JP2002265720A - Aromatic vinyl compound resin composition - Google Patents

Abstract

[PROBLEMS] To provide an aromatic vinyl compound-based resin composition which has excellent mechanical properties, is easy to produce, and is useful as an extruded or injection-molded product, and as a film or sheet. . A resin composition containing an aromatic vinyl compound-based polymer and a novel cross-copolymerized olefin-aromatic vinyl compound-diene copolymer having a specific composition and structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aromatic vinyl compound-based polymer (component (A)) and a novel cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)). To an aromatic vinyl compound-based resin composition.

More specifically, an aromatic vinyl compound polymer (component (A)) and a novel aromatic vinyl compound content of 1 mol% or more and 96 mol% or less, and a diene content of 0.1 mol% or less.
Olefin-aromatic vinyl having an olefin-aromatic vinyl compound-diene copolymer in which the content of the aromatic vinyl compound is at least 5 mol% different from that of the olefin-aromatic vinyl compound-diene copolymer, which is at least 0001 mol% and at most 3 mol% and the balance is olefin. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer ((B)), wherein the compound copolymer and / or the olefin-aromatic vinyl compound-diene copolymer is cross-copolymerized. Component), which is excellent in mechanical properties and heat resistance, is easy to produce, and is useful as an extruded or injection-molded product, and is useful as a film or sheet.

[0003]

2. Description of the Related Art An aromatic vinyl compound polymer is a material having excellent shape stability and rigidity, but has a drawback of poor mechanical properties, especially toughness. In order to improve its toughness,
A method of discontinuously dispersing an elastic rubber phase in a hard resin is generally used. At that time, it is common to add a styrene-butadiene random copolymer, a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, etc. due to a double bond of butadiene or isoprene in the copolymer. Therefore, there is a point that the resin is liable to undergo thermal deterioration during molding. For this reason, hydrogenated styrene-butadiene block copolymers and the like in which the double bond is hydrogenated have been developed, but there is a problem that the rigidity of the resin composition is significantly reduced and the heat resistance is also reduced. In addition, a block copolymer of an aromatic vinyl compound and a diene compound and a hydrogenated aromatic vinyl-diene block copolymer obtained by hydrogenating the same are produced by anionic living polymerization and subsequent hydrogenation. It is expensive as a manufacturing process. Further, the rigidity, heat resistance and surface hardness of the obtained composition are insufficient.

[0004] A resin composition comprising a polyphenylene ether (polyphenylene oxide) having good compatibility with a polystyrene resin as an aromatic vinyl compound polymer is known as a high temperature thermoplastic engineering resin. However, the resin composition composed of the polystyrene resin and the polyphenylene ether also has a drawback of poor toughness.

A so-called pseudo-random copolymer of an aromatic vinyl compound and ethylene (a head of an aromatic vinyl compound)
WO98-10014 reports on a copolymer having no tail chain structure) and an aromatic vinyl compound-based resin composition. WO 99-48972 reports a resin composition of a so-called random copolymer of an aromatic vinyl compound and ethylene and an aromatic vinyl compound-based resin. However, the rigidity, heat resistance, and surface hardness of these resin compositions cannot be said to be sufficient.

JP-A-12-198918 discloses a resin composition comprising an aromatic vinyl compound, a so-called random copolymer of ethylene, a styrene resin and polyphenylene ether. However, these resin compositions cannot be said to have sufficient rigidity, heat resistance and surface hardness.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to improve the drawbacks of the conventional aromatic vinyl compound-based polymers, to have excellent mechanical properties, to be easily manufactured, and to extrude or injection mold. The product is composed of an aromatic vinyl compound-based polymer (component (A)) and a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) which are useful as films and sheets. To provide an aromatic vinyl compound-based resin composition.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that aromatic vinyl compound-based polymer (component (A)) 5 to 95% by weight, A vinyl compound content of 1 mol% or more and 96 mol% or less,
The content of the aromatic vinyl compound is different from that of the olefin-aromatic vinyl compound-diene copolymer having a diene content of 0.0001 mol% or more and 3 mol% or less and a balance of olefin of 5 mol% or more as compared with the copolymer. A novel cross-copolymerized olefin-aromatic vinyl compound-diene, wherein the olefin-aromatic vinyl compound copolymer and / or the olefin-aromatic vinyl compound-diene copolymer is cross-copolymerized. Copolymer (component (B)) 5
The present inventors have found that the above object is achieved by an aromatic vinyl compound-based resin composition containing 95% by weight, and completed the present invention.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aromatic vinyl compound polymer (component (A)) and a novel cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)).
Is an aromatic vinyl compound-based resin composition. Hereinafter, each component will be described in detail.

[Aromatic vinyl compound polymer (component (A))] The aromatic vinyl compound polymer (component (A)) used in the present invention is a polymer of an aromatic vinyl compound alone,
It is a polymer containing a copolymer of one or more monomers copolymerizable with an aromatic vinyl compound and an aromatic vinyl compound. Examples of the aromatic vinyl compound monomer used in the aromatic vinyl compound-based polymer (component (A)) include styrene and various substituted styrenes such as para-methylstyrene, meta-methylstyrene, ortho-methylstyrene,
Ortho-tert-butylstyrene, meta-tert-butylstyrene, para-tert-butylstyrene, para-chlorostyrene, meta-chlorostyrene, α
-Methylstyrene and the like; and compounds having a plurality of vinyl groups in one molecule such as divinylbenzene. Further, a copolymer between these plural aromatic vinyl compounds is also used. Furthermore, the stereoregularity between the aromatic groups of the aromatic vinyl compound may be any of atactic, isotactic and syndiotactic.

[0011] Monomers copolymerizable with the aromatic vinyl compound include butadiene, isoprene, other conjugated dienes, methyl acrylate, methyl methacrylate,
Examples include acrylic acid such as butyl acrylate and butyl methacrylate, ester derivatives of methacrylic acid, acrylonitrile, amide derivatives, and maleic anhydride. The copolymerization type may be either block copolymerization or random copolymerization.
The aromatic vinyl compound-based polymer (component (A)) used in the present invention is a composition of the above-described polymer or copolymer of the aromatic vinyl compound alone, other resin and rubber components,
It may be a graft composition. For example, polyphenylene ether, polybutadiene, polyisoprene, styrene-
Block copolymers such as isoprene-styrene block copolymer and styrene-butadiene-styrene block copolymer; water such as hydrogenated styrene-butadiene-styrene block copolymer and hydrogenated styrene-isoprene-styrene block copolymer A rubber-reinforced polystyrene-based resin containing an addition block copolymer or the like can be used. The aromatic vinyl compound-based polymer (component (A)) needs to have a weight average molecular weight in terms of styrene of preferably 30,000 or more, more preferably 50,000 or more, in order to exhibit the performance as a practical resin. is there. Preferably 30 styrene monomer units
A styrene-based resin and / or a rubber-reinforced styrene-based resin containing at least% by weight; And a rubber-reinforced acrylonitrile-styrene copolymer, a styrene-butadiene-styrene copolymer, and a composition of a styrene resin and polyphenylene ether.

[Cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B))] Cross-copolymerized olefin-aromatic vinyl compound constituting the aromatic vinyl compound-based resin composition of the present invention -The diene copolymer (component (B)) (hereinafter referred to as cross copolymer) has an aromatic vinyl compound content of 1 mol% or more and 96 mol% or less, and a diene content of 0.0001 mol% or more and 3 mol% or less. The remainder being an olefin-an aromatic vinyl compound-
The aromatic vinyl compound content is 5 mol% in the diene copolymer.
A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer obtained by cross-copolymerizing the above-mentioned different olefin-aromatic vinyl compound copolymer and / or olefin-aromatic vinyl compound-diene copolymer. It is a polymer.

As used herein, the term “cross-copolymer” means that a main-chain olefin-aromatic vinyl compound-diene copolymer and a vinyl compound polymer are linked via a diene unit at one or more points as shown in FIG. Bond with cross strand (cross-link)
It is a copolymer mainly having the structure shown below. Such a cross structure can be rephrased as a star structure. In addition, classification by the American Chemical Society POLY subcommittee
graded star copolymer
(Polymer prints, 1998,
March). Hereinafter, the olefin-aromatic vinyl compound copolymer and / or the olefin-aromatic vinyl compound-diene copolymer cross-linked to the main chain olefin-aromatic vinyl compound-diene copolymer is referred to 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 a 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. It is believed that excellent strength of the structural interface is obtained, giving high mechanical properties.

The cross-copolymer constituting the aromatic vinyl compound resin composition of the present invention has an aromatic vinyl compound content of 1 mol% to 96 mol% and a diene content of 0.0001 mol% to 3 mol%. Mol% or less, and the remainder is an olefin-aromatic vinyl compound-diene copolymer and an olefin-aromatic vinyl compound copolymer and / or
Or a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer obtained by cross-copolymerizing an olefin-aromatic vinyl compound-diene copolymer, wherein the cross-linked aromatic vinyl A cross-copolymerized olefin-aromatic compound characterized in that the compound content is different from the aromatic vinyl compound content of the main chain olefin-aromatic vinyl compound-diene copolymer by 5 mol% or more before cross-copolymerization. It is an aromatic vinyl compound-diene copolymer. More preferably, the cross-copolymer constituting the aromatic vinyl compound-based resin composition of the present invention has an aromatic vinyl compound content of 1 mol% to 96 mol%, and a diene content of 0.0001 mol% to 3 mol. % Or less, and the olefin-aromatic vinyl compound-diene copolymer whose balance is olefin is cross-copolymerized with the olefin-aromatic vinyl compound copolymer and / or the olefin-aromatic vinyl compound-diene copolymer. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer characterized in that the content of the aromatic vinyl compound is compared with that of the olefin-aromatic vinyl compound-diene copolymer before cross-copolymerization. And a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer characterized by a difference of at least 5 mol% or more. Aromatic vinyl compound - - Cross-copolymerized olefin, characterized in that there is a diene copolymer.

The cross copolymer used in the present invention is:
Not only is it a concept showing the cross copolymer itself,
Cross copolymer, and the first polymerization step shown below, non-cross-linked olefin obtained in the second polymerization step-
The term includes a composition containing an aromatic vinyl compound copolymer and / or an olefin-aromatic vinyl compound-diene copolymer in an arbitrary ratio. The composition containing such a cross copolymer can be obtained by the following production method.

An example of the method for producing the cross-copolymer used in the present invention will be described, but is not limited to the following production method. The cross-copolymer production method is preferably uniform and can be produced with efficiency and economy suitable for industrialization.

That is, as a first polymerization step, an olefin monomer, an aromatic vinyl compound monomer and a diene monomer are copolymerized to synthesize an olefin-aromatic vinyl compound-diene copolymer, and then as a second polymerization step. ,
In this production method, a cross-copolymer is obtained by cross-copolymerizing the copolymer with an olefin and an aromatic vinyl compound monomer and, if necessary, a diene monomer. A coordination polymerization catalyst is preferably used in both the first polymerization step and the second polymerization step, and a single-site catalyst is particularly preferable.

The aromatic vinyl compound content of the olefin-aromatic vinyl compound-diene copolymer polymerized in the first polymerization step and the olefin-aromatic vinyl compound copolymer polymerized in the second polymerization step (first polymerization When the polymerization solution obtained in the step is used as it is in the second polymerization step, a small amount of residual diene is copolymerized in the polymer obtained here), and the content of the aromatic vinyl compound differs by at least 5 mol% or more. It is necessary to be. Preferably at least 10 mol%,
Most preferably, they differ by at least 15 mol%. Preferably, the olefin obtained in the first polymerization step
The aromatic vinyl compound content of the aromatic vinyl compound-diene copolymer and the aromatic vinyl compound content of the finally obtained cross-copolymerized olefin-aromatic vinyl compound-diene copolymer are at least 5 mol%, preferably at least 5 mol%. Is different by 10 mol% or more.

The olefins used in the first polymerization step include ethylene, α-olefins having 3 to 20 carbon atoms,
That is, propylene, 1-butene, 1-hexene, 4-
Examples include methyl-1-pentene, 1-octene and cyclic olefins, ie, cyclopentene and norbornene. Preferably, ethylene, ethylene and propylene, 1
Α- such as butene, 1-hexene or 1-octene
A mixture with an olefin, an α-olefin such as propylene is used, and more preferably, ethylene, ethylene and α
A mixture of olefins is used, particularly preferably ethylene.

Styrene is preferably used as the aromatic vinyl compound used in the first polymerization step, but other aromatic vinyl compounds such as p-chlorostyrene, p-tert-butylstyrene, α-methylstyrene, vinyl Naphthalene, p-methylstyrene, vinyl naphthalene,
Vinyl anthracene or the like can be used, and a mixture thereof may be used.

As the diene used in the first polymerization step, a diene capable of coordination polymerization is preferably used. For example, butadiene, isoprene, chloroprene and the like described in JP-A-6-136060, and paradivinylbenzene and metadivinylbenzene described in JP-A-11-124420 are exemplified. Preferably 1,4-hexadiene, 1,5-
Hexadiene, ethylidene norbornene, dicyclopentadiene, norbornadiene, 4-vinyl-1cyclohexene, 3-vinyl-1cyclohexene, 2-vinyl-
1-cyclohexene, 1-vinyl-1-cyclohexene, paradivinylbenzene, metadivinylbenzene or a mixture thereof is used. 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. Preferably, dienes in which one of the double bonds (vinyl group) is used for coordination polymerization and the remaining double bond in the polymerized state is coordinatively polymerizable, most preferably para, meta divinyl Benzene and mixtures thereof are preferably used.

The olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step has an aromatic vinyl compound content of 1 mol% to 96 mol%, and a diene content of 0.0001 mol% to 3 mol%. The balance is an olefin, preferably an aromatic vinyl compound content of 1 mol% to 50 mol%, a diene content of 0.001 mol% to less than 0.5 mol%, and a balance of olefin. When the content of the aromatic vinyl compound is 1 mol% or less, the compatibility with the aromatic vinyl compound-based polymer is deteriorated. When the content is 96 mol% or more, the flexibility unique to the cross copolymer is not obtained.

When the first polymerization step is carried out at a diene concentration higher than the required amount, a large amount of the crosslinked structure of the polymer is formed during the polymerization to cause gelation or the like. It is not preferable because the processability and physical properties of the polymer deteriorate. For example, if the first polymerization step is performed at a diene concentration higher than the required amount, the residual diene concentration in the polymerization liquid will increase. Also, the obtained cross-copolymer similarly deteriorates processability and physical properties.
Conversely, if the first polymerization step is carried out at a diene concentration less than the required amount, the crossing density is small and the crossing effect is not sufficient. When the gel content of the cross-copolymer is 10% by weight or more, moldability such as fluidity is remarkably reduced, which is disadvantageous when the molded article is recycled. From these, the amount of the diene used in the first polymerization step is preferably 1/100 or less with respect to the amount of the aromatic vinyl compound used in a molar ratio.
/ 50,000 or more, more preferably 1/400 or less
It is 20,000 or more.

