Title of Invention: Method for manufacturing diester-based material
technical field
[One]
Cross Citation with Related Applications
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0119987 dated September 27, 2019, and all contents disclosed in the literature of the Korean patent application are incorporated as a part of this specification.
[3]
[4]
technical field
[5]
The present invention relates to a method for producing a diester-based material having improved reactivity and productivity.
[6]
background
[7]
Phthalate-based plasticizers accounted for 92% of the global plasticizer market by the 20th century (Mustafizur Rahman and Christopher S. Brazel "The plasticizer market: an assessment of traditional plasticizers and research trends to meet new challenges" Progress in Polymer Science 2004, 29, 1223-1248), mainly used to impart flexibility, durability, and cold resistance to polyvinyl chloride (hereinafter referred to as PVC) and to improve processability by lowering the viscosity during melting. From hard products such as pipes to soft products that are soft and stretchable and can be used for food packaging, blood bags, flooring, etc. .
[8]
However, in spite of the compatibility with PVC of phthalate-based plasticizers and excellent softness imparting properties, recently, when PVC products containing phthalate-based plasticizers are used in real life, little by little leakage to the outside of the product causes endocrine disorders (environmental hormones) estimated substances and levels of heavy metals. Controversy has arisen that it may act as a carcinogen (NR Janjua et al. "Systemic Uptake of Diethyl Phthalate, Dibutyl Phthalate, and Butyl Paraben Following Whole-body Topical Application and Reproductive and Thyroid Hormone Levels in Humans" Environmental Science and Technology 2008, 42, 7522-7527). In particular, in the 1960s, after a report was announced that di-(2-ethylhexyl) phthalate (DEHP), the most used among phthalate-based plasticizers in the United States, leaked outside PVC products, in the 1990s, environmental hormones Global environmental regulations, including various studies on the harmfulness of phthalate-based plasticizers to the human body, began to be made with increased interest in
[9]
In order to respond to environmental hormone problems and environmental regulations caused by the leakage of phthalate-based plasticizers, particularly di(2-ethylhexyl) phthalate, many researchers have In addition to developing a phthalate-based plasticizer or a phthalate-based plasticizer that can replace di(2-ethylhexyl) phthalate that is phthalate-based, but the outflow of the plasticizer is suppressed and can be used for industrial purposes, as well as the leakage of phthalate-based plasticizer Research is being carried out to develop a spill control technology that can significantly reduce human risk by suppressing the chemical and also meet environmental standards.
[10]
As such, as an ester-based plasticizer, materials free from environmental problems that can replace di(2-ethylhexyl) phthalate, which have environmental problems, are being actively developed. As well as research, research on facilities for manufacturing such a plasticizer is being actively conducted, and a more efficient, economical and simple process design is required in terms of process design.
[11]
On the other hand, the process of manufacturing the above ester-based plasticizer is a batch process applied in most industrial sites, and as a batch process, the invention relates to a gas-liquid separation system for reflux of unreacted substances and efficient removal of side reactants in the reactor (Korea Patent Publication) Publication No. 10-2019-0027622) and an invention regarding a system that integrates facilities of the first direct esterification reaction and the second transesterification reaction in order to simplify the facilities of the batch process (Korean Patent Application Laid-Open No. 10-2019 -0027623) are being introduced.
[12]
However, in the case of the batch process introduced in these inventions, the purpose is to improve the reaction through simplification of equipment or change of equipment. difficult to do Accordingly, there is a need to develop a process capable of optimizing the reaction through modification and control of process conditions.
[13]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[14]
An object of the present invention is to provide a method for producing a diester-based material in which process efficiency is improved by improving productivity by improving the reaction rate through control of reaction conditions in manufacturing a diester-based material, and reducing energy consumption.
[15]
means of solving the problem
[16]
According to an embodiment of the present invention in order to solve the above problems, the steps of preparing a raw material mixture by mixing a dicarboxylic acid and a mono-alcohol having 4 to 10 carbon atoms (S1); and a step (S2) of reacting the raw material mixture under a catalyst to obtain a product mixture including a diester-based material and product water (S2), wherein at least one of the following conditions A to C is applied. In the above conditions A to C, the division of the initial reaction and the late reaction is provided based on the reaction control point, which is a time point selected from when the conversion rate of the reaction is 10% to 80%.
[17]
The conditions A to C are as follows.
[18]
Condition A: the reactor temperature at the initial stage of the reaction is set to 150 to 220 °C, the reactor temperature at the late stage of the reaction is set to 180 to 250 °C, but the late temperature is set to be higher than the initial temperature;
[19]
Condition B: 40 to 90% by weight is added at the beginning of the reaction, and 10 to 60% by weight is added at the end of the reaction with respect to the total amount of monoalcohol, and
[20]
Condition C: 10 to 50% by volume was added at the beginning of the reaction, and 50 to 90% by volume was added at the end of the reaction with respect to the total amount of inert gas.
[21]
Effects of the Invention
[22]
The method for producing a diester-based material according to the present invention can provide a method for producing a diester-based material with high efficiency by increasing the reaction rate, so productivity can be improved, and energy consumption can be improved to reduce process costs. have.
[23]
Modes for carrying out the invention
[24]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention. The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of ​​the present invention.
[25]
[26]
Definition of Terms
[27]
The term "composition" as used herein includes reaction products and decomposition products formed from materials of the composition, as well as mixtures of materials comprising the composition.
