KR102484658B1 - Process for hydrogenation of phthalate compound - Google Patents

Abstract

The present invention relates to a method for hydrogenating phthalate compounds. Specifically, in one embodiment of the present invention, the average temperature inside the reactor and the maximum-minimum temperature deviation during the hydrogenation reaction of the phthalate compound are adjusted to satisfy a specific range, respectively, so that the aromaticity is controlled to 2.5 to 5.5%. It provides a method for obtaining a hydrogenated reaction product.

Description

Method for hydrogenating phthalate compounds {PROCESS FOR HYDROGENATION OF PHTHALATE COMPOUND}

The present invention relates to a method for hydrogenating phthalate compounds.

A phthalate-based compound is a material widely used as a plasticizer for plastics, particularly polyvinyl chloride (PVC). For example, electrical and electronic products, pharmaceuticals, paint pigments, lubricants, binders, surfactants, adhesives, tiles, food containers, packaging materials, and the like are indeed very diverse.

However, as some phthalate compounds are known as substances that can cause environmental pollution and human endocrine disorders, regulations on their use are being strengthened, especially in developed countries such as Europe and the United States. In particular, among phthalate-based plasticizers, di (2-ethylhexyl) phthalate (DEHP)), butyl benzyl phthalate (BBP), di-n-butyl phthalate (di-n-butyl phthalate) , DBP) is an endocrine disrupter that interferes with or disrupts human hormone activity, and is suspected of being an endocrine disruptor, and there is a movement to regulate it.

Accordingly, efforts have been made to develop eco-friendly plasticizers free from the endocrine disruptor controversy while exhibiting performance equivalent to those of conventional plasticizers.

The hydrogenation reaction product of the phthalate compound has reduced viscosity and surface migration compared to the phthalate compound as a starting material, and may contribute to improving dispersibility and processability of a resin composition including the same as a plasticizer.

However, volatilization loss may increase according to the hydrogenation reaction of the phthalate compound. When a hydrogenation reaction product having a high volatilization loss is used as a plasticizer, the amount of the plasticizer released from the resin composition may increase.

Therefore, in preparing an eco-friendly plasticizer through a hydrogenation reaction of a phthalate compound, it is necessary to control physical properties such as viscosity, surface migration, and volatilization loss of the product within an appropriate range.

The present invention, in order to provide an eco-friendly plasticizer whose physical properties such as viscosity, surface migration, and volatilization loss are all within an appropriate range, the average temperature and maximum-minimum temperature deviation inside the reactor during the hydrogenation reaction of a phthalate compound are simultaneously controlled, It relates to a method for obtaining a product whose aromaticity is controlled within a specific range.

Specifically, in one embodiment of the present invention, a hydrogenation method of a phthalate compound is provided to obtain a hydrogenation reaction product having an aromaticity of 2.5 to 5.5% according to the following formula 1:

[Equation 1] Aromaticity (%) = 100 * (B / A)

In Equation 1, A and B are H-NMR measurement values of the hydrogenation reaction product, respectively, A is the total number of hydrogen atoms included in the hydrogenation reaction product, and B is included in the aromatic functional group in the hydrogenation reaction product. is the number of hydrogen atoms present.

More specifically, during the hydrogenation reaction of a phthalate compound comprising reacting a phthalate compound with hydrogen in the presence of a hydrogenation catalyst in the reactor to obtain a hydrogenation product whose aromaticity is controlled within the above range, inside the reactor The average temperature of is controlled within the range of 125 to 160 ° C, and the maximum-minimum temperature deviation is controlled within the range of 4.5 to 9.0 ° C.

According to the above embodiment, the hydrogenation reaction product having aromaticity controlled to 2.5 to 5.5% by controlling the average temperature and the maximum-minimum temperature deviation inside the reactor during the hydrogenation reaction of the phthalate compound to satisfy a specific range, respectively. can be obtained.

Since the hydrogenation reaction product, whose aromaticity is controlled within the above range, exhibits physical properties such as viscosity, surface migration, and volatilization loss throughout an appropriate range, it can be provided as a plasticizer of improved quality.

1 is a diagram schematically showing a hydrogenation reaction apparatus used in the hydrogenation method of the present invention.

Since the present invention can apply various transformations and have various embodiments, specific embodiments will be exemplified and described in detail. However, it should be understood that this is not intended to limit the present invention to specific embodiments, and includes all transformations, equivalents, and substitutes included in the spirit and scope of the present invention. In describing the present invention, if it is determined that a detailed description of related known technologies may obscure the gist of the present invention, the detailed description will be omitted.

In addition, terms including ordinal numbers such as first and second to be used below may be used to describe various components, but the components are not limited by the terms. These terms are only used for the purpose of distinguishing one component from another. For example, a first element may be termed a second element, and similarly, a second element may be termed a first element, without departing from the scope of the present invention.

Singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, the terms "include" or "have" are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is not precluded.

Hereinafter, a method for hydrogenating a phthalate compound according to an embodiment will be described in detail with reference to the drawings.

The present invention relates to a method for hydrogenating a phthalate compound comprising reacting the phthalate compound with hydrogen in the presence of a hydrogenation catalyst in a reactor.

In general, when a phthalate compound is reacted with hydrogen in the presence of a hydrogenation catalyst, the hydrogenation reaction product has reduced aromaticity compared to the phthalate compound as a starting material.

As the aromaticity of the hydrogenation reaction product decreases, viscosity and surface migration decrease, while volatiles loss tends to increase. Here, the 'volatility loss' may be affected by various factors such as molecular weight, molecular structure, and polarity of the compound.

As the viscosity and surface migration of the hydrogenation reaction product decrease, it may be advantageous to improve dispersibility, processability, etc. of a resin composition to which it is applied as a plasticizer.

However, volatilization loss may increase according to the hydrogenation reaction of the phthalate compound. When a hydrogenation reaction product having a high volatilization loss is used as a plasticizer, the amount of the plasticizer released from the resin composition may increase.

Therefore, it is necessary to control the aromaticity of the hydrogenation reaction product within an appropriate range to reduce the viscosity and surface migration while reducing volatilization loss within an appropriate range.

One embodiment of the present invention, which was derived in accordance with the above needs, provides a method for obtaining a hydrogenation product having an aromaticity of 2.5 to 5.5%. The hydrogenation reaction product whose aromaticity is controlled within this range expresses physical properties such as viscosity, surface migration, and volatilization loss throughout an appropriate range, and can be provided as a plasticizer of improved quality.

Specifically, in one embodiment of the present invention, a phthalate compound comprising the step of reacting a phthalate compound with hydrogen in the presence of a hydrogenation catalyst in a reactor to obtain a hydrogenation product whose aromaticity is controlled within the above range. During the hydrogenation reaction, the average temperature inside the reactor is controlled within the range of 125 to 160 °C, and the maximum-minimum temperature deviation is controlled within the range of 4.5 to 9.0 °C.

In fact, in the experimental examples described later, when the average temperature inside the reactor during the reaction of the phthalate compound is controlled within the range of 125 to 160° C., and the maximum-minimum temperature deviation is controlled within the range of 4.5 to 9.0° C.; Unlike the case where the average temperature is the same but the maximum-minimum temperature deviation exceeds the upper limit of the above range, a hydrogenation reaction product having an aromaticity of 2.5 to 5.5% is obtained, and when the aromaticity within this range is satisfied, the viscosity, surface It was confirmed that the degree of implementation and loss of volatilization were within the appropriate range.

Compared to a general hydrogenation reaction, this lowers the maximum-minimum temperature difference (Δt) when the average temperature (T) inside the reactor is the same, so that a uniform reaction occurs in the entire reactor area, so that the aromaticity is appropriate. It corresponds to a method for obtaining a product with a controlled range. Here, the temperature deviation means the difference between the maximum temperature and the minimum temperature in the reactor, and can be measured from a plurality of temperature sensors installed according to the height of the reactor.

The aromaticity of the product obtained according to the above embodiment is a factor controllable by changing the average temperature inside the reactor, the maximum-minimum temperature deviation, or both within the ranges given above.

For example, while the average temperature inside the reactor during the hydrogenation reaction is 125 ° C or higher, 126 ° C or higher, 127 ° C or higher, 128 ° C or higher, 129 ° C or higher, or 130 ° C or higher, 160 ° C or lower, 159 ° C or lower, 158 ° C or lower, It can be 157°C or less, 156°C or less, or 155°C or less.

In addition, while the maximum-minimum temperature deviation inside the reactor during the hydrogenation reaction is 4.5 ° C or more, 4.6 ° C or more, 4.7 ° C or more, 4.8 ° C or more, 4.9 ° C or more, 5.0 ° C or more, or 5.1 ° C or more, 9.0 ° C or less, 8.9 ° C or more °C or less, 8.8 °C or less, 8.7 °C or less, 8.6 °C or less, 8.5 °C or less, 8.4 °C or less, 8.3 °C or less, 8.2 °C or less, 8.1 °C or less, 8.0 °C or less, or 7.9 °C or less.

By changing the average temperature inside the reactor, the maximum-minimum temperature deviation, or both within each of the above exemplified ranges, the aromaticity of the obtained product is 2.5% or more, 2.6% or more, 2.7% or more, 2.8% or more, 2.9% or more, or 3.0% or more, and can be adjusted within the range of 5.5% or less, 5.4% or less, 5.3% or less, 5.2% or less, 5.1% or less, or 5.1% or less.

