DE2709884A1 - Olefin dimerisation using nickel and aluminium catalyst - prepd. from vinyl pyridine grafted rubber, nickel salt and (organo)aluminium cpd. - Google Patents

Abstract

olefins are dimerised by mixing with a catalyst (I) in an opt. halogenated hydrocarbon solvent (II) at 0-100 degrees C and 1-40 atm. (I) is a grafted copolymer of natural or synthetic rubber and vinyl pyridine, which swells in (II) and contains 0.5-40 wt. % polyvinylpyridine sequences with which is complexed a Ni salt of an (i)organic acid as well as 2-50 mole % -AlRX units (R is 8C alkyl, X is halogenated), the Al atom being linked to the main chain of the polymer via a C atom and the Al/Ni ratio being 1-20. The catalyst has high selectivity: dimerisation of ethylene gives a mixt. of butenes contg. 92-96% butene-1, and that of propylene gives 90-95% methypentenes. Unlike prior art catalysts, (I) do not crumble, can be easily regenerated, very stable and can be used for an extended period while maintaining its activity.

Description

description

The invention relates to the field of petroleum technology, in particular aur process for the dimerization of olefins. The olefin hydrocarbons obtained can be used as monomers and comonomers in the manufacture of polyolefins, and as Raw material for the production of synthetic rubber, etc.

use.

Processes for dimerizing olefins by mixing are known of olefins with different catalysts of homogeneous or heterogeneous type (safe for example the journal U £ Jpechi chiinii, 37, 1835 (1968), in Russian; J. Chem.

Soc. (C), 1971, 1117).

The homogeneous catalysts, which consist of an organaluminium rule Compounds and a compound of a transition metal with elements of V. and VI. Containing group of the periodic table (nitrogen, oxygen, phosphorus, sulfur) low molecular weight If there are ligands, there are a number of disadvantages on. A particularly significant disadvantage of the same is the difficulty of separation of the end products in pure form, because they are used to separate those in one phase Components special methods are applied, the difficulty of continuous Create processes; namely, all processes are usually discontinuous. In addition, the homogeneous catalysts are relatively unstable over time and leave not regenerate.

The use of heterogeneous catalysts makes the process possible for the dimerization of olefins not only periodically, but also continuously perform.

However, while working with heterogeneous catalysts it comes about the stirring or the conveyance of the reaction mass to a comminution of the Catalyst and, as a result, significant losses of catalyst.

In addition, the well-known homogeneous and heterogeneous catalysts do it not possible, butene- (l) by dimerization of ethylene in practically high yield to erllalten (you get mainly butene- (cis-2) and butene-trans- (2) with a Content from 85 to 98%); In the dimerization of propylene is the production of Methylpentelien impossible in high yield (the methylpentene content of the dimerizate does not exceed 69%).

EB is currently known a process for the dimerization of olefins with a maximum of 12 carbon atoms by mixing it medium of hydrocarbon or calogenic hydrocarbon solvents at a temperature of (-50) to (+150) ° C and a pressure of 1 to 100 atm. of at least one of the sewn Olefins with a two-component catalyst consisting of an organoaluminum compound of the general formula RnAIX3-n, where R is alkyl with a maximum of 12 carbon atoms, 1 is halogen, n is 1 or 2, and a copolymer of vinyl pyridine with a polyvinyl-substituted aromatic compound (e.g. divinylbenzene, Trivinylbenzene), said copolymer being 75 to 90 percent by weight Polyvinylpyridine fragments to which a nickel salt of an organic or inorganic Acid complex is bound, contains and the molar ratio of the organoaluminum Connection to the nickel salt is 1 to 100 (see U SPs 3 737 474).

The catalyst used in the process described, which is described in is insoluble in the reaction medium, all the disadvantages of the known heterogeneous Catalysts on.

The purpose of the present invention is to eliminate the above Disadvantage.

