Dimerization of low .alpha.-olefins

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for dimerization of a lower .alpha.-olefin, using a nickel-containing catalyst.
2. Description of the Related Art
Dimers of lower .alpha.-olefins such as ethylene, propylene, butene, etc. are useful as important raw materials in the production of agricultural chemicals, pharmaceuticals, medicines, perfumes, cosmetics and other chemicals or as monomers of polymers. It is known that the dimers are prepared by dimerizing the lower .alpha.-olefin in the presence of a nickel-containing catalyst system. Known nickel-containing catalyst systems for dimerization of the lower .alpha.-olefins are, for example, a catalyst system comprising a nickel compound, a trialkylaluminum, a phosphorous compound and a halogenated phenol (cf. Japanese Patent Kokai Publication No. 39004/1979), a catalyst system comprising a nickel compound, a trialkylaluminum, a phosphorous compound, a halogenated phenol and water (cf. Japanese Patent Kokai Publication No. 167932/1982), a catalyst system comprising a nickel compound, a bisdialkylaluminoxane, a phosphorous compound and a halogenated phenol (cf. Japanese Patent Kokai Publication No. 169433/1982) and a catalyst system comprising a nickel compound, a trialkylaluminum, a phosphorous compound and a fluorinated isopropyl alcohol (cf. Japanese Patent Kokai Publication Nos. 158225/1987 and 221335/1989).
SUMMARY OF THE INVENTION
An object of the present invention is to find a nickel-containing catalyst system which effectively catalyzes dimerization of lower .alpha.-olefins and to provide a process for preparing the dimers of the lower .alpha.-olefins in high yield and with high selectivity.
It has been found that the addition of sulfur compounds such as sulfonic acids, dialkyl sulfates, etc., to the nickel-containing catalyst system improves the yield and the selectivity in dimerization of lower .alpha.-olefins.
Accordingly, the present invention provides a process for preparing a dimer of a lower .alpha.-olefin comprising dimerizing the .alpha.-olefin in the presence of a catalyst system (Catalyst (A)) which comprises:
(1) at least one nickel compound selected from the group consisting of organic acid salts, inorganic acid salts and complex compounds of nickel,
(2) a trialkylaluminum,
(3) at least one compound selected from the group consisting of halogenated phenols of the general formula: ##STR1## wherein X.sub.1 to X.sub.5 independently represent a halogen atom, a hydrogen atom, or a hydroxyl group, with the proviso that at least one of them is a halogen atom, and a fluorinated isopropyl alcohol,
(4) at least one phosphorous compound selected from the group consisting of compounds of the formulae:
PR.sup.1 R.sup.2 R.sup.3 (II)
P(NR.sup.4.sub.2).sub.3 (III)
P(OR.sup.5).sub.3 (IV)
and
PR.sup.6 R.sup.7 (CH.sub.2).sub.n PR.sup.6 R.sup.7 (V)
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 independently represent an alkyl group, a cycloalkyl group, an aralkyl group or a phenyl group optionally substituted by alkyl groups or alkoxy groups and n is an integer from 1 to 6, and
(5) at least one sulfur compound selected from the group consisting of sulfonic acids and dialkyl sulfates; a catalyst system (Catalyst (B)) which comprises:
(1) at least one nickel compound selected from the group consisting of organic acid salts, inorganic acid salts and complex compounds of nickel,
(2) a trialkylaluminum,
(3) a fluorinated isopropyl alcohol,
(4) at least one phosphorous compound selected from the group consisting of compounds of the formulae:
PR.sup.1 R.sup.2 R.sup.3 (II)
P(NR.sup.4.sub.2).sub.3 (III)
P(OR.sup.5).sub.3 (IV)
and
PR.sup.6 R.sup.7 (CH.sub.2).sub.n PR.sup.6 R.sup.7 (V)
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, and n are the same as defined above,
(5) a sulfonic acid, and
(6) water; or a catalyst system (Catalyst (C)) which comprises:
(1) at least one nickel compound selected from the group consisting of organic acid salts, inorganic acid salts and complex compounds of nickel,
(2) a trialkylaluminum;
(3) a halogenated phenol represented by the general formula: ##STR2## wherein X.sub.1 to X.sub.5 are the same as defined above, (4) at least one phosphorous compound selected from the group consisting of compounds of the formulae:
PR.sup.1 R.sup.2 R.sup.3 (II)
P(NR.sup.4.sub.2).sub.3 (III)
and
P(OR.sup.5).sub.3 (IV)
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are the same as defined above,
(5) a sulfonic acid, and
(6) water.
Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

DETAILED DESCRIPTION OF THE INVENTION
The present invention will be illustrated in details hereinafter.
First, the preparation of Catalyst (A) will be illustrated.
The nickel compounds of the component (1) in Catalyst (A) used in accordance with the present invention include, for example, organic salts such as nickel naphthenate, nickel formate, nickel acetate, nickel benzoate, nickel oxalate, etc.; inorganic salts such as nickel chloride, nickel bromide, nickel iodide, nickel fluoride, nickel nitrate, nickel sulfate, etc.; and complex compounds of nickel such as nickel bis-(acetylacetonate), nickel bis-(ethylacetoacetate), nickel bis-(dimethylglyoximate), etc. Two or more nickel compounds may be used in combination.
The trialkylaluminums of the component (2) in Catalyst (A) include, for example, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-isopropylaluminum, tri-n-butylaluminum, tri-isobutylaluminum, tri-n-pentyaluminum, tri-n-hexylaluminum, tricyclohexylaluminum, etc.
Amount of the trialkylaluminum is usually 2-500 moles, preferably 2-100 moles, more preferably 2-50 moles per mole of the nickel compound.
The halogenated phenols of the component (3) in Catalyst (A) which are represented by the formula (I) include, for example, o-, m- and p-chlorophenol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-dichlorophenol, 2,4,5,- and 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol, pentachlorophenol, 2,3-dichlorohydroquinone, 2,6-dichlorohydroquinone, tetrachlorohydroquinone, 4,6-dichlororesorcine, 2,4,6-trichlororesorcine and tetrachlorocatechol and halogenated phenols in which the chlorine atoms in the compounds mentioned above are substituted by at least one fluorine, bromine or iodine atom.