More specifically, within each of the above exemplified ranges, as the maximum-minimum temperature deviation increases while increasing the average temperature inside the reactor during the hydrogenation reaction, the aromaticity of the obtained product decreases, and the initial viscosity as much as the aromaticity decreases and surface migration is reduced, and volatiles loss may be increased.

In this regard, the aromaticity of the product is designed in consideration of physical property targets such as viscosity, surface migration, and volatilization loss, and process conditions in each of the above exemplified ranges accordingly (i.e., average temperature inside the reactor and maximum-minimum temperature deviation) ) can be adjusted.

On the other hand, when the average temperature and maximum-minimum temperature deviation in the reactor are more sensitively adjusted during the hydrogenation reaction to satisfy the relationship of Equation 2 below, to obtain a product having aromaticity of the product within the desired range and physical properties accordingly It may be more advantageous to:

[Equation 2] 0.13*T-12.3 ≤ Δt ≤ 0.13*T-10.3

In Equation 2, T is the average temperature inside the reactor (° C.) during the reaction; Δt is the difference (° C.) between the maximum temperature and the minimum temperature inside the reactor during the reaction.

In order to satisfy the relationship of Equation 2, the reactor can be operated to avoid local heat generation by controlling the temperature deviation per unit length (m) of the reactor during the hydrogenation reaction to be maintained at 3 ° C or less, for example, 2 ° C or less. there is. Since the lower the temperature deviation value per unit length of the reactor, the better, the lower limit is not limited, but may be, for example, 1 ° C. or more, and preferably 0 ° C. This temperature deviation can be measured from a number of temperature sensors installed along the height of the reactor.

In addition, during the hydrogenation reaction, the maximum reaction amount per actual reaction volume (m ³ ) of the reactor filled with the catalyst is maintained at 20 kmol/h or less, for example, 15 kmol/hr or less, so as not to generate local heat in the reactor. can do. Here, the amount of reaction can be calculated through the concentration change value by sampling each product according to the height of the reactor.

In order to adjust the reaction amount in the reactor, as described above, the flow rate or concentration of the reactants is adjusted, or for this purpose, an inert gas or an inert liquid is added together with the reactants, and the amount is adjusted. A method of adjusting and the like may be used.

For example, the mass flow rate of the phthalate compound introduced into the reactor, that is, the flow rate per unit area (m ² ) of the reactor filled with the catalyst (mass flux) may be 10,000 to 15,000 kg*hr ^-1 *m ^-2 , Specifically, it may be 10,000 to 13,000 kg*hr ^-1 *m ^-2 .

If the mass flow rate of the phthalate compound is less than 10,000 kg*hr ^-1 *m ^-2 per unit area (m ² ), the input amount of the raw material is not sufficient, resulting in a decrease in productivity, and 15,000 kg*hr ^-1 *m ^-2 If it exceeds, the amount of liquid raw material injected into the reactor at once becomes too large, and the film thickness of the liquid raw material on the surface of the catalyst increases, and accordingly, hydrogen penetration becomes difficult, making it difficult for hydrogenation to occur, and side reactions increase. , local heat generation occurs, causing a problem in that the temperature deviation of the reactor intensifies.

Meanwhile, in order to minimize side reactions and improve process productivity by optimizing the ratio between reactants, the amount of hydrogen introduced into the reactor is 3 moles or more, or 4 moles or more, and 300 moles or less, or 100 moles or less, based on 1 mole of the phthalate compound. may be up to 50 moles, or up to 50 moles, or up to 30 moles.

If the amount of hydrogen is too small, less than 3 moles relative to 1 mole of the phthalate compound, the conversion rate of the reaction is low and a conversion rate of 95% or more cannot be obtained. It may be shortened, resulting in a lower conversion rate, an increase in by-products, or a rapid decrease in catalyst life. From this point of view, the amount of hydrogen can be controlled within the above range.

In addition, as a method for controlling the temperature deviation and reaction amount in the reactor, a method of dispersing reaction heat by installing a cooling member through which a refrigerant circulates inside or outside the reactor may be used.

At this time, as the refrigerant, a refrigerant known in the art may be used without limitation, such as cooling water, a methane-based refrigerant, a mixed refrigerant of ether and a lower alkane having 1 to 5 carbon atoms substituted or unsubstituted with fluorine. The type of the cooling member is not particularly limited, but an indirect cooling method such as a heat exchanger or a cooling jacket or a direct cooling method such as an inert gas or an inert liquid may be used.

In this way, when the hydrogenation reaction is performed by controlling the temperature deviation in the reactor, the reaction occurs uniformly in the reactor, which not only controls the aromaticity of the hydrogenation product, but also increases the catalyst lifespan because the catalysts above and below the reactor are evenly loaded. can be improved

The subject of the hydrogenation reaction is a phthalate compound, and hydrogen is added to the benzene ring of the phthalate compound by hydrogenation to convert it into a cyclohexane dicarboxylate compound corresponding thereto.

