Title of Invention: Citrate-based plasticizer composition and resin composition comprising same
technical field
[One]
Cross Citation with Related Applications
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0005440 dated January 15, 2020, and all contents disclosed in the literature of the Korean patent application are incorporated as a part of this specification.
[3]
[4]
technical field
[5]
The present invention relates to a citrate-based plasticizer composition comprising a hybrid citrate of lower and higher alkyl radicals of components in the composition, and a resin composition comprising the same.
[6]
background
[7]
Plasticizers typically react with alcohols with 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 harmful to the human body, research on plasticizer compositions that can replace phthalate-based plasticizers such as terephthalate, adipate, and other polymer-based plasticizers is continuing.
[8]
[9]
On the other hand, regardless of the plastisol industry such as flooring, wallpaper, soft and hard sheet, calendaring industry, and extrusion/injection compound industry, the demand for these eco-friendly products is increasing, and the quality characteristics, processability and In order to enhance productivity, an appropriate plasticizer should be used in consideration of discoloration, transferability, and mechanical properties.
[10]
In these various areas of use, additives such as plasticizers, fillers, stabilizers, viscosity reducing agents, dispersants, defoamers, foaming agents, etc. will do
[11]
For example, among the plasticizer compositions applicable to PVC, when di(2-ethylhexyl) terephthalate (DEHTP), which is relatively inexpensive and most commonly used, is applied, hardness or sol viscosity is high and the absorption rate of the plasticizer is relatively slow, and the transferability and stress transferability were not good.
[12]
As an improvement to this, as a composition containing DEHTP, it may be considered to apply the product of the transesterification reaction with butanol as a plasticizer, but the plasticization efficiency is improved, but the loss of heating or thermal stability is poor, and mechanical properties Improvement of physical properties is required, such as a slight decrease in this, and there is currently no solution other than adopting a method to compensate for this through mixing with other secondary plasticizers in general.
[13]
However, when a secondary plasticizer is applied, it is difficult to predict the change in physical properties, and it may act as a factor in increasing the unit price of the product. The downside is that there are no problems.
[14]
In addition, when a substance such as tri(2-ethylhexyl) trimellitate or triisononyl trimellitate is applied as a trimellitate-based product in order to improve the poor transferability and weight loss characteristics of the DEHTP product, transferability or While the weight loss characteristics are improved, the plasticization efficiency is poor, and there is a problem that a considerable amount must be added to give an appropriate plasticizing effect to the resin. .
[15]
Accordingly, as an existing product, there is a need to develop products for solving environmental issues of phthalate-based products or products with improved poor physical properties of eco-friendly products for improving environmental issues of phthalate-based products.
[16]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[17]
The present invention is a plasticizer composition, which includes citrates in which lower and higher alkyl radicals are appropriately controlled and combined, thereby improving mechanical properties and stress resistance compared to conventional plasticizers, and at the same time improving migration resistance and weight loss characteristics and plasticizing efficiency. An object of the present invention is to provide a plasticizer composition capable of balanced improvement and improving heat resistance (residual rate characteristic).
[18]
means of solving the problem
[19]
According to one embodiment of the present invention in order to solve the above problems, a citrate-based composition including three or more citrates of Formula 1 is included, and the alkyl group of the citrate is derived from C4 alcohol and C7 alcohol, The C4 alcohol includes at least one selected from n-butanol and isobutanol, and the C7 alcohol includes at least one selected from an n-heptyl group and a branched heptyl group.
[20]
[Formula 1]
[21]

