JP3506147B2 - Ethylene / α-olefin copolymer and thermoplastic resin composition containing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel ethylene / α-olefin copolymer and a thermoplastic resin composition containing the same, more specifically, ethylene and 3 to 20 carbon atoms.
It is derived from the α-olefin of the above, and the activation energy of the melt flow can be controlled, the processing characteristics are excellent, and the physical properties such as density, melting point, and crystallinity can be controlled. The present invention relates to an ethylene / α-olefin copolymer having various characteristics such as being capable of modification, and a thermoplastic resin composition containing the same.

[0002]

2. Description of the Related Art Conventionally, polyethylene and ethylene-α-olefin copolymers have been prepared by adding a third component such as molecular weight, molecular weight distribution, copolymerizability (randomness, blockiness, branching degree distribution) and diene. The primary structure has been controlled by introducing branches. By the way, there are various molding methods of ethylene polymers, and as typical molding methods, for example, injection molding, extrusion molding, blow molding, inflation molding, compression molding, vacuum molding and the like are known. In such a molding method, in order to improve the processing characteristics and reduce the processing cost, attempts have been made for many years to impart high-speed moldability and to reduce the energy of the molding process, which is suitable for each application. It is an important issue to give optimum physical properties and mold with optimum processing characteristics.

In recent years, homogeneous metallocene catalysts have been
It was revealed that the copolymerization property between olefins is excellent, the molecular weight distribution of the obtained polymer is narrow, and the catalyst activity is extremely high as compared with conventional vanadium catalysts. Therefore, it is expected that such characteristics will be applied to various fields of application. On the other hand, however, the polyolefin obtained from the metallocene catalyst has many problems in its molding and processing characteristics, and has a drawback in that it cannot avoid restrictions during blow molding and inflation molding.

Conventionally known low density polyethylene (L
DPE) is obtained by high-pressure radical polymerization of ethylene, and has a structure having both long-chain branch and short-chain branch. It is said that the long-chain branch is formed by an intermolecular hydrogen transfer reaction between the radical-growing terminal of the polymer and the polymer. On the other hand, various explanations have been made on the mechanism of forming short chain branches. For example, a back-biting mechanism has been proposed [J. Am. Chem. Soc.] Vol. 75, "Journal of American Chemical Society".
Page 6110 (1953)]. This is a rational explanation for the formation of butyl branches by hydrogen transfer via a 6-membered ring intermediate at the terminal of the growing radical. In addition, butyl branching occurs again due to hydrogen transfer reaction at the terminal of the growing radical with the ethylene 2-molecule association produced under high pressure.
It has been reported that ethyl branching is introduced by the production of butene-1 by hydrogen transfer reaction in the molecular association [Makromol. Che.
m.) "Vol. 181, 2811 (1981)
Year)〕. Furthermore, it has been reported that the formation of ethyl branches is due to hydrogen transfer from the polymer main chain to ethyl branched radicals [Journal of Polymer Science (J. Polym. Sci.) Vol. 34, Vol. Page 569 (1
959)].

As described above, the formation of long-chain branch or short-chain branch of low-density polyethylene is based on radical polymerization (1) hydrogen transfer reaction, and (2) change in radical polymerization reactivity due to ethylene molecule association under high pressure. It is a generally accepted reaction mechanism. Therefore, in the above reaction process, it is impossible to arbitrarily control the abundance of long-chain branch or short-chain branch, and the number of carbon atoms of the short-chain branch, especially methyl branch, propyl branch, hexyl branch, and branched α-
There is a limitation in introducing or controlling a short chain branch derived from an olefin (for example, 4-methylpentene-1 branch). Such low-density polyethylene has excellent melt-tension and melt-flow activation energy due to long-chain branching, and thus has excellent high-speed moldability and is suitable for films and the like, but has a wide molecular weight distribution and low molecular weight components. To include,
It has the drawbacks of low environmental stress crack resistance (ESCR) and low impact resistance.

On the other hand, various ethylene polymers in which a long-chain branch is introduced into a high-density polyethylene skeleton have been disclosed.
For example, (1) an α, ω-diene, an olefin-based copolymer having a long chain branch using a cyclic endomethylene-based diene (JP-A-47-34981), (2) a non-conjugated diene and an olefin When the copolymerization is carried out, the polymerization is carried out in two steps, and a method for producing a copolymer in which the content of non-conjugated diene in the high molecular weight part is higher than that in the low molecular weight part (JP-A-59-5
6412), (3) ethylene / α-olefin / 1,5-using a metallocene / aluminoxane catalyst.
Hexadiene copolymer (Japanese Patent Publication No. 1-501555), (4) Copolymerizing α, ω-dienes with ethylene using a zero-valent or divalent nickel compound and a specific aminobis (imino) compound as a catalyst. According to the method of introducing a long-chain branch (JP-A-2-261809), (5) a short-chain branched long-chain branch obtained by polymerizing only ethylene using the same catalyst component as in (4) above. Polyethylene containing both (JP-A-3-277610) is disclosed.

However, in the above-mentioned copolymer (1), the diene component is involved in the formation of long-chain branching, and at the same time, a crosslinking reaction is simultaneously generated to generate a gel at the time of film formation, and the melting property is reversed. However, the control range is extremely narrow, the copolymerization reactivity is low, and there are problems such as deterioration of physical properties due to the formation of low molecular weight substances. In the method for producing a copolymer of (2), since the long-chain branch is introduced into the high-molecular weight component, the increase in the molecular weight due to cross-linking is remarkable, and insolubilization and gelation may occur at the same time. Small,
Copolymerization reactivity is also low, and there are problems such as deterioration of physical properties due to formation of low molecular weight substances. Further, the copolymer (3) has a narrow molecular weight distribution and is disadvantageous for blow molding, film molding, etc., and also forms a branch point due to the progress of cyclization reaction of 1,5-hexadiene. There are drawbacks such as low effective monomer concentration. Furthermore, the method (4) of introducing long chain branching has problems such as gel generation and a narrow control range of physical properties. Further, the polyethylene (5) is a polymer containing no ethyl branch or butyl branch, and since physical properties such as density are controlled by the methyl branch, there is a problem that mechanical properties tend to deteriorate. is doing.

In addition, a method for producing an ethylene-based polymer imparted with a processing property by a copolymerization method, for example, a high molecular weight product ([η] = 10 to 20 deciliter / g) is produced by prepolymerization, and then ethylene is produced by main polymerization. A method for producing a / α-olefin copolymer has been disclosed (Japanese Patent Laid-Open No. Hei 4 (1998) -19984).
-55410 publication). However, in this method, although the melt characteristics of the obtained copolymer are changed and the melt tension is increased, there is a drawback that film gel is likely to occur. Furthermore, an ethylene-based polymer using a metallocene-based catalyst and a method for producing the same, for example, (1) a method for producing an ethylene-based polymer using a constrained geometry type catalyst, and an ethylene-based copolymer obtained by the method (Japanese Patent Laid-Open No. HEI 3) -163088), and (2) a method for producing a polyolefin by a supported metallocene catalyst using a porous inorganic oxide (aluminum compound) as a carrier (JP-A-4-100808).

However, in the above technique (1), the ethylene polymer obtained is said to exhibit non-Newtonian properties, but it is still insufficient, and L-LDPE,
Has sufficient mechanical properties in the density range of HDPE,
At the same time, there is a problem that a large restriction cannot be escaped in order to give processing characteristics. Moreover, in the manufacturing method of (2),
The copolymer of ethylene and α-olefin obtained is said to have a large die swell ratio, but when the relationship of the die swell ratio to the melting point of the ethylene / butene-1 copolymer disclosed herein is examined, the melting point is It is clear that the die swell ratio decreases with increasing. Therefore, it is not possible to provide a copolymer in which the die swell ratio related to neck-in, which is a problem when forming a film or sheet, is controlled in a wide melting point range.

[0010]

Under these circumstances, the present invention is capable of controlling the activation energy of melt flow, is excellent in processing characteristics, and has excellent density, melting point, crystallinity, and the like. It has the characteristics that the physical properties can be controlled and that various modifications using terminal vinyl groups are possible, and it can be used for ordinary high-density polyethylene (HDPE), linear low-density polyethylene (L-LDPE) and LDPE. The purpose of the invention is to provide a novel ethylene / α-olefin copolymer different from the above.