[28]
The term "straight vinyl chloride polymer" as used herein, as one of the types of vinyl chloride polymer, may mean polymerized through suspension polymerization or bulk polymerization, and has a size of tens to hundreds of micrometers. It refers to a polymer having a form of porous particles with a large amount of pores distributed, no cohesiveness, and excellent flowability.
[29]
The term "paste vinyl chloride polymer" as used herein, as one of the types of vinyl chloride polymer, may mean polymerized through microsuspension polymerization, microseed polymerization, or emulsion polymerization, etc., It refers to a polymer having a size of several thousand nanometers and has poor flowability as fine, dense void-free particles.
[30]
The prefix "iso-" as used herein generally means that a methyl branch is bonded to the end of the alkyl group, but unless otherwise defined in the present specification, in the present specification, a methyl group or an ethyl group is attached to the main chain of the alkyl group. refers to an alkyl group bonded to a branched chain, and is used to encompass an alkyl group in which a methyl group or an ethyl group is bonded to the main chain as a branched chain, including those bonded to a terminal, and includes the meaning of a mixture of these alkyl groups.
[31]
The terms 'comprising', 'having' and their derivatives are not intended to exclude the presence of any additional component, step or procedure, whether or not they are specifically disclosed. For the avoidance of any doubt, all compositions claimed through use of the term 'comprising', unless stated to the contrary, contain any additional additives, adjuvants, or compounds, whether polymeric or otherwise. may include In contrast, the term 'consisting essentially of' excludes from the scope of any subsequent description any other component, step or procedure, except as is not essential to operability. The term 'consisting of' excludes any component, step or procedure not specifically described or listed.
[32]
[33]
Method for producing diester-based material
[34]
According to an embodiment of the present invention, dicarboxylic acid and a mono-alcohol having 4 to 10 carbon atoms are mixed to prepare a raw material mixture (S1); and a step (S2) of reacting the raw material mixture under a catalyst to obtain a product mixture including a diester-based material and product water (S2), wherein at least one of the following conditions A to C is applied. In the above conditions A to C, the division of the initial reaction and the late reaction is provided based on the reaction control point, which is a time point selected from when the conversion rate of the reaction is 10% to 80%.
[35]
The conditions A to C are as follows.
[36]
Condition A: the reactor temperature at the initial stage of the reaction is set to 150 to 220 °C, the reactor temperature at the late stage of the reaction is set to 180 to 250 °C, but the late temperature is set to be higher than the initial temperature;
[37]
Condition B: 40 to 90% by weight is added at the beginning of the reaction, and 10 to 60% by weight is added at the end of the reaction with respect to the total amount of monoalcohol, and
[38]
Condition C: 10 to 50% by volume was added at the beginning of the reaction, and 50 to 90% by volume was added at the end of the reaction with respect to the total amount of inert gas.
[39]
[40]
Raw material mixture preparation step (S1)
[41]
The manufacturing method according to an embodiment of the present invention starts from preparing a raw material mixture, wherein the raw material mixture includes dicarboxylic acid and a mono-alcohol having 4 to 10 carbon atoms, and in some cases, the dicarboxylic acid and mono-alcohol. One type of alcohol may be used, but a mixture of two or more types may be used.
[42]
The raw material mixture is preferably introduced into the reactor in a state of mixing as uniformly as possible through mixing before being introduced into the reactor, rather than being directly introduced into the reactor in which the reaction is performed. It is not excluded that dicarboxylic acid and mono-alcohol are directly introduced as a raw material mixture into the reactor, but in the case of mixing in advance and inputting the raw material mixture in the form of a raw material mixture, in particular, preheat the raw material mixture in advance, but react with sufficient preheating through waste heat utilization. can proceed with ease. In addition, in this case, the reaction catalyst is generally separated and introduced into the reactor. In this case, the reaction catalyst is preheated and then brought into contact with the raw material mixture, thereby preventing side reactions that occur when the temperature is raised from the beginning together with the catalyst.
[43]
The dicarboxylic acid contained in the raw material mixture is, for example, isophthalic acid, terephthalic acid, succinic acid, adipic acid, cyclohexane 1,2-dicarboxylic acid, cyclohexane 1,3-dicarboxylic acid and cyclohexane 1 It may include at least one selected from the group consisting of ,4-dicarboxylic acid.
[44]
In addition, the mono-alcohol may have 4 to 10 carbon atoms, preferably 5 to 9 carbon atoms, and more preferably 6 to 9 carbon atoms. For example, the mono alcohol is n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, n-octanol, 2-ethyl It may include one or more selected from the group consisting of hexanol, n-nonanol, isononanol, decanol, isodecanol and 2-propylheptanol, and a mixture of two or more alcohols may be used, It is also possible to prepare a diester-based material as a composition using a mixture of regioisomers.
[45]
[46]
esterification reaction step (S2)
[47]
In the manufacturing method according to an embodiment of the present invention, a step of preparing a raw material mixture and subjecting it to an esterification reaction under specific conditions to obtain a diester-based material and product water is subsequently performed.
[48]
In the esterification reaction, more specifically, a catalyst may be added to a raw material mixture, which is a mixture of dicarboxylic acid and monoalcohol, and reacted under a nitrogen atmosphere.