The single-site coordination polymerization catalyst preferably used in the first polymerization step includes a polymerization catalyst comprising a transition metal compound and a co-catalyst, soluble Zieglar-N
Atta catalysts, transition metal compound catalysts activated with methylaluminoxane, boron compounds, and the like (so-called metallocene catalysts, half-metallocene catalysts, CGCT catalysts, and the like) are exemplified. Specifically, polymerization catalysts described in the following documents and patents can be used. For example, in the case of metallocene catalysts, US Pat.
No. 88, JP-A-6-49132, Polym
er Preprints, Japan, 42, 229
2 (1993), Macromol. Chem. ,
Rapid Commun. , 17, 745 (199
6), JP-A-9-309925, EP08724
92A2, JP-A-6-184179. In half metallocene catalysts, Makromol. Chem.
191, 387 (1990). For CGCT catalysts, JP-A-3-1630088, JP-A-7-53618, and EP-A-416815. Soluble Zieg
For the lar-Natta catalyst, JP-A-3-250007
No., Stud. Surf. Sci. Catal. ,
517 (1990). 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 a copolymer having such a uniform composition, Zieglar
It is difficult with a -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.). ).

The most preferably used single-site coordination polymerization catalyst is a polymerization catalyst comprising a transition metal compound represented by the following chemical formula (1) and a co-catalyst. When a polymerization catalyst composed of a transition metal compound represented by the following chemical 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 reduce the amount of diene used in the first polymerization step and the amount of unreacted diene remaining in the polymerization solution.

Further, when a polymerization catalyst comprising a transition metal compound represented by the following chemical formula (1) and a cocatalyst is used, an olefin-aromatic vinyl compound having a high activity and a uniform composition suitable for industrialization- It is possible to produce diene copolymers. An olefin-aromatic vinyl compound-diene copolymer having isotactic stereoregularity and a head-tail styrene chain structure in a composition having an aromatic vinyl compound content of 1 mol% or more and 96 mol% or less. Can be.

Embedded image In the formula, A and B are each independently a group selected from an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, or 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. Also, Y
May have a cyclic structure such as a cyclohexylidene group or a cyclopentylidene group. X is each independently hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms,
An aryl group having 10 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 hydrogen, or a hydrogen atom having 1 to 22 carbon atoms. An amide group having a hydrocarbon substituent. 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. And a polymerization catalyst.

As the cocatalyst used in the first polymerization step, known cocatalysts and alkylaluminum compounds conventionally used in combination with a transition metal compound can be used. (Or as methylalumoxane or MAO)
Alternatively, a boron compound is suitably used. Examples of cocatalysts and alkylaluminum compounds used include EP
-0872492A2, JP-A-11-13080
No. 8, JP-A-9-309925, WO00 /
Co-catalysts and alkylaluminum compounds described in JP-A-20426, EP0985689A2, and JP-A-6-184179.

In producing the olefin-aromatic vinyl compound-diene copolymer, each monomer, metal complex (transition metal compound) and co-catalyst exemplified above are brought into contact with each other. Can be used.

As the method of the first polymerization step, a method of polymerizing in a liquid monomer without using a solvent, or pentane, hexane, heptane, cyclohexane, benzene, toluene, ethylbenzene, xylene, chloro-substituted benzene, chloro-substituted toluene , Methylene chloride, chloroform and the like using a saturated or aromatic hydrocarbon or a halogenated hydrocarbon alone or in a mixed solvent. Preferably, a mixed alkane solvent, cyclohexane, toluene, or ethylbenzene is used. The polymerization form may be either solution polymerization or slurry polymerization. If necessary, known methods such as batch polymerization, continuous polymerization, and multistage polymerization can be used.

It is also possible to use a single linear or loop, or a plurality of connected pipes. In this case, the pipe-shaped polymerization can includes various known mixers such as a dynamic or static mixer and a static mixer that also serves 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
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 co-catalyst, a boron atom / complex metal atom ratio of 0.01 to 1 is used.
It is used at a ratio of 00, preferably 0.1 to 10, particularly preferably 1. 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% and more than 50% of the olefin partial pressure at the start of the polymerization. However, the olefin partial pressure in the first polymerization step is preferably kept constant during the polymerization.

The olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step is preferably an ethylene-styrene-diene copolymer, an ethylene-α-olefin-styrene-diene copolymer, or An ethylene-cyclic olefin-styrene-diene copolymer, particularly preferably an ethylene-styrene-divinylbenzene copolymer is used. In addition, the olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step may have a cross structure or a cross-linked structure in the diene monomer unit included, but the gel content is 10% of the whole.
Less than 1% by weight, preferably less than 1% by weight.

The typical and preferred ethylene-styrene-divinylbenzene copolymer used in the present invention will be described below. The ethylene-styrene-divinylbenzene copolymer obtained in the first polymerization step has a head-tail styrene unit chain structure attributed to a peak observed at 40 to 45 ppm by 13C-NMR measurement based on TMS. And preferably 42.3-43.1 ppm, 43.7-44.5 p
pm, 40.4-41.0 ppm, 43.0-43.6
It preferably has a chain structure of styrene units assigned by the peak observed in ppm.

Further, an ethylene-styrene-divinylbenzene copolymer obtained by using a metallocene catalyst capable of producing isotactic polystyrene by homopolymerization of styrene and producing polyethylene by homopolymerization of ethylene. Coalescing is preferred. Therefore, the obtained ethylene-styrene-divinylbenzene 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-divinylbenzene copolymer obtained in the first polymerization step, which is preferably used, has a phenyl group having an alternating structure of styrene and ethylene represented by the following general formula (1) contained in the structure. Is a copolymer having a stereoregularity of isotactic dyad fraction (or meso dyad fraction) Pm of more than 0.5, preferably more than 0.75, particularly preferably more than 0.95. The isotactic dyad fraction Pm of the alternating copolymer structure of ethylene and styrene has a peak area Ar derived from an r-structure of a methylene carbon peak appearing at around 25 ppm by 13C-NMR measurement based on TMS, and an m-structure. From the area Am of the peak derived,
It can be obtained by the following equation (1). Pm = Am / (Ar + Am) General formula (1) The appearance position of the peak may be slightly shifted depending on the measurement conditions and the solvent. The m structure is a meso diad structure,
The r structure represents a racemic diad structure.

The ethylene-styrene-divinylbenzene copolymer obtained in the first polymerization step has an alternating structure having a ratio of an alternating structure of styrene and ethylene represented by the following general formula (2) contained in the copolymer structure. The index λ is smaller than 70, larger than 0.01, preferably smaller than 30,
Preferably, the copolymer is greater than 0.1. λ = A3 / A2 × 100 General formula (2) Here, A3 is obtained by 13 C-NMR measurement and has three types of peaks a, b, and 3 derived from an ethylene-styrene alternating structure represented by the following chemical formula (2) This is the sum of the areas of c. A2 is 13C-NMR based on TMS.
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.

