WO2017183877A1 - Plasticizer composition, and resin composition comprising same - Google Patents

Abstract

The present invention relates to a plasticizer composition and resin composition and a method for preparing same and can provide a plasticizer and a resin composition comprising same, wherein the plasticizer can improve physical properties, such as plasticizing efficiency, migration, tensile strength, elongation rate, stress migration, and light stability, which are required from a sheet prescription when the plasticizer is used as a plasticizer of a resin composition, by making improvement on bad physical properties which have occurred due to structural limits.

Description

Plasticizer composition and resin composition containing same

[Citations with Related Applications]

The present invention claims the benefit of priority based on Korean Patent Application No. 10-2016-0049081 filed on Apr. 22, 2016 and Korean Patent Application No. 10-2017-0047832 filed on Apr. 13, 2017, All content disclosed in the literature is included as part of this specification.

[Technical Field]

The present invention relates to a plasticizer composition and a resin composition comprising the same.

Typically, plasticizers react with alcohols to polycarboxylic acids such as phthalic acid and adipic acid to form the corresponding esters. In addition, in consideration of domestic and international regulations on phthalate-based plasticizers that are harmful to humans, research on plasticizer compositions that can replace phthalate-based plasticizers such as terephthalate-based, adipate-based, and other polymer-based plastics is being continued.

On the other hand, regardless of the plastisol industry such as flooring, wallpaper, soft and hard sheets, calendaring industry, extrusion / injection compound industry, there is an increasing demand for such eco-friendly products, quality characteristics, processability and In order to enhance productivity, appropriate plasticizers should be used in consideration of discoloration, transferability, and mechanical properties.

In these various fields of use, plasticizers, fillers, stabilizers, viscosity-reducing agents, dispersants, antifoaming agents, foaming agents, etc. are blended with PVC resins according to the characteristics required for different industries such as tensile strength, elongation, light resistance, transition, gelling or absorption rate. Done.

For example, among the plasticizer compositions applicable to PVC, when the most widely used di (2-ethylhexyl) terephthalate is applied, the hardness or sol viscosity is high and the absorption rate of the plasticizer is relatively high. It was slow, and the performance and stress performance were not good.

Although the hydrogenated material of di (2-ethylhexyl) terephthalate can be considered as an improvement, the plasticization efficiency is improved, while the migration efficiency and thermal stability are poor, and the production cost is increased due to the hydrogenation reaction. Having difficulty with

In order to overcome this problem, a mixed composition having better physical properties in terms of physical properties than the hydrogenated di (2-ethylhexyl) terephthalate di (2-ethylhexyl) 1,4-cyclohexanoate, or a novel derivative thereof There is a continuing need for the development of new composition products, and research on the development of products and uses as an environmentally friendly plasticizer for vinyl chloride-based resins continues.

The present invention is a plasticizer which can improve the physical properties such as plasticization efficiency, transferability, gelling properties, etc. required for the prescription of calendering sheet, plastisol and extrusion / injection compound as a plasticizer used in the resin composition and a manufacturing method thereof. And to provide a resin composition comprising them.

Specifically, the present invention can improve the performance by mixing a certain amount of citrate plasticizers in order to solve the problems of the migration and plasticization efficiency and economical efficiency of the hydrogenated di (2-ethylhexyl) terephthalate, In view of the fact that a mixed hydrogenation composition having two or more compositions is superior to a single hydrogenated material, two or more kinds of 1,4- are superior in terms of plasticizing efficiency and transferability, plasticizer absorption rate and stress transferability. A plasticizer composition comprising a cyclohexane diester-based material and a citrate-based material is provided.

According to an embodiment of the present invention to solve the above problems, two or more cyclohexane 1,4-diester material; And citrate-based material, wherein the weight ratio of the cyclohexane 1,4-diester-based material and the citrate-based material is 99: 1 to 1:99.

The citrate-based material may include any one selected from the group consisting of a hybrid alkyl substituted citrate-based material having 4 to 10 carbon atoms and a non-hybrid alkyl substituted citrate-based material having 4 to 10 carbon atoms.

The plasticizer composition may further comprise an epoxidized material.

The epoxidized material may further include 1 to 100 parts by weight based on 100 parts by weight of the mixed weight of the cyclohexane 1,4-diester-based material and the citrate-based material.

According to an embodiment of the present invention to solve the above problems, a step of producing a cyclohexane 1,4-diester material by hydrogenation of a terephthalate-based material in the presence of a metal catalyst; And blending the cyclohexane 1,4-diester-based material and the citrate-based material in a weight ratio of 99: 1 to 1:99 to obtain a plasticizer composition, wherein the terephthalate-based material is a mixture. Provided is a method of preparing a plasticizer composition.

According to an embodiment of the present invention to solve the above problems, 100 parts by weight of resin; And 5 to 150 parts by weight of the plasticizer composition of claim 1 is provided.

The resin may be at least one member selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomers.

When used in a resin composition, the plasticizer composition according to an embodiment of the present invention may provide excellent physical properties such as migration resistance and volatility, as well as excellent plasticization efficiency and tensile strength and elongation.

1 is an image showing the improvement of heat resistance according to the addition of the epoxidized material.

Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.

The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

As used herein, the term “butyl” refers to an alkyl group having 4 carbon atoms, and may be used as a term including both straight and branched chains, and may be, for example, n-butyl, isobutyl, or t-butyl. But preferably n-butyl or isobutyl.

As used herein, the terms “octyl” and “2-ethylhexyl” are alkyl groups having 8 carbon atoms, and may be used in combination with octyl as an abbreviation of 2-ethylhexyl, and in some cases, may refer to octyl which is a linear alkyl group. However, it can be interpreted to mean a branched alkyl group, 2-ethylhexyl.