[0011]

DISCLOSURE OF THE INVENTION The present inventors have conducted extensive studies to develop a novel ethylene / α-olefin copolymer having the above-mentioned preferable properties, and as a result, they have been derived from ethylene and α-olefin. It was done, 135
The specific relationship is the ratio of the Huggins constant of a linear ethylene polymer that is soluble in decalin at ℃, does not contain at least quaternary carbon in the main chain skeleton, and has the same intrinsic viscosity [η] as the copolymer. And an ethylene / α-olefin copolymer obtained by hydrogenating a carbon-carbon unsaturated bond containing a terminal vinyl type unsaturated bond in this ethylene / α-olefin copolymer. It has been found that coalescence can meet its purpose. The present invention has been completed based on such findings.

That is, according to the present invention, ethylene and 3 carbon atoms are used.
In a copolymer derived from an α-olefin of 20 to 20 by a linear ethylene polymer having the same intrinsic viscosity [η] and a decalin solvent of the copolymer, the Huggins constant (k ) Ratio of the formula 1.12 <k ¹ / k ² ≦ 5 (where k ¹ is the Huggins constant of the copolymer and k ² is the Huggins constant of the linear ethylene polymer). An ethylene / α-olefin copolymer characterized by satisfying and containing no quaternary carbon in the polymer main chain, and a carbon containing a terminal vinyl type unsaturated bond in the ethylene / α-olefin copolymer An ethylene / α-olefin copolymer obtained by hydrogenating a carbon unsaturated bond, and a thermoplastic resin composition containing these ethylene / α-olefin copolymers are provided.

The ethylene / α-olefin copolymer of the present invention does not contain quaternary carbon in at least the polymer main chain,
It has a relatively large Huggins constant and is soluble in a decalin solvent at a temperature of 135 ° C.
Different from L-LDPE and LDPE. This difference can be determined by the following (A) primary structure evaluation and (B) physical property evaluation.

(A) Judgment by evaluation of primary structure Comparison with HDPE, L-LDPE and LDPE ¹³ C-nuclear magnetic resonance spectrum measurement shows that at least HDPE, L-LDPE and LDPE have different structures. . (A) Comparison with HDPE (relatively low molecular weight substance) Ordinary HDPE (relatively low molecular weight substance) has a terminal structure

[0015]

[Chemical 1]

A: 13.99, B: 22.84, C: 30.0
0, D: 32.18 (unit: ppm) (however, A, B, D
Is a slight peak. ), And there is no peak due to branching. (B) Comparison with ethylene / α-olefin copolymer (ethylene-butene-1 copolymer) ethylene-butene-
The 1-copolymer has a structure near the branch point,

[0017]

[Chemical 2]

A: 11.14, B: 26.75, C: 27.3
5, D: 30.00, E: 30.49, F: 34.11, G:
It has a structure represented by 39.75 (unit: ppm). (Ethylene-hexene-1 copolymer) The ethylene-hexene-1 copolymer has a structure in the vicinity of the branch point,

[0019]

[Chemical 3]

A: 4.08, B: 23.36, C: 27.3
3, D: 29.57, E: 30.00, F: 30.51, G:
34.22, H: 34.61, I: 38.23 (unit: ppm)
It has a structure represented by (Ethylene / 4-methylpentene-1 copolymer) The ethylene / 4-methylpentene-1 copolymer has a structure in the vicinity of a branch point.

[0021]

[Chemical 4]

A: 23.27, B: 26.05, C: 27.1
4, D: 30.00, E: 30.51, F: 34.88, G:
36.03, H: 44.83 (unit: ppm). (Ethylene / octene-1 copolymer) The ethylene / octene-1 copolymer has a structure in the vicinity of the branch point,

[0023]

[Chemical 5]

A: 4.02, B: 22.88, C: 27.2
8, D: 27.33, E: 30.00, F: 30.51, G:
32.20, H: 34.59, I: 38.25 (unit: ppm)
It has a structure represented by (Ethylene / Propylene Copolymer) The ethylene / propylene copolymer has a structure near the branch point

[0025]

[Chemical 6]

A: 19.98, B: 27.47, C: 30.0
It has a structure represented by 0, D: 33.31, E: 37.59 (unit: ppm). The above ethylene / α-olefin copolymer has short chain branches derived from α-olefin and does not have long chain branches.

(C) Comparison with LDPE The ¹³ C-NMR spectrum of LDPE is complicated, and short-chain branches (ethyl, butyl branches) and long-chain branches (at least hexyl branches or more) are present. It is considered that the structure near the point mainly has the following structures (a) to (e). (A) Isolated branch (Bn)

[0028]

[Chemical 7]

(B) Ethyl-ethyl (1,3) branch (peq) bonded to a tertiary carbon

[0030]

[Chemical 8]

(C) Isolated ethyl-ethyl (1,3)
Branch

[0032]

[Chemical 9]

(D) Isolated ethyl-propyl (1,
3) Branch (pep)

[0034]

[Chemical 10]

(E) Isolated methyl-ethyl (1,4)
Branch (pme)

[0036]

[Chemical 11]

LDPE is considered to mainly have the structures of (a) to (e) above, and identifications corresponding to these have been made ["Macromolecules (Macromolecules)".
s) ", Vol. 17, p. 1756 (1984)]. According to this document, the identification was made as shown in Table 1, and long-chain branching of at least hexyl branching (32.18 pp
The presence of m) and an ethyl branch has been confirmed, and an additional 10
There is absorption indicating the presence of quaternary carbon in the region of ppm or less.

[0038]

[Table 1]

By ¹³ C-nuclear magnetic resonance spectrum,
Attempts to confirm the presence of long-chain branches A method for confirming and quantifying the presence of hexyl branches by comparing ethylene / octene-1 copolymers with hexyl branches has been proposed [[Macromolecules (Macromolecules
molecules) ", Volume 14, Page 215 (1981)
, 17: 1756 (1984)
Year)〕. According to them, ¹³ C of the peak appearing in the vicinity of 27.3ppm is, that differ from the peaks appearing in the ethylene / octene-1 copolymer, a blend of LDPE
-It is said that it was clarified from the measurement of the nuclear magnetic resonance spectrum. Further, in normal C ₃₆ H ₇₄ used as a model substance for long chain branching, the third carbon signal from the end is 32.
Appears at 18 ppm. On the other hand, ethylene / octene-1
From the end of the hexyl branch of the copolymer, the third carbon signal appears at 32.22 ppm. Taking advantage of the difference in chemical shift depending on the branch chain length, ethylene / octene-1 copolymer and LDPE with long chain branch are blended, and ¹³ C-nuclear magnetic resonance spectrum is measured, and two peaks appear. Therefore, the long chain branch of LDPE can be identified and quantified. By such a method, it was confirmed that LDPE has long chain branching.

(B) Judgment by Evaluation of Physical Properties Method by Analysis of Melt Fluid The long chain branching is involved in the flow behavior of the melt such as melt viscosity and viscoelastic property, and the processability of the resin, optical properties, or
It is known that important influences are exerted on mechanical properties such as environmental stress crack resistance, and their existence can be indirectly revealed by measuring and evaluating them.
In addition, the following facts can be cited as the reason for backing the existence of long chain branching. The relationship between MI-Mw of LDPE is
As the number of long-chain branches increases, linear polyethylene (HDP
Deviation from the relationship of E), that is, LDPE shows smaller MI at the same Mw. In addition, the activation energy (Ea) obtained from the shift factor was examined using HDPE.
Is as small as 6 kcal / mol, while LDPE is about 1
Since it is as large as 2 kcal / mol, it can be confirmed that the fluidity is affected by long chain branching. The analysis of such a melt fluid strongly suggested that the polyethylene of the present invention has a long chain branch.

