KR20140132656A - Method for preparing ester composition and resin composition - Google Patents

Abstract

The present invention relates to a process for producing an ester composition and a resin composition containing the same, and it is an object of the present invention to provide a process for producing an ester composition and a resin composition containing the same, have.

Description

[0001] The present invention relates to a method for preparing an ester composition,

The present invention relates to a process for producing an ester composition and a resin composition, and more particularly, to a process for producing an ester composition and a process for producing the same, ≪ / RTI >

Typically, the plasticizer reacts with the polycarboxylic acid, such as phthalic acid and adipic acid, to form the corresponding ester. Commercially important examples include adipates of C8, C9 and C10 alcohols, such as di (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate; And phthalates of C8, C9 and C10 alcohols such as di (2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate.

In particular, the di (2-ethylhexyl) phthalate has been widely used as an antioxidant in the manufacture of toys, films, shoes, paints, flooring, gloves, wallpaper, artificial leather, sealants, tarpaulins, Foam mats, and soundproofing panels, and can also be used to produce the exterior and insulation of PVC cables, as well as other calendered, plastic PVC products.

Di (2-ethylhexyl) adipate is particularly used in films and is used at low levels in other products such as wallpaper, artificial leather, car floor coatings, gloves, and sealants. Di (2-ethylhexyl) adipate is especially used when the product is intended to be used at low temperatures and / or when a plastisol is used as the process intermediate.

Apart from the di (2-ethylhexyl) adipate, research on environmentally friendly plasticizers is continuing due to environmental problems of phthalate plasticizers.

Accordingly, the inventors of the present invention have been studying environmentally friendly plasticizers and have found that among alkyl-substituted terephthalate compounds of mixed branch type, non-hybrid non-branch type, and non-hybrid branch type, alkyl- substituted terephthalate compounds The ester composition contained within this specific range improves the processability due to the absorption rate and short melting time for the resin and is excellent in the prescription of sheets such as wire, automobile interior material, film, sheet, tube, wallpaper, And thus the present invention has been accomplished.

That is, an object of the present invention is to provide a process for producing an alkyl-substituted terephthalate compound of a mixed branch type, an uncombined unbranched type, and an unblended branched type as an environmentally friendly plasticizer, And to provide an ester composition contained within this specific range.

Another object of the present invention is to provide a resin composition comprising the ester composition.

According to the present invention, there is provided a process for producing an alkyl-substituted terephthalate-based alkyl-substituted terephthalate-based compound, wherein the alkyl-substituted terephthalate-based compound of the mixed branched type, the non-hybrid branched type, The present invention provides a method for producing an ester composition,

Further, according to the present invention, there is provided an ester composition produced by the above method and a resin composition comprising the resin.

Hereinafter, the present invention will be described in detail.

That is, in the present invention, an alkyl-substituted terephthalate compound of a mixed branch type, an uncombined unbranched type, and an unblended branched type is prepared, wherein the mixed branched type alkyl-substituted terephthalate compound is contained in a specific range Ester compositions of the present invention.

The term "hybrid branched type" used in the present invention refers to a structure in which alkyl groups substituted at symmetrical positions of the phenyl group are different from each other and include one branching chain unless otherwise specified.

The term "non-hybrid non-branched type" used in the present invention refers to a structure in which alkyl groups substituted at symmetrical positions of the phenyl group are the same and include two kinds of linear hydrocarbons without branching.

Furthermore, the term "non-hybrid branched type" used in the present invention refers to a structure in which the alkyl group substituted at the symmetrical position of the phenyl group is the same and includes two kinds of branch chains, unless otherwise specified.

According to the present invention, there is provided an alkyl-substituted terephthalate-based alkyl-substituted terephthalate-based alkyl-substituted terephthalate-based alkyl-substituted terephthalate-based alkyl- The compound may be contained in the range of 1 to 70 wt%, 5 to 50 wt%, 10 to 50 wt%, 20 to 50 wt%, or 25 to 50 wt%. The above content range can be achieved by controlling the esterification reaction conditions.

