A method of obtaining a polymer, the method of obtaining metallocene, double-linked metallocene

 

(57) Abstract:

Describes a method of obtaining a polymer involving contacting unsaturated monomer in a suitable polymerization conditions with double-linked metallocene formula I or formula II, where each Z represents the same or different cyclopentadienylsodium radicals; R represents alkalinity radical having 1-20 carbon atoms, or a divalent organic ellenby radical, which connects the two Z radicals; x is 1 or 0; R' represents a hydrocarbon radical, which connects Z and Me in such a way that there are only four atoms separating the associated Z and Me, and these atoms are carbon atoms; Me represents a transition metal selected from Ti, Zr and HF, and Q is a halogen; R" is a divalent organic radical linking Z and Me, and R" is so radical that the number of atoms separating the respective associated Z and Me, was 2. Describes new doubly linked metallocene formula I or formula II and the way they are received. These connections - double-linked metallocene are used as catalysts for polymerization activity, this invention relates to metallocene containing at least one cyclopentadienyls radical, which is linked to the transition metal metallocene as through PI-communication (communication), and carbon Sigma-bond (connection) Deputy of this cyclopentadienyls radical. Another objective of the present invention is the use of metallocenes for polymerization olefin-unsaturated monomers.

The term "Metallocene" used in the description of the invention, refers to a derivative of cyclopentadienide, which is a derivative of a metal containing at least one cyclopentadienyls component, which is connected with the transition metal. Transition metal selected from groups IVB, VB and VIB, preferably IVB and VIB. Examples include titanium, zirconium, hafnium, chromium, vanadium, and rare earth metals. It was found that a number metallocenes suitable for the polymerization of olefins. Usually the preferred catalysts are metallocene Zr, Hf or Ti. The term "sandwich-linked metallocene" used in the patent refers to metallocene having at least two cyclopentadienyls group, which are both connected to the PI-bond with the same transition metal atom.

Accordingly one object of the present invention is to propose a new class metallocenes.

Another object of the present invention is to propose methods for such metallocenes.

Another object of the present invention is a method of obtaining a polymer by the polymerization of olefins using twice the United metallocenes.

Other features, objectives and advantages of the present invention will be apparent from the following about what llorena, having cyclopentadienylsodium radical, which is connected with the transition metal, as a PI-bond and carbon Sigma-bond substituent of the same cyclopentadienylsodium radical, comprising the reaction of a particular type of metallocene with a reducing agent, and metallocene of a certain type is metallocene selected from the group consisting of metallocenes with cyclopentadienylsodium radical having at least one unsaturated Deputy, preferably olefins other than metallocene connected in bridge connection, having as their organic ligands (cyclopentadienyl) (cyclopentadienyl) (indenyl)-(dimethyl) methane). In accordance with another objective of the present invention, a method for obtaining a polymer comprising contacting at least one olefin monomer in a suitable polymerization conditions with double-linked metallocene.

The term double-linked metallocene includes metallocene with cyclopentadienylsodium radical, or which (1) is associated with the same transition metal as a PI-bond, and Sigma-bond substituent that cyclopentadienylsodium radical or (2) is connected with odnako metallocene predecessor carbon Sigma-bond substituent that cyclopentadienyls radical. Examples of the first type twice the United metallocene include metallocene formula

< / BR>
where Z represent the same or different cyclopentadienylsodium radicals, R is a divalent organic radical linking the two radicals Z, x is 1 or O, and R' represents a bivalent organic radical, which connects Z and Me in such a way that there are only four atoms separating the associated Z and Me, and these atoms are carbon atoms, Me represents a transition metal, and Q is chosen from the group consisting of hydrocarbon, hydrocarbonsoluble and Halogens.

Examples of the second type double-associated metallocenes include metallocene having at least one unit of formula

< / BR>
where Z, Me, Q and x have the above values and where R" is a divalent organic radical linking the Z with Me, and R" is so radical that the number of atoms separating the respective associated Z and Me was either 2 or 3 or more than 4.

Generally, if Q is a hydrocarbon radical, it will contain 1-20 carbon atoms, more preferably 1-4 carbon atoms, R' may be selected from a wide range of EOS is from a wide variety of organic radicals, usually it will contain 1-20 carbon atoms. R may be selected from any divalent organic radicals, known in this area as suitable for the formation of bridging ties between the two cyclopentadienyls radicals. Examples include saturated divalent hydrocarbon radicals, such as, for example, alkylene radicals having 1-20 carbon atoms, a divalent organic silylene radicals, such as, for example, dihydrocarbamazepine divalent silylene radicals, such as dimethylsilane, diphenylsilane and methyldiphenylamine, and divalent radicals dihydrocarvone, such as, for example, dimethyl - and diphenylurea. Usually R will have 1-20 carbon atoms. In the preferred embodiment of the invention R is selected from divalent organic radicals such that R had only one atom, which separates the two radicals Z, R" may be selected from a wide variety of organic radicals. Usually Me preferably selected from Zr, Hf and Ti.

