JP2002241449A - Cross-copolymerized olefin-aromatic vinyl compound- diene copolymer and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cross-copolymerized olefin-diene copolymer, especially a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer, which is excellent in dynamic properties, high-temperature properties, and compatibility and has a high uniformity; a composition of the same; and a production method thereof. SOLUTION: This cross-copolymer is prepared by subjecting an olefin-diene copolymer comprising aromatic vinyl compound units in a content of 5 mol% or higher but 50 mol% or lower, diene units in a content of 0.0001 mol% or higher but 3 mol% or lower, and olefin units accounting for the rest to cross- copolymerization with an olefin copolymer containing aromatic vinyl compound units in a content of 2.2 mol% or lower.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (hereinafter sometimes abbreviated as cross-copolymer), a composition thereof, and a composition thereof. It relates to a manufacturing method.

[0002]

2. Description of the Related Art Ethylene-aromatic vinyl compound (styrene) copolymer obtained by using a so-called homogeneous Ziegler-Natta catalyst system comprising a transition metal catalyst component and an organoaluminum compound. Some copolymers and a method for producing the same are known. JP-A-3-1630088 and JP-A-7-53618 disclose that a normal (ie, head-to-tail) styrene chain having a styrene content of 50 mol% or less obtained by using a complex having a so-called constrained geometric structure exists. No ethylene-styrene copolymers, so-called pseudo-random copolymers, are described. JP-A-6-49132, and Polymer Preprints, Japan,
42 , 2292 (1993) include a bridged metallocene system Z
Method for producing an ethylene-styrene copolymer having no aromatic vinyl compound chain and having an aromatic vinyl compound content of 50 mol% or less, that is, a so-called pseudo-random copolymer, using a catalyst comprising an r complex and a cocatalyst Is described. These copolymers do not have stereoregularity derived from aromatic vinyl compound units.

[0003] More recently, a specific bridged bisindenyl Zr complex, ie, racemic [ethylenebis (indenyl) zirconium dichloride] has been used at an extremely low temperature (-2
Under the condition of 5 ° C.), an ethylene-aromatic vinyl compound copolymer having a stereoregularity close to an alternating copolymer has been reported. (Macromol. Chem., RapidC.
ommun. , 17 , 745 (1996). )However,
The copolymer obtained with the present complex has a molecular weight that is not practically sufficient and has a large composition distribution. Also, JP-A-9-309
925 and JP-A-11-130808,
It has a styrene content of 1 to 55 mol% and 1 to 99 mol%, has ethylene-styrene alternating structure and styrene chain structure, has isotactic stereoregularity, and has head-tail styrene chain structure. And a high molecular weight novel ethylene-styrene copolymer having a copolymer alternating degree (λ value in the present specification) of 70 or less. Also,
This copolymer has high transparency.

[0004] Although the various ethylene-styrene random copolymers described above have various excellent features, in order to put them to practical use, improvement of their heat resistance and physical properties especially at high temperatures is desired. .

[0005] Further, the conventional ethylene-styrene copolymer has a remarkable change in softness (Shore-A hardness, D hardness) depending on the styrene content. For example, the Shore-A hardness of a copolymer having a styrene content of about 5 mol% is about 95, and decreases to about 85 at 10 mol%. I do. However, when the styrene content of the copolymer increases, its heat resistance rapidly decreases. On the other hand, the cold resistance (brittleness temperature) is -60 ° C. with a copolymer having a low styrene content.
Although it is excellent as follows, the cold resistance deteriorates as the styrene content increases, and reaches about -10 ° C. at around 30 mol% and room temperature at around 50 mol%. Styrene content 1
A copolymer in the vicinity of 5 to 50 mol% has a feel, flexibility and stress relaxation properties similar to those of PVC, and is useful as a substitute for PVC. In addition, it has excellent vibration damping and soundproofing properties. However, its heat resistance and cold resistance are poor and it is difficult to use it as it is.

When used as a stretch film, a copolymer having a styrene content of about 30 to 50 mol% exhibits slow elongation recovery at room temperature like a PVC stretch film, but becomes too hard under refrigerated or frozen conditions. . Further, if this film is to be manufactured by extrusion processing using a T-die or inflation molding, the films adhere to each other during winding because the film itself has high self-adhesiveness. Although a certain degree of self-adhesiveness is effective especially for replacing a PVC film as a stretch film for food packaging, it is difficult to achieve compatibility with film formability.

[0007] Ethylene having a styrene content of 40 mol% or more
Styrene copolymers have excellent printability and coloring properties, and also have improved compatibility with styrene resins. Especially styrene content 2
When the copolymer is 0 mol% or less, the printability and the colorability are poor, but the compatibility with the polyolefin resin is excellent. As described above, the physical properties and compatibility of these random ethylene-styrene copolymers vary significantly depending on the composition, and various properties excellent in one composition (for example, heat resistance, cold resistance, stress relaxation properties, and flexibility). ) Cannot be satisfied at the same time.

Conventionally, in order to solve such a problem,
Ethylene-styrene copolymers having different compositions are mixed together to form a composition (Japanese Patent Laid-Open No. 2000-129043, WO98 / 1018), or a composition with a polyolefin (WO98 / 1015),
A method of crosslinking (US Pat. No. 5,869,591) has been proposed. However, ethylene-styrene copolymers having greatly different compositions have poor compatibility with each other, and their compositions and compositions with polyolefins are opaque, and mechanical properties may be impaired, thus limiting the applications. In addition, when crosslinked, there is a problem that the secondary moldability and the recyclability are lost and the production cost is increased.

Ethylene-α-olefin copolymer Ethylene-α-olefin copolymer obtained by copolymerizing ethylene with 1-hexene, 1-octene, etc., so-called LLDPE
Is flexible and transparent and has high strength,
It is widely used as general-purpose films, packaging materials, containers and the like. However, the fate of the polyolefin resin is poor in printability and paintability, and a special treatment such as corona treatment is required for printing and painting. Furthermore, since it has low affinity with aromatic vinyl compound polymers such as polystyrene and polar polymers, it is necessary to use other expensive compatibilizers in order to obtain a composition having good mechanical properties with these resins. There was sex.

General Grafted Copolymer Conventionally, as a method for obtaining a graft copolymer, an olefin-based polymer or an olefin-based polymer can be prepared by a general known radical grafting method during polymerization or molding. A method for obtaining a graft copolymer of a styrene copolymer is known. However, in this method, it is difficult to obtain a high graft efficiency, which is disadvantageous in terms of cost, and the obtained graft copolymer is non-uniform and partially gels and becomes insoluble, or impairs moldability. And the like. The thus obtained grafted copolymer generally has a graft chain branched one by one from the polymer main chain, but when this is used as a composition or as a compatibilizer, the grafted copolymer has a polymer microstructure interface. The strength is not enough.

[0011]

SUMMARY OF THE INVENTION The present invention provides mechanical properties,
Cross-copolymerized olefin with excellent high temperature properties and compatibility
An object of the present invention is to provide an aromatic vinyl compound-diene copolymer and a composition thereof, and further provide an industrially excellent production method of the cross copolymer and the composition.

[0012]

DISCLOSURE OF THE INVENTION The present invention firstly solves the above-mentioned problems of the prior art, and provides a cross-copolymerized olefin-aromatic compound which satisfies heat resistance, various mechanical properties and compatibility. This is an industrially excellent method for producing a vinyl compound-diene copolymer and a composition thereof, and furthermore, this cross copolymer. The present invention is, secondly, the use of the cross-copolymer of the present invention, and solves the problems of the conventional various resin compositions and moldings, and various resin compositions including the improved cross-copolymer and It is a molded product.

Hereinafter, the present invention will be described in detail. <Cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (cross-copolymer)> In the present invention, the olefin-aromatic vinyl compound-diene copolymer is
It shows a copolymer composed of units derived from olefin, aromatic vinyl compound and diene monomers. In the present specification, the aromatic vinyl compound content of the copolymer indicates the content of units derived from the aromatic vinyl compound monomer contained in the copolymer.
The same applies to the olefin content and the diene content. The cross copolymer of the present invention comprises an olefin-aromatic vinyl compound-diene copolymer containing an olefin copolymer having an aromatic vinyl compound content of 2.2 mol% or less (which may contain a diene). It is a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer obtained by cross-copolymerization. Preferably, the cross copolymer of the present invention has an olefin-aromatic content in which the content of the aromatic vinyl compound is 5 mol% or more and 50 mol% or less, the diene content is 0.0001 mol% or more and 3 mol% or less, and the balance is olefin. An olefin copolymer (which may contain a diene) having an aromatic vinyl compound content of 2.2 mol% or less is cross-copolymerized with the vinyl compound-diene copolymer. It is a polymerized olefin-aromatic vinyl compound-diene copolymer. Further, the cross copolymer of the present invention preferably has an olefin copolymer (which may contain a diene) having an aromatic vinyl compound content of 2.2 mol% or less as a cross chain, and Is a cross-copolymerized olefin-aromatic vinyl compound having an aromatic vinyl compound content of 5 mol% to 50 mol%, a diene content of 0.0001 mol% to 3 mol%, and a balance of olefin. -A diene copolymer. That is, the cross copolymer of the present invention finally has a composition in which the content of the aromatic vinyl compound is 5 mol% or more and 50 mol% or less, the diene content is 0.0001 mol% or more and 3 mol% or less, and the balance is olefin. Can be. More preferably, the cross-copolymer of the present invention finally has an aromatic vinyl compound content of 5 mol%.
It can have a composition of not less than 50 mol%, not more than 0.001 mol% and less than 0.5 mol%, and the balance being olefin.

The weight average molecular weight of the cross copolymer of the present invention is preferably 10,000 or more, more preferably 30,000 or more, particularly preferably 60,000 or more, and 1,000,000 or less, preferably 500,000 or less. The molecular weight distribution (Mw / Mn) is 1
0 or less, preferably 7 or less, most preferably 5 or less,
1.5 or more. In the specification of the present invention, a cross copolymer is a polymer that can be directly obtained by the production method of the present invention.

Further, the present invention is a cross-copolymer which preferably comprises the structure shown in FIG. 1 or preferably mainly comprises the structure shown in FIG. That is, as shown in FIG. 1, a main chain olefin-aromatic vinyl compound-diene copolymer and a vinyl compound polymer are interposed via a diene unit,
It is a copolymer mainly having a structure that is bonded (cross-linked) to a cross chain at one or more points. Such a cross structure can be rephrased as a star structure.
In addition, classification by the American Chemical Society POLY subcommittee
eggated star copolymer (Po
lymer prints, March 1998). Hereinafter, an olefin-aromatic vinyl compound copolymer or olefin (co) cross-linked to a main chain olefin-aromatic vinyl compound-diene copolymer
The polymer is described as a cross-chain.

On the other hand, as shown in FIG. 2, a graft copolymer known to those skilled in the art is a copolymer mainly having a polymer chain branched from one or more points of the main chain. A structure in which the polymer main chain and other polymer chains cross-link (cross-link) (also referred to as a star structure) generally has a higher polymer microstructure than a grafted structure when used as a composition or compatibilizer. Excellent strength of the structural interface is obtained,
It is believed to provide high mechanical properties. The cross copolymer of the present invention (in the present specification, a cross-copolymerized olefin-
Synonymous with aromatic vinyl compound-diene copolymer. ) Has a cross-chain aromatic vinyl compound content of 2.2.
Mol% or less, and therefore has a characteristic that it can have a high crystal melting point (heat resistance, high temperature mechanical properties). The cross-copolymer of the present invention therefore has a D
According to SC, at least one melting point peak is 80 ° C or higher and 1
It is observed at a temperature of 40 ° C. or lower, preferably 100 ° C. or higher and 140 ° C. or lower, and has a crystal melting heat of 10 J / g to 150 J / g, preferably 20 J / g to 120 J.
/ G or less. Further, preferably, the cross copolymer of the present invention has a crystal structure based on an ethylene chain structure. This crystal structure can be formed by a known method, for example, X
It can be confirmed by a line diffraction method.

