]] − 1.3 More preferably, log [MT] ≧ 3.7 log [[η]]-1.1 Particularly preferably, log [MT] ≧ 3. 7log [[η]] − 1.0 is satisfied.

The α-olefin / polyene copolymer (i) forming the α-olefin / polyene copolymer-containing polymer [I] is a copolymer of an α-olefin having 3 or more carbon atoms and a polyene. When the olefin polymer (ii) is polypropylene, the α-olefin / polyene copolymer-containing polymer [I] has a log [MT] ≧ 3.7 log [[η]]-1.50. Satisfies the relationship expressed by log [MT] ≧ 3.7 log [[η]] − 1.45, particularly preferably log [MT] ≧ 3.7 log [[η]] − 1.40.

Further, for example, the α-olefin / polyene copolymer-containing polymer [I] comprises the above-mentioned ethylene / polyene copolymer (i) and polyethylene (ii), and the density of this olefin polymer is When 0.92 g / cm ³ and intrinsic viscosity [η] are 1.8 dl / g, the melt tension of the olefin polymer is 2.5 g or more, preferably 3.5 g or more, more preferably 4.0 g or more. And more preferably at least 4.5 g, particularly preferably at least 5.0 g.

The melt tension is measured as follows. Using an MT measuring device manufactured by Toyo Seiki Seisaku-Sho, an orifice, 7 g of polymer, and a cylinder held at a polymer melting temperature (230 ° C. for polypropylene)
Insert in piston order. After 5 minutes, the piston is pushed down at a speed of 10 mm / min, and the molten polymer is pushed out from the orifice at the bottom of the cylinder. The extruded strand is drawn into a filament, passed through a pulley of a load detector, and taken up by a take-up roller at a speed of 25 m / min. At this time,
The stress applied to the pulley is measured, and this value is used as the melt tension of the polymer.

Next, the catalyst component of the transition metal compound [A] used in producing the above-mentioned α-olefin / polyene copolymer-containing polymer will be described. In the present invention, the [A] transition metal compound catalyst component includes a compound containing a transition metal selected from Groups III to VIII of the periodic table, and is preferably Ti, Zr, Hf, Nb, Ta,
Examples include compounds containing at least one transition metal selected from Cr and V.

The catalyst component of the transition metal compound [A] includes all known catalyst components, and specifically includes, for example, a solid titanium catalyst component containing titanium and halogen. More specifically, as an example of such a solid titanium catalyst component, titanium, magnesium, halogen and, if necessary, an electron donor (a)
And a solid titanium catalyst component [A-1].

Such a solid titanium catalyst component [A-1]
The method of preparing is described in detail in, for example, the following gazettes. 46-34
No.092, JP-B-53-46799, JP-B-60-3
No. 323, JP-B-63-54289, JP-A-1-26
1404, JP-A-1-261407, JP-B-47-
41676, JP-B-47-46269, JP-B-48
-19794, JP-A-60-262803, JP-A-59-147004, JP-A-59-149911,
JP-A-1-201308, JP-A-61-151211
JP-A-53-58495, JP-A-53-8799
No. 0, JP-A-59-206413, JP-A-58-20
No. 6613, JP-A-58-125706, JP-A-63
-68606, JP-A-63-69806, JP-A-63-69806
0-81210, JP-A-61-40306, JP-A-51-281189, JP-A-50-126590,
JP-A-51-92885, JP-B-57-45244.
No., JP-B-57-26613, JP-B-61-5483
No., JP-A-56-811, JP-B-60-37804.
No., JP-B-59-50246, JP-A-58-8300
6, JP-A-48-16986, JP-A-49-659
No. 99, JP-A-49-86482, JP-B-56-39
No. 767, JP-B-56-32222, JP-A-55-2.
9591, JP-A-53-146292 and JP-A-57-146292.
-63310, JP-A-57-63311, JP-A-5-6311
7-63312, JP-A-62-273206, JP-A-63-69804, JP-A-61-21109, JP-A-63-264607, JP-A-60-23404
No., JP-A-60-44507, JP-A-60-1582
04, JP-A-61-55104, JP-A-2-282
No. 01, JP-A-58-196210, JP-A-64-5
4005, JP-A-59-149905, JP-A-61-61905
-145206, JP-A-63-302, JP-A-63-302
-225605, JP-A-64-69610, JP-A-1-168707, JP-A-62-104810, JP-A-62-104811, and JP-A-62-104812.
And JP-A No. 62-104813.

The solid titanium catalyst component [A-1] is prepared by, for example, using a titanium compound, a magnesium compound and, if necessary, an electron donor (a) and bringing these compounds into contact.

Examples of the titanium compound used for preparing the solid titanium catalyst component [A-1] include a tetravalent titanium compound and a trivalent titanium compound. Examples of such a tetravalent titanium compound include a compound represented by the following formula.

Ti (OR) _g X _{4-g In the} formula, R is a hydrocarbon group, X is a halogen atom, and 0 ≦ g ≦ 4. Specific examples of such compounds include titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and TiI ₄ , Ti (OCH ₃ ) Cl ₃ , and Ti (OC ₂ H ₅ ) Cl _3.
, Ti (On-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (O
-iso-C ₄ H ₉₎ trihalide, alkoxy titanium such as _{Br 3, Ti (OCH 3)} 2 Cl 2, Ti (OC 2 H 5) 2 Cl 2, Ti
Dialkoxytitanium dihalides such as (On-C ₄ H ₉ ) ₂ Cl ₂ and Ti (OC ₂ H ₅ ) ₂ Br ₂ , Ti (OCH ₃ ) ₃ Cl, Ti (O
_{C 2 H 5) 3 Cl,} Ti (On-C 4 H 9) 3 Cl, Ti (OC 2 H 5) 3 B
r and other monohalogenated trialkoxy titanium, Ti (O
CH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₄ H ₉ ) ₄ , Ti
Examples thereof include tetraalkoxy titanium such as (O-iso-C ₄ H ₉ ) ₄ and Ti (O-2-ethylhexyl) ₄ .

Among these, preferred are titanium tetrahalides, and particularly preferred is titanium tetrachloride. These titanium compounds may be used alone or in combination of two or more. Alternatively, it may be used after being diluted with a hydrocarbon or a halogenated hydrocarbon. Titanium trichloride is used as the trivalent titanium compound.

As such titanium trichloride, for example, titanium tetrachloride is brought into contact with hydrogen, a metal such as metallic magnesium, metallic aluminum, metallic titanium or an organometallic compound such as an organomagnesium compound, an organoaluminum compound or an organozinc compound. Titanium trichloride obtained by the reduction is preferably used.

The magnesium compound used for preparing the solid titanium catalyst component [A-1] includes a magnesium compound having a reducing ability and a magnesium compound having no reducing ability.

The magnesium compound having a reducing ability includes, for example, an organic magnesium compound represented by the following formula. X _n MgR _{2-n In the} formula, n is 0 ≦ n <2, and R is hydrogen or carbon atom 1
20 to 20 alkyl groups, aryl groups or cycloalkyl groups. When n is 0, two Rs may be the same or different, and X is a halogen.

Specific examples of such an organomagnesium compound having a reducing ability include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, and the like.
Dialkyl magnesium compounds such as dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, octyl butyl magnesium, and ethyl butyl magnesium; alkyl magnesium such as ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, and amyl magnesium chloride Examples thereof include alkyl magnesium alkoxides such as halide, butyl ethoxy magnesium, ethyl butoxy magnesium and octyl butoxy magnesium, and other butyl magnesium hydrides.

Specific examples of magnesium compounds having no reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride, methoxymagnesium chloride, and the like.
Alkoxy magnesium halides such as ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride, etc., allyloxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride, ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octo And magnesium carboxylate such as magnesium magnesium laurate, magnesium stearate, etc .; alkoxymagnesium such as xoxymagnesium and 2-ethylhexoxymagnesium; allyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium; In addition, magnesium metal and magnesium hydride can be used.

The magnesium compound having no reducing ability may be a compound derived from the magnesium compound having the reducing ability described above or a compound derived at the time of preparing the catalyst component. In order to derive a magnesium compound having no reducing ability from a magnesium compound having reducing ability, for example, a magnesium compound having reducing ability is converted into a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, and a halogen. What is necessary is just to contact with a containing compound or a compound having an OH group or an active carbon-oxygen bond.

The magnesium compound having the reducing ability and the magnesium compound having no reducing ability are as follows.
Organometallic compounds described below, for example, complex compounds with other metals such as aluminum, zinc, boron, beryllium, sodium and potassium, may form complex compounds, or may be mixtures with other metal compounds Good. Further, the magnesium compound may be used alone, or two or more of the above compounds may be used in combination. The magnesium compound may be used in a liquid state or a solid state.
When the magnesium compound is a solid, the electron donor (a)
The liquid state can be obtained by using alcohols, carboxylic acids, aldehydes, amines, metal acid esters, and the like described below.

