JP2000143733A - Aromatic vinyl compound-ethylene copolymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain in practically high activity the subject copolymer of high randomness (low alternateness) with no crystallinity derived from alternate structure recognizable. SOLUTION: This copolymer satisfies the following requirements: (1) aromatic vinyl compound content is 1-99 mol%, (2) the stereoregularity of the alternate structure composed of aromatic vinyl compound unit and ethylene unit stands at >=0.75 in terms of isotactic diad, and (3) crystallinity derived from the aromatic vinyl compound-ethylene alternate structure cannot be observed even after taking an action for promoting sufficient crystallization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel aromatic vinyl compound-ethylene copolymer and a method for producing the same.

[0002]

2. Description of the Related Art There are known several styrene-ethylene copolymers obtained using a so-called single-site catalyst system comprising a transition metal catalyst component and an organoaluminum compound, and a method for producing the same. JP-A-3-1630088 and JP-A-7-53618 disclose a normal styrene chain (head of styrene unit) obtained using a complex having a so-called constrained geometric structure (CGCT catalyst).
A styrene-ethylene copolymer having no (tail chain), a so-called pseudo-random copolymer is described.
In addition, styrene may be described as St below. The inability of the polymerization catalyst, in this case the CGCT catalyst, to form a head-tail styrene chain structure imposes a constraint on the polymer chain growth reaction. For example,
If the polymer end is a styrene unit, styrene cannot coordinate and must wait for ethylene to come. Such constraint of the monomer species during the polymer growth process will significantly reduce the activity of the catalyst as compared to the unconstrained catalyst. Also, due to the absence of styrene chains, the styrene content cannot exceed 50 mol%. Further, the phenyl group having a styrene-ethylene alternating structure present in the pseudorandom copolymer has no stereoregularity.

JP-A-6-49132 and Pol
ymer Preprints, Japan, vol.
42, 2292 (1993) discloses a bridged metallocene system Z
The same normal St was obtained using a catalyst consisting of an r complex and a co-catalyst.
A method for producing a styrene-ethylene copolymer having no chain, that is, a so-called pseudo-random copolymer is described.
However, Polymer Preprints, Jap
an, vol. 42, 2292 (1993),
The phenyl group of the alternating styrene-ethylene structure present in the pseudorandom copolymer has no substantial stereoregularity. Also, as in the case of complexes having a constrained geometry, the absence of normal styrene chains prevents the styrene content from exceeding 50 mol%. Activity,
Practically insufficient. More recently, certain bridged bisindenyl Zr complexes, ie, rac [ethylene
bis (indenyl) zirconium dic
hloride] [racemic [ethylenebis (indenyl) zirconium dichloride]] at very low temperatures (-2
Under the condition of 5 ° C.), a styrene-ethylene copolymer having a stereoregularity close to an alternating copolymer has been reported. (Ma
cromol. Chem. , Rapid Commu
n. , Vol. 17, 745 (1996). However, it is clear from the published 13 C-NMR spectrum and the description of the article that there is no head-tail styrene linkage in this copolymer. Furthermore,
When copolymerization is carried out at a polymerization temperature of room temperature or higher using this complex, only a copolymer having low styrene content and low molecular weight can be obtained.

On the other hand, T having a substituted phenolic ligand
Styrene-ethylene alternating copolymers obtained using i-complexes are known (JP-A-3-250007,
And Stud. Surf. Sci. Catal. , 51
7 (1990)). This copolymer is characterized by being substantially composed of an alternating structure of ethylene and styrene. Other structures such as an ethylene chain, a structure composed of an ethylene chain and styrene, a head-head bond and a tail-tail bond of styrene ( Such structures are hereinafter substantially not included. The alternating degree (λ value in the present specification) of the copolymer is 70 or more, substantially 90 or more. That is, the obtained copolymer is a copolymer having a very high alternating property and containing substantially only an alternating structure. Therefore, the composition ratio of 50 mol% of ethylene and 50 mol% of styrene in the copolymer is reduced. It is practically difficult to change.

JP-A-9-309925 discloses that a styrene content of 1 to 55 mol%, an alternating structure of styrene and ethylene has isotactic stereoregularity, and a degree of alternation of a copolymer (λ in the present specification). Value) is 70 or less. This copolymer has a relatively high degree of alternation, has crystallinity based on an alternating structure, and has a characteristic that it can provide a melting point, a heat of fusion of crystal of about 10 J / g or more, and an X-ray diffraction peak. However, when used in applications where crystallinity is unfavorable, such as applications where dimensional stability is required during molding, or when the physical properties of the resin or the resin composition cause problems such as a change over time due to slow crystallization, Yes, lower alternating (low λ
Value) copolymer, i.e., a lower crystallinity level,
Alternatively, the appearance of a styrene-ethylene random copolymer having no crystallinity has been expected. Further, a method for producing such a copolymer with practically high activity has been awaited.

[0006]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention is directed to an aromatic vinyl compound-ethylene random copolymer having high randomness (low alternating) and no crystallinity derived from an alternating structure. An object of the present invention is to provide a polymer and a method for producing the polymer with practical high activity.

[0007]

SUMMARY OF THE INVENTION The present invention is an aromatic vinyl compound-ethylene copolymer having the following characteristics. (1) The content of the aromatic vinyl compound is 1 mol% or more and 99 mol% or less. (2) The stereoregularity of the alternating structure of the aromatic vinyl compound unit and the ethylene unit is 0.75 or more by isotactic dyad. (3) No crystallinity derived from the aromatic vinyl-ethylene alternating structure is observed even after taking measures to sufficiently promote crystallization. Further, the present invention is an aromatic vinyl compound-ethylene copolymer having a head-tail chain structure of two or more aromatic vinyl compound units. Further, no melting point is observed between 70 ° C. and 200 ° C. by DSC measurement, and the content of the aromatic vinyl compound is preferably 15 mol% or more and 85 mol% or less, particularly preferably 4 mol% or less.
It is an aromatic vinyl compound-ethylene copolymer characterized by being at least 0 mol% and at most 85 mol%, most preferably at least 50 mol% and at most 85 mol%.

Further, the alternating structure index λ given by the following formula (i) satisfies the following relational formula (ii): an aromatic vinyl compound content of 15 mol% to 85 mol%, preferably 40 mol% or less. It is an aromatic vinyl compound-ethylene copolymer in an amount of from 85% by mole to 85% by mole. λ = A3 / A2 × 100 Expression (i) Relational expression (ii) When 15 ≦ x <50, 1 ≦ λ <x−10 Expression (ii) When 50 ≦ x ≦ 85, 1 ≦ λ <90-x Formula (ii) Here, x is an aromatic vinyl compound content (mol%). In the formula (i), A3 represents three kinds of peaks a derived from an aromatic vinyl compound-ethylene alternate structure represented by the following general formula (1) and obtained by 13C-NMR measurement,
This is the sum of the areas b and c. A2 is the total area of peaks derived from main chain methylene and main chain methine carbon observed in the range of 0 to 50 ppm by 13C-NMR based on TMS.