The phthalate compound may be at least one selected from phthalate, terephthalate, isophthalate, and a carboxylic acid corresponding thereto.

First, the phthalate compound may be represented by Chemical Formula 1 below.

[Formula 1]

In Formula 1, R1 and R1' are each independently different from or the same, and contain hydrogen, 1 to 20 carbon atoms, preferably 4 to 20 carbon atoms, more preferably 5 to 20 carbon atoms, and still more preferably 5 to 10 carbon atoms. is a straight-chain or branched-chain alkyl group of

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

The terephthalate compound may be represented by Chemical Formula 2 below.

[Formula 2]

In Formula 2, R2 and R2' are each independently different from or the same, and contain hydrogen, 1 to 20 carbon atoms, preferably 4 to 20 carbon atoms, more preferably 5 to 20 carbon atoms, and still more preferably 5 to 10 carbon atoms. is a straight-chain or branched-chain alkyl group of

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

The isophthalate compound may be represented by Chemical Formula 3 below.

[Formula 3]

In Formula 3, R3 and R3' are each independently different from or the same, and contain hydrogen, 1 to 20 carbon atoms, preferably 4 to 20 carbon atoms, more preferably 5 to 20 carbon atoms, and still more preferably 5 to 10 carbon atoms. is a straight-chain or branched-chain alkyl group of

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

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

The purity of the phthalate compound may be about 99% or more, preferably about 99.5% or more, and more preferably about 98% or more, but is not limited thereto, and commercially available phthalate compounds of any quality and purity may be used. .

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

The temperature and pressure conditions of the gaseous raw material and liquid raw material introduced into the reactor are not particularly limited, but the gaseous raw material is at a pressure of about 100 to about 200 bar, preferably about 130 to about 160 bar and about 100 to about 200 ° C. , Preferably it can be adjusted to be in the range of about 130 to about 180 ℃, the liquid raw material is about 100 to about 200 bar, preferably about 130 to about 160 bar pressure and about 100 to about 200 ℃, preferably It can be adjusted to be in the range of about 130 to about 180 °C.

In this regard, the step of increasing the pressure and temperature of the liquid phthalate compound before the reaction; further comprising supplying the increased pressure and temperature of the liquid phthalate compound and gaseous hydrogen to the reactor filled with the hydrogenation catalyst, and the reactor It is possible to react the liquid phthalate compound and gaseous hydrogen under the hydrogenation catalyst in the elevated pressure and temperature. Of course, the average temperature and the maximum-minimum temperature deviation inside the reactor must be controlled as described above.

The hydrogenation catalyst may include a transition metal as an active component, preferably at least one selected from the group consisting of ruthenium (Ru), palladium (Pd), rhodium (Rh), and platinum (Pt). there is.

Such a hydrogenation catalyst may be used by being supported on a carrier, and at this time, a carrier known in the art may be used without limitation as the carrier. Specifically, carriers such as zirconia (ZrO ₂ ), titania (TiO ₂ ), alumina (Al ₂ O ₃ ), and silica (SiO ₂ ) may be used.

When the hydrogenation catalyst is supported on a carrier, the amount of the active ingredient of the hydrogenation catalyst is preferably 3 parts by weight or less, 2 parts by weight or less, or 1 part by weight or less, and 0.1 parts by weight or more, or 0.3 parts by weight or less, based on 100 parts by weight of the carrier. It may be more than one part by weight. If the amount of the hydrogenation catalyst exceeds 3 parts by weight with respect to 100 parts by weight of the carrier, the reaction proceeds rapidly on the surface of the catalyst, and in this process, side reactions also increase, resulting in a rapid increase in the amount of by-products. If it is less than the above range, the yield of the hydrogenation reaction may decrease due to insufficient catalyst amount, so the above range is preferable.

In the present invention, 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 does not occur well, and there may be various problems such as consumption of an excessive amount of catalyst and increase of by-products due to the residence time being too long. The above range is preferable because energy such as excessive electric power is required and the manufacturing cost of equipment such as a reactor may greatly increase.

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

After the reaction is completed, the resulting liquid hydrogenation reaction product and the unreacted gaseous raw material are separated. The separated gaseous raw material may be recycled to the hydrogenation process. In addition, the recovered hydrogenation reaction product can be finally separated through a process of reducing pressure and cooling.

1 is a diagram illustrating a hydrogenation reaction apparatus used in the hydrogenation method of the present invention. According to FIG. 1, the hydrogenation reaction device may include heat exchangers (a, b), a reactor (c), and a gas-liquid phase separator (d).

The heat exchangers (a, b) serve to increase the temperature of the gaseous raw material 1 and the liquid raw material 3 before being introduced into the reactor (c), and may be omitted if necessary.