Identification by analysis of polymer solution (a) Judgment by Huggins Coefficients Reduced viscosity η _sp / c (deciliter / g), intrinsic viscosity [η] (deciliter / g), Huggins constant k and polymer It is known that the relationship between the concentration c (g / deciliter) and the general formula (Huggins' formula) η _sp / c = [η] + k [η] ² C is established. The Huggins constant k is a value indicating the intermolecular interaction of the polymer in a dilute solution state, and is considered to be influenced by the molecular weight of the polymer, the molecular weight distribution, and the presence of branches. Introducing branching into the polymer structure has been shown to increase the Huggins constant in styrene / divinylbenzene copolymers [Journal of Polymer Sanence (J. Pol.
ymer Sci.) ", Volume 9, Page 265 (1952)
Year)〕. In addition, LDPE having a long chain branch and linear HDP
It has been shown that the Huggins constant of E is large in LDPE ["Polymer Handbook"]
Published by John Wiley Sons (1975)].

It has been confirmed that the ratio of the Huggins constant of the ethylene / α-olefin copolymer of the present invention to the Huggins constant of the linear ethylene polymer having the same intrinsic viscosity has the following relational expression. There is. (B) Judgment based on the relationship between the intrinsic viscosity [η] and the molecular weight obtained by gel permeation chromatography or light scattering method The intrinsic viscosity [η] determined from a dilute solution of polyethylene and the solute height by using the above Huggins equation and the like. The relationship with the molecular weight by gel permeation chromatography (GPC) method or light scattering method, which determines the molecular weight according to the size of the molecule, is
It is known to reflect the branched structure of macromolecules. For example, the relationship between the intrinsic viscosity of linear HDPE and the molecular weight by the GPC method is different from that of LDPE having a long chain branch,
When compared at the same intrinsic viscosity, LDPE has been shown to show a lower molecular weight than HDPE.

Next, the characteristics of the ethylene / α-olefin copolymer of the present invention will be described. Ethylene of the present invention /
The α-olefin copolymer is soluble in a decalin solvent at a temperature of 135 ° C. Since the copolymer does not become insoluble and infusible over a wide density range and does not contain gel,
It is dissolved in decalin at a temperature of 135 ° C. In addition, it exhibits good solubility in aromatic hydrocarbons (such as tetrachlorobenzene) and high-boiling point hydrocarbons other than decalin during normal heating. LDPE obtained by high pressure radical polymerization
In the above, in view of the formation mechanism, formation of a part of gel is observed.

Further, the ethylene / α-olefin copolymer of the present invention does not contain at least quaternary carbon in the main chain skeleton, and is different from the high pressure method LDPE. Furthermore, in the Huggins constant (k) determined by the relationship between the polymer concentration and the reduced viscosity measured at a temperature of 135 ° C. in a decalin solvent, the ethylene / α-olefin copolymer of the present invention is identified by the following ratio of Huggins constants. To be done.
That is, in the linear ethylene polymer having the same intrinsic viscosity [η] measured in a decalin solvent at a temperature of 135 ° C. and the ethylene / α-olefin copolymer of the present invention, the ratio of their Huggins constants (k) is Where, 1.12 <k ¹ / k ² ≦ 5 (where k ¹ is the Huggins constant of the ethylene / α-olefin copolymer of the present invention, and k ² is the Huggins constant of the linear ethylene polymer). ) Ethylene / α-
It is an olefin copolymer. Also, this ratio k ¹ / k
² is preferably 1.13 ≦ k ¹ / k ² ≦ 4.0, more preferably 1.14 ≦ k ¹ / k ² ≦ 3.7, still more preferably 1.15 ≦ k ¹ / k ² ≦ 3.6. Most preferably, the relationship of 1.18 ≦ k ¹ / k ² ≦ 3.4 is satisfied.

Further, the specific examples of the linear ethylene polymer shown here are the ethylene polymers currently produced on an industrial scale, or the above polymers produced at a laboratory level. As a manufacturing method, a normal Ziegler-based catalyst,
For example, a catalyst mainly composed of a combination of a transition metal compound such as titanium, zirconium, hafnium or chromium compound and an organometallic compound such as triethylaluminum or tributylaluminum, especially an organoaluminum compound is used. Also, magnesium compounds,
The above catalyst system using a silicon compound as a carrier is also included in this production method. Also, the control of the intrinsic viscosity [η] is
It can be controlled by hydrogen, polymerization temperature, monomer charge, catalyst amount, etc.

The measurement was carried out in a decalin solvent at a temperature of 135 ° C.
The determined intrinsic viscosity [η] is the ethylene / α-ole of the present invention.
Obtained with a Ziegler-based catalyst that is identical to the fin copolymer
Of linear ethylene / α-olefin copolymer
Constant k³And the ethylene / α-olefin of the present invention
Huggins constant k of the copolymer¹And above k³Ratio k ¹
/ K³In the case of 1.02 <k¹/ K³≤5.0 Preferably 1.03 <k¹/ K³≦ 4 More preferably 1.04 <k¹/ K³≤3.5 More preferably 1.05 <k¹/ K³≤3.2 Most preferably 1.06 <k¹/ K³≤3.0 Meet the relationship. From this point as well, the conventional ethylene-α-
It is also different from the olefin copolymer. Furthermore, the ratio
The above linear ethylene / α-olefin copolymer used for comparison
Α-olefin species and α-olefin copolymerization group in the body
Effect on the Huggins constant is relatively small, but the same
To compare with the same resin density using α-olefin species
desirable.

The intrinsic viscosity [η] and the Huggins constant k in the above relational expressions can be obtained as follows. That is, between the reduced viscosity η _sp / c (deciliter / g), the intrinsic viscosity [η] (deciliter / g), the Huggins constant k and the polymer concentration c (g / deciliter), as described above, the Huggins equation η It is known that the relationship of _sp / c = [η] + k [η] ² c holds. So first,
Reduced viscosity η _{SP / c} , solvent: decalin, polymer concentration: 2.
0 g / deciliter or less, measurement temperature: 135 ° C ± 0.01
Measure at 5 ° C or higher at 5 ° C, at approximately equal intervals of polymer concentration, and in a viscosity tube: Ubbelohde type condition. Regarding the measurement accuracy, the relative viscosity was measured within the range of 1.1 or more at each measurement point, the relative viscosity was within ± 0.04%, and the number of measurements at each polymer concentration was 5 times or more. Is. Also,
The measurement point on the lowest concentration side needs to be 45% or less of the concentration on the measurement point on the highest concentration side.

The above method can determine the Huggins constant only when the relationship between the reduced viscosity and the polymer concentration is clearly linear. If the linear relationship cannot be obtained, the cause is that the polymer concentration is high or the molecular weight is large, and therefore it is necessary to reduce the polymer concentration and measure again. However, if the polymer concentration is extremely reduced, there may be a region where the reduced viscosity does not depend on the polymer concentration and a region where the reduced viscosity increases as the polymer concentration decreases. In this region, the Huggins constant should be calculated. I can't. Also, when another measurement point when the measurement point with the highest concentration (C _n ) and the measurement point with the lowest concentration (C ₁ ) are connected by a straight line is clearly present below,
The Huggins constant cannot be calculated in this region. However, this is not the case if the following conditions are met.
That is, whether or not the linear relationship is established is determined as follows. In FIG. 1, the highest concentration measurement point (C _n ) and the lowest concentration measurement point (C ₁ ) are connected by a straight line. Furthermore, each measurement point is regressed with a smooth curve.
Here, the most distant distance between the straight line and the curve ([η _sp / c] ^H −
[Η _sp / c] ^L ) is calculated and ([η _sp / c] ^H − [η _sp /
determining a straight line with the c] ^L) / [C _n -C _1] is 0.001 or less.

The ethylene / α-olefin copolymer of the present invention may be any one having the above-mentioned characteristics, and more preferably, the activation energy (Ea) of its melt flow is 8 to. 20 kcal / mol, more preferably 8.5-19 kcal / mol, particularly preferably 9-1
It is in the range of 8 kcal / mol. If the activation energy (Ea) of the melt flow is less than 8 kcal / mol, sufficient processing characteristics tend not to be obtained. The activation energy (Ea) of the melt flow is 1
Frequency dependence of dynamic viscoelasticity at 70 ° C, 190 ° C, 210 ° C and 230 ° C (10 ^-2 to 10 ^-2 rod / se
c) is measured, and the value is calculated by the Arrhenius equation from the reciprocal of the shift factors of G ′ and G ″ and the absolute temperature at each temperature using 170 ° C. as the reference temperature and the temperature-time conversion rule.

