BRPI1102655B1 - supported metallocene catalytic system, synthesis process and use - Google Patents

Abstract

supported metallocene catalytic system, synthesis process and use thereof, high density polyethylene, and low or ultra low density linear polyethylene. The present invention relates to a catalytic system composed of metallocene on a hybrid silica magnesium support synthesized by the sol-gel method, to the process of preparing the metallocene catalytic system supported from a hybrid silica magnesia synthesized by the method. sol-gel, and the higher α-olefin incorporation ethylene polymers and copolymers prepared using this catalytic system.

Description

“CATALYTIC SYSTEM OF THE SUPPORTED METALOCENE TYPE, SYNTHESIS PROCESS AND USE OF THE SAME” [1] The olefin polymerization processes with the use of catalysts can be classified into: solution process, slurry process (in Portuguese, mud) and process in gas phase.

[2] One type of catalyst used in the polymerization of olefins is metallocene. In the slurry and gas phase processes, this catalyst must be supported, otherwise the polymer adheres to the reactor walls, damaging the equipment, which can even cause a plant to stop. However, when supporting metallocene, catalytic activity is reduced considerably when compared to unsupported metallocene catalysts.

[3] Among the different supports existing in the state of the art, the silica-based support is one of the most used.

[4] Several routes of metallocene immobilization on the silica surface have been described in the literature and can be classified into: (i) direct immobilization, (ii) immobilization on silica functionalized with methylaluminoxane (MAO) or with other types of cocatalysts; (iii) immobilization on modified silicas with spacers; (iv) in situ synthesis on the support and (v) synthesis on hybrid silica.

[5] Route (i) consists of the reaction between silane groups of silica and the leaving group of metallocene (chloride or hydride) in the presence of an organic solvent. Route (ii) essentially comprises the pre-contact of the support with MAO or common aluminum alkyls, followed by the immobilization of the metallocene. In route (iii), the catalytic sites are generated or removed from the surface (vertical spacers) or between themselves (horizontal spacers). In both cases, the objective is to increase the catalytic activity of these supported metallocene catalysts. In route (iv), the silanol groups on the silica surface are reacted with compounds of the MCI4 type (M = Ti, Zr) and later with indenyl or cyclopentadienyl ions or the silanol groups

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2/30 of the silica surface organosilanes are reacted with binders of the cyclopentadiene or indene type, which, by deprotonation, generate aromatic ions that can be metallized with MCI4 type reagents (M = Ti, Zr). Route (v) consists of obtaining a silica containing organic groups on the surface of the cyclopentadienyl or indenyl type, obtained by the sol-gel method, followed by the reaction with titanium chloride or zirconium chloride. This route differs from the previous routes in that, while in the other routes the silica used is commercial, previously synthesized, in this route, the silica is synthesized already containing the organic binders (hybrid silicas). In the state of the art examples of these five routes are commented on in G.G. Hlatky, Chem. Rev. 100 (2000) 1347 and by J. R. Sevem, J. C. Chadwick, R. Duchateau, N. Friederichs, Chem. Rev. 105 (2005) 4073.

[6] In parallel with the development of immobilization routes, alternatives to the use of silica as a support have been investigated. Examples of other supports found in the literature include alumina (MFV Marques, M. de Alcantara, J. Polym. Sci. A: Polym. Chem. 42 (2003) 9), magnesium chloride (MFV Marques, A Conte, Eur. Polym. Joum. 37 (2001) 1887), the zeolites (MFV Marques, SC Moreira, J. Mol. Catai. A: Chem. 192 (2003) 93) and the MCM-41 (H. Rahiala , I. Beurroies, T. Eklund, K. Hakala, R. Gougeon, P. Trains and JB Rosenholm, J. Catai. 188 (1999) 14).

[7] All of these systems have drawbacks, such as leaching of active species during the polymerization process, incomplete fragmentation of the support and significant reduction of catalytic activity in relation to homogeneous systems. In an attempt to improve the performance of the supported metallocene catalysts, the use of silica bispheres with metal oxides, such as titania (AG Fisch, NSM Cardozo, AR Secchi, FC Stedile, PR Livotto, DS de Sá, ZN da Rocha, JHZ dos Santos, Appl. Catai. A: General 354 (2009) 88) and zirconia

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3/30 (T. Pothirat, Β. Jongsomjit, Ρ. Praserthdam, Catai. Lett. 121 (2008) 266) appear as an alternative. Another alternative are silica magnesia bisectors, which have been used in the preparation of hybrid catalytic systems Ziegler-Natta / metallocene (H.S. Cho, D.J. Choi, W.Y. Lee, J. App. Polym. Sei. 78 (2000) 2318). These bis supports are prepared by precipitation reactions of sodium silicates with magnesium chloride.

[8] Patent document EP0416815, owned by DOW, describes the preparation of a catalyst with tensioned geometry (CGC). This geometry gives metallocene the property of incorporating comonomers, such as 1-octene or 1-decene, and has the differential of not having to be supported. Thus, this catalyst is used in the copolymerization of ethylene with α-olefins, such as propylene, 1-butene, 1-hexene, 4-methyl1-pentene and 1-octene, but only in solution processes.

[9] Patent document EP0705849, owned by Idemitsu Kosan Co. Ltd., describes the synthesis of a CGC metallocene type catalytic complex and its application in the copolymerization of ethylene with aolefins. The patent also reports that the catalyst can be used immobilized on an inorganic support such as, for example, silica, alumina, magnesia and bi-supports of these oxides. The resulting copolymer had an octene incorporation content of up to 30% (molar base).

[10] Another example of supported CGC metallocene is described in EP0662979 for the copolymerization of ethylene with α-olefins. The synthesis of the supported catalyst consisted basically of immobilizing the catalytic complex on a silica previously modified with methylaluminoxane. However, the activation of this system was carried out with organoborans, which in addition to having high cost contain aromatic groups that are polluting and also cause damage to health.

[11] In the open literature, the heterogenization of CGC catalysts has been carried out through in situ synthesis on commercial silica and

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4/30 comprises the grafting of aminosilane groups on the silica surface, followed by the reaction with alkylillithium, reaction with tetramethyl-cyclopentadienylchlorosilane and metallization. A variation of this method uses aminopropyl modified silica prepared by hydrolyzing an imine. However, the catalytic activities of these systems, in the order of 30 kg of PE (mol of Ti.h.atm) · ¹ (or 12 g of PE (g of cat) ¹ ), are still very low from an industrial point of view ( MW McKittrick, CW Jones, J. Catai. 227 (2004) 186-201).

[12] Another supported catalytic system for the polymerization of ethylene with long-chain α-olefins, particularly 1-octene, was developed by Soga et. al., in Macromolecular Rapid Communications 18 (1997) 9. In this work, a commercial silica was modified with aminopropylsilane groups using the grafting method. The metallocene catalyst was immobilized on this functionalized support. This system showed catalytic activity in the copolymerization of ethylene with 1-octene in the order of 2 kg of polymer (mol of Ti.h.atm) ¹ . The copolymers of ethylene with 1-octene showed a comonomer incorporation content of up to 37%. In addition, the product of the reactivity ratios r _E. ro> 0.42 indicated the formation of random copolymers.