[49]
[50]
According to an embodiment of the present invention, in the esterification reaction, a specific time point is designated as a reaction control point, the initial reaction and the late reaction are divided based on this reaction control point, and conditions A to C are applied, and the reaction control point is the reaction It is selected when the conversion is between 10% and 80%, and the conversion range that can be selected as the reaction control point may be preferably 15%, more preferably 20%, even more preferably 25% as the lower limit, and as the upper limit, Preferably 75%, more preferably 70%, even more preferably 60%. When the reaction control point is selected as a time point lower than the conversion rate of 10%, the energy consumption may be large even though the improvement in the reaction rate is not large, so that it is not significantly different from the case where the condition is not applied, and compared to the time point when the conversion rate is 80% Selecting the reaction control point after the reaction has progressed rather becomes a factor that worsens the reaction rate, and the meaning of changing the reaction conditions may be faded.
[51]
That is, in order to realize the effects of both improvement of reaction rate and improvement of energy consumption, it may be preferable that the reaction control point is selected within the above range, and the initial reaction means until the reaction control point passes, and the reaction control point is late. may mean a conversion rate after the reaction control point has passed.
[52]
According to an embodiment of the present invention, the controlled conditions A to C are as follows.
[53]
Condition A: the reactor temperature at the beginning of the reaction is set to 150 to 220 °C, and the reactor temperature at the late stage of the reaction is set to 180 to 250 °C;
[54]
Condition B: 40 to 90% by weight is added at the beginning of the reaction, and 10 to 60% by weight is added at the end of the reaction with respect to the total amount of monoalcohol, and
[55]
Condition C: 10 to 50% by volume was added at the beginning of the reaction, and 50 to 90% by volume was added at the end of the reaction with respect to the total amount of inert gas.
[56]
In the case of the conditions A to C, after the reaction raw material is added and the catalyst is added, the condition A may be a set value of the reactor, and the conditions B and C may be to control the input amount.
[57]
[58]
On the other hand, the manufacturing method is carried out in a reactor, wherein the reactor is a vaporized material connected to the upper part of the reactor, and a stripper for gas-liquid separation of unreacted mono-alcohol and product water, and a condenser for condensing and separating the gas discharged from the stripper and a decanter, and may be a component of a reaction unit, and the reaction of step S2 may be performed in this reaction unit.
[59]
Specifically, when the raw material mixture of dicarboxylic acid and mono-alcohol is introduced into the reactor to start the reaction, the reaction temperature is higher than the boiling point of the mono-alcohol, so vaporization occurs, and water (product water) is produced as a reaction by-product together with the diester-based material. As it is formed, vaporization takes place. As the esterification reaction is an equilibrium reaction, the product water must be continuously removed and the vaporized unreacted mono-alcohol must be returned back to the reactor for the reaction to proceed smoothly. Accordingly, the mixed gas of the product water and the unreacted mono-alcohol is separated through a stripper, a condenser and a decanter, the mono-alcohol is recycled back to the reactor, and the product water can be discharged to the outside of the system or used as process water in the process.
[60]
Hereinafter, in the reaction environment as described above, it will be described whether it is effective to control which conditions and how to improve the energy consumption and the reaction rate.
[61]
[62]
control of reaction temperature
[63]
According to an embodiment of the present invention, condition A among the controlled conditions is to change the temperature value of the reactor. The reaction is performed by setting the set value of the reactor temperature in the range of 150 to 220 ° C. during the initial reaction, and then changing the temperature setting of the reactor to a temperature of 180 to 250 ° C. at the time when the reaction control point passes. In this case, the reactor temperature at the late stage of the reaction is set to be higher than the reactor temperature at the beginning of the reaction.
[64]
The set temperature of the reactor is not necessarily the same as the reactant therein, and even if the temperature of the reactor is set to 200 ° C, the reactant may be a process in which the temperature is raised toward 200 ° C. However, it may be a lower value due to reflux or the like.
[65]
When the temperature of the reactor is initially controlled between 150 and 220°C, the initial reflux of the mono-alcohol can be suppressed, unnecessary heat loss can be prevented, and when set to a temperature lower than 150°C, the reaction rate is too slow, The side reaction rate increases, and if the temperature is set higher than 220°C, unnecessary heat loss occurs and the reactants may be thermally damaged. have.
[66]
After the reaction control point has passed, since a certain level of reaction is performed, the temperature must be raised to an appropriate level in order to maximize the reaction conversion, in this case, it is necessary to set a value between 180 and 250 °C. When the temperature is lower than 180 ℃, the conversion rate cannot be achieved up to 99%, so the purity of the product cannot be met. Alternatively, the occurrence of scale due to the catalyst is high, and furthermore, the time required for the conversion to exceed 99% may be long or impossible to achieve due to an increase in the amount of reflux at the end of the reaction.
[67]
Accordingly, as described above, when the reactor set temperature is selected as the control condition, the set value of the initial reactor temperature is selected from 150 to 220 ° C., and the late reaction is changed to a value between 180 and 250 ° C. It can be effective in preventing problems in advance and achieving improvement in energy consumption, and preferably, the reactor temperature at the initial stage of the reaction can be set to 160 to 190°C, and the reactor temperature at the later stage of the reaction can be set to 200 to 250°C.