The invention was based on the object, go in the Ver for the dimerization of olefins with 2 to 4 carbon atoms on a catalyst the basis of connections of the Nikkiel and aluminum to develop which it makes possible to obtain butene (l) and methyl pöntene in high yield, a high Has stability, can be easily regenerated and it allows the process to be carried out both periodically and continuously.

This object is achieved in that a method for nimerization of olefins having 2 to 4 carbon atoms by mixing at least one of the mentioned olefins with a catalyst in the medium of hydrocarbon or halogenated hydrocarbon solvents at a temperature of 0 to (+100) ° C and a pressure of 1 to 40 atm is suggested; is used as a catalyst according to the invention, one in the hydrocarbon or ijalogenohydrocarbon solvents swellable graft copolymer of natural or synthetic carbocatenary rubber with Vinylpyridine, where the said polymerizate 0.5 to 40 percent by weight of polyvinylpyridine fragments, to which a nickel salt of an organic or inorganic acid is complexly bound is, and 2 to 50 mole percent - AlRX members, where R is alkyl with at most 8 Carbon atoms, X is halogen, contains, the aluminum atom with the Main chain of the copolymer is connected via a carbon atom and that AltNi atom contains 1 to 20.

The catalyst is distinguished by its high selectivity. By the dimerization of ethylene is obtained butene- (l) in high yield (the content of the butene mixture obtained in butene- (l) reaches 92 to 96% j; in dimerization of propylene is essentially obtained methylpentene (the content of the Dimerisates of methyl pentenes reached 90 to 95s) In contrast to the known heterogeneous catalysts crumble in the process according to the invention gel-like catalyst is not used, it can be easily regenerated and can used in the process for a long time while maintaining the original activity will.

The inventive method for the dimerization of olefins with 2 to 4 carbon atoms is obtained by mixing at least one of the olefins mentioned with the catalyst in the medium of hydrocarbon solvents (aliphatic, aromatic hydrocarbons) or halogenated hydrocarbon solvents a temperature of 0 to (+100) 0C, preferably 20 to 700C, and a pressure of 1 to 40 atm, preferably 1 to 10 atm, in reactors with periodic operation (below Stirring) or in continuous flow tube reactors. In the process of dimerization, both individual olefins (ethylene, Propylene, butene) and their mixtures (for example a mixture of ethylene with propylene or a mixture of ethylene with butene).

As stated above, one uses in the method according to the invention as a catalyst a graft copolymer swellable in the abovementioned solvents of natural or synthetic carbon chain rubber with vinyl pyridine, said M Copolymer 0.5 to 40 percent by weight of polyvinylpyridine fragments to which a nickel salt of an organic or inorganic acid is bound in a complex, as well as 2 to 50 mole percent -AlRZ-Glleder, where R is alkyl with at most 8 carbon atoms, preferably 2 to 4 carbon atoms, x is aloene, preferably chlorine, contains, the aluminum atom with the main chain of the Xischpolymerisates through a carbon atom is connected and the Al / Ni atomic ratio is 1 to 20, preferably 3 to 6.

Both Nature- as well as synthetic carbon chain rubber, for example polybutadiene (1,2), Polybutadiene cis and trans, isoprene rubber, ternary copolymers of ethylene, Propylene and non-conjugated diene.

The rubber (60 to 99.5 percent by weight) is subjected to one radical graft copolymerization with 0.5 to 40 percent by weight vinylpyridine, for example 4-vinylpyridine, 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, in the medium of hydrocarbon or halogenated hydrocarbon solvents a temperature of 40 to 70 ° C. As initiators of radical copolymerization one uses, for example, azobisisobutyronitrile. After the interpolymerization has been carried out one takes the crosslinking of the ischpolymerisat it 'with the use of peroxide initiators, for example benzoyl peroxide.

