Catalyst and method for (co)polymerization of alpha-olefins

 

(57) Abstract:

The catalyst for polymerization of alpha-olefins contains (a) bis(cyclopentadienyl bis-amide)-derived element of group IVB of the Periodic table of the elements of the formula I:

in which M represents a metal of group IVB; R1, R2, R3and R4- C1-4alkyl and Cp have the meanings indicated in the description, and b) luminosity socialization. The specified catalyst exhibits high catalytic activity in the polymerization and copolymerization of ethylene and alpha-olefins. 2 S. and 4 C.p. f-crystals.

The invention concerns a catalyst derived from bis(cyclopentadienyl)bis(amide)-derived element of group IVB of the Periodic system of elements and iluminating co-catalyst, and its use for the (co)polymerization of ethylene and other alpha-olefins.

It is known that ethylene or even alpha-olefins can be polimerizuet in the process at low pressure using a catalyst of the Ziegler-Natta.

The catalysts used for these purposes, usually obtained from the compound of the transition metal elements of groups IV-VIII of the Periodic table of the elements), in a mixture with the ORGANOMETALLIC compound and the I or diluent. Cm. the work of J. Boor. The catalysts of the Ziegler-Natta and polymerization, Academic Press, new York (1979).

A special class of catalysts active for the polymerization, is a combination iluminacin with cyclopentadienyl derivative of such a metal, such as titanium, zirconium and hafnium (group IVB), which is referred to also as "metallocene", and corresponds to the following formula

< / BR>
in which

M represents a metal of group IVB of the Periodic table of elements, each R represents a halogen atom, an alkyl or aryl group and each Cf represents independently from each other cyclopentadienyl-, indenyl or fluorenyl group. In this regard, see H. Sinn, W. Kaminsky Adv. Were obtained. Chem. 18, 99 /1980/ and U.S. patent N 4.542.199.

Such catalysts reveal a high catalytic activity with obtaining polymers with desired properties, which are caused, in particular, used catalytic composition and the olefin or mixture of olefins which undergo polymerization. Cm. for example, the U.S. patents NN 4.530.914, 4.935.474, 4.937.299 and 5.001.205 and European patent application NN 35.242, 318.049, 384.17 and 387.609.

Was established in accordance with the invention that the joint isponre, exhibit high catalytic activity in the polymerization of olefins.

Therefore, the aim of the present invention is the development of a catalyst for the polymerization process, derived from metallocene containing a substituted amide group, and iluminacin.

In addition, the subject invention includes the development of the method of (co)polymerization of ethylene and other alpha-olefins using this catalyst.

Thus, the present invention relates primarily to a catalyst for polymerization or copolymerization of ethylene and other alpha-olefins, containing a) a bis(cyclopentadienyl)bis(amido)derived element of group IVB of the Periodic table of elements corresponding to the formula

< / BR>
in which

M represents a metal of group IVB of the Periodic table of elements;

R1, R2, R3and R4are each independently from each other alkyl group with 1-8 C-atoms, cycloalkyl group with 5 to 8 C-atoms or phenyl group, and

and each Cp independently represents a cyclopentadienyl-, indenyl or fluorenyl group, which may contain one or more C1-4alkylsulfate,

the specified Cp-tructure and b) luminosity socializaton.

In particular, in the formula (1) metal M should be chosen from the group of titanium, zirconium and hafnium, and the most appropriate should be considered zirconium and hafnium.

Preferably, if R1, R2, R3and R4in the formula (1) independently from each other represent an alkyl group with 1-4 C-atoms and optimally if all the radicals R1, R2, R3and R4represent ethyl.

In the formula (1) Cp is preferably selected from the group: cyclopentadienyl, indenyl and fluorenyl, which can be substituted or containing one or more C1-4-deputies. If both Cp groups in the compound (1) are connected to each other by bridge structures, it is preferable if these bridge structures formed from linear or branched, alkylene groups with 1-4 C atoms, or represent dialkylzinc and, more preferably, dimethylsilane group. The examples of the United bridging ties Cp-groups can be considered as bis(cyclopentadienyl)ethylene, bis(indenyl)ethylene (cyclopentadienyl-1-fluorenyl)and isopropyl bis(cyclopentadienyl)dimethylsilane.

