Propane tricarboxylate plasticizer composition and resin composition containing the same

Abstract

The invention is characterized in that the alkyl group thereof is derived from propane tricarboxylate of an isomer mixture of hexanol and benzyl alcohol, and when the propane tricarboxylate is applied to resin, excellent migration resistance, volatilization loss and stress resistance as well as high plasticization efficiency can be obtained.

Description

Technical Field

[0001] The present invention relates to a plasticizer composition comprising propane tricarboxylate having an alkyl group derived from an isomer mixture of hexyl alcohol and benzyl alcohol, and a resin composition comprising the same. Background Art

[0002] Generally, in the case of plasticizers, alcohols react with polycarboxylic acids such as phthalic acid and adipic acid to form esters corresponding thereto. In addition, in view of domestic and foreign regulations restricting phthalate plasticizers that are harmful to the human body, research on plasticizer compositions that can replace phthalate plasticizers, such as terephthalate plasticizers, adipate plasticizers, and other polymer plasticizers has been continuing.

[0003] At the same time, there is an increasing demand for environmentally friendly products in the plastisol industry, calendaring industry and extrusion / injection compounding industry, such as flooring, wallpaper, soft and hard sheets, and in order to improve the quality characteristics, processability and productivity of each final product, it is necessary to use suitable plasticizers while considering factors such as discoloration, migration properties and mechanical properties.

[0004] Supplementary materials such as plasticizers, fillers, stabilizers, viscosity reducers, dispersants, defoamers and blowing agents are mixed with PVC resins according to the properties required in the industry in different fields of use, such as tensile strength, elongation, light resistance, migration properties, gelling properties or absorption rate.

[0005] For example, in the plasticizer combination suitable for PVC, when the most commonly used di(2-ethylhexyl) terephthalate with relatively low cost is applied, the hardness or sol viscosity is high, the absorption speed of the plasticizer is relatively slow, and the migration performance and stress migration performance are poor.

[0006] In order to overcome the above limitations, as a composition containing DEHTP, the product obtained by ester exchange with butanol can be considered as a plasticizer. In this case, the use of the product can improve the plasticizing efficiency, but it will lead to volatilization loss or poor thermal stability, a slight decrease in mechanical properties, and the need to improve physical properties. Therefore, in addition to generally using a secondary plasticizer together to make up for the shortcomings, there is currently no other solution.

[0007] However, the use of secondary plasticizers brings with it the following unexpected drawbacks: changes in physical properties are difficult to predict, the unit cost of the product may increase, the improvement in physical properties is not significant except in certain cases, and compatibility with the resin may be problematic.

[0008] In addition, when trimellitic acid ester materials, such as tri(2-ethylhexyl) trimellitic acid ester or triisononyl trimellitic acid ester, are used to improve the poor migration and loss properties of DEHTP products, the migration or loss properties may be improved, but the plasticizing efficiency may decrease, and a considerable amount of material needs to be added to provide a resin with appropriate plasticizing properties, and the relatively high unit price of the product makes it impossible to sell the product on the market.

[0009] Therefore, it is necessary to develop a product for solving the environmental problems caused by phthalate products which are commonly used products, or to develop a product that corrects the bad physical properties of environmentally friendly products to solve the environmental problems of phthalate products. Summary of the invention

[0010] Technical issues

[0011] One aspect of the present invention provides a plasticizer composition which can improve mobility, plasticizing efficiency and volatility loss, and can also maintain mechanical properties and stress resistance at least at the same level as those of conventional plasticizers by comprising propane tricarboxylate in which the alkyl group is derived from an isomeric mixture of hexanol and benzyl alcohol.

[0012] Technical Solution

[0013] In order to solve the above-mentioned problems, the present invention provides a plasticizer composition and a resin composition comprising the plasticizer composition.

[0014] (1) According to one aspect of the present invention, there is provided a trimalt plasticizer composition comprising a propane trimalt composition containing at least one propane trimalt of the following formula 1:

[0015] The alkyl group of the propane tricarboxylate is derived from an alcohol composition comprising an isomeric mixture of hexanol and benzyl alcohol, and

[0016] The isomeric mixture of hexanol comprises two or more selected from the group consisting of 1-hexanol, 1-methylpentanol, 2-methylpentanol, 3-methylpentanol, 4-methylpentanol, 1,1-dimethylbutanol, 1,2-dimethylbutanol, 1,3-dimethylbutanol, 2,2-dimethylbutanol, 2,3-dimethylbutanol, 3,3-dimethylbutanol, 1-ethylbutanol, 2-ethylbutanol, 3-ethylbutanol and cyclopentylmethanol,

[0017] [Formula 1]

[0018]

[0019] In the above formula 1,

[0020] R1 to R3 are each independently n-hexyl, branched hexyl, cyclopentylmethyl or benzyl.

[0021] (2) The present invention provides the plasticizer composition as described in (1) above, wherein

[0022] The propane tricarboxylate composition comprises at least one propane tricarboxylate selected from the following formulas 2 to 7:

[0023] [Formula 2]

[0024]

[0025] [Formula 3]

[0026]

[0027] [Formula 4]

[0028]

[0029] [Formula 5]

[0030]

[0031] [Formula 6]

[0032]

[0033] [Formula 7]

[0034]

[0035] Wherein, in the above formulas 2 to 7,

[0036] R a are each n-hexyl, branched hexyl or cyclopentylmethyl, and

[0037] R b It's benzyl.

[0038] (3) The present invention provides the plasticizer composition as described in (1) above, wherein the degree of branching of the isomer mixture of hexanol is 2.0 or less.

[0039] (4) The present invention provides the plasticizer composition as described in any one of (1) to (3) above, wherein the degree of branching of the isomer mixture of hexanol is 1.5 or less.