The reaction of the mixture polymer obtained is then carried out Nickel salt, for example nickel dichloride, nickel dibromide, nickel oleate, nickela ciety acet onate, in the medium of the above solvents at a temperature from 10 to 500C through. This gives something that is swellable in the solvents mentioned Graft copolymer containing 0.5 to 40 percent by weight of polyvinylpyridine fragments contains, to which the nickel salt is bound in a complex. Vas preserved nickel-containing Uischpolymerisat is carefully washed with the solvent to remove any possible Traces of the converted nickel salt.

The nickel-containing copolymer obtained is subjected to the medium an absolute hydrocarbon solvent implementation with dialkyl aluminum hydride, preferably diisobutyl aluminum hydride, at one temperature from 0 to (+100) 0C or with trialkyl aluminum, preferably triisobutyl aluminum, at a temperature of 100 to 1600C. The amount of dialkyl aluminum hydride respectively of the trialkylaluminum is, based on the link of the rubber chain, 2 to 50 mole percent. The product obtained is subjected to the above-mentioned in the medium Solvent of the reaction with a stoichiometric amount (compared to the aluminum content in rubber) of chlorine, or aluminum halide, preferably of aluminum chloride, or alkyl aluminum dihalide, preferably ethyl aluminum dichloride, or isobutyl aluminum dichloride, or with a (compared to the stoichiometry not less than tenfold) excess of dialkyl aluminum halide, preferably diisobutyl aluminum chloride, at one Temperature from 20 to 50 ° C.

The gel-like catalyst obtained is carefully washed with the Solvent to remove possible traces of the unreacted low molecular weight organometallic compounds.

The catalyst used in the process according to the invention are used in the form of 0.1 to 5 mm in the above solvents swollen granules. These granules are in the whole volume for the molecules slightly permeable to the reagents and the reaction products that are formed.

For a better understanding of the present invention, the following are made Examples of the implementation of the dimerization of Olefins listed.

Example 1. Place in an ampoule with a capacity of 75 ml 1 g of polybutadiene - (1,2), 0.11 g of 4-vinylpyridine and 40 ml of heptane. After the dissolution of the rubber, the solution is degassed and 0.04 g of azobisisobutyronitrile is added to 5 ml of benzene. The ampoule is kept at a temperature of 700C for 10 hours. then 0.04 g of benzoyl peroxide in 5 ml of benzene is introduced into the ampoule. The ampoule it is kept at a temperature of 80 ° C. for 10 hours. The graft copolymer obtained the rubber with 4-vinylpyridine is filtered off and washed twice with small portions (each with a rope 10 ml) of benzene and dry in vacuo. The said copolymer swells in the raw hydrogen and halogenated hydrocarbon solvents. The content of the Copolymer of poly-4-vinylpyridine fragments is qv 13 percent by weight.

The graft copolymer obtained is 2 to 3 mm in size Granules are placed in a quantity of 1 g in a glass reactor with a capacity of 75 ml, provided with stirrer, a. 0.24 g of nickel acetylacetonate are placed in the same reactor and 30 ml of heptane. The reaction mixture is stirred at a temperature of 20 ° C for 20 hours.

Then the polymeric granules are washed several times (4 to 6 times) with portions of 10 ml each of heptane to remove the unreacted xickel acetylacetonate and dries in a vacuum.

This gives a graft copolymer containing poly-4-vinylpyridine fragments contains, to which the nickel acetylacetonate molecules are coordinated (nickel-containingo cliché polymer).

The nickel content of the copolymer is 1.3 percent by weight.

The resulting nickel-containing copolymer is added in vacuo 10 ml 0.5 molar solution of diisobutyl aluminum hydride in absolute heptane and 20 ml of absolute heptane. The resulting mixture is kept at a temperature of 60 ° C for 3 hours and then at a temperature of 100 ° C for 3 hours. then one brings into the reactor 10 ml of 0.5 molar solution of ethylaluminum dichloride in absolute heptane and keeps the mixture at a temperature of 20 ° C 10 hours. Then the granules of the catalyst are washed, the 10 mol percent -Al (iso-Bu) contains Cl members, carefully mixed with absolute heptane for removal of the low molecular weight organoaluminum compounds and dries in vacuo.

