Polymerization method of alpha-olefines

The invention relates to a process for polymerization of olefins in the presence of solvent and catalyst.

It is known that α / fa-olefin polymers, namely polyethylene or ethylene / a // <2-olefin copolymers are obtained by processes in which ethylene is polymerized or ethylene and αΖ / α-olefin are copolymerized in the presence of a titanium catalyst. consisting of a titanium compound and an organo-aluminum compound, or a vanadium-based catalyst consisting of a vanadium compound and an organo-aluminum compound.

In general, ethylene / aZ / â-olefin copolymers obtained with titanium catalyst have a wide molecular weight distribution and have low transparency, low non-adhesion and weak dynamic properties. The ethylene / izZ / a-olefin copolymers obtained in the presence of vanadium-based catalysts have a close molecular weight distribution, compared to the ethylene / aZ / a-olefin copolymers obtained with the titanium-based catalyst and have a fairly good transparency enhancement. , non-adhesion, and dynamic properties, but said ethylene / aZ / holefin copolymers are insufficient for the practical purposes where such properties are required.

It is therefore desirable that the physico-mechanical properties of the ethylene / αΖ / α-olefin copolymers be improved. Under such conditions, on the one hand, recent processes have been proposed for the preparation of ethylene / α / α-olefin copolymers using zirconium and alumonoxy catalysts as a new type of Ziegler catalysts for polymerization of olefins.

A process for the preparation of ethylene / α / α-olefin copolymers is known, which consists in the polymerization of ethylene and one or at least two αΖ / α-olefins with 3 ... 12 carbon atoms at a temperature between -80 and 200 ° C, in the presence of a catalyst consisting of a compound containing transition metal represented by the general formula:

(Cyclopentadienyl)₂ MeRHal wherein R is cyclopentadienyl, 1-6 alkyl carbon or halogen, Me is a transition metal and Hal is 5 halogen and a linear aluminoxane is the following general formula:

A1₂OR₄ (A1 (R) -O) "where R is methyl or ethyl and n is an integer from 4 to 20, or a minoxane cycloalk1θ represented by the general formula:

(Al (R) -0-)_{n + 2}where R and n are similar to those defined above. The mode of regulation of ', the resulting polyethylene density is presented, the polymerization being done in the presence of small quantities of up to 10% by weight of aZ / ef-olefins with almost long chain or mixtures thereof.

Another known process refers to the preparation of linear aluminoxane represented by the following general formula:

^R R ^R \ l-0 (-Al-o) —Al⁷/ ^V \

RR wherein n is a number from 2 to 40, and R is an alkyl radical of 1 to 6 carbon atoms, and a cyclic aluminoxane represented by the general formula:

(A1 (R) -0-),_{i + 2} wherein n and R are similar to those defined above 35.

In this process, it is specified that when the polymerization of ethylene is carried out, in the presence of a mixture containing aluminoxane prepared as above, for example 40 pi, methylaluminoxane and a biscyclopentadienyl) -zimonium compound or a to- (cyclopentadienyl) -titan compound is obtained. at least 25 mg of polyethylene per g of transition metal and per 1 .h.

Another well-known documentary material (Japanese Patent Publication LCP No. 35005/1985) presents a process for preparing the olefin polymerization catalyst which consists first of reaction in the formation of an aluminoxanic compound representing 103648 of the general formula:

R, R, where R 1 is alkyl of 1 to 10 carbon atoms R_a is R; or R_arepresents the -O- bond with a magnesium compound, and then the chlorination of the reaction product, followed by treatment with a titanium, vanadium, zirconium or chromium compound. This material describes the fact that the catalysts prepared by the above process are used in the copolymerization of ethylene and α-olefins with 3 to 12 carbon atoms. Another known procedure. is the Japanese patent publication no. 35006/1985) having a catalyst containing a combination of (a) two or more different mono-, di- or trz-cyclopentadienyls or their transition metal derivatives and (b) an aluminoxane as a catalyst for the preparation of reactive mixed polymers. Example 1 of this LOP patent publication shows that ethylene and propylene are polymerized in the presence of a catalyst consisting of & z's- (pentamethylcyclo-pentamethylcyclopentadienyl) -dimethylzirconium and an aluminoxane to obtain polyethylene having a weight of 36 %4 and4 molecular weight4,4 propylene. Example 2 of this publication shows that ethylene and propylene are polymerized in the presence of the catalyst containing bis-pentamethylcyclopentadienejl-zirconium dichloride and / us- (methylcyclopentadienyl) -circonium dichloride and an aluminoxane to obtain a mixture of polyethylene and polyethylene / consisting of a toluene soluble portion with a molecular weight of 2200 and an average molecular weight of 11.9000 and · containing 30% molar propylene component and a portion insoluble in toluene, having an average molecular weight of 3000 and an average molecular weight of 7400, containing 4.8% molar propylene component. The mixture has an average molecular weight of

8300 and contains 7.1% molar propylene component. Similarly, Example 3 shows a mixture of ethylene polymer and an ethylene / propylene copolymer consisting of a soluble portion having a molecular weight distribution (Mw / Mn) 4.57 and containing 20.6% molar propylene component and an insoluble portion having molecular weight distribution of 3.04 and containing 2.9% molar-component-propylene.