Plasticizer composition

According to one embodiment of the present invention, it is possible to provide a plasticizer composition including two or more cyclohexane 1,4-diester-based materials. Specifically, the cyclohexane 1,4-diester material is 1 to 99% by weight, 20 to 99% by weight, 40 to 99% by weight, 50 to 95% by weight or 60 to 90% by weight based on the total weight of the composition The content selected in the range of the like may be applied.

The cyclohexane 1,4-diester material may be a compound represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1, R ₁ and R ₂ may be the same or different and may be selected from alkyl groups having 1 to 12 carbon atoms, respectively.

In the present specification, the cyclohexane 1,4-diester-based material may be named, for example, dialkyl cyclohexane-1,4-diester when R1 and R2 are the same, and alkyl (if R1 and R2 are different). R 1) alkyl (R 2) cyclohexane-1,4-diester.

The cyclohexane 1,4-diester-based material is butyl (2-ethylhexyl) cyclohexane-1,4-diester (1,4-BOCH), (2-ethylhexyl) isononyl cyclohexane- 1,4-diester (1,4-OINCH), butylisononyl cyclohexane-1,4-diester (1,4-BINCH), pentylisononyl cyclohexane-1,4-diester (1,4-PINCH), isononyl (2-propylheptyl) cyclohexane-1,4-diester (1,4-IPHCH), dibutyl cyclohexane-1,4-diester (1,4 -DBCH), dipentyl cyclohexane-1,4-diester (1,4-DPCH), diisononyl cyclohexane-1,4-diester (1,4-DINCH), di (2-ethyl Hexyl) cyclohexane-1,4-diester (1,4-DOCH), di (2-propylheptyl) cyclohexane-1,4-diester mixture of two or more selected from the group consisting of have.

More specifically, the cyclohexane 1,4-diester-based material may be a mixture of three cyclohexane 1,4-diester-based material, for example, di (2-ethylhexyl) cyclohex First mixture, diisononyl cyclo, hexane-1,4-diester, butyl (2-ethylhexyl) cyclohexane-1,4-diester and dibutyl cyclohexane-1,4-diester Second mixture of hexane-1,4-diester, butylisononyl cyclohexane-1,4-diester and dibutyl cyclohexane-1,4-diester, di (2-ethylhexyl 3) a mixture of cyclohexane-1,4-diester, (2-ethylhexyl) isononyl cyclohexane-1,4-diester and diisononyl cyclohexane-1,4-diester Or di (2-propylheptyl) cyclohexane-1,4-diester, isononyl (2-propylheptyl) cyclohexane-1,4-diester and diisononyl Quaternary mixture of chlorhexane-1,4-diester or dipentyl cyclohexane-1,4-diester, pentylisononyl cyclohexane-1,4-diester and diisononyl cyclohex It may be a fifth mixture in which stein-1,4-diester is mixed.

Specifically, in the case of the first to the fifth mixture, it may have a specific composition ratio, the first mixture is di (2-ethylhexyl) cyclohexane-1,4-diester 3.0 to 99.0 mol%; Butyl (2-ethylhexyl) cyclohexane-1,4-diester 0.5 to 96.5 mol% and dibutyl cyclohexane-1,4-diester 0.5 to 96.5 mol%; wherein the second mixture is Diisononyl cyclohexane-1,4-diester 3.0 to 99.0 mol%; 0.5 to 96.5 mol% of butyl isononyl cyclohexane-1,4-diester and 0.5 to 96.5 mol% of dibutyl cyclohexane-1,4-diester; wherein the third mixture is di (2- Ethylhexyl) cyclohexane-1,4-diester 3.0 to 99.0 mol%; 0.5 to 96.5 mol% of (2-ethylhexyl) isononyl cyclohexane-1,4-diester and 0.5 to 96.5 mol% of diisononyl cyclohexane-1,4-diester; and the fourth mixture Silver di (2-propylheptyl) cyclohexane-1,4-diester 3.0 to 99.0 mol%; 0.5 to 96.5 mol% of isononyl (2-propylheptyl) cyclohexane-1,4-diester and 0.5 to 96.5 mol% of diisononyl cyclohexane-1,4-diester; and the fifth mixture Silver dipentyl cyclohexane-1,4-diester 3.0 to 99.0 mol%; Pentylisononyl cyclohexane-1,4-diester 0.5 to 96.5 mol% and diisononyl cyclohexane-1,4-diester 0.5 to 96.5 mol%;

The composition ratio may be a mixture composition ratio produced by the esterification reaction, and may be an intended composition ratio by additionally mixing a specific compound, and the mixture composition ratio may be appropriately adjusted to suit desired physical properties.

As such, when the cyclohexane 1,4-diester-based material is a mixture of two or more kinds, the transition characteristics may be improved, the mechanical properties may be considerably excellent, and the plasticization efficiency may be increased.

In addition, according to an embodiment of the present invention, the plasticizer composition comprises a citrate-based material, the citrate-based material is a mixed alkyl substituted citrate-based material having 4 to 10 carbon atoms and a non-hybridized alkyl substitution having 4 to 10 carbon atoms It may include one or more compounds selected from the group consisting of citrate-based materials.

