Catalytic trimerisation of olefin monomers

FIELD: chemistry.

SUBSTANCE: claimed invention relates to catalyst of olefin monomers trimerisation. Described is catalytic composition for olefin monomers trimerisation, which contains a) source of chrome, molybdenum or tungsten; b) ligand if general formula (I), in which X stands for bivalent organic group, selected from substituted or non-substituted alkylene groups, in case of substituted groups, substituents represent hydrocarbon groups; R1 and R3 represent cycloaromatic groups, which do not contain polar substituents in none of orto-positions; R2 and R4 are independently selected from obligatory substituted cycloaromatic groups, each of R2 and R4 having polar substituent in at least one orto-position; and c) cocatalyst. Also described is method of olefin monomers trimerisation, including interaction of at least one olefin monomer in conditions of trimerisation reaction with said above catalytic composition.

EFFECT: selective obtaining 1-hexagen from ethylene, reducing level of formation of by-products, especially C10.

10 cl, 2 tbl, 12 ex

 

The technical field to which the invention relates

The present invention relates to a catalyst for the trimerization of olefinic monomers. The present invention also relates to a method for the trimerization of olefinic monomers, in particular the production of 1-hexene from ethylene in the presence of the above catalyst.

The prior art inventions

Effective catalytic trimerization of olefinic monomers, such as trimerization of ethylene to 1-hexene, is an area of heightened interest to get olefin trimers different degrees of commercial value. In particular, 1-hexene is a valuable comonomer for linear low density polyethylene (LLDPE). 1-hexene can also be obtained in the usual way oligomerization using transition metal, although the path of trimerization is more preferable, as it largely avoids undesirable olefins.

The prior art describes several different catalytic systems for the trimerization of ethylene to 1-hexene. A number of these catalysts based on chromium.

US-A-5198563 (Phillips) describes catalysts based on chromium containing monodentate amine ligands suitable for the trimerization of olefins.

US-A-5968866 (Phillips) describes a method of oligomerization/trimerization of ethylene, which is used in the of eshet catalyst, containing a complex of chromium, which contains asymmetric tridentate coordinating postanowi, arsenovic or stipanovic ligand and alumoxane to obtain alpha-olefins, which are enriched with 1-hexene.

U.S. patent 5523507 (Phillips) describes the catalyst on the basis of the source of chromium, 2.5 to dimethylpyrrole ligand and alkylamino activator for use in the trimerization of ethylene to 1-hexene.

Chem. Commun., 2002, 8, 858-859 (BP) describes the chromium complexes with ligands of the type Ar2PN(Me)PAr2(Ar=ortho-methoxy-substituted aryl group) as catalysts for the trimerization of ethylene.

WO 02/04119 (BP) describes a catalyst for the trimerization of olefins containing a source of chromium, molybdenum or tungsten, the ligand containing at least one atom of phosphorus, arsenic or antimony, is associated with at least one hydrocarbon or heteropaternal group having a polar Deputy, but excluding the case where all such polar substituents are Fofanova, arsenovi or stipanovi group and possibly the activator. The ligand used in most examples, represents a (2-methoxyphenyl)2PN(Me)P(2-methoxyphenyl)2.

Although the catalysts described in the above-mentioned documents BP, have good selectivity for 1-hexene inside a fraction With the6, has a relatively high level on the education side products (e.g., datenow). It would therefore be desirable to provide a catalyst for the trimerization of olefinic monomers, especially for the trimerization of ethylene to 1-hexene, which reduces the formation of by-products (for example, datenow) while maintaining selectivity for 1-hexene.

Unexpectedly, it was found that the composition of the catalysts and methods of the present invention provide an effective path for selective derivation of 1-hexene from ethylene at lower level of education by-products, especially With10.

The invention

According to one aspect of the present invention is proposed composition of the catalyst for the trimerization of olefinic monomers, which contains

a) a source of chromium, molybdenum or tungsten;

b) a ligand of General formula (I):

(R1)(R2)P-X-P(R3)(R4)(I)

in which

X means a bivalent organic bridging group containing from 1 to 10 carbon atoms in the bridge;

R1and R3independently selected from a hydrocarbon, substituted hydrocarbon, heterogenicity and substituted heterogenicity groups with the proviso that when R1and R3mean cycloaromatization group, they do not contain polar substituents in any the m of the ortho-positions;

R2and R4independently selected from optionally substituted cycloaromatization groups, and each R2and R4has a polar substituent in at least one of the ortho-positions; and

(C) socialization.

According to an additional aspect of the present invention proposes a method for the trimerization of olefinic monomers, including the interaction of at least one olefinic monomer in the reaction conditions of the trimerization with the aforementioned catalyst composition.

The composition of the catalysts of the present invention are particularly suitable for the trimerization of olefinic monomers, especially for the trimerization of ethylene to 1-hexene. The composition of the catalysts and the method according to the present invention unexpectedly provide, essentially, the low concentration side of olefinic products (for example, datenov, predominantly 1-mission, which is obtained by adding two ethylene monomers to produce 1-hexene) while maintaining a high selectivity for 1-hexene. In addition, the composition of the catalysts of the present invention demonstrate improved velocity profiles activity/attenuation compared to Cr(III)(2-methoxyphenyl)2PN(Me)P(2-methoxyphenyl)2the catalysts described in WO 02/04119 mentioned above. In particular, the compositions of the catalysts of the present invention show horologically activity but less rapid decay than Cr(III)(2-methoxyphenyl)2PN(Me)P(2-methoxyphenyl)2the catalysts.

Detailed description of the invention

Used in this description, the term "trimerization" means the catalytic trimerization of olefinic monomers with obtaining the composition of the product, enriched compound obtained by the reaction of the three mentioned olefinic monomers. The term trimerization includes cases where all of olefinic monomers in the flow of raw materials are identical, as are cases when the flow of raw material contains two or more different olefinic monomers.

In particular, the term "trimerization", when used in relation to the trimerization of ethylene means the trimerization of ethylene to form with6alkene, especially 1-hexene.

The term "trimerization selectivity"when used in relation to the trimerization of ethylene to 1-hexene, means the amount received From the6fractions in the composition of the product.

The term "selectivity for 1-hexene", when used in relation to the trimerization of ethylene to 1-hexene, means the amount of 1-hexene in the composition of the product. The total yield of 1-hexene in the trimerization of ethylene is the result of multiplying the "selectivity of trimerization" on "selectivity for 1-hexene".

The composition of the catalyst according to the present invention contains

a) history the nick of chromium, molybdenum or tungsten;

b) ligand;

(C) socialization.

Each of these three essential components are described in detail below.

The source of chromium, molybdenum or tungsten, component (a), for the composition of the catalyst may include simple inorganic or organic salts of chromium, molybdenum or tungsten. Examples of simple inorganic or organic salts are the halides, acetylacetonates, carboxylates, oxides, nitrates, sulfates and the like. Additional sources of chromium, molybdenum or tungsten may also include the coordination or ORGANOMETALLIC complexes, such as complex trichloride chrome tetrahydrofuran, benzene)tricarbonylchromium, hexacarbonylchromium and the like.

The source of chromium, molybdenum or tungsten may also include a mixture of simple inorganic salts, simple organic salts, coordination complexes and ORGANOMETALLIC complexes.

In preferred embodiments of this invention component (a) is a chromium, particularly chromium (III).

Preferred sources of chromium for use in this invention are inorganic and organic salts of chromium. Preferred sources of chromium for use in this invention are halide is chromium, such as chromium chloride, chromium bromide, chromium fluoride and iodide chromium. Particularly preferred source of chromium for use in this invention is a chromium chloride, CrCl3.

The ligand composition of the catalyst according to the present invention, the component (b)has the General formula (I):

(R1)(R2)P-X-P(R3)(R4)(I)

in which

X means a bivalent organic bridging group containing from 1 to 10 carbon atoms in the bridge;

R1and R3independently selected from a hydrocarbon, substituted hydrocarbon, heterogenicity and substituted heterogenicity groups with the proviso that when R1and R3are cycloaromatization group, they do not contain polar substituents in any of the ortho-positions;

R2and R4independently selected from optionally substituted cycloaromatization groups, and each R2and R4has a polar substituent in at least one of the ortho-positions.

In the General formula (I), X denotes a divalent organic bridging group containing from 1 to 10, preferably from 2 to 6, more preferably from 2 to 4 and especially 2 to 3 carbon atoms in the bridge. The preferred option is sushestvennee has 2 carbon atoms in the bridge.