As the magnesium compound used for the preparation of the solid titanium catalyst component [A-1], many magnesium compounds can be used other than those described above, but the finally obtained solid titanium catalyst component [A-] In [1], it is preferable to take the form of a halogen-containing magnesium compound. Therefore, when a halogen-free magnesium compound is used, it is preferable to carry out a contact reaction with the halogen-containing compound during the preparation.

Among these, magnesium compounds having no reducing ability are preferred, and halogen-containing magnesium compounds are particularly preferred. Of these, magnesium chloride, alkoxymagnesium chloride and allyloxymagnesium chloride are preferred.

In the preparation of the solid titanium catalyst component [A-1], the electron donor (a) is preferably used. Such electron donors (a) include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, esters of organic or inorganic acids, ethers, diethers, acid amides , Acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, ammonias,
Examples include nitrogen-containing electron donors such as amines, nitriles, pyridines, and isocyanates. More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropyl benzyl Alcohols having 1 to 18 carbon atoms such as alcohols and halogen-containing alcohols having 1 to 18 carbon atoms such as trichloromethanol and trichloroethanol and trichlorohexanol, phenol, cresol, xylenol, ethylphenol,
C6-20 phenols which may have a lower alkyl group such as propylphenol, nonylphenol, cumylphenol and naphthol, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone,
C3-C15 ketones such as benzophenone and benzoquinone, acetaldehyde, propionaldehyde,
C2 to C15 aldehydes such as octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, Ethyl herbate,
Methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoate Benzyl acid, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethyl carbonate, etc. C2 to C18 organic acid esters, acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, and other C2 to C15 acid halides, methyl ether, ethyl ether, isopropyl ether, butyl ether , Amyl ether, tetrahydrofuran, anisole, ethers having 2 to 20 carbon atoms, such as diphenyl ether, acetic acid N, N-dimethylamide,
Acid amides such as benzoic acid N, N-diethylamide and toluic acid N, N-dimethylamide; amines such as trimethylamine, triethylamine, tributylamine, tribenzylamine and tetramethylethylenediamine; nitriles such as acetonitrile, benzonitrile and trinitrile And pyridines such as pyridine, methylpyridine, ethylpyridine and dimethylpyridine, and acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride.

Preferred examples of the organic acid ester include a polyvalent carboxylic acid ester having a skeleton represented by the following general formula.

[0058]

Embedded image

(Wherein, R ¹ is a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ , and R ⁶ are hydrogen or a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ are hydrogen or a substituted or unsubstituted group. It is an unsubstituted hydrocarbon group, preferably at least one is a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ may be linked to each other to form a cyclic structure. When the hydrogen groups R ^{1 to} R ⁶ are substituted, the substituent contains a different atom such as N, O, S, and, for example, C—O
-C, COOR, COOH, OH, SO 3 H, -C-N
-C-, having a group such as NH _2. Examples of such polyvalent carboxylic acid esters include aliphatic polycarboxylic acid esters, alicyclic polycarboxylic acid esters,
Examples thereof include aromatic polycarboxylic acid esters and heterocyclic polycarboxylic acid esters.

Preferred examples are n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadicate, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, and di-n-butyl phthalate. Butyl, 2-phthalic acid
Examples include ethylhexyl and dibutyl 3,4-furandicarboxylate.

Particularly preferred polycarboxylic acid esters include phthalic acid esters. Further, compounds represented by the following general formula are mentioned as diether compounds.

[0062]

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(Wherein, n is an integer of 2 ≦ n ≦ 10, and R ^{1 to} R ²⁶ are at least one kind selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon) is a substituent having an element, any R ¹ ~
R ²⁶ , preferably R ^{1 to} R ^2n, may together form a ring other than a benzene ring, and the main chain may contain atoms other than carbon. ) Preferred examples include 2,2-
Diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3 -Dimethoxypropane and the like.

The electron donor (a) as described above can be used in combination of two or more. In addition, the solid titanium catalyst component [A-1] used in the present invention may be prepared by preparing an organic compound containing silicon, phosphorus, aluminum, or the like used as a carrier compound and a reaction aid, in addition to the compounds described above. And an inorganic compound or the like.

Examples of such a carrier compound include Al
₂ O ₃ , SiO ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ ,
_{ZnO, SnO 2, BaO, ThO} , styrene - like resins such as divinylbenzene copolymer. Among them, Al ₂ O ₃ , SiO ₂ and styrene-divinylbenzene copolymer are preferred.

The solid titanium catalyst component [A-1] used in the present invention is prepared by bringing a titanium compound, a magnesium compound and preferably an electron donor (a) into contact with each other.

The method for preparing the solid titanium catalyst component [A-1] using these compounds is not particularly limited. However, in the case of using a tetravalent titanium compound, several examples of this method are given below. Briefly described. (1) A method comprising contacting and reacting a solution comprising a magnesium compound, an electron donor (a) and a hydrocarbon solvent with an organometallic compound to precipitate a solid, or contacting and reacting with a titanium compound while precipitating. (2) A method in which a complex comprising a magnesium compound and an electron donor (a) is contact-reacted with an organometallic compound, followed by a contact reaction with a titanium compound. (3) A method in which a contact product of an inorganic carrier and an organic magnesium compound is contact-reacted with a titanium compound. At this time, the above-mentioned contact product may be brought into contact with a halogen-containing compound, an electron donor (a) and / or an organometallic compound in advance. (4) a magnesium compound, an electron donor (a), and optionally a mixture of a solution containing a hydrocarbon solvent and an inorganic or organic carrier, to obtain an inorganic or organic carrier on which a magnesium compound is supported, and then a titanium compound. How to make contact. (5) Magnesium compound, titanium compound, electron donor
(a) A method of obtaining a [A-1] solid titanium catalyst component carrying magnesium and titanium by optionally contacting a solution containing a hydrocarbon solvent with an inorganic or organic carrier. (6) A method of contacting a liquid state organomagnesium compound with a halogen-containing titanium compound. (7) A method in which a liquid state organomagnesium compound is brought into contact with a halogen-containing compound and then brought into contact with a titanium compound. (8) A method of contacting an alkoxy group-containing magnesium compound with a halogen-containing titanium compound. (9) A method of contacting a complex comprising an alkoxy group-containing magnesium compound and an electron donor (a) with a titanium compound. (10) A method comprising contacting a complex comprising an alkoxy group-containing magnesium compound and an electron donor (a) with an organometallic compound and then contacting the complex with a titanium compound. (11) A method of contacting and reacting a magnesium compound, an electron donor (a), and a titanium compound in an arbitrary order. In this reaction, each component may be pretreated with an electron donor (a) and / or a reaction auxiliary such as an organometallic compound or a halogen-containing silicon compound. (12) A method in which a liquid magnesium compound having no reducing ability is reacted with a liquid titanium compound in the presence of an electron donor (a), if necessary, to precipitate a solid magnesium / titanium composite. (13) A method in which a titanium compound is further reacted with the reaction product obtained in (12). (14) A method in which the reaction product obtained in (11) or (12) is further reacted with an electron donor (a) and a titanium compound. (15) A method in which a solid obtained by pulverizing a magnesium compound, a titanium compound and, if necessary, an electron donor (a) is treated with any of a halogen, a halogen compound and an aromatic hydrocarbon. This method may include a step of pulverizing only the magnesium compound, or a complex compound composed of the magnesium compound and the electron donor (a), or a magnesium compound and a titanium compound. Further, after the pulverization, a preliminary treatment with a reaction aid may be performed, followed by a treatment with a halogen or the like. Examples of the reaction aid include an organometallic compound and a halogen-containing silicon compound. (16) A method of pulverizing a magnesium compound and then contacting and reacting with a titanium compound. At this time, an electron donor (a) or a reaction aid may be used at the time of pulverization and / or contact / reaction. (17) A method of treating the compound obtained in the above (11) to (16) with a halogen, a halogen compound or an aromatic hydrocarbon. (18) A method of contacting a reaction product of a metal oxide, an organomagnesium and a halogen-containing compound with a titanium compound and, if necessary, an electron donor (a). (19) A method in which a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium is reacted with a titanium compound and / or a halogen-containing hydrocarbon and, if necessary, an electron donor (a). (20) A method of contacting a hydrocarbon solution containing at least a magnesium compound and alkoxytitanium with a titanium compound and / or an electron donor (a). At this time, if necessary, a halogen-containing compound such as a halogen-containing silicon compound may be further contacted. (21) reacting a magnesium compound in a liquid state having no reducing ability with an organometallic compound to form a solid magnesium compound;
A method in which a metal (aluminum) complex is precipitated, and then a titanium compound and, if necessary, an electron donor (a) are reacted.

