JP3468429B2 - Polyethylene and thermoplastic resin composition containing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polyethylene. More specifically, it is derived from ethylene monomer only, it is possible to control the activation energy of melt flow, it has excellent processing characteristics, and polyethylene can control physical properties such as density, melting point and crystallinity. You can
Furthermore, the present invention relates to polyethylene having characteristics such that various modifications using unsaturated groups are possible.

[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.], No. 75, "Journal of the American Chemical Society".
Vol. 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 due to hydrogen transfer reaction between the ethylene bimolecular association product generated under high pressure and the growth radical terminal, and butene-1 due to hydrogen transfer reaction in the ethylene bimolecular association product.
It has been reported that ethyl branching is introduced by the production of [(Makromol.
Chem.) "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, this method shows the effect of changing the melting characteristics of the obtained copolymer and increasing the melt tension, but has the 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), (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), and (3) a specific hafnium-based catalyst. The ethylene / α-olefin copolymer has a narrow molecular weight distribution derived from ethylene and α-olefin and has improved melt flow characteristics (JP-A-2-276).
No. 807) is disclosed.

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. On the other hand, what is disclosed in (3) is a copolymer containing an α-olefin unit as an essential unit, and does not include a copolymer having a resin density of more than 0.92 g / cm ³ . In addition, in (1) and (3), ethylene / α
-The melting point of the olefin copolymer is greatly lowered and the mechanical strength is also lowered.

[0010]

Under the above circumstances, the present invention is capable of controlling the activation energy of melt flow and is excellent in processing characteristics. In addition, polyethylene alone has a density, melting point, and crystallinity. It has the characteristics that physical properties such as properties can be controlled, and that various modifications using unsaturated groups are possible.
PE), linear low density polyethylene (L-LDPE) and L
It was made for the purpose of providing a novel polyethylene different from DPE.

[0011]

Means for Solving the Problems As a result of intensive studies to develop a novel polyethylene having the above-mentioned preferable properties, the present inventors have found that it is derived from only an ethylene monomer and a polymer. Does not contain quaternary carbon in the main chain,
In addition, the activation energy (Ea) of melt flow is in a specific range, the Huggins constant and the intrinsic viscosity have a specific relationship, and polyethylene that is soluble in decalin at 135 ° C. It has been found that polyethylene obtained by hydrogenating carbon unsaturated bonds can meet the purpose. The present invention has been completed based on such findings.

That is, according to the present invention, in a polymer derived from an ethylene monomer, (a) the polymer main chain does not contain quaternary carbon, and (b) the activation energy (Ea) of melt flow is 8 to 20 kcal / mol,
(C) The Huggins constant (k) and the intrinsic viscosity [η] determined by the relationship between the polymer concentration and the reduced viscosity measured at a temperature of 135 ° C. in a decalin solvent are expressed by the formula k ≧ 0.2 + 0.0743 × [η] And (d) a polyethylene which is soluble in a decalin solvent having a temperature of 135 ° C., and in this polyethylene, a carbon-carbon unsaturated bond containing a terminal vinyl type unsaturated bond is hydrogenated. The present invention provides treated polyethylene, and a thermoplastic resin composition containing these polyethylenes. INDUSTRIAL APPLICABILITY The polyethylene of the present invention does not contain quaternary carbon in the polymer main chain, has an activation energy of melt flow within a specific range, has a relatively large Huggins constant, and is soluble in a decalin solvent at a temperature of 135 ° C. Normal HDPE, L
-Different from 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

[0014]

[Chemical 1]

A: 13.99, B: 22.84, C: 30.0
0, D: 32.18 (unit: ppm) [However, A, B and D are minute peaks. ], 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,

[0016]

[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,

[0018]

[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.

[0020]

[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,

[0022]

[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

[0024]

[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 LD C has a complicated ¹³ C-NMR spectrum, and has short-chain branches (ethyl, butyl branches) and long-chain branches (at least hexyl branches), It is considered that the structure near the point mainly has the following structures (a) to (e). (A) Isolated branch (Bn)

[0027]

[Chemical 7]

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

[0029]

[Chemical 8]

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

[0031]

[Chemical 9]

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

[0033]

[Chemical 10]

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

[0035]

[Chemical 11]

LDPE is considered to mainly have the structures of (a) to (e), and identifications corresponding to these have been performed ["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.

[0037]

[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 and optical properties of the resin 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 [J. Polymer Sci., Vol. 9, Vol. , 265 (1952)]. LDPE with long chain branching
It is shown that the Huggins constant of linear and HDPE is large in LDPE [[Polymer Handbook (Polyme
r Handbook) "John Wiley Sons published (1975
Year)〕.

In the polyethylene of the present invention, it has been confirmed that the following relational expression holds between the Huggins constant and the intrinsic viscosity [η]. (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 polyethylene of the present invention will be described.