Under the "bridge" you know the shortest connection between the two phosphorus atoms.

Suitable bridging groups include substituted and unsubstituted alkylene group. Alkylene group may contain one or more heteroatoms in the bridge, such as N, S, Si or O. Preferably, if Allenova group contains only carbon atoms in the bridge.

Alkylene group may be substituted by one or more substituents. The substituents can be attached to any part of the connection.

Deputy alkalinous bridge groups can contain carbon atoms and/or heteroatoms. Suitable substituents include a hydrocarbon group which may be linear or branched, saturated or unsaturated, aromatic or non-aromatic. Hydrocarbon substituents can contain heteroatoms such as Si, S, N or O. Suitable aromatic hydrocarbon substituents include cycloaromatization group, preferably having from 5 to 10 carbon atoms in the cycle, such as phenyl and C1-C4alkylphenyl group. Suitable non-aromatic hydrocarbon substituents include linear or branched, alkyl or cycloalkyl group, preferably having from 1 to 10 carbon atoms, more pre is respectfully from 1 to 4 carbon atoms.

Other suitable substituents alkalinous bridging groups include halides such as chloride, bromide and iodide, thiol, HE AND1-O-, -S-A1, -CO-A1, -NH2, -NHA1, -NA1A2, -CO-NA1A2, -PO4, -NO2, -CO, -SO2that And1and2independently represent a non-aromatic group, preferably having from 1 to 10 carbon atoms, more preferably from 1 to 4 carbon atoms, for example methyl, ethyl, propyl and isopropyl.

When Allenova bridge group is substituted, preferred substituents are hydrocarbon groups. Particularly preferred hydrocarbon substituents are1-C4alkyl group, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, most preferably methyl.

Examples of unsubstituted alkilinity bridging groups include methylene, ethylene and trimethylene group. Examples of substituted alkilinity bridging groups include 2,2-dimethyl-trimethylene, 2,2-diethyl-trimethylene, 2,2-dimethyl-tetramethylene, 2-methyl, 2-hydroxymethyl-trimethylene and 2,2-di-hydroxymethyl-trimethylene.

Particularly preferred organic alkylene bridge group for use in this invention are unsubstituted alkylene mos is iMovie group. Particularly preferred organic bridging group is an ethylene, that is,- CH2-CH2-.

Other suitable bridging groups are those where the connection forms part of a non-aromatic or aromatic ring structure. Such bridging groups contain one or more substituted or unsubstituted, saturated or unsaturated non-aromatic ring structures and/or one or more substituted or unsubstituted cycloaromatization (including heteroaromatic) ring structures. Non-aromatic ring structure may be interrupted by one or more heteroatoms, such as N, S, Si or O. Preferably, such a bridge group contains from 2 to 6 carbon atoms in the bridge.

Suitable non-aromatic ring structure include cyclopentane, cyclohexane, cyclohexene, cyclopentene, 3,4-furan and 3,4-thiophene.

Suitable aromatic ring structures include phenylene, especially 1,2-phenylene and naftilan, especially 1,8 - or 1,2-naphthylene.

These ring structures may be substituted for any type of substituent, including heteroatoms, alkyl groups, cycloalkyl group and cycloaromatization group. Suitable substituents include the substituents mentioned above in relation to alkilinity bridge groupprincipal, when two atoms of phosphorus added to the round Robin system in the neighboring positions, i.e. positions 1 and 2.

R1and R3independently selected from a hydrocarbon, substituted hydrocarbon, heterogenicity and substituted heterogenicity groups, provided that when R1and R3are cycloaromatization group, they do not contain polar substituents in any of the ortho-positions.

Used in this description, the term "hydrocarbon" refers to a group containing the atoms of only carbon and hydrogen. The hydrocarbon group may be saturated or unsaturated, linear or branched, non-aromatic ring or cycloaromatization ring. Preferred for use in this invention the hydrocarbon groups contain from 1 to 20 carbon atoms.

Used in this description, the term "substituted hydrocarbon" refers to hydrocarbon groups that contain one or more functional groups containing inert heteroatoms. Under "functional groups containing inert heteroatoms", understand that these functional groups do not interfere to any substantial degree the trimerization process.

Used in this description, the term "heterogenicity" refers to a hydrocarbon group in which one or more is about of the carbon atoms replaced by a heteroatom, such as S, N or O. Used in this description, the term "substituted heterogenicity" refers to heterorhabditis groups that contain one or more functional groups containing inert heteroatoms.

Used in this description, the term "cycloaromatization" refers to monocyclic or polycyclic, aromatic or heteroaromatic ring having from 5 to 14 ring atoms, optionally containing 1 to 3 heteroatoms selected among N, O and S. Cycloaromatization groups are preferably monocyclic or polycyclic aromatic rings, such as cyclopentadienyl, phenyl, naphthyl or anthracene. Even more preferred cycloaromatization groups are monocyclic or polycyclic aromatic ring having 5 to 10 ring atoms. Especially preferred cycloaromatization groups are monocyclic aromatic ring containing from 5 to 6 carbon atoms, such as phenyl and cyclopentadienyl, and the most preferred cycloaromatization group is a phenyl group.

Used in this description, the term "substituted cycloaromatization" means that cycloaromatization group may be substituted by one or more substituents. The approach is the following substituents include substituents, mentioned above in relation to alkilinity bridging groups.

In one preferred embodiment, R1and R3independently selected from substituted or unsubstituted cycloaromatization groups that do not contain a polar substituent at any of the ortho-positions. In an even more preferred embodiment, R1and R3independently selected from optionally substituted phenyl groups, which do not contain a polar substituent at any of the ortho-positions. In a particularly preferred embodiment, R1and R3represent unsubstituted phenyl groups.

Preferably, R1and R3the groups were the same.

R2and R4independently selected from optionally substituted cycloaromatization groups, and each R2and R4the group has polar Deputy, at least one of the ortho-positions. For the avoidance of doubt, the phrase "each R2and R4the group has polar Deputy, at least one of the ortho-positions" means that the same ligand R2substituted with a polar substituent in one or both of its ortho-positions, and R4substituted with a polar substituent in one or both of its ortho-positions.

The term "possibly substituted" in relation to R2and R4means that, on the addition to polar Deputy, in at least one of the ortho-positions, R2and R4groups can contain one or more substituents. Suitable substituents include the substituents mentioned above in relation to alkilinity bridging groups.

Preferably, if R2and R4independently selected from optionally substituted cycloaromatization groups having from 5 to 14 ring atoms, preferably 5 to 10 ring atoms, each of R2and R4has polar Deputy, at least one of the ortho-positions.

In one preferred embodiment, R2and R4independently selected from a possibly substituted phenyl group, and each of R2and R4has polar Deputy, at least one of the ortho-positions.

Preferably, if each of R2and R4has polar Deputy, at least one of the two ortho-positions.

Used in this description, the term "polar Deputy" means the Deputy, which includes electronegative center.

Suitable for use in this invention, the polar substituents include, but are not limited to, optionally branched C1-C20alkoxygroup, i.e. hydrocarbon group associated with R2and R4cycloaromatization to what lcom through bridging oxygen atom; optionally substituted C5-C14alloctype, i.e. optionally substituted cycloaromatization group associated with R2and R4cycloaromatization ring through bridging oxygen atom; optionally branched C1-C20alkyl(C1-C20)alkoxygroup, i.e. With1-C20hydrocarbon group having From1-C20alkoxygroup; hydroxyl; amino; (di)1-C6alkylamino; nitro; C1-C6alkylsulfanyl; C1-C6alkylthio1-C6alkyl groups; and tselnye group.

Examples of suitable polar substituents include methoxy, ethoxy, isopropoxy, phenoxy, Pantothenate, trimethylsiloxy, dimethylamino, methylsulfonyl, tosyl, methoxymethyl, methylthiomethyl, 1,3-oxazolyl, hydroxyl, amino, sulfate, nitro and the like.

Preferably, if the polar substituents for R2and R4independently selected from optionally branched C1-C20alkoxygroup, optionally substituted C5-C14aryloxy and optionally branched C1-C20alkyl(C1-C20)alkoxygroup. More preferably, if the polar substituents for R2and R4independently selected from optionally branched C1-C20alkoxygroup, especially optional is about branched C 1-C6alkoxygroup, such as, for example, methoxy, ethoxy or isopropoxy. Especially preferred polar Deputy for R2and R4is methoxy.