Used in the present invention, the term cyclopentadienyls radical refers to radicals having the structure of cyclopentadienyl, examples include substituted or unsubstituted, formattitle such cyclopentadienylsodium radicals can if they are, essentially to be of any shape which does not interfere with the desired reactions. Typically, the substituents, if present, are organic radicals, usually hydrocarbon radicals or hydrocarbonoclasticus, usually containing 1 to 20 carbon atoms. Preferred specific metallocene source reagent having two communication halogen-transition metal.

The stage of restoration required to obtain a double-linked metallocene, can be performed using a large number of well-known methods of recovery. Usually metallocene, preferably metallocene with halogen, associated with the transition metal, is subjected to the interaction with the reducing agent in a suitable liquid diluent. Usually apply the same conditions, which are known to be acceptable to obtain reagent Schwartz and similar compounds. Some examples of such techniques are described in U.S. patent 4147709. For example, a certain type of metallocene source reagent, which is one of dicyclopentadienyltitanium radicals is Deputy containing unsaturated bond, can be subjected to the interaction of a reducing agent, such as LiAlH4or Li the reducing agent is used in an amount of about 1 mole per mole of metallocene reagent. You can apply any suitable liquid diluent. Used in the invention, the term "liquid diluent" includes hydrocarbons, such as isobutane, pentane, benzene, toluene, etc. and ethers, such as diethyl ether and tetrahydrofuran, and organohalogen fluid, for example, dichloromethane.

Another example includes processing a certain metallocene solution NaAlH2(OCH2CH2OCH3)2of benzene. Another technique includes processing the source metallocene metallic magnesium in tetrahydrofuran. Another method involves the reaction of metallocene with molecular hydrogen in the presence of an elemental metal selected from group IA of the Periodic table of elements, in a solvent for metallocene, which prevents the formation of the target product.

Reaction conditions can vary within wide limits depending on the specific desired results. Obviously, it is desirable to limit the temperature to a temperature below that at which may occur in the decomposition of the target product.

It is found that the double-linked metallocene suitable as components of catalytic systems for polymerization. Catalytic systems the Examples of such olefins include ethylene, propylene, butene-1, penten-1, 3 - methylbutan-1, hexene-1, 4-methylpentene-1, 3-methylpentene-1, hepten - 1, octene-1, mission-1, 4,4-dimethyl-1-penten, 4,4-diethyl-1-hexene, 3,4-dimethyl-1-hexene and the like olefins, and mixtures thereof. These catalysts are also suitable for obtaining copolymers of ethylene and propylene and copolymers of ethylene or propylene and heavier olefins. Styrene and butadiene are also examples of olefin unsaturated monomers.

The polymerization can be conducted in a wide range of conditions depending on the specific applicable metallocene and specific desired results. It is believed that the catalytic system of the present invention suitable for carrying out the polymerization in solution, suspension or gas phase.

When the polymerization is carried out in the presence of liquid diluents, obviously, it is important to use a solvent that does not adversely affect the catalytic system. Typical liquid diluents include propylene, propane, butane, isobutane, pentane, hexane, octane, cyclohexane, methylcyclohexane, toluene, xylene and so on, Usually the temperature of polymerization may vary within wide limits, the temperature usually in the range of from about -60oC to the eye and polymerization is in the range of from about 1 to about 500 atmospheres or even higher. The catalytic system of the invention, particularly suitable for the polymerization carried out in the form of particles, i.e., in conditions such as suspension polymerization.

Usually metallocene of the invention is used with suitable socialization. Examples of suitable socialization include any of those ORGANOMETALLIC socialization, which were previously used in combination with containing transition metal catalysts for the polymerization of olefins. Some typical examples include ORGANOMETALLIC compounds of metals of groups IA, IIA and IIIB of the Periodic table of elements. Examples of such compounds include ORGANOMETALLIC halide compounds, ORGANOMETALLIC hydrides and even metal hydrides. Some specific examples include triethylaluminum, triisobutylaluminum, diethylaluminum, diethylaluminium, etc. are Other examples of known acetalization include the use of stable recoordination protivougonnykh of acetalization (an example of such socializaton described in U.S. patent 5155080), for example the use of tetrakis(pentafluorophenyl)boronate triphenylarsine. Another example is the use of a mixture of trimethylaluminum and dimethylformamide, such as described Zam connection, containing a cation which will irreversibly react with at least one ligand contained in metallocene, and coordinational anion which is a single coordination complex containing a variety of lipophilic radicals covalently coordinated to the Central formally containing a charge of the metal atom and protecting this atom, or metalloid atom or anion containing many atoms of boron, for example Priaralye boron, carbonates and metallacarborane.