Another documentary material (the Japanese patent publication LOP no. 35007/1985) presents a process in which the ethylene and an // â-o] efine polymerized with 3 or more carbon atoms in the presence of a catalyst system containing metallocene and an aluminoxane represented by the general formula:

The (R) -0-)_{n + 2} wherein R is an alkyl group of 1 to 5 carbon atoms and n is an integer of 1 to about 20, aluminum-linear linear represented by the general formula:

R - (- Al (R) -O -) - LRA₂ where R is similar to that defined above, and n is similar to that defined above.

According to this process, the obtained polymers have an average molecular weight of about 500 to about 1,400,000 and a molecular weight distribution of

1.5 to 4.0.

Another known process (Japanese Patent Publication No. 35008/1985) discloses that polyethylene polymers or ethylene - alpha olefin copolymers with 3 to 10 carbon atoms having a wide molecular weight distribution are prepared by using the catalytic system comprising at least 2 metallocene and aluminoxan. According to this process copolymers having a distributed molecular weight (Mw / Mn) from 2 to 50 are obtained._:

Other known processes (Japanese patent publications LOP Nos. 260602 1985 and 130604/1985) contain the polymerization of olefins by using catalysts formed from a mixture of organo-aluminum compound consisting of a transition metal compound, aluminoxane and an organo-aluminum compound. The activity of the polymerization reaction per unit of transition metal is enhanced by the addition of the organo-aluminum compound.

In each of the processes mentioned above, as a problem, the activity per unit of aluminoxane of the catalyst used is still low. Furthermore, it is difficult to obtain polymers having a sufficiently high molecular weight when olefins, for example, ethylene and propellin, are copolymerized by the use of catalysts composed of transition metal and aluminoxane compounds hitherto known.

The object of the invention is to obtain a polymer with a narrow molecular weight distribution.

The problem to be solved by the invention is the use of a specific catalyst in the polymerization process to achieve the proposed purpose.

The present invention removes the above disadvantages by the fact that, in the reaction medium, a catalyst consisting of (A) is introduced into a transition metal compound of group IV of the periodic table which is a zirconium compound containing a group having as a ligand a conjugate electron π, ie a monoadentate ligand containing a cyclopentadienyl or cyclopentadiene group substituted with an alkyl group or a multi-bonded ligand containing at least two groups selected from an indenyl group or a substituted indenyl group and partial hydrides thereof, these groups being linked by a lower alkylene group, (B) a compound represented by aluminoxane; (C) optionally an organo-aluminum compound containing a hydrocarbon group other than n-alkyl, represented by the trialkylaluminum, tricycloalkylaluminum, alkenylaluminum, dialkylaluminum hydrides, alkylaluminium alkali and alkyl aluminum dihalogens.

The following are examples of embodiments of the invention.

Example 1. Preparation of aluminoxane. A 400 ml flask completely blown with nitrogen is loaded with 37 g of A1₂(SO₄)₃-14 H₂O and 12.5 ml of toluene and cool to 0 ° C. Then 500 mmol of triethylaluminium diluted with 12.5 ml of toluene is added dropwise. The temperature of the flask mass is then raised to 40 ° C and the reaction is continued at the same temperature for 10 hours. After completion of the reaction, the mixture obtained is subjected to separation by liquid solid filtration. The toluene is removed from the filtrate to give 12 g of aluminoxane as a white solid. The aluminoxane thus obtained is dissolved in toluene again and the solution is used to prepare the catalysts with which the polymers are produced.

The aluminoxane thus prepared has a molecular weight of 870 determined by decreasing the freezing point in benzene, the value m of the catalytic component (B) was 13.

Preparation of the catalyst and polymerization.

A 1.51 glass autoclave is purged completely with nitrogen and charged with 500 ml of toluene containing 0.50 mmol of water and 400 ml of 4-methyl-1-pentene. Then the temperature rises to 50 ° C. Thereafter, the aluminoxane thus prepared as above is added in an amount of 5 mg in aluminum atom and stirred at 50 ° C for 15 min. Thereafter, 0.02 mmol Z? / - (cyclopentadienyl)-zirconium dichloride, to initiate polymerization. The polymerization was carried out at atmospheric pressure at 50 ° C for 2h, and then 20 ml of water was added to stop the polymerization. After removal of the residual catalyst with hydrochloric acid and water, toluene and unpolymerized 4-methyl-1-pentene are removed, using an evaporator, and then dried under vacuum at 120 ° C, remaining overnight. As a result, 62 g of poly4-methyl-1-pentene liquid having Mn = 1300 and Mw / Mn = 2.20 are obtained.

Comparative example 1.

A polymerization catalyst for olefins is prepared in the same manner as that prepared in Example 1 except that fapane is used 500 ml toluene without water content.

With this catalyst, 4-methyl-1-pentene is polymerized under the same conditions as described in Example 1, giving 48 g of poly-4-methyl-1-pentene liquid having Mw / Mn = 2.15

Example 2 and 3. Olefin polymerization catalysts are prepared by repeating the methodology of the example

1, but using the components presented in the example in Table 1. Using the catalysts thus prepared, 4-methyl-1-pentene is polymerized under the same conditions as those described in Example 1, obtaining poly-4-methyl-1-pentene and having the properties presented in table 1.