The substituted alkyl may be, for example, an alkyl group having 3 to 10 carbon atoms. In another example, considering the ease of processing (plasticizing efficiency) and the migration loss depending on the fast absorption rate with the resin, An alkyl group having 1 to 4 carbon atoms, and an alkyl group having 8 to 10 carbon atoms.

As another example, the alkyl-substituted terephthalate-based compound of the hybrid branch type may be represented by the following formula 1.

[Chemical Formula 1]

As another example, the non-hybrid non-branched type alkyl-substituted terephthalate-based compound may be represented by the following formula (2).

(2)

As another example, the alkyl-substituted terephthalate-based compound of the non-hybrid branched type may be represented by the following formula (3).

(3)

As another example, the blending ratio of the non-hybrid unbranched type and the non-hybrid branched type alkyl-substituted terephthalate compound is 1:99 to 40:60 Weight ratio, weight ratio of 1:99 to 15:85, 1:99 to 9.9: 90.1, or 1:99 to 9.6: 90.4. Within the above range, processability such as absorption rate and melting time and other physical properties can be improved.

The esterification reaction conditions for satisfying the above-mentioned observations can be performed, for example, by mixing a non-branched alcohol and a branched alcohol.

The unbranched alcohol may be, for example, an unbranched aliphatic alcohol having an alkyl group of C3-C4, and may include 1 to 80% by weight, or 15 to 50% by weight of 100% by weight of the alcohol. As another example, the unbranched alcohol may be n-butyl alcohol.

The branched alcohols are, for example, branched aliphatic alcohols having C8-C10 alkyl groups, and may be contained in an amount of 99 to 20% by weight or 80 to 20% by weight based on 100% by weight of the alcohol. As another example, the branched alcohol may be 2-ethylhexanol.

The esterification reaction conditions for satisfying the above-mentioned aspects may be, for example, using terephthalic acid having an average particle size of 30 to 100 mu m or 39 to 91 mu m. Within this range, the reaction time can be shortened and the productivity can be improved.

As a specific example, the terephthalic acid may be pulverized to the above-mentioned range and then mixed with the alcohol, or may be mixed with the alcohol and then pulverized to the above-mentioned range.

The pulverization may be carried out, for example, by dry pulverization or wet pulverization. As a specific example, a high-speed rotary wet grinding apparatus such as a cavitron, a homogenizer or the like can be used.

As another example, the condition of the high-speed rotation may be from 3,000 to 50,000 rpm, or from 10,000 to 50,000 rpm, so as to quickly reach the desired average particle diameter distribution.

Wherein the terephthalic acid and the alcohol are contained in an amount of 10 to 40 mol% of terephthalic acid and 90 to 60 mol% of alcohol, 20 to 30 mol% of terephthalic acid and 80 to 70 mol% of alcohol, 29 mol% and the alcohol in the range of 79 to 71 mol%. For reference, it is possible to increase the concentration of the reactant in the esterification reaction, which is a reversible reaction within the above range, and increase the reaction rate by suppressing the reverse reaction.

A carboxylic acid, a polycarboxylic acid, an anhydride thereof and the like, if necessary.

The esterification reaction conditions for satisfying the above-mentioned conditions are, for example, 1 to 10 hours at a reaction temperature of 130 to 250 ° C, 130 to 220 ° C, or 180 to 220 ° C, or a reaction time of 5 to 7 hours It may be an alkoxide compound of a metal or an acid catalyst as a reaction catalyst.

Examples of the alkoxide compound of the metal include titanium tetraalkoxide [Ti (OR) ₄ ] such as tetraisobutyl titanate and tetraisopropyl titanate, tin dialkoxide [Sn (OR) ₂ ] such as dibutyl tin oxide and the like It may be at least one selected.

The acid catalyst may be at least one selected from para-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, sulfuric acid, and the like.

