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 郑在钦 丁基泽 金孝锡 朴圣慜 李京一 李惠媛 于 2018-11-01 设计创作，主要内容包括：本发明涉及一种苯二甲酸酯化合物的氢化方法。根据本发明,氢化反应的立体选择性增加,并且氢化反应产物中顺式异构体的含量增加,因此可以提高产物作为增塑剂的品质。(The invention relates to a hydrogenation method of phthalate compounds. According to the present invention, the stereoselectivity of the hydrogenation reaction is increased, and the cis-isomer content in the hydrogenation reaction product is increased, so that the quality of the product as a plasticizer can be improved.)

1. A process for hydrogenating a phthalate compound, comprising the step of reacting the phthalate compound with hydrogen in the presence of a hydrogenation catalyst in a reactor,

wherein the temperature deviation in the reactor during the reaction is from 0 to 30 ℃, and

the cis-isomer content in the hydrogenation product separated after the reaction is 70% or more.

2. The method for hydrogenating the phthalate compound according to claim 1, wherein a temperature deviation per unit length (m) of the reactor during the reaction is 10 ℃ or less.

3. The method of hydrogenating the phthalate compound of claim 1 wherein during the reaction the reactor is operated per unit volume (m) of the reactor³) The reaction amount of (3) is 100kmol/h or less.

4. The process for hydrogenating the phthalate compound according to claim 1, wherein said reactor comprises externally mounted cooling means, wherein a coolant is circulated in said cooling means.

5. The process for hydrogenating the phthalate compound of claim 1 wherein the phthalate compound is introduced into said reactor per unit area (m)²) The mass flow of (A) is from 10,000 to 100,000kg h^-1*m^-2。

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

7. 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.

8. The method for hydrogenating the phthalate compound according to claim 1, wherein a gas phase raw material is fed from an upper portion or a lower portion of said reactor, and a liquid raw material is fed from an upper portion of said reactor.

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

10. The method for hydrogenating the phthalate compound according to claim 1, wherein the amount of the hydrogenation catalyst is 3% by weight or less based on 100% by weight of the carrier.

11. A hydrogenated phthalate or terephthalate compound prepared by the process according to any one of claims 1 to 10.

12. A plasticizer comprising the hydrogenated phthalate or terephthalate compound of claim 11.

13. A resin composition comprising the plasticizer of claim 12 and a resin selected from ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, polybutadiene, silicone, thermoplastic elastomers or copolymers thereof.

Technical Field

Cross Reference to Related Applications

This application claims the benefit of korean patent application No. 10-2017-0161952, filed on 29.11.2017 with the korean intellectual property office, the entire contents of which are incorporated herein by reference.

The invention relates to a hydrogenation method of phthalate compounds. In particular, the present invention relates to a method for hydrogenating phthalate compounds, which can increase the stereoselectivity of the reaction to increase the cis-isomer content in the hydrogenated product.

Background

Phthalate-based compounds are materials widely used as plasticizers for plastics, especially polyvinyl chloride (PVC). For example, it is used in various applications such as electric and electronic products, medicines, paints, lubricants, adhesives, surfactants, adhesives, tiles, food containers, packaging materials, and the like.

However, several phthalate compounds are known to cause environmental pollution and human endocrine disruption, and regulations for use are also being strengthened in advanced 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) or di-n-butyl phthalate (DBP), are considered as endocrine disruptors that interfere with or confound the hormonal actions of humans, and thus, there are regulations governing them.

Therefore, efforts are being made to develop an environmentally friendly plasticizer showing the same performance as the conventional plasticizer without the problem of environmental hormones, in which one method is to use a compound in which the benzene ring contained in the phthalate compound is hydrogenated.

As hydrogenation of aromatic compounds such as benzene rings, a method using a catalyst comprising a transition metal (such as ruthenium) on a support as an active ingredient is known. For example, korean registered patent No. 1556340 proposes a hydrogenation method of reacting a phthalate compound with hydrogen in the presence of a hydrogen catalyst and an alcohol, and discloses that the performance and life of the catalyst are improved according to the method.

