Ethylene copolymer, thermoplastic resin composition containing the same, and process for producing ethylene copolymer

ES 2 179 066 T3

DESCRIPTION

Ethylene copolymer, thermoplastic resin composition that contains it, and production process for this copolymer.

Technical field

The present invention relates to a new ethylene copolymer, to a thermoplastic resin composition containing it, and to a new process for the preparation of said ethylene copolymer. More specifically, the present invention relates to an ethylene copolymer that can be derived from an olefin having 3 to 20 carbon atoms, and in which control of the activation energy of the melt flow is possible, as well as control of phasic properties, such as density and melting point and crystallinity; a thermoplastic resin composition containing said ethylene copolymer; and a process for efficiently preparing the ethylene copolymer in which non-Newtonian properties are improved and which is excellent in working properties.

Background of the invention

To date, the primary structure of polyethylene or ethylene-a-olefin copolymer has been controlled by adjusting the molecular weight, molecular weight distribution or copolymerization properties (random properties, blocking tendency and distribution of the degree of branching), or adding a third component such as diene, to introduce the branches.

On the other hand, for ethylanic polymers, various molding methods can be applied, including among the typical known examples of molding methods, injection molding, extrusion, blow molding, inflation, compression molding and vacuum forming. In such molding methods, research has been going on for a long time to impart high speed molding properties and a reduction of molding energy, in order to improve the working properties and thus reduce the working cost; thus, the issue of imparting optimal phasic properties suitable for each use, and of being able to carry the molding with optimal working properties, is important.

In recent years, it has been elucidated that a uniform metallocene catalyst is excellent for copolymerization properties between olefins, being able to obtain a polymer with a narrow molecular weight distribution, and having a much higher catalytic activity compared to catalysts. conventional vanadium. Therefore, it is expected that metallocene catalysts will be developed in various technical fields to take advantage of these characteristics. However, polyolefins obtained by using a metallocene catalyst have poor molding and working properties and, for this reason, the application of metallocene catalysts for blow molding and inflation is inevitably limited.

A conventional known low density polyethylene (LDPE) can be obtained by high pressure radical polymerization of ethylene, having both long chain branches and short chain branches. It has been considered that long chain branches can be formed through the intermolecular hydrogen transfer reaction between the radical growth terminal of the polymer and the polymer. On the other hand, with regard to the mechanism of formation of short branches, various theories have been described. For example, a counter-cutting mechanism has been suggested [J. Am. Chem. Soc. Vol., 75, p. 6110 (1953)]. Said theory explains in a rational way that butyl branching can be formed by hydrogen transfer after the formation of a six-membered intermediate at the terminal of growth radicals. According to another theory, it has been described that the butyl branching is formed by virtue of the production of an associate of two ethylene molecules at high pressure and a hydrogen transfer reaction at the radical growth terminal, and can be introduce an ethyl branch due to the production of 1-butene through the hydrogen transfer reaction in the associate of two ethylene molecules [Makromol. Chem. Vol., 181, p. 2811 (1981)]. In accordance with yet another theory, it has been described that the formation of the ethyl branch is completed by the transfer of hydrogen from the main chain of the polymer to an ethyl branch radical [J. Polym. Sci., Vol. 34, p. 569 (1959)].

To understand all of the above, it can be concluded that the formation of long chain branches and short chain branches in low-density polyethylene is carried out through (1) the hydrogen transfer reaction based on polymerization of radicals and (2) the change of the reactivity of radical polymerization by association of ethylene molecules at high pressure, this being a normally recognized reaction mechanism. Accordingly, in the above-mentioned reaction process, it is impossible to optionally control the amounts of long chain branches and the

ES 2 179 066 T3 existing short chain branches, as well as the number of carbon atoms in the short chain branches. In particular, the introduction and control of a methyl branch, a propyl branch, a hexyl branch, and a short-chain branch derived from a branched α-olefin (eg, a 4-methyl-pentene-1 branch) was limited. .

Such low-density polyethylene has a large melt stress and a large melt flow activation energy by virtue of the long chain branching and is therefore excellent in its high speed molding properties and suitable for the formation of films. However, because it has a wide molecular weight distribution and contains a low molecular weight component, low density polyethylene is undesirably deficient in its resistance to environmental stress cracking (ESCR) and impact resistence.

On the other hand, various ethyloenic polyomers have been described in which long chain branches are introduced into a high-density polyethylene structure. For example, (1) an olefin copolymer having the long chain branches obtained by using an α, ω-diene or a cyclic endomethylene diene has been described (Japanese Patent Application Laid-Open No. 34981/1972), ( 2) a process for preparing a copolymer having a higher unconjugated diene content in the high molecular weight segment than in the low molecular weight segment, which consists of carrying out the polymerization in two stages to copolymerize the unconjugated diene with an olefin (Japanese patent application open No. 56412/1984), (3) an ethylene-a-olefin-1,5-hexadiene copolymer obtained by using a metallocene / aluminoxane catalyst (Japanese Patent Application PCT- Open No.^° 501555/1989), (4) a process for introducing long chain branches by copolymerization of α, ω-diene and ethylene in the presence of a catalyst that includes a divalent or zero valence nickel compound and a specific aminobis (imino) compound ( Japanese Patent Application Open N^° 261809/1990), and (5) a polyethylene containing both short chain branches and long chain branches that can be obtained by polymerization of ethylene alone by using the same catalytic component as mentioned above in (4) ( Japanese Patent Application Open N^° 277610/1991).

However, in the copolymer of (1) mentioned above, a crosslinking reaction takes place simultaneously with the formation of the long chain branches by the diene component, and at the same time as a film is formed, a gel. On the other hand, the melt properties deteriorate inversely, and the control range is extremely narrow. On the other hand, there is a problem that the copolymerization reactivity is low, so that low molecular weight polyomers are produced, which leads to the deterioration of the phosphorous properties in an inconvenient way. In the process of preparing the copolymer described in (2) above, the long chain branches are introduced into the high molecular weight component, so that the molecular weight increases considerably due to the crosslinking and, therefore, is they can inconveniently produce insolubilization, lack of fusion or gelation. On the other hand, the control range is narrow, the copolymerization reactivity is also low, and therefore there is a problem that due to the production of low molecular weight polyomers, the phosphorous properties are disadvantageously deteriorated. In the aforementioned copolymer (3), the molecular weight distribution is narrow, and for this reason, the copolymer is not suitable for blow molding and film forming. On the other hand, since branch points are formed by the progress of the 1,5-hexadiene cyclization reaction, the effective monoomer concentration is inconveniently low. In the mentioned long chain branching process (4), there is a problem that the range to control the generation of a gel and the phosphoric properties is limited. Also, the aforementioned polyethylene (5) is a polymer that does not contain ethyl branches or butyl branches, and consequently the control of the phosphoric properties, for example, the density control, is carried out by the branches of methyl, so that the physical properties of polyethylene tend to deteriorate.

Likewise, a method has been described to prepare an ethylenic polymer in which working properties are imparted through the use of copolymerization, for example, a method consisting of the formation of a polymer ([η] = 10-20 dl / g ) by preliminary polymerization, and then preparing an ethylene-a-olefin copolymer by main polymerization (Japanese Patent Application Laid-Open No. 55410/1992). This method has the effect that the melt tension can be increased by changing the melt properties of the obtained copolymer, but has the disadvantage that film gel tends to be produced.

Additionally, ethylene polymers obtained in the presence of a metallocene catalyst and methods for their preparation have been described, such as (1) a method for preparing an ethylene polymer in the presence of a limited geometric catalyst and an ethylene copolymer obtained through

ES 2 179 066 T3 this method (Japanese open patent application No. 163088/1991 and WO93 / 08221), (2) a method for preparing a polyolefin in the presence of a metallocene catalyst containing a porous inorganic oxide (a compound of aluminum) as a support (Japanese Patent Application Open N^° 100808/1992), and (3) an ethylene-to-olefin copolymer which can be derived from ethylene and α-olefin in the presence of a specific hafnium catalyst and which has a narrow molecular weight distribution and improved flow properties of cast (Japanese Patent Application Open No.^° 276807/1990).

However, in the technique of the above-mentioned (1), density control and the like can be achieved by introducing an α-olefin unit into an ethylene chain, the resulting product being a substantially linear polymer. According to the preparation method (2) mentioned above, the copolymer obtained from ethylene and α-olefin has a wide swelling ratio in the die (ratio of the diameter of the extrudate to the diameter of the die), although having Taking into account the correlation between the swelling ratio at the nozzle and the melting point of the ethylene-good copolymer, it is evident that the swelling ratio at the nozzle deteriorates with rising melting point. Accordingly, it is not possible to provide any copolymer in which the swelling ratio at the nozzle in terms of inward beading does not pose a problem at the time of film or film formation, which can be controlled within a wide range of the melting point.

On the other hand, the copolymer described in the above method (3) contains an α-olefin unit as an essential unit and does not cover a copolymer having a resin density greater than 0.92 g / cm³Additionally, in their examples, only copolymers having resin densities of 0.89 g / cm are described³ or less. On the other hand, in the mentioned methods (1) and (3), when branches are introduced, the melting point and mechanical strength of the ethylene-α-olefin copolymer are considerably deteriorated.

Description of the invention

Under these circumstances, the present invention has been studied. One of the objects of the present invention is to provide a new ethylene copolymer with which the activation energy of the melt flow can be controlled, which is excellent in its working properties, in which the properties can be controlled. physics such as density, melting point and crystallinity mainly, which has a higher melting point under conditions of the same density and which is different from normal high density polyethylene (HDPE), as well as ethylene-α-olefin copolymer and low density polyethylene (LDPE) described in the application aforementioned Japanese patent open N^°163088/1991, WO93 / 08221 and Japanese Patent Application Laid-Open No.^° 276809/1990.

The authors of the present invention have carried out an exhaustive study to achieve the aforementioned objective and, as a result, have observed that a copolymer derived from ethylene and an olefin having from 3 to 20 carbon atoms is suitable to fulfill said objective. That is, this type of copolymer has a polymeric backbone containing no quaternary carbons and an activation energy (Ea) of the melt flow in a specific range. On the other hand, in the copolymer of the present invention, (1) the Huggins coefficients of the copolymer and the straight chain ethylene polymer having the same intrinsic viscosity remain in a specific relationship with each other; (2) the molar ratio [CH3 / CH2] of the methyl group and the methylene group present in the molecular chain is within a specific range and this molar ratio and the melting point (Pf) satisfy a specific relative equation; (3) Weight average molecular weight (Mw) and die swell ratio (DR) satisfy a specific relative equation. On the other hand, it has been observed that when a specific catalyst is used for polymerization, the activation energy of the melt flow and the Huggins coefficient can be controlled to efficiently obtain an ethylene copolymer having better non-Newtonian properties. and excellent working properties. Accordingly, the present invention has been completed based on this knowledge.

That is, according to the present invention, it can be provided:

(1) an ethylene copolymer [1] which is derived from ethylene and an olefin having 3 to 20 carbon atoms and in which (1) no quaternary carbon atom is present in the polymeric backbone; (2) the activation energy (Ea) of the melt flow is in the range of 8 to 20 kcal / mol; and (3) the relationship between the Huggins coefficients (k) of the copolymer and a straight chain ethylene hompolymer having the same intrinsic viscosity [η] measured at a temperature of 135^°C in a decalin solvent satisfy the relation of the equation:

1.2 <k¹/ k² < 5

ES 2 179 066 T3 where k¹ is the Huggins coefficient of the copolymer, and k² is the Huggins coefficient of the straight chain ethylene homopolymer.

(2) An ethylene copolymer [2] which is derived from ethylene and an olefin having 3 to 20 carbon atoms and in which (1) no quaternary carbon atom is present in the polymeric backbone; (2) the activation energy (Ea) of the melt flow is within the range of 8 to 20 kcal / mol; and (3) the molar ratio [CH3 / CH2] of the methyl group in the region of 0.8 to 1.0 ppm to the methylene group in the region of 1.2 to 1.4 ppm observed according to the resonance spectrum method. nuclear magnetic of protoin (¹H-NMR) is in the range of 0.005 to 0.1, and the melting point (Pf) and the molar ratio [CH3 / CH2] observed with a differential scanning calorimeter (DSC) satisfy the equation:

Mp> 131-1340 [CH₃/ CH₂] (3) A copolymer of ethylene [3] which is derived from ethylene and an olefin of 3 to 20 carbon atoms and in which (1) no quaternary carbon atoms are present in the polymeric backbone; (2) the activation energy (Ea) of the melt flow is within the range of 8 to 20 kcal / mol; and (3) the relationship between the weight average molecular weight (Mw) as regards polyethylene measured according to the gel permeation chromatography method and the nozzle swelling ratio (DR) satisfies the equation:

DR> 0.5 + 0.125 x logPm.

Additionally, according to the present invention, an ethylene copolymer obtained by hydrogenation treatment of any of the aforementioned ethylene copolymers can be provided, as well as a thermoplastic resin composition that includes any of these ethylene copolymers.

Moreover, according to the present invention, A process can be provided to prepare an ethylene copolymer that includes the step of copolymerizing ethylene and at least one olefin having 3 to 20 carbon atoms in the presence of a catalyst consisting of (a) a transition metal compound. where the relationship between the monomer charge composition [the molar ratio [M] of 1-octene / (ethylene + 1-octene)] and the product of the enthalpy of crystallization (ΔΗ) and the melting point (Pf ) of the copolymer produced satisfies the equation:

<ΔΗ + Pf <27000 - 21600 [M]⁰,⁵⁶ (under polymerization conditions in which component (a) is used together with an aluminoxane), (b) a transition metal compound capable of forming a terminal vinyl group in the homopolymerization of ethylene or the copolymerization of ethylene and at least an olefin having 3 to 20 carbon atoms (under polymerization conditions in which component (b) is used together with the aluminoxane), and (c) a compound capable of forming an ioan complex from the aforementioned components (a) and (b) or their derivatives (the transitional metal compounds of the aforementioned components (a) and (b) are compounds containing metals from groups 3 to 10 or the lanthanide series of the periodic table).

Brief description of the graphics

Figure 1 is a graph for judging whether or not the polymer concentration and the reduced viscosity remain in a linear relationship with respect to each other.

Figure 2 shows the spectrum of ¹³C-NMR of the ethylene-1-butene copolymer obtained in the example

1.

Figure 3 is a graph showing the dependence of the shear rate on the melt viscosity of the ethylene copolymer obtained in Example 14 and Comparative Example 3.

Best mode of realization of the invention

The ethylene copolymer of the present invention is different from the usual HDPE, L-LDPE (a linear low-density polyethylene) and LDPE (a high-pressure method), and some differences can be judged through (A) the evaluation of the primary structure. and (B) the evaluation of the phasic properties that will be described later.

ES 2 179 066 T3 (A) Judgment through evaluation of the primary structure (1) Comparison with HDPE, L-LDPE and LDPE

According to the measurement of nuclear magnetic resonance spectra ¹³C, it is evident that the ethylene copolymer of the present invention is different from HDPE, L-LDPE and LDPE in its structure.

(a) Comparison with HDPE (a relatively low molecular weight polymer)

The end structure of a normal HDPE (a relatively low molecular weight polymer) is represented by:

CDBA -CH2 -CH2 -CH2 -CH3

A = 13.99, B = 22.84, C = 30.00 and D = 32.18 (unit = ppm) (A, B and D are minimal peaks) peaks that are based on branching are not present.

(b) Comparison with ethylene-a-olefin copolymers Ethylene-1-butene copolymer

Ethylene-1-butene copolymer has the structure represented by:

DECFG -CH2 -CH2 -CH2 -CH2 -CH- CH2 ^|

CH2 -CH3 BA

A = 11.4, B = 26.75, C = 27.35; D = 30.00

E = 30.49; F = 34.11 and G = 39.75 (unit = ppm) as a structure in the vicinity of a branch point.

Ethylene-1-hexene copolymer

Ethylene-1-hexene copolymer has a structure represented by:

<td>I CH2 -CH- I</td><td>H CH2 -</td><td>C CH2 -</td><td>F CH2 -</td><td>AND CH2</td>

<td>^|CH2 -</td><td>CH2 -</td><td>CH2 -</td><td>CH3</td><td></td>

<td>G</td><td>D</td><td>B</td><td>TO</td><td></td>

A = 14.08, B = 23.36; C = 27.33; D = 29.57,

E = 30.00; F = 30.51; G = 34.22; H = 34.61, and I: 38.23 (unit = ppm) as structure in the vicinity of the branch point.

Ethylene-4-methylpentene-1 copolymer

Ethylene-4-methylpentene copolymer has the structure represented by:

ES 2 179 066 T3

<td>G</td><td>F</td><td>C</td><td>AND</td><td>D</td>

<td>CH-^|</td><td>CH2 - B</td><td>CH2 -</td><td>CH2 -</td><td>CH2</td>

<td>CH2 -</td><td>CH-</td><td>CH3</td><td></td><td></td>

<td>H</td><td>^|CH3</td><td>TO</td><td></td><td></td>

A = 23.27; B = 26.05; C = 27.14; D = 30.00,

E = 30.51; F = 34.88; G = 36.03; and H = 44.83 (unit = ppm) as structure in the vicinity of the branch point.