The amount of the halogenated phenol is usually 0.4-20 moles, preferably 1-10 moles per mole of the trialkylaluminum.
The fluorinated isopropyl alcohols of the component (3) in Catalyst (A) include, for example, 1,1,3,3-tetrafluoroisopropyl alcohol, 1,1,1,3-tetrafluoroisopropyl alcohol, 1,1,1,3,3-pentafluoroisopropyl alcohol, 1,1,1,3,3,3-hexafluoroisopropyl alcohol, etc. Among them, 1,1,1,3,3,3-hexafluoroisopropyl alcohol is particularly preferred.
The amount of the fluorinated isopropyl alcohol is usually 0.2-10 moles, preferably 0.5-5 moles per mole of the trialkylaluminum.
The amount of the halogenated phenol or the fluorinated isopropyl alcohol used has a relationship to the composition of the dimers produced. For example, in the case of the dimerization of propylene, the selectivity of 2,3-dimethyl-2-butene produced tends to increase with the increase of the amount of the halogenated phenol or the fluorinated isopropyl alcohol.
The phosphorous compounds of the component (4) in Catalyst (A) include, for example, the phosphines represented by the formula [II] such as trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triisobutylphosphine, tri-tert-butylphosphine, tri-sec-butylphosphine, tricyclopropylphosphine, tricyclohexylphosphine, triphenylphosphine, tri-p-tolylphosphine, tri-p-methoxyphenylphosphine, tri-2,4,6-trimethylphenylphosphine, phenyl-diisopropylphosphine, diethylisopropylphosphine, ethyl-di-tert-butylphosphine, diethyl-tert-butylphosphine, ethyldicyclohexylphosphine, methylphenylbenzylphosphine, diethylphenylphosphine, ethyldiphenylphosphine, dimethylphenylphosphine, methyldiphenylphosphine, diisopropyl-ethylphosphine etc.; the aminophosphines represented by the formula [III] such as trisdimethylaminophosphine, trisdiethylaminophosphine, trisdi-n-propylaminophosphine, trisdiisopropylaminophosphine, trisdi-n-butylaminophosphine, trisdiisobutylaminophosphine, trisdi-tert-butylaminophosphine, trisdicyclohexylaminophosphine, etc.; the phosphites represented by the formula [IV] such as trimethylphosphite, triethylphosphite, tri-n-propylphosphite, triisopropylphosphite, tri-n-butylphosphite, triisobutylphosphite, tri-tert-butylphosphite, tricyclohexylphosphite, triphenylphosphite, tri-p-tolylphosphite, tri-p-methoxyphenylphosphite, etc.; and the bidentate phosphines represented by the formula [V] such as bisdiphenylphosphinomethane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,5-bis(diphenylphosphino)pentane, 1,6-bis(diphenylphosphino)hexane, 1,2-bis(dimethylphosphino)ethane, 1,2-bis(diethylphosphino)ethane, 1,2-(diethylphosphino)ethane, 1,2-bis(dicyclohexylphosphino)ethane, 1,2-bis(dipentafluorophenylphosphino)ethane, etc.
There is a relationship between the kind of the phosphorous compound used and the composition of the dimers produced. For example, in the case of the dimerization of propylene, the use of a phosphine such as triisopropylphosphine, tricyclohexylphosphine, tri-sec-butylphosphine, ethyl-di-tert-butylphosphine, and the like provides predominantly 2,3-dimethylbutenes, while the use of the bidentate phosphine, such as 1,2-bis(diphenylphosphino)ethane, provides predominantly methylpentenes.
The amount of the phosphorous compound is usually 0.1-50 moles, preferably 0.1-20 moles, more preferably 0.1-2 moles per mole of the nickel compound.
As the sulfur compound of the component (5) in Catalyst (A), there is used at least one compound selected from sulfonic acids and dialkyl sulfates. The sulfonic acids include, for example, aliphatic sulfonic acids such as methanesulfonic acid and ethanesulfonic acid; aromatic sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid and ethylbenzenesulfonic acid; and halogen-containing sulfonic acid such as chlorosulfonic acid and trifluoromethanesulfonic acid. The dialkyl sulfates include, for example, dimethyl sulfate and diethyl sulfate. These sulfur compounds may be used in admixture of two or more compounds. Particularly, the combined use of the sulfonic acids and the dialkyl sulfates provides an increased activity and selectivity of the catalyst for the dimerization of the lower .alpha.-olefin.
The amount of the sulfur compound is usually 0.1-20 moles, preferably 0.1-10 moles per mole of the nickel compound.
The catalyst according to the invention is usually prepared in the presence of an inert solvent. The inert solvents include, for example, aromatic hydrocarbons such as benzene, toluene, xylene, etc.; aliphatic hydrocarbons such as hexane, heptane, cyclohexane, etc.; and halogenated hydrocarbons such as dichloromethane, dichloroethane, chlorobenzene, dichlorobenzene, etc.
In the preparation of the catalysts, the order of addition of the components is not specified, but any order may be applicable. Especially, the catalysts of high stability are preferably prepared in the presence of a conjugated diene such as butadiene, isoprene, 1,2-pentadiene and 2,3-dimethyl-1,3-butadiene. If the conjugated diene is present in an excess amount, the dimerization of the lower .alpha.-olefin is prevented. Therefore, a molar amount of the conjugated diene is preferably from 1 to 200 times the amount the nickel compound.
The catalyst may usually be prepared at a temperature of -78 to 100.degree. C., preferably -50 to 30.degree. C.
The preparation of Catalyst (B) will be also illustrated as follows:
The nickel compounds of the component (1) in Catalyst (B) are the same as those in Catalyst (A).
The trialkylaluminums of the component (2) in Catalyst (B) are also the same as those in Catalyst (A) and are used in similar amounts to those in Catalyst (A).
