KR20190074948A - Paraffin mixture and preparation method thereof - Google Patents

Abstract

The present invention relates to a paraffin mixture and a method for manufacturing the same. The paraffin mixture of the present invention is excellent in fluidity even at a low temperature and has a high flash point to be stable at a high temperature. Thus, the mixture can be used as a solvent for paint, insecticide, printer toner and the like, or a solvent for synthesizing polymers such as LDPE, and can be used for various purposes such as metal processing oil, a cleaning agent, a cosmetic product, and an edible product. Further, according to the method for manufacturing the paraffin mixture of the present invention, a paraffin mixture in which the content of impurities such as sulfur and/or an aromatic compound is remarkably low can be manufactured.

Description

[0001] PARAFFIN MIXTURE AND PREPARATION METHOD THEREOF [0002]

The present invention relates to paraffin mixtures and processes for their preparation.

Paraffin solvents provide a variety of industrial applications. Commercially available paraffin solvents include NORPAR solvents (Exxon Chemical Company) consisting essentially of C ₁₀ -C ₁₅ linear or normal paraffins (n-paraffin), highly branched paraffins having very low n-paraffin content, And an ISOPAR solvent (Exxon Chemical Company) composed of a mixture of paraffins.

The normal paraffin solvent is produced by molecular sieve using kerosene as a raw material. Because of its high selective dissolving power, low reactivity and relatively low viscosity, it is used as a diluting solvent for aluminum rotary rolling oil and carbonless copy paper. Is used. The normal paraffin solvent has a relatively low viscosity, but it has a drawback that the low-temperature characteristics are deteriorated because it has a high pour point.

On the other hand, branched paraffin or isoparaffin solvents (hereinafter referred to as isoparaffin solvents) are derived from alkaline base water (typically produced by alkylation). Isoparaffinic solvents are used in food-related applications and have high purity, low odor, excellent oxidation stability, low pour point, and excellent low temperature characteristics. However, isoparaffinic solvent has high viscosity, unlike normal paraffinic solvent.

Accordingly, development of a solvent having desirable properties of a normal paraffin solvent and an isoparaffin solvent, that is, a low viscosity of a normal paraffin solvent and a low temperature characteristic of an isoparaffin solvent is desired. In addition, the paraffin solvent has been produced through the refining process of petroleum. In this case, impurities in petroleum such as sulfur and aromatic compounds are mixed and the purity of the solvent is lowered.

The present invention aims to provide a paraffin mixture which exhibits a low pour point, a high flash point and a high stability.

Another object of the present invention is to provide a process for producing a paraffin mixture which can produce the paraffin mixture in high purity.

According to an aspect of the present invention,

60 to 85 parts by weight of normal paraffin;

10 to 30 parts by weight of isoparaffin; And

1 to 5 parts by weight of naphthene.

The paraffin mixture may have 14, 16, 18 and 20 carbon atoms.

The paraffin mixture may have a sulfur content of 0.05 part by weight or less based on 100 parts by weight of the paraffin mixture.

The paraffin mixture may have an aromatic compound content of 0.05 part by weight or less based on 100 parts by weight of the paraffin mixture.

The paraffin mixture may have a pour point of less than -40 占 폚.

The paraffin mixture may have a flash point of 130 ° C or higher.

The present invention also relates to a process for the preparation of olefin oligomerization catalysts comprising the steps of: a) oligomerizing olefins in the presence of an olefin oligomerization catalyst system;

b) distilling the reaction mixture in step a) to separate hydrocarbons having less than 10 carbon atoms and hydrocarbons having 10 or more carbon atoms; And

c) hydrogenating the hydrocarbons having 10 or more carbon atoms in the presence of a hydrogenation catalyst; Lt; / RTI >

Wherein the olefin oligomerization catalyst system comprises a transition metal compound, a ligand compound and a cocatalyst, or

Wherein the ligand compound comprises an organic transition metal compound coordinated to a transition metal,

Wherein the ligand compound is represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, A is represented by the following Formula 2,

(2)

X is an alkylene of 1 to 20 carbon atoms or an arylene of 6 to 14 carbon atoms,

Each of R 1 to R 4 is independently selected from the group consisting of C 1-20 alkyl, C 2-20 alkenyl, C 6-14 aryl, C 6-14 aryl substituted with C 1-4 alkyl, and C 6-14 aryl Lt; / RTI > is aryl having from 1 to 4 alkyl or from 6 to 14 carbons substituted with from 1 to 4 alkoxy,

R5 to R14 are each independently selected from the group consisting of hydrogen, C1-20 alkyl, C2-20 alkenyl, C6-14 aryl, C6-14 aryl substituted with C1-4 alkyl, and C6-14 aryl Alkyl having 1 to 4 carbon atoms or aryl having 6 to 14 carbon atoms substituted with 1 to 4 alkoxy.