[13] The preparation of metallocene catalysts containing alkylalkoxysilane groups and their method of immobilization are described in patent document EP0839836. The immobilization route consists of grafting the metallocenes onto the silica, where the alkylalkoxysilane groups are the sites for attachment to the support. These catalytic systems can be used for the copolymerization of ethylene with α-olefins of up to eight carbon atoms. However, the copolymers obtained have a random distribution, and the α-olefin incorporation content is of the order of only 1%.

[14] Patent EP0927201B1, owned by Hyundai Petrochemical Co. Ltd., describes the preparation of metallocene catalysts

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5/30 supported for the copolymerization of ethylene with α-olefins that can be activated without the use of methylaluminoxane. These supported catalytic systems can be prepared through two distinct routes: (i) direct immobilization of the catalytic complex on alumina or magnesium chloride and subsequent reaction with alkyl aluminum (ii) modification of silica or alumina with methylaluminoxane, immobilization of the metallocene on this modified support and reaction with alkyl aluminum. However, the fixed metallocene content is limited by the amount and accessibility of hydroxyl groups on the surface of the support.

[15] Thus, despite several attempts to synthesize supported metallocene catalytic systems, these systems continue to have the drawback of low catalytic activity.

[16] In this way, the present invention overcomes the problems of the state of the art, presenting a new catalytic system that, in addition to being synthesized by a totally new process, has as a differential the high catalytic activity, when compared with other supported metallocene catalysts .

DESCRIPTION OF THE INVENTION [17] The present invention relates to a catalytic system composed of metallocene on a hybrid silica-magnesia support synthesized by the sol-gel method, to the process of preparing the metallocene-based catalytic system supported from a silica -hybrid magnesia synthesized by the sol-gel method, and to polymers and copolymers of ethylene with a high content of incorporation of superior α-olefins prepared using this catalytic system.

[18] In addition to the presence of Mg, which generates Lewis acid sites, the support of the present invention features organic groups with amino functionality for anchoring the metallocene. In this catalytic system, the amino groups of the organic compound chemically bound to the

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6/30 support makes up the metal coordination sphere and the organic part plays a role of surface spacer, which together with the characteristics of the immobilized metallocene complex, produces less sterically hindered sites for the coordination of olefins. The textural properties of this supported catalyst are identical to those obtained for the catalytic support of hybrid silica-magnesia.

[19] The metal content of the supported metallocene catalyst of the present invention is up to 10 times higher than the levels obtained by an immobilization route via grafting (conventional).

[20] The supported catalytic system of the present invention has catalytic activity in the polymerization of ethylene and in the copolymerization of ethylene with α-olefins in the range of 100 to 10,000 kg of polymer / (mol Ti.h.atm). The ethylene homopolymers obtained with this system have an average molecular mass in the range of 1000 to 2000 kg / mol, and polydispersity between 2 and 30. Thus, the catalytic system of the present invention allows the obtainment of ethylene copolymers with superior α-olefins with incorporation levels in the range of 1-70% (mol / mol) and alternate distribution of the comonomer units.

Catalytic System [21] The catalytic system of the present invention is composed of a silica-hybrid (silica / magnesia) support synthesized by the sol-gel process, containing organic aminoalkyl groups as sites for metallocene bonding.

[22] Preferably, the organic groups are aminoalkyls of 1 to 18 carbons, more preferably, the organic group comprises 1 to 9 carbons.

[23] The metallocene of the present invention comprises a structure according to formula I,

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7/30

L ¹ I?

\ /

M

Formula I where,

M is a transition metal of groups 4 or 5,

L ¹ is a bulky cyclopentadienyl (Cp), indenyl (Ind) or fluorenyl (Flu) type, whether or not substituted by hydrogen, alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl,

L ² , L ³ and L ⁴ can be halogens, alkoxides or alkyl groups.

[24] Preferably, the transition metals of groups 4 or 5 are Ti, Zr or Hf.

[25] The metallocene catalyst content of the present invention is about 0.1 to 10% (w / w).

[26] The hybrid silica-magnesia catalytic support of the present invention consists of a material formed predominantly by silica gel, with Mg contents on the surface of about 0.1 to 12% (w / w). The content of covering the support by organic aminoalkyl groups on the surface of said support is about 1 to 200 pmol / m ² . The specific areas and the average pore diameter of this hybrid support are about 10 to 500 m ² / g and 10 to 100 Â, respectively.

DETAILED DESCRIPTION OF THE INVENTION [27] The process of synthesizing a metallocene catalytic system supported from a hybrid silica-magnesia synthesized by the solgel method of the present invention is divided into two parts: (i) preparation of the hybrid catalytic support and (ii) synthesis of the supported metallocene catalyst, which will be described below.

i. Preparation of the hybrid catalytic support (a) Preparation of a solution of an acid in an alcohol;

(b) Reaction of a tetraalkylortosilicate solution on with

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8/30 the solution obtained in (a);

(c) Reaction of a magnesium salt with the solution obtained in (b);

(d) Reaction of a trialkoxideorganosilane containing amino functionality with the suspension obtained in (c);

(e) Removal of the solvent, washing and drying of the product of the reaction obtained in (d).

[28] The reactions involved in the process of preparing the hybrid catalytic support are illustrated in Scheme 1 below.

+ MgL, + NHjíCH ^ SifORhj

Hp / H

ΝΉ ₂ (ΟΗρ _π εί (ΟΗ} ₃

OH

Jz

Ml

HO --- Si --- OH

L.

OH

NH,

OH

NH,

NH,

NHj

OH

OH

Scheme 1 where,

Rx and Ry are alkyl groups,

L can be halide ions, nitrate or alkoxide groups, and

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9/30 n is a number between 1 and 6.

[29] In step (a) of the present invention an aqueous solution of an acid with a concentration in the range of 0.1 to 5 mol / L is diluted in an alcohol. Preferably acid with a concentration of 2 mol / L is used. The dilution factor is about 2 to 100. Preferably the dilution factor used in the present invention is 20.

[30] In step (b) of the present invention, an alcoholic solution of tetraalkylortosilicate is added over the solution obtained in (a).

[31] The volumetric ratio of tetraalkylortosilicate to alcohol is about 1: 100 to 1: 1. Preferably, the volumetric ratio of tetraalkylortosilicate and alcohol used in the present invention is about 1: 2.

[32] The reaction time is about 1 to 48 hours, preferably about 24 hours. In step (c) of the present invention, an aqueous suspension of a magnesium salt is carried out to the suspension obtained in (b).

[33] The molar ratio of magnesium salt to tetraalkylortosilicate used in the present invention should be in the range of 1:50 to 2: 1. Preferably, a 1: 5 molar ratio should be used.

[34] Optionally, this step can be carried out concurrently with step (b).

[35] The reaction time is about 1 to 48 hours, preferably about 8 hours.

[36] In step (d) the preparation process of the supported catalytic system of the present invention, the addition of a trialkoxideorganosilane containing amino functionality in the form of an alcoholic solution is carried out in the suspension obtained in (c).