[22]
In Formula 1, R 1 to R 3 are each independently an alkyl group having 4 or 7 carbon atoms, and R 4 is hydrogen or an acetyl group.
[23]
[24]
According to another embodiment of the present invention in order to solve the above problems, 100 parts by weight of the resin; And 5 to 150 parts by weight of the above-mentioned plasticizer composition; is provided a resin composition comprising.
[25]
The resin may be at least one selected from the group consisting of straight vinyl chloride polymer, paste vinyl chloride polymer, ethylene vinyl acetate copolymer, ethylene polymer, propylene polymer, polyketone, polystyrene, polyurethane, natural rubber and synthetic rubber.
[26]
Effects of the Invention
[27]
The plasticizer composition according to an embodiment of the present invention, when used in a resin composition, improves mechanical properties and stress resistance compared to conventional plasticizers, and at the same time improves weight loss characteristics and plasticization efficiency, and improves migration resistance and residual rate characteristics. can be improved
[28]
Modes for carrying out the invention
[29]
The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of ​​the present invention.
[30]
[31]
Definition of Terms
[32]
The term "composition" as used herein includes reaction products and decomposition products formed from materials of the composition, as well as mixtures of materials comprising the composition.
[33]
As used herein, "straight vinyl chloride polymer" is one of the types of vinyl chloride polymer, and is polymerized through suspension polymerization or bulk polymerization. The polymer is a porous particle having a plurality of pores, has a size of several tens to several hundreds of micrometers, has no cohesiveness, and has excellent flowability.
[34]
As used herein, "paste vinyl chloride polymer" is one of the types of vinyl chloride polymer, and is polymerized through microsuspension polymerization, microseed polymerization, or emulsion polymerization. This polymer is fine, dense particles without pores, has a size of several tens to thousands of nanometers, is cohesive, and has poor flowability.
[35]
The terms 'comprising', 'having' and their derivatives are not intended to exclude the presence of any additional component, step or procedure, whether or not they are specifically disclosed. For the avoidance of any doubt, all compositions claimed through use of the term 'comprising', unless stated to the contrary, contain any additional additives, adjuvants, or compounds, whether polymeric or otherwise. may include In contrast, the term 'consisting essentially of' excludes from the scope of any subsequent description any other component, step or procedure, except as is not essential to operability. The term 'consisting of' excludes any component, step or procedure not specifically described or listed.
[36]
[37]
measurement method
[38]
In the present specification, analysis of the content of components in the composition is performed through gas chromatography measurement, and Agilent's gas chromatography instrument (product name: Agilent 7890 GC, column: HP-5, carrier gas: helium (flow rate 2.4 mL/min)) , detector: FID, injection volume: 1uL, initial value: 70℃/4.2min, end value: 280℃/7.8min, program rate: 15℃/min).
[39]
In the present specification, 'hardness' means the shore hardness (Shore "A" and / or Shore "D") at 25 ° C using ASTM D2240, measured under the conditions of 3T 10s, and plasticized It can be an index to evaluate the efficiency, and the lower it is, the better the plasticization efficiency is.
[40]
In the present specification, 'tensile strength' is a crosshead speed of 200 mm/min (1T) using a test device, UTM (manufacturer; Instron, model name; 4466), according to the ASTM D638 method. ), measure the point at which the specimen is cut, and calculate by Equation 1 below.
[41]
[Equation 1]
[42]
Tensile strength (kgf/cm 2 ) = load value (kgf) / thickness (cm) x width (cm)
[43]
In the present specification, the 'elongation rate' refers to the point at which the specimen is cut after pulling the cross head speed to 200 mm/min (1T) using the UTM according to the ASTM D638 method. Then, it is calculated by Equation 2 below.
[44]
[Equation 2]
[45]
Elongation (%) = length after stretching / initial length x 100
[46]
In the present specification, 'migration loss' refers to obtaining a test piece having a thickness of 2 mm or more according to KSM-3156, attaching a glass plate to both sides of the test piece, and then applying a load of 1 kgf/cm 2 . After leaving the test piece in a hot air circulation oven (80°C) for 72 hours, take it out and cool it at room temperature for 4 hours. Then, after removing the glass plate attached to both sides of the test piece, measure the weight before and after leaving the glass plate and the specimen plate in the oven to calculate the transfer loss by Equation 3 below.
[47]
[Equation 3]
[48]
Transition loss (%) = {[(initial weight of specimen at room temperature) - (weight of specimen after leaving in oven)] / (weight of initial specimen at room temperature)} x 100
[49]
In the present specification, 'volatile loss' refers to measuring the weight of the specimen after working the specimen at 80°C for 72 hours.
[50]
[Equation 4]
[51]
Loss on heating (wt%) = {[(initial specimen weight - after working specimen weight)] / (initial specimen weight)} x 100
[52]
In the case of the various measurement conditions, detailed conditions such as temperature, rotation speed, time, etc. may be slightly different depending on the case, and in the case of different conditions, the measurement method and conditions are separately specified.
[53]
[54]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[55]
According to an embodiment of the present invention, the plasticizer composition includes a citrate-based composition including three or more citrates of Formula 1, wherein the alkyl group of the citrate is derived from C4 alcohol and C7 alcohol, and the C4 alcohol includes at least one selected from n-butanol and isobutanol, and the C7 alcohol includes at least one selected from n-heptyl group and branched heptyl group.
[56]
[Formula 1]
[57]