The mixed alkyl substituted citrate-based material having 4 to 10 carbon atoms may be, for example, 1,2-dibutyl 3- (2-ethylhexyl) 2-hydroxypropane-1,2,3-tricarboxylate, 1,3-dibutyl 2- (2-ethylhexyl) 2-hydroxypropane-1,2,3-tricarboxylate, 1-butyl 2,3-di (2-ethylhexyl) 2-hydroxypropane 4 and 8 carbon atoms, such as -1,2,3-tricarboxylate or 2-butyl 1,3-di (2-ethylhexyl) 2-hydroxypropane-1,2,3-tricarboxylate Citrate having a combination substituent of an alkyl group; 1,2-dipentyl 3-heptyl 2-hydroxypropane-1,2,3-tricarboxylate, 1,3-dipentyl 2-heptyl 2-hydroxypropane-1,2,3-tricarboxyl Rate, 1-pentyl 2,3-diheptyl 2-hydroxypropane-1,2,3-tricarboxylate, or 2-butyl 1,3-diheptyl 2-hydroxypropane-1,2,3- Citrate having a combination substituent of an alkyl group having 5 and 7 carbon atoms, such as tricarboxylate, and the like. In addition to this, a citrate having a combination substituent of two alkyl groups having 4 to 10 carbon atoms and having different carbon atoms may be selected. This may be applied, the alkyl group may be straight or branched chain.

In the non-hybrid alkyl substituted citrate-based material having 4 to 10 carbon atoms, the alkyl group having 4 to 10 carbon atoms may be linear or branched. For example, tributyl citrate (TBC) and tripentyl citrate (TPC). , Trihexyl citrate (THC), triheptyl citrate (THPC), tri (2-ethylhexyl) citrate (TOC), trinonyl citrate (TNC), tri (2-propylheptyl) citrate (TPHC) The butyl group to nonyl group may be applied to each of the structural isomers such as isobutyl group for butyl group, 2-ethylhexyl group for octyl group, isononyl group for 2-nonheptyl group, and 2-propylheptyl group. In this case, all of isodecyl may be included.

Although not limited thereto, non-hybrid alkyl substituted citrate materials having 4 to 10 carbon atoms may be preferred, compared to hybrid alkyl substituted citrate materials, and tributyl citrate and / or tri (2-ethylhexyl) sheets. The rate may be used at a slightly more frequent frequency.

On the other hand, trialkyl citrate, or dinalkyl-malkyl citrate, such as the hybrid or non-hybrid alkyl substituted citrate compound, may be applied. When the acetyl group is present in the citrate-based material, the physical properties of the plasticizer, particularly There exists a possibility that workability and gelling property may deteriorate with the fall of plasticization efficiency.

In other words, when the citrate-based material is an acetyl citrate compound in which an acetyl group is substituted for hydrogen of the remaining hydroxy group in addition to the three ester groups, the plasticization efficiency is lowered, the amount of plasticizer to be overcome is increased, and the product price is increased. Due to such problems, deterioration in various aspects such as marketability, economic feasibility and physical properties may be a problem.

Here, the cyclohexane 1,4-diester-based material and the citrate-based material in the plasticizer composition, the upper limit is 99: 1, 95: 5, 90:10, 85:15, 80:20, 70 by weight ratio : 30 or 60:40 and the lower limit may be 1:99, 5:95, 10:90, 15:85, 20:80, 30:70 or 40:60. Preferably 90:10 to 20:80, more preferably 90:10 to 30:70.

The plasticizer composition may include a cyclohexane 1,4-diester-based material and a citrate-based material, and may further include an epoxidized material.

In the case of the mixed plasticizer composition of the cyclohexane 1,4-diester-based material and the citrate-based material, among the various physical properties, the heat resistance may not be excellent, and the heat resistance may further include the epoxidized material. This can be supplemented.

The addition amount of the epoxidized material for supplementing the heat resistance property may be 1 to 100 parts by weight based on 100 parts by weight of the mixed weight of cyclohexane 1,4-diester-based material and citrate-based material, preferably 5 to 80 parts by weight Can be. When the epoxidation material is added in the above range, the heat resistance property can be compensated for. However, when the amount of the epoxidized material is added in excess, the cyclohexane 1,4-diester material and the citrate material are relatively low. There is a fear that the physical properties of the basic plasticizer is included, it is necessary to adjust the content.

The epoxidized material is, for example, epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized palm oil (epoxidized stearate), epoxidized oleate, epoxidized tallate and epoxidized linoleate or mixtures thereof. Preferably, epoxidized soybean oil (ESO), epoxidized linseed oil (ELO) and epoxidized ester derivatives thereof may be applied, but are not limited thereto.

Method of Preparation of Plasticizer Composition

According to one embodiment of the invention, the step of hydrogenating the terephthalate-based material in the presence of a metal catalyst to prepare a cyclohexane 1,4-diester-based material; And blending the cyclohexane 1,4-diester-based material and the citrate-based material in a weight ratio of 99: 1 to 1:99 to obtain a plasticizer composition.

The terephthalate-based material is a direct esterification reaction of at least two alcohols selected from the group consisting of 2-ethylhexyl alcohol, isononyl alcohol, 2-propylheptyl alcohol, butyl alcohol and isobutyl alcohol and terephthalic acid; Phthalate based materials can be prepared.

The direct esterification may include adding terephthalic acid to an alcohol, then adding a catalyst and reacting under a nitrogen atmosphere; Removing unreacted alcohol and neutralizing unreacted acid; And dehydration and filtration by distillation under reduced pressure.

The alcohol may be used in 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 terephthalic acid.

On the other hand, the catalyst is, for example, acid catalysts such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, paratoluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, alkyl sulfuric acid, aluminum lactic acid, lithium fluoride, potassium chloride, cesium chloride, Metal salts such as calcium chloride, iron chloride, aluminum phosphate, metal oxides such as heteropolyacids, natural / synthetic zeolites, cation and anion exchange resins, tetraalkyl titanate and organic metals such as polymers thereof. . As a specific example, the catalyst may use tetraalkyl titanate.