[68]
[69]
Controlling the amount of alcohol used
[70]
According to an embodiment of the present invention, condition B among the controlled conditions is the divided dose of alcohol. The amount of alcohol input to the reactor or mixer at the beginning of the reaction is 40 to 90 wt% with respect to the total input amount, and 10 to 60 wt%, which is the remainder of the amount added at the beginning of the reaction from the total input amount at the end of the reaction after the reaction control point, is added will be. At this time, the alcohol can be added in batches at the start of the reaction based on the reaction control point, continuous input over all time points, or divided input within the initial input amount of the reaction. The same method may be applied, and the input method may be independently applied to each of the initial and late stages of the reaction.
[71]
In general, the alcohol may be used within the range of 150 to 500 mol%, 200 to 400 mol%, 200 to 350 mol%, 250 to 400 mol%, or 270 to 330 mol% based on 100 mol% of the dicarboxylic acid. . With an amount selected within the above range to be added as 100 wt%, 40 to 90 wt% may be added at the initial stage of the reaction and the remainder may be added at the end of the reaction.
[72]
When the mono-alcohol is added, if less than 40% by weight of the total amount is added at the beginning of the reaction, the reaction rate may not be improved at all, and only the energy consumption may increase. That is, it means that more than 60% by weight is added at the end of the reaction, and since it means that the amount of alcohol added to the reactant after the temperature has already been raised exceeds 60% by weight, the reaction is suppressed in terms of heat of reaction phenomena may occur. In addition, since the reaction does not proceed predominantly in the forward reaction and water is not removed due to an increase in the amount of monoalcohol that forms an azeotrope with the remaining water, deactivation of the catalyst or a prevailing reverse reaction situation may occur during the reaction, so the reaction rate is slowed and energy consumption can be large.
[73]
In addition, when an amount greater than 90% by weight is added at the initial stage of the reaction, energy consumption may rapidly increase. If a large amount of mono-alcohol is present in the reactor, the reaction rate is expected to be fast due to the forward reaction dominance effect.
[74]
Accordingly, when the mono-alcohol input amount is selected as the control condition, the amount of alcohol input at the beginning of the reaction is set to 40 to 90 wt% with respect to the total input amount, and the balance of the total amount added at the end of the reaction is set to 10 to 60 wt% This may be effective in reducing energy consumption and improving reaction rate. In addition, in the case of controlling the amount of alcohol input within this range, in terms of controlling the input of the excess amount added more than the equivalent of the alcohol input amount, unlike the theoretical prediction, the diester-based material and Reactivity improvement can be expected by improving the reaction contact area of ​​the mono-alcohol, and preferably, the amount of alcohol added at the beginning of the reaction is set to 40 to 80% by weight based on the total input amount, and set to 20 to 60% by weight at the end of the reaction. and more preferably 40 to 70% by weight at the beginning of the reaction, and 30 to 60% by weight at the end of the reaction.
[75]
[76]
Inert gas dosage condition control
[77]
According to an embodiment of the present invention, condition C among the controlled conditions is the divided input amount of the inert gas. The inert gas input to the reactor during the initial reaction is 10 to 50 volume % of the total input amount, and the inert gas input amount in the late reaction period, that is, after the reaction control point, is 50 to 90 volume %, which is the remainder excluding the initial input amount from the total input amount. At this time, the input of the inert gas is based on the reaction control point, when the reaction is started, the reactant is put in a batch, or it is continuously added over all time points, or it is added by dividing the input within the initial input amount of the reaction. In addition, the same method may be applied to the latter stage of the reaction, and the input method may be independently applied to each of the initial stage and the late stage of the reaction.
[78]
The inert gas may be at least one selected from the group consisting of nitrogen, argon and helium, which serves to control the reflux amount for discharging the product water. % may cause a problem of energy consumption due to an increase in reflux, and if it is less than 10% by weight, it may be difficult to discharge the generated water, resulting in a problem of reaction delay. Accordingly, when the inert gas input amount is controlled within the above range, reactivity and productivity can be improved, and preferably 10 to 40 vol% of the total input is added at the beginning of the reaction, and 60 to 90 vol% is added at the end of the reaction can do.
[79]
[80]
According to an embodiment of the present invention, at least one of the conditions A to C is applied in step S2 of the manufacturing method. The problem when each condition is not applied in each of the conditions A to C may mean that each condition is not satisfied when all of A to C are not applied. For example, when condition A is applied, the condition The problem may be partially offset when B and C do not apply, and the same may be true for the case where condition B applies and the remainder does not apply, and the case where condition C applies and the remainder does not.
[81]
When the above-mentioned reactor temperature (condition A), mono-alcohol input amount (condition B), and inert gas input amount (condition C) are controlled based on a specific conversion rate in combination or independently of each other, even if only one case is applied, the existing It is possible to expect an epoch-making effect to improve contrast reactivity, and if two or more or all of the above conditions are applied by separating the reaction in the early and late stages based on a specific conversion rate, it is possible to produce a diester-based material with optimal efficiency. have.
[82]
That is, preferably, in terms of energy consumption improvement and reaction rate improvement, two or more of Conditions A to C may be applied, and among these, Conditions A and B may be more preferably applied, and most preferably Conditions A to C can all be applied.
[83]
The manufacturing method according to an embodiment of the present invention controls the reaction conditions such as the reactor temperature, the amount and time of input of the mono-alcohol, the amount and time of the inert gas as the reaction conditions as the reaction conditions, based on the conversion rate of the reaction. Reactivity and productivity can be improved by designing the reaction conditions, and thus energy consumption or product purity and reaction time can reach an excellent level.