The reaction catalyst may be 0.1 to 15 parts by weight, 0.1 to 10 parts by weight, 0.1 to 7 parts by weight, or 0.1 to 5.0 parts by weight based on 100 parts by weight of the reaction raw material terephthalic acid. For reference, the reaction efficiency may be lowered below the above range, and the product may be discolored when the range is exceeded.

The esterification reaction can be carried out under a nitrogen atmosphere for blocking the outside air of the reaction system and nitrogen can be bubbled into the reaction solution to remove water generated during the reaction by the condensation of the esterification reaction. For this purpose or for other purposes, the reaction may be carried out under pressure or under reduced pressure, if necessary.

The resulting plasticizer composition, that is, the ester composition, can be obtained at a purity of from 96 to 99.99%, or from 96.1 to 99.1%, after a usual post-treatment such as neutralization, water washing, and de-alcohol.

The ester composition is, for example, composed of alkyl-substituted terephthalate-based compounds of the mixed branch type, non-hybrid non-branched type, and non-hybrid branched type, wherein the mixed branched type alkyl-substituted terephthalate- By weight, 1 to 19.5% by weight, 1 to 19% by weight, or 5 to 12% by weight, respectively.

The ester composition may be combined with a resin to provide a resin composition. The resin may be at least one selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, thermoplastic elastomer and polylactic acid.

As the resin composition, for example, the absorption rate of the plasticizer is 1 to 10 minutes, 3 to 8 minutes, or 4 to 7 minutes. Within this range, the resin composition has an excellent workability and processability.

The resin and the plasticizer were mixed with each other using a blender (product name: Brabender, P600) under the mixing conditions of 77 ° C, 66 rpm, PVC (product name: LS100, manufactured by LG Chemical Co., Ltd.) and 400 g of plasticizer The time until the torque becomes stabilized is measured and evaluated.

The stabilization of the torque means a state in which the resin is first charged in order to measure the absorption rate, and when the plasticizer is injected, the torque peak is initially increased and then gradually decreased while the torque peak gradually decreases. .

Further, the resin composition has a sol viscosity of 4000 to 15000 cp, 5000 to 11000 cp, or 6000 to 9000 cp, and has an effect of securing stable processability within this range.

The sol viscosity is measured using a Brookfield (LV type) viscometer and the spindle used is # 4 and measured at 6 rpm and 12 rpm. Samples PVC (PB900, LG Chemical) 100phr, plasticizers 75phr, stabilizers (KSZ111XF) 4phr, blowing agent _{(W1039) 3phr, TiO 2 (} TMCA100) 13phr, CaCO3 (OMYA10) 130phr, viscosity-reducing agents (Exa-sol) 10phr, a dispersing agent ( BYK3160) to make a plastisol, and after storage at 25 ° C for 1 hour, measure.

The resin composition may be, for example, a resin composition which is lower in the amount of the viscosity reducing agent than that of the conventional product, or which is not used, that is, a viscosity reducing agent-free resin composition.

The viscosity reducing agent free composition of the present invention means that it does not contain any viscosity reducing agent for controlling the viscosity of the resin composition.

The ester composition may be formulated in an amount of, for example, 5 to 150 parts by weight, or 5 to 100 parts by weight, based on 100 parts by weight of the resin. A plasticizer composition selected from at least one of dioctyl phthalate (DOP), dibutyl phthalate (DBP), dioctyl terephthalate (DOTP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) More preferably 5 to 150 parts by weight, or 5 to 100 parts by weight, based on the weight of the composition.

Further, the resin composition may contain 0.5 to 7 parts by weight of the stabilizer and 0.5 to 3 parts by weight of the lubricant, and if necessary, conventional additives may further be added.

The resin composition may further include a filler, for example.

The filler is not particularly limited as long as it is a filler commonly used in the art to which the present resin composition belongs.

The filler may be, for example, 10 to 300 parts by weight, 50 to 200 parts by weight, or 100 to 200 parts by weight based on 100 parts by weight of the resin.