[0040] (5) The present invention provides the plasticizer composition as described in any one of (1) to (4) above, wherein the isomer mixture of hexanol comprises 1-hexanol, 2-methylpentanol and 3-methylpentanol.

[0041] (6) The present invention provides the plasticizer composition as described in any one of (1) to (5) above, wherein the isomer mixture of hexanol contains 40 parts by weight or more of branched alcohols relative to 100 parts by weight of the isomer mixture of hexanol.

[0042] (7) The present invention provides a plasticizer composition as described in any one of (1) to (6) above, wherein the isomer mixture of hexanol contains 50 parts by weight to 95 parts by weight of branched alcohol relative to 100 parts by weight of the isomer mixture of hexanol.

[0043] (8) The present invention provides the plasticizer composition as described in any one of (1) to (7) above, wherein the isomer mixture of hexanol contains 40 parts by weight or less of 1-hexanol relative to 100 parts by weight of the isomer mixture of hexanol.

[0044] (9) The present invention provides the plasticizer composition as described in any one of (1) to (8) above, wherein the isomer mixture of hexanol comprises 1-hexanol, 2-methylpentanol, 3-methylpentanol and cyclopentylmethanol.

[0045] (10) The present invention provides a plasticizer composition as described in any one of (1) to (9) above, wherein the isomer mixture of hexanol contains 20 parts by weight or less of cyclopentylmethanol relative to 100 parts by weight of the isomer mixture of hexanol.

[0046] (11) The present invention provides the plasticizer composition as described in any one of (1) to (10) above, wherein the weight ratio of the isomer mixture of hexanol to benzyl alcohol is 90:10 to 10:90.

[0047] (12) According to another aspect of the present invention, there is provided a resin composition comprising:

[0048] 100 parts by weight of a resin; and 5 to 150 parts by weight of the plasticizer composition described in any one of (1) to (11) above.

[0049] (13) The present invention provides a resin composition as described in (12) above, wherein the resin is one or more selected from the group consisting of linear vinyl chloride polymers, paste vinyl chloride polymers, ethylene-vinyl acetate copolymers, ethylene polymers, propylene polymers, polyketones, polystyrene, polyurethanes, polylactic acid, natural rubber and synthetic rubber.

[0050] Beneficial Effects

[0051] When the plasticizer composition according to an embodiment of the present invention is used in a resin composition, it can maintain and improve mechanical properties and stress resistance, at least to the same level as conventional plasticizers, and can also improve properties such as loss performance, migration performance and plasticization efficiency. DETAILED DESCRIPTION

[0052] It should be understood that the words or terms used in the specification and claims of the present invention should not be interpreted as being limited to the meanings defined in common dictionaries. It will be further understood that these words or terms should be interpreted as having meanings consistent with their meanings in the relevant technical background and the technical concept of the present invention, based on the principle that the inventor can appropriately define the meanings of these words or terms to best explain the present invention.

[0053] Definition of terms

[0054] As used herein, the term "composition" encompasses compositions comprising a mixture of materials, as well as reaction products and decomposition products formed from the materials of the composition.

[0055] As used herein, the term "linear vinyl chloride polymer" is a vinyl chloride polymer that is polymerized by suspension polymerization or bulk polymerization, and refers to a polymer in the form of porous particles in which a large number of pores with a size of tens to hundreds of microns are distributed, with no cohesive force and good fluidity.

[0056] As used herein, the term "paste vinyl chloride polymer" is a vinyl chloride polymer that is polymerized by microsuspension polymerization, microseed polymerization or emulsion polymerization, and refers to a polymer in the form of fine, compact, non-porous particles with a size of tens to thousands of nanometers, cohesiveness and poor fluidity.

[0057] The terms "comprising" and "having" and their derivatives are not meant to exclude the presence of any additional ingredients, steps or procedures, whether or not they are specifically disclosed. To avoid any uncertainty, all compositions claimed through the use of the term "comprising", whether polymeric or otherwise, may include any additional additives, adjuvants or compounds unless otherwise specified. Conversely, the term "consisting essentially of excludes any other ingredients, steps or procedures from the scope of any subsequent description and excludes those ingredients that are not essential to operability. The term "consisting of excludes any ingredient, step or procedure not specifically described or listed.

[0058] Measurement method

[0059] In the specification, the analysis was performed by gas chromatography using a gas chromatograph (Agilent 7890GC, manufactured by Agilent Technologies Inc., column: HP-5, carrier gas: helium (flow rate 2.4 mL / min), detector: FID, injection volume: 1 μL, initial value: 70°C / 4.2 minutes, final value: 280°C / 7.8 minutes, program rate: 15°C / min).

[0060] In this specification, "hardness" refers to the Shore hardness (Shore "A" and / or Shore "D") measured at 25°C according to ASTM D2240. Hardness is measured under the condition of 3T 10s and can be used as an index for evaluating plasticization efficiency. Low hardness indicates excellent plasticization efficiency.

[0061] In the specification, "tensile strength" is measured according to ASTM D638 as follows: A 1T specimen is pulled at a crosshead speed of 200 mm / min using a universal testing machine (UTM; 4466 manufactured by Instron), and then the point at which the specimen breaks is determined and substituted into the following equation 1.

[0062] [Equation 1]

[0063] Tensile strength (kgf / cm 2 ) = load value (kgf) / thickness (cm) × width (cm)

[0064] In this specification, "elongation" is measured according to ASTM D638 as follows: A 1T specimen is pulled at a crosshead speed of 200 mm / min using UTM, and then the time point at which the specimen breaks is determined and substituted into the following Equation 2.