[84]
In this way, if the reaction conditions are controlled in a complex way, the effects such as control of the amount of reflux in consideration of energy consumption, improvement of reactivity through improvement of reaction rate and temperature increase rate, and improvement of product quality through smooth discharge of generated water are all optimized. can be obtained
[85]
[86]
On the other hand, the catalyst is, for example, sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, para-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, an acid catalyst such as alkyl sulfuric acid, aluminum lactate, lithium fluoride, potassium chloride, cesium chloride, Metal salts such as calcium chloride, iron chloride, aluminum phosphate, metal oxides such as heteropolyacid, natural/synthetic zeolites, cation and anion exchange resins, tetraalkyl titanate and organic metals such as polymers thereof may be at least one selected from the group consisting of . As a specific example, the catalyst may be tetraalkyl titanate.
[87]
The amount of catalyst used may vary depending on the type, for example, in the case of a homogeneous catalyst, 0.01 to 5% by weight, 0.01 to 3% by weight, 1 to 5% by weight, or 2 to 4% by weight based on 100% by weight of the total reactants. and in the case of a heterogeneous catalyst, it may be in the range of 5 to 200 wt%, 5 to 100 wt%, 20 to 200 wt%, or 20 to 150 wt% of the total amount of reactants.
[88]
[89]
Neutralization step of the product mixture (S3)
[90]
According to an embodiment of the present invention, the manufacturing method may further include a step (S3) of neutralizing by adding a neutralizing agent including alkali metal hydroxide and water to the product mixture obtained in step S2 (S3).
[91]
As the alkali metal hydroxide used for the neutralization, sodium hydroxide or potassium hydroxide may be applied, and 0.1 to 10% of the alkali metal hydroxide may be dissolved in water and applied in an aqueous solution state. The neutralization step may be a process of inactivating the catalyst remaining in the product mixture by adding the above aqueous alkali metal hydroxide solution, and at this time, a salt is generated and removed as a solid product, and an organic layer containing a diester-based material and water are included. It can be separated and discharged into a layer-separated aqueous layer.
[92]
The product mixture that has undergone the neutralization step is discharged as an organic layer containing a diester-based material, and the discharged organic layer undergoes a predetermined purification process to produce a diester-based material, and the aqueous layer is monolithic through a wastewater treatment system The alcohol is recovered and the water can be recycled to process water or the like.
[93]
[94]
Plasticizer composition and resin composition
[95]
According to another embodiment of the present invention, there is provided a plasticizer composition comprising a diester-based material prepared according to the above-described manufacturing method.
[96]
The plasticizer composition may include commonly used components, and is not particularly limited thereto.
[97]
The plasticizer composition includes the above-mentioned epoxidized alkyl ester composition, and the plasticizer composition including the epoxidized alkyl ester composition may be used alone, or a mixed plasticizer may be applied by containing a secondary plasticizer in addition.
[98]
The secondary plasticizer is a terephthalate-based material, an isophthalate-based material, a phthalate-based material, a cyclohexane 1,4-diester-based material, a cyclohexane 1,2-diester-based material, a cyclohexane 1,3-diester-based material Substances, trimellitate-based materials, citrate-based materials, epoxidized oils, succinate-based materials, benzoate-based materials, glycol-based materials, etc. may be applied, and a mixture thereof may be applied as a secondary plasticizer.
[99]
Specifically, all of the materials listed as secondary plasticizers are materials having an ester group, and the alkyl group bonded to the ester group includes n-butyl group, isobutyl group, n-pentyl group, isopentyl group, n-hexyl group, iso A hexyl group, n-heptyl group, isoheptyl group, 2-ethylhexyl group, octyl group, n-nonyl group, isononyl group, 2-propylheptyl group, decyl group, isodecyl group, etc. may be applied.
[100]
[101]
According to another embodiment of the present invention, there is provided a resin composition comprising the plasticizer composition and the resin.
[102]
As the resin, a resin known in the art may be used. For example, at least one selected from the group consisting of straight vinyl chloride polymer, paste vinyl chloride polymer, ethylene vinyl acetate copolymer, ethylene polymer, propylene polymer, polyketone, polystyrene, polyurethane, natural rubber, synthetic rubber, and thermoplastic elastomer Mixtures and the like may be used, but the present invention is not limited thereto.
[103]
The plasticizer composition may be included in an amount of 5 to 150 parts by weight, preferably 5 to 130 parts by weight, or 10 to 120 parts by weight based on 100 parts by weight of the resin.
[104]
In general, the resin in which the plasticizer composition is used may be manufactured into a resin product through melt processing or plastisol processing, and the melt processing resin and the plastisol processing resin may be produced differently according to each polymerization method.
[105]
For example, when a vinyl chloride polymer is used for melt processing, solid resin particles with a large average particle diameter are used because it is prepared by suspension polymerization, etc., and this vinyl chloride polymer is called a straight vinyl chloride polymer, and is used for plastisol processing. In this case, a resin in a sol state is used as a fine resin particle prepared by emulsion polymerization, etc., and such a vinyl chloride polymer is called a paste vinyl chloride resin.