The most preferred acetalization is alumoxane. Such compounds include compounds having the repeating unit of the formula

< / BR>
where R is typically a hydrocarbon group having 1-5 carbon atoms.

Alumoxane can be produced by various methods known in this field. For example, aluminiuim can be treated with water, dissolved in an inert organic solvent, or it can be subjected to interaction with the hydrated salt, such as gidratirovannym copper sulfate, suspended in an inert organic solvent, obtaining alumoxane. To obtain a mixture of linear and cyclic types alumoxane offered are usually what aluminiumoxide), well known in this field, they usually get a reaction hydrocarboncontaminated connection with water. Such methods of obtaining described in U.S. patent 3242099 and 4808561, which are included in the description of the present invention as a reference. Preferred alumoxane socializaton currently derived from trimethylaluminum or triethylaluminum, they are sometimes referred to as poly(methylaluminoxane) and poly(ethylaluminum), respectively. In the scope of the present invention also includes the use of alumoxane in combination with trialkylaluminium described in U.S. patent N 4794096, which is included in the present description by reference.

In a particular preferred embodiment of the invention, double-linked metallocene can be used in combination with solid organoaluminum, which is essentially insoluble in the diluent for the polymerization reaction, when carrying out the polymerization using the catalyst in the form of particles. Organoaluminum component used to obtain the solid catalyst system of the present invention, includes oligomeric aluminum compounds having the repeating unit of the formula

< / BR>
Some examples organosiloxane represents a C1-C5is an alkyl radical, for example methyl, ethyl, propyl, butyl or pentyl, and "n" is an integer from 1 to 50. Most preferably R represents methyl and n is at least 4. Such solid alumoxane can be obtained by the interaction of the solution organosiloxane with organobromine under conditions sufficient for the formation of a solid product. Another way of getting insoluble organoaluminum includes the contacting of the solution organoaluminum with water or a compound having an active hydrogen, as described in U.S. patent 4990640.

Another way of getting solid socializaton includes contacting organosiloxane with organic boranova compound that does not contain acidic hydrogen, as described in U.S. patent 5354721, which is included in the present description by reference. Another method involves contacting organosiloxane with organoboron compound with acid functionality of boron, i.e.- BOH, as described in U.S. patent 5414189, which is included in the present description by reference.

The preferred method of obtaining solid organoaluminum of socializaton includes contacting the organic solution is, as indicated in U.S. patent 5411925, which is included in the present description by reference.

In the most preferred embodiment of the present invention double-linked metallocene subjected to preliminary polymerization olefin to obtain a solid catalytic system, which can then be used for the polymerization of olefins. This method is especially suitable for suspension polymerization or polymerization in the form of particles.

To get a solid pre-polymerized catalyst system metallocen and alumoxane combine in the presence of a suitable liquid for formation of a liquid catalyst system. Preferably, the liquid catalytic system was obtained with the application of organic liquid in which alumoxane at least partially soluble. Preferred liquids are hydrocarbons, such as hexane or toluene. Usually used aromatic liquid solvent. Examples include benzene, toluene, ethylbenzene, diethylbenzene, and so on, the Amount of applied liquid is almost non-critical. However, the amount should preferably be such as to dissolve at least a portion of the product is tion and to ensure good mixing. The temperature is preferably kept lower than the temperature, which may cause decomposition of metallocene. Usually the temperature is in the range from -50oC to 100oC. Preferably metallocene, alumoxane and liquid diluent combine at room temperature, i.e. about 10-30oC. the Reaction between alumoxanes and metallocene relatively fast. The reaction rate may vary depending on the ligand metallocene. Usually it is desirable that they were in contact during the time from at least about one minute to about 1 hour.

In the scope of the present invention also includes the production of the liquid catalytic system in the presence of solid substances in the form of particles, which can be applied any number of solids. Typically, the carrier can be any organic or inorganic solid substance that does not interfere with achieving the desired end result. Examples include porous media, such as talc, inorganic oxides, and resinous materials-media such as polyolefins in the form of particles. Examples of materials such as inorganic oxides include oxides of metals of groups II, III, IV or V, for example silicon dioxide, aluminium oxide, aluminium silicate and D. see Other suitable materials for the media that can be used include such materials as duplissy magnesium and powdered polyolefins, such as polyethylene. In the scope of the present invention also includes the use of mixtures of one or more solids in the form of particles.

