• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a process for selectively dimerizing ethylene to butene-1 using a catalytic composition comprising at least one alkoxy or aryloxy compound of titanium, at least one additive chosen from ether-type compounds and at least one compound. aluminum.
    公开号:FR3023285A1
    申请号:FR1456470
    申请日:2014-07-04
    公开日:2016-01-08
    发明作者:Lionel Magna；Helene Olivier-Bourbigou
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the selective dimerization of ethylene to butene-1. An object of the invention is to provide a process for dimerizing ethylene using a particular catalyst composition.
    [0002] Prior art Of the catalytic systems capable of selectively dimerizing ethylene to butene-1, it is possible to identify in the literature vanadium-based catalyst systems (S. Zhang et al., Organometallics 2009, 28, 5925; Nomura et al Inorgan Chem 2013, 52, 2607), iron or cobalt (S. Song et al., J. Organomet.
    [0003] Chem., 2011, 696, 2594; V. Appukuttan et al. Organometallics 2011, 30, 2285), tungsten (H. Olivier et al J. Mol Catal A: Chem 1999, 148, 43, R. Tooze et al., Sasol Technology W02005089940A2, 2005), tantalum (S McLain et al J. Am Chem Soc., 1978, 100 (4), 1315, R. Schrock et al., Pure & App., Chem., 1980, 52, 729), nickel (S. Mukherjee and Organometallics 2009, 28, 3074, K. Wang et al.
    [0004] Catal. Common. 2009, 10, 1730; H. Liu et al. Dalton Trans. 2011, 40, 2614; J. Flapper et al. Organometallics 2009, 28, 3272, K. Song et al. Eur. J. Inorg. Chem. 2009, 3016) or Ti (A. W. Al-Sa'doun, Applied Catalysis A: General, 1993, 105, 1-40).
    [0005] Among these systems, those based on titanium occupy by far a privileged position. In U.S. Patent 2,943,125, K. Ziegler has described a method for dimerizing ethylene to butene-1 using a catalyst obtained from the mixture of trialkylaluminum and a titanium tetraalkoxide of zirconium. During the reaction, a certain amount of high molecular weight polyethylene is also formed, which considerably hampers the implementation of the process. Several improvements have been proposed to reduce the polyethylene content, in particular in US Pat. No. 3,686,350, which recommends the use of organic phosphorus compounds in conjunction with the elements of the catalyst, in US Pat. No. 4,101,600, which describes the treatment of polyethylene. catalyst with hydrogen or in US Patent 3,879,485 which describes the use of various ethers as solvents of the reaction medium. Although these modifications of the initial catalytic system provide an improvement in the selectivity of the reaction, they prove to be impractical, particularly in an industrial process in which butene-1 must be separated from the solvent leaving only traces of polar compound in butenes.
    [0006] From this point of view, patent FR 2 552 079 of the applicant, has demonstrated that the implementation of a catalyst obtained by the interaction of a trialkylaluminium on the one hand, with the other hand a preformed mixture of alkyl titanate and ether additive in stoichiometric amount, appreciably improves the activity and selectivity of these catalysts for the dimerization of ethylene to butene-1. Patent FR 2,552,079 also teaches that the use of said ether type additives in molar ratios greater than 10 relative to the alkyl titanate considerably slows down the reaction and results in a lower selectivity.
    [0007] If it is known that the increase in the molar ratio between alkylaluminium and alkyl titanate leads to an improvement in productivity, this is done under the conditions of patent FR 2 552 079, to the detriment of the operability of the process since increasing amounts of polymer are observed.
    [0008] The increase in the temperature of the reaction also leads to the same effects, in particular with a decrease in the stability of the catalyst and an increase in the proportion of polymer. The main disadvantage of the titanium-based catalyst systems used for the selective formation of butene-1 is therefore the formation of a significant amount of polymers. This polymer formation can cause a rapid deactivation of the catalyst and an increased difficulty of operability. An object of the invention is to provide a process for the selective dimerization of ethylene to butene-1 with reduced or almost zero polyethylene production and greatly improved operability.
