阅读说明：本技术 苯二甲酸酯化合物的氢化方法 (Method for hydrogenating phthalate compound ) 是由 金孝锡 丁基泽 朴圣慜 李京一 李惠媛 郑在钦 于 2018-11-01 设计创作，主要内容包括：本发明提供了一种苯二甲酸酯化合物的氢化方法。根据本发明,可以提高氢化反应的立体选择性,因此可以增加产物中顺式异构体的含量。结果,可以改善氢化产物作为增塑剂的品质。(The invention provides a hydrogenation method of phthalate compounds. According to the present invention, the stereoselectivity of the hydrogenation reaction can be improved, and thus the cis-isomer content in the product can be increased. As a result, the quality of the hydrogenated product as a plasticizer can be improved.)

1. A process for the hydrogenation of a phthalate compound, the process comprising the steps of: introducing a gas-phase raw material containing hydrogen and a liquid-phase raw material containing a phthalate compound into a reactor and reacting the hydrogen and the phthalate compound in the presence of a hydrogenation catalyst,

wherein the Reynolds number of the liquid phase raw material is 1 to 100, and the content of the cis-isomer in the hydrogenation product separated after the reaction is 70% or more.

2. The method for hydrogenating the phthalate compound of claim 1 wherein the amount of hydrogen introduced into the reactor is 3 to 300 moles per 1 mole of the phthalate compound.

3. The method for hydrogenating the phthalate compound according to claim 1, wherein the phthalate compound is one or more selected from the group consisting of phthalates, terephthalates, isophthalates, and carboxylic acid compounds thereof.

4. The process for hydrogenating the phthalate compound according to claim 1, wherein said vapor phase feedstock is fed to an upper portion or a lower portion of said reactor and said liquid phase feedstock is fed to an upper portion of said reactor.

5. The method for hydrogenating the phthalate compound according to claim 1, wherein an active ingredient of the hydrogenation catalyst is one or more selected from ruthenium (Ru), rhodium (Rh), palladium (Pd), and platinum (Pt).

6. The method for hydrogenating the phthalate compound according to claim 1, wherein the hydrogenation catalyst comprises 3% by weight or less of a catalyst active ingredient relative to 100% by weight of the carrier.

7. A hydrogenated phthalate or terephthalate compound prepared by the process according to any one of claims 1 to 6.

8. A plasticizer comprising the hydrogenated phthalate or terephthalate compound of claim 7.

9. A resin composition comprising the plasticizer according to claim 8 and a resin selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, polybutadiene, silicone, thermoplastic elastomers, and copolymers thereof.

Technical Field

Cross Reference to Related Applications

The present application is based on and claims priority from korean patent application No. 10-2017-0161950, filed on 29/11/2017, the entire contents of which are incorporated herein by reference.

The present invention relates to a process for the hydrogenation of phthalate compounds. In particular, the present invention relates to a method for hydrogenating phthalate compounds, which is capable of increasing the cis-isomer content in the hydrogenated products by improving the stereoselectivity of the reaction.

Background

Phthalate-based compounds are materials widely used as plasticizers for plastics, especially polyvinyl chloride (PVC). For example, phthalate-based compounds are widely used in a variety of applications, such as electrical and electronic products, pharmaceuticals, paint pigments, lubricants, cements, surfactants, adhesives, tiles, food containers, packaging materials, and the like.

However, since some phthalate compounds are known to be substances causing environmental pollution and problems of endocrine disorders in human body, their use has been limited in developed countries such as europe, the united states, and the like. In particular, among phthalate-based plasticizers, some products such as di (2-ethylhexyl) phthalate (DEHP), butylbenzyl phthalate (BBP), and di-n-butyl phthalate (DBP) are suspected to be environmental hormones, i.e., endocrine disruptors that inhibit or destroy hormonal effects in the human body, and thus there is a tendency to regulate these products.

For this reason, efforts have been made to develop an environmentally friendly plasticizer which is not controversial in terms of environmental hormones while having the same properties as existing plasticizers. As one of the efforts, there is a method using a compound prepared by hydrogenating a benzene ring contained in a phthalate compound.

As the hydrogenation reaction of aromatic compounds such as benzene rings, a method using a catalyst in which a transition metal such as ruthenium is contained on a support as an active ingredient is known.