The fluorinated isopropyl alcohols of the component (3) in Catalyst (B) are the same as those in Catalyst (A) and are also used in similar amounts to those in Catalyst (A).
There is a relationship between the amount of the fluorinated isopropyl alcohol used and the composition of the dimers produced. For example, in the case of the dimerization of propylene, the increased amount of the fluorinated isopropyl alcohol leads to the increase in the selectivity of 2,3-dimethyl-2-butene produced.
The phosphorous compounds of the component (4) in Catalyst (B) are the same as those in Catalyst (A) and used in similar amounts to those in Catalyst (A).
There is a relationship between the kind of the phosphorous compound used and the composition of the dimers produced. For example, when propylene is dimerized, the use of the phosphines such as trisopropylphosphine, tricyclohexylphosphine, tri-sec-butylphosphine or ethyl-di-tert-butylphosphine provides predominantly 2,3-dimethylbutenes, while the use of the bidentate phosphines such as 1,2-bisdiphenylphosphinoethane gives predominantly methylpentenes.
The sulfonic acids of the component (5) in Catalyst (B) are the same as those in Catalyst (A), and used in similar amounts to those in Catalyst (A).
The amount of water of the catalyst component (6) in Catalyst (B) is usually 0.1-10 moles, preferably from 1 to 5 moles per mole of the nickel compound, and is usually 0.1-2 moles, preferably 0.2-1 moles per mole of the trialkylaluminum.
Catalyst (B) can be prepared under the similar conditions to those employed in the preparation of Catalyst (A).
Finally the preparation of Catalyst (C) will be illustrated as follows.
The nickel compounds of the component (1) in Catalyst (C) are the same as those in Catalyst (A).
The trialkylaluminums of the component (2) in Catalyst (C) are also the same as those in Catalyst (A), and are used in similar amounts to those in Catalyst (A),
The halogenated phenols of the component (3) in Catalyst (C) are the same as those in Catalyst (A) and are used in similar amounts to those in Catalyst (A)
The phosphines of the formula (II), the aminophosphines of the formula (III) and the phosphites of the formula (IV) which are used as the component (3) in Catalyst (C) are the same as those in Catalyst (A) and are used in similar amounts to those in Catalyst (A).
There is a relation between the kind of the phosphorous compound used and the composition of the dimers produced. For example, in the dimerization of propylene, the use of a phosphine such as triisopropylphosphine, tricyclophosphine, tri-sec-butylphosphine, ethyl-di-tert-butylphosphine provides predominantly 2,3-dimethylbutenes.
The sulfonic acids of the component (5) in Catalyst (C) are the same as those in Catalyst (A) and are used in similar amounts to those in Catalyst (A).
The water of component (6) in Catalyst (C) is used in a similar amount to that in Catalyst (A).
Catalyst (C) can be prepared under the similar conditions to those employed in the preparation of Catalyst (A).
The dimerization of the lower .alpha.-olefin can be carried out in the inert solvent described above, using either of Catalyst (A), Catalyst (B) and Catalyst (C) in an amount of 10.sup.-5 to 10.sup.-1 mol/liter in terms of the concentration of the nickel component.
A dimerization temperature is usually from -70.degree. to 150.degree. C., preferably from -50.degree. to 100.degree. C., more preferably from -20.degree. to 50.degree. C., and dimerization pressure is usually from 0 to 30 Kg/cm.sup.2 G.
The lower .alpha.-olefins to be dimerized by the process of the present invention include, for example, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1 -hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene and the like. Among them, ethylene, propylene and 1-butene are preferably used.
After the reaction is completed, the product can be isolated by stopping the reaction in a per se conventional manner, removing the catalyst, and distillating the residue. The desired dimer is thereby obtained. According to the present invention, the dimer of the lower .alpha.-olefin can be obtained in a high yield and with high selectivity.
PREFERRED EMBODIMENTS OF THE INVENTION
The invention will be illustrated by the following examples, which, however, limit the present invention in no way.
Examples 1 and 2
In a 50 ml Schlenk-type tube which had been cooled to 5.degree. C. and filled with nitrogen, 1.35 ml of toluene containing 0.1 mmol of nickel naphthenate, 0.1 mmol of tricyclohexylphosphine (in 20% toluene solution) and 8 mmol of isoprene were charged at 5.degree. C., followed by the addition of 2 ml of toluene containing 2 mmol of triethylaluminum. The mixture was heated to 18.degree. C. with stirring.
Then the mixture was cooled to 5.degree. C. and methanesulfonic acid was added thereto in an amount shown in Table 1. Further 3.5 ml of toluene containing 3.5 mmol of 2,4,6-trichlorophenol was added in such manner that the internal temperature in the tube did not exceed 20.degree. C.
In a stainless steel 500 ml autoclave which had been filled with nitrogen, the catalyst solution which had been prepared as described above and 18 ml of toluene were added at 20.degree. C. and then propylene was injected to a pressure of 4 Kg/cm.sup.2 G to react at 20.degree. C. for 3 hours.
After the reaction was completed, the reaction mixture was cooled to 5.degree. C., followed by purging of unreacted propylene from the mixture. Then the reaction mixture was analyzed by gas chromatography. The results are shown in Table 1.
TON(turnover number)=the amount of the dimers produced (mmol)/ the amount of the nickel metal used (mmol)
Selectivity of dimer (%)=[the amount of the dimers produced (g)/ the amount of the propylene reacted (g)].times.100
Dimers: DMB-1+DMB-2+2M1P+2M2P+4M1,2P+Hex (DMB-1: 2,3-dimethyl-1-butene, DMB-2: 2,3-dimethyl-2-butene, 2M1P: 2-methyl-1-pentene, 2M2P: 2-methyl-2-pentene, 4M1,2P: 4-methyl-l-pentene+4-methyl-2-pentene, Hex: Hexene)
Comparative Example 1
Example 1 was repeated except that 0.8 mmol of water was used in place of methanesulfonic acid. The results are given in Table 1.
