Catalyst and method for the polymerization of olefins

 

(57) Abstract:

The invention relates to a catalyst intended for use in polymerization by Ziegler and containing ORGANOMETALLIC compound and complex (transition metalloidal). The complex contains at least one aminogroup associated with the transition metal, and allgroups the complex is o, O-disubstituted phenyl group. The invention also relates to a method of polymerization of olefin according to Ziegler, namely, that the olefins are subjected to polymerization in the presence of the above catalyst. There is a high catalytic activity output for diarylamino-ligand compared to dialkylamide-ligand or alkylsilane-ligand. Increased activity of the catalyst causes a corresponding and proportional decrease in the concentration of the transition metal in the resulting polymer. 2 S. and 11 C. p. F.-ly, 1 table.

The invention relates to a catalyst which is suitable for the method for polymerization of olefins according to Ziegler and contains the ORGANOMETALLIC compound and complex (transition metal-aminoaryl).

From patent US-A-5086023 known catalyst, which is applicable to floor the ü catalyst contains a complex of vanadium trichloride - kidomaru - toluene).

The disadvantage of such a catalyst for polymerization of olefins according to Ziegler is that its activity is low (approximately 3 times lower than existing catalysts, as can be seen from the results of experiments with the same catalyst, presented in the patent US-A-5086023.

According to the invention with the new catalyst obtained significantly higher yield of polymer relative to the amount of the transition metal.

The catalyst according to the invention differs from the known fact that the complex (transition metal - aminoaryl) contains at least one aminogroup associated with the transition metal, and aryl group in the complex is o,O-disubstituted phenyl group.

Under aminogroups here refers to a group which is derived from the amine separation of a hydrogen atom; in the context of the invention aminogroups is a nitrogen-containing group in which the nitrogen atom is connected by a simple relationship with the transition metal.

Unexpectedly, it was found that due to the combination associated with transition metal aminogroup, imido, O-substituted phenyl group is unique is active in the beginning but also has a much more constant activity profile. The activity profile is changed from type "collapse" to "active for a long period of time". Thanks to the inclusion of specific groups that are not currently described in the literature, obtained catalysts, which has a catalytic activity that is significantly different from the behavior of transition metal compounds, which are still widely used in the Ziegler reaction. This is evident, for example, from differences in the outputs (per unit transition metal), various configurations of polymers and differences in the percentage of comonomers, when multiple olefins, so that should be the conclusion about the presence of different catalytic center.

The above high activity is not achieved, if instead of aminogroup in complex with a transition metal are connected alkoxide and halogen groups.

The above stability of the catalyst is not achieved, if the aryl group amido-aryl complex differs from that of the group according to the invention, namely, O-disubstituted phenyl group. In particular, this applies to the case of using complex (trichlorosilane in the complex has the General formula-NR1R2where R1and R2independently from each other, independently from each other represent an alkyl group, alkenyl group, aryl group, the silicon-containing hydrocarbonyl group, and each group contains 1 to 20 carbon atoms.

Here and further in this complex transition metal - aminoaryl) refers to a group of compounds having the following General formula 1

R-N=M-XnYm(NR1R2)p< / BR>
where

R-o,O - disubstituted phenyl group;

M is a transition metal of groups 3 to 6;

X is halogen;

Y - alkoxy group, aryloxy group, amide group or silicon-containing hydrocarbon-group or different ligand group, described below.

R1and/or R2-alkyl-group, alkenyl group, aryl group or silicon-containing hydrocarbon group,

n= 0-2, m= 0-2, p=1-3 [depending on the valence of R-N=M-group, i.e. n+m+p=(valence of M-2)].

R-N=-aminoaryl-ligand.

Separate groups of the complex are discussed below.

Aryl group (P in formula 1) is o,O-substituted phenyl group, which optionally can also be substituted in the meta - and para-position. Substituents present in o-(ortho)-put doctitle are substituents, having 1 to 8 C-atoms, such as methyl, ethyl, isopropyl and isobutyl. More preferably, the Deputy is methyl or isopropyl group. The respective substituents in the meta - and para-positions of the R groups may be alkyl, aralkyl, alkoxide, aryloxy, halogen, amino, nitro, thiol and carboxyl. These and other substituents are known in the art, and their suitability can be determined in a simple way.