Preferably, when R2and R4groups are the same and have the same number and type of polar substituents. Particularly preferably, if R2has only one polar substituent in one of the two ortho-positions, and if R4has only one polar substituent in one of the two ortho-positions.

The ligands according to formula (I) can be prepared using techniques known to experts in the art or described in the published literature. Examples of such compounds are

(2-methoxyphenyl)(phenyl)DCL2CH2P(2-methoxyphenyl)(phenyl),

(2-methoxyphenyl)(phenyl)DCL2P(2-methoxyphenyl)(phenyl),

(2-methoxyphenyl)(phenyl)DCL2CH2CH2P(2-methoxyphenyl)(phenyl),

(2-ethoxyphenyl)(phenyl)DCL2CH2P(2-ethoxyphenyl)(phenyl),

(2-ethoxyphenyl)(phenyl)DCL2P(2-ethoxyphenyl)(phenyl),

(2-ethoxyphenyl)(phenyl)DCL2CH2CH2P(2-ethoxyphenyl)(phenyl),

(2-isopropoxyphenyl)(phenyl)DCL2CH2P(2-isopropoxyphenyl)(phenyl),

(2-isopropoxyphenyl)(phenyl)DCL2P(2-isopropoxyphenyl)(phenyl),

(2-isopropoxyphenyl)(phenyl)DCL2 CH2CH2P(2-isopropoxyphenyl)(phenyl).

Particularly preferred ligand for use in this invention is a (2-methoxyphenyl)(phenyl)DCL2CH2P(2-methoxyphenyl)(phenyl).

The source of chromium, molybdenum or tungsten, component (a), and the ligand, component (b)may be present in the composition of the catalyst according to the present invention in a ratio in the range from 10000:1 to 1:10000, preferably from 100:1 to 1:100, more preferably from 10:1 to 1:10. Most preferably, components (a) and (b) are present in a ratio ranging from 3:1 to 1:3. Usually the number of (a) and (b) are approximately equal, i.e. the ratio in the range from 1.5:1 to 1:1,5.

Socialization, component (C)may in principle be any compound or mixture of compounds that form an active catalyst with a source of chromium, molybdenum or tungsten, component (a) and ligand, component (b).

Compounds which are suitable as socializaton include alumoorganic compounds, organoboron compounds and inorganic acids and salts, such as athirat terraforming acid, tetrafluoroborate silver, hexafluoroantimonate sodium and the like.

Particularly preferred socializaton are alumoorganic connection. Suitable for use in this invention alumino the content of inorganic fillers compounds are compounds, having the formula AlR3in which each R group is independently selected from C1-C30of alkyl, oxygen or halides or compounds, such as LiAlH4and similar. Non-limiting examples of suitable alumoorganic compounds include trimethylaluminum (TMA), triethylaluminium (tea), triisobutylaluminum (CHIBA), tri-n-octylamine, dichloride methylalanine, dichloride ethylamine, chloride dimethylamine, chloride diethylamine and alumoxane. The mixture alumoorganic compounds are also suitable for use in this invention.

In a preferred embodiment of the present invention acetalization is alumoxanes socialization. These alumoxane socializaton can contain any alumoxane combination or mixture alumoxane compounds. Alumoxane can be prepared regulated by the addition of water to alkylamino connection, such as connection mentioned above or commercially available. In this context it should be noted that the term "alumoxane"used in this description, includes commercially available alumoxane, which may contain a proportion, usually about 10 wt.%, but possibly up to 50 wt.%, the corresponding trialkylaluminium. For example, commercial methylalumoxane (MAO) typically contains approximately > 10% of trimethylaluminum (TMA), while the modified methylalumoxane (MMAO) contains both TMA and triisobutylaluminum (CHIBA). The molar ratio of water to the connection of aluminum in the preparation of alumoxanes preferably lies in the range from 0.01:1 to 2.0:1, more preferably from 0.02:1 to 1.2:1, more preferably from 0.4:1 to 1:1, especially of 0.5:1. These alumoxane compounds may be linear, cyclic frames or mixtures thereof. Preferred alumoxane represent linear alumoxane formula R5(R6AlO)nin which n denotes a number from about 2 to 50, and R5and R6denote alkyl groups from C1to C6. The most preferred alumoxane are methylalumoxane (MAO) or modified methylalumoxane (MMAO), which contains both TMA and CHIBA.

Other suitable socializaton include socializaton described in WO 02/04119.

The number of socializaton used in the present invention, it is generally sufficient to provide a ratio in the range from 0.1 to 20000, preferably from 1 to 2000 atoms of aluminium or boron per atom of chromium, molybdenum or tungsten.

The composition of the catalyst according to the present invention can also be mixed with at least one other catalyst for trimerization.

Three important components of the catalyst (the), (b) and (C) may be added together simultaneously or sequentially in any order to provide an active catalyst. Three important components of the catalyst can interact in the presence of any suitable solvent. Suitable solvents known to specialists in this field of technology. Examples of suitable solvents are the solvents described in WO 02/04119.

The composition of the catalyst according to the present invention can be prepared either in the presence (i.e. "in-situ"), or in the absence of olefin monomer. Three significant component of the composition of the catalyst can be merged completely in the absence of olefin monomer or olefin monomer can be added to interaction of the catalyst components, simultaneously with the components of the catalyst or at any time during the interaction of the catalyst components.

Three important components of the catalyst can be deposited or applied on a material carrier. Examples of suitable materials media can be found in WO 02/04119.

Olefinic monomers suitable for use in the method of trimerization of the present invention, can be any olefin monomers that can be turned into a trimer. Suitable olefin monomers include, but are not limited to, ethylene, propylene, not necessarily OSVETLENIE 4-C20α-olefins, optionally branched C4-C20internal olefins, optionally branched C4-C20vinylidene olefins, optionally branched C4-C20cyclic olefins and optionally branched C4-C20dieny, as well as optionally branched C4-C20functionalityand olefins. Examples of suitable olefin monomers include, but are not limited to, ethylene, propylene, 1-butene, 1-penten, 1-hexene, 4-methylpent-1-ene, 1-hepten, 1-octene, 1-none, 1-mission 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecane, 1-hexadecene, 1-heptadecene, 1 octadecene, 1-nonadecane, 1 achozen, styrene, 2-butene, 1-ethyl-1-hexene, cyclohexene, norbornene and the like.

A mixture of olefinic monomers can also be used in the method according to the present invention.

Preferred olefin monomers for use in the method of trimerization of the present invention are propylene and ethylene. Particularly preferred ethylene.

The composition of the catalyst and the method according to the present invention is particularly suitable for the trimerization of ethylene to 1-hexene.

The way the trimerization of the present invention can be implemented in a wide range of conditions, known to experts in the art or described in the SDA is likovnoj literature, such as, for example, the conditions described in WO 02/04119.

The trimerization reaction can be performed in solution, slurry, gas phase or in mass.

When the trimerization is carried out in solution or suspension, you can apply a diluent or solvent which is essentially inert under the conditions of trimerization. Suitable diluents or solvents are aliphatic and aromatic hydrocarbons, halogenated hydrocarbons and olefins, which are essentially inert under the conditions of trimerization, such as solvents, are described in WO 02/04119.

The way the trimerization of the present invention can be implemented in a wide range of conditions that are well known to specialists in this field of technology. Typically, the temperature ranges from -100°C to 200°C, preferably from 0°C to 150°C and more preferably from 25°C. to 100°C. Typically, the pressure is in the range from 0 to 100 bar, preferably from 1 to 50 bar.

The way the trimerization of the present invention may be implemented in any of a number of suitable reactors, which are well known to specialists in this field of technology. Usually the way the trimerization of the present invention is carried out in a periodic, properities or continuous mode.

The division of the product of the reactant and the catalyst can be performed using any technology, it is GII, well-known experts in the art, such as distillation, filtration, centrifugation, separation of liquid/liquid extraction, etc.

Additional details regarding suitable reaction conditions for the trimerization, including further details of the reactors, solvents, separation technologies and the like, can be found in WO 02/04119.

The use of a composition of the catalyst and method according to the present invention for the catalytic trimerization of ethylene to 1-hexene provides very high selectivity for 1-hexene over all other products formed in this reaction.

