JPH11158085A - Production of hydrocarbon solvent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a nonpollution type hydrocarbon solvent produced from propylene as a raw material and consisting essentially of an isoparaffin, especially 2,3-dimethylbutane and 2-methylpentane. SOLUTION: This method for producing a hydrocarbon solvent comprises carrying out a dimerizing reaction of propylene, then hydrogenating and distilling the resultant dimerized substance obtained by the reaction and including >=90 mass % of 2,3-dimethylbutane and/or 2-methylpentane therein.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a pollution-free hydrocarbon solvent, and more particularly, to a method of dimerizing, hydrogenating, and distilling propylene as a raw material to eliminate aromatics and olefins. The present invention relates to a method for producing a hydrocarbon mixture having excellent volatility.

[0002]

2. Description of the Related Art Organic solvents are used in various applications such as reaction solvents, ink solvents, wet copy solvents, paint solvents, aerosol spray solvents, base oils for lubricating oils having high low-temperature fluidity, and base oils for cosmetics and fragrances. ing. Due to recent environmental problems, the use of aromatic compounds and olefinic compounds has been shunned. Recently, since chlorofluorocarbon-based solvents cause environmental destruction and the like, alternative solvents have been demanded.However, aromatic hydrocarbon solvents such as benzene, toluene, and xylene are regulated by the Ordinance on Prevention of Organic Solvent Poisoning. Those having a benzene content of more than 1% by volume, as specified second-class substances, are subject to strict restrictions on how to handle them.

[0003]

SUMMARY OF THE INVENTION Therefore, Japanese Patent Publication No. Sho 61
As disclosed in JP-A-21986, JP-A-53-146278 and JP-A-55-56199, naphthenic solvents have been developed, while aliphatic hydrocarbon solvents such as normal hexane have also been developed. It is attracting attention and used as an alternative solvent. However, in recent years, the amount of normal hexane used is being restricted similarly to aromatic hydrocarbons such as benzene, toluene and xylene. It is desired to develop an alternative solvent which has various physical properties similar to normal hexane and is excellent in volatility with little environmental destruction. Therefore, the present invention has been made in view of such practical use, and an object of the present invention is to provide an isoparaffin, particularly 2,3-dimethylbutane and 2-methylpentane, which is produced from propylene as a raw material. An object of the present invention is to provide a method for producing a pollution type hydrocarbon solvent.

[0004]

In order to achieve the above object, the present invention provides a method for producing a hydrocarbon solvent, which comprises carrying out a dimerization reaction of propylene, and then hydrogenating and dimerizing the dimer obtained by the reaction. It is distilled to contain 90 mass% or more of 2,3-dimethylbutane and / or 2-methylpentane.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the contents of the present invention will be described in detail. As propylene that can be used in the present invention, high-purity propylene, which can be used as a petrochemical raw material, can of course be used, but heavy gas oil such as vacuum gas oil obtained by vacuum distillation of crude oil and residual oil under atmospheric distillation. Gas mixture containing propylene produced by catalytic cracking of petroleum fractions, as well as propylene fractions obtained by catalytic cracking of vacuum distillation residual oil and propylene purified to high purity (in this case, sulfur, arsenic Minutes should be removed)
Also, a mixed gas containing propylene obtained by decomposition of naphtha can be used as propylene. In the method of the present invention, propylene is first dimerized,
Any method can be used for the dimerization. For example, a method using a solid phosphoric acid catalyst, a method using a strong base catalyst suspended in an organic solvent, a method using organic aluminum as a catalyst, an organic nickel complex Among them, a method using an organic nickel complex catalyst is particularly useful because of its high catalytic activity and dimer selectivity, and easy control of product selectivity. .