However, the transition metal catalyst has a problem in that its activity rapidly decreases as the reaction proceeds, resulting in a decrease in yield. Therefore, efforts have been made to solve the problems of the hydrogenation reaction in order to improve the productivity and economic efficiency of the process. For example, korean patent No. 1556340 discloses a hydrogenation method in which a phthalate compound is reacted with hydrogen in the presence of a hydrogenation catalyst and an alcohol, thereby improving the performance and life of the catalyst.

Meanwhile, the hydrogenation reaction is accompanied by side reactions. As the by-product content increases, the manufactured product becomes acidic. If the acid value of the product exceeds a certain level, odor is generated and the purity is lowered, resulting in quality problems as a plasticizer. In addition, the by-products also reduce the activity of the hydrogenation catalyst, and therefore, there is a need for a novel method for hydrogenating phthalate compounds, which can suppress the production of by-products, to improve the productivity and economic efficiency of the method, and to improve the product quality.

[ Prior Art document ]

Patent document 1: korean patent No. 1556340, "hydrogenation method of phthalate compound"

Disclosure of Invention

[ problem ] to provide a method for producing a semiconductor device

The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for hydrogenating a phthalate compound, which is capable of increasing the cis-isomer content in the hydrogenated product.

[ technical solution ] A

In order to achieve the above object, there is provided a method for hydrogenating a phthalate compound, comprising the steps of: introducing a gas-phase raw material containing hydrogen and a liquid-phase raw material containing a phthalate compound into a reactor and reacting the hydrogen and the phthalate compound in the presence of a hydrogenation catalyst,

wherein the Reynolds number of the liquid phase raw material is 1 to 100, and the content of the cis-isomer in the hydrogenation product separated after the reaction is 70% or more.

The amount of hydrogen introduced into the reactor may be 3 moles to 300 moles with respect to 1 mole of the phthalate compound.

The phthalate compound may be one or more selected from the group consisting of phthalates, terephthalates, isophthalates, and carboxylic acid compounds thereof.

The gas-phase raw material may be fed to the upper or lower portion of the reactor, and the liquid-phase raw material may be fed to the upper portion of the reactor.

The active component of the hydrogenation catalyst may be one or more selected from ruthenium (Ru), rhodium (Rh), palladium (Pd), and platinum (Pt).

The hydrogenation catalyst may contain 3% by weight or less of the catalyst active ingredient relative to 100% by weight of the support.

Further, there is provided a hydrogenated phthalate or terephthalate compound prepared by the above process.

The hydrogenated phthalate or terephthalate compounds may be used as plasticizers.

Further, provided is a resin composition comprising a plasticizer; and a resin selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, polybutadiene, silicone, thermoplastic elastomers, and copolymers thereof.

[ PROBLEMS ] the present invention

According to the hydrogenation method of phthalate compounds of the present invention, the stereoselectivity of the hydrogenation reaction can be improved, and thus the cis-isomer content in the product can be increased. As a result, the quality of the hydrogenated product as a plasticizer can be improved.

Drawings

FIG. 1 is a schematic diagram of a hydrogenation reaction apparatus used in the hydrogenation process of the present invention.

Detailed Description

The present invention is susceptible to various modifications and embodiments, and the specific embodiments will be shown by way of example and described in detail. However, the present invention is not limited to the exemplary embodiments described herein, but all modifications, equivalents, and substitutions within the spirit and scope of the present invention are also included in the present invention. In addition, when it is determined that detailed description of known technologies related to the present invention may make the gist of the present invention unclear, the detailed description thereof will be omitted.

In addition, terms such as first, second, etc. ordinal numbers that will be used below may be used to describe various components. However, these components are not limited to these terms. These terms are only used to distinguish one component from another. For example, a "first" component may be termed a "second" component, and a "second" component may be similarly termed a "first" component, without departing from the scope of the present invention.

The singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms such as "comprising," "having," and the like, used in this specification are intended to specify the presence of stated features, integers, steps, operations, configuration elements, components, or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, operations, configuration elements, components, or groups thereof.

Hereinafter, the hydrogenation method of phthalate compounds according to the present invention will be described in detail with reference to the accompanying drawings.

According to a preferred embodiment of the present invention, there is provided a method for hydrogenating a phthalate compound, which comprises the steps of: introducing a gas-phase raw material containing hydrogen and a liquid-phase raw material containing a phthalate compound into a reactor and reacting the hydrogen and the phthalate compound in the presence of a hydrogenation catalyst,

wherein the Reynolds number of the liquid phase feedstock is from 1 to 100 and the content of the cis-isomer in the hydrogenation product separated after the reaction is 70% or more.