The composition of the catalyst of the present invention provides a total output of 1-hexene by trimerization of ethylene, which is more than the total yield of 1-hexene by trimerization of ethylene using the equivalent composition of the catalyst, which does not contain a ligand of this type, as described in the present invention (but which, for example, contains a ligand of the formula PN(CH3)P-, as described in WO 02/04119), under identical reaction conditions. Preferably, if the composition of the catalyst of the present invention provides a total output of 1-hexene by trimerization of ethylene, which is up to 35% more than the total yield of 1-hexene by trimerization of ethylene using the equivalent composition of the catalyst is, which does not contain a ligand of this type, as described in the present invention, in an identical reaction conditions. More preferably, if the composition of the catalyst according to the present invention will provide full output 1-hexene by trimerization of ethylene, at least 5% more than the total yield of 1-hexene by trimerization of ethylene using the equivalent composition of the catalyst, which does not contain a ligand of this type, as described in the present invention, in an identical reaction conditions.

The number of 1-hexene obtained by trimerization of ethylene using the catalyst composition of the present invention, is at least 80 wt.%, preferably, at least 85 wt.%, more preferably at least 90 wt.% and especially at least 95 wt.%, from the composition of the final product.

The trimerization selectivity (i.e. the number of fractions With6in the composition of the product) for the trimerization of ethylene using the catalyst composition of the present invention is at least 80 wt.%. Preferably, if the trimerization selectivity for trimerization of ethylene using the catalyst composition of the present invention is greater than the selectivity for trimerization receive6compounds by trimerization of ethylene with ISOE what Itanium equivalent to the composition of the catalyst, which does not contain a ligand of this type, as described in the present invention (but which, for example, contains a ligand of the formula PN(CH3)P-, as described in WO 02/04119), under identical reaction conditions. Preferably, if the trimerization selectivity for trimerization of ethylene using the catalyst composition of the present invention up to 40% more than the trimerization selectivity for trimerization of ethylene using the equivalent composition of the catalyst, which does not contain a ligand of this type, as described in the present invention, in an identical reaction conditions. It is also preferred that the composition of the catalyst according to the present invention has the trimerization selectivity for trimerization of ethylene, which is at least 5% more than the trimerization selectivity for trimerization of ethylene using the equivalent composition of the catalyst, which does not contain a ligand of this type, as described in the present invention, in an identical reaction conditions.

The education side With10connections by trimerization of ethylene using the catalyst composition of the present invention is preferably not more than 60% of the level of adverse10compounds formed by the trimerization of ethylene using the equivalent composition of the catalyst, which is not who will win ligand of this type, as described in the present invention (for example, Cr(III)(2-methoxyphenyl)2)PN(CH3)P(2-methoxyphenyl)2), under identical reaction conditions. More preferably, when the receiving side connections10when the trimerization of ethylene using the catalyst according to the present invention is not more than 50% of the level of side connections10obtained by trimerization of ethylene using the equivalent composition of the catalyst, which does not contain a ligand of this type, as described in the present invention, under identical reaction conditions. Even more preferably, when receiving products of compounds With10when the trimerization of ethylene using the catalyst according to the present invention is not more than 30% from the level of the side connections10obtained by trimerization of ethylene using the equivalent composition of the catalyst, which does not contain a ligand of this type, as described in the present invention, under identical reaction conditions. In a particularly preferred embodiment, the receiving side connections10when the trimerization of ethylene using the catalyst according to the present invention is not more than 20% from the level of the side connections10obtained by trimerization of ethylene using equivalent compositions cat who lyst which does not contain a ligand of this type, as described in the present invention, under identical reaction conditions.

Catalytic composition and method according to the present invention are illustrated in the following non-limiting examples.

EXAMPLES

Several compositions (compositions 1, 2 and 3)containing the component of the ligand and a source of chromium, received for use in the trimerization reactions described below.

Composition 1

(2-Methoxyphenyl)(phenyl)PCH2CH2P(2-methoxyphenyl)(phenyl) in a 1:1 ratio with CrCl3

(2-methoxyphenyl)(phenyl)PCH2CH2P(2-methoxyphenyl)(phenyl) ligand was obtained by the following method.

In a nitrogen atmosphere to a solution of o-bromoanisole (0.54 mol) in pentane (150 ml) was slowly added with constant stirring a solution of n-utility (337 ml, 0.54 mol). The mixture was stirred overnight, after which the stirring was stopped and the suspension was allowed to spread. Liquid decantation and the solid precipitate on-resilite washed with pentane and dried in high vacuum.

0.20 mol o-resilite was dissolved in diethyl ether (400 ml) and cooled to -20°C. To the resulting solution was slowly added with constant stirring to 0.1 mol of ethylvinylacetate. Then the solution was allowed to reach 25°C, after which the solution was boiled under reflux for 2 hours Then the solution was allowed to cool, after which was added 0,1M hydrochloric acid (150 ml). The product was extracted with three portions of 50 ml of dichloromethane. The combined organic layers were dried using magnesium sulfate. The solvents were then removed with obtaining oil and then the excess anisole was removed by heating (70°C) in vacuum. The last traces of anisole was removed by washing the obtained white precipitate ((2-methoxyphenyl)(phenyl)phosphine oxide) in diethyl ether followed by crystallization from a mixture of chloroform/diethyl ether.

40 mmol (2-methoxyphenyl)(phenyl)phosphine oxide was added to tetrahydrofuran (600 ml) and the resulting solution was added a solution of n-utility (25 ml, 40 mmol) at 0°C. the Resulting orange homogeneous solution of lithium salt was then stirred for 1 hour at room temperature and then was cooled to 0°C. To this solution was added 1,2-attendeelist (20 ml). The temperature of the solution then was allowed to increase to room temperature. The suspension was formed by heating of the solution is boiled under reflux during the night. The mixture is then cooled and the reaction was suppressed by addition of water (150 ml). The product was then extracted with dichloromethane (3×100 ml) followed by drying with magnesium sulfate. The concentration of the solution leads to the product 1,2-ethandiyl(2-methoxyphenyl)(phenyl)phosphine oxide as white TV is Gomu substance.

To 2 mmol of a solution of the product 1,2-ethandiyl(2-methoxyphenyl)(phenyl)phosphine oxide in tetrahydrofuran (250 ml) was added dropwise to alumoweld (AlH3×1/3(C2H5)2O, 20 mmol). The solution is then boiled under reflux until completion (usually during the night), after which the reaction was suppressed by the addition of methanol (10 ml) followed by filtration of the precipitate aluminum salt. The filtrate was then concentrated. Adding methanol leads to a crystalline product (2-methoxyphenyl)(phenyl)PCH2CH2P(2-methoxyphenyl)(phenyl).

Composition 2 (comparative)

(2-Methoxyphenyl)2PN(CH3)P(2-methoxyphenyl)2in the ratio of 1:1 with CrCl3

(2-methoxyphenyl)2PN(CH3)P(2-methoxyphenyl)2the ligand was prepared by the primary education of a solution of 1.59 g (5 mmol) (2-methoxyphenyl)2PNEt2in 20 ml of diethyl ether. To this solution was added a solution of 10 ml of 1M HCl in diethyl ether (10 mmol HCl) in an inert atmosphere at room temperature. Thus obtained suspension was stirred over night. Diethyl ether was removed from the product under vacuum, was added 20 ml of dry toluene. The resulting solution was filtered and the toluene was removed from the filtrate in vacuo to obtain the product as a white precipitate (2-methoxyphenyl)2The PCl.

A solution of 0.51 g (5 mmol) of triethylamine in 20 ml of dry dihl smetana was added to (2-methoxyphenyl) 2PCl product. To the mixture was added a solution of 1.25 ml of 2M H2NMe in THF (2.5 mmol) and left with stirring overnight. The solvent was removed from the resulting solution under vacuum, was added 20 ml of dry toluene. The mixture is then filtered. The toluene was removed from the filtrate in vacuo and after adding 10 ml of methanol. The suspension was filtered again and was isolated white solid product (2-methoxyphenyl)2PN(CH3)(2-methoxyphenyl)2.

Composition 3 (comparative)

(2-Methoxyphenyl)(phenyl)PN(CH3)P(2-methoxyphenyl)(phenyl) in a 1:1 ratio with CrCl3

(2-methoxyphenyl)(phenyl)PN(CH3)P(2-methoxyphenyl)(phenyl) ligand was prepared primary education suspension of 0.42 g of lithium (60 mmol) in 80 ml of THF, to which was added to 9.66 g of the ligand (2-methoxyphenyl)2P(phenyl) (30 mmol) at 0°C in an argon atmosphere. The mixture was stirred for 4 hours, after which was added an aliquot of the methanol 5 ml 60 ml of toluene was added to the mixture, after which the solution was extracted with two 40 ml of water. Extracted in toluene solution is then concentrated to a volume of approximately 20 ml, which led to the formation of a suspension. A concentrated toluene solution was filtered and the toluene filtrate was added 4.6 g2Cl6(24 mmol), which was then stirred for 2 hours at 90°C. Gaseous HCl, you is Eleusis from the reaction mixture, "caught" alkaline bath. The mixture was then cooled to room temperature and purged with nitrogen to remove all residual HCl present in solution.