The amount of the 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 heterogeneous catalysts, it may be in the range of 5 to 200%, 5 to 100%, 20 to 200%, or 20 to 150% by weight of the total amount of reactants.

The direct esterification reaction is 10 minutes to 10 hours, preferably 30 minutes to 8 hours, more preferably 1 to 6 hours in the temperature range of 80 ℃ to 270 ℃, preferably 150 ℃ to 250 ℃ It is preferably carried out in, it is possible to effectively obtain a terephthalate-based material in the appropriate temperature, catalyst and time range in consideration of the boiling point of alcohol and the like.

When the terephthalate-based material is a mixture, cyclohexane 1,4-diester-based material is also a mixture, for example, trans esterification of di (2-ethylhexyl) terephthalate and butyl alcohol; Trans esterification of diisononyl terephthalate and butyl alcohol; Or trans esterification of di (2-ethylhexyl) terephthalate and diisononyl alcohol, trans esterification of diisononyl terephthalate and 2-propylheptyl; It may be to prepare a terephthalate-based material through such.

In addition, the mixture may produce the same mixture even when the alkyl groups of the terephthalate and the alcohol are interchanged. For example, the product of the trans esterification reaction of di (2-ethylhexyl) terephthalate and diisononyl alcohol may be the same as the product of the trans esterification reaction of diisononyl terephthalate and 2-ethylhexyl alcohol.

As used in the present invention, "trans esterification reaction" refers to a reaction in which an alcohol and an ester react with each other, as shown in Scheme 1 below, so that R of the ester is interchanged with R 'of an alcohol.

Scheme 1

According to an embodiment of the present invention, when the trans-esterification reaction is carried out when the alkoxide of the alcohol attacks the carbon of two ester (RCOOR ″) groups present in the ester compound; When attacking the carbon of one ester (RCOOR ”) group present in the ester compound; In the three cases, three kinds of ester compositions may be generated by water.

In addition, the trans-esterification reaction has the advantage that does not cause a waste water problem compared to the acid-alcohol esterification reaction, and can proceed under a non-catalyst, it can solve the problem when using an acid catalyst.

For example, di (2-ethylhexyl) terephthalate and butyl alcohol may be prepared by the trans-esterification reaction, such as di (2-ethylhexyl) terephthalate, butyl (2-ethylhexyl) terephthalate and dibutyl terephthalate. Can be produced, wherein the three terephthalates are formed in amounts of 3.0% to 70%, 0.5% to 50%, and 0.5% to 85% by weight relative to the total weight of the mixture, respectively. And may be specifically formed in amounts of 10% to 50%, 0.5% to 50%, and 35% to 80% by weight. Within this range, there is an effect of obtaining a terephthalate-based material (mixture) having high process efficiency and excellent processability and absorption rate.

In addition, the mixture prepared by the trans-esterification reaction can control the composition ratio of the mixture according to the amount of alcohol added.

The addition amount of the alcohol may be 0.1 to 89.9 parts by weight, specifically 3 to 50 parts by weight, and more specifically 5 to 40 parts by weight based on 100 parts by weight of the terephthalate-based material.

Since the molar fraction of the terephthalate compound participating in the trans-esterification reaction will increase as the terephthalate compound contains more alcohol, the content of the two terephthalate compounds as a product in the mixture may increase. And, correspondingly, the content of the unreacted terephthalate compound may show a tendency to decrease.

According to one embodiment of the present invention, the molar ratio of the reactant terephthalate compound and the alcohol is, for example, 1: 0.005 to 5.0, 1: 0.05 to 2.5, or 1: 0.1 to 1.0, within this range, high process efficiency and processability There is an effect of obtaining an ester plasticizer composition excellent in an improvement effect.

However, the composition ratio of the mixture of the three terephthalates is not limited to the above range, and may be added to any one of the three terephthalates to change the composition ratio, and possible mixed composition ratios are as described above. .

The ester composition prepared by the trans esterification step may include all of the single attack ester compound, the double attack ester compound, and the reaction residual ester compound, and control the composition ratio of the ester composition according to the amount of the alcohol added. can do.

The addition amount of the alcohol may be 0.1 to 89.9 parts by weight, specifically 3 to 50 parts by weight, and more specifically 5 to 40 parts by weight based on 100 parts by weight of the terephthalate.

The more terephthalate-based material is added to the alcohol, the greater the mole fraction of the terephthalate participating in the trans esterification reaction (mole fraction), and thus the tere produced by attacking only one ester group in the plasticizer composition The content of phthalates and terephthalates attacked by two ester groups may increase.

In addition, the content of residual terephthalate present in the unreacted correspondingly may tend to decrease.

The molar ratio of the terephthalate and alcohol may be, for example, 1: 0.005 to 5.0, 1: 0.05 to 2.5, or 1: 0.1 to 1.0, and may provide a plasticizer composition having high process efficiency and excellent processability improvement effect within this range. Terephthalate-based materials can be obtained.

The trans esterification reaction is carried out at a reaction temperature of 120 ° C to 190 ° C, preferably 135 ° C to 180 ° C, more preferably 141 ° C to 179 ° C, for 10 minutes to 10 hours, preferably 30 minutes to 8 hours, more Preferably it is carried out in 1 to 6 hours. It is possible to effectively obtain a mixture that is a terephthalate-based material of a desired composition ratio within the temperature and time range. In this case, the reaction time may be calculated from the time point at which the reaction temperature is reached after the reaction temperature is raised.

The trans esterification reaction may be performed under a non-catalyst, but in some cases, may be performed under an acid catalyst or a metal catalyst, in which case the reaction time may be shortened.