Table 1

<td>Ex. no.</td><td>Catalytic components Name</td><td>(A) mmol</td><td>Aluminum (mg atom A)</td><td>Mmol water</td><td>Yield g</td><td>Mn</td><td>Mw / Mn</td>

<td> 2</td><td>Bis- (cyclic pentadienyl zirconium dichloride</td><td> 0,2</td><td> 5</td><td> 0,25</td><td> 66</td><td> 1100</td><td> 2,10</td>

<td> 3</td><td>Bis- (methylthio, cyclopentadienyl) -circonium dichloride</td><td> 0,02</td><td> 5</td><td> 0,50</td><td></td><td> 1400</td><td> 2,24</td>

Example 4. A glass autoclave of 500 ml capacity is purged with nitrogen and 10 is charged with 250 ml of toluene containing 0.125 mmol of water and aluminoxane prepared as described in example 1 in an amount of 1.25 mg expressed as an aluminum atom, and then stir at 15 ° C for 10 minutes. Thereafter, a mixture of ethylene and propylene gas (60 1 / h and 40 1 / h respectively) is introduced into the autoclave, and stirred for 5 min. After that, add 5 x 10 '⁴ mmol 20 of 6z5- (cyclopentadienyl) zirconium chloride for initiation of polymerization. After polymerization under atmospheric pressure conditions at 25 ° C for 30 minutes while adding the above-mentioned gas mixture, a small amount of methanol is added to stop the polymerization. To the polymer solution obtained, an excess amount of matanol is added to precipitate the polymer, then dried in vacuo at 130 ° C for 12 hours. As a result, 7.8 g of polymer with an MFR of 0.69 g / 10 min are obtained, 88.2 mol% of ethylene content as shown in 35 of the spectrum ¹³C-NMR, Mw / Mn of 1.94 and B's value of 1.12.

Comparative example 2.

The same polymer as described in Example 4 is prepared except that 25 ml of toluene is used which does not contain water, giving 6.7 g of polymer having an MFR of 2.02 g / 10 min, the ethylene content being 91, 5% molar, Mw / Mn of 1.98 and B value of 1.11.

Example 5. A 400 ml nitrogen-purged glass flask is charged with 57 ml of toluene, 0.94 g of A1₂(SO₄)₃-13H₂A fine spray and 50 ml toluene solution of alumminoxane prepared according to the point of example 1 (Al 2,14 mol / 1). The temperature of the flask is raised to 40 ° C for the reaction to take place, for 72 hours. The slurry thus obtained is used for the following polymerization.

The same apparatus as described in Example 4 is charged with 250 ml of toluene and the mixture of ethylene and propylene gas (60 1 / h respectively 40 1 / h) is passed through toluene. After that, add 1.25 ml of slurry obtained above and 5 x IO '⁴ mmoles of bis (cyclopentadienyl) - zirconium dichloride are added in the same manner as in Example 4. 10.7 g of polymer is obtained, having an MFR of 0.56 g / 10 min, the ethylene content of 86.2% molar, Mw / Min of 2.03 and the value of B 1.12.

Example 6. The same polymerization as in Example 5 is performed except that bis (cyclopentadienyl) zirconium dichloride used in example 5 is used to (methylcyclopentadienyl)-zirconium dichloride, thereby obtaining 10.2 g. of polymer, having a MFR of 0.49 g / 10 min, the ethylene content of 86.9% molar, Mw / Mn of 2.11 and the B value of 1.12.

Example 7. A 400 ml capacity glass flask, charged with nitrogen, is charged with 57 ml of toluene, 0.94 g of A1₂(SO₄)₃-13H₂A fine spray and 50 ml toluene aluminoxane solution obtained in the same manner as in Example 1 (Al 2.14 moles / 1). The temperature is raised to 40 ° C for the reaction to take place, for 72 hours. The sludge thus contained is used in the following polymerization reaction.

A stainless steel autoclave of 2 1 capacity is purged with nitrogen and charged with 900 ml of 4-methyl-1-pentene and 1 mmol of triisobutyl aluminum. The temperature of the autoclave is raised to 100 ° C. Afterwards 0.2 ml slurry contained above and 8 x IO '⁴mmoles of the (methylcyclopentadienyl) zirconium dichloride are contacted in 40 ml of cyclohexane for 2 min at room temperature and then introduced, together with ethylene, into the polymerization system to initiate the polymerization reaction. The polymerization is continued at a total pressure of 20 Kg / cm², for 40 minutes, while ethylene is continuously fed into the system. A small amount of methanol is added to stop polymerization. The polymer solution is added in excess methanol to precipitate the polymer, followed by vacuum drying at 80 ° C for 12 hours. As a result, 111 g of the polymer is obtained with an MFR of 1.6 g / 10 min. , the density of 0.302 g / cm³, Mw / Mn of 2.14 and the soluble portion in n-decane of 1.6% by weight.

Comparative example 3.