At room temperature was added 5-ml aliquot of triethylamine to a concentrated toluene solution and left for a few minutes, after which was added 6 ml of 2M H2NMe (12 mmol) in a few drops at a time. The suspension was filtered and washed with 20 ml of toluene. Toluene filtrate and washed with toluene fraction was pooled. The combined toluene fractions were evaporated to dryness and was added 30 ml of methanol. The methanol solution was left overnight at -35°C, while in the solution formed a white precipitate (2-methoxyphenyl)(phenyl)PN(CH3)P(2-methoxyphenyl)(phenyl). Precipitated ligand was then allocated.

Precipitated ligand consisted of two isomers, racemic isomer (RR and/or SS enantiomers of the ligand) and mesosoma (RS enantiomer of the ligand). The ratio of these two isomers was determined using the31P NMR peak at 63,18 ppm and 64,8 ppm, related to two different isomers, respectively. Two samples (2-methoxyphenyl)(phenyl)PN(CH3)P(2-methoxyphenyl)(phenyl) used in the examples. These two sample consisted of a mixture as racemic isomer, and mesosoma with the mass ratio of 57/43 and 92/8, respectively.

Methods of work to install/p>

Examples 1-8 were performed using the following setup and methodology. "Installation" (trade mark Argonaut Technologies, Inc.) represents multireactor installation, containing eight coated glass reactor 15 ml used for carrying out reactions under pressure (30 bar). These reactions were performed in a volume of 5 to 10 ml.

Methodology the trimerization of ethylene to 1-hexene was performed as follows.

The reactor was purged three times with ethylene at 100°C and a pressure of 30 bar. Then the reactor was allowed to cool to room temperature, maintaining at this time, the pressure of ethylene of 20-30 bar. Inlet valve ethylene was closed and the reactor was left for the night. Moreover, the control pressure of ethylene inside the reactor during the night the reactor was checked for leakage. Then the reactors were prepared for carrying out reactions the next day.

Pre-mixed catalytic solution was prepared for the respective catalyst must be used. Pre-mixed catalytic solution was prepared by weighing 10 µmol composition 1, 2 or 3, the addition of 7.4 g of dry toluene, and the addition of 1.26 g (3 mmol) of the modified solution methylalumoxane (denoted here as MMAO) (6,4 wt.% Al in heptane, obtained from Witco Co.). Thus, pre-prepared mixed solution of 10 ml) contained a total of 10 µmol Cr and 3 mmol of Al (1 mm Cr, 0,3M Al), and, hence, the ratio of Al:Cr was 300:1. A pre-mixed solution was stirred overnight under nitrogen atmosphere at room temperature and atmospheric pressure.

0,2M, MAO absorbing solution (5 ml) were prepared by addition of 1 mmol (422 mg) quantities of MAO (to 6.4 wt.% Al in heptane) to a 3.9 g of toluene.

The reactor was then loaded the appropriate number of 0,2M absorbing solution, MAO and 2.5 ml of additional toluene. The reactor then was heated up to 80°C and was filled with ethylene to the desired reaction pressure. To start the trimerization reaction, an aliquot of pre-mixed solution was injected into the reactor. An additional 0.5 ml of toluene was then introduced to clear a line of input from the remaining pre-mixed catalytic solution.

The reaction was stopped or when the maximum absorption of ethylene, or after a set time, closing the inlet valve of ethylene, cooling to room temperature, relieving pressure and opening the reactor. The expression "he stopped at the maximum absorption of ethylene", when used herein, means that the amount of ethylene absorbed in the corresponding reaction corresponds to the amount of ethylene required to obtain the desired amount of 1-hexene. For example, if the desirable is th final volume of 1-hexene is equal to 5 ml (0.04 mol), the number of moles of ethylene required to obtain 5 ml final volume of 1-hexene, should be 0.12 mol, thus, the flow of ethylene into the reactor must be stopped when the rotation of 0.12 mol of ethylene. It is important that the volume of the reactor on the "installation" was approximately 15 ml and thus the desired final volume of the product and any remaining starting materials was less than 15 ml Usually desirable final volume of 5-10 ml

The mixture of products was collected and weighed. Weighted number was analyzed using gas chromatography (GC) (50 m CPSIL 5 CB y 0,25 column, carrier gas, helium, PID (flame ionization detector) with a known number of hexylbenzene as an internal standard.

Example 1

In this experiment, the reactor containing 0.5 ml of 0.2m, MAO absorbing solution and heated to 80°C, was filled with ethylene to a pressure of 8 bar. An aliquot of 0.5 ml pre-mixed catalytic solution containing composition 1, was introduced into the reactor to start the reaction (ratio of Al:Cr 500:1). The reaction was stopped when it was achieved the maximum absorption of ethylene (161 minutes).

The mixture of products was analyzed by GC. The results are presented in table 1.

Example 2

In this experiment, the reactor containing 0.5 ml of 0.2m, MAO absorbing solution and heat is th 80°C, filled with ethylene until a pressure of 20 bar. An aliquot of 0.5 ml pre-mixed catalytic solution containing composition 1, was introduced into the reactor to start the reaction (ratio of Al:Cr 500:1). The reaction was stopped when it was achieved the maximum absorption of ethylene (96 min).

The mixture of products was analyzed by GC. The results are presented in table 1.

Example 3

In this experiment, the reactor containing 0.5 ml of 0.2m, MAO absorbing solution and heated to 80°C, was filled with ethylene to a pressure of 8 bar. An aliquot of 0.5 ml pre-mixed catalytic solution containing composition 1, was introduced into the reactor to start the reaction (ratio of Al:Cr 500:1). The reaction was stopped after 1 hour.

The mixture of products was analyzed by GC. The results are presented in table 1.

Example 4

In this experiment, the reactor containing 0.35 ml of 0.2m, MAO absorbing solution and heated to 80°C, was filled with ethylene to a pressure of 15 bar. An aliquot of 0.35 ml pre-mixed catalytic solution containing composition 1, was introduced into the reactor to start the reaction (ratio of Al:Cr 500:1). The reaction was stopped after 1 hour.

The mixture of products was analyzed by GC. The results are presented in table 1.

Example 5 (comparative)

In this experiment the reactor, sod is Rashi 0.5 ml of 0.2m, MAO absorbing solution and heated to 80°C, filled with ethylene to a pressure of 8 bar. An aliquot of 0.5 ml pre-mixed catalytic solution containing composition 2, was introduced into the reactor to start the reaction (ratio of Al:Cr 500:1). The reaction was stopped when it was achieved the maximum absorption of ethylene, 105 minutes.

The mixture of products was analyzed by GC. The results are presented in table 1.

Example 6 (comparative)

In this experiment, the reactor containing 0.5 ml of 0.2m, MAO absorbing solution and heated to 80°C, was filled with ethylene until a pressure of 20 bar. However, due to the high reaction rate greater than the feed rate of the feedstock in the reactor, the pressure during the reaction was only 7-10 bar. An aliquot of 0.5 ml pre-mixed catalytic solution containing composition 2, was introduced into the reactor to start the reaction (ratio of Al:Cr 500:1). The reaction was stopped when it was achieved the maximum absorption of ethylene, 96 minutes.

The mixture of products was analyzed by GC. The results are presented in table 1.

Example 7 (comparative)

In this experiment, the reactor containing 0.5 ml of 0.2m, MAO absorbing solution and heated to 80°C, was filled with ethylene to a pressure of 8 bar. An aliquot of 0.5 ml pre-mixed catalytic solution containing composition 2, was introduced reactor, to start the reaction (ratio of Al:Cr 500:1). The reaction was stopped after 1 hour.

The mixture of products was analyzed by GC. The results are presented in table 1.

Example 8 (comparative)

In this experiment, the reactor containing 0.35 ml of 0.2m, MAO absorbing solution and heated to 80°C, was filled with ethylene to a pressure of 15 bar. An aliquot of 0.35 ml pre-mixed catalytic solution containing composition 2, was introduced into the reactor to start the reaction (ratio of Al:Cr 500:1). The reaction was stopped after 1 hour.