Usually it is desirable solid before applying fully degidratiruth, preferably dehydration so that it had during annealing the mass loss of less than 1%. Thermal dehydration can be carried out in a vacuum or by blowing dry inert gas such as nitrogen, at a temperature of from about 20oC to about 1000oC, preferably from about 300oC to about 800oC. Pressure thermal processing non-critical. The duration of the heat treatment can be from about 1 to about 24 hours. However, you can use a shorter or a longer processing time, provided that establishes the equilibrium with surface hydroxyl groups.

Dehydration may be accompanied by chemical treatment of solid substances in order to remove water and reduce the concentration of surface hydroxyl groups. Chemical treatment is usually capable ol the chemical agents are, for example, trimethylaluminum, ethylaniline, chloro silanes, for example, SiCl4, disilane, trimethylchlorosilane, dimethylaminomethylene and similar agents.

Chemical dehydration may be accompanied by suspendirovanie particles of inorganic material, such as silicon dioxide, in an inert, low-boiling hydrocarbon, such as, for example, hexane. During treatment for chemical dehydration of the silica should be incubated in an atmosphere containing no moisture and oxygen. A suspension of silicon dioxide were then added, the solution in the low-boiling inert hydrocarbon chemical dehydrating, such as, for example, dichloromethylsilane. The solution is added to the suspension slowly. Temperature range during the chemical reaction of dehydration can be from about 0oC to about 120oC, however, it is possible to use higher or lower temperatures. Preferably the temperature should be from about 15oC to about 100oC. Procedure the chemical dehydration should be continued until the removal of the material of the carrier in the form of particles substantially all the reactive groups, as indicated by cessation of gas evolution. Usually the chemical reaction a chemical dehydration of the solid material in the form of particles can be filtered in a nitrogen atmosphere and washed one or more times dry, not containing oxygen with an inert solvent. Solvents, reagents and diluents used for the formation of a suspension or solution of the chemical dehydrating, may be any suitable inert hydrocarbon. Examples of such hydrocarbons are pentane, heptane, hexane, toluene, isopentane and the like hydrocarbons.

Another chemical treatment that can be applied to solid inorganic oxides, for example of silicon dioxide, includes the restoration by contacting such a solid oxide with carbon monoxide at an elevated temperature sufficient to convert essentially all of the water and hydroxyl groups in a relatively inactive group.

The specific particle size of the carrier or inorganic carrier, surface area, pore volume and the number of hydroxyl groups critical for its application in the practical use of the invention. However, these characteristics often determine the number of used media to obtain a catalytic composition, and also affect the morphology of the particles formed polymers. Characteristics of the carrier or substrate should nevertheless be taken into account when wynia also includes the addition of such solid material in the form of particles in a liquid catalytic system after its formation and the preliminary polymerization in the presence of this solid material.

The number alumoxane and metallocene used for the formation of liquid crystalline system for the preliminary polymerization may vary within wide limits. Usually, however, the molar ratio of aluminum in alumoxane to the transition metal in metallocene is in the range from about 1:1 to about 20,000: 1, more preferably employ a molar ratio from about 50:1 to about 2000:1. If you use a solid material in the form of particles, for example silicon dioxide, it is used usually in an amount such that the mass ratio of metallocene to solid material in the form of particles was in the range of from about 0,00001:1 to 1:1, more preferably of 0.0005:1-0,2:1.

The preliminary polymerization is carried out in liquid catalytic system, which can be a solution, suspension or gel in the liquid. For prepolymerisation can apply to a wide range of olefins. Usually prepolymerisation carried out using olefin, preferably selected from ethylene and non-aromatic alpha-olefins, such as propylene. In the scope of the present invention also includes the use of a mixture of olefins, for prepolymerisation can be used such as ethylene and higher alpha-olefin.

Prepolymerisation you, RETA low temperatures, intended to prevent local degradation resulting from high concentrations of localized heat. Prepolymerisation usually carried out at temperatures ranging from about -30oC to about +110oC, more preferably in the range from about +10oC to about +30oC. the Number of prepolymer may vary, but will usually range from about 1 to about 95 wt. % get prepolymerized solid catalytic system, more preferably from about 5 to 80 wt.%. Usually it is desirable to prepolymerisation at least to the point where essentially all metallocen is solid, not liquid form, because it maximalism application metallocene.