The same polymerization as in Example 7 is performed except that 0.2 mg atom, as an aluminum atom, of aluminum oxide prepared according to example 1, as used, is obtained without contacting it with water, that is, without using AL / SO ^ j + 13H₂O, thus obtaining 75 g of polymer having an MFR of 6.2 g / 10 min, density of 0.904 cm₃, Mw / Mn of 2.20 and the n-dean portion of 1.6% by weight.

Examples 8-10. The same polymerization reaction, as in Example 4, is carried out with the 4-methyl-1-pentene monomer, the catalysts each comprising the catalytic components presented in the example in Table 2, the polymers presented in table 2 being obtained.

Example 11. A 400 ml flask of nitrogen-purged glass is charged with 57 ml of toluene, 0.47 g A1₂SO₄)₃-13H₂O and 50 ml of toluene aluminoxane solution prepared in the same manner as described in Example 1. The reaction is carried out at 40 ° C for 48 h. To 10 ml of slurry thus obtained add 40 ml of toluene and 0.1 mmol bis (cyclopentadienyl)-zirconium dichloride and then contacted at room temperature for 10 min. The polymerization is carried out in the same manner as that described in Example 7, but using 0.1 ml sludge thus treated and 1 mmol of triisobutyl aluminum. 88 g of polymer is obtained with MFR of 2.1 g / 10 min, density 0.903 g / cm³ Mw / Mn of 2.31 and the soluble portion in n-decane of 1.6% by weight.

According to the invention, catalysts having an increased activity are used in the polymerization process, being able to give olefinic polymers having a high molecular weight. Also, by using catalysts in the process, olefin polymers are obtained having a close molecular weight distribution for olefin homopolymers and olefin copolymers with a close distribution of the composition when copolymers with two or more olefin molecules are prepared.

Table 2

Polymerization results

<td rowspan="2">Nr. example</td><td rowspan="2">The Sort component</td><td rowspan="2">cat (A) mmol</td><td rowspan="2">aluminoxane ml</td><td colspan="2">Organicaluminiu</td><td rowspan="2">Yield %</td><td rowspan="2">MFR g / io min</td><td rowspan="2">Density g / cm³</td><td rowspan="2">mw * Mn</td><td rowspan="2">X</td>

<td>The kind</td><td>mmol</td>

<td> 8</td><td>Bis- (cyclopentadienyl) zirconium dichloride</td><td>2x10 '³</td><td> 0,2</td><td>triisobutyl aluminum</td><td> 1</td><td> 74</td><td> 2,8</td><td> 0,903</td><td> 2,29</td><td> 1,7</td>

<td> 9</td><td>Bis-cyclopentadienyl) zirconium dichloride</td><td>2xl0 '³</td><td> 0,2</td><td>tri- (2- ethyl hexyl) -aluminum</td><td> 1</td><td> 69</td><td> 2,5</td><td> 0,902</td><td> 2,34</td><td> 1,8</td>

<td> 10</td><td>Bis- (indenyl) zirconium dichloride</td><td>8xl0 '⁴</td><td> 0,2</td><td>triisobutylaluminum</td><td> 1</td><td> 76</td><td> 4,1</td><td> 0,904</td><td> 2,45</td><td> 2,0</td>

+ slam obtained in example 7

X = the amount of n-dean that has a soluble portion in it (%)

The present invention aims to solve the problems raised by the known processes, namely to provide olefin polymerization catalysts that can give olefinic polymers having a distribution in 5 molecular weights close when it is intended to obtain homopolymers of the olefins, a close distribution of the composition is obtained copolymers of two or more 10 olefins and more, catalysts that exhibit improved polymerization activities and when the amounts of aluminoxanes used are small and can easily give olefinic polymers having a high molecular weight.

The process according to the present invention provides a process for the polymerization of olefins, using olefin polymerization catalysts, of the type 20 mentioned above.

A first olefin polymerization catalyst according to the present invention consists of: A) a transition metal compound belonging to group IV of the periodic table and elements; B) an aluminoxan; C) water.

A second olefin polymerization catalyst according to the present invention is typically characterized by:

A) a compound of a transition metal belonging to the IVB group of the periodic table of the elements; B) an aluminoxan; C) water and D) an organo-aluminum compound.

A first process for the polymerization of olefins, according to the present invention, has its characteristics in that the olefins are polymerized or copolymerized in the presence of a catalyst consisting of:

A) a compound belonging to a transition metal in group IVB of the periodic table of elements; B) an aluminoxan, and C) water.

A second process of polymerization of olefins, according to the present invention, has its characteristics in that the olefins are polymerized or copolymerized in the presence of a catalyst consisting of:

A) a compound of a transition metal belonging to group IV B of the periodic table of the elements.

B) an aluminoxan; C) water and D) an organo-aluminum compound.

The olefin polymerization catalysts according to the present invention and the olefin polymerization processes according to the present invention and the olefin polymerization processes using said olefin polymerization catalysts are illustrated and illustrated in detail below.

In the description of the present invention, the term polymerization is sometimes used in the sense that it includes not only homopolymerization but also copolymerization and also the term polymer is sometimes used in the sense that it includes not only homopolymers but also copolymers.