Embedded image (In the formula, Ph represents a phenyl group, x represents the number of repeating units, and represents an integer of 2 or more.)

In particular, a copolymer having a high isotactic stereoregularity in the ethylene-styrene alternating structure and having an alternating structure index λ of less than 70 is preferred as the copolymer of the present invention. -A copolymer having a styrene chain of a tail, and having an isotactic stereoregularity in an ethylene-styrene alternating structure, and having an alternating structure index λ value of less than 70 is particularly preferred as the copolymer of the present invention. .

That is, the olefin-aromatic vinyl compound-diene copolymer obtained in the preferred first polymerization step used in the present invention has an alternating structure of ethylene and styrene having high stereoregularity and simultaneously various lengths. It is characterized by having various structures such as ethylene chains, styrene hetero bonds, and styrene chains of various lengths. Also,
The olefin-aromatic vinyl compound-diene copolymer of the present invention has an alternating structure ratio of 0 in the λ value obtained by the above formula depending on the polymerization catalyst used, the polymerization conditions, and the content of the aromatic vinyl compound in the copolymer. Various changes can be made within a range of greater than 0.01 and less than 70.

The olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step suitably used in the present invention, particularly the ethylene-styrene-divinylbenzene copolymer described above, is preferably prepared by the above-mentioned chemical formula ( It can be obtained by a polymerization catalyst comprising the transition metal compound represented by 1) and a co-catalyst.

As described above, olefin-aromatic vinyl compound-
The representative and preferred example of the ethylene-styrene-divinylbenzene copolymer obtained in the first polymerization step in producing the diene copolymer has been described, but of course the olefin-aromatic vinyl compound used in the present invention -The diene copolymer is not limited to this.

The weight average molecular weight of the olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step is as follows:
It is 10,000 or 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 may be adjusted within a range described above by a known method using a chain transfer agent such as hydrogen, or by changing the polymerization temperature if necessary. Can be adjusted. The olefin obtained in the first polymerization step
The aromatic vinyl compound-diene copolymer may partially have a cross structure or a branched structure via the included diene unit.

Next, the second polymerization step will be described. The second polymerization step here may be composed of a plurality of polymerization steps having different conditions and the like. As the second polymerization step, coordination polymerization using a single-site coordination polymerization catalyst is preferably employed. More preferably, a single-site coordination polymerization catalyst comprising the same transition metal compound represented by the chemical 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 chemical formula (1) and the co-catalyst forms a residual coordination polymerizable double bond of a diene unit copolymerized in a polymer main chain, particularly, divinylbenzene. Because it can be copolymerized with high efficiency,
It is also preferred as a catalyst for the second polymerization step. The copolymer obtained in the second polymerization step preferably has the same structure as the copolymer in the first polymerization step, but the composition is such that the content of the aromatic vinyl compound is that of the copolymer in the first polymerization step. It is necessary that the difference be at least 5 mol%.

In the second polymerization step, for example, a method similar to the polymerization method used in the first polymerization step is used. In this case, olefins and aromatic vinyl compounds used in the first polymerization step, and diene monomers remaining as needed or remaining in the polymerization solution can be used. The second polymerization step is preferably performed following the first polymerization step using the polymerization liquid obtained in the first polymerization step. However, the copolymer obtained in the first polymerization step is recovered from the polymerization solution, dissolved in a new solvent, and a monomer such as an olefin is newly added. A two-polymerization step may be performed.

The olefin-aromatic vinyl compound copolymer or olefin-aromatic vinyl compound which is polymerized in the second polymerization step compared to the olefin-aromatic vinyl compound-diene copolymer polymerized in the first polymerization step The aromatic vinyl compound content of the diene copolymer (when the polymerization solution obtained in the first polymerization step is used as it is in the second polymerization step, a small amount of residual diene is copolymerized in the obtained polymer) is at least It is necessary that they differ by 5 mol%. Preferably it differs by at least 10 mol%, most preferably by at least 15 mol%. The aromatic vinyl compound content of the polymer obtained in the first polymerization step and the aromatic vinyl compound content of the finally obtained cross-copolymer are at least 5%.
Preferably, they differ by at least mol%.

If the aromatic vinyl compound content of the polymer obtained in the first polymerization step and the polymer obtained in the second polymerization step do not differ by at least 5 mol%, the polymer obtained in the first polymerization step as a cross-copolymer And only the average physical properties of the polymer obtained in the second polymerization step are obtained, whereas if the aromatic vinyl compound content is different by 5 mol% or more, the polymer obtained in the first polymerization step and the polymer obtained in the second polymerization step The characteristics of both the obtained polymers appear. The features include, for example, flexibility, heat resistance, permanent compression set, rheological properties, chemical resistance, moldability, and the like. These features are combined, and various properties can be simultaneously provided. Further, the aromatic vinyl compound content of the polymer obtained in the first polymerization step and the aromatic vinyl compound content of the finally obtained cross-copolymer are preferably different from each other by 5 mol% or more. When the aromatic vinyl compound content of the polymer obtained in the polymerization step and the aromatic vinyl compound content of the finally obtained cross-copolymer differ from each other by 5 mol% or more, the polymer obtained in the first polymerization step and the second polymerization step The characteristics of both of the polymers obtained in the above appear.

The polymer obtained in the second polymerization step may have a branched structure via the diene unit contained.

A specific manufacturing method satisfying the above is described below. That is, as a first polymerization step, an aromatic vinyl compound monomer, an olefin monomer and a diene monomer are copolymerized using a coordination polymerization catalyst to synthesize an olefin-aromatic vinyl compound-diene copolymer, and then As a second polymerization step having different polymerization conditions, at least two polymerization using a coordination polymerization catalyst in the presence of the olefin-aromatic vinyl compound-diene copolymer and at least an olefin, an aromatic vinyl compound, and if necessary a diene. This is a step polymerization method. Further, the production method preferably satisfies at least one or more of the following conditions. 1) The olefin partial pressure of the polymerization solution in the second polymerization step is 1 to the olefin partial pressure immediately before the start of the polymerization in the first polymerization step.
50% or more or 50% or less. 2) The concentration of the aromatic vinyl compound in the polymerization liquid immediately before the start of the polymerization in the second polymerization step is 30% or less, or 20% or less, of the concentration of the aromatic vinyl compound immediately before the start of the polymerization in the first polymerization step.
0% or more. 3) Use different single-site coordination polymerization catalysts in the first polymerization step and the second polymerization step. 4) In the first polymerization step and the second polymerization step, the type of olefin used for the polymerization is different. Here, the first polymerization step and the second polymerization step are distinguished when the operation for changing these conditions is started.

The change satisfying the above conditions is performed as rapidly as possible and completed, preferably within 50%, more preferably within 30%, even more preferably within 10% of the polymerization time of the second polymerization step. It is preferable to complete. Further, the polymerization temperature in the first polymerization step and the polymerization temperature in the second polymerization step are preferably the same. If different, a temperature difference within about 100 ° C. is appropriate.