Such a solid titanium catalyst component [A-1]
Is usually at -70 ° C to 200 ° C, preferably at -50 ° C.
It is carried out at a temperature of between 150C and 150C. The solid titanium catalyst component [A-1] thus obtained contains titanium, magnesium, halogen and preferably an electron donor (a).

In the solid titanium catalyst component [A-1], halogen / titanium (atomic ratio) is 2 to 200, preferably 4 to 90, and magnesium / titanium (atomic ratio) is 1 to 100, Preferably, it is 2 to 50.

Also preferably, the electron donor (a) is usually
When the electron donor (a) / titanium (molar ratio) is 0.01 to 10
0, preferably 0.05 to 50. In the present invention, the solid titanium catalyst component [A-1] as described above
Has been described above using a titanium compound. However, in the above-mentioned titanium compound, titanium may be replaced with zirconium, hafnium, vanadium, niobium, tantalum or chromium.

In the present invention, a conventionally known [A-2] titanium trichloride-based catalyst component can be used as another example of the solid titanium catalyst component exemplified as the transition metal compound catalyst component [A].

The method of preparing the [A-2] titanium trichloride-based catalyst component is described in detail in, for example, the following gazettes. JP-A-63-1
7274, JP-A-64-38409, JP-A-56-38
No. 34711, JP-A-61-287904, JP-A-6-287904
JP-A-3-75007, JP-A-63-83106, JP-A-59-13630, JP-A-63-108008, JP-A-63-27508, JP-A-57-70110,
JP-A-58-219207, JP-A-1-144405
JP-A-1-292011, JP-A-1-29201
No. 1, etc.

Examples of the [A-2] titanium trichloride-based catalyst component include the above-mentioned titanium trichloride. Further, such titanium trichloride can be used together with the above-mentioned electron donor (a) and / or tetravalent titanium compound or after being brought into contact therewith.

Further, in the present invention, [A-3] a metallocene compound can be used as the catalyst component of the transition metal compound [A]. Details of such a method for preparing the [A-3] metallocene compound are described in, for example, the following gazettes.

JP-A-63-61010, JP-A-63-61010
No. 152608, JP-A-63-264606, JP-A-63-280703, JP-A-64-6003, JP-A-1-95110, JP-A-3-62806, JP-A-1-259004, JP-A-64-45406, JP-A-60-106808, JP-A-60-137911
JP-A-58-19309, JP-A-60-3500
6, JP-A-60-35007, JP-A-61-296
008, Patent Publication 63-501369, JP-A-61-61
JP-A-221207, JP-A-62-121707, JP-A-63-66206, JP-A-2-22307, JP-A-2-173110, JP-A-2-302410, JP-A-1-129003, JP-A-1-129003 No. 1-210404,
JP-A-3-66710, JP-A-3-70710, JP-A-1-207248, JP-A-63-222177
JP-A-63-222178, JP-A-63-222
No. 179, Japanese Patent Application Laid-Open No. 1-12407, Japanese Patent Application Laid-Open No. 1-301
704, JP-A-1-319489, JP-A-3-74
412, JP-A-61-264010, JP-A 1-2
No. 75609, JP-A-63-251405, JP-A-6-251405
4-74202, JP-A-2-41303, JP-A-2-42
JP-A-131488, JP-A-3-56508, JP-A-3-3508
-70708, JP-A-3-70709 and the like.

As the [A-3] metallocene compound, a compound represented by the following formula is specifically mentioned. ML _{x wherein} M is a transition metal selected from the group consisting of Zr, Ti, Hf, V, Nb, Ta and Cr, L is a ligand coordinated to the transition metal, and at least one L is a ligand having a cyclopentadienyl skeleton, and L other than a ligand having a cyclopentadienyl skeleton has 1 to 1 carbon atoms.
2, a hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, an SO ₃ R group (where R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen), a halogen atom Or a hydrogen atom, and x is the valence of the transition metal. Examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group, a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group,
Tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadiene Examples include alkyl-substituted cyclopentadienyl groups such as enyl group, methylbutylcyclopentadienyl group and hexylcyclopentadienyl group, or indenyl group, 4,5,6,7-tetrahydroindenyl group and fluorenyl group. Can be. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

Among the ligands which coordinate to these transition metals, an alkyl-substituted cyclopentadienyl group is particularly preferred. When the compound represented by the above general formula contains two or more groups having a cyclopentadienyl skeleton,
Groups having a cyclopentadienyl skeleton are substituted with an alkylene group such as ethylene and propylene, a substituted alkylene group such as isopropylidene and diphenylmethylene, a silylene group or a dimethylsilylene group, a diphenylsilylene group, and a methylphenylsilylene group. They may be bonded via a silylene group or the like.

Specific examples of the ligand L other than the ligand having a cyclopentadienyl skeleton include the following. Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Group, butyl group, etc., cycloalkyl group, cyclopentyl group, cyclohexyl group, etc., aryl group, phenyl group, tolyl group, etc., and aralkyl group, benzyl group, neophyl group, etc. And the like.

As the alkoxy group, a methoxy group,
An ethoxy group, a butoxy group and the like are exemplified. As the aryloxy group, a phenoxy group and the like are exemplified. As the halogen, fluorine, chlorine, bromine, iodine and the like are exemplified.

Examples of the ligand represented by SO ₃ R include a p-toluenesulfonato group, a methanesulfonato group and a trifluoromethanesulfonato group. Including a ligand having such a cyclopentadienyl skeleton [A-3]
When the valence of the transition metal is 4, for example, the metallocene compound is more specifically represented by the following formula.

R ² _k R ³ _l R ⁴ _m R ⁵ _n M (wherein M is the above transition metal, R ² is a group (ligand) having a cyclopentadienyl skeleton, and R ³ , R ⁴ and R ⁵ are a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, an SO ₃ R group, a halogen atom or a hydrogen atom. And k is an integer of 1 or more, and k + 1 + m + n = 4.) In the present invention, in the above formula R ² _k R ³ _l R ⁴ _m R ⁵ _n M,
A metallocene compound in which at least two of R ² , R ³ , R ⁴ and R ⁵ , that is, R ² and R ³ are groups (ligands) having a cyclopentadienyl skeleton is preferably used. These groups having a cyclopentadienyl skeleton include alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, and silylene groups or substituted silylene groups such as dimethylsilylene, diphenylsilylene and methylphenylsilylene groups. May be connected via R ⁴ and R ⁵ are a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, SO ₃
R, a halogen atom or a hydrogen atom.

Specific examples of the transition metal compound in which M is zirconium are shown below. Bis (indenyl) zirconium dichloride, bis (indenyl)
Zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato) bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylene Bis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconiumbis (methanesulfonato), ethylenebis ( Indenyl) zirconium bis (p-toluenesulfonate), ethylenebis (indenyl) zirconiumbis (trifluoromethanesulfonate), ethylenebis (4,5,6,7 -Tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (cyclopentadienyl) zirconium dichloride, Dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylene Bis (indenyl) zirconium bis (trifluoromethanesulfonate), dimethylsilicone Bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylsilylenebis (indenyl) zirconium dichloride, bis (Cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl)
Methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl)
Benzyl zirconium monochloride, bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) methyl zirconium monohydride, bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diphenyl zirconium, Bis (cyclopentadienyl) dibenzyl zirconium, bis (cyclopentadienyl)
Zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxycyclolide, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (cyclo (Pentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl)
Zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxycyclolide, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadiyl) Enyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl)
Zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl) ) Zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride,
Bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl)
Zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride.

In the above examples, disubstituted cyclopentadienyl ring includes 1,2- and 1,3-substituted, and tri-substituted cyclopentadienyl ring includes 1,2,3- and 1,2,4-substituted Including the body. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert-
And isomers.

In the above zirconium compound, a compound in which zirconium is replaced by titanium, hafnium, vanadium, niobium, tantalum or chromium can also be used.

These compounds may be used alone,
Two or more kinds may be used in combination. It may be used after being diluted with a hydrocarbon or a halogenated hydrocarbon.
In the present invention, as the metallocene compound [A-3], a zirconocene compound in which the central metal atom is zirconium and which has a ligand having at least two cyclopentadienyl skeletons is preferably used.

Further, the metallocene compound [A-3] as described above can be used by being brought into contact with a particulate carrier compound and carried on a carrier. As the carrier compound, SiO 2
₂ , Al ₂ O ₃ , B ₂ O ₃ , MgO, ZrO ₂ , CaO, Ti
Inorganic carrier compounds such as O ₂ , ZnO, SnO ₂ , BaO, and ThO, and resins such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, and styrene-divinylbenzene copolymer can be used. it can.

These carrier compounds can be used in combination of two or more. Of these, SiO ₂ , Al
₂ O ₃ and MgO are preferably used. Next, Group I to Periodic Table of the Periodic Table for forming the prepolymerized catalyst [I] according to the present invention.
The organometallic compound catalyst component [B] containing a metal selected from Group III will be described.