The transition metal complex (M in General formula 1) is selected from groups 3 to 6 of the periodic system of elements (including a new list of IUPAC, as shown in the liner Handbook of Chemistry, 70 th Edt, 1989-90).

Preferably, the transition metal is selected from the group consisting of Ti, Zr, V, Nb, Cr and Mo. More preferably, the transition metal is Ti or V. To obtain an amorphous copolymers are most preferred is the use of vanadium as a transition metal.

Aminogroup in the catalyst and, in particular, -NR1R2the group is at least only (p= 1 in General formula 1), but the presence of several aminogroup is also acceptable. In aminogroup R1group and R2group, independently from each other represent an alkyl group, alkenyl-g 1 - 20 C-atoms. Preferably, the alkyl - or alkenyl-group contains 1 to 8 C-atoms; the aryl group preferably contains 6 to 15 C-atoms.

As the alkyl group can be mentioned, for example, methyl, ethyl, propyl, isopropyl and higher homologues. As alkenyl groups can be specified, for example, vinyl, 1-propenyl, allyl and 1,3-butadienyl. As the aryl group can be mentioned, for example, tolyl, phenyl and Naftali. Preferred is the use of phenyl groups. As the silicon-containing hydrocarbonyl group can be specified trimethylsilyl, triethylsilyl, dimethylethylene and similar groups. Alkyl-, alkenyl-, aryl - or silicon-containing hydrocarbonyl-groups may also contain substituents, such as aryl or alkyl group, an alkoxide, aryloxy-, halogen-, amino-, nitro-, thiol - or carboxyl group.

Preferably, R1and R2are the aryl group and more preferably R1and R2are phenyl group.

Aminogroup may also be heterocyclic system such as imidazole group, carbazole group or piperidino group.

Also with the transition metal may be associated with one or two ATO is CLASS="ptx2">

Preferably, the complex contains at least one halogen, more preferably at least one atom of chlorine, which is associated with a transition metal (i.e., n1). Also suitable are mixtures of the above halogen-free.

In the above General formula IV may be selected from the group consisting of alkoxide, aryloxy, amine, amide, S - or P - connection, cyclopentadienyl or a silicon-containing hydrocarbonsoluble, and mixtures are also possible.

Complexes of transition metal - aminoaryl, especially in the form of canadianization complexes, known as such: see, for example, D. D. DeVore fabric et al.,in J. Am. Chev. Soc., Vol. 109/24/, pp. 7408-16 (1987).

This article also shows how can be obtained complexes containing vanadium as the transition metal. As examples there may be mentioned the reaction of VOCl3with para-substituted arylisocyanate. To obtain complexes based on other transition metals in the literature there are special methods of preparation. Reference may be made to the article W. A. Nugent and B. L. Haymore in Coord. Chem. Rev. 31(1990), pp.123-175.

Amigaremix according to the invention can be obtained in several ways. Can be used, for example, shadowdale and amidon alkali metal (Me-NR1R2where Me means, for example, Li, Ne, or),

b) aminogroup obtained by reaction of midorigaoka transition metal with an amine in the presence of halogen-trap (for example, the base Lewis such as triethylamine),

c) as linked above, by reacting a substituted amine, and the Deputy is easy tsepliaeva group, such as trimethylamine.

Therefore, several ways of synthesis are available and known to experts.

The catalyst also contains an ORGANOMETALLIC compound of groups 1,2,12 or 13 as socializaton (also according to the new IUPAC-list). At least one hydrocarbon group is bonded directly to the metal atom through a carbon atom.

Compounds of Na, Li, Zn, Mg and especially Al can be specified as compounds of such metals, in which at least one hydrocarbon group is bonded directly to the metal ion via a carbon atom. Hydrocarbon group that is associated with the metal atom in these compounds, preferably containing 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Examples of appropriate compounds are aminotri, utility, dieters is of trialkylamine (such as triethylaluminium), hydrides alkylamine (such as hydride diisobutylaluminum), compounds alkylalkoxysilane and halogenated aluminum compounds (such as diethylaluminium, diisobutylaluminium, monoethylglycinexylidide and ethylaminoethanol). Can also be used mixtures of such compounds.

The molar ratio of ORGANOMETALLIC compound and complex transition metal may vary in a wide interval. Basically, this ratio lies between 1:1 and 1500:1. Preferably, it is selected between 2:1 and 300:1, more preferably between 3:1 and 50:1.