As a method of changing the monomer composition ratio in the polymerization liquid, for example, the olefin partial pressure of the polymerization liquid in the second polymerization step is set to 150% or more, preferably 200% or more, most preferably to the first polymerization step. There is a method to change it to 300% or more. As an example, when ethylene is used as the olefin, when the first polymerization step is performed at an ethylene pressure of 0.2 MPa, 0.3 MPa is used in the second polymerization step.
Above, preferably at least 0.4 MPa, most preferably at least 0.6 MPa. In addition, the olefin partial pressure of the polymerization solution in the second polymerization step is 5 relative to the first polymerization step.
It may be changed to 0% or less, preferably 20% or less. For example, when the first polymerization step is performed at an ethylene pressure of 1.0 MPa, the second polymerization step is performed at 0.5 MPa or less, preferably 0.2 MPa or less. 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 an example of a method for changing the monomer composition ratio in the polymerization liquid, the concentration of the aromatic vinyl compound in the polymerization liquid immediately before the start of the polymerization in the second polymerization step is compared with that immediately before the start of the polymerization in the first polymerization step. 30% or less, preferably 20% or less, or 200% or more, preferably 500%
The above-mentioned changing method is also applicable. For example, when styrene 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 liquid, 0.3 mol / L or less, preferably 0.1 mol / L or less in the second polymerization step. It is carried out at 2 mol / L or less, or 2 mol / L or more, preferably 5 mol / L or more. 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, and an olefin and an aromatic vinyl compound monomer are added. 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 polymerization step, the kind of the olefin used for the polymerization is changed to reduce the content of the aromatic vinyl compound in the copolymer polymerized in the first polymerization step and the second polymerization step. It is also possible to change as described above.

Further, the second polymerization step is carried out subsequent to the first polymerization step using the polymerization solution obtained in the first polymerization step, and without adding a new aromatic vinyl compound monomer. When the monomer remaining in the liquid is used in the second polymerization step, the conversion of the aromatic vinyl compound monomer species through all the polymerization steps is preferably 50% by weight or more, particularly preferably 60% by weight or more. is there. 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, preferably, among the conditions described in paragraph [0049], 1)
Alternatively, a manufacturing method that satisfies 2) is adopted, and among the above conditions, a manufacturing method that satisfies 1) is more preferably adopted. In the production method that satisfies 1), a method is more preferably employed in which the olefin partial pressure of the polymerization solution in the second polymerization step is changed to 300% or more with respect to the first polymerization step. When the olefin partial pressure in the first polymerization step is not constant, that is, when the olefin partial pressure fluctuates within the above range, the polymerization in the second polymerization step is preferably performed with respect to the olefin partial pressure immediately before the start of the polymerization in the first polymerization step. A method is employed in which the olefin partial pressure of the polymerization liquid immediately before the start is maintained at 300% or more.

The proportion of the copolymer obtained in the first polymerization step is at least 10% by weight or more, preferably 30% by weight or more of the finally obtained cross copolymer. The amount of the polymer (including the cross chain weight) obtained in the second polymerization step is at least 10% of the finally obtained cross copolymer.
% By weight, preferably 30% by weight or more. If either of them is 10% by weight or less or 90% by weight or more, the characteristics of the polymer having a small amount of components are not sufficiently exhibited. For example, flexibility, heat resistance, permanent compression set, rheological properties, chemical resistance, moldability, and the like are mentioned.
If the content is more than 10% by weight, these features cannot be provided together, and as a result, various properties as exemplified above cannot be simultaneously provided. Here, the aromatic vinyl compound content of the finally obtained cross copolymer is preferably from 1 mol% to 96 mol%, and the diene content is 0.0001 mol%.
It is preferably at least 3 mol%.

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. Cross-copolymerization of olefins, aromatic vinyl compounds, and dienes using a coordination polymerization catalyst in a single reactor while continuously changing the olefin or aromatic vinyl compound concentration You can also.

The physical properties of the cross-copolymerized ethylene-styrene-divinylbenzene copolymer as a typical example of the cross-copolymer of the present invention will be described below. The cross copolymer (component (B)) used in the present invention has, for example, thermoplastic elastomer-like properties. Further, it is characterized in that the composition of the main chain and the cross chain (styrene content in the case of the cross-copolymerized ethylene-styrene-divinylbenzene copolymer) is largely different. Either the main chain or the cross chain can have a composition having a low styrene content (that is, a crystal structure derived from an ethylene chain). 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. This is because the cross copolymer functions as these compatibilizers, and thus can have various characteristics.

Since the cross copolymer can have a crystal structure derived from an ethylene chain, it has good heat resistance. Further, the ethylene-styrene copolymer having a low styrene content can have characteristics such as a low glass transition temperature, a low embrittlement temperature (−50 ° C. or lower), and high mechanical properties (rupture strength, tensile elastic modulus). . In addition, since it can have a composition having a relatively high styrene content in either the main chain or the cross chain, it can have characteristics of an ethylene-styrene copolymer having a relatively high styrene content shown below. . That is, a relatively low tensile modulus, surface hardness, flexibility, a tan δ component (0.05 to 0.80 at 0 ° C. or 25 ° C.) near room temperature in the viscoelastic spectrum, scratch resistance, and PVC-like feel , Coloring and printing properties. That is, as a feature, compared to the conventional ethylene-styrene copolymer, heat resistance, compatibilization, scratch resistance,
Excellent wear resistance, chemical resistance, etc.

The cross copolymer used in the present invention is D
The melting point is preferably from 65 ° C to 140 ° C by SC,
More preferably, at least one is observed at 80 ° C. or more and 130 ° C. or less, and its melting point is 10 J / g or more,
J / g or less, preferably 20 J / g or more and 120 J / g or less. The cross copolymer used in the present invention preferably has a crystal structure based on an ethylene chain structure. This crystal structure can be confirmed by a known method, for example, an X-ray diffraction method. further,
The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer has an aromatic vinyl compound content of 5 mol% or more and 5 mol% or more.
0 mol% or less, the aromatic vinyl compound content,
Heat of crystal fusion measured by DSC is 10 J / g or more and 150 J
/ G or less preferably satisfies the following relationship. (5 ≦ St ≦ 20) −3 · St + 125 ≦ Tm ≦ 140 (20 <St ≦ 50) 65 ≦ Tm ≦ 140 Tm; The heat of crystal fusion measured by DSC is 10 J / g or more and 1
Melting point (° C.) not more than 50 J / g St; Aromatic vinyl compound content (mol%) Known so-called pseudo-random copolymers, JP-A-9-309925, JP-A-11-13
No. 0808 discloses that the cross-copolymer has a higher melting point than the olefin-aromatic vinyl compound random copolymer.

When the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer has an aromatic vinyl compound content of 5 to 20 mol%, the aromatic vinyl compound content and the Vicat softening point are as follows. It is preferable to satisfy the relationship. (5 ≦ St ≦ 20) −3 · St + 120 ≦ Tvicat ≦ 140 Tvicat; Vicat softening point (° C.) St; Aromatic vinyl compound content (mol%) So-called pseudo-random copolymers known from JP-A-163088 and JP-A-7-53618, JP-A-9-309925, JP-A-11-13
No. 0808 discloses that the cross-copolymer has a higher Vicat softening point than the olefin-aromatic vinyl compound random copolymer.

The components (A) and (B) have been described above. Next, the amounts of these components will be described. The compounding amount of the aromatic vinyl compound-based polymer as the component (A) is preferably 5 to 95% by weight, and more preferably 50 to 80% by weight in the aromatic vinyl compound-based resin composition of the present invention. When the amount is less than 5% by weight, the high rigidity and the like characteristic of the aromatic vinyl compound polymer are not sufficiently satisfied. When the amount exceeds 95% by weight, the flexibility and the like which are characteristics of the cross copolymer are not sufficiently satisfied.