The ethylene / α-olefin copolymer of the present invention having such characteristics usually has the following properties. That is, the resin density (D) is usually 0.86 to
0.97 g / cm ³ , preferably 0.865 to 0.960 g /
cm ³ , more preferably 0.870 to 0.955 g / cm ^3.
Is the range. The density is a value obtained by forming a press sheet at a temperature of 190 ° C., quenching it, and measuring it with a density gradient tube. In addition, the differential scanning calorimeter (DS
The melting point (Tm) observable by C) is usually 50 to 1
37 ° C, preferably 55 to 136 ° C, more preferably 5
It is in the range of 8 to 135 ° C., and also includes an ethylene / α-olefin copolymer that does not substantially show a melting point (Tm) under the measurement conditions described later. Furthermore, the crystallization enthalpy (ΔH) observable by the DSC usually satisfies the relation of 0 ≦ ΔH ≦ 250. The enthalpy of crystallization was measured by using a DSC (manufactured by Perkin Elmer, DSC7 type) at a temperature of 190 ° C.
After melting at 0 ° C for 5 minutes, -50 at a rate of 10 ° C / minute
It is a value obtained from the exothermic peak of crystallization observed when the temperature is lowered to ℃, and the melting point is a value obtained from the temperature at the maximum peak position of the endothermic peak of melting when the temperature is further raised at a rate of 10 ° C / min. Is.

Further, in the ethylene / α-olefin copolymer of the present invention, a gel permeation chromatograph (GPC) method [apparatus: Waters ALC / GPC]
150C, column: Tosoh product, TSK HM + GMH
6 × 2, flow rate 1.0 ml / min, solvent: 1, 2, 4
The ratio Mw / Mn between the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polyethylene measured by trichloropentene, 135 ° C.] is usually in the range of 2.0 to 150, depending on the molding and the purpose. You can control. On the other hand, the intrinsic viscosity [η] measured in decalin at a temperature of 135 ° C. is usually 0.01 to 20 deciliter / g, preferably 0.05 to
It is in the range of 17 deciliter / g, more preferably 0.1 to 15 deciliter / g. If this [η] is less than 0.01 deciliter / g, the mechanical properties will not be sufficiently expressed, and if it exceeds 20 deciliter / g, the processing characteristics will deteriorate.

Further, in the ethylene / α-olefin copolymer of the present invention, a vinyl type unsaturated group is usually present at the molecular end, and the unsaturated group is pressed at a temperature of 190 ° C. (thickness 100). .About.500 .mu.m) and measuring the infrared absorption spectrum of this product, it can be easily identified and quantified. Type of terminal unsaturated group Absorption position (cm ⁻¹ ) Vinylene group 963 Vinylidene group 888 Vinyl group 907 In the ethylene / α-olefin copolymer, the generation ratio of the terminal vinyl group is relative to the total amount of the unsaturated groups. , Usually 3
It is 0 mol% or more, preferably 40 mol% or more, more preferably 50 mol% or more. The amount of the terminal vinyl group is represented by the formula n = 0.114A ₉₀₇ / [D · t] (where n is the number of terminal vinyl groups per 100 carbons, A ₉₀₇ is the absorbance at ₉₀₇ cm ⁻¹ , and D is the resin). The density (g / cm ³ ) and t are the thickness (mm) of the film.

It is generally known that the terminal unsaturated group amount and the molecular weight have a correlation, but in the polyethylene of the present invention, the terminal vinyl type unsaturated content (U),
The reciprocal of the intrinsic viscosity [η] measured in decalin at a temperature of 135 ° C. is usually in the relation of 0 ≦ U ≦ 15 × [η] ⁻¹ , preferably 0 ≦ U ≦ 14 × [η] ^−1. More preferably 0 ≦ U ≦ 13 × [η] ^−1, most preferably 0 ≦ U ≦ 12 × [η] ⁻¹ (where U is the number of terminal vinyl groups per 1000 carbons). Is desirable.

With respect to the ethylene / α-olefin copolymer having a high terminal vinyl group content within the above range, modification of the vinyl group causes the disadvantages of polyolefin such as adhesiveness, printability, paintability, phase and It is possible to add various functions such as solubilization, moisture permeability, and barrier properties, and at the same time, it is expected that processing characteristics based on branching will be improved. Furthermore, it can be used as a branched macromonomer in the production of various graft copolymers. On the other hand, regarding the ethylene / α-olefin copolymer having a small terminal vinyl group content within the above range, the thermal stability is improved, and the processing characteristics based on branching can be expected to be improved. Regarding the addition of functions such as adhesion and printability, ethylene /
Even α-olefin copolymers exhibit sufficient functions by modification in practice. The present invention also provides an ethylene / α-olefin copolymer obtained by hydrogenating a carbon-carbon unsaturated bond containing such a terminal vinyl type unsaturated bond. The ethylene / α-olefin copolymer having the unsaturated group reduced or eliminated has improved thermal stability.

The ethylene / α-olefin copolymer (ethylene / α-olefin copolymer before hydrogenation treatment, ethylene / α-olefin copolymer after hydrogenation treatment) of the present invention is mixed with another thermoplastic resin. Can be used. Examples of other thermoplastic resins include polyolefin-based resins, polystyrene-based resins, condensation-type high-molecular polymers, and addition-polymerization high-molecular polymers. Specific examples of the polyolefin resin include high-density polyethylene; low-density polyethylene; poly-3-methylbutene-1; poly-4-methylpentene-1; butene-1 as a comonomer component; hexene-1; octene-1; 4-methylpentene-1; 3-
Linear low-density polyethylene obtained by using methylbutene-1, etc., ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer , Ethylene-based ionomers, polypropylene and the like. Specific examples of the polystyrene-based resin include general-purpose polystyrene, isotactic polystyrene, and high-impact polystyrene (rubber-modified). Specific examples of the condensation type high molecular weight polymer include polyacetal resin,
Examples thereof include polycarbonate resin, polyamide resin such as nylon 6, nylon 6/6, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polyphenylene oxide resin, polyimide resin, polysulfone resin, polyether sulfone resin, polyphenylene sulfide resin and the like. Examples of the addition polymerization type high molecular weight polymer include, for example, a polymer obtained from a polar vinyl monomer and a polymer obtained from a diene monomer, specifically, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-butadiene copolymer, acrylonitrile. Examples thereof include a butadiene-styrene copolymer, a diene polymer in which a diene chain is hydrogenated, and a thermoplastic elastomer. The thermoplastic resin composition of the present invention,
Other thermoplastic resin or elastomer is blended in an amount of 2 to 500 parts by weight, preferably 3 to 300 parts by weight, based on 100 parts by weight of the ethylene / α-olefin copolymer of the present invention.

The ethylene / α-olefin copolymer (before hydrogenation treatment) of the present invention comprises ethylene and α-C3-20 carbon atoms.
It can be produced by polymerizing an olefin in the presence of a polymerization catalyst such that an ethylene / α-olefin copolymer having the above-mentioned properties can be obtained. The α-olefin having 3 to 20 carbon atoms used here is not particularly limited, but for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1
-Dodecene, 1-tetradecene, 1-hexadecene, 1
Examples include linear α-olefins such as -octadecene and 1-eicosene, branched α-olefins such as 3-methyl-1-butene and 4-methyl-1-pentene, and these may be used alone, or You may use it in combination of 2 or more type. Examples of such a polymerization catalyst include those containing (A) a transition metal compound and (B) a compound capable of forming an ionic complex from the transition metal compound or a derivative thereof as a main component. As the transition metal compound of the component (A) in the catalyst, there are 3 to 1 of the periodic table.
A transition metal compound containing a metal belonging to Group 0 or a lanthanoid series metal can be used. As the transition metal, titanium, zirconium, hafnium, vanadium, niobium, chromium and the like are preferable.

As such a transition metal compound, various compounds can be mentioned, and a compound containing a transition metal of Groups 4, 5 and 6 can be preferably used. In particular the general formulas ^{_{CpM 1 R 1 a R 2 b}} R 3 c ··· (I) Cp 2 M 1 R 1 a R 2 b ··· (II) (Cp-A e -Cp) M 1 R 1 a R ² _b ··· (III) or a compound represented by the general formula ^{_{M 1 R 1 a R 2 b}} R 3 c R 4 d ··· (IV) or its derivative is preferable.