The organometallic compound catalyst component [B]
Examples thereof include [B-1] an organoaluminum compound, a complex alkyl compound of a Group I metal and aluminum,
An organic metal compound of a Group II metal or the like can be used.

As the organic aluminum compound [B-1], for example, an organic aluminum compound represented by the following formula can be exemplified. During R ^a _n AlX _3-n (wherein, R ^a is a hydrocarbon group having 1 to 12 carbon atoms, X
Is halogen or hydrogen, and n is 1-3. ) In the above formula, ^Ra is a hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Examples include an isobutyl group, a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, and a tolyl group. Specific examples of such an organoaluminum compound include the following compounds.

Trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri2-
Trialkyl aluminum such as ethylhexyl aluminum.

Alkenyl aluminum, such as isoprenyl aluminum. Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide.

Alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide.

Alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride and ethyl aluminum dibromide.

Alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; [B-1] As the organoaluminum compound, a compound represented by the following formula can also be used.

R ^a _n AlY _{3-n In the} above formula, R ^a is the same as above, and Y is -OR
^b group, -OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂ group, -
A SiR ^f ₃ group or a —N (R ^g ) AlR ^h ₂ group, wherein n is 1
And R ^b , R ^c , R ^d and R ^h are methyl groups,
Ethyl, isopropyl, isobutyl, cyclohexyl, phenyl, etc., ^Re is hydrogen, methyl, ethyl, isopropyl, phenyl, trimethylsilyl, etc., and R ^f and R ^g are methyl, And an ethyl group.

As the organic aluminum compound [B-1], specifically, the following compounds are used. _{^{(i) R a n Al (}} OR b) 3-n dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum _{^{methoxide, (ii) R a n Al}} (OSiR c 3) 3-n Et 2 Al (OSiMe ₃₎ (such as _{iso-Bu) 2 Al (OSiMe} 3) (iso-Bu) 2 Al (OSiEt 3), (iii) R a n Al (OAlR d 2) 3-n Et 2 AlOAlEt 2 (iso-Bu) such as _{2 AlOAl (iso-Bu) 2} , (iv) R a n Al (NR e 2) 3-n Me 2 AlNEt 2 Et 2 AlNHMe Me 2 AlNHEt Et 2 AlN (Me 3 Si) 2 (iso-Bu) 2 AlN etc. _{(Me 3 Si) 2, (} v) R a n Al etc. ^{_{(SiR f 3) 3-n}} (iso-Bu) 2 AlSiMe 3, (vi) R a n Al [n (R ^g) -AlR ^h etc. _{2] 3-n Et 2 AlN (Me} ) -AlEt 2 (iso-Bu) 2 AlN (Et) Al (iso-Bu) 2.

[0097] As [B-1] organoaluminum compounds mentioned _{^{above, R a 3 Al, R a}} n Al (OR b) 3-n, R
an organoaluminum compound represented by _{^{a n Al (OAlR d 2)}} 3-n may be mentioned as preferred examples.

Examples of the complex alkylated product of Group I metal and aluminum include compounds represented by the following general formula. M ¹ AlR ^j ₄ (where M ¹ is Li, Na, K, and R ^j is C 1
To 15) More specifically, LiAl (C _{2
H 5) 4, LiAl (C} 7 H 15) 4 and the like.

Examples of the organometallic compounds of Group II metals include compounds represented by the following general formula. R ^k R ¹ M ² (where R ^k and R ¹ are a hydrocarbon group having 1 to 15 carbon atoms or halogen, and may be the same or different from each other, except when both are halogen. M ² Is M
g, Zn, and Cd). Specific examples include diethyl zinc, diethyl magnesium, butyl ethyl magnesium, ethyl magnesium chloride, and butyl magnesium chloride.

These compounds can be used in combination of two or more kinds. Specific examples of the [B-2] organoaluminum oxy compound include aluminoxanes represented by general formulas (1) and (2).

[0101]

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(In the general formulas (1) and (2), R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group, and a butyl group, preferably a methyl group, an ethyl group, particularly preferably a methyl group. Yes, m is 2 or more, preferably 5
It is an integer of 40. Here, the aluminoxane is an alkyloxyaluminum unit represented by the formula (OAl (R ¹ )) and an alkyloxyaluminum unit represented by the formula (OAl (R ² )) wherein R ¹ and R ²
Can be exemplified by the same hydrocarbon groups as R, and R ¹ and R ² represent different groups.]. In that case, the methyloxyaluminum unit (OAl
(CH ₃ )) is at least 30 mol%, preferably at least 50 mol%
As described above, aluminoxane formed from a mixed alkyloxyaluminum unit containing at least 70 mol% is particularly preferable.

The [B-2] organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminum oxy compound found by the present applicants. You may.

As a method for producing such an aluminoxane, for example, the following method can be exemplified. (1) Compounds containing water of adsorption or salts containing water of crystallization, such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as trialkylaluminum to a hydrocarbon medium suspension of the above to react. (2) A method in which water is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) Decane, benzene, organoaluminum compounds such as trialkylaluminum in a medium such as toluene,
A method of reacting an organotin compound such as dimethyltin oxide and dibutyltin oxide.

Among these methods, it is preferable to employ the method (1). The aluminoxane may contain a small amount of an organic metal component other than aluminum. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered aluminoxane solution by distillation, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used in the production of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum and triisopropylaluminum.
n-butyl aluminum, triisobutyl aluminum,
Trisec-butyl aluminum, tritert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, trialkyl aluminum such as tridecyl aluminum, tricyclohexyl aluminum, tricycloalkyl aluminum such as tricyclooctyl aluminum, dimethyl aluminum Dialkylaluminum halides such as chloride, diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride, dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide, diethylaluminum And dialkylaluminum aryloxides such as ammonium phenoxide.

Further, isoprenyl aluminum represented by the following general formula can also be used. (I-C ₄ H ₉ ) x Aly (C ₅ H ₁₀ ) z (where x, y, and z are positive numbers and z ≧ 2x). Of these, trialkylaluminum is particularly preferred. .

The above-mentioned organoaluminum compounds are used alone or in combination. Solvents used in the production of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic solvents such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. Hydrocarbons, cyclopentane, cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclopentane, petroleum fractions such as gasoline, kerosene, gas oil, and the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons; Examples thereof include hydrocarbon solvents such as halides, especially chlorides and bromides, and ethers such as ethyl ether and tetrahydrofuran. Of these, aromatic hydrocarbons are particularly preferably used.

When the transition metal compound catalyst component [A] is a solid titanium catalyst component [A-1] or a titanium trichloride catalyst component [A-2], an organometallic compound catalyst component [B] Is preferably [B-1] an organoaluminum compound, and when [A] the transition metal compound catalyst component is [A-3] a metallocene compound, [B] the organometallic compound catalyst component is [B-2]. ] It is preferable that it is an organic aluminum oxy compound.

In preliminarily polymerizing an α-olefin and a polyene compound with the catalyst component [A] and the catalyst component [B], the electron donor (a) is optionally used. Alternatively, the following electron donor (b) may be used.

As such an electron donor (b), an organosilicon compound represented by the following general formula can be used. R _n Si (OR ') in _4-n (wherein, R and R' is a hydrocarbon group, 0 <n <4
Specific examples of the organosilicon compound represented by the above general formula include the following compounds.

Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane,
t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane , Screw p-
Tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, Methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-
Aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyl Dimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane,
Methyl triaryloxy silane, vinyl tris (β-methoxyethoxy silane), vinyl triacetoxy silane, dimethyl tetraethoxy disiloxane, cyclopentyl trimethoxy silane, 2-methyl cyclopentyl trimethoxy silane, 2,3-dimethyl cyclopentyl trimethoxy Silane, cyclopentyltriethoxysilane, dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, Dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, hexenyltrimethoxysilane, dicyclopentylmethylethoxysilane Orchids, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentyldimethylethoxysilane.

Of these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, Bis-p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane,
Cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltriethoxysilane, dicyclopentyldimethoxysilane, hexenyltrimethoxysilane, cyclopentyltriethoxysilane, tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane, etc. It is preferably used.

These organic silicon compounds can be used in combination of two or more. Further, in the present invention, as the electron donor (b), 2,6-substituted piperidines, 2,5-substituted piperidines, N, N, N ', N'-tetramethylmethylenediamine, N, N, N' N-containing electron donors such as substituted methylenediamines such as N, N'-tetraethylmethylenediamine, substituted methylenediamines such as 1,3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine; Phosphorus-containing electron donors such as phosphites such as phytite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, tri-isobutyl phosphite, diethyl n-butyl phosphite and diethyl phenyl phosphite And oxygen-containing electron donors such as 2,6-substituted tetrahydropyrans and 2,5-substituted tetrahydropyrans.

