JPH0517892B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION The present invention relates to a method for producing a codimer by reacting ethylene and styrenes in the presence of a catalyst. According to the method of the present invention, a codimer of ethylene and styrene can be produced in high yield by reacting ethylene and styrene using a very small amount of a catalyst that is easily available and easy to handle. can. The codimer of ethylene and styrenes obtained by the method of the present invention has a polymerizable double bond, and can not only form a homopolymer but also copolymerize with other vinyl monomers such as ethylene and propylene. It also provides coalescence and is industrially useful. Prior Art Regarding a method for producing 3-phenyl-1-butenes obtained by codimerizing ethylene and styrenes with good selectivity, a method using a palladium compound and a rhodium compound is known. However, this method had problems in that the catalyst was expensive and the catalyst activity was low. On the other hand, Japanese Patent Application Laid-Open No. 48-22379 discloses a complex complex of nickel, (Here, O/ represents a phenyl group and Z represents an aromatic substituent) is used as a catalyst to codimerize ethylene and styrene. However, although this method is superior in that a codimer of ethylene and styrene can be obtained in high yield, it has the drawback that the synthesis of the nickel complex catalyst used is complicated, such as using a Grignard reagent, and it is difficult to obtain. Ta. Summary of the Invention In order to overcome the problems of the above-mentioned known techniques, and as a result of intensive studies to carry out the catalytic reaction more advantageously, the present inventors have discovered that by using an extremely small amount of an easily available compound, The present invention has been completed by discovering that the catalytic activity is expressed simply by mixing, which is advantageous in handling the catalyst, and that the desired codimer of ethylene and styrene can be produced in high yield. That is, the present invention provides a method of co-dimerizing ethylene and styrene by reacting them in the presence of a catalyst, wherein the catalyst is (a) a nickel (zero-valent) complex, (b) general formula: PR ¹ ₃ A compound represented by (where R ¹
represents a _C1-12 alkyl group, a _C6-15 cycloalkyl group, a _C6-15 aryl group or a _C7-15 aralkyl group), (c) represented by the general formula: ^R2X compound (where
R ² is a C _1-12 alkyl group, a C _2-12 alkylene group, a C _6-15 aryl group, a C _7-15 aralkyl group, or a C _6-15 cycloalkyl group, and X is a base, bromine or iodine, respectively) and (d) a compound represented by the general formula: AY (where A
is boron or aluminum, and Y is a halogen atom). Detailed Description of the Invention (Styrenes) As the styrenes, which are one of the raw materials used in the method of the present invention, a compound represented by the general formula () is used. (In the formula, R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, halogen atoms, C _1-12 alkyl groups, C _6-15 aryl groups, chloromethyl groups, hydroxycarbonyl groups,
selected from a C _2-12 alkoxycarbonyl group, trichloromethyl group, hydroxy group, and trimethylsilyl group, each of which may be the same or different, and R ⁵ and R ⁶ are a hydrogen atom or a C _1-13 alkyl group ). More specifically, styrene, o-, m-, p-
Fluorostyrene, 2,3-, 2,4-, 2,5-
Difluorostyrene, o-, m-, p-chlorostyrene, 2,3-, 2,4-, 2,5-dichlorostyrene, o-, m-, p-methylstyrene, o
-, m-, p-ethylstyrene, o-, m-, p
-butylstyrene, o-, m-, p-decylstyrene, o-, m-, p-phenylstyrene, o
-, m-, p-chloromethylstyrene, 2,3
-, 2,4-, 2,5-, 3,4-dichloromethylstyrene, o-, m-, p-hydroxycarbonylstyrene, 2,3-, 2,4-, 2,5-,
3,4-dihydroxycarbonylstyrene, o
-, m-, p-methoxycarbonylstyrene, o
-, m-, p-ethoxycarbonylstyrene, o
-, m-, p-butoxycarbonylstyrene, o
-, m-, p-hexoxycarbonylstyrene,
o-, m-, p-desoxycarbonylstyrene,
2,3-,2,4-,2,5-,3,4-dimethoxycarbonylstyrene, 2,3-,2,4-,
2,5-,3,4-diethoxycarbonylstyrene, 2,3-,2,4-,2,5-,3,4-dibutoxycarbonylstyrene, o-, m-, p-
Trifluoromethylstyrene, 2,3-,2,4