The acid catalyst may be, for example, sulfuric acid, methanesulfonic acid or p-toluenesulfonic acid, and the like, and the metal catalyst may be, for example, an organometallic catalyst, a metal oxide catalyst, a metal salt catalyst, or the metal itself.

The metal component may be any one selected from the group consisting of tin, titanium and zirconium, or a mixture of two or more thereof.

In addition, the method may further include distilling off the unreacted alcohol and reaction by-products, for example, an ester compound after the trans-esterification reaction.

The distillation may be, for example, two-stage distillation separately using the boiling point difference of the alcohol and the reaction by-product.

In another example, the distillation may be mixed distillation. In this case, there is an effect that the ester plasticizer composition can be relatively stable at a desired composition ratio. The mixed distillation means distilling butanol and reaction by-products simultaneously.

The hydrogenation step may be a step of converting a terephthalate-based material into a cyclohexane 1,4-diester-based material by hydrogenating a terephthalate-based material, which is a single compound or a mixture, in the presence of a metal catalyst.

The hydrogenation step is a reaction for removing the aromaticity of the benzene ring of the terephthalate-based materials by adding hydrogen in the presence of a metal catalyst, may be a kind of reduction reaction.

The hydrogenation reaction is a reaction of the terephthalate-based material with hydrogen under a metal catalyst to synthesize a cyclohexane 1,4-diester-based material, the reaction conditions of the benzene without affecting the carbonyl group substituted in the benzene It may include all conventional reaction conditions capable of hydrogenating only the ring.

The hydrogenation reaction may be performed by further including an organic solvent such as ethanol, but is not limited thereto. As the metal catalyst, a Rh / C catalyst, a Pt catalyst, a Pd catalyst, and the like, which are generally used to hydrogenate a benzene ring, may be used. However, the metal catalyst is not limited thereto.

For example, the pressure during hydrogenation in the hydrogenation reaction may be about 3 to 15 MPa, the reaction may be carried out for about 2 to 10 hours, it may be carried out at a temperature of about 80 ℃ to 200 ℃.

The above-described reaction step may be an example, and the final hydrogenated cyclohexane 1,4-diester-based material may be hydrogenated with a terephthalate of a single material first to produce a hydrogenated cyclohexane 1,4-diester-based material of the single material. After the material is prepared, a mixed cyclohexane 1,4-diester-based composition may be prepared by hydrogenation by trans esterification with alcohol.

In other words, the final product may be prepared by performing a direct ester reaction using terephthalic acid and / or terephthalate and / or a trans ester reaction followed by hydrogenation, or after the hydrogenation of the terephthalate prepared through the ester reaction, followed by trans esterification. Any method for producing a hydrogenated mixture through the oxidization reaction can be applied.

Meanwhile, the three hydrogenated final mixed compositions prepared through the trans esterification reaction may generally include two substances having the same alkyl group of the diester and one substance having different alkyl groups of the diester. In this case, one substance having different alkyl groups from the diester may serve as a main factor affecting the physical properties of the plasticizer, but it may be impossible to commercially and technically separate it as a single substance.

For example, the same alkyl groups bonded to the diesters at the 1,4 positions may be prepared as a single substance through direct esterification, respectively, but the alkyl groups bonded to the diesters at the 1,4 positions of the cyclohexane may be different from each other. Different things can only be prepared through trans esterification reaction, in which case it is impossible to separate only one material from which the alkyl group of the diester differs from each other, and even if only a small amount can be separated through excessive iteration at the laboratory level.

Therefore, alternatively, as a final composition state, it is possible to apply the method to perform the optimal physical properties through the control of the carbon number of the alkyl group or the ratio of the three compositions.

The blending may be performed by blending the cyclohexane 1,4-diester-based material and the citrate-based material in which the terephthalate-based material is converted through a hydrogenation reaction in a ratio of 1:99 to 99: 1 by weight. A plasticizer composition may be prepared, and the cyclohexane 1,4-diester-based material may be dependent on whether the terephthalate-based material is a single compound or a mixture, and is characterized in that each is a single compound or a mixture.

Since the content, type, and mixing ratio of the cyclohexane 1,4-diester-based material and the citrate-based material mixed during the blending have been described above, the description thereof is omitted.

After the blending, the method may further include adding an epoxidized material. Since the content in the case of adding the said epoxidation material further, and the kind of epoxidation material were mentioned above, the description is abbreviate | omitted.

The aforementioned direct esterification and trans esterification reactions can also be used to prepare the above-mentioned hybrid or non-hybrid citrate compounds. In this case, like the cyclohexane 1,4-diester-based material, the citrate-based material may also be prepared in a mixed ratio in a predetermined ratio, and the composition ratio of the resulting mixture may be controlled by controlling the content of alcohol as a reaction raw material. have. In addition, when the citrate compound is prepared through a direct esterification reaction or a trans esterification reaction, the contents thereof may be applied in the same manner as the contents applied to preparing the terephthalate-based material.

According to another embodiment of the present invention, there is provided a resin composition comprising the plasticizer composition and the resin described above.

The resin may be a resin known in the art. For example, one or more mixtures selected from ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, thermoplastic elastomer, and polylactic acid may be used, but is not limited thereto.

The plasticizer composition may be included in 5 to 150 parts by weight based on 100 parts by weight of the resin.

However, the content of the plasticizer may be changed according to the method of processing the resin composition. For example, in the case of a resin in which melt processing such as extrusion, injection, or calendering is performed, the plasticizer is preferably 5 to 100 parts by weight of the resin. 100 parts by weight, 5 to 60 parts by weight, or 5 to 50 parts by weight.

In addition, in the case of a resin in which plastisol processing such as spread coating, spray coating or dip coating is performed, a plasticizer may be included as 30 to 150 parts by weight, 40 to 130 parts by weight, and 60 to 120 parts by weight.

