前苏联专利SU784740A3 Catalyst composition for diolefin dimerization

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1466463 Dimerizing dienes SOC NATIONALE DES PETROLES D'AQUITAINE and INSTITUT FRANCAIS DU PETROLE DES CARBURANTS ET LUBRIFIANTS 11 April 1974 [12 April 1973] 16337/74 Heading C5E [Also in Division B1] Diolefins may be dimerized in the liquid phase at 20-120‹ C. using a catalyst which is the reaction product of a transition metal carbonyl M<SP>1</SP> m (CO)<SP>-</SP> n where m and n are integers and a co-ordinated transition metal halide or pseudohalide of formula [M<SP>2</SP>L p X q ] r where L is a co-ordinate group that can furnish 3 electrons, e.g. nitrosyl, trihaptoallyl or substituted or unsubstituted pentadienyl; X is halogen, cyanide, sulphocyanide or isocyanate; p and q are 1, 2 or 3; and r is an integer (see Division B1). The dimerization may be effected at 0À5-10 kg./cm.<SP>2</SP> with a diolefin to halide or pseudohalide molar ratio of about 300 in the presence of a solvent, e.g. hexane, cyclohexane, benzene, toluene, ethyl ether, anisole, tetrahydrofuran or the hydrocarbon product of the dimerization. The diolefins may be conjugated, e.g. butadiene, isoprene or dimethyl butadiene or non-conjugated, e.g. norbornadiene. The feed may be a mixture of butadiene and butene obtained from refineries. The examples describe the dimerization of butadiene to give mainly vinyl-4-cyclohexene together with a minor proportion of cyclooctadiene and some cyclododecatriene- 1,5,9 and C 12+ oligomers.
公开号:SU784740A3
申请号:SU742031654
申请日:1974-04-11
公开日:1980-11-30
发明作者:Ткаченко Игорь
申请人:Сосьете Насьональ Де Петроль Д"Акитэн (Фирма)；Энститю Франсэ Дю Петроль (Фирма)；
IPC主号:

专利说明:

