Polyethylene, thermoplastic resin composition containing the same, and process for producing polyethylene.

IS 2 178 648 T3

DESCRIPTION

Polyethylene, a thermoplastic resin composition that contains it, and a polyethylene production process.

Technical field

The present invention relates to a new ethylene homopolymer, to a thermoplastic resin composition containing it, and to a new process for the preparation of said ethylene homopolymer. More specifically, the present invention relates to an ethylene homopolymer which can be derived from an ethylene monomer uonic, which is excellent in working properties and has good film moldability and blow mouldability, and in the that it is possible to control the activation energy of the melt flow, as well as to control the phosphoric properties, such as density and melting point and crystallinity, mainly in the homopolymer state; a thermoplastic resin composition containing said ethylene homopolymer and a process for efficiently preparing the ethylene homopolymer 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, the molecular weight distribution or the 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 ethyloenic polyomers, various molding methods can be applied, including topical known examples of molding methods, injection molding, extrusion, blow molding, inflation, compression molding and vacuum forming. In such molding methods, the way to impart high-speed molding properties and a reduction of molding energy has been investigated for a long time, in order to improve the working properties and also reduce the working cost; Therefore, the question of imparting suitable or optimal phosphorous properties for each use is important, and of being able to carry the molding with the optimal working properties.

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)]. This theory rationally explains that butyl branching can be formed by transfer of hydrogen 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 partner of two ethylene molecules [Makromol. Chem. Vol., 181, p. 2811 (1981)]. According to 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, being

ES 2 178 648 T3 is a normally recognized reaction mechanism. Accordingly, in the above-mentioned reaction process, it is impossible to optionally control the amounts of the existing long chain branches and the 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) is 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, since it has a wide broad 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 resistance.

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 (open Japanese patent application No. 56412/1984), (3) an ethylene-a-olefin-1,5-hexadiene copolymer obtained by using a metallocene / aluminoxane catalyst (Japanese PCT-Open Patent Application No.^° 501555/1989), (4) a process to introduce 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 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 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 polymerization reactivity is low, so that low molecular weight polymers are produced, which leads to the deterioration of physical 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 polymers, the physical 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 monoimer concentration is inconveniently low. In the process of introducing long chain branches mentioned in (4), there is a problem that the range to control the generation of a gel and the physical properties is limited. Also, the polyethylene of (5) mentioned is a polymer that does not contain ethyl branches and butyl branches, and consequently the control of the physical 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 that consists 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 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, ethylenic polymers obtained in the presence of a me3 catalyst have been described.

ES 2 178 648 T3 talocene and methods for its preparation, such as (1) a method for preparing an ethylenic polymer in the presence of a limited geometric catalyst and an ethylene copolymer obtained through this method (Japanese patent application open 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 (an aluminum compound) as a support (Japanese Patent Application Laid-Open No.^° 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 (1) above, 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 at the die (ratio of the extrudate diameter with respect to the die diameter), 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 die in terms of inward beading does not pose a problem at the time of film or line 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 / cm³On the other hand, in the methods (1) and (3) mentioned, when branches are introduced, the melting point and the mechanical strength of the ethylene-a-olefin copolymer deteriorate considerably.

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 polytylene which can be derived from a single ethylene monoimer, with which the activation energy of the melt flow can be controlled, which is excellent in terms of its working properties. , which has good film formability and blow moldability, in which physical properties such as density, melting point and crystallinity can be controlled mainly in the homopolymer state, 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 the ethylene-a-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 polyethylene derived from a single ethylene monoimer is suitable to achieve said objective. That is, this type of ethylene homopolymer 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 ethylene homopolymer of the present invention, (1) the Huggins coefficient and the 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; or (4) in the measurement of the elastic modulus of loss, an e-relaxation peak is present within the range of 0 to 100 ° C. 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 relationship between the Huggins coefficient and the intrinsic viscosity can be controlled to efficiently obtain the ethylene homopolymer. having better non-Newtonian properties and excellent working properties. Accordingly, the present invention has been completed on the basis of this knowledge.

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

(1) a polyethylene [1] which is derived from an ethylene monomer 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 Huggins coefficient (k) and the intrinsic viscosity [η], which are decided according to the relationship between polymer concentration and viscosity.

ES 2 178 648 T3 reduced measured at a temperature of 135 ° C in a decalin solvent satisfy the relation of the equation:

k> 0.2 + 0.0743 x [η] (2) A polyethylene [2] which is derived from an ethylene monoomer and in which (1) no quaternary carbon atom was present in the polymer 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. proton nuclear magnetic¹H-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 calorometer (DSC) satisfy the equation:

Mp> 131-1340 [CH3 / CH2] (3) A polyoethylene [3] which is derived from an ethylene monomer and in which (1) no quaternary carbon atom is present in the monomeric 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 the homopolymer measured according to the gel permeation chromatography method and the nozzle swelling ratio (DR) satisfies the equation:

DR> 0.5 + 0.125 x logPm.

(4) A polyethylene [4] which is derived from an ethylene monomer and in which (1) no quaternary carbon atom was 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) in the measurement of the loss elastic modulus, the β-relaxation peak is present in the range of 0 to -100 ° C.

On the other hand, according to the present invention, an ethylene homopolymer obtained by hydrogenation treatment of any of the aforementioned ethylene homopolymers can be provided, as well as a thermoplastic resin composition that includes any of these ethylene homopolymers.

On the other hand, according to the present invention, A process can be provided to prepare a polyethylene that includes the step of homopolymerizing ethylene in the presence of a catalyst consisting of (a) a transition metal compound in which the ratio between the monoomer charge composition [the molar ratio [M] of 1-octene / (ethylene + 1-octene)] and the product of the enthalpoe of crystallization (ΔΗ) and the melting point (Pf) of the produced copolymer satisfies the equation:

<ΔΗ + Pf <27000 - 21600 [M]⁰,⁵⁶ (under polymerization conditions using compound (a) together with an aluminoxane), (b) a transition metal compound capable of forming a terminal vinyl group in ethylene homopolymerization (under polymerization conditions where component (b) together with the aluminoxane), and (c) a compound capable of forming an ionic 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 from the lantoanide 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 each other.

Figure 2 is a graphical representation for calculating the area of ​​the β-relaxation peak of an ethylene homopolymer.

Figure 3 is a graph showing the relationship between the polymer concentration and the reduced viscosity in the ethylene homopolymer obtained in Example 1.

Figure 4 shows the spectrum of ¹³C-NMR of the ethylene homopolymer obtained in Example 1.

Figure 5 shows the spectrum of ¹³C-NMR of the ethylene homopolymer obtained in Example 3.

IS 2 178 648 T3

Figure 6 shows the dispersion behavior of the solid viscoelasticity temperature of the ethylene homopolymer obtained in Example 13.

Figure 7 shows the dispersion behavior of the solid viscoelasticity temperature of the ethylene homopolymer obtained in comparative example 3.

Figure 8 shows the dependence of the shear rate on the melt viscosity of the ethylene homopolymer obtained in Example 16.

Figure 9 is a graph showing the measured results (ΔΗ) of the temperature drop using a differential scanning calorimeter obtained in catalyst evaluation No. 3

2.

Figure 10 is a graph showing the measured results (Pf) of the temperature rise by means of a differential scanning calorometer obtained in the N^°3 catalyst evaluation 2.

Best mode of carrying out the invention

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

(A) Judgment through the 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 homopolymer 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 terminal 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 mononymous peaks) peaks that are based on branching are not present.

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

The 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

IS 2 178 648 T3

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

(Ethylene-1-hexene copolymer)

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

IHCFE

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

CH2 -CH2 -CH2 -CH3 GDBA

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:

<td>GF</td><td>CED</td>

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

<td>| B</td><td></td>

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

<td>H |</td><td>TO</td>

<td>CH3</td><td></td>

<td>A = 23.27; B = 26.05; C = 27.14; D = 30.00,</td><td></td>

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:

IHDFE

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

CH2 -CH2 -CH2 -CH2 -CH2 -CH3 HCEGBA

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:

IS 2 178 648 T3

CBED

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

CH3

TO

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

and E = 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.

(C-1) Isolated branch (Bn) γ β α br

- CH₂ - CH₂ - CH₂ - CH - CH₂ - CH₂ - n branching ^| nCH2 1 methyl | 2 ethyl n-1CH2 3 propyl. 4 butyl. 5 pentyl. 6 hexyl

3CH2 nm days long ^|

2CH2 ^|

1CH3

[xBn] (n = 1, 2, 3, ..., n) (n = 1, 2, 3 ..., n, α, β, γ ...) (C-2) Ethyl branching- ethyl (1,3) attached to a quaternary carbon (peq) (R) γ β α br α '| α β

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

2CH2 CH2 2 ||

1CH3 CH3 1

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

ES 2 178 648 T3 (C-3) Isolated ethyl-ethyl branch (1,3) (pee) γ β α br α '

-CH2 -CH2 -CH2 - CH - CH2 - CH - CH2 -CH2 -

<td></td><td>2CH2</td><td>CH2</td><td> 2</td>

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

<td>[(xB2) pee]</td><td></td><td></td><td></td>

<td>(C-4) Branching</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>αβ</td>

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

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

[(xB2) pep, (xB3) pep] (C-5) Isolated methyl-ethyl branch (1,4) (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 Figure 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.

IS 2 178 648 T3

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>2B 6 —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>^αΒ 4 —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> 1,01</td><td>1B2 or</td>

<td></td><td></td><td>Main chain</td><td></td><td> 10,85</td><td>^{(1 B}2) pee</td>

<td> 13</td><td> 27,33</td><td>βΒ 4 —n</td><td></td><td> 8,15</td><td></td>

<td> 14</td><td> 25,99</td><td>βΒ'2</td><td> 22</td><td> 7,87</td><td>1B'2</td>

(2) Confirmation test for the presence of long chain branching by nuclear magnetic resonance spectrum ¹³C.

A technique has been suggested that confirms the presence of hexyl branching and determines hexyl branching in comparison to an ethylene-1-octene copolymer having hexyl branching [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.

(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, viscoelastic properties, and the like of a melt, and exerts an important influence on mechanical properties, such as workability, optical 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 relation between MI and Pm of LDPE deviates from the relation 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 Instroin type capillary rheoimeter, fluid characteristics can be examined, and the displacement factor can be used to determine the activation energy (Ea) of HDPE. 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

ES 2 178 648 T3 are affected by long chain branching.

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

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

nsp / c = [η] + k [n]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 the branching.

It has been elucidated that when 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 intronsic viscosity [η] and the molecular weight measured through the gel permeation chromatography method or the light scattering method.

It is known that the relationship between the intronsic viscosity [η] determined in a dilute polyethylene solution by using the Huggins equation mentioned above and the molecular weight measured through the gel permathion chromatography (GPC) method to determine 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 relation between the intronsic viscosity and the molecular weight measured through the GPC method, and it has been concluded that when the comparison is made being the constant intronsic viscosity, the molecular weight of LDPE is less than that of HDPE.