[0009]

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(In the formula, Ph is an aromatic group, x is the number of repeating units and is an integer of 2 or more.) Further, it has a peak at 40 to 45 ppm by 13 C-NMR measurement based on TMS, preferably 4
0.4-41.0 ppm, 42.3-43.6 ppm,
43.0-43.6 ppm, 43.7-44.5 ppm
, Particularly preferably from 42.3 to 43.6.
It is an aromatic vinyl compound-ethylene copolymer having a peak at 43.7 to 44.5 ppm. The amount of the aromatic vinyl compound unit having a head-tail chain structure giving the above peak is 0.1% of the total amount of the aromatic vinyl compound unit contained in the copolymer.
It is at least 1%, preferably at least 1.0%, and the content of the aromatic vinyl compound is preferably at least 1 mol% and less than 30 mol%. Preferably, the aromatic vinyl compound-ethylene copolymer of the present invention has a polystyrene equivalent weight average molecular weight of 10,000 or more and a molecular weight distribution (Mw / Mn) of 6 or less. The random copolymer in the present invention is a copolymer containing both a chain structure in which the aromatic vinyl compound unit is bonded by a head-tail, a chain structure in which the ethylene unit is bonded, and a structure in which the aromatic vinyl compound unit and the ethylene unit are bonded. It is united. Depending on the content of the aromatic vinyl compound or the polymerization conditions such as the polymerization temperature, the proportion of these structures in the copolymer varies. The proportions of these structures and the distribution of the structures are not restricted by the structure distribution by a specific statistical calculation. Hereinafter, a styrene-ethylene copolymer which is an example of the aromatic vinyl compound-ethylene copolymer of the present invention will be described as an example. However, the present invention is not limited to this. Its structure is determined by nuclear magnetic resonance (NMR).

The copolymer of the present invention has main peaks at the following positions in 13 C-NMR based on TMS. Peaks derived from main chain methylene and main chain methine carbon were around 24 to 25 ppm, around 27 ppm, and 30 ppm.
Around 34 to 37 ppm, around 40 to 41 ppm and around 42 to 46 ppm, and peaks derived from five carbons not bonded to the polymer main chain among the phenyl groups around 126 ppm and 128 ppm. Among them, a peak derived from one carbon bonded to the polymer main chain is shown at around 146 ppm.

The styrene-ethylene copolymer of the present invention comprises:
It is a copolymer satisfying the following conditions. (1) The content of the aromatic vinyl compound is 1 mol% or more and 99 mol% or less. (2) The stereoregularity of the alternating structure of the aromatic vinyl compound unit and the ethylene unit is 0.75 or more by isotactic dyad. (3) No crystallinity derived from the aromatic vinyl-ethylene alternating structure is observed even after taking measures to sufficiently promote crystallization. Further, the styrene-ethylene copolymer of the present invention may comprise two or more aromatic vinyl compound units.
It is an aromatic vinyl compound-ethylene copolymer having a tail chain structure. Aromatic vinyl compound content is 1H-NM
It can be determined by R. Styrene unit head of styrene-ethylene copolymer of the present invention-
The chain structure linked by the tail is a chain structure of two or more styrenes represented by the following structures.

[0013]

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Here, n is an arbitrary integer of 2 or more. Ph
Is a phenyl group. The chain structure in which two styrene units are linked by a head-tail is, based on TMS, 13C-NMR measurement using heavy tetrachloroethane as a solvent, at around 42 to 43 ppm, around 43 to 45 ppm, preferably 42.3 ppm. 43.6 ppm, 43.7-44.
Gives a peak at 5 ppm. A chain structure in which three or more styrene units are linked by a head-tail is, in the same measurement, around 40 to 41 ppm, around 43 to 44 ppm,
Preferably 40.4-41.0 ppm, 43.0-4
It also gives a peak at 3.6 ppm. Accordingly, a chain structure in which two or more styrene units are linked by a head-tail is around 40 to 45 ppm, preferably 40.4 to 41.0 ppm, 42.3 to 43.
6 ppm, 43.0-43.6 ppm, 43.7-4
Gives a peak at 4.5 ppm. On the other hand, in the case of a conventionally known so-called pseudo-random copolymer, a head-tail chain structure of styrene cannot be found even at a maximum styrene content of around 50 mol%. Further, even if homopolymerization of styrene is attempted using a catalyst for producing a pseudorandom copolymer, no polymer can be obtained. A very small amount of atactic styrene homopolymer may be obtained depending on the polymerization conditions, etc., which is understood to be formed by cationic polymerization by coexisting methylalumoxane or alkylaluminum mixed therein, or by radical polymerization. Should. Such an atactic styrene homopolymer can be easily separated by solvent separation or the like.

In the styrene-ethylene copolymer of the present invention, the isotactic structure in which the stereoregularity of the phenyl group in the alternating copolymer structure of ethylene and styrene is the isotactic structure is defined as the isotactic diad fraction m (or meso diad). Fraction) is greater than 0.75, preferably 0.85
Above, more preferably a structure showing 0.95 or more. The isotactic dyad fraction m of the alternating copolymer structure of ethylene and styrene is represented by a peak area Ar derived from the r structure of the methylene carbon peak appearing at around 25 ppm.
And the area Am of the peak derived from the m structure, and can be determined by the following formula (iii). m = Am / (Ar + Am) Formula (iii) 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 (73.89 ppm) of the triplet of heavy tetrachloroethane is used as a reference, the peak derived from the r structure is 25.3 to 2
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. In the styrene-ethylene copolymer of the present invention,
A peak attributed to the r structure in the alternating copolymer structure of ethylene and styrene is not substantially observed.

[0016] The copolymer of the present invention can be treated with known crystallization measures such as annealing, a nucleating agent, and a crystallization aid.
It does not show a crystal structure based on an ethylene-styrene alternating structure. Specifically, it does not show a crystal diffraction peak attributed to an ethylene-styrene alternate structure by X-ray diffraction. Here, the crystal diffraction peak based on the ethylene-styrene alternating structure is a diffraction peak obtained by using a Cu radiation source,
A diffraction peak at 2θ which has an intensity at least 3 times the noise level in the range of 15 to 40 ° and a peak area of 1% or more of the halo-peak area, or 2θ.
Means a peak having a half width of 3 ° or less. X-ray diffraction peaks derived from the ethylene-styrene alternating structure are described in JP-A-9-309925, Macromol.
Rapid Commun. , Vol. 19,327
(1998), Macromol. RapidCom
mun. , Vol. 17, 745 (1996). The copolymer of the present invention has a crystal structure derived from polyethylene in a low aromatic vinyl compound content region (about 15 mol% or less) and an isotactic polystyrene in a high aromatic vinyl compound content region (about 90 mol% or more). It may contain a crystal structure derived from it. Further, the aromatic vinyl compound-ethylene copolymer of the present invention has a melting point not observed between 70 ° C. and 200 ° C. by DSC measurement, and the content of the aromatic vinyl compound is preferably from 15 mol% to 85 mol%. The aromatic vinyl compound-ethylene copolymer is particularly preferably 40 mol% or more and 85 mol% or less. DS
The fact that no melting point was observed between 70 ° C. and 200 ° C. by the C measurement means that a crystal structure having a melting point in this temperature range (a crystal structure derived from the styrene-ethylene alternating structure, a polyethylene chain structure, a polystyrene chain, etc.). Crystal structure derived from the structure) does not exist.

Further, the aromatic vinyl compound-ethylene copolymer of the present invention has a styrene content of 15 to 85% or less,
A styrene-ethylene random copolymer having preferably 40 mol% to 85 mol%, wherein the alternating structure index λ given by the following formula (i) satisfies the following relational expression (ii). It is an aromatic vinyl compound-ethylene copolymer. λ = A3 / A2 × 100 Expression (i) Relational expression (ii) When 15 ≦ x <50, 1 ≦ λ <x−10 Expression (ii) When 50 ≦ x ≦ 85, 1 ≦ λ <90-x Formula (ii) Here, x is an aromatic vinyl compound content (mol%). In the formula (i), A3 represents three kinds of peaks a derived from an aromatic vinyl compound-ethylene alternate structure represented by the following general formula (1) and obtained by 13C-NMR measurement,
This is the sum of the areas b and c. A2 is the total area of peaks derived from main chain methylene and main chain methine carbon observed in the range of 0 to 50 ppm by 13C-NMR based on TMS.