Examples of compounds of formula (1) include: bis(cyclopentadienyl)bis(etelemed)zirconium, is elemid)hafnium and isopropyl(cyclopentadienyl-fluorenyl)bis(etelemed)hafnium.

In the catalysts intended for the production of polyolefins with a wide molecular weight distribution, you can use the compound (1) containing two metal M, which differ from each other.

Connection (1), in which both Cp-radical represent a cyclopentadienyl group, and all radicals R1, R2, R3and R4represent ethyl, can be obtained in accordance with data described G. Chandra and M. F. Zapper in J. Am. Soc. (A), 1968, p. 1940.

In accordance with the present invention in combination with the above-described compound (1) as socializaton used iluminacin.

As you know, iluminacin are compounds having Al-O-Al-due to the different ratio of O:Al, which can be obtained by the reaction of alkylamine or alkylhalogenide in controlled conditions with water, and in the case of trimethylaluminum with a hydrate, such as uranyl aluminium sulfate pentahydrate of copper sulfate and iron sulfate pentahydrate. In particular, this invention the catalyst specified iluminacin the compound (1) contained in such proportions that the atomic ratio of aluminum contained in luminescene, to the metal of group IVB, the ptx2">

The catalytic system according to the invention is used for polymerization of ethylene with obtaining linear polyethylene, as well as for the polymerization of propylene or higher alpha-olefins with getting atactic, syndiotactic or isotactic polymers, due, in particular, the catalytic composition and the specific conditions of polymerization. The catalytic system also catalyze the copolymerization of ethylene with propylene and/or other olefins (formation of linear low density polyethylene) and terpolymerization ethylene, propylene and diene (triple polymerization).

The polymerization can be performed using a slurry method in an inert diluent, or in gas phase at temperatures from 20 to 120oC under a pressure of from 1 to 300 bar, when using the means of regulating the molecular weight, such as hydrogen.

For a clearer illustration of the invention, the following examples of its implementation.

Example 1. In an autoclave of 5 l stainless steel type Bringnole, equipped with a magnetic anchor stirrer, under the control of the temperature by means of electric resistors upload:

n-hexane (purity for polymerizat homemage methylalumoxane in 10% toluene (by weight) 40 ml

the molecular weight regulator (H2) 0,5 bar

ethylene 14,43 bar

The polymerization is carried out at an atomic ratio of Al : Zr equal to 2,500 : 1, with a total pressure of 15 bar and a temperature of 70oC. the duration of the polymerization process 1 h under such conditions get 0,258 kg polyethylene, which corresponds to a yield of 34.4 kg of polymer product per gram of catalyst and accordingly 138 kg of polymer per gram of zirconium in the catalyst.

Example 2. Ethylene will polimerizuet in accordance with the method described in example 1, using the following modification of the catalyst:

the catalyst Cp2Zr[N(C2H5)2]20,00191 g

socialization (solution oligomeric methylalumoxane in 10% toluene (by weight) of 8.7 ml

The polymerization is carried out at an atomic ratio of Al:Zr = 2,500:1. The duration of polymerization for 1.5 hours under such conditions get 0,1625 kg of polyethylene with the release of 85 kg of polymer product per gram of catalyst, which corresponds to 341 kg of polymer product per gram of zirconium in the catalyst.

Example 3. Ethylene will polimerizuet by the above method (see example 1/, using the following modification of the catalyst:

the catalyst Cp2Zr[N(C2H) 11 ml

The polymerization is carried out at an atomic ratio of Al:Zr = 2,500:1. the duration of polymerization is 1.16 hours In such conditions get 0,198 kg of polyethylene with a yield of 99 kg of polymer product per gram of catalyst, which corresponds to 398 kg of polymer product per gram of zirconium in the catalyst.

The resulting polyethylene has a melt flow index (ASTM 1238 (E) (1.78 g/10 min.

Example 4. Ethylene polimerizuet in the same reactor as in example 1 under the following conditions:

hexane /purity for polymerization/ 1,900 ml

the catalyst Cp2Zr[N(C2H5)2]20.001 g

socialization /solution oligomeric methylalumoxane in 10% toluene (by weight) of 5.1 ml

the molecular weight regulator (H2) 0,5 bar

ethylene 14,5 bar

The polymerization is carried out at an atomic ratio of Al:Zr = 2,500:1 with a total pressure of 15 bar at a temperature of 70oC for 1.5 h under these conditions receive 0,166 kg of polyethylene with exit 166 kg of polymer product per gram of catalyst, which corresponds 664 kg of polymer product per gram of zirconium in the catalyst.