    [0009] The invention relates to a process for selective dimerization of ethylene to butene-1 using a catalyst composition comprising at least one alkoxy or aryloxy compound of titanium, at least one additive selected from ether compounds and at least one compound of aluminum, in which the molar ratio between the additive and the titanium compound is strictly greater than 10 and the molar ratio between the aluminum compound and the alkoxy or aryloxy compound of titanium is strictly greater than 4. It has now It has been found that a process employing a catalytic composition comprising at least one alkoxy or aryloxy compound of titanium, at least one additive selected from ether-type compounds and at least one aluminum compound, wherein the molar ratio between the additive and the alkoxy or aryloxy compound of the titanium is strictly greater than 10 and the molar ratio between the aluminum compound and the alkoxy or aryloxy compound of the Ti tane is strictly greater than 4, allowed to obtain a very high selectivity for the selective dimerization of ethylene to butene-1 and this with a reduced or even zero polyethylene production. DETAILED DESCRIPTION OF THE INVENTION In the rest of the text and in the foregoing, the molar ratio between the additive and the titanium compound will, unless otherwise indicated, be expressed in mole of additive per mole of titanium. In the rest of the text and in the foregoing, the molar ratio between the aluminum compound and the alkoxy or aryloxy titanium compound will, unless otherwise indicated, be expressed in mole of aluminum per mole of titanium.
    [0010] The invention relates to a process for selective dimerization of ethylene to butene-1 using a catalyst composition comprising at least one alkoxy or aryloxy compound of titanium, at least one additive selected from ether compounds and at least one compound of aluminum, in which the molar ratio between said additive and the titanium compound is strictly greater than 10 and the molar ratio between the aluminum compound and the alkoxy or aryloxy compound of titanium is strictly greater than 4.
    [0011] Advantageously, the molar ratio between the additive and the alkoxy or aryloxy compound of the titanium of the catalytic composition is between 11 and 19. Advantageously, the molar ratio between the aluminum compound and the titanium alkoxy or aryloxy compound of the composition The titanium alkoxy compound used in the present invention advantageously corresponds to the general formula [Ti (OR) 4] in which R is a linear or branched alkyl radical containing from 2 to 30 carbon atoms. The radical R can comprise substituents based on nitrogen heteroatom, phosphorus, sulfur and oxygen. Among the preferred alkoxy radicals, mention may be made by way of non-limiting example: tetraethoxy, tetraisopropoxy, tetra-n-butoxy, tetra-2-ethylhexyloxy.
    [0012] The aryloxy compound of titanium used in the present invention advantageously corresponds to the general formula [Ti (OR ') 4] in which R' is an aryl radical substituted or not by alkyl, aryl or aralkyl groups comprising from 2 to 30 carbon atoms. carbon. The radical R 'may comprise substituents based on nitrogen, phosphorus, sulfur and oxygenated heteroatoms. Among the preferred aryloxy radicals, mention may be made by way of non-limiting example: phenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy, 4-methylphenoxy, 2-phenylphenoxy , 2,6-diphenylphenoxy, 2,4,6-triphenylphenoxy, 4-phenylphenoxy, 2-tert-butyl-6-phenylphenoxy, 2,4-ditertbutyl-6-phenylphenoxy, 2,6-diisopropylphenoxy, , 2,6-ditert-butylphenoxy, 4-methyl-2,6-ditert-butylphenoxy, 2,6-dichloro-4-tert-butylphenoxy and 2,6-dibromo-4-tert-butylphenoxy, biphenoxy radical, binaphthoxy, 1,8-naphthalenedioxy.
    [0013] The aluminum compound according to the invention is advantageously chosen from the group consisting of hydrocarbylaluminium compounds, tris (hydrocarbyl) aluminum compounds, chlorinated or brominated hydrocarbylaluminium compounds and aluminoxanes. The tris (hydrocarbyl) alcohols and chlorinated or brominated hydrocarbylaluminum compounds are represented by the general formula ## STR2 ## wherein R "is a hydrocarbyl radical, preferably alkyl having 1 to 6 carbon atoms, Y is a chlorine or bromine atom, preferably a chlorine atom and m is a number from 1 to 3.
    [0014] Preferably, the aluminum compound is chosen from the group formed by dichloroethylaluminum (EtAIC12), ethylaluminium sesquichloride (Et3Al2Cl3), chlorodiethylaluminum (Et2AlCl), chlorodiisobutylaluminum (i-Bu2AlCl), triethylaluminum (AlTE3), tripropylaluminum (Al (n-Pr) 3), triisobutylaluminum (Al (i-Bu) 3). The preferred aluminum compound is triethylaluminum (AIEt3).