The polyethylene of the present invention does not contain quaternary carbon in the polymer main chain and is different from the high pressure LDPE. Further, the activation energy (Ea) of the melt flow is 8 to
20 kcal / mol, preferably 8.5-19 kcal /
It is necessary to be in the range of moles, more preferably in the range of 9 to 18 kcal / mol, and if the activation energy (Ea) is less than 8 kcal / mol, sufficient processing characteristics cannot be obtained. The activation energy (Ea) was measured at a temperature of 150
Frequency viability of dynamic viscoelasticity at ℃, 170 ℃, 190 ℃, 210 ℃, 230 ℃ (10 ^-2 -10 ² rod / s
ec) was measured, and the value was calculated by the Arrhenius equation from the reciprocal of the shift factors of G ′ and G ″ at each temperature and the absolute temperature using the temperature-time conversion rule with 170 ° C. as the reference temperature. The polyethylene of the present invention is soluble in a decalin solvent at a temperature of 135 ° C. That is, it does not insolubilize or infusate over a wide range of densities and does not contain a gel, so that the temperature of 135
Dissolve in decalin at ℃. In addition, it exhibits good solubility in aromatic hydrocarbons (such as tetrachlorobenzene) and high-boiling point hydrocarbons other than decalin during normal heating. In addition, in LDPE obtained by high-pressure radical polymerization,
From the mechanism of its formation, some gel formation is recognized.

Further, in the polyethylene of the present invention, the Huggins constant (k) and the intrinsic viscosity [η] determined by the relationship between the polymer concentration and the reduced viscosity measured at a temperature of 135 ° C. in a decalin solvent are expressed by the formula k ≧ 0. It is necessary to satisfy the relationship of 0.2 + 0.0743 × [η], preferably 20 ≧ k ≧ 0.2 + 0.0743 × [η], more preferably 15 ≧ k ≧ 0.22 + 0.0743 × [η] More preferably, it is desirable to satisfy the relationship of 10 ≧ k ≧ 0.24 + 0.0743 × [η]. A preferred specific range of the Huggins constant (k) is 5 ≧ k ≧ 0.41.

The Huggins constant (k) may behave differently when the intrinsic viscosity [η] is extremely large, but the polyethylene of the present invention is also specified by the following ratio of Huggins constants. That is, in the linear high-density polyethylene having the same intrinsic viscosity [η] measured at 135 ° C. in a decalin solvent and the polyethylene of the present invention, the ratio k / k ′ of their Huggins constants is 1.05 to 5. The polyethylene is in the range of 0 (k: the Huggins constant of the polyethylene of the present invention, k ': the Huggins constant of the linear high-density polyethylene). Also, this ratio k / k 'is
It is preferably 1.07 ≤ k / k '≤ 4.0, more preferably 1.08 ≤ k / k' ≤ 3.7, still more preferably 1.10 ≤ k / k '≤ 3.6, and most preferably 1.13. The relationship of ≦ k / k ′ ≦ 3.4 is satisfied.

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:
Less than 2.0 g / deciliter, measurement temperature: 135 ° C ± 0.0
1 ℃, measurement points: 5 points or more, polymer concentration at almost equal intervals,
Viscosity tube: Measured under Ubbelohde conditions. 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. Further, the measurement point on the lowest density side needs to be 45% or less of the concentration on the measurement point on the highest density side.

Then, (1) the relationship between the reduced viscosity and the polymer concentration is linearly regressed by the minimum double method to calculate the intrinsic viscosity [η], and (2) at the same time with the above Huggins equation.
Kraemer's formula ln η _rel / c = [η] + k ₂ [η] ² c and Schulz-Blashke's formula η _sp / c = [η] + k ₃ [η] η _sp [where η _rel is the relative viscosity, η _sp Is the specific viscosity, k ₂ and k ₃ are constants, and others are the same as the Huggins equation. Note that ln
Indicates the natural logarithm. ], The intrinsic viscosity [η] is determined by extrapolating the polymer concentration or the specific viscosity. Furthermore, after confirming that this intrinsic viscosity shows good agreement with all three methods, the Huggins constant is calculated according to the above method (1) from the average value of these intrinsic viscosities and the Huggins equation.

In any of the above methods (1) and (2),
The Huggins constant can be determined 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 of the highest concentration (C _n ) and the measurement point of the lowest concentration (C ₁ ) are connected by a straight line is clearly present below, the Huggins constant is also in this region. Cannot be calculated. 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 ([η _sp / c] ^H − [η _sp / c] ^L ) between the straight line and the curve is calculated and calculated as ([η _sp / c] ^H − [η _sp / c] ^L ) / [C _n- C
₁ ] is 0.001 or less, it is determined to be a straight line.

Also, the activation energy of the melt flow (E
a) is 8 to 20 kcal / mol, preferably 8.5 to 19
It is necessary to be in the range of kcal / mol, more preferably in the range of 9 to 18 kcal / mol, and if this activation energy (Ea) is less than 8 kcal / mol, sufficient processing characteristics cannot be obtained. The activation energy (Ea) is
Temperature 150 ℃, 170 ℃, 190 ℃, 210 ℃, 230
Frequency dependence of dynamic viscoelasticity at ℃ (10 ^-2 -10 ²
rod / sec), the temperature-time conversion rule is used with 170 ° C. as the reference temperature, and the values are calculated by the Arrhenius equation from the reciprocal of the shift factors of G ′ and G ″ at each temperature and the absolute temperature.