The first olefin polymerization catalysts of the present invention which consists of three catalytic components (A), (B) and (C) as shown above, is further illustrated in detail.

The catalytic component (A) used in the olefin polymerization catalyst according to the process of the present invention is a component belonging to a transition metal in the IVB group of the periodic table of elements and selected from the group consisting of titanium, zirconium, and hafnium in compact mass. Of the transition metals used in the catalytic component (A), preferred are titanium and zirconium, preferably zirconium.

As a transition metal compound belonging to the IVB group of the periodic table of elements used in the catalytic component (A), the zirconium compound preferably containing a group having ligand π-conjugated electrons can preferably be mentioned.

Examples of zirconium compound containing a group having π-conjugated electrons as ligands may be cited as those of the compounds represented by the following general formula I:

R, R_;²R "³R ,,⁴Zr (I) wherein R¹ is a cycloalkadienyl group R², R³ and R⁴ are individually cycloalkadienyl group, aryl group, alkyl group, aralkyl group, halogen or hydrogen atom, k is greater than 1, and K + l + m + l + n is 4.

Examples of the cycloalkadienyl group are cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, pentamethylc herein open 14 tadienyl, indenyl, and tetrahydroindenyl. Examples of alkyl groups representing R², R³ and R⁴ they are methyl, ethyl, propyl, isopropyl and butyl groups. Examples of aryl groups are phenyl groups and foils. Examples of aralkyl groups are the groups, for example, benzyl, neophenyl. Halogen atoms may include, for example, fluorine, chlorine and bromine.

Examples of a zirconium compound containing a group having π electrons conjugated as a ligand may be: his- (cyclopentadienyl) zirconium monohydrate monohydrate; hzs- (cyclopenta dienyl) -circonium monohydrate monohydrate; bzs- (cyclopentadienyl) -methylcirconium hydride; bis ((opentadienyl) -ethylcirconia) hydride; his- (cyclopentadienyl) -phenyl zirconium hydride; bis (cyclopentadienyl) -phenyl zirconium hydride; hydride hzs^,- (cyclopentadienyl) -benzyl zirconium, h / s-cyclopentadienyl) -neopentylcirconium hydride; hzs- (methylcyclopentadienyl) -monoclor hydride; bis- (indenyl) zirconium moiioclura monohydrate; hzs- (cyclopentadienyl)-zirconium dichloride; hz's- (cyclopentadienyl) -circone dibromide, hz5- (cyclopentadienyl) -methylcircone monochloride, hzs- (cyclopentadienyl) -ethylcircone monochloride; &amp; lt; (cyclopentadienyl-cyclohexyl zirconium monochloride; bis (cyclopentadienyl) -phenyl-zirconium monochloride; to- (cyclopentadienyl) -benzyl zirconium monochloride; bzs- (methylcyclopentandienyl) zirconium dichloride; hz - (5-butylcyclopentadienyl) -circonia dichloride; &amp; zs- (pentamethylcyclopentadienyl) -circonium dichloride; bis- (indenyl) -circonium dichloride; Z? Zs- (indenyl) -circone dibromide; hzs- (cyclopentadienyl) "zirconium methyl, bzs- (cyclopentadienyl) -circonium diphenyl; hz \ - (cyclopentadiphenyl) zirconium dibenzyl.

Further, the zirconium compound used as catalytic component (A) for olefin polymerization according to the present invention may include zirconium compounds as ligands, a multidentate compound wherein at least two groups selected from the group consisting of an indenyl group, a substituted indenyl group and an indenyl group, a substituted indenyl group and partial hydrides thereof are linked to one another by the lower alkylene group.

Examples of such zirconium compounds as mentioned above are: ethylene- / ns- (indenyl) -dimethyl zirconium; Ws ethylene (indenyl) diethyl zirconium; ethylene bis (indenyl) -phenyl zirconium; ethylene-bzs- (indenyl) -methylcirconium monochloride; ethylbenzo- (indenyl) -ethylcirconium monochloride, ethylenbis- (indenyl) m ethylcirconium monobromide, ethylene benzene ((indenyl) -circonia dichloride, ethylene-to- (idenyl) -circone dibromide;

ethylene-bis- (4, 5, 6, 7-tetrahydro-1- (indenyl) -dimethyl-zirconium; ethylene-bis- (4_t. 5, 6, 7-tetrahydro-1-indenyl) -methyl-zirconium monochloride; ethylene-Zus- (4, 5, 6, 7-tetrahydro-1- (indenyl) -circonium dichloride; ethylene-άύ - (4, 5, 6, 7-tetrahydro-1- (indenyl) -circonium bromide; ethylene- Zs- (4-methyl-1-indenyl) -circonium dichloride; ethylene-b / s- (5-methyl-1 (indenyl) -circonium dichloride; ethylene-1'-x (6-methyl-1-indenyl) - chloride zirconium; ethylene-bzs- (7-methyl-1-indenyl) -circonium dichloride; ethylene-his^,- (5-methoxy-1-indenyl) zirconium dichloride; ethylene-Z? - (2,3-dimethyl-1-indenyl) -circonium dichloride, ethylene-hh '- (4,7-dimethyl-1-indenyl) -circonia dichloride and ethylene-hz'v- (4, 7-dimethoxy-1-indenyl) -circonium dichloride.