The blending amount of the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (B) is 5 to 95% by weight or less, preferably 5 to 95% by weight, in the aromatic vinyl compound resin composition of the present invention. 20 to 50% by weight. If the amount is less than 5% by weight, the aromatic vinyl compound polymer as the component (A) cannot be improved in toughness and the like, and if the amount exceeds 95% by weight, the aromatic component (A) will not be improved. Rigidity, heat resistance, surface hardness, and the like, which are characteristics of the aromatic group vinyl compound polymer, are not sufficiently satisfied.

Further, in addition to the essential components (A) and (B), other additional components (optional components) can be added to the aromatic vinyl compound resin composition of the present invention. Examples of such additional components include rubber such as ethylene-α-olefin copolymer rubber such as ethylene-propylene rubber and ethylene-butene rubber, and resin such as polyethylene and polypropylene. In addition, known additives can be added. That is, phenolic and phosphorus antioxidants, hindered amines,
Benzophenone-based and benzotriazole-based anti-light deterioration inhibitors, nucleating agents such as organoaluminum compounds and organophosphorus compounds, dispersants represented by metal salts of stearic acid, coloring substances such as phthalocyanine, titanium oxide and carbon black, calcium carbonate , Talc, clay, calcium silicate, magnesium carbonate, magnesium hydroxide, mica,
Inorganic additives such as barium sulfate, titanium oxide, aluminum hydroxide, and silica; fillers such as carbon black, wood flour and wood pulp; and mineral oil softeners such as paraffin, naphthene, aroma-based process oils, and liquid paraffin ,
Castor oil, linseed oil, olefin wax, mineral wax, plasticizers such as various esters, and the like.

The aromatic vinyl compound-based resin composition of the present invention can be obtained by uniformly mixing and kneading the essential components (A) and (B) and, if necessary, additional optional components and additives. Although there is no particular limitation on the method, dry blending is performed using a mixer such as a Henschel mixer or a tumbler that is generally performed, and an extruder, a Banbury mixer, a roll, a kneader such as a kneader, and a set temperature of 180 ° C. It is manufactured by kneading at 250 ° C. Among these, it is preferable to manufacture using an extruder, especially a twin-screw extruder.

The aromatic vinyl compound resin composition of the present invention is excellent in mechanical properties, heat resistance and the like, is easy to produce, and
It is useful as an extruded or injection-molded product, as a film or sheet.

[0068]

The present invention will be described below with reference to examples.
The present invention is not limited to the following examples. The copolymer obtained in each of the following Reference Examples was analyzed by the following means. The 13C-nmr measurement was performed using a device manufactured by JEOL Ltd. α-50.
0, the solvent used was heavy 1,1,2,2-tetrachloroethane, and the measurement was performed based on tetramethylsilane (TMS). Here, the measurement based on TMS is as follows. First, weight 1,1, based on TMS
The shift value of the central peak of the triplet 13C-nmr peak of 2,2-tetrachloroethane was determined. Next, the copolymer was dissolved in heavy 1,1,2,2-tetrachloroethane to obtain 1
3C-nmr was measured, and each peak shift value was
Calculated based on the triplet center peak of 1,2,2-tetrachloroethane. The shift value of the triplet center peak of heavy 1,1,2,2-tetrachloroethane is 73.89 pp.
m. The measurement was carried out using 3 parts of the copolymer against these solvents.
The dissolution was performed by weight / volume%. Further, the amount of divinylbenzene in the polymerization liquid was determined by gas chromatography measurement of the polymerization liquid extracted at the end of the first polymerization step and at the end of the second polymerization step, and the divinylbenzene consumed in the first polymerization step and the second polymerization step was determined. The amount obtained, from this value divinylbenzene content of the polymer obtained in the first polymerization step and,
The divinylbenzene content of the finally obtained cross copolymer was determined.

The determination of the styrene content in the copolymer is as follows.
The peak was derived from a phenyl group proton based on TMS using a 1,1,2,2-tetrachloroethane solvent (6. H-nmr). 5 to 7.5 ppm) and a proton peak derived from an alkyl group (0.8 to 3 ppm). The molecular weight was determined using GPC (gel permeation chromatography) in terms of standard polystyrene. The measurement was performed using tetrahydrofuran (THF) as a solvent and HLC-8020 manufactured by Tosoh Corporation as a measuring instrument. The DSC was measured using a DSC200 manufactured by Seiko Denshi Co., Ltd. at a temperature rising rate of 10 ° C./min under a nitrogen stream. For a copolymer insoluble in THF at room temperature, ortho-dichlorobenzene was used as a solvent, and Tosoh HLC-812 was used as a measuring instrument.
The measurement was performed at 145 ° C. using No. 1. The gel content was measured as follows according to ASTM D-2765-84. About 1.0 g of the precisely weighed 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 net bag and weighed accurately. After extracting this in boiling xylene for about 5 hours, the net bag is collected,
Dried in vacuum at 90 ° C for more than 10 hours. After cooling sufficiently, the net bag was precisely weighed, and the amount of polymer gel was calculated by the following equation. [Gel content (%)] = [weight of polymer remaining in mesh bag after test (g)] / [weight of polymer in mesh bag before test (g)] × 100 Vicat softening point is measured according to JIS K7206. The Vicat softening point was measured at a load of 200 gf according to the above.

The physical properties of the resin compositions of the examples were evaluated by the following methods. The molded piece is PS20 manufactured by Nissei Plastic Industry Co., Ltd.
Molding was performed using an E5ASE type injection molding machine. (1) Flexural modulus: 23 ° C. according to ASTM D790
The measurement was performed at a bending speed of 15 mm / min using an injection molded product having a thickness of 1/4 inch. (2) Vicat softening point: The Vicat softening point was measured under a load of 5 kgf according to JIS K7206. (3) Surface hardness: Durometer hardness of type D was measured according to JIS K-7215.

[Raw materials] (1) Aromatic vinyl heavy (component (A)) Polystyrene: Toyo Styrol GP- manufactured by Toyo Styrene Co.
1 was used. In the table, it is described as GP. Rubber reinforced methyl methacrylate-styrene copolymer: TP polymer TP-URX50 manufactured by Denki Kagaku Kogyo was used. In the table, it is described as TP. Polystyrene resin / polyphenylene ether resin composition: Iupiace AN30 manufactured by Mitsubishi Engineering-Plastics Corporation was used. In the table, it is described as PPE. (2) Cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) was synthesized by the method described in Reference Examples 1 to 3. (3) Ethylene-styrene copolymer in Comparative Example Reference Example 4 To 6 were synthesized.

Reference Example 1 <Synthesis of cross-copolymerized ethylene-styrene-divinylbenzene copolymer (C-1)> rac-dimethylmethylenebis (4,5-benzo-1-indenyl) was used as a catalyst.
It carried out as follows using zirconium dichloride. Polymerization was carried out using an autoclave having a capacity of 10 L, a stirrer and a jacket for heating and cooling. Toluene 440
0 mL, 400 mL of styrene, and 0.5 mL of divinylbenzene (purity: 80%, manufactured by Aldrich) were charged, and heated and stirred at an internal temperature of 70 ° C. About 100 L of nitrogen was bubbled through to purge the system and the polymerization solution. Triisobutylaluminum 8.4 mmol, methylalumoxane (manufactured by Tosoh Akzo Co., Ltd., PMAO-s) is 21 based on Al.
mmol, ethylene was immediately introduced, and the pressure was 0.2
After stabilizing at 5 MPa (1.5 kg / cm 2 G), 8.4 μmol of rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride and 1 mmol of triisobutylaluminum were added from a catalyst tank installed on an autoclave. About 50 ml of the dissolved toluene solution was added to the autoclave. 70 internal temperature
The polymerization was carried out for 46 minutes while maintaining the pressure at 0.25 MPa at ° C (first polymerization step).