In the present invention, the stereoselectivity of the hydrogenation reaction of the phthalate compound can be improved by operating while controlling the Reynolds number of the liquid phase raw material within a specific numerical range. In other words, according to the present invention, the hydrogenated product has a high cis-isomer content of 70% or more, and such a hydrogenated product can exhibit excellent plasticization efficiency to PVC resin, high absorption rate and transparency of the product after curing, and has excellent properties as a plastic plasticizer since the leaching rate from the surface of the product is low even after its long-term use. Therefore, the present invention can be applied to the production of high-quality plasticizers.

The reaction target of the hydrogenation process of the present invention is a phthalate compound, and hydrogen is added to the benzene ring of the phthalate compound by hydrogenation to be converted into a cyclohexanedicarboxylate compound corresponding to the phthalate compound.

The phthalate compound may be one or more selected from the group consisting of phthalates, terephthalates, isophthalates, and carboxylic acid compounds corresponding thereto.

First, the phthalate compound may be represented by the following chemical formula 1:

[ chemical formula 1]

In chemical formula 1, R1 and R1' are each independently the same as or different from each other, and are hydrogen or a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 4 to 20 carbon atoms, more preferably 5 to 20 carbon atoms, most preferably 5 to 10 carbon atoms.

Specific examples of the phthalate compound may include dibutyl phthalate (DBP), dihexyl phthalate (DHP), dioctyl phthalate (DOP), di-n-octyl phthalate (DnOP), diisononyl phthalate, diisodecyl phthalate (DIDP), etc., but are not limited thereto. These compounds may be used alone or in admixture thereof.

The terephthalate compound may be represented by the following chemical formula 2:

[ chemical formula 2]

In chemical formula 2, R2 and R2' are each independently the same as or different from each other, and are hydrogen or a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 4 to 20 carbon atoms, more preferably 5 to 20 carbon atoms, most preferably 5 to 10 carbon atoms.

Specific examples of the terephthalate compound may include dibutyl terephthalate (DBTP), dioctyl terephthalate (DOTP), diisononyl terephthalate (DINTP), or diisodecyl terephthalate (DIDTP), but are not limited thereto. These compounds may be used alone or in admixture thereof.

The isophthalic acid compound may be represented by the following chemical formula 3:

[ chemical formula 3]

In chemical formula 3, R3 and R3' are the same as or different from each other independently and are hydrogen or a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 4 to 20 carbon atoms, more preferably 5 to 20 carbon atoms, most preferably 5 to 10 carbon atoms.

Specific examples of the isophthalate compound may include dibutyl isophthalate (DBIP), dioctyl isophthalate (DOIP), diisononyl isophthalate (DINIP), diisodecyl isophthalate (DIDIP), and the like, but are not limited thereto. These compounds may be used alone or in admixture thereof.

Preferably, dioctyl terephthalate (DOTP) may be used as the phthalate compound.

The phthalate compound may have a purity of about 99% or more, preferably about 99.5% or more, and more preferably about 98% or more, but is not limited thereto. Any phthalate compound of commercially available quality and purity can be used.

The hydrogenation of the phthalate compound may be carried out in the liquid or gas phase. In the present invention, the phthalate compound is contained in the liquid-phase raw material and hydrogen is contained in the gas-phase raw material, which are introduced into the reactor packed with the hydrogenation catalyst.

In the present invention, the reynolds number of the liquid-phase raw material introduced into the reactor may be 1 to 100.

Reynolds number (N)_RE) Is the ratio of the "inertial force" to the "viscous force" of the fluid, represented by equation 1 below:

[ equation 1]

μ: viscosity ρ: density u_z: axial linear velocity D_p: diameter of flow path

In fluid flow, when the viscous force is greater, laminar flow occurs, in which elements in the fluid move parallel to each other in the transport direction; when the inertial force is greater, turbulence occurs, in which elements in the fluid move randomly in the transport direction. The reynolds number is a value used to determine whether the flow in a pipe is laminar or turbulent. When the Reynolds number is about 2000 or less, laminar flow is determined; and when the reynolds number is greater than 2000, turbulence is determined. In other words, a lower reynolds number for the fluid indicates that the flow is stable and free of turbulence.

In the process for hydrogenating the phthalate compound of the present invention, the Reynolds number of the liquid phase raw material may be 1 or more, or 5 or more, or 10 or more, or 20 or more, and 100 or less, or 90 or less, or 80 or less, or 50 or less, or 30 or less.