Next, reference is made to the characteristics of the ethylene homopolymer of the present invention.

In each of the ethylene homopolymers [1] to [4] of the present invention, it is necessary that no quaternary carbon atom is present in the polymeric main chain, and that the activation energy (Ea) of the melt flow It is comprised within the range of 8 to 20 kcal / mol, preferably between 8.5 and 19 kcal / mol, being more preferable between 9 and 18 kcal / mol. If the activation energy (Ea) is less than 8 kcal / mol, sufficient working properties cannot be achieved. Therefore, the activation energy (Ea) is a value obtained as follows. First, the frequency dependencies (10^-2 a10² rad / sec) of the dynamomic 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 temperature-time conversion rule to the standard temperature of 170 ° C.

On the other hand, the ethylene homopolymers [1] to [4] of the present invention can satisfy the above-mentioned requirements and have the following characteristics.

That is, in the ethylene homopolymer [1], the Huggins coefficient (k) and the intrinsic viscosity [η], which are decided according to the relationship between the polymer concentration and the reduced viscosity measured at a temperature of 135 ° C in a decalin solvent must satisfy the relation of the equation:

k&gt; 0.2 + 0.0743 x [η], preferably,&gt; k&gt; 0.2 + 0.0743 x [η], more preferably,

ES 2 178 648 T3&gt; k&gt; 0.22 + 0.0743 x [η], with&gt; k&gt; 0.24 + 0.0743 x [η] being most preferable.

The preferable topical range of this Huggins coefficient (k) is 5&gt; k&gt; 0.41.

The Huggins coefficient (k) mentioned above shows a different behavior at times when the intronsic viscosity [η] is extremely large, but the ethylene homopolymer [1] of the present invention can also be specified through the relationship that is exposed then between the Huggins coefficients. That is, if the straight chain high density polyethylene and the ethylene homopolymer [1] of the present invention have the same intronsic viscosity [η] measured at 135^°C in decalin solvent, ethylene homopolymer [1] has a k / k 'ratio of its Huggins coefficients in the range of 1.05 to 5.0, k being the Huggins coefficient of polyethylene [1] herein invention and k ', the Huggins coefficient of straight chain high-density polyethylene.

Preferably, the ratio k / k 'can satisfy the ratio 1.07 &lt;k / k' &lt;4.0 m or more preferably

1.08 &lt;k / k '&lt;3.7 mas preferably auón

1.10 &lt;k / k &lt;3.6 being above all preferable

1.13 &lt;k / k '&lt;3.4

The intronsic 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 intronsic viscosity [η] (dl / g), the Huggins coefficient k and the polymer concentration c (g / dl ), using the Huggins equation nsp / c = [η] + 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^°Cen5omor points of measurement, at a range of a substantially constant polymer concentration using a Ubbelohde viscometer. The measurement precision is such that the relative viscosity is 1.1 or more and the relative viscosity error 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 measuring point on the side of the minimum concentration is 45% or less of the polymer concentration at the measuring point on the side of the maximum concentration.

Next, (1) the relationship between the reduced viscosity and the polymer concentration through a straight line is represented according to the method of mononymous squares and then the intronsic viscosity [η] is calculated. Alternatively, (2) the intronsic viscosity [η] can also be obtained by applying the Huggins equation mentioned above, the Kraemer equation:

1nnrei / c = [η] + k2 [n]²c and the Schulz-Blashke equation:

nsp^{/ c} = ^[n^] + ^k3 ^[n^]nsp

ES 2 178 648 T3 (where r¡_rel is the relative viscosity; r_sp is the specific viscosity; k₂ and k₃ they are constant; 1n represents a natural logarithm; and the other signs are as defined for the Huggins equation), to extrapolate the polymer concentration or the specific viscosity. On the other hand, after confirming that the intrinsic viscosities [r] obtained through the three mentioned methods coincide with each other, the Huggins coefficient can be calculated as a function of the mean value of said intrinsic viscosities and the Huggins equation according to the aforementioned method (1).

In both the above-mentioned methods (1) and (2), 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 measurement point is apparently present below the straight line represented by connecting the measurement point (Cn) at the maximum concentration with the measurement point (C1) at the minimum concentration, in this region, no 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 described 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. The corresponding measuring points are then connected to each other with a smooth curve. Here, the distance between the straight line and the curve is calculated ([r] sp / C]^H - [rsp / C]^L) and if ([rsp / C]^H - [rsp / C]^L) / [Cn -C1] is 0.001 or less, it can be judged that the linear relationship is established.

This ethylene homopolymer [1] is neither indissoluble nor infusible over a wide density range and therefore does not contain gel, so polyethylene [1] dissolves in decalin at a temperature of 135^°C. On the other hand, ethylene homopolymer [1] exerts good solubility in aromaitic 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 formation of the gel is partially observed in view of its production mechanism.

Ethylene homopolymer [1] does not normally contain any ethyl branching as branching, so it is different from LDPE obtained through the high pressure method. On the other hand, ethylene homopolymer [1] is also different from conventional polyethylene in having butyl branching.

Likewise, the melting point (Pf) of the ethylene homopolymer [1] that can be observed by the differential scanning calorimeter (DSC) is normally in the range of 116 to 132^°C, preferably 116 to 131.5^°C, more preferably 117 to 131^°C, and the enthalpy of crystallization (ΔΗ) and the melting point (Pf) of the ethylene homopolymer [1] that can be observed by DSC normally satisfies the equation:

&lt;ΔΗ &lt;250 and the equation

0.02 x ΔΗ + 116 &lt;Pf &lt;0.02 x ΔΗ + 126 preferably

0.02 x ΔΗ + 117 &lt;Pf&gt; 0.02 x ΔΗ + 125 being more preferable

0.02 x ΔΗ + 118 &lt;Pf &lt;0.02 x ΔΗ + 124.

Ethylene homopolymer [1] is a polymer that has a relatively high melting point but in which the enthalpy of crystallization changes considerably, and can exert characteristics such as

ES 2 178 648 T3 elastomer with low crystallinity and high melting point in the category of an ethyloenic polymer. Therefore, the enthalpoe of crystallization is a value obtained from an exothelial 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 cooled 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 endotothermic melting peak at the moment in which the temperature is raised at a rate of 10^°C / minute.

In the ethylene homopolymer [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 calorometer (DSC) satisfy the equation:

Mp&gt; 131-1340 [CH3 / CH2] preferably

Mp&gt; 131-1230 [CH3 / CH2] more preferably

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]. On the other hand, the melting point is normally 135^°C or less.

The melting point (Pf) is the value obtained from the temperature at the position of the maximum peak of the endotothermic melting peak at the moment in which the pressed lamina 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 it is heated at a speed of 10^°C / min. In the ethylene homopolymer [2] of the present invention, the branched α-olefin having 5 to 20 carbon atoms is not present, for example the short chain branching derived from 3-methylbutene-1 or 4-methylpentene -1. When obtaining an ethylene-a-olefin copolymer through a known polymerization method, if the conversion of α-olefin to the polymer is improved remarkably by using a batch polymerizer, the ethylene-copolymer is produced. α-olefin and a high density polyethylene, so that the relationship between the melting point and [CH3 / CH2] could apparently deviate. However, it is a mixture of different types of polymers, which does not fall within the present invention.

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

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

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

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

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

At this point, the swelling ratio at the nozzle (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) = 1,275 mm, length (L) = 51.03 mm, L / D0 = 40, and an inlet angle = 90^°] at an extrusion speed of 1.5 mm / min (shear speed = 10 sec^-1), at a temperature of 190^°C, using the

ES 2 178 648 T3 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 of 5 cm from the nozzle outlet).

On the other hand, the ethylene homopolymer [4] of the present invention has a peak of β-relaxation in the range of 0 to 100 ° C, preferably 5 to -70 ° C as a modulus of elastic loss. The β-relaxation peak (area) as an index of the β-relaxation peak intensity is obtained as follows. First, the temperature dispersion is measured (in a temperature range of -150 to 200^°C) of the solid viscoelasticity at a frequency of 1 Hz in an amount of stress of 0.15% using an RSA-II model manufactured by Leometric Co., Ltd., and then the elastic modulus in storage ( E '), an elastic loss modulus (E ") and a dissipation ratio (tan £) as a function of the temperature dispersion of the solid viscoelasticity. Next, the peak of β-relaxation of the elastic modulus of loss (E ”) in the temperature dispersion behavior of the calculated saline viscoelasticity is read by means of a digitizer, and its area is then calculated using a graphical measurement program (MEAS1 ). To calculate the area of ​​the β-relaxation peak, as shown in figure 2, a reference line is decided in a temperature range from -100 to 0^°C. As a sample to be measured, a film having a thickness of 100 μm is used that is prepared by heating and melting the polyethylene at 190^°C, pressure molding and then cooled. No particular restriction is placed on the area of ​​the β-relaxation peak, and it depends on the density of the polyethylene, but it is 0.3 or more, preferably in the range of 0.5 to 30.

The ethylene homopolymers [1] to [4] of the present invention usually have the following phasic properties.

(1) The 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 9,000 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 weight average molecular 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 homopolymers [1] to [4] 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 molecule. pressed sheet (thickness = 100 to 500 μm) formed at a temperature of 190 ° C.

<td>Terminal unsaturated group type</td><td>Absorption position (cm ¹)</td>

<td>Vinylene group</td><td> 963</td>

<td>Vinylidene group</td><td> 888</td>

<td>Vinyl group</td><td> 907</td>

In each ethylene homopolymer, the production ratio of the terminal vinyl group is normally

IS 2 178 648 T3

30% by mole, preferably 40% by mole or more, more preferably 50% by mole or more, based on 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 interrelationship is present between the amount of terminal unsaturated groups and the molecular weight, but in the ethylene homopolymers of the present invention, the content of terminal vinyl-type unsaturated groups (U) and the number The reciprocal of the intrinsic viscosity [η] measured in decalin at a temperature of 135 ° C normally satisfies the equation:

0.1 x [η]^-1 &lt;u &lt;7 x [η]^-1 preferably

0.1 x [η]^-1 &lt;U &lt;6.5 x [η]^-1 more preferably,

0.15 x [η]^-1 &lt;U &lt;6.5 x [η]^-1 being above all preferable, or, 15 x [η]^-1 &lt;u &lt;6 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 a polyethylene having a high content of unsaturated groups in the terminal through the modification of the unsaturated group and, simultaneously, the improvement of the working properties can be expected as a function of the branching. Additionally, polyethylene having a high content of terminal vinyl groups can be used as a branched micromonoemer for the manufacture of various graft copolymers. On the other hand, in polyethylene having a low content of terminal unsaturated groups, thermal stability can be improved and working properties based on branching can be expected. Functions such as adhesive properties and printability can be sufficiently influenced through practical modification even in the case of a polyethylene having a low content of terminal unsaturated groups.