Further, such transition metal compounds may be used to those obtained by substituting zirconium metal from the abovementioned zirconium compounds with titanium or hafnium metal.

The catalytic component (B) used in the olefin polymerization catalyst according to the present invention is an aluminoxane. The aluminoxane used may be an organo-aluminum compound represented by the general formula II or III:

R₂Al - (- OAl-), „-OA1R₂... (II).

R (III) r

In aluminoxanes of general formula H or III, R is a hydrocarbon group such as methyl, ethyl, propyl, or butyl, preferably methyl or ethyl, preferred being

<img file="RO103648B1_D0001.tif" />

methyl group, and m is an integer of at least 2, preferably from 5 to 40. This aluminoxane is illustrated above and may be formed by the aluminum alkoxy units 5 comprising the alkyloxyaluminum unit of formula - (OA1) - and a alkyloxy unit^Rand aluminum of formula - (OA1) - wherein R_x and 10. |^R2

R₂ they may be represented by the same hydrocarbon radical as R of formula II or III and may be represented by different (radical) groups of 15 hydrocarbons. In this case the preferred aluminoxanes are those formed from mixed aluminoalkyloxy units containing at least 30% molar preferably at least 70 molar units of methyloxialuminum units - (OA1) -.

| ch₃

Aluminoxane as mentioned above can be prepared for example by the following methods:

(1) A method comprising reacting a suspension of a compound containing absorbent water or a salt containing crystallizing water, such as, for example, magnesium chloride hydrate, 30 copper and aluminum sulfate hydrate, hydrated nickel sulfate or chloride hydrate of cerium, in hydrocarbon medium with a trialkylammonium.

(2) A method comprising reacting direct trialkylaluminium with water in medium 35 such as benzene, toluene, ethyl ether or tetrahydrofuran.

Of the above-mentioned methods the method is preferred (1). The aluminoxanes prepared by these methods may contain small amounts of 40 organomethyl compounds.

The catalytic component (C) used in the olefin polymerization catalyst according to the present invention is water and the water may, for example, be dissolved or dispersed water in such polymerization solvents as will be mentioned later, or the water contained in the compounds or salts. used in the preparation of the catalytic component (B).

In the manner thus described, the first catalytic polymerization of the olefin polymerization according to the present invention consists of (A) a transition metal compound belonging to group IV B of the periodic table of elements, (B) an aluminoxane and (C) water. The catalyst of this type can be. prepared by the process comprising mixing components (A), (B) and (C) together, simultaneously, in hydrocarbon or olefin medium, or by a process which first comprises mixing the catalytic components together to prepare a mixture and then mixing of this mixture with the remaining catalytic component of the catalyst composition. In the preparation of the mixture of two catalytic components, it is first preferable to mix the catalytic component (B) with the catalytic component (C).

At the preliminary mixing of the catalytic component (B) with the catalytic component (C) a concentration of aluminoxane in terms of aluminum atom is usually 5 x 10 '⁴ at 3 g atom / 1, preferably 1 x IO '³ at 2 g atom / 1, and the water concentration is usually 2.5 x IO '⁵ at 2 moles / 1, preferably 5 x IO '⁵ at 1.5 moles / 1. The molar ratio of mixing of the aluminum atom to water (A1 / H₂O) is 0.5 to 50, preferably 1 to 40. The temperature at which the preliminary mixing is performed is usually -50 ° to + 100 ° C, and the mixing time is usually from 0.1 min to 200 h.

The atomic ratio of the transition metal constituting the catalytic component (A) to aluminum constituting the aluminoxane (Al / transition metal) is usually 20 to 1 x IO⁴ , preferably 50 to 5 x 10³, a concentration of the transition metal is usually 1 x 10 '⁸ 1.5 x 10 '¹ atom g / l, preferably lx IO '⁷ 1 x 10 '¹ g / l atom, and the concentration of the aluminum atom is usually 5 x 10^s at 3 g / l atom, preferably 1 x IO '⁴ the 2 g atom / 1. When mixing the preliminary mix of the catalytic components (B) and (C) with the catalytic component (A), the temperature used is usually from -50 ° C to 200 ° C, and the mixing time is usually 0.1 min to 50 h. .

The second olefin polymerization catalyst according to the present invention is illustrated below. This olefin polymerization catalyst consists of (D) and the additional organo-aluminum compound in (A) the transition metal compound belonging to the metal in group IVB of the periodic table of elements, (B) aluminoxane and (C) water as mentioned above. .

Usually the organo-aluminum compounds as mentioned above are concretely represented as shown below.

Trialkylaluminum compounds such as trimethylaluminium triethylaluminium, triisoproilaluminum, triisobutylaluminum, trz-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri2-methylpental aluminum, trz-3-methylpentylaluminum, trzyl-4-methyl-aluminum -methylhexylaluminum, trioxylaluminium etc., tricycloalkylaluminum compounds such as tricyclohexylaluminum and triarylaluminum compounds such as triphenylaluminum, tritolylaluminum etc. or alkenylaluminum compounds, such as isoprenylaluminum.