[37] The volumetric ratio of trialkoxyorganosilane containing amino functionality to alcohol is about 1: 100 to 1: 1.

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10/30

Preferably, the volumetric ratio is about 1: 2.

[38] In steps (a), (b), (c) and (d), the mixing speed of the mixture is about 50 rpm to 40,000 rpm, being preferably about 100 to 300 rpm, and the temperature reaction time (in steps (b), (c) and (d)) is about 0 to 70 ° C, preferably about 20 to 30 ° C.

[39] The molar ratio of trialkoxyorganosilane containing amino functionality to the tetraalkylortosilicate used in the present invention is about 1:50 to 1: 0. Preferably, the molar ratio is about 1:20.

[40] The reaction time (step (d)) is about 5 to 90 hours, preferably about 10 to 60 hours.

[41] In step (e) the solvent is removed, the product is dried and washed from the reaction obtained in (d).

[42] The solvent can be removed by evaporation at room temperature, filtration, centrifugation or reduced pressure. Preferably, filtration and drying are carried out under reduced pressure for 12 hours.

[43] The product is washed with alcohol. After washing, the product is dried under reduced pressure for 12 hours.

[44] The nitrogen content in the catalytic supports obtained in the present invention was between 0.1 and 30%, precisely between 0.5% and 20%.

[45] The specific areas of the catalytic supports obtained in the present invention were between 10 and 500 m ² / g.

[46] The average pore diameter was between 20 and 100 o

THE.

[47] Thus, the catalytic support of the present invention is prepared by the reaction of hydrolytic sol-gel in an acidic medium from a tetraalkylortosilicate, a magnesium salt and a

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11/30 trialkoxideorganosilane.

[48] Non-limiting examples of tetraalkylortosilicates that can be used in the present invention include tetramethylortosilicate (TMOS), tetraethylortosilicate (TEOS), tetrapropylortosiliacate (TPOS) and tetrabutylortosilicate (TBOS). Preferably TEOS should be used.

[49] Non-limiting examples of acids that can be used in the present invention include hydrochloric, hydrofluoric and nitric acids, or mixtures thereof. Preferably, the acid used in the present invention is hydrochloric acid.

[50] Non-limiting examples of trialkoxyorganosilanes containing amino functionality that can be used in the present invention include aminomethyltrimethoxysilane (AMTMS), 2-aminoethyltrimethoxysilane (AETMS),

3-aminopropyltrimethoxysilane (APTMS), 4-aminobutyltrimethoxysilane (ABTMS), 5-aminopentyltrimethoxysilane (APETMS), 6-aminohexyltrimethoxysilane (AHTMS), aminomethyltriethoxysilane (AMTES), 2aminoethyltriethoxyl (3) 5-aminopentyltriethoxysilane (APETES) and 6-aminohexyltriethoxysilane. Preferably, the trialkoxideorganosilane used in the present invention is APTES.

[51] Non-limiting examples of alcohols that can be used in the present invention include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 1-hexanol and 2-hexanol, or mixtures thereof. Preferably, the alcohol used in the present invention is ethanol.

[52] Non-limiting examples of magnesium salts that can be used in the present invention include magnesium nitrate, magnesium sulfate and magnesium chloride. Preferably, the magnesium salt used in the present invention is magnesium chloride.

[53] Cocatalysts are usually applied to activate

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12/30 metallocene catalysts, because in polymerization they generate the cationic species due to its Lewis acid character. In the present invention, the addition of organic aminoalkyl groups was expected to reduce the activation of the catalyst due to its basic character, inhibiting the Lewis acid sites. However, despite the presence of the aminoalkyl groups, the magnesium salt generated some Lewis acid sites on the hybrid support surface and maintained the acidic characteristic of the activation sites. In this way, the amino-acid groups present on the support surface became the binding sites of the metallocene complex.

II. Synthesis of the supported metallocene catalyst (f) Heat treatment of the product obtained in (e);

(g) Reaction of the product obtained in (f) with an organometallic compound based on group I transition metal in an inert organic solvent;

(h) removal of the solvent from the product obtained in (g);

(i) Reaction of the solid product obtained in (h) with a solution of metallocene based on the transition metal of groups 4 or 5 of the periodic table in an inert organic solvent;

(j) Washing and removing solvent from the product of the reaction obtained in (i).

[54] Scheme 2 illustrates the synthesis of the metallocene catalyst with the catalytic support with subsequent immobilization of the ML4 complex.

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13/30

Γ nh ₂ NH, | NH, 1 OH -J / _ζ Μ8. _λ ° \ L · Ma OH I OH ·' ] ' O O 1 si ---- Ο- Ι 1 --Si — o I --- Si ---- 0 I --- Si --- 0 I ---- Si ---- O - Si — o ----- Si ---- O --- Si --- 1 O 1 O 1 O 1 O O O O I O I Si ---- O- --- Si --- O - Sl · —o --- Si ---- O ---- Si ---- O ---- Si --- 0 1 --Si - 1 • 0 ---- si ---- ^-

I 1 ι | I ι

OH o ·

1. Heat treatment

1 r OH OH J / \ l NH M I NH M ” NH 1 M ΝΗ'1-Γ Ma .Mg 1 (CH,) _n CCH,) _n OH (CH,) _n O O I I Si ---- O --- Si --- O --- si- -O ---- Si ---- O - Si - o 1 1 --Si - Q - Si - o I 1 O O O HI Hi 1 1 the o Si --- O --Si — o-- si- - O 1 ---- Si ---- 1 O --- Si --- 0 --- Si --- O --- Si --- O

”O-Si

I

I

I

- O --- si --- O --- si --- O --- Si

NH ^X L j nh’m 1 .NtS '1 (CH _{J? N} OH <CH,) _n O I  1 'o I 1 Si --- 0 ____ ς i — O --- Si --- O 1 --Si — o I 1 --Yes - I O Ç ) O 1 O 1 O

Scheme 2 where,

M is a transition metal of groups 4 or 5,

L ¹ is a bulky cyclopentadienyl (Cp), indenyl (Ind) or fluorenyl (Flu) type, whether or not substituted by hydrogen, alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl,

L ² , L ³ and L ⁴ can be halogens, alkoxides or alkyl groups, and

n is a number between 1 and 6.

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14/30 [55] In step (f) of the process of preparing the supported catalytic system of the present invention, a heat treatment of the product obtained after step (e) is carried out.

[56] The treatment temperature is about 40 to 220 ° C. Preferably, the temperature is about 90 to 200 ° C.

[57] The treatment time is about 1 to 200 hours, preferably about 8 to 24 hours.

[58] Heat treatment can be carried out at atmospheric pressure or reduced pressure.

[59] In step (g), the product obtained in (f) is reacted with an organometallic compound based on group I transition metal in an inert organic solvent, followed by cooling in a temperature range of about 0 at -80 ° C.

[60] Non-limiting examples of inert organic solvents that can be used to suspend the product obtained in (f) are cyclohexane, n-hexane, n-heptane and n-octane. Preferably n-hexane should be used.