-, 2,5-, 3,4-bis(trifluoromethyl)styrene, o-, m-, p-hydroxystyrene, 2,3-, 2,4-, 2,5-, 3,4-
Bis(trimethylsilyl)styrene, α-methylstyrene, α-methyl-4-chlorostyrene, α
-Methyl-3-ethoxycarbonylstyrene, α
-ethyl-chloromethylstyrene, α-propyl-4-trifluoromethylstyrene, ω-methylstyrene, ω-methyl-3-chlorostyrene, ω-
ethyl-4-prokypoxycarbonylstyrene,
ω-Methyl-3-chloromethylstyrene, ω-methyl-4-trifluoromethylstyrene, ω-methyl-3,4-dichlorostyrene, ω-methyl-4
-Methylstyrene and the like. Incidentally, the co-dimerization reaction between ethylene and styrenes carried out in the method of the present invention is shown as follows. (R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the formula are the same as defined above). (Catalyst) As the nickel (zero-valent) complex [component (a)] as one component of the catalyst used in the method of the present invention, one in which an electron donor such as olefin or phosphine is stabilized by coordination with nickel is used. It will be done. At this time, when a complex in which phosphine is coordinated is used, it is also possible to omit component (b) of the catalyst components described below. It is also possible to prepare the catalyst by synthesizing a nickel (zero-valent) complex in situ and then sequentially adding the catalyst components (b), (c), and (d) described below. It is. For example, a nickel (zero-valent) complex may be synthesized by adding a reducing agent such as an organometallic compound to a nickel organic acid compound in the presence of phosphine for reduction. To give specific examples of nickel (zero-valent) complexes, examples with olefin coordination include bis(cyclooctadiene)nickel, bis(acrolein)nickel, bis(acrylonitrile)nickel, and bis(cyclooctatetraene)nickel. , bis(π
Examples of phosphine-coordinated complexes include tetrakis(triphenylphosphine)nickel, tetrakis(triethylphosphine)nickel, tetrakis(tributylphosphine)nickel, etc.; Examples of phosphine-coordinated complexes include ethylene bis(triphenylphosphine) nickel, acrolein bis(triphenylphosphine) nickel, acrylonitrile bis(triphenylphosphine) nickel, and the like. Preferred examples include bis(cyclooctadiene)nickel, tetrakis(triphenylphosphine)nickel, and ethylenebis(triphenylphosphine)nickel. Further, nickel tetracarbonyl etc. to which carbon monoxide is coordinated can also be used. General formula of component (b) of the catalyst used in the present invention:
Specific examples of compounds represented by PR ¹ ₃ (where R ¹ represents a C _1-12 alkyl group, a C _6-15 cycloalkyl group, a C _6-15 aryl group, a C _7-15 aralkyl group) When R ¹ is alkyl, it is trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, trilaurylphosphine, etc., and when R ¹ is a cycloalkane group, it is tricyclohexylphosphine, Tri(methylcyclohexyl)phosphine, tri(ethylcyclohexyl)phosphine, tri(hexylcyclohexyl)phosphine, etc.
When R ¹ is an aryl group, triphenylphosphine, tritolylphosphine, tri(ethylphenyl)phosphine, tri(butylphenyl)phosphine, tri(hexylphenyl)phosphine, tri(methoxyphenyl)phosphine, tri(phenylphenyl)phosphine, Examples include trinaphthylphosphine, tri(methylnaphthyl)phosphine, tri(ethylnaphthyl)phosphine, tri(butylnaphthyl)phosphine, tri(amylnaphthyl)phosphine, etc. When R ¹ is an aralkyl group, tribenzylphosphine, tri(methylbenzyl)phosphine, tri(ethylbenzyl)phosphine, tri(butylbenzyl)phosphine,
Examples include tri(hexylbenzyl)phosphine, tri(naphthylmethyl)phosphine, tri(naphthylethyl)phosphine, and the like. Preferred examples include triphenylphosphine, tritolylphosphine, and trinaphthylphosphine. Component (c) of the catalyst used in the method of the present invention is a compound represented by the general formula: ^R2X (where ^R2 is _C1-12
an alkyl group of _C2-12 , an alkylene group of C6-15, an aryl group of _C6-15 , an aralkyl group of _C7-15 or a cycloalkyl group of _C6-15 , X represents a base, bromine or iodine, respectively). To give a concrete example, R ²
When is an alkyl group, methyl bromide, methyl iodide,
Ethyl bromide, ethyl iodide, isopropyl chloride, t-butyl chloride, isobutyl bromide, isobutyl iodide, t-butyl bromide, t-butyl iodide, 2-, 3
-Hexyl chloride, hexyl bromide, isohexyl bromide, hexyl iodide, isohexyl iodide, 2-, 3
-, 4-octyl chloride, 2-, 3-, 4-, 5