In the above general formulas (I) to (IV), M ¹
Represents a transition metal such as titanium, zirconium, hafnium, vanadium, niobium, and chromium, and Cp represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group. Group, a cyclic unsaturated hydrocarbon group such as a fluorenyl group or a substituted fluorenyl group, or a chain unsaturated hydrocarbon group. R ¹ , R ² , R ³ and R
Each of ⁴ independently represents a σ-bonding ligand, a chelating ligand, a ligand such as a Lewis base. As the σ-bonding ligand, specifically, a hydrogen atom, an oxygen atom, Halogen atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group or arylalkyl group, carbon number 1 to 2
Examples thereof include an acyloxy group of 0, an allyl group, a substituted allyl group, and a substituent containing a silicon atom, and examples of the chelating ligand include an acetylacetonato group and a substituted acetylacetonato group. A indicates crosslinking by covalent bond. a, b, c and d are each independently 0 to 4
, And e is an integer of 0 to 6. Two or more of R ¹ , R ² , R ³ and R ⁴ may combine with each other to form a ring. When Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. In the formulas (II) and (III), the two Cp's may be the same or different from each other.

Substituted cyclohexyl in the above formulas (I) to (III)
Examples of the pentadienyl group include methylcyclopenta
Dienyl group, ethylcyclopentadienyl group; isopro
Pyrcyclopentadienyl group; 1,2-dimethylcyclo
Pentadienyl group; tetramethylcyclopentadienyl
Group; 1,3-dimethylcyclopentadienyl group; 1,
2,3-trimethylcyclopentadienyl group; 1,2,
4-trimethylcyclopentadienyl group; pentamethyl
Cyclopentadienyl group; trimethylsilylcyclopen
Examples thereof include a tadienyl group. In addition, the above (I)
R in formula (IV) ¹~ R^FourFor example,
Fluorine atom, chlorine atom, bromine atom as halogen atom,
Iodine atom, methyl as an alkyl group having 1 to 20 carbon atoms
Group, ethyl group, n-propyl group, isopropyl group, n-
Butyl group, octyl group, 2-ethylhexyl group, carbon number
Methoxy group and ethoxy as the alkoxy group of 1 to 20
Group, propoxy group, butoxy group, phenoxy group, carbon number
6 to 20 aryl groups, alkylaryl groups or
Phenyl group, tolyl group, xylyl as reel alkyl group
Group, benzyl group, and acyloxy group having 1 to 20 carbon atoms
The heptadecylcarbonyloxy group and silicon atom.
Trimethylsilyl group as a substituent, (trimethylsilyl group
) Methyl group, dimethyl ether as a Lewis base, di-
Ethers such as ethyl ether and tetrahydrofuran
, Thioethers such as tetrahydrothiophene,
Esters such as tylbenzoate, acetonitrile;
Nitriles such as benzonitrile, trimethylamine;
Triethylamine; tributylamine; N, N-dimethyl
Luaniline; pyridine; 2,2'-bipyridine; phena
Amines such as nitroline, triethylphosphine;
Phosphines such as Liphenylphosphine, chain unsaturated
As hydrocarbons, ethylene; butadiene; 1-pente
Isoprene; Pentadiene; 1-Hexene and this
As a derivative thereof, as a cyclic unsaturated hydrocarbon, benzene;
Ruene; Xylene; Cycloheptatriene; Cyclooctane
Tadiene; Cyclooctatriene; Cyclooctatetra
Examples thereof include ene and derivatives thereof. Also, above
Examples of the covalent cross-linking of A in the formula (III) include
For example, methylene bridge, dimethylmethylene bridge, ethylene
Cross-linked, 1,1'-cyclohexylene cross-linked, dimethylsilyl
Lene cross-link, dimethyl germylene cross-link, dimethyl stannile
And cross-linking.

Further, as the component (A), in the general formula (III), two substituted or unsubstituted conjugated cyclopentadienyl groups (provided that at least one is a substituted cyclopentadienyl group). A group 4 transition metal compound having a multicoordinating compound as a ligand, which is bonded to each other via an element selected from group 14 of the periodic table, can be preferably used. Examples of such compounds include those represented by the general formula (V)

[0061]

[Chemical 12]

Examples of the compound represented by
be able to. Y in the general formula (V)¹Is carbon, Kei
Element, germanium or tin atom, R^Five _t-C_FiveH_4-tOver
And R^Five _u-C_FiveH_4-uAre each substituted cyclopentadiene
The nyl group, t and u represent an integer of 1 to 4. Where R^Five
Are hydrogen atoms, silyl groups or hydrocarbon groups,
It may be one or different. Also, at least one piece
The other cyclopentadienyl group is Y¹Is bound to
R on at least one carbon next to the carbon^FiveExists.
R⁶Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or carbon
An aryl group of formula 6 to 20, an alkylaryl group or
Indicates an arylalkyl group. M²Is titanium, zirconium
Or a hafnium atom, X¹Is a hydrogen atom, halogen
Atom, alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Aryl group, alkylaryl group or aryl group of
It shows a alkyl group or an alkoxy group having 1 to 20 carbon atoms. X
¹R may be the same or different from each other, and R⁶Also
They may be the same or different from each other.

Examples of the substituted cyclopentadienyl group in the above general formula (V) include methylcyclopentadienyl group; ethylcyclopentadienyl group; isopropylcyclopentadienyl group; 1,2-dimethylcyclopentadienyl group. Group; 1,3-dimethylcyclopentadienyl group; 1,2,3-trimethylcyclopentadienyl group;
Examples include 1,2,4-trimethylcyclopentadienyl group. Specific examples of X ¹ include F, Cl, Br, I as a halogen atom, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an octyl group as an alkyl group having 1 to 20 carbon atoms, 2-ethylhexyl group, methoxy group as an alkoxy group having 1 to 20 carbon atoms,
Examples of the ethoxy group, propoxy group, butoxy group, phenoxy group, aryl group having 6 to 20 carbon atoms, alkylaryl group or arylalkyl group include phenyl group, tolyl group, xylyl group and benzyl group. Specific examples of R ⁶ include a methyl group, an ethyl group, a phenyl group, a tolyl group, a xylyl group and a benzyl group. Furthermore, general formula (VI)

[0064]

[Chemical 13]

The compounds represented by are also included. The general formula
In the compound of (VI), Cp is cyclopentadienyl
Group, substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, tetrahydroindenyl group, substituted tetra
Hydroindenyl group, fluorenyl group or substituted fluorescein
Cyclic unsaturated hydrocarbon group such as nyl group or chain unsaturated carbonization
Indicates a hydrogen group. M³Is titanium, zirconium or hafni
X represents a um atom²Is hydrogen atom, halogen atom, carbon
C1-C20 alkyl group, C6-C20 aryl
Group, alkylaryl group or arylalkyl group, or
Represents an alkoxy group having 1 to 20 carbon atoms. Z is Si
R⁷ ₂, CR⁷ ₂, SiR⁷ ₂SiR⁷ ₂, CR⁷ ₂CR⁷ ₂, CR
⁷ ₂CR⁷ ₂CR⁷ ₂, CR⁷= CR⁷, CR⁷ ₂SiR⁷ ₂Or
GeR⁷ ₂Indicates Y ²Is -N (R⁸)-, -O-, -S-
Or -P (R⁸) -Indicates. R above⁷Is a hydrogen atom or 2
Alkyl, aryl, silyl having up to 0 non-hydrogen atoms
And alkyl halides, aryl halides and
R is a group selected from these combinations,⁸Has 1 to 1 carbon atoms
An alkyl group having 10 or an aryl group having 6 to 10 carbon atoms
Yes, or one or more R⁷And up to 30
May form a fused ring system of non-hydrogen atoms. w is 1 or
2 is shown.