In addition, the known composition may further include at least one selected from the group consisting of a pigment, a dye, a processing aid, a dispersant, a foaming agent, a defoaming agent, and a viscosity reducing agent.

The pigments, dyes, processing aids, dispersants, foaming agents, antifoaming agents and viscosity reducing agents may be, for example, 0.1 to 20 parts by weight, or 1 to 15 parts by weight, based on 100 parts by weight of the resin.

The resin composition can be used, for example, as a sheet prescription for wires, an automobile interior material, a film, a sheet, a tube, a wallpaper, a toy, a flooring, etc., and a compound prescription product.

According to the present invention, it is possible to appropriately prepare a plasticizer composition capable of providing an improvement in processability by having an absorption rate and a short melting time for the resin.

1 is an optical microscope photograph (x50) of Example 1, Comparative Examples 1 and 2 alone, Dioctyl phthalate (DOP) alone, Diisononyl phthalate (DINP) alone, DOP alone, DINP alone, Comparative Example 2, Comparative Example 1, and Example 1.
2 is an optical microscope photograph (x50) of Example 2, Comparative Examples 1 and 2, Dicophthalate (DOP) alone, Diisononyl Phthalate (DINP) alone, DOP alone, DINP alone, Comparative Example 2, Comparative Examples 1 and 2.

Hereinafter, the present invention will be described in detail with reference to Examples. However, the following examples are only illustrative of the present invention and do not limit the scope of the present invention.

< Example  1>

Terephthalic acid was pulverized using Caviatron and a pulverized product having an average particle size (measured by a laser scattering analyzer (Nicomp 380 instrument)) of 30 to 100 탆 was prepared. 440 g of ground terephthalic acid, 302 g of n-butanol and 530 g of 2-ethylhexanol were esterified under 32 g of 70% methane sulfonic acid at 130 ° C for 7 hours, neutralized with Na2CO3, After the recovery of the solvent, it was dehydrated by heating under reduced pressure to obtain a plasticizer composition.

The obtained plasticizer composition was continuously heated to 280 DEG C at a rate of 10 DEG C per minute for 3 minutes at an initial temperature of 70 DEG C for 5 minutes after being heated by a GC-Mass analyzer (product name: Agilent 7890 GC, column: HP- ). As a result, it was confirmed that the material was composed of materials having the following formulas (1), (2) and (3).

[Chemical Formula 1]

(2)

(3)

It was confirmed that the weight ratio of the formula 1: Formula 2: Formula 3 was 50:10:40.

< Example  2>

440 g of ground terephthalic acid, 98 g of n-butanol and 823 g of 2-ethylhexanol were reacted in the same manner as in Example 1 except that the reaction was carried out at 32 ° C under 70 g of methane sulfonic acid at 140 ° C. for 6 hours The same experiment as in Example 1 was repeated to prepare a plasticizer composition. As a result of analysis by GC-Mass spectrometer, it was confirmed that the weight ratio of Formula 1: Formula 2: Formula 3 was 25: 3: 72.

< Example 3 >

440 g of ground terephthalic acid, 49 g of n-butanol and 909 g of 2-ethylhexanol were reacted in the same manner as in Example 1 except that the reaction was carried out at 32 DEG C under 70% methane sulfonic acid at 140 DEG C for 6 hours The same experiment as in Example 1 was repeated to prepare a plasticizer composition. As a result of analyzing with a GC-Mass analyzer, it was confirmed that the weight ratio of Formula 1: Formula 2: Formula 3 was 12: 2: 86.

< Example 4 >

440 g of ground terephthalic acid, 25 g of n-butanol and 951 g of 2-ethylhexanol were reacted in the same manner as in Example 1 except that the reaction was carried out at 32 ° C under 70% of methane sulfonic acid at 140 ° C. for 6 hours The same experiment as in Example 1 was repeated to prepare a plasticizer composition. Further, analysis by a GC-Mass spectrometer showed that the weight ratio of the above-mentioned Formula 1: Formula 2: Formula 3 was 5: 1: 94.