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

The ethylene homopolymers (unhydrogenated ethylene homopolymers and hydrogenated ethylene homopolymers) of the present invention can be mixed with other thermoplastic resins and used later. 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, straight chain low-density polyethylenes obtained by using 1 -butene, 1-hexene, 1-octene, 4-methylpentene-1 and 3-methylbutene-1 as comoneomer components, ethylene-vinyl acetate copolymers, saponified ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ether copolymers, ethylene ionomer 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 weight polymers

ES 2 178 648 T3 molecular series of adicioin polymerization include polymers made from polar vinyl monomers and polymers made from diene monoimers, typically, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-butadiene copolymer, acrylonitrile copolymer -butadienestyrene, diene polymers in which the diene chain is hydrogenated and thermoplastic elastíomers.

The thermoplastic resin composition of the present invention can be obtained by mixing 100 parts by weight 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 thermoplastic elastiomer).

The ethylene homopolymers [1] to [4] of the present invention can be prepared by polymerization of an ethylene monoimer in the presence of a suitable polymerization catalyst so as to allow the preparation of polyethylene having the aforementioned characteristics.

An example of such a polymerization catalyst contains as main components (A) a transition metal compound and (B) a compound capable of forming an ionic 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 lantianide series can be used. Preferable examples of the transition metal include titanium, zirconium, hafnium, vanadium, niobium, and chromium.

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

CpM¹R¹aR_b²Rc³ ... (I)

Cp2M¹R¹aR_b² ... (II) (Cp-Ae-Cp) M¹R¹aR_b² ... (III) or the general formula:

M¹R¹aRb²Rc³R⁴d ... (IV) and its derivatives.

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. In this connection, 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 They independently represent a δ-binding ligand, a chelate ligand or a ligand such as a Lewis base, including among the 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 junction cross-linked 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 substituent is preferably an alkyl group having 1 to 20 carbon atoms. In formulas (II) and (III), the two Cps can be the same or different from each other.

Examples of the substituted cyclopentadienyl group in formulas (I) to (III) above 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

ES 2 178 648 T3 pentamethylcyclopentadienyl group and a trimethylsilylcyclopentadienyl group. Also, among the topical examples of R¹ aR⁴ in the above-mentioned formulas (I) to (IV), a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are included as halogen atom; 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 dimethyl 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 '-pyrididine 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 coclic unsaturated hydrocarbons such as benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraen and its derivatives as Lewis base. On the other hand, examples of crosslinking by the covalent bond of A in formula (III) include a methylene crosslinking, a dimethylmethylene crosslinking, an ethylene crosslinking, a 1,1'-cyclohexylene crosslinking, a crosslinking dimethylsilylene, a dimethylgermylene crosslink and a dimethyltanylene crosslink.

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) trimetilzirconio, (methylcyclopentadienyl) trifenilzirconio, (methylcyclopentadienyl) tribencilzirconio, (methylcyclopentadienyl) triclorozirconio, (methylcyclopentadienyl) dimethyl (methoxy) zirconium, (dimethylcyclopentadienyl) triclorozirconio, (trimethylcyclopentadienyl) triclorozirconio, (trimethylcyclopentadienyl ) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium, and compounds in which zirconium is replaced by titanium or hafnium.

IS 2 178 648 T3

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) dichlorozironohydride (cyclopentadienyl) dichlorozironohydrozirconium (cyclopentadienyl) dichlorozironohydride (cyclopentadienyl) dichlorozironohydride (cyclopentadienyl) dichlorozirconium (cyclopentadienyl) dichlorohydrogen monohydrozirconium bis (methylcyclopentadienyl) dimethylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclopentadienyl) dibenzylzirconium, 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 (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (9 - fluorenyl) zirconium dimethyl, isopropylidene (cyclopentadienyl ) (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-flupentadienyl) (cyclopentylidene (9-flupentadienyl) (cyclopentylidene (9-flupentadienyl) (cyclopentyl) - (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, tetrabenzyl zirconium, tetramethoxyzirconium, tetraethoxyzirconium, tetrabutoxyzirconium, tetrachlorozirconium, tetrabromozirconium, butoxytrichlorozirconium, dibutoxyzirconium (2,5-buthoxy-dichloro-dimethyl-dichlorozirconium) , bis (2,5, - di-t-butylphenoxy) dichlorozirconium, bis (acetylacetonate) zirconium, as well as these compounds in which the zirconium is replaced by titanium or hafnium.

Topical examples of the vanadium compound include vanadium trichloride, vanadyl trichloride, vanadium triacetylacetonate, vanadium tetrachloride, vanadium tributooxide, vanadyl dichloride, vanadyl bisacetylacetonate, vanadyl triacetylacetonate, vanadyl vanadyl triacetonate, dicyclovanadyl 19

ES 2 178 648 T3 dienylvanadium, dicyclopentadienylvanadium dichloride, cyclopentadienylvanadium dichloride and dicyclopentadienylmethylvanadium.

Also, topical examples of the chromium compound include tetramethylchromium, tetra (tbutoxy) chromium, bis (cyclopentadienyl) chromium, hydridotricacarbonyl (cyclopentadienyl) chromium, hexacarbonyl (cyclopentadienyl) chromium, bis (benzene) chromium, tricarbonylphostris (triphenyl) chromium tris (allyl) chromium, triphenyltris (tetrahydrofuran) chromium and tris (acetylacetonate) chromium.

Likewise, as component (A), a group 4 transition compound 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) with each other through an element selected from group 14 of the periodic table.

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

^ (R5 - C5 H 4-t) ··· / X¹

R6 and¹ ··· M² .. (V) ^X(RU -C5 H 4-u) ···· ^XX¹ 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 one represents a substituted cyclopentadienyl group, 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 otoms, 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 topical 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.

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

Z --- Y²

Cp --- M³ ... (SAW)

X²,,

IS 2 178 648 T3

In the compound of the general formula (VI), 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. 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 1 to 20 carbon atoms carbon. Z represents SiR2⁷, CR⁷2, SiR₂⁷Sir⁷2, CR₂⁷CR2⁷, CR⁷2CR⁷two CR⁷2, CR⁷ = CR⁷, CR2⁷SiR2⁷ oGeR⁷two , hey² represents -N (R⁸ ) -, -O-, -S- io -P (R⁸ ) -. 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 atoms, an aryl group, a silyl group, a halogenated alkyl group, a halogenated aryl group, and a combination of them, and R⁸ is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, or R⁸ can form a condensed ring of one or more R⁷ and 30 or less non-hydrogen atoms. On the other hand, w represents 1 or 2.

Typical examples of the compound represented by the general formula (V) include (tert-butylamido) (tetramethyl-r⁵ - cyclopentadienyl) -1, 2-ethanediylzirconium, (tert-butylamido) dichloride (tetramethyl-r ⁵ - cyclopentadienyl) -1,2-ethanediiltitanium, (methylamido) dichloride (tetramethyl-r⁵ - cyclopentadienyl) -1,2-ethanediylzirconium, (methylamido) dichloride (tetramethyl-r⁵ cyclopentadienyl) -1,2-ethanediiltitanium, (ethylamido) dichloride (tetramethyl-r⁵ - cyclopentadienyl) methylene titanium, (tert-butylamido) dimethyl (tetramethyl-r dichloride ⁵ - cyclopentadienyl) silanetitanium, (tert-butylamido) dimethyl - (tetramethyl-r ⁵ - cyclopentadienyl) silanozirconium dibenzyl, (benzylamido) dimethyl (tetramethyl-r dichloride⁵ - cyclopentadienyl) -silanetitanium and (phenylphosphide) dimethyl (tetramethyl-r⁵ 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 halogen atoms and the alkoxy group with the central metal and any of the diols represented by the general formulas (VII) to (XII):

(VII)

HO - R⁹ - (Y³) m -R¹⁰ - OH

<img file="ES2178648T3_D0001.tif" />

(VIII)

<img file="ES2178648T3_D0002.tif" />

... (IX)

<img file="ES2178648T3_D0003.tif" />

... (X)

ES 2 178 648 T3 (XI)

<img file="ES2178648T3_D0004.tif" />

(xii)

In the compounds represented by the general formulas (VII) to (XII), R⁹ and R¹⁰ are each a hydrocarbon group having 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:

<td></td><td></td><td>OR II</td><td></td><td></td><td></td><td>OR II</td><td>R¹⁵ |</td>

<td>O-, -S-, - S - S -,</td><td>- S-, II</td><td>- S-, II</td><td>- C-, II</td><td>-N-, |</td><td>- P-, |</td><td>- P - o |</td><td>¹- Yes - |</td>

<td></td><td>II OR</td><td>OR</td><td>OR</td><td>¹R¹⁵</td><td>¹R¹⁵</td><td>¹R¹⁵</td><td>¹R¹⁵</td>

where R¹⁵ is a hydrocarbon group that has 1 to 6 carbon atoms. Among the examples of hydrocarbon group having 1 to 20 carbon atoms that is represented by R⁹, R¹⁰ and Y³ include methylene, ethylene, trimethylene, propylene, diphenyl-methylene, ethylidene, n-propylidene, isopropylidene, n-butylidene, and isobutylidene, with methylene, ethylene, ethylidene, isopropylidene, and isobutylidene being most preferred. n is an integer of 0 or more, with 0 to 1 being particularly preferable.

On the other hand, R¹¹, R¹², R¹³ and R¹⁴ They are each a hydrocarbon group having 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 to an aromatic ring, e, y, y ', z and z' are each an integer between 0 and 4, e, y "and z" are each an integer between 0 and 2 , where y ”'and z”' are each an integer between 0 and 3.

An example of 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) v O E3, (Y⁴) ^ / \ ... (xiii)

EO^XXE1

IS 2 178 648 T3

In the general formula (XIII), M¹ is as defined before, E¹ yE² are each a hydrocarbon group having 1 to 20 carbon atoms, v and x are each 0 or e 1, and E¹ yE² form a reticulation structure through Y⁴.AND³ yE⁴ 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 atom of oxygen or an atom of sulfur, and m is an integer between 0 and 4. E⁵ yE⁶ are each a hydrocarbon group having 1 to 20 carbon atoms, and Y⁵ it is a carbon atom or a silicon group.

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

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

<img file="ES2178648T3_D0005.tif" />

On the other hand, the compound of the general formula (XIII) also includes a compound represented by the general formula (XIV):

_OR16 ^|

R¹⁶ O- (M⁴ -OR-)₂ R¹⁶ ... (XIV) ^|_OR16

In the general formula (XIV), the R¹⁶ are each an alkyl group or an acyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or an aryl group, an alkylaryl group or an arylalkyl group having 6 to 20 carbon atoms, and the R¹⁶

Corresponding ES 2 178 648 T3 may 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 lantianide series, and z is an integer between 2 and 20.