    [0015] The additive of the catalytic composition according to the invention is advantageously chosen from the group formed by diethyl ether, diisopropyl ether, 2-methoxy-2-methylpropane, 2-methoxy-2-methylbutane and 2,5-dihydrofuran. tetrahydrofuran, 2-methoxytetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,3-dihydropyran, tetrahydropyran, 1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, dimethoxyethane, di (2-methoxyethyl) ether and benzofuran, alone or as a mixture. A particular composition according to the invention is a composition in which the titanium compound is [Ti (OnBu) 4], the additive is THF and is in a molar ratio (mol / mol) relative to the titanium compound ( THF / Ti) strictly greater than 10, preferably between 11 and 19, and the aluminum compound is triethylaluminium in a molar ratio (mol / mol) relative to the titanium compound (AIEt3 / Ti) strictly greater than 4, preferably between 5 and 15.30 Process for preparing the catalytic composition used in the process according to the invention The catalytic composition according to the invention; that is, the alkoxy or aryloxy compound of titanium, the ether additive and the aluminum compound; may be used in admixture with a solvent selected from the group consisting of aliphatic and cycloaliphatic hydrocarbons such as hexane, cyclohexane, heptane, butane or isobutane, with an unsaturated hydrocarbon such as a monoolefin or a diolefin comprising for example from 4 to 20 carbon atoms, with an aromatic hydrocarbon such as benzene, toluene, ortho-xylene, mesitylene, ethylbenzene or with a chlorinated hydrocarbon such as chlorobenzene or dichloromethane, pure or mixed. Aliphatic hydrocarbons such as cyclohexane or n-heptane and aromatic hydrocarbons such as toluene and ortho-xylene are advantageously used.
    [0016] According to a mode of preparation of the catalytic composition according to the invention, the aluminum compound is added in a solution containing the additive and the alkoxy or aryloxy compound of titanium present in a molar ratio strictly greater than 10, preferably in a ratio between 11 and 19, the molar ratio of the aluminum compound to the titanium compound being strictly greater than 4, preferably between 5 and 15. The concentration of titanium in the catalytic solution is advantageously between 1.10-9 to 1 mol / L, preferably between 1.10-6 and 0.5 mol / L. The temperature at which the components of the catalytic composition are mixed is advantageously between -40 and + 250 ° C., preferably between 0 and 150 ° C., for example at a temperature close to room temperature (15 to 30 ° C.). VS). The mixing can be carried out under an atmosphere of ethylene or inert gas. Dimerization Reaction The process according to the invention is a process for selective dimerization of ethylene to butene-1 using the catalytic composition described above.
    [0017] The dimerization reaction of ethylene is advantageously carried out under a total pressure of 0.5 to 20 MPa, preferably of 0.5 to 10 MPa, and at a temperature of 20 to 180 ° C., preferably 40 to at 140 ° C.
    [0018] According to one embodiment, the dimerization reaction is carried out batchwise. A selected volume of the catalytic composition, constituted as described above, advantageously in solution, is introduced into a reactor provided with the usual stirring, heating and cooling devices, and then pressurized with ethylene, advantageously with desired pressure, and the temperature is adjusted, preferably to the desired value. The dimerization reactor is maintained at constant pressure by introduction of ethylene until the total volume of fluid produced is, for example, from 2 to 50 times the volume of the catalytic solution originally introduced. The catalyst is then destroyed by any usual means known to those skilled in the art, then the reaction products and the solvent are removed and separated. According to another preferred embodiment, the catalytic dimerisation reaction of ethylene is carried out continuously. In a first variant, a solution containing the titanium compound and the additive is injected separately into a reactor maintained under constant pressure of ethylene, and on the other hand a solution containing the aluminum compound of in order to produce the catalytic composition according to the invention. Said reactor is stirred by conventional mechanical means known to those skilled in the art or by an external recirculation. The temperature and the ethylene pressure are kept constant at the desired values using conventional means known to those skilled in the art. The reaction mixture is withdrawn by means of a valve controlled at the liquid level so as to keep it constant. The catalyst is continuously destroyed by any usual means known to those skilled in the art, then the products from the reaction and the solvent are separated, for example by distillation. Ethylene that has not been converted can be recycled to the reactor. The catalyst residues included in a heavy fraction can be incinerated.