The product prepared by hydrogenation is obtained as a mixture of cis and trans isomers. Here, since the cis-isomer content is high, excellent plasticization efficiency for PVC resin, a fast absorption speed and high product transparency after curing are exhibited, and leaching does not occur on the surface of the product even after long-term use, thus exhibiting excellent properties as a plasticizer.

Therefore, in order to obtain a plasticizer having excellent quality, a hydrogenation method of a phthalate compound having improved stereoselectivity so that the content of cis-isomer is high is required.

[ Prior art documents ]

Patent document 1: korean registered patent No. 1556340, "Process for hydrogenating phthalate ester"

Disclosure of Invention

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

In order to solve the above problems, it is an object of the present invention to provide a novel process for hydrogenating phthalate compounds, which can increase the cis-isomer content in the hydrogenated products.

[ technical solution ] A

To achieve the object, there is provided a method for hydrogenating a phthalate compound, which comprises the step of reacting the phthalate compound with hydrogen in the presence of a hydrogenation catalyst in a reactor,

wherein the temperature deviation in the reactor during the reaction is from 0 to 30 ℃, and

the cis-isomer content in the hydrogenation product separated after the reaction is more than 70%.

Here, the temperature deviation per unit length (m) of the reactor during the reaction may be 10 ℃ or less.

During the reaction, per unit volume (m) of the reactor³) The reaction amount of (3) may be 100kmol/h or less.

The reactor may include an externally mounted cooling member in which a coolant is circulated.

Per unit area (m) of phthalate compound introduced into the reactor²) The mass flow rate of (A) may be 10,000 to 100,000kg h^-1*m^-2。

The amount of hydrogen introduced into the reactor may be 3 to 300mol per 1mol 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 from the upper or lower part of the reactor, and the liquid raw material may be fed from the upper part of the reactor.

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

The amount of the hydrogenation catalyst may be 3 wt% or less based on 100 wt% of the support.

Also provided are hydrogenated phthalate or terephthalate compounds prepared by the above process.

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

Also provided is a resin composition comprising a plasticizer, and a resin selected from ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, polybutadiene, silicone, thermoplastic elastomer, or a copolymer thereof.

[ Effect of the invention ]

According to the process of the present invention, the stereoselectivity of hydrogenation is increased and the cis isomer content in the hydrogenated product is increased, so that the quality of the product as a plasticizer can be improved.

Drawings

Figure 1 schematically shows a hydrogenation apparatus for use in the hydrogenation process of the present invention.

FIG. 2 shows the results of determination of the cis-isomer content in the hydrogenated products of examples and comparative examples.

Detailed Description

While the present invention is susceptible to various modifications and alternative forms, specific examples will be described and illustrated in detail below. It should be understood, however, that these examples are not intended to limit the invention to the particular disclosure, and that the invention includes all modifications, equivalents, and alternatives thereof without departing from the spirit and technical scope of the invention.

As used herein, terms including ordinal numbers such as "first", "second", and the like, are used to explain various structural elements, but the structural elements are not limited by the terms. The term is used only to distinguish one structural element from another. For example, a first structural element may be referred to as a second structural element, and similarly, a second structural element may be referred to as a first structural element.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise or is clear from the context to be expected. As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," and the like, are intended to denote the presence of stated features, quantities, steps, elements, or combinations thereof, in practice, and they are not intended to exclude the presence or increased likelihood of one or more other features, quantities, steps, elements, or combinations thereof.

Hereinafter, the hydrogenation method of phthalate compounds according to the present invention will be explained 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 step of reacting the phthalate compound with hydrogen in the presence of a hydrogenation catalyst in a reactor,

wherein the temperature deviation in the reactor during the reaction is from 0 to 30 ℃, and

the cis-isomer content in the hydrogenation product separated after the reaction is 70% or more.