Ethylene-1-octene copolymer

Ethylene-1-octene copolymer has the structure represented by:

<td>I CH2 -CH- I</td><td>H CH2 -</td><td>D CH2 -</td><td>F CH2 -</td><td colspan="2">AND CH2 -</td>

<td>^|CH2 -</td><td>CH2 -</td><td>CH2 -</td><td>CH2 -</td><td>CH2 -</td><td>CH3</td>

<td>H</td><td>C</td><td>AND</td><td>G</td><td>B</td><td>TO</td>

A = 14.02, B = 22.88; C = 27.28; D = 27.33, E = 30.00; F = 30.51; G = 32.20; H = 34.59, and I = 38.25 (unit = ppm) as structure in the vicinity of the branch point.

Ethylene-propylene copolymer

The ethylene-propylene copolymer has a structure represented by:

CBE -CH2 -CH2 -CH2

D

CH-CH2 ^|

CH3

TO

A = 19.98; B 0 27.47; C = 30.00; D = 33.31;

yE = 37.59 (unit = ppm) as structure in the vicinity of the branch point.

In each of the above-mentioned ethylene-a-olefin copolymers, a short chain branch derived from α-olefin is present, but no long chain branch is present.

(c) Comparison with LDPE

The spectrum of ¹³C-NMR of LDPE is complex and indicates that short chain branches (ethyl and butyl branches) and long chain branches (at least one hexyl branch and the like) are present in LDPE. On the other hand, LDPE is considered to have mainly the following structures (C-1) to (C-5) in the vicinity of the branches.

ES 2 179 066 T3 (C-1) Isolated branch (Bn) γ β α br

<td colspan="2">-CH2 -CH-CH2 -CH2 -n</td><td>branch</td>

<td>n</td><td>1 CH2^|</td><td>1 methyl 2 ethyl</td>

<td>n-1</td><td>CH2</td><td>3 propyl 4 butyl 5 pentyl 6 hexyl</td>

<td> 3</td><td>CH2_|</td><td>n longest</td>

<td> 2</td><td>^|CH2 I</td><td></td>

<td> 1</td><td>^|CH3</td><td></td>

[xBn] (n = 1, 2, 3, ..., n) (n = 1, 2, 3 ..., n, α, β, γ ...) (C-2) Ethyl branch- ethyl (1,3) attached to a quaternary carbon (small)

[(xB2) pee] (R)

[(XB2) small, (xB'2) small]

<td>γ β α br α '</td><td>^|</td><td>α</td><td>^β</td>

<td>-CH2 -CH2 -CH2 -CH-CH2 I</td><td>-C - I</td><td>CH2</td><td>-CH2</td>

<td>^|2CH2 I</td><td>^|CH2 I</td><td> 2</td><td></td>

<td>^|1CH3</td><td>^|CH3</td><td> 1</td><td></td>

<td>ethyl-ethyl (1,3) isolated (pee)</td><td></td><td></td><td></td>

<td>γ β α br α '</td><td></td><td></td><td></td>

<td>-CH2 -CH2 -CH2 -CH-CH2 - I</td><td>CH- I</td><td>CH2</td><td>-CH2</td>

<td>^|2CH2</td><td>^|CH2</td><td> 2</td><td></td>

<td>_|1CH3</td><td>_|CH3</td><td> 1</td><td></td>

<td>ethyl-propyl (1,3) isolated (pep)</td><td></td><td></td><td></td>

<td>γ β α br α '</td><td>br</td><td>α</td><td>^β</td>

<td>-CH2 -CH2 -CH2 -CH-CH2 I</td><td>-CH I</td><td>-CH2</td><td>-CH2</td>

<td>^|2CH2</td><td>^|CH2 I</td><td> 3</td><td></td>

<td>_|1CH3</td><td>^|CH2 I</td><td> 2</td><td></td>

<td></td><td>^|CH3</td><td> 1</td><td></td>

[(xB2) pep, (xB3) pep]

ES 2 179 066 T3 (C-5) Isolated methyl-ethyl (1,4) branch (pme) γ β α br α 'α ”br α β

-CH2 -CH2 -CH2 -CH-CH2 -CH2 -CH-CH2 -CH2 ||

2CH2 CH3 1 ^|

1CH3

[(XB2) pme^{, (xB}1⁾pme^]

LDPE is considered to mainly have the structures (C-1) to (C-5) mentioned above, said structures having been identified [Macromolecules, vol., 17, p. 1756 (1984)].

In accordance with this literature document, the identification has been carried out as shown in table 1, and the presence of the long chain branch (32.18 ppm) of at least one hexyl branch and one hexyl branch has been confirmed. ethyl.

TABLE 1

<td>No.</td><td>Displacement chemical</td><td>Assignment</td><td>No.</td><td>Displacement chemical</td><td>Assignment</td>

<td> 1</td><td> 42,86</td><td></td><td> 15</td><td> 24,36</td><td>β-C ^</td>

<td> 2</td><td> 39,75</td><td>brB2</td><td></td><td></td><td>(attached to the carbonyl group)</td>

<td> 3</td><td> 39,19</td><td></td><td> 16</td><td> 23,36</td><td>2B₄</td>

<td> 4</td><td> 38,23</td><td>brB₄-n</td><td> 17</td><td> 22,88</td><td>2B₄</td>

<td> 5</td><td> 37,38</td><td>(brB2) pee</td><td></td><td> 22,84</td><td>2B6-n</td>

<td> 6</td><td> 35,99</td><td></td><td> 18</td><td> 20,15</td><td>2B3</td>

<td> 7</td><td> 35,00</td><td></td><td></td><td> 20,04</td><td>1Bi</td>

<td> 8</td><td> 34,61</td><td>^αΒ4 —N</td><td> 19</td><td> 14,59</td><td>1B3</td>

<td> 9</td><td> 34,22</td><td>4B₄</td><td> 20</td><td> 14,08</td><td>1 B₄</td>

<td> 10</td><td> 32,70</td><td>3B5</td><td></td><td> 14,02</td><td>^{1 B}5-n</td>

<td> 11</td><td> 32,18</td><td>3Bn</td><td> 21</td><td> 11,22</td><td></td>

<td> 12</td><td> 30,00</td><td>CH2</td><td></td><td> 11,01</td><td>1B2 or</td>

<td></td><td></td><td>Main chain</td><td></td><td></td><td>^{(1 B}2) pee</td>

<td> 13</td><td> 27,33</td><td>β B4-n</td><td></td><td> 10,85</td><td></td>

<td> 14</td><td> 25,99</td><td>β B'2</td><td> 22</td><td> 8,15</td><td>1B'2</td>

<td></td><td></td><td></td><td></td><td> 7,87</td><td></td>

(2) Test for confirmation of the presence of long chain branching by nuclear magnetic resonance spectrum ¹³ C

A technique has been suggested which confirms the presence of the hexyl branch and determines the hexyl branch in comparison to an ethylene-1-octene copolymer having hexyl branch [Macromolecules, vol., 14 p. 215 (1981), and idem, vol. 17, p. 1756 (1984)]. According to these publications, it has been concluded from the measurement of the nuclear magnetic resonance spectrum¹³C of a blend with LDPE that the peak observed at about 27.3 ppm is different from the peak observed in the case of the ethylene-1-octene copolymer. On the other hand, in normal C36H74 which is used as the model substance for long chain branching, the third carbon signal from its terminal appears at 32.18 ppm. On the other hand, the third carbon signal from the terminal of the hexyl branch of the ethylene-1-octene copolymer appears at 32.22 ppm. To take advantage of the fact that the presence of the long chain branching influences the chemical shift, when the ethylene-1-octene copolymer is mixed with the LDPE having the long chain branching and the nuclear magnetic resonance spectrum is measured. from ¹³C, two peaks appear, by virtue of which the long chain branching of LDPE can be identified and determined.

Through these techniques it can be confirmed that LDPE has the long chain branching.

ES 2 179 066 T3 (B) Judgment of evaluation of physical properties (1) Judgment by melt analysis

Long-chain branching is known to be related to the fluid behavior of melt viscosity, viscoeleastic properties, and the like of a melt, and exerts an important influence on mechaenic properties, such as workability, optic properties. and the resistance to environmental stress cracking of the resin. Therefore, by measuring and evaluating them, the presence of the long chain can be confirmed.

On the other hand, among the reasons that exist to confirm the presence of the long chain branching, the following facts can be mentioned. The relationship between MI and Pm of LDPE deviates from the relationship in the case of a straight chain polyethylene (HDPE), since the number of long chain branches increases. That is, the LDPE has a lower MI when the Pm is the same. Also, with an Instréon type capillary rheometer, fluid characteristics can be examined, and the displacement factor can be used to determine the melt flow activation energy (Ea). Said measured activation energy (Ea) of HDPE is only 6 kcal / mol, while the Ea of LDPE is up to approximately 12 kcal / mol. Consequently, it can be confirmed that the fluid characteristics are affected by long chain branching.

According to this melt flow analysis, it has been firmly deduced that the ethylene copolymer of the present invention has long chains.

(2) Discrimination by polymer solution analysis (a) Judgment by Huggins coefficient

It is known that a relationship can be established between the reduced viscosity r,_sp/ C (dl / g), intrinsic viscosity [η] (dl / g), Huggins coefficient k and polymer concentration c (g / dl) with the following general equation (Huggins equation).

rsp / c = [r] + k [r]²c

The Huggins coefficient k is a value that represents the intermolecular interaction of a polymer in a state of dilute solution, and therefore, it is considered that this coefficient k affects the molecular weight of the polymer, the molecular weight distribution and the presence of they branched it.

It has been elucidated that when the branching is introduced into the polymer structure, the Huggins coefficient increases in the case of styrene-divinylbenzene copolymer [J. Polymer Sci., Vol. 9, p. 265 (1952)]. On the other hand, it has also been reported that the Huggins coefficient of LDPE having long chain branching is higher than that of straight chain HDPE [Polymer Handbook, published by John Wiley Sons, (1975)].

(b) Judgment of the relationship between the introinsic viscosity [r] and the molecular weight measured through the gel permeation chromatography method or the light scattering method.

It is known that the relationship between the intrinsic viscosity [r], determined in a dilute polyethylene solution using the Huggins equation mentioned above, and the molecular weight measured through the gel permacian chromatography (GPC) method to determining the molecular weight according to the size of a solute polymer or the light scattering method, can reflect the branching structure of the polymer. For example, the straight chain HDPE is different from the LDPE which has the long chain branching in the relationship between the intrinsic viscosity and the molecular weight measured through the GPC method, and it has been concluded that when the comparison is made being the constant intrinsic viscosity, the molecular weight of LDPE is less than that of HDPE.

Next, reference will be made to the characteristics of the ethylene copolymer [1] to [3] of the present invention.

In each of the ethylene copolymers [1] to [3] of the present invention, it is necessary that no quaternary carbon atom be present in the polymeric main chain, and that the activation energy (Ea) of the melt flow is within the range of 8 to 20 kcal / mol, preferably between 8.5 and 19 kcal / mol, more preferably between 9 and 18 kcal / mol. If the melt flow activation energy (Ea) is less than 8 kcal / mol, working properties cannot be achieved.

ES 2 179 066 T3 sufficient. Therefore, the melt flow activation energy (Ea) is a value obtained as follows. First, the frequency dependencies (10^-2 a10² rad / sec) of the dynamic viscoelastic properties at temperatures of 150^°C, 170^°C, 190^°C, 210^°C and 230^°C, and then the activation energy (Ea) is calculated as a function of the displacement factors G ', G ”at the corresponding temperatures, and the reciprocal number of an absolute temperature according to the Arrhenius equation applying a conversion rule temperature-time at the standard temperature of 170^°C.

On the other hand, the ethylene copolymers [1] to [3] of the present invention can satisfy the above-mentioned requirements and have the following characteristics.

First, the ethylene copolymer [1] can be specified by the following relationship between the Huggins coefficients (k), which are decided by the relationship between the polymer concentration and the reduced viscosity measured at a temperature of 135^°C in a decalin solvent. That is, if the straight chain ethylene homopolymer and the ethylene copolymer [1] of the present invention have the same intrinsic viscosity [η] measured at a temperature of 135^°C in decalin solvent, the ethylene copolymer [1] satisfies the relationship between the Huggins coefficients (k) represented by the following equation:

1.12 &lt;k¹/ k² &lt;5 where k¹ is the Huggins coefficient of the ethylene copolymer [1] of the present invention and k² is the Huggins coefficient of the straight chain ethylene homopolymer.

This correspondence k¹/ k² preferably satisfies the relation:

1.13 &lt;k¹/ k² &lt;4.0 mais preferably,

1.14 &lt;k¹/ k² &lt;3.7 or more preferably,

1.15 &lt;k¹/ k² &lt;3.6 being above all preferable

1.18 &lt;k¹/ k² &lt; 3,4

A typical example of the referred straight chain ethylene homopolymer is an ethylene polymer currently being produced on an industrial scale or a laboratory produced ethylene polymer.

The homopolymer is made using a common Ziegler catalyst, such as a Ziegler catalyst system titanium tetrachloride / triethylaluminum. On the other hand, the mentioned catalyst, in which a magnesium compound or a silicon compound is used as the support, can also be used in the preparation process. The intrinsic viscosity [η] can be controlled by the use of hydrogen, the polymerization temperature, the amount of monomer charged, the amount of catalyst, and the like.

Assuming that the Huggins coefficient of the straight chain ethylene / α-olefin copolymer, which is obtained with a Ziegler catalyst and in which the intrinsic viscosity [η] measured at a temperature of 135^°C in decalin solvent is the same as that of the ethylene copolymer [1] of the present invention, it is represented by k³, the relationship k¹/ k³ between the Huggins coefficient k¹ of the ethylene copolymer [1] of the present invention and the k³ normally satisfy the relationship:

1.02 &lt;k¹/ k³ &lt;5.0 preferably,

1.03 &lt;k¹/ k³ &lt; 4

ES 2 179 066 T3 more preferably,

1.05 &lt;k¹/ k³ &lt; 3,5

Also at this point, the ethylene copolymer [1] of the present invention is different from the conventional ethylene / α-olefin copolymer.

On the other hand, the α-olefin fractions or the α-olefin copolymer compositions in the above-mentioned straight chain ethylene / α-olefin copolymer, which can be used for comparative purposes, has a relatively small influence on the coefficient Huggins, although it is desirable to make the comparison using the same type of α-olefin and the same resin density.

The intrinsic viscosity [η] and the Huggins coefficient k in the aforementioned relationship equations can be obtained as follows.

That is, it is known that a relationship can be established between the reduced viscosity nsp / c (dl / g), the intrinsic viscosity [η] (dl / g), the Huggins coefficient k and the polymer concentration c (g / dl ), using the Huggins equation nsp / c = [n] + k [n]²c

First, the reduced viscosity n is measured_sp/ c in decalin solvent at a polymer concentration of 2.0 g / dl or less at a measurement temperature of 135 ° C ± 0.01 ° C at 5 or more measurement points, within a range of a concentration of substantially constant polymer using a Ubbelohde visceometer. The precision of measurement is such that the relative viscosity is 1.1 or more and the error of the relative viscosity is ± 0.04 or less at each measurement point, the measurement being carried out 5 times or more at each polymer concentration. On the other hand, it is necessary that the polymer concentration at the measurement point on the minimum concentration side is 45% or less of the polymer concentration at the measurement point on the maximum concentration side.

In the mentioned method, the decision of the Huggins coefficient is possible only when the relationship between the reduced viscosity and the polymer concentration is definitely in a linear relationship. When the polymer concentration is high or the molecular weight of the polymer is large, the linear relationship is not obtained and therefore it is necessary to perform the measurement again after decreasing the polymer concentration. However, if the polymer concentration is too low, a region in which the reduced viscosity does not depend on the polymer concentration and a region in which the reduced viscosity increases with decreasing polymer concentration could be present, and in such regions, the Huggins coefficient cannot be calculated.

On the other hand, if the measuring point is apparently present below the straight line represented by connecting the measuring point (Cn) at the maximum concentration with the measuring point (C1) at the minimum concentration, in this region, do not the Huggins coefficient can be calculated. However, this is not applicable as long as the following conditions are satisfied. That is, you can judge whether or not the linear relationship is established in the way that is written below. In figure 1, the measuring point (Cn) at the maximum concentration is first connected with the measuring point (C1) at the minimum concentration with a straight line. Next, the corresponding measurement points are connected to each other with a smooth curve. Here, the distance between the straight line and the curve is calculated ([nsp / C]^H - [nsp / C]^L) and if ([nsp / C]^H - [nsp / C]^L) / [Cn -C1] is 0.001 or less, it can be judged that the linear relationship is established.

This ethylene copolymer [1] is dissolved in decalin at a temperature of 135^°C. Normally, this copolymer is neither insoluble nor infusible within a wide density range and therefore does not contain gel, so the ethylene copolymer [1] dissolves in decalin at a temperature of 135^°C. On the other hand, the ethylene copolymer [1] exerts good solubility in aromatic hydrocarbons (tetrachlorobenzene and the like) and high-boiling hydrocarbons other than decalin, usually when heated. In LDPE obtained by radical polymerization at high pressure, the gel formation is partially observed in view of its production mechanism.