The electron donor (b) as described above may be used in combination of two or more. In the present invention, when forming the α-olefin / polyene copolymer-containing polymer, first, the above-mentioned [A] transition metal compound catalyst component and [B]
The α-olefin and the polyene compound are copolymerized with the organometallic compound catalyst component to form a prepolymerized catalyst containing the α-olefin / polyene copolymer (i).

In the present invention, when the [A] transition metal compound catalyst component and [B] organometallic compound catalyst component are preliminarily polymerized with an α-olefin and a polyene compound, the polyene compound is added to 1 mol of the α-olefin. Usually 0.0001 to 10 mol, preferably 0.0005 to 5 mol
It is preferred to use them in moles, particularly preferably in amounts of 0.001 to 2 moles.

The copolymerization of the α-olefin with the polyene compound can be carried out by any of a liquid phase polymerization method such as solution polymerization and suspension polymerization or a gas phase polymerization method. When the polymerization is carried out in a liquid phase, the polymerization can be carried out in the presence of an inert solvent described later. Further, the polymerization can be carried out using the olefin and the polyene compound used in the polymerization as a solvent or in a state substantially without a solvent.

In the present invention, this pre-copolymerization can be carried out in the co-presence of an inert solvent described later, and the above-mentioned olefin, polyene compound and catalyst component are added to the inert solvent, and the reaction is carried out under relatively mild conditions. Is preferred. At this time, the reaction may be carried out under a condition in which the produced prepolymer is dissolved in the polymerization medium, or may be carried out under a condition in which the prepolymer is not dissolved.

In the present invention, the above-mentioned prepolymerized catalyst can be prepared more specifically as follows. i) In an inert solvent, [A] a transition metal compound catalyst component, [B] an organometallic compound catalyst component and, if necessary, an electron donor are brought into contact in advance to form a prepolymerization catalyst,
A method in which an α-olefin and the polyene compound are copolymerized with the catalyst to form a prepolymerized catalyst. ii) in a mixture of an α-olefin and a polyene compound, [A] a transition metal compound catalyst component, [B] an organometallic compound catalyst component and, if necessary, an electron donor to previously contact to form a catalyst, A method in which an α-olefin and a polyene compound are copolymerized with the catalyst to form a prepolymerized catalyst.

Examples of the inert solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene.
Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as α-olefin chloride and chlorobenzene; and mixtures thereof. .

Among these, it is particularly preferable to use an aliphatic hydrocarbon. The prepolymerization can be performed in any of a batch system, a continuous system, and a semi-continuous system.

The concentration of the catalyst component in the prepolymerization varies depending on the catalyst component used, but the concentration of the transition metal compound catalyst component is usually about 0.001 to 5000 mmol per transition volume of liter of polymerization metal atom. , Preferably about 0.01 to 1000 mmol, particularly preferably 0.1 to 500 mmol.

The organometallic compound catalyst component is used in an amount of 0.01 to 2000 g, preferably 0.03 to 1000 g, more preferably 0.05 to 20 g per gram of the transition metal compound catalyst component.
It is used in an amount such that 0 g of a polymer is produced, and is usually about 0.1-1000 mol, preferably about 0.5-500 mol, particularly preferably about 1 mol of transition metal atom in the transition metal compound catalyst component. It is used in an amount of 1 to 100 mol.

When an electron donor is used, the electron donor is used in an amount of 0.01 to 50 mol, preferably 0.05 to 50 mol per mol of transition metal atom in the transition metal compound catalyst component.
It is used in an amount of 30 mol, more preferably 0.1 to 10 mol.

The reaction temperature during the prepolymerization is usually about -20.
To + 100 ° C, preferably about -20 to + 80 ° C, and more preferably about -10 to + 40 ° C.
In the preliminary polymerization, a molecular weight regulator such as hydrogen may be used.

The prepolymerized catalyst according to the present invention comprises the above-mentioned [A] transition metal compound catalyst component and [B] organometallic compound catalyst component per 1 g of the transition metal compound catalyst component.
0.01 to 2000 g, preferably 0.03 to 1000 g,
More preferably, it is obtained by copolymerizing an α-olefin and a polyene compound in an amount of 0.05 to 200 g.

The prepolymerized catalyst containing the α-olefin / polyene copolymer (i) is usually obtained in a suspended state. Such a prepolymerized catalyst can be used as it is in a suspended state in the subsequent polymerization, or can be used by separating the prepolymerized catalyst from the suspension.

The prepolymerized catalyst obtained in the above suspension state was
In the main polymerization step described below, the organometallic compound catalyst component or the electron donor may not need to be further added. In the present invention, prior to the above preliminary copolymerization,
An olefin can be preliminarily polymerized on the [A] transition metal compound catalyst component and [B] the organometallic compound catalyst component.

As the olefin, the above-mentioned olefins are used. Of these, α-olefins are preferable, and propylene is more preferable. When the olefin is preliminarily polymerized in the olefin polymerization catalyst prior to the precopolymerization as described above, for example, the following effects can be specifically obtained. That is, when the olefin is preliminarily polymerized in the olefin polymerization catalyst prior to the precopolymerization as described above, a prepolymerized catalyst excellent in particle shape such as particle size distribution and particle size distribution can be obtained.

In the present invention, the above-mentioned olefin is polymerized or copolymerized with the prepolymerized catalyst obtained as described above to form an olefin polymer (ii). In forming the olefin polymer (ii), the prepolymerization catalyst is
Usually, about 0.001 to 100 mmol, preferably about 0.0100, in terms of transition metal atoms per liter of polymerization volume.
It is used in an amount of from 0.5 to 20 mmol.

In this case, if necessary, an organometallic compound catalyst component or an electron donor may be used together with the prepolymerization catalyst. When the organometallic compound catalyst component [B] is used, the organometallic compound catalyst component [B] is
The metal atom in the catalyst component [B] is usually about 1 to 200 moles per 1 mole of the transition metal atom in the prepolymerization catalyst in the polymerization system.
It is used in an amount such that it is 0 mol, preferably about 2 to 500 mol. When an electron donor is used, the electron donor is generally used in an amount of about 0.001 mol to 10 mol, preferably 0.01 mol to 1 mol, per 1 mol of the metal atom in the organometallic compound catalyst component [B]. Used in an amount of 5 mol.

When hydrogen is used during the polymerization, the molecular weight of the obtained polymer can be adjusted, and a polymer having a high melt flow rate can be obtained. In the present invention, the olefin can be polymerized by any of a liquid phase polymerization method such as solution polymerization and suspension polymerization or a gas phase polymerization method. Further, it can be carried out by any of a batch system, a semi-continuous system and a continuous system.

When the polymerization takes a reaction form of slurry polymerization, the above-mentioned inert organic solvent or a liquid olefin at the reaction temperature can be used as the reaction solvent.

The polymerization conditions vary depending on the olefin used in the polymerization, but the polymerization temperature is usually from -20 to 300.
° C, preferably about -20 to 150 ° C, more preferably -10 to 130 ° C, and the polymerization pressure is usually normal pressure to 10
0 kg / cm ² , preferably about ² to 50 kg / cm ² .

Further, the olefin polymerization can be carried out in two or more stages. At this time, the reaction conditions in each stage may be the same or different. The olefin polymer (ii) thus formed is a homopolymer of olefin,
It may be a random copolymer or a block copolymer composed of two or more olefins.

The α-olefin / polyene copolymer-containing olefin polymer as described above has a higher melt tension than a conventional olefin polymer. The foam molded article according to the present invention is obtained by heating a foam molding composition comprising the olefin polymer as described above, a foaming agent, an organic peroxide, if necessary, and a crosslinking aid. Can be manufactured.

The foaming agent is a chemical substance which is liquid or solid at room temperature and generates a gas upon heating. Specifically, azodicarbonamide, barium azodicarboxylate, N, N'-dinitrosopentamethylenetetramine , 4,4-
Oxybis (benzenesulfonylhydrazide), diphenylsulfone-3,3-disulfonylhydrazide, p-toluenesulfonylsemicarbazide, trihydrazinotriazine, biurea, zinc carbonate and the like are used. Among these, azodicarbonamide, N, N'-dinitrosopentamethylenetetramine, and trihydrazinotriazine, which generate a large amount of gas and the gas generation end temperature is sufficiently lower than the thermal degradation start temperature of the olefin polymer, are particularly preferable. preferable.

Such a blowing agent is an olefin polymer 1
It is preferably present in an amount of from 1 to 20 parts by weight, especially from 2 to 5 parts by weight, based on 00 parts by weight. The organic peroxide is used to crosslink the foam molded article. As this organic peroxide, organic peroxides and organic peroxyesters are mainly used, and specifically, the following compounds are used.