The polyethylene of the present invention having such characteristics usually has the following properties. That is,
The polymer main chain does not contain quaternary carbon, and the resin density is
Usually 0.86 to 0.97 g / cm ³ , preferably 0.865 to
0.960 g / cm ³ , more preferably 0.870 to 0.95
It is in the range of 5 g / cm ³ . The density is 190 ° C.
It is a value measured by a density gradient tube after quenching a press sheet prepared at the temperature of. The melting point (Tm) that can be observed by a differential scanning calorimeter (DSC) is
Usually 116 to 132 ° C, preferably 116 to 131.5
C., more preferably in the range of 117 to 131.degree. C., and the crystallization enthalpy (.DELTA.H) and melting point (Tm) observable by DSC usually satisfy the relation of 0.ltoreq..DELTA.H.ltoreq.250, and 0. 02 × ΔH + 116 <Tm <0.02 × ΔH + 126, preferably 0.02 × ΔH + 117 <Tm <0.02 × ΔH + 125, more preferably 0.02 × ΔH + 118 <Tm <0.02 × ΔH + 124. The polyethylene of the present invention is a polymer having a relatively high melting point and a large change in enthalpy of crystallization, and also exhibits the properties as an elastomer having a high melting point and low crystallinity in the range of ethylene-based polymers. It is possible. The crystallization enthalpy is DS
C (manufactured by Perkin Elmer Co., Ltd., DSC7 type) was used to press a press sheet prepared at a temperature of 190 ° C. at a temperature of 150 ° C. for 5 minutes.
It is a value obtained from the exothermic peak of crystallization observed when the temperature is lowered to −50 ° C. at a rate of 10 ° C./minute after melting for a minute, and the melting point is a value when the temperature is further raised at a rate of 10 ° C./minute. It is a value obtained from the temperature at the maximum peak position of the endothermic peak of melting.

In the polyethylene of the present invention,
Gel permeation chromatograph (GPC) method [apparatus: Waters ALC / GPC 150C, column:
Manufactured by Tosoh, TSK HM + GMH6 × 2, flow rate 1.0 ml / min, solvent: 1,2,4-trichlorobenzene, 135 ° C.] and the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polyethylene. Ratio of
w / Mn is usually 2.1 to 70, preferably 2.3 to 60,
The range is more preferably 2.4 to 50. On the other hand, temperature 1
The intrinsic viscosity [η] measured in decalin at 35 ° C is usually
0.01 to 20 deciliters / g, preferably 0.05 to 1
It is in the range of 7 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.
If it exceeds 20 deciliters / g, the processing characteristics will deteriorate.

Further, in the polyethylene of the present invention, an unsaturated group is present at the terminal end of the molecule, and the unsaturated group is pressed at a temperature of 190 ° C. (thickness 100 to 50).
0 μm) and the infrared absorption spectrum of this product can be measured to easily identify and quantify it. Type of terminal unsaturated group Absorption position (cm ^-1 ) Vinylene group 963 Vinylidene group 888 Vinyl group 907 In the polyethylene, the production ratio of the terminal vinyl group is usually 30 mol% or more based on the total of the unsaturated groups. , 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. Density (g / cm ³ ), t is film thickness (mm). ] It is possible to calculate.

Generally, it is known that the amount of unsaturated group at the terminal and the molecular weight are in correlation, but in the polyethylene of the present invention, the terminal vinyl type unsaturated content (U).
And the reciprocal of the intrinsic viscosity [η] measured in decalin at a temperature of 135 ° C. are usually in the relationship of 0.1 × [η] ⁻¹ ≦ U ≦ 7 × [η] ⁻¹ , preferably 0 .1 × [η] ⁻¹ ≦ U ≦ 6.5 × [η] ^−1, more preferably 0.15 × [η] ⁻¹ ≦ U ≦ 6.5 × [η] ^−1, most preferably 0.15 X [η] ^-1 ≤ U ≤ 6 x [η] ^-1 [wherein U is the number of terminal vinyl groups per 1000 carbons. ] Is desirable.

With respect to polyethylene having a high unsaturated group content within the above range, modification of the unsaturated group causes the disadvantages of polyolefin such as adhesiveness, printability, paintability, compatibilizing ability, moisture permeability, It is possible to add various functions such as barrier properties, and at the same time, improvement of processing characteristics based on branching can be expected. Furthermore, polyethylene having a high terminal vinyl group content can be used as a branched macromonomer for the production of various graft copolymers. On the other hand, within the above range, polyethylene having a small unsaturated group content is expected to have improved thermal stability and improved processing characteristics due to branching. Further, with regard to imparting functions such as adhesion and printability, even polyethylene having a low unsaturated group content can sufficiently exhibit its function by modification in practice.