[106]
In this case, in the case of the straight vinyl chloride polymer, the plasticizer is preferably included in the range of 5 to 80 parts by weight based on 100 parts by weight of the polymer, and in the case of the paste vinyl chloride polymer, in the range of 40 to 120 parts by weight based on 100 parts by weight of the polymer. It is preferable to include in
[107]
The resin composition may further include a filler. The filler may be 0 to 300 parts by weight, preferably 50 to 200 parts by weight, more preferably 100 to 200 parts by weight based on 100 parts by weight of the resin.
[108]
As the filler, any filler known in the art may be used, and the filler is not particularly limited. For example, it may be a mixture of one or more selected from silica, magnesium carbonate, calcium carbonate, coal, talc, magnesium hydroxide, titanium dioxide, magnesium oxide, calcium hydroxide, aluminum hydroxide, aluminum silicate, magnesium silicate and barium sulfate.
[109]
In addition, the resin composition may further include other additives such as a stabilizer, if necessary. Other additives such as the stabilizer may be, for example, 0 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the resin.
[110]
The stabilizer may include, for example, a calcium-zinc (Ca-Zn-based) stabilizer or a barium-zinc-based (Ba-Zn-based) stabilizer such as a calcium-zinc complex stearate salt, but is not particularly limited thereto. it is not
[111]
The resin composition may be applied to both melt processing and plastisol processing as described above, for example, melt processing may include calendering processing, extrusion processing, or injection processing, and plastisol processing may include coating processing, etc. This can be applied.
[112]
[113]
Example
[114]
Hereinafter, examples will be given to describe the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described in detail below. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.
[115]
[116]
(1) Application of condition A
[117]
Examples, Reference Examples and Comparative Examples
[118]
After premixing 498 g of isophthalic acid as dicarboxylic acid and 1172 g of 2-ethylhexanol as mono alcohol, it was put into a 3.0 L reactor, and tetrabutyl titanate was added as a catalyst to carry out the reaction, each Example and Standard Example And the reaction conditions of Comparative Examples are as described in Table 1 below.
[119]
[Table 1]
　 Reaction temperature (℃) Alcohol input (wt%) Inert gas input (vol.%) Conversion rate (%)
Early review
Example 1-1 160 250 100 100 10
Example 1-2 180 220 100 100 20
Examples 1-3 200 220 100 100 20
Examples 1-4 200 220 100 100 80
standard example 220 220 100 100 -
Comparative Example 1-1 230 250 100 100 80
Comparative Example 1-2 230 250 100 100 10
Comparative Example 1-3 140 220 100 100 10
Comparative Example 1-4 140 220 100 100 80
[120]
[121]
Experimental Example 1
[122]
For the Examples, Reference Examples and Comparative Examples, the degree of energy improvement and the degree of reactivity improvement were indexed and displayed, and the index was indexed according to the following measurement standards, and the results are shown in Table 2 below.
[123]
1) Energy improvement index : Based on the standard example, when the energy consumption of the standard example is 0, it is divided into steps from -5 to 10, where -3 indicates a large amount of energy consumption, and as it goes to 10, energy consumption is small and the degree of improvement is large. did. The energy consumption is the sum of the energy consumed to put the alcohol refluxed to the upper part of the reactor back into the reactor and the energy consumed to apply the heat of reaction. The flow rate was measured and evaluated, and the heat of reaction was measured as the amount of steam required to set the reactor temperature.
[124]
2) Reactivity improvement index : When the reactivity of the reference example is 5 based on the reference example, it is divided into steps from 1 to 10 and the reactivity is smaller than that of the reference example (the reaction rate is slow, and it takes time to achieve 99% conversion rate) When it takes a long time), it is expressed close to 1, and when the reactivity is excellent (the reaction rate is fast and it takes a long time to achieve the conversion rate of 99%) It is expressed close to 10, and it takes the time to achieve the conversion rate of 99% It was evaluated based on the reaction time.
[125]
[Table 2]
　 Energy improvement index Responsiveness improvement index
Example 1-1 5 4
Example 1-2 7 5
Examples 1-3 5 5
Examples 1-4 4 6
standard example 0 5
Comparative Example 1-1 -3 5
Comparative Example 1-2 -5 4
Comparative Example 1-3 0 2
Comparative Example 1-4 - -
[126]
Referring to Table 2, in the case of Examples 1-1 to 1-4, in which the reactor temperature in the initial and late stages of the reaction was set within the scope of the present invention and the temperature was increased, it was found that the energy improvement and the reactivity improvement were excellent. can be checked On the other hand, in the case of Comparative Example 1-1 in which the reactor temperature at the initial stage of the reaction was set too high and the conversion rate was maintained up to 80%, it was confirmed that the energy improvement was worse than that of the reference example in which the reaction was performed without changing the temperature, and the conversion rate was 10% In the case of Comparative Example 1-2, which was changed in , it can be seen that the initial initial reactor temperature was too high, so that the energy consumption was further deteriorated and the reactivity was also deteriorated. Furthermore, in the case of Comparative Example 1-3, in which the reactor temperature at the initial stage of the reaction was set too low, it was confirmed that the reactivity was at a poor level, and when the temperature was changed after maintaining this low reactor temperature up to a conversion rate of 80%, the reaction was performed up to a conversion rate of 99%. This was not progressed, so it was not possible to measure energy improvement and reactivity improvement.