More specifically, the cross-copolymer of the present invention has at least one of an aromatic vinyl compound content and a melting point peak having a crystal fusion heat of 10 J / g or more and 150 J / g or less measured by DSC. One that satisfies the following relationship: an aromatic vinyl compound content of 5 mol% or more and 50 mol% or less, a diene content of 0.0001 mol% or more and 3 mol% or less, and a balance of ethylene or two or more containing ethylene It is preferable that the olefin is a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer. (5 ≦ St ≦ 15) −3 · St + 125 ≦ Tm ≦ 140 (15 <St ≦ 50) 80 ≦ Tm ≦ 140 Tm; Melting point (° C.) by DSC measurement St; Aromatic vinyl compound content (mol%)

More preferably, in the cross-copolymer of the present invention, at least one of the aromatic vinyl compound content and the melting point peak having a crystal fusion heat of 10 J / g or more and 150 J / g or less measured by DSC is not more than one. The aromatic vinyl compound content is characterized by satisfying the relationship of 5 mol%
Not less than 50 mol% and the diene content is 0.0001 mol%
This is a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer in which at least 3 mol% and the balance is ethylene or two or more olefins containing ethylene. (5 ≦ St ≦ 10) −2 · Xc + 120 ≦ Tm ≦ 140 (10 <St ≦ 50) 100 ≦ Tm ≦ 140 Tm; Melting point (° C.) by DSC measurement St; Aromatic vinyl compound content (mol%)

Most preferably, the cross-copolymer of the present invention has an aromatic vinyl compound content and at least one of melting point peaks having a heat of crystal fusion of 10 J / g or more and 150 J / g or less measured by DSC, wherein The aromatic vinyl compound content is 5 mol% or more and 30 mol% or less, the diene content is 0.0001 mol% or more and 3 mol% or less, and the balance includes ethylene or ethylene.
Cross-copolymerized olefins which are at least one kind of olefin
It is an aromatic vinyl compound-diene copolymer. (5 ≦ St ≦ 10) −2 · St + 120 ≦ Tm ≦ 140 (10 <St ≦ 30) 100 ≦ Tm ≦ 140 Tm; Melting point (° C.) by DSC measurement St; Aromatic vinyl compound content (mol%) More preferably , A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer having one melting point observed by DSC and having the melting point satisfying the above relationship. The melting point of the cross-copolymer of the present invention represented by the above formula is significantly higher than the relationship between the melting point and the aromatic vinyl compound content of the ethylene-based copolymer having an α-olefin or styrene as an aromatic vinyl compound. , Are distinguished.

The cross-copolymer of the present invention is characterized in that a cross-copolymerized olefin characterized in that an aromatic vinyl compound is copolymerized in the main chain and the cross chain or only in the main chain.
It is an aromatic vinyl compound-diene copolymer. By using an aromatic vinyl compound, it is possible to have mechanical properties similar to a soft vinyl chloride resin and excellent compatibility with a styrene resin, other resins, and additives. Among the cross copolymers of the present invention, the cross-copolymerized ethylene-styrene-divinylbenzene copolymer is preferably at 30 ° C.
Below, it can have at least one glass transition point in the range of −30 ° C. or higher. The glass transition point is a glass transition point determined by a tangent method (on set method) in DSC measurement.

Further, the present invention is preferably carried out at 230 ° C.
MFR measured under a load of 5 kg is 0.1 g / 10 min or more,
More preferably, it is a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer which is 1 g / 10 min or more and which is more excellent in moldability. Further, the present invention provides
The boiling xylene insoluble matter (gel content) determined by ASTM D-2765-84 is less than 10% by mass, preferably less than 1% by mass, most preferably less than 0.1% by mass, low in gel content, or Cross-copolymerized olefins substantially free of gel content-aromatic vinyl compounds-
It is a diene copolymer. The present invention is a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer, wherein the olefin is preferably ethylene or two or more olefins containing ethylene.

The cross copolymer of the present invention is a copolymer obtainable by the following production method.
The cross-copolymer of the present invention is not only a concept showing the cross-copolymer itself, but also the cross-copolymer, and the first polymerization step, the second and subsequent polymerization steps (hereinafter sometimes referred to as the second polymerization step). The concept of a composition containing the olefin copolymer (olefin-aromatic vinyl compound copolymer or the like) which is not cross-crosslinked and obtained in any ratio. A composition containing such a cross copolymer can be obtained by the production method of the present invention.

Since the cross-copolymer of the present invention has significantly different aromatic vinyl compound contents between the main chain and the cross-chain, the olefin-aromatic vinyl compound copolymers having different compositions (aromatic vinyl compound content) obtained in each polymerization step are different. It is thought that even if the polymer is contained, it functions as a compatibilizer for these.
Therefore, the cross copolymer obtained by the production method of the present invention is considered to have excellent mechanical properties, high heat resistance, transparency, and processability as compared with a normal olefin-aromatic vinyl compound copolymer. . Further, the present invention provides a method for producing a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer excellent in economical efficiency, and a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer obtained by the method. A polymer is provided. These cross copolymers are extremely useful in a wide range of applications.

<Method for producing cross-copolymerized olefin-aromatic vinyl compound-diene copolymer> The present invention provides a cross-copolymer, ie, cross-copolymerized olefin-aromatic, obtainable by the following production method. It is an aromatic vinyl compound-diene copolymer. In addition, the present cross copolymer production method is to produce a cross copolymer having uniformity, excellent heat resistance, good processability, and transparency and mechanical properties with efficiency and economy suitable for industrialization. Can be.

That is, in the present invention, as a first polymerization step (main chain polymerization step), an olefin monomer, an aromatic vinyl compound monomer and a diene monomer are copolymerized using a coordination polymerization catalyst, and an olefin-aromatic vinyl compound is obtained. A diene copolymer is synthesized, and then, as a second polymerization step (cross-forming step), an olefin-aromatic vinyl compound is prepared by using the copolymer, an olefin, an aromatic vinyl compound, and a coordination polymerization catalyst if necessary. This is a production method for obtaining a cross copolymer obtained by cross-copolymerizing a copolymer. This manufacturing method
This is a production method using two or more polymerization steps including the first polymerization step (main chain polymerization step) and the second polymerization step (cross-forming step).

A) First polymerization step (main chain polymerization step) Olefin-aromatic vinyl compound used in the present invention
The diene copolymer is obtained by copolymerizing an olefin monomer, an aromatic vinyl compound monomer and a diene monomer in the presence of a single-site coordination polymerization catalyst. The olefins used in the present invention include ethylene, α-olefins having 3 to 20 carbon atoms, ie, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and cyclic olefins, ie, cyclopentene. , Norbornene or an alicyclic olefin, that is, one or more of vinylcyclohexane. Preferably, ethylene and / or C3-20
Α-olefin is used, and particularly preferably, ethylene and propylene, ethylene and 1-butene, and ethylene and 1-
Hexene, ethylene and 1-octene, and ethylene and norbornene are used. Most preferably, ethylene is used.

Styrene is preferably used as the aromatic vinyl compound used in the present invention. Other aromatic vinyl compounds such as p-chlorostyrene, p-tert-butylstyrene, α-methylstyrene, vinylnaphthalene, p-chlorostyrene -Methylstyrene, vinylnaphthalene, vinylanthracene and the like can be used, and a mixture thereof may be used.

As the diene used in the present invention, a diene capable of coordination polymerization is used. Preferably 1,4-hexadiene, 1,5-hexadiene, ethylidene norbornene, dicyclopentadiene, norbornadiene, 4-vinyl-1-cyclohexene, 3-vinyl-
1 cyclohexene, 2-vinyl-1 cyclohexene, 1
-Vinyl-1 cyclohexene, orthodivinylbenzene, paradivinylbenzene, metadivinylbenzene or mixtures thereof. Further, a diene in which a plurality of double bonds (vinyl groups) are bonded via a hydrocarbon group having 6 to 30 carbon atoms containing one or more aromatic vinyl ring structures can be used. In addition, Japanese Patent Application Laid-Open No. 6-1
Dienes described in 36060 and JP-A-11-124420 can also be used in the present invention. Preferably, dienes in which one of the double bonds (vinyl group) is used for coordination polymerization and the double bond remaining in the polymerized state is coordinatively polymerizable, most preferably ortho, para, meta Of various divinylbenzenes and mixtures thereof are preferably used.

In the present invention, the amount of the diene used in the main chain polymerization step is 1/100 to 1 / 50,000 or more, preferably 1/400 to 1/20000 or more, in terms of molar ratio, of the amount of the aromatic vinyl compound used. It is. When the main chain polymerization step is carried out at a diene concentration higher than this, a large amount of the crosslinked structure of the polymer is formed during the polymerization and gelation occurs, or the processability of the cross copolymer finally obtained through the crossing step is improved. It is not preferable because physical properties deteriorate. Also,
When the main-chain polymerization step is performed at a diene concentration higher than this, the residual diene concentration in the polymerization liquid increases, so that when this polymerization liquid is used as it is in the cross-forming step, many crosslinked structures are generated and obtained. Similarly, the cross-copolymer may have poor processability and physical properties. The olefin-aromatic vinyl compound-diene copolymer polymerized in the first polymerization step (main chain polymerization step) of the present invention has an aromatic vinyl compound content of 5 mol% or more and 50 mol% or less and a diene content of 0.1 mol% or less.
It has a composition in which the content is from 0001 mol% to 3 mol%, with the balance being olefin. In particular, in order to obtain a cross copolymer having excellent flexibility, the olefin-aromatic vinyl compound-diene copolymer polymerized in the first polymerization step (main chain polymerization step) has an aromatic vinyl compound content of about 15%. It is preferred that the composition has a composition in which the content of diene is from 0.001 mol% to less than 0.5 mol%, and the balance is olefin. In particular, characteristics similar to soft PVC (tactile sensation such as softness, tan around room temperature in viscoelastic spectrum)
In order to obtain a cross copolymer having the δ component), the aromatic vinyl compound is particularly preferably styrene,
In this case, an olefin-aromatic vinyl compound-diene copolymer having a styrene content of about 20 mol% to 50 mol%, a diene content of 0.001 mol% to less than 0.5 mol%, and the balance being olefin is used. . In order to obtain a cross copolymer having both softness and cold resistance, it is necessary to use an olefin polymerized in the first polymerization step (main chain polymerization step).
The aromatic vinyl compound-diene copolymer has a composition in which the content of the aromatic vinyl compound is from 10 mol% to 30 mol%, the content of the diene is from 0.001 mol% to less than 0.5 mol%, and the balance is olefin. Is preferred. The diene content of the olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step (main chain polymerization step) is 0.0001 mol% or more and 3 mol% or less, preferably 0.001 mol% or more. It is less than 0.5 mol%, most preferably 0.01 mol% or more and less than 0.3 mol%. If the diene content in the copolymer becomes higher, the processability of the cross copolymer finally obtained through the second polymerization step (cross-forming step) deteriorates, which is not preferable.

As the transition metal compound catalyst used in the first polymerization step (main chain polymerization step), a polymerization catalyst composed of a soluble transition metal compound and a cocatalyst, ie, a soluble Zi
eglar-Natta catalysts, transition metal compound catalysts activated with methylaluminoxane, boron compounds and the like (so-called metallocene catalysts, half metallocene catalysts, CGCT
Catalyst). Specifically, polymerization catalysts described in the following documents and patents can be used. For example, in the case of metallocene catalysts, US Pat. No. 5,324,800, JP-B-7-37488, JP-A-6-49132, Polymer Preprints, Japan
n, 42 , 2292 (1993), Macromol.
Chem. , Rapid Commun. , 17 ,
745 (1996), JP-A-9-309925,
EP0872492A2, JP-A-6-18417
No. 9 publication. For half metallocene catalysts, Makromomo
l. Chem. 191 , 2387 (1990). CGC
For the T catalyst, Japanese Patent Application Laid-Open Nos.
No. 53618, EP-A-416815,
WO 99/14221. Soluble Zieglar-Nat
For the ta catalyst, JP-A-3-250007, Stu
d. Surf. Sci. Catal. , 517 (199
0).