The mixture of products was analyzed by GC. The results are presented in table 1.

Table 1
ExampleCatalystPressureTime (minutes)OZ
(1-C6)
PTS
(1-C6)
C10
(wt.%)
With6
(wt.%)
1-C6
(wt.%)*
Total product (g)
11816172100 2690015,783,198,8the 3.65
212096138000862509,9of 87.894,56,63
3186020300203001,696,898,80,88
41156081800818008,390,699,32,66
5**28105832004750033,965,399,45,31
6**220107952005340036,263,199,36,35
7**2860482004820027,771,599,42,83
8**21560551005510027,471,299,42,28
† The inverse, OZ = mol product/mol catalyst
The inverse frequency, PTS = mol product/mol catalyst × time (hours)).
*% 1-hexene wt. from C6part of the composition of the product.
** Comparative example.
With6Hydrocarbons containing 6 carbon atoms.
With10Hydrocarbons containing 10 carbon atoms.
1-C61-hexene.

Methods the 1-liter batch reactor, the

1-liter batch reactor, the heated in nitrogen atmosphere to 70°C, washed with N2three times and was evacuated for 5 minutes. The reactor was placed a solution of 250 ml of dry toluene and 1 g of a solution of MAO (5,11% Al in toluene) to "etch" the reactor for at least 2 hours at 70°C.

Toluene and MAO solution for "treatment" was removed and the reactor was evacuated for 5 minutes, maintaining the reactor at a temperature of 70°C. the Reactor is then filled with 250 ml of dry toluene was pumped ethylene to the reaction pressure and introduced a corresponding number of absorber MAO. The solution then was stirred for at least 5 minutes at 70°C.

Pre-mixed catalytic solution was prepared by weighing 10 µmol composition 1, 2 or 3, the addition of 7.1 g of dry toluene, and the addition of 1.59 g (3 mmol) of a solution of MAO (5,11% Al in toluene). Thus, the obtained pre-mixed solution (10 ml) contained a total of 10 µmol Cr and 3 Microm Al (1 mm Cr, 0,3M Al) and had a ratio of Al:Cr equal to 300:1.

After stirring was started, the trimerization reaction by introducing aliquots catalytic pre-mixed solution in a pressurized reactor. The reactor then was heated to the reaction temperature is 80°C. the Reaction was carried out over a known period of time, while supports the elk reaction pressure, and then stopped, quickly cooling the reactor to about 30°C (approximately 5 minutes). The contents of the reactor were removed from the bottom of the 1-liter reactor periodic action.

The resulting mixture of the product was collected and weighed. Weighted number used for GC analysis hexylbenzene as an internal standard.

Example 9

An aliquot of 10 ml of pre-mixed catalytic solution prepared using composition 1, was injected into the 1-liter reactor containing 3 mmol of MAO as an absorber (1,59 g of a solution of MAO). The reaction was conducted at 80°C and a pressure of 15 bar atmosphere of ethylene. The reaction was stopped after 5 hours. It was totally absorbed 275 liters of ethylene.

The product mixture was analyzed by GC. The results are presented in table 2.

Example 10 (comparative)

An aliquot of 2 ml of pre-mixed catalytic solution prepared using composition 1, was injected into the 1-liter reactor containing 0.6 mmol of MAO as an absorber (317 mg of a solution of MAO). The reaction was conducted at 80°C and a pressure of 15 bar atmosphere of ethylene. After 205 minutes have introduced an additional 2 ml of pre-mixed catalytic solution. The reaction was stopped after 4.5 hours. It was totally absorbed 325 liters of ethylene.

The product mixture was analyzed by GC. Results the ATA presented in table 2.

Example 11 (comparative)

An aliquot of 2 ml of pre-mixed catalytic solution prepared using composition 3 in the ratio of 57/43, was injected into the 1-liter reactor containing 0.6 mmol of MAO as the absorber (317 mg of a solution of MAO). The reaction was conducted at 80°C and a pressure of 15 bar atmosphere of ethylene. The reaction was stopped after 3 hours. It was totally absorbed in 250 liters of ethylene.

The mixture of products was analyzed by GC. The results are presented in table 2.

Example 12 (comparative)

An aliquot of 2 ml of pre-mixed catalytic solution prepared using composition 3 in the ratio of 92/8, was injected into the 1-liter reactor containing 0.6 mmol of MAO as an absorber (317 mg of a solution of MAO). The reaction was conducted at 80°C and a pressure of 15 bar atmosphere of ethylene. The reaction was stopped after 4.5 hours. It was totally absorbed 308 liters of ethylene.

The mixture of products was analyzed by GC. The results are presented in table 2.

Table 2
ExampleCatalystTime (hours)OZ
(1-C6)
PTS
(1-C6)
With6
(wt.%)
1-C6
(wt.%)*
Total product (g)
915343000686007,292,399,45311,8
10**24,591472816631412,586,4of 99.75355,7
11**3 (57/43)3130945546216121,874,299,36296,8
12**3 (92/8)4,5133753429723028,569,399,42324,7
† The reverse is the value, OZ = mol product/mol catalyst
The inverse frequency (PTS) = mol product/mol catalyst × time (hours)).
*% 1-hexene wt. from C6part of the composition of the product.
** Comparative example.
With6Hydrocarbons containing 6 carbon atoms.
With10Hydrocarbons containing 10 carbon atoms.
1-C61-hexene.

From the results given above in table 1 and table 2 it is evident that the use of the catalytic composition of the present invention, containing the ligand of formula (I) as defined above, namely, (methoxyphenyl)(phenyl)PCH2CH2P(methoxyphenyl)(phenyl), leads to the decrease of the output side products10compared with the use of under equivalent reaction conditions are equivalent catalytic composition containing a ligand having the formula (2-methoxyphenyl)2PN(CH3)P(2-methoxyphenyl)2(disclosed in the examples of WO 02/04119) or a ligand having the formula (2-methoxyphenyl)(phenyl)PN(CH3)P(methoxyphenyl)(phenyl), none of which misses the formula (I)as defined above.

1. Catalytic composition for the trimerization of olefinic monomers containing
a) a source of chromium, molybdenum or tungsten;
b) a ligand of General formula (I)

in which X denotes a bivalent organic bridging group selected from substituted the s or unsubstituted alkilinity groups, moreover, in the case of the substituted groups, the substituents are hydrocarbon groups;
R1and R3are cycloaromatization groups that do not contain polar substituents in any of the ortho-positions;
R2and R4independently selected from optionally substituted cycloaromatization groups, each of R2and R4has polar Deputy, in at least one ortho-positions; and
c) socialization.

2. The catalytic composition according to claim 1, in which the bivalent organic bridging group X is alkylenes group that contains from 2 to 6 carbon atoms in the bridge.

3. The catalytic composition according to claim 1 or 2, in which a bivalent organic bridging group X is-CH2-CH2-.

4. The catalytic composition according to claim 1 or 2, in which R1and R3independently selected from optionally substituted phenyl groups, which do not contain polar substituents in any of anthopology.

5. The catalytic composition according to claim 1 or 2, in which R2and R4independently selected from optionally substituted phenyl groups, while the polar substituents are optionally branched C1-C20alkoxygroup.

6. The catalytic composition according to claim 1 or 2, in which R2and R4mean-metoksifenilny group.

7. The catalytic composition according to claim 1 or 2, in which socialization choose from methylalumoxane or modified methylalumoxane.

8. The catalytic composition according to claim 1 or 2, in which component a) is a source of chromium.

9. The catalytic composition of claim 8 in which the source of chromium is a CrCl3.

10. The way the trimerization of olefinic monomers, including the interaction of at least one olefinic monomer in the reaction conditions of the trimerization with a catalytic composition according to any one of claims 1 to 9.



 

Same patents:

FIELD: polymerization catalysts.

SUBSTANCE: supported olefin trimerization and oligomerization catalyst is characterized by molar productivity equal to 50% of that shown by the same but non-supported catalyst. Catalyst comprises: source of transition group 6 metal; ligand depicted by formula (R1)(R2)X-Y-X(R3)(R4) or X(R1)(R2)(R3), wherein X represents phosphorus, arsenic, or antimony atom, Y is linking group, and each of R1, R2, R3, R4, independently of each other, represents optionally substituted hydrocarbon group, optionally substituted heterohydrocarbon group, wherein each of the formulas has polar substituent, which is other than phosphane, arsane, or stibane group; and optionally activator. Polymerization of olefins or olefin blends is an integrated process in one or different reactors, in particular olefin monomer or olefin blend is brought into contact with above-described catalyst under trimerization conditions and then with additional catalyst suitable for olefin polymerization, which results in that trimerization products are incorporated into higher-molecular weight polymer. Process may be accomplished in a reaction circuit. Invention also claims supported α-olefin trimerization and polymerization catalyst comprising above-indicated components and optionally one or several olefin polymerization suitable catalysts.