[0065] [Equation 2]

[0066] Elongation (%) = elongated length / initial length × 100

[0067] In this specification, "migration loss" is measured as follows in accordance with the provisions of KSM-3156. Prepare a sample with a thickness of 2 mm or more, attach glass plates to both sides of the sample, and then apply 1 kgf / cm 2 The sample was placed in a hot air convection oven (80°C) for 72 hours, then removed from the oven and cooled at room temperature for 4 hours. After that, the glass plates attached to both sides of the sample were removed, and the weight of the sample and the glass plates before and after being placed in the oven was measured to determine the migration loss using the following equation 3.

[0068] [Equation 3]

[0069] Migration loss (%) = {(initial weight of sample - weight of sample after removal from oven) / initial weight of sample} × 100

[0070] In the specification, "volatile loss" is measured by treating a sample at 80°C for 72 hours and then weighing the sample.

[0071] [Equation 4]

[0072] Volatilization loss (wt%) = {(initial weight of sample - weight of sample after treatment) / initial weight of sample} × 100

[0073] In the case of the above-mentioned various measurement methods, detailed conditions such as temperature, rotation speed, time, etc. may slightly change in some cases, and when the detailed conditions change, the measurement method and conditions are specified separately.

[0074] Hereinafter, the present invention will be described in detail to help understanding of the present invention.

[0075] According to an embodiment of the present invention, a trimalt plasticizer composition is provided, comprising a propane trimalt composition containing at least one propane trimalt of the following formula 1, wherein the alkyl group of the propane trimalt comes from an alcohol composition comprising an isomer mixture of hexanol and benzyl alcohol, and the isomer mixture of hexanol comprises two or more selected from 1-hexanol, 1-methylpentanol, 2-methylpentanol, 3-methylpentanol, 4-methylpentanol, 1,1-dimethylbutanol, 1,2-dimethylbutanol, 1,3-dimethylbutanol, 2,2-dimethylbutanol, 2,3-dimethylbutanol, 3,3-dimethylbutanol, 1-ethylbutanol, 2-ethylbutanol, 3-ethylbutanol and cyclopentylmethanol.

[0076] [Formula 1]

[0077]

[0078] In the above formula 1,

[0079] R1 to R3 are each independently n-hexyl, branched hexyl, cyclopentylmethyl or benzyl.

[0080] The plasticizer composition may be a product produced by direct esterification between 1,2,3-propanetricarboxylic acid or a derivative thereof and an alcohol composition comprising an isomer mixture of hexanol and benzyl alcohol, or by transesterification between trialkyl 1,2,3-propanetricarboxylate and an alcohol composition, in which case the hexanol mixture used may be a hexanol mixture having different structures, i.e., a mixture of structural isomers. More specifically, the isomer mixture of hexanol may include two or more selected from the group consisting of 1-hexanol, 1-methylpentanol, 2-methylpentanol, 3-methylpentanol, 4-methylpentanol, 1,1-dimethylbutanol, 1,2-dimethylbutanol, 1,3-dimethylbutanol, 2,2-dimethylbutanol, 2,3-dimethylbutanol, 3,3-dimethylbutanol, 1-ethylbutanol, 2-ethylbutanol, 3-ethylbutanol and cyclopentylmethanol.

[0081] In the above-mentioned esterification or transesterification, the alkyl groups of R1 to R3 of the above-mentioned Formula 1 may be determined according to the composition ratio between the hexanol mixture and benzyl alcohol in the alcohol composition, or the alcohol contained in the hexanol isomer mixture, and in the final composition, a diversified composition of three, two, or one and three alkyl groups in combination of the hexanol isomer alkyl group and the benzyl alcohol may be included, and the component ratio in the final composition may be determined by the ratio of the respective structural isomer components in the hexanol mixture subjected to the reaction and the ratio between the hexanol mixture and benzyl alcohol in the alcohol composition.

[0082] As described above, with regard to the use of the trimesic acid ester plasticizer, when an alkyl group derived from an alcohol composition comprising an isomer mixture of hexanol and benzyl alcohol is used, improved migration, volatilization loss and tensile strength can be shown compared to an alkyl group derived only from the isomer mixture of hexanol, excellent mechanical properties can be provided compared to an alkyl group derived from an alcohol having less than 6 carbon atoms, and more particularly, tensile strength, elongation and volatilization loss may be significantly improved, and excellent plasticizing efficiency, migration resistance and stress resistance may be achieved compared to an alkyl group having more than 6 carbon atoms.

[0083] More specifically, the propane trimalate-based composition may include at least one of the propane trimalates of the following Formulae 2 to 7, and may particularly preferably include all of the propane trimalates of the following Formulae 2 to 7:

[0084] [Formula 2]

[0085]

[0086] [Formula 3]

[0087]

[0088] [Formula 4]

[0089]

[0090] [Formula 5]

[0091]

[0092] [Formula 6]

[0093]

[0094] [Formula 7]

[0095]

[0096] Wherein, in the above formulas 2 to 7,

[0097] R a is n-hexyl, branched hexyl or cyclopentylmethyl, and

[0098] R b It's benzyl.

[0099] The triformate represented by the above formulae 2 to 7 represents a triformate in which all alkyl groups are derived from an isomeric mixture of hexanol (Formula 2), a triformate in which two alkyl groups are derived from an isomeric mixture of hexanol and one alkyl group is derived from benzyl alcohol (Formulae 3 and 4), a triformate in which one alkyl group is derived from an isomeric mixture of hexanol and two alkyl groups are derived from benzyl alcohol (Formulae 5 and 6), and a triformate in which all alkyl groups are derived from benzyl alcohol (Formula 7). In the plasticizer composition of the present invention, the relative proportion of each triformate represented by the above formulae 2 to 7 can be varied according to the composition ratio of the isomeric mixture of hexanol and benzyl alcohol in the alcohol composition used for esterification or transesterification.