[127]
Through this, it can be seen that energy improvement and reactivity improvement can be achieved at the same time when the reaction is performed by setting the reactor temperature in the initial and late stages of the reaction within the scope of the present invention and increasing the temperature.
[128]
[129]
(2) Application of condition B
[130]
Examples, Reference Examples and Comparative Examples
[131]
After premixing 498 g of isophthalic acid as dicarboxylic acid and 1172 g of 2-ethylhexanol as mono alcohol (total amount added in the initial and late stages), it was put into a 3.0 L reactor, and tetrabutyl titanate was added as a catalyst to proceed with the reaction. , Reaction conditions of each Example, Reference Example and Comparative Example are as described in Table 3 below.
[132]
[Table 3]
　 Reaction temperature (℃) Alcohol input (wt%) Inert gas input (vol.%) Conversion rate (%)
Early review
Example 2-1 220 40 60 100 10
Example 2-2 220 70 30 100 55
Example 2-3 220 90 10 100 55
Example 2-4 220 90 10 100 80
Example 2-5 220 70 30 100 10
Example 2-6 220 70 30 100 80
standard example 220 100 - 100 -
Comparative Example 2-1 220 95 5 100 80
Comparative Example 2-2 220 95 5 100 10
Comparative Example 2-3 220 20 80 100 10
Comparative Example 2-4 220 20 80 100 80
Comparative Example 2-5 220 70 30 100 5
Comparative Example 2-6 220 70 30 100 90
[133]
[134]
Experimental Example 2
[135]
For the Examples, Reference Examples, and Comparative Examples, the degree of energy improvement and the degree of reactivity improvement were indexed and displayed, and the results were measured and indexed by the same standards and methods as in Experimental Example 1, and the results are shown in Table 4 below.
[136]
[Table 4]
　 Energy improvement index Responsiveness improvement index
Example 2-1 8 7
Example 2-2 8 8
Example 2-3 2 7
Example 2-4 3 6
Example 2-5 4 6
Example 2-6 9 7
standard example 0 5
Comparative Example 2-1 2 5
Comparative Example 2-2 One 5
Comparative Example 2-3 3 3
Comparative Example 2-4 - -
Comparative Example 2-5 One 6
Comparative Example 2-6 3 3
[137]
Referring to Table 4, in the case of Examples 2-1 to 2-6, in which the total amount of alcohol was well divided and added in the initial and late stages of the reaction, it can be confirmed that the energy improvement and the reactivity improvement degree are very excellent, whereas the comparative example In the case of 2-1 and 2-2, it can be confirmed that the degree of energy improvement and reactivity improvement are very insignificant due to the excessive injection of alcohol at the beginning, and this is the same even if the divided injection timing is changed, and in the case of Comparative Example 2-3 It can be confirmed that the degree of energy improvement is negligible while the reactivity is rather deteriorated by injecting too little alcohol in the initial stage, and Comparative Example 2-4 is a time point at which the divided input is changed in Comparative Example 2-3 to a time point having a conversion rate of 80%. In this case, the reaction did not proceed and it was at a level that could not be measured. In addition, when comparing Examples 2-5 and Comparative Examples 2-5, it was found that there was a difference of three steps in the degree of energy improvement despite a difference of only 5% in the conversion rate. It is confirmed, and when comparing Example 2-6 and Comparative Example 2-6, the degree of energy improvement and the degree of improvement in reactivity are significantly different even though all conditions are the same except for applying at the time when the conversion rate exceeds 80% and is 90% is confirmed to be present.
[138]
Through this, it can be confirmed that energy improvement and reactivity improvement can be achieved at the same time when alcohol is divided in an appropriate amount in the initial and late stages of the reaction.
[139]
[140]
(3) Application of condition C
[141]
Examples, Reference Examples and Comparative Examples
[142]
After premixing 498 g of isophthalic acid as a dicarboxylic acid and 1172 g of 2-ethylhexanol as a mono alcohol, it was put into a 3.0 L reactor, and tetrabutyl titanate was added as a catalyst to carry out the reaction, each Example and Standard Example And the reaction conditions of Comparative Examples are as described in Table 5 below.
[143]
[Table 5]
　 Reaction temperature (℃) Inert gas input (vol.%) Alcohol input (wt%) Conversion rate (%)
Early review
Example 3-1 220 10 90 100 50
Example 3-2 220 30 70 100 50
Example 3-3 220 40 60 100 50
standard example 220 100 - 100 -
Comparative Example 3-1 220 70 30 100 50
[144]
[145]
Experimental Example 3
[146]
With respect to the Examples, Reference Examples and Comparative Examples, the degree of energy improvement and the degree of reactivity improvement were indexed and displayed, and the results were measured and indexed by the same standards and methods as in Experimental Example 1, and the results are shown in Table 6 below.
[147]
[Table 6]
　 Energy improvement index Responsiveness improvement index
Example 3-1 3 6
Example 3-2 2 6
Example 3-3 One 5
standard example 0 5
Comparative Example 3-1 -2 4
[148]
Referring to Table 6, in the case of Examples 3-1 to 3-3, in which the total amount of inert gas was well divided and added in the initial and late stages of the reaction, it can be confirmed that the degree of energy improvement and reactivity improvement is relatively excellent, whereas , in the case of Comparative Example 3-1, it can be seen that both the energy improvement and the reactivity deteriorated due to excessive input of the inert gas at the beginning. Through this, when the inert gas is divided in an appropriate amount in the initial and late stages of the reaction, energy It can be seen that the improvement and responsiveness improvement are achievable at the same time.