[0018]

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Wherein Ph is an aromatic group such as a phenyl group;
x represents the number of repeating units and represents an integer of 2 or more. )

The copolymer has an alternating structure index λ satisfying the relationship of the formula (ii) at various styrene contents,
Since it has a feature that the styrene content is less than 40 even at 50 mol%, it indicates that the copolymer has lower alternating property and higher randomness. Therefore, in the present copolymer, even after taking measures by a known method of promoting crystallization, the crystal structure derived from the styrene-ethylene alternating structure of the copolymer isotactic is not observed by X-ray diffraction. There are features. Furthermore, it has a feature that it has no melting point derived from any crystal structure between 70 ° C. and 200 ° C. by DSC measurement. Furthermore, in any styrene content range, ethylene chain structure,
The copolymer has various structures such as a styrene head-tail chain structure and a structure in which a styrene unit and an ethylene unit are bonded to each other. Even when the styrene content of the copolymer is from 50 mol% to 90 mol%, a chain structure of ethylene is observed by ordinary 13C-NMR measurement. This copolymer in which ethylene chains are present randomly and uniformly in the main chain of the copolymer having a high styrene content is characterized by being non-crystalline and having high impact strength and high transparency.

Low styrene content 1 mol% to 50 mol%
In the copolymer (1), two or three or more head-tail styrene chain structures are observed by ordinary 13C-NMR measurement. This copolymer, in which the head-tail styrene chain is present randomly and uniformly in the main chain of such a low styrene content copolymer, breaks the crystallinity of the polyethylene chain, and is flexible, rupture strength, and transparent. Both have the feature of being high. In the present invention, when the aromatic vinyl compound unit having a head-tail chain structure giving the above-mentioned peaks has an aromatic vinyl compound content of 1 mol% or more and less than 30 mol%, the total amount contained in the copolymer It is at least 0.1%, preferably at least 1% of the amount of the aromatic vinyl compound unit. The ratio 量 of the amount of the aromatic vinyl compound units derived from the head-tail chain structure of the aromatic vinyl compound units to the total amount of the aromatic vinyl compound units contained in the copolymer was determined by the following formula. χ = χa / χb × 100 Here, χa is the sum of the peak areas derived from the main chain methine carbon in the head-tail chain structure of two or more aromatic vinyl compound units. For example, in 13C-NMR measurement based on TMS, 40.4 to 41.
Peak (n) observed at 0 ppm and 42.3-43.
Sum of peaks (j) observed at 6 ppm. χb is the sum of the peak areas derived from the main chain methine carbon of the whole aromatic vinyl compound unit contained in the copolymer.

Further, in the styrene-ethylene random copolymer of the present invention, the stereoregularity of the phenyl group in the chain structure of the styrene unit is isotactic. Isotacticity of the stereoregularity of the phenyl group in the styrene unit chain structure is defined as isotactic dyad fraction ms
(Or also referred to as meso dyad fraction) is greater than 0.5, preferably 0.7 or more, more preferably 0.8
This refers to the structure described above. The stereoregularity of the chain structure of the styrene unit is 43 to 43 observed by 13C-NMR.
Peak position of methylene carbon around 44 ppm, and 1H
-Determined by the peak position of the main chain proton observed by NMR.

The peak of the methylene carbon of the structure derived from the hetero-bond of styrene in the conventional pseudorandom copolymer having no stereoregularity is 34.0 to 34.5 ppm and 34.5.
It is known to be in two regions of ~ 35.2 ppm. (For example, Polymer Preprints,
Japan, vol. 42, 2292 (1993)) In the styrene-ethylene random copolymer of the present invention, a peak attributed to a methylene carbon of a heterogeneous bond structure derived from styrene is observed in a region of 34.5 to 35.2 ppm. It is hardly observed at 34.0 to 34.5 ppm. This shows one of the characteristics of the copolymer of the present invention,
This shows that the high stereoregularity of the phenyl group is maintained even in a heterogeneous bond structure derived from styrene as shown in the following formula.

[0024]

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The weight average molecular weight of the styrene-ethylene random copolymer of the present invention is at least 10,000, preferably at least 30,000, particularly preferably at least 80,000, and has a practically high molecular weight. The molecular weight distribution (Mw / Mn) is 6 or less, preferably 4 or less, particularly preferably 3 or less. The weight average molecular weight of the copolymer of the present invention is 1,000,000 or less, preferably 500,000 or less, in consideration of its processability. 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.

Further, the styrene-ethylene random copolymer of the present invention has an alternating structure of ethylene and styrene having high stereoregularity, and simultaneously has ethylene chains of various lengths, heterogeneous bonds of styrene, and various lengths of styrene. It is characterized by having various structures such as styrene chains. Also,
Styrene-ethylene random copolymer of the present invention, depending on the content of styrene in the copolymer, or polymerization temperature,
Under polymerization conditions such as monomer concentration, the ratio of the alternating structure can be variously changed within a range where the λ value satisfies the above specific relational expression.

The copolymer of the present invention has high performances such as initial tensile modulus, hardness, breaking strength, solvent resistance, etc. in each St content region and various degrees of crystallinity. It exhibits physical properties characteristic of a conductive resin, a thermoplastic elastomer, and a transparent soft resin. Further, by changing the styrene content, the glass transition point can be changed in a wide range. Further, the styrene-ethylene copolymer of the present invention, which does not basically contain an elutable plasticizer or a halogen, has a basic feature of high safety (small environmental load). The copolymer of the present invention exhibits the following characteristics at each styrene content. A copolymer having a styrene content of 1 to 10 mol% has high tensile strength and transparency, is flexible, and exhibits properties as a plastomer or an elastomer. The copolymer having a styrene content of 10 to 25 mol% has high tensile strength, elongation, transparency, flexibility, and recoverability, and exhibits properties as an elastomer. The copolymer having the above composition is used alone or as an alloy of the copolymers having different styrene contents.
Alternatively, it can be suitably used as an alloy with a polyolefin such as polypropylene, for example, for a stretch film for packaging. A copolymer having a styrene content of 50 mol% or more and 85 mol% or less and having a low crystallization ratio is a highly transparent plastic, and has a high shrink property at a temperature higher than the glass transition point and a temperature lower than the glass transition point. It has high dimensional stability at a temperature of, for example, and is useful as a shrink film for packaging. Also, once heated above the melting point and rapidly cooled to below the glass transition point, the fixed shape is deformed under the temperature condition between the glass transition point and the melting point and cooled to below the glass transition point to deform and fix the shape. However, if the film is heated again to a temperature not lower than the glass transition point and not higher than the melting point, the original shape can be recovered. That is, it has shape memory properties. The copolymer having a styrene content of 15 to 50 mol% is
As an alloy with polyolefin such as polypropylene or polyethylene, polystyrene, or other resin, or a composition obtained by partially cross-linking, it is suitably used for a substitute for soft PVC. The copolymer of this composition is used as a compatibilizer for styrene-based resin and polyolefin, as an additive to styrene-based resin and polyolefin-based resin, as a rubber modifier, and as a component of pressure-sensitive adhesive. Agent)
Useful as By changing the styrene content, the copolymer of the present invention can arbitrarily change the glass transition point from -40 to 90 ° C., and has a large tan δ peak in the viscoelastic spectrum, so that it can support a wide temperature range. It is useful as a vibration damping material. The styrene-ethylene copolymer has been described above as a typical example of the aromatic vinyl compound-ethylene copolymer of the present invention. However, the above description can be generally applied to an aromatic vinyl compound-ethylene copolymer using the above aromatic vinyl compound.