After prepolymerisation educated hard prepolymerisation the catalyst is separated from the liquid reaction mixture. For this stage you can apply various methods known in this field. For example, the material can be separated by filtration, decantation or evaporation in a vacuum. Currently, however, prefer to abandon evaporation in a vacuum, because take into account the fact that & it is desirable to remove essentially all Rastko catalyst prior to its storage or use for subsequent polymerization. After separation of the solid part from the liquid received the hard part is preferably washed with a hydrocarbon and then dried using high vacuum to remove substantially all the liquid and other volatile components, which may be associated with the solid component. Vacuum drying is preferably carried out under relatively mild conditions, i.e. at temperatures below 100oC. As a rule, prepolymerized solid material is dried in a high vacuum at a temperature of about 30oto achieve essentially constant weight. In the preferred method is used, at least one initial flushing aromatic hydrocarbon, for example toluene, and subsequent washing paraffin hydrocarbon, for example hexane, and then dried in vacuum.

In the scope of the present invention also includes the contacting of the product (mixture) reaction prepolymerisation with the liquid in which prepolymer poorly soluble, i.e. protorestoration for prepolymer to assist the precipitation of soluble prepolymer from the solution. This fluid is also suitable for the subsequent washing prepolymerized solid material.

In the scope of the present invention, whodini, this solid material can be added to the liquid product prepolymerisation to add protoveratrines. Thus, soluble prepolymer precipitated on the surface of a solid material to help the selection of the filtrate in the form of particles and prevent agglomeration during the drying process. The liquid mixture obtained by prepolymerisation or solid prepolymerized catalyst can be treated with ultrasound, so that, if desirable, to help to break down the particles.

In addition, if desired, selected solid prepolymerized catalytic system can be sifted to obtain particles having a size that meets your specific requirements for a particular type of polymerization.

Another way is to combine selected solid prepolymerized catalytic system of the present invention with an inert hydrocarbon, such as hydrocarbon type that is used as the washing liquid, and then removing the liquid under vacuum. In this way, it is sometimes desirable resulting mixture is treated with ultrasound to remove the liquid.

The obtained solid prepolymerisation metallosoderzhashhie catalytic system is more alumoxane. It may be that in some cases it is desirable to apply a small amount alyuminiiorganicheskikh compound as acceptor for poisons. The term alyuminiiorganicheskikh connection includes such compounds as triethylaluminum, trimethylaluminum, diethylaluminum, ethylaminoethanol, ethylaminoethanol etc. Preferred trialkylaluminium connection. In some cases it may be desirable to use a small amount of anti-static tools that help to prevent agglomeration of the polymer particles in the polymerization process. In addition, when the catalytic system of the present invention is added to the reactor in suspension in a liquid, it is sometimes desirable to add dried solid material in the form of particles as an additive that improves the fluidity of the suspension. Preferably, this solid material is dried using one of the methods described earlier. In particular, the preferred inorganic oxides such as silicon dioxide. Preferably the use of fume silica, for example dioxide, which is sold under the trade name Cab-o-Sil. Usually fuming silica is dried by applying heat and trimethylaluminum.

TV is Susannah polymers. Such a polymerization can be carried out in the gas phase, phase, solution or phase of the suspension. The applicable conditions are usually similar to the conditions used in the case of use for the polymerization of other solid metallocene. One difference is that usually there is no need to apply additional socialization solid prepolymerized catalyst.

The polymers produced with the catalysts described in this invention have various applications, which should be obvious to the skilled in the art from the physical properties of the respective polymers. Includes areas such as molded articles, films, adhesives, etc.

Further understanding of the present invention, its various incarnations, objectives and advantages will clearly from the following examples:

Example I

Not containing bridge (remotecopy) metallocen (cyclopentadienyl) (omega - butylcyclopentadienyl)zirconiated, which can also be called (cyclopentadienyl) (1-but-3-enciklopediey)zirconiated, number 3 mmole was dissolved in tetrahydrofuran together with 0,79 g (3.11 mmole) socialwise three - tert-butylacrylamide and was stirred over night at connatre. The resulting liquid was concentrated by evaporation, and then was led by adding n-hexane. Double-associated remotecopy metallocene product, (cyclopentadienyl) (1-butylcyclopentadienyl) zirconium (IV) chloride, identified as PMR and13C NMR spectroscopy as having butanol attached to the zirconium Sigma bond and two cyclopentadienyls group, United with zirconium PI-bonds.

A similar reaction was carried out using the following different metallocenes, namely bridge, sandwich the United metallocenes ((1-butene-3-enciklopediey) (fluorenyl) (dimethyl)methane) zirconiated, ((omega-butylidene) (fluorenyl) (dimethyl)silane)zirconiated and ((fluorenyl) (1 - athentication) (dimethyl) methane) zirconiated. Selected products identified PMR and13C NMR spectroscopy as a double-linked metallocene.