Typical examples represented by the general formula (XIV) include BuO [Zr (OBu) 2 O] 4Bu, EtO [Zr (OEt) 2 O] 4-Et, iPrO [Zr (OiPr) 2O] 4-iPr, nPrO [Zr (OnPr) 2O] 4-nPr, BuO [Zr (OBu) 2 O] 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 hompolymer 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 should 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 present invention, the transition 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 which can be used as component (B) in the polymerization catalyst and which is capable of forming an ionic complex from the transition metal compound of component (A) or its derivative include (B-1) an ionic 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 ioin compound of component (B-1), any ioin compound can be used as long as it reacts with the transition metal compound of component (A) to form the ion 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 anion in which several groups are attached to. an element. The compound that includes a cation and an anion in which several groups are attached to one element is a compound represented by the general formula:

([L¹-R¹⁷)^{k +})p.m¹⁵Z¹Z² ... Zⁿ] ⁽what^{h — g—)} ... (XV) or

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

[In the forms (XV) and (XVI), L¹ is a Lewis base; M⁵ and M⁶ they are each an item selected from groups 5, 6, 7, 8-10, 11, 12, 13, 14, and 15 of the periodic table, preferably an item selected from groups 13, 14, and 15; M⁷ and M⁸ they are each an element selected from groups 3, 4, 5, 6, 7, 8-10, 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 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms carbon, an aryl group, an alkylaryl group or an arylalkyl group having 6 to 20 carbon atoms, a halogen-substituted hydrocarbon having 1 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms carbon, an organic metalloid group or a halogen atom, and Z¹ aZⁿthey can be joined together to form a ring. R¹⁷ is 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; 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 cyclic ligand like 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 ion of [L¹ -R¹⁷] or [L²] y is an integer between 1 and 7, and p is an integer of 1 or mine, and q = (pxk) / (h - g).

At this point, among the typical examples of Lewis base 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

ES 2 178 648 T3 as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane, thioethers such as diethyl thioether and tetrahydrothiophene and an ester such as ethyl benzoate.

Likewise, among the topical examples of M⁵ and M⁶ include B, Al, Si, P, As and Sb, with B and P being preferred. Topical examples of M⁷ include Li, Na, Ag, Cu, Br, and I, and topical examples of M⁸ include Mn, Fe, Co, Ni, and Zn. Among the topical 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, alkylrayl 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 thyrmethylsilyl group, a trimethylgermyl group, a diphenylarsine group, a dicyclohexylanantimony group and a diphenylboron group as orgaonic metalloid groups. Among the topical examples of R¹⁷, R²⁰ the aforementioned are included. Among the topical 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 formulas (XV) and (XVI), the compounds in which M⁵ and M⁶ they are boron. Of the compounds of the general formulations (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, pentaluorophenyl tetrakis (pentafluorophenyl) borate) borate triphenylammonium, 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) methyl tetrakis (pentafluorophenyl) 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, pentafluorophenyl) bokis (pentafluorophenyl) bokisor tetrakis (pentafluorophenyl) borate - cyanopyridinium), tetrakis (pentafluorophenyl) borate (N-methylpyridinium), tetrakis (pentafluorophenyl) borate (N-benzylpyridinium), tetrakis (pentafluorophenyl) borate (2-cyano-N-methylpyridinium), (4-cyano-N-methylpyridinium) tetrakis (pentafluorophenyl) borate, (4-cyano-N-benzylpyridinium) tetrakis (pentafluorophenyl) borate, trimethylsulfonium tetrakis (pentafluorophenyl) borate, benzyldimethylsulfonium tetrakis (pentafluorophenyl) borate tetraphenylphosphonium pentafluorophenyl) borate, dimethylanilinium tetrakis (3,5-ditrifluoromethylphenyl) borate, tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) dimethylanilinium borate, tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) triethylammonium borate, tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) pyridinium borate, tris (pentafluorophenyl) - () pentafluorofluoro-trifluoro-trifluoro-trifluoro-trifluoro (2-cyano-N-methylpyridinium) trifluoromethyltetrafluorophenyl) borate, tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) borate, tris (pentafluorophenyl), tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) triphenylphosphonium borate, tris (pentafluorophenyl) (2,3,5,6-tetrafluoropyridinyl) borate, dimethylanopyridinium, tris (pentafluorophenyl) - (2,3,5pyrid) triethylammonium, tris (pentafluorophenyl) (2,3,5,6-tetrafluoropyridinyl) borate pyridinium, tris (pentafluorophenyl) (2,3,5,6-tetrafluoropyridinyl) borate (N-methylpyridinium), (2-cyano-N-methylpyridinium) tris (pentafluorophenyl) (2,3,5,6-tetrafluoropyridinyl) -borate, (4-cyano- N-benzylpyridinium), triphenylphos25 tris (pentafluorophenyl) (2,3,5,6-tetrafluoropyridinyl) borate

ES 2 178 648 T3 Phonium, dimethylanilinium tris (pentafluorophenyl) (phenyl) borate, dimethylanilinium tris (pentafluorophenyl) [3,5-di (trifluoromethyl) phenyl] borate, dimethylanilinium tris (pentafluorophenyl) (4-trifluoromethylphenyl) borate Dimethylanilinium triphenyl (pentafluorophenyl) borate and trimethylammonium hexafluoroarsenate.

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 of tetraphenylporphyriniron, tetrakis (pentafluorophenyl) borate of 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 ionic compound, which is the component (B-1), capable of forming an ionic complex, may be a polycational 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—)_s-—₂ By ... (XVII) / | \ _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; y s represents the degree of polymerization, and is an integer normally between 3 and 50, preferably between 7 and 40);

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

_|--(To the-_|^||| ^|| | R 22 | (XVIII) (in which the R²² and s are as defined above).

Among the compounds of the general formulations (XVII) and (XVIII), aluminoxanes having a degree of polymerization of 7 or more are preferable. When using an aluminoxane having a degree of polymerization of 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 formulas (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 preparing the mentioned aluminoxanes, mention can be made of a method 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, it is possible to carry out the They reacted in any of the known ways. For example, there is a method (1) that consists of the dissolution of an organic aluminum compound in an orgaonic solvent and the subsequent contact of the solution with water, (2) a method that consists in the first addition of a compound of orgaonic aluminum at the time of polymerization, and the subsequent addition of water, (3) a method that consists of the reaction

ES 2 178 648 T3 of water of crystallization contained in a methyl 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 mine 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 in combination of two or more of them.

In the present invention, as the catalyst component (B), the above-mentioned components (B-1), (B-2) and (B-3) can be used, alone or by 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 can be used which is represented by the general formula (XIX):

R_r²³AlQ 3 — r ... (XIX) in which R²³ is an alkyl group having 1 to 10 carbon atoms; Q is an atom of hydrogen, 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, diethylaluminumhydrysinide, diethylaluminum dihydrochloride, diethylaluminum dichloride, diethylaluminum hydridethylaluminumide, 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 afterwards.

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 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-divnylbenzene copolymers, polyethylenes, polypropylenes, polystyrenes and substituted polyacrylates, staridoin 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, it is preferred27

ES 2 178 648 T3 may be 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 polymer particles 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 m²/ 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 1 / 0.1 to 1/100, preferably 1 / 0.5 to 1/10, mine 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 1/2000 to 1/1, preferably 1/1000 to 1/5, more preferably 1/500 to 1/10.

On the other hand, in the case (3) that the 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 present invention, an ethylene homopolymer having better non-Newtonian properties and excellent working properties can be efficiently obtained, wherein the Huggins coefficient and intrinsic viscosity [r] measured in a decalin solvent, at a temperature of 135^°C satisfy the relation of the equation:

k&gt; 0.2 + 0.0743 x [r] for example, as in the case of the ethylene homopolymer [1] mentioned above, by homopolymerization of ethylene in the presence of a catalyst consisting of (a) a metal compound of transition in which the relationship between the monomer charge composition [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 satisfy the equation:

&lt;ΔΗ-Pm &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 transitional metal compound capable of forming a terminal vinyl group in the

ES 2 178 648 T3 homopolymerization of ethylene (however, under the polymerization conditions in which component (b) is used together with the aluminoxane), and (c) a compound capable of forming an iogenic complex from the components (a) and (b) mentioned above or their derivatives, selecting said components (a), (b) and (c) between transition metal compounds of components (A) containing a metal from groups 3 to 10 of the periodic table or from the lanthanide series, preferably titanium, zirconium, hafnium, chromium, vanadium or a metal from the lantaenid 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 catalytic activity of each component, and therefore cannot be radically decided, although when the ratio of component (b) is increased ( a), an ethylene homopolymer having superior nonewtonian 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 is 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 homopolymer can be obtained that has non-Newtonian properties. It is believed that the fact that the ethylene homopolymer 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 ethylene is produced. comb shape, but also forms a branch in the branched chain of 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.

Typically, the formation of the terminal vinyl group is considered to be due to chain transfer of elimination of the growing terminal β hydrogen and β alkyl group in a polymerization system involving ethylene and propylene. It can be determined by evaluating the polymer produced by polymerization 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 as a function of 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 so calculated terminal vinyl groups, 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.

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 end groups and that can easily react the vinyl groups with the monomer to form the branches, the number of vinyl groups is ultimately reduced. In contrast, when using a catalyst that can easily form finyl groups and has poor copolymerization properties, many vinyl groups remain.

IS 2 178 648 T3

Therefore, it is necessary to inspect the ease of formation of branches. This can be evaluated by the relationship between the number average molecular weight Mn as regards polyethylene measured by gel permeation chromatography (GPC) and the number average molecular weight Mn calculated as a function of the relationship between the methylene groups. in the main chain and end groups measured by¹ H-NMR. When carrying out the evaluation of the branching as a function of this Mn ratio, it is necessary to judge and globally 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.

Preferable examples of the transition metal compound of the catalyst component (b) having such terminal vinyl group formation properties include:

(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) Cp2M¹R¹aRb² ... (II) (3) (CP-Ae-Cp) M¹R¹aR_b² ... (III) (where Cp, A, M¹, R¹, R², a, bye are as defined above).

(b) Copolymerization properties

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

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

&lt;ΔΗ-Pf &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 were evaluated by selecting excellent polymerization conditions using the transition metal compound of component (a) and the aluminoxane.

(Method to verify the relation 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 when 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 cooled to -50^°C at a speed of 10^°C / min.