An olefin-aromatic vinyl compound-diene copolymer having a uniform composition in which the diene is uniformly contained in the polymer is preferably used to obtain the cross copolymer of the present invention. It is difficult to obtain a copolymer having such a uniform composition with a Zieglar-Natta catalyst, and a single-site coordination polymerization catalyst is preferably used. A single-site coordination polymerization catalyst is a polymerization catalyst composed of a transition metal compound and a co-catalyst, and a transition metal compound catalyst activated by methylaluminoxane, boron compound, or the like (a so-called metallocene catalyst, half metallocene catalyst, CGCT catalyst, etc.). ).

In the present invention, the most preferably used single-site coordination polymerization catalyst is a polymerization catalyst comprising a transition metal compound represented by the following general formula (1) and a co-catalyst. When a polymerization catalyst comprising a transition metal compound represented by the following general formula (1) and a cocatalyst is used, it is possible to copolymerize a diene, particularly divinylbenzene, with a polymer with high efficiency. It is possible to greatly reduce the amount of diene used in the first polymerization step (main chain polymerization step) and the amount of unreacted diene remaining in the polymerization solution.

If the amount of diene used in the main chain polymerization step is high, that is, if the concentration is high, a large amount of cross-linking of the polymer occurs during the main chain polymerization with the diene unit structure as a cross-linking point, resulting in gelation and insolubilization, and eventually cross-linking. It deteriorates the processability of the copolymer or cross copolymer. In addition, if a large amount of unpolymerized dienes remains in the polymerization solution obtained in the main chain polymerization step, the degree of cross-linking of the cross chains will be significantly increased during the subsequent cross-polymerization step, and the resulting cross-linked The copolymer or the cross-copolymer is insolubilized, gelled, or deteriorates in processability.

Further, when a polymerization catalyst comprising a transition metal compound represented by the following general formula (1) and a cocatalyst is used, an olefin-aromatic vinyl having a very high activity and a uniform composition suitable for industrialization. It is possible to produce a compound-diene copolymer, especially an olefin-aromatic vinyl compound-diene copolymer. In addition, a highly transparent copolymer can be provided. Further, it is possible to provide an olefin-aromatic vinyl compound-diene copolymer having isotactic stereoregularity and a head-tail styrene chain structure excellent in mechanical properties.

[0035]

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In the formula, A and B are each independently selected from an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, and an unsubstituted or substituted fluorenyl group. Group. Y has a bond with A and B, and further contains a group containing hydrogen or a hydrocarbon having 1 to 20 carbon atoms (this group is 1 to
(Which may contain three nitrogen, boron, silicon, phosphorus, selenium, oxygen or sulfur atoms) as a substituent. The substituents may be different or the same. Further, Y may have a cyclic structure such as a cyclohexylidene group and a cyclopentylidene group. X independently has hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 8 to 12 carbon atoms, and a hydrocarbon substituent having 1 to 4 carbon atoms. A silyl group, an alkoxy group having 1 to 10 carbon atoms, hydrogen, or an amide group having a hydrocarbon substituent having 1 to 22 carbon atoms. n is an integer of 0, 1 or 2.
M is zirconium, hafnium, or titanium.
Particularly preferably, at least one of A and B is a group selected from an unsubstituted or substituted benzoindenyl group or an unsubstituted or substituted indenyl group, and the transition metal compound of the above general formula (1) and a cocatalyst. It is a polymerization catalyst composed of

An unsubstituted or substituted benzoindenyl group is
It can be represented by the following Chemical Formulas 3 to 5. In the following chemical formulas, R1b to R3b are each independently hydrogen, 1 to 3 nitrogen, boron, silicon, phosphorus, selenium, an alkyl group having 1 to 20 carbon atoms which may contain an oxygen or sulfur atom, and 6 to 6 carbon atoms.
10 aryl groups, alkylaryl groups having 7 to 20 carbon atoms, halogen atoms, OSiR ₃ groups, SiR ₃ groups, NR ₂ groups or PR ₂ groups (R represents a hydrocarbon group having 1 to 10 carbon atoms) It is. In addition, these adjacent groups may be combined to form a single or plural 5- to 10-membered aromatic or aliphatic rings. R1a to R3a are:
Each independently hydrogen, 1 to 3 nitrogen, boron, silicon,
Phosphorus, selenium, an alkyl group having 1 to 20 carbon atoms which may contain an oxygen or sulfur atom, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, a halogen atom, an OSiR ₃ group, a SiR ₃ group , An NR ₂ group or a PR ₂ group (R represents a hydrocarbon group having 1 to 10 carbon atoms), and is preferably hydrogen.

[0038]

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[0039]

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[0040]

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As unsubstituted benzoindenyl groups, 4,5
-Benzo-1-indenyl, (also known as benzo (e) indenyl), 5,6-benzo-1-indenyl, and 6,7-benzo-1-indenyl were substituted with α-acenaphth-1- as a substituted benzoindenyl group. Examples thereof include indenyl, 3-cyclopenta [c] phenanthryl, and 1-cyclopenta [l] phenanthryl. Particularly preferably, as an unsubstituted benzoindenyl group, 4,5-benzo-1-indenyl (also called benzo (e) indenyl) is used, and as a substituted benzoindenyl group, α-acenaphth-1-indenyl, 3-cyclopenta [ c] phenanthryl, 1-cyclopenta [l] phenanthryl group and the like. The unsubstituted or substituted indenyl group, unsubstituted or substituted fluorenyl group or unsubstituted or substituted cyclopentadienyl group can be represented by the following formulas 6 to 8.

[0042]

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[0043]

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[0044]

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R4b and R6 each independently represent hydrogen, 1 to
Three nitrogen, boron, silicon, phosphorus, selenium, oxygen or sulfur
An alkyl group having 1 to 20 carbon atoms which may contain a yellow atom,
Aryl group having 6 to 10 primes, alkyl having 7 to 20 carbons
Aryl group, halogen atom, OSiR_ThreeGroup, SiR_ThreeGroup,
NR_TwoGroup or PR_TwoGroup (R is a group having 1 to 10 carbon atoms
Represents a hydrocarbon group). In addition, these adjacent groups
Is a single or plural 5- to 10-membered ring (6
A ring or a non-membered ring)
May be. R5 is each independently hydrogen, 1 to 3 nitrogen atoms;
Element, boron, silicon, phosphorus, selenium, oxygen or sulfur atom
C1-C20 alkyl group, C6-C6 which may be contained
10 aryl groups, alkyl aryl having 7 to 20 carbon atoms
Group, halogen atom, OSiR _ThreeGroup, SiR_ThreeGroup, NR_TwoBase
Or PR_TwoGroup (R is a hydrocarbon having 1 to 10 carbon atoms)
Represents an elementary group). In addition, these adjacent groups are integrated
And a single or a plurality of 5- to 10-membered aromatic rings
Alternatively, an alicyclic ring may be formed. R4a is
Independently hydrogen, 1 to 3 nitrogens, boron, silicon, phosphorus, selenium
Carbon atoms which may contain oxygen, oxygen or sulfur atoms
0 alkyl group, 6-10 carbon aryl group, carbon number
7-20 alkylaryl groups, halogen atoms, OSi
R_ThreeGroup, SiR_ThreeGroup, NR_TwoGroup or PR_TwoGroup (R is any
Also represents a hydrocarbon group having 1 to 10 carbon atoms),
It is preferred that

When both A and B are unsubstituted or substituted benzoindenyl groups or unsubstituted or substituted indenyl groups, they may be the same or different. In producing the copolymer used in the present invention, A, B
It is particularly preferred that at least one of them is an unsubstituted or substituted benzoindenyl group. Most preferably, both are unsubstituted or substituted benzoindenyl groups. In the above general formula (1), Y is A, B
And a hydrogen atom or a carbon atom having 1 as a substituent.
A group containing up to 20 hydrocarbons (this group is one to three nitrogens,
A methylene group, a silylene group, an ethylene group, a germylene group, or a boron residue having a boron, silicon, phosphorus, selenium, oxygen or sulfur atom). The substituents may be different or the same. Further, Y may have a cyclic structure such as a cyclohexylidene group and a cyclopentylidene group.

Preferably, Y has a bond with A and B,
Hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a substituted methylene group or a substituted boron group substituted with an amino group or a trimethylsilyl group. Most preferably, Y is
A substituted methylene group which has a bond with A and B and is substituted by hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon substituent include an alkyl group, an aryl group, a cycloalkyl group, and a cycloaryl group. The substituents may be different or the same. Preferred examples, Y _{is, -CH 2 -, - CMe 2} -, - CEt 2 -, -
CPh _2- , cyclohexylidene, cyclopentylidene and the like. Here, Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group.

X is independently hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 8 to 12 carbon atoms,
A silyl group having a hydrocarbon substituent of 4 having 1 to 10 carbon atoms
Or an amide group or an amino group having hydrogen or a hydrocarbon substituent having 1 to 22 carbon atoms. n is an integer of 0, 1 or 2. Halogen is chlorine, bromine, fluorine, etc., alkyl is methyl, ethyl, etc., aryl is phenyl, etc., alkylaryl is benzyl, silyl is trimethylsilyl, etc. And alkoxy groups include methoxy group, ethoxy group, isopropoxy group and the like, and amide groups such as dialkylamide groups such as dimethylamide group and arylamide groups such as N-methylanilide, N-phenylanilide and anilide group. Is mentioned. Further, as X, US Patent Publication No. 5859276,
The groups described in US Pat. No. 5,892,075 can also be used. M is zirconium, hafnium, or titanium. Particularly preferred is zirconium.

Examples of such transition metal compounds include EP
-0872492A2, JP-A-11-130808
JP, JP-A-9-309925, WO 00/2
0426, EP0985689A2, JP-A-6
And transition metal compounds described in JP-A-184179. Particularly preferably, EP-0872492
A2, JP-A-11-130808, JP-A-9
It is a transition metal compound having a substituted methylene bridge structure specifically exemplified in JP-A-309925.

As the cocatalyst used in the production method of the present invention, known cocatalysts and alkylaluminum compounds conventionally used in combination with a transition metal compound can be used. Aluminoxanes (or methylalumoxane or MAO) or boron compounds are preferably used. Examples of the cocatalyst and the alkylaluminum compound to be used are disclosed in EP-0872492A2 and JP-A-11-1.
No. 30808, JP-A-9-309925, W
Co-catalysts and alkylaluminum compounds described in O00 / 20426, EP0985689A2, and JP-A-6-184179. Further, the co-catalyst used at that time is represented by the following general formula (2):
The aluminoxane (or alumoxane) represented by (3) is preferred.

[0051]

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In the formula, R is an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or hydrogen, and m is 2 to 10 carbon atoms.
It is an integer of 0. Each R may be the same or different.

[0053]

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In the formula, R ′ is an alkyl group having 1 to 5 carbon atoms;
An aryl group having 6 to 10 carbon atoms or hydrogen, and n is 2 to 1
It is an integer of 00. Each R 'may be the same or different.

In producing the olefin-aromatic vinyl compound-diene copolymer used in the present invention,
Each monomer, metal complex (transition metal compound) and cocatalyst exemplified above are brought into contact with each other, and the order of contact and the contacting method may be any known methods. As a method of the above copolymerization or polymerization, a method of polymerizing in a liquid monomer without using a solvent, or pentane, hexane, heptane, cyclohexane, benzene, toluene,
There is a method using a saturated aliphatic or aromatic hydrocarbon or a halogenated hydrocarbon alone or a mixed solvent such as ethylbenzene, xylene, chloro-substituted benzene, chloro-substituted toluene, methylene chloride and chloroform. Preferably, a mixed alkane solvent, cyclohexane, toluene, or ethylbenzene is used. The polymerization form may be either solution polymerization or slurry polymerization.

The polymerization may be of a batch type, a batch type or a continuous type. As the polymerization apparatus, a known apparatus such as a tank type, a single linear or loop type or a plurality of connected pipes, or a tower type can be used. In this case, the pipe-shaped polymerization apparatus includes various known mixers such as a dynamic or static mixer and a static mixer also serving as heat removal, a cooler equipped with a heat removal thin tube, and the like. It may have various known coolers. Moreover, you may have a batch type pre-polymerization can. Further, a method such as gas phase polymerization can be used.