The compound of formula (1) may be any one selected from the group consisting of the following compounds.

Wherein the transition metal compound comprises a chromium compound and the chromium compound is selected from the group consisting of chromium (III) acetylacetonate, chromium tristrifluoromethane trichloride, chromium (III) -2-ethylhexanoate, (III) benzoyl acetonate, chromium (III) hexafluoro-2,4-pentene indionate and chromium (III) acetate hydrate And < RTI ID = 0.0 > a < / RTI >

In the above production process, the cocatalyst may be at least one selected from the group consisting of compounds represented by the following formulas (3) to (5).

(3)

_{- [Al (R 20) -O} ] c -

In the general formula (3), R 20 are the same or different from each other and each independently represent a halogen, an alkyl of 1 to 20 carbon atoms, or a haloalkyl of 1 to 20 carbon atoms, c is an integer of 2 or more,

[Chemical Formula 4]

D (R _{21) 3}

In Formula 4,

D is aluminum or boron, R21 is the same or different from each other and is independently hydrogen or halogen, alkyl having 1 to 20 carbon atoms or haloalkyl having 1 to 20 carbon atoms,

[Chemical Formula 5]

[LH] ⁺ [Q (E) ₄ ] ^-

In Formula 5,

L is a neutral Lewis base, [LH] ⁺ is a Bronsted acid, Q is boron or aluminum in the +3-oxidation state, E is independently in each occurrence 6 to 20 carbon atoms or 1 to 20 carbon atoms, The aryl group having 6 to 20 carbon atoms or the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one substituent selected from the group consisting of halogen, C 1-20 alkyl, C 1-20 alkoxy and phenoxy.

In the above production method, the hydrogenation catalyst may be at least one selected from the group consisting of nickel (Ni), copper (Cu), ruthenium (Ru), palladium (Pd), rhodium (Rh) and platinum (Pt).

In the above production process, the olefin may be one comprising ethylene.

The paraffin mixture of the present invention is excellent in fluidity even at a low temperature and has a high flash point and is stable at a high temperature. Thus, it can be used as a solvent for a solvent such as paint, insecticide, printer toner, or a polymer such as LDPE, and can be used for various purposes such as a metal processing oil, a cleaning agent, a cosmetic product, and an edible product. Further, according to the paraffin mixture preparation method of the present invention, a high-purity paraffin mixture having a small amount of impurities such as sulfur and / or an aromatic compound can be obtained.

The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprises", "comprising", or "having" are used to designate the presence of stated features, steps, components, or combinations thereof, and are not intended to preclude the presence of one or more other features, Components, or combinations thereof, as a matter of convenience, without departing from the spirit and scope of the invention.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Hereinafter, the present invention will be described in detail.

Paraffin mixture

The present invention relates to a paraffin mixture capable of realizing both the advantages of a normal paraffin solvent and an isoparaffin solvent, and it relates to a paraffin mixture which contains paraffin having a low pour point, a high flash point and a high stability ≪ / RTI >

Due to such characteristics, the paraffin mixture of the present invention can be used in various applications such as industrial detergents, paints, insecticides, solvent for printer toners, polymerization solvents, metal processing oils, cleaning agents, cosmetics and foods.

More specifically,

60 to 85 parts by weight of normal paraffin;

10 to 30 parts by weight of isoparaffin; And

1 to 5 parts by weight of naphthene.

The n-paraffin refers to a hydrocarbon compound having a linear structure of carbons in a molecule, and iso-paraffin refers to a hydrocarbon compound having at least one branched structure in a molecule. Also, naphthene means a hydrocarbon compound containing a ring structure of a single bond.

Specifically, the isoparaffin is not particularly limited as long as it is a hydrocarbon compound containing an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, propyl, etc. in the main chain. For example, the isoparaffin may include at least one methyl group. The naphthene may be cyclohexane, cyclopentane or the like containing an alkyl group having 1 to 20 carbon atoms.