3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, succinic peroxide,
Acetyl peroxide, tert-butylperoxy (2-ethylhexanoate), m-toluoyl peroxide, benzoyl peroxide, tert-butylperoxyisobutyrate, 1,1-bis (tert-butylperoxy) -3,5,5
-Trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, tert-butylperoxymaleic acid, tert-butylperoxylaurate, tert
-Butylperoxy-3,5,5-trimethylcyclohexanoate, cyclohexanone peroxide, tert-butylperoxyisopropyl carbonate, 2,5-dimethyl-
2,5-di (benzoylperoxy) hexane, tert-butylperoxyacetate, 2,2-bis (tert-butylperoxy) butane, tert-butylperoxybenzoate, n-butyl-4,4-bis (tert-butylperoxy) ) Valerate, di-tert-butylperoxyisophthalate,
Methyl ethyl ketone peroxide, α, α'-bis (te
rt-butylperoxyisopropyl) benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylcumyl peroxide, diisopropylbenzene hydroperoxide, di-t
ert-butyl peroxide, paramenthane hydroperoxide, 2,5-dimethyl-2,5- (tert-butylperoxy) -3-
Hexin, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, cumene hydroperoxide, tert-butylhydroxy peroxide and the like.

Among them, 1,1-bis (tert-butylperoxy) cyclohexane, tert-butylperoxymaleic acid, tert-butylperoxylaurate,
-Butylperoxy-3,5,5-trimethylcyclohexanoate, cyclohexanone peroxide, tert-butylperoxyisopropyl carbonate, 2,5-dimethyl-
2,5-di (benzoylperoxy) hexane, tert-butylperoxyacetate, 2,2-bis (tert-butylperoxy) butane, tert-butylperoxybenzoate, n-butyl-4,4-bis (tert-butylperoxy) ) Valerate, di-tert-butylperoxyisophthalate,
Methyl ethyl ketone peroxide, α, α'-bis (te
rt-butylperoxyisopropyl) benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylcumyl peroxide, diisopropylbenzene hydroperoxide, di-t
ert-butyl peroxide, paramenthane hydroperoxide, 2,5-dimethyl-2,5- (tert-butylperoxy) -3-
Hexine, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, cumene hydroperoxide and tert-butylhydroxyperoxide are preferred.

The organic peroxide is an olefin polymer 1
0.01 to 5 parts by weight, especially 0.01 to 100 parts by weight
Preferably it is used in an amount of up to 1 part by weight. Crosslinking aids stabilize polymer radicals by allowing the hydrogens of the olefin polymer to be abstracted by the organic peroxide and the resulting polymer radicals reacting with the crosslinking aids faster than causing a cleavage reaction. It serves to enhance the crosslinking efficiency.

Examples of the cross-linking assistant having such a function include:
Usually, unsaturated compounds having one or more double bonds, oxime compounds, nitroso compounds, maleimide compounds and the like can be mentioned. These are used in one kind or in a mixture of two or more kinds.

Specific examples of such a crosslinking aid include unsaturated compounds such as divinylbenzene, triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, diallyl phthalate, and pentayl phthalate. Oxime compounds such as erythritol triacrylate, neopentyl glycol diacrylate, 1,6-hexanediol dimethacrylate, quinone dioxime, benzoquinone dioxime, paranitrosophenol, and N, N-metaphenylenebismaleimide. Of these, neopentyl glycol diacrylate and 1,6-hexanediol dimethacrylate are preferred.

The foamed molded article according to the present invention may have any shape, such as a block shape, a sheet shape and a monofilament shape. To produce the foamed molded article according to the present invention from the olefin polymer as described above,
A conventionally known foam molding apparatus can be used. As the molding conditions, conventionally known conditions can be adopted.

For example, the olefin polymer (A) described above,
An organic peroxide (B), a crosslinking assistant (C), a foaming agent (D) and, if necessary, a heat-resistant stabilizer (E) in the above range with a Henschel mixer, a V-blender, a ribbon blender,
The organic peroxide (B) is decomposed while absorbing unnecessary volatile substances from a vent installed after the high-temperature heating unit using a composition mixed with a tumbler blender or the like using an extruder, preferably a vented extruder. Is kneaded in a temperature range where the foaming agent (D) does not decompose, and the extruder is attached to the extruder.
-Obtaining a crosslinked modified foamable sheet comprising substantially undecomposed blowing agent (D) through a die or an annular die,
Known foaming methods, namely, a press foaming method in which a foaming agent is decomposed under pressure under pressure, a molten salt bath heating foaming method in which a foaming agent is thermally decomposed under normal pressure, a hot air oven method, a radiant heat ray heating foaming method, A method of producing a foam by foaming by a method such as a high-frequency heating foaming method or a combination of two or more of these methods can be exemplified.

The olefin polymer forming the foamed molded article according to the present invention comprises at least one of a phenol stabilizer, an organic phosphite stabilizer, a thioether stabilizer, a hindered amine stabilizer and a higher fatty acid metal salt. Preferably, it contains more than one species.

Such a compound is an olefin polymer 1
0.005 to 5 parts by weight with respect to 00 parts by weight,
Preferably, it is used in an amount of 0.01 to 0.5 part by weight.

As the phenolic stabilizer, conventionally known phenolic stabilizers can be used without any particular limitation. Specifically, the following compounds are used. 2,6-di-t-butyl
-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-diphenol
-t-Amyl-4-methylphenol, 2,6-di-t-octyl
-4-n-propylphenol, 2,6-dicyclohexyl-4-n
-Octylphenol, 2-isopropyl-4-methyl-6-t
-Butylphenol, 2-t-butyl-2-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-5-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, styrene Cresol, dl-
α-tocophenol, t-butylhydroquinone, 2,2′-methylenebis (4-methyl-6-t-butylphenol), 4,4 ′
-Butylidenebis (3-methyl-6-t-butylphenol)
, 4,4'-thiobis (3-methyl-6-t-butylphenol)
, 2,2'-thiobis (4-methyl-6-t-butylphenol)
, 4,4'-methylenebis (2,6-di-t-butylphenol)
, 2,2'-methylenebis [6- (1-methylcyclohexyl) -p
-Cresol], 2,2'-ethylidenebis (4,6-di-t-butylphenol), 2,2'-butylidenebis (2-t-butyl
-4-methylphenol), 1,1,3-tris (2-methyl-4-
(Hydroxy-5-t-butylphenyl) butane, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2'-thiodiethylenebis [3-
(3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di -t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4
-t-butylbenzyl) isocyanurate, 1,3,5-tris
[(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tris (4-t-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 2,4- Bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, tetrakis [methylene-3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate] methane, bis (3,5-di-t
-Ethyl butyl-4-hydroxybenzylphosphonate) calcium, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate) nickel, bis [3,3-bis (3-t
-Butyl-4-hydroxyphenyl) butyric acid]
Glycol ester, N, N'-bis [3- (3,5-di-t-butyl
-4-hydroxyphenyl) propionyl] hydrazine,
2,2'-Ogizamide bis [ethyl-3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate], bis [2-t-
Butyl-4-methyl-6- (3-t-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 1,3,5-trimethyl-2,4,6-tris (3,5-di- t-butyl-4-hydroxybenzyl) benzene, 3,9-bis [1,1-dimethyl-2- (β
-(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2-bis [4- ( 2- (3,5-di-t-butyl-4-hydroxyhydrocinnamoyloxy)) ethoxyphenyl] propane and stearyl-β- (4-hydroxy-3,5-di-tert-butylphenol) propionate β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester and the like.

Among them, 2,6-di-tert-butyl-4-
Methylphenol, stearyl-β- (4-hydroxy-
3,5-di-tert-butylphenol) propionate, 2,2 '
-Ethylidenebis (4,6-di-tert-butylphenol),
Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane is preferred.

As the phosphite-based stabilizer, specifically, the following compounds are used. Trioctyl phosphite, trilauryl phosphite, tristridecyl phosphite, tris isodecyl phosphite,
Phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, Tris (2,4-di-t-butylphenyl) phosphite, tris (butoxyethyl) phosphite, tetratridecyl-4,4'-butylidenebis (3-methyl-6-t-butylphenol) -diphosphite, 4, 4'-isopropylidene-diphenol alkyl phosphite (where alkyl is about 12 to 15 carbon atoms), 4,4'-isopropylidenebis (2-t-butylphenol) di (nonylphenyl) phosphite, tris ( Biphenyl) phosphite, tetra (g Decyl) -
1,1,3-tris (2-methyl-5-t-butyl-4-hydroxyphenyl) butane diphosphite, tris (3,5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenated -4,4 '
-Isopropylidene diphenol polyphosphite, bis (octylphenyl) bis [4,4'-butylidenebis (3-methyl-6-t-butylphenol)]-1,6-hexaneoldiphosphite, hexatridecyl- 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenol) diphosphite, tris [4,4′-isopropylidenebis (2
-t-butylphenol)] phosphite, tris (1,3-
Distearoyloxyisopropyl) phosphite, 9,
10-dihydro-9-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite, distearylpentaerythritol diphosphite, (Nonylphenyl) pentaerythritol diphosphite, phenyl-4,4'-isopropylidenediphenolpentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and phenylbisphenol-A-pentaerythritol diphosphite.