The ethylene / α-olefin copolymer of the present invention can be obtained by various production methods, and the method is not particularly limited, but it can be obtained by selecting these catalysts and polymerization conditions. As the catalyst in this case, an alkoxytitanium compound or a titanium or zirconium compound having a crosslink between ligands is preferably used. In the polymerization catalyst used in the present invention, the transition metal compound as the component (A) may be used alone or in combination of two or more kinds. On the other hand, in the polymerization catalyst, as the compound used as the component (B), a compound capable of forming an ionic complex from the transition metal compound of the component (A) or a derivative thereof is (B-
1) An ionic compound that reacts with the transition metal compound of the component (A) to form an ionic complex, and (B-2) an aluminoxane. As the compound of the component (B-1), any compound can be used as long as it can react with the transition metal compound of the component (A) to form an ionic complex. A compound composed of an anion bonded to an element, particularly a coordination complex compound composed of a cation and an anion having a plurality of groups bonded to the element can be preferably used. As a compound composed of such a cation and an anion in which a plurality of groups are bound to an element, a compound represented by the general formula ([L ¹ -R ⁷ ] ^{k +} ) _p ([M ⁴ Z ¹ Z ² ·· Z ⁿ ] ^{(hg) -} ) _Q ·· (VII) or ([L ² ] ^{k +} ) _p ([M ⁵ Z ¹ Z ² ·· Z ⁿ ] ^(hg)- ) _q ·· (VIII) (where L ² is M ⁶ , R ⁸ R ⁹ M ⁷ , R ¹⁰ ₃ C or R ¹¹
M ⁷ ), where L ¹ is a Lewis base, M ⁴ and M ⁵
Are the 5th, 6th, 7th, 8th-10th groups of the periodic table,
Elements selected from Groups 11, 12, 13, 14, and 15, preferably elements selected from Groups 13, 14 and 15, M ⁶ and M ⁷ are Group 3 and 4 of the periodic table, respectively.
Tribe, five, six, seven, eight to ten, one, eleven, two
An element selected from Group 12, Group 12 and Group 17, Z ^{1 to} Z ⁿ are a hydrogen atom, a dialkylamino group, and a carbon number of 1 to 2, respectively.
0 alkoxy group, C6-20 aryloxy group, C1-20 alkyl group, C6-20 aryl group, alkylaryl group, arylalkyl group,
C1-C20 halogen-substituted hydrocarbon group, C1-C1
20 represents an acyloxy group, an organic metalloid group or a halogen atom, and two or more of Z ^{1 to} Z ⁿ may be bonded to each other to form a ring. R ⁷ is a hydrogen atom, having 1 to 1 carbon atoms
20 alkyl group, aryl group having 6 to 20 carbon atoms, alkylaryl group or arylalkyl group, wherein R ⁸ and R ⁹ are cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group or fluorenyl group,
R ¹⁰ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ¹¹ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. g is an valence of M ⁴ and M ⁵ and is an integer of 1 to 7, h is an integer of 2 to 8 and k is [L ¹ -R ¹⁶ ],
The ion valence of [L ² ] is an integer of 1 to 7, p is an integer of 1 or more, and q = (p × k) / (h−g). ) Is a compound represented by.

Specific examples of the Lewis base represented by L ¹ are ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, tri-n-butylamine, N. , N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N
-Amines such as dimethylaniline, phosphines such as triethylphosphine, triphenylphosphine and diphenylphosphine, ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, dioxane, thioethers such as diethylthioether and tetrahydrothiophene, ethylbenzoate And the like.

Specific examples of M ⁴ and M ⁵ are:
B, Al, Si, P, As, Sb, etc., preferably B or P, M ⁶ are exemplified by Li, Na, Ag, C.
Specific examples of M ⁷ , such as u, Br, and I, include Mn and F.
e, Co, Ni, Zn, etc. may be mentioned. Specific examples of Z ^{1 to} Z ⁿ include, for example, a dimethylamino group as a dialkylamino group; a diethylamino group, a methoxy group, an ethoxy group, an n-butoxy group, and a carbon number of 6 to 20 as an alkoxy group having 1 to 20 carbon atoms. Phenoxy group as an aryloxy group; 2,6-dimethylphenoxy group; naphthyloxy group, methyl group as an alkyl group having 1 to 20 carbon atoms;
Ethyl group; n-propyl group; isopropyl group; n-butyl group; n-octyl group; 2-ethylhexyl group, aryl group having 6 to 20 carbon atoms; phenyl group as an alkylaryl group or arylalkyl group; p-tolyl group Benzyl group; 4-t-butylphenyl group; 2,6-dimethylphenyl group; 3,5-dimethylphenyl group; 2,4-
Dimethylphenyl group; 2,3-dimethylphenyl group; p-fluorophenyl group as halogen-substituted hydrocarbon group having 1 to 20 carbon atoms; 3,5-difluorophenyl group; pentachlorophenyl group; 3,4,5-trifluoro group Phenyl group; pentafluorophenyl group; 3,5-di (trifluoromethyl) phenyl group, F, C as halogen atom
1, Br, I, pentamethylantimony group as organic metalloid group, trimethylsilyl group, trimethylgermyl group,
Examples thereof include diphenylarsine group, dicyclohexylantimony group, and diphenylboron group. Specific examples of R ⁷ and R ¹⁰ are the same as those mentioned above.
Specific examples of the substituted cyclopentadienyl group for R ⁸ and R ⁹ include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. To be Here, the alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups is an integer of 1 to 5. Among the compounds represented by the general formulas (VII) and (VIII), those in which M ⁴ and M ⁵ are boron are preferable. As the component (B-1), a compound that reacts with the transition metal compound of the component (A) to form an ionic complex may be used alone or in combination of two or more. Further, the component composed of the transition metal compound of the component (A) and the compound capable of forming an ionic complex of the component (B-1) may be a polycation complex. On the other hand, the aluminoxane as the component (B-2) is represented by the general formula (IX)

[0069]

[Chemical 14]

(In the formula, R ¹² is an alkyl group, an alkenyl group, an aryl group having 1 to 20 carbon atoms, preferably 1 to ¹² carbon atoms,
A hydrocarbon group such as an arylalkyl group, s represents the degree of polymerization, and is generally an integer of 3 to 50, preferably 7 to 40. ) A chain aluminoxane represented by the general formula (X)

[0071]

[Chemical 15]

A cyclic aluminoxane represented by the formula (wherein R ¹² and s are the same as above) can be mentioned. Among the compounds of the general formulas (IX) and (X), aluminoxane having a degree of polymerization of 7 or more is preferable. When the aluminoxane having a degree of polymerization of 7 or more or a mixture thereof is used, high activity can be obtained. Further, modified aluminoxane which is insoluble in a general solvent obtained by modifying the aluminoxane represented by the general formulas (IX) and (X) with a compound having active hydrogen such as water can also be preferably used.

As a method for producing the aluminoxane, there may be mentioned a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other, but the means therefor is not particularly limited, and the reaction may be carried out according to a known method. For example, an organoaluminum compound is dissolved in an organic solvent, a method of contacting it with water, a method of initially adding an organoaluminum compound at the time of polymerization, and a method of subsequently adding water, water of crystallization contained in a metal salt, Method of reacting water adsorbed to an inorganic substance or organic substance with an organoaluminum compound, reaction of tetraalkyldialuminoxane with trialkylaluminum, and further reaction of water, treatment of aluminoxane with water or alcohol, and insolubility in general solvent There is a way to do it. These aluminoxanes may be used alone or in combination of two or more.

In the present invention, as the catalyst component (B), only the component (B-1) may be used, or (B-
The component (2) may be used alone, or the component (B-1) and the component (B-2) may be used in combination. In the polymerization catalyst used in the present invention, if desired, as the component (C), a compound represented by the general formula (XI) R ¹² _r AlQ _3-r ... (XI) (wherein R ¹² is the same as the above, Q represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms or a halogen atom, and r
Is a number from 1 to 3. ) An organoaluminum compound represented by In particular, when a compound which reacts with the transition metal compound of the component (A) shown as the component (B-1) to form an ionic complex is used as the component (B), the organoaluminum compound (C) is used in combination. High activity can be obtained by.

Next, in the present invention, the above (A),
At least one of (B) and the (C) catalyst component used as desired can be used by supporting it on a suitable carrier. The type of the carrier is not particularly limited, and any of an inorganic oxide carrier, other inorganic carriers and organic carriers can be used, but an inorganic oxide carrier or another inorganic carrier is particularly preferable. As the inorganic oxide carrier,
Specifically, SiO ₂ , Al ₂ O ₃ , MgO, Zr
O ₂ , TiO ₂ , Fe ₂ O ₃ , B ₂ O ₃ , CaO, Zn
Examples include O, BaO, ThO ₂ and mixtures thereof, such as silica alumina, zeolite, ferrite, and glass fiber. Among these, especially SiO ₂ , A
1 ₂ O ₃ is preferred. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate and the like.