At this stage, the consumption of ethylene was about 100 L under the standard condition. A part of the polymerization solution was sampled, and a polymer sample (polymer 1-A) in the first polymerization step was obtained by meta-precipitation. Ethylene was introduced rapidly and 25
The pressure in the system was brought to 1.1 MPa over a period of minutes. By increasing the pressure of ethylene, polymerization was promoted, and the internal temperature was temporarily increased from 70 ° C to 80 ° C. Pressure 1.1MP
Polymerization was carried out for 25 minutes while maintaining at a (second polymerization step). 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. 860 g of a polymer (Polymer 1-C) was obtained. Table 1 shows the polymerization conditions of Reference Example 1, and Table 2 shows the analysis results of the cross-copolymerized ethylene-styrene-divinylbenzene copolymer obtained. Further, the calculated values of the polymer (1-B) produced in the second polymerization step calculated from the polymerization conditions of Table 2 and the analysis results of the polymer 1-A and the polymer 1-C are shown in the table.

Reference Examples 2 and 3 Polymerization and post-treatment were carried out in the same manner as in Reference Example 1 under the conditions shown in Table 1. Table 2 shows the analysis results of the obtained cross-copolymerized ethylene-styrene-divinylbenzene copolymers. The results of calculating the components generated in the second polymerization step from the polymerization conditions and the polymerization results shown in Tables 1 and 2 are also 2-B,
Also shown in Table 2 as 3-B.

[0075]

[Table 1]

[0076]

[Table 2]

Reference Example 4 Polymerization was carried out using a polymerization vessel having a capacity of 150 L, a stirrer and a jacket for heating and cooling. After the inside of the system was replaced with nitrogen, 67 L of dehydrated cyclohexane and 5 L of dehydrated styrene were charged into a polymerization vessel, and heated and stirred at an internal temperature of 55 ° C. 84 mmol of triisobutylaluminum and 84 mol of methylalumoxane (PMAO-s, manufactured by Tosoh Akzo Co., Ltd.) based on Al
mmol was added. Immediately introduced ethylene, pressure 1.
After stabilizing at 0 MPa, the catalyst, rac dimethyl methylene bis (4,5-
75 μmol of benzo-1-indenyl) zirconium dichloride, 2 mmol of triisobutylaluminum
About 100 ml of a toluene solution in which was dissolved was added to the polymerization vessel. The polymerization was carried out for 120 minutes while maintaining the internal temperature at 55 ° C. and the ethylene pressure at 1.0 MPa. After depressurizing ethylene,
The polymerization vessel gas phase was purged several times with nitrogen. Next, the polymerization solution was put into 150 L of 85 ° C. heated water containing a dispersant (Pluronic P-103; manufactured by Asahi Denka Co., Ltd.) with vigorous stirring over 1 hour. After stirring at 97 ° C for 30 minutes,
Hot water containing crumbs was put into the cooling water, and the crumbs were collected. The crumb was air-dried at 50 ° C. to obtain 6 kg of a copolymer (SE1) having a crumb shape with a size of about several mm and having a good shape. The composition ratio of styrene and ethylene was 11 mol% and 8 respectively.
9 mol%. Table 3 shows the polymerization conditions of Reference Example 4, and Table 4 shows the analysis results of the obtained ethylene-styrene random copolymer.

<Reference Examples 5 and 6> Polymerization and post-treatment were carried out in the same manner as in Reference Example 4 under the conditions shown in Table 3. Table 3 shows the polymerization conditions of Reference Example 5, and Table 4 shows the analysis results of the obtained styrene-ethylene random copolymer.

[0079]

[Table 3]

[0080]

[Table 4]

[0081]

Examples 1 to 7 and

Comparative Examples 1 to 5 Compounds were added in the proportions shown in Tables 5, 6 and 7, and tetrakis [methylene-3- (3′5′-di-t) was used as a heat stabilizer with respect to 100% by weight of the composition. -Butyl 4'-hydroxyphenyl) propionate] methane (IRGA manufactured by Ciba Specialty Chemicals)
NOX1010) 0.1% by weight was mixed and mixed for 3 minutes with a super mixer manufactured by Kawada Seisakusho, and then kneaded and granulated at a set temperature of 220 ° C. using a twin-screw kneader (PCM30) manufactured by Ikegai Kikisha. A vinyl compound-based resin composition was obtained. The measurement was performed according to the above various measurement methods. The evaluation results are shown in Tables 5, 6 and 7.

[0082]

[Table 5]

[0083]

[Table 6]

[0084]

[Table 7]

As shown in Tables 5, 6, and 7, the composition containing the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer was more flexible than the olefin-aromatic vinyl compound random copolymer. It is an aromatic vinyl compound resin composition having excellent heat resistance, heat resistance and surface hardness.

[0086]

The aromatic vinyl compound resin composition of the present invention contains an aromatic vinyl compound polymer and a novel cross-copolymerized olefin-aromatic vinyl compound-diene copolymer, and has rigidity and heat resistance. It is a novel resin composition having excellent surface hardness and the like, and which is suitably used for applications such as injection molded products and extruded molded products.

[Brief description of the drawings]

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

FIG. 2 is a conceptual diagram showing the structure of a conventional grafted copolymer.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 71/12 C08L 71/12 F-term (Reference) 4F071 AA12X AA14 AA15 AA20X AA22 AA33X AA34X AA51 AA75X AA77 AA83 AA87 AB06 AC18 AE06A AF13 AF25 AF26 AF43Y AF45 AF53 AF53Y AG02 AG27 AH19 BA01 BB05 BB06 BC01 4J002 AC03W AC06W BB033 BB053 BB123 BB153 BC00W BC01W BC03W BC05W BC06W BC07W BC08A BC11W FD00 BN00XW 030 BN00XW AC19 AC34 BA02 BA05 BA07 BA45 BB03 BB04 DA02 DA05 DA17 DB02 DB17 DB23 FA03 GA01 4J028 AA01A AB00A AB01A AC01A AC09A AC10A AC27A AC28A BA00A BA01B BB00B BB01B BC12B BC15B BC25B EB01 EB02 EB03 EB02 EB03 EB02 EB03 EB02 EB03 EB02 EB03 ED05 ED06 FA02 GA14 GA19 4J128 AA01 AB00 AB01 AC01 AC09 AC10 AC27 AC28 AD00 BA00A BA01B BB00B BB01B BC12B BC15B BC25B EB01 EB02 EB03 EB04 EB05 EB07 EB09 EB10 EB12 EB15 EB18 EB21 EC04 EC06 ED01 ED02 ED03 ED04 ED05 ED06 FA02 GA14 GA19

Claims (21)