The Al / Ni atomic ratio is 6. The degree of swelling of the catalyst granules is as follows: 0.1 g of granules sucked 0.7 ml of heptane at a temperature of 200C on.

In a glass reactor with a capacity of 50 ml equipped with a stirrer 0.2 g of the catalyst obtained and 15 ml of absolute heptane are introduced. That The mixture is stirred for 30 minutes at a temperature of 4000, then into the reactor Introduces ethylene at a temperature of 40 ° C and a pressure of 2 atm. To The reaction is interrupted after 2 hours. The dimerization products one distills off and collects in the template. 3g of butenes are obtained, which is 92% Butene- (l) included.

Example 2. To a 75 ml flask fitted with a stirrer 1 g of granules of the graft copolymer of polybutadiene (l, 2) with 4 vinylwhich 9 weight percent poly-4-vinylpyridinepyridine fragments contains (the copolymer was obtained analogously to Example 1), 0.13 g of nickel chloride and 30 ml of heptane. The reaction mixture is stirred at a temperature of 200.degree for 20 hours. The polymeric granules are then washed several times with heptane to remove the unreacted nickel chloride and dry in vacuo. The salary of the copolymer of nickel is 1.2 percent by weight.

The resulting nickel-containing copolymer is added in vacuo 10 ml 0.5 molar solution of diisobutyl aluminum hydride in absolute heptane and 20 ml of absolute heptane. The mixture obtained is kept at 60 ° C. for 3 hours and then 3 hours at 10,000. 10 ml of 0.5 molar solution of ethylaluminum dichloride are then introduced into the reactor in absolute heptane and holds the mixture at 2000 for 10 hours. Thereafter the granules of the catalyst, which contains 20 mole percent -Al (iso-Bu) Cl members, are washed contains, carefully with absolute heptane to remove the low molecular weight organoaluminum Compounds and dry in vacuum. The Al / Ni M om ratio in the catalyst it is 10. The degree of swelling of the catalyst is as follows: 0.1 g of granules absorbs 0.4 ml of heptane at 20 ° C.

The catalyst obtained is placed in a tubular reactor and 20 ml of absolute dean. Then ethylene is passed through. The dimerization will carried out at a temperature of 200C and a pressure ton 3 atm. The dimerization products is collected in the template. Samples and are taken at certain time intervals analyzes the composition the butenes that are formed according to the Gas-liquid chromatography method. The results are given in the table.

Table time, min content of butene- (1) in the dimer,% 10 96.0 30 95.0 60 95.1 120 94.9 Example 3. In an ampoule of 75 ml capacity is brought to 0.6 g granules of the crosslinked graft copolymer, obtained by radical copolymerization of polybutadiene - (1,2) with ternary Copolymer of ethylene, propylene and ethylidene norbornene and with 4-vinylpyridine (The polymerization conditions are analogous to Example 1, the weight ratio of the components mentioned is 1: 4: 1), a. Then 0.15 is placed in the reactor g of nickel oleate and 30 ml of heptane. The reaction mixture is stirred at one temperature of 20 ° C for 10 hours. The granules obtained are then washed several times Heptane to remove the unreacted nickel oleate and dry in vacuo. Man contains nickel-containing mixed polymer (the nickel content is 1.45 percent by weight).

The resulting nickel-containing copolymer is added in the 5.3 ml of 0.5 molar solution of diethylaluminum hydride in absolute heptane and vacuum 20 ml of absolute heptane too.

The reaction mixture is kept for 5 hours at a temperature of 50 ° C, 5.3 ml of 0.5 molar solution of ethylaluminum dibromide are then introduced into the reactor in absolute heptane and keeps the mixture at a temperature of 200C during 10 hours1 Then the granules of the catalyst, which is 7 mole percent -Al (ethyl) contains Br links, carefully mixed with absolute heptane for removal of the unreacted low molecular weight organoaluminum compounds and dries in the Vacuum. The Al / Ni atomic ratio is ~ 3. The degree of swelling of the catalyst granules is as follows: 0.1 g of granules absorbs 0.55 ml of heptane at 20 ° C.