Further, depending on the polymerization conditions and the like, a small amount of an atactic homopolymer obtained by heat, radical, or cation polymerization of an aromatic vinyl compound may be contained, but the amount is 10% by weight or less of the whole. Such a homopolymer can be removed by solvent extraction, but if there is no particular problem in physical properties, it can be used while containing it. Further, blending with other polymers is also possible for the purpose of improving physical properties. Blends of the copolymers of the present invention having different styrene contents are also possible.

The aromatic vinyl compound-ethylene copolymer of the present invention can be produced by a polymerization catalyst comprising a metallocene compound and a cocatalyst shown below.

[0030]

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In the formula, A is the following general formula:
Is an unsubstituted or substituted cyclopentaphenanthryl group.

[0032]

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[0033]

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(In the above Chemical Formulas 7 and 8, R1 and R2 are each hydrogen, an alkyl group having 1 to 20 carbon atoms, 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 or PR ₂ groups (R represents a hydrocarbon group having 1 to 10 carbon atoms),
R1 and R2 may be the same or different from each other. In addition, adjacent R1 and R2 groups are integrated into 5 to 8
It may form a membered aromatic or aliphatic ring. R1 ',
R2 'is the same substituent as R1 and R2, respectively, and preferably R1' and R2 'are hydrogen. Specific examples of the unsubstituted cyclopentaphenanthryl group include a 3-cyclopenta [c] phenanthryl group and a 1-cyclopenta [l] phenanthryl group.

B is an unsubstituted or substituted cyclopentaphenanthryl group represented by the same chemical formula as A, an unsubstituted or substituted benzoindenyl group represented by formulas 9 to 11, or An unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group or an unsubstituted or substituted fluorenyl group represented by Chemical formula 14.

[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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(In the above chemical formulas 9, 10 and 11, R3,
R4 and R5 are each hydrogen, an alkyl group having 1 to 20 carbon atoms, 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 or a PR ₂ group (R is any of R3, R4, and R5 may be the same or different from each other. In addition, adjacent R3, R
The 4, R5 groups may together form a 5- to 8-membered aromatic or aliphatic ring. However, this does not apply to the case where it becomes an unsubstituted cyclopentaphenanthrene group. (In the above chemical formulas 12, 13, and 14, R6, R7, R
Each of the eight groups is hydrogen, an alkyl group having 1 to 20 carbon atoms, 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, or a PR ₂ group (R Each represents a hydrocarbon group having 1 to 10 carbon atoms), and R6, R7, and R8 may be the same or different. When both A and B are unsubstituted or substituted cyclopentaphenanthryl groups, they may be the same or different.

In producing the copolymer of the present invention, both A and B are preferably unsubstituted or substituted cyclopentaphenanthryl groups.

As unsubstituted benzoindenyl groups, 4,5
-Benzo-1-indenyl, (also known as benzo (e) indenyl), 5,6-benzo-1-indenyl, 6,7-benzo-1-indenyl is substituted with α-acenaphth-1- as a substituted benzoindenyl group. Examples include an indenyl group. An unsubstituted cyclopentadienyl group is cyclopentadienyl, and a substituted cyclopentadienyl group is 4
-Aryl-1-cyclopentadienyl, 4,5-diaryl-1-cyclopentadienyl, 5-alkyl-4
-Aryl-1-cyclopentadienyl, 4-alkyl-5-aryl-1-cyclopentadienyl, 4,5-
Examples thereof include dialkyl-1-cyclopentadienyl, 5-trialkylsilyl-4-alkyl-1-cyclopentadienyl, and 4,5-dialkylsilyl-1-cyclopentadienyl.

The unsubstituted indenyl group is 1-indenyl, and the substituted indenyl group is 4-alkyl-1-indenyl, 4-aryl-1-indenyl, 4,5-dialkyl-1-indenyl, 4,6-dialkyl -1-
Indenyl, 5,6-dialkyl-1-indenyl,
4,5-diaryl-1-indenyl, 5-aryl-
1-indenyl, 4-aryl-5-alkyl-1-indenyl, 2,6-dialkyl-4-aryl-1-indenyl, 5,6-diaryl-1-indenyl, 4,
5,6-triaryl-1-indenyl and the like. Examples of the unsubstituted fluorenyl group include a 9-fluorenyl group, and examples of the substituted fluorenyl group include a 7-methyl-9-fluorenyl group and a benzo-9-fluorenyl group.

In the above general formula (4), Y represents A, B
Carbon, silicon, and boron having a bond with other substituents
Or an ethylene group, which is hydrogen or has 1 to 1 carbon atoms.
Methylene group having 5 hydrocarbon groups, silylene group, boro group
And a 1,2-ethylene group. The substituents are
They may be different or the same. Y is cyclohexyl
Having a cyclic structure such as a lidene group or a cyclopentylidene group
May be. Preferably, Y has a bond with A, B,
Hydrogen or a group substituted by a hydrocarbon group having 1 to 15 carbon atoms
Is a substituted methylene group. Alkyl hydrocarbons include
Group, aryl group, cycloalkyl group, cycloaryl
And the like. Substituents are the same even if different
May be. Particularly preferably, Y is -CH_Two-, -CM
e_Two-, -CEt_Two-, -CPh _Two-, Cyclohexyl
And a cyclopentylidene group. Where Me is
A methyl group, Et represents an ethyl group, and Ph represents a phenyl group.
X is hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms,
Aryl group having 6 to 10 carbon atoms, alkyl having 8 to 12 carbon atoms
Aryl group, having a hydrocarbon substituent having 1 to 4 carbon atoms
Silyl group, alkoxy group having 1 to 10 carbon atoms, or carbon
Dialkylamide group having alkyl substituent of formulas 1 to 6
It is. Halogen includes chlorine and bromine, etc.
As a methyl group, an ethyl group, etc., and as an aryl group,
When a phenyl group or the like is an alkylaryl group,
And a silyl group such as a trimethylsilyl group.
Lucoxy groups include methoxy, ethoxy and isopro
And a dialkylamide group such as dimethyl group.
Luamide group and the like. M is zirconium, hafni
Or titanium. Particularly preferred zirconium
It is.