[0100] The degree of branching of the isomeric mixture of hexanol contained in the alcohol composition of the present invention can be below 2.0, preferably below 1.5, and particularly preferably below 1.0. Specifically, the degree of branching can be below 1.5, below 1.3, more preferably below 1.1. In addition, the degree of branching can be more than 0.1, more than 0.2, more than 0.3, most preferably more than 0.7. In the triformate plasticizer composition produced with hexanol, the degree of branching of the isomeric mixture of hexanol can also remain unchanged. When the degree of branching is too high, the balance between the physical properties may be broken, so that the product cannot meet any one or more evaluation criteria, but within the preferred range below 1.5, the improvement of migration loss and volatilization loss and mechanical properties can be further optimized, and a good balance between the physical properties can be obtained.

[0101] In this case, the degree of branching may represent the number of branched carbons of the alkyl group combined with the material contained in the composition, and may be determined according to the weight ratio of the corresponding materials. For example, when the alcohol mixture comprises 60% by weight of n-hexanol, 30% by weight of methylpentanol, and 10% by weight of ethylbutanol, the number of branched carbons of each alcohol is 0, 1, and 2, and the degree of branching may be determined as 0.5 according to [(60×0)+(30×1)+(10×2)] / 100. Meanwhile, with regard to the definition of the degree of branching in the present invention, the number of branched carbons of cyclopentylmethanol is considered to be 0.

[0102] The isomeric mixture of n-hexanol may contain 1-hexanol and 2-methylpentanol. Therefore, when 1-hexanol and 2-methylpentanol are contained together, a balance between physical properties can be maintained and a good effect can be achieved in terms of volatility loss. Preferably, the isomeric mixture of hexanol may further contain 3-methylpentanol, in which case the balance between physical properties is quite good.

[0103] Relative to 100 parts by weight of the isomer mixture, the content of the branched hexanol including 2-methylpentanol can be 40 parts by weight or more, 50 parts by weight or more, 60 parts by weight or more, preferably 65 parts by weight or more, 70 parts by weight or more. The content of the branched hexanol including 2-methylpentanol can be 100 parts by weight or less, 99 parts by weight or less, 98 parts by weight or less, preferably 95 parts by weight or less, or 90 parts by weight or less. When the branched hexanol is included within this range, improvement in mechanical properties can be expected.

[0104] In addition, the content of the straight-chain alcohol of 1-hexanol can be less than 50 parts by weight, less than 40 parts by weight, and preferably less than 30 parts by weight relative to 100 parts by weight of the isomer mixture. 1-hexanol may not be present in the component, but it can be packed in an amount of at least 2 parts by weight, and in this case, the balance between the physical properties can be maintained and improved mechanical properties can also be achieved. In theory, it is known that straight-chain alcohols show excellent performance, but in the present invention, different results are obtained, confirming that even better balance between physical properties can be obtained using an isomer mixture containing branched alcohols.

[0105] In addition, the isomeric mixture of hexanol may contain 1-hexanol, 2-methylpentanol, 3-methylpentanol and cyclopentylmethanol. Preferably, by further adding cyclopentylmethanol, the mechanical properties can be slightly improved.

[0106] In this case, the content of cyclopentylmethanol may be 20 parts by weight or less, preferably 15 parts by weight or less, or absent, or at least 2 parts by weight relative to 100 parts by weight of the isomer mixture, thereby obtaining its effect.

[0107] Specifically, according to the ratio of branched alkyl groups in the total alkyl groups in the final composition, and further according to the ratio of specific branched alkyl groups in the branched alkyl groups, the balance between plasticizing efficiency and physical properties, such as migration / loss properties, can be controlled, and mechanical properties such as tensile strength and elongation and stress resistance can be maintained at least at the same level, which can be achieved by the above-mentioned components of hexanol isomers and their component ratios.

[0108] By the above manner, a plasticizer composition can be provided that can prevent the environmental problems of common phthalate products and further improve the loss performance, and has significantly improved migration and loss performance compared to common terephthalate products.

[0109] Meanwhile, in the alcohol composition of the present invention, the weight ratio of the isomer mixture of hexanol and benzyl alcohol may be 90:10 to 10:90, preferably 90:10 to 30:70, particularly preferably 90:10 to 50:50. Within the above range, the plasticizer composition may have excellent plasticizing efficiency and excellent anti-migration and anti-stress properties.

[0110] As a method of preparing the plasticizer composition according to an embodiment of the present invention, any method of preparing the above-mentioned plasticizer composition well known in the art may be applied without particular limitation.

[0111] For example, the composition can be prepared by direct esterification between 1,2,3-propanetricarboxylic acid or its anhydride and an alcohol composition comprising an isomeric mixture of hexanol and benzyl alcohol, or by transesterification between trialkyl 1,2,3-propanetricarboxylate and an alcohol composition comprising an isomeric mixture of hexanol and benzyl alcohol.

[0112] The plasticizer composition according to an embodiment of the present invention is a material prepared by appropriately performing esterification, and the preparation method thereof is not particularly limited as long as the above conditions are satisfied and the weight ratio between the trisaccharides of each family is appropriately adjusted.

[0113] For example, direct esterification can be carried out in the following manner: injecting 1,2,3-propanetricarboxylic acid or a derivative thereof and an alcohol composition comprising an isomer mixture of hexanol and benzyl alcohol, then adding a catalyst, inducing a reaction in a nitrogen environment; removing unreacted raw materials; neutralizing (or deactivating) unreacted raw materials and catalyst; and removing (e.g., using reduced pressure distillation) and filtering impurities.