The present invention also provides a polyethylene obtained by hydrogenating such a carbon-carbon unsaturated bond. The polyethylene whose unsaturated group is reduced or eliminated by this hydrogenation treatment is The stability is improved. The polyethylene of the present invention (polyethylene before hydrogenation treatment,
The hydrogenated polyethylene) can be mixed with another thermoplastic resin and used as a thermoplastic resin composition. 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-as a comonomer component
1; hexene-1, octene-1, 4-methylpentene-1, 3-methylbutene-1, linear low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer Examples thereof include saponified products, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, ethylene-based ionomers and polypropylene. Specific examples of the polystyrene-based resin include general-purpose polystyrene, isotactic polystyrene, and high-impact polystyrene (rubber-modified). Specific examples of the condensation polymer include polyacetal resin, polycarbonate resin, nylon 6,
Examples thereof include polyamide resins such as nylon 6/6, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyphenylene oxide resins, polyimide resins, polysulfone resins, polyether sulfone resins and polyphenylene sulfide resins.
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 is the above-mentioned polyethylene 100 of the present invention.
By blending 2 to 500 parts by weight, preferably 3 to 300 parts by weight, of another thermoplastic resin (including an elastomer) with respect to parts by weight, moldability is improved and a molded article having excellent physical properties is obtained. Obtainable.

The polyethylene of the present invention (before hydrogenation treatment) is
It can be produced by polymerizing an ethylene monomer in the presence of a polymerization catalyst capable of obtaining polyethylene having the above-mentioned characteristics. 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, a transition metal compound containing a metal belonging to Group 3 to 10 of the periodic table 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 ligand such as a σ-bonding ligand, a chelating ligand, and a Lewis base. Specific examples of the σ-bonding ligand include a hydrogen atom and an oxygen atom. , Halogen atom, C1-C20 alkyl group, C1-C20
Alkoxy group, aryl group having 6 to 20 carbon atoms, alkylaryl group or arylalkyl group, 1 to carbon atoms
Examples thereof include 20 acyloxy groups, allyl groups, substituted allyl groups, and substituents containing a silicon atom. Examples of chelating ligands include acetylacetonate groups and substituted acetylacetonate groups. A indicates crosslinking by covalent bond. a, b, c, and d each independently represent an integer of 0 to 4, and e represents an integer of 0 to 6. R ¹ ,
Two or more of 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, ethylene;
Butadiene; 1-Pentene; Isoprene; Pentadie
Chain-unsaturated such as 1-hexene and their derivatives
Hydrocarbons, Benzene; Toluene; Xylene; Cyclohep
Tatriene; Cyclooctadiene; Cyclooctatriene
Such as cyclooctatetraene and derivatives thereof
Examples include cyclic unsaturated hydrocarbons. Also, the above (II
Examples of the covalent cross-linking of A in the formula (I) include
For example, methylene bridge, dimethylmethylene bridge, ethylene bridge
Bridge, 1,1'-cyclohexylene bridge, dimethylsilyle
Crosslinking, dimethylgermylene crosslinking, dimethylstannylene
Examples include crosslinking.

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 cyclopentadi
The enyl group, t and u represent an integer of 1 to 4. Where R
^FiveAre hydrogen atoms, silyl groups or hydrocarbon groups, and
It may be the same or different. Also, at least
One cyclopentadienyl group contains Y¹Is bound to
R on at least one carbon next to the carbon^FiveExists
It R⁶Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or
C6-C20 aryl group, alkylaryl group
Represents an arylalkyl group. M²Is titanium, zirco
X represents a nitrogen or hafnium atom, and X¹Is a hydrogen atom,
Rogen atom, C1-C20 alkyl group, C6-C
20 aryl groups, alkylaryl groups or aryl
Represents an alkyl group or an alkoxy group having 1 to 20 carbon atoms
You X¹May be the same or different from each other,
R⁶May be the same as 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.

Further, the transition metal compound of the component (A) is at least two halogen atoms or alkoxy groups among the transition metal compounds represented by the general formula (IV),
Alternatively, a transition metal compound in which two halogen atoms and an alkoxy group are bonded to a central metal, and a compound represented by the general formula (VII)
(XII)

[0067]

[Chemical 14]

A reaction product with a diol represented by: can also be used. In the compounds represented by the above general formulas (VII) to (XII), R ⁹ and R ¹⁰ are hydrocarbon groups having 1 to 20 carbon atoms, which may be the same or different from each other, and Y ³ Is a hydrocarbon group having 1 to 20 carbon atoms,

[0069]

[Chemical 15]

A group represented by (where R¹⁵Has 1 to 1 carbon atoms
6 shows a hydrocarbon group of 6. ). R ⁹, R^TenAnd Y³
For example, the hydrocarbon group having 1 to 20 carbon atoms represented by
Methylene, ethylene, trimethylene, propylene, di
Phenylmethylene, ethylidene, n-propylidene, a
Sopropylidene, n-butylidene, isobutylidene groups
Examples of these include methylene and ethyl
, Ethylidene, isopropylidene and isobutylidene
Groups are preferred. n represents an integer of 0 or more, but especially 0 or
Is preferably 1.

R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, a nitro group,
It represents a nitrile group, a hydrocarbyloxy group or a halogen atom, which may be the same or different.
Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl,
Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, n-
Hexyl, n-heptyl, n-octyl, n-decyl,
Examples thereof include alkyl groups such as n-dodecyl group, aryl groups such as phenyl and naphthyl groups, cycloalkyl groups such as cyclohexyl and cyclopentyl groups, alkenyl groups such as propenyl group, and aralkyl groups such as benzyl group. Of these, an alkyl group having 1 to 10 carbon atoms is preferable. y, y ', y'',y''', z, z ', z''
And z ″ ′ represent the number of substituents bonded to the aromatic ring, y, y ′, z and z ′ are integers of 0 to 4, and y ″ and z ″ are 0 to 0. The integer of 2, y ''', and z''' show the integer of 0-3.