The gaseous raw material 2 and the liquid raw material 4 are introduced into a tubular reactor c filled with a hydrogenation catalyst, and a hydrogenation reaction proceeds. The reactor may further include an outer jacket for heat removal in order to control reaction heat. At this time, the gaseous raw material 2 may be supplied from the top or bottom of the reactor, and the liquid raw material 4 may be supplied from the top of the reactor.

In the hydrogenation reaction of the phthalate compound, since gaseous reaction raw materials and liquid reaction raw materials react on the surface of the solid catalyst, a flow rate sufficient to form a film on the surface of the solid catalyst in the liquid phase must flow. Therefore, it is appropriate to operate in a way in which liquid raw materials are gradually shed by gravity from the top. On the other hand, when the liquid phase is introduced into the lower part, since the solid phase catalyst is submerged by the liquid phase reactant, it is difficult for the gas phase reactant to penetrate the solid phase catalyst, which may not be appropriate.

The reaction mixture (5) from the reactor (c) is passed to a gas-liquid separator (d), where a liquid reaction product (7) and a gaseous unreacted material (6) are separated. The separated reaction product 7 can be recovered and subjected to additional purification, and the gaseous unreacted material 6 is recycled for discharge or reuse.

However, since the location of each device in FIG. 1 can be changed and other devices not shown in FIG. 1 can be included as needed, the hydrogenation method of the present invention is not limited to the devices and process sequences shown in FIG. .

The product whose aromaticity is controlled according to the hydrogenation method of the embodiment has low viscosity and surface mobility, and relatively little leaching to the product surface even after long-term use, and thus exhibits excellent properties as a plastic plasticizer.

The hydrogenated phthalate or terephthalate compound prepared in this way can be usefully used as a plasticizer. Specifically, the plasticizer containing the phthalate or terephthalate compound may be suitably used as a plasticizer for a resin selected from polystyrene, polyurethane, polybutadiene, silicone, thermoplastic elastomer, or copolymers thereof.

A resin composition containing the resin may be used in a variety of products. For example, it can be used for products such as stabilizers, paints, inks, liquid foaming agents (Masterbatch type), adhesives, and the like. In addition, food packaging film (eg, wrap), industrial film, compound, decorative sheet, decorative tile, soft sheet, hard sheet, wire and cable, wallpaper, foam mat, leather, flooring, tarpaulin, gloves, sealant, refrigerator Gaskets, hoses, medical devices, geogrids, mesh tarpaulins, toys, stationery, insulation tapes, clothing coatings, PVC labels used for clothing or stationery, bottle cap liners, stoppers for industrial or other purposes, artificial baits, It may be used in the manufacture of electronic device parts (eg, sleeves), automobile interior materials, adhesives, coatings, etc., but is not limited thereto.

Hereinafter, the action and effect of the invention will be described in more detail through specific examples of the invention. However, these embodiments are only presented as examples of the invention, and the scope of the invention is not determined thereby.

<Example>

Example 1

Dioctyl terephthalate (DOTP) having a purity of 99% was injected into the reactor, and a hydrogenation reaction was performed at a reaction pressure of 150 bar.

The mass flow rate per unit area (m ² ) of DOTP was 12,000 kg*hr ^-1 *m ^-2 , and the amount of hydrogen was added at a hydrogen/DOTP molar ratio of 6.

The reactor was in the form of a single tube, and the length of the part filled with the catalyst in the tube was 2.0 m in total, and the average temperature inside the reactor during the reaction was 155 ° C. The minimum temperature deviation was controlled to satisfy 7.9 °C. In addition, the reaction amount per unit volume (m ³ ) of the reactor during the reaction was 20 kmol/h or less.

The catalyst used in the reactor is a ruthenium (Ru) catalyst, and the ruthenium content is 0.5 parts by weight based on 100 parts by weight of an alumina (Al ₂ O ₃ ) carrier. It is a cylindrical shape with a diameter of 3 mm and a height of 3 mm. did

For reference, the reactor average temperature and maximum-minimum temperature deviation among each reaction of Examples 2 and 3 and Comparative Examples 1 to 9 below, including Example 1, are recorded in Table 1 below, and each condition corresponds to Equation 2 Satisfaction was evaluated.

Example 2

In Example 1, the average temperature inside the reactor during the hydrogenation reaction was changed to 140 °C and the maximum-minimum temperature deviation was changed to 6.4 °C, and the hydrogenation reaction was carried out in the same manner as the rest.

Example 3

In Example 1, during the hydrogenation reaction, the average temperature inside the reactor was changed to 130 °C and the maximum-minimum temperature deviation was changed to 5.1 °C, and the rest of the hydrogenation reactions were carried out in the same manner.

Comparative Example 1

Dioctyl terephthalate (DOTP) having a purity of 99% was used as Comparative Example 1 without hydrogenation.