Of these, tris (2,4-di-tert-
Butylphenyl) phosphite, tris (nonylphenyl) phosphite and tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite are preferred, and tris (2,4-di- Particularly preferred is (t-butylphenyl) phosphite.

As the organic thioether-based stabilizer, it is preferable to use dialkylthiodipropionates and polyhydric alcohol esters of alkylthiopropionic acids. As the dialkylthiodipropionate used here, a dialkylthiodipropionate having an alkyl group having 6 to 20 carbon atoms is preferable. Further, as the polyhydric alcohol ester of alkylthiopropionic acid,
Polyhydric alcohol esters of alkylthiopropionic acid having an alkyl group having 4 to 20 carbon atoms are preferred. In this case, examples of the polyhydric alcohol constituting the polyhydric alcohol ester include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and trishydroxyethyl isocyanurate.

Specific examples of such a dialkylthiodipropionate include dilaurylthiodipropionate, dimyristylthiodipropionate and distearylthiodipropionate.

Examples of polyhydric alcohol esters of alkylthiopropionic acids include glycerin tributylthiopropionate, glycerin trioctyl thiopropionate, glycerin trilauryl thiopropionate and glycerin tristearyl thiopropionate; Methylol ethane tributyl thiopropionate, trimethylol ethane trioctyl thiopropionate, trimethylol ethane trilauryl thiopropionate and trimethylol ethane tristearyl thiopropionate; pentaerythritol tetrabutyl thiopropionate, pentaerythritol tetra Octylthiopropionate, pentaerythritol tetralaurylthiopropionate and pentaerythritol tetrastearylthione Propionate can be mentioned.

Among these, it is preferable to use dilauryl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetralauryl thiopropionate.

Specific examples of the hindered amine stabilizer include the following compounds. Screw (2,2,
6,6-tetramethyl-4-piperidyl) sebacate, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-succinate
2,2,6,6-tetramethylpiperidine polycondensate, poly [[6
-(1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexa Methylene [(2,2,6,6-tetramethyl-4-piperidyl) imino], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxy Rate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis- (1,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-tert-butyl-4 -Hydroxybenzyl) -2-n-butylmalonate, bis- (N-methyl-2,2,
6,6-tetramethyl-4-piperidyl) sebacate, 1,1'-
(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3 , 4-butanetetracarboxylate, (mixed 1,2,2,6,6-pentamethyl-4-
Piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed {2,2,6,6-tetramethyl-4-
Piperidyl / β, β, β ', β'-tetramethyl-3,9- [2,4,
8,10-Tetraoxaspiro (5,5) undecane] diethyl {-1,2,3,4-butanetetracarboxylate, mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β , β,
β ', β'-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,
6,6-pentamethyl-4-piperidyl) amino] -6-chloro-
1,3,5-triazine condensate, poly [6-N-morpholyl-1,3,5
-Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4
-Piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imide], N, N'-bis (2,2,
Condensation product of 6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane, [N- (2,2,6,6-
Tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6,6-
Tetramethyl-4-piperidyl) imino] propionamide.

Among these hindered amine stabilizers, the following compounds are particularly preferred. Dimethyl succinate
-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [6- (1,1,3,3-tetramethylbutyl) imino-1, 3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) Imino], tetrakis (2,2,6,6-tetramethyl
-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis- (1,2,6,6-pentamethyl-4-piperidyl) -2-
(3,5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate, 1,1 ′-(1,2-ethanediyl) bis (3,
3,5,5-tetramethylpiperazinone), (mixed 2,2,
6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,
4-butanetetracarboxylate, (mixed 1,2,2,
6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,
4-butanetetracarboxylate, mixed ｛2,2,6,
6-tetramethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1, 2,3,4-butanetetracarboxylate, mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- [2, 4,8,1
0-Tetraoxaspiro (5,5) undecane] diethyl｝-
1,2,3,4-butanetetracarboxylate, N, N'-bis (3
-Aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensation Compound, poly [6-N-morphoryl-1,3,5-triazine-2,4-diyl] [(2,2,6,6-
Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imide],
A condensate of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane,
[N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl
-2- (2,2,6,6-tetramethyl-4-piperidyl) imino] propionamide.

Examples of the metal salts of higher fatty acids include magnesium salts of higher fatty acids such as stearic acid, oleic acid, lauric acid, capric acid, arachidic acid, palmitic acid, behenic acid, 12-hydroxystearic acid, ricinoleic acid and montanic acid. Alkaline earth metal salts such as calcium salts and barium salts, cadmium salts, zinc salts, lead salts, alkali metal salts such as sodium salts, potassium salts and lithium salts are used. Specifically, the following compounds are used.

Magnesium stearate, magnesium laurate, magnesium palmitate, calcium stearate, calcium oleate, calcium laurate, barium stearate, barium oleate, barium laurate, barium arachidate, barium behenate, zinc stearate, olein Zinc acid, zinc laurate, lithium stearate, sodium stearate, sodium palmitate, sodium laurate, potassium stearate, potassium laurate, 12-
Calcium hydroxystearate, calcium montanate and the like.

The foamed molded article according to the present invention may further comprise other heat stabilizers, weather stabilizers, antistatic agents, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils , Wax and the like.

Further, the foamed molded article according to the present invention may contain silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, hydroxide, as long as the object of the present invention is not impaired. Magnesium, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, guffite, Aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber,
A filler such as polyethylene fiber, polypropylene fiber, polyester fiber, and polyamide fiber may be included.

[0162]

According to the present invention, (i) α-olefin
There is provided a foam molded article comprising an α-olefin / polyene copolymer-containing olefin polymer comprising a polyene copolymer and (ii) an olefin polymer.

This foamed article can be foamed to a high foaming ratio, and the foam cells are dense and the size of the foam cells is uniform. For this reason, it is excellent in bending characteristics. Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

[0164]

EXAMPLE 1 The reactor of the "solid titanium catalyst component [A] Preparation of" 4.5 m ^3, anhydrous magnesium chloride 240 Kg, decane 11
00 liter and 2-ethylhexyl alcohol 990
After charging Kg and heating at 130 ° C. to make a homogeneous solution, 54 Kg of phthalic anhydride was added to this solution,
The mixture was stirred at 0 ° C. to dissolve phthalic anhydride. After cooling the homogeneous solution thus obtained to room temperature,
The whole homogeneous solution was dripped into 6.7 m ^{3 of} titanium tetrachloride held in the flask while stirring. Temperature after charging is approx.
20 ° C. The temperature of the mixture was raised to 11 over 4 hours.
The temperature was raised to 0 ° C., and when the temperature reached 110 ° C., 13 kg of diisobutyl phthalate (DIBP) was added, and the mixture was stirred and maintained at the same temperature for 2 hours.

After completion of the reaction, a solid portion was collected by hot filtration.
This solid portion was resuspended in 7.3 m ³ of titanium tetrachloride and then heated again at 110 ° C. for 2 hours. After the completion of the reaction, the solid portion was collected again by hot filtration, and sufficiently washed with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution.

Through the above operations, a solid titanium catalyst component [A] was obtained. The composition of the solid titanium catalyst component [A] thus obtained was 2.2% by weight of titanium and 61% of chlorine.
% By weight, magnesium by 19% by weight, and DIBP by 12.7% by weight.

"Preliminary polymerization of solid titanium catalyst component [A]" In a 80-liter reactor equipped with a stirrer, 40 liters of purified hexane and 0.1 ml of triethylaluminum were added under a nitrogen atmosphere.
After adding 9 mol and 0.3 mol of the solid titanium catalyst component [A] in terms of titanium atom, 1.66 kg of propylene was supplied to the reactor at a temperature of 20 ° C., and prepolymerization was performed for 2 hours.

After the completion of the reaction, the inside of the reactor was replaced with nitrogen, and a washing operation comprising removing the supernatant and adding purified hexane was performed three times to obtain a prepolymerized catalyst [B]. Then, at 0 ° C
68.4 liters of hexane, 1,9-decadiene 1.
After adding 6 liters and 2.1 moles of diethylaluminum ethoxide, ethylene was fed to the reactor. During the polymerization reaction, the temperature was kept at 0 ° C, and when 4650 liters of ethylene had reacted, the supply of ethylene was stopped.

When the supply of ethylene was completed, the inside of the reactor was replaced with nitrogen, and a washing operation including removal of a supernatant and addition of purified hexane was performed five times to obtain a prepolymerized catalyst [C].
I got The prepolymerized catalyst [C] was resuspended in purified hexane and stored.