TABLE 1______________________________________Methanesulfonic Selectivity TONacid/Ni of dimers Total DMB-1 +(molar ratio) (%) dimers DMB-2______________________________________Example 1 3 75 8,786 7,046Example 2 5 77 11,021 8,784Comp. -- 62 6,856 5,862Exam. 1.sup.1)______________________________________ .sup.1 Water/Nickel (molar ratio) = 8
Example 3
Example 1 was repeated except that 0.1 mmol of trifluoromethanesulfonic acid was used in place of methanesulfonic acid and that the reaction was carried out for 2 hours. The selectivity of the dimers was 90.1%, and the TON of the total dimers and DMB-1+DMB-2 were 17,080 and 8,400, respectively.
Example 4
Example 3 was repeated except that the reaction was carried out at a temperature of 10.degree. C. for 1 hour. After the reaction was completed, the reaction mixture was analyzed by gas chromatography. The selectivity of the dimers was found to be 94.6%, and the TON of the total dimers and DMB-1+DMB-2 to be 28,830 and 17,696, respectively.
Example 5
Example 4 was repeated except that 0.02 mmol of nickel naphthenate, 0.02 mmol of tricyclohexylphosphine, 0.02 ml of trifluoromethanesulfonic acid, 0.16 mmol of isoprene, 0.40 mmol of triethylaluminum and 0.70 mmol of 2,4,6-trichlorophenol were used. After the reaction was completed, the reaction mixture was analyzed by gas chromatography. The selectivity of the dimers was found to be 99.4%, and the TON of the total dimers and DMB-1+DMB-2 to be 70,906 and 39,227, respectively.
Example 6
Example 5 was repeated except that the reaction was carried out at a pressure of 6 Kg/cm.sup.2 for 40 minutes. After the reaction was completed, the reaction mixture was analyzed by gas chromatography. The selectivity of the dimers was found to be 94.1%, and the TON of the total dimers and DMB-1+DMB-2 to be 112,778 and 51,495, respectively.
Example 7
Into a 50 ml Schlenk-type tube which had been cooled to 5.degree. C. and filled with nitrogen, 0.375 ml toluene containing 0.01 mmol of nickel naphthenate, 0.01 mmol of tricyclohexylphosphine (in 20% toluene solution) and 0.8 mmol of isoprene were charged at 5.degree. C., followed by the addition of 0.2 ml of toluene containing 0.2 mmol of triethylaluminum. The mixture was heated to 18.degree. C. with stirring.
Then the mixture was cooled to 5.degree. C. and 0.02 mmol of dimethyl sulfate was added thereto. Further, 0.7 ml of toluene containing 0.7 mmol of 2,4,6-trichlorophenol was added in such manner that the internal temperature in the tube did not exceed 20.degree. C.
In a stainless steel 100 ml autoclave which had been filled with nitrogen, the catalyst solution which had been prepared as described above and 2 ml of toluene were added at 15.degree. C. and propylene was injected to a pressure of 6 Kg/cm.sup.2 G to react at 15.degree. C. to 20.degree. C. for 1 hour.
After the reaction was completed, the reaction mixture was cooled to 5.degree. C., followed by purging unreacted propylene from the mixture. Then it was analyzed by gas chromatography. The results are given in Table 2.
Example 8
Example 7 was repeated except that dimethyl sulfate was used in an amount of 0.03 mmol. The results are given in Table 2.
Example 9
Example 7 was repeated except that o-dichlorobenzene was used in place of toluene and that dimethyl sulfate was used in an amount of 0.04 mmol. The results are given in Table 2.
Example 10
Example 7 was repeated except that diethyl sulfate was used in an amount of 0.03 mmol in place of dimethyl sulfate. The results are given in Table 2.
TABLE 2______________________________________ Selectivity of TON dimers (%) Total dimers DMB-1 DMB-2______________________________________Example 7 64 28,339 17,496 4,420Example 8 68 29,552 17,295 4,337Example 9 64 30,514 18,606 4,341Example 10 72 21,335 14,144 2,177______________________________________
Example 11
In a 50 ml Schlenk-type tube which had been cooled to 5.degree. C. and filled with nitrogen, 0.68 ml of toluene containing 0.05mmol of nickel naphthenate, 0.05 mmol of tricyclohexylphosphine (in 20% toluene solution) and 4 mmol of isoprene were charged at 5.degree. C., followed by the addition of 1 ml of toluene containing 1 mmol of triethylaluminum. The mixture was heated to 18.degree. C. with stirring.
Then the mixture was cooled to 5.degree. C. and 0.15 mmol of dimethyl sulfate was added thereto. Further 3.5 ml of toluene containing 3.5 mmol of 2,4,6-trichlorophenol was added in such manner that the internal temperature in the tube did not exceed 20.degree. C.
In a stainless steel 500 ml autoclave which had been filled with nitrogen, the catalyst solution prepared as described above and 18 ml of toluene were introduced at 15.degree. C. and then propylene was injected to a pressure of 4 Kg/cm.sup.2 G to react at 20.degree. C. for 2 hours.
After the reaction was completed, the reaction mixture was cooled to 5.degree. C., followed by purging unreacted propylene from the mixture. Then it was analyzed by gas chromatography. The results are given in Table 3.
Example 12
Example 11 was repeated except that triethylaluminum was used in an amount of 0.75 mmol, dimethyl sulfate in an amount of 0.115 mmol and 2,4,6-trichlorophenol in an amount of 2.5 mmol. The results are given in Table 3.
TABLE 3______________________________________ Selectivity of TON dimers (%) Total dimers DMB-1 DMB-2______________________________________Example 11 68 18,121 2,156 11,852Example 12 68 16,349 11,011 1,921______________________________________
Example 13
In a 50 ml Schlenk-type tube which had been cooled to 5.degree. C. and filled with nitrogen, 0.375 ml of toluene containing 0.01 mmol of nickel naphthenate, 0.01 mmol of triisopropylphosphine and 0.8 mmol of isoprene were charged at the same temperature, followed by the addition of 0.15 ml of toluene containing 0.15 mmol of triethylaluminum. The mixture was heated to 18.degree. C. with stirring.