< Comparative Example  1>

A plasticizer was prepared in the same manner as in Example 1, except that 440 g of terephthalic acid and 890 g of n-butanol were reacted at 130 캜 for 13 hours.

The obtained plasticizer was analyzed by a GC-Mass analyzer, and as a result, a compound having the following formula 2 could be identified.

(2)

< Comparative Example  2>

The same procedure as in Example 1 was repeated except that 440 g of terephthalic acid and 1,060 g of 2-ethylhexanol were reacted at 220 캜 for 5 hours using 1.6 g of tetraisopropyl titanate catalyst to obtain a plasticizer A composition was prepared.

The obtained plasticizer was analyzed by a GC-Mass analyzer, and as a result, a compound having the following formula (3) was confirmed.

(3)

<Application example>

5 to 100 parts by weight of the plasticizer, DOP alone, and DINP obtained in Examples 1-4 and Comparative Examples 1-2 were added to 100 parts by weight of a vinyl chloride resin, and a stabilizer, a lubricant and a foaming agent were added and extruded And the physical properties such as the absorption rate and the workability were evaluated.

The dissolution rate (Fusion Test) of Example 1 was 244 seconds when measured under the conditions of 77 ° C, 60 rpm / PVC (LS 100) 400 Plasticizer, and 244 seconds when using dioctyl phthalate (DOP) alone ), And was superior to that of dioctyl terephthalate (DOTP) of Comparative Example 2 alone (428 seconds). As a result of measurement, the melting test of Example 1 was 32 sec.

Also, the anti-migratory property of Example 1 was 3.75%, which was calculated by measuring the loss of the plasticizer due to migration after heating at 80 DEG C for 72 hours, as a migration loss.

1, the foamability of the wallpaper prepared with the sample of Example 1 was evaluated by measuring the cell state after foaming with an optical microscope, using dioctyl phthalate (DOP ) Alone, diisononyl phthalate (DINP) alone, and dioctyl terephthalate (DOTP) alone were observed to have uniform cell size, shape and arrangement.

The dissolution rate (Fusion Test) of Example 2 was 280 seconds when the mixing time was measured under the condition of 200 g of a plasticizer of 60 rpm / PVC (product name: LS 100) at 77 DEG C and when using dioctyl phthalate (DOP) alone 306 seconds) and showed a much better level than that of dioctyl terephthalate (DOTP) of Comparative Example 2 as in Example 1. [ The melting test result of Example 2 was 38 sec, and the result of the measurement of the anti-fogging property was 3.46%.

2, the foamability of the wallpaper prepared with the sample of Example 1 was evaluated by measuring the cell state after foaming by means of an optical microscope, using dioctyl phthalate (DOP) It was observed that cell size, shape, and arrangement were homogeneous when used alone, diisononyl phthalate (DINP) alone, and dioctyl terephthalate (DOTP) alone.

On the other hand, the absorption rate of Comparative Example 1 was 100 seconds when the mixing time was measured under the conditions of 77 rpm / 60 rpm / PVC (product name: LS 100) 400 Plasticizer, and when using dioctyl phthalate (DOP) alone Which was much lower.

Also, the migration loss calculated from the loss of plasticizer after heating at 80 ℃ for 72 hours showed 10.56%, which is higher than 3.95% when using DOP alone. This indicates that the product of Comparative Example 1 has increased migration due to the low molecular weight and the disadvantageous structure compared to DOP. In Comparative Example 2, the migration loss was only 0.22%.

Further, as shown in FIGS. 1 and 2, the foamability of the wallpaper prepared in Comparative Example 1 was observed to be more uniform in the size, shape, and arrangement of cells after foaming than when using DOP alone, DINP alone, or DOTP alone. The result of the melting test of Comparative Example 1 was 138 sec, and the result of measurement of the inner resistance was 3.54%.