In the present invention, normal paraffin is used as a main component, and isoparaffin and naphthene are contained at a certain ratio to improve the low temperature characteristics and solubility of the paraffin mixture. If the content of isoparaffin is out of the above range, sufficient low-temperature characteristics can not be obtained. If the content of naphthene is out of the above range, the solubility is lowered and it may not be suitable for application to a solvent for polymerization. The content of paraffin and naphthene preferably satisfies the above range.

Further, in order to secure the above-mentioned effect, the paraffin mixture of the present invention may contain 70 to 80 parts by weight of normal paraffin, 15 to 25 parts by weight of isoparaffin, and 1 to 5 parts by weight of naphthene. Alternatively, the paraffin mixture may comprise 75 to 80 parts by weight of normal paraffin, 17 to 22 parts by weight of isoparaffin, and 2 to 3 parts by weight of naphthene.

In the present invention, the normal paraffin, isoparaffin, and naphthene have carbon atoms of 14 to 20, respectively, and satisfy the carbon number range and the content range described above, thereby exhibiting the low pour point and the high flash point effect of the present invention. In order to further improve the effect of the present invention, the normal paraffin, isoparaffin and naphthene may have carbon atoms of 14, 16, 18, or 20, respectively.

On the other hand, the paraffin mixture of the present invention has a lower impurity amount than the conventional paraffin solvent and exhibits high purity. Specifically, the paraffin mixture of the present invention may have a sulfur content of 0.05 parts by weight, 0.03 parts by weight, or 0.01 parts by weight or less based on 100 parts by weight of the paraffin mixture. Also, the paraffin mixture of the present invention may contain 0.05 part by weight, 0.03 part by weight, or 0.01 part by weight, based on 100 parts by weight of the paraffin mixture, of an aromatic compound such as benzene, toluene, xylene, have.

As such exhibits a low sulfur content and an aromatic compound content, the paraffin mixture of the present invention can be used as a solvent for polymer polymerization.

Such a low impurity content can be achieved by a process for producing a paraffin mixture of the present invention to be described later. That is, since the production method of the present invention does not use petroleum as a raw material unlike the conventional production method of a paraffin solvent, the content of sulfur and / or an aromatic compound derived from petroleum can be greatly reduced and thus a high quality paraffin mixture can be provided have.

The paraffin mixture of the present invention satisfies the above-mentioned composition, thereby having both low viscosity properties of normal paraffin and low temperature characteristics of isoparaffin. Specifically, the paraffin mixture exhibits excellent low temperature characteristics at a pour point of -40 캜 or lower.

Further, the paraffin mixture has a flash point of 130 ° C or higher, or 135 ° C or higher, and exhibits sufficient stability even at a high temperature. Therefore, when it is used for cleaning, metal working, and the like, safety of the operator can be secured, which is preferable.

The paraffin mixture of the present invention described above can be applied to all applications in which conventional paraffin solvents are used. Specifically, the paraffin mixture of the present invention has excellent wetting ability, excellent degreasing ability, low residue, and low odor due to low surface tension, and can be used as an industrial detergent such as wood, plastic, metal And the like.

The paraffin mixture has a low surface tension and spreads well on a metal surface, and can be used as a metal processing oil for reducing friction, lubrication, heat removal, removal of metal chips and dirt, And can also be used for protection of metal from moisture (rust prevention). Particularly, the paraffin mixture of the present invention is preferable because it has a small odor and very few impurities harmful to human body such as an aromatic compound, contributing to the safety of the operator.

The paraffin mixture has significantly less impurities such as sulfur and aromatic compounds than commercially available paraffin solvents. Therefore, it can be used as a catalyst for polymerization reaction of an olefin or the like, and can also be used as a solvent for an initiator solvent or a catalyst. The paraffin mixture of the present invention is suitable for use in a polymerization reaction or the like because it contains a certain amount of naphthene and is excellent in solubility in a resin and inert to most polymers.

The method for producing the paraffin mixture of the present invention described above is not particularly limited, and the production method of the paraffin mixture known in the art can be used without limitation. However, in order to obtain a high-quality paraffin mixture by minimizing the content of impurities such as sulfur and / or an aromatic compound, it is preferable to produce it according to the production method of the present invention described below.

Preparation method of paraffin mixture

According to the present invention,

a) oligomerizing the olefin in the presence of an oligomerization catalyst system;

b) distilling the reaction mixture in step a) to separate hydrocarbons having less than 10 carbon atoms and hydrocarbons having 10 or more carbon atoms; And

c) hydrogenating the hydrocarbons having 10 or more carbon atoms in the presence of a hydrogenation catalyst.