Comparative Example 2

In Example 1, during the hydrogenation reaction, the average temperature inside the reactor was changed to 100 °C and the maximum-minimum temperature deviation was changed to 1.8 °C, and the hydrogenation reaction was carried out in the same manner as the rest.

Comparative Example 3

In Example 1, during the hydrogenation reaction, the average temperature inside the reactor was changed to 110 °C and the maximum-minimum temperature deviation was changed to 2.8 °C, and the hydrogenation reaction was carried out in the same manner as the rest.

Comparative Example 4

In Example 1, during the hydrogenation reaction, the average temperature inside the reactor was changed to 120 °C and the maximum-minimum temperature deviation was changed to 3.9 °C, and the rest of the hydrogenation reactions were carried out in the same manner.

Comparative Example 5

In Example 1, the average temperature inside the reactor during the hydrogenation reaction was changed to 180 °C and the maximum-minimum temperature deviation was changed to 13 °C, and the hydrogenation reaction was carried out in the same manner as the rest.

Comparative Example 6

In Example 1, the mass flow rate per unit area (m ² ) of DOTP was 20,000 kg*hr ^-1 *m ^-2 , the average temperature inside the reactor during the reaction was 140 °C, and the maximum-minimum temperature deviation was 10.6 °C. , The reaction amount per unit volume (m ³ ) of the reactor during the reaction was changed to 30 kmol/h or less, and the hydrogenation reaction was performed in the same manner as the rest.

Comparative Example 7

In Example 1, the mass flow rate per unit area (m ² ) of DOTP was 20,000 kg*hr ^-1 *m ^-2 , the average temperature inside the reactor during the reaction was 155 °C, and the maximum-minimum temperature deviation was 13.1 °C. , The reaction amount per unit volume (m ³ ) of the reactor during the reaction was changed to 30 kmol/h or less, and the hydrogenation reaction was performed in the same manner as the rest.

Comparative Example 8

In Example 1, the mass flow rate per unit area (m ² ) of DOTP was 20,000 kg*hr ^-1 *m ^-2 , the average temperature inside the reactor during the reaction was 165 °C, and the maximum-minimum temperature deviation was 14.3 °C. , The reaction amount per unit volume (m ³ ) of the reactor during the reaction was changed to 30 kmol/h or less, and the hydrogenation reaction was performed in the same manner as the rest.

Comparative Example 9

In Example 1, the mass flow rate per unit area (m ² ) of DOTP was 20,000 kg*hr ^-1 *m ^-2 , the average temperature inside the reactor during the reaction was 175 °C, and the maximum-minimum temperature deviation was 15.2 °C. , The reaction amount per unit volume (m ³ ) of the reactor during the reaction was changed to 30 kmol/h or less, and the hydrogenation reaction was performed in the same manner as the rest.

Hydrogenation reaction conditions Evaluation of whether equation 2 of hydrogenation reaction conditions is satisfied average temperature
(℃) maximum minimum
Temperature range
(℃) 0.13*T-12.3
(℃) 0.13*T-10.3
(℃) evaluation Example 1 155 7.9 7.85 9.85 O Example 2 140 6.4 5.9 7.9 O Example 3 130 5.1 4.6 6.6 O Comparative Example 1 (Hydrogenation reaction does not proceed) Comparative Example 2 100 1.8 0.7 2.7 O Comparative Example 3 110 2.8 2 4 O Comparative Example 4 120 3.9 3.3 5.3 O Comparative Example 5 180 13 11.1 13.1 O Comparative Example 6 140 10.6 5.9 7.9 X Comparative Example 7 155 13.1 7.85 9.85 X Comparative Example 8 165 14.3 9.15 11.15 X Comparative Example 9 175 15.2 10.45 12.45 X

<Experimental Example 1>

After completion of the hydrogenation reaction in Examples and Comparative Examples, unreacted gaseous raw materials were separated from the reaction mixture, and each hydrogenation reaction product was obtained.

For each hydrogenation reaction product, the physical properties were evaluated by the following method, and the physical property evaluation results were recorded in Table 2 below.

Aromaticity : Each hydrogenation reaction product was analyzed by H-NMR, and aromaticity was evaluated according to Equation 1 below, and the results were recorded in Table 2 below.

[Equation 1] Aromaticity (%) = 100 * (B / A)

In Equation 1, A and B are H-NMR measurement values of the hydrogenation reaction product, respectively; A is the total number of hydrogen atoms included in the hydrogenation reaction product; B is the number of hydrogen atoms included in the aromatic functional group in the hydrogenation reaction product.