The transition metal compound and the above-mentioned general formula (VII)
As an example of a reaction product with a diol represented by (XII), a compound represented by the general formula (XIII)

[0073]

[Chemical 16]

Examples thereof include compounds represented by:
In the general formula (XIII), M ¹ has the same meaning as described above, E ¹ and E ² are hydrocarbon groups having 1 to 20 carbon atoms, v and x each represent 0 or 1, and E ¹ And E
² forms a crosslinked structure via Y ⁴ . E
³ and E ⁴ represent a σ-bonding ligand, a chelating ligand or a Lewis base, which may be the same or different. v ′ and x ′ each represent an integer of 0 to 2 [an integer of v ′ + x ′ (valence of M ¹ −2)]. Y
⁴ represents a hydrocarbon group having 1 to 20 carbon atoms, E ⁵ E ⁶ Y ⁵ , an oxygen atom or a sulfur atom, and m represents an integer of 0 to 4. E
⁵ and E ⁶ are hydrocarbon groups having 1 to 20 carbon atoms, and Y ⁵ is a carbon atom or a silicon atom. The polyethylene 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 at this time, an alkoxy titanium compound,
Alternatively, 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 of the component (A) may be used alone,
You may use it in combination of 2 or more type. On the other hand, in the polymerization catalyst
In addition, the component (A) used as the component (B)
Ionic complexes from transition metal compounds of
The compound that can be formed includes (B-1) the component (A)
It forms an ionic complex by reacting with transition metal compounds.
Illustrates an on-type compound and (B-2) aluminoxane.
be able to. As the compound of the component (B-1),
An ionic complex by reacting with the transition metal compound of component (A).
Anything that can form a body can be used
However, a cation and an anion in which multiple groups are bound to an element
Compounds consisting of, especially cations and multiple groups bound to an element
Coordination complex compound consisting of
You can do it. Such cations and multiple groups bind to the element.
The compound consisting of the combined anion has the general formula ([L¹-R¹⁶]^{k +})_p([M^FourZ¹Z²..Zⁿ]^(hg)-)_q  .. (XIV) Or ([L²]^{k +})_p([M^FiveZ¹Z²..Zⁿ]^(hg)-)_q        .. (XV) (However, L²Is M⁶, R¹⁷R¹⁸M⁷, R¹⁹ ₃C or R²⁰
M⁷Is. ) [In the formula, L¹Is Lewis base, M^FourAnd M^FiveRespectively
Periodic Table 5th, 6th, 7th, 8th-10th, 11th, 1
Elements selected from groups 2, 13, 14 and 15
More preferably, elements selected from the 13th, 14th and 15th groups,
M⁶And M⁷Are the 3rd, 4th, and 5th groups of the periodic table, respectively.
Tribe, 6 family, 7 family, 8-10 family, 1 family, 11 family, 2 family, 1
Element selected from Group 2 and Group 17, Z¹~ ZⁿIs it
Hydrogen atom, dialkylamino group, each having 1 to 20 carbon atoms
Alkoxy group, aryloxy group having 6 to 20 carbon atoms, charcoal
Alkyl group having a prime number of 1 to 20, aryl having a carbon number of 6 to 20
Group, alkylaryl group, arylalkyl group, carbon number
1-20 halogen-substituted hydrocarbon groups, 1-20 carbon atoms
Acyloxy group, organic metalloid group or halogen atom
Shows, Z¹~ ZⁿIs a ring formed by connecting two or more of them to each other.
It may be formed. R ¹⁶Is a hydrogen atom, having 1 to 20 carbon atoms
Alkyl group, aryl group having 6 to 20 carbon atoms, alkyl
An aryl group or an arylalkyl group, R¹⁷And R
¹⁸Are a cyclopentadienyl group and a substituted cyclopentyl group, respectively.
Entadienyl group, indenyl group or fluorenyl group, R
¹⁹Is an alkyl group, aryl group, or alkyl group having 1 to 20 carbon atoms.
A ruaryl group or an arylalkyl group is shown. R²⁰Is
Macrocycles such as traphenylporphyrin and phthalocyanine
Shows a ligand. g is M^Four, M^FiveValence of 1 to 7
Number, h is an integer from 2 to 8, k is [L¹-R¹⁶], [L²]
Is an integer of 1 to 7 in the valence of p, p is an integer of 1 or more, q =
(P × k) / (h−g). In the compound represented by
is there.

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.

As specific examples of M ⁴ and M ⁵ ,
Specific examples of B, Al, Si, P, As, Sb, and preferably B or P, M ⁶ include Li, Na, Ag, and 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 ¹⁶ and R ¹⁹ are the same as those mentioned above. Specific examples of the substituted cyclopentadienyl group for R ¹⁷ and R ¹⁸ 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,
The number of substituted alkyl groups is an integer of 1-5.