The organic nickel complex catalyst includes (A) at least one nickel compound selected from nickel organic acid salts, nickel inorganic acid salts and nickel complex compounds as its constituent components; (B) a compound represented by the following general formula (1): The organic phosphorus compound represented by PX ¹ X ² X ³ (1) (wherein X ¹ X ² and X ³ each represent a halogen atom, a hydrogen atom, or a hydrocarbon residue having 1 to 12 carbon atoms). ) Organoaluminum compounds are typical examples. Also,
As an optional catalyst component, these three components are used as a basis. In order to further improve activity and selectivity, as a component (D), at least one compound represented by any of the following general formulas MX _n , MR _n , and MR ′ _{n, MXlR m, MXlR 'm} , M
R ¹ R ′ _m , M ¹ (BR ₄ ) _p and R ″ (BR ₄ ) (wherein M represents an element selected from Mg, Ti, Zr, B and Sn, and M ¹ represents Li, Na, K, X represents a halogen atom or a hydrogen atom, R represents a hydrocarbon group having 1 to 12 carbon atoms, and R ′ represents an oxygen-containing hydrocarbon group having 1 to 12 carbon atoms. , R ″ represents a hydrocarbon group having 1 to 20 carbon atoms or an ammonium group, n represents a valence of M, l and m are natural numbers satisfying n = l + m, and p represents a valence of M ¹ Or (E) a compound having a carbon-halogen bond, or (F) an oxo acid and / or a salt thereof, or (G) a sulfonic acid derivative compound. Further, an olefinic compound may be appropriately added. The organic nickel complex catalyst can be obtained by bringing the above (A) to (C) or (D), (E), (F) or (G) into contact with each other.

The nickel compound of component (A) is one or more nickel compounds selected from nickel organic acid salts, nickel inorganic acid salts and nickel complex compounds. As the nickel organic acid salt, a carboxylic acid salt of nickel is preferable, and specific examples thereof include nickel formate, nickel acetate, nickel propionate, nickel octylate, nickel stearate, nickel 2-ethylhexanoate, and the like. A saturated aliphatic carboxylic acid nickel,
Nickel naphthenate and the like can be mentioned. Examples of the nickel inorganic acid salt include nickel halides such as nickel chloride, nickel bromide, nickel fluoride, and nickel iodide, nickel sulfate, nickel nitrate, nickel hydroxide, nickel oxide, and the like. Examples of the nickel complex compound include nickel halides such as nickel iodide, nickel sulfate, nickel nitrate, nickel hydroxide, nickel oxide and the like. Nickel complex compounds include bis- (1,5-cyclooctadiene) -nickel, dichlorobis (triphenylphosphine) nickel, biscyclopentadienylnickel, bis (acetylacetonato) nickel, bis (ethylacetoacetate) nickel , Nickel carbonyl and the like. Among these, nickel chloride, bis- (1,5-cyclooctadiene) -nickel, nickel acetate, nickel naphthenate, nickel 2-ethylhexanoate and nickel bis (acetylacetonate) are preferred, and nickel naphthenate, Nickel ethylhexanoate, nickel bis (acetylacetonate), bis- (1,5-cyclooctadiene) -nickel and the like are more preferred. These may be used alone or in combination of two or more.