Also, the melting point (Pf) of the ethylene copolymer [1] that can be observed by the differential scanning calorimeter (DSC) is normally in the range of 50 to 137^°C, preferably 55 to 136^°C, more preferably 58 to 135^°C, and the ethylene copolymer [1] also includes an ethylene-olefin copolymer that does not substantially exhibit the melting point (MP).

ES 2 179 066 T3

On the other hand, the enthalpy of crystallization (ΔΗ) of the ethylene copolymer [1] that can be observed by DSC normally satisfies the equation:

by &lt;ΔΗ &lt;250

The enthalpy of crystallization is a value obtained from an exothermic crystallization peak observed at the moment in which a pressed sheet formed at a temperature of 190 melts.^°C by using the DSC (model DSC7, manufactured by Perkin Elmer Co., Ltd) at a temperature of 150^°C for 5 minutes and then cool down to -50^°C at a speed of 10^°C / minute. On the other hand, the melting point is a value obtained from a temperature at the position of the maximum peak of the endothermic melting peak at the moment in which the temperature rises at a rate of 10^°C / minute.

In the ethylene copolymer [2] of the present invention, the molar ratio [CH3 / CH2] of a methyl group in the region of 0.8 to 1.0 ppm to a methylene group in the region of 1.2 to 1 , 4 ppm obtained through the proton nuclear magnetic resonance spectrum method (¹H-NMR) is within the range of 0.005 to 0.1, and it is necessary that the melting point (Pf) and the ratio [CH3 / CH2] observed by differential scanning calorimeter (DSC) satisfy the equation:

Mp&gt; 131-1340 [CH₃/ CH₂] preferably

Mp&gt; 131-1260 [CH3 / CH2] more preferably

Mp&gt; 131-1190 [CH3 / CH2].

being still more preferable

Mp&gt; 131-1120 [CH3 / CH2].

Here, [CH3 / CH2] can be decided through a known technique. That is, if the integrated value of the peak present in the region of 0.8 to 1.0 ppm is considered as A and the integrated value of the peak present in the region of 1.2 to 1.4 ppm is considered as B, [CH3 / CH2] can be represented as [A / 3] / [B / 2].

The melting point (Pf) is the value obtained from the temperature at the position of the maximum peak of the endothermic melting peak at the moment in which the pressed sheet formed at a temperature of 190 melts.^°C by using DSC (model DSC7, manufactured by Perkin Elmer Co., Ltd.) at a temperature of 150^°C for 5 minutes, cool to -50^°C at a speed of 10^°C / min, and then heats up at a speed of 10^°C / min.

In the ethylene copolymer [3] of the present invention, it is necessary that the weight average molecular weight (Mw) as regards polyethylene measured by gel permeation chromatography (GPC) and the swelling ratio at the nozzle (DR) satisfy the equation:

DR&gt; 0.5 + 0.125 x log Pm, preferably,

1.80&gt; DR&gt; 0.36 + 0.159 x log Pm more preferably,

1.75&gt; DR&gt; 0.16 + 0.21 x log Pm, being above all preferable,

1.70&gt; DR&gt; -0.11 + 0.279 x log Pm,

At this point, the nozzle swelling ratio (DR) is a value (D1 / D0) that is obtained by measuring the diameter (D1, mm) of a strand formed by extrusion through a capillary nozzle [diameter (D0) = 1.275mm, length (L) = 51.03mm, L / D0 = 40, and entry angle = 90^°] at a speed

ES 2 179 066 T3 1.5 mm / min extruder (shear speed = 10 sec^-1), at a temperature of 190 ° C, by using a capillograph manufactured by Toyo Seiki Seisakusho Co., Ltd., and then dividing this diameter by the diameter of the capillary nozzle.

The diameter (D1) of the aforementioned strand is an average value of the values ​​obtained by measuring the long axes and the short axes of central positions of 5 samples having an extruded strand length of 5 cm (length 5 cm from the nozzle outlet).

The ethylene copolymers [1] to [3] of the present invention usually have the following phasic properties.

(1) Weight average molecular weight (Mw) as regards polyethylene measured by Gel Permeation Chromatography (GPC) [apparatus = Waters ALC / GPC 150C, column = manufactured by Toso Co., Ltd., TSK HM * GMH6x2, flow rate = 1.0 ml / min, and solvent = 1,2,4-trichlorobenzene, 135 ° C] is normally within the range of 5,000 to 2,000,000 preferably 7,000 to 1,500,000, more preferably 10,000 to 1,000,000. If this average weight molecular weight (Mw) is less than 5,000, its influence on the mechanical properties is small and, if it is more than 2,000,000, the working properties deteriorate.

(2) The Mw / Mn ratio between molecular weight average weight (Mw) and number average molecular weight (Mn) for polyethylene measured by the GPC method is normally in the range of 1 5 to 70, preferably 1.6 to 60, most preferably 2.0 to 50.

(3) The density of resin is normally within the range of 0.85 to 0.96 g / cm³, preferably 0.860 to 0.955 g / cm³, more preferably 0.870 to 0.950 cm³. This resin density is the value obtained when measuring with a density gradient tube, the pressed sheet formed at a temperature of 190^°C and cooled afterwards.

(4) The intrinsic viscosity [η] measured in decalin at a temperature of 135^°C is normally in the range of 0.01 to 20 dl / g, preferably 0.05 to 17 dl / g, more preferably 0.1 to 15 dl / g. If said [η] is less than 0.01 dl / g, the influence on the mechanical properties is little, and if it is more than 20 dl / g, the working properties deteriorate.

On the other hand, in the ethylene copolymers [1] to [3] of the present invention, an unsaturated group is present at the terminal of each molecule, and said unsaturated group can be easily identified and determined by measuring the infrared absorption spectra of the pressed sheet (thickness = 100 to 500 μm) formed at a temperature of 190 ° C.

Terminal unsaturated group type Absorption position (cm^-1)

Vinylene Group 963

Vinylidene Group 888

Vinyl group 907

In each ethylene copolymer, the production ratio of terminal vinyl groups is usually 30% by mole, preferably 40% by mole or more, more preferably 50% by mole or more, relative to the sum of the unsaturated groups mentioned. In this regard, the amount of terminal vinyl groups can be calculated according to the equation, n = 0.114 A907 / [dt] where n is the number of terminal vinyl groups with respect to 100 carbon atoms; A907 is the absorbance at 907 cm^-1; d is the density of resin (g / cm³); and t is the thickness of the film (mm).

In general, it is known that an interrelation is present between the amount of terminal unsaturated groups and the molecular weight, but in particular in the ethylene copolymer [1] of the present invention, the content of terminal vinyl-type unsaturated groups ( U) and the reciprocal number of the intrinsic viscosity [η] measured in decalin at a temperature of 135^°C normally satisfies the equation:

&lt;U &lt;15 x [η]^-1 preferably &lt;U &lt;14 x [η]^-1

ES 2 179 066 T3 more preferably, or &lt;υ &lt;13 x [η] ¹ being above all preferable, o &lt;υ &lt;12 x [η] ¹ where U is the number of terminal vinyl groups with respect to 1000 carbon atoms.

Various functions, such as adhesive properties, printability, coating properties, compatibility, moisture permeability and barrier properties, which are insufficient in a polyolefin, can be imparted to ethylene copolymers [1] to [3] that have a high content of unsaturated groups at the terminal through modification of the unsaturated group and, simultaneously, the improvement of the working properties can be expected as a function of the branching. Additionally, ethylene polymers having a high content of terminal vinyl groups can be used as branched micromonaomer for the manufacture of various graft copolymers. On the other hand, in ethylene copolymers having a low content of terminal unsaturated groups, the thermal stability can be improved and working properties as a function of branching can be expected. Functions such as adhesive properties and printability can be sufficiently influenced by practical modification even in the case of ethylene copolymers which have a low content of terminal unsaturated groups.

The present invention also provides an ethylene copolymer in which the unsaturated carbon-carbon union is hydrogenated, it being possible to improve the thermal stability of the ethylene copolymer in which the unsaturated groups are reduced or lost by said hydrogenzone treatment.

The ethylene copolymers (unhydrogenated ethylene copolymers and hydrogenated ethylene copolymers) of the present invention can be mixed with other thermoplastic resins and used thereafter. Examples of other thermoplastic resins include polyolefin resins, polystyrene resins, condensation series high molecular weight polymers, and addition polymerization series high molecular weight polymers. Typical examples of polyolefin resins include high-density polyethylenes, low-density polyethylenes, poly-3-methyl-butene-1-, poly-4-methylpentene-1, linear chain low-density polyethylenes obtained by using 1-butene, 1-hexene, 1-octene,

4-methylpentene-1 and 3-methylbutene-1 as comonoamer components, ethylene-vinyl acetate copolymers, saponified ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, ionamers ethylanic and polypropylene. Typical examples of polystyrene resins include multipurpose polystyrenes, isotactic polystyrenes and high impact (rubber modified) polystyrenes. Typical examples of condensation series high molecular weight polymers include polyacetal resins, polycarbonate resins, polyamide resins such as 6-nylon and 6,6-nylon, polyester resins such as polyethylene terephthalates and polybutylene terephthalates, polyphenylene oxide resins, polyimide resins, polysulfone resins, polyethersulfone resins, and polyphenylene sulfide resins. Examples of high molecular weight polymerization series polymers of adicon include polymers made from polar vinyl monomers and polymers made from diene monoamers, typically, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, diene polymers in which the diene chain is hydrogenated and thermoplastic elastaomers.

The thermoplastic resin composition of the present invention can be obtained by mixing 100 parts by weight of the mentioned ethylene copolymer of the present invention with 2 to 500 parts by weight, preferably 3 to 300 parts by weight, more preferably 5 to 200 parts. by weight of the other thermoplastic resin (or the thermoplastic elastaomer).

The ethylene copolymer of the present invention can be obtained by copolymerizing ethylene with an olefin having 3 to 2 carbon atoms, being able to include the olefin having 3 to 2 carbon atoms α-olefins, calcium olefins and styrenos.

Examples of α-olefins include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1 -octadecene, 1-eicosene and 3-methyl-1-butene.

Examples of calcium olefins include norbornene, 5-methylnorbornene, 5-ethylnorbornene,

5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene

ES 2 179 066 T3 neno, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidene norbornene, 1,4,5,8-dimethanol-1,2,3,4,4a, 5,8,8aoctahydronaphthalene, 2-methyl- 1,4,5,8-dimethanol-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethane-1,2,3,4, 4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethane-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1, 4,5,8-dimethane-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene, 5,6-dicarboxynorbornene anhydride, 5-dimethylaminonorbornene, 5-cyanonorbornene, 2-ethyl-1,4,5,8-dimethane- 1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethane-1,2,3,4,4a, 5,8,8a- octahydronaphthalene, 2-hexyl-1,4,5,8-dimethanol-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethane-1, 2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethane-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and 1,5-dimethyl-1,4,5,8-dimethanol-1, 2,3,4,4a, 5,8,8a-octahydronaphthalene. Norbornene and its derivatives are particularly suitable.

Examples of styrene include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-chlorostyrene, pt-butylstyrene, p-phenylstyrene, and p-trimethylstyrene.

These comonoemers can be used alone or by combining two or more of them.

The ethylene copolymers (unhydrogenated) of the present invention can be prepared by polymerizing ethylene with an olefin having 3 to 20 carbon atoms in the presence of a polymerization catalyst that can allow the preparation of an ethylene copolymer having the features that have been mentioned above.

An example of such a polymerization catalyst contains as main components (A) a transition metal compound and (B) a compound capable of forming an ion complex from a transition metal compound or its derivative.

As the transition metal compound of component (A) in the polymerization catalyst, a transition metal compound containing a metal from groups 3 to 10 of the periodic table or a metal from the lantheanide series can be used. Preferable examples of the transition metal include titanium, zirconium, hafnium, vanadium, niobium, and chromium.

Examples of such a transition metal compound include various types of compound, in particular, compounds containing group 4, 5 and 6 transition metals can be suitably used. The compounds represented by the formulas are particularly suitable. general:

<td></td><td>CpM¹R¹aR²bR³c Cp2M¹R¹aR²b (Cp-Ae-Cp) M¹R¹aR²b</td><td>(I) (II) (III)</td>

<td>the general formula:</td><td></td><td></td>

<td>Their derivatives.</td><td>M¹R¹aR²bR³cR⁴d</td><td>(IV)</td>

In the general formulas (I) to (IV) mentioned above, M¹ represents a transition metal such as titanium, zirconium, hafnium, vanadium, niobium and chromium, and Cp represents a cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group such as a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group , a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group. Related to this, a part of the carbon atoms in the cyclopentadienyl group can be replaced by a heteroatom such as nitrogen or phosphorus. R¹, R², R³ yR⁴ independently represent a δ-binding ligand, a chelate ligand or a ligand such as a Lewis base, including typical examples of a δ-binding ligand a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, an alkyl aryl group or an arylalkyl group having 6 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an allyl group, a substituted allyl group, and a substituent containing a silicon atom. On the other hand, examples of the chelate ligand include an acetylacetonate group and a substituted acetylacetonate group. A represents a bond crosslinked by a covalent bond. a, b, c and d are independently an integer between 0 and 4, and e is an integer between 0 and 6. Two or more of the R¹, R², R³ yR⁴ they can be joined together to form a ring. When the aforementioned Cp has a substituent, said

ES 2 179 066 T3 substituent is preferably an alkyl group having 1 to 20 carbon atoms. In faormulas (II) and (III), the two Cps can be the same or different from each other.

Examples of the substituted cyclopentadienyl group in the above formulas (I) to (III) include a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an isopropylcyclopentadienyl group, a 1,2-dimethylcyclopentadienyl group, a tetramethylcyclopentadienyl group, a 1,3 group -dimethylcyclopentadienyl, a 1,2,3-trimethylcyclopentadienyl group, a 1,2,4-trimethylcyclopentadienyl group, a pentamethylcyclopentadienyl group and a trimethylsilylcyclopentadienyl group. Likewise, among the typical examples of R¹ aR⁴ in the above-mentioned phaormules (I) to (IV), a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are included as halogen atoms; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an octyl group and a 2-ethylhexyl group as alkyl groups having 1 to 20 carbon atoms; a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a phenoxy group as alkoxy groups having 1 to 20 carbon atoms; a phenyl group, a tolyl group, a xylyl group and a benzyl group as aryl groups, the alkylaryl groups or the arylalkyl groups having 6 to 20 carbon atoms; a heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms; a trimethylsilyl group and a (trimethylsilyl) methyl group as a substituent containing a silicon atom; and ethers such as dimethalic ether, diethyl ether, and tetrahydrofuran, a thioether such as tetrahydrothiophene, an ester such as ethyl benzoate, nitriles such as acetonitrile and benzonitrile, amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline ', 2, 2-pyridine bipyridine and phenanthroline, phosphines such as triethylphosphine and triphenylphosphine, unsaturated chain hydrocarbons such as ethylene, butadiene, 1-pentene, isoprene, pentadiene, 1-hexene and its derivatives and unsaturated caclic hydrocarbons such as benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraen and its derivatives as Lewis base. On the other hand, examples of crosslinking by covalent bonding of A in formula (III) include a methylene crosslinking, a dimethylmethylene crosslinking, an ethylene crosslinking, a 1,1'-cyclohexylene crosslinking, a dimethylsilylene, a dimethylgermylene crosslinker and a dimethyltanylene crosslinker.

Examples of the compound represented by the general formula (I) include: (Pentametilciclpentadienilo) trimetilzirconio, (pentamethylcyclopentadienyl) trifenilzirconio, (pentamethylcyclopentadienyl) tribencilzirconio, (pentamethylcyclopentadienyl) triclorozirconio, (pentamethylcyclopentadienyl) trimetoxizirconio, (pentamethylcyclopentadienyl) trietoxizirconio, (cyclopentadienyl) trimetilzirconio, (cyclopentadienyl) trifenilzirconio, (cyclopentadienyl) tribencilzirconio, (cyclopentadienyl) triclorocirconio, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) triethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium, (methylcyclopentadienyl) trimethylzirconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzirconium, (methylcyclopentadienyl) trichlorozirobyclodienyl (methyl) trichlorozircyclocyrconium (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzirconium, (methylcyclopentadienyl) trichlorozirfoxycyclozirconium (methylcyclopentadienyl)

ES 2 179 066 T3 (trimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium, and compounds in which zirconium is replaced by titanium or hafnium.

Examples of the compound represented by the general formula (II) include: bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) diethylzirconium, bis (cyclopentadienyl) dibenzyl zirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium (cyclopentadienyl) dichlorohydrogen monohydronozirconium (cyclopentadienyl) dichlorozironohydride (cyclopentadienyl) dichlorozironohydride (cyclopentadienyl) dichlorozironohydride (cyclopentadienyl) dichlorohydrozirconium (cyclopentadienyl) dichlorohydrozirconium (methylcyclopentadienyl) dimethylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclopentadienyl) dibenzirconium, bis (pentamethylcyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) dichlorozirconium, bis (pentamethylcyclopentadienyl) dibencilzirconio, bis (pentamethylcyclopentadienyl) clorometilzirconio, bis (pentamethylcyclopentadienyl) hidridometilzirconio, (cyclopentadienyl) (pentamethylcyclopentadienyl) dichlorozirconium, and these same compounds wherein zirconium is replaced with titanium or hafnium.