In a reactor with a capacity of 50 ml equipped with a stirrer 0.3 g of granules of the catalyst obtained and 20 ml of absolute heptane are added a. Then one leads the reactor ethylene at a temperature of 200C and one Pressure of 1 atm too. After 1 hour, the butenes formed are removed from the reactor. The dimerization rate of ethylene is 1.5 kg butenes / g Ni in the Hour. The butene (l) content of the butene mixture obtained is 95%.

The temperature in the reactor is then increased to 4000.

The dimerization of ethylene is carried out at the temperature mentioned and a pressure of 1 atm. After 1.5 hours, the butenes formed are removed from the reactor. The rate of polymerization of ethylene is 1.1 kg Butene / g Ni per hour. The butene- (l) content of the butene mixture obtained is 94%.

The temperature in the reactor is then increased to 60 ° C. and carried out the dimerization of ethylene at said th temperature and a pressure of 2 atm through. After 1 hour, the reaction products are removed from the reactor. the The rate of dimerization of ethylene is 0.7 kg butenes / g Ni per hour. The butene (I) content of the butene mixture obtained is 96%.

Example 4. Into a reactor containing 0.3 g of that used in Example 3 Contains catalyst, one brings ncc the removal of the products of dimerization of the ethylene and the solvent, 20 ml of absolute heptane. Then you lead that Reactor to propylene and carries out the dimerization of propylene at a temperature of 40 ° C and a pressure of 1.5 atm. After 1 hour you remove from the Reactor the reaction products and the solvent. The rate of dimerization of propylene is 0.8 kg hexene / g Ni per hour. The content of the received Hexene mixture of methyl pentenes is ~ 95%.

Then 20 ml of absolute chlorobenzene are introduced and the dimerization is carried out of propylene at a temperature of 0 ° C and a pressure of 1 atm. To The reaction products and the solvent are removed from the reactor for 1 hour. The dimerization rate of propylene is 0.9 kg hexene / g Ni in the Hour. The content of the obtained witch mixture of methyl pentenes is 92%.

Example 5. Put 0.3 g of the example in a reactor 3 (the Al / Ni atomic ratio is 1) and 20 ml of absolute toluene. Then ethylene is fed to the reactor and the dimerization is carried out at a temperature of 4000 and a pressure of 1 atm. Removed after 1 hour the Dinr'erisierungsprodukte from the reactor. The rate of dimerization of ethylene is 1.1 kg of butene / g I per hour, the content of the butene mixture obtained of butene- (1) is 94%.

The temperature in the reactor is then increased to 10002 and the process is carried out the dimerization of ethylene at a pressure of 10 atm for 1 hour. The rate of dimerization of ethylene is 0.3 kg of butenes / g of iti in the Hour.

The butene (l) content of the butene mixture obtained is 95%.

Example 6. The mixture is placed in a reactor equipped with a stirrer 0.3 g of granules of the crosslinked graft copolymer obtained by free radicals Copolymerization of polybutadiene (1,2) with the ternary copolymer of Ethylene, propylene and ethylidene norbornene (the weight ratio of the reagents is 2: 1) and with 4-vinylpyridine (the content of the crosslinked graft copolymer Poly-4-vinylpyridine fragments is 40% by weight), a. Then you bring into the reactor 0.12 g of nickel bromide and 30 ml of heptane. The reaction mixture is stirred one at a temperature of 200C for 10 hours.

The polymeric granules are then washed several times with heptane to remove them of the unreacted nickel bromide and dried in vacuo.