On the other hand, as an inorganic carrier other than the above, MgC
Examples thereof include magnesium compounds such as l ₂ and Mg (OC ₂ H ₅ ) ₂ and complex salts thereof, and organomagnesium compounds represented by MgR ¹³ _i X ³ _j . here,
R ¹³ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, X ³ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms,
i is 0 to 2, and j is 0 to 2. Examples of the organic carrier include polystyrene, polyethylene, polypropylene, substituted polystyrene, polymers such as polyarylate, starch, and carbon. Here, the properties of the carrier used vary depending on the type and production method, but the average particle size is usually 1 to 300 μm, preferably 10 to
It is 200 μm, more preferably 20 to 100 μm.

When the particle size is small, the amount of fine powder in the polymer increases,
If the particle size is large, coarse particles in the polymer increase, which causes a decrease in bulk density and clogging of the hopper. The specific surface area of the carrier is usually 1 to 1000 m ² / g, preferably 50 to
500 m ² / g, pore volume is usually 0.1-5 cm ³ / g,
It is preferably 0.3 to ³ cm ³ / g. If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and pore volume are
For example, it can be determined from the volume of nitrogen gas adsorbed according to the BET method (Journal of American
See Chemical Society, Volume 60, page 309 (1983)). Further, the carrier is usually 15
It is desirable to use by firing at 0 to 1000 ° C, preferably 200 to 800 ° C. The method of loading on a carrier is not particularly limited, and a conventionally used method can be used.

Next, the use ratio of each catalyst component in the present invention will be described. When (1) (A) component and (B-1) component are used as the catalyst component, (A) component /
The component (B-1) has a molar ratio of 1 / 0.1 to 1/100, preferably 1 / 0.5 to 1/10, and more preferably 1/1 to 1 /.
It is desirable to use both components so as to be in the range of 5.
(2) When the component (A), the component (B-1) and the component (C) are used, the molar ratio of the component (A) / the component (B-1) is the same as the case (1). However, the molar ratio of component (A) / component (C) is 1/2000 to 1/1, preferably 1/10.
It is desirable to be in the range of 00 to 1/5, more preferably 1/500 to 1/10.

When component (3) (A) and component (B-2) are used, the molar ratio of component (A) / component (B-2) is 1/20 to 1/10000, preferably 1/100
To 1/5000, more preferably 1/200 to 1/20
It is desirable to use both components so that they are in the range of 00.
(4) When the component (A), the component (B-2) and the component (C) are used, the molar ratio of the component (A) / the component (B-2) is the same as the case (3). However, the molar ratio of component (A) / component (C) is 1/2000 to 1/1, preferably 1/10.
It is desirable to be in the range of 00 to 1/5, more preferably 1/500 to 1/10. The polymerization method is not particularly limited, and solvent polymerization methods (suspension polymerization, solution polymerization) using an inert hydrocarbon or the like, bulk polymerization method in which polymerization is performed in the absence of a substantially inert hydrocarbon solvent, and gas phase A polymerization method can also be used.

Examples of the hydrocarbon solvent used in the polymerization include butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane and other saturated hydrocarbons, benzene, toluene,
Examples thereof include aromatic hydrocarbons such as xylene, chlorine-containing solvents such as chloroform, dichloromethane, ethylene dichloride and chlorobenzene. The polymerization temperature is -10
0 to 200 ° C., polymerization pressure is normal pressure to 100 kg / c
m ² is generally used, but preferably -50 to 1
00 ° C., normal pressure to 50 kg / cm ² , more preferably 0
˜100 ° C., normal pressure˜20 kg / cm ² The molecular weight of the obtained polymer may be controlled by a commonly used method. For example, it can be controlled by hydrogen, temperature, monomer concentration, catalyst concentration and the like.

[0081]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Example 1 (1) Preparation of catalyst component After replacing 100 ml of Nasflavco with dry nitrogen, 30 ml of toluene and 3.6 ml of a n-butyllithium hexane solution (1.66 mol / l) were added. , -78 ° C. To this, 0.56 g of cyclopentanol was added dropwise, then over 60 minutes at -50 ° C.
The temperature was raised to. To this, 26 ml of a toluene solution of pentamethylcyclopentadient chloride chloride titanium (0.0769 mol / l) was added dropwise over 60 minutes. Further, the temperature was raised to -25 ° C, the reaction was performed for 120 minutes, the temperature was raised to 20 ° C, and the mixture was left for 24 hours. The reaction solution was pale yellow, and a white precipitate of lithium chloride was formed at the bottom. (2) Preparation of methylaluminoxane In a glass container having an inner volume of 500 ml replaced with argon, 200 ml of toluene, 17.8 g (71 mmol) of copper sulfate pentahydrate (CuSO ₄ .5H ₂ O) and 24 ml of trimethylaluminum ( (250 mmol) was added, and the mixture was reacted at 40 ° C. for 8 hours. afterwards,
From the solution obtained by removing the solid components, toluene was further distilled off under reduced pressure to obtain a catalyst product (methylaluminoxane) 6.
7 g was obtained. Further, this was heat-treated at 120 ° C. under reduced pressure for 10 hours, and dissolved and dispersed in toluene. (3) Production of ethylene / butene-1 copolymer To a 1 liter flask equipped with a stirrer, under nitrogen atmosphere, 300 ml of toluene and 30 mmol of methylaluminoxane prepared in the above (2) were added. 60 ℃
The temperature was raised to 0 and ethylene gas was introduced under normal pressure distribution conditions to saturate. Further, butene-1 was continuously supplied. To this, 9 ml of only the solution portion of the catalyst component prepared in (1) above was added. Polymerization was carried out for 120 minutes while controlling the reaction temperature at 60 ° C. and continuously supplying ethylene and butene-1. At this time, the total amount of butene-1 supplied was 5.5 g. After completion of the polymerization, the mixture was poured into a large amount of methanol, washed, and dried under reduced pressure to give ethylene / butene-1.
15.4 g of copolymer was obtained.

(4) Evaluation of Ethylene / Butene-1 Copolymer (a) Measurement of Huggins Constant 0.044 g of the copolymer obtained in (3) above was added to Decalin 15.
Dissolved in 691 g at 135 ° C. The polymer concentration at this time is 0.2237 g / deciliter, assuming that the density of decalin at 135 ° C. is 0.79055 g / ml.
The reduced viscosity at 135 ° C. measured with an Ubbelohde viscometer was 2.778 deciliter / g. Further, this viscosity measurement was carried out in the same manner while using the above-mentioned polymer solution as a mother liquor while diluting with decalin, and was carried out at approximately equal intervals at 6 points. The Huggins constant determined from this was 0.494, the intrinsic viscosity [η] was 2.22 deciliters / g, and the correlation coefficient was 0.2.
It was 998. In addition, the Huggins constant of a linear ethylene polymer having an [η] of 2.22 deciliter / g, which was produced using a titanium tetrachloride / triethylaluminum catalyst system, was 0.36.
5, the ratio was 1.35. Furthermore, titanium tetrachloride /
[Η] produced with triethylaluminum catalyst system is 2.2
A 2 deciliter / g ethylene / butene-1 copolymer had a Huggins constant of 0.410 and a ratio of 1.21.

(B) Structural analysis by NMR ¹³ C-NMR [measurement temperature 130 ° C., solvent 1,2,4-trichlorobenzene / deuterated benzene (molar ratio 8/2), 10
0 MHz] was measured. The result is shown in FIG. L
8.15 pp methyl group near quaternary carbon found in DPE
No absorption was observed at m, and ethyl branching was found at 11.14 ppm. In addition, methine carbon at 38 to 39 ppm, 34 to
From the presence of methylene carbon at 36 ppm, it is considered that long chain branching is also present. (C) Evaluation of thermal behavior Using a sheet obtained by hot pressing at 190 ° C. as a sample, measurement was performed by a DSC7 differential scanning calorimeter manufactured by Perkin Elmer. After melting for 5 minutes at 150 ℃, 10 ℃
The temperature was decreased to −50 ° C. at a rate of / min, and the crystallization enthalpy (Δ
H) was calculated. Further, the temperature was further raised at a rate of 10 ° C./min, and the melting point (Tm) was determined from the endothermic peak observed in this process. As a result, ΔH and Tm were not observed and it was an amorphous substance.