Then the mixture was cooled to 5.degree. C. and was added 0.025 mmol of dimethyl sulfate thereto. Further, 0.5 ml of toluene containing 0.5 mmol of 2,4,6-trichlorophenol was added in such manner that the internal temperature in the tube did not exceed 20.degree. C.
In a stainless steel 100 ml autoclave which had been filled with nitrogen, the catalyst solution prepared as described above and 2 ml of toluene were introduced at 15.degree. C. and then propylene was injected to a pressure of 6 Kg/cm.sup.2 G to react at a temperature of 15.degree. C. to 20.degree. C. for 1 hour.
After the reaction was completed, the reaction mixture was cooled to 5.degree. C., followed by purging unreacted propylene from the mixture. Then it was analyzed by gas chromatography. The results are given in Table 4.
Example 14
Example 13 was repeated except that 0.01 mmol of triethylphosphine was used in place of triisopropylphosphine. The results are given in Table 4.
Example 15
Example 13 was repeated except that 0.01 mmol of diethylphenylphosphine was used in place of triisopropylphosphine. The results are given in Table 4.
TABLE 4__________________________________________________________________________Selectivity of TONdimers (%) Total dimers DMB-1 DMB-2 2M1P 2M2P 4M1,2P__________________________________________________________________________Example 13 64 11,484 7,763 1,088 1,072 393 1,064Example 14 90 16,821 4,499 169 2,469 4,151 4,971Example 15 87 9,618 2,424 263 1,903 2,503 2,525__________________________________________________________________________
Example 16
In a 50 ml Schlenk-type tube which had been cooled to 5.degree. C. and filled with nitrogen, 0.68 ml of toluene containing 0.05 mmol of nickel naphthenate, 0.05 mmol of tricyclohexylphosphine (in 20% toluene solution) and 4 mmol of isoprene were charged at 5.degree. C., followed by the addition of 0.9 ml of toluene containing 1 mmol of triethylaluminum. The mixture was heated to 18.degree. C. with stirring.
Then the mixture was cooled to 5.degree. C. and 0.09 mmol of dimethyl sulfate was added thereto. Further, 2.5 ml of toluene containing 2.5 mmol of 2,4,6-trichlorophenol was added in such manner that the internal temperature in the tube did not exceed 20.degree. C.
In a stainless steel 500ml autoclave which had been filled with nitrogen, the catalyst solution prepared as described above and 18 ml of toluene were introduced at 15.degree. C. and then propylene was injected to a pressure of 4 Kg/cm.sup.2 G to react at 20.degree. C. for 2 hours.
After the reaction was completed, the reaction mixture was cooled to 5.degree. C., followed by purging unreacted propylene from the mixture. Then it was analyzed by gas chromatography. The results are given in Table 3.
Example 17
Example 16 was repeated except that 0.125 mmol of methanesulfonic acid was further added after the addition of 0.09 mmol of diethyl sulfate. The results are given in Table 5.
Example 18
Example 16 was repeated except that 0.15 mmol of methanesulfonic acid was further added after the addition of 0.09 mmol of diethyl sulfate. The results are given in Table 5.
Example 19
Example 16 was repeated except that 0.2 mmol of methanesulfonic acid was further added after the addition of 0.09 mmol of diethyl sulfate. The results are given in Table 5.
TABLE 5______________________________________ Selectivity of TON dimers (%) Total dimers DMB-1 DMB-2______________________________________Example 16 66.9 9,399 4,993 2,028Example 17 70.4 24,124 16,195 2,742Example 18 77.5 28,822 20,631 2,138Example 19 76.5 23,760 16,751 2,043______________________________________
Example 20
In a 50 ml Schlenk-type tube which had been cooled to 5.degree. C. and filled with nitrogen, 1.24 ml of toluene containing 0.1 mmol of nickel naphthenate, 0.1 mmol of 1,2-bis(diphenylphosphino)ethane and 8 mmol of isoprene were charged at 5.degree. C., followed by the addition of 2 ml of toluene containing 2 mmol of triethylaluminum.
Then 0.3 mmol of trifluoromethanesulfonic acid was added at 5.degree. C. and further 3.5 ml of toluene containing 3.5 mmol of 2,4,6-trichlorophenol was added in such manner that the internal temperature in the tube did not exceed 20.degree. C.
In a stainless steel 500 ml autoclave which had been filled with nitrogen, the catalyst solution prepared as described above and 12 ml of toluene were introduced at 10.degree. C. and then propylene was injected to a pressure of 4.5 Kg/cm2G to react at the same temperature for 2 hours.
After the reaction was completed, the reaction mixture was cooled to 0.degree. C., followed by purging unreacted propylene from the mixture. Then it was analyzed by gas chromatography. The results are given in Table 6.
Example 21
Example 20 was repeated except that 0.1 mmol of 1,6-bis(diphenylphosphino)hexane was used in place of 1,2-bis(diphenylphosphino)ethane. The results are given in Table 6.
TABLE 6______________________________________ TON Selectivity of Total dimers (%) dimers 4M1,2P Methylpentenes______________________________________Example 20 97.8 8,110 4,480 7,650Example 21 100 26,600 9,120 15,140______________________________________
Example 22
In a 50 ml Schlenk-type tube which had been cooled to 5.degree. C. and filled with nitrogen, 0.375 ml of toluene containing 0.01 mmol of nickel naphthenate, 0.01 mmol of tricyclohexylphosphine (in 20% toluene solution) and 0.8 mmol of isoprene were charged at 5.degree. C., followed by the addition of 0.2 ml of toluene containing 0.2 mmol of triethylaluminum. The mixture was heated to 18.degree. C. with stirring.
Then the mixture was cooled to 5.degree. C. and 0.025 mmol of dimethyl sulfate was added thereto. Further, 0.3 ml of toluene containing 0.3 mmol of 1,1,1,3,3,3-hexafluoroisopropyl alcohol was added in such manner that the internal temperature in the tube did not exceed 20.degree. C.
In a stainless steel 100ml autoclave which had been filled with nitrogen, the catalyst solution prepared as described above and 2 ml of toluene were introduced at 15.degree. C. and then propylene was injected to a pressure of 6 Kg/cm.sup.2 G to react at 20.degree. C. for 1 hour.