The products obtained can be attributed to ((fluorenyl) (1-butanol-cyclopentadienyl) (dimethyl) methane) zirconium (IV) chloride, (fluorenyl) (butylidene)(dimethyl)silane)zirconium(IV)chloride and poly(fluorenyl) (ethylcyclopentadienyl) (dimethyl)methane) zirconium (IV) chloride, example double-linked metallocene formue as described in example I, i.e. metallocene formula (I), were evaluated for their efficiency in the polymerization of ethylene. In addition, comparative polymerization using double-linked metallocene, (cyclopentadienyl) (cyclopentadienyl) (dimethyl) methane (1 indenyl) zirconium (IV) chloride, i.e. the compounds of formula (4) described in the above article in J. Orgnomet. Chem. Polymerization consisted of getting solution of the catalyst by adding about 1-2 mg metallocene in the tube Slinka and mixing it with 1 ml of 30% by weight solution methylalumoxane in toluene. The solution then was diluted with toluene so that from about 0.2 to about 0.5 mg of metallocene complex was dissolved in about 10 ml. of Ethylene was polymerizable at room temperature in the tube Slinka, applying a slight pressure. Monitored the color of the reaction mixture. In each case, the reduction in color was indicated that the complex was immobilizovana on the formed polymer, i.e., there was evidence that metallocen was introduced into the polymer.

Example III

Using four different double-linked metallocene received four different solid catalytic system.

First, poly((1-ethylcyclopentadienyl) (PL what dimetilaminom, the treated silicon dioxide Davidson 948. In a dry tank, this solid material was combined with 20 ml of a 1.1 molar solution methylalumoxane obtained from Schering in toluene. The resulting mixture was stirred 1 hour and then washed and filtered two times 25 ml of hexane. Color wash water had traces of coloring metallocene. Selected solid was placed in a high vacuum for 2 hours and was isolated as a solid catalytic system A.

In another case, 0.27 g double-linked metallocene, ((1 - butylcyclopentadienyl) (fluorenyl) (dimethyl) methane) zirconium (IV) chloride, mixed with a 25.1 ml of a 1.1 molar solution methylalumoxane obtained from Schering in toluene. To this mixture was added 2.5 g of trimethylaluminum (TMA), treated with silica Davidson 948. The resulting mixture was stirred 20 minutes and Then at room temperature, the mixture was subjected to interaction with ethylene at a pressure of 0,352 ATM for 1 hour. The color was changed from reddish-orange to red in about 5 min after the start of feeding of ethylene. The obtained solid material was washed and filtered twice using 20 ml of toluene and twice using 20 ml of hexane. Then this solid 2 hours and was kept in a high vacuum, floor linked metallocene, ((fluorenyl) (butylidene) (dimethyl) (silane)zirconium-chloride, mixed with 23 ml of a 1.1 molar solution methylalumoxane received from Schring in toluene. To this mixture was added 2.5 g of the TMA-treated silica Davidson 948. The resulting mixture was stirred 20 min, then was treated with ethylene at a pressure of 0,352 ATM to conduct prepolymerisation. The color was changed from reddish-brown to dark-red within 10 min after the start of feeding of ethylene. After 1 hour, the solid material was isolated and washed and filtered twice using 20 ml of toluene and twice using 20 ml of hexane. The obtained solid product was then placed in a high vacuum for 2 hours, resulting in the solid prepolymerized catalytic system C.

Another solid catalyst was obtained by mixing 0,265 g double-linked metallocene (cyclopentadienyl)- ((cyclopentadienyl) (dimethyl) methane (indenyl) zirconium (IV) chloride from 27.4 ml of a 1.1 molar solution methylalumoxane obtained from Schering in toluene. To this mixture was added 2.5 g of the TMA-treated silica Davidson 948, and the resulting mixture was stirred for 2 hours. Then typed ethylene under pressure 0,352 ATM and at room temperature. After 1 hour, the obtained tverd was stirred for 2 h under high vacuum, getting prepolymerisation catalytic system D.

Example IV

Each of the catalysts A-D are separately used in the polymerization. These reactions were carried out in a reactor-autoclave at 3,78533 l with stirring. The catalytic system was loaded into the autoclave. Into the autoclave was introduced 2 l of isobutane and the temperature was raised to about 90oC. Hydrogen was added from a vessel of 300 ml, and then the vessel was created increased pressure to the total pressure of ethylene in the reactor 31,64 ATM. All the polymerization reaction, with the exception of experiment 1, continued for 1 hour. The reactor was then cooled, the outlet was opened and the solid polymer was discharged. The results are summarized in table.

Solid catalytic systems A, B and D formed polymers having a narrow molecular weight distribution of the type normally associated with the use of metallocene catalysts with "one phase", i.e., with H1less than 3. The solid catalyst C was given a relatively broad molecular weight distribution.