(D) Measurement of Density A sample formed by hot pressing at 190 ° C. was used and measured by a density gradient tube method. As a result, the density was 0.886 g / ml. Moreover, the annealing treatment of the sample was not performed. (E) Measurement of terminal vinyl group A pressed sheet having a thickness of 100 μm was prepared and its transmitted infrared absorption spectrum was measured. From the absorbance (A ₉₀₇ ) based on the terminal vinyl group near ₉₀₇ cm ⁻¹ , the film thickness (t), and the resin density (D), the following equation n = 0.114A ₉₀₇ / [D · t] (where D: g / cm ³ , t: mm, n: 100 carbon
It was determined according to the number of vinyl groups per piece). As a result, the amount of terminal vinyl groups was 0.67 / 1000 carbons.

(F) Measuring apparatus for molecular weight distribution: Waters ALC / GPC150C, column:
Tosoh, TSK HM + GMH6 × 2, solvent: 1,
2,4-trichlorobenzene, temperature: 135 ° C, flow rate:
The molecular weight was measured in terms of polyethylene by the GPC method under the condition of 1 ml / min. As a result, the ratio Mw / Mn of the weight average molecular weight to the number average molecular weight was 3.05, and the weight average molecular weight (Mw) was 153,000. (G) Melt flow activation energy (Ea) Rheometrics RMS E-605 was used as a measuring device, and the melt flow activation energy (Ea) was measured according to the following method. That is, the measurement temperature is 150 ° C, 1
Frequency dependence of dynamic viscoelasticity at 70 ℃, 190 ℃, 210 ℃ and 230 ℃ (10 ^-2 to 10 ^-2 rod / sec)
Was measured, and the activation energy (Ea) was calculated by the Arrhenius equation from the shift factors of G ′ and G ″ at each temperature and the reciprocal of absolute temperature using 170 ° C. as a reference temperature and the temperature-time conversion rule. As a result, the activation energy (Ea) was 12.0 kcal / mol.
The Ea of HDPE is 6.3 kcal / mol [[Polymer Engineering Science (Polym.
Eng. Sci.) ", Volume 8, Page 235 (1968)
Year)〕.

Example 2 (Ethylene / Butene-1 Copolymer) In a pressure-resistant autoclave equipped with a 1-liter stirrer, 400 ml of toluene and a toluene solution of triisobutylaluminum (2 mol / liter) in a nitrogen atmosphere were used.
5 ml of 30 mmol of methylaluminoxane prepared in Example 1 (2) was added, and the temperature was raised to 70 ° C. 3.26 g of butene-1 was added to this, and the mixture was stirred for 5 minutes, then saturated with ethylene at a partial pressure of 9.0 kg / cm ² G, and then 9 ml of the catalyst component prepared in Example 1 (1) was added. It was charged through a balance line to start polymerization. Polymerization was carried out for 60 minutes while controlling the ethylene pressure so that the total pressure would be 9.6 kg / cm ² G. After the polymerization was completed, the polymer was recovered. The results are shown in Table 2.

[0088] Example 3 (ethylene / octene-1 copolymer) In Example 2, octene-1 was used instead of butene-1.
Was used in 2 ml and prepared in Example 1 (2)
10 mmol of methylaluminoxane, Example 1 (1)
1.5 ml of the catalyst component prepared in
7.5 kg / cm ²G, except that the polymerization temperature was 70 ° C.
It carried out like Example 2. The results are shown in Table 2.

Example 4 (Ethylene / Butene-1 Copolymer) In Example 1 (2), 0.25 ml of a toluene solution of triisobutylaluminum (2 mol / l) was added to a polymerization system after adding a toluene solvent. An ethylene / butene-1 copolymer was produced in the same manner as in Example 1 except that 0.4 mmol of anilinium tetrakis (pentafluorophenyl) borate was added in place of methylaluminoxane. The results are shown in Table 2.

[0090]

[Table 2]

(Note) k ¹ : Huggins constant of the copolymer shown in the example k ² : Huggins constant of linear ethylene polymers having the same [η] k ³ : straight chain having the same [η] Huggins constant Tm of ethylene / α-olefin copolymer (the density is substantially the same as that of this example): melting point ΔH: enthalpy of crystallization Mw: weight average molecular weight Mn: number average molecular weight * 1: 8.15 ppm absorption, 11. Ethyl branching at 14 ppm * 2: No 8.15 ppm absorption, hexyl branching at 14.02 ppm

Example 5 The ethylene / octene-1 copolymer produced in Example 3 was placed in a decalin solvent at a temperature of 140 ° C. and the polymer concentration was 2 wt.
%, Hydrogen partial pressure 30 kg / cm ² G, carbon supported ruthenium catalyst (Ru content 5 wt%) concentration 4 wt%, reaction time 6 hours. Then, the obtained polymer was isolated from the reaction solution. When a press sheet having a thickness of 300 μm was prepared and the infrared absorption spectrum was measured, absorption of unsaturated groups present in the range of 885 to 970 cm ⁻¹ was not recognized.

Example 6 Ethylene / butene-1 copolymer (density 0.920 g / cm
³ , MI 1.0 g / 10 min) 80% by weight and the ethylene / butene-1 copolymer 20% by weight of Example 1 using a Labo Blast Mill [Toyo Seiki Co., Ltd., internal volume 30 ml] 190 A resin composition was obtained by melt-kneading at 50 ° C. and 50 rpm for 5 minutes. A film having a thickness of 100 μm was prepared from this resin composition. The physical properties of the obtained film were as follows. Tensile modulus of elasticity: 1,800kg / cm ² breaking strength: 370kg / cm ² elongation: 690%

[0094]

INDUSTRIAL APPLICABILITY The ethylene / α-olefin copolymer of the present invention is derived from ethylene and α-olefin and is different from ordinary HDPE, L-LDPE and LDPE, and it has an effect of activating melt flow. Energy can be controlled, processing characteristics are excellent, and physical properties such as density, melting point, and crystallinity can be controlled. Furthermore, various modifications using terminal vinyl groups are possible. is doing. Further, the product obtained by hydrogenating the ethylene / α-olefin copolymer has the above-mentioned properties and is excellent in thermal stability.

[Brief description of drawings]

FIG. 1 is a graph for determining whether a polymer concentration and a reduced viscosity have a linear relationship.

2 is a ¹³ C-NMR spectrum diagram of the ethylene / Bunte-1 copolymer obtained in Example 1. FIG.

Front page continuation (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08F 210/16-210/18 C08F 8/04 C08L 23/08 C08L 23/26-23/36

Claims (5)

(57) [Claims] 1. A copolymer derived from ethylene and an α-olefin having 3 to 20 carbon atoms, which is a linear ethylene polymer having the same intrinsic viscosity [η] and a decalin solvent of the copolymer, The ratio of the Huggins constant (k) measured at a temperature of 135 ° C. is calculated by the formula 1.12 <k ¹ / k ² ≦ 5 (where k ¹ is the Huggins constant of the copolymer and k ² is a linear ethylene polymer). Huggins constant of 1) is satisfied, and a quaternary carbon is not contained in the polymer main chain, an ethylene / α-olefin copolymer. 2. The ethylene / α-olefin copolymer according to claim 1, wherein the activation energy (Ea) of melt flow is 8 to 20 kcal / mol. 3. The relationship between the reciprocal of the intrinsic viscosity [η] measured at a temperature of 135 ° C. in a decalin solvent and the terminal vinyl group content (U) is expressed by the formula 0 ≦ U ≦ 15 × [η] ⁻¹ (however, , U represents the number of terminal vinyl groups per 1000 carbons.) The ethylene / α-olefin copolymer according to claim 1 or 2. 4. An ethylene / α-olefin copolymer obtained by hydrotreating the ethylene / α-olefin copolymer according to claim 3. 5. A thermoplastic resin composition containing the ethylene / α-olefin copolymer according to any one of claims 1 to 4.