Examples of such transition metal catalyst components include the following compounds in addition to the substituted methylene bridged transition metal compounds specifically exemplified in European Patent Publication EP0872492A2. For example, dimethylmethylenebis (3-cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylenebis (3-cyclopenta [c]
Phenanthryl) zirconium bisdimethylamide, di-n-propylmethylenebis (3-cyclopenta [c] phenanthryl) zirconium dichloride, dii-propylmethylenebis (3-cyclopenta [c] phenanthryl) zirconium dichloride, cyclohexylidenebis (3- Cyclopenta [c] phenanthryl) zirconium dichloride, cyclopentylidenebis (3-cyclopenta [c] phenanthryl) zirconium dichloride,
Diphenylmethylenebis (3-cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylene (4,5-benzo-1-indenyl) (3-cyclopenta [c] phenanthryl) zirconium dichloride,
Dimethylmethylene (5,6-benzo-1-indenyl)
(3-cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylene (6,7-benzo-1
-Indenyl) (3-cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (3-cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylene (1-indenyl) (3-cyclopenta [c] phenanthryl ) Zirconium dichloride, dimethylmethylene (1-fluorenyl) (3-cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylene (4-phenyl-1-indenyl) (3-cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylene (4 -Naphthyl-1-indenyl) (3-
Cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylene (3-cyclopenta [c] phenanthryl) (4,5-naphth-1-indenyl) zirconium dichloride, dimethylmethylene (3-cyclopenta [c] phenanthryl) (α-acenaphtho- 1-
Indenyl) zirconium dichloride, dimethylmethylenebis (1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylenebis (1-cyclopenta [l] phenanthryl) zirconium bisdimethylamide, di-n-propylmethylenebis (1-cyclopenta [l] Phenanthryl) zirconium dichloride, dii-propylmethylenebis (1-cyclopenta [l] phenanthryl) zirconium dichloride, cyclohexylidenebis (1-cyclopenta [l] phenanthryl) zirconium dichloride, cyclopentylidenebis (1-cyclopenta [l] phenanthryl ) Zirconium dichloride, diphenylmethylenebis (1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene 4,5-benzo-1-indenyl) (1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene (5,6-benzo-1-indenyl) (1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene ( 6,7-benzo-1-indenyl) (1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene (1-indenyl) ( 1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene (1-fluorenyl) (1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene (4-phenyl-1-i Denier) (1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene (4-naphthyl -
1-indenyl) (1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene (1
-Cyclopenta [l] phenanthryl) (4,5-naphth-1-indenyl) zirconium dichloride, dimethylmethylene (1-cyclopenta [l] phenanthryl)
(Α-acenaphth-1-indenyl) zirconium dichloride, dimethylmethylene (1-cyclopenta [l] phenanthryl) (3-cyclopenta [c] phenanthryl) zirconium dichloride and the like. Although the zirconium complex has been exemplified above, the same compounds as described above are preferably used for the titanium and hafnium complexes. Further, a mixture of a racemic body and a meso body may be used. Preferably, racemic or pseudo-racemic is used. In these cases, a D-form or an L-form may be used. As the co-catalyst used in the present invention, a co-catalyst conventionally used in combination with a transition metal catalyst component can be used. As such a co-catalyst, an aluminoxane (or alumoxane) or a boron compound is used. It is preferably used. Further, the co-catalyst used at that time has the following general formula (5):
The aluminoxane (or alumoxane) represented by (6) is preferred.

[0048]

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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.

[0050]

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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. As the aluminoxane, methylalumoxane, ethylalumoxane and triisobutylalumoxane are preferably used, and methylalumoxane is particularly preferably used. If necessary, a mixture of these different alumoxanes may be used. These alumoxanes may be used in combination with alkylaluminums, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, and alkylaluminums containing halogen, for example, dimethylaluminum chloride. The addition of the alkyl aluminum is effective for removing a polymerization inhibitor such as a polymerization inhibitor in styrene, styrene, water in a solvent, and other substances that inhibit polymerization, and rendering the polymerization reaction harmless. However, by pre-distilling styrene, solvent, etc., bubbling with a dry inert gas, or reducing these amounts to a level that does not affect the polymerization by a known method such as passing through a molecular sieve,
Alternatively, slightly increase the amount of alumoxane used,
Alternatively, if it is added, it is not always necessary to add the alkyl aluminum during the polymerization. In the present invention, a boron compound can be used as a promoter together with the above transition metal catalyst component.

The boron compound used as a co-catalyst is
The boron compounds specifically exemplified in European Patent Publication EP0872492A2 can be used similarly. These boron compounds and the above-mentioned organoaluminum compounds may be used simultaneously. In particular, when a boron compound is used as a co-catalyst, the addition of an alkyl aluminum compound such as triisobutyl aluminum is effective for removing impurities such as water contained in the polymerization system that adversely affect the polymerization.

The aromatic vinyl compound used in the present invention includes styrene and various substituted styrenes such as p
-Methylstyrene, m-methylstyrene, o-methylstyrene, ot-butylstyrene, mt-butylstyrene, pt-butylstyrene, p-chlorostyrene,
Examples thereof include o-chlorostyrene, α-methylstyrene, and the like, and compounds having a plurality of vinyl groups in one molecule such as divinylbenzene. Further, vinyl naphthalene, vinyl anthracene, or the like can be used.
Industrially preferably styrene, p-methylstyrene,
p-Chlorostyrene, particularly preferably styrene, is used. The copolymer of the present invention can be copolymerized with another monomer as a third component other than the aromatic vinyl compound and ethylene as long as the effects of the present invention are not impaired.
Examples of the monomer of the third component include α-olefins having 2 to 20 carbon atoms, ie, ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and cyclic olefins, ie, cyclopentene, norbornene. And norbornadiene are suitable. Two or more of these olefins may be used. Butadiene, 1,4-hexadiene, 1,5-hexadiene,
Dienes such as ethylidene norbornene and dicyclopentadiene are also suitably used as the third component monomer. The content of these dienes is preferably 0.05 mol% or more and 5 mol% or less. In producing the copolymer of the present invention, ethylene, the aromatic vinyl compound exemplified above, and if necessary, the third component monomer are brought into contact with a transition metal catalyst component which is a metal complex and a cocatalyst. Any known method can be used for the order and the contact method. As the above copolymerization method, 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 Such as a saturated aliphatic or aromatic hydrocarbon or a halogenated hydrocarbon alone or in a mixed solvent. Also, if necessary,
Methods such as batch polymerization, continuous polymerization, batch polymerization, slurry polymerization, preliminary polymerization, and gas phase polymerization can be used. Conventionally, when styrene is used as a monomer component, gas-phase polymerization cannot be adopted because of its low vapor pressure. However, when a catalyst composed of the transition metal catalyst component for polymerization of the present invention and a cocatalyst is used, the copolymerization ability of styrene is extremely high, so that copolymerization is possible even at a low styrene monomer concentration. That is, copolymerization of olefin and styrene is possible even under a low styrene partial pressure under gas phase polymerization conditions. In this case, the transition metal catalyst component for polymerization and the cocatalyst may be used by being supported on a suitable known carrier.

The copolymerization or 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. Furthermore, industrially preferably, it is 0 ° C to 160 ° C, particularly preferably 30 ° C to 160 ° C.
It is. The pressure at the time of copolymerization is suitably from 0.1 to 1000 atm, preferably from 1 to 50 atm, particularly preferably from 1 to 30 atm. When an organoaluminum compound (alumoxane) is used as a promoter,
The metal atom of the complex has an aluminum atom / complex metal atom ratio of 0.1 to 100,000, preferably 10 to 10,000.
Used in the ratio of 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 using a boron compound as a promoter,
It is used at a boron atom / complex metal atom ratio of 0.01 to 100, 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.

[0055]

The present invention will be described below with reference to examples.
The present invention is not limited to the following examples. In the following description, Cp is a cyclopentadienyl group, In
d is a 1-indenyl group, BInd is 4,5-benzo-1
-Indenyl group, Flu represents a 9-fluorenyl group, Me represents a methyl group, Et represents an ethyl group, tBu represents a tertiary-butyl group, and Ph represents a phenyl group.

The copolymers obtained in each of the examples and comparative examples were analyzed by the following means. The 13C-NMR spectrum was measured using a heavy chloroform solvent or a heavy 1,1,2,2-tetrachloroethane solvent using α-500 manufactured by JEOL Ltd. with reference to TMS. Here, the measurement based on TMS is as follows.
First, the triple line 1 of tetrachloroethane based on TMS
The shift value of the center peak of the 3C-NMR peak was determined.
Next, the copolymer was dissolved in tetrachloroethane to obtain 13C.
-The NMR was measured, and each peak shift value was calculated based on the triplet center peak of tetrachloroethane. The shift value of the triplet center peak of tetrachloroethane is 73.
It was 89 ppm. Quantification of peak area 13C-
The NMR spectrum measurement was performed by a proton gate decoupling method in which NOE was eliminated, using a pulse of 45 ° pulse width 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 result was consistent with the case of the repetition time of 5 seconds within the range of the measurement error.