Among the compounds represented by the general formulas (XIV) and (XV), those in which M ⁴ and M ⁵ are boron are preferable. This (B
The compound that reacts with the transition metal compound of the component (A), which is the component (-1), 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 (XVI)

[0079]

[Chemical 17]

[Wherein R ²¹ 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 (XV
II)

[0081]

[Chemical 18]

[In the formula, R ²¹ and s are the same as defined above. ] The cyclic aluminoxane represented by these can be mentioned. Among the compounds of the above general formulas (XVI) and (XVII), 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 (XVI) and (XVII) 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 adding water later, crystal water contained in a metal salt, There are a method of reacting water adsorbed to an inorganic substance or an organic substance with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting with water. These aluminoxanes may be used alone or in combination of two or more.

In the present invention, as the catalyst component (B), only the above-mentioned 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 following general formula (XVIII) R ²² _r AlQ _3-r (XVIII) [wherein R ²² has 1 to 10 carbon atoms] An alkyl group, Q is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and r is a number of 1 to 3. ] The organoaluminum compound represented by the following can be used. 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, an inorganic carrier other than that, and an organic carrier can be used, but an inorganic oxide carrier or another inorganic carrier is particularly preferable. Specific examples of the inorganic oxide carrier include SiO ₂ , Al ₂ O ₃ , MgO and 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 ²³ _i X ³ _j . here,
R ²³ 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. Further, examples of the organic carrier include polymers such as polystyrene, styrene-divinylbenzene copolymer, polyethylene, polypropylene, substituted polystyrene and 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 200 μm, and more preferably 20 to 100 μm.

When the particle size is small, 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 (3) the component (A) and the component (B-2) are used, the molar ratio of the component (A) / the 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.

In the present invention, there are no particular restrictions on the polymerization method for producing polyethylene, and there are no particular restrictions on the solvent polymerization method (suspension polymerization, solution polymerization) using an inert hydrocarbon or a substantially inert hydrocarbon solvent. A bulk polymerization method or a gas phase polymerization method in which the polymerization is carried out under the condition of not existing can also be used. Examples of the hydrocarbon solvent used in the polymerization include butane,
Saturated hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorine-containing solvents such as chloroform, dichloromethane, ethylene dichloride, chlorobenzene, etc. Can be mentioned. The polymerization temperature is generally -100 to 200 ° C, and the polymerization pressure is generally atmospheric pressure to 100 kg / cm ² , but preferably -50 to 100 ° C and atmospheric pressure to 50 k.
g / cm ² , more preferably 0 to 100 ° C., normal pressure to 2
It is in the range of 0 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.

Further, as the hydrogenation catalyst (hydrogenation catalyst) used for the hydrogenation treatment (hydrogenation treatment) of the polyethylene obtained above, in addition to the ones described in detail above, generally in the hydrogenation treatment of an olefin compound. Any catalyst can be used as long as it is used, and it is not particularly limited, but examples thereof include the following. As the heterogeneous catalyst, nickel, palladium, platinum, or a solid catalyst in which these metals are supported on a carrier such as carbon, silica, diatomaceous earth, alumina, or titanium oxide, for example, nickel / silica, nickel / diatomaceous earth, palladium /carbon,
Palladium / silica, palladium / diatomaceous earth, palladium / alumina and the like can be mentioned. Examples of the nickel-based catalyst include Raney nickel catalyst, and examples of the platinum-based catalyst include platinum oxide catalyst and platinum black. As the homogeneous catalyst, one based on a metal of Group 8 to 10 of the periodic table, for example, cobalt naphthenate / triethylaluminum, cobalt octenoate / n-butyllithium, nickel acetylacetonate / triethylaluminum, Ni, Co, etc. Compounds and Periodic Table 1, 2,
Composed of an organometallic compound of a metal selected from Group 3
Or Rh compound etc. can be mentioned.

Further, a Ziegler-based hydrogenation catalyst [Journal of the American Chemical Society (J. A
m. Chem. Soc.) Volume 85, Page 4014 (1983)
Year)] can also be used effectively. Examples of these catalysts include the following. _{Ti (O-iC 3 H 7} ) 4 - (iC 4 H 9) 3 Al, Ti (O-iC 3 H 7) 4 - (C 2 H 5) 3 Al, (C 2 H 5) 2 TiCl 2 - _{(C 2 H 5) 3 Al} , Cr (acac) 3 - (C 2 H 5) 3 Al ( wherein, a
cac is an acetyl acetonate), Na (acac) - ( iC 4 H 9) 3 Al, Mn (acac) 3 - (C 2 H 5) 3 Al, Fe (acac) 3 - (C 2 H 5) _{3 Al, Ca (acac) 2} - (C 2 H 5) 3 Al, (C 7 H 5 COO) 3 Co- (C 2 H 5) 3 Al.

Regarding the amount of the catalyst used in the hydrogenation treatment, the molar ratio of the residual unsaturated group content in polyethylene to the hydrogenation catalyst component is 10 ⁷ : 1 to 10: 1, preferably 10
^It is desirable to select it in the range of ⁶ : 1 to 10 ² : 1. Also, the pressure of hydrogen is normal pressure to 50 kg / c.
A range of m ² G is desirable. Furthermore, the reaction temperature is preferably as high as possible within the range in which the polyethylene obtained in the polymerization step is not decomposed, and is usually −100 ° C. to 300 ° C., preferably −5.
It is selected in the range of 0 to 200 ° C, more preferably 10 to 180 ° C.