[0008] The organophosphorus compound of the component (B) is an organophosphorus compound represented by the following general formula (1). PX ¹ X ² X ³ (1) (wherein, X ¹ , X ² and X ³ each independently represent a halogen atom, a hydrogen atom, a carbon number of 1 to 12, preferably 1 to 8
Represents a hydrocarbon residue. When one or more of X ¹ , X ² and X ³ in the general formula (1) is a hydrocarbon residue, the hydrocarbon residue may be an alkyl group, an aryl group, an aralkyl group, an alkoxy group,
Any such as an aryloxy group may be used,
More specifically, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, isopropyl, isopropoxy, butyl, isobutyl, pentyl, cyclopentyl, hexyl, hexyl, cyclohexyl, phenyl, Any of a phenoxy group, a tolyl group, a xylyl group and a benzyl group may be used. X
^One or more of X ¹ , X ² and X ³ may be halogen, in which case the halogen may be chlorine, bromine,
Fluorine and the like can be mentioned, and chlorine is preferable, but X ¹ , X ² ,
X ³ is preferably the hydrocarbon residue described above. Preferred examples of the organic phosphorus compound include trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tributylphosphine, tripentylphosphine, tricyclopentylphosphine, trihexylphosphine, tricyclohexylphosphine, triphenylphosphine, and tolylphosphine. Diphenylphosphine, diphenylpropylphosphine, diphenylmethylphosphine, diphenylchlorophosphine, trimethylphosphite, triethylphosphite, tripropylphosphite, tributylphosphite, tripentylphosphite, tricyclopentylphosphite, trihexylphosphite, tricyclohexyl Phosphite, triphenyl phosphite, tolyl Sufaito and the like, in particular a phosphine compound. These compounds can be used alone or in a mixture. The type of the organic phosphorus compound used as the component (B) greatly affects the selectivity of the dimer formed in the oligomerization reaction of the present invention. That is, in order to obtain a highly volatile solvent containing a high proportion of 2,3-dimethylbutane and 2-methylpentane precursors, it is preferable to use triisopropylphosphine or tricyclohexylphosphine. When other trimethylphosphine, triethylphosphine, triarylphosphine represented by triphenylphosphine such as alkylphosphine such as tributylphosphine, a 2-methylpentane precursor is obtained,
A normal hexane precursor is formed. Therefore, aside from using hexene by-produced for some special purpose, it is desirable to use tricyclohexylphosphine or triisopropylphosphine in order to selectively obtain the product of the present invention.

As the organoaluminum compound of the component (C), there may be mentioned an aluminum compound represented by the following general formula (2). _{AlR1 p X '3-p (} 2) ( wherein, R1 has 1 to 20 carbon atoms, preferably 1 to 12
X ′ represents a hydrogen atom or a halogen atom, and p is a number satisfying the range of 0 ≦ n ≦ 3. ) P in the general formula (2) is not necessarily an integer, for example, a _{p = 1.5 AlR1 1.5 X '1.5} , i.e., R1 ₃ Al ₂ X' also sesquichloride compound represented by _3, It is included in the general formula (2). The hydrocarbon group R1 in the general formula (2) may be any of an alkyl group, an aryl group, an aralkyl group, an alkylaryl group and the like, and more specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples thereof include a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a phenyl group, a tolyl group, a xylyl group, and a benzyl group, which may be the same or different. Also,
When X in the general formula (2) is a halogen atom, the halogen atom is any of fluorine, chlorine, bromine, and iodine. Specific examples of the organoaluminum compound represented by the general formula (2) include trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, tripentylaluminum, tricyclopentylaluminum, trihexylaluminum, and tricyclohexylaluminum. , Triphenylaluminum, tritolylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum dichloride, isobutylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum hydride, diisobutylaluminum hydride, aluminum chloride, etc. Diethylaluminum chloride, ethyl aluminum sesquichloride preferred. These can be used alone or in combination of two or more. As the component (C), a modified organoaluminum compound obtained by modifying an organoaluminum compound represented by the above general formula (2) with an active proton compound exemplified by alcohol, phenol and the like can be used. One of such modified organoaluminum compounds can be represented by the following general formula (3). AlR ² q (OR ³ ) _3-q (3) (wherein R ² and R ³ each independently represent a hydrocarbon group having 1 to 20, preferably 1 to 12 carbon atoms, and q is 0 <q ≦ 3
Is a number in the range. The hydrocarbon group R ² or R ³ in the general formula (3) may be any of an alkyl group, an aryl group, an aralkyl group, an alkylaryl group and the like.
Any of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, cyclopentyl, hexyl, cyclohexyl, phenyl, tolyl, xylyl, benzyl, etc. . Specific examples of the modified organoaluminum compound usable as the component (C) include dimethylmethoxyaluminum, dimethylethoxyaluminum, dimethylphenoxyaluminum, dimethyl- (2,6-di-t
Butyl-4-methylphenoxy) -aluminum, methyldimethoxyaluminum, methyldiethoxyaluminum, methyldiphenoxyaluminum, methyl-di (2,6-dibutyl-4-methylphenoxy) -aluminum, diethylmethoxyaluminum, diethylethoxy Aluminum, diethylphenoxyaluminum, diethyl- (2,6-di-tbutyl-4-methylphenoxy) -aluminum, ethyldimethoxyaluminum, ethyldiethoxyaluminum, ethyldiphenoxyaluminum, ethyl-di (2,6-ditbutyl) -4
-Methylphenoxy) -aluminum and the like;
In addition, an organoaluminum compound modified with a polyfunctional active proton compound such as water or a diol compound can be used, and specific examples thereof include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, and isobutylaluminoxane. The organoaluminum compounds listed above can be used alone or in combination of two or more.