[61] The group I transition metal-based organometallic compound used in the present invention comprises Formula II:

C _n H2n + lM

Formula II where,

M is a transition metal of group 1;

n is a number between 1 and 6.

[62] Non-limiting examples of organometallic compounds of the present invention are methyl lithium, 2-ethyl lithium, 3-propyl lithium and n-butyl lithium. Preferably, the organometallic compound of the present invention is n-butyl lithium. The amount of this compound used is dependent on the amount of trialkoxideorganosilane containing amino functionality added in the

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15/30 step (d). An excess of organometallic compound should be added in relation to the latter.

[63] Alternatively to the use of group I organometallic compounds, group I metal hydrides can be used. Non-limiting examples of these compounds are sodium hydride, potassium hydride and lithium hydride. The amount of this compound used is dependent on the amount of trialkoxideorganosilane containing amino functionality added in step (d). An excess of group I metal hydride in relation to the latter must be added.

[64] The reaction time is about 1 to 20 hours. Preferably, reaction time is about 4 to 16 hours.

[65] In step (h) of the present invention, removal of the solvent from the product obtained in (g) is carried out;

[66] The solvent can be removed by evaporation at room temperature, filtration, centrifugation or reduced pressure. Preferably, solvent removal is done by drying under reduced pressure for about 2 hours.

[67] In step (i) of the process of the present invention, the solid product obtained in (h) is reacted with a metallocene solution in an inert organic solvent.

[68] The metallocene of the present invention comprises a structure according to Formula I:

L ¹ I?

\ /

M

Formula I where,

M is a transition metal of groups 4 or 5,

L ¹ is a bulky cyclopentadienyl (Cp), indenyl (Ind) or fluorenyl (Flu) type, whether or not substituted by hydrogen, alkyl,

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16/30 cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl,

L ² , L ³ and L ⁴ can be halogens, alkoxides or alkyl groups.

[69] Preferably, the transition metals of groups 4 or 5 are Ti, Zr or Hf. Preferably, L ¹ is a cyclopentadienyl. Preferably, L ² , L ³ and L ⁴ are halogens.

[70] Representative, but not limiting, examples of compounds having Formula I include CpTiCl ₃ , CpZrCl ₃ , CpHfCl ₃ , CpVCl ₃ , IndTiCl ₃ , IndZrCl ₃ , IndHfCl ₃ , IndVCl ₃ , FluTiCl ₃ , FluZrCl ₃ , FluZfCl ₃ , F1uVC1 ₃ , (MeCp) TiCl ₃ , (MeCp) ZrCl ₃ , (MeCp) HfCl ₃ , (MeCp) VCl ₃ , (nBuCp) TiCl ₃ , (nBuCp) ZrCl ₃ , (nBuCp) HfCl ₃ , (nBuCp) VCl ₃ , (Me ₅ Cp) TiCl ₃ , (Me ₅ Cp) ZrCl ₃ , (Me ₅ Cp) HfCl ₃ , (Me ₅ Cp) VCl ₃ (4,7-Me2Ind) TiCl ₃ , (4,7-Me ₂ Ind ) ZrCl ₃ , (4.7Me ₂ Ind) HfCl ₃ , (4.7-Me ₂ Ind) VCl ₃ , (2-MeInd) TiCl ₃ , (2-MeInd) ZrCl ₃ , (2MeInd) HfCl ₃ , (2 -MeInd) VCl ₃ , (2-arylInd) TiCl ₃ , (2-arylInd) ZrCl ₃ , (2arylInd) HfCl ₃ , (2-arylInd) VCl ₃ , (4,5,6,7-H4lnd) TiCl ₃ , (4,5,6,7-H4lnd) ZrCl ₃ , (4,5,6,7-H4lnd) HfCl ₃ , (4,5,6,7-H4lnd) VCl ₃ , (9-MeFlu) TiCl ₃ , (9-MeFlu) ZrCl ₃ , (9-MeFlu) HfCl ₃ , (9-MeFlu) VCl ₃ .

[71] Non-limiting examples of inert organic solvents that can be used to suspend said metallocene are: hexane, toluene, o-xylene and p-xylene. Toluene should preferably be used.

[72] The amount of said metallocene of the present invention is about 0.1-10% by weight of metal relative to the mass of the hybrid catalytic support, preferably being about 0.1-5%.

[73] The reaction temperature is about 0 to 60 ° C, preferably about 10 to 30 ° C.

[74] The reaction time is about 0.1 to 24 hours, preferably about 0.5 to 5 hours.

[75] In step (j) of the process of the present invention, the supported metallocene obtained in step (i) is washed. This washing is performed with 5 to 10 aliquots of 10 to 50 mL of organic solvent. THE

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17/30 wash temperature can vary from room temperature to about 70 ° C.

[76] Non-limiting examples of organic solvents that can be used for washing the supported metallocene catalyst obtained in step (i) include: toluene, o-xylene and p-xylene. The removal of the solvent from the product of the reaction obtained in (i) is done with reduced pressure in about 1 to 24 hours.

[77] The supported metallocene catalysts of the present invention are suitable for use in the process of homopolymerization of ethylene and copolymerization of ethylene with α-olefins in gas or slurry phases.

[78] The cocatalyst used in the process of homopolymerization of ethylene and copolymerization of ethylene with α-olefins, using the supported complex of the present invention, is an alkyl aluminum, preferably MAO, TMAL, TEAL or TIBAL. The Al / M molar ratio in the ethylene homopolymerization and copolymerization process is about 150 to 700, preferably about 200 to 650. An advantage of the supported metallocene catalysts described in the present invention over most other supported metallocene catalysts present in the state of the art it is the possibility of activation with the use of low amount of cocatlisator without significant loss of catalytic activity. This reduction in the amount of cocatalyst used in polymerization will possibly translate into a lower cost for using these catalysts in industrial processes compared to other supported metallocene catalysts. Variations in the order of addition of cocatalysts have not been investigated, but in the future they may be carried out.

[79] The supported metallocene catalysts of the present invention are advantageously used in homopolymerization of ethylene and copolymerization of ethylene with α-olefins such as, propene, 1-butene, 1hexene, 4-methyl-1-pentene, 1-octene, 1- decene, 1-dodecene, up to 1

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18/30 octadecene. In addition, the catalyst system of the present invention allows obtaining copolymers with up to 70% long-chain α-olefin incorporation content, which is a content considered high compared to most other supported metallocene catalysts. This greater incorporation occurs without reducing the catalytic activity of the supported systems in comparison to their performance in ethylene homopolymerization reactions, that is, even if a high comonomer content is added, there is no reduction in the catalytic activity and the activity is the same. homopolymerization order.

DESCRIPTION OF THE FIGURES [80] Figure 1 illustrates a spectrum of fluorescence emission in the region of 350 to 550 nm for the PBA on the surface of the supports of the present invention, where (a) refers to the PBA of Example 1; (b) refers to the PBA in Example 2 and (c) refers to the PBA in Example 3.

[81] Figure 2 illustrates the DSC curves for the ethylene-1-octene and ethylene-1-decene copolymers obtained with the catalytic system of example 6.