The determination of the styrene content in the copolymer was determined by 1H
-Performed by NMR, the equipment was α-500 and B manufactured by JEOL Ltd.
AC-250 manufactured by RUCKER was used. Using a heavy chloroform solvent or heavy 1,1,2,2-tetrachloroethane, based on TMS, a peak derived from a phenyl group proton (6.5 to 7.5 ppm) and a proton peak derived from an alkyl group (0.8 to 7.5 ppm). 3 ppm). For the molecular weight in the examples, a weight average molecular weight in terms of standard polystyrene was determined using GPC (gel permeation chromatography). A copolymer soluble in THF at room temperature can be obtained by using THF as a solvent and HLC-802 manufactured by Tosoh Corporation.
0 was measured. The copolymer insoluble in THF at room temperature is
HLC manufactured by Tosoh Corporation using o-dichlorobenzene as a solvent
It measured at 145 degreeC using the -8121 apparatus. The DSC measurement was performed using Seiko Denshi DSC200. 6
A 10 mg sample treated at 0 to 70 ° C. for about 10 hours was heated from room temperature to 250 ° C. under a N ₂ gas flow at a rate of 20 ° C./mi.
The temperature was raised at n and measured, and the presence or absence of a melting point between 70 ° C and 250 ° C was confirmed. (1st-run), 10 at 250 ° C
After quenching with liquid nitrogen,
The temperature was raised at a rate of 10 ° C./min from 2 ° C. to 280 ° C. (2nd-run), and the glass transition point (Tg) was measured. X-ray diffraction is performed by using a high-power X-ray diffractometer MXP-18 manufactured by Mac Science, Inc.
405 angstroms).

The tensile modulus, tensile elongation at break, and tensile strength at break were measured by the hot press method (200 ° C., 4 minutes, 50 k
g / cm ² G), a sheet was formed to a thickness of 1 mm, the sheet was punched out in the shape of a No. 2 dumbbell, and measured according to JIS K-7113. The total light transmittance and haze were determined using a sheet having a thickness of 1 mm obtained in the same manner and using a turbidimeter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K-7105. Surface hardness (Shore-A, D hardness) is JISK-7
215.

Experimental Example <Synthesis of transition metal catalyst component A> rac-dimethylmethylenebis (3-cyclopenta [c] phenanthryl) zirconium dichloride of the following formula (also known as rac @ CpPh)
_{en-CMe 2 -CpPhen} ZrCl 2} ) was synthesized as follows. CpPhen represents cyclopenta [c] phenanthryl).

[0060]

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1H or 3H-cyclopenta [c] phenanthrene is described in the literature Organometallics,
vol. 16, 3413 (1997).

A-1 Isopropylidenebis (cyclopenta [c] phenanthrene) Under an Ar atmosphere, 32 g of 1H or 3H-cyclopenta [c] phenanthrene was added to 3.0 g of potassium hydroxide.
Was added to suspended 40 ml of dimethoxyethane, and the mixture was stirred at room temperature for 30 minutes.
Stirred at C for 2 hours. After neutralization by adding 10% phosphoric acid aqueous solution, the mixture was extracted with methylene chloride, the organic phase was washed with water and dried, and methylene chloride was distilled off. By recrystallization from a methylene chloride-diethyl ether solution, white crystalline isopropylidenebis (cyclopenta [c] phenanthrene) was obtained in an amount of 1.5%.
g was obtained. By 1H-NMR spectrum measurement, 1.93.
ppm (6H, s), 4.20 ppm (4H, d),
6.89 ppm (2H, t), 7.5-7.9 ppm
It has a peak at (14H, m), 8.91 ppm (2H, d). The measurement was performed using CDCl ₃ based on TMS.
Was used as a solvent.

A-3 Synthesis of rac-dimethylmethylenebis (3-cyclopenta [c] phenanthryl) zirconium dichloride 2.0 mmol of isopropylidenebis (cyclopenta [c] phenanthrene) and 2.0 mmol under an Ar gas flow.
l of zirconium tetrakisdimethylamide, Zr
(NMe ₂ ) ₄と と も に together with 20 ml of toluene
The mixture was stirred under reflux for 7 hours. Under reduced pressure, toluene was distilled off, 50 ml of methylene chloride was added, and the mixture was cooled to -50 ° C. Dimethylamine hydrochloride (4.0 mmol) was slowly added, and the mixture was slowly warmed to room temperature and further stirred for 2 hours. After distilling off the solvent, the obtained solid was washed with pentane and then with a small amount of methylene chloride to remove the meso form and the ligand.
ac-dimethylmethylenebis (3-cyclopenta [c]
0.36 g of yellowish yellow crystals of phenanthryl) zirconium dichloride were obtained. According to 1H-NMR spectrum measurement, 2.55 ppm (6H, s) and 6.49 ppm (2
H, d), 7.55-8.02 ppm (16H, m),
It has a peak at a position of 8.82 ppm (2H, d).
The measurement was performed using CDCl ₃ as a solvent based on TMS.

Example 1 <Synthesis of styrene-ethylene random copolymer> As a catalyst, the catalyst obtained in the above-mentioned synthesis A of transition metal catalyst component, ra
Using c-dimethylmethylenebis (3-cyclopenta [c] phenanthryl) zirconium dichloride, the procedure was carried out as follows under the conditions shown in Table 1. Polymerization was carried out using an autoclave having a capacity of 10 L, a stirrer and a jacket for heating and cooling. 800 ml of dehydrated toluene and 4000 ml of dehydrated styrene were charged and heated and stirred at an internal temperature of 50 ° C. About 100 L of nitrogen is bubbled through the system to purge the system, 8.4 mmol of triisobutylaluminum, and methylalumoxane (MMAO-3A, manufactured by Tosoh Akzo).
Was added in an amount of 84 mmol based on Al. Immediately, ethylene was introduced to replace the inside of the autoclave, and the pressure was 0.1 MPa.
(0 kg / cm ² G, atmospheric pressure), and then the catalyst obtained by the above-mentioned synthesis A of the transition metal catalyst component, rac-dimethylmethylenebis (3-cyclopenta [c]) was taken from the catalyst tank installed on the autoclave. About 50 ml of a toluene solution of 21 μmol of phenanthryl) zirconium dichloride and 0.84 mmol of triisobutylaluminum were added to the autoclave. The polymerization was carried out for 2.5 hours while maintaining the internal temperature at 50 ° C. and the pressure at 0.1 MPa. After the completion of the polymerization, the resulting polymerization solution was poured little by little into excess methanol which was vigorously stirred to precipitate the produced polymer. After drying under reduced pressure at 60 ° C. until no change in weight was observed, 504 g of a polymer was obtained.

Examples 2 to 7 (excluding Example 3) Polymerization was carried out in the same manner as in Example 1 under the conditions shown in Table 1. PMAO or MMAO manufactured by Toso-Akzo was used.