The catalyst may be introduced into the polymerization reactor in the form of a solution (in this case, preferably, is selected solvent or dispersing agent, which is also used in the corresponding liquid-phase polymerization), and with at least one of the components, which is used as the carrier. Several methods for the implementation of the latter case is known in themselves for professionals. As the carrier can be used, for example, silica, alumina, zeolite, MgCl2and so on, This so-called heterogenization catalyst makes Cosmonautilor in several ways, to make it more suitable for the production of polyolefins by polymerization by Ziegler.

For example, the catalyst may also contain a promoter that is a compound that improves the yield of polymer on the catalyst. Particularly suitable promoters are halogenated compounds. Preference is given to using as promoters for obtaining copolymers of ethylene special connections with a low content of halogen so as to avoid too high a concentration of the halogen in the resulting polymer. Essentially and preferably these compounds contain the largest 2 of the halogen atom in the molecule, for example, alkyl - or alkoxyalkyl - esters of phenyl mono-or diplodocuses acid. For these and other relevant promoters reference may be made to U.S. patent US-A-4435552.

The catalyst according to the invention can also contain a Lewis acid. This acid is able to increase the activity of the catalyst according to the invention. Examples of appropriate Lewis acids include, but are not limited to) AlCl3, AlBr3, GaCl3, Gabr data member3, BCl3or SiCl4.

Another possibility is that predlagaemym catalytic effect. Examples of Lewis bases include, but are not limited to esters, ethers, ketones, alcohols, amines, etc.

Another possibility influence on the catalytic activity is the (partial) replacement of the halogen group (or groups) X complex transition metal - aminoaryl on various ligands (i.e., Y is a group of General formula 1). Examples of such ligands include, but are not limited to):

alkoxygroup,

alloctype,

the amino group or amide group,

S - connection (such as, for example, sulfide, sulfite, sulfate, Teesport, sulfinate),

P connection (such as, for example, phosphine, postit, phosphate),

cyclopentadienyl, substituted or unsubstituted,

silicon hydrocarbon connection.

The above modifications can be applied to the catalyst or they may be made in the polymerization process using known methods.

The invention relates also to a method in which the catalyst according to the invention is used to obtain a polyolefin by polymerization by Ziegler, in particular, polymer-based olefin selected from the group consisting of-olefins, the olefins with nekozumi dvoje relates to a method for the polymerization of olefins. Alpha-olefins, preferably selected from the group containing ethylene, propylene, butylene, Panten, hapten and octene; can also be used mixtures thereof. More preferably, the olefin is ethylene and/or propylene. The use of such olefins leads to the formation of crystalline homopolymers and copolymers of polyethylene, both high and low-density (HDPE, LDPE, LLDPE and so on) and homopolymers and copolymers of polypropylene and EPS). Required for such products, monomers and methods used are well known to the experts.

The method according to the invention is most suitable for the production of amorphous and kauchukopodobnoe copolymers based on ethylene and other olefins. As another-olefin, preferably propylene is used, resulting in an ethylene-propylene rubber. Also, in addition to ethylene and another-olefin can be used Dien, resulting in so-called EADM-rubber, in particular ternary ethylene-propylene-diene rubber (Sept).

Under an amorphous copolymer hereinafter refers to a copolymer, which at room temperature and higher temperatures has a degree crystallization has a degree of crystallinity of 1%.

The olefin may polymerization in a known manner as in the gas phase and in the liquid reaction medium. As the mortar, and suspension polymerization are suitable for the latter case. The method according to the invention will be explained below on the example of a ternary ethylene-propylene-diene copolymer which is known in itself. For other polymers based on olefins, there are many publications on this subject.

Alpha-olefins which are suitable for use in obtaining EA/L/M-polymer, are propylene, butylene-1, penten-1, hexene-1, octene-1 or their branched isomers, such as 4-methylpentene-1, and, in addition, the styrene-methylsterol. Can also be used mixtures of these alkenes, and in this case, preferred is propylene and/or butylene-1.