[0114] The components of the isomer mixture of hexanol and the weight ratio of each component are the same as above. The alcohol composition comprising the isomer mixture of hexanol and benzyl alcohol can be used in the range of 200 mol% to 900 mol%, 200 mol% to 700 mol%, 200 mol% to 600 mol%, 250 mol% to 600 mol% or 270 to 600 mol% relative to 100 mol% of the acid, and by controlling the amount of the alcohol, the ratio of the components in the final composition can be controlled.

[0115] The catalyst can be, for example, selected from acid catalysts such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid and alkyl sulfate, metal salts such as aluminum lactate, lithium fluoride, potassium chloride, cesium chloride, calcium chloride, ferric chloride and aluminum phosphate, metal oxides such as heteropolyacids, natural / synthetic zeolites, cation and anion exchange resins, and organic metals such as tetraalkyl titanates and polymers thereof One or more. Specifically, the catalyst can use, for example, tetraalkyl titanates. Preferably, p-toluenesulfonic acid, methanesulfonic acid, etc. may be suitable as acidic catalysts with low activation temperature.

[0116] The amount of the catalyst used may vary depending on its type, for example, the amount of a homogeneous catalyst used may be 0.01 wt % to 5 wt %, 0.01 wt % to 3 wt %, 1 wt % to 5 wt %, or 2 wt % to 4 wt % relative to 100 wt % of the total amount of reactants; the amount of a heterogeneous catalyst used may be 5 wt % to 200 wt %, 5 wt % to 100 wt %, 20 wt % to 200 wt %, or 20 wt % to 150 wt % relative to the total amount of reactants.

[0117] In this case, the reaction temperature may be in the range of 100 to 280°C, 100 to 250°C, or 120 to 230°C.

[0118] In another example, the transesterification may be a reaction between a trialkyl 1,2,3-propane tricarboxylate and an alcohol composition comprising an isomeric mixture of hexanol and benzyl alcohol. In terms of minimizing impurities, the alkyl group of the trialkyl 1,2,3-propane tricarboxylate may preferably be a hexyl group or a benzyl group, in which case, when the hexyl group of the tricarboxylate is linear, the isomeric mixture of hexanol is set to contain a branched alcohol, or when the hexyl group of the tricarboxylate is branched, the isomeric mixture of hexanol is set to contain a linear alcohol, so that the alkyl group of the finally obtained 1,2,3-propane tricarboxylate may contain both linear and branched hexyl groups.

[0119] As used herein, "ester exchange" refers to the reaction between an alcohol and an ester as shown in the following reaction formula 1, whereby the R" of the ester is exchanged with the R' of the alcohol:

[0120] [Reaction 1]

[0121]

[0122] Generally speaking, during the ester exchange process, when there are two types of alkyl groups, four types of ester compositions can be produced according to the following four situations: a situation where the alkoxide of the alcohol attacks the carbons of three ester (RCOOR") groups present in the ester compound; a situation where the alkoxide of the alcohol attacks the carbons of two ester (RCOOR") groups present in the ester compound; a situation where the alkoxide of the alcohol attacks the carbons of one ester (RCOOR") group present in the ester compound; and an unreacted situation where no reaction occurs.

[0123] However, in the tris-formic acid ester contained in the plasticizer composition according to the present invention, when two ester groups are exchanged or one ester group is exchanged according to the bonding position of the ester group, each may form three types, and therefore, a maximum of 8 types of compounds may exist in the final composition. However, in the isomer mixture of hexanol according to the present invention, there are two types of alkyl groups, and thus the types may be more diverse.

[0124] Furthermore, unlike acid-alcohol esterification, transesterification does not cause wastewater problems.

[0125] The composition ratio of the mixture prepared by the transesterification reaction can be controlled according to the amount of alcohol added. The amount of alcohol added can be 0.1 to 200 parts by weight, particularly 1 to 150 parts by weight, and more particularly 5 to 100 parts by weight relative to 100 parts by weight of the trialkyl 1,2,3-propane tricarboxylate compound. For reference, the component ratio in the final composition can be determined by the amount of alcohol added in the direct esterification.

[0126] According to an embodiment of the present invention, the transesterification can be 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 1 hour to 6 hours. When the temperature and time are within the above range, the composition ratio of the final plasticizer composition can be effectively controlled. In this case, the reaction time can be determined from the point at which the reaction temperature is reached after the reactant temperature is raised.

[0127] The transesterification may be carried out in the presence of an acid catalyst or a metal catalyst, in which case the reaction time can be shortened.

[0128] The acid catalyst may include, for example, sulfuric acid, methanesulfonic acid, or p-toluenesulfonic acid, and the metal catalyst may include, for example, an organic metal catalyst, a metal oxide catalyst, a metal salt catalyst, or a metal itself.

[0129] For example, 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.

[0130] In addition, after the esterification process, it is further possible to include removing unreacted alcohol and reaction byproducts by distillation. For example, the distillation can be, for example, a two-stage distillation, by which the boiling point difference is utilized to separate alcohol and byproducts separately. In another example, the distillation can be a mixed distillation, in which case a relatively stable ester-based plasticizer composition with a desired ratio can be obtained. Mixed distillation means that unreacted alcohol and byproducts are distilled together.

[0131] According to another embodiment of the present invention, a resin composition including a plasticizer composition and a resin is provided.

[0132] As the resin, resins known in the art can be used. For example, one or more mixtures selected from the following group can be used without limitation: linear vinyl chloride polymers, pasty vinyl chloride polymers, ethylene-vinyl acetate copolymers, ethylene polymers, propylene polymers, polyketones, polystyrene, polyurethane, polylactic acid, natural rubber, synthetic rubber, and thermoplastic elastomers.