By operating the reactor while controlling the temperature deviation of the reactor during the reaction, the stereoselectivity of the hydrogenation of the phthalate compound is improved. Specifically, according to the method of the present invention, the cis-isomer content in the hydrogenated product is as high as 70% or more, and the product exhibits excellent plasticization efficiency, a fast absorption speed, and high transparency of the product after curing for PVC resin, and does not undergo leaching on the surface of the product even after long-term use, thus exhibiting excellent plasticizer properties. Thus, the present invention can be used to produce plasticizers.

The hydrogenation object is a phthalate compound, and by hydrogenation, hydrogen is added to the benzene ring of the phthalate compound and the phthalate compound is converted into the corresponding cyclohexanedicarboxylate.

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

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

[ chemical formula 1]

In chemical formula 1, R₁And R₁' are the same or different from each other, and are each independently hydrogen, or a C1 to C20, preferably C4 to C20, more preferably C5 to C20, even more preferably C5 to C10 straight or branched chain alkyl group.

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

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

[ chemical formula 2]

In chemical formula 2, R₂And R₂' are the same or different from each other, and are each independently hydrogen, or a C1 to C20, preferably C4 to C20, more preferably C5 to C20, even more preferably C5 to C10 straight or branched chain alkyl group.

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 combination.

The isophthalate compound can be represented by the following chemical formula 3.

[ chemical formula 3]

In chemical formula 3, R₃And R₃' are the same or different from each other, and are each independently hydrogen, or a C1 to C20, preferably C4 to C20, more preferably C5 to C20, even more preferably C5 to C10 straight or branched chain alkyl group.

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

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

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, and a commercially available phthalate compound of any quality and purity may be used.

The hydrogenation of the phthalate compound may be carried out in the liquid or gas phase. According to one embodiment of the present invention, the hydrogenation process may be carried out with a liquid phthalate compound and gaseous hydrogen.

Per unit area (m)²) The mass flow rate of the phthalate compound introduced into the reactor, i.e., the mass flow rate per unit area (m) of the reactor packed with the catalyst²) The mass flow of (c) may preferably be from 10,000 to 100,000kg h^-1*m^-2More preferably 17,000 to 50,000kg h^-1*m^-2。

If per unit area (m)²) The mass flow rate of the phthalate compound is less than 10,000kg^-1*m^-2The input amount of raw materials may be insufficient, resulting in a decrease in productivity. And if more than 100,000kg h^-1*m^-2In this case, the amount of the liquid raw material introduced into the reactor at one time may excessively increase, the thickness of the raw material film on the surface of the catalyst may increase, and thus hydrogen may be difficult to permeate, and the hydrogenation reaction may hardly occur, and thus the side reaction may increase and local heating may occur, thereby increasing the temperature deviation of the reactor.

Meanwhile, in order to minimize side reactions and optimize the ratio between reaction materials to increase productivity, the amount of hydrogen introduced into the reactor may be 3mol or more, or 4mol or more, or 7mol or more, and 300mol or less, or 100mol or less, or 50mol or less, or 30mol or less, based on 1mol of the phthalate compound.

If the amount of hydrogen is less than 3mol per 1mol of the phthalate compound, the reaction conversion may be reduced and a conversion of 95% or more may not be obtained; whereas if the amount of hydrogen is more than 300mol, the residence time of the liquid droplets of the liquid raw material may be shortened by the hydrogen, and thus, the conversion rate may be decreased or the by-products may be increased, or the catalyst life may be rapidly shortened. In this regard, the amount of hydrogen is preferably within the above range.

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, but the gas-phase raw material may be controlled to a pressure of about 100 to about 200 bar, preferably about 130 to about 160 bar, and a temperature of about 100 to about 200 ℃, preferably about 130 to about 180 ℃, and the liquid-phase raw material may be controlled to a pressure of about 100 to about 200 bar, preferably about 130 to about 160 bar, and a temperature of about 100 to about 200 ℃, preferably about 130 to about 180 ℃.