On the other hand, the copolymerization conditions are (1) that the polymerization can be carried out under atmospheric pressure or with an increase in pressure, (2) that a discontinuous polymerization in which the polymer is continuously fed is acceptable. ethylene alone (however, the monoimer conversion is 20% 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 an actual mixed catalyst system, (4) that the copolymerization reaction is initiated once the composition ratio between ethylene and comonomer and the total concentration have reached a constant state, (5) that the molecular weight of the copolymer produced is higher 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) than the Ethylene concentration and gaseous monoimer concentration are calculated as a function of the weight of ethylene or monomer that is dissolved in a polymerization solvent and with which the polymerization solvent is saturated at a given

ES 2 178 648 T3 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 are unacceptable polymerization conditions in which the monomer composition of the system changes by diffusion of ethylene or gaseous monomer, (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 catalytic components is such that the ratio between the transition metal compound (a) and the aluminoxane is in the range of 1/100 to 1/2000.

The relationship between the proportion of the monomeric monomer charge composition [M] and the product of recrystallization enthalpo (ΔΗ) and the melting point (Pf) of the ethyl 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 transition 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 still &lt;ΔΗ.Ρί &lt;27,000 - 24,000 [M]⁰,⁴⁷ more preferably still &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

Preferable examples of the transition metal compound which is the catalyst component (a) having such copolymerization properties include the compounds represented by the general formulas:

CpMXR2R3 ... (I) (Cp-Ae-Cp) M¹RaR2 ... (III)

Z --- Y²

Cp --- M³

XW and

(AND¹) v O E3, (Y⁴)^ / \

AND ^XFORMER

.. (SAW)

... (XIII) in which Cp, A, E, E¹, E², E³, E⁴, X², Y², Y⁴, Z, R¹ to R³, a, b, c, e, w, m, v, v ', x and x' are as defined before and M¹ and M³ represent titanium, zirconium or vanadium. The compounds represented by formulas (VI) and (III) are especially preferred, as they have a high polymerization activity.

IS 2 178 648 T3

Polymerization can be carried out using the above-mentioned catalyst through one-stage polymerization or through 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 in a wide range is possible. Also, in the two-stage copolymerization, the ethylene homopolymer can be provided in which the amount of unsaturated carbon-carbon bonds in the produced ethylene homopolymer is decreased and the thermic stability is improved. On the other hand, the ethylene homopolymer obtained through one-stage polymerization is suitable as a material for a chemically modifiable ethylenic polymer, thanks to the presence of relatively large unsaturated groups.

In the present invention, no particular restriction is established as to the polymerization method for preparing the ethylene homopolymer, and therefore, a solvent polymerization method using an inert hydrocarbon or the like (suspension polymerization or the like can be used). solution polymerization), a block 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 was 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 homopolymer, 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, 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 oxide, for example nickel- silica, nickel-diatomaceous earth, palladium-carbon, palladium-silica, palladium-diatomaceous earth, and palladium-alloumin. Examples of the nickel catalyst include Raney nickel catalysts, and examples of platinum catalysts include platinum black and platinum oxide catalysts. Examples of homogeneous catalysts include catalysts containing metals from groups 8 to 10 of the Periodic table as base components, for example catalysts including Ni and Co compounds and orgaonic 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,

IS 2 178 648 T3

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 to be 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 polyethylene and (II) 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 a gauge pressure of 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, with 10 to 180 being more preferable^°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 methylaluminoxane (MAO)

200 ml of toluene, 17.8 g (71 mmol) of copper sulfate pentahydrate (CuSO4.5H2O) and 24 ml (250 mmol) of trimethylalumino were placed in a 500 ml glass container that had been purged with argon, and then the mixture was reacted at 40^°C for 8 hours.

Next, toluene was distilled from the solution obtained by separating the solid components, under reduced pressure, to obtain 6.7 g of a catalytic product (methylaluminoxane).

(2) 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. Subsequently, 0.56 g of cyclopentanol was added, drop by drop and then the solution was tempered 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 will be more limited until -25^°Afterwards, the reaction will be carried out for 120 minutes. Next, the solution will be displayed until 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.

(3) Ethylene polymerization

300 ml of toluene and 60 mmol of the methylaluminoxane prepared in step (1) above were placed, under a nitrogen atmosphere, in a 1 liter flask equipped with a stirrer. The solution was then heated to 60^°C and ethylene gas was then introduced under atmospheric flow conditions. Next, 6.0 ml of the solitary solution portion of the catalyst component prepared in step (2) above was poured into the flask.

IS 2 178 648 T3

The reaction temperature was controlled at 60 ° C and polymerization was carried out for 120 minutes at the same time that ethylene was continuously introduced. After completion of the polymerization, a large amount of methanol was poured in and the resulting product was washed; and then it was dried under reduced pressure to obtain 8.5 g of an ethylene homopolymer.

(4) Evaluation of the ethylene hompolymer (a) Measurement of the Huggins coefficient

0.1005 g of the ethylene homopolymer obtained in step (3) above was dispersed in 17.996 g of decalin, and then the mixture was melted at 135 ° C. The concentration of the polymer obtained when the density of the decalin at 135 ° C was 0.79055 g / ml was 0.4415 g / dl.

This polymer was transferred to a Ubbelode viscoometer, and once the temperature of the polymer had reached a constant temperature of 135 ° C, the measurement was started. The measurement was repeated 6 times, and as a result, the average result obtained was 3.043 dl / g as regards the reduced viscosity.

On the other hand, the viscosity reduced by 5 points was measured, in the same way as described, at the same time that the polymer was diluted with decalin as mother liquor. Figure 3 shows the relationship between the polymer concentration [c] and the reduced viscosity.

The Huggins coefficient obtained at 5 points was 0.412 and the intronsic viscosity [η] was 2.18 dl / g. On the other hand, its correlation coefficient was 0.999.

On the other hand, the relationship between a HDPE with the same intronsic viscosity [η] and the Huggins coefficient was 1.14.

(b) NMR measurement

The measurement of ¹³C-NMR [100 MHz, measuring temperature = 130 ° C, solvent 1,2,4-trichlorobenzene / heavy benzene (molar ratio = 8/2)]. As a result, no absorption of the ethyl branched methyl group was present at 11.14 ppm. However, judging from the fact that methylene carbon at 38-39 ppm, methylene carbon at 34-36 ppm and the methyl group at 13.8-14.1 ppm are present in the polymer chain, it can be consider that a long chain branching is present. On the other hand, no absorption was observed at 8.15 ppm, which shows that no quaternary carbon is present.

On the other hand, an absorption based on butyl branching was observed at 29.57 pp. The spectrum graph is shown in figure 4.

(c) Assessment of the thermic behavior

A heat-pressed sheet was used as a sample at a temperature of 190 ° C, and the measurement was carried out by using a difference exploration calorometer model DSC7 manufactured by Perkin Elmer Co., Ltd. That is, the enthalpoe of crystallization (ΔΗ) as a function of the exothermic peak of crystallization observed at the time when the sheet was melted at a temperature of 150 ° C for 5 minutes, then cooled to -50 ° C at a rate of 10 ° C min. A melting point (MP) was obtained from the endotothermic peak observed at the time the loamine was heated at a rate of 10 ° C / min.

As a result, the enthalpoe of crystallization (ΔΗ) was 5 J / g, and the melting point (MP) was 121 ° C.

(d) Density measurement

A sample molded by hot pressing at 190 ° C was used and the measurement was carried out according to the density gradient tube method. As a result, the density was 0.887 g / cm³. Additionally, no anelation treatment was carried out on the sample.

(e) Measurement of terminal vinyl groups.

A pressed 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

ES 2 178 648 T3 in 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 0.2 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 weight average molecular weight (Mw) was 258,000, the number average molecular weight (Mn) was 14,700, and the Mw / Mn ratio was 17.6.

(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 dynamic viscoelastic properties, at measuring 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 used 170^°C as the standard temperature.

As a result, the activation energy (Ea) was 12.1 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

Under a stream of nitrogen, 400 ml of toluene, 0.5 mmol of triisobutylaluminum and 10 mmol of the methylaluminoxane prepared in example 1- (1) were placed in a stainless steel autoclave and then the mixture was heated to 70^°C. Subsequently, 1.5 ml of the solution portion of the catalytic component prepared in example 1 (2) was added and ethylene was continuously introduced for 10 minutes at a pressure of 6 kg / cm²M to polymerize ethylene.

After completion of the polymerization, the ethylene pressure was released and a large amount of methanol was poured in. The solution was washed and then dried to obtain 3.6 g of an ethylene homopolymer.

From the ethylene homopolymers obtained in Examples 1 and 2, films were formed and tensile tests were carried out. Table 2 shows the results. On the other hand, Table 3 shows the results of the evaluation.

TABLE 2

<td></td><td>Modulus of elasticity (kg / cm²)</td><td>Breaking strength (kg / cm²)</td><td>Extent of rupture (%)</td>

<td>Example 1</td><td> 360</td><td> 100</td><td> 470</td>

<td>Example 2</td><td> 9.000</td><td> 230</td><td> 1.030</td>

Example 3

The same procedure as in Example 2 was carried out with the exception that the ethylene feed pressure was set at a gauge pressure of 735 kPa (7.5 kg / cm²M) to get

8.5 g of an ethylene homopolymer. The ethylene homopolymer thus obtained was evaluated. Table 3 shows the results. The spectrum of¹³C-NMR of the ethylene homopolymer obtained appears in Figure 5.

IS 2 178 648 T3

TABLE 3

<td></td><td>Example 2</td><td>Example 3</td>

<td>Huggins coefficient</td><td> 0,799</td><td> 0,504</td>

<td>(correlation coefficient)</td><td> (0,999)</td><td> (0,999)</td>

<td>¹³C-NMR</td><td>No absorption at 8.15 ppm and 11.14 ppm Absorption was present at 29.57 ppm</td><td>No absorption at 8.15 ppm and 11.14 ppm Absorption was present at 29.57 ppm</td>

<td>Melting point (° C)</td><td> 124,0</td><td> 125,2</td>

<td>Enthalpy of crystallization (J / g)</td><td> 191,2</td><td> 200,2</td>

<td>Density (g / cm³)</td><td> 0,957</td><td> 0,958</td>

<td>End vinyl groups (for 1000 carbon atoms)</td><td> 4,5</td><td> 3,7</td>

<td>Pm / Mn¹)</td><td> 21,6</td><td> 30,7</td>

<td>Intrinsic viscosity [r] (dl / g)</td><td> 1,07</td><td> 1,20</td>

<td>k / k '²⁾</td><td> 2,75</td><td> 1,71</td>

<td>Melt flow activation energy</td><td> 11,5</td><td> 11,2</td>

Melt flow activation energy: kcal / moles.

Notes: 1) Mw / Mn = weight average molecular weight / number average molecular weight.

2) The relationship between the Huggins coefficients of polyethylene and an HDPE under conditions of the same [r].

Example 4

The ethylene homopolymer obtained in Example 2 was hydrogenated under conditions of a temperature of 140^°C, an ethylene homopolymer concentration of 9% by weight, a hydrogen pressure of 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 from the reaction solution.