EXAMPLES [82] Examples of the present invention are provided below. The examples described herein are not to be considered as limiting the invention.

[83] In the examples of the present invention, TEOS (Merck,> 98% purity), magnesium chloride (Sigma Aldrich,> 99.9% purity), 3aminopropyltriethoxysilane (Aldrich, 98% purity), ethanol (Merck, 99.8% purity), hydrochloric acid (Merck, 37% in HCl), n-butyl lithium (Sigma Aldrich, 1.6 M solution in hexane) TEAL (Akzo), MAO (Akzo) and cyclopentadienyl titanium chloride (IV) (Sigma Aldrich,> 97% purity) are used without prior purification. Toluene (Nuclear, 98% pure) and 1-octene (Merck, 98% pure), used in the preparation of the catalytic system and in the copolymerization of ethylene with alpha-olefins, are dried according to

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19/30 usual techniques. All manipulations were performed using an inert nitrogen atmosphere with a maximum limit of 1.5 ppm of moisture.

Preparation of the hybrid catalytic support

Example 1 [84] This example illustrates the use of TEOS and 3-aminopropylsilane, at a 20: 1 molar ratio, as reagents for preparing the hybrid catalytic support.

[85] In a solution of ethanol, hydrochloric acid and water with a pH of about 2.0, with stirring of 250 rpm, TEOS diluted in ethanol is added. The suspension is left under mechanical stirring at 250 rpm for 24 hours. After this period, a pre-calculated amount of magnesium chloride suspended in water is added to the suspension. The TEOS: MgC12 molar ratio added is 5: 1. After 8 hours of reaction, 3-aminopropyltriethoxysilane (APTES) diluted in ethanol was added to the reaction system. The added TEOS: APTES molar ratio is 20: 1. The reaction mixture is kept under stirring at 250 rpm until product formation (additional 16 hours). The suspension is filtered and the product washed with 10 aliquots of 5 ml of ethanol. After washing, the product is dried under reduced pressure for 12 hours.

[86] The obtained compound was characterized, presenting the following characteristics:

• N content: 0.8% (w / w) • Mg content: 4.3 (w / w) • Specific area (Sbet): 235 m ² / g • Average pore diameter (D _p ): 94 Â • APTES content: 0.6 mmol / g

Example 2 [87] This example illustrates the use of TEOS and 3-aminopropylsilane, in a 5: 1 molar ratio, as reagents for preparing the hybrid catalytic support.

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20/30 [88] In a solution of ethanol, hydrochloric acid and water with a pH of around 2.0, with stirring of 250 rpm, TEOS diluted in ethanol is added. The suspension is left under mechanical stirring at 250 rpm for 24 hours. After this period, a pre-calculated amount of magnesium chloride suspended in water is added to the suspension. The TEOSrMgCh molar ratio added is 5: 1. After 8 hours of reaction, 3-aminopropyltriethoxysilane (APTES) diluted in ethanol is added to the reaction system. The added TEOS: APTES molar ratio is 5: 1. The reaction mixture is kept under stirring at 250 rpm until product formation (additional 16 hours). The suspension is filtered and the product washed with 10 aliquots of 5 ml of ethanol. After washing, the product is dried under reduced pressure for 12 hours.

[89] The component obtained was characterized, presenting the following characteristics:

• N content: 1.5% (w / w) • Mg content: 4.3 (w / w) • Specific area (Sbet): 43 m ² / g • Average pore diameter (D _p ): 40 Â • APTES content: 1.1 mmol / g

Example 3 [90] This example illustrates the use of TEOS and 3-aminopropylsilane, in a 2: 1 molar ratio, as reagents for preparing the hybrid catalytic support.

[91] In a solution of ethanol, hydrochloric acid and water with a pH around 2.0, with stirring of 250 rpm, TEOS diluted in ethanol is added. The suspension is left under mechanical stirring at 250 rpm for 24 hours. After this period, a pre-calculated amount of magnesium chloride suspended in water is added to the suspension. The TEOSrMgCh molar ratio added is 5: 1. After 8 hours of reaction, 3-aminopropyltriethoxysilane (APTES) diluted in ethanol is added to the reaction system. The TEOS molar ratio: APTES

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21/30 added is 2: 1. The reaction mixture is kept under stirring at 250 rpm until product formation (additional 16 hours). The suspension is filtered and the product washed with 10 aliquots of 5 ml of ethanol. After washing, the product is dried under reduced pressure for 12 hours.

[92] The component obtained was characterized, presenting the following characteristics:

• N content: 3.3% (w / w) • Mg content: 4.3 (w / w) • Specific area (Sbet): 25 m ² / g • Average pore diameter (D _p ): 32 Â • APTES content: 2.4 mmol / g

Example 4-Comparative example [93] This Example illustrates the use of TEOS as a reagent for preparing the catalytic support, directly on silica.

[94] In a solution of ethanol, hydrochloric acid and water with a pH around 2.0, with stirring of 250 rpm, TEOS diluted in ethanol is added. The reaction mixture is left under mechanical stirring at 250 rpm until product formation (48 h). The suspension is filtered and the product washed with 10 aliquots of 5 ml of ethanol. After washing, the product is dried under reduced pressure for 12 hours.

[95] The component obtained was characterized, presenting the following characteristics:

• Specific area (Sbet): 105 m ² / g • Average pore diameter (D _p ): 60 Â

Example 5-Comparative example [96] This Example illustrates the use of TEOS and MgCE, in a 5: 1 molar ratio, as reagents for preparing the catalytic support.

[97] In a solution of ethanol, hydrochloric acid and water with a pH around 2.0, with stirring at 250 rpm, TEOS diluted in ethanol is added.

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The suspension is left under mechanical stirring at 250 rpm for 24 hours. After this period, a pre-calculated amount of magnesium chloride suspended in water is added to the suspension. The TEOS: MgCE molar ratio added is 5: 1. The reaction mixture is left under mechanical stirring at 250 rpm until product formation (additional 24 hours). The suspension is filtered and the product washed with 10 aliquots of 5 ml of ethanol. After washing, the product is dried under reduced pressure for 12 hours.

[98] The component obtained was characterized, presenting the following characteristics:

• Mg content: 4.3 (w / w) • Specific area (Sbet): 379 m ² / g • Average pore diameter (D _p ): 30 Â [99] In order to determine the relative separation between the aminopropylsilane groups present in the catalytic supports of the present invention, the fluorescence emission spectra were obtained, through excitation at 330 nm, of the supports grafted with 1-pyrenobutyric acid (PBA), as shown in Figure 1.

[100] Thus, according to Figure 1, the fluorescence emission spectrum of the PBA grafted onto the surface of the support of Example 1 has three well-defined bands at 377, 397 and 419 nm, which can be attributed to the monomeric form of the PBA. In addition to these bands, there is also a broad band between 425-550 nm, which can be attributed to the presence of excimers. For the PBA system / Example 2 (Figure 1b), it is possible to observe in the spectrum a reduction in the intensity of the bands attributed to the monomeric form of the PBA and an increase in the intensity of the band attributed to the excimers. Finally, for the PBA system / Example 3 (Figure 1c), it can be seen in the fluorescence spectrum a very significant reduction in the bands attributed to the monomeric form of the PBA and an increase in the intensity and width of the excimer band. The ratios between the intensities of the

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23/30 excimers (at 425-550 nm) and the monomer band (at 377 nm) were calculated for the different systems, as shown in Table 1.