Hydrogenation reaction conditions hydrogenation reaction product average temperature
(℃) Maximum-minimum temperature difference
(℃) aromaticity
(%) Example 1 155 7.9 3.0 Example 2 140 6.4 4.2 Example 3 130 5.1 5.0 Comparative Example 1 (Hydrogenation reaction does not proceed) 10.5 Comparative Example 2 100 1.8 8.4 Comparative Example 3 110 2.8 7.4 Comparative Example 4 120 3.9 6.3 Comparative Example 5 180 13 2.1 Comparative Example 6 140 10.6 6.1 Comparative Example 7 155 13.1 5.3 Comparative Example 8 165 14.3 5.1 Comparative Example 9 175 15.2 5.1

<Experimental Example 2>

100 parts by weight of polyvinyl chloride, 65 parts by weight of each plasticizer composition (hydrogenation reaction product) of the above examples and comparative examples, 140 parts by weight of filler (OMYA-10), 4 parts by weight of fat sugar (TiO ₂ ), stabilizer (LFX-035H) Plastisol was prepared by mixing 1.6 parts by weight, 0.5 parts by weight of a dispersant, 5 parts by weight of a diluent (D240R), and 8.8 parts by weight of a viscosity lowering agent (BYK 5130) for 10 minutes in a Mathis mixer. Each plastisol of Example and Comparative Example prepared according to this method was evaluated as follows.

Initial viscosity and viscosity change rate with time: each plastisol was aged in a constant temperature oven at 25° C. for 1 hour, and then measured using a Brookfield viscometer (spindle #4, 20 RPM). In addition, the change in viscosity after 1 day under the same conditions was measured, and the rate of change in viscosity over time was calculated according to Equation 3 below.

[Equation 3]

Change rate (%) of viscosity after 1 day = {(initial viscosity of plastisol)/(viscosity of plastisol after 1 day)}

Migration loss : Using Mathis Oven, prepare a specimen with a thickness of 2 mm or more of each plastisol according to KSM-3156, attach oil paper to both sides of the specimen, place a 5 kg weight on it, and store in an oven at 60 ° C for 7 days. did Then, after removing the oil paper attached to both sides of each specimen taken out of the oven, the weight before and after being left in the oven was measured, and the migration loss was calculated according to Equation 4 below.

[Equation 4]

Migration loss (%) = [(initial weight of specimen at room temperature - weight of specimen after leaving in oven) / initial weight of specimen at room temperature] x 100

Heating loss : On the other hand, after storing 30 g of each plasticizer composition (hydrogenation reaction product) prepared in the above Examples and Comparative Examples in an oven at 200 ° C. for 1 hour, the heating loss was calculated from the weight change according to Equation 5 below.

[Equation 5] Heating loss (% by weight) = [(weight of initial plasticizer composition-weight of plasticizer composition after storage at 200 ° C. for 1 hour) / weight of initial plasticizer composition] Х100

Hydrogenation reaction conditions Evaluation of physical properties of hydrogenation reaction products average temperature
(℃) maximum minimum
Temperature range
(℃) aromaticity
(%) initial viscosity
(1hr, 20rpm) 1 day later
viscosity
(20rpm) viscosity
change over time surface
degree of fulfillment
(%) volatilization loss
(%) Example 1 155 7.9 3.0 3240 3310 1.02 9.10 0.41 Example 2 140 6.4 4.2 3460 3500 1.01 9.25 0.39 Example 3 130 5.1 5.0 3600 3700 1.03 9.29 0.38 Comparative Example 1 - 10.5 5770 5940 1.03 10.44 0.34 Comparative Example 2 100 1.8 8.4 4550 4750 1.04 9.88 0.36 Comparative Example 3 110 2.8 7.4 4110 4350 1.06 9.81 0.37 Comparative Example 4 120 3.9 6.3 3860 4060 1.05 9.80 0.38 Comparative Example 5 180 13 2.1 3060 3180 1.04 8.98 0.44 Comparative Example 6 140 10.6 6.1 3820 4010 1.05 9.79 0.38 Comparative Example 7 155 13.1 5.3 3680 3830 1.04 9.73 0.39 Comparative Example 8 165 14.3 5.1 3640 3790 1.04 9.70 0.39 Comparative Example 9 175 15.2 5.1 3640 3790 1.04 9.70 0.39

According to Table 2, the hydrogenation products of Examples 1 to 3 as well as Comparative Examples 2 to 9 have reduced aromaticity compared to the phthalate compound (ie, Comparative Example 1) as a starting material. , and the viscosity and surface migration rate decrease, which is due to the addition of hydrogen to benzene included in the phthalate compound.

However, as the aromaticity of the hydrogenated product decreases, the volatiles loss may increase, and it is important to control the volatiles loss within an appropriate range to obtain a plasticizer in harmony with other physical properties.