After the reaction was completed, the reaction mixture was cooled to 5.degree. C., followed by purging unreacted propylene from the mixture. Then it was analyzed by gas chromatography. The results are given in Table 7.
Example 23
Example 22 was repeated except that 0.07 mmol of methanesulfonic acid was used in place of dimethyl sulfate. The results are given in Table 7.
Example 24
Example 22 was repeated except that 0.1 mmol of triethylaluminum and 0.15 mmol of 1,1,1,3,3,3-hexafluoroisopropyl alcohol were used and that 0.01 mmol of trifluoromethanesulfonic acid was used in place of dimethyl sulfate. The results are given in Table 7.
Example 25
Example 22 was repeated except that 0.15 mmol of triethylaluminum was used. The results are given in Table 7.
Example 26
Example 22 was repeated except that 0.4 mmol of 1,1,1,3,3,3-hexafluoroisopropyl alcohol was used. The results are given in Table 7.
Example 27
Example 24 was repeated except that 0.02 mmol of chlorosulfonic acid was used in place of trifluoromethanesulfonic acid. The results are given in Table 7.
Comparative Example 2
Example 22 was repeated except that 0.02 mmol of nickel naphthenate, 0.02 mmol of tricyclohexylphosphine, 1.6 mmol of isoprene were and 0.60 mmol of 1,1,1,3,3,3-hexafluoroisopropyl alcohol used, and that dimethyl sulfate was not used. The results are given in Table 7.
Comparative Example 3
Example 22 was repeated except that 0.02 mmol of nickel naphthenate, 0.02 mmol of tricyclohexylphosphine, 1.6 mmol of isoprene and 0.15 mmol of 1,1,1,3,3,3-hexafluoroisopropyl alcohol were used, and no dimethyl sulfate was used. The results are given in Table 7.
TABLE 7______________________________________ Selectivity of TON dimers (%) Total dimers DMB-1 DMB-2______________________________________Example 22 43 9,322 7,679 562Example 23 50 15,407 7,226 6,163Example 24 65 17,317 13,903 62Example 25 44 11,881 2,337 7,786Example 26 53 17,607 1,265 13,560Example 27 97 8,210 6,041 8Comp. 37 4,149 283 3,339Exam. 2Comp. 34 2,466 2,184 50Exam. 3______________________________________
Example 28
In a 50 ml Schlenk-type tube which had been cooled to 5.degree. C. and filled with nitrogen, 1.35 ml of toluene containing 0.1 mmol of nickel naphthenate, 0.1 mmol of tricyclohexylphosphine (in 20% toluene solution) and 0.8 mmol of isoprene were charged at 5.degree. C., followed by the addition of 1 ml of toluene containing 1 mmol of triethylaluminum. The mixture was heated to 18.degree. C. with stirring.
Then the mixture was cooled to -5.degree. C. and 0.1 mmol of trifluoromethanesulfonic acid was added thereto. Further, 1.5 ml of toluene containing 1.5 mmol of 1,1,1,3,3,3-hexafluoroisopropanol was added in such manner that the internal temperature in the tube did not exceed 20.degree. C.
In a stainless steel 500 ml autoclave which had been filled with nitrogen, the catalyst solution prepared as described above and 18 ml of toluene were introduced at 15.degree. C. and then propylene was injected to a pressure of 4 Kg/cm.sup.2 G to react at 20.degree. C. for 2 hours.
After the reaction was completed, the reaction mixture was cooled to 5.degree. C., followed by purging of unreacted propylene from the mixture. Then the reaction mixture was analyzed by gas chromatography. The results are given in Table 8.
Example 29
Example 28 was repeated except that 0.05 mmol of trifluoromethanesulfonic acid was used. The results are given in Table 8.
Example 30
Example 28 was repeated except that 0.05 mmol of nickel naphthenate, 0.05 mmol of tricyclohexylphosphine, 4 mmol of isoprene, 0.5 mmol of triethylaluminum and 0.75 mmol of 1,1,1,3,3,3-hexafluoroisopropyl alcohol were used, and that 0.075 mmol of trifluoromethanesulfonic acid and 0.05 mmol of dimethyl sulfate were used in place of 0.1 mmol of trifluoromethanesulfonic acid. The results are given in Table 8.
Example 31
Example 28 was repeated except that 0.05 mmol of nickel naphthenate, 0.05 mmol of tricyclohexylphosphine, 4 mmol of isoprene, 0.5 mmol of triethylaluminum and 0.75 mmol of 1,1,1,3,3,3-hexafluoroisopropyl were used, and that 0.125 mmol of trifluoromethanesulfonic acid and 0.05 mmol of dimethyl sulfate were used in place of 0.1 mmol of trifluoromethanesulfonic acid. The results are given in Table 8.
Example 32
Example 28 was repeated except that 0.05 mmol of nickel naphthenate, 0.05 mmol of tricyclohexylphosphine, 4 mmol of isoprene, 0.5 mmol of triethylaluminum and 0.75 mmol of 1,1,1,3,3,3-hexafluoroisopropyl alcohol were used and that 0.125 mmol of trifluoromethanesulfonic acid and 0.05 mmol of diethyl sulfate were used in place of 0.1 mmol of trifluoromethanesulfonic acid. The results are given in Table 8.
TABLE 8______________________________________ TONSelectivity of DMB-1 +dimers (%) Total dimers DMB-1 DMB-2______________________________________Example 28 83.9 19,179 14,937 15,081Example 29 78.9 13,119 10,182 10,988Example 30 86.2 25,290 19,007 19,646Example 31 84 26,332 20,087 20,241Example 32 86.2 23,983 18,044 18,218______________________________________
Example 33
Example 24 was repeated except that 0.01 mmol of triisopropylphosphine was used in place of tricyclohexylphosphine. The results are given in Table 9.
Example 34
Example 24 was repeated except that 0.01 mmol of triethylphosphine was used in place of tricyclohexylphosphine. The results are given in Table 9.