    [0019] In a second variant, a solution containing the titanium compound and the additive and, on the other hand, the aluminum compound are injected into a first reactor / mixer in order to produce the catalytic composition according to the invention. invention, said composition is then introduced continuously into a reactor maintained under constant pressure of ethylene. This mixture in the first reactor / mixer can be carried out under an inert atmosphere or under an ethylene atmosphere. The reaction mixture is withdrawn by means of a valve controlled at the liquid level so as to keep it constant. The catalyst is continuously destroyed by any usual means known to those skilled in the art, then the products from the reaction and the solvent are separated, for example by distillation. Ethylene that has not been converted can be recycled to the reactor. The catalyst residues included in a heavy fraction can be incinerated. Products Obtained The process according to the invention allows the selective production of butene-1. This compound finds use as comonomers with ethylene in the manufacture of linear low density polyethylene. The following examples illustrate the invention without limiting its scope. EXAMPLES Examples 1-4: The ethylene dimerization tests presented in Table 1 below were carried out in a stainless steel autoclave of useful volume. 500 mL, equipped with a double jacket to regulate the temperature by circulation of oil. Stirring is provided by a Rushton blade with mechanical drive. 40 mL of n-heptane and 5 mL of a 0.085 mol / L solution of the titanium compound in n-heptane are introduced into this reactor under an ethylene atmosphere and at ambient temperature. Once the temperature of the reactor has been raised to 53 ° C., the quarter-volume of desired aluminum-based cocatalyst (previously diluted in 5 ml of n-heptane) is introduced under ethylene pressure. The ethylene pressure is maintained at 23 MPa and the temperature at 53 ° C. After 1 hour of reaction, the introduction of ethylene is stopped and the reactor cooled to 25 ° C. The reactor is then degassed through a gas meter. This gas is analyzed by gas chromatography. The liquid phase contained in the reactor is then weighed and analyzed by gas chromatography. The produced polymer is recovered, dried and weighed.
    [0020] The composition of the products obtained is given in Table 1 below. In this table, the activity is defined as the mass of ethylene consumed per gram of initially introduced titanium per hour. The C4 (% C4) distribution is the amount of olefins with a carbon number equal to 4 in the total distribution.
    [0021] The percentage% C4-1 represents the selectivity to butene-1 linear product in the C4 cut. The amount of polymer (% PE) corresponds to the mass of polymer recovered, brought back into the total distribution. Table 1: Ex. Compound Additive Molar Ratio Co-Ratio T. t Activity% C 41)% Ti (TiO / Ti) molar catalyst PE 1 [Ti (OnBu) 4] THF 4 AlEt 3 3.0 53 87 6200 94 (99+) 0.05 2 [Ti (OnBu 4] THF 4 AIEt3 6.8 53 62 12400 94 (99+) 0.30 3 [Ti (OnBu) 4] THF 10.7 AIEt3 6.8 53 114 6800 94 (99+) nd * 4 [Ti (OnBu) 4] THF 18.8 AIEt3 6.9 125 125 7500 95 (99+) nd * * nd = not detected (this denomination characterizes the total absence of polymer) In this table, Examples 1 and 2 show that the compositions having a THF / Ti <10 molar ratio (examples Comparative non-compliant with the invention), increasing the molar ratio AIEt3 / Ti from 3 to 6.8 leads to a significant increase in the production of polyethylene.
    [0022] Examples 3 and 4 in accordance with the invention demonstrate that compositions having a THF / Ti molar ratio strictly greater than 10 have a very good activity and selectivity for dimerization at an AEt3 / Ti ratio of 6.8 (see Ex.2). selective ethylene to butene-1 and this without the production of polyethylene.15
    权利要求:
    Claims (16)
    [0001]
    REVENDICATIONS1. A process for the selective dimerization of ethylene to butene-1 using a catalyst composition comprising at least one alkoxy or aryloxy compound of titanium, at least one additive chosen from ether-type compounds and at least one aluminum compound, in wherein the molar ratio of the additive to the alkoxy or aryloxy compound of titanium is strictly greater than 10 and the molar ratio of the aluminum compound to the alkoxy or aryloxy compound of titanium is strictly greater than 4.