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

Example 5 (1) Preparation of catalyst component

A titanium catalyst component was prepared in the same manner as in Example 1- (2).

(2) Ethylene polymerization.

Under a stream of nitrogen, 200 ml of toluene, 4 mmol of triisobutylaluminum (TIBA), 0.4 mmol of a boron compound [Me2PhNH] [B (C6F5) 4] and 0.05 mmol were placed, relative to the titanium, from a titanium catalytic component prepared in step (1) above, in a stainless steel autoclave and then the mixture was heated to 30^°C. Then, ethylene was continuously introduced for 60 minutes to polymerize the ethylene.

After completion of the polymerization, the polymer was poured into a large quantity of methanol and the solution was washed off; then it was dried to obtain 5.0 g of an ethylene homopolymer. The procedures and results of the evaluation of the ethylene homopolymer obtained are described below. On the other hand, figures 4 and 5 show the conditions and results of the polymerization.

ES 2 178 648 T3 (3) Evaluation of polyethylene (a) Measured by NMR

The measure of ¹H-NMR [400 MHz, measurement temperature = 130^°C, solvent = 1,2,4-trichlorobenzene / heavy benzene (molar ratio = 8/2)]. As a result, the molar ratio [CH3 / CH2] 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 0.007. 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, observed in an LDPE.

(b) Assessment of thermal behavior

A heat-pressed sheet was used as a sample at a temperature of 190^°C and the measurement was carried out using a differential scanning calorimeter model DSC7 manufactured by Perkin Elmer Co., Ltd. That is, a melting point (Pf) was obtained from the endothermic peak observed at the time when laléamina 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 131.1^°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 0.945 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 210,000, the number average molecular weight (Mn) was 46,600 and the Pm / Mn ratio was 4.5.

(e) Measurement of the 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 12.5 kcal / mol.

Example 6 (1) Preparation of methylaluminoxane (MAO)

The same procedure as in example 1- (1) was repeated to obtain 6.7 g of a catalytic product (methylaluminoxane) and then the product was subjected to heat treatment at 120^°C for 10 hours, under reduced pressure to dissolve and disperse it in toluene.

(2) Preparation of the catalytic component

The same procedure as in Example 1- (2) was repeated, except that the cyclopentanol from Example 1- (2) was replaced with 0.38 g of isopropanol, to prepare a catalytic component.

(3) Ethylene polymerization

The same procedure as in Example 5- (2) was followed under the conditions shown in Table 4 to prepare an ethylene homopolymer. The conditions and results of the polymerization are shown in Tables 4 and 5.

Examples 7 and 8

Ethylene was polymerized under the conditions indicated in Table 4 to prepare an ethylene homopolymer, followed by its evaluation. Table 5 shows the results.

IS 2 178 648 T3

TABLE 4 (I)

<td rowspan="2"></td><td rowspan="2">Toluene (ml)</td><td rowspan="2">TIBA (mmol)</td><td rowspan="2">[B] (mmol)</td><td rowspan="2">MAO (mmol)</td><td colspan="2">Transition components</td>

<td>kind</td><td>moles</td>

<td>Example 5</td><td> 200</td><td> 4</td><td> 0,4</td><td> -</td><td>Titanium component (I)</td><td> 0,2</td>

<td>Example 6</td><td> 300</td><td> -</td><td> -</td><td> 60</td><td>Titanium component (II)</td><td> 0,3</td>

<td>Example 7</td><td> 300</td><td></td><td></td><td> 60</td><td>Titanium component (II) Zirconium component</td><td> 0,3 0,001</td>

<td>Example 8</td><td> 300</td><td></td><td></td><td> 60</td><td>Zirconium component (II) Zirconium component</td><td> 0,3 0,002</td>

TABLE 4 (II)

<td></td><td>Ethylene pressure (kg / cm²M)</td><td>Temperature (^°C)</td><td>Weather (min)</td><td>Performance⁽g)</td>

<td>Example 5</td><td>Flowable</td><td> 30</td><td> 60</td><td> 5,0</td>

<td>Example 6</td><td>Flowable</td><td> 60</td><td> 60</td><td> 8,4</td>

<td>Example 7</td><td>Flowable</td><td> 60</td><td> 60</td><td> 20,7</td>

<td>Example 8</td><td>Flowable</td><td> 60</td><td> 60</td><td> 29,5</td>

[Notes] [B]: [Me2PhNH] [B (C6F5) 4].

Titanium component [I]: Catalyst prepared in Example 5- (1). Titanium component [II]: Catalyst prepared in Example 6- (1). Zirconium component: Et [Ind] 2ZrCl2.

TABLE 5 (I)

<td></td><td>Density (g / cm³)</td><td>Grade branch</td><td>Weight molecular weight average (Mw)</td><td>Molecular weight distribution (Pm / Mn)</td>

<td>Example 5</td><td> 0,945</td><td> 0,007</td><td> 210.000</td><td> 4,5</td>

<td>Example 6</td><td> 0,890</td><td> 0,062</td><td> 265.000</td><td> 2,9</td>

<td>Example 7</td><td> 0,922</td><td> 0,045</td><td> 178.000</td><td> 2,2</td>

<td>Example 8</td><td> 0,935</td><td> 0,017</td><td> 165.000</td><td> 2,2</td>

[Note]: Degree of branching: A [CH3 / CH2] molar ratio calculated by ¹H-NMR.

IS 2 178 648 T3

TABLE 5 (II)

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

<td>Example 5</td><td> 12,5</td><td> 131,1</td>

<td>Example 6</td><td> 12,5</td><td> 125,9</td>

<td>Example 7</td><td> 12,0</td><td> 117,9</td>

<td>Example 8</td><td> 11,8</td><td> 123,0</td>

Example 9

The polyethylene obtained in Example 7 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 was isolated of the reaction solution.

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 activation energy of the fluid were the same as in Example 7.

Comparative Example 1

An ethylene / 1-octene copolymer was prepared under the conditions shown in Table 6. Tables 6 and 7 show the polymerization conditions and the evaluation results.

TABLE 6

<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 80 twenty 57.5</td>

[Note]

1-octene: 40 mol.

Titanium component [III]: (tert-Butylamido) -diemethyl (tetramethyl-n⁵-cyclopentadienyl) silanetitanium.

^* = 8 kg / cm²M

IS 2 178 648 T3

TABLE 7

<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>Activation energy flow</td><td> 7,5</td>

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

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

Example 10 (1) Preparation of methylaluminoxane (MAO)

The same procedure as in Example 1- (1) was repeated to obtain 6.7 g of a catalyst product (methylaluminoxane).

(2) Preparation of titanium catalyst component.

A titanium catalyst component was prepared in the same manner as in Example 1- (2).

(3) Preparation of the catalyst component.

A 50 ml flask was dried and purged with nitrogen and 20 ml of toluene, 0.1 ml of the titanium catalyst component prepared in step (2) above and 0.02 mmol of (tert-butylamido) dichloride were introduced dimethyl (tetramethyl-n⁵-cyclopentadienyl) silanetitanium in the flask, followed by stirring at 25 ° C. Next, 0.6 mmol of the aluminoxane prepared in step (1) above was added, and then the reaction was carried out for 2 hours.

The resulting reaction product was used as a catalyst component.

(4) Polyethylene preparation.

600 ml of toluene, 15 mmol of the methylaluminoxane prepared in the previous step (1) and 0.3 mmol of triisobutylaluminum (TIBA) were placed in a pressure resistant stainless steel autoclave with a capacity of 1 liter and the mixture was heated afterwards. at 90 ° C. Then, 0.036 mmol, based on titanium, of the catalyst component prepared in the above-mentioned step (3) was added.

Ethylene was then continuously introduced into the autoclave under a gauge pressure of 313 kPa (3.2 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 homopolymer was collected, washed with methanol and then dried to obtain 35 g of the polyethylene.

(5) Evaluation of the ethylene homopolymer (a) Density measurement

The measurement was carried out in the same way as in Example 1- (4) - (d). As a result, the density was 0.928 g / cm³. On the other hand, the anelating treatment of the sample was not carried out.

(b) 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 85,000, the number average molecular weight (Mn) was 25,000 and the Pm / Mn ratio was 3.4.

ES 2 178 648 T3 (c) 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 12.1 kcal / mol.

(d) 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, L / D0 = 40, and an 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 capilograph 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 1.41.

(e) NMR measurement

I will carry out the measure¹³C-NMR and, as a result, no absorption was observed at 8.15 ppm of the methyl group in the vicinity of the quaternary carbon, as observed in an LDPE.

Example 11 (1) Preparation of titanium catalyst component

A 100 ml oval plant-type flask was dried and purged with nitrogen, and then 30 ml of toluene and 3.6 ml of a solution of n-butyllithium in hexane (1.66 mol / liter) were introduced, followed cooling of the solution to -78 ° C. Next, 0.49 g of n-butanol was added dropwise and then the solution was made up to -50^°C for 60 minutes.

Then, 26 ml of a solution of pentamethylcyclopentadiene titanium trichloride in toluene (0.0769 mol / liter) was added dropwise to the solution over 60 minutes. The solution was fixed until -25^°After the reaction was carried out for 120 minutes. Then, the solution was fixed up to 20^°Afterwards, it was left to stand 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.

(2) Preparation of the catalytic component.

The same procedure as in example 10- (3) was repeated with the exception that the titanium catalytic component obtained in example 10- (2) was replaced by 0.25 mmol of the titanium catalytic component obtained in step ( 1) above and 0.01 mmol of (tert-butylamido) dimethyl (tetramethyl-η⁵-cyclopentadienyl) silanetitanium and 0.8 mmol of methylaluminoxane, to prepare the catalytic component.

(3) Preparation of the ethylene homopolymer.

The same procedure as that of Example 10- (4) was carried out under the conditions indicated in Table 8 to prepare an ethylene homopolymer. Table 8 shows the results.

Comparative Example 2

An ethylene homopolymer was prepared under the conditions indicated in table 8. The results are shown in table 8.

IS 2 178 648 T3

TABLE 8 (I)

<td></td><td>Example 11</td><td>Comparative Example 1</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> 45,9</td><td> 42,7</td>

MAO: Methylaluminoxane

Catalyst from Example 11: catalyst component prepared in Example 11- (2).

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

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

TABLE 8 (II)

<td></td><td>Example 11</td><td>Comparative Example 1</td>

<td>Density (g / cm³)</td><td> 0,912</td><td> 0,962</td>

<td>Weight Average Molecular Weight (Pm)</td><td> 60.000</td><td> 71.400</td>

<td>Molecular weight distribution (Pm / Mn)</td><td> 3,7</td><td> 3,4</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> 1,35</td><td> 1,06</td>

(Note) In both Example 11 and Comparative Example 2, the results measured in the ¹³C-NMR indicate that no absorption was present at 8.15 ppm.