According to the above production method, since petroleum is not used as a raw material for the paraffin mixture, the content of impurities such as sulfur and / or aromatic compounds in the finally prepared paraffin mixture can be remarkably reduced. Specifically, according to the above production method, the paraffin mixture finally produced has a sulfur content of 0.05 wt% or less, and an aromatic compound content of 0.05 wt% or less. Hereinafter, the production method of the paraffin mixture of the present invention will be described step by step.

The step a) is an oligomerization step of the olefin. The term " olefin oligomerization " used in the present invention means olefin polymerization. When the three olefins are polymerized, they are called trimerization. When the four olefins are polymerized, they are called tetramerization. When the olefins are so polymerized, the process of producing a low molecular weight material is generally referred to as multimerization ).

At this time, the kind of the olefin which can be used is not particularly limited, but ethylene can be used according to a preferred embodiment of the present invention. Oligomerization of ethylene can produce industrially useful alpha olefins having less than 10 carbon atoms, such as 1-butene, 1-hexene, 1-octene, etc. As a by-product thereof, an alkane, cycloalkane, linear olefin, branched olefin having 10 or more carbon atoms , And cyclic olefins are also produced. The olefin may have a double bond in the molecule or at the end, and the number of double bonds in the molecule may be one or more.

In the present invention, the above-mentioned paraffin mixture of the present invention is prepared from hydrocarbons having 10 or more carbon atoms, which are produced as byproducts in the production of alpha-olefins having less than 10 carbon atoms.

The step a) is carried out in the presence of an oligomerization catalyst system of olefins.

The olefin oligomerization catalyst system may include a transition metal compound, a ligand compound and a cocatalyst, or may include an organic transition metal compound in which a ligand compound is coordinated to a transition metal.

In the present invention, the olefin oligomerization catalyst system may be used without limitation as is known in the art. Preferably, the ligand compound of the olefin oligomerization catalyst system includes a diphosphine moiety, Lt; / RTI >

[Chemical Formula 1]

In Formula 1, A is represented by the following Formula 2,

(2)

X is an alkylene of 1 to 20 carbon atoms or an arylene of 6 to 14 carbon atoms,

Each of R 1 to R 4 is independently selected from the group consisting of C 1-20 alkyl, C 2-20 alkenyl, C 6-14 aryl, C 6-14 aryl substituted with C 1-4 alkyl, and C 6-14 aryl Lt; / RTI > is aryl having from 1 to 4 alkyl or from 6 to 14 carbons substituted with from 1 to 4 alkoxy,

R5 to R14 are each independently selected from the group consisting of hydrogen, C1-20 alkyl, C2-20 alkenyl, C6-14 aryl, C6-14 aryl substituted with C1-4 alkyl, and C6-14 aryl Alkyl having 1 to 4 carbon atoms or aryl having 6 to 14 carbon atoms substituted with 1 to 4 alkoxy.

The alkyl may be linear or branched and specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert- butyl, sec- Butyl, pentyl, isopentyl, neopentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, Butyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, , n-nonyl, 2,2-dimethylheptyl, 1-ethylpropyl, 1,1-dimethylpropyl, isohexyl, 2-methylpentyl, 4-methylhexyl and 5-methylhexyl. It does not.

The alkenyl may be linear or branched and specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-butenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl- (Diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group But are not limited to these.

The aryl may be a monocyclic or polycyclic aryl, and the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, or the like, but is not limited thereto. Examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a klycenyl group and a fluorenyl group.

The ligand compound containing the diphosphine moiety represented by the above formula (1) has an effect of increasing the activity and selectivity of the catalyst and is suitable for use in the present invention.

Preferably, X is methylene or phenylene.

Preferably, R ₁ to R ₄ are the same as each other. More preferably, R ₁ to R ₄ are phenyl.

Preferably, R ₅ and R ₆ are hydrogen.

Also preferably, R ₇ and R ₈ are the same as each other and are hydrogen or methyl.

Also preferably, R ₉ is hydrogen or iso-propyl. Also, preferably, R ₁₀ is hydrogen.

Preferably, R ₁₁ to R ₁₃ are hydrogen.

Also preferably, R < ₁₄ > is hydrogen or methyl.