On the other hand, examples of the compound represented by the general formula (III) include: ethylenebis (indenyl) zirconium dimethyl, ethylenebis (indenyl) dichlorozirconium, ethylenebis (tetrahydroindenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium, dimethylsilylenebis (cilopentadienil) dimethylzirconium, dimethylsilylenebis (cilopentadienil) dichlorozirconium, isopropylidene (cilopentadienil) (9-fluorenyl) zirconium dimethyl, isopropylidene (cilopentadienil ) (9-fluorenyl) dichlorozirconium, [phenyl (methyl) methylene] (9-fluorenyl) - (cyclopentadienyl) -dimethylzirconium, diphenylmethylene (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclohexalidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclopentylidene (9-fluorenyl) -fluorenyl) (cyclopentylidene (9-fluorenyl) -fluorenyl) (cyclopentylidene (9-flupentadienyl) - (cyclopentadienyl) dimethylzirconium, dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium, dimethylsilienbis (2,3,5-trimethylcyclopentadienyl) dimethylzirconium, dimethylsilylenebis- (indenyl) dichlorozirconium, isopropylidenebis (cyclopentadienyl) dichlorozirconium and these same compounds in which zirconium is replaced by titanium or hafnium.

Likewise, examples of compounds represented by the general formula (IV) include tetramethylzirconium, tetrabenzylzirconium, tetramethoxyzirconium, tetraethoxyzirconium, tetrabutoxyzircon.

ES 2 179 066 T3 nium, tetrachlorozirconium, tetrabromozirconium, butoxytrichlorozirconium, dibutoxydichlorozirconium, bis (2,5-di-tbutylphenoxy) -dimethylzirconium, bis (2,5, -di-t-butylphenoxy) dichlorozirconium, bis (2,5-di-t-butylphenoxy) dichlorozirconium) dichlorozirconium, bis (2,5-di-tbutylphenoxy) as well as these compounds in which the zirconium is replaced by titanium or hafnium.

Typical examples of the vanadium compound include vanadium trichloride, vanadyl trichloride, vanadium triacetylacetonate, vanadium tetrachloride, vanadium tributoxide, vanadyl dichloride, vanadyl bisacetylacetonate, vanadyl triacetylacetonate, dicyclopentadiene, dicyclovaniovaniovanium, dicyclopentadiene, dicyclovaniovaniovanium cyclopentadienylvanadium dichloride and dicyclopentadienylmethylvanadium.

Also, typical examples of the chromium compound include tetramethyl chromium, tetra (tbutoxy) chromium, bis (cyclopentadienyl) chromium, hydridotricacarbonyl (cyclopentadienyl) chromium, hexacarbonyl (cyclopentadienyl) chromium, bis (benzene) chromium, tricarbonyltris (triphenylphos), tris (allyl) chromium, triphenyltris (tetrahydrofuran) chromium and tris (acetylacetonate) chromium.

Also, as component (A), a transition compound of group 4 having as ligand, a multiple ligand compound in which, in the above-mentioned general formula (III), two conjugated cyclopentadienyl groups are attached can be suitably used. substituted or unsubstituted (at least one of them being a substituted cyclopentadienyl group) to each other through an element selected from group 14 of the perfodic table.

An example of such a compound is a compound represented by the general formula (V):

(R⁵t-C5H4-t) \ X¹

<img file="ES2179066T3_D0001.tif" />

(R⁵u-C5H4-u) X¹ . . (V) or its derivative.

In the general formula (V) above, Y¹ represents a carbon atom, a silicon atom, a germanium atom, or a tin atom, R⁵-C₅H_4-t and RU-C₅H_4-u each represent a substituted cyclopentadienyl group, with t and u each being an integer between 1 and 4. Here, the R⁵ they represent a hydrogen atom, a silyl group or a hydrocarbon group, and can be the same or different from each other. In at least each of the cyclopentadienyl groups, R⁵ is present in at least each of the carbon atoms adjacent to the carbon atom attached to Y¹. R⁶ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, an alkylaryl group or an arylalkyl group having 6 to 20 carbon atoms. M² represents a titanium atom, a zirconium atom, or a hafnium atom, X¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group having 6 to 20 carbon atoms, or an alkoxy group having it has 1 to 20 carbon atoms. The X¹ may be the same or different from each other, and similarly, the R⁶ they can be the same or different from each other.

Also, examples of the substituted cyclopentadienyl group in the general formula (V) include a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an isopropylcyclopentadienyl group, a 1,2-dimethylcyclopentadienyl group, a 1,3-dimethylcyclopentadienyl group, a 1 group, 2,3-trimethylcyclopentadienyl and a 1,2,4-trimethylcyclopentadienyl group. Among the typical examples of X¹ F, Cl, Br and I are included as halogen atoms; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an octyl group, and a 2-ethylhexyl group as an alkyl group having 1 to 20 carbon atoms; a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a phenoxy group as alkoxy groups having 1 to 20 carbon atoms; and a phenyl group, a tolyl group, a xylyl group and a benzyl group as the aryl group, the alkylaryl group or the arylalkyl group having 6 to 20 carbon atoms. Among the typical examples of R⁶ A methyl group, an ethyl group, a phenyl group, a tolyl group, a xylyl group, and a benzyl group are included.

Examples of compounds having the general formula (V) include dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) titanium dichloride and dimethylsilylenebis (2,3 , 5-trimethylcyclopentadienyl) hafnium.

ES 2 179 066 T3

On the other hand, the compound having the general formula (V) also includes compounds represented by the general formula (VI):

<img file="ES2179066T3_D0002.tif" />

In the general formula compound (VI), Cp represents a ceyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group such as a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group. M³represents a titanium atom, a zirconium atom or a hafnium atom, X² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group having 6 to 20 carbon atoms, or an alkoxy group having it has 1 to 20 carbon atoms. Z represents SiR2⁷, CR⁷2, SiR₂⁷Sir⁷2, CR₂⁷CR2⁷, CR⁷two CR⁷2CR⁷2, CR⁷= CR⁷, CR2⁷SiR2⁷ oGeR⁷2, eY² represents -N (R⁶) -, -O-, -S- oé -P (R⁶ ) -. The R⁷ The aforementioned is a group selected from the group consisting of a hydrogen atom, an alkyl group having 20 or less non-hydrogen atom, an aryl group, a silyl group, a halogenated alkyl group, a halogenated aryl group and a combination of them, and R⁶ is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, or R⁶ can form a condensed ring of one or more R⁷ and 30 minus non-hydrogen atoms. On the other hand, w represents 1 or e 2.

Typical examples of the compound represented by the general formula (VI) include (tert-butylamido) (tetramethyl-n⁵ -cyclopentadienyl) -1,2-ethanediylzirconium, (tert-butylamido) dichloride (tetramethyl-n⁵-cyclopentadienyl) -1,2-ethanediiltitanium, (methylamido) (tetramethyl-n dichloride⁵ -cyclopentadienyl) -1,2-ethanediylzirconium, (methylamido) (tetramethyl-n dichloride⁵ -cyclopentadienyl) -1,2-ethanediiltitanium, (ethylamido) (tetramethyl-n dichloride⁵ -cyclopentadienyl) -methylene titanium, (tert-butylamido) dimethyl (tetramethyl-n⁵ -cyclopentadienyl) silanetitanium, (tert-butylamido) dimethyl- (tetramethyl-n⁵cyclopentadienyl) silanozirconium dibenzyl, (benzylamido) dimethyl (tetramethyl-n dichloride⁵-cyclopentadienyl) -silanetitanium and (phenylphosphide) dimethyl (tetramethyl-n⁵-cyclopentadienyl) silanozirconium dibenzyl.

On the other hand, as the transition metal compound that is component (A), a reaction product of a transition metal compound represented by the general formula (IV) in which at least two atoms are bound can be used. of halogen, an alkoxy group or the two atoms of halogen and the alkoxy group with the central metal and any of the diols represented by the general formulations (VII) to (XII):

HO - R⁹ - (Y³) n -R¹⁰ -OH ... (VII)

<img file="ES2179066T3_D0003.tif" />

<img file="ES2179066T3_D0004.tif" />

ES 2 179 066 T3

<img file="ES2179066T3_D0005.tif" />

<img file="ES2179066T3_D0006.tif" />

In the compounds represented by the general faormulas (VII) to (XII), R⁹ yR¹⁰ are each a hydrocarbon group that has 1 to 20 carbon atoms, and can be the same or different from each other, and³ is a hydrocarbon group that has 1 to 20 carbon atoms, or a group represented by:

OOR ¹⁵

<td>—O -, - S -, - S — S -, - S—,</td><td>—S—,</td><td>—C—,</td><td>—N—,</td><td>—P—,</td><td>—P—</td><td>or if-</td>

<td>II OR</td><td>OR</td><td>OR</td><td>^|_R15</td><td>^|_R15</td><td>^|_R15</td><td>^|_R15</td>

where R¹⁵ It is a hydrocarbon group that has 1 to 6 carbon atoms. Among the examples of hydrocarbon group having 1 to 20 carbon atoms which is represented by R⁹ , R¹⁰ hey³ Methylene, ethylene, trimethylene, propylene, diphenylmethylene, ethylidene, n-propylidene, isopropylidene, n-butylidene and isobutylidene are included, with methylene, ethylene, ethylidene, isopropylidene and isobutylidene being most preferred. n is an integer of 0 or more, with 0 or 1 being particularly preferable.

On the other hand, R¹¹, R¹², R¹³ yR¹⁴ they are each a hydrocarbon group having from 1 to 20 carbon atoms, a hydroxyl group, a nitro group, a nitrile group, a hydrocarbyloxy group or a halogen atom, and they may be the same or different from each other. Examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, n-hexyl, n-heptyl, n-octyl, n-decyl and n-dodecyl; aryl groups such as phenyl and naphthyl; cycloalkyl groups such as cyclohexyl and cyclopentyl; an alkenyl group such as propenyl; and an aralkyl group such as benzyl, especially alkyl groups having 1 to 10 carbon atoms being preferred, and, y ', y ”, y”', z, z ', z ”and z”' are each the number of substituents attached

ES 2 179 066 T3 to an aromatic ring, e, y, y ', z and z' are each an integer between 0 and 4, e, y "yz" are each an integer between 0 and 2 , where y ”'and z”' are each an integer between 0 and 3.

The reaction product of the transition metal compound and each of the diols represented by the general formulas (VII) to (XII) is a compound represented by the general formula (XIII):

(and¹) »Or E3, (Y⁴) m M¹ . . (XIII) \ / \ (E²) x OE £,

In the general formula (XIII), M¹ is as defined before, E¹ and E² are each a hydrocarbon group having 1 to 20 carbon atoms, v and x are each 0 and 1, and E¹ and E² form a crosslinking structure through Y⁴. AND³ and E⁴ they are each a δ-binding ligand, a chelate ligand, or a Lewis base, and may be the same or different from each other.

v 'and x' are each an integer between 0 and 2 (v '+ x' = an integer of (the valence M¹-two)]. Y⁴ is a hydrocarbon group that has 1 to 20 carbon atoms, E⁵AND⁶Y⁵, an oxygen atom or a sulfur atom, and m is an integer between 0 and 4. E⁵ and E⁶ are each a hydrocarbon group having 1 to 20 carbon atoms, and Y⁵ it is a carbon atom or a silicon group.

Examples of the compound represented by the general formula (XIII) include:

<img file="ES2179066T3_D0007.tif" />

<img file="ES2179066T3_D0008.tif" />

<img file="ES2179066T3_D0009.tif" />

<img file="ES2179066T3_D0010.tif" />

<img file="ES2179066T3_D0011.tif" />

On the other hand, the compound of general formula (XIII) by general formula (XIV):

also includes a compound depicted

ES 2 179 o66 T3 _OR16 ^|

R¹⁶O— (M⁴ —O—) z — R¹⁶ . . . (XIV)^|_OR16

In the general formula (XIV), the R¹⁶ are each an alkyl group or an acyl group having 1 to 2 carbon atoms, a cycloalkyl group having 6 to 2 carbon atoms, or an aryl group, an alkylaryl group or an arylalkyl group having 6 to 2 carbon atoms, and the R¹⁶corresponding can be the same or different from each other. M⁴ is a metallic element of group 3 or 4 of the periodic table or of the lanthanide series, and z is an integer between 2 and 2.

Typical examples represented by the general phaormula (XIV) include BuO [Zr (OBu) 2O] 4Bu EtO [Zr (OEt) 2O] 4-Et, iPrO [Zr (OiPr) 2O] 4-iPr, nPrO [Zr (OnPr) 2O] 4-nPr, BuO [Zr (OBu) 2O] 3-Bu, BuO [Zr (OBu) 2O] 2-Bu, and these same compounds in which zirconium is replaced by titanium and hafnium. In these formulas Bu is a butyl group, Et is an ethyl group, iPr is an isopropyl group, and nPr is a normal propyl group.

The ethylene copolymer of the present invention can be obtained through various preparation methods, there being no particular restriction on said method, although the catalyst and polymerization conditions must be properly selected. In such case, preferable examples of the catalyst include alkoxy titanium compounds and titanium zirconium compounds in which a crosslinking is present between the ligands.

In the polymerization catalyst for use in the preparation of the ethylene copolymer of the present invention, the transitional metal compounds constituting component (A) can be used alone or by combining two or more of them.

On the other hand, examples of the compound that can be used as component (B) in the polymerization catalyst and that is capable of forming an ionic complex from the transitional metal compound of component (A) or its derivative include (B-1) an ioanic compound for its reaction with the transition metal compound of component (A) to form an ionic complex, (B-2) an aluminoxane, and (B-3) a Lewis acid.

As the ionic compound of component (B-1), any ioanic compound can be used, as long as it reacts with the transitional metal compound of component (A) to form the ioan complex. However, a compound that includes a cation and an anion in which several groups are attached to an element can be suitably used, in particular, a coordinate complex compound that includes a cation and an anioan in which several groups are attached to. an element. The compound that includes a cathioan and an anioan in which several groups are attached to an element is a compound represented by the general formula:

([L¹-R¹⁷]^{k +})p.m¹⁵Z¹Z²... Zⁿ]^(hg-)q ... (XV) or

([L²]^{k +})p.m⁶Z¹Z²... Zⁿ]^(hg)-) q (XVI) in which L² is M⁷, R¹⁸R¹⁹M⁸, R₃²⁰CoR²¹M¹⁸.

[In the faormulas (XV) and (XVI), L¹ is a Lewis base; M⁵ and M⁶ they are each an element selected from groups 5, 6, 7, 8-1o, 11, 12, 13, 14, and 15 of the periodic table, preferably an element selected from groups 13, 14 and 15; M⁷ and M⁸ they are each an element selected from groups 3, 4, 5, 6, 7, 8-1o, 1, 11, 2, 12, and 17 of the periodic table; Z¹ aZⁿ they are each a hydrogen atom, a dialkylamino group, an alkoxy group having 1 to 2 carbon atoms, an aryloxy group having 6 to 2 carbon atoms, an alkyl group having 1 to 2 carbon atoms carbon, an aryl group, an alkylaryl group or an arylalkyl group having 6 to 2 carbon atoms, a halogen substituted hydrocarbon having 1 to 2 carbon atoms, an acyloxy group having 1 to 2 carbon atoms carbon, an organic metalloid group or a halogen atom, and Z¹ aZⁿthey can be joined together to form a ring. R¹⁷ is an atom of hydrogen, an alkyl group that has

ES 2 179 066 T3 of 1 to 20 carbon atoms, or an aryl group, an alkylaryl group or an arylalkyl group having 6 to 20 carbon atoms; R¹⁸ yR¹⁹ they are each a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, or a fluorenyl group; and R²⁰ is an alkyl group having 1 to 20 carbon atoms; an aryl group, an alkylaryl group, or an arylalkyl group. R²¹ it is a large calcium ligand such as tetraphenylporphyrin or phthalocyanine. g is a valence of each M⁵ and M⁶ y is an integer from 1 to 7; h is an integer between 2 and 8; k is a valence of iáon of [L¹ - R¹⁷] or [L²] y is an integer between 1 and 7, yp a round of 1 or more, and q = (pxk) / (h - g).

At this point, among the typical Lewis base examples represented by L¹ include ammonia, amines such as methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, tri-n-butylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline and p- nitro-N, N-dimethylaniline, phosphines such as triethylphosphine, triphenylphosphine and diphenylphosphine, ethers such as dimethalic ether, diethalic ether, tetrahydrofuran and dioxane, thioethers such as diethyl thioether and tetrahydrothiophene and an ester such as benzoate.