When the reynolds number of the liquid-phase raw material is too low to be less than 1, the axial linear velocity is too low or the viscosity is too high, and therefore liquid-phase distribution does not generally occur. When the reynolds number is too high in excess of 100, turbulence of random movement becomes strong, and reactivity may be reduced without forming stable trickle flow. From this viewpoint, the reynolds number of the liquid-phase raw material is preferably in the above range.

In investigating the method of increasing the cis-isomer content of the product during hydrogenation of phthalate compounds, the present inventors have discovered that the reynolds number of the liquid phase feed affects the stereoselectivity of the reaction. In other words, the higher the content of cis-isomer, the lower the reynolds number of the liquid phase feed, which may be attributed to: since the fluidity of the raw material on the surface of the catalyst is improved, the rate of addition of hydrogen to the benzene ring of the phthalate compound is increased.

In the present invention, the temperature and pressure conditions of the gas-phase raw material and the liquid-phase raw material introduced into the reactor are not particularly limited. However, the raw material to be introduced may generally have the same pressure as the hydrogenation conditions, and in terms of temperature conditions, the raw material may preferably have the same temperature as the hydrogenation conditions. Optionally, a feedstock having a temperature below the hydrogenation conditions may be introduced into the reactor to control heat generation in the reactor.

In the present invention, the method of controlling the reynolds number of the liquid-phase raw material introduced into the reactor is not particularly limited. For example, the reynolds number of the liquid phase feed may be controlled by temperature, catalyst size, reactor diameter, amount of liquid phase feed across the cross-sectional area, and the like. In one embodiment of the present invention, the reynolds number may be controlled by changing the reactor diameter, flow rate, etc. after the catalyst is sized, but the present invention is not limited thereto.

Further, in order to ensure the above-mentioned effects, the amount of hydrogen introduced into the reactor may be 3 moles or more, or 4 moles or more, or 7 moles or more, and 300 moles or less, or 100 moles or less, or 50 moles or less, or 30 moles or less, relative to 1 mole of the phthalate compound. If the amount of hydrogen is too small to be less than 3 moles with respect to 1 mole of the phthalate compound, the reactivity is lowered to a level lower than the equivalence ratio. If the amount is too large to exceed 300 moles, the size of the reactor, the back-end gas phase treatment apparatus and the instruments becomes too large, so that the equipment cost may increase. From this viewpoint, the amount of hydrogen is preferably within the above range.

The hydrogenation catalyst may include a transition metal as an active ingredient, and may preferably include one or more selected from ruthenium (Ru), palladium (Pd), rhodium (Rh), and platinum (Pt).

The hydrogenation catalyst may be used after being supported on a carrier. In this regard, as the carrier, any carrier known in the art may be used without limitation. Specifically, a material such as zirconium oxide (ZrO) may be used₂) Titanium oxide (TiO)₂) Alumina (Al)₂O₃) Silicon oxide (SiO)₂) And the like.

When the hydrogenation catalyst is supported on a carrier, the amount of the active ingredient of the hydrogenation catalyst is preferably 3% by weight or less, 2% by weight or less, or 1% by weight or less, and 0.1% by weight or more, or 0.3% by weight or more, relative to 100% by weight of the carrier. If the amount of the hydrogenation catalyst is more than 3% by weight with respect to 100% by weight of the carrier, the reaction rapidly occurs on the surface of the catalyst, and in the process, side reactions also increase, which may cause a problem that the amount of by-products rapidly increases. If the amount is less than 0.1 wt%, the yield of the hydrogenation reaction may be reduced due to an insufficient amount of the catalyst. Therefore, the above range is preferable.

In the present invention, the hydrogenation reaction conditions are not particularly limited. However, the reaction pressure may be, for example, 50 bar or more, or 100 bar or more, or 130 bar or more, and 200 bar or less, or 180 bar or less, or 150 bar or less. If the reaction pressure is less than 50 bar, there are various problems in that the solubility of hydrogen in the liquid is too low, and thus the reactivity may be lowered. If the reaction pressure exceeds 200 bar, there is a problem in that the equipment cost increases because the high pressure increases the size of the equipment. Therefore, the above range is preferable.

The reaction temperature may be 100 ℃ or higher, 120 ℃ or higher, 130 ℃ or higher, and 300 ℃ or lower, 250 ℃ or lower, or 200 ℃ or lower. If the reaction temperature is lower than 100 ℃, there is a problem in that reactivity may be reduced due to a low temperature. If the reaction temperature is higher than 300 ℃, there is a problem in that by-products increase due to decomposition or the like.