    [0002]
    2. Method according to claim 1 wherein the molar ratio between the additive and the titanium alkoxy or aryloxy compound of the catalytic composition is between 11 and 19.
    [0003]
    3. A process according to claim 1 or 2 wherein the molar ratio of the aluminum compound to the titanium alkoxy or aryloxy compound of the catalyst composition is from 5 to 15.
    [0004]
    4. Method according to one of claims 1 to 3 wherein the alkoxy compound of titanium has the general formula [Ti (OR) 4] wherein R is a linear or branched alkyl radical having from 2 to 30 carbon atoms.
    [0005]
    5. Method according to one of claims 1 to 3 wherein the aryloxy compound of titanium has the general formula [Ti (OR ') 4] wherein R' is an aryl radical substituted or not with alkyl groups, aryl or aralkyl having 2 to 30 carbon atoms.
    [0006]
    The process according to one of the preceding claims wherein the aluminum compound is selected from the group consisting of hydrocarbyl aluminum compounds, tris (hydrocarbyl) aluminum compounds, chlorinated or brominated hydrocarbyl aluminum compounds and aluminoxanes.
    [0007]
    7. Process according to claim 6, in which the aluminum compound is chosen from the group formed by dichloroethylaluminum (EtAIC12), ethylaluminium sesquichloride (Et3Al2C13), chlorodiethylaluminum (Et2AlCl) and chlorodiisobutylaluminum (i-Bu2AlCl). triethylaluminum (AIEt3), tripropylaluminum (Al (n-Pr) 3), triisobutylaluminum (Al (i-Bu) 3).
    [0008]
    8. Process according to one of the preceding claims using a composition in which the titanium compound is [Ti (OnBu) 4], the additive is THF and is in a molar ratio relative to the titanium compound ( THF / Ti) strictly greater than 10 and the aluminum compound is triethylaluminum in a molar ratio relative to the titanium compound (AIEt3 / Ti) strictly greater than 4.
    [0009]
    9. Method according to one of the preceding claims wherein the additive is selected from the group consisting of diethyl ether, diisopropyl ether, 2-methoxy-2-methylpropane, 2-methoxy-2-methylbutane, 2, 5-dihydrofuran, tetrahydrofuran, 2-methoxytetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,3-dihydropyran, tetrahydropyran, 1,3-dioxolane, 1,3-dioxane, 1,4 dioxane, dimethoxyethane, di (2-methoxyethyl) ether and benzofuran, alone or as a mixture.
    [0010]
    10. Method according to one of the preceding claims wherein the catalytic composition is used in admixture with a solvent selected from the group consisting of aliphatic and cycloaliphatic hydrocarbons, an unsaturated hydrocarbon such as a monoolefin or a diolefin comprising for example from 4 to 20 carbon atoms, by a hydrocarbon or a chlorinated hydrocarbon, pure or in mixture.
    [0011]
    11. Method according to one of the preceding claims implemented under a total pressure of 0.5 to 20 MPa and a temperature of 20 to 180 ° C.
    [0012]
    12. Method according to one of the preceding claims implemented in a discontinuous or continuous embodiment.
    [0013]
    13. Method according to one of the preceding claims wherein a selected volume of the catalyst composition according to one of claims 1 to 10 is introduced into a reactor equipped with stirring, heating and cooling devices, then pressurized by ethylene and adjust the temperature.
    [0014]
    14. A process for the selective dimerization of ethylene to butene-1 according to one of the preceding claims implemented as is introduced separately, in a reactor maintained under constant pressure of ethylene, on the one hand a solution containing the compound. titanium and the additive, and secondly a solution containing the aluminum compound so as to produce the catalyst composition as defined according to one of claims 1 to 10.
    [0015]
    15. A process for selectively dimerizing ethylene to butene-1 according to one of the preceding claims implemented as is introduced into a first reactor / mixer, on the one hand a solution containing the titanium compound and the additive. and on the other hand the aluminum compound so as to produce the catalytic composition as defined in one of claims 1 to 10, said composition then being introduced continuously into a reactor maintained under constant pressure of ethylene.