The polymerization temperature is suitably from -78 ° C to 200 ° C. A polymerization temperature lower than -78 ° C is industrially disadvantageous, and a temperature higher than 200 ° C is not suitable because decomposition of the metal complex occurs. Industrially preferably, it is 0 ° C to 160 ° C.
° C, particularly preferably 30 ° C to 160 ° C. The pressure during the polymerization is generally from 0.1 to 1000 atm, preferably from 1 to 100 atm, particularly preferably from 1 to 30 atm.

When an organoaluminum compound is used as a cocatalyst, an aluminum atom /
The complex metal atom ratio is 0.1 to 100,000, preferably 1
It is used at a ratio of 0 to 10,000. If it is less than 0.1, the metal complex cannot be activated effectively, and if it exceeds 100,000, it is economically disadvantageous. When a boron compound is used as a cocatalyst, a boron atom / complex metal atom ratio of 0.01
To 100, preferably 0.1 to 1
0, particularly preferably 1, is used. If it is less than 0.01, the metal complex cannot be activated effectively, and if it exceeds 100, it is economically disadvantageous. The metal complex and the cocatalyst may be mixed and prepared outside the polymerization tank, or may be mixed in the tank during polymerization.

In the first polymerization step of the present invention, the olefin partial pressure can be changed continuously or stepwise within a range of less than 150% or more than 50% of the olefin partial pressure at the start of the polymerization. The olefin partial pressure in the first polymerization step is preferably kept constant during the polymerization. In the first polymerization step of the present invention, the concentration of the aromatic vinyl compound in the polymerization solution is higher than 30% and higher than the concentration at the start of polymerization by 200%.
It can be changed continuously or stepwise in a lower range. Also preferably, the conversion of the aromatic vinyl compound monomer is less than 70% (the concentration of the aromatic vinyl compound is higher than 30% as compared with the time of the initiation of the polymerization) without dispensing the aromatic vinyl compound monomer. Is good.

<Olefin-Aromatic Vinyl Compound-Diene Copolymer Used in the Present Invention> It is synthesized from each monomer of aromatic vinyl compound, olefin, and diene using a polymerization catalyst. The olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step (main chain polymerization step) of the present invention is preferably ethylene-α-
Olefin-aromatic vinyl compound-diene copolymer or ethylene-cyclic olefin-aromatic vinyl compound-
Diene copolymer or ethylene-alicyclic olefin-
An aromatic vinyl compound-diene copolymer, particularly preferably an ethylene-aromatic vinyl compound-diene copolymer is used. The ethylene-aromatic vinyl compound-diene copolymer obtained in the first polymerization step (main chain polymerization step) of the present invention is preferably an ethylene-styrene-diene copolymer or ethylene-styrene-α-olefin- An aromatic vinyl compound-diene copolymer or an ethylene-styrene-cyclic olefin-aromatic vinyl compound-diene copolymer, particularly preferably an ethylene-styrene-diene copolymer, is used. Further, the olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step (main chain polymerization step) of the present invention may have a cross structure or a cross-linked structure in the diene monomer unit contained therein. Having a gel content of less than 10% by mass, preferably 0.1% by mass.
It must be less than mass%.

The typical and preferred ethylene-styrene-diene copolymer used in the present invention will be described below. The ethylene-styrene-diene copolymer obtained in the first polymerization step (main chain polymerization step) is 1 based on TMS.
It preferably has a chain structure of styrene units of the head-tail attributed by a peak observed at 40 to 45 ppm by 3C-NMR measurement, and further,
42.3-43.1 ppm, 43.7-44.5 pp
m, 40.4-41.0 ppm, 43.0-43.6p
It preferably has a chain structure of styrene units assigned by the peak observed in pm. Further, the copolymer suitably used in the present invention is an ethylene-styrene-diene copolymer obtained by using a metallocene catalyst capable of producing isotactic polystyrene by homopolymerization of styrene, and An ethylene-styrene-diene copolymer obtained using a metallocene catalyst capable of producing polyethylene by homopolymerization of ethylene.

Therefore, the obtained ethylene-styrene-
The diene copolymer can have both an ethylene chain structure, a head-tail styrene chain structure, and a structure in which an ethylene unit and a styrene unit are bonded in the main chain.

The ethylene-styrene-diene copolymer obtained in the first polymerization step (main chain polymerization step) preferably used in the present invention is a styrene represented by the following general formula (4) contained in its structure. The stereoregularity of the phenyl group in the alternating structure of styrene and ethylene is greater than 0.5, preferably greater than 0.75, particularly preferably greater than 0.95 in isotactic dyad fraction (or meso dyad fraction) m. It is a copolymer. The isotactic dyad fraction m of the alternating copolymer structure of ethylene and styrene is represented by r of the methylene carbon peak appearing at around 25 ppm.
The peak area Ar derived from the structure and the area Am of the peak derived from the m structure can be determined by the following formula (ii). m = Am / (Ar + Am) Formula (ii) The appearance position of the peak may be slightly shifted depending on the measurement conditions and the solvent. For example, using deuterated chloroform as a solvent,
Based on TMS, the peak derived from the r structure is
The peak derived from the m-structure appears around 25.4 to 25.5 ppm, and around 25.2 to 25.3 ppm. Also,
When heavy tetrachloroethane is used as a solvent and the center peak of the triplet of heavy tetrachloroethane is defined as 73.89 ppm, the peak derived from the r structure is 25.3 to 25.3.
Around 5.4 ppm, the peak derived from the m-structure was 25.
Appears around 1-25.2 ppm. Note that the m structure represents a meso diad structure, and the r structure represents a racemic diad structure.

The ethylene-styrene-diene copolymer obtained in the first polymerization step (main chain polymerization step) has a ratio of an alternating structure of styrene and ethylene represented by the general formula (4) contained in the copolymer structure. The copolymer preferably has an alternating structure index λ (represented by the following formula (i)) of less than 70, more than 0.01, preferably less than 30, and more than 0.1. λ = A3 / A2 × 100 Formula (i) Here, A3 is three kinds of peaks a and b derived from an ethylene-styrene alternating structure represented by the following general formula (4 ′) and obtained by 13 C-NMR measurement. , C is the sum of the areas. A2 is 13C-NM based on TMS.
It is the sum of the areas of peaks derived from main chain methylene and main chain methine carbon observed in the range of 0 to 50 ppm by R.

[0065]

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[0066]

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(In the formula, Ph represents a phenyl group, x represents the number of repeating units and represents an integer of 2 or more.) An ethylene-styrene-diene copolymer having a diene content of 3 mol% or less, preferably less than 1 mol% Having a head-tail styrene chain and / or having an isotactic stereoregularity in an ethylene-styrene alternating structure and / or having an alternating structure index λ value of less than 70 means high transparency. It is effective because it is an elastomer copolymer having high mechanical strength such as breaking strength, and a copolymer having such characteristics can be suitably used in the present invention. In particular, the ethylene-styrene alternating structure has a high isotactic stereoregularity and an alternating structure index λ
A copolymer having a value of less than 70 is preferable as the copolymer of the present invention. Further, the copolymer has a head-tail styrene chain, and has an ethylene-styrene alternating structure having isotactic stereoregularity, Copolymers having a structure index λ value smaller than 70 are particularly preferred as the copolymer of the present invention.

That is, the preferred ethylene-styrene-diene copolymer of the present invention comprises an alternating structure of ethylene and styrene having high stereoregularity, an ethylene chain of various lengths, a heterogeneous bond of styrene, and various lengths of styrene. It has the feature of having various structures such as styrene chains. Further, the ethylene-styrene-diene copolymer of the present invention, the polymerization catalyst and polymerization conditions to be used, the ratio of the alternating structure depending on the styrene content in the copolymer, the λ value obtained from the above formula is from 0.01 to λ value. Various changes can be made in a large range of less than 70. An alternating index λ value of less than 70 means that the crystalline polymer has significant mechanical strength,
It is important to provide solvent resistance, toughness, and transparency, and to be a partially crystalline polymer or an amorphous polymer.

The olefin-aromatic vinyl compound-diene copolymer, particularly the ethylene-styrene-divinylbenzene copolymer, which is preferably used in the present invention, is as described above.
It can be obtained by a polymerization catalyst composed of the transition metal compound represented by the general formula (1) and a co-catalyst. As described above, the ethylene-styrene-diene copolymer as a representative and preferred example of the olefin-aromatic vinyl compound-diene copolymer used in the present invention has been described. The vinyl compound-diene copolymer is not limited to this.

The weight average molecular weight of the olefin-aromatic vinyl compound-diene copolymer used in the present invention is preferably 10,000 or more, more preferably 30,000 or more, particularly preferably 60,000 or more, and 1,000,000 or less. , Preferably 500,000 or less. The molecular weight distribution (Mw / Mn) is at most 6, preferably at most 4, most preferably at most 3. Here, the weight average molecular weight refers to a molecular weight in terms of polystyrene obtained by using GPC with standard polystyrene. The same applies to the following description. The weight average molecular weight of the olefin-aromatic vinyl compound-diene copolymer used in the present invention is within the above range as required by a known method using a chain transfer agent such as hydrogen, or by changing the polymerization temperature. It is possible to adjust. The olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step (main chain polymerization step) of the present invention may have a partial cross structure or a branched structure via a diene unit contained therein. good.

B) Second Polymerization Step (Cross-forming Step) As the second polymerization step of the present invention, coordination polymerization using the above-mentioned single-site coordination polymerization catalyst is employed. Preferably, a single-site coordination polymerization catalyst comprising a transition metal compound represented by the same general formula (1) and a cocatalyst as in the first polymerization step is employed. The single-site coordination polymerization catalyst composed of the transition metal compound represented by the general formula (1) and a cocatalyst is a diene unit copolymerized in a polymer main chain,
In particular, the present invention is preferable in the present invention because the residual coordination polymerizable double bond of divinylbenzene can be copolymerized with high efficiency. The copolymer obtained in the second polymerization step of the present invention preferably has the same structure as that of the copolymer in the first polymerization step, that is, the type and stereoregularity of the contained monomer unit. In the second polymerization step of the present invention, the same method as the polymerization method used in the first polymerization step is used. In this case, monomers of aromatic vinyl compounds such as olefins and aromatic vinyl compounds used in the first polymerization step can be used. The second polymerization step of the present invention is preferably carried out using the polymerization solution obtained in the above-mentioned first polymerization step and subsequently to the first polymerization step. However, the copolymer obtained in the first polymerization step is recovered from the polymerization solution,
The second polymerization step may be carried out in the presence of a single-site coordination polymerization catalyst by dissolving in a new solvent and adding the monomer to be used.

The olefin copolymer or olefin-aromatic vinyl compound-diene copolymer polymerized in the second and subsequent polymerization steps (cross-forming step) of the present invention (the polymerization liquid obtained in the first polymerization step When used in the second and subsequent polymerization steps, a small amount of residual diene is copolymerized in the obtained polymer).
It is as follows. In an extreme case, the content of the aromatic vinyl compound in the olefin copolymer polymerized in the second and subsequent polymerization steps (cross-forming step) may be 0 mol%. In this case, it is preferable that the copolymer is recovered from the polymerization solution obtained in the first polymerization step, dissolved in a new solvent, a catalyst, a cocatalyst, and an olefin are added, and the second polymerization step is performed. Further, the aromatic vinyl compound may be removed from the polymerization solution obtained in the first polymerization step by an appropriate means, and the second polymerization step may be performed. When the polymerization liquid obtained in the first polymerization step is used in the second polymerization step, unreacted diene remaining in the polymerization liquid is copolymerized in the second polymerization step, and the diene content is determined by the second polymerization step. In the olefin-aromatic vinyl compound copolymer (including cross chains) obtained in the step, it is usually in the range of 0.0001 mol% to 3 mol%, preferably 0.001 mol% to 0.5 mol. %. If the diene content is higher than this, the finally obtained cross-copolymer is insolubilized, gelled, or deteriorates in processability, which is not preferable. However, the polymer obtained in the second polymerization step (cross-chain polymerization step) of the present invention may partially have a cross structure or a branched structure via a small amount of a diene unit contained.