In the prepolymerized catalyst [C] thus obtained, 10.2 g / g of the transition metal compound catalyst component was used.
g of ethylene / 1,9-decadiene copolymer was produced. "Polymerization" Insert 450 liters of purified n-hexane into a reactor with a stirrer having an internal volume of 1000 liters, and in a propylene atmosphere at 60 ° C., 400 mol of triethylaluminum,
Cyclohexylmethyldimethoxysilane (CMMS) 8
0 moles and 8 parts of the prepolymerized catalyst [C] in terms of titanium atoms.
Mole Ti was charged.

After introducing 90 liters of hydrogen and raising the temperature to 70 ° C., the temperature was maintained for 3.2 hours to carry out propylene polymerization. The pressure during the polymerization was kept at 6 kg / cm ² G. After completion of the polymerization, the pressure was released, and the slurry containing the produced solid was centrifuged and dried with a drier to obtain 200 kg of a white powdery polymer.
I got

For the obtained polymer, boiling heptane extraction residual ratio, MFR, [η], apparent bulk specific gravity and melt tension were measured or calculated, and the results of concentration of the liquid phase portion are shown in Table 1.

"Foam molding" 100 parts by weight of the polypropylene powder obtained above, 0.1 part by weight of dicumyl peroxide as an organic peroxide, 1.0 part by weight of divinylbenzene as a crosslinking aid, a blowing agent The foaming polypropylene sheet molding composition comprising 3 parts by weight of azodicarbonamide was mixed using a high-speed mixer (Henschel mixer manufactured by Mitsui Miike Seisakusho Co., Ltd.), granulated by an extruder having a diameter of 65 mm, and pelletized. The resin temperature at this time was 170 ° C.

The pellet sheet thus obtained was supplied to a sheet forming machine (65 mm extruder, die width 550 mm, lip opening 1.0 mm) to produce a sheet-like foamable polypropylene sheet. The sheet molding temperature was about 170 ° C., and no resin foaming was observed during sheet molding. The thickness of the obtained sheet was 1.0 mm.

The obtained foamable polypropylene sheet was heated by a ceramic heater of a vacuum forming machine for about 90 seconds,
The foamable polypropylene sheet was foamed to form a foamed polypropylene layer. At this time, the set temperature of the ceramic heater was 400 ° C., and the surface temperature of the expandable polypropylene sheet was 210 ° C. This foam sheet was cooled by air spray for about 60 seconds.

The thickness of the obtained expanded polypropylene sheet is about 6.7 mm, the density is 0.14 g / cm ³ ,
The expansion ratio was about 6.7 times. [Evaluation of Molded Article] (1) Expansion ratio: Indicated by the ratio of the thickness of the unfoamed sheet to the thickness of the foamed sheet. The thickness was measured with a caliper. (2) Foamed state: Determined by the state of cells in the cross section of the foamed sheet. The state of the cell was visually determined.

Micro-uniform cell: Uniform cell: 〇 Non-uniform cell, coarse cell: 不良 Poor foaming ^* : × (* coarse cell + non-uniform cell) (3) Cell size: Measured from a micrograph, average cell diameter I asked. (4) Bending characteristics: The foamed sheet which has not yet been cooled in a foamed state was pressed and cooled by sandwiching it between press plates. The interval between the press plates was 4.5 mm.

The following test piece for bending measurement was cut out from the foamed press sheet thus obtained. Size: 50mm width, 150mm length Bending test: 3-point bending test Distance between spans: 100mm Bending speed: 50mm / min. Temperature: 23 ° C, 80 ° C, 110 ° C Direction: Vertical, horizontal (1) to (3) The results are shown in Table 2, and the result of (4) is shown in Table 3.

[0179]

Example 2 Polymerization Polymerization was carried out in the same manner as in Example 1 except that 150 liters of hydrogen were used.

Table 1 shows the results. "Foam molding" The foam molding was carried out in the same manner as in Example 1 using the polypropylene powder obtained above.

[Evaluation of Molded Article] (1) Expansion ratio (2) Expanded state (3) Cell size (4) Flexural properties were evaluated in the same manner as in Example 1.

Table 2 shows the results of (1) to (3).
Table 3 shows the results of (4).

[0183]

Example 3 “Foam molding” Using the same resin as used in Example 1,
The organic peroxide described in Example 1, the crosslinking aid, and the foaming agent were added in the amounts described in Example 1, and 15 parts by weight of GF (glass fiber) was further added. Molding was performed. "Evaluation of molded article" (1) Expansion ratio (2) Expanded state (3)
The cell size was evaluated in the same manner as in Example 1.

Table 2 shows the results.

[0185]

[Comparative Example 1] "Foam molding" A commercially available polypropylene resin powder (made by Mitsui Petrochemical Co., Ltd., brand name J300P, MFR = 2.0) without using the polypropylene obtained in Example 1
dg / min., [η] = 2.64 dl / g, MT = 2.2).

[Evaluation of Molded Article] As in Example 1,
(1) Expansion ratio (2) Expanded state (3) Cell size (4)
The bending characteristics were evaluated, and the results of (1) to (3) are shown in Table 2 and the result of (4) is shown in Table 3.

[0187]

[Comparative Example 2] "Foam molding" Using the same resin as used in Comparative Example 1,
The organic peroxide described in Example 1, the crosslinking aid, and the foaming agent were added in the amounts described in Example 1, and 15 parts by weight of GF (glass fiber) was further added. Molding was performed. However, the foam cell was broken by the GF, and the gas generated from the foaming agent escaped, so that a foam molded article could not be obtained.

[0188]

Comparative Example 3 Polymerization of propylene was carried out in the same manner as in Example 2, except that the “polymerization” prepolymerization catalyst [B] was used.

The results are shown in Table 1. "Foam molding" Using the polypropylene powder obtained above, foam molding was performed in the same manner as in Example 1.
Gas generated from the foaming agent escaped, and a foamed molded article could not be obtained.

[0190]

[Table 1]

[0191]

[Table 2]

[0192]

[Table 3]

Continued on front page (31) Priority claim number Japanese Patent Application No. 3-204467 (32) Priority date August 14, 1991 (1991.8.14) (33) Priority claim country Japan (JP) (72) Inventor Toshio Kobayashi 3 Chigusa Coast, Ichihara City, Chiba Prefecture, Mitsui Oil Chemical Industry Co., Ltd. (72) Inventor Mamoru Kioka 1-2-1, Waki, Wakimachi, Kuga County, Yamaguchi Prefecture Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-62-32105 (JP, A) JP-A-59-56412 (JP, A) JP-A-2-311507 (JP, A) JP-A-4-159312 (JP, A) Kaihei 4-170440 (JP, A) U.S. Pat. No. 5,021,382 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/60-4/70 C08F 10/00-10/14 C08L 23/00-23/36 C08J 9/00-9/42 CA (STN) EPAT (QUESTEL) REGISTRY (STN) WPI / L (QUESTEL)

Claims (6)

(57) [Claims] 1. A catalyst composition comprising: [A] a transition metal compound catalyst component;
Organic gold containing metals selected from Groups I to III of the Periodic Table
Α-olefins and polyenes
Composition derived from α-olefin obtained by copolymerization
When the unit is 99.999 to 50 mol%, the polyene compound
From 0.001 to 50 mol% of structural units derived from
Α-olefin / polyene copolymer
The olefin is polymerized using a prepolymerization catalyst containing (i).
Polymerize or copolymerize to form the olefin polymer (ii)
A foamed molded article comprising the α-olefin / polyene copolymer-containing olefin polymer obtained in the above . 2. The α-olefin / polyene copolymer-containing olefin polymer comprises: (i) an α-olefin / polyene copolymer in an amount of 0.001 to 0.001;
The foamed molded article according to claim 1, wherein the foamed molded article contains (ii) an olefin polymer in an amount of 99.999 to 85% by weight in an amount of 15% by weight. 3. The olefin polymer containing an α-olefin / polyene copolymer, wherein [A] a transition metal compound catalyst component selected from Ti, Zr, Hf, Cr and V, and [B] a period. The organometallic compound catalyst component containing a metal selected from Groups I to III of the Table includes an α-olefin and a polyene compound in an amount of 0.01 to 2000 g per 1 g of the [A] transition metal compound catalyst component. Α-olefin / polyene copolymer
An olefin polymer is obtained by polymerizing or copolymerizing an olefin with a prepolymerization catalyst containing (i).
3. An α-olefin / polyene copolymer-containing polymer obtained by forming (ii).
The foam molded article according to the above. 4. The foam molded article according to claim 1, wherein the polyene compound is a polyene compound having olefinic double bonds at both ends. 5. The polyene compound is an aliphatic polyene compound and / or an alicyclic polyene compound having an olefinic double bond at both terminals and has 7 or more carbon atoms. 4. The foam molded article according to 2 or 3. 6. The method according to claim 1, wherein the olefin polymer (ii) is polypropylene or polyethylene.
4. The foam molded article according to 2 or 3.