As a diene in such amorphous copolymer should use a polyunsaturated compound which is able to introduce an unsaturated bond in the polymer; this compound contains at least two C=C-bond and may be aliphatic or alicyclic. Aliphatic polyunsaturated compounds usually contain 3 to 20 carbon atoms, the double bond can be as terbutalin-1,3, 2-ethylbutane-1,3, piperylene, MIRCEN, allene, 1,2-butadiene, 1,4,9-decatriene, 1,4-hexadiene, 1,5-hexadiene and 4-methyl-hexadiene-1,4. Alicyclic polyunsaturated compounds that can contain or not contain a bridging group can be monocyclic or polycyclic. Examples of such compounds are (but are not limited to) norbornadiene and its alkyl derivatives; alcaligenaceae, in particular 5-alcaligenaceae-2, which alkyliden-group contains 1 to 20, preferably 1 to 8 carbon atoms; alkenylamine, in particular 5-alkenylsilanes-2, which alkenyl-group contains 2 to 20, preferably 2 to 10, carbon atoms, for example, vinylnorbornene, 5-(2'-methyl-2'-butenyl)-norbornene-2 and 5-(3'-methyl-2'-butenyl)-norbornene-2; Dicyclopentadiene and polyunsaturated compounds bicyclo-(2,2,1)-heptane, bicyclo-(2,2,2)-octane, bicyclo-(3,2,1)-octane and bicyclo-(3,2,2)-nonane, where at least one of the rings is unsaturated. Besides can be used compounds such 4,7,8,9-tetrahydroindene and isopropylideneuridine. In particular, are Dicyclopentadiene, 5-methylene -, or 5-ethylidenenorbornene-2 or hexadiene-1,4. Can also be used mixtures of the above compounds.

Along with or instead of the diene in the copolymer can be (optional) is added to the unsaturated compound having one or more functional groups such as halogen atoms, OH, OR, -COOH, COOR or NH2group, in an amount up to 20 wt.%.

The molar ratio of monomers used in the invention depends on the desired composition of the polymer. Since the rate of polymerization of the monomers differ slightly, can be taken normally used outside of molar ratios. In the case of copolymerization of ethylene and propylene are usually chosen molar ratio of from 1:1 to 1:5. If lightly copolymerized polyunsaturated connection, this molar ratio to ethylene is usually from 0.0001:1 to 1:1.

The polymerization reaction is usually conducted at a temperature of from 40 to 200oC, preferably at 10 to 80oC. the Pressure is usually 0.1 to 5 MPa, but can be used for higher or lower pressure. Preferably, the method is continuous, but it can be semi-continuous or periodic.

The time of polymerization reaction may vary from a few hours. Generally preferred is the reaction time is from several minutes to hours.

the, in one or more saturated aliphatic hydrocarbons (such as butane, pentane, hexane, heptane, pentamethylheptane or oils); aromatic hydrocarbons (e.g. benzene or toluene) or a halogenated aliphatic or aromatic hydrocarbons (e.g. trichloroethylene). Working temperature and pressure can be such that one or more of the monomers used, in particular, olefin, such as propylene, is liquid and is present in such large quantities that serves as a dispersing agent. Then there is no need for another dispersing agent. The method according to the invention can be carried out in a polymerization reactor, filled with gas and fluid, and the reactor is filled completely with liquid. The use of heterogeneous catalyst according to the invention makes it possible to conduct the polymerization in suspension or in the gas phase.

Molecular weight can be set to known methods. In particular, it can be adjusted by using the controls, chain length, such as diethylzinc and, preferably, hydrogen. Very small amounts of hydrogen are already having a noticeable effect on the molecular weight.

Amorphous copolymers, obtained using the method of the invention typically contain 25 to 85 wt.% of ethylene. Preferred are products with ethylene content of 40 to 75 wt.%. The copolymers are suitable for various applications, for example for the manufacture of hoses, conveyor belts and preformed gaskets. Optionally, the copolymers can vulcanizates known standard methods using substances that give free radicals such as peroxide or using sulfur.

In order to receive the product, processed as rubber, the copolymer is miscible with oil. Preferably, this is done in the polymerization process. Adding agents to the copolymer to obtain the so-called "free-flowing mixture is known. This can be made azizia, described herein containing inorganic separating agent, thickening agent and an anionic dispersant, is very suitable for use with the products of the invention.

Hereinafter the invention is described with reference to the following examples and comparative experiments, without any limitations.