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

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

In the case where 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, 0.3% by weight or more, based on 100% by weight of the carrier. If the amount of the hydrogenation catalyst is more than 3% by weight based on 100% by weight of the carrier, the reaction may rapidly proceed on the surface of the catalyst and in the process, side reactions may also increase and by-products may rapidly increase, while if less than 0.1% by weight, the yield of the hydrogenation reaction may decrease due to an insufficient amount of the catalyst, and thus the above range is preferred.

The hydrogenation reaction conditions are not particularly limited, but for example, the reaction pressure may be 50 bar or more, or 100 bar or more, or 130 bar or more, and 220 bar or less, or 200 bar or less, or 180 bar or less. If the reaction pressure is less than 50 bar, the reaction may not easily occur, and thus an excessive amount of catalyst may be consumed, and the residence time may be excessively prolonged, thereby increasing byproducts, while if it is more than 200 bar, excessive energy may be required during the operation of the process, and the manufacturing cost of a reactor or the like may be significantly increased, and thus the above range is preferable.

The reaction temperature may be 100 ℃ or higher, 120 ℃ or higher, 130 ℃ or higher, 300 ℃ or lower, 250 ℃ or lower, or 200 ℃ or lower. If the reaction temperature is lower than 100 c, the reaction speed may be too slow and thus the reaction may not be smoothly performed, and if the temperature is higher than 300 c, the by-products may rapidly increase. In addition, it may also affect the catalyst life, and therefore the above range is preferred.

By this hydrogenation reaction, the aromatic ring of the phthalate compound is hydrogenated and the phthalate compound is converted into the corresponding cyclohexanedicarboxylate compound.

The reaction is controlled so that the temperature deviation in the reactor during the hydrogenation reaction can be maintained at 0 to 30 ℃, preferably 0 to 20 ℃, and more preferably 0 to 10 ℃, thereby minimizing the production of trans-isomer and improving the selectivity to cis-isomer. Here, the temperature deviation means a difference between the highest temperature and the lowest temperature in the reactor, and may be measured by a plurality of temperature sensors installed according to the height of the reactor.

Alternatively, the reaction is controlled such that the temperature deviation per unit length (m) of the reactor during the hydrogenation reaction is kept below 10 ℃ or below 5 ℃, thereby avoiding local heating and thus minimizing the production of trans-isomer and improving the selectivity to cis-isomer. The lower limit is not limited as the temperature deviation per unit length of the reactor is better, but for example, the lower limit may be 3 ℃ or more, preferably 0 ℃. Such temperature deviation may be measured by a plurality of temperature sensors installed according to the height of the reactor.

Also, according to an embodiment of the present invention, during the hydrogenation reaction, the reactor filled with the catalyst has a volume per actual reaction volume (m)³) Is kept below 100kmol/h, or below 50kmol/h, preferably below 30kmol/h, in order to avoid local heating in the reactor and thus to increase the selectivity towards the cis-isomer. Wherein the reaction amount can be determined according to the reactionThe height of the vessel was calculated from the concentration change values by sampling the product individually.

To control the amount of reaction in the reactor, the mass flow or concentration of the reactants may be controlled as described above, and for this purpose, an inert gas or an inert liquid may be added together with the reactants, and the amount may be controlled.

The method for controlling the temperature deviation and the reaction amount in the reactor is not particularly limited, and any method known in the art may be used. For example, a method of installing a cooling member in which a coolant circulates inside or outside the reactor to diffuse reaction heat may be used.

Here, as the coolant, any coolant known in the art, for example, cooling water, a methane-based coolant, a mixed coolant of fluorine substituted or unsubstituted C1-C5 lower alkane and ether, and the like, may be used without limitation. The kind of the cooling member is not particularly limited, and indirect cooling methods such as a heat exchanger, a cooling jacket, and the like, and direct cooling methods such as an inert gas, an inert liquid, and the like can be used.