Dialkylaluminium hydrides can be diisobutylaluminium hydride, alkylaluminium alkoxides, such as isobutylaluminium methoxide, isobutylaluminium ethoxide, isobutylaluminium isopropoxide, etc. and dialkylaluminium halides such as dimethylaluminium chloride, diethylaluminium chloride, diisopropylaluminium chloride, diisobutylaluminium chloride, dimethylaluminium bromide etc.

Alkylaluminium sesquhalogens may be methylaluminium sesquichloride, ethylaluminium sesquichloride, isopropylaluminium sesquichloride, isobutylaluminium sesquichloride, ethylaluminium sesquichloride etc.

Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, isobutylaluminum, dichloride, ethylaluminum dibromide etc.

Of the aforementioned organoaluminum compounds, the preferred are the trialkylaluminum compounds, and additionally the trialkylaluminum compounds having a n-alkyl hydrocarbon group. Specifically preferred are compounds: triisopropylaluminum, triisobutyl aluminum, trz-2-methylbutylaluminum, tri-3-methylbutylaluminum, irz-2-methylpentylaluminum, trz-3-methylpentylaluminum, r / 'z-4-methylpentylaluminum, tri-2-methyl, tri-2-methyl -3-methylhexylaluminum and trz-2-ethylenexylaluminum.

Moreover, such compounds as those of which the above-mentioned organometallic compounds are formed in the polymerization system, for example, halogenated aluminum and lithium alkyl, or halogenated aluminum and alkylmagnesium, can also be used as a catalytic component (D).

The catalyst of this type can be prepared by a process comprising simultaneously mixing all the catalytic components (A), (B), (C) and (D) in hydrocarbon or olefin medium, a process comprising the preliminary mixing of two components. catalysts for the preparation of a mixture and then mixing the remaining part of the other two catalytic components, or a process comprising the preliminary mixing of three catalytic components for preparing a mixture and then mixing the part comprises the preliminary mixing of three catalytic components for preparing a mixture and then mixing it with the remaining part of a catalytic component. In these cases, the preliminary mixing of the catalytic component (B) with the catalytic component (C) is preferred.

In the same manner as in the above mentioned case for the first catalyst for the olefin polymerization according to the present invention, a concentration of aluminoxane in an aluminum atom is used in the preliminary mixing of the catalytic components, preferably 1 x IO '.⁷ the 1 x 10³ g / 1 atom and the catalytic component (B) present in the polymerization system are used. In such amount, that aluminum atoms resulting from said catalytic component (B) in the polymerization system are less than. 3 mg atom / 1 preferably 0.01-2 mg atom / 1 and more preferably 0.02lmg atom / 1.

The above-mentioned olefin polymerization catalysts can also be used as solid catalysts by depositing catalytic components on inorganic compounds such as silica and alumina or organic compounds such as polyethylene, polypropylene and polystyrene.

The olefin polymerization catalysts of the present invention as illustrated above are used in the preparation of olefin polymers. The olefins that can be polymerized by using the plomerization catalysts of the present invention include ethylene and alpha olefins with 3 to 20 carbon atoms, for example, propylene, 1-butene, 1-pentene, 1-hexane, 4-methyl-1-pentene, 1. -th octave, k-decade, 1-twelfth, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-elcoena. If necessary, pollen such as diene can be copolymerized with the aforementioned olefins. The polymerization reaction of the olefins using the catalysts of the process according to the present invention is usually carried out in the gas phase or in the liquid phase, for example, in solution. When the polymerization reaction is carried out in the liquid phase, an inert hydrocarbon may be used as the solvent, or the olefin itself may be used as the solvent.

Hydrocarbons used as solvents in the above polymerization reaction include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane, alicyclic hydrocarbons and cyclopentane, cyclopentane, cyclopentane , aromatic hydrocarbons such as benzene, toluene and xylene and oil fractions such as gasoline, kerosene and light oil.

The temperature at which polymerization of the olefins using the above catalysts in the polymerization process according to the present invention is usually -50 to 200 ° C, preferably 0 ° -120 ° C. The polymerization pressure used in this case is usually from atmospheric pressure to 100 kg / cm² preferably 1 x IO '⁷ ί x 10 '³ gram atom / 1 and the catalytic component (B) present in the polymerization system is used in such an amount that the aluminum atoms resulting from said catalytic component (B) in the polymerization system are less than 3 mg / atom / 1 preferably 0, 01-2 mg atom / 1 and more preferably 0.02-1 mg atom / 1.

The above-mentioned olefin polymerization catalysts can also be used as solid catalysts by depositing catalytic components on inorganic compounds such as silica and alumina or organic compounds such as FIPS, polypropylene and polystyrene.

Catalysts in the olefin polymerization process of the present invention as illustrated above are used in the preparation of olefin polymers, Olefin which can be polymerized by using the polymerization catalysts of the present invention include ethylene and alpha olefins with 3 to 20 carbon atoms, for example , propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decade, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecena and 1eococena. If necessary, pollen such as diene can be copolymerized with the aforementioned olefins. The polymerization reaction of the olefins using the olefin polymerization catalysts of the present invention is usually carried out in the gas phase or in the liquid phase, for example, in solution. When the polymerization reaction is carried out in the liquid phase, an inert hydrocarbon may be used as the solvent, or the olefin itself may be used as the solvent.