Thus obtained polyethylene has the following characteristics:

flow index BR> density /23oC/ 0,9630 g/ml

Example 5. Ethylene will polimerizuet in the same reactor as in example 1 under the following conditions:

n-hexane /purity for polymerization/ 1,900 ml

the catalyst Cp2Zr[N(C2H5)2]20,0007 g

socialization /solution oligomeric methylalumoxane in 10% toluene (by weight) of 3.8 ml

the molecular weight regulator (H2) 0,5 bar

ethylene 14,5 bar

The polymerization is carried out at an atomic ratio of Al:Zr = 2,500:1 with a total pressure of 15 bar and a temperature of 40oC for 1.5 hours under such conditions get 0,166 kg of polyethylene with the release of 33 kg of polymer product per gram of catalyst, which corresponds to 132 kg of polymer product per gram of zirconium in the catalyst.

The resulting polyethylene has the following characteristics:

the melt flow index /ASTM D 1238 E/ 6,01 g/10 min

the melt flow index /ASTM D 1238 F/ 162,9 g/10 min

sensitivity to slice 27,1

Example 6. Ethylene will polimerizuet in the same reactor as in example 1 under the following conditions:

hexane (purity for polymerization) 1,900 ml

the catalyst Cp2[N(C2H5)2]20,0007 g

socialization /solution oligomeric methylalumoxane is merisalu carried out in the atomic ratio of Al:Zr = 2500:1 with a total pressure of 15 bar and a temperature of 120oC for 1.5 hours under such conditions get 0.0333 kg of polyethylene with the release of 48 kg of polymer product per gram of catalyst, which corresponds to 191 kg of polymer product per gram of zirconium in the catalyst.

Thus obtained polyethylene has the following characteristics:

the melt flow index (ASTM D 1238 (E) of 4.12 g/10 min

the melt flow index (ASTM D 1238 (F) of 72.3 g/10 min

sensitivity to slice 17,6

density (23oC) 0,9517 g/ml

1. The catalyst for polymerization of alpha-olefins, in particular ethylene, characterized in that it contains a) bis-(cyclopentadienyl)-bis(amide)-derived element of group IVB of the Periodic system of the elements of the General formula I

< / BR>
in which M represents a metal selected from zirconium and hafnium;

R1, R2, R3and R4- each represent an alkyl group with 1 to 4 C-atoms,

and each Cp independently represents a cyclopentadienyl-, indenyl or fluorenyl, which may contain one or more C1-4-alkyl substituents,

moreover, these Cp-groups can be linked together using bridge structures C-atoms or alkylsilane structures is UB>, R3and R4in formula I are each independently ethyl group.

3. The catalyst p. 1, characterized in that the Deputy Cp in the formula I has the following values: cyclopentadienyl-, indenyl and fluorenyl group which may be unsubstituted or may contain one or more C1-4is an alkyl substituent, or both Cp groups may together represent a bis(cyclopentadienyl)ethylene, bis(indenyl)ethylene (cyclopentadienyl-1-fluorenyl)and isopropyl bis(cyclopentadienyl)dimethylsilane group.

4. The catalyst p. 1, characterized in that the said compound I is chosen from the group of bis(cyclopentadienyl)bis(ethylamino)zirconium, bis(cyclopentadienyl)bis(ethylamino) hafnium, ethylene-bis(indenyl)bis(ethylamino)zirconium, ethylene(bis)indenyl)bis(etelemed)hafnium and isopropyl(cyclopentadienyl-fluorenyl)bis(ethylamino)hafnium.

5. The catalyst p. 1, characterized in that the atomic ratio contained in socializaton b) aluminum contained in the connection I metal, group IVB, is from 10 : 1 to 108: 1, preferably from 102: 1 to 104: 1.

6. The method of (co)polymerization of alpha-olefins, particularly ethylene, with ispolzovanije: (a) a bis-(cyclopentadienyl)-bis(amide)-derived element of group IVB of the Periodic system of the elements of the General formula I

< / BR>
where M is a metal selected from zirconium and hafnium;

Cp, R1, R2, R3and R4have the values listed in paragraph 1,

and b) luminosity socialization.

 

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