In the case of performing the reaction while controlling the temperature deviation in the reactor, the stereoselectivity of the hydrogenation is remarkably improved, and the cis-isomer content in the hydrogenated product is as high as 70% or more. Therefore, the quality of the hydrogenated product as a plasticizer can be improved. Also, the reaction can occur uniformly inside the reactor, and the catalyst of the upper/lower portion of the reactor can be uniformly loaded, thereby remarkably extending the life span of the catalyst.

After the completion of the reaction, the liquid-phase hydrogenation product and the unreacted gas-phase raw material are separated. The separated gas phase feed may be recycled to the hydrogenation process, while the recovered hydrogenation product may be subjected to a pressure reduction and cooling process and finally separated.

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

Referring to fig. 1, the hydrogenation apparatus may consist of heat exchangers (a, b), a reactor (c), a gas-liquid phase separator (d), and the like.

The heat exchangers (a, b) are used to raise the temperature before introducing the gas-phase feedstock (1) and the liquid-phase feedstock (3) into the reactor (c), and may be omitted as required.

The vapor-phase raw material (2) and the liquid-phase raw material (4) are introduced into a tubular reactor (c) filled with a hydrogenation catalyst, thereby carrying out hydrogenation. The reactor may further comprise an external jacket for removing heat to remove the heat of reaction. Here, the gas-phase raw material (2) may be fed from the upper or lower portion of the reactor, and the liquid-phase raw material (4) may be fed from the upper portion of the reactor.

Since the hydrogenation of the phthalate compound causes a reaction between the gas-phase raw material and the liquid-phase raw material on the surface of the solid catalyst, the liquid-phase raw material should flow at a flow rate capable of forming a film on the surface of the solid catalyst. Therefore, it is appropriate to gradually flow the liquid-phase raw material from the upper portion by gravity. In contrast, in the case of introducing the liquid phase from the lower portion, the solid catalyst may be submerged by the liquid reactant, and thus the gas-phase reactant may have difficulty in penetrating the solid catalyst, which is not suitable.

The reaction mixture (5) discharged from the reactor (c) is transferred to a gas-liquid phase separator (d) in which the liquid phase reaction product (7) and the gas phase unreacted material (6) are separated. The separated reaction product (7) may be recovered and subjected to additional purification processes, and the gas phase unreacted feed (6) may be recycled for discharge or reuse.

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

According to the hydrogenation process of the present invention, the stereoselectivity of hydrogenation can be improved to obtain a reaction product having a cis-isomer content of 70% or more. The product exhibits excellent plasticizing efficiency and rapid absorption speed, as well as excellent product transparency after curing, and does not undergo leaching on the product surface even after long-term use, thus exhibiting excellent properties as a plasticizer.

The hydrogenated phthalate or terephthalate compound thus produced can be effectively used as a plasticizer. Specifically, the plasticizer containing a phthalate or terephthalate compound can be used for a stabilizer, paint, ink, liquid foaming agent (masterbatch type), adhesive, and the like.

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

The resin composition including the phthalate or terephthalate compound prepared according to the above method as a plasticizer and including the above resin may be used for various products. For example, it can be used for preparing films for food packaging (e.g., packaging materials), industrial films, compounds, decorative sheets, decorative tiles (decortiles), films, hard sheets, electric wires and cables, wallpaper, foam pads, artificial leather, floors, tarpaulins, gloves, sealants, refrigerator gaskets, hoses, medical instruments, geogrids, net-shaped tarpaulins, toys, stationery, insulating tapes, clothing paints, PVC labels for clothing or stationery, plug liners, plugs for industrial or other uses, artificial baits, parts in electronic devices (e.g., sleeves), automotive interior materials, adhesives, paints, and the like, but is not limited thereto.

Hereinafter, the action and effect of the present invention will be described in more detail by specific examples. However, these embodiments are merely examples, and the scope of the present invention is not determined thereby.

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