Also preferably, X is methylene or phenylene, R ₁ to R ₄ are phenyl, R ₅ and R ₆ are hydrogen, R ₇ and R ₈ are the same as each other and are hydrogen or methyl, R ₉ is hydrogen or Isopropyl, R ₁₀ to R ₁₃ are hydrogen, and R ₁₄ is hydrogen or methyl.

Representative examples of the compound represented by the formula (1) are as follows:

The compound represented by the general formula (1) includes all possible optical isomers.

(III) acetylacetonate, chromium tristrifluoride tetrahydrofuran, chromium (III) -2, and the like. The transition metal source is preferably a transition metal, (III) tris (2,2,6,6-tetramethyl-3,5-heptohydronate), chromium (III) benzoyl acetonate, chromium (III) hexafluoro-2, 4-pentene indonate, and chromium (III) acetate hydroxide.

The cocatalyst is an organometallic compound containing a Group 13 metal and is not particularly limited as long as it can be used for mass-producing olefins under the catalyst of a transition metal compound. Specifically, the promoter may be at least one selected from the group consisting of compounds represented by the following formulas (3) to (5).

(3)

_{- [Al (R 20) -O} ] c -

In the general formula (3), R 20 are the same or different from each other and each independently represent a halogen, an alkyl of 1 to 20 carbon atoms, or a haloalkyl of 1 to 20 carbon atoms, c is an integer of 2 or more,

[Chemical Formula 4]

D (R _{21) 3}

In Formula 4,

D is aluminum or boron, R21 is the same or different from each other and is independently hydrogen or halogen, alkyl having 1 to 20 carbon atoms or haloalkyl having 1 to 20 carbon atoms,

[Chemical Formula 5]

[LH] ⁺ [Q (E) ₄ ] ^-

In Formula 5,

L is a neutral Lewis base, [LH] ⁺ is a Bronsted acid, Q is boron or aluminum in the +3-oxidation state, E is independently in each occurrence 6 to 20 carbon atoms or 1 to 20 carbon atoms, The aryl group having 6 to 20 carbon atoms or the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one substituent selected from the group consisting of halogen, C 1-20 alkyl, C 1-20 alkoxy and phenoxy.

Examples of the compound represented by Formula 3 include methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane.

Examples of the compound represented by the formula (4) include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, dimethyl isobutyl aluminum, dimethylethyl aluminum, diethyl chloro aluminum, Isopropylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, Aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron or tributyl boron.

Examples of the compound represented by Formula 5 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl Boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (p-trifluoromethylphenyl) boron, trimethylammoniumtetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N, N -Diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium (P-tolyl) aluminum, trimethylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, (P-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammoniumtetra (ptrifluoromethylphenyl) aluminum, trimethylammoniumtetra (ptrifluoromethylphenyl) Aluminum, tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetrapenta Fluorophenyl aluminum, diethylammonium tetrapentafluorophenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenylal (P-trifluoromethylphenyl) boron, or triphenylcarbonium tetrapentafluorophenylboron, which may be used alone or in combination of two or more of them. have.

The catalyst system for olefin oligomerization may have a molar ratio of the ligand compound: transition metal source: promoter of about 1: 1: 1 to about 10: 1: 10,000, preferably about 1: 1 : 100 to about 5: 1: 3,000.

In the catalyst system for olefin oligomerization comprising the ligand compounds, transition metal sources and cocatalysts described above, the three components may be added simultaneously or in any order, in any suitable solvent, together with or without the presence of monomers, Lt; / RTI > Suitable solvents include, but are not limited to, heptane, toluene, 1-hexene, diethyl ether, tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol, acetone and the like.

The olefin oligomerization according to the present invention can be carried out in the presence of an inert solvent in the presence or absence of an inert solvent using a conventional apparatus and contact technique with the catalyst system for olefin oligomerization, a slurry reaction in which the catalyst system is partially or completely dissolved , Two-phase liquid / liquid reactions, or bulk-phase or gas-phase reactions in which the product olefins act as the main medium, and a homogeneous liquid phase reaction is preferred.

The olefin oligomerization reaction can be carried out in any inert solvent that does not react with the catalyst compound and the activator. Suitable inert solvents include, but are not limited to, benzene, toluene, xylene, cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, hexane, pentane, butane and isobutane. At this time, the solvent can be used by removing a small amount of water or air acting as catalyst poison by treating with a small amount of alkylaluminum.