Likewise, among the typical examples of M⁵ and M⁶ include B, Al, Si, P, As and Sb, with B and P being preferred. Typical examples of M⁷ include Li, Na, Ag, Cu, Br, and I, and typical examples of M⁸ Mn, Fe, Co, Ni, and Zn are included. Among the typical examples of Z¹ aZⁿ a dimethylamino group and a diethylamino group are included as a dialkylamino group; a methoxy group, an ethoxy group and an n-butoxy group as an alkoxy group having 1 to 20 carbon atoms; a phenoxy group, a 2,6-dimethylphenoxy group and a naphthyloxy group as an aryloxy group having 6 to 20 carbon atoms; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-octyl group and a 2-ethylhexyl group as alkyl groups having 1 to 20 carbon atoms; a phenyl group, a p-tolyl group, a benzyl group, a 4-t-butylphenyl group, a 2,6-dimethylphenyl group, a

3.5-dimethylphenyl, a 2,4-dimethylphenyl group and a 2,3-dimethylphenyl group as aryl groups, alkylaryl groups or arylalkyl groups having 6 to 20 carbon atoms; a p-fluorophenyl group, a group

3.5-difluorophenyl, a pentachlorophenyl group, a 3,4,5-trifluorophenyl group, a pentafluorophenyl group and a 3,5-di (trifluoromethyl) phenyl group as halogen substituted hydrocarbons having 1 to 20 carbon atoms; F, Cl, Br and I as halogen atoms; and a pentamethylanthimonium group, a trimethylsilyl group, a trimethylgermyl group, a diphenylarsine group, a dicyclohexylanantimony group and a diphenylboron group as organic metalloid groups. Among the typical examples of R¹⁷, R²⁰ the aforementioned are included. Among the typical examples of the substituted cyclopentadienyl group of R¹⁸ yR¹⁹Included are groups substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group and a pentamethylcyclopentadienyl group. At this point, the alkyl group usually has 1 to 6 carbon atoms, the number of substituted alkyl groups being an integer from 1 to 5.

Among the compounds represented by the general faormulas (XV) and (XVI), the compounds in which M⁵ and M⁶ they are boron. Of the compounds of the general formulas (XV) and (XVI), topically, the following examples are particularly preferably used.

Examples of the compound of general formula (XV) include triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl-tri (n-butyl) ammonium tetraphenylborate, benzyltri tetraphenylborate. (n-Butyl) -ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl (2-cyanopyridinium) tetraphenylborate, trimethylsulfonium tetraphenylborate, benzylmethylsulfonium tetraphenylborate, triethylammonium tetrakis (pentafluorophenyl) -borate, tetrakis (pentaluorophenyl) -tetrakis (pentaluorophenyl) -butofyl triphenylammonium borate, tetrakis (pentafluorophenyl) -tetrabutylammonium borate, tetrakis (pentafluorophenyl) -tetraethylammonium borate, [Methyltri (n-butyl) ammonium] tetrakis (pentafluorophenyl) borate, [benzyltri (n-butyl) ammonium] tetrakis (pentafluorophenyl) borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) tetrakis (methyldiphenyl) borate Dimethyldiphenyl ammonium pentafluorophenyl) borate, anilinium tetrakis (pentafluorophenyl) borate, methylanilinium tetrakis (pentafluorophenyl) borate, dimethylanilium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, dimethyl (m-nitroanilinium) tetrakis (pentafluorophenyl) borate, dimethyl (p-bromoanilinium) tetrakis (pentafluorophenyl) borate, pyridinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate) -cyanopyridinium), tetrakis (pentafluorophenyl) borate (N-methylpyridinium), tetrakis (pentafluorophenyl) borate (N-benzylpyridinium), tetrakis (pentafluorophenyl) borate (2-cyano-Nmethylpyridinium), (4-cyano-N-methylpyridinium) tetrakis (pentafluorophenyl) borate, (4-cyano-N-benzylpyridinium) tetrakis (pentafluorophenyl) borate, trimethylsulfonium tetrakis (pentafluorophenyl) borate, benzylsulfonium tetrakis (pentafluorophenyl) borate Pentafluorophenyl) tetraphenylphos24 borate

ES 2 179 066 T3 phonium, dimethylanilinium tetrakis (3,5-ditrifluoromethylphenyl) borate, tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) dimethylanilinium borate, tris (pentafluorophenyl) (p-trifluorofluorofhenyl) (p-trifluorofluoromethyl) pyridinium p-trifluoromethyltetrafluorophenyl) borate, tris (pentafluorophenyl) - (N-methylpyridinium p-trifluoromethyltetrafluorophenyl) borate, (2-cyano-N-methylpyridinium) tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) borate, tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) borate (4-cyano-N-benzylophenyl pentafluoriphenyl) (trifluorophenyl pentafluoromethyl) borate ) trisphenylphosphonium borate, tris (pentafluorophenyl) (2,3,5,6-tetrafluoropyridinyl) orate, dimethylanilinium, tris (pentafluorophenyl) - (2,3,5,6-tetrafluoropyridinyl) triethylammonium borate, pyridinium tris- (pentafluorophenyl) (2,3,5,6-tetrafluoropyridinyl) borate, tris (pentafluorophenyl) (2,3,5,6-tetrafluoropyridinyl) borate, tris (pentafluorophenyl) (2, 3,5,6-tetrafluoropyridinyl) -borate (2-cyano-N-methylpyridinium), tris (pentafluorophenyl) (2,3,5,6-tetrafluoropyridinyl) borate (4-cyano-N-benzylpyridinium), tris (pentafluorophenyl) Triphenylphosphonium (2,3,5,6-tetrafluoropyridinyl) borate, dimethylanilinium tris (pentafluorophenyl) (phenyl) borate, Dimethylanilinium tris (pentafluorophenyl) [3,5-di (trifluoromethyl) phenyl] borate, dimethylanilimethyl tris (pentafluorophenyl) (4-trifluoromethylphenyl) borate, dimethylanilimethyl triphenyl (pentafluorophenyl) borate and dimethylanilimethylammonium hexafluoroenmonium borate).

On the other hand, examples of the compound of the general formula (XVI) include ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrinmanganese tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) 1'-dimethylferrocenium), decamethylferrocenium tetrakis (pentafluorophenyl) borate, acetylferrocenium tetrakis (pentafluorophenyl) borate, formylferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) cyanoferrocenium borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, lithium pentafluorophenyl tetrakis (bontafluorophenyl) borate) tetraphenylporphyrinmanganese pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetraphenylporphyriniron chloride, tetrakis (pentafluorophenyl) borate, tetraphenylporphyrinzinc chloride, silver tetrafluoroborate, silver hexafluoroarsenate and silver hexafluoroantimonate.

In addition to the compounds of the general formulas (XV) and (XVI) mentioned above, for example tris (pentafluorophenyl) boron, tris [3,5-di (trifluoromethyl) phenyl] boron and triphenylboron can also be used.

The ionic compounds, which are the components (B-1) capable of reacting with the transition metal compound of the above-mentioned component (A) to form an ionic complex, can be used alone or by combining two or more of them. On the other hand, the component including the transition metal compound of the component (A) and the iogenic compound, which is the component (B-1), capable of forming an ionic complex, may be a polycatiogenic complex.

On the other hand, as the aluminoxane of the component (B-2), a chain aluminoxane represented by the general formula (XVII) can be mentioned:

_R22 _R22 \/

Al - O -— Al - O ——- Al ... (XVII) _{/ |}^{s 2}_\_R22 _R22 _R22 (in which the R²² are each independently a halogen atom, or a hydrocarbon group such as, for example, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an arylalkyl group having 1 to 20 carbon atoms, preferably 1 at 12 carbon atoms, the alkyl group being the most preferable; and s represents the degree of polymerization, and is an integer normally between 3 and 50, preferably between 7 and 40);

and a ceclic aluminoxane represented by the general formula (XVIII):

-(TO_| the _|^|R22 _|^|

... (XVIII) (in which the R²² and s are as defined above).

Among the compounds of the general formula (XVII) and (XVIII), aluminoxanes having a degree of polymerization of 7% are preferable. When using an aluminoxane that have a grade

ES 2 179 066 T3 of polymerization 7 or more, or a mixture of said aluminoxanes, a high activation can be obtained. On the other hand, modified aluminoxanes that can be obtained by modifying the aluminoxanes represented by the general formulations (XVII) and (XVIII) with a compound such as water, which has an active hydrogen and is insoluble in solvents, can also be suitably used. usual.

As a method of preparation of the mentioned aluminoxanes, a method can be mentioned in which an aluminum alkyl is brought into contact with a condensing agent such as water, although no particular restriction is established on the medium, being able to carry out the Reaction follows any of the known modes. For example, there is a method (1) that consists of the dissolution of an organic aluminum compound in an organic solvent and the subsequent contact of the solution with water, (2) a method that consists in the first addition of a compound of organic aluminum at the time of polymerization, and the subsequent addition of water, (3) a method consisting of the reaction of water of crystallization contained in a metal salt or water absorbed in an inorganic substance or an organic substance with an organic aluminum compound, and (4) a method consisting of the reaction of tetraalkyldialuminoxane with a trialkylaluminum, and the subsequent reaction with water. Said aluminoxanes can be used alone or by combining two or more of them.

On the other hand, no particular restriction is established as to the Lewis acid which is the component (B-3), said Lewis acid can be an organic compound or a solid inorganic compound. Among the organic compounds, the use of boron compounds and aluminum compounds is preferable, and as the organic compound, the use of magnesium compounds and aluminum compounds is preferable. Said Lewis compounds can be used alone or by combining two or more of them.

In the present invention, to obtain the ethylene copolymer of the present invention, as catalytic component (B), the components (B-1), (B-2) and (B-3) mentioned above can be used alone. or combining two or more of them.

In the polymerization catalyst, which can be used in the present invention, if desired, as component (C), an organic aluminum compound which is represented by the general formula (XIX):

R²³rAlQ3-r. . . (XIX) in which R²³ is an alkyl group having 1 to 10 carbon atoms; Q is a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group, having 6 to 20 carbon atoms, or a halogen atom; and r is an integer from 1 to 3.

In particular, when the ionic compound (B-1) is used as component (B) which is capable of reacting with the transition metal compound of component (A) to form an ionic complex, together with the organic aluminum compound ( C), high activity can be obtained.

Typical examples of the compound represented by the general formula (XIX) include trimethylaluminum, triethylaluminum triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, diethylaluminum hydrideylaluminumide, diethylaluminum dichloride, diethylaluminum hydrofluoride, and ethylaluminum sesquichloride.

Hereinafter, in the present invention a support can be included in at least one of the catalyst components (A), (B) and, if desired (C) and used later.

No particular restriction is established on the type of support, it being possible to use inorganic oxide supports, other inorganic supports and organic supports, although inorganic oxide supports and other inorganic supports are particularly preferable.

Typical examples of inorganic oxide supports include SiO2, Al2O3, MgO, ZrO2, TiO2, Fe2O3, B2O3, CaO, ZnO, BaO, ThO2, and mixtures thereof, for example silica-alumina, zeolite, ferrite, sepiolite, and fiber. of glass. Among them, SiO2 and Al2O3 are especially preferable. Related to this, the above-mentioned inorganic oxide support may contain a small amount of carbonate, nitrate, sulfate or the like.

On the other hand, examples of supports other than those mentioned include magnesium compounds such as MgCl2 and Mg (OC2H5) 2 and their complex salts, as well as organic magnesium compounds represented by the general formula MgR_i²⁴X_j³ . At this point, R²⁴ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group

ES 2 179 066 T3 having 6 to 20 carbon atoms; X³ is a halogen atom or an alkyl group having 1 to 20 carbon atoms; i is 0 to 2; and j is 0 to 2.

On the other hand, examples of organic supports include polymers such as polystyrenes, styrene-divinylbenzene copolymers, polyethylenes, polypropylenes, polystyrenes and substituted polyacrylates, starch and carbon.

The state of the support that can be used here depends on the type of manufacturing process, although its mean particle diameter is normally within the range of 1 to 300 µm, preferably 10 to 200 µm, more preferably 20 to 100 µm. .

If the particle diameter is small, the fine polymer powder increases, and if the particle diameter is large, the number of coarse particles of the polymer increases, causing deterioration of block density and jamming of the hopper.

On the other hand, the specific surface area of ​​the support is normally within the range of 1 to 1000 μm.²/ g, preferably 50 to 500 m²/ g, and its pore volume is normally within the range of 0.1 to 5 cm³/ g, preferably 0.3 to 3 cm³/ g.

If both the specific surface area and the pore volume deviate from the mentioned ranges, sometimes the activity of the catalyst deteriorates. In this regard, the specific surface area and pore volume can be calculated from the adsorbed nitrogen gas volume according to the BET method [see Journal of the American Chemical Society, vol., 60, p. 309 (1983)].

On the other hand, it is desirable to calcine the aforementioned support, when used, at 150-1000^°C, preferably 200-800^°C.

No particular restriction is established as to the method for including the catalytic components in the support, and any of the usual methods may be used.

Next, the relationship between the corresponding catalyst components that can be used in the present invention will be described. In the case (1) in which the catalytic components (A) and (B-1) are used, both components are suitably used so that the molar ratio of component (A) / component (B-1) can be within in the range of 1 / 0.1 to 1/100, preferably 1 / 0.5 to 1/10, more preferably 1/1 to 1/5. In the case (2) that catalytic components (A), (B-1) and (C) are used, the molar ratio of component (A) / component (B1) is the same as that of case (1) mentioned above, but the molar ratio of component (A) / component (C) is within the range of 1 / 2,000 to 1/1, preferably 1 / 1,000 to 1/5, more preferably 1/500 to 1/10.

On the other hand, in the case (3) that catalytic components (A) and (B-2) are used, both components are suitably used so that the molar ratio of component (A) / component (B-2) is It is within the range of 1/20 to 1 / 10,000, preferably 1/100 to 1 / 5,000, more preferably 1/200 to 1 / 2,000. In the case (4) that catalytic components (A), (B-2) and (C) are used, the molar ratio between component (A) / component (B-2) is the same as in the case (3) mentioned above, but the molar ratio of component (A) / component (C) is within the range of 1 / 2,000 to 1/1, preferably 1 / 1,000 to 1/5, more preferably 1/500 to 1/10.

On the other hand, in the case (5) that catalytic components (A) and (B-3) are used, both components are used appropriately so that the molar ratio between component (A) / and component (B- 3) is within the range of 1 / 0.1 to 1 / 2,000, preferably 1 / 0.2 to 1 / 1,000, more preferably 1 / 0.5 to 1/500. In the case (6) that catalytic components (A), (B-3) and (C) are used, the molar ratio between component (A) and component (B-3) is the same as in previous case (5), but the molar ratio between component (A) and component (C) is within the range of 1 / 2,000 to 1/1, preferably 1 / 1,000 to 1/5, more preferably 1/500 to 1/10.

In the process of the present invention, an ethylene copolymer can be efficiently obtained in which the activation energy (Ea) of the melt flow and the Huggins coefficient can be controlled, which has better non-Newtonian properties, as well as excellent working properties, by polymerization of ethylene and an olefin having 3 to 20 carbon atoms in the presence of a catalyst consisting of (a) a transition metal compound in which the ratio of the monoimer charge composition [a molar ratio [ M] of 1-octene / (ethylene + 1-octene)] and the product of the enthalpy of crystallization (ΔΗ) and the melting point (Pf) of the produced copolymer satisfies the equation:

ES 2 179 066 T3 &lt;ΔΗ.Ρί &lt;27,000 - 21 - 600 [M]⁰,⁵⁶ (however, under the polymerization conditions in which component (a) is used together with an aluminumxane), (b) a transition metal compound capable of forming a terminal vinyl group in the homopolymerization of ethylene or the copolymerization of ethylene and at least one ethylene selected from olefins having 3 to 20 carbon atoms (however, under polymerization conditions in which component (b) is used together with aluminoxane), and (c) a compound capable of forming an ioenic complex from the aforementioned components (a) and (b) or their derivatives, said components (a), (b) and (c) being selected from among transition metal compounds. of components (A) containing a metal from groups 3 to 10 of the periodic table or from the lantaenide series, preferably titanium, zirconium, hafnium, chromium, vanadium or a metal from the lantaenide series.

Likewise, when said polymerization catalyst is used, as described above, the organogenic aluminum compound which is the aforementioned component (C) can be additionally used, and at least one of the catalytic components can be supported on a support. suitable. On the other hand, the practical relationship between component (a) and component (b) depends on the unique catalytic activity of each component, and therefore cannot be radically decided, although when the ratio of component (a) is increased , an ethylene copolymer having superior non-Newtonian properties can be obtained. In general, the molar ratio between component (a) and component (b) is selected within the range of 1/1000 to 1,000/1, preferably 1/500 to 500/1, more preferably 1/300 to 300/1. .

The transition metal compound that constitutes component (a) has the catalytic component whose copolymerization properties are in a specific range and, on the other hand, the transition metal compound that is component (b) is a catalytic component. capable of forming a terminal vinyl group. When these two types of transition metal compounds are combined and used, an ethylene copolymer can be obtained which has non-Newtonian properties. It is believed that the fact that the ethylene copolymer has the non-Newtonian properties is due to the presence of long chain branches and, in view of the mechanism of formation of the branches, it can be assumed that not only one polymer of comb shape, but also a branch is formed in the branched chain in the system.

Next, reference is made to the formation of the terminal vinyl group and the properties of copolymerization by the aforementioned catalyst.