The resulting nickel-containing copolymer is mixed with dioctylaluminum hydride and then with ethylaluminum dichloride under the analogues described in Example 1 Conditions around. The granules of the catalyst obtained, the 50 mole percent -Al (octyl) Cl members contains, it is carefully washed with absolute beptane to remove the low molecular weight organoaluminum compounds and dries in vacuo.

The Al / Ni atomic ratio is 12.

It is then introduced into the reactor containing the catalyst obtained 20 ml of butene- (l) and feeds ethylene.

At a temperature of OOC and a pressure of 2 atm, the Dimerization of a mixture of butene- (l) with ethylene. After 1 hour will be the reaction products are distilled off and analyzed. 0.3 g of hexene are obtained 50% of methyl pentenes and 50% of linear hexenes.

Example 7. The mixture is placed in a reactor equipped with a stirrer 1 g of crosslinked graft copolymer obtained by radical copolymerization of natural rubber with polybutadiene- (1,2) and 2-vinylpyridine (the conditions of The copolymerization is carried out analogously to Example 1; the weight ratio from natural rubber to polybutadiene - (1,2) is 9: 1, the content of the crosslinked Graft copolymer of poly-2-vinylpyridine fragments 0.5 percent by weight), a. 0.05 g of nickel acetylacetonate is then introduced into the reactor and 25 ml of heptane and carries out the implementation of said Äischpolymerisates with the Nickel acetylacetonate under the conditions analogous to Example 1 by. The received Nickel-containing copolymer is set under the conditions analogous to Example 1 with 2 ml of 0.5 molar solution of diisobutylaluminum hydride in absolute heptane and then with 2 ml of 0.5 molar solution of ethylaluminum dichloride in absolute heptane around. The granules of the catalyst, which contains 2 mole percent -Al (iso-butyl) Cl members, it is carefully washed with absolute heptane to remove the low molecular weight Compounds and dry in vacuum. The AlZ atom ratio is «20. The degree of swelling of the catalyst is as follows: 0.1 g of granules is absorbed by 0.8 ml of heptane at 200.degree.

Then the dimerization of ethylene is carried out at one temperature of 700C and a pressure of 40 atm in the medium of absolute heptane. To The reaction is interrupted for 2 hours and butenes (0.8 g) are collected in the receiver, which ~ 95 »contain butene- (l).

Example 8. In a flow-through reactor with a stirrer to which a compressor is connected for circulation, add 0.5 g granules of the catalyst, analogous to that used in Example 3 (Al / Ni atomic ratio = 5), and 40 ml absolute Dean a. Lian supplies ethylene and performs dimerization at one temperature of 300C, a pressure of 2 atm by circulating the ethylene. The rate of circulation is 20 to 50 g of ethylene per hour. The dimerization products are circulated by the current of the led from Ethylene diverted out of the reactor and collected in the catcher. The process will last during 100 Hours carried out. The space-time yield of the catalyst is 120 kg of nickel. A mixture of butenes (butene- (1), butene- (cis-2) and (trans-2)) is obtained, which Contains ~ 94% butene- (1).

Claims (1)

Process for the dimerization of olefins. PATENT CLAIM Process for the dimerization of olefins having 2 to 4 carbon atoms by mixing at least one of said olefins with a catalyst based on compounds of nickel and aluminum in the medium of hydrocarbon or halogenated hydrocarbon solvents at a temperature of 0 to (+100) 0 C and a pressure of 1 to 40 atm, thereby g e -k e n n n e i c h n e t that the catalyst used in the hydrocarbon or halogenated hydrocarbon solvents swellable graft copolymer of Natural or synthetic carbon chain rubber with vinyl pyridine used, where said copolymer 0.5 to 40 percent by weight of polyvinylpyridine fragments, to which a nickel salt of an organic or inorganic acid is complexly bound is, and 2 to 50 mole percent -AlRX members, where R is alkyl with at most 8 Carbon atoms, X stands for halogen, the aluminum atom with the Main chain of the copolymer is connected by a carbon atom and that Al / Ni atomic ratio is 1 to 20.