-,6-dodecyl chloride, dodecyl bromide, isododecyl bromide, dodecyl iodide, isododecyl iodide, etc., and preferably isopropyl bromide, isopropyl iodide, isobutyl bromide, isobutyl iodide, etc. When R ² is an alkylene group, ethylene bromide, ethylene iodide, allyl chloride, allyl bromide, allyl iodide, 1-chloride-2-butene, bromide butene, iodide butene, 1-chloride-2-hexene ,
Hexene bromide, hexene iodide, 3-octene chloride, octene bromide, octene iodide, 6-4-dodecene chloride, dodecene bromide, dodecene iodide,
Examples thereof include cinnamyl chloride, cinnamyl bromide, cinnamyl iodide, and preferable examples include allyl bromide, allyl iodide, cinnamyl chloride, cinnamyl bromide, and cinnamyl iodide. When R ² is an aryl group, benzene chloride, benzene bromide, benzene iodide, o-, m-, p-chlorotoluene, o-, m
-, p-bromotoluene, o-, m-, p-iodotoluene, -2,3-xylyl chloride, -
2,4-xylyl, 2,5-xylyl chloride, 2,6-xylyl chloride, 3,4-xylyl chloride, 3,5-xylyl chloride, 2,3-xylyl bromide, 2,4-xylyl, bromide-2,5
-Xylyl, bromide-2,6-xylyl, bromide-
3,4-xylyl, 3,5-xylyl bromide, 2,6-xylyl iodide, o-, m-, p-cumenyl chloride, o-, m-, p-cumenyl bromide, o-,
m-, p-Cumenyl iodide, mesityl chloride, mesityl bromide, mesityl iodide, -4-biphenylyl chloride, -4-biphenylyl bromide, -4-biphenylyl iodide, -1-naphthyl chloride, -1 bromide -naphthyl, 1-naphthyl iodide, 1,3-dimethyl-2-naphthyl chloride, 1,3-dimethyl-2 bromide
-naphthyl, 1,3-dimethyl-2-naphthyl iodide, 1,2-, 1,3-, 1,4-dichlorobenzene, 1,2-, 1,3-, 1,4-dibromobenzene, 1,2-, 1,3-, 1,4-diotobenzene, 1-bromo-2-chlorobenzene,
1-bromo-3-chlorobenzene, 1-bromo-
4-chlorobenzene, 1-bromo-2-iodobenzene, 1-bromo-4-iodobenzene, 1-
Examples include bromo-4-chloro-2,6-xylene, and preferred are benzene bromide, o-bromotoluene, o-iodotoluene, 2,6-xylyl bromide, and 2,6-xylyl iodide. etc. When R ² is an aralkyl group, benzyl chloride,
Benzyl bromide, benzyl iodide, phenethyl chloride,
Phenethyl bromide, phenethyl iodide, α-methylbenzene chloride, α-methylbenzene bromide, α-methylbenzene iodide, 1-methyl-1-bromide
Phenethyl, 1-methyl-1-phenethyl iodide, benzhydryl bromide, benzhydryl iodide,
Examples include cinnamyl chloride, cinnamyl bromide, cinnamyl iodide, and preferable examples include benzyl chloride, bromide, benzyl iodide, and phenethyl iodide. ^R2
When is a cycloalkyl group, cyclohexyl bromide, cyclohexyl iodide, methylcyclohexyl bromide, methylcyclohexyl iodide, ethylcyclohexyl bromide, ethylcyclohexyl iodide, betylcyclohexyl bromide, butylhexyl iodide, bromodecaline, iodo Examples include decalin, and preferred examples include methylcyclohexyl bromide, dimethylxylyl bromide, and dimethylxylyl iodide. Component (d) of the catalyst used in the method of the present invention is a compound represented by the general formula: AY (where A represents boron or aluminum, and Y represents a halogen atom such as fluorine, chlorine, bromine, or iodine, respectively). It is. Specific examples of this include boron trifluoride, boron trichloride, aluminum fluoride, aluminum chloride, etc., and preferably boron trifluoride, aluminum chloride, etc. Further, examples include compounds in which ether, carboxylic acid, ketone, etc. are coordinated to these compounds, and boron trifluoride ethyl ether is preferred. (Reaction) In the method of the present invention, ethylene and styrene react in equivalent amounts, but these raw materials do not necessarily have to be present in the reaction system in an equivalent relationship. can be used in an amount of 0.1 to 10 mol. There is no particular restriction on the amount of the catalyst used, but the nickel (zero-valent) complex, which is the component (a) of the catalyst, is usually used in an amount of 0.00001 to 0.1 mol, preferably 0.0001 to 0.01 mol, per 1 mol of styrene. The phosphorus compound represented by the general formula PR ¹ ₃ , which is the component (b) of the catalyst, is 0.05 to 10 mol per mol of the nickel (zero-valent) complex,
The amount of the organic halide represented by the general formula: R ² The amount of boron halide or aluminum halide of the compound represented by the general formula: AY, which is the component (d) of the catalyst, is preferably 0.1 to 3 mol.