EFFECT: excluded loss of catalyst activity in supported form.

36 cl, 25 ex

FIELD: chemical technology, catalysts.

SUBSTANCE: invention relates to a nickel-containing catalyst and to a method for the oligomerization reaction of ethylene to a mixture of olefin products with high degree of linearity. Invention describes a composition of catalyst comprising product prepared by interaction of the following components in a polar organic solvent in the presence of ethylene: (a) bivalent nickel simple salt with solubility at least 0.001 mole per liter in indicated polar organic solvent; (b) boron hydride-base reducing agent; (c) water-soluble base; (d) ligand chosen from o-dihydrocarbylphosphinobenzoic acids and their alkaline metal salts; (e) trivalent phosphite wherein the molar ratio of ligand to phosphite is in limits from about 50:1 to about 1000:1. Also, invention describes a method for preparing the catalyst composition and a method for synthesis of a mixture of olefin products showing the high degree of linearity. Invention provides preparing the economically effective catalyst useful in synthesis of olefin substances showing the high degree of linearity.

EFFECT: improved and valuable properties of catalyst.

10 cl, 2 tbl, 3 ex

The invention relates to new furifosmin formula I

< / BR>
where n denotes an integer of 1 or 2; R1denotes a hydrophilic group selected from the following groups: -SO2M, -SO3M, -CO2M, -PO3M, where M represents inorganic or organic cationic residue selected from a proton, cations, alkaline or alkaline earth metals, ammonium cations -- N(R)4where R denotes hydrogen or C1-C14alkyl, and the other cations are based on metals, salts with acids: fullsleeve, fullcarbon, fullsleeve or furylphosphonous soluble in water; m denotes an integer of 1; R2denotes a hydrophilic group,- SO2M, -SO3M, -CO2M, RHO3M, where M denotes hydrogen or an alkaline metal salt with the acid fullsleeve, fullcarbon, fullsleeve or fullfactorial soluble in water, R denotes an integer from 0 to 2
The invention relates to a catalytic composition comprising at least one compound of Nickel in the form of a mixture or in the form of a complex with at least one tertiary phosphine dissolved at least partially in non-aqueous ionic nature, resulting from the contacting of at least one aluminum halide (C) at least one Quaternary ammonium (A) at least one hydrocarbon (S) and with organic derivative of aluminum (D), characterized in that the hydrocarbon (C) is an aromatic hydrocarbon, and as an organic derivative of aluminum (D) use of the compound of General formula AlRxX3-xwhere R denotes a linear or branched alkyl radical with 2-8 carbon atoms; X denotes chlorine or bromine; x = 1,2 or 3

The invention relates to the field of petrochemical synthesis, in particular, to a method for producing 2-alkyl substituted 1,3-dienes of General formula

,

where

R = C4H9C6H13C9H19

FIELD: chemistry.

SUBSTANCE: invention relates to the catalyst for synthesising the 2- and 4-picolines, method for its producing and the method for producing the 2- and 4-picolines. The catalyst which can be used in synthesis of 2- and 4-picolines containing the heteropolyacid from the group containing the silicon tungsten acid, phosphorus tungsten acid and the vanadium tungsten acid applied upon the silica gel substrate with the particles size of 6-14 mesh, is described. The method for producing the catalyst is also described, which includes the dissolution of heteropolyacid in distilled water, stirring the obtained mixture with the needed amount of the silica gel to obtain the suspension; mixing the suspension till even impregnation, air drying the suspension at 200-250°C up to 1.5 hour; following heating the suspension at 300 to 400°C within 0.5 to 1.5 hours and cooling the obtained product till the room temperature in the exiccator to obtain the needed catalyst. The method for producing the of 2- and 4-picolines is described which includes the interaction of acetaldehyde and ammonium hydrate at heating in presence of the said catalyst.

EFFECT: stable highly selective and active catalyst is available.

14 cl, 3 ex

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention concerns catalytic process for obtaining isooctane fractions via alkylation of isobutane with butylene fractions. Process involves catalytic complex having following composition: MexOy*aAn-*bCnClmH2n+2-m, wherein Me represents group III-IV metal, x=1-2, y=2-3, and An- anion of oxygen-containing acid selected from sulfuric, phosphoric, molybdenic, and tungstenic acid, or mixture thereof in any proportions; a=0.01-0,2, b=0.01-0.1; bCnClmH2n+2-m is polychlorine-substituted hydrocarbon with n=1-10 and m=1-22, dispersed on porous support and containing hydrogenation component. Alkylation process is carried out at temperature not exceeding 150°C, mass flow rate of starting mixture not higher than 3 g/g cat*h, pressure not higher than 40 atm, and in presence of 10 mol % hydrogen.

EFFECT: increased catalyst stability and selectivity.

5 cl, 3 tbl, 20 ex

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention provides catalyst composed of heteropolyacid: phosphorotungstic acid and/or phosphoromolybdenic acid, at least one precious metal deposited on essentially inert inorganic amorphous or crystalline carrier selected from group including titanium dioxide, zirconium dioxide, aluminum oxide, and silicon carbide, which catalyst retains characteristic structure of heteropolyacid confirmed by oscillation frequencies of the order 985 and 1008 cm-1 recorded with the aid of laser combination scattering spectroscopy and which has specific surface area larger than 15 m2/g, from which surface area in pores 15 Å in diameter is excluded. Method of converting hydrocarbon feedstock containing C4-C24-paraffins in presence of above-defined catalyst is likewise described.

EFFECT: increased catalyst selectivity and enhanced hydrocarbon feedstock conversion.

5 cl, 7 tbl, 7 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention relates to catalytic methods of isomerizing n-paraffins and provides catalyst constituted by catalytic complex of general formula MexOy*aAn-*bCnXmH2n+2-m, where Me represents group III and IV metal, x=1-2, y=2-3, An- oxygen-containing acid anion, a=0.01-0.2, b=0.01-0.1; CnXmH2n+2-m is polyhalogenated hydrocarbon wherein X is halogen selected from a series including F, Cl, Br, I, or any combination thereof, n=1-10, m=1-22, dispersed on porous carrier with average pore radius at least 500 nm and containing hydrogenation component. Method of preparing this catalyst is also disclosed wherein above-indicated catalytic complex is synthesized from polyhalogenated hydrocarbon CnXmH2n+2-m wherein X, n, and m are defined above, group III and IV metal oxide, and oxygen-containing acid anion, and dispersed on porous carrier with average pore radius at least 500 nm, hydrogenation component being introduced either preliminarily into carrier or together with catalytic complex. Process of isomerizing n-paraffins utilizing above-defined catalyst is also described.

EFFECT: lowered isomerization process temperature and pressure and increased productivity of catalyst.

17 cl, 3 tbl, 25 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention relates to catalytic methods of isomerizing n-butane into isobutane and provides catalyst constituted by catalytic complex of general formula MexOy*aAn-*bCnXmH2n+2-m, where Me represents group III and IV metal, x=1-2, y=2-3, An- oxygen-containing acid anion, a=0.01-0.2, b=0.01-0.1; CnXmH2n+2-m is polyhalogenated hydrocarbon wherein X is halogen selected from a series including F, Cl, Br, I, or any combination thereof, n=1-10, m=1-22, dispersed on porous carrier with average pore radius at least 500 nm and containing hydrogenation component. Method of preparing this catalyst is also disclosed wherein above-indicated catalytic complex is synthesized from polyhalogenated hydrocarbon CnXmH2n+2-m wherein X, n, and m are defined above, group III and IV metal oxide, and oxygen-containing acid anion, and dispersed on porous carrier with average pore radius at least 500 nm, hydrogenation component being introduced either preliminarily into carrier or together with catalytic complex. Process of isomerizing n-butane into isobutane utilizing above-defined catalyst is also described.

EFFECT: lowered butane isomerization process temperature and pressure and increased productivity of catalyst.