Example 12

The ethylene homopolymer obtained in Example 10 was hydrogenated under conditions of a temperature of 140 ° C, a polyethylene concentration of 9% by weight, a gauge pressure of hydrogen 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 from the solution was isolated. of reaction.

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, 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 10.

IS 2 178 648 T3

Example 13 (1) Preparation of methylaluminoxane (MAO)

The same procedure as in example 1- (1) was repeated to obtain 6.7 g of a catalytic product (methylaluminoxane).

(2) Preparation of the catalyst component.

A titanium catalyst component was prepared in the same way as in Example 11- (1).

(3) Ethylene polymerization

300 ml of toluene and 30 mmol of the methylaluminoxane prepared in step (1) above were placed in a 1 liter flask equipped with a stirrer, under a nitrogen atmosphere. The solution was then heated to 60^°C, and then ethylene gas was introduced under atmospheric flow conditions. Next, 6.0 ml (0.2 mmol) of the solitary solution portion of the catalyst component prepared in step (2) above was poured into the flask.

The reaction temperature was controlled at 60^°C and polymerization was carried out for 120 minutes at the same time ethylene was continuously introduced. After completion of the polymerization, a large amount of methanol was introduced and the resulting product was washed; then, it was dried under reduced pressure to obtain 10.2 g of ethylene homopolymer.

(4) Evaluation of the ethylene hompolymer.

(a) Density measurement

The density measurement was carried out in the same way as in Example 1- (4) - (d). As a result, the density was 0.887 g / cm³. On the other hand, no annealing treatment was carried out on the sample.

(b) 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 3.05 and the weight average molecular weight ^ m) was 114,000.

(c) Structure analysis by NMR

The measurement of ¹³C-NMR [measurement temperature = 130^°C, solvent = 1,2,4-trichlorobenzene / heavy benzene (molar ratio = 8/2), and 100 M ^]. As a result, no absorption was observed at 8.15 ppm of the methyl group in the vicinity of the quaternary carbon, as observed in an LDPE.

(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 12.8 kcal / mol.

(e) Measurement of solid viscoelasticity; Measurement of the β-relaxation peak (area) (1) In general, when the temperature dispersion of the viscoelasticity of the ethylene homopolymer is measured, as dispersion peaks of its temperature dispersion behavior, it is mainly observed (at ) an α-relaxation (at about 60 ° C) caused by a molecular shift in a crystal region, (b) a β-relaxation (at about -50 ° C to -20 ° C) which is the so-called main dispersion caused by the displacement of segment of the main chain containing branch points in an amorphous region, and (c) a γ-relaxation (at about -130 ° C to -100 ° C) that is caused by the amorphous region or the irregular portions of the crystals.

At the same time, the β-relaxation that is the main dispersion cannot be observed in a normal ethylene homopolymer, but can be observed in an ethylene / α-olefin copolymer or a homo43

ES 2 178 648 T3 ethylene polymer having a long chain branching. Therefore, great attention was paid here to the β-relaxation which was the main dispersion and the comparison was made.

(2) Regarding the solid viscoelasticity of a sample, the elastic modulus in storage (E '), the elastic modulus of loss (E ”) and the dissipation ratio (tan £) were calculated as a function of the behavior temperature dispersion in a temperature range of -150 to 200^°Under conditions of a frequency of 1 Hz and an amount of stress of 0.15% using an RSA-II model manufactured by Leometric Co., Ltd. (Fig. 6).

(3) From the dispersion behavior of the solid viscoelasticity temperature shown in figure 6, the curve of the β-relaxation peak of the elastic modulus of loss (E ”) is obtained by determining the temperature interval (- 100 to 0^°C), making a reading with a fingering device and then going to a graphic measurement program (MEAS1). The size of this area was calculated based on a plotted graph that had the temperature on the abscissa axis from -150 to 100^°Cy an E ', E ”on the ordinate axis of 1 x 10⁶ a1x10¹¹ dynes / cm² (5 points) obtained with the aforementioned measuring device. As a result, the area of ​​β-relaxation was 23.1.

On the other hand, the peak temperature of β-relaxation was -56.5 ° C and at this temperature, the elastic modulus in storage (E ') was 9.96 x 10⁹ dynes / cm², the elastic modulus of loss (E ”) was 2.1 x 10⁹ dynes / cm², the dissipation ratio (tan £) was 0.211.

Example 14, 15 and Comparative Examples 3 and 4

Ethylene polymerization was carried out under the conditions indicated in Table 9 to prepare an ethylene homopolymer and its evaluation was carried out. Table 10 shows the results. Likewise, the measured values ​​of solid viscoelasticity appear in table 11.

Figure 7 shows the temperature dispersion behavior of the solid viscoelasticity of the ethylene homopolymer (the straight chain ethylene hompolymer) of the comparative example.

3.

As can be deduced from this graph, the peak of β-relaxation that was the main dispersion was not observed.

TABLE 9 (I)

<td rowspan="2"></td><td rowspan="2">Toluene (ml)</td><td rowspan="2">MAO¹(mmol)</td><td colspan="2">transition metal component</td>

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

<td>Example 14</td><td> 100</td><td> 20</td><td>Component titanium²Component₃zirconium³</td><td> 0,1 0,00067</td>

<td>Example 15</td><td> 400</td><td> 10</td><td>Component titanium²</td><td> 0,05</td>

<td>Ex. Comp. 3</td><td> 100</td><td> 20</td><td>Component₃zirconium³</td><td> 0,00067</td>

<td>Ex. Comp. 4</td><td> 400</td><td> 10</td><td>Component titanium⁴</td><td> 0,002</td>

IS 2 178 648 T3

TABLE 9 (II)

<td></td><td>Ethylene pressure (kPa) *</td><td>Temperature (° C)</td><td>Time (min)</td><td>Performance⁽g)</td>

<td>Example 14</td><td>Pressure atmospheric</td><td> 60</td><td> 70</td><td> 15,4</td>

<td>Example 15</td><td> 588(6)</td><td> 70</td><td> 60</td><td> 59,6</td>

<td>Eg comp. 3</td><td>Pressure atmospheric</td><td> 60</td><td> 70</td><td> 13,2</td>

<td>Ex. Comp. 4</td><td> 588(6)</td><td> 70</td><td> 60</td><td> 25,0</td>

(Notes):

(1) MAO: Methylaluminoxane prepared in Example 13- (1) (2) Titanium catalyst component prepared in Example 13- (2) (3) Ethylenebisindenylzirconium dichloride.

(4) (tert-Butylamido) dimethyl (tetramethyl-n dichloride⁵-cyclopentadienyl) silanetitanium ^* The value in kg / cm²M is indicated in parentheses.

TABLE 10 (I)

<td></td><td>Density (g / cm³)</td><td>Weight molecular weight average (Mw)</td><td>Molecular weight distribution (Pm / Mn)</td><td>Structure analysis by NMR</td>

<td>Example 14</td><td> 0,889</td><td> 258.000</td><td> 5,0</td><td>TO</td>

<td>Example 15</td><td> 0,925</td><td> 148.500</td><td> 2,9</td><td>TO</td>

<td>Ex. Comp. 3</td><td> 0,960</td><td> 232.000</td><td> 6,9</td><td>TO</td>

<td>Ex. Comp. 4</td><td> 0,958</td><td> 86.000</td><td> 3,0</td><td>TO</td>

TABLE 10 (II)

<td></td><td>Melting point (° C)</td><td>Melt flow activation energy (Ea) (kcal / mol)</td><td>Peak area of ​​β relaxation</td>

<td>Example 14</td><td> 70,121</td><td> 13,5</td><td> 22,8</td>

<td>Example 15</td><td> 118,5</td><td> 12,0</td><td> 1,6</td>

<td>Ex. Comp. 3</td><td> 132,0</td><td> 6,3</td><td> -</td>

<td>Ex. Comp. 4</td><td> 129,0</td><td> 7,5</td><td> -</td>

(Note):

A: No absorption was present at 8.15 ppm.

IS 2 178 648 T3

TABLE 11

<td></td><td>Peak temperature of βrelaxation (° C)</td><td>Elastic storage module (E ') (dynes / cm²)</td><td>Elastic loss modulus (E ”) (dynes / cm²)</td><td>Dissipation ratio (tan δ)</td>

<td>Example 14</td><td> -53,4</td><td>9.8 x 10⁹</td><td>1.95x10⁹</td><td> 0,199</td>

<td>Example 15</td><td> -11,6</td><td>1.14x10¹⁰</td><td>7.9x10⁸</td><td> 0,07</td>

Example 16 (1) Preparation of methylaluminoxane (MAO)

The same procedure as in example 1- (1) was repeated to obtain 6.7 g of a catalytic product (methylaluminoxane).

(2) Preparation of the catalytic component.

A titanium catalyst component was prepared in the same way as in Example 1- (2).

(3) Preparation of polyethylene

400 ml of toluene and 0.25 mml of triisobutylaluminum in toluene (2 mmol / liter) were introduced into a 1 liter pressure resistant autoclave, equipped with a stirrer, followed by stirring at 20 ° C. for 5 minutes. Next, 10 mmol of the methylaluminoxane prepared in step (1) above was added, and the solution was heated to 70 ° C. Then,

1.5 ml of the titanium catalyst component prepared in step (2) above and 2 μmol of (tert-butylamido) dimethyl (tetramethyl-η dichloride⁵-cyclopentadienyl) silanetitanium to the solution, and then ethiene was introduced under a partial gauge pressure of 588 kPa (6 kg / cm²M) to start polymerization. The reaction was carried out at 70^°C for 30 minutes, while maintaining the total pressure constantly.

(4) Evaluation of polyethylene (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 131 J / g, and the melting point (Pf) was 118 , 5 ° C.

(b) Density measurement

The measurement was carried out in the same way as in example 1- (4) - (d), and as a result, the density was 0.925 g / cm³. On the other hand, no aging treatment was performed on the sample.

(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 2, 85.

(d) Measurement of intrinsic viscosity

Intrinsic viscosity was measured in decalin at 135^°C and, as a result, the intrinsic viscosity [η] was 2.41 dl / g.

Related to this, Table 12 shows the physical properties of the ethylene homopolymer. Example 17

The same procedure as in example 16- (3) was repeated, with the exception that the titanium catalytic component prepared in example 16- (2) was replaced by 0.01 mmol of titanocene dichloride, the temperature was established polymerization at 80^°C and the feeding pressure was established

ES 2 178 648 T3 of ethylene at a gage pressure of 608 kPa (6.2 kg / cm²M), to thereby prepare a polyethylene.