Cat. 1 = VOCl3< / BR>
Cat. 2 = FRN=VCl2N(Et)2< / BR>
Cat. 3 = FRN=VCl2N(Et)(Ph)

Cat. 4 = FRN=VCl2N(Ph)2< / BR>
Cat. 5 = FRN=VCl2-carbanilide

Cat. 6 = FRN=VCl2-(N-ethyl)2,4-dichloraniline,

where Ar-o,o-diisopropylphenyl, Ph is phenyl, Et is ethyl.

DHFM - dichlorphenoxy ethyl ester.

EACH - ethylaminoethanol3-sod. mass content of propylene units in the polymer

The output is either the absolute yield in grams of polymer (g) or kilograms per 1 g of the transition metal (kg/g M).

Comparative experiment AND

In a glass autoclave with a capacity of 1 l is loaded 400 ml of gasoline and 0.1 mmol of EACH. Using purified monomers pressure in the reactor is brought to 8 bar, and the reactor is cooled so that the ratio of propylene:ethylene in the gas phase is equal to 2:1. The temperature in the reactor is maintained at 30oC. Then, the polymerization concentration of monomers are supported as far as possible constant supply of propylene (200 nl/h/ and ethylene/100 nl/h/ in the reactor).

After 10 min of the polymerization reaction is not observed, the pressure in the reactor is discharged, the solution is collected and dried. Obtained amorphous copolymer of ethylene and propylene. The results obtained are given in the table.

Example 1. Using the same polymerization installation as in comparative experiment A. as a component of the catalyst is now used complex (transition metal - aminoaryl) according to the invention, namely the cat. 2. Reaction conditions are maintained the same as in comparative experiment A. the Catalyst remains active in time; after 60 minutes of polymerization the pressure in the reactor is discharged.

Obtained amorphous polymer.

Example 2. Example 1 is repeated, only now as a component of the catalyst used cat. 3. There is a stable behavior of the catalyst in the polymerization process; after 50 min, the polymerization reaction is stopped with the pressure relief of the reactor.

Examples 3 and 4. Example 1 is repeated using catalysts cat. 4 to 6, respectively, and the polymerization time is set to 60 minutes

The results are given in the table.

Presented in the table resulta invention. This is clearly evidenced by the increase in the yield of the polymer per 1 g of the transition metal. Moreover, there is a high catalytic activity output for diarylamino-ligand compared to dialkylamide-ligand or alkylsilane-ligand.

Increased activity of the catalyst causes a corresponding and proportional decrease in the concentration of the transition metal in the obtained polymer (10 times from the comparative experiment And example III).

1. The catalyst for polymerization of olefins according to Ziegler, containing organometallics connection and a complex of a transition metal - aminoaryl, characterized in that the complex of the transition metal - aminoaryl contains at least one amino group that is associated with a transition metal, and the aryl group represents a complex of o,O-disubstituted phenyl and ORGANOMETALLIC compound contains aluminum.

2. The catalyst p. 1, characterized in that aminogroup has the formula

-NR1R2,

where R1and R2- independently from each other alkyl, Alchemilla, aryl group or silicon-containing gidrolabilna group.

3. The catalyst p. 2, characterized in that R1and R2- Arilyn an O-dimethylaniline or O-diisopropylphenyl group.

5. The catalyst PP.1 to 4, characterized in that the complex of the transition metal - aminoaryl contains vanadium.

6.The catalyst PP.1 to 5, characterized in that it contains a promoter.

7. The catalyst p. 6, characterized in that the promoter contains not more than two halogen molecule.

8. The catalyst according to any one of paragraphs.1 to 7, characterized in that it also contains a Lewis acid or Lewis base.

9. The method of polymerization of olefin to Ziegler, characterized in that the olefin is subjected to polymerization in the presence of a catalyst according to any one of paragraphs.1 - 8.

10. The method according to p. 9, characterized in that the olefin is chosen from the group comprising - olefin, the olefin with nekozumi double bonds, diolefin or their mixture.

11. The method according to p. 10, wherein the - olefin is chosen from the group selected from ethylene, propylene, butylene, pentene, octene, or mixtures thereof.

12. The method according to PP.9 to 11, characterized in that the polymer is produced on the basis of ethylene and/or propylene.

13. The method according to p. 12, characterized in that koutsokoumnis polymer is produced on the basis of ethylene, propylene, optionally, a diene.

 

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