13 cl, 1 tbl, 24 ex

The invention relates to a method of continuous hydration of ethylene, propylene or mixtures thereof with water in the vapor phase to the corresponding alcohols in the presence of salts heteroalicyclic as a catalyst at a molar ratio of water to olefin passing through the reactor, in the range of 0.1 to 3.0, an average hourly rate of gas supply water/olefin through the catalytic system 0,010 - 0.25 g/min/cm3concentrations of heteroalicyclic 5 to 60 wt.% from the total mass of the catalytic system, at a temperature of 150 - 350oC and a pressure ranging from 1000 to 25000 kPa

The invention relates to a catalyst based on aluminum, which contains, calculated on the weight content of the oxide 2-10 wt.% of cobalt oxide COO, 10-30 wt.% molybdenum oxide of Moo3and 4-10 wt.% oxide of phosphorus P2ABOUT5with a surface area by BET method in the range of 100 - 300 m2/g crushing strength CSH more than 1.4 MPa and an average diameter of pores in the range of 8-11 nm, the volume of pores of diameter greater than 14 nm is less than 0.08 ml/g, volume of pores with a diameter of less than 8 nm is not more than 0.05 ml/g and a volume of pores with a diameter of 8 to 14 nm in the range 0,20 - 0,80 ml/g

The invention relates to catalysts and methods of hydroperiod of crude oil

The invention relates to the refining catalysts, in particular catalysts for Hydrotreating of crude oil

The invention relates to the production of odorants for natural gas, in particular waste-free way to obtain mercaptan, as well as to a method for producing a catalyst, providing a higher degree of interaction between methyl alcohol and hydrogen sulfide and the use of such a method of producing hydrogen sulfide, which provides waste reduction production in General

FIELD: chemistry.

SUBSTANCE: claimed invention relates to catalyst of olefin monomers trimerisation. Described is catalytic composition for olefin monomers trimerisation, which contains a) source of chrome, molybdenum or tungsten; b) ligand if general formula (I), in which X stands for bivalent organic group, selected from substituted or non-substituted alkylene groups, in case of substituted groups, substituents represent hydrocarbon groups; R1 and R3 represent cycloaromatic groups, which do not contain polar substituents in none of orto-positions; R2 and R4 are independently selected from obligatory substituted cycloaromatic groups, each of R2 and R4 having polar substituent in at least one orto-position; and c) cocatalyst. Also described is method of olefin monomers trimerisation, including interaction of at least one olefin monomer in conditions of trimerisation reaction with said above catalytic composition.

EFFECT: selective obtaining 1-hexagen from ethylene, reducing level of formation of by-products, especially C10.

10 cl, 2 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: present invention refers to catalytic system and to the method of reduction of nitrogen oxides emissions using the said system. The described catalytic system for NOx reduction contains: the catalyst containing the metal oxide substrate, catalytic metal oxide which is gallium oxide or silver oxide or both of them and initiating metal chosen from the group consisting of silver, cobalt, molybdenum, wolfram, indium, bismuth and their mixtures, gas flow containing the organic reducing agent and sulfur-containing substance. The described catalytic system for NOx reduction contains: the catalyst consisting of (i) the metal oxide substrate, containing aluminium oxide, (ii) catalytic metal oxide which is gallium oxide or silver oxide or both of them in quantity 1-31 mole %; and (iii) initiating metal or their combination selected from the group consisting of silver, cobalt, molybdenum, wolfram, indium, bismuth, indium and wolfram, silver and cobalt, indium and molybdenum, indium and silver, bismuth and silver, bismuth and indium and molybdenum and indium in quantity 1-31 mole %, gas flow containing (A) water in quantity 1-15 mole %; (B) gaseous oxygen in quantity 1-15 mole %; and (C) organic reducing agent selected from the group consisting of alcanes, alkenes, alcohols, ethers, esters, carboxylic acids, aldehydes, ketones, carbonates and their combinations; and sulfur oxide; where at the specified organic reducing agent and NOx are present in approximate molar ratio carbon to NOx from 0.5:1 to 24:1. The described method of NOx reducing includes the stages of gaseous mixture containing NOx, organic reducing agent and sulfur-containing substance inflow and of said gaseous mixture contact with specified catalyst. The described method of NOx reduction includes: inflow of gaseous mixture containing (A) NOx, (B) water in quantity 1-15 mole %; (C) oxygen in approximate quantity 1-15 mole %; (D) organic reducing agent selected from the group consisting of alcanes, alkenes, alcohols, ethers, esters, carboxylic acids, aldehydes, ketones, carbonates and their combinations and (E) sulfur oxide; and contact of said gaseous mixture with catalyst described above and containing the specified components in the defined molar ratio.

EFFECT: improved action of the catalyst.

35 cl, 10 tbl, 84 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts for pyrazinamide synthesis during reaction of oxidative ammonolysis methylpyrazine. Alkyl-substituted pyrazines and their derivatives have high biological activity, which enables their wide use as medicinal agents for different purposes. Described is a catalyst for synthesis of oxidative ammonolysis methylpyrazine containing vanadium pentoxide and titanium dioxide and modifying additives from a group of elements of oxidative nature such as tungsten W or molybden Mo, with the following content of components, wt %: V2O5 10-29, TiO2 70-79, WoO3 or MoO3 1-10. Also described is a method of producing pyrazinamide through oxidative ammonolysis methylpyrazine in the presence the catalyst described above.

EFFECT: proposed catalysts enable production of pyrazinamide in a single step and increase total output of pyrazinamide and pyrazinonitrile.

2 cl, 8 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst system and a method of reducing nitrogen oxide emissions. The described catalyst system for reducing NOx contains: a catalyst having a support which contains at least one compound selected from a group consisting of aluminium oxide, titanium dioxide, zirconium dioxide, cerium oxide, silicon carbide and mixtures thereof, a catalytic metal oxide containing at least one of gallium oxide or silver oxide and at least one activating metal selected from a group consisting of silver, cobalt, molybdenum, tungsten, indium or mixtures thereof; and a gas stream containing oxygen ranging from approximately 1 mol % to approximately 12 mol % and an organic reducing agent selected from a group consisting of alcohol, carbonate or combinations thereof, where the said organic reducing agent and the said NOx are present in molar ratio carbon: NOx ranging from approximately 0.5:1 to approximately 24:1. A catalyst system for reducing NOx which contains the following is described: a catalyst consisting of (i) metal oxide support which contains aluminium oxide, (ii) at least one of the following oxides: gallium oxide or silver oxide, present in amount ranging from approximately 5 mol % to approximately 31 mol %; and (iii) an activating metal or a combination of activating metals, present in amount ranging from approximately 1 mol % to approximately 22 mol % and selected from a group consisting of silver, cobalt, molybdenum, tungsten, indium and molybdenum, indium and cobalt, and indium and tungsten; and a gas stream containing (A) water in range from approximately 1 mol % to approximately 12 mol %; (B) oxygen in the range from approximately 1 mol % to approximately 15 mol %; and (C) an organic reducing agent containing oxygen and selected from a group consisting of methanol, ethanol, butyl alcohol, propyl alcohol, dimethyl carbonate or combinations thereof; where the said organic reducing agent and NOx are present in molar ratio carbon: NOx ranging from approximately 0.5:1 to 24:1. Also described are methods of reducing NOx which involve the following steps: providing a gas mixture and bringing the said gas mixture into contact with above described catalysts for reducing NOx (versions).

EFFECT: reduced ill effects of air contamination caused by by-products of incomplete high-temperature combustion of organic substances.

21 cl, 34 ex, 4 tbl

FIELD: oil and gas industry.

SUBSTANCE: invention refers to catalysts intended to open naphthene rings. There described is catalyst for opening naphthene rings, which includes platinum component, ruthenic component and modifying component, and they are all dispersed on a substrate from high-melting non-organic oxide, and is characterised by the fact that at least 50% of platinum and ruthenic components is present in the form of particles, where on particle surface there is concentration of ruthenium, which is higher than that in the centre of particles. There also described is method for obtaining acyclic paraffins from cyclic ones, which involves contact of flow of raw material containing cyclic paraffins with the catalyst containing platinum component, ruthenic component and modifying component, and they are all dispersed on a substrate from high-melting non-organic oxide, in conditions of opening the ring in order to prevent at least some part of cyclic paraffins to acyclic paraffins; at that, catalyst is characterised by the fact that at least 50% of platinum and ruthenic components is in the form of particles, where on particle surface there is concentration of ruthenium, which is higher than that in the centre of particles.

EFFECT: increased synergism of Pt/Ru catalysts.

10 cl, 8 ex, 6 tbl, 2 dwg

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