[0133] The content of the plasticizer composition may be 5 to 150 parts by weight, preferably 5 to 130 parts by weight, or 10 to 120 parts by weight, relative to 100 parts by weight of the resin.

[0134] Generally, a resin product can be prepared from a resin using a plasticizer composition by melt processing or plasto processing, and a resin obtained by melt processing and a resin obtained by plasto processing can be produced in different ways according to each polymerization method.

[0135] For example, when a vinyl chloride polymer is used for melt processing, solid resin particles with a larger average particle size are prepared by suspension polymerization or the like and used, and this type of vinyl chloride polymer is called a linear vinyl chloride polymer. When a vinyl chloride polymer is used for plastic solution processing, a sol-state resin as tiny resin particles is prepared by emulsion polymerization or the like and used, and this type of vinyl chloride polymer is called a paste-like vinyl chloride resin.

[0136] In this case, in the case of a linear vinyl chloride polymer, the content of the plasticizer is preferably 5 to 80 parts by weight relative to 100 parts by weight of the polymer, and in the case of a paste vinyl chloride polymer, the content of the plasticizer is preferably 40 to 120 parts by weight relative to 100 parts by weight of the polymer.

[0137] The resin composition may further include a filler. The filler may be used in an amount of 0 to 300 parts by weight, preferably 50 to 200 parts by weight, and more preferably 100 to 200 parts by weight, relative to 100 parts by weight of the resin.

[0138] As fillers, fillers known in the art can be used, and are not particularly limited. For example, the filler can be a mixture of one or more selected from silicon dioxide, magnesium carbonate, calcium carbonate, hard coal, talc, magnesium hydroxide, titanium dioxide, magnesium oxide, calcium hydroxide, aluminum hydroxide, aluminum silicate, magnesium silicate and barium sulfate.

[0139] In addition, the resin composition may further include other additives such as stabilizers when necessary. The content of other additives such as stabilizers is, for example, 0 to 20 parts by weight, preferably 1 to 15 parts by weight, relative to 100 parts by weight of the resin.

[0140] For example, the stabilizer may be a calcium zinc type (Ca-Zn type) stabilizer such as calcium zinc complex stearate or a barium zinc type (Ba-Zn type) stabilizer, but is not particularly limited.

[0141] The resin composition can be applied to the above-mentioned melt processing and plasto processing, and a calendering process, an extrusion process, or an injection process can be applied to the melt processing, and a coating process or the like can be applied to the plasto processing.

[0142] Example

[0143] Below, the present invention will be described in detail with reference to embodiment. However, embodiments according to the present invention may be modified into other various forms, and the scope of the present invention should not be construed as being limited only to the embodiments described below. Examples of the present invention are provided to more fully describe the present invention to those skilled in the art.

[0144] Example 1

[0145] In a reactor equipped with a stirrer, a condenser and a decanter, 500.2 g of 1,2,3-propanetricarboxylic acid, 867.5 g of an isomer mixture of hexanol, 371.8 g of benzyl alcohol and 1.5 g of tetrabutyl titanate (TnBT) were added and esterified in nitrogen. After the reaction was terminated, the catalyst and the product obtained therefrom were neutralized with an alkaline aqueous solution, and unreacted alcohol and water were purified to finally obtain a plasticizer composition.

[0146] The alcohol composition of the hexanol isomer mixture used herein is a mixture of 1-hexanol, 2-methylpentanol, 3-methylpentanol, and cyclopentylmethanol in a weight ratio of 10:40:45:5.

[0147] Example 2

[0148] A plasticizer composition was obtained in the same manner as in Example 1, except that a hexanol isomer mixture of 1-hexanol, 2-methylpentanol, and 3-methylpentanol mixed in a weight ratio of 20:35:45 was used.

[0149] Example 3

[0150] A plasticizer composition was obtained in the same manner as in Example 1, except that a hexanol isomer mixture of 1-hexanol, 2-methylpentanol, 3-methylpentanol, and cyclopentylmethanol mixed in a weight ratio of 10:45:30:15 was used.

[0151] Example 4

[0152] A plasticizer composition was obtained in the same manner as in Example 1, except that the total weight of the isomer mixture of hexanol and benzyl alcohol was the same, but the weight ratio between the two alcohols was 90:10.

[0153] Example 5

[0154] A plasticizer composition was obtained in the same manner as in Example 1, except that the total weight of the isomer mixture of hexanol and benzyl alcohol was the same, but the weight ratio between the two alcohols was 50:50.

[0155] Comparative Example 1

[0156] Dioctyl phthalate (DOP, LG Chem) was used as a plasticizer.

[0157] Comparative Example 2

[0158] Diisononyl phthalate (DINP, LG Chemical) was used as a plasticizer.

[0159] Comparative Example 3

[0160] Di(2-ethylhexyl) terephthalate (GL300, LG Chemical) was used as a plasticizer.

[0161] Comparative Example 4

[0162] A composition (GL500, LG Chem) was used as a plasticizer, which contained 6.3 wt% of dibutyl terephthalate (DBTP), 38.8 wt% of butyl (2-ethylhexyl) terephthalate (BEHTP), and 54.9 wt% of di(2-ethylhexyl) terephthalate (DEHTP).

[0163] Comparative Example 5

[0164] A plasticizer composition was obtained in the same manner as in Example 1, except that 326.4 g of citric acid was used instead of 1,2,3-propanetricarboxylic acid.

[0165] Comparative Example 6

[0166] A plasticizer composition was obtained in the same manner as in Example 5, except that after esterification, acetic anhydride was added and acetylation was performed.

[0167] Comparative Example 7

[0168] A plasticizer composition was obtained in the same manner as in Example 1, except that only 1239.3 g of the isomer mixture of hexanol was used instead of benzyl alcohol.