Tables 12 and 13 show the mechanical properties and the results of the evaluation. Example 18

400 ml of toluene and 0.25 mml of a solution of triisobutylaluminum in toluene (2 moles / liter) were introduced into a 1 liter pressure resistant glass autoclave equipped with a stirrer, followed stirring at 20 ° C for 5 minutes. Subsequently, 10 mmol of methylaluminoxane prepared in Example 16- (1) was added and the solution was then heated to 70^°C. Next, 0.01 mmol of titanocene dichloride was added to the solution and ethylene was then introduced under a partial gauge pressure of 392 kPa (4 kg / cm²M) to initiate polymerization. The reaction was carried out at 70^°C for 20 minutes, while keeping the total pressure constant. Then, while keeping the solution at 70^°C, the pressure was released and part of the resulting polymerization reaction product was extracted with a syringe and then poured into methanol. As a result, the formation of a white polymer was confirmed.

Likewise, 2 micromoles of (tert-butylamido) -dimethyl (tetramethyl-n⁵cyclopentadienyl) silanetitanium to the reaction system and then ethylene was introduced under a partial gauge pressure of 588 kPa (6 kg / cm²M) and polymerization was carried out at 70^°C for 30 minutes, while keeping the total pressure constant. After completion of the polymerization, the polymer was collected in the same way as in Example 16- (3).

Tables 12 and 13 show the mechanical properties and the results of the evaluation. Example 19

The same procedure as that of example 16- (3) was carried out with the exception that the aluminoxane was replaced by 25 μmol of anilinium tetrakis (pentafluorophenyl) borate and that the titanium compound prepared in example 16- (2) per 0.01 mmol of titanocene dichloride, to prepare an ethylene homopolymer. Table 13 shows the results.

Example 20

The same procedure as in Example 16- (3) was carried out with the exception that the polymerization time was set at 15 minutes. The pressure was then released from the unreacted ethylene and the remainder of the ethylene was removed using nitrogen. Next, a hydrogen gauge pressure of 588 kPa (6 kg / cm²M) and while the pressure was maintained, the reaction was carried out for 5 hours. Once the hydrogenation treatment was completed, the pressure was released and the same procedure as in Example 16- (3) was repeated to obtain the ethylene homopolymer. Table 13 shows the results.

Example 21

The same procedure as in Example 16- (3) was carried out with the exception that (tert-butylamido) dimethyl (tetramethyl-n⁵-cyclopentadienyl) silanetitanium per 0.1 micromole of ethylenebisindenylzirconium dichloride [Et (Ind) 2ZrCl2], to prepare a polyethylene roast.

Tables 12 and 13 show the mechanical properties and the results of the evaluation. Comparative Example 5

The same procedure as that of Example 16- (3) was carried out with the exception that the titanium compound prepared in Example 16- (2) was not used to prepare a polyethylene roast. Table 13 shows the results.

IS 2 178 648 T3

TABLE 12

<td></td><td>Modulus of elasticity (kg / cm²)</td><td>Breaking strength (kg / cm²)</td><td>Extension of break (%)</td>

<td>Example 16</td><td> 3.900</td><td> 480</td><td> 640</td>

<td>Example 17</td><td> 10.600</td><td> 330</td><td> 670</td>

<td>Example 18</td><td> 13.100</td><td> 330</td><td> 950</td>

<td>Example 19</td><td> 6.800</td><td> 330</td><td> 750</td>

TABLE 13 (I)

<td></td><td>Yield (g)</td><td>Melting point (° C)</td><td>Density (g / cm³)</td>

<td>Example 16</td><td> 45,7</td><td> 118,5</td><td> 0,925</td>

<td>Example 17</td><td> 46,0</td><td> 135,0</td><td> 0,952</td>

<td>Example 18</td><td> 37,0</td><td> 132,3</td><td> 0,958</td>

<td>Example 19</td><td> 18,4</td><td> 133,6</td><td> 0,945</td>

<td>Example 20</td><td> 22,9</td><td> 118,3</td><td> 0,924</td>

<td>Example 21</td><td> 45,6</td><td> 127,2</td><td> 0,940</td>

<td>Ex. Comp. 5</td><td> 30,8</td><td> 138,0</td><td> 0,962</td>

TABLE 13 (II)

<td></td><td>Intrinsic viscosity (dl / g)</td><td>Molecular weight distribution (Pm / Mn)</td><td>ΔH (J / g)</td>

<td>Example 16</td><td> 2,41</td><td> 2,85</td><td> 131</td>

<td>Example 17</td><td> 1,98</td><td> 3,23</td><td> 208</td>

<td>Example 18</td><td> 2,80</td><td> 12,1</td><td> 211</td>

<td>Example 19</td><td> 1,77</td><td> 12,1</td><td> 196</td>

<td>Example 20</td><td> 2,41</td><td> 2,84</td><td> 131</td>

<td>Example 21</td><td> 1,44</td><td> 3,24</td><td> 178</td>

<td>Ex. Comp. 5</td><td> 2,92</td><td> 2,33</td><td> 189</td>

Polymer Evaluation 1

The dependence of the melt viscosity [η] and the shear rate ω of the ethylene homopolymer obtained in Example 16 was obtained as described below, by virtue of which the non-Newtonian properties were evaluated.

An RMS E-605 model manufactured by Rheometrics Co., Ltd. was used as the apparatus and a sinusoidal vibration was given at 190^°C in an amount of effort of 10% to measure the dynamic viscoelastic properties. The results are shown in Figure 8.

Polymer Assessment 2

The viscosities of ethylene homopolymers 16 to 21 and Comparative Example 5 were measured in a state of dilute solution, and the Huggins coefficient k was calculated according to the viscosity equation:

nsp / c = [η] + k [n]²c.

IS 2 178 648 T3

The reduced viscosities n_sp/ c changing the concentration of polymer C in a decalin solvent at 135 ° C at 5 or more points in a range where the linear relationship is recognized. The linear correlation coefficient was 0.995 or more. At this point, [η] is the intronsic viscosity. Table 14 shows the results.

TABLE 14

<td></td><td>k</td>

<td>Example 16</td><td> 0,515</td>

<td>Example 17</td><td> 0,726</td>

<td>Example 18</td><td> 0,524</td>

<td>Example 19</td><td> 0,619</td>

<td>Example 20</td><td> 0,514</td>

<td>Example 21</td><td> 0,456</td>

<td>Ex. Comp. 5</td><td> 0,340</td>

Catalyst Assessment 1

The ethylene polymerization properties of the titanium catalyst of Example 16 and the titanocene dichloride of Example 17 were evaluated by carrying out the polymerization under the conditions mentioned below and then determining the terminal vinyl groups.

Titanium catalyst from Example 16

The same procedure as in Example 16- (3) was repeated with the exception that (tert-butylamido) dimethyl) tetramethyl-n dichloride was not used.⁵-cyclopentadienyl) silanetitanium, to prepare a homopolymer of ethylene.

Titanocene dichloride from example 17

The same procedure of Example 17 was repeated, with the exception that (tert-butylamido) dimethyl) tetramethyl-n dichloride was not used.⁵-cyclopentadienyl) silanetitanium, to prepare an ethylene homopolymer. (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 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 = d / ml, T = mm, and n = number of vinyl groups in relation to 100 carbon atoms.

As a result, the number of terminal vinyl groups was 4.5 groups / 1,000 carbon atoms, in the case of the titanium catalyst of Example 16, and 0.04 groups / 1,000 carbon atoms in the case of the titanocene dichloride of the example. 17.

Catalyst evaluation 2 (Evaluation of copolymerization properties)

The copolymerization of ethylene and 1-octene was carried out in the presence of (tert-butylamido) dimethyl) tetramethyl-n dichloride.⁵-cyclopentadienyl) silanetitanium (I) used in Example 16 and ethylenebisindenylzirconium dichloride (II) used in Example 21 under the conditions indicated in Table 15, and then the enthalpoa of crystallization (ΔΗ) and the point of fusion (MP) of the resulting copolymer. The measured results of the copolymer obtained in No. 3 by using a differential scanning calorimeter at the time it cooled are shown in Figure 9, and the results of the measurement at the time it heated appear in figure 10.

IS 2 178 648 T3

TABLE 15 (I)

Toluene (ml) TIBA⁴ (mmol) MAO (mmol) Metal compound ^ moles) Temperature (^°C) Monoomer charge ratio³[M]

Time (min)

<td>N^°1</td><td>N ° 2</td><td>N ° 3</td>

<td> 400</td><td> 400</td><td> 400</td>

<td> 0,5</td><td> 0,5</td><td> 0,5</td>

<td> 10</td><td> 10</td><td> 10</td>

<td>(I) 2</td><td>(I) 2</td><td>(II) 0.2</td>

<td> 70</td><td> 80</td><td> 70</td>

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

<td> 10</td><td> 10</td><td> 10</td>

TABLE 15 (II)

<td></td><td>N ° 1</td><td>N ° 2</td><td>N ° 3</td>

<td>Yield (g)</td><td> 16,5</td><td> 19,2</td><td> 29,3</td>

<td>TM⁴ (° C)</td><td> 93,6</td><td> 90,4</td><td> 116,5</td>

<td>ΔΗ⁵ (J / g)</td><td> 75</td><td> 61</td><td> 130</td>

<td>AH.Pf</td><td> 7020</td><td> 5514</td><td> 15145</td>

<td>AH.Pf. calculated according to the general equation⁶</td><td> 17492</td><td> 17107</td><td> 17492</td>

1) TIBA: Triisobutylaluminum

2) MAO: Methylaluminoxane prepared in example 16- (1)

3) It was calculated based on 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 will be measured in the same way as in example 16- (4)

5) (ΔΗ): ​​Enthalpy of crystallization, which was measured in the same way as in example 16- (4).

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

The copolymerization was carried out according to example 16- (3), but the metal compounds (I) and (II) were added after dissolving the ethylene to a state of saturation at the polymerization temperature, by virtue of which 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 in the closest position. Likewise, the area 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

In ES 2 178 648 T3 catalytic component, an organic 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 state of saturation 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 other catalytic components were added, 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 catalyst to carry out the evaluation again.

After carrying out the polymerization for a specified period of time, the ethylene feed was stopped and the pressure was immediately released to remove the 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.

Example 22

A resin composition was cast consisting of 80 parts by weight of an ethylene-butene copolymer (density = 0.922 g / cm³) and 20 parts by weight of polyethylene (density 0.887 g / cm³) obtained in Example 1, at a blowing speed of 2.7 by inflation molding to form a film.

The moldability of the film was good.

Possibility of industrial application

The ethylene homopolymer of the present invention is derived from a single ethylene monomer and does not contain any quaternary carbon in the main chain of the polymer, being different from the usual HDPE, L-LDPE and LDPE. Ethylene homopolymer is characterized by controllable melt flow activation energy, excellent working properties, and phosphoric properties, such as density, melting point and crystallinity, which can be controlled mainly in the homopolymer state. On the other hand, the ethylene homopolymer subjected to hydrogenation treatment not only has the characteristics that have been mentioned, but also is excellent in terms of its thermic stability.

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