A specific method for producing the cross copolymer of the present invention satisfying the above conditions will be described below. That is, as a first polymerization step (main chain polymerization step), an aromatic vinyl compound such as an aromatic vinyl compound, an olefin monomer, and a diene monomer are copolymerized using a coordination polymerization catalyst to obtain an olefin-aromatic vinyl compound- A diene copolymer is synthesized, and then a second polymerization step (cross-linking step) having different polymerization conditions from the diene copolymer is performed in the presence of at least an olefin and an aromatic vinyl compound with the olefin-aromatic vinyl compound-diene copolymer. A method for producing a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer produced by using at least a two-stage polymerization method in which a polymerization is carried out using a coordination polymerization catalyst, and more preferably at least the following This is a manufacturing method that satisfies one or more of the conditions.

1) The olefin partial pressure of the polymerization liquid in the second and subsequent polymerization steps is 150% or more of the olefin partial pressure at the start of the first polymerization step. On the other hand, in the present invention, the olefin partial pressure in the first polymerization step is adjusted to a range higher than 50% and lower than 150% of the olefin pressure at the start of the polymerization, but it is more preferable that the olefin partial pressure is constant. 2) The concentration of the aromatic vinyl compound in the polymerization liquid at the start of the second and subsequent polymerization steps is 30% or less of the concentration of the aromatic vinyl compound at the start of the first polymerization step. However, the aromatic vinyl compound concentration in the first step in the present invention is maintained in a range higher than 30% of the concentration at the start of polymerization. 3) Different single-site coordination polymerization catalysts are used in the first polymerization step and the second and subsequent polymerization steps. 4) The type of olefin used for the polymerization is different between the first polymerization step and the second and subsequent polymerization steps.

The first polymerization step and the second polymerization step are distinguished from each other when the operation for changing these conditions is started.
The change that satisfies the above conditions is performed as rapidly as possible and is completed, and preferably, the polymerization time of the second polymerization step is 50 minutes.
%, More preferably within 30%, most preferably 1%
It is preferably completed within 0% of the time. It is preferable that the polymerization temperatures of the first polymerization step and the second polymerization step are the same. If different, up to 100 ° C, preferably 70 ° C
A temperature difference within ° C is appropriate. As a method of changing the monomer composition ratio in the polymerization liquid, the olefin partial pressure of the polymerization liquid in the second and subsequent polymerization steps is set to 15 with respect to the first polymerization step.
0% or more, preferably 200%, most preferably 300%
There is a way to change it to% or more. For example, when ethylene is used as the olefin, an ethylene pressure of 0.2 MPa
When the first polymerization step is performed in the second polymerization step, the first polymerization step is performed at 0.3 MPa or more, preferably 0.4 MPa or more, and most preferably 0.6 MPa or more.

The olefin partial pressure in the second polymerization step may be constant during the polymerization, or may be changed stepwise or continuously as long as the above conditions are satisfied. Further, as a method of changing the monomer composition ratio in the polymerization liquid, the concentration of the aromatic vinyl compound in the polymerization liquid at the start of the polymerization in the second and subsequent polymerization steps is 30% or less, preferably 20%, with respect to the first polymerization step. The following changing method is also applicable. For example, when styrene, which is an aromatic vinyl compound, is used as the aromatic vinyl compound, when the first polymerization step is started at a styrene concentration of 1 mol / L in the polymerization solution, 0.5 mol / L is used in the second polymerization step. It is carried out at a concentration of preferably 0.2 mol / L or less. Furthermore, you may apply combining the said olefin partial pressure and the change of an aromatic vinyl compound density | concentration.

The copolymer obtained in the first polymerization step is recovered from the polymerization solution, dissolved in a new solvent, an olefin and an aromatic vinyl compound monomer are added, and the copolymer is added in the presence of a single-site coordination polymerization catalyst. When performing the two polymerization step,
A single site polymerization catalyst different from the first polymerization step can be used. In the first polymerization step and the second and subsequent polymerization steps, by changing the type of olefin used for the polymerization, the aromatic vinyl compound content of the copolymer polymerized in the first polymerization step and the second polymerization step, the final It is also possible to change the aromatic vinyl compound content of the cross copolymer to be obtained as described above. The conversion rate of the aromatic vinyl compound monomer species to be polymerized in the second polymerization step is preferably 1% by mass or more at the start of the second polymerization step, particularly preferably 1% by mass.
0 mass% or more. Further, the second polymerization step is carried out subsequent to the first polymerization step using the polymerization liquid obtained in the first polymerization step, and in the first polymerization step polymerization liquid without addition of a new aromatic vinyl compound monomer When the remaining monomer is used in the second polymerization step, the conversion of the aromatic vinyl compound monomer species through all polymerization steps is preferably 40% by mass or more, particularly preferably 60% by mass or more. The higher the conversion of the aromatic vinyl compound monomer through the second polymerization step or all the polymerization steps, the higher the probability that the polymerizable double bond of the diene unit of the copolymer main chain is cross-copolymerized.

In the production of the cross copolymer of the present invention, a production method which satisfies 1) or 2) among the above conditions is preferably employed. Further, in the production of the cross-copolymer of the present invention, a production method that satisfies 1) among the above conditions is most preferably employed. In the production of the cross-copolymer of the present invention, a method is preferably employed in which the olefin partial pressure of the polymerization liquid in the second and subsequent polymerization steps is changed to 300% or more with respect to the first polymerization step. Further, when the olefin partial pressure of the first polymerization step is not constant, that is, when the olefin partial pressure fluctuates within the above range, most preferably, the olefin partial pressure at the start of the first polymerization step, the second and subsequent polymerization steps. The method is adopted in which the olefin partial pressure of the polymerization liquid is changed so as to maintain 300% or more.

The proportion of the copolymer obtained in the first polymerization step needs to account for at least 10% by mass or more of the finally obtained cross copolymer. Further, the amount of the polymer (including the cross chain mass) obtained in the second polymerization step needs to account for at least 10% by mass or more of the finally obtained cross copolymer. If the proportion of the copolymer obtained in the first polymerization step or the second polymerization step is less than 10% by weight of the finally obtained cross copolymer, the characteristics of the copolymer having a small amount of components will not be sufficiently exhibited. The cross copolymer of the present invention comprises a main chain copolymer (a copolymer component obtained in the first polymerization step) and a cross chain copolymer (a copolymer component obtained in the second polymerization step). By changing the weight ratio of the resin, even in the category of a soft resin, from a relatively hard resin (88 or more in Shore-A hardness) to a soft resin (87 or less in Shore-A hardness)
Above), the hardness can be arbitrarily changed.
In particular, in order for the Shore-A hardness of the cross copolymer of the present invention to be 87 or less, the copolymer obtained in the first polymerization step is substantially non-crystalline and this substantially non-crystalline It is particularly preferred that the copolymer occupies at least 60% by mass or more of the finally obtained cross copolymer. Here, the term “substantially non-crystalline” means that the melting point of the crystal peak observed in DSC is 50 ° C. or less, more preferably the heat of fusion is 10 J / g or less, or a crystal calculated by an X-ray diffraction method. It means that the degree of crystallization (crystallinity) is 10% or less. Further, the Shore-A hardness of the cross copolymer of the present invention is such that the glass transition point of the copolymer obtained in the first polymerization step is 5 ° C. or lower, preferably 0 ° C. or lower, at room temperature is 87 or lower. Important for.

The first polymerization step and the second polymerization step can be carried out in different reactors. These steps can also be performed using a single reactor. In these cases, the conditions are distinguished at the time when the above-described condition changing operations 1) to 4) are started. The cross-copolymer of the present invention, in a single reactor, while continuously changing the olefin or aromatic vinyl compound concentration, the copolymerization of olefin, aromatic vinyl compound, diene using a coordination polymerization catalyst It can also be manufactured. It suffices that at least one of the above conditions 1) to 4) is substantially satisfied between the initial stage and the final stage of the polymerization. The cross copolymer of the present invention can be produced by a production method including the first polymerization step (main chain polymerization step) and the second polymerization step (cross-forming step). The process can use any known method. For example, a method in which the first polymerization step is performed by batch polymerization or continuous polymerization (batch polymerization) of complete mixing, and the second polymerization step is performed by the same batch polymerization or continuous polymerization (batch polymerization), or a method in which the first polymerization step is performed. Is performed by batch polymerization or continuous polymerization (batch polymerization) of complete mixing,
A method in which the second polymerization step is performed by plug flow polymerization is exemplified. Here, the complete mixing type polymerization is, for example, a known method using a tank-shaped, tower-shaped or loop-shaped reactor. This is a polymerization method capable of having a uniform composition. Also, plug flow polymerization is
This is a polymerization method in which mass transfer is restricted in the reactor and the polymerization liquid has a continuous or discontinuous composition distribution from the inlet to the outlet of the reactor. In the second polymerization step of the present invention, from the viewpoint of performing efficient heat removal because the viscosity of the polymerization liquid increases, various coolers, having a mixer,
A loop-type or plug-flow polymerization method having a pipe shape is preferred.

Hereinafter, physical properties of the cross-copolymerized ethylene-styrene-divinylbenzene copolymer as a typical example of the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer of the present invention and its use will be described. The cross-copolymer of the present invention is characterized by having a main chain having a relatively high styrene content and a cross-chain having a very low styrene content. That is, the cross chains (components obtained after the second polymerization step) have high crystallinity derived from polyethylene. Further, the cross-copolymer of the present invention can be obtained by optionally preparing an ethylene-styrene copolymer having a different styrene content (which may contain a small amount of divinylbenzene) corresponding to the styrene content of the main chain and the cross-chain, respectively. Can be included in proportions. However, since the cross copolymer functions as a compatibilizer, it is possible to have various characteristics and high transparency.

Since the cross copolymer of the present invention has a crystal structure derived from an ethylene chain, it has good heat resistance. Furthermore, the low glass transition temperature and low embrittlement temperature of an ethylene-styrene copolymer having a low styrene content (−
(At 50 ° C. or lower) and high mechanical properties (rupture strength, tensile modulus). Also,
Since it can have a composition having a relatively high styrene content in either the main chain or the cross chain, it can have the following characteristics of an ethylene-styrene copolymer having a relatively high styrene content. That is, a relatively low tensile modulus, surface hardness, flexibility, a tan δ component near room temperature in the viscoelastic spectrum (0.05 to 0.80 at 0 ° C. or 25 ° C.), scratch resistance,
It can have a PVC-like feel, coloring property, and printability.

The cross-copolymerized ethylene-styrene-diene copolymer of the present invention can be used alone and suitably used as a substitute for known transparent soft resins such as soft PVC.
The cross-copolymer of the present invention includes a stabilizer, an antioxidant, a light resistance improver, an ultraviolet absorber, a plasticizer, a softener, a lubricant, a processing aid, a colorant, and an antistatic agent which are usually used in resins. , An antifogging agent, an antiblocking agent, a crystal nucleating agent, and the like. These can be used alone or in combination of two or more. The cross-copolymer of the present invention is, because of its excellent characteristics, a simple film or a composition mainly containing itself, as a substitute for a known transparent soft resin such as soft PVC, a stretch film, a shrink film or a package material, and a sheet. Can be suitably used as a tube or hose

When the cross-copolymer of the present invention is used as a film or a film for stretch packaging, the thickness thereof is not particularly limited, but it is generally 3 μm to 1 mm, preferably 10 μm to 0.1 μm.
5 mm. In order to use it suitably as a stretch packaging film for foods, it is preferably 5 to 100.
μm, more preferably 10 to 50 μm. In order to produce a transparent film or a film for stretch packaging comprising the cross copolymer of the present invention, a usual extrusion film forming method such as an inflation method or a T-die method can be employed. The film of the present invention or the film for stretch wrapping, for the purpose of improving the physical properties, other suitable films, for example, isotactic or syndiotactic polypropylene, high-density polyethylene,
Low density polyethylene (LDPE or LLDPE),
It can be multilayered with a film of polystyrene, polyethylene terephthalate, ethylene-vinyl acetate copolymer (EVA) or the like.