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.

The filler may be a filler known in the art, it is not particularly limited. For example, it may be at least one mixture selected from silica, magnesium carbonate, calcium carbonate, hard coal, talc, magnesium hydroxide, titanium dioxide, magnesium oxide, calcium hydroxide, aluminum hydroxide, aluminum silicate, magnesium silicate and barium sulfate.

In addition, the resin composition may further include other additives such as stabilizers, 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.

The stabilizer may be, for example, a calcium-zinc-based (Ca-Zn-based) stabilizer such as calcium stearate salts, but is not particularly limited thereto.

The resin composition may be applied to all resins used for melt processing and plastisol processing, and may be applied to compound industries such as extrusion or injection, calendering and plastisol, for example. Examples of the product may include various electric wires, flooring materials, automotive interior materials, films, sheets, wallpaper, toys, and the like.

Example

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Production Example  One: DEHTP Of BEHTP Of DBTP's  Preparation of Hydrogenation Mixture

One) Esterification  reaction

2,000 g of dioctyl terephthalate and 340 g of n-butanol (17 parts by weight based on 100 parts by weight of DOTP) were added to a reactor equipped with a stirrer, a condenser, and a decanter, followed by a reaction temperature of 160 ° C. under a nitrogen atmosphere. Trans-esterification reaction for 2 hours at 4.0 wt%, 35.0 wt% and 61.0 wt% The ester plasticizer composition contained in the range was obtained.

The reaction product was mixed and distilled to remove butanol and 2-ethylhexyl alcohol and finally a mixed composition was prepared.

2) hydrogenation reaction

In a 1.5L high pressure reactor, 1,000 g of the composition produced by the esterification reaction and 20 g of ruthenium catalyst (NE chemcat) were charged with raw materials, hydrogen was added at a pressure of 8 MPa, and hydrogenation was performed at a temperature of 150 ° C. for 3 hours. The reaction was completed. After the reaction was completed, the catalyst was filtered, and a mixture composition hydrogenated in a yield of 99% was prepared through a conventional purification process.

Production Example  2: DINTP Of EHINTP Of Of DEHTP  Preparation of Hydrogenation Mixture

One) Esterification  reaction

498.0 g of purified terephthalic acid (PTA), 975 g of 2-ethylhexyl alcohol (2-EH) A molar ratio of EH (1.0) :( 2.5)) and 216.5 g of isononyl alcohol (INA) (molar ratio of PTA: INA (1.0) :( 0.5)) were added and a titanium-based catalyst (TIPT, tetra isopropyl titanate) was used as a catalyst. Was added 1.54 g (0.31 parts by weight based on 100 parts by weight of PTA), and the temperature was gradually increased to about 170 ° C. The production of water was started at about 170 ° C., and the reaction was carried out for about 4.5 hours while nitrogen gas was continuously added at a reaction temperature of about 220 ° C. and atmospheric pressure. The reaction was terminated when the acid value reached 0.01.

After the reaction is completed, distillation is performed under reduced pressure for 0.5 to 4 hours to remove unreacted raw materials. In order to remove unreacted raw materials below a certain content level, steam extraction is performed under reduced pressure using steam for 0.5 to 3 hours, the reaction solution temperature is cooled to about 90 ° C., and neutralization is performed using an alkaline solution. . In addition, washing with water may be performed, and then the reaction solution is dehydrated to remove moisture. The filtrate was added to the reaction solution from which the water was removed, the mixture was stirred for a predetermined time, and then filtered to obtain a mixed composition.

2) hydrogenation reaction

In the same manner as in Preparation Example 1, the mixed composition was hydrogenated to prepare a hydrogenated mixed composition.

Production Example  3: DINTP Of BINTP Of DBTP's  Preparation of Hydrogenation Mixture

Instead of using isononyl alcohol and 2-ethylhexyl alcohol during the esterification reaction in Preparation Example 2, hydrogenation was performed by performing esterification and hydrogenation in the same manner as Preparation Example 2 using isononyl alcohol and butyl alcohol. A composition was obtained.

Production Example  4: DINTP Of PHINTP Of Of DPHTP  Preparation of Hydrogenation Mixture

Instead of using isononyl alcohol and 2-ethylhexyl alcohol during esterification in Preparation Example 2, esterification and hydrogenation were carried out in the same manner as in Preparation Example 2, using isononyl alcohol and 2-propylheptyl alcohol. A hydrogenated mixed composition was obtained.

Production Example  5: Preparation of TBC

384 g of citric acid and 580 g of butanol were used as reaction raw materials, and finally, 706 g (yield: 98%) of tributyl citrate were obtained.

Production Example  6: Of TOC  Produce

Finally, 1,029 g (yield: 98%) of tri-2-ethylhexyl citrate were obtained using 384 g of citric acid and 1,014 g of 2-ethylhexanol as reaction raw materials.

Production Example  7: TiNC  Produce

384 g of citric acid and 1,123 g of isononanol were used as reaction raw materials to finally obtain 1,111 g (yield: 98%) of triisobutyl citrate.

Production Example  8: TPHC  Produce

384 g of citric acid and 1,235 g of 2-propylheptanol were used as reaction raw materials to finally obtain 1,200 g of tri (2-propylheptyl citrate) (yield: 98%).

Production Example  9: Of BOC  Produce

Transesterification was performed using 1,000 g of TOC prepared in Preparation Example 6 and 300 g of n-butanol as reaction raw materials, and finally 840 g of butyloctyl citrate was obtained. For reference, the product is a composition, the main components are divided into alkyl groups bonded to the three ester groups of the citrate compound, BOC two butyl groups, BOC one butyl group and TOC unbutylated, respectively The ratio of was about 20%, 50% and 30% by weight.