The component (D) includes magnesium chloride, titanium tetrachloride, tetraisopropoxy titanium, tetrabutoxy zirconium, boron fluoride diethyl ether complex,
Triphenyltin chloride, dibutyltin dichloride, sodium tetraphenylborate and the like. Component (E) includes perfluorocyclohexane,
Perfluoromethylcyclohexane, perfluorodecalin, hexafluorobenzene, octafluoronaphthalene, 1,2-bistrifluoromethylbenzene, 1,
Examples thereof include 3-bistrifluoromethylbenzene and 1,4-bistrifluoromethylbenzene. As the component (F), H ₂ WO ₄ , H ₂ MoO ₄ , H ₃ PW
₁₂ O ₄₀ , H ₄ SiW ₁₂ O ₄₀ , H ₃ GeW ₁₂ O ₄₀ , H ₅ B
_{W 12 O 40, H 3 PMo} 12 O 40, H 4 SiMo 12 O 40,
These salts are exemplified. Component (G) includes methanesulfonic acid, paratoluenesulfonic acid, trifluoromethanesulfonic acid and the like. In addition, their salts, esters, amides and the like can also be used. Further, in addition to the above components, 2-methyl-1,3-butadiene,
An olefin component such as 5-cyclooctadiene, vinyl norbornene, and ethylidene norbornene can also be added.

The contact of each component is performed in an organic solvent such as benzene, toluene, xylene, hexane, heptane, decane, dodecane, cyclohexane, chlorobenzene or the like in a closed container replaced with an inert gas such as nitrogen or argon. Usually done. When the component (G) is added as an optional component, the component (G) is preferably soluble in an organic solvent. When the component (G) is hardly soluble, dichloromethane, chloroform, carbon tetrachloride, acetonitrile , Benzonitrile, dimethylformamide,
Polar solvents such as dimethyl sulfoxide, acetone, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethyl acetate and the like can be replaced with some or all of the organic solvents described above. The contact temperature of each component is selected in the range of -100C to 200C, preferably -50C to 100C, and the contact time is selected in the range of 1 second to 24 hours. When the components are brought into contact with each other, the nickel compound of the component (A) and the organoaluminum compound of the component (C) are brought into contact with each other in the absence of the organic phosphorus compound of the component (B). When the component (A) and the component (C) are in contact with each other, it is preferable that the component (B) is present in the field of the contact in advance. Can be contacted. In addition, each of the individual components may be divided into a plurality of portions, and each of the plurality of portions may be brought into contact with an arbitrary order. When the optional components (D) to (G) are used in combination, the components can be brought into contact with the basic components (A) to (D) of the catalyst in any order. In the case of adding, it is preferable to add the components (A) and (C) after bringing them into contact. When the olefin component is added, the order of addition is not particularly limited. Among them, when the component (A) and the component (C) come into contact with each other, the olefin component and the component ( It is preferred that B) coexists. Regarding the use ratio of each component in obtaining the organonickel complex catalyst of the present invention, component (B) is usually 0.01 to 100 mol, preferably 0.1 to 10 mol, per 1 mol of component (A). Preferably, it is used in the range of 0.5 to 5 mol. Component (C) is used in an amount of usually 0.01 to 10000 mol, preferably 0.1 to 1 mol, per 1 mol of component (A).
It is used in the range of 1 to 1000 mol, more preferably 1 to 100 mol. Optional components (D) to (G) are component (A)
Usually 0.001 to 100 mol, preferably 0.01 to 100 mol per 1 mol, usually 0.01 to 100 mol.
It is used in the range of 00 mol, preferably 0.1 to 1000 mol, more preferably 1 to 100 mol. The optional components (D) to (G) are usually used in an amount of 0.0 to 1 mol of the component (A).
It is used in the range of from 01 to 100 mol, preferably from 0.01 to 10 mol, more preferably from 0.1 to 5 mol. When an olefin component is used, the amount of the olefin component can be arbitrarily selected.
It is used in an amount of 0 mol or less, preferably 0.01 to 100 mol, more preferably 0.1 to 50 mol.