0.01 to 10 moles, preferably 0.1 to 3 moles
It is a mole. The codimerization reaction in the method of the invention is preferably carried out using a solvent. This solvent is
Aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons and halogenated hydrocarbons are used. Among these, aromatic hydrocarbons, which contribute to solubilization and stabilization of the complex catalyst used in the reaction, are preferred solvents. To give a concrete example of this, benzene,
Toluene, xylene, ethylbenzene, cumene,
Examples include tetralin, fluorinated benzene, and the like. Of course, a substantially solvent-free reaction is also possible using styrene, which is a type of aromatic compound and one of the substrates of the present invention, as a solvent. The reaction temperature of the codimeric reaction in the method of the present invention is −50 to
The temperature is 150°C, preferably -10 to 120°C. The reaction pressure may be normal pressure, but under pressure of ethylene 0.5 to 100 kg/
cm ² G, particularly 1 to 50 Kg/cm ² G is preferred. The catalyst used for the co-dimerization reaction in the method of the present invention is a nickel (zero-valent) complex and a general formula: PR ¹ ₃
A mixture of phosphorus compounds represented by the general formula:
Preferably, the catalyst is prepared by adding an organic halide represented by R ² used for. Experimental Example 1 Autoclave with electromagnetic induction stirrer (inner volume
500 ml) was replaced with nitrogen, and then 200 ml of toluene, bis(cyclooctadiene)nickel (0.55 g, 2 mmol), triphenylphosphine (1.05 g, 4 mmol), and mesityl bromide (0.40 g, 2 mmol) were replaced under a nitrogen gas flow.
g, 2 mmol), boron fluoride etherate (0.248 ml, 2 mmol), styrene (100 ml, 0.90 m
mol), and after sealing, ethylene gas was introduced to maintain the pressure at 5 kg/cm ² G. The mixture was kept at 20°C and reacted for 1 hour. Next, take out the reaction solution and adjust to 1N
After catalytic decomposition with 50 ml of HCl/methanol (50/50), the product was analyzed by gas chromatography, and the conversion rate of styrene was almost 100%. The yield was 92%. Examples 2 to 20 The styrene in Example 1 was replaced with various styrene derivatives shown in Table 1, and the number of moles of the catalyst was changed to various nickel (zero-valent) complexes [Ni (zero-valent) complex] shown in Table 1. ], an organic phosphorus compound (abbreviated as PR ¹ ₃ ), an organic halide (abbreviated as R ² X), and a boron halide or aluminum halide (abbreviated as AY). The reaction was carried out in the same manner as in Example 1,
Catalytic decomposition and product analysis were performed. The results are shown in Table 1.

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Claims (1)

[Claims] 1. A method of co-dimerizing ethylene and styrene by reacting them in the presence of a catalyst, wherein the catalyst is (a) a nickel (zero-valent) complex, (b) general formula: PR ¹ ₃ (where R ¹
represents a _C1-12 alkyl group, a _C6-15 cycloalkyl group, a _C6-15 aryl group or a _C7-15 aralkyl group), (c) represented by the general formula: ^R2X compound (where
R ² is a C _1-12 alkyl group, a C _2-12 alkylene group, a C _6-15 aryl group, a C _7-15 aralkyl group, or a C _6-15 cycloalkyl group, and X is a base, bromine or iodine, respectively) and (d) a compound represented by the general formula: AY (where A
is boron or aluminum, and Y is a halogen atom).