[0094]

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 (1) Preparation of methylaluminoxane 200 ml of toluene, 17.8 g (71 mmol) of copper sulfate pentahydrate (CuSO ₄ .5H ₂ O) and trimethylaluminum were placed in a glass container having an inner volume of 500 ml and purged with argon. 24 ml (250 mmol) was added, and the reaction was carried out 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. (2) Preparation of catalyst component A 100 ml eggplant-shaped flask was dried and purged with nitrogen, and then 30 ml of toluene and 3.6 ml of a hexane solution of n-butyllithium (1.66 mol / liter) were added and the temperature was adjusted to -78 ° C. Cooled. To this, 0.56 g of cyclopentanol was added dropwise, and it took 60 minutes thereafter-
The temperature was raised to 50 ° C. Then, 60 ml of 26 ml of a toluene solution of pentamethylcyclopentadiethylene chloride titanium (0.0769 mol / l) was added thereto.
It was dripped over a period of minutes. Further, the temperature is raised to -25 ° C, and 1
After reacting for 20 minutes, the temperature was raised to 20 ° C. and left for 24 hours. The reaction solution was pale yellow, and a white precipitate of lithium chloride was formed at the bottom.

(3) Polymerization of ethylene To a 1 liter flask equipped with a stirrer, 300 ml of toluene and 60 mmol of methylaluminoxane prepared in the above (1) were added under a nitrogen atmosphere. This was heated to 60 ° C., and ethylene gas was introduced under normal pressure distribution conditions. To this, 6.0 ml of only the solution portion of the catalyst component prepared in (2) above was added. Polymerization was carried out for 120 minutes while controlling the reaction temperature at 60 ° C. and continuously supplying ethylene. After completion of the polymerization, the mixture was poured into a large amount of methanol, washed and dried under reduced pressure to obtain 8.5 g of polyethylene.

(4) Evaluation of polyethylene (a)) Measurement of Huggins constant 0.105 g of polyethylene obtained in (3) above was dispersed in 17.996 g of decalin and dissolved at 135 ° C. The polymer concentration obtained with the density of decalin at 135 ° C. as 0.79055 g / ml was 0.4415 g / deciliter. Load this into an Ubbelohde viscometer,
After reaching a constant temperature of 135 ° C., the measurement was started. It was measured 6 times, and the average value was a reduced viscosity of 3.043 deciliters /
It was g. Further, in this viscosity measurement, the reduced viscosity was measured by the same method while using the above-mentioned polymer concentration as a mother liquor and diluting with decalin. The relationship between the polymer concentration [C] and the reduced viscosity is shown in FIG. The Huggins constant determined from the above 5 points was 0.412, and the intrinsic viscosity [η] was 2.18 deciliter / g. The correlation coefficient was 0.999. The ratio of the Huggins constant to HDPE having the same intrinsic viscosity [η] was 1.14.

(B) Measurement by NMR ¹³ C-NMR [100 MHz, measurement temperature 130 ° C., solvent 1,2,4-trichlorobenzene / deuterium benzene (molar ratio 8/2)] was measured. As a result, there was no absorption of 11.14 ppm of ethyl-branched methyl groups. However, in the polymer chain, methylene carbon 38-39ppm, methylene carbon 34-36ppm, methyl group 13.8-14.1p.
From the existence of pm, it is considered that long chain branching exists. Further, since there is no absorption at 8.15 ppm, it can be seen that there is no quaternary carbon. Furthermore, absorption based on butyl branching was observed at 29.57 ppm. The spectrum chart is shown in FIG.

(C) Evaluation of Thermal Behavior A sheet obtained by hot pressing at 190 ° C. was used as a sample and measured 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, the crystallization enthalpy (ΔH) is 5 J
/ G, melting point (Tm) was 121 ° C.

(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 0.887 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
The number of vinyl groups per piece]. As a result, the amount of terminal vinyl groups was 0.2 / 1000 carbons.

(F) Measuring device 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 weight average molecular weight (Mw) was 258,000, and the number average molecular weight (Mw
n) was 14700 and Mw / Mn was 17.6.

(G) Melt flow activation energy (E
Using Rheometrics' RMS E-605 as a measuring device of a), the activation energy (Ea) of the melt flow was measured according to the following method. That is, the measurement temperature is 150 ° C, 1
Frequency dependence of dynamic viscoelasticity at 70 ° C, 190 ° C, 210 ° C, 230 ° C (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 12.1 kcal / mol.
The Ea of HDPE is 6.3 kcal / mol [[Polymer Engineering Science (Polym.
Eng. Sci.) ", Volume 8, p. 235 (1968)
Year)〕. The mechanical properties of polyethylene are shown in Table 2.