[0012] The catalyst concentration in the dimerization reaction can be arbitrarily selected according to the reaction mode such as solution polymerization, gas phase polymerization, bulk polymerization and the like. The catalyst of the present invention is generally used in the range of 0.0001 mmol to 100 mol in terms of nickel concentration, preferably in the range of 0.001 mmol to 1 mol, more preferably 0.01 mmol to 1 mol. Used in the range of 100 mmol. The reaction temperature is selected in the range of -100C to 200C, preferably in the range of -50C to 100C, and more preferably in the range of 0C to 50C. Reaction pressure is 10 kPa · G-10MP
a · G, preferably from 100 kPa · G to
5 MPa · G, more preferably 200 kPa · G to 3M
It is selected in the range of Pa · G (G means gauge pressure). The reaction time is not particularly limited, but in the case of a batch reaction, it is usually in the range of 1 minute to 1 week, and a continuous reaction in which propylene and a catalyst are continuously added and a product is continuously withdrawn. In this case, the residence time is usually about 1 second to 6 hours. The reaction form of the dimerization reaction may be any of solution polymerization, gas phase polymerization and bulk polymerization,
Particularly, solution polymerization and bulk polymerization are preferred. Any kind of solvent can be used for the solution polymerization as long as it does not inhibit the dimerization of the present invention, but usually, the solvents and the like exemplified above as the solvent used when preparing the catalyst of the present invention are used. You. In this case, it is preferable to use the same solvent as the solvent used for preparing the catalyst in the solution polymerization, but a different solvent can be used in the solution polymerization. It is also possible to react with propylene itself as a solvent. The dimerization reaction is started by introducing a catalyst solution into a pressure-resistant vessel and introducing propylene. After the completion of the reaction, the pressure-resistant container is depressurized and released in the air, and the reaction product is washed with dilute hydrochloric acid, then with a saturated saline solution, and dried with magnesium sulfate. For purification of the product, a distillation method is preferably used.

The C6 olefin component is mainly produced by the dimerization reaction of propylene.
Dimethyl-1-butene and 2,3-dimethyl-2-butene, further 2-methyl-1-pentene and 2-methyl-2-pentene, further 4-methyl-1-pentene and 4-methyl-2-pentene; Further, they are 1-hexene and 2-hexene, and their boiling points are shown in Table 1. Further, in addition to these compounds, a polymer of an isomer having a slight movement of an olefinic position, a trimer or more is obtained. Among these compounds, the solvent component precursor of the present invention can be 2,3-dimethyl-1-butene, 2,3-dimethyl-2-butene, 2-methyl-1-pentene, 2-methyl- 2-pentene, 4-methyl-1-pentene and 4-methyl-2-pentene. 2,3-dimethyl-
2-Butene and 2-methyl-2-pentene have high boiling points, and a dimerization reaction catalyst further acts on 2,3-dimethyl-1-butene and 2-methyl-1-pentene, respectively, to form a certain secondary reaction. This is a component that is distilled off along with 1-hexene and 2-hexene when distillation is performed.