Table 1

System Aminopropylsilane content (mmol NH2 g ¹ support) Iexc / Imon PBA / Example 1 0.6 0.42 PBA / Example 2 1.1 0.91 PBA / Example 3 2.4 5.98

[101] According to Table 1, the increase in the aminopropylsilane content in the silica-magnesia-aminopropyl supports results in an increase in the I _and xc / Imon ratio, that is, in the amount of excimers in the materials. For example, the PBA / Example 1 system has an Iexc / Imon ratio equal to 0.42, which is approximately 14 times less than that observed for the PBA / Example 3 system, whose ratio is 5.98. This result can be attributed to a larger population of monomeric PBA molecules, which are further apart than 10 Â, in the PBA / Example 1 system, compared to the PBA / Example 3 system. Therefore, considering that the aminopropylsilane groups are the sites of binding of the PBA molecules, it can be inferred that the increase in the APTES content in the supports results in an increase in the population of aminopropylsilane groups with spacing less than 10 Â. Therefore, the support of example 1 obtained the best spacing.

Preparation of the supported metallocene catalyst

Examples 6-10 [102] The hybrid catalytic support obtained according to the examples described above is treated at a temperature of 200 ° C for 8 hours under vacuum. This treated support is suspended in hexane and the suspension is cooled to -10 ° C. The system is maintained under 250 rpm mechanical agitation. A pre-calculated volume of 1.6 M n-butyl lithium solution is added to this suspension. The mol amount used for this reagent is greater than the number of moles of aminopropyl present in the support. The reaction is kept under stirring for 4 hours. After that period, the solvent is removed under reduced pressure. Then, the solid is suspended in toluene and to that suspension is

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24/30 a solution of cyclopentadienyl titanium (IV) chloride was added. The molar amount of this catalytic complex that is used is equivalent to the number of moles of n-butyl lithium previously added. The suspension is left under stirring at room temperature for 4 hours. The solvent is removed by decanting / siphoning and the solid is washed with 5 10 ml aliquots of toluene. After washing, the supported catalyst is dried under vacuum for 8 hours. The results of Ti content (measured by the Rutherford backscatter spectroscopy technique) and Ti 2p binding energy (EL) (determined using the X-ray photoelectronic spectroscopy technique) for the supported metallocene catalysts obtained with the hybrid catalytic supports of the examples 1-5 are shown in Table 2.

Table 2

Hybrid catalytic support Metallocene catalyst supported Ti / SiCh content (% w / w) Ti 2p EL (eV) Example 1 Example 6 1.6 459.1 Example 2 Example 7 3.5 458.5 Example 3 Example 8 4.4 458.4 Example 4 Example 9 0.9 458.8 Example 5 Example 10 0.7 459.6

[103] According to Table 2, supported catalysts prepared according to examples 6-8 have a higher metallocene fixation content compared to the catalysts in comparative examples 9 and 10. In addition, the catalysts in examples 6-8 present different catalytic sites in relation to those of the systems of comparative examples 9 and 10. These differences can be evidenced through the differences in the binding energies of Ti 2p.

Polymerizations [104] In a 0.1 L capacity steel Parr® reactor, equipped with temperature and pressure controller and mechanical stirring, hexane is added under a nitrogen atmosphere. A 10 mL amount of TEA is added for flushing the reactor. The washing time is at least thirty minutes. The washing liquid is removed from the reactor by siphoning. After washing, toluene is added to the reactor and mixed

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25/30

TEA: MAO in the proportion of 1: 1 at a temperature of 40 ° C, and then the reactor is purged with ethylene. After purging, the pre-catalyst dissolved in toluene is added to the reactor, forming a catalytic system with [Ti] = 5 x 10 ' ⁶ mol and Al / Ti molar ratio equal to 500. In copolymerizations, 10 ml of 1 -octene or 1-decene. The ethylene pressure is adjusted to 1.5 bar and the stirring to 250 rpm. After a period of 1 hour, the reactor is drained in a 10% (v / v) acidified ethanol solution with HCl in a Becker beaker, to deactivate the catalytic system and precipitate the polymer. The mixture is filtered and washed with distilled water, successive times until the elimination of toluene and catalytic residues. The polymer retained in the filter is dried under vacuum at 40 ° C and 10 ¹ bar, until it has a constant weight. The results of catalytic activity of the supported catalysts of examples 6-10 are shown in Table 3.

Table 3

Metallocene catalyst supported Catalytic activity (kg in / mol Ti.h.atm) Tm (° C) Xc (%) Mw (kg mol ¹ ) Mw / Mn Example 6 520 138 51 1380 2.8 Example 7 310 138 58 ND ND Example 8 170 140 58 1720 26.2 Example 9 20 134 38 170 2.3 Example 10 110 138 43 220 2.7

ND = not determined.

[105] According to Table 3, the activities of the catalysts of examples 6-8 are superior to those observed for the catalysts of comparative examples 9-10. For example, the supported catalyst of example 6 has an activity 26 times greater than that observed for the system of comparative example 9.

[106] The greater catalytic activity of the systems of examples 6-8 compared to the system of example 9 can be attributed to the reduction of the cationic character of the Ti centers with the presence of the aminopropylsilane groups. Although a moderate cationic character on Ti favors the coordination of olefin and leads to an increase in catalytic activity, the very strong cationic character of the metal center tends to strongly coordinate the olefin, which

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26/30 should in turn translate into a decrease in the speed of propagation of the growth of the chain, reducing catalytic activity. Therefore, the reduction of the cationic character of Ti with the presence of aminopropylsilane should increase the speed of propagation of the growth of the chain, resulting in an increase in catalytic activity. However, the increase in the content of aminopropylsilane groups in the supports resulted in a decrease in the activity of the supported catalysts. This behavior can be attributed to three main factors. The first is the reduction of the specific area of the supports and catalysts supported with an increase in the content of aminopropylsilane groups. Another factor that may be contributing to the reduction of catalytic activity is the decrease in the average spacing between the aminopropylsilane groups with the increase in the content of these groups in the supports. A smaller spacing of these groups on the surface can result in a greater number of tridentated catalytic species, inactive to polymerization. In addition, this smaller spacing should cause an increase in molecular deactivation reactions due to the greater proximity between the metallocene centers. The third factor is the increase in the electronic density of the Ti atom with an increase in the content of aminopropylsilane groups, resulting in a lower tendency for olefin coordination and, consequently, a decrease in catalytic activity.

[107] The melting and crystallinity temperatures of the polyethylenes obtained with these systems are characteristic of high density polyethylene. The polyethylenes obtained with the catalytic systems of the present invention have molecular weight between 1000 and 2000 kg mol ¹ and polydispersion in the range of 2-30.