(a) Formation of the terminal vinyl group

Normally, the formation of the terminal vinyl group is considered to be due to the elimination chain transfer of the β hydrogen and β alkyl group at the growing terminal in a polymerization system involving ethylene and propylene. It can be determined by evaluating the polymer produced by polymerization or copolymerization of ethylene using the transition metal compound of component (b) and the aluminoxane, whether or not the catalyst has the ability to form the terminal vinyl group. However, when polymer production is low, it is necessary to employ polymerization conditions to reduce molecular weight, such as increasing catalyst concentration and decreasing monoomer concentration.

The determination of the terminal vinyl group can be carried out by calculating the number n of terminal vinyl groups in relation to 100 carbon atoms based on the terminal vinyl group peak that appears at 907 cm^-1 in the measure of IR, according to the following equation:

n = 0.114 x A907 / (dx T) where A907 is the absorbance at 907 cm^-1, d is the density (g / ml); and T is the thickness of the film to be measured.

As the catalytic component that the polymer having a large number of terminal vinyl groups thus calculated, that is, the properly usable transition metal compound of component (b), can be mentioned, there can be mentioned compounds containing a metal such as titanium, zirconium, hafnium, vanadium or chromium.

ES 2 179 066 T3

The number of terminal vinyl groups does not always mean an ease of production of the vinyl groups, since when the catalyst is used that can easily produce the groups and that can easily make the vinyl groups react with the monomer to form the branches, the numberer of vinyl groups is finally reduced. On the contrary, when using a catalyst that can easily form vinyl groups and has poor copolymerization properties, many vinyl groups remain.

Therefore, it is necessary to inspect the ease of branching formation. This can be evaluated by the relationship between the number average molecular weight Mn as regards polyethylene as measured by gel permeation chromatography (GPC) and the number average molecular weight Mn calculated based on the relationship between the methylene groups. in the main chain and end groups measured by¹H-NMR. When carrying out the evaluation of the branching based on this Mn ratio, it is necessary to globally judge and determine the Mn ratio taking into account (1) that the Mn measured by GPC does not always represent a real molecular weight when the polymer it has a branching structure, and (2) that when the molecular weight distribution is wide, the precision of the Mn value is low.

The transition metal compound of the catalytic component (b) having such terminal vinyl group forming properties includes:

(1) Compounds having a -OR group (where R is an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, a cycloalkyl group, a halogenated alkyl group, or a halogenated aryl group having 1 at 20 carbon atoms), (2) compounds represented by the formula (II)

Cp2M¹R¹aR²b ... (II) (3) compounds represented by the formula (III) (CP - Ae - Cp) M¹R¹aR²b ... (III) (where Cp, A, R¹, R², a, bye are as defined before and M¹ is titanium, zirconium or hafnium).

(b) Copolymerization properties

To copolymerize the formed vinyl end group with ethylene or another comonoemer, superior copolymerization properties are required. In particular, the copolymerization properties of a higher α-olefin tend to deteriorate enormously, since the number of carbon atoms decreases, also decreasing the ratio of the vinyl group per molecular weight.

In the process of the present invention, a copolymerization system is required in which the ratio between the proportion of the monoomer composition [a molar ratio [M] of 1-octene / (ethylene + 1octene)] and the product of the recrystallization enthalpy (ΔΗ) and melting point (Pf) of the produced copolymer satisfy the equation:

&lt;ΔΗ.Γί &lt;27,000 - 21,600 [M]⁰,⁵⁶ and that to satisfy the requirements, a transition metal compound is used which is component (a). On the other hand, the polymerization conditions are evaluated by selecting excellent polymerization conditions using the transition metal compound of component (a) and the aluminoxane. Method to verify the relationship of the previous equation

The enthalpy of crystallization (ΔΗ) can be obtained as follows. That is, the enthalpy of crystallization (ΔΗ) (unit = J = g) can be calculated as a function of the exothermic peak of crystallization observed at the moment in which a heat-pressed sample sheet melts at a temperature of 190^°C, at a temperature of 150^°C for 5 minutes using a differential scanning calorimeter (model DSC7, manufactured by Perkin Elmer Co., Ltd.) and then cool to -50^°C at a speed of 10^°C / min.

On the other hand, the copolymerization conditions are (1) that polymerization can be carried out under atmospheric pressure or with increased pressure, (2) that polymerization is acceptable.

ES 2 179 o66 T3 discontinuous in which the ethylene alone is fed continuously (anyway, the monoomer conversion is 2o% or less), or a continuous polymerization, (3) that the polymerization temperature is within the range of ± 10 ° C of the temperature at which the maximum polymerization activity is obtained, or a temperature at which the polyethylene polymer with non-Newtonian properties can be prepared in a real mixed catalyst system, (4) that the copolymerization reaction starts once the composition ratio between ethylene and the comonomer and the total concentration have reached a constant state, (5) that the molecular weight of the copolymer produced is greater than a critical molecular weight and that the polymerization should not be carried out in a region where the melting point increases with an increase in molecular weight, (6) that the ethylene concentration and the gaseous monoomer concentration are calculated as a function of the weight of the ethylene or monomer that dissolves in a polymerization solvent and with which the polymerization solvent is saturated at a certain temperature, (7) that in the case of gaseous polymerization, the monomer charge composition ratio is calculated as a function of the partial pressure of the monomer feed ratio, (8) that polymerization conditions in which the monomer composition of the system is changed by diffusion of ethylene or gaseous monomer are unacceptable, (9) that polymerization should not continue under conditions in which ethylene is not consumed by polymerization, and (10) that the molar ratio between the corresponding catalyst components is such that the ratio between the transition metal compound (a) and the aluminoxane is in the range of 1/100 to 1 / 2,000.

The relationship between the ratio of the monomeric monomer charge composition [M] and the product of recrystallization enthalpa (ΔΗ) and the melting point (Pf) of the ethylanic polymer produced must satisfy the equation:

&lt;ΔΗ.Ρί &lt;27,000 - 21,600 [M]⁰,⁵⁶ and if the product of the ΔΗ and the melting point (MP) exceeds this range, the transitional metal compound (a) does not exert the preferable copolymerization properties.

Said ratio is preferably &lt;ΔΗ.Ρί &lt;27,000 - 22,000 [M]⁰,⁵³ more preferably, &lt;ΔΗ.Ρί &lt;27,000 - 23,000 [M]⁰,⁵³ more preferably auán &lt;ΔΗ.Ρί &lt;27,000 - 24,000 [M]⁰,⁴⁷ more preferably auán &lt;ΔΗ.Ρί &lt;27,000 - 26,000 [M]⁰,⁴⁰ being above all &lt;ΔΗ.Ρί &lt;27,000 - 27,000 [M]⁰,²⁷

Among the compounds of transition metal that is the catalytic component (a) that have said copolymerization properties include the compounds represented by the general formulas:

CpM¹R¹aR²bR³c ... (I) (Cp - Ae - Cp) M¹R¹aR²b ... (III)

ES 2 179 066 T3 (VI)

<img file="ES2179066T3_D0012.tif" />

(Y⁴) μ ϊ

<img file="ES2179066T3_D0013.tif" />

y * (E¹) v OR EV, \ / _M1

... (XIII) / \ (E²) xO EX,

<img file="ES2179066T3_D0014.tif" />

<img file="ES2179066T3_D0015.tif" />

have been defined before and M¹ represent titanium, zirconium or hafnium. The compounds represented by the formulas (VI) and (III) are particularly preferred, as they have a high polymerization activity.

The polymerization using the above-mentioned catalyst can be carried out through a one-stage polymerization or through the two-stage polymerization described below, in the presence of catalytic components (a), (b) and (c) . That is, ethylene is homopolymerized in the presence of a catalytic system consisting of components (b) and (c) to substantially produce the polymer, and the catalytic component (a) is then added to the polymerization system to continue polymerization. According to this process, control of the molecular weight distribution is possible, and the distribution of the degree of branching can be changed. Therefore, a molecular design that meets the requirement of physical properties over a wide range is possible. Also, in the two-stage polymerization, the ethylene copolymer can be provided in which the amount of unsaturated carbon-carbon bonds in the produced ethylene copolymer is decreased and the thermal stability is improved. On the other hand, the ethylene copolymer obtained through one-stage polymerization is suitable as a material for a chemically modifiable ethylene polymer, thanks to the presence of relatively large unsaturated groups. In such a two-stage polymerization, the comoneomer can be introduced into the polymerization stage constituting the second stage, or it can be introduced into both stages of polymerization, that is, the first and the second stage.

In the present invention, no particular restriction is placed on the polymerization method for preparing the ethylene copolymer, and therefore a solvent polymerization method using an inert hydrocarbon or the like (suspension polymerization or the like can be used). solution polymerization), a bulk polymerization method in which polymerization is carried out in the substantial absence of an inert hydrocarbon solvent, and a gas phase polymerization method.

Examples of the hydrocarbon solvent that can be used in the polymerization include saturated hydrocarbons such as butane, heptane, hexane, heptane, octane, nonane, decane, cyclopentane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; and chlorine-containing solvents such as chloroform, dichloromethane, ethylene dichloride, and chlorobenzene.

The polymerization temperature is normally between -100 and 200^°C, preferably between -50^°C and 100^°C, more preferably between 0 and 100^°C, and the polymerization pressure is normally between atmospheric pressure and 9.8 MPa (100 kg / cm²), preferably between atmospheric pressure and 4.9 MPa (50 kg / cm²), more preferably between atmospheric pressure and 1.9 MPa (20 kg / cm²).

The control of the molecular weight of the polymer obtained is carried out through the usual means, such as, for example (1) hydrogen, (2) temperature, (3) the monoomer concentration or (4) the catalyst concentration.

In the hydrogenation treatment of the above obtained ethylene copolymer, a hydrogenation catalyst can be used. No particular restriction is established on the type of hydrogenation catalyst, the above-mentioned catalysts in detail and the catalysts that are usually used at the time of hydrogenation of an olefin compound can be used. For example,

ES 2 179 066 T3 the following catalysts can be mentioned.

Examples of heterogeneous catalysts include nickel, palladium, and platinum, as well as solid catalysts obtained by including a support on these metals, such as carbon, silica, diatomaceous earth, alumina, and titanium ioxide, for example, nickel- Silica, Nickel-Diatomaceous Earth, Palladium-Carbon, Palladium-Silica, Palladium-Diatomaceous Earth, and Palladium-Aluminum. Examples of the nickel catalyst include Raney nickel catalysts, and examples of platinum catalysts include platinum black and platinum ioxide catalysts. Examples of homogeneous catalysts include catalysts that contain metals from groups 8 to 10 of the periodic table as basic components, for example catalysts that include Ni and Co compounds and organo-metal compounds of metals selected from groups 1, 2 and 3 of the periodic table, such as cobalt naphthenate-triethylaluminum, cobalt octenoate-n-butyllithium, nickel acetylacetonate-triethylaluminum and Rh compounds.

On the other hand, the Ziegler hydrogenation catalysts described by MS Saloan et al., [J. Am. Chem. Soc., 85, p. 4014 (1983)]. Examples of these catalysts include the following compounds.

Ti (O-iC3H7) 4- (iC4H9) 3Al,

Ti (O-iC3H7) 4- (C2H5) 3Al, (C2H5) 2TiCl2- (C2H5) 3Al,

Cr (acac) 3- (C2H5) 3Al, (where acac represents acetylacetonate),

Na (acac) - (iC4H9) 3Al, Mn (acac) 3- (C2H5) 3Al, Fe (acac) 3- (C2H5) 3Al, Ca (acac) 2- (C2H5) 3Al, and (C7H5COO) 3Co- ( C2H5) 3Al.

The amount of the catalyst that is used in the hydrogenation stage is suitably selected so that the molar ratio of the remaining unsaturated groups to the hydrogenation catalyst components in the ethylene copolymer can be in the range of 10⁷: 1 to 10: 1, preferably between 10⁶: 1 and 10²:1.

On the other hand, the hydrogen loading pressure is suitably within the range between atmospheric pressure and 4.9 MPa (50 kg / cm²M). Also, the reaction temperature is preferably on the upper side within the range in which the polyethylene obtained in the polymerization process does not decompose and is normally selected in the range of -100 to 300.^°C, preferably -50^°C to 200^°C, being more preferable from 10 to 180^°C.

In the following, the present invention will be described in more detail with reference to the examples, although the scope of the present invention should not be limited by such examples.

Example 1 (1) Preparation of catalyst component

A 100 ml oval plant type flask was dried and purged with nitrogen. Next, 30 ml of toluene and 3.6 ml of a solution of n-butyllithium in hexane (1.66 mol / liter) were placed in the flask, followed by cooling the solution to -78 ° C. Next, 0.56 g of cyclopentanol was added dropwise and then the solution was warmed to -50^°C for 60 minutes.

Subsequently, 26 ml of a solution of pentamethylcyclopentadiene titanium trichloride in toluene (0.0769 mol / l) was added dropwise to the solution over 60 minutes. The solution was made up to -25^°Cydespuíes the reaction was carried out for 120 minutes. Next, the solution was set up to 20^°C and then left to rest for 24 hours. The resulting reaction solution was light yellow, and a white precipitate of lithium chloride also occurred at the bottom of the flask.

ES 2 179 066 T3 (2) Preparation of methylaluminoxane

200 ml of toluene, 17.8 g (71 mmol) of copper sulfate pentahydrate (CuSO4.5H2O) and 24 ml (250 mmol) of trimethylaluminum, and the mixture was then reacted at 40 C for 8 hours. Then, it was extracted by distillation from the solution obtained by separating the solid components, toluene, under reduced pressure to obtain 6.7 g of a catalytic product (methylaluminoxane). Also, this product was subjected to heat treatment at 120 ° C for 10 hours under reduced pressure, and then dissolved and dispersed in toluene.

(3) Preparation of ethylene / 1-butene copolymer

300 ml of toluene and 30 mmol of the methylaluminoxane previously prepared in step (2) were introduced, under a nitrogen atmosphere, into a 1 liter flask equipped with a stirrer. Next, the solution is heated to 60 ° C, and then ethylene gas was introduced under atmospheric flow conditions to saturate the flask with ethylene gas. Also, 1-butene was continuously fed. Next, 9 ml of the solitary solution portion of the catalyst component prepared in step (1) above was introduced into the flask.

The reaction temperature will be controlled at 60^°C, and polymerization will be carried out for 120 minutes while continuously feeding ethylene and 1-butene. At this time, the total amount of the 1-butene introduced was 5.5 g. After completion of the copolymerization, a large amount of methanol was introduced, followed by washing and subsequent drying, under reduced pressure, to obtain 1.54 g of ethylene-1-butene copolymer.

(4) Evaluation of the ethylene-1-butene copolymer (a) Measurement of the Huggins coefficient

In 15.691 g of decalin, 0.0444 g of the copolymer obtained in step (3) above was dispersed at 135^°C. The concentration of the polymer obtained when the density of the decalin is 135^°C was 0.79055 g / ml was 0.2237 g / dl. The reduced viscosity of the polymer to 135^°C measured with a Ubbelode viscaometer was 2,778 dl / g. Also, this 6-point viscosity measurement was carried out at a substantially equivalent range, in the same manner as described above, at the same time as the polymer as mother liquor was diluted with decalin.

The Huggins coefficient determined according to the method of measurement that has been described was 0.494, the intrinsic viscosity [η] was 2.22 dl / g. and the correlation coefficient was 0.998. On the other hand, the Huggins coefficient of the straight chain ethylene polymer with an [η] of 2.22 dl / g prepared by using a titanium tetrachloride / triethylaluminum catalyst was 0.365 and the relationship between these Huggins coefficients It was 1.35.

On the other hand, the Huggins coefficient of the ethylene / 1-butene copolymer with an [η] of 2.22 dl / g prepared by using a titanium tetrachloride / triethylaluminum catalyst was 0.410 and the ratio between both coefficients of Huggins was 1.21.

(b) NMR structure analysis

The measurement of ¹³C-NMR [100 MHz, measurement temperature = 130^°C, 1,2,4-trichlorobenzene / heavy benzene solvent (molar ratio = 8/2), 100 MHz]. The results are shown in figure 2.

No absorption of the methyl group will be observed in the vicinity of the quaternary carbon atom which will be observed at 8.15 ppm in an LDPE, and an ethyl branching will be observed at 11.14 ppm. However, judging from the fact that the methyl carbon and methylene carbon absorptions are present at 38-39 ppm and 34-36 ppm, respectively, it can be considered that long chain branching is also present.

(c) Evaluation of thermal behavior

A heat-pressed sheet at a temperature of 190 was used as a sample.^°C, and the measurement will be performed using a difference scanning calorimeter model DSC7 manufactured by Perkin

ES 2 179 066 T3

Elmer Co., Ltd. That is, the enthalpy of crystallization (ΔΗ) was calculated as a function of the exothermic peak of crystallization observed at the time the laminum melted at a temperature of 150^°C for 5 minutes, then cooled to -50^°C at a speed of 10^°C / min. A melting point (Pf) was obtained from the endothermic peak observed at the time the lamin was heated at a rate of 10^°C / min.

As a result, neither the enthalpy of crystallization (ΔΗ) nor the melting point (Pf) was observed, so the lamin was amorphous.