Further, the film of the present invention or the film for stretch packaging can have self-adhesiveness and adhesiveness by appropriately selecting the composition of the main chain or the cross chain. However, when stronger self-adhesiveness is required, a multilayer film with another film having self-adhesiveness can be used. Further, when it is desired to form a film for stretch packaging having a non-adhesive surface and an adhesive surface on the front and back, an ethylene-styrene copolymer having a higher styrene content or a linear low-density having a density of 0.916 g / cm ³ or more is formed on the non-adhesive surface. 5-30 high density polyethylene based on total thickness
%, An ethylene-styrene copolymer used in the present invention in the intermediate layer, a liquid polyisobutylene, liquid polybutadiene, etc. added to the ethylene-styrene copolymer used in the present invention in the adhesive layer in an amount of 2 to 10% by mass, Or the density is 0.
What added liquid polyisobutylene, liquid polybutadiene, etc. to 2-10 mass% to 916 g / cm < ³ > or less linear low density polyethylene, or laminated | stacked the ethylene-vinyl acetate copolymer about 5-30% with respect to the total thickness It can also be a multilayer film. Further, an appropriate amount of a tackifier may be added and used.

Although the specific application of the film of the present invention is not particularly limited, it is useful as a general packaging material or container.
It can be used for packaging films, bags, pouches and the like. In particular, it can be suitably used for stretch packaging films for food packaging, pallet stretch films, and the like. The molded article of the present invention, particularly a film or a film for stretch packaging, can be subjected to surface treatment such as corona, ozone, plasma, etc., antifogging agent application, lubricant application, printing and the like as required. Among the molded products of the present invention, the film or the film for stretch packaging can be produced as a stretched film which is stretched uniaxially or biaxially as required. The film of the present invention, or the film for stretch packaging, if necessary, heat, ultrasonic waves, fusion by a method such as high frequency, the film between by a method such as adhesion with a solvent or the like, and other materials such as thermoplastic resin and the like Can be joined. When used as a stretch packaging film for food, it can be suitably packaged by an automatic packaging machine or a manual packaging machine. Furthermore, when the film of the present invention has a thickness of, for example, 100 μm or more, a packaging tray for foods, electric products, and the like can be formed by a method such as vacuum forming, compression molding, or pressure forming.

Furthermore, since the cross copolymer of the present invention basically does not contain an eluting plasticizer or halogen, it has a basic feature of high environmental adaptability and safety. The cross copolymer of the present invention may be used as a composition with another polymer. Conventionally, polymers and additives known as a composition with an ethylene-styrene copolymer can be used as a composition with the cross copolymer of the present invention. Examples of such polymers and additives include the following. The following polymer is used in an amount of 1 to 99% by mass, preferably 30% by mass, based on the composition using the cross copolymer of the present invention.
It can be added in the range of up to 95% by mass. In addition, the cross copolymer of the present invention can be used as a compatibilizer between the “aromatic vinyl compound polymer” and the “olefin polymer”. The cross-copolymer of the present invention can significantly change the olefin / aromatic vinyl compound content ratio of the main chain and the cross-chain, so that it is possible to enhance the compatibility with each polymer, Therefore, it can be suitably used as a compatibilizer. In this case, the cross copolymer of the present invention can be used in an amount of 1 to 50% by mass, preferably 1 to 20% by mass, based on the composition.
Further, in the case of "filler" or "plasticizer", it can be used in an amount of 1 to 80% by mass, preferably 5 to 50% by mass based on the composition.

"Aromatic vinyl compound polymer" The content of the aromatic vinyl compound containing at least 10% by mass of the polymer of the aromatic vinyl compound alone and at least one monomer component copolymerizable with the aromatic vinyl compound is preferable. Is a copolymer of 30% by mass or more. Examples of the aromatic vinyl compound monomer used in the aromatic vinyl compound-based polymer include styrene and various substituted styrenes such as p-methylstyrene and m-styrene.
-Methylstyrene, o-methylstyrene, ot-butylstyrene, mt-butylstyrene, pt-butylstyrene, α-methylstyrene and the like. And the like. Further, a copolymer between these plural aromatic vinyl compounds is also used. The stereoregularity between the aromatic groups of the aromatic vinyl compound may be any of atactic, isotactic and syndiotactic.

Examples of the monomer copolymerizable with the aromatic vinyl compound include butadiene, isoprene, other conjugated dienes, acrylic acid, methacrylic acid, amide derivatives and ester derivatives, and maleic anhydride and derivatives thereof. The copolymerization method may be any of block copolymerization, tapered block copolymerization, random copolymerization, and alternating copolymerization. Further, a polymer obtained by graft-polymerizing the aromatic vinyl compound to a polymer composed of the above-mentioned monomer and containing the aromatic vinyl compound in an amount of 10% by mass or more, preferably 30% by mass or more may be used. The above aromatic vinyl compound-based polymer needs to have a weight average molecular weight in terms of styrene of 30,000 or more, preferably 50,000 or more, in order to exhibit the performance as a practical resin.

As the aromatic vinyl compound resin used, for example, isotactic polystyrene (IP
S), syndiotactic polystyrene (s-PS),
Atactic polystyrene (a-PS), rubber-reinforced polystyrene (HIPS), acrylonitrile-butadiene-styrene copolymer (ABS) resin, styrene-acrylonitrile copolymer (AS resin), styrene-methyl methacrylate copolymer, etc. Styrene-methacrylate copolymer, styrene-diene block / tapered copolymer (SBS, SIS, etc.), hydrogenated styrene-diene block / tapered copolymer (SEBS, SEPS, etc.), styrene-diene copolymer ( SBR), hydrogenated styrene-diene copolymer (hydrogenated SBR, etc.), styrene-maleic acid copolymer, and styrene-imidized maleic acid copolymer. The concept also includes petroleum resin.

"Olefin polymers" such as low density polyethylene (LDPE) and high density polyethylene (HDP)
E), linear low-density polyethylene (LLDPE), isotactic polypropylene (i-PP), syndiotactic polypropylene (s-PP), atactic polypropylene (a-PP), propylene-ethylene block copolymer, Propylene-ethylene random copolymer, ethylene-propylene-diene copolymer (EPD
M), cyclic olefin polymers such as ethylene-vinyl acetate copolymer, polyisobutene, polybutene and polynorbornene, and cyclic olefin copolymers such as ethylene-norbornene copolymer. If necessary, an olefin resin obtained by copolymerizing dienes such as butadiene and α-ω diene may be used. The above-mentioned olefin-based polymer needs to have a styrene-equivalent weight average molecular weight of 10,000 or more, preferably 30,000 or more, in order to exhibit the performance as a practical resin.

[Other Resins, Elastomers, and Rubbers] For example, polyamides such as nylon, polyesters such as polyimide and polyethylene terephthalate, polyvinyl alcohol, SBS (styrene-butadiene block copolymer), SEBS (hydrogenated styrene-butadiene block) Styrene (styrene-isoprene block copolymer), SEPS (hydrogenated styrene-isoprene block copolymer), SBR (styrene-butadiene block copolymer), styrene-based block copolymer such as hydrogenated SBR And natural rubber, silicone resin, and silicone rubber which do not fall into the category of the aromatic vinyl compound-based resin.

[Filler] Known fillers can be used. Preferred examples are calcium carbonate, talc,
Examples include clay, calcium silicate, magnesium carbonate, magnesium hydroxide, mica, barium sulfate, titanium oxide, aluminum hydroxide, silica, carbon black, wood flour, wood pulp, and the like. Further, a conductive filler such as glass fiber, known graphite, and carbon fiber can be used. "Plasticizer" Known mineral oil-based softeners such as paraffin, naphthene, aroma-based process oil, liquid paraffin, castor oil, linseed oil, olefin wax, mineral wax, various esters and the like are used.

In order to produce the polymer composition of the present invention, a known suitable blending method can be used. For example,
Melt mixing can be performed using a single-screw or twin-screw extruder, a Banbury mixer, a plast mill, a co-kneader, a heating roll, or the like. Before performing melt mixing, use a Henschel mixer, ribbon blender, super mixer,
Each raw material may be uniformly mixed with a tumbler or the like. The melting and mixing temperature is not particularly limited, but may be 100 to 30.
0 ° C., preferably 150-250 ° C. is common.

As the molding method of the various compositions of the present invention, known molding methods such as vacuum molding, injection molding, blow molding, extrusion molding, and extrusion molding can be used. Compositions containing the cross-copolymer of the present invention, various films and packaging materials, sheets, tubes and hoses, gaskets,
Further, it can be suitably used as a building material such as a floor material and a wall material, and as an interior material of an automobile.

[0096]

The present invention will be described below with reference to examples.
The present invention is not limited to the following examples. Analysis of the copolymers obtained in each of the examples and comparative examples was performed by the following means. The 13C-NMR spectrum was determined using α-500 (manufactured by JEOL Ltd.), using a heavy chloroform solvent or heavy
The measurement was based on MS. Here, the measurement based on TMS is as follows. First, the shift value of the center peak of the triplet 13C-NMR peak of heavy 1,1,2,2-tetrachloroethane was determined based on TMS. Next, the copolymer was dissolved in heavy 1,1,2,2-tetrachloroethane, and 13 C-NMR was measured.
Calculated based on the center line of the overlap line. Weight 1,1,2,
The shift value of the center line of the triplet of 2-tetrachloroethane was 73.89 ppm. The measurement was performed by dissolving 3% by mass / volume of the polymer in these solvents.

The 13C-NMR spectrum measurement for quantifying the peak area was performed by a proton gate decoupling method with NOE eliminated, using a pulse width of 45 ° and a repetition time of 5 seconds as a standard. By the way, under the same conditions, except that the repetition time was changed to 1.5 seconds, the measurement was performed.
The measurement time coincided with the case of the repetition time of 5 seconds within the measurement error range. Determination of the styrene content in the copolymer was determined by 1H-NMR
The equipment is α-500 and BRUCK manufactured by JEOL Ltd.
AC-250 manufactured by ER was used. It was dissolved in heavy 1,1,2,2-tetrachloroethane, and the measurement was performed at 80 to 100 ° C. The intensity was compared with the peak derived from the phenyl group proton (6.5 to 7.5 ppm) and the proton peak derived from the alkyl group (0.8 to 3 ppm) based on TMS. The diene (divinylbenzene) content in the copolymer is
Performed by 1H-NMR.

The molecular weight in the examples was determined by GPC (gel permeation chromatography) using a weight average molecular weight in terms of standard polystyrene. The copolymer soluble in THF at room temperature is obtained by using Tosoh HLC
It measured using -8020. For a copolymer insoluble in THF at room temperature, measurement was performed using ortho-dichlorobenzene as a solvent.
It measured at 145 degreeC using HLS-8121 apparatus made by Tosoh. The detector used was a RI (differential refractometer).
In the cross-copolymer of this example, the main chain component and the cross-chain component, since the refractive index to the solvent orthodichlorobenzene is inverted, the molecular weight of the cross copolymer obtained by the RI detector is not accurate, It is a reference value. D
The SC measurement was performed using a DSC 200 manufactured by Seiko Denshi Co., Ltd.
_The heating was performed at a heating rate of 10 ° C./min under _two air streams. Sample 1
Using 0 mg, the mixture was heated to 240 ° C. at a heating rate of 20 ° C./min, quenched with liquid nitrogen to −100 ° C. or less (pretreatment),
Next, the temperature was raised at a rate of 10 ° C./min from −100 ° C. to 240 ° C.
An SC measurement was performed to determine the melting point, heat of crystal fusion, and glass transition point. As a sample for evaluating physical properties, a sheet having a thickness of 1.0 mm formed by a hot press method (temperature: 180 ° C., time: 3 minutes, pressure: 50 kg / cm ² ) was used.