Example 3 Polymerization was carried out using a polymerization vessel having a capacity of 150 L, a stirrer and a jacket for heating and cooling. Dehydrated cyclohexane 3
6L, 36L of dehydrated styrene are charged and the internal temperature is about 50 ℃
And heated and stirred. Triisobutyl aluminum 84mm
ol, methylalumoxane (MMA, manufactured by Tosoh Akzo)
840 mmol of O-3A) was added based on Al. Immediately introduced ethylene, pressure 0.3MPa (2Kg / cm
After stable at ² G), from the installation catalyst tank onto the polymerization vessel, wherein the transition metal catalyst component A, rac- dimethylmethylenebis (3-cyclopenta [c] phenanthryl)
About 100 ml of a toluene solution of 105 μmol of zirconium dichloride and 10 mmol of triisobutylaluminum was added to the polymerization vessel. Thereafter, polymerization was carried out at about 50 ° C. for 3.0 hours while maintaining the pressure at 0.2 MPa. After completion of the polymerization, the obtained polymerization solution was degassed, and then treated by the crumb forming method as described below to recover the polymer. Dispersant (Pluronic: trade name) obtained by diluting the polymerization solution with 72 L of cyclohexane and stirring vigorously
Was poured into 300 L of heated water at 85 ° C. for 2 hours. Then, after stirring at 97 ° C. for 1 hour, hot water containing crumbs was poured into cold water to collect crumbs. By air drying the crumb at 50 ° C and then vacuum degassing at 60 ° C,
A good crumb-shaped polymer of about several mm in size,
9.5 kg were obtained.

[0067] <Synthesis B of transition metal catalyst component> rac- dimethylmethylene (3-cyclopenta [c] phenanthryl) (1-indenyl) zirconium dichloride (also known _{as, rac {CpPhen-CMe 2 -Ind} } ZrC
l ₂ ) was synthesized as follows. CpPhen represents cyclopenta [c] phenanthryl). Synthesis of B-11,1-isopropylidene-3-cyclopenta [c] phenanthrene Can. J. Chem. , Vol. 62, 1751 (1
984), with reference to the synthesis of 6,6-diphenylfulvene. However, as a starting material, acetone was used instead of benzophenone, and 1H or 3H-cyclopenta [c] phenanthrene was used instead of cyclopentadiene. B-2 Synthesis of isopropylidene (1-indene) (3-cyclopenta [C] phenanthrene) Under Ar atmosphere, 14 mmol of indene was added to 50 ml of T
Dissolved in HF, added an equivalent amount of BuLi at 0 ° C., and stirred for about 10 hours. TH in which 14 mmol of 1,1-isopropylidene-3-cyclopenta [c] phenanthrene is dissolved
F20 ml was added, and the mixture was stirred at 0 ° C. to room temperature overnight. Water 5
0 ml and 100 ml of diethyl ether were added and shaken.
The organic phase was separated, washed with saturated saline, dried over sodium sulfate, and the solvent was distilled off under reduced pressure. Further purification with a column gave isopropylidene (1-indene) (3-cyclopenta [C] phenanthrene). Yield 32%. B-3 Synthesis of rac-dimethylmethylene (3-cyclopenta [c] phenanthryl) (1-indenyl) zirconium dichloride In the same manner as in the synthesis of rac-dimethylmethylenebis (3-cyclopenta [c] phenanthryl) zirconium dichloride of A-3. Synthesized. Yellow orange powder. Yield 28%.
2.43 ppm by 1H-NMR spectrum measurement
(3H, s), 2.47 ppm (3H, s), 6.28
ppm (1H, d), 6.36 ppm (1H, d),
6.71 (1H, dd), 7.08-7.97 ppm
It has a peak at the position of (12H, m), 8.88 ppm (1H, d). The chloroform H peak in deuterated chloroform was observed at 7.254 ppm, and the impurity toluene peak was observed at 2.3499 ppm. The measurement was CDCl ₃
Was used as a solvent.

Example 8 Synthesis of transition metal catalyst component as a catalyst
8.4 μm of pPhen-CMe ₂ -Ind @ ZrCl ₂
The polymerization was carried out under the conditions shown in Table 1 using mol.

Reference Example Table 2 shows the results of homopolymerization of styrene using the catalyst used in Example 1. It is understood that the catalyst of the present invention can sufficiently perform homopolymerization of styrene.

Comparative Examples 1-2 The catalyst was rac isopropylidenebisindenyl zirconium dichloride; rac @ Ind-C (Me) _2- I
Polymerization was carried out using nd @ ZrCl ₂ under the conditions shown in Table 1.

Table 1 shows the polymerization conditions and results of the examples and comparative examples.

[0072]

[Table 1]

Table 2 shows the styrene content of the obtained polymer, the molecular weight determined by GPC, and the glass transition point and melting point determined by DSC.

[0074]

[Table 2]

FIGS. 1 and 2 show a GPC chart and a DSC chart of the copolymer obtained in Example 1 as typical examples of the styrene-ethylene copolymer of the present invention. In the GPC measurement of the polymer obtained in each example, as shown in FIG. 1, it was confirmed that the GPC curves obtained by the different detectors (RI and UV) matched within the error range of the experiment. It shows that the coalescence has a very uniform composition distribution. The single glass transition point obtained by DSC in Table 2 also indicates a uniform composition of the copolymer. The copolymer obtained in this example was press-molded at 180 ° C., annealed at 50 ° C. for 1 week, and subjected to X-ray diffraction analysis.
Shown in In the copolymer of this example, no diffraction peak derived from the ethylene-styrene alternating structure was observed. In the copolymer having a styrene content of about 15 mol% or less, a diffraction peak derived from an ethylene chain structure (polyethylene) crystal was observed. On the other hand, in the copolymer of Comparative Example, a diffraction peak derived from an ethylene-styrene alternating structure was clearly observed. FIG. 3 shows, as an example, a diffraction spectrum after annealing the copolymer of Example 1, and FIG. 4 shows a diffraction spectrum of a copolymer having a crystal structure derived from an ethylene-styrene alternating structure. Table 5 shows the copolymer sample obtained in Example 1 and 50
The physical properties of the sample annealed at ℃ for one week are shown.
Mechanical properties and hardness by annealing treatment. No major change was seen in transparency or the like. In addition, it can be seen that the copolymer has high transparency and low haze in both samples before and after annealing.

13C of the polymer obtained in Examples 2 and 5
-The NMR spectrum is shown in FIGS.

The styrene-ethylene random copolymer of the present invention is a copolymer which can contain a typical structure represented by the following general formula at an arbitrary ratio. 1
In the methine and methylene carbon regions of the 3C-NMR spectrum, peaks attributable to the following can be shown. a ~
o is a symbol indicating carbon shown in the following chemical structural formulas of Chemical Formulas 17 to 26. Based on the center peak (73.89 ppm) of the triplet of heavy tetrachloroethane, the following peaks are shown. (1) Alternating structure of styrene and ethylene

[0078]

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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.) That is, the methine carbon connected to the Ph group and the three 1 shows a structure consisting of a methylene carbon.

[0080]

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In the following general formula, hydrogen atoms are omitted for simplification. (2) Chain structure of ethylene

[0082]

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(3) Structure consisting of an ethylene chain and one unit of styrene

[0084]

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(4) Structure composed of inversion of styrene unit (tail-to-tail structure)

[0086]

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(5) a structure comprising an ethylene unit or a head-tail chain of two ethylene chains and two styrene units;

[0088]

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Or a structure in which a styrene unit and a styrene-ethylene alternate structural unit are randomly bonded.