(d) Density measurement

A sample was used hot press molded at 190^°C and the measurement was carried out according to the density gradient tube method. As a result, the density was 0.886 g / cm³. Additionally, no anelation treatment was carried out on the sample.

(e) Measurement of terminal vinyl groups

A press sheet having a thickness of 100 µm was prepared, and the transmitted infrared absorption spectrum was measured. The number of vinyl groups was calculated as a function of absorbance (A907) based on the terminal vinyl groups in the vicinity of 907 cm^-1, a film thickness (t) and a resin density (d) according to the equation:

n = 0.114 A907 / [dt] where d = g / cm³, t = mm, and n = number of vinyl groups in relation to 100 carbon atoms. As a result, the number of terminal vinyl groups was 0.67 relative to 1,000 carbon atoms.

(f) Measurement of molecular weight distribution

The molecular weight for polyethylene was measured using a Waters ALC / GPC150C apparatus, a TSK HM * GMH6x2 column manufactured by Toso Co., Ltd. a 1,2,4-trichlorobenzene solvent, a temperature of 135^°C and a flow rate of 1.0 ml / min according to the GPC method. As a result, the Mw / Mn ratio between the weight average molecular weight and the number average molecular weight was 3.05, and the weight average molecular weight (Mw) was 153,000.

(g) Measurement of activation energy (Ea) of melt flow

The activation energy (Ea) of the melt flow was measured using an RMS E-605 apparatus manufactured by Rheometrics Co., Ltd. according to the following procedure. That is, the frequency dependencies were measured (10^-2 a10² rad / sec) of the dynamic viscoelastic properties, at measurement temperatures of 150^°C, 170^°C, 190^°C, 210^°C and 230^°C, and then the activation energy (Ea) was calculated as a function of the displacement factors of G ', G ”at the corresponding temperatures and the reciprocal number of the absolute temperature according to the Arrhenius equation by using a temperature-time conversion rule in which it was used 170^°C as standard temperature.

As a result, the activation energy (Ea) was 12.0 kcal / mol. Related to this, the Ea of a HDPE was 6.3 kcal / mol [Polym. Eng. Sci. Vol., 8, p. 235 (1968)].

Example 2

Ethylene-1-Butene Copolymer

Under a nitrogen atmosphere, 400 ml of toluene, 0.25 mmol (2 moles / liter) of a solution of triisobutylaluminum in toluene and 30 mmol of the methylaluminoxane prepared in Example 1- (2) were placed in a resistant autoclave. 1 liter capacity pressure equipped with stirrer and then the solution was heated up to 70^°C. Next, 3.26 g of 1-butene was poured into the solution, followed by stirring for 5 minutes. The autoclave was then saturated with ethylene at a pressure of 9.0 kg / cm²M and 9 ml of the catalyst prepared in Example 1- (1) was poured through an equilibrium line to initiate polymerization.

At the same time that the ethylene pressure was controlled so that the total pressure could be a gauge pressure of 941 KPa (9.6 kg / cm²M), polymerization was carried out for 60 minutes. After completion of the polymerization, the resulting polymer was collected. Table 2 shows the

ES 2 179 066 T3 results.

Example 3

Ethylene-1-octene copolymer

The same procedure as that of example 2 was carried out with the exception that 2 ml of 1-octene were used instead of 1-butene and that 10 mmol of the methylaluminoxane prepared in example 1- (2), 1 were used, 5 ml of the catalyst component prepared in Example 1- (1), an ethylene gauge pressure of 735 kPa (7.5 kg / cm²M) and a polymerization temperature of 70^°C. Table 2 shows the results.

Example 4

Ethylene-1-Butene Copolymer

The same procedure as in Example 1 was carried out, with the exception that in Example 1 (2), 0.25 ml (2 moles / liter) of a solution of triisobutylaluminum in toluene was poured into a toluene solvent and then the solution was added to the polymerization system, and 0.4 mmol of anilinium tetrakis (pentafluophenyl) borate was added instead of methylaluminoxane, thus preparing an ethylene-1-butene copolymer. Table 2 shows the results.

TABLE 2

<td></td><td colspan="4">Example</td>

<td></td><td> 1</td><td> 2</td><td> 3</td><td> 4</td>

<td>Yield (g)</td><td> 15,4</td><td> 31,1</td><td> 8,6</td><td> 16,3</td>

<td>Intrinsic viscosity [η]</td><td> 2,22</td><td> 3,51</td><td> 0,89</td><td> 2,79</td>

<td>^{(dl /}g)</td><td></td><td></td><td></td><td></td>

<td>k¹</td><td> 0,494</td><td> 0,594</td><td> 0,394</td><td> 0,458</td>

<td>k²</td><td> 0,365</td><td> 0,472</td><td> 0,275</td><td> 0,395</td>

<td>k³</td><td> [0,410]</td><td> [0,478]</td><td> [0,325]</td><td> [0,410]</td>

<td>k¹/ k²</td><td> 1,35</td><td> 1,26</td><td> 1,43</td><td> 1,16</td>

<td>k¹/ k³</td><td> 1,21</td><td> 1,24</td><td> 1,21</td><td> 1,12</td>

<td>Mp (° C)</td><td> -</td><td> 89,1</td><td> 123,1</td><td> 114,2</td>

<td>ΔΗ (J / g)</td><td> -</td><td> 125</td><td> 195</td><td> 115</td>

<td>Density (g / cm³)</td><td> 0,886</td><td> 0,909</td><td> 0,957</td><td> 0,904</td>

<td>¹³C-NMR</td><td> *1</td><td>^*1^*</td><td> *2</td><td> *1</td>

<td>P.m</td><td> 153000</td><td> 258000</td><td> 48100</td><td> 273000</td>

<td>Pm / Mn</td><td> 3,05</td><td> 92,2</td><td> 16,1</td><td> 30,5</td>

<td>Terminal vinyl groups (groups / 1000 atoms of</td><td> 0,67</td><td> 2,4</td><td> 3,5</td><td> 0,16</td>

<td>carbon)</td><td></td><td></td><td></td><td></td>

<td>Melt flow activation energy</td><td> 12,0</td><td> 12,1</td><td> 11,5</td><td> 9,7</td>

Melt flow activation energy: (kcal / mol) (notes) k¹: Huggins coefficient of the copolymer of each example.

k²: Huggins coefficient of a straight chain ethylene polymer with the same [η] k³: Huggins coefficient of a straight chain ethylene-a-olefin copolymer (whose density is substantially the same as in each of the examples) having the same [η] 35

ES 2 179 066 T3

Pf: melting point

ΔΗ: Enthalpy of crystallization

Pm: Weight Average Molecular Weight

Mn: Number average molecular weight * 1: No absorption was present at 8.15 ppm, and an ethylene branch was present at 11.14 ppm.

^*2: No absorbency was present at 8.15 ppm, and an ethyl branch was present at 14.02 ppm.

Example 5

The ethylene / 1-octene copolymer obtained in Example 3 was hydrogenated under conditions of a temperature of 140^°C, a polymer concentration of 2% by weight, a hydrogen gauge pressure of 2.9 MPa (30 kg / cm²M), a concentration of ruthenium catalyst supported on carbon (Ru content = 5% by weight) of 4% by weight and a reaction time of 6 hours, in decalin solvent, and then the polymer obtained in the reaction solution.

From this polymer, a hot-pressed sheet having a thickness of 300 µm was formed and the infrared absorption spectrum was measured. As a result, no absorption of unsaturated groups was observed in the range of 885 to 907 cm.^-1 .

Example 6 (1) Preparation of catalyst component

The same procedure as that of Example 1- (1) was carried out, except that 0.56 g of cyclopentanol was substituted for 0.38 g of isopropanol, to prepare a catalyst component.

(2) Preparation of methylaluminoxane

Methylaluminoxane was prepared in the same way as Example 1- (2).

(3) Preparation of ethylene / 1-octene copolymer

200 ml of toluene, 2 ml of 1-octene and 20 mmol of the methylaluminoxane (MAO) prepared in step (2) above were introduced into a stainless steel autoclave, under a stream of nitrogen, and the mixture was then heated to 60^°C. Subsequently, the nitrogen was replaced by ethylene and ethylene was introduced for 10 minutes, while the solution was stirred. Then 0.1 mmol relative to the titanium of the titanium catalytic component prepared in step (1) above and 0.67 micromoles of ethylenebisindenylzirconium dichloride were added thereby initiating the copolymerization of ethylene and 1-octene.

At the same time as ethylene was introduced, the reaction was carried out for 120 minutes, and then the reaction solution was poured into methanol to sufficiently remove the ashes and wash the solution, and then dried under reduced pressure to obtain 16 , 5 g of ethylene / 1-octene copolymer.

(4) Evaluation of ethylene / 1-octene copolymer (a) Measured by NMR

The measurement of 'II-HMN [400 Mllz. measuring temperature = 130 ° C, solvent 1,2,4-trichlorobenzene / heavy benzene (molar ratio = 8/2)]. As a result, the molar ratio of ^ Η₃© Η₂] calculated as a function of the integrated value of the absorption of the methyl group at 0.8-1.0 ppm and the absorption of the methylene group at 1.2-1.4 ppm was 0.015. On the other hand, the¹³C-NMR in the same way and, as a result, no absorption was observed at 8.15 ppm of the methyl group in the vicinity of the quaternary carbon atom as would be observed in an LDPE. On the other hand, no absorption was observed at 14.02, 22.28 and 27.28 ppm considered as corresponding to a hexyl branch.

ES 2 179 066 T3 derived from 1-octene.

(b) Evaluation of thermal behavior

A heat-pressed sheet at a temperature of 190 ° C was used as a sample and the measurement was carried out by using a differential scanning calorimeter model DSC7 manufactured by Perkin Elmer Co., Ltd. That is, a melting point was obtained. (Pf) from the endothermic peak observed at the moment when the amino acid melted at a temperature of 150^°C for 5 minutes, cooled to -50^°C at a speed of 10^°C / min, and then heated at a speed of 10^°C / min.

As a result, the melting point (Pf) was 99.6^°C.

(c) Density measurement

The measurement was carried out in the same way as in example 1- (4) - (d). As a result, the density was 0.9023 g / cm³. On the other hand, the aging treatment of the sample was not carried out.

(d) Measurement of molecular weight distribution

The measurement was carried out in the same way as in Example 1- (4) - (f), and as a result, the weight average molecular weight (Mw) was 139,000, the number average molecular weight (Mn) was 63,000 and the Pm / Mn ratio was 2.2.

(e) Measurement of activation energy (Ea) of melt flow

The measurement was carried out in the same way as in Example 1- (4) - (g) and, as a result, the activation energy (Ea) was 11.8 kcal / mol.

Examples 7 to 9

Each of the ethylene copolymers was prepared according to the conditions indicated in Table 3. Table 4 shows the results.

TABLE 3 (I)

<td rowspan="2"></td><td rowspan="2">Toluene (ml)</td><td rowspan="2">1-octene (mmol)</td><td rowspan="2">1-hexene (mmol)</td><td rowspan="2">MAO (mmol)</td><td colspan="2">Transition metal components</td>

<td>Kind</td><td>(mmol)</td>

<td>Example 6</td><td> 200</td><td> 2</td><td> -</td><td> 20</td><td>Component titanium Component zirconium</td><td> 0,1 0,0067</td>

<td>Example 7</td><td> 200</td><td></td><td> 1</td><td> 20</td><td>Component titanium Component zirconium</td><td> 0,1 0,0067</td>

<td>Example 8</td><td> 200</td><td> 1</td><td></td><td> 20</td><td>Component titanium Component zirconium Component zirconium</td><td> 0,1 0,01 0,001</td>

<td>Example 9</td><td> 400</td><td> 1</td><td></td><td> 20</td><td>Component titanium Component zirconium</td><td> 0,1 0,02</td>

ES 2 179 066 T3

TABLE 3 (II)

<td></td><td>Ethylene pressure (Ρ *)</td><td>Temperature (° C)</td><td>Weather (min)</td><td>Performance⁽g)</td>

<td>Example 6</td><td>Flowable</td><td> 30</td><td> 120</td><td> 16,5</td>

<td>Example 7</td><td>Flowable</td><td> 60</td><td> 100</td><td> 17,0</td>

<td>Example 8</td><td>Flowable</td><td> 90</td><td> 120</td><td> 7,0</td>

<td>Example 9</td><td>Flowable</td><td> 60</td><td> 120</td><td> 43,2</td>

[Notes]

Titanium Component: Catalyst prepared in Example 6- (1), and "mmol" was the value relative to titanium.

Zirconium component: ethylenebisindenylzirconium dichloride.

TABLE 4 (I)

<td></td><td>Density (g / cm³)</td><td>Grade ramification</td><td>Weight medium weight molecular ^ m)</td><td>Molecular weight distribution ^ m / Mn)</td>

<td>Example 6</td><td> 0,902</td><td> 0,026</td><td> 141.000</td><td> 2,8</td>

<td>Example 7</td><td> 0,907</td><td> 0,023</td><td> 145.000</td><td> 2,3</td>

<td>Example 8</td><td> 0,916</td><td> 0,020</td><td> 93.000</td><td> 2,7</td>

<td>Example 9</td><td> 0,935</td><td> 0,012</td><td> 234.000</td><td> 2,5</td>

[Note]: Degree of branching: A [C ^ / C ^] molar ratio calculated by ¹II-HMN.

TABLE 4 (II)

<td></td><td>Melt flow activation energy [Ea] (kcal / mol)</td><td>Melting point (° C)</td><td>¹³C-NMR</td>

<td>Example 6</td><td> 11,8</td><td> 99,6</td><td>TO</td>

<td>Example 7</td><td> 12,1</td><td> 95,0</td><td>B</td>

<td>Example 7</td><td> 12,0</td><td> 110,3</td><td>TO</td>

<td>Example 9</td><td> 11,8</td><td> 117,5</td><td>TO</td>

[Notes]: A: no absorptors were present at 8.15 ppm, and absorptors were present at 14.02, 22.08, 27.88 ppm.

B: No absorption was present at 8.15 ppm, and absorption was present at 14.08 and 23.36 ppm. Example 10

The ethylene / 1-octene copolymer obtained in Example 6 was hydrogenated under conditions of a temperature of 140^°C, a polyethylene concentration of 9% by weight, a hydrogen gauge pressure of 2.9 MPa (30 kg / cm²M), a concentration of ruthenium catalyst supported on carbon (Ru content = 5% by weight) of 4% by weight and a reaction time of 6 hours in a decalin solvent, and then the polymer obtained is isolated of the reaction solution.

ES 2 179 066 T3

From this polymer, a pressed sheet with a thickness of 300 µm was formed, and then the infrared absorption spectrum was measured. As a result, no absorption of the unsaturated groups present in the range of 885 to 970 cm was observed.^-1 .

On the other hand, the density, molecular weight, melting point, and fluid activation energy were the same as in Example 6.

Comparative Example 1

An ethylene / 1-octene copolymer was prepared under the conditions shown in Table 5. Tables 5 and 6 show the polymerization conditions and the evaluation results.

TABLE 5

<td></td><td>Comparative Example 1</td>

<td>Toluene (ml) MAO (mmol) Transition metal component (mmol) Ethylene pressure (KPa) * Temperature (° C) Time (minutes) Yield (g)</td><td>400 3 Titanium (III) component 1 784 (8) 80 twenty 57.5</td>

[Note]

1-octene: 40 ml.

Titanium component [II]: (tert-butylamido) -dimethyl (tetramethyl-r⁵-cyclopentadienyl) silanetitanium.

* the value in kg / cm²M is expressed in parentheses.

TABLE 6

<td></td><td>Comparative Example 1</td>

<td>Density (g / cm³)</td><td> 0,868</td>

<td>Degree of branching</td><td> 0,052</td>

<td>Weight Average Molecular Weight (Pm)</td><td> 230.000</td>

<td>Molecular weight distribution</td><td> 9,9</td>

<td>(Pm / Mn)</td><td></td>

<td>Flow Activation Energy</td><td> 7,5</td>

<td>melt [Ea] (kcal / mol)</td><td></td>

<td>Melting point (° C)</td><td> 56,4</td>

Example 11 (1) Preparation of titanium catalyst component

A titanium catalyst component was prepared in the same way as in Example 1- (1).

(2) Preparation of methylaluminoxane

The same procedure as in Example 1- (2) was repeated to prepare methylaluminoxane.

ES 2 179 066 T3 (3) Preparation of the catalytic component

A 50 ml flask was dried and purged with nitrogen and 20 ml of toluene, 0.5 mmol of the titanium catalytic component prepared in step (1) above and 0.02 mmol of (tert-butylamido) dichloride were introduced dimethyl (tetramethyl- n ⁵ -cyclopentadienyl) silanetitanium in the flask, followed by shaking at 25^°C. Next, 0.6 mmol of the methylaluminoxane prepared in step (2) above was added, and then the reaction was carried out for 2 hours.

The resulting reaction product was used as a catalyst component.

(4) Preparation of ethylene / 1-octene copolymer

400 ml of toluene, 20 ml of 1-octene and 30 mmol of the methylaluminoxane prepared in step (2) above were placed in a 1 liter capacity stainless steel pressure-resistant autoclave and the mixture was then heated to 90^°C. Next, 0.026 mmol, relative to titanium, of the catalytic component prepared in step (3) mentioned above was added.