    [0016]
    16. Process for preparing the catalytic composition according to one of claims 1 to 10 wherein the aluminum compound is added in a solution containing the additive and the alkoxy or aryloxy compound of titanium present in a molar ratio strictly greater than 10, the molar ratio of the aluminum compound to the titanium compound being strictly greater than 4.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP0885656B1|2002-01-02|Catalytic composition and ethylene oligomerization, especially in 1-butene and/or 1-hexene
    CA2896007A1|2016-01-04|Catalytic composition and selective dimerization process of ethylene into butene-1
    EP2388069A1|2011-11-23|Method for dimerisation of ethylene into butene-1 using a composition including a titanium complex and an alcoxy ligand functionalised by a heteroatom
    EP1110930B1|2003-09-10|Catalytic composition and process for the oligomerisation of ethylene, to primarily 1-hexene
    EP2567752B1|2018-11-21|New nickel-based catalytic composition and method for oligomerising olefins using said composition
    CA2886105A1|2015-09-25|New catalytic composition and process for the oligomerization of ethylene into 1-hexene
    CA2916195A1|2016-01-04|Improved selective dimerization process for ethylene into butene-1
    JP2011506069A|2011-03-03|Catalyst composition for oligomerization of ethylene, oligomerization process and preparation method thereof
    WO2008142295A1|2008-11-27|Method for oligomerising olefins using a catalytic composition comprising an organometal complex containing a phenoxy ligand functionalised by a heteroatom
    BE1015290A3|2005-01-11|Catalyst composition and method for improved oligomerization ethylene, particularly in hexene-1.
    FR2960235A1|2011-11-25|OLEFIN OLIGOMERIZATION METHOD USING A COMPOSITION COMPRISING AN ORGANOMETALLIC COMPLEX CONTAINING A HETERO ATOMIC FUNCTIONALIZED ALCOXY LIGAND
    FR2857964A1|2005-01-28|Treatment of crude product from ethylene oligomerisation, e.g. for the production of hexene-1, involves addition of amine, alcohol or acid, e.g. 2-ethyl-hexanoic acid, to eliminate catalyst before distillation
    EP2572782B1|2014-10-22|Method for separating butene-2 from a C4 cut containing butene-2 and butene-1 by selective oligomerisation of the butene-1
    EP1354627A1|2003-10-22|Organometallic complexes with phosphonite ligands and their use as catalysts for olefin oligomerisation
    WO2019105844A1|2019-06-06|New catalytic composition based on nickel and a phosphonium, and use thereof for the oligomerisation of olefins
    WO2022023028A1|2022-02-03|Ethylene oligomerisation process comprising in situ preparation of the catalytic composition
    WO2022023027A1|2022-02-03|Novel chromium-based catalytic composition and associated method for the trimerisation of ethylene to hexene-1
    FR3112342A1|2022-01-14|OLIGOMERIZATION PROCESS USING A GAS/LIQUID EXCHANGER
    FR3099476A1|2021-02-05|OLIGOMERIZATION PROCESS IMPLEMENTING GAS SKY RECYCLE
    FR3008697A1|2015-01-23|METHOD FOR SELECTIVELY DIMERIZING ETHYLENE TO BUTENE-1 USING A CATALYTIC COMPOSITION COMPRISING AN ADDITIVE TITANIUM COMPLEX IN ASSOCIATION WITH A HETERO-ATOMIC FUNCTIONALIZED ALCOXY LIGAND
    FR3074493A1|2019-06-07|METHOD FOR DIMERIZING ETHYLENE COMPRISING A STEP FOR TREATING REACTION EFFLUENT
    FR3074064A1|2019-05-31|NOVEL NICKEL CATALYTIC COMPOSITION, PHOSPHORUS COMPOUND AND SULFONIC ACID AND USE THEREOF FOR OLIGOMERIZING OLEFINS
    FR3051793A1|2017-12-01|NICKEL COMPLEXES AND SECONDARY PHOSPHINE OXIDE TYPE LIGANDS AND USE THEREOF IN A METHOD OF OLIGOMERIZING OLEFINS
    同族专利:
    公开号 | 公开日
    TW201609612A|2016-03-16|