In the present invention, the propylene dimer thus obtained is subjected to hydrogenation and distillation to remove unnecessary solvents, catalyst components and polymers, thereby obtaining 2,3-dimethylbutane and / or 2-dimethylbutane. 90 methyl pentane
A hydrocarbon solvent containing at least mass% is obtained. The order of hydrogenation and distillation at this time is not particularly limited, but is preferably changed depending on the production ratio of 2,3-dimethyl-2-butene and 2-methyl-2-pentene. That is, 2,
When the production ratio of 3-dimethyl-2-butene and 2-methyl-2-pentene is low and can be neglected in terms of quantity, distillation is carried out first with olefin, and 2-methyl-1-pentene and 4-methyl Preferably, only a mixture of -1-pentene, 4-methyl-2-pentene and 2,3-dimethyl-1-butene is obtained and hydrogenated. On the other hand, when the production ratio of 2,3-dimethyl-2-butene and 2-methyl-2-pentene is high, these components and 1-hexene,
It is preferred that the 2,3-dimethylbutane and 2-methylpentane components are separated by distillation after hydrogenation so that hexene can be separated.

Examples of the catalyst for hydrogenation include VI of the periodic table.
The metals belonging to Group A and Group VIII can be used in combination or alone.For example, ruthenium, rhodium, palladium, a single metal such as platinum or the like dispersed or supported on carbon, Raney nickel or , Cobalt-molybdenum, nickel-chromium, palladium-molybdenum, nickel-cobalt-molybdenum, nickel sulfide, tungsten sulfide and the like are used as preferred catalysts. In the case of a continuous system, the reaction conditions for hydrogenation are usually set at 0 ° C. in order to suppress carbon deposition on the catalyst and selectively achieve saturation of unsaturated components.
４５０450 ° C., pressure 0.01MP60 MPa, hydrogen / solvent precursor ratio 40〜100 Nm ³ / kl, space velocity LHSV 1１０10 h
A range of r ^-1 is used. At high temperatures exceeding 450 ° C,
Decomposition of the hydrocarbon itself occurs, and carbon deposition on the catalyst surface is remarkable, which shortens the life of the catalyst, which is not preferable.
The reaction pressure mainly affects the life of the catalyst and the degree of purification of the treated oil. As the pressure is increased, the production of carbon is suppressed, and the life of the catalyst is prolonged. If the pressure is increased more than necessary, the material and structure of the device will be affected.
It is preferable to set the pressure to a or less. In the case of a batch type, a catalyst is introduced into an autoclave, and a raw material unsaturated hydrocarbon is added, if necessary, a solvent, usually at a temperature of 0 to 450 ° C,
Hydrogenation can be performed by applying a hydrogen pressure of 0.01 to 200 MPa.

The distillation operation can be carried out by arbitrarily setting the number of columns and the number of stages. For example, the number of towers is 1 under normal pressure
It is preferable that the number of steps is 1 to 100 or about 2.
The solvent which is the object of the present invention can be obtained by collecting a fraction not exceeding 62 ° C. which is usually the boiling point of 2-methylpentane. Further fractionation can be performed for the purpose of increasing the content of 2,3-dimethylbutane. The composition of the solvent obtained by the method of the present invention is extremely specified by limiting various conditions as described above. That is, the main components thereof are 2,3-dimethylbutane and 2-methylpentane, which are hydrocarbons having 6 carbon atoms, and these are contained in an amount of 90 mass% or more.