<MFR> Measured according to JIS K7210. Measurement temperature is 230 ° C, load is 5kg or 1
It was measured at 0 kg. <Tensile test> According to JIS K-6251, the sheet was cut into a No. 1 type test piece shape, and Shimadzu AGS
Using a -100D type tensile tester, a tensile speed of 500 mm /
It was measured in min.

<Measurement of dynamic viscoelasticity> Loss tangent tan δ
Is a dynamic viscoelasticity measuring device (RSA-
II) using a frequency of 1 Hz and a temperature range of −120 ° C.
The measurement was performed in the range of + 150 ° C. (the measurement temperature range was slightly changed depending on the sample characteristics). A sample for measurement (3 mm × 4
0 mm). <X-ray diffraction> X-ray diffraction is measured by MacP
A -18 type high-power X-ray diffractometer was used, and the radiation source was measured using a Cu-enclosed counter electrode (wavelength: 1.5405 Å). <Hardness> For the hardness, the durometer hardness of types A and D was determined according to the durometer hardness test method of JIS K-7215 plastic. <Divinylbenzene> The divinylbenzene used in the following polymerization has a purity of 80% manufactured by Aldrich.
1 ml per 400 ml of styrene in the following polymerization
When used, the amount of divinylbenzene is 1/640 of the amount of styrene in molar ratio.

<Synthesis of Ethylene-Styrene-Divinylbenzene Copolymer> Example 1 Using rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride as a catalyst, the reaction was carried out as follows. Polymerization was carried out using an autoclave having a capacity of 10 L, a stirrer and a jacket for heating and cooling. 4000 ml of toluene, 800 ml of styrene and 4.0 ml of divinylbenzene were charged, and heated and stirred at an internal temperature of 70 ° C. About 200 L of nitrogen was bubbled through to purge the system and the polymerization solution. 8.4 mmol of triisobutylaluminum and 21 mmol of methylalumoxane (manufactured by Tosoh Akzo Co., Ltd., PMAO-3A) were added based on Al,
Immediately, ethylene was introduced and the pressure was 0.5 MPa (1.5
After stabilization at Kg / cm ² G), 8.4 μmol of rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride and 0.84 mmol of triisobutylaluminum were added from a catalyst tank installed on the autoclave. Approximately 50m of dissolved toluene solution
1 was added to the autoclave. The polymerization (first polymerization step) was carried out for 86 minutes while maintaining the internal temperature at 50 ° C. and the pressure at 0.5 MPa. After the polymerization is completed, the obtained polymer liquid is
The polymer was added little by little into a large amount of vigorously stirred methanol liquid to recover the polymer. The polymer was air-dried at room temperature for 24 hours, and then dried at 80 ° C. in vacuo until no change in mass was observed. 657 g of polymer (P-1) was obtained.

Examples 2 to 4 Polymerization was carried out in the same manner as in Example 1 under the conditions shown in Table 1 to obtain an ethylene-styrene-divinylbenzene copolymer. Table 1 also shows the results of analysis of the obtained copolymer.

<Synthesis of Cross Copolymer> Example 5 The procedure was as follows, using rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride as a catalyst. Polymerization was carried out using an autoclave having a capacity of 10 L, a stirrer and a jacket for heating and cooling. 4700 ml of toluene and 100 g of the polymer (P-2) were charged into an autoclave, and dissolved by heating at an internal temperature of 70 ° C. with stirring. About 200 L of nitrogen was bubbled through to purge the system and the polymerization solution. 8.4 mmol of triisobutylaluminum and 21 mmol of methylalumoxane (manufactured by Tosoh Akzo Co., Ltd., PMAO-3A) were added based on Al,
Immediately, ethylene was introduced at a pressure of 0.3 MPa (2.0
After stabilization at Kg / cm ² G), 8.4 μmol of rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride and 0.84 mmol of triisobutylaluminum were added from a catalyst tank installed on the autoclave. Approximately 50m of dissolved toluene solution
1 was added to the autoclave. While maintaining the internal temperature at 70 ° C. and the pressure at 0.3 MPa, polymerization was carried out for 30 minutes.
After completion of the polymerization, the obtained polymer solution was added little by little into a large amount of vigorously stirred methanol solution to recover the polymer. After air drying the polymer at room temperature all day and night, 8
It was dried in a vacuum at 0 ° C. until no change in mass was observed. 250 g of polymer (P-5) was obtained.

Examples 6 to 9 Under the conditions shown in Table 2, polymerization was carried out in the same manner as in Example 5.
However, in Example 6, the styrene monomer was 200 ml,
4500 ml of toluene was used.

<One-Pot Synthesis of Cross Copolymer> Example 10 Using rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride as a catalyst, the reaction was carried out as follows. Polymerization was carried out using an autoclave having a capacity of 10 L, a stirrer and a jacket for heating and cooling. 4400 ml of toluene, 400 ml of styrene and 1.0 ml of divinylbenzene were charged, and the mixture was heated and stirred at an internal temperature of 90 ° C. About 200 L of nitrogen was bubbled through to purge the system and the polymerization solution. 8.4 mmol of triisobutylaluminum and 21 mmol of methylalumoxane (manufactured by Tosoh Akzo Co., Ltd., PMAO-3A) were added based on Al,
Immediately, ethylene was introduced, and the pressure was 0.25 MPa (1.
After stabilizing at 5 kg / cm ² G), 8.4 μmol of rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride and 0.84 mmol of triisobutylaluminum were added from a catalyst tank installed on the autoclave. Approximately 50 dissolved toluene solution
ml was added to the autoclave. The polymerization (first polymerization step) was performed for 110 minutes while maintaining the internal temperature at 90 ° C. and the pressure at 0.25 MPa. The integrated flow rate (consumption amount) of ethylene at this stage was about 200 L in a standard state. A part of the polymerization solution was sampled, and a polymer sample (P-10A) of the first polymerization step was obtained by meta-precipitation. Ethylene was rapidly introduced, and the pressure in the system was adjusted to 1.1 MPa over 17 minutes. Polymerization was performed for 35 minutes while maintaining the pressure at 1.1 MPa (second polymerization step). By increasing the pressure of ethylene, the polymerization was promoted, and the internal temperature was temporarily increased from 90 ° C to 95 ° C. After completion of the polymerization, the obtained polymer solution was added little by little into a large amount of vigorously stirred methanol solution to recover the polymer. The polymer was air-dried at room temperature for 24 hours, and then dried at 80 ° C. in vacuo until no change in mass was observed. 842 g of the polymer (P-1
0C).

Examples 11 and 12 Polymerization was carried out in the same manner as in Example 10 under the conditions shown in Table 3. Tables 1, 2, and 3 summarize the polymerization conditions of each example. Tables 4 and 5 show the analysis results of the polymers obtained in the respective examples. Cross copolymer P obtained in Examples 5, 7, 8, and 9
-5, P-7, P-8, and P-9 perform ethylene homopolymerization in the second polymerization step (cross-forming step) without using a styrene monomer in the presence of an ethylene-styrene-divinylbenzene copolymer. Therefore, the copolymer (cross chain) obtained in the second polymerization step (cross-forming step) becomes a polyethylene chain. Cross copolymer P- obtained in Example 6
About No. 6, the mass and composition of the used ethylene-styrene-divinylbenzene copolymer P-1 and the obtained mass and composition of P-6 were used to obtain a mass balance in the second polymerization step (cross-forming step). When the composition of the obtained copolymer (cross chain) was determined, the styrene content was 2.0 mol%. Table 5 shows that the polymer (P-
10A), the mass and composition of the polymer (P-10B) polymerized in the second polymerization step, in addition to the polymer (P-10C, etc.) finally obtained through the second polymerization step, are determined by mass balance. Values are also shown. As a result, in Examples 10 to 12, when the composition of the copolymer (cross chain) obtained in the second polymerization step (cross-forming step) was determined, each was 2.2.
Mol% or less.

In Examples 10 to 12, the amount of residual divinylbenzene in the polymerization solution was determined by gas chromatography analysis of the polymerization solution extracted at the end of the first polymerization step, and the amount of divinylbenzene consumed in the first polymerization step was determined. Was. From the value, the divinylbenzene content in the copolymer obtained in each of the first polymerization steps was determined. P-10A, P-12
A is about 0.04 mol%, P11-A is about 0.03 mol%
Met. The value of the structural index λ of the cross-copolymer obtained in each example and the value of the isotactic dyad fraction m of the styrene unit-ethylene unit alternating structure were determined according to the above formulas (i) and (ii), respectively. The λ values of P-1 to P-4 obtained in Examples 1 to 4 were all in the range of 12 to 22. In addition, the m value was 0.95 or more in each case, indicating high isotactic stereoregularity. Λ of P-10C to P-12C obtained in Examples 10 to 12
All values were in the range of 7-15. In addition, the m value was 0.95 or more in each case, indicating high isotactic stereoregularity.

Comparative Examples 1 to 6 rac-dimethylmethylenebis (4,5-benzo-1-
Indenyl) zirconium dichloride as a catalyst,
EP-0 using methylalumoxane (MAO) as a co-catalyst
Table 6 shows the results of analysis of ethylene-styrene copolymers having various styrene contents, which were obtained by polymerization according to the methods disclosed in JP-A-872492A2 and JP-A-11-130808.

Table 7 shows the results of the physical property tests of the polymers of the examples. It can be seen that the cross-copolymerized styrene-ethylene-divinylbenzene copolymer of this example has good mechanical properties (elongation, strength) and high heat resistance (melting point). When the physical properties of an ethylene-styrene copolymer having the same composition (styrene content) are compared with those of the ethylene-styrene copolymer, a remarkably high melting point can be exhibited. Further, it is shown that by changing the composition of the main chain and the cross chain and the ratio thereof, the elastic modulus and the hardness can be changed in a wide range while maintaining high heat resistance (melting point). That is, since the cross copolymer of this example has a cross chain having a low content of the aromatic vinyl compound (styrene), it can have a high melting point, have good mechanical properties, and have various elastic modulus and hardness. Can be changed. Further, the cross-copolymer P-12C obtained in Example 12 was used.
Is that the copolymer obtained in the first polymerization step is substantially non-crystalline (the melting point of the crystalline peak observed in DSC is 50
° C or less, and the heat of fusion is 10 J / g or less), and the substantially non-crystalline copolymer accounts for 60% by mass or more of the finally obtained cross copolymer. It has a characteristic of being excellent in softness, having a Shore-A hardness of 87 or less. Further, since the glass transition point of P-12A obtained in the first polymerization step is 0 ° C. or less, the cross copolymer P-
12C is soft and has a Shore-A hardness of 87 at room temperature.
It can take the following values:

FIG. 3 shows the relationship between the styrene content and the DSC melting point of the cross-copolymer obtained in this example and the ethylene-styrene copolymer of the comparative example. Furthermore, the cross-copolymerized styrene-ethylene-diene copolymer obtained in this example has relatively good workability (MFR, load 10 kg,
MFR measured at 230 ° C. is 0.1 g / 10 min. Above). The gel content of the cross-copolymer was measured according to ASTM D-2765-84. That is, a precisely weighed 1.0 g polymer (molded product having a diameter of about 1 mm and a length of about 3 mm) was wrapped in a 100-mesh stainless steel mesh bag and weighed precisely. After extracting this in boiling xylene for about 5 hours, the net bag was recovered and dried in vacuum at 90 ° C. for 10 hours or more. After cooling sufficiently, the net bag was precisely weighed, and the amount of polymer gel was calculated by the following equation.

Amount of gel = A / B × 100 A = weight of polymer remaining in net bag B = weight of initial polymer As a result, all were 0% (measurement lower limit: 0.1% by weight). It shows a very low gel content of the coalescence, a degree of crosslinking. This is because the coordination polymerization catalyst used in this example is
This is because the diene can be copolymerized with high efficiency, and the cross-linking proceeds sufficiently at a very low level of the diene used. It is considered that when the amount / concentration of the residual diene in the polymerization solution is sufficiently small, crosslinking of the copolymer in the diene unit during polymerization is suppressed to an extremely low level, and generation of a gel component is suppressed. Also in the crossing step, the generation of the gel component is suppressed because the residual diene amount / concentration is low. Therefore, it is considered that good moldability can be obtained. X-ray diffraction confirmed that all the cross-copolymers of this example had a crystal structure derived from an ethylene chain.