[0090]

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Alternating structure unit

[0092]

Embedded image

[0093]

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(6) Structure comprising a head-tail chain of three or more styrene units

[0095]

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25.1 to 25.2 ppm (c) 36.4 to 36.5 ppm (b) 44.8 to 45.4 ppm (a) 29.4 to 29.9 ppm (g) 36.5 to 36.8 ppm (E) 27.2 to 27.6 ppm (f) 45.4 to 46.1 ppm (d, h) 34.5 to 34.9 ppm (i) 42.3 to 43.6 ppm (j) 43.7 to 44 5.5 ppm (k) 35.6-36.1 ppm (l) 24.0-24.9 ppm (m) 40.4-41.0 ppm (n) 43.0-43.6 ppm (o) A slight shift, a microstructure of a peak, or a peak shoulder may occur due to the influence of measurement conditions, a solvent, or the like, or a long-range effect from an adjacent structure.

These peaks were assigned by Macromo
recules, vol. 13, 849 (1980),
J. Appl. Polymer Sci. , Vol. 5
3, 1453 (1994); Polymer Ph
ys. Ed. , Vol. 13,901 (1975), M
acromolecules, vol. 10,773
(1977), EP 416815, JP-A-Hei.
-130114, 13C-NMR In
adequat method, DEPT method, and 13C-NMR
The peak shift was predicted by a database STN (Specinfo). Table 3 shows the 13C-NMR beak position of the copolymer obtained in each example.

The structural index λ of the copolymer obtained in each Example
The value was determined according to equation (i) above. Table 6 shows the λ value and m value obtained in each of the examples and comparative examples. The isotactic dyad (meso dyad) fraction m of the alternating structure is given by the above equation (iii). By performing the 13C-NMR measurement, a clear peak derived from the styrene chain structure of the head-tail can be observed. The ratio 量 of the amount of the aromatic vinyl compound units derived from the head-tail chain structure of the aromatic vinyl compound units to the total amount of the aromatic vinyl compound units contained in the copolymer was determined by the following formula. χ = χa / χb × 100 Here, χa is the sum of the peak areas derived from the main chain methine carbon in the head-tail chain structure of two or more aromatic vinyl compound units. For example, in 13C-NMR measurement based on TMS, 40.4 to 41.
Peak (n) observed at 0 ppm and 42.3-44.
Sum of peaks (j) observed at 6 ppm. χb is the sum of the peak areas derived from the main chain methine carbon of the whole aromatic vinyl compound unit contained in the copolymer. Table 6 shows the χ values of the copolymers of the examples.

[0099]

[Table 3]

[0100]

[Table 4]

[0101]

[Table 5]

[0102]

[Table 6]

As a result of 13 C-NMR measurement, two and three
Peaks derived from more than one head-tail styrene chain structure were observed. The aromatic vinyl compound-ethylene copolymer of the present invention has a head-tail styrene chain even when the styrene content is as low as 10 mol% or less and the usual 13C-NMR measurement (about 20,000 times). A clear peak derived from the structure can be observed. Further, the aromatic vinyl compound-ethylene copolymer of the present invention is a copolymer having a high λ value (low alternating property) with a λ value satisfying the relationship of the formula (ii).

[0104]

According to the present invention, (1) the content of the aromatic vinyl compound is 1 mol% or more and 99 mol% or less. (2) The stereoregularity of the alternating structure of the aromatic vinyl compound unit and the ethylene unit is 0.75 or more by isotactic dyad. (3) No crystallinity derived from the aromatic vinyl compound-ethylene alternating structure is observed even after taking measures to sufficiently promote crystallization. It has the above characteristics, and further has a head-tail chain structure of two or two or more aromatic vinyl compound units, and the alternating structure index λ value is a specific relational expression (the above relational expression (ii)) Is satisfied, the randomness is high (the alternation is low), and a non-crystalline aromatic vinyl compound-ethylene random copolymer can be obtained, which is extremely useful in various applications.

[Brief description of the drawings]

FIG. 1 is a GPC chart of the copolymer obtained in Example 1.

FIG. 2 is a DSC chart of the copolymer obtained in Example 1.
G

FIG. 3 is an X-ray diffraction diagram of the copolymer obtained in Example 1.

FIG. 4 is an X-ray diffraction diagram of a copolymer having a crystal structure derived from an ethylene-styrene alternate structure.

FIG. 5: 13C-NM of the copolymer obtained in Example 2
R spectrum (methine-methylene region)

FIG. 6: 13C-NM of the copolymer obtained in Example 5
R spectrum (methine-methylene region)

Claims (11)

[Claims] 1. An aromatic vinyl compound-ethylene copolymer having the following characteristics. (1) The content of the aromatic vinyl compound is 1 mol% or more and 99 mol% or less. (2) The stereoregularity of the alternating structure of the aromatic vinyl compound unit and the ethylene unit is 0.75 or more by isotactic dyad. (3) No crystallinity derived from the aromatic vinyl compound-ethylene alternating structure is observed even after taking measures to sufficiently promote crystallization. 2. The aromatic vinyl compound-ethylene copolymer according to claim 1, which has a head-tail chain structure of two or more aromatic vinyl compound units. 3. From 70 ° C. to 200 ° C. according to DSC measurement.
2. The aromatic vinyl compound-ethylene copolymer according to claim 1, wherein no melting point is observed during the reaction, and the content of the aromatic vinyl compound is from 15 mol% to 85 mol%. 4. The aromatic vinyl compound-ethylene copolymer according to claim 3, wherein the content of the aromatic vinyl compound is from 50 mol% to 85 mol%. 5. The aromatic vinyl compound-ethylene copolymer according to claim 3, wherein the alternating structure index λ given by the following formula (i) satisfies the following relational formula (ii). λ = A3 / A2 × 100 Expression (i) Relational expression (ii) When 15 ≦ x <50, 1 ≦ λ <x−10 Expression (ii) When 50 ≦ x ≦ 85, 1 ≦ λ <90-x Formula (ii) Here, x is an aromatic vinyl compound content (mol%). In the formula (i), A3 represents three kinds of peaks a derived from an aromatic vinyl compound-ethylene alternate structure represented by the following general formula (1) and obtained by 13C-NMR measurement,
This is the sum of the areas b and c. A2 is the total area of peaks derived from main chain methylene and main chain methine carbon observed in the range of 0 to 50 ppm by 13C-NMR based on TMS. Embedded image (Wherein Ph represents an aromatic group, x represents the number of repeating units, and 2
Represents the above integer. ) 6. The aromatic vinyl compound according to claim 2, which has a peak observed at 40 to 45 ppm by 13 C-NMR measurement based on TMS.
Ethylene copolymer. 7. 40.4 to 41.0 ppm, 42.3 to 43.3 by 13 C-NMR measurement based on TMS.
6 ppm, 43.0-43.6 ppm, 43.7-4
The aromatic vinyl compound-ethylene copolymer according to claim 2, which has a head-tail chain structure of an aromatic vinyl compound unit assigned by a peak observed at 4.5 ppm. 8. A 42.3 to 43.6 ppm, 43.7 to 44.3 ppm by 13 C-NMR measurement based on TMS.
The aromatic vinyl compound-ethylene copolymer according to claim 2, which has a head-tail chain structure of an aromatic vinyl compound unit assigned by a peak observed at 5 ppm. 9. An aromatic vinyl compound unit having a head-tail chain structure is 0.1% or more of the total amount of aromatic vinyl compound units contained in the copolymer, and the aromatic vinyl compound content is 1 mol. 3. The aromatic vinyl compound-ethylene copolymer according to claim 2, wherein the amount is at least 30% by mole. 10. A polystyrene equivalent weight average molecular weight of 1
The aromatic vinyl compound-ethylene copolymer according to claim 1, which has a molecular weight distribution (Mw / Mn) of 6 or less and 6 or less. 11. The method for producing an aromatic vinyl compound-ethylene copolymer according to claim 1, wherein the production is carried out using a polymerization catalyst comprising a metallocene compound and a cocatalyst.