1. A method of obtaining a polymer involving contacting unsaturated monomer in a suitable polymerization conditions with double-linked metallocene, distinguish the fight the same or different cyclopentadienylsodium radicals, R represents alkalinity radical having 1 to 20 carbon atoms, or a divalent organic ellenby radical, which connects the two Z radicals; x is 1 or 0; R is a hydrocarbon radical, which connects Z and Me in such a way that there are only four atoms separating the associated Z and Me, and these atoms are carbon atoms; Me represents a transition metal selected from Ti, Zr and Hf, and Q is a halogen or metallocene containing at least one unit of formula II

< / BR>
where Z, R, Me, Q and x have the above values and where R" is a divalent organic radical linking Z and Me, and R" is so radical that the number of atoms separating the respective associated Z and Me, was 2.

2. The method according to p. 1, characterized in that the polymerization is carried out in the presence of socializaton to metallocene.

3. The method according to p. 2, characterized in that the unsaturated monomer used alpha-olefin having 2 to 10 carbon atoms.

4. The method according to p. 3, characterized in that socialization contains organoaluminum compound having the repeating unit of the formula

< / BR>
where R is alistar is methylalumoxane.

6. The method according to p. 5, characterized in that the double-linked metallocene formula I is (cyclopentadienyl)(butylcyclopentadienyl)zirconium (IV)chloride.

7. The method according to p. 5, characterized in that the double-linked metallocene formula I is ((fluorenyl)(butylcyclopentadienyl)(dimethyl)methane)zirconium(IV)chloride.

8. The method according to p. 5, characterized in that the double-linked metallocene formula I is ((fluorenyl)(butylidene)-(dimethyl)silane)zirconium(IV)chloride.

9. The method according to p. 5, characterized in that the double-linked metallocene has the formula I, x is 1 and R is selected from dialkylamino and dialkylanilines.

10. The method according to p. 9, wherein R' represents butanol.

11. The method according to p. 5, characterized in that the double-linked metallocene has the formula I and x is 0.

12. The method according to p. 11, wherein R' represents butanol.

13. The method according to p. 11, wherein R' represents an end indenolol group, which is connected with Me, and indayla group separated from connected with her group Z one atom.

14. The method according to p. 5, characterized in that the double-linked metallocene selected from metallocenes of form ((fluorenyl)(atenciosamente)(dimethyl)methane)zirconiated.

16. The method according to p. 14, characterized in that the double-linked metallocene selected from those in which x is 1 and R" is a divalent saturated ethylene radical.

17. The method according to p. 14, characterized in that the double-linked metallocene chosen from those in which Z is attached to R" represents a cyclopentadienyl and the other Z is fluorenyl and R is a divalent saturated dimethylethylene radical.

18. The method according to p. 5, where metallocene used as a solid catalyst system obtained by the interaction of metallocene and methylalumoxane dry inorganic carrier in the form of particles, followed by drying the mixture using vacuum.

19. The method according to p. 5, where metallocene used as a solid catalyst system obtained by the interaction of metallocene and methylalumoxane, contacting the resulting mixture with the olefin to form prepolymer, followed by drying the obtained solid material with application of vacuum.

20. The method according to p. 19, where metallocen and methylalumoxane combine with dry inorganic carrier in the form of particles before prepolymerisation.

21. The way the floor is PI-communication, and carbon Sigma-bond substituent of the same cyclopentadienylsodium radical, including the interaction of metallocene with a reducing agent, and metallocene selected from the group consisting of metallocenes with cyclopentadienylsodium radical having at least one unsaturated Deputy, other than metallocene, having as their organic ligands combination of (cyclopentadienyl) (cyclopentadienyl)(indenyl)(dimethyl)methane.

22. The method according to p. 21, wherein the receive double-linked metallocene selected from metallocenes formula I

< / BR>
where each Z represents the same or different cyclopentadienylsodium radicals; R represents alkalinity radical having 1 to 20 carbon atoms, or a divalent organic ellenby radical, which connects the two Z radicals; x is 1 or 0; R' represents a hydrocarbon radical, which connects Z and Me in such a way that there are only four atoms separating the associated Z and Me, and these atoms are carbon atoms; Me represents a transition metal selected from Ti, Zr and Hf, and Q represents a halogen, or metallocenes, containing at least one SV is th organic radical, connecting Z with Me, and R" is so radical that the number of atoms separating the respective associated Z and Me, was 2, provided that metallocene formula I do not include sandwich United metallocene, having as their organic ligands combination (cyclopentadienyl) and ((cyclopentadienyl)(indenyl)-(dimethyl)methane).