Example 35
Example 24 was repeated except that 0.01 mmol of diethylphenylphosphine was used in place of tricyclohexylphosphine. The results are given in Table 9.
TABLE 9__________________________________________________________________________Selectivity of TONdimers (%) Total dimers DMB-1 DMB-2 2M1P 2M2P 4M1,2P__________________________________________________________________________Example 24 65 17,317 13,903 62 1,874 166 1,136Example 33 76.3 16,544 12,210 33 1,754 165 2,200Example 34 89.3 14,661 5,665 146 3,596 2,715 2,304Example 35 92 20,872 5,560 272 4,701 5,223 4,053__________________________________________________________________________
Example 36
Example 28 was repeated except that 0.12 ml of toluene containing 0.1 mmol of nickel naphthenate and 0.1 mmol of tri-sec-butylphosphine were used, and that the reaction was carried out at a temperature of 10.degree. C. for 1 hour. The results are given in Table 10.
Example 37
Example 36 was repeated except that 0.06 ml of toluene containing 0.05 mmol of nickel naphthenate, 0.05 mmol of diisopropylethylphosphine, 4 mmol of isoprene, 0.5 mmol of triethylaluminum, 0.05 mmol of trifluoromethanesulfonic acid and 0.75 mmol of 1,1,1,3,3,3-hexafluoroisopropyl alcohol were used. The results are given in Table 10.
Example 38
Example 37 was repeated except that 0.05 mmol of triisopropylphosphine was used in place of diisopropylethylphosphine. The results are given in Table 10.
Example 39
Example 36 was repeated except that 0.10 mmol of triisopropylphosphine was used in place of tri-sec-butylphosphine and that 0.08 mmol of trifluoromethanesulfonic acid was used. The results are given in Table 10.
TABLE 10______________________________________ TONSelectivity of DMB-1 +dimers (%) Total dimers DMB-1 DMB-2______________________________________Example 36 80.9 22,694 17,454 17,500Example 37 85.9 49,807 27,397 27,566Example 38 94.5 34,878 26,625 26,753Example 39 85.5 28,006 14,618 14,755______________________________________
Example 40
In a 50 ml Schlenk-type tube which had been cooled to 5.degree. C. and filled with nitrogen, 1.35 ml of toluene containing 0.1 mmol of nickel naphthenate, 0.1 mmol of tricyclohexylphosphine (in 20% toluene solution) and 8 mmol of isoprene were charged at 5.degree. C., followed by the addition of 1 ml of toluene containing 1 mmol of triethylaluminum. The mixture was heated to 18.degree. C. with stirring.
Then the mixture was cooled to 5.degree. C. and 0.1 mmol of trifluoromethanesulfonic acid was added thereto. Then 1.5 ml of toluene containing 1.5 mmol of 1,1,1,3,3,3-hexafluoroisopropyl alcohol was added in such manner that the internal temperature in the tube did not exceed 20.degree. C.
In a stainless steel 1,500ml autoclave which had been filled with nitrogen, the catalyst solution prepared as described above and 40 ml of toluene were introduced at 15.degree. C. and then propylene was injected to a pressure of 3 Kg/cm.sup.2 G to react at 10.degree. C. for 2 hours.
After the reaction was completed, the reaction mixture was cooled to 5.degree. C., followed by purging unreacted propylene from the mixture. Then it was analyzed by gas chromatography. The results are given in Table 10.
Example 41
In the same manner as in Example 40 except that 0.15 mmol of nickel naphthenate, 0.15 mmol of tricyclohexylphosphine, 12 mmol of isoprene, 1.5 mmol of triethylaluminum, 0.15 mmol of trifluoromethanesulfonic acid and 2.25 mmol of 1,1,1,3,3,3-hexafluoroisopropyl alcohol were used, the catalyst was prepared.
In a stainless steel 1,500 ml autoclave which had been filled with nitrogen, one third of the catalyst prepared as described above and 36 ml of toluene were introduced at 15.degree. C. and then propylene was injected to a pressure of 3 Kg/cm.sup.2 G to start the reaction at 10.degree. C. The remaining catalyst solution was divided into two portions and added to the reaction mixture after 1 and 2 hours from the start of the reaction respectively, and the reaction was continued for additional 1 hour.
After the reaction was completed, the reaction mixture was cooled to 5.degree. C., followed by purging unreacted propylene from the mixture. Then it was analyzed by gas chromatography. The results are given in Table 11.
Example 42
Example 41 was repeated except that propylene was injected to a pressure of 4 Kg/cm.sup.2 G. The results are given in Table 11.
TABLE 11______________________________________ TONSelectivity of DMB-1 +dimers (%) Total dimers DMB-1 DMB-2______________________________________Example 40 74.5 48,737 38,210 38,210Example 41 83.1 45,009 35,487 35,737Example 42 78.3 56,209 42,700 43,843______________________________________
Example 43
In a 50 ml Schlenk-type tube which had been cooled to 5.degree. C. and filled with nitrogen, 1.2 ml of toluene containing 0.05 mmol of nickel naphthenate, 0.05 mmol of 1,2-bis(diphenylphosphino)ethane and 4 mmol of isoprene were charged at 5.degree. C., followed by the addition of 0.5 ml of toluene containing 0.5 mmol of triethylaluminum. The mixture was heated to 18.degree. C. with stirring.
Then the mixture was cooled to 5.degree. C. and 0.1 mmol of trifluoromethanesulfonic acid was added thereto. Further, 0.75 ml of toluene containing 0.75 mmol of 1,1,1,3,3,3-hexafluoroisopropyl alcohol was added in such manner that the internal temperature in the tube did not exceed 20.degree. C.
In a stainless steel 500 ml autoclave which had been filled with nitrogen, the catalyst solution prepared as described above and 18 ml of toluene were introduced at 15.degree. C. and then propylene was injected to a pressure of 4 Kg/cm.sup.2 G to react at 20.degree. C. for 2 hours.
After the reaction was completed, the reaction mixture was cooled to 5.degree. C., followed by purging unreacted propylene from the mixture. Then it was analyzed by gas chromatography. The results are given in Table 12.