The embrittlement temperature of the cross copolymer of this example was J
It was measured according to IS K-6723, K-7216. As a result, each of the cross copolymers P-11C and P-12C showed an embrittlement temperature of −60 ° C. or less. On the other hand, a transparent soft PVC compound (DENKA, VINICON S2100-5)
0) indicated an embrittlement temperature of approximately -25 ° C. FIG. 4 shows a viscoelastic spectrum (measured at 1 Hz) of the cross-copolymer film obtained in Example 12. E ′ (storage modulus) of the cross copolymer of this example is 10 ° C. at 110 ° C.
^It shows a value of ⁶ Pa or more, and the temperature at which the temperature drops to 10 ⁶ Pa is about 120 ° C., which indicates that it has high heat resistance.

<Kneading and C Set Measurement> Using a Brabender Plasticorder (PLE331, Brabender), after melting the polymer, kneading was performed at 200 ° C., 60 rpm, for 10 minutes, with the composition shown in Tables 8 to 10 to obtain a sample. Produced. The sample was press-molded, the mechanical properties were measured, and the residual compression set (C-set) after pressure heat treatment at 70 ° C. for 20 hours was measured in accordance with JIS K6262. FIG. 8 shows the results. The C-set of the cross-copolymer alone (containing only the stabilizer) of Example 13 was prepared in Example 13,
14, 17, 20, 22, and 24.
Each of them has a good C-set value of 60% or less. This indicates that the cross-copolymer has good elastic recovery (7
High deformation recovery at 0 ° C.). Also, 1
Even in a heat resistance test at 20 ° C. for 2 hours (a dumbbell was hung in a gear oven and deformation was observed), it did not melt and showed high heat resistance. On the other hand, ethylene-
The styrene copolymer shows a high C-set value of 90 to 100% or more, and it is understood that the elastic recovery at high temperatures is low (that is, the heat resistance is low). Further, in the heat resistance test at 120 ° C., it melted within 15 minutes (for example, Comparative Example 7).

As comparative examples of the cross copolymer of this example, the main chain of the cross copolymer (copolymer obtained in the first polymerization step) and the cross chain (copolymer obtained in the second polymerization step) Ethylene-styrene copolymers corresponding to (R-
6: R-1) was mixed at a mass ratio of 7: 3, and a blend sample was subjected to C-set measurement and heat resistance test. Mixed samples were obtained by mechanical mixing and solution mixing methods. That is, a sample in which two types of ethylene-styrene copolymers were mixed with Brabender under the same conditions as in the example (Comparative Example 8).
And a solution (mixed solution) at 120 ° C. for 2 hours using toluene as a solvent, and then collected by methanol precipitation and dried to prepare a sample (Comparative Example 9). Further, ethylene-styrene copolymers (R-
6: R-1) was prepared at a weight ratio of 5: 5 to prepare a blend sample, and a C-set and a heat resistance test were performed (Comparative Example 10). As a result, all of these C-sets were 100% and melted at 120 ° C. within 15 minutes.

Further, the C-set of a sample (Comparative Example 11) in which ethylene-styrene copolymer R-6 having a composition corresponding to the main chain of the cross-copolymer examples and polyethylene were mixed at a mass ratio of 7: 3. Was 100%. The blend ratios in these comparative examples are similar to the cross copolymers of Examples 9 and 12. From the above results, it can be seen that the cross copolymer of this example has a high-temperature elastic recovery property and a heat resistance that are significantly superior to those of the ethylene-styrene copolymer and its composition. Further, the cross-copolymer of this example has a C-set value improved by blending with a plasticizer and a polyolefin, and has a hardness of about 90 to 90.
It is also possible to adjust in the range of about 70 (Example 1)
5, 16, 18, 19, 21, 23, 25-27). The cross-copolymer composition containing a polyolefin such as polyethylene or polypropylene and an oil as a plasticizer exhibited a high heat resistance of about 40 to 70% C-set.

[0116]

[Table 1]

[0117]

[Table 2]

[0118]

[Table 3]

[0119]

[Table 4]

[0120]

[Table 5]

[0121]

[Table 6]

[0122]

[Table 7]

[0123]

[Table 8]

[0124]

[Table 9]

[0125]

[Table 10]

[0126]

According to the present invention, mechanical characteristics, high temperature characteristics,
The present invention provides a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer having excellent compatibility and a composition thereof, and further provides an industrially excellent method for producing the cross copolymer and a composition thereof.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram showing a cross-linked copolymer of the present invention.

FIG. 2 is a conceptual diagram showing a conventional grafted copolymer.

FIG. 3 is a graph showing the relationship between the composition and the melting point of the cross-linked copolymer and ethylene-styrene copolymer of the present invention.

FIG. 4 shows the (P) of the cross copolymer obtained in Example 12.
-12C) Viscoelastic spectrum.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 23/00 C08L 23/00 51/00 51/00 (72) Inventor Masaki Nakajima Asahimachi, Machida-shi, Tokyo 3-5-1 No. 1 F-term in the Central Research Laboratory of Denka Kagaku Kogyo Co., Ltd. (reference) 4F071 AA15X AA22X AA77 AA87 BC01 BC17 4J002 AE03Y AE05Y BB03X BB06X BB12X BB16X BN03W BP02X FD02Y 4J026 A03 A02BA03 A18 ABA18 DB17 EA02 4J028 AA01A AB01A AC01A AC19A AC27A BA00A BA01B BB00A BB01B BC25B EA02 EB02 EB15 EB21 EC04 ED01 ED06 ED09 FA02 GA19 4J128 AA01 AB01 AC01 AC19 AC27 AD00 BA00A BA01B EB01 EB01 EB01 EB00 BB00B EB00

Claims (26)

[Claims] 1. The olefin-aromatic vinyl compound-diene copolymer has an aromatic vinyl compound content of 2.2 mol%.
A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer obtained by cross-copolymerizing the following olefin copolymer (which may contain a diene). 2. An olefin-aromatic vinyl compound-diene copolymer having an aromatic vinyl compound content of 5 to 50 mol%, a diene content of 0.0001 to 3 mol%, and a balance of olefin. A cross-copolymerized olefin-aromatic vinyl obtained by cross-copolymerizing an olefin copolymer (which may contain a diene) having an aromatic vinyl compound content of 2.2 mol% or less. Compound-diene copolymer. 3. An aromatic vinyl compound content of 2.2 mol%.
It has the following olefin copolymer (which may contain a diene) as a cross chain, and the overall composition is such that the aromatic vinyl compound content is 5 mol% or more and 50 mol% or less, and the diene content is 0.0001 mol%. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer characterized in that at least 3 mol% and the balance is olefin. 4. At least one melting point peak is observed in the range of 100 ° C. or more and 140 ° C. or less by DSC measurement, and the heat of crystal fusion is 10 J / g or more and 150 J / g.
4. The method according to claim 1, wherein:
Item 14. The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer according to the above item. 5. A crystalline structure derived from an ethylene chain structure, at least one of an aromatic vinyl compound content and a melting point having a crystal melting heat of 10 J / g or more measured by DSC satisfies the following relationship: The aromatic vinyl compound content is 5 mol% or more and 50 mol% or less, and the diene content is 0.0 mol% or less.
A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer, wherein 001 mol% or more and 3 mol% or less, the balance being ethylene or two or more olefins containing ethylene. (5 ≦ Xc ≦ 10) −2 × Xc + 120 ≦ Tm ≦ 140 (10 <Xc ≦ 50) 100 ≦ Tm ≦ 140 Tm; Melting point (° C.) by DSC measurement Xc; Aromatic vinyl compound content (mol%) 6. The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer according to claim 1, wherein the cross chain is polyethylene. 7. The first polymerization step (main chain polymerization step)
An olefin monomer, an aromatic vinyl compound monomer, and a diene monomer are copolymerized using a coordination polymerization catalyst to synthesize an olefin-aromatic vinyl compound-diene copolymer. In the step (cross-forming step), polymerization is carried out using a coordination polymerization catalyst in the presence of the olefin-aromatic vinyl compound-diene copolymer, at least an olefin and, if necessary, an aromatic vinyl compound and a diene. The cross-copolymerized olefin-aromatic vinyl compound- according to any one of claims 1 to 5, which is produced by using a stage polymerization method.
A method for producing a diene copolymer. 8. The amount of the diene used in the first polymerization step is 1/100 or less of the amount of the aromatic vinyl compound used.
The method according to claim 7, wherein the molar ratio is 50,000 or more. 9. The method according to claim 1, wherein the polymerization liquid obtained in the first polymerization step is used in a polymerization step after the second polymerization step without separating and recovering an olefin-aromatic vinyl compound-diene copolymer. The manufacturing method according to claim 7, wherein 10. The production method according to claim 7, wherein the aromatic vinyl compound and the diene monomer used in the polymerization step after the second polymerization step are unreacted monomers in the first polymerization step. 11. An olefin-aromatic vinyl compound obtained by separating and recovering from the polymerization solution obtained in the first polymerization step.
The method according to claim 7, wherein the diene copolymer is used in a polymerization step after the second polymerization step. 12. The aromatic vinyl compound used in the polymerization step after the second polymerization step and, if necessary, a diene monomer are monomers newly added in the second polymerization step. 7. The production method according to 7. 13. The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer according to claim 1, wherein the olefin is ethylene or two or more olefins containing ethylene. Coalescing. 14. The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer according to claim 1, wherein the aromatic vinyl compound is styrene. 15. The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer according to claim 1, wherein the diene is divinylbenzene. 16. The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer according to claim 1, wherein the gel content is less than 10% by mass. 17. The coordination polymerization catalyst used in the first polymerization step and the second polymerization step is a single-site coordination polymerization catalyst composed of a transition metal compound and a cocatalyst. Manufacturing method. 18. The coordination polymerization catalyst used in the first polymerization step and the second polymerization step is a polymerization catalyst comprising a transition metal compound represented by the following general formula (1) and a cocatalyst. The method according to claim 17, wherein: Embedded image In the formula, A and B represent an unsubstituted or substituted cyclopentaphenanthryl group, an unsubstituted or substituted benzoindenyl group,
It is a group selected from an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, and an unsubstituted or substituted fluorenyl group. Y has a bond to A and B, and further contains a hydrogen or a hydrocarbon group having 1 to 20 carbon atoms (this group has 1 to 3 nitrogen, boron, silicon, phosphorus, selenium, oxygen or sulfur atom. (Which may be included) as a substituent. The substituents may be different or the same. Further, Y may have a cyclic structure such as a cyclohexylidene group and a cyclopentylidene group. X is each independently hydrogen, halogen, carbon number 1
An alkyl group having 15 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 8 to 12 carbon atoms, a silyl group having a hydrocarbon substituent having 1 to 4 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or It is an amide group having hydrogen or a hydrocarbon substituent having 1 to 22 carbon atoms. n is an integer of 0, 1 or 2. M is zirconium, hafnium, or titanium. 19. Among A and B in the general formula (1),
19. The method according to claim 18, wherein at least one is a group selected from an unsubstituted or substituted cyclopentaphenanthryl group, an unsubstituted or substituted benzoindenyl group, and an unsubstituted or substituted indenyl group. 20. A molded product obtained by molding the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer according to any one of claims 1 to 6. 21. A film comprising the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer according to any one of claims 1 to 6. 22. A composition comprising 0.1 to 99.9% by mass of the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer according to claim 1. Description: . 23. A molded article obtained by molding the composition according to claim 22. 24. A composition comprising the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer according to any one of claims 1 to 6 and a plasticizer. 25. A composition comprising the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer according to any one of claims 1 to 6 and a polyolefin. 26. A composition comprising the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer according to any one of claims 1 to 6, a polyolefin, and a plasticizer.