By the hydrogenation reaction, the aromatic ring of the phthalate compound is hydrogenated to be converted into a cyclohexanedicarboxylate compound corresponding thereto.

After the reaction is terminated, the resulting liquid-phase hydrogenated product and the unreacted gaseous starting material are separated from each other. The separated gas phase feed can be recycled in the hydrogenation process. In addition, the recovered hydrogenation product may be finally separated by a decompression and cooling process.

The hydrogenation process according to the present invention, wherein the gas phase and liquid phase feedstocks are introduced into the reactor by controlling the reynolds number, improves the stereoselectivity of the hydrogenation reaction and the cis isomer content in the product is as high as 70% or more, more preferably 80% or more. Thus, the hydrogenated product prepared by the present invention can exhibit excellent plasticization efficiency, high absorption rate and excellent product transparency after curing due to the increase of cis-isomer content, and has excellent properties as a plasticizer for plastics due to low leaching rate from the surface of the product even after long-term use.

Fig. 1 shows a hydrogenation reaction apparatus used in the hydrogenation process of the present invention.

Referring to fig. 1, the hydrogenation reaction apparatus may be composed of heat exchangers a and b, a reactor c, and a gas-liquid separator d, etc.

The heat exchangers a and b are used to heat the vapor-phase raw material 1 and the liquid-phase raw material 3 before introducing them into the reactor c, and may be omitted as needed.

The gas-phase raw material 2 and the liquid-phase raw material 4 passed through the heat exchanger are introduced into a tubular reactor c, the inside of which is filled with a hydrogenation catalyst, and a hydrogenation reaction is carried out. The reactor may further comprise an external jacket for heat removal in order to control the heat of reaction. In this regard, the gas-phase raw material 2 may be fed to the upper or lower portion of the reactor, and the liquid-phase raw material 4 may be fed to the upper portion of the reactor. The liquid feedstock flows by gravity over the catalyst from the upper to the lower part of the reactor and shows a trickle flow according to the reynolds number, so that the hydrogenation proceeds with effective reactivity.

The reaction mixture 5 discharged from the reactor c is transferred to a gas-liquid separator d, in which a liquid-phase reaction product 7 and an unreacted gas phase 6 are separated from each other. The separated reaction product 7 can be recovered and further subjected to a purification process, and the unreacted gas phase 6 is recycled so as to be discharged or recycled.

However, the location of each of the devices shown in FIG. 1 may be changed, and other devices not shown in FIG. 1 may be included, if desired. Thus, the hydrogenation process according to the present invention is not limited to the apparatus and process sequence shown in FIG. 1.

According to the above hydrogenation method of the present invention, the stereoselectivity of the hydrogenation reaction is improved, thereby obtaining a reaction product having a cis isomer content of 70% or more. The product exhibits excellent plasticizing efficiency, high absorption rate, and excellent transparency of the cured product, and has excellent properties as a plasticizer for plastics since the leaching rate from the surface of the product is low even after long-term use.

The hydrogenated phthalate or terephthalate compounds prepared as described above can be effectively used as plasticizers. Specifically, a plasticizer containing a phthalate or terephthalate compound may be applied to products such as a stabilizer, a coating material, an ink, a liquid-phase foaming agent (master batch), an adhesive, and the like.

The hydrogenated phthalate or terephthalate compound prepared according to the present invention has excellent purity and high cis-isomer content, and thus is excellent in quality as a plasticizer. Therefore, it may be suitably used as a plasticizer for a resin selected from ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, polybutadiene, silicone, thermoplastic elastomer, and copolymers thereof.

The resin composition comprising the phthalate or terephthalate compound prepared according to the present invention as a plasticizer and the above resin may be used in various products. For example, the resin composition can be used for preparing food packaging films (e.g., wrapping paper), industrial films, compounds, decorative sheets, decorative tiles, flexible sheets, hard sheets, electric wires and cables, wallpaper, foam pads, leather, flooring materials, tarpaulins, gloves, sealants, refrigerator gaskets, hoses, medical devices, geogrids, waterproof tarpaulins, toys, stationery, insulating tapes, garment coatings, PVC labels for clothing or stationery, bottle cap liners, stoppers for industrial or other uses, artificial baits, parts (e.g., sleeves) in electronic devices, automotive interior materials, adhesives, coating agents, but is not limited thereto.

Hereinafter, the action and effect of the present invention will be described in more detail with reference to specific examples thereof. However, these examples are for illustrative purposes only, and the scope of the present invention is not intended to be limited thereto.

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