The olefin oligomerization reaction may be carried out at a temperature of from about 5 ° C to about 200 ° C, preferably from about 30 ° C to about 150 ° C. In addition, the olefin oligomerization reaction can be carried out at a pressure of from about 1 bar to about 300 bar, preferably from about 2 bar to about 150 bar.

The range of the temperature and the pressure may be a condition of the proprietary reaction in which the olefin is mass-reacted. When the olefin is made large in the temperature range and the pressure range, the amount of the by-product may be reduced, And reduce costs.

Step b) is a step of separating hydrocarbons having less than 10 carbon atoms and hydrocarbons having 10 or more carbon atoms from the reaction mixture in which step a) has been completed. In the present invention, step b) is by distillation of the reaction mixture.

In the present invention, the distillation column used in step b) may be selected from a distillation column commonly used in a distillation process in a general industrial field, including a main tower, a condenser and / or a reboiler.

The theoretical number, the inner diameter, the reflux ratio of the upper and lower discharge, etc. of the main tower are not particularly limited and can be appropriately adjusted according to the component to be separated.

The condenser is a device for taking the heat of vaporization of the mixture in the gaseous state and condensing it, and the condenser used in the conventional chemical engineering device is not limited.

The re-boiling is an apparatus for providing vaporization heat to a liquid mixture to vaporize it, and it is possible to use the reboiler used in conventional chemical engineering equipment without limitation.

The reaction mixture in which the step a) has been completed can be introduced into the distillation column and the separation process can be carried out at a pressure of 1 to 100 bar and a temperature range of 100 to 400 ° C, preferably 270 to 330 ° C.

The hydrogenation reaction in the step c) is a step of hydrogenating the hydrocarbon having 10 or more carbon atoms separated in the step b) to prepare the paraffin mixture of the present invention.

The hydrogenation process can be carried out by a conventional method known in the art. For example, the hydrogenation process may be performed in a reactor such as an autoclave, and may be performed by injecting hydrogen gas in the presence of a hydrogenation catalyst. Alternatively, a method may be used in which hydrocarbons having 10 or more carbon atoms pass through a fixed bed catalyst under a hydrogen atmosphere.

The type of the catalyst used in the hydrogenation reaction is not particularly limited, and a catalyst generally used in the hydrogenation reaction is applicable. For example, the hydrogenation catalyst includes at least one selected from the group consisting of nickel (Ni), copper (Cu), ruthenium (Ru), palladium (Pd), rhodium (Rh) can do.

Such a hydrogenation catalyst can be used by being supported on a support. As the support, a carrier known in the art can be used without limitation. Specifically, a carrier such as zirconia (ZrO ₂ ), titania (TiO ₂ ), alumina (Al ₂ O ₃ ), silica (SiO ₂ ) or diatomaceous earth may be used. Specifically, the above-mentioned hydrogenation process may use a nickel-supported catalyst, but is not limited thereto.

The hydrogenation reaction conditions in the present invention are not particularly limited. For example, the reaction pressure may be 30 to 100 bar or 50 to 70 bar, and the reaction temperature may be 50 to 300 ° C, or 150 to 270 ° C, or 200 to 250 ° C Lt; / RTI > The hydrogenation reaction time can be appropriately controlled so that the hydrogenation of the hydrocarbon can be sufficiently advanced, for example, it may range from 1 to 10 hours.

The paraffin mixture prepared by the above-mentioned method has a remarkably low content of impurities such as sulfur and / or an aromatic compound and exhibits high purity in comparison with a conventional paraffin mixture prepared from petroleum, Detergents, metalworking oils, polymerization solvents, and the like. In addition, the paraffin mixture contains normal paraffins, isoparaffins and naphthenes having 14 to 20 carbon atoms in a specific composition. Therefore, the paraffin mixture is excellent in fluidity even at low temperatures and stable at high temperatures due to its high flash point. Thus, it can be used as a solvent for a solvent such as paint, insecticide, printer toner, or a polymer such as LDPE, and can be used for various purposes such as a metal processing oil, a cleaning agent, a cosmetic product, and an edible product.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.

[Example]

≪ Synthesis of ligand compound &

All reactions proceeded under argon using the Schlenk technique or glove box. The synthesized ligands were analyzed by ¹ H (500 MHz) and ³¹ P (202 MHz) NMR spectra using a Varian 500 MHz spectrometer. Chemical shifts were expressed in ppm downfield from TMS with residual solvent peak as reference. Phosphorous probe was calibrated with aqueous H ₃ PO ₄ .