    CN105294376A|2016-02-03|
    KR20160004935A|2016-01-13|
    JP2016027038A|2016-02-18|
    TWI662012B|2019-06-11|
    FR3023285B1|2017-10-27|
    JP6677979B2|2020-04-08|
    CN105294376B|2020-10-02|
    EP2963004A1|2016-01-06|
    CA2916195A1|2016-01-04|
    US9499455B2|2016-11-22|
    US20160002123A1|2016-01-07|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3879485A|1974-01-25|1975-04-22|Gennady Petrovich Belov|Method of producing butene-1|
    EP0516852A1|1990-12-07|1992-12-09|Okhtinskoe Nauchno-Proizvodstvennoe Obieninenie "Plastopolimer"|Method of obtaining butene-i|
    EP0722922A1|1995-01-19|1996-07-24|Indian Petrochemicals Corporation Limited|Manufacture of linear alpha-olefins|
    US2943125A|1954-08-07|1960-06-28|Ziegler|Production of dimers and low molecular polymerization products from ethylene|
    DE1420575A1|1956-07-25|1968-10-10|Montedison Spa|Process for the production of linear, high molecular weight, highly crystalline ethylene polymers|
    GB1312974A|1969-05-29|1973-04-11|Toyo Soda Mfg Co Ltd|Process and catalyst for dimerization of alpha-olefins|
    SU681032A1|1976-02-23|1979-08-25|Грозненский филиал Охтинского научно-производственного объединения "Пластполимер"|Process for the preparation of dimers and codimers of alpha-olefins|
    FR2552079B1|1983-09-20|1986-10-03|Inst Francais Du Petrole|IMPROVED PROCESS FOR THE SYNTHESIS OF BUTENE-1 BY DIMERIZATION OF ETHYLENE|
    GB0406039D0|2004-03-17|2004-04-21|Sasol Technology Uk Ltd|Tungsten based catalyst system|US10154382B2|2013-03-12|2018-12-11|Zendrive, Inc.|System and method for determining a driver in a telematic application|
    WO2015087304A2|2013-12-13|2015-06-18|Saudi Basic Industries Corporation|Catalyst compositions for selective dimerization of ethylene|
    FR3023183A1|2014-07-04|2016-01-08|IFP Energies Nouvelles|CATALYTIC COMPOSITION AND METHOD FOR SELECTIVE DIMERIZATION OF ETHYLENE TO BUTENE-1|
    US10362482B2|2016-12-21|2019-07-23|T-Mobile Usa, Inc.|Network operation and trusted execution environment|
    法律状态:
    2015-07-15| PLFP| Fee payment|Year of fee payment: 2 |
    2016-01-08| PLSC| Search report ready|Effective date: 20160108 |
    2016-07-19| PLFP| Fee payment|Year of fee payment: 3 |
    2017-07-31| PLFP| Fee payment|Year of fee payment: 4 |
    2018-07-25| PLFP| Fee payment|Year of fee payment: 5 |
    2019-07-25| PLFP| Fee payment|Year of fee payment: 6 |
    2020-07-28| PLFP| Fee payment|Year of fee payment: 7 |
    2021-07-26| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1456470A|FR3023285B1|2014-07-04|2014-07-04|IMPROVED METHOD FOR SELECTIVE DIMERIZATION OF ETHYLENE TO BUTENE-1|FR1456470A| FR3023285B1|2014-07-04|2014-07-04|IMPROVED METHOD FOR SELECTIVE DIMERIZATION OF ETHYLENE TO BUTENE-1|
    EP15305860.7A| EP2963004A1|2014-07-04|2015-06-05|Improved process for the selective dimerisation of ethylene to 1-butene|
    CA2916195A| CA2916195A1|2014-07-04|2015-06-30|Improved selective dimerization process for ethylene into butene-1|
    KR1020150092911A| KR20160004935A|2014-07-04|2015-06-30|Improved process for the selective dimerisation of ethylene to 1-butene|
    JP2015132370A| JP6677979B2|2014-07-04|2015-07-01|Improved method for the selective dimerization of ethylene to 1-butene|
    TW104121387A| TWI662012B|2014-07-04|2015-07-01|Improved process for the selective dimerisation of ethylene to 1-butene|
    US14/790,734| US9499455B2|2014-07-04|2015-07-02|Process for the selective dimerisation of ethylene to 1-butene|
    CN201510383858.5A| CN105294376B|2014-07-04|2015-07-03|Improved process for selective dimerization of ethylene to 1-butene|
    [返回顶部]