Hydrocarbons used as solvents in the above polymerization reaction include aliphatic hydrocarbons such as butane isobutane, pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane, alicyclic hydrocarbons such as aromatic hydrocarbon, toluene and xylene and oil fractions such as gasoline, kerosene and light oil.

The temperature at which polymerization of olefins takes place, using the polymerization catalysts of the present invention, is usually -50 ... 200 ° C, preferably 0 ...

120 ° C. The polymerization pressure used in this case is usually from atmospheric pressure to 100 kgf / cm², preferably from atmospheric pressure to 50 kgf / cm² and 5 the polymerization reaction may be carried out in a block, semi-continuous or continuous manner, thereafter the reaction may be carried out in two or more steps under different reaction conditions. The molecular weight of the obtained olefin polymers 10 can be adjusted with the help of hydrogen and / or the polymerization temperature used.

In the case of polymerization of olefins by using the polymerization catalysts 15 of the present invention, high molecular weight olefinic polymers with high molecular weight distribution are obtained. In case two or more olefins are copolymerized by the use of the aforementioned polymerization catalysts, olefinic copolymers are obtained having the distribution of the near molecular weight and the distribution of the close composition and a high molecular weight. Furthermore, the 25 catalysts used in the process according to the invention have a high catalytic activity and in this way the amount of aluminoxane can be reduced.

In the text examples, the values ​​of Mw / Mn 30 were determined by the following procedure in accordance with those described in the literature (Tackeuchi, Gel Permeation Chromatography, Mazuzen. Tokyo).

(1) Using a standard polystyrene having 35 known molecular weight (a standard polystyrene, a monodisperse polystyrene) the molecular weight and gel chromatographic permeability (GPC) recorded for the sample are measured for the purpose of plotting the molecular weight calibration curve (M ) and the elution volume (EV).

The concentration of the sample used is maintained at 0.02% by weight.

(2) GP C chromatography of the sample is 45 performed by measuring GPC, and the average number of molecular weight Mn and average weight of molecular weight, in terms of polystyrene, then calculated from the above calibration curve mentioned in process (1) for getting value

Mw / Mn. in case 1 we refer to the conditions in which the sample was prepared and the conditions in which the GPC was measured are the following:

Preparation of the sample (a) The sample is placed in an Erlanayer flask together with odiclorbenzene so that the sample weighs 0.1% by weight.

(b) The Erlenmyer flask is heated to 140 ° C for 30 minutes to dissolve the sample in o-dichlorobenzene.

(c) the o-dichlorobenzene filtered solution is subjected to GPC chromatography.

/ GBC measurement conditions /

The measurements were performed under the following conditions:

(a) 150 C-ALC / GPC machine (manufactured by Waters Co.) (b) GMH column (Toyo manufactured type)¹Soda KK) (c) The sample quantity used 400 microliters (d) Temperature 140 ° C (e) Flow rate 1 ml / min. Further, the B value of the ethylene copolymer obtained according to the present invention is defined as follows:

<img file="RO103648B1_D0002.tif" />

2P₀P_d where P_E represents the molar fraction of the ethylene component in the copolymer, P_a represents the molar fraction of the componentofolefinic content contained in the copolymer, and P_OErepresents the molar fraction of alpha-olefin-ethylene chain in the total length of the chain.

The value B is an index that shows the state of the distribution of the monomers in the polymer chain, and is calculated by obtaining the above-mentioned P_E, P._a and P_OE (based on those reported by GJRay (Macromolecules, 10, 773 (1988)), JC Randall (Macromolecules, 15, 353 (1982)), J. Polymer Science, Polymer

Physics Ed., 11, 275 (1973)) and K. Kimura (Polymer, 25, 441 (1984)). The higher the value of B. mentioned above, the smaller the block chain of the copolymer, and the distribution of ethylene and alpha-olefins24 is uniform, thus indicating that the copolymer having a high value of B has a composition evenly distributed and close.

The value B is calculated by such a process as spectrum recording ¹³C-NMR of the sample obtained by the homogeneous dissolution of approximately 200 mg of copolymers in 1 ml of hexachlorobutadiene in a test tube of 0 = 10 mm, usually under conditions of temperature measurement of 120 ° C, measurement of frequency of 25.05 MHz, spectrum width of 1500 Hz, filter width of 1500 Hz, pulse repetition time of 4.2 s, pulse width of 7 microseconds, and integration time of 2000-5000 times. From this spectrum the values ​​for P are obtained_E, P._a and P_0E.

Further, the amount of n-decane soluble portion of the ethylene copolymer obtained by the present invention (the smaller the amount of n-soluble portion the closer the distribution of the copolymer composition) was measured by dissolving about 3 g of ethylene copolymer in 450 ml n-decane at 145 ° C, cooling the solution to 23 ° C, removing the insoluble portion in the n-decane by filtration, and recovering the n-decane soluble portion of the filtrate.

The present invention has the advantage of obtaining a polymer of high molecular weight, having a narrow distribution of molecular weight.

claims