Example 2 400 ml of toluene and 0.5 of triisobutylaluminum were added to a stainless steel autoclave under a nitrogen stream.
Mmol and 10 mmol of methylaluminoxane prepared in Example 1- (1) were added, and the temperature was raised to 70 ° C.
To this, 1.5 ml of the solution portion of the catalyst component prepared in Example 1 (2) was added, and ethylene was added at 6 kg / cm ^2.
Polymerization of ethylene was carried out by continuously supplying at a pressure of G for 10 minutes. After the polymerization was completed, ethylene was depressurized, and the polymer was put into a large amount of methanol, washed and dried to obtain 3.6 g of polyethylene. The mechanical properties of polyethylene obtained are shown in Table 2 and the evaluation results are shown in Table 3.

[0103]

[Table 2]

Example 3 In Example 2, the ethylene supply pressure was 7.5 kg / cm.
Example 2 was repeated except that ² G was used.
8.5 g of polyethylene was obtained. The evaluation results of the obtained polyethylene are shown in Table 3. A ¹³ C-NMR spectrum chart is shown in FIG.

[0105]

[Table 3]

Example 4 The polyethylene obtained in Example 2 was mixed in a decalin solvent at a temperature of 140 ° C., a polyethylene concentration of 9% by weight, a hydrogen pressure of 30 kg / cm ² G, a carbon-supported ruthenium catalyst (Ru content of 5% by weight). %) After hydrogenation under the conditions of a concentration of 4% by weight and a reaction time of 6 hours, the obtained polymer was isolated from the reaction solution. Using this polymer, a thickness of 300
When a press sheet of μm was prepared and the infrared absorption spectrum was measured, absorption of unsaturated groups existing in the range of 885 to 970 cm ⁻¹ was not recognized.

Example 5 Ethylene / butene-1 copolymer (density 0.922 g / cm
³ ) A resin composition comprising 80 parts by weight and 20 parts by weight of the polyethylene (density 0.887 g / cm ³ ) obtained in Example 1 was blow-molded at a blow ratio of 2.7 to produce a film. did. The film moldability was good.

[0108]

INDUSTRIAL APPLICABILITY The polyethylene of the present invention is derived from only an ethylene monomer and contains quaternary carbon in the polymer main chain, but has long chain branching and has a vinyl group at the end. , Which is different from ordinary HDPE, L-LDPE, and LDPE, it is possible to control the activation energy of the melt flow and is excellent in processing characteristics. In addition, polyethylene alone has physical properties such as density, melting point and crystallinity. It has a feature that it can be controlled and that various modifications using an unsaturated group are possible. Further, the product obtained by hydrogenating the above-mentioned polyethylene has the above-mentioned characteristics and is excellent in thermal stability.

[Brief description of drawings]

FIG. 1 is a graph for determining whether or not a polymer concentration and a reduced viscosity have a linear relationship.

FIG. 2 is a graph showing the relationship between polymer concentration and reduced viscosity in the polyethylene obtained in Example 1.

FIG. 3 ¹³ C—N of polyethylene obtained in Example 1
The MR spectrum is shown.

FIG. 4 ¹³ C—N of polyethylene obtained in Example 3
The MR spectrum is shown.

Claims (8)

(57) [Claims] 1. A polymer derived from an ethylene monomer, wherein (a) the polymer main chain does not contain quaternary carbon, and (b) the activation energy (Ea) of melt flow is 8 to 8.
20 kcal / mol, (c) the Huggins constant (k) and the intrinsic viscosity [η] determined by the relationship between the polymer concentration and the reduced viscosity measured at a temperature of 135 ° C. in a decalin solvent are expressed by the formula k ≧ 0. A polyethylene characterized by satisfying the relationship of 2 + 0.0743 × [η] and (d) being soluble in a decalin solvent having a temperature of 135 ° C. 2. The polyethylene according to claim 1, which does not contain at least an ethyl branch as a branch. ^3. The crystallization enthalpy (ΔH) and melting point (Tm), which have a resin density in the range of 0.86 to 0.97 g / cm ³ and can be observed by a differential scanning calorimeter, are expressed by the formula 0 ≦ ΔH ≦ The polyethylene according to claim 1, which is present in a range that simultaneously satisfies the relationship of 250 and 0.02 × ΔH + 116 <Tm <0.02 × ΔH + 126. 4. The polyethylene according to claim 1, wherein the ratio Mw / Mn of the weight-average molecular weight and the number-average molecular weight in terms of polyethylene measured by gel permeation chromatography is in the range of 2.1 to 70. 5. The polyethylene according to claim 1, having a melting point (Tm) observed by a differential scanning calorimeter of 116 to 132 ° C. 6. Content of terminal vinyl type unsaturated bond (U)
And the reciprocal of the intrinsic viscosity [η] measured at a temperature of 135 ° C. in decalin are expressed by the formula 0.1 × [η] ⁻¹ ≦ U ≦ 7 × [η] ⁻¹ [where U is per 1000 carbons] It is the number of terminal vinyl groups. ] The polyethylene of Claim 1 which satisfy | fills the relationship of]. 7. The polyethylene according to claim 6, wherein
Polyethylene obtained by hydrogenating a carbon-carbon unsaturated bond. 8. A thermoplastic resin composition containing the polyethylene according to any one of claims 1 to 7.