for, cobalt or nickel to the compound mtsh, -, equal to 0.5 - 1.0. .
A composition of this composition has an increased activity and selectivity, for example, when dimerizing butadiene, the yield of vinylcyclohexane | san reaches 97.5% with a selective teat on vinylcyclohexane of 100%,
The proposed catalyst may be manufactured on site or separately, depending on the nature of the coordination L constituting the compound. When L N0, prepare the catalyst on site: two or three components dissolved in an appropriate solvent are introduced directly into the reactor in which the dimerization. On the contrary, the L code is a trigapto-allyl group; it is preferable that both components introduced into the corresponding solvent undergo photohigmatic activation before they enter the reactor.
Dimerisation of the diolefins is carried out by adding a certain amount of liquid diolefins to the catalytic mixture. The reaction is carried out in an autoclave, under the pressure necessary to maintain the reaction medium in a liquid state. The reaction temperature may range from 20 to, preferably from 40 to 80 ° C.
Solvents, especially suitable for the dimerization of diolefins, must be inert with respect to catalysts. In particular, these are saturated hydrocarbons — hexanes, cyclohexanes, aromatic hydrocarbons — benzene, toluene, as well as aliphatic aromatic or alicyclic ethers, ethyl ether, anisole, tetrahydrofuran. VTSG is also suitable: it has the advantage of being used in that it allows the recovery of vinyl diclohexane (EDC) by simple distillation, which does not require preliminary solvent separation.
Diolefins, which can be dimerized using the catalysts described in the invention, are very diverse. First of all, it is possible to carry out the dimerization of conjugated diolefins as butadiene, isoprene, dimethylbutadiene, and even sodimerize these: diolefins among themselves. Isolated double bond diolefins, such as norbornadiene (bicyclo-2,1,1-heptadiene), can also be dimerized.
The catalysts only allow dimerization of diolefins, which are in a mixture of diolefins and monoolefins, to the detriment of monoolefins, which do not change. The separation of dimer and olefin is very easy.
Experiments carried out in a stainless steel autoclave, with a 125 ml bone, equipped with a double thermostatting jacket, are described. In each experiment, a catalyst was introduced into the autoclave, cooled to -20 ° C in a nitrogen or argon atmosphere:
previously prepared in the case when L (h -CjHg), obtained by activation under normal illumination, is a mixture of a certain amount of metal carbonyl and bistrihaptallyl bromo-nickel in a solution of the aforementioned solvent,
or a catalyst formed in situ when L N0, which is obtained by reacting a certain amount of metal carbonyl with an appropriate amount of nitrosyl metal halide,.
or by the reaction of a certain amount of iron pentacarbonyl or tetra.carbonyl nickel with a given amount of metallic nitrosyl chloride and potassium iodide.
Then, an appropriate amount of liquid diolefin is introduced: butadiene, isoprene, Cd fractions, etc. Then the autoclave is thermostatic with constant stirring for a specified time. The catalyst is deactivated by introducing hydrochloric acid and bubbling air flow. The resulting reaction product is distilled to isolate the solvent. All the various products are subjected to angstise and determination using gas chromatography.
Examples 1-20 (table 1).
These examples show the effect on the conversion of butadiene into the oligomer mixture of the catalytic composition CjHg) NiBrJ ,, + carbonyl metal temperature and reaction time.
To a solution containing in 5 ml of toluene 1-mol,. T. That is, 359 mg of bistrihaptoallylbromonikkel, is added a solution containing 5 ml of toluene (2 mol) of the metal carbonyl as defined above. from compounds made by the methods described in the literature. The resulting mixture is stirred in an inert atmosphere at room temperature and under light. A precipitate formed which was removed after two hours by photochemical activation of the mixture. The purified solution was placed in an autocooled chill, cooled to, and 27 g of liquid butadiene was added. The molar ratio between butadiene and nickel contained in- (hr-C-ijH) N i Вг is 250. The autoclave is brought to the desired temperature and maintained at this temperature for a predetermined time. The catalytic composition is destroyed with dilute hydrochloric acid; the reaction mixture is distilled and studied by gas chromatography. The results are presented in s table. 1. They indicate the degree of con-version of the butadiene and the selectivity of vinylcyclohexane (VCH), cycdo-octadiene 1.5 (DPC), cyclododecatriene 1.5 (CDT), and higher oligomers. It can be established that the dimerization of a butadien by the compositions (L-CaH) N i Br | 1 „+
the wearing of BCG / COX varies with the iteMnura, the formation of VCG is favored by low temperatures, but this formation is almost independent of the reaction time.
Table + carbonyl metal
Examples 21-27 (table 2). The significance of the method for the preparation of a catalytic composition using bistriheptoapli bromonikel and multi-core carbonyl iron Fe2 (COlfc. Catalytic, the mixture is prepared as described above, but the relative proportion of both components, the nature of the solvent, and the method for purifying the catalytic solution are shown. Table 2. Untreated toluene solutions thus lead to the formation of oligomers C, j. Replacing toluene with ether prevents this oligomerization of butadiene, but also reduces the reaction The chemical activity of the cata-chic composition. Photochemical activation is necessary and the best yields are obtained for the Ni / Fe 1 ratio. These experiments were performed for 2 hours. Examples 28-31 (Table of LC shows that in the case of C, i B Ni (CO) toluene replacement ether is accompanied by a clear decrease in the proportion of oligomers l / Cij.Examples 32–4 (table 4) show that the replacement of the coordination component of triheptoallyl by nitrosyl is accompanied by a marked increase in reactivity and selectivity in dimization of butadiene to form vinyl-1-cyclohexane. In addition, the preparation of the catalyst is carried out directly in a reactor cooled to –20 ° C. Thus, a solution of pentacarbonyl nickel or tetrakrbonyl nickel in 5 ml toluene is added to a solution containing 5 ml of toluene with 1 mol of dinitrosyl iron halide or cobalt, then injected at -20 16.2 g (300 mol) of liquid butadiene. Reactions conducted at for 3 hours. Examples. 12-15 (table 4). It is shown that there is no need for a stoichiometric ratio between iron pentacarbonyl and nitrosyl metal halide. -If an excess of first results in worse results, its use in smaller amounts of Bak, which is 1: 1, gives very interesting results. Examples 46-47 (table t) Show that the use of chloride dinitrozil iron together with iron pentacarbonyl and a given amount of potassium iodide leads to almost the same result as the use of Podide iron dinitrozil together with iron pentacarbonyl. The addition of second potassium and potassium iodide does not give additional improvement. Examples -18-49 (table 4). These are controlled experiments that show that compounds
Dimerization of .butadiene with cpc composite- Effect of preparation
21
Raw
Toluene
0.5
Purified
(h -CT, Ht;) N i Rr + Fe
(with:
0.5 77
ten
95
12
0.5 45.5
36
32 fe (NO) Co (NO), C ijxj, scr. - / s. - J 2. encased separately, do not give butadiene conversion, EXAMPLE 50. Dimerization of isoprene. The catalyst obtained according to the described method (Example 46) was autoclaved with 20.4 g (300: Jvlo) isoprene. The temperature of the autoclave is brought to 80 ° C and maintained for 5 hours. After decomposition of the catalyst with dilute hydrochloric acid and distilling off the solvent, isoprene dimers are selected. The conversion of isoprene is 88% and the selectivity relative to the dimer is 99%. PRI me R 51. Dimerization of norbornadiene. The analytical composition described in Example 46 is applied. Catalytic composition is introduced into tube 1 of Lenka, then 15 g of bicyclo-2,2,1-heptadiene (norbornadiene), the mixture is heated to 85 ° C E for 5 liters. The catalyst is destroyed with dilute hydrochloric acid and the solvent is distilled. 98% of the nrbordiene is converted into a dimer. L m rime 52. The use of the fraction. The catcher, prepared according to the method described above, consists of cobalt dinitrosyl iodide and iron pentacarbonyl iodide in solution in toluene. After the introduction of the catalyst, 20 g of the steam cracking fraction C containing 38% butadiene are introduced into the autoclave cooled to -20 ° C. The temperature of the autoclave is adjusted to and maintained for 5 hours. 65% of the butadiene present in this fraction is converted to BCG and gas chromatography does not show the presence of other compounds. Table 2
Dimerization of butadiene with the composition (H5) N i (COL Improvement made by ether