23. The method according to p. 21, wherein the receive metallocen (cyclopentadienyl)(butylcyclopentadienyl)zirconium (IV)chloride.

24. The method according to p. 21, wherein the receive metallocen ((fluorenyl)(butylcyclopentadienyl)(dimethyl)methane)zirconium(IV)chloride.

25. The method according to p. 21, wherein the receive metallocen ((fluorenyl)(butylidene)dimethylsilane)zirconium(IV)chloride.

26. The method according to p. 21, characterized in that metallocen formula II, where Z, is attached to R is cyclopentadienyl; the other Z represents fluorenyl; R represents dimethylmethylene; R" is a saturated bivalent ethylene radical; Me is Zr and Q represents Cl.

27. Double-linked metallocene selected from metallocenes formula I

< / BR>
where each Z represents the same or razlichna, or divalent organic ellenby radical, which connects the two Z radicals; x is 1 or 0; R' represents a hydrocarbon radical, which connects Z and Me in such a way that there are only four atoms separating the associated Z and Me, and these atoms are carbon atoms; Me represents a transition metal selected from Ti, Zr and Hf, and Q represents a halogen, or metallocene containing at least one unit of formula

< / BR>
where Z, R, Me, Q and x have the above values and where R" is a divalent organic radical, connecting Z with Me, and R" is so radical that the number of atoms separating the respective associated Z and Me, was 2, provided that metallocene formula I do not include sandwich United metallocene, having as their organic ligands combination (cyclopentadienyl) and ((cyclopentadienyl)(indenyl)(dimethyl)methane).

28. Metallocen on p. 27, having the name (cyclopentadienyl)(butylcyclopentadienyl)zirconium(IV)chloride.

29. Metallocen on p. 27, having the name (fluorenyl)(butylcyclopentadienyl)(dimethyl)methane)zirconium(IV)chloride.

30. Metallocen on p. 27, having the name (fluorenyl)(BU is United to R", represents a cyclopentadienyl; the other Z is fluorenyl; R represents dimethylmethylene; R" is a saturated bivalent ethylene radical; Me is Zr and Q represents Cl.

 

Same patents:

The invention relates to the synthesis of low molecular weight branched polyethylene in the presence of efficient homogeneous catalytic systems based on metallocene or pseudometallic complexes IVC group, alyuminiiorganicheskikh compounds and perftoralkil borates

The invention relates to the components of the catalyst for polymerization of olefins comprising the product obtained by the reaction of compounds of the transition metal M selected from Ti, Zr, HF containing at least one M--communication with the porous polymer carrier, representing a prepolymer obtained by polymerization of one or more olefins of the General formula CH2=CHR, in which R is hydrogen or alkyl with 1-12 carbon atoms, with a complex catalyst comprising the product obtained by contacting connection Ti with a halide of magnesium in the form of particles with an average crystallite size below 300it called the halide of magnesium contained in the above-mentioned prepolymer in amounts of between 50 and 50000 h

The invention relates to the chemistry of polymers, and to methods of producing stereoregular polypropylene, and can be used in the chemical industry in the manufacture of plastics

The invention relates to a method for metallocenes with bridging ties carried out in situ, the resulting metallocene can be used as a component of catalysts suitable for the polymerization of olefins

The invention relates to new colophony to zirconocenes (TP), namely the ANSA-zirconocenes with cyclogeranyl bridge, functionalized directly on the bridge, which can be used as catalysts in the chemical industry for production of polyolefins (PO)

The invention relates to new ANSA-zirconocenes, namely zirconocenes with unsaturated 2,5-dihydro-1H-silydianin bridge, which can be used as catalysts in the chemical industry for production of polyolefins

The invention relates to the components of the catalyst for polymerization of olefins comprising the product obtained by the reaction of compounds of the transition metal M selected from Ti, Zr, HF containing at least one M--communication with the porous polymer carrier, representing a prepolymer obtained by polymerization of one or more olefins of the General formula CH2=CHR, in which R is hydrogen or alkyl with 1-12 carbon atoms, with a complex catalyst comprising the product obtained by contacting connection Ti with a halide of magnesium in the form of particles with an average crystallite size below 300it called the halide of magnesium contained in the above-mentioned prepolymer in amounts of between 50 and 50000 h

The invention relates to the chemistry of polymers, and to methods of producing stereoregular polypropylene, and can be used in the chemical industry in the manufacture of plastics

The invention relates to a technology for obtaining a polymer of olefins and their use in polymer alloys and molded articles, in particular metallocene catalyst and method for producing a copolymer of cycloolefin, and also to polymeric alloy and molded product comprising at least one copolymer of cycloolefin
Up!