Ethylene was then continuously introduced into the autoclave under a gauge pressure of 294 kPa (3.0 kg / cm²M) to carry out the polymerization reaction for 60 minutes.

After completion of the polymerization reaction, the pressure was released and the resulting ethylene-1-octene copolymer was collected, washed with methanol and then dried to obtain 75.2 g of ethylene-1-octene copolymer.

(5) Evaluation of the ethylene-1-octene copolymer (a) NMR structure analysis

The measurement of ¹³C-NMR and as a result, no absorption of methyl groups was observed in the vicinity of the quaternary carbon atom, as could be observed in an LDPE at 8.15 ppm.

(b) Density measurement

The measurement was carried out in the same way as in Example 1- (4) - (d). As a result, the density was 0.895 g / cm³. On the other hand, the aging treatment of the sample was not carried out.

(c) Measurement of molecular weight distribution

The measurement was carried out in the same way as in Example 1- (4) - (f) and as a result, the weight average molecular weight (Mw) was 126,000, the number average molecular weight (Mn) was 45,000 and the Pm / Mn ratio was 2.8.

(d) Measurement of the activation energy (Ea) of the melt flow

The measurement was carried out in the same way as in Example 1- (4) - (g) and as a result, the activation energy (Ea) was 13.2 kcal / mol.

(e) Measurement of the inflation ratio at the nozzle

The nozzle swelling ratio (DR) was obtained as (D1 / D0) by measuring the diameter (D1, mm) of a strand formed by extrusion through a capillary nozzle [diameter (D0) = 1,275 mm, length (L ) = 51.03 mm, UD0 = 40, and entry angle = 90^°], at an extrusion speed of 1.5 mm / min (shear speed = 10 sec^-1), at a temperature of 190^°C by using a capillograph manufactured by Toyo Seiki Seisakusho Col., Ltd. and then dividing this diameter by the diameter of the capillary nozzle.

The diameter (D1) of the strand was a mean value of the values ​​obtained by measuring the long axes and the short axes of the central portions of 5 samples having an extruded strand length of 5 cm (a length of 5 cm from nozzle outlet).

As a result, the swelling ratio at the nozzle was 1.52.

ES 2 179 066 T3

Example 12 (1) Preparation of titanium catalyst component

The same procedure as in example 1- (1) will be carried out, with the exception that 0.56 g of cyclopentanol was replaced by 0.49 g of n-butanol, thus preparing a titanium catalyst component.

(2) Preparation of catalyst component

The same procedure as in example 11- (3) will be repeated with the exception that the titanium catalyst component obtained in example 11- (1) is replaced by 0.25 mmol of the titanium catalyst component obtained in step ( 1) above and 0.01 mmol of (tert-butylamido) dimethyl (tetramethyl-n⁵-cyclopentadienyl) silanetitanium and 0.8 mmol of methylaluminoxane, to thus prepare the catalyst component.

(3) Preparation of ethylene / 1-hexene copolymer

The same procedure as in example 11- (4) will be carried out under the conditions indicated in table 7, with the exception that 10 ml of 1-hexene were used instead of 1-octene, to prepare thus an ethylene / 1-hexene copolymer. Table 7 shows the results.

The measure will be carried out¹³C-NMR and as a result, no absorption of methyl groups will be observed in the vicinity of the quaternary carbon atom, as can be seen in an LDPE, at 8.15 ppm.

Comparative Example 2

The same procedure as that of Example 12- (3) will be followed under the conditions shown in Table 7, to thus prepare an ethylene / 1-hexene copolymer. Table 7 shows the results.

TABLE 7 (I)

<td></td><td>Example 12</td><td>Comparative Example 2</td>

<td>Toluene (ml)</td><td> 400</td><td> 400</td>

<td>MAO (mmol)</td><td> 30</td><td> 10</td>

<td>Catalyst (mmol)</td><td> 0,26</td><td> 0,01</td>

<td>Temperature (° C)</td><td> 90</td><td> 150</td>

<td>Ethylene (kPa *)</td><td> 294 (3)</td><td> 784 (8)</td>

<td>Time (min)</td><td> 60</td><td> 30</td>

<td>Yield (g)</td><td> 52,7</td><td> 52,3</td>

MAO: Methylaluminoxane

Catalyst from example 12: catalyst component prepared in example 12- (2).

Catalyst from Comparative Example 2: (tert-butyl-amido) dimethyl (tetramethyl-n dichloride⁵cyclopentadienyl) silanetitanium.

* The value in kg / cm²M is indicated in parentheses.

ES 2 179 066 T3

TABLE 7 (II)

<td></td><td>Example 12</td><td>Comparative Example 2</td>

<td>Density (g / cm³)</td><td> 0,902</td><td> 0,937</td>

<td>Weight Average Molecular Weight (Pm)</td><td> 45.000</td><td> 62.000</td>

<td>Molecular weight distribution (Pm / Mn)</td><td> 3,2</td><td> 3,8</td>

<td>Melt flow activation energy [Ea] (kcal / mol)</td><td> 12,5</td><td> 11,5</td>

<td>Nozzle inflation ratio (DR)</td><td> 1,40</td><td> 1,06</td>

Example 13

The ethylene / 1-octene copolymer obtained in Example 11 was hydrogenated under conditions of a temperature of 140^°C, a polyethylene concentration of 9% by weight, a hydrogen gauge pressure of 2.94 MPa (30 kg / cm²M), a concentration of ruthenium catalyst supported on carbon (Ru content = 5% by weight) of 4% by weight and a reaction time of 6 hours in decalin solvent, and then the polymer obtained from the solution was isolated of reaction.

From this polymer, a hot-pressed sheet with a thickness of 300 µm was formed, and then the infrared absorption spectrum was measured. As a result, it was observed that no absorption of unsaturated groups was present in the range of 885 to 970 cm.^-1.

On the other hand, the density, molecular weight, melting point, and fluid activation energy were the same as in Example 11.

Example 14 (1) Preparation of the catalyst component

A catalyst component was prepared in the same way as in Example 1- (1).

(2) Preparation of methylaluminoxane (MAO)

The same procedure as in Example 1- (2) was repeated to obtain methylaluminoxane.

(3) Ethylene / 1-hexene copolymer polymerization

400 ml of toluene, 20 ml of 1-hexene and 0.25 ml of a solution of triisobutylaluminum in toluene (2 moles / liter) were placed in a 1-liter flask equipped with a stirrer (2 moles / liter), followed by stirring at 20 ° C for 5 minutes. Next, 10 mmol of the methylaluminoxane prepared in step (2) above was added and the solution was heated to 70^°C. Subsequently, 1.5 ml of the titanium catalyst component prepared in step (1) above were introduced, 2 micromoles of (tert-butylamido) dimethyl (tetramethyl-n dichloride) were added⁵-cyclopentadienyl) silanetitanium, and ethylene was introduced at a partial gauge pressure of 735 kPa (7.5 kg / cm²M) to initiate polymerization. At the same time that the total pressure was kept constant, the reaction was carried out at 70^°C for 30 minutes.

After completion of the reaction, the pressure was released and the resulting reaction product was poured into methanol and then filtered to collect the polymer.

The polymer was then dried to 85^°C for 10 hours under reduced pressure. As a result, 60.5 g of ethylene-1-hexene copolymer was obtained.

ES 2 179 066 T3 (4) Evaluation of ethylene-1-hexene copolymer (a) Evaluation of thermal behavior

The measurement was carried out in the same way as in example 1- (4) - (c) and as a result the enthalpea of ​​crystallization (ΔΗ) was 80 J / g and the melting point (Pf) was 104.0 C .

(b) Density

The density measurement was carried out in the same way as in Example 1- (4) - (d). As a result, the density was 0.902 g / cm³. On the other hand, no anelating treatment of the sample was carried out.

(c) Measurement of molecular weight distribution

The measurement was carried out in the same way as in Example 1- (4) - (f), and as a result the Mw / Mn ratio between the weight average molecular weight and the number average molecular weight was 7.79 .

(d) Measurement of intrinsic viscosity

The intrinsic viscosity in decalin was measured at 135 ° C, and as a result, the intrinsic viscosity [η] was 2.42 dl / g.

(e) Evaluation of non-Newtonian properties

A model RMS E-605 manufactured by Rheometrics Co., Ltd. was used as the apparatus and a sinusoidal vibration was given at 190^°C in an amount of stress of 10% to measure the dynamic viscoeleastic properties, by virtue of which the dependence of the shear rate ω on the melt viscosity [η] was obtained and the non-Newtonian properties were evaluated. The results are shown in Figure 3, the activation energy of the melt flow was 12.2 kcal / mole.

(5) Huggins coefficient measure (k)

The viscosities of the ethylene copolymer were measured in a state of dilute solution, and then the IIuggiiis coefficient (k) was calculated according to the viscosity equation:

nsp / c 0 [η] + k [n]²c

The reduced viscosities n_sp/ c changing the concentration of polymer c in a decalin solvent to 135^°Cen5omae points in an interval in which the linear relationship was recognized. The linear correlation coefficient was 0.995 or less. Here, [η] is the intrinsic viscosity. The Huggins coefficient (k) was 0.439.

(6) Film evaluation

The traction modulus, breaking strength and elongation of the film were 760 kg / cm², 420 kg / cm² and 660%, respectively.

(7) Evaluation of the catalyst (a) Evaluation 1 of the catalyst

The ethylene polymerization properties of the titanium catalytic component prepared in step (1) above were evaluated by preparing polyethylene in the same manner as in step (3) above, with the exception that (tert-butylamidodichloride ) dimethyl (tetramethyl-n⁵-cyclopentadienyl) silanetitanium and 1-hexene and that the partial gauge pressure of ethylene was established at 588 kPa (6 kg / cm²M) and then the terminal vinyl groups were determined.

Measurement of terminal vinyl groups

A pressed sheet with a thickness of 100 µm was formed, and the transmitted infrared absorption spectrum was measured. The number of terminal vinyl groups n was calculated as a function of the absorbance

ES 2 179 066 T3 (A907) based on the terminal vinyl groups in the vicinity of 907 cm^-1, a film thickness (t) and a resin density (d) according to the equation:

n = 0.114 A907 / [dT] where d = d / ml, T = mm, and n = number of vinyl groups relative to 100 carbon atoms. As a result, the number of terminal vinyl groups was 4.5 groups / 1000 carbon atoms.

Evaluation 2 of the catalyst (Evaluation of the properties of copolymerization)

The copolymerization of ethylene and 1-octene was carried out in the presence of (tert-butylamido) dimethyl) tetramethyl-r dichloride.⁵-cyclopentadienyl) silanetitanium (I) under the conditions indicated in Table 8, and then the enthalpea of ​​crystallization (ΔΗ) and the melting point (Pf) of the resulting copolymer were measured. Table 8 shows the measured results.

TABLE 8 (I)

<td></td><td>N ° 1</td><td>N ° 2</td>

<td>Toluene (ml)</td><td> 400</td><td> 400</td>

<td>TIBA⁴ (mmol)</td><td> 0,5</td><td> 0,5</td>

<td>MAO (mmol)</td><td> 10</td><td> 10</td>

<td>Compound</td><td> 2</td><td> 2</td>

<td>metallic ^ moles)</td><td></td><td></td>

<td>Temperature (° C)</td><td> 70</td><td> 80</td>

<td>Load ratio</td><td> 0,231</td><td> 0,248</td>

<td>from monémero³©</td><td></td><td></td>

<td>Time (min)</td><td> 10</td><td> 10</td>

TABLE 8 (II)

<td></td><td>N ° 1</td><td>N ° 2</td>

<td>Yield (g)</td><td> 16,5</td><td> 19,2</td>

<td>TM⁴ (° C)</td><td> 93,6</td><td> 90,4</td>

<td>ΔΗ⁵ (J / g)</td><td> 75</td><td> 61</td>

<td>ΔΗ. Pf</td><td> 7020</td><td> 5514</td>

<td>ΔΗ ^ ί calculated according to the general equation⁶</td><td> 17492</td><td> 17107</td>

1) TIBA: Triisobutylaluminum

2) MAO: Methylaluminoxane prepared in Example 14- (2)

3) It was calculated as a function of the weight of ethylene dissolved at the polymerization temperature in a mixed solvent prepared from 400 ml of toluene and 7.15 g of 1-octene at 25^°C.

4) Pf: melting point, which was measured in the same way as in example 14- (4).

5) (ΔΗ): ​​Enthalpea of ​​crystallization, which was measured in the same way as in Example 14- (4).

6) AII.Pf: It was calculated according to 27,000 - 21,000 [M]^0,56.

7) (tert-butylamido) dimethyl (tetramethyl-r⁵-cyclopentadienyl) silanetitanium.

The copolymerization was carried out according to Example 14- (3), but the metal compound was added after dissolving the ethylene to a state of saturation at the polymerization temperature, by virtue of

ES 2 179 066 T3 from which the polymerization started.

Specifically, the evaluation was carried out by applying the following apparatus and method.

That is, as the polymerization reactor, a pressure-resistant stainless steel autoclave was used having a volume of 1.76 liters and an internal diameter of 114 mm. This autoclave was equipped with an anchor blade (thickness = 1.5 mm) as a stirrer, and the space between the end of the blade and the inner wall of the reactor was 17 mm at the nearest position. Likewise, the air of one of the surfaces of the blade was 13 cm². When the blade was used, it was set in such a state that 70% or more of it could be immersed in the solvent.

As an evaluation procedure, the aforementioned autoclave was sufficiently dried, and 400 ml (volume at 25^°C) of dry toluene (moisture content = 5 ppm or less) in the autoclave, at room temperature, under a nitrogen atmosphere and also introduced in a previously determined amount by weight of 1-octene (water content = 5 ppm or less). Additionally, as a catalytic component, an orgagenic metal compound (eg, aluminoxane, an aluminum alkyl or the like) was introduced. The solution was then stirred at room temperature for 3 minutes. The solution was then heated to the polymerization temperature in a closed state and, once the pressure reached a constant level, ethylene was introduced into the autoclave. Subsequently, the ethylene feed was stopped and the saturation state was confirmed by the fact that the pressure did not drop.

At this time, the stirring speed was constant at 500 rpm. At the same time that this state was maintained, the metal compound that is being evaluated was added, which was another catalytic component, with which the copolymerization began.

Once the copolymerization had started, it was necessary to control the flow rate of ethylene to 3 normal liters / min, or less under a previously determined pressure and a temperature within ± 2^°C from a previously determined polymerization temperature.

If this control is not carried out, it is necessary to change the amount of the catalyst to carry out the evaluation again.

After carrying out the polymerization for a specified period of time, it was stopped, fed with ethylene and immediately released under pressure to remove unreacted ethylene. Then, the deactivation was carried out with methanol.

In this case, the total amount of solvent in the catalyst components was adjusted to be 1% or less based on the total volume of toluene and 1-octene, which were the polymerization solvents.

Comparative example 3

The same procedure as in Example 14 was repeated with the exception that the titanium catalyst component prepared in Example 14- (1) was not used, to prepare 43.5 g of ethylene / 1-hexene copolymer.

The results of the evaluation were the following:

Melting Point (Pf): 75.0^°C

Density: 0.908 g / cm³

Intrinsic viscosity [η]: 2.32 dl / g

Molecular weight distribution (Mw / Mn): 6.99

Enthalpe of crystallization (ΔΗ): ​​50 J / g

Huggins coefficient (k): 0.345

On the other hand, the dependence ω of the shear rate of the melt viscosity [η] was obtained in the same way as in Example 14- (4) - (e), by virtue of which the non-Newtonian properties were evaluated . The results are shown in Figure 3.

ES 2 179 066 T3

Example 15

80% by weight of ethylene / 1-butene copolymer (density 0.920 g / cm³, Ml = 1.0 g / 10 min) and 20% by weight of the ethylene / 1-hexene copolymer of example 14 and they were kneaded at 190^°C for 5 minutes at 50^°C by using a laboratory mill (Toyo Seiki Seikusho Co., Ltd., internal volume = 30 ml) to obtain a resin composition.

From this resin composition, a film was formed having a thickness of 100 µm. The physical properties of the film thus formed were as follows.

Traction modulus: 2000 kg / cm²

Breaking strength: 380 kg / cm²

Elongation: 670%

Possibility of industrial application

The ethylene copolymer of the present invention is derived from ethylene and an olefin that has 3 to 20 carbon atoms and does not contain any quaternary carbon in the main chain of the polymer, being different from the usual HDPE, L-LDPE and LDPE. The ethylene copolymer is characterized by controllable melt flow activation energy, excellent working properties, and controllable physical properties such as density, melting point and crystallinity. On the other hand, the ethylene copolymer subjected to hydrogenation treatment not only exhibits the characteristics that have been mentioned, but is also excellent in terms of its heat stability.

On the other hand, according to the process for preparing the ethylene copolymer of the present invention, an ethylene copolymer can be efficiently prepared in which the activation energy of the melt flow and the Huggins coefficient can be controlled and in which the non-Newtonian properties are improved, in addition to presenting excellent working properties.