权利要求:
Claims (1)
[1]
Table 3. Formula of the invention Catalytic composition for dimerization of diolefins in a liquid phase in a solution of an inert solvent g, containing transition metal geshogenide 1a and a coordination group together with a reducing agent, characterized in that, in order to increase the activity and selectivity of the catalytic composition, as a reducing agent it contains carbonyls of iron, cobalt or nickel, and as a transition metal halide and coordination group a compound of the formula., 012 where M is iron, cobalt or nickel, L is a coo The reduction component is trihaptoallyl (h-C-Hg), nitroel (N0), X is chlorine, bromine, iodine, and the molar ratio of transition metal carbonyl to MUXj is 0.5-1.0. Sources of information taken into account during the examination 1. QUA patent No. 3G55793, cl. 260-6G6, published. 1972. 2, Patent of France 1502141,. С 07 С, published. 1967 (prototype)

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引用文献:

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GB908778A|1958-02-26|1962-10-24|Montedison Spa|Improved polymerisation catalyst and polymerisation of butadiene therewith|

US3377397A|1965-10-22|1968-04-09|Phillips Petroleum Co|Dimerization of diolefins|

CH490418A|1967-09-15|1970-05-15|Lonza Ag|Process for the preparation of allyl ruthenium tricarbonyl halides|

US3567731A|1967-12-26|1971-03-02|Phillips Petroleum Co|Metal nitrosyl halide complexes|

US3703561A|1968-03-28|1972-11-21|Phillips Petroleum Co|Olefin conversion using complexes of cu,ag and au with organoaluminums|

US3767593A|1970-12-10|1973-10-23|Phillips Petroleum Co|Catalyst system for dimerizing conjugated dienes comprising a dinitrosyliron halide and a reducing agent|JPS5371647U|1976-11-16|1978-06-15|

FR2409972B1|1977-11-29|1980-10-17|Charbonnages Ste Chimique|

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US5112451A|1989-05-08|1992-05-12|The Dow Chemical Company|Electrochemical preparation of iron nitrosyl carbonyl and its use as a catalyst|

US4973568A|1989-05-08|1990-11-27|The Dow Chemical Company|Preparation of a catalyst useful in the dimerization of butadiene|

US5182246A|1989-12-26|1993-01-26|Sagami Chemical Research Center|Catalyst for hydrogenation, dehydrosilylation or hydrosilylation and use thereof|

US5096870A|1990-09-05|1992-03-17|The Dow Chemical Company|Preparation of iron nitrosyl carbonyl catalyst|

US5057469A|1990-09-05|1991-10-15|The Dow Chemical Company|Preparation of iron nitrosyl carbonyl catalyst|

US5043504A|1990-09-05|1991-08-27|The Dow Chemical Company|Inhibition of butadiene-polymerization during the conversion of butadiene to vinylcyclohexene|

US5922780A|1995-01-10|1999-07-13|The Procter & Gamble Company|Crosslinked polymers made from 1,3,7-octatriene and like conjugated polyenes|

US5767168A|1995-03-30|1998-06-16|The Proctor & Gamble Company|Biodegradable and/or compostable polymers made from conjugated dienes such as isoprene and 2,3-dimethyl-1, 3-butadiene|

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法律状态:

优先权:

申请号 | 申请日 | 专利标题

FR7313293A|FR2225401B1|1973-04-12|1973-04-12|

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