The solvent of the present invention may be any one of organic acids such as alcohol, citric acid, tartaric acid and phthalic acid, a preservative, a rust preventive, a defoaming agent, and the like, as long as the effect is not impaired.
You may make it mix | blend an antioxidant, an enzyme for washing | cleaning, etc. Solvents obtained by the present invention include, for example, paints, inks, rubbers, adhesives and adhesives, water repellents and oil repellents, sealants, degreasing detergents for precision parts and metal materials, and degreasing for plastic materials and the like. It can be used for various applications such as cleaning agents and cleaning solvents. When used as a degreasing cleaning agent, the above solvent alone shows sufficient detergency, but depending on the type and degree of the object to be cleaned and the stain, for example, perfluoroalkane, perfluorocycloalkane, perfluoroether, perfluorocycloether It can also be mixed with perfluoro organic compounds such as to reduce flammability,
Surfactants and the like can be mixed. Further, in the case of washing with a hydrocarbon solvent obtained by using the present invention, a conventionally known method can be adopted. For example,
First, ultrasonic cleaning is performed in an ultrasonic cleaning tank containing the above-mentioned hydrocarbon solvent, then immersion cleaning is performed in a liquid bath filled with the same solvent, and finally, steps such as shower cleaning and steam cleaning using the same solvent are continuously performed. Can be used effectively.
When used as a sealant, conventionally known sealing compounds can be used, for example,
Styrene-butadiene copolymer rubber is used. Or, if necessary, natural rubber, other acrylonitrile-butadiene rubber, polyisobutylene rubber, isoprene-isobutylene rubber, chloroprene rubber, silicone rubber, polyvinyl ether, synthetic rubber such as chlorinated rubber, further rosins, terpenes , Phenolic resin,
Pressure-sensitive adhesives such as petroleum resins, thickeners such as karaya gum, methylcellulose, and polyvinyl alcohol; fillers such as silica, calcium carbonate, kaolin, clay, and talc;
A mixture obtained by adding and mixing additives such as a preservative, an antioxidant, a surfactant, and a pH adjuster can be used as a sealing compound.

As described above, the hydrocarbon solvent obtained according to the present invention can be used for various applications as described above, and has no toxicity to the human body because it contains substantially no aromatic hydrocarbon. It is excellent in volatility and does not destroy the environment.

[0019]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

<Example> Dimerization of propylene Under a nitrogen atmosphere, 3 ml of dry toluene was introduced into a 50 ml dry eggplant type flask. While stirring, a toluene solution of nickel 2-ethylhexanoate (0.032 ml, 0.03 ml
2 mmol), vinyl norbornene (0.16 mmol) and tricyclohexylphosphine (0.032 mmol) were added, and the mixture was cooled to -78 ° C. Further, a toluene solution of ethyl aluminum sesquichloride (0.64 ml, Al 0.64 mmol) was added, a toluene solution of zirconium tetrabutoxide (1 ml, 0.032 mmol) was added, and the mixture was stirred for 10 minutes to obtain a catalyst solution. 5 well dried
Propylene (2Kg, 47.6mol) at 0 ° C in L autoclave
Was introduced with stirring, the catalyst solution was added, and
The reaction was carried out at ℃. After completion of the reaction, unreacted propylene was expelled, a small amount of water was added to deactivate the catalyst, and the mixture was washed with saturated saline and dried over magnesium sulfate. Analysis was performed by gas chromatography, and the following results were obtained. Catalytic efficiency 1245 Converted propylene kmol / nickel mol Dimer selectivity 96% Dimethylbutene selectivity 50% Methylpentene selectivity 48% Hexene selectivity 2%

Hydrogenation of propylene dimer Palladium carbon (palladium content 1 mass%, 1 g) was introduced into a 2 L autoclave, and the mixture (500 ml) obtained by the above dimerization reaction was added. Hydrogen pressure 500k
The mixture was added until the pressure became Pa, followed by stirring at 50 ° C. for 24 hours. After completion of the reaction, hydrogen was expelled and the catalyst was filtered off to obtain a hydride. 100 ml of distilled hydride of propylene dimer hydride was taken and rectified by a rotary band rectifier. The pressure was normal pressure, and the reflux ratio was 30. From the start of distillation, a portion that is stable at 58 ° C., which is the boiling point of 2,3-dimethylbutane, is fractionated, and is taken as a fraction a, which starts to rise from 58 ° C. and reaches 62 ° C., which is the boiling point of 2-methylpentane. The fraction was collected and designated as component b. The portion stable at 62 ° C. was taken as fraction c. The bottom was the d component.
These components were analyzed by gas chromatography, and the results are shown in Table 2. Table 2 Composition of hydrocarbon solvents a b cd d Lights 0.0 0.0 0.0 0.0 2,3-dimethylbutane 97.3 48.2 1.5 0.0 2-methylpentane 2.7 51.8 98.5 10.5 normal hexane 0.0 0.0 0.1 50.5 toluene 0.0 0.0 0.0 25.0 methylcyclohexane 0.0 0.0 0.0 0.0 4.0 Heavy 0.0 0.0 0.0 10.0