Synthesis Example 1

5-amino-1,3,3-trimethylcyclohexanemethylamine (5 mmol) and triethylamine (3-10 equivalents) were dissolved in dichloromethane (80 mL) under an argon atmosphere. While the flask was immersed in a water bath, chlorodiphenylphosphine (20 mmol) was slowly added thereto and stirred overnight. The solvent was removed in vacuo, THF was added and stirred well, and the triethylammonium chloride salt was removed with an air-free glass filter. The solvent of the filtrate was removed to obtain the target compound.

Example 1

Under the argon gas, Cr (acac) ₃ (17.5 mg, 0.05 mmol) and the ligand of Synthesis Example 1 (1.1 eq. To Cr) were placed in a flask, and 100 mL of methylcyclohexane was added and stirred to prepare a 0.5 mM solution.

A Parr reactor with a capacity of 600 mL was prepared and vacuumed at 120 ° C for 2 hours, then the temperature was lowered to 60 ° C and the inside was replaced with argon. Then, 1.6 mL (Al / Cr = 1200) of 140 g of methylcyclohexane and MMAO (8.6 wt% iso-heptane solution) was injected and 5 mL (2.5 mol) of the 0.5 mM solution was injected into the reactor. A valve of the ethylene line set at 60 bar was opened, the inside of the reactor was filled with ethylene, and the mixture was stirred at 500 rpm for 15 minutes. The ethylene line valve was closed, Deactivator was added and stirred.

Fractions containing C14, C16, C18 and C20 were separated by distillation at a temperature of 270 to 330 ° C and hydrogenation was carried out to obtain a paraffin mixture having the composition shown in Table 1.

Example 2

A paraffin mixture having the composition shown in Table 1 was obtained in the same manner as in Example 1, except that the distillation temperature was 260 to 290 캜.

Example 3

A paraffin mixture having the composition shown in Table 1 was obtained in the same manner as in Example 1, except that the distillation temperature was 270 to 300 캜.

Comparative Examples 1 and 2

Isopar V from Exxon, a commercially available isoparaffin solvent, was used as Comparative Example 1, and Linpar 1416V from Sasol Company as a normal paraffin solvent was used as Comparative Example 2.

Experimental Example 1

The flash point, pour point and aromatic compound content of each paraffin mixture in the above Examples and Comparative Examples were measured, and the results are shown in Table 1 below. The measurement method of each property is as follows.

(1) Flash point measurement: The flash point was measured according to ASTM D-93.

(2) Measurement of pour point: The pour point was measured according to ASTM D97.

(3) Measurement of aromatic compound content: The spectrum in the wavelength range of 200 to 300 nm was measured with an ultraviolet spectrophotometer, and the content of aromatic compound was calculated using 260 to 280 nm peak.

characteristic Example 1 Example 2 Example 3 Comparative Example 1
(Isopar V) Comparative Example 2
(Linpar 1416V) Carbon number 14, 16, 18, 20 14, 16 14, 16, 18 14-19 14-16 Paraffin type
(Parts by weight) Normal paraffin 79.8 75.2 76.5 - 97.5 Isoparaffin 17.5 22.0 21.2 Major - Naften 2.7 2.8 2.3 - - Flash point ( ^o C) 135 132 135 130 118 Pour Point ( ^o C) <-40 <-40 <-40 <-50 37 Aromatic compound content (parts by weight) ND ND ND 0.1 0.5

* ND: Not Detected

Referring to Table 1, the paraffin mixtures of Examples 1 to 3 had the composition of the present invention and had a high flash point of 132 ° C or higher and a pour point of -40 ° C or lower, and thus, the conventional paraffin solvent and normal paraffin solvent It can be confirmed that it exhibits excellent physical properties.

Further, Examples 1 to 3 were produced according to the production method of the present invention, and an aromatic compound was not detected unlike a commercial paraffin solvent.

From the above experimental results, the paraffin mixture of the present invention exhibits excellent high-temperature stability and low-temperature characteristics including normal paraffins, isoparaffins and naphthenes having a carbon number of 14 to 20 in a specific content ratio, It can be confirmed that such a paraffin mixture can be produced by the production method of the present invention.