Example  1 to 10 and Comparative example  1 to 5

The structure of the Example and the comparative example was carried out as Table 1 below.

division	Hydrogenated Mixed Composition	Citrate	Mixing ratio
Example 1	Preparation Example 1	TBC	7: 3
Example 2	Preparation Example 1	TBC	3: 7
Example 3	Preparation Example 1	TOC	8: 2
Example 4	Preparation Example 2	BOC	7: 3
Example 5	Preparation Example 2	TOC	2: 8
Example 6	Preparation Example 2	TPHC	6: 4
Example 7	Preparation Example 3	TINC	6: 4
Example 8	Preparation Example 3	TBC	5: 5
Example 9	Preparation Example 4	TOC	5: 5
Example 10	Preparation Example 4	TBC	5: 5
Comparative Example 1	1,4-DEHCH	TBC	7: 3
Comparative Example 2	1,4-DBCH	TOC	6: 4
Comparative Example 3	1,2-DINCH	TBC	7: 3
Comparative Example 4	Preparation Example 3	-
Comparative Example 5	-	TOC

Example  11 and 12

In order to confirm the heat resistance improvement using the epoxidized material, Example 11 and Example 12 were configured as shown in Table 2 below.

division	Hydrogenated Mixed Composition	Citrate	Mixing ratio
Example 11	Example 1	ESO	8: 2
Example 12	Example 4	ESO	7: 3

Experimental Example  1: Physical property evaluation

Experimental specimens were prepared using the plasticizer compositions of Examples and Comparative Examples described in Tables 1 and 2.

The specimen is prepared by referring to ASTM D638, 40 parts by weight of the plasticizer composition of Examples 1 to 10 and Comparative Examples 1 to 5, 3 parts by weight of a stabilizer (BZ-153T) in 100 parts by weight of PVC (LS100S) 3L super mixer ( after mixing at 98 and 700 rpm in a super mixer, and then working with a roll mill for 4 minutes at 160 ° C. to produce 5 mm sheets, press work at 180 ° C. for 2.5 minutes at low pressure and 2 minutes at high pressure, and then make 1T and 3T sheets. Specimen was produced. Each specimen was used to evaluate physical properties according to the test items below, and the results are summarized in Tables 3 and 4 below.

<Test item>

Hardness Measurement

Using ASTM D2240, measurements were taken at 25 ° C. shore (A) hardness, 3T and 10s conditions.

Tensile strength measurement

By the ASTM D638 method, the cross head speed was pulled to 200 mm / min (1T) using a test instrument, UTM (manufacturer; Instron, model name; 4466), and the point where the specimen was cut was measured. . Tensile strength was calculated as follows:

Tensile Strength (kgf / mm2) = Load Value (kgf) / Thickness (mm) × Width (mm)

Elongation (elongation rate) measurement

By using the ASTM D638 method, the crosshead speed was pulled to 200 mm / min (1T) using the U.T.M, and then measured at the point where the specimen was cut, the elongation was calculated as follows:

Elongation (%) = [length after extension / initial length] x 100 was calculated.

Migration loss measurement

Specimens with a thickness of 2 mm or more were obtained according to KSM-3156. A PS plate was attached to both sides of the specimen and a load of 1 kgf / cm ² was applied. The specimen was left in a hot air circulation oven (80 ° C.) for 72 hours and then taken out and cooled at room temperature for 4 hours. Then, after removing the PS attached to both sides of the test piece, the weight before and after leaving in the oven was measured and the transfer loss was calculated by the following equation.

Transfer loss (%) = [(Initial weight of specimen at room temperature-weight of specimen after leaving the oven) / Initial weight of specimen at room temperature] × 100

Measurement of volatile loss

After working the prepared specimen at 80 ℃ for 72 hours, the weight of the specimen was measured.

Heating loss (%) = [(initial specimen weight-specimen weight after operation) / initial specimen weight] x 100.

Stress testing

In the stress test, the specimen was bent at room temperature for a period of time, and then observed the degree of transition (the degree of bleeding), and the degree was expressed as a numerical value, the closer to 0, the better and the closer to 3, the worse. It is a characteristic.

Thermal stability test

The thermal stability of the specimen against high temperature contact was tested by moving 0.5T specimen prepared by roll-mill operation using Mathis Oven at a speed of 10mm / 25sec at 220 ℃.

division	Shore "A"	Tensile Strength (kg / cm 2 )	% Elongation	Performance loss (%)	Heating loss (%)	Stress test
Example 1	82.5	211.7	296.2	1.56	3.10	0
Example 2	78.5	215.2	287.1	1.89	3.51	0
Example 3	85.0	221.6	292.8	1.31	1.84	0
Example 4	85.0	232.2	307.7	1.60	1.95	0
Example 5	88.0	228.5	283.1	0.50	0.54	0.5
Example 6	86.0	221.1	296.7	1.87	0.87	1.0
Example 7	86.0	235.1	301.5	1.55	0.35	0.5
Example 8	84.0	217.0	284.6	1.90	2.14	0.5
Example 9	85.5	229.7	288.5	1.62	0.39	0.5
Example 10	82.0	220.4	278.1	1.45	2.02	0.5
Comparative Example 1	85.5	204.5	256.4	2.28	3.05	0.5
Comparative Example 2	88.0	207.1	223.1	1.50	1.32	1.0
Comparative Example 3	85.0	210.8	266.7	2.40	1.66	1.0
Comparative Example 4	87.0	201.3	221.0	2.86	1.56	2.0
Comparative Example 5	92.0	189.5	201.3	0.47	0.47	1.5

division	Shore "A"	Tensile Strength (kg / cm 2 )	% Elongation	Performance loss (%)	Heating loss (%)	Stress test
Example 11	83.5	235.1	307.5	1.20	2.66	0
Example 12	86.5	298.0	314.2	0.84	1.03	0

Referring to Table 3, in Comparative Examples 1 to 3 using the cyclohexane 1,4-diester-based material as a single material, it can be seen that the elongation characteristics are significantly poor compared to the examples, the tensile strength is also It can be confirmed that it is not superior to the embodiments. In addition, in the case of Comparative Examples 4 and 5 that do not contain any one of the citrate-based material or cyclohexane 1,4-diester-based material, the hardness is slightly higher, which may adversely affect the plasticization efficiency, It can be seen that the tensile strength and elongation characteristics are poorly shown.