[108] The activities of the catalytic system of example 6 in ethylene copolymerization reactions with 1-octene and 1-decene were 490 and 470 kg pol / mol of Ti.h.atm, respectively, which are up to 250 times greater than activities observed for the supported catalytic system of Soga et. beyond

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Macromolecular Rapid Communications 18 (1997) 9.

[109] Ethylene copolymers with α-olefins were characterized in terms of melting temperatures and crystallinity by the differential scanning calorimetry (DSC) technique. Figure 2 shows the DSC curves for the ethylene-1-octene and ethylene-1-decene copolymers obtained with the catalytic system of example 6.

[110] According to Figure 2, the copolymers of ethylene-1-octene and ethylene-1-decene have extended DSC curves with maxima centered between 50-100 ° C. The low magnitudes of the melting endotherms show the formation of amorphous polymers and are characteristic of copolymers with a high comonomer content. The melting temperature and crystallinity values for the ethylene-1-octene and ethylene-1decene copolymers, obtained with some of the catalytic systems, are presented in Table 4. For comparative purposes, the crystallinity temperature values of the ethylene homopolymers were also added to the table.

Table 4

System Polymer Tm (° C) Xc (%) CpTiCl ₃ Polyethylene 133 44 Ethylene-1-octene copolymer 55 <1 Ethylene-1-decene copolymer 56 <1 Example 10 Polyethylene 134 43 Ethylene-1-octene copolymer 118 19 Ethylene-1-decene copolymer 105 12 Example 6 Polyethylene 137 51 Ethylene-1-octene copolymer 57 <1 Ethylene-1-decene copolymer 88 6

[111] According to Table 4, the copolymers of ethylene-1-octene and ethylene-1-decene have melting temperatures (Tm) in the range of 55118 ° C. The crystallinity of the copolymers was between 1 and 19%. These values of Tm and Xc are lower than those observed for ethylene homopolymers and this decrease is attributed to the insertion of branches in the polyethylene chain, which make these polymers more amorphous. The comparison between the temperature and crystallinity values of the copolymers obtained with the different catalytic systems allows us to infer that,

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28/30 for the same amount of long-chain α-olefin added to the feed, the CpTiCfi and example 6 systems produce copolymers that can be classified as very low density polyethylene. The copolymers obtained with the system of Example 10, on the other hand, exhibit values of Tm and Xc characteristic of low density linear polyethylenes.

[112] Results regarding the content and distribution of 1-octene or

1-decene in ethylene copolymers obtained with some catalysts are shown in Table 5.

Table 5

System Copolymer rccci TECC1 TECE] [EEE] rCECl [EEC] Π Γε rc Γε · r _c CpTiCl ₃ Ethylene-1-octene - - - - - - 28.6 ^a - - - Ethylene-1-decene 3.0 8.8 16.3 32.9 6.4 32.6 28.1 9.9 0.08 0.79 Example 10 Ethylene-1-octene 0 0 5.4 83.7 0 10.9 5.4 89.2 0 0 Ethylene-1-decene 0 0 9.2 72.4 0 18.4 9.2 38.6 0 0 Example 6 Ethylene-1-octene 2.4 2.3 21.2 16.8 8.8 48.5 26.1 8.1 0.02 0.16 Ethylene-1-decene 0.8 5.8 15.2 43.1 4.6 30.5 21.8 13.3 0.04 0.53 Comparative ^b Ethylene-1-octene 6.7 13.7 16.3 8.0 14.1 41.2 36.8 4.5 0.1 0.45

^a : Determined by Ή NMR Spectroscopy;

^b : Reference data 13. Catalytic system prepared by immobilizing Cp * TiC13 on commercial silica modified with aminopropylsilane groups via grafting. Polymerization conditions: [Ti] = 1 (H mol; Cocatalyst = MAO; Al / Ti = 500; Reaction medium: toluene (100 mL); Temperature = 40 ° C. Ethene pressure = 1 atm; Comonomer volume = 7 mL; Time = 60 min Catalytic activity of the order of 2.0 kg PE (mol Ti.h.atm) ¹ [113] According to Table 5, the unsupported CpTiCfi system produces an ethylene-1-octene copolymer with 28.6% octene built in. For this polymer, it was not possible to re-perform the ¹³ C NMR analysis, and consequently, the calculation of the relative percentages of each triad, due to the high catalytic residue content. 10, despite being more active in copolymerizing ethylene with 1-octene compared to the CpTiCfi system, produces a copolymer with a low total content of 1-octene incorporated (5.4%). that the copolymer is exclusively formed by the triads [ECE] and [EEE], which results in a product of the reactivation ratios comonomer (γε. rc) equal to zero, which is characteristic of an alternating copolymer. In the case of the ethylene-1-octene copolymer obtained with the catalytic system of example 6, an octene incorporation content of 26.1% can be observed. This content is of the same order of magnitude as that obtained for the

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29/30 copolymer prepared with unsupported CpTiCfi catalyst. With respect to the distribution of octene, it can be verified that the triads [ECE], [EEE] and [CEE] are majorities, leading to a product of the comonomer reactivity ratios (r _E. Rc) equal to 0.16. The closer to zero is the value of r _E. rc, more alternate is the distribution of the comonomer branches in the copolymer. Thus, the use of catalysts of the present invention in copolymerizing ethylene with 1-octene results in polymers with a higher octene content compared to those obtained with the use of CpTiCh catalysts supported on silica-magnesia. However, the addition of aminopropylsilane to the catalytic support results in a more random distribution of octene in the resulting copolymer. In comparison to the supported catalyst by Soga et. al. (1997), the catalyst of example 6, prepared by immobilizing CpTiCh on the modified silica-magnesia support with aminopropylsilane groups, produces a less random 1-octene ethylene copolymer, that is, more alternate, which can be verified by the value of r _E. rc closer to zero. Another difference between the performance in the copolymerization of ethylene with 1-octene of the catalyst of example 6 and that of Soga et. al. (1997) is observed in catalytic activity. The catalyst of example 6 is approximately 250 times more active than the catalyst of Soga et. al, (1997). Therefore, the catalytic system of the present invention has high activity in copolymerizing ethylene with 1-octene and produces copolymer with high octene content. It should be noted that these are characteristics of catalysts with tensioned geometry (CGC), which is not expected for a supported metallocene catalyst. The catalytic system of example 6, therefore, can be applied in gas or suspension phase (sludge) processes, since it is a supported catalyst.

[114] The same behavior observed for the different catalytic systems in the copolymerization of ethylene with 1-octene is verified in the copolymerization of ethylene with 1-decene, that is, that the use of

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30/30 catalysts synthesized by immobilizing CpTiCh on silica-magnesia supports modified with aminopropylsilane groups in copolymerization of ethylene with 1-decene results in copolymers with higher decene content compared to those obtained with the use of CpTiCh catalysts supported on silica -magnesia. In addition, the addition of aminopropylsilane to the catalytic support results in a more random distribution of decene in the resulting copolymer.