The measured values are summarized in Table 1 below.

division DOP alone DINP alone Comparative Example 2 Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Absorption rate
(min: sec) 5:06 6:20 7:08 1:40 4:04 4:40 5:21 6:35 Melting test (sec) 32 45 138 22 32 38 68 95 Transitability (%) 3.95 3.29 3.54 10.56 3.75 3.46 3.40 3.41

As a result, in the case of Examples 1-4 in which ester plasticizers containing all of the ester plasticizers in an appropriate mixing ratio were compared with the measurement results of Examples 1-4 and Comparative Examples 1-2, preferable results were obtained in terms of all physical properties .

On the other hand, in the case of Comparative Example 1 in which the compound of Formula 2 alone was used, (In this case, rather, the gelation is promoted to deteriorate the workability and foaming properties), but the disadvantage that the degree of migration is increased as much as that.

Further, in the case of Comparative Example 2 in which the compound of the formula (3) was used singly, migration did not occur, but a disadvantage that absorption and melting took a long time was confirmed.

Claims (19)

Wherein the mixed branched type alkyl-substituted terephthalate-based compound is in the range of 1 to 70 wt%, and the mixed branched type alkyl-substituted terephthalate- Lt; RTI ID = 0.0 &gt; of: &lt; / RTI &gt; The method according to claim 1,
Wherein the mixed branched type alkyl-substituted terephthalate compound is contained in an amount of 1 to 20% by weight. The method according to claim 1,
Wherein the esterification reaction is carried out in the presence of an acid catalyst. The method according to claim 1,
Wherein the mixed branched type alkyl-substituted terephthalate compound is represented by the following formula 1. &lt; EMI ID = 1.0 &gt;
[Chemical Formula 1]

The method according to claim 1,
Wherein the non-hybrid non-branched type alkyl-substituted terephthalate compound is represented by the following formula (2).
(2)

The method according to claim 1,
Wherein the non-hybrid branched type alkyl-substituted terephthalate compound is represented by the following formula (3).
(3)

The method of claim 1, wherein
The blending ratio of the non-hybrid unbranched type and the non-hybrid branched type alkyl-substituted terephthalate compound is 1:99 to 40:60 By weight based on the total weight of the ester composition. The method according to claim 1,
Wherein said esterification reaction is carried out using an acid catalyst at 130-250 &lt; 0 &gt; C for 1 to 10 hours with terephthalic acid, unbranched alcohol and branched alcohols. The method of claim 1, wherein
Wherein the unbranched alcohol comprises an unbranched aliphatic alcohol having a C3-C4 alkyl group in an amount of 1 to 80% by weight based on 100% by weight of the alcohol. The method according to claim 1,
Wherein the branched alcohol comprises a branched aliphatic alcohol having a C8-C10 alkyl group in a range of 99 to 20% by weight based on 100% by weight of the alcohol. The method according to claim 1,
Wherein the terephthalic acid, the unbranched alcohol and the branched alcohol are used in an amount of 10 to 40 mol% of terephthalic acid and 90 to 60 mol% of unbranched alcohol and branched alcohol, based on the sum of the moles of the total reactants. Way. The method of claim 3,
Wherein the acid catalyst is at least one member selected from para-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid and sulfuric acid. A resin composition comprising an ester composition prepared by the process of any one of claims 1 to 12 and a resin. 14. The method of claim 13,
Wherein the resin composition has an absorption rate of 1 minute to 10 minutes. 14. The method of claim 13,
Wherein the resin composition has a sol viscosity of 4000 to 13000 cp.
14. The method of claim 13,
Wherein the resin is at least one selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, thermoplastic elastomer and polylactic acid. 14. The method of claim 13,
Wherein the ester composition is in a range of 5 to 150 parts by weight based on 100 parts by weight of the resin. 14. The method of claim 13,
Wherein the resin composition further comprises a filler. 14. The method of claim 13,
Wherein the resin composition further comprises at least one member selected from the group consisting of a stabilizer, a lubricant, a pigment, a dye, a processing aid, a dispersant, a foaming agent, a defoaming agent and a viscosity reducing agent.

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