Through this, in order to prepare a resin having satisfactory physical properties in all aspects of mechanical properties (tensile strength and elongation), physical properties related to the total amount of plasticizer (migration loss and heating loss) and processability (hardness), cyclohexane 1 It was confirmed that it is preferable to use a, 4-diester material as the mixing composition and to mix the citrate material.

In addition, referring to Table 4, Examples 11 and 12 were added to the epoxidized soybean oil in Examples 1 and 4, respectively, it can be confirmed that the heating loss and transition loss is lowered, mechanical strength such as tensile strength, elongation It can be confirmed that even physical properties can be improved.

Furthermore, referring to FIG. 1, in Examples 1 and 4 without adding the epoxidation material, it was confirmed that the specimen was burned and burned to a degree close to black, but in Example 11, discoloration was hardly achieved. It can be seen that the naked eye, and accordingly it can be seen that the thermal stability can be improved through the addition of the epoxidized material.

In other words, when the epoxidized material is mixed so as to act as a 'plasticizer' to more than 10 parts by weight, rather than a secondary stabilizer, it can be seen that there are improvements in all physical properties.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of rights.

Claims (13)

1. Two or more cyclohexane 1,4-diester materials; And citrate-based materials;

   The plasticizer composition of the cyclohexane 1,4-diester-based material and the citrate-based material is 99: 1 to 1:99.
2. The method of claim 1,

   The plasticizer composition of the cyclohexane 1,4-diester-based material and the citrate-based material is 95: 5 to 50:50.
3. The method of claim 2,

   The plasticizer composition of the cyclohexane 1,4-diester-based material and the citrate-based material is 95: 5 to 60:40.
4. The method of claim 1,

   The cyclohexane 1,4-diester-based material is butyl (2-ethylhexyl) cyclohexane-1,4-diester (1,4-BOCH), (2-ethylhexyl) isononyl cyclohexane- 1,4-diester (1,4-OINCH), butylisononyl cyclohexane-1,4-diester (1,4-BINCH), isononyl (2-propylheptyl) cyclohexane-1, 4-diester (1,4-IPHCH), dibutyl cyclohexane-1,4-diester (1,4-DBCH), diisononyl cyclohexane-1,4-diester (1,4- DINCH), di (2-ethylhexyl) cyclohexane-1,4-diester (1,4-DOCH), di (2-propylheptyl) cyclohexane-1,4-diester Plasticizer composition in which two or more are mixed mixtures.
5. The method of claim 4, wherein

   The cyclohexane 1,4-diester material,

   Di (2-ethylhexyl) cyclohexane-1,4-diester, butyl (2-ethylhexyl) cyclohexane-1,4-diester and dibutyl cyclohexane-1,4-diester mixed First mixture,

   A second mixture of diisononyl cyclohexane-1,4-diester, butylisononyl cyclohexane-1,4-diester and dibutyl cyclohexane-1,4-diester,

   Di (2-ethylhexyl) cyclohexane-1,4-diester, (2-ethylhexyl) isononyl cyclohexane-1,4-diester and diisononyl cyclohexane-1,4-diester Tertiary mixture mixed with

   Di (2-propylheptyl) cyclohexane-1,4-diester, isononyl (2-propylheptyl) cyclohexane-1,4-diester and diisononyl cyclohexane-1,4-diester The fourth mixture mixed with, or

   Dipentyl cyclohexane-1,4-diester, pentylisononyl cyclohexane-1,4-diester, and diisononyl cyclohexane-1,4-diester; Plasticizer composition.
6. The method of claim 5,

   Each component of the first to fifth mixtures is 3.0 to 99.0 mol%, in order of component description; 0.5 to 96.5 mol% and 0.5 to 96.5 mol%; plasticizer composition.
7. The method of claim 1,

   The citrate-based material is a plasticizer composition comprising any one selected from the group consisting of a 4 to 10 carbon-based alkyl substituted citrate-based material and a 4 to 10 carbon-based non-hybrid alkyl substituted citrate-based material.
8. The method of claim 1,

   The citrate-based material is a non-hybrid alkyl substituted citrate-based material having 4 to 10 carbon atoms,

   Plasticizer composition of the alkyl group having 4 to 10 carbon atoms of the citrate-based material is a straight chain or branched chain.
9. The method of claim 1,

   A plasticizer composition further comprising an epoxidation material.
10. The method of claim 9,

    The epoxidation material is a plasticizer composition further comprises 1 to 100 parts by weight based on 100 parts by weight of the mixed weight of cyclohexane 1,4-diester-based material and citrate-based material.
11. The method of claim 9,

    The epoxidized material is epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearate Plasticizer composition comprising one or more selected from the group consisting of epoxidized oleate, epoxidized tallate and epoxidized linoleate.
12. 100 parts by weight of resin; And 5 to 150 parts by weight of the plasticizer composition of claim 1.
13. The method of claim 12,

    The resin composition is one or more selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomer.

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