[0169] Comparative Example 8

[0170] A plasticizer composition was obtained in the same manner as in Example 1, except that only 1239.3 g of benzyl alcohol was used instead of the isomer mixture of hexanol.

[0171] Comparative Example 9

[0172] A plasticizer composition was obtained in the same manner as in Example 1, except that 867.5 g of 2-methylpentanol single compound was used instead of the isomer mixture of hexanol.

[0173] Comparative Example 10

[0174] A plasticizer composition was obtained in the same manner as in Example 1, except that 820 g of a single compound of n-butanol was used instead of the isomer mixture of hexanol.

[0175] Comparative Example 11

[0176] A plasticizer composition was obtained in the same manner as in Example 1, except that 1440 g of 2-ethylhexanol single compound was used instead of the isomer mixture of hexanol.

[0177] The types of acids and alcohols used in Examples and Comparative Examples are shown in Table 1 below.

[0178] [Table 1]

[0179]

[0180] PTCA: Propanetricarboxylic Acid

[0181] CA: Citric acid

[0182] ACA: Acetyl Citric Acid

[0183] 1-H: 1-Hexanol

[0184] 2-MP:2-Methylpentanol

[0185] 3-MP:3-Methylpentanol

[0186] CYP-M: Cyclopentylcarbinol

[0187] BA: Benzyl alcohol

[0188] Experimental Example 1: Sheet Performance Evaluation

[0189] Using the plasticizers of Examples and Comparative Examples, test specimens were prepared according to ASTM D638 and the following formulations and preparation conditions.

[0190] (1) Formulation: 100 parts by weight of linear vinyl chloride polymer (LS100S), 40 parts by weight of plasticizer and 3 parts by weight of stabilizer (BZ-153T).

[0191] (2) Stirring: Stir at 700 rpm at 98°C

[0192] (3) Preparation of samples: 1T, 2T and 3T sheets were prepared by rolling at 160° C. for 4 minutes and by pressing at 180° C. for 2.5 minutes (low pressure) and 2 minutes (high pressure).

[0193] (4) Evaluation items

[0194] 1) Hardness: Shore hardness at 25°C (Shore "A" and "D") is measured using a 3T test specimen for 10 seconds using ASTM D2240. When the a value is smaller, the plasticizing efficiency is determined to be excellent.

[0195] 2) Tensile strength and tensile strength retention: According to the method of ASTM D638, the sample was pulled at a crosshead speed of 200 mm / min using a UTM tester (manufacturer: Instron, model name: 4466), and the breaking point of the 1T sample was determined. The tensile strength was determined as follows.

[0196] Tensile strength (kgf / cm 2 ) = load value (kgf) / thickness (cm) × width (cm)

[0197] The tensile strength retention rate refers to the ratio of the tensile strength remaining in the sample after the sample is placed in an oven at 100°C for 168 hours. The determination method is the same as the tensile strength determination method mentioned above.

[0198] 3) Measurement of tensile elongation and tensile elongation retention: According to the method of ASTM D638, a sample was pulled at a crosshead speed of 200 mm / min using a UTM testing machine, and the breaking point of the 1T sample was determined.

[0199] Tensile elongation (%) = elongated length / initial length × 100

[0200] The tensile elongation retention rate refers to the ratio of the tensile elongation remaining in the sample after the sample is placed in an oven at 100° C. for 168 hours. The determination method is the same as the above-mentioned tensile elongation determination method.

[0201] 4) Measurement of migration loss: According to KSM-3156, obtain a sample with a thickness of more than 2 mm, attach glass plates to both sides of the 1T sample, and apply 1 kgf / cm 2 The sample was placed in a hot air convection oven (80°C) for 72 hours, then removed from the oven and cooled at room temperature for 4 hours. After that, the glass plates attached to both sides of the sample were removed, and the weight of the sample together with the glass plates before and after being placed in the oven was measured, and the migration loss was determined by the following equation.

[0202] Migration loss (%) = {(initial weight of the sample at room temperature - weight of the sample after being placed in the oven) / initial weight of the sample at room temperature} × 100

[0203] 5) Measurement of volatilization loss: The sample prepared above was treated at 80°C for 72 hours, and the weight of the sample was measured.

[0204] Volatilization loss (wt%) = initial sample weight - (sample weight after treatment at 80°C for 72 hours) / initial sample weight × 100

[0205] 6) Stress test (stress resistance): Place a 2 mm thick specimen in a bent state at 23°C for 168 hours, observe its migration degree (exudation degree), and report the result in numerical form. When the value is close to 0, it indicates excellent performance.

[0206] (5) Evaluation results

[0207] The evaluation results of the project are shown in Tables 2 and 3 below.

[0208] [Table 2]

[0209]

[0210] [Table 3]

[0211]

[0212] With reference to Table 2 and Table 3 above, it can be seen that Examples 1 to 5 using the plasticizer composition according to the embodiment of the present invention show significantly superior plasticizing efficiency and mobility, as well as excellent tensile and elongation properties compared to Comparative Examples 1 and 2 using commonly used products. Comparative Examples 1 and 2 show excellent performance, but belong to commonly used phthalate products that are not environmentally friendly. The above results show that the plasticizer composition of the present invention is environmentally friendly because it does not contain phthalates, can fully replace commonly used products and further provide greater improved performance.

[0213] In addition, Comparative Examples 3 and 4 are environmentally friendly products used as substitutes for Comparative Examples 1 and 2, but the migration and stress resistance they exhibit are significantly inferior to those of common products and Examples 1 to 5 of the present invention, and the plasticization efficiency is also worse than that of Examples 1 to 5 of the present invention.