Claims (12)

60 to 85 parts by weight of normal paraffin;
10 to 30 parts by weight of isoparaffin; And
1 to 5 parts by weight of naphthene. The method according to claim 1,
14, 16, 18 and 20 carbon atoms. The method according to claim 1,
Based on 100 parts by weight of the paraffin mixture,
Wherein the sulfur content is 0.05 parts by weight or less. The method according to claim 1,
Based on 100 parts by weight of the paraffin mixture,
Wherein the aromatics content is 0.05 parts by weight or less. The method according to claim 1,
A paraffinic mixture having a pour point of -40 캜 or lower. The method according to claim 1,
A paraffin mixture having a flash point of 130 ° C or higher. a) oligomerizing the olefin in the presence of an olefin oligomerization catalyst system;
b) distilling the reaction mixture in step a) to separate hydrocarbons having less than 10 carbon atoms and hydrocarbons having 10 or more carbon atoms; And
c) hydrogenating the hydrocarbons having 10 or more carbon atoms in the presence of a hydrogenation catalyst; Lt; / RTI &gt;
Wherein the olefin oligomerization catalyst system comprises a transition metal compound, a ligand compound and a cocatalyst, or
Wherein the ligand compound comprises an organic transition metal compound coordinated to a transition metal,
The method of producing a paraffin mixture according to claim 1, wherein the ligand compound is represented by the following formula (1).
[Chemical Formula 1]

In Formula 1, A is represented by the following Formula 2,
(2)

X is an alkylene of 1 to 20 carbon atoms or an arylene of 6 to 14 carbon atoms,
Each of R 1 to R 4 is independently selected from the group consisting of C 1-20 alkyl, C 2-20 alkenyl, C 6-14 aryl, C 6-14 aryl substituted with C 1-4 alkyl, and C 6-14 aryl Lt; / RTI &gt; is aryl having from 1 to 4 alkyl or from 6 to 14 carbons substituted with from 1 to 4 alkoxy,
R5 to R14 are each independently selected from the group consisting of hydrogen, C1-20 alkyl, C2-20 alkenyl, C6-14 aryl, C6-14 aryl substituted with C1-4 alkyl, and C6-14 aryl Alkyl having 1 to 4 carbon atoms or aryl having 6 to 14 carbon atoms substituted with 1 to 4 alkoxy.
8. The method of claim 7,
The process for producing a paraffin mixture according to claim 1, wherein the compound of formula (1) is any one selected from the group consisting of the following compounds.

8. The method of claim 7,
Wherein the transition metal compound comprises a chromium compound and the chromium compound is selected from the group consisting of chromium (III) acetylacetonate, chromium tristrifluoromethanesulfonate, chromium (III) -2-ethylhexanoate, chromium (III) Chromium (III) benzoyl acetonate, chromium (III) hexafluoro-2,4-pentene indionate and chromium (III) acetate hydroxide Wherein the paraffin mixture is at least one selected from the group consisting of:
8. The method of claim 7,
Wherein the cocatalyst is at least one selected from the group consisting of compounds represented by the following Chemical Formulas 3 to 5:
(3)
_{- [Al (R 20) -O} ] c -
In the general formula (3), R 20 are the same or different from each other and each independently represent a halogen, an alkyl of 1 to 20 carbon atoms, or a haloalkyl of 1 to 20 carbon atoms, c is an integer of 2 or more,
[Chemical Formula 4]
D (R _{21) 3}
In Formula 4,
D is aluminum or boron, R21 is the same or different from each other and is independently hydrogen or halogen, alkyl having 1 to 20 carbon atoms or haloalkyl having 1 to 20 carbon atoms,
[Chemical Formula 5]
[LH] ⁺ [Q (E) ₄ ] ^-
In Formula 5,
L is a neutral Lewis base, [LH] ⁺ is a Bronsted acid, Q is boron or aluminum in the +3-oxidation state, E is independently in each occurrence 6 to 20 carbon atoms or 1 to 20 carbon atoms, The aryl group having 6 to 20 carbon atoms or the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one substituent selected from the group consisting of halogen, C 1-20 alkyl, C 1-20 alkoxy and phenoxy.
8. The method of claim 7,
Wherein the hydrogenation catalyst comprises at least one selected from the group consisting of nickel (Ni), copper (Cu), ruthenium (Ru), palladium (Pd), rhodium (Rh) &Lt; / RTI &gt;
8. The method of claim 7,
The process of claim 1, wherein the olefin comprises ethylene.