[Claims] 1. An aromatic vinyl compound-based resin composition containing the following components (A) and (B). Component (A): 5 to 95% by weight of an aromatic vinyl compound polymer. Component (B): The aromatic vinyl compound content is 1 mol% or more and 9
6 mol% or less, diene content is 0.0001 mol% or more, 3
Olefin-aromatic vinyl compound-diene copolymer in which the content of aromatic vinyl compound differs from the olefin-aromatic vinyl compound-diene copolymer by 5 mol% or less as compared with the copolymer, And / or 5 to 95% by weight of a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer, wherein the olefin-aromatic vinyl compound-diene copolymer is cross-copolymerized. Here, the total of the components (A) and (B) is 100% by weight.
It is. 2. An aromatic vinyl compound-based resin composition containing the following components (A) and (B). Component (A): 5 to 95% by weight of an aromatic vinyl compound polymer. Component (B): The aromatic vinyl compound content is 1 mol% or more and 9
6 mol% or less, diene content is 0.0001 mol% or more, 3
Mol% or less, and the olefin-aromatic vinyl compound-diene copolymer whose balance is olefin is cross-copolymerized with the olefin-aromatic vinyl compound copolymer and / or the olefin-aromatic vinyl compound-diene copolymer. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer characterized by comprising an olefin-aromatic vinyl compound-diene copolymer having an aromatic vinyl compound content before cross-copolymerization. A cross-copolymerized olefin characterized by a difference of at least 5 mol%
5 to 95% by weight of an aromatic vinyl compound-diene copolymer. Here, the total of the components (A) and (B) is 100% by weight. 3. A cross-copolymerized olefin comprising 50 to 90% by weight of an aromatic vinyl compound-based polymer (component (A)).
The aromatic vinyl compound-based resin composition according to claim 1 or 2, wherein the content of the aromatic vinyl compound-diene copolymer (component (B)) is 10 to 50% by weight. Here, the total of the components (A) and (B) is 100% by weight. 4. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) is obtained by using a coordination polymerization catalyst as a first polymerization step to obtain an aromatic vinyl compound monomer, an olefin monomer and a diene copolymer. A monomer is copolymerized to synthesize an olefin-aromatic vinyl compound-diene copolymer, and then, as a second polymerization step having different polymerization conditions therefrom, the olefin-aromatic vinyl compound-diene copolymer and at least an olefin The monomer according to any one of claims 1 to 3, wherein the copolymer is produced by using at least a two-stage polymerization method in which polymerization is performed using a coordination polymerization catalyst in the presence of an aromatic vinyl compound monomer. Aromatic vinyl compound resin composition. 5. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) comprising 10 to 90% by weight of the polymer produced in the first polymerization step, and second polymer. 90% by weight to 10% by weight of polymer produced in the process
The aromatic vinyl compound-based resin composition according to claim 4, wherein Here, the total of the polymer produced in the first polymerization step and the polymer produced in the second polymerization step is 1
00% by weight. 6. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) having a gel content of 10
The aromatic vinyl compound-based resin composition according to any one of claims 1 to 5, wherein the content is less than 10% by weight. 7. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) is produced by a single-site coordination polymerization catalyst comprising a transition metal compound and a co-catalyst. The aromatic vinyl compound-based resin composition according to any one of claims 1 to 6. 8. A coordination polymerization catalyst for producing a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) comprises a transition metal compound represented by the following chemical formula (1): The aromatic vinyl compound-based resin composition according to claim 7, which is a polymerization catalyst comprising a catalyst. 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. 9. The olefin of the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) is ethylene or two or more olefins containing ethylene. 8. The aromatic vinyl compound-based resin composition according to any one of 8). 10. The aromatic vinyl according to claim 9, wherein the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) has a crystal structure derived from an ethylene chain structure. Compound-based resin composition. 11. An aromatic vinyl compound of the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) is styrene.
10. The aromatic vinyl compound-based resin composition according to any one of 10. 12. The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) wherein the diene is divinylbenzene.
The aromatic vinyl compound-based resin composition according to any one of the preceding claims. 13. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) having an aromatic vinyl compound content of 5 to 50 mol% and a diene content of 0.0001 mol%. The aromatic vinyl compound-based resin composition according to any one of claims 1 to 12, wherein at least 3 mol% and the balance is ethylene or two or more olefins containing ethylene. 14. The olefin of the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) is ethylene or two or more olefins containing ethylene, and the cross-copolymerized olefin-aromatic is used. The aromatic vinyl compound-diene copolymer (component (B)) has a crystal structure derived from an ethylene chain structure, and the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) 14. A DSC, wherein at least one melting point of 65 ° C. or more and 140 ° C. or less is observed, and a heat of crystal fusion corresponding to the melting point is 10 J / g or more and 150 J / g or less. Item 14. The aromatic vinyl compound-based resin composition according to the above item. 15. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) having an aromatic vinyl compound content of 5 mol% to 50 mol% and a diene content of 0.0001 mol%. Not less than 3 mol%, the balance being ethylene or two or more olefins containing ethylene, having a crystal structure derived from an ethylene chain structure, characterized in that it is a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer. The content of the aromatic vinyl compound in the union and the cross-copolymerized olefin-aromatic vinyl compound-
2. The melting point of the diene copolymer (component (B)) whose crystal heat of fusion measured by DSC measurement is 10 J / g or more and 150 J / g or less satisfies the following relationship. 15. The aromatic vinyl compound-based resin composition according to any one of claims 14 to 14. (5 ≦ St ≦ 20) −3 · St + 125 ≦ Tm ≦ 140 (20 <St ≦ 50) 65 ≦ Tm ≦ 140 Tm; heat of crystal fusion measured by DSC is 10 J / g or more;
Melting point (° C.) of 150 J / g or less St: Content of aromatic vinyl compound (mol%) 16. The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) has an aromatic vinyl compound content of 5 to 20 mol% and a diene content of 0.0001 mol. The aromatic vinyl compound-based resin composition according to any one of claims 1 to 15, wherein the amount of the aromatic vinyl compound-based resin composition is not less than 3% by mole and not more than 3% by mole, with the balance being ethylene or two or more olefins containing ethylene. 17. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) having an aromatic vinyl compound content of 5 to 20 mol% and a diene content of 0.0001 mol. 17. The aromatic vinyl compound according to claim 16, wherein the content of the aromatic vinyl compound and the Vicat softening point satisfy the following relationship. Compound-based resin composition. (5 ≦ St ≦ 20) −3 · St + 120 ≦ Tvicat ≦ 140 Tvicat; Vicat softening point (° C.) St; Aromatic vinyl compound content (mol%) 18. An aromatic vinyl compound-based polymer (component (A)) containing at least 30% by weight of a styrene monomer unit in at least one kind selected from styrene-based resins and rubber-reinforced styrene-based resins. The aromatic vinyl compound-based resin composition according to any one of claims 1 to 17, which is a polymer. 19. An aromatic vinyl compound-based polymer (component (A)) containing 30% by weight or more of styrene monomer units, such as polystyrene, rubber-reinforced polystyrene, methyl methacrylate-styrene copolymer, and rubber-reinforced methyl methacrylate-styrene copolymer. Coalesced, acrylonitrile-styrene copolymer, rubber-reinforced acrylonitrile-styrene copolymer,
The aromatic vinyl compound-based resin composition according to any one of claims 1 to 18, wherein the composition is at least one or more aromatic vinyl compound-based polymers selected from styrene-butadiene-styrene block copolymers. object. 20. The aromatic compound according to claim 1, wherein the aromatic vinyl compound polymer (component (A)) is a resin composition comprising a styrene resin and polyphenylene ether. Vinyl compound resin composition. 21. A molded article comprising the aromatic vinyl compound resin composition according to claim 1.