Example 44
Example 43 was repeated except that 0.05 mmol of bisdiphenylphosphinomethane was used in place of 1,2-bis(diphenylphosphino)ethane. The results are given in Table 12.
Example 45
Example 43 was repeated except that 0.05 mmol of 1,6-bis(diphenylphosphino)hexane was used in place of 1,2-bis(diphenylphosphino)ethane, and that 0.05 mmol of trifluoromethanesulfonic acid was used. The results are given in Table 12.
Example 46
Example 43 was repeated except that 0.05 mmol of nickel naphthenate, 0.05 mmol of 1,2-bis(diphenylphosphino)ethane, 4 mmol of isoprene and 0.75 mmol of 1,1,1,3,3,3-hexafluoroisopropyl alcohol were used, and that 0.05 mmol of trifluoromethanesulfonic acid and 0.1 mmol of dimethyl sulfate were used in place of 0.1 mmol of trifluoromethanesulfonic acid. The results are given in Table 12.
TABLE 12______________________________________ TONSelectivity of 4M1,2P +dimers (%) Total dimers 4M1,2P 2M1,2P______________________________________Example 43 74.4 30,100 13,900 26,800Example 44 81.1 19,700 9,250 17,000Example 45 50.6 22,800 4,290 18,200Example 46 79.1 25,600 11,200 22,400______________________________________ (2M1,2P:2M1P + 2M2P)
Example 47-49
In a 50 ml Schlenk-type tube which had been cooled to 5.degree. C. and filled with nitrogen, 4.7 ml of toluene containing 0.1 mmol of nickel naphthenate, 0.1 mmol of tricyclohexylphosphine (in 20% toluene solution) and 8 mmol of isoprene were charged, followed by the addition of 1 ml of toluene containing 1 mmol of triethylaluminum. The mixture was then heated to 18.degree. C. with stirring.
The mixture was again cooled to 5.degree. C. and water in an amount shown in Table 12 was gradually added thereto. Then 0.12 mmol of trifluoromethanesulfonic acid was added and 1.5 ml of toluene containing 1.5 mmol of 1,1,1,3,3,3-hexafluoroisopropyl alcohol was added in such manner that the internal temperature in the tube did not exceed 20.degree. C.
In a stainless steel 500 ml autoclave which had been filled with nitrogen, the catalyst solution prepared as described above and 15 ml of toluene were introduced at 15.degree. C. and the propylene was injected to a pressure of 4 Kg/cm.sup.2 G to react at 10.degree. C. for 1.5 hours.
After the reaction was completed, the reaction mixture was cooled to 5.degree. C., followed by purging unreacted propylene from the mixture. Then it was analyzed by gas chromatography. The results are given in Table 13.
TABLE 13______________________________________ Selectivity TON Water/Ni of Dimers Total DMB-1 + (in mole) (%) dimers DMB-2______________________________________Example 47 3 61 4,500 4,020Example 48 1.5 58 17,400 14,500Example 49 0.5 70 17,400 13,700______________________________________
Example 50
Example 47 was repeated except that 1,2-bisdiphenylphosphinoethane was used in place of tricyclohexylphosphine and that trifluoromethanesulfonic acid was used in an amount of 0.2 mmol instead of 0.12 mmol. The results are given in Table 14.
TABLE 14______________________________________ Selectivity TON of dimers 4M1,2P + (%) Total dimers 4M1,2P 2M1,2P______________________________________Example 47 100 10,800 5,610 8,590______________________________________
Example 51-53
In a 50 ml Schlenk-type tube which had been cooled to 5.degree. C. and filled with nitrogen, 0.375 ml of toluene containing 0.01 mmol of nickel naphthenate, 0.01 mmol of tricyclohexylphosphine (in 20% toluene solution) and 0.8 mmol of isoprene were charged at 5.degree. C., followed by the addition of 0.2 ml of toluene containing 0.2 mmol of triethylaluminum. The mixture then was heated to 18.degree. C. with stirring.
The mixture was again cooled to 5.degree. C. and 0.03 mmol of water was gradually added to it. Then methanesulfonic acid in an amount given in Table 14 was added and 0.7 ml of toluene containing 0.7 mmol of 2,4,6-trichlorophenol was added in such manner that the internal temperature in the tube did not exceed 20.degree. C.
In a stainless steel 100 ml autoclave which had been filled with nitrogen, the catalyst solution prepared as described above and 2 ml of toluene were introduced at 15.degree. C. and then propylene was injected to a pressure of 6 Kg/cm.sup.2 G to react at a temperature between 15.degree. C. and 20.degree. C. for 1 hour.
After the reaction was completed, the reaction mixture was cooled to 5.degree. C., followed by purging unreacted propylene from the mixture. Then it was analyzed by gas chromatography. The results are given in Table 15.
Comparative Example 4
Example 51 was repeated except that methanesulfonic was not used. The results are given in Table 15.
TABLE 15______________________________________Methanesulfonic Selectivity of TONacid/Ni dimers Total DMB-1 +(molar ratio) (%) dimers DMB-2______________________________________Example 51 3 72 46,633 30,358Example 52 5 65 42,768 27,264Example 53 7 66 45,641 29,072Comp. -- 55 6,020 5,069Exam. 4______________________________________
The invention being thus described, it will be obvious that the same way be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims.

Number	Date	Country
4-116044	May 1992	JPX
4-136730	May 1992	JPX
4-147202	Jun 1992	JPX
4-270087	Oct 1992	JPX
4-346027	Dec 1992	JPX

Number	Name	Date
4487847	Knudsen	Dec 1984
4709112	Sato et al.	Nov 1987
4992610	Sato et al.	Feb 1991

Number	Date	Country
54-39004	Mar 1979	JPX
57-167932	Oct 1982	JPX
57-169433	Oct 1982	JPX

Dimerization of low .alpha.-olefins

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Chemical Abstract, 98: 88802v, 1983.
Chemical Abstract, 98: 106775v, 1983.