[0214] In addition, in Comparative Examples 5 and 6, in which the isomer mixture of hexanol was used in the same manner as in Examples 1 to 3 of the present invention, but citric acid or acetylcitric acid was used instead of 1,2,3-propanetricarboxylic acid, the plasticizing efficiency, tensile properties, elongation properties, migration and stress resistance shown in Comparative Example 5 using citric acid were not as good as those in Examples 1 to 5. Comparative Example 6 using acetylcitric acid showed plasticizing efficiency and elongation properties that were not as good as those in Examples 1 to 5, and showed migration loss and stress resistance that were slightly inferior to those in Examples 1 to 5.

[0215] Meanwhile, in Comparative Examples 7 and 8 using only any one of the isomer mixture of hexanol and benzyl alcohol as the alcohol composition, Comparative Example 7 using only the isomer mixture of hexanol showed tensile strength, mobility and volatilization loss inferior to those of Examples 1 to 5, and Comparative Example 8 using only benzyl alcohol showed plasticizing efficiency, elongation, mobility and stress resistance inferior to those of Examples 1 to 5. The above results show that when the isomer mixture of hexanol and benzyl alcohol are used together, the overall physical properties are improved due to the synergistic effect between the two alcohols, and the balance between the physical properties can be well maintained.

[0216] Finally, Comparative Example 9, in which 2-methylpentanol (one of the hexanols) was used alone instead of the isomer mixture of hexanol, showed tensile properties, elongation properties, mobility, and volatility loss inferior to those of Examples 1 to 5. In Comparative Examples 10 and 11, in which an alcohol having 4 carbon atoms was used instead of hexanol as the alcohol used with benzyl alcohol (Comparative Example 10), or an alcohol having 8 carbon atoms was used (Comparative Example 11), Comparative Example 10 showed significantly poor tensile properties and volatility, while Comparative Example 11 showed significantly poor plasticizing efficiency, elongation properties, mobility, and stress resistance. The results show that only when an alcohol composition containing an isomer mixture of hexanol and benzyl alcohol is used as an alcohol to react with 1,2,3-propanetricarboxylic acid, can excellent physical properties such as Examples 1 to 5 of the present invention be obtained, and when another alcohol is used instead of any of the two alcohols, some physical properties are deteriorated, and therefore, a plasticizer composition having excellent properties may not be provided.

[0217] The above results indicate that when the esterification product of 1,2,3-propanetricarboxylic acid and an alcohol composition comprising an isomer mixture of hexanol and benzyl alcohol is used as a plasticizer as in the examples of the present invention, a plasticizer can be obtained that can fully replace common products and exhibit excellent performance.

Claims

1. A trimesic acid ester plasticizer composition, comprising a propane trimesic acid ester composition containing at least one propane trimesic acid ester of the following formula 1, wherein the alkyl group of the propane tricarboxylate is derived from an alcohol composition comprising an isomeric mixture of hexanol and benzyl alcohol, and The isomeric mixture of hexanol comprises two or more selected from the group consisting of 1-hexanol, 1-methylpentanol, 2-methylpentanol, 3-methylpentanol, 4-methylpentanol, 1,1-dimethylbutanol, 1,2-dimethylbutanol, 1,3-dimethylbutanol, 2,2-dimethylbutanol, 2,3-dimethylbutanol, 3,3-dimethylbutanol, 1-ethylbutanol, 2-ethylbutanol, 3-ethylbutanol and cyclopentylmethanol, and in, The degree of branching of the isomer mixture of hexanol is less than 1.5, [Formula 1] Among them, in formula 1, R1 to R3 are each independently n-hexyl, branched hexyl, cyclopentylmethyl or benzyl.

2. The plasticizer composition according to claim 1, wherein The propane tricarboxylate composition comprises at least one propane tricarboxylate selected from the following formulas 2 to 7: [Formula 2] [Formula 3] [Formula 4] [Formula 5] [Formula 6] [Formula 7] Wherein, in the above formulas 2 to 7, R a are each n-hexyl, branched hexyl or cyclopentylmethyl, and R b It's benzyl.

3. The plasticizer composition according to claim 1, wherein The isomeric mixture of hexanol comprises 1-hexanol, 2-methylpentanol and 3-methylpentanol.

4. The plasticizer composition according to claim 1, wherein The isomer mixture of hexanol includes 40 parts by weight or more of branched alcohol relative to 100 parts by weight of the isomer mixture of hexanol.

5. The plasticizer composition according to claim 1, wherein The isomer mixture of hexanol includes 50 to 95 parts by weight of branched alcohol relative to 100 parts by weight of the isomer mixture of hexanol.

6. The plasticizer composition according to claim 1, wherein The isomer mixture of hexanol contains 40 parts by weight or less of 1-hexanol relative to 100 parts by weight of the isomer mixture of hexanol.

7. The plasticizer composition according to claim 1, wherein The isomeric mixture of hexanol comprises 1-hexanol, 2-methylpentanol, 3-methylpentanol and cyclopentylmethanol.

8. The plasticizer composition according to claim 7, wherein The isomer mixture of hexanol includes 20 parts by weight or less of cyclopentylmethanol relative to 100 parts by weight of the isomer mixture of hexanol.

9. The plasticizer composition according to claim 1, wherein The weight ratio of the isomer mixture of hexanol to benzyl alcohol is 90:10 to 10:

90.

10. A resin composition comprising: 100 parts by weight of a resin; and 5 to 150 parts by weight of the plasticizer composition of claim 1.

11. The resin composition according to claim 10, wherein The resin is one or more selected from the group consisting of linear vinyl chloride polymers, pasty vinyl chloride polymers, ethylene-vinyl acetate copolymers, ethylene polymers, propylene polymers, polyketones, polystyrenes, polyurethanes, polylactic acid, natural rubbers, and synthetic rubbers.

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