Claims (22)

1. Catalytic system of the supported metallocene type, characterized by the fact that it comprises a hybrid silica-magnesia support synthesized by the sol-gel process and organic groups with amino functionality, said groups being aminoalkyls from 1 to 18 carbons, in which said metallocene is defined according to formula I: Where, M is a transition metal of groups 4 or 5, L ¹ is a bulky cyclopentadienyl (Cp), indenyl (Ind) or fluorenyl (Flu) type, whether or not substituted by hydrogen, alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl, L ² , L ³ and L ⁴ can be halogens, alkoxides or alkyl groups. 2. Catalytic system, according to claim 1, characterized by the fact that the organic groups comprise from 1 to 9 carbons. 3. Catalytic system, according to claim 1, characterized by the fact that the content of covering the support by the organic groups on the surface of said support is from 1 to 200 pmol / m ² . 4. Catalytic system according to any one of claims 1 to 3, characterized in that the transition metal of groups 4 or 5 is Ti, Zr or Hf. Catalytic system according to any one of claims 1 to 4, characterized by the fact that the metallocene catalyst content is 0.1 to 10% (w / w). 6. Catalytic system according to any one of claims 1 to 5, characterized in that the catalytic support of hybrid silica-magnesia consists of a material formed predominantly Petition 870180160652, of 12/10/2018, p. 54/59 2/5 per silica gel, with Mg contents on the surface of 0.1 to 12% (w / w). Catalytic system according to any one of claims 1 to 6, characterized by the fact that it comprises a specific area and average pore diameter of 10 to 500 m ^z / g and 10 to 100 A, respectively. 8. Process of synthesis of the supported metallocene-type catalytic system, as defined in claim 1, characterized by the fact that it comprises the following steps: (i) preparation of the hybrid catalytic support comprising: The. preparation of a solution of an acid with a concentration in the range of 0.1 to 5 mol / L in an alcohol, with a dilution factor of 2 to 100; B. reaction of a solution of tetraalkylortosilicate with the solution obtained in (a), so that the volumetric ratio of tetraalkylortosilicate on alcohol is from 1: 100 to 1: 1; ç. reaction of a magnesium salt with the solution obtained in (b), for a reaction time of 1 to 48 hours, in which the molar ratio of the magnesium salt to the tetraalkylortosilicate is in the range of 1:50 to 2: 1 ; d. reaction of a trialkoxideorganosilane containing amino functionality with the suspension obtained in (c), in which the volumetric ratio of trialkoxideorganosilane to alcohol is from 1: 100 to 1: 1; and. removing the solvent, washing and drying the product of the reaction obtained in (d); and (ii) Synthesis of the supported metallocene catalyst which comprises: f. heat treatment of the product obtained in (e) at a temperature of 40 to 220 ° C, for a period of 1 to 200 hours; Petition 870180160652, of 12/10/2018, p. 55/59 3/5 g. reaction of the product obtained in (f) with an organometallic compound based on group I transition metal in an inert organic solvent, for a period of 1 to 20 hours, followed by cooling to a temperature between 0 and -80 ° C, in which said organometallic compound comprises formula II: C _n H2n + iM Formula II where M is a transition metal of group 1 and n is a number between 1 and 6; H. removing solvent from the product obtained in (g); i. reaction of the solid product obtained in (h) with a solution of metallocene based on transition metal of groups 4 or 5 of the periodic table in an inert organic solvent, at a temperature between 0 and 60 ° C, for a period of time between 0, 1h and 24h, in which the metallocene is defined according to formula I: Where, M is a transition metal of groups 4 or 5, L ¹ is a bulky cyclopentadienyl (Cp) type binder, indenyl (Ind) or fluorenyl (Flu), whether or not substituted by hydrogen, alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl, alkyl; L ² , L ³ and L ⁴ can be halogen, alkoxide or j groups. washing and removing solvent from the reaction product obtained in (i). 9. Synthesis process, according to claim 8, characterized by the fact that the tetraalkylortosilicate used in step b. the process of preparing the hybrid catalytic support is selected from among the Petition 870180160652, of 12/10/2018, p. 56/59 4/5 group comprising: tetramethylortosilicate (TMOS), tetraethylortosilicate (TEOS), tetrapropylortosiliacate (TPOS) and tetrabutylortosilicate (TBOS). 10. Synthesis process, according to claim 9, characterized by the fact that the tetraalkylortosilicate used in step b. of the process of preparing the hybrid catalytic support is tetraethylortosilicate (TEOS). 11. Synthesis process according to any one of claims 8 to 10, characterized by the fact that step (c) is carried out concurrently with step (b). 12. Synthesis process, according to claim 8, characterized by the fact that the trialoxideorganosilane used in step (d) of the preparation process of the hybrid catalytic support is selected from the group comprising: aminomethyltrimethoxysilane (AMTMS), 2aminoethyltrimethoxysilane (AETMS ), 3-aminopropyltrimethoxysilane (APTMS), 4-aminobutyltrimethoxysilane (ABTMS), 5-aminopentyltrimethoxysilane (APETMS), 6-aminohexyltrimethoxysilane (AHTMS), aminomethyltriethoxysilane (AMTES), 2-aminoethyltriethoxysilane (AETES), 3-aminopropyltrietho (3-aminopropyltriethoxy) (APETES) and 6-aminohexyltriethoxysilane. 13. Synthesis process, according to claim 12, characterized by the fact that the trialcosideorganosilane used in step (d) of the process of preparation of the hybrid catalytic support is 3aminopropyltriethoxysilane (APTES). Synthesis process according to any one of claims 8 to 13, characterized in that the mixing speed of the steps in steps (a), (b), (c) and (d) is 50 rpm at 40,000 rpm and the reaction temperature in steps (b), (c) and (d) is 0 to 70 ° C. 15. Synthesis process according to any one of claims 8 to 14, characterized by the fact that the molar ratio of Petition 870180160652, of 12/10/2018, p. 57/59 5/5 trialkoxideorganosilane containing amino functionality in relation to tetraalkylortosilicate is 1:50 to 1: 0. 16. Synthesis process according to claim 8, characterized by the fact that the group I transition metal-based organometallic compound is selected from methyl lithium, 2-ethyl lithium, 3-propyl lithium and n -butyl-lithium. 17. Synthesis process according to claim 8 or 16, characterized by the fact that the group I transition metal-based organometallic compound is replaced by a group I metal hydride. 18. Synthesis process according to claim 8, characterized by the fact that the transition metal of groups 4 or 5 is Ti, Zr or Hf. 19. Synthesis process according to claim 8, characterized by the fact that the metallocene catalyst content is 0.1 to 10% (w / w) · 20. Use of the supported metallocene type catalytic system as defined in claim 1, characterized by the fact that it is in the process of homopolymerization of ethylene or copolymerization of ethylene with long chain olefins in gas or sludge phase. 21. Use of the catalytic system according to the claim 20, characterized by the fact that the homopolymerization or copolymerization process uses an alkyl aluminum as a cocatalyst. 22. Use of the catalytic system according to the claim 21, characterized by the fact that the homopolymerization or copolymerization process uses methylaluminoxane (MAO) as a cocatalyst.