Each of the produced hydrocarbon solvents was evaluated as follows. (1) Detergency test piece (cold rolled steel sheet JIS G-3141, 120 ×
After immersing a part (70 cm ² ) in a processing oil shown in Table 3, using a hydrocarbon solvent, normal hexane and 1,1,1-trichloroethane obtained by the above method. Ultrasonic cleaning was performed. The determination of the degree of cleaning was performed visually. Table 3 shows the results.

[0023]Table 3 Detergency test Water-soluble processing oil Water-insoluble processing oil Wax Trichloroethane Some cloudiness remains Some cloudiness remains Fully washed Normal hexane Partially washed Some clouding remains Fully washed Fraction a Partially washed Some clouding remains Fraction b that has been completely washed Fraction b has been partially washed Some clouding has been completely washed Fraction c Has been partially washed Clouding has been partially washed completely Have been

(2) Drying property 25 μl of the hydrocarbon solvent obtained by the above method was dropped on the glass surface and the metal surface, and the drying time was measured. As an evaluation method, the drying time of 1,1,1-trichloroethane was used as a reference, and expressed as a magnification relative to the drying time. Table 4 shows the results.

(3) Swellability test A test piece (50 × 20 × 2 mm) made of the material shown in Table 5
The hydrocarbon solvent obtained by the above method, norma
Hexane (abbreviated as HEX in the table) and 1,1,1-
Normal temperature to trichloroethane (abbreviated as 1,1,1-TCE in the table)
After immersion for 22 hours in each, the weight change rate and body
The product change rate was measured. Table 5 shows the results.Table 5 Swellability test Weight change rate Volume change rate1,1,1-TCE HEX cut abc 1,1,1-TCE HEX cut abc EPDM 55 55 55 33 33 33 Natural rubber 55 55 55 43 33 33 Fluorine rubber 21 11 11 11 11 11 NBR 5 11 11 11 11 11 Polyethylene 11 1 1 1 1 1 1 1 1 1 Polypropylene 2 2 2 2 2 1 1 1 1 1 1 ABS dissolution 1 1 1 1 Dissolution 1 1 1 1 EPDM: Ethylene-propylene-diene copolymer rubber NBR: Acrylonitrile-butadiene rubber ABS: Acrylonitrile-butadiene-styrene copolymer Evaluation criteria 1: Change rate 5% or less 2: Change rate 6 to 10% 3: Change rate 11 to 11 25% 4: Change rate 26 to 50% 5: Change rate 50% or more

[0026]

In summary, according to the present invention, the dimerization of propylene is carried out, and then the propylene obtained by the reaction is obtained.
By hydrogenating and distilling the quantified product and containing 90 mass% or more of 2,3-dimethylbutane and / or 2-methylpentane, it can be easily used in various applications as an alternative solvent to normal hexane, In addition, it is possible to produce a hydrocarbon solvent which is particularly excellent in volatility and excellent in that it does not adversely affect the human body.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 7/50 C11D 7/50 // C07B 61/00 300 C07B 61/00 300

Claims (1)

[Claims] 1. A dimerization reaction of propylene is carried out, and then a dimer obtained by the reaction is hydrogenated and distilled to contain 90 mass% or more of 2,3-dimethylbutane and / or 2-methylpentane. A method for producing a hydrocarbon solvent.