[149]
[150]
(4) Applying two or more conditions
[151]
Examples, Reference Examples and Comparative Examples
[152]
After premixing 498 g of isophthalic acid as dicarboxylic acid and 1172 g of 2-ethylhexanol as mono alcohol (total amount added in the initial and late stages), it was put into a 3.0 L reactor, and tetrabutyl titanate was added as a catalyst to proceed with the reaction. , Reaction conditions of each Example, Reference Example and Comparative Example are as described in Table 7 below.
[153]
[Table 7]
　 Reaction temperature (℃) Alcohol input (wt%) Inert gas input (vol.%) Conversion rate (%)
Early review Early review Early review
Example 4-1 220 220 70 30 10 90 10
Example 4-2 220 220 70 30 10 90 80
Example 4-3 180 220 100 - 10 90 20
Example 4-4 180 220 70 30 100 - 50
Example 4-5 220 220 70 30 10 90 55
Example 4-6 180 220 70 30 10 90 50
standard example 220 220 100 - 100 - -
Comparative Example 4-1 180 220 70 30 100 - 5
Comparative Example 4-2 180 220 70 30 100 - 90
[154]
[155]
Experimental Example 4
[156]
For the Examples, Reference Examples and Comparative Examples, the degree of energy improvement and the degree of reactivity improvement were indexed and displayed, and the results were measured and indexed in the same manner as in Experimental Example 1, and the results are shown in Table 8 below.
[157]
[Table 8]
　 Energy improvement index Responsiveness improvement index
Example 4-1 5 6
Example 4-2 10 7
Example 4-3 8 6
Example 4-4 9 8
Example 4-5 9 8
Example 4-6 10 10
standard example 0 5
Comparative Example 4-1 0 5
Comparative Example 4-2 3 One
[158]
Referring to Table 8, in Examples 4-1 to 4-6, when two or more of the reaction conditions A to C were applied, it was confirmed that the degree of energy and reactivity improvement improved significantly compared to the reference example. On the other hand, in the case of Comparative Examples 4-1 and 4-2, the reaction control point was not properly selected when the conditions were applied. showed an extreme difference and the degree of reactivity improvement was also the same, and it can be confirmed that when the reaction control point setting is wrong, it is the same as that in which the condition is not applied. It is confirmed that the reactivity is rather deteriorated and the energy improvement is at a negligible level. Through this, it can be confirmed that it is preferable to apply two or more of the conditions A to C in order to achieve the energy improvement and the reactivity improvement at the same time, Furthermore, it is confirmed that the difference in effect is very large according to the selection of the reaction control point.
Claims
[Claim 1]
preparing a raw material mixture by mixing a dicarboxylic acid and a mono-alcohol having 4 to 10 carbon atoms (S1); and a step (S2) of reacting the raw material mixture under a catalyst to obtain a product mixture including a diester-based material and product water (S2), wherein at least one of the following conditions A to C is applied. In the above conditions A to C, the division of the initial reaction and the late reaction is based on the reaction control point, which is a time point selected from when the conversion rate of the reaction is 10% to 80%: Condition A: Reactor at the beginning of the reaction The temperature is set to 150 to 220 ° C, the reactor temperature in the late reaction is set to 180 to 250 ° C, but the late temperature is set to be higher than the initial temperature, Condition B: 40 to 90 weight at the beginning of the reaction with respect to the total amount of monoalcohol % added, 10 to 60% by weight added at the end of the reaction, and Condition C: 10 to 50% by volume was added at the beginning of the reaction with respect to the total amount of inert gas added, and 50 to 90% by volume was added at the end of the reaction.
[Claim 2]
The method according to claim 1, wherein in step (S2), two or more of the conditions A to C are applied.
[Claim 3]
The method according to claim 1, wherein in the step (S2), the conditions A and B are applied.
[Claim 4]
The method according to claim 1, wherein in step (S2), all of the conditions A to C are applied.
[Claim 5]
The method according to claim 1, wherein the condition A is to set the reactor temperature at the initial stage of the reaction to 160 to 190 °C, and set the reactor temperature to 200 to 250 °C at the late stage of the reaction.
[Claim 6]
The method according to claim 1, wherein the condition B is 40 to 85% by weight at the beginning of the reaction, and 15 to 60% by weight at the end of the reaction, based on the total amount of monoalcohol.
[Claim 7]
The method according to claim 1, wherein in step (S1), the raw material mixture is preheated to a temperature of 150° C. or less in a non-catalytic state.
[Claim 8]
The method according to claim 1, further comprising the step of neutralizing alkali metal hydroxide and water by adding alkali metal hydroxide and water to the product mixture (S3), wherein the water includes the water produced in step (S2).
[Claim 9]
According to claim 1, wherein the dicarboxylic acid is isophthalic acid, terephthalic acid, succinic acid, adipic acid, cyclohexane 1,2-dicarboxylic acid, cyclohexane 1,3-dicarboxylic acid and cyclohexane 1,4- A method comprising at least one selected from the group consisting of dicarboxylic acids.
[Claim 10]
The method according to claim 1, wherein the mono-alcohol has 5 to 9 carbon atoms.