Specifically, in Comparative Examples 2 to 9, products having an aromaticity of more than 5.0% were obtained, and the volatilization loss of each product was appropriate within the range of 0.36 to 0.44%, with an initial viscosity ranging from a minimum of 3640 to a maximum of 4550, After that, the viscosity was further increased to reach a minimum of 3790 and a maximum of 4750, and the surface transition rate was confirmed to reach a minimum of 9.70 and a maximum of 9.88.

On the other hand, in Examples 1 to 3, products having an aromaticity in the range of 3.0 to 5.0% were obtained, and the volatilization loss of each product was the same as that of Comparative Examples 2 to 9, but the initial viscosity was 3600 or less, and the viscosity after 1 day 3700 or less, the surface migration rate is 9.29% or less, and it is confirmed that the viscosity and surface migration rate are significantly improved.

Unlike Comparative Examples 2 to 9, these Examples 1 to 3 are significant in that the viscosity and surface migration can be lowered while controlling the volatilization loss of the product to an appropriate level by adjusting the hydrogenation process conditions of the phthalate compound within a specific range there is.

However, Examples 1 to 3 are examples of the above-described embodiment, and the average temperature inside the reactor where the hydrogenation reaction of the phthalate compound occurs is controlled within the range of 125 to 160 ° C., and the maximum-minimum temperature deviation inside the reactor When (Δt) is controlled within the range of 4.5 to 9.0 ° C so that a uniform reaction occurs in the entire reactor area, a product with 2.5 to 5.5% aromaticity, low viscosity and surface migration, and a suitable range of volatilization loss will be able to obtain

More specifically, the aromaticity of the hydrogenation reaction product corresponds to a factor controllable by changing the average temperature inside the reactor, the maximum-minimum temperature deviation, or both within the ranges indicated above, and particularly the average temperature and the maximum-minimum temperature difference. It will also be possible to manufacture a product with desired physical properties by sensitively adjusting the reaction conditions so that the relationship between the minimum temperature deviation satisfies Equation 2 above.

a, b: heat exchanger
c: reactor
d: gas-liquid separator
1, 2: vapor phase raw material
3, 4: liquid raw material
5: reaction mixture
6: vapor phase unreacted
7: liquid reaction product

Claims (16)

A method for hydrogenating a phthalate compound comprising reacting a phthalate compound with hydrogen in the presence of a hydrogenation catalyst in a reactor,
During the reaction, the average temperature inside the reactor is controlled within the range of 130 to 155 ° C, and the maximum-minimum temperature deviation is controlled within the range of 5.1 to 7.9 ° C,
Obtaining a hydrogenation reaction product having an aromaticity of 3.0 to 5.0% according to Formula 1 below,
The average temperature and maximum-minimum temperature deviation inside the reactor during the reaction satisfy the relationship of Equation 2 below,
Method for hydrogenating phthalate compounds:
[Equation 1]
Aromaticity (%) = 100*(B/A)
In Equation 1 above,
A and B are H-NMR measurement values of the hydrogenation reaction product, respectively,
A is the total number of hydrogen atoms included in the hydrogenation reaction product,
B is the number of hydrogen atoms included in the aromatic functional group in the hydrogenation reaction product,
[Equation 2]
0.13*T-12.3 ≤ Δt ≤ 0.13*T-10.3
In Equation 2 above,
T is the average temperature inside the reactor (° C.) during the reaction,
Δt is the deviation (° C.) between the maximum temperature and the minimum temperature inside the reactor during the reaction.
delete delete delete delete According to claim 1,
The reaction amount per unit volume (m ³ ) of the reactor during the reaction is 20 kmol / h or less, a method for hydrogenating a phthalate compound.
According to claim 1,
The reactor is a method for hydrogenating a phthalate compound, in which a cooling member through which a refrigerant is circulated is installed outside.
According to claim 1,
The mass flow rate per unit area (m ² ) of the phthalate compound introduced into the reactor is 10,000 to 15,000 kg*hr ⁻¹ *m ⁻² , a method for hydrogenating a phthalate compound
According to claim 1,
The amount of hydrogen introduced into the reactor is 3 to 300 moles per mole of the phthalate compound, a method for hydrogenating a phthalate compound.
According to claim 1,
The phthalate compound is at least one selected from the group consisting of phthalates, terephthalates, isophthalates, and carboxylic acid compounds thereof, a method for hydrogenating a phthalate compound.
According to claim 1,
A method for hydrogenating a phthalate compound, wherein the gaseous raw material is supplied from the top or bottom of the reactor, and the liquid raw material is supplied from the top of the reactor.
According to claim 1,
The hydrogenation catalyst is at least one selected from the group consisting of ruthenium (Ru), rhodium (Rh), palladium (Pd) and platinum (Pt), a method for hydrogenating a phthalate compound.
According to claim 1,
The hydrogenation catalyst is a method for hydrogenating a phthalate compound, wherein the catalyst is 3% by weight or less based on 100% by weight of the carrier.
delete delete delete

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