[58]
In Formula 1, R 1 to R 3 are each independently an alkyl group having 4 or 7 carbon atoms, and R 4 is hydrogen or an acetyl group.
[59]
[60]
Specifically, the citrate-based composition includes a lower non-hybridized citrate having a C4 alcohol-derived alkyl group and a lower hybrid citrate having a C4 alcohol-derived alkyl group and a C7 alcohol-derived alkyl group, but having more C4 alcohol-derived alkyl groups. based citrate; and higher alkyl-based citrates including higher hybrid citrates having C4 alcohol-derived alkyl groups and C7 alcohol-derived alkyl groups but having more C7 alcohol-derived alkyl groups and higher non-hybridizing citrates having C7 alcohol-derived alkyl groups; there is.
[61]
More specifically, according to an embodiment of the present invention, the citrate-based composition included in the plasticizer composition includes a total of four types of citrate, and a higher alkyl-based citrate in which two or more C7 alkyl groups are bonded (Formula 1- 4 to 1-6) and a lower alkyl-based citrate in which two or more C4 alkyl groups are bonded (Formulas 1-1 to 1-3). In addition, the lower alkyl-based citrate is a lower non-hybridized citrate (Formula 1-1) in which all three ester groups of the citrate are bonded to a C4 alkyl group, and a lower hybrid citrate in which a C4 alkyl group is bonded to two ester groups ( Formulas 1-2 and 1-3), and higher alkyl-based citrates are also classified into higher non-hybridized citrates (Formulas 1-6 and higher hybrid citrates (Formulas 1-4 and 1-5) Specifically, in the case of citrates represented by Formulas 1-3 and 1-5, optical isomers may exist due to the presence of chiral carbon, but in the present specification, they are not treated separately as other compounds. .
[62]
Here, the 'alkyl group bonded' may mean an alkyl group bonded to the three ester groups of the citrate.
[63]
In addition, the 'non-hybrid' or 'hybrid' is based on the alkyl group bonded to the triester, and distinguishes whether the alkyl radicals are bonded only with the same number of carbon atoms or are bonded with those with different carbon numbers, and the three ester groups When all alkyl groups having the same carbon number are bonded to each other, it may be referred to as 'non-hybrid', and when alkyl groups having different carbon atoms are mixed and bonded to the three ester groups, it may be referred to as 'hybrid'. In detail, the hybrid and non-hybridization are distinguished based on the number of carbon atoms, and for example, in the case where the heptyl group is bound to the same number of carbon atoms, even if the n-heptyl group and the branched heptyl group are hybridized together, in the present specification, the number of carbon atoms is Since it is the same, it means 'immiscible', and the same is true for the butyl group.
[64]
Chemical formulas 1-1 to 1-6 representing each of the higher alkyl-based citrate and the lower alkyl-based citrate in the citrate-based composition are as follows.
[65]
[Formula 1-1]
[66]

[67]
[Formula 1-2]
[68]

[69]
[Formula 1-3]
[70]

[71]
[Formula 1-4]
[72]

[73]
[Formula 1-5]
[74]

[75]
[Formula 1-6]
[76]

[77]
In Formulas 1-1 to 1-6, R L is an n-butyl group or an isobutyl group, R H is an n-heptyl group or a branched heptyl group, and R a is hydrogen or an acetyl group.
[78]
The plasticizer composition is a direct esterification reaction of a mixture of citric acid or a citric acid derivative and an alcohol having an alkyl group having 4 and 7 carbon atoms, or a citrate having an alkyl group having 4 (or 7) carbon atoms and 7 (or 4) carbon atoms. It may be a product produced by the transesterification reaction of phosphorus alcohol, in which case the alcohol to be applied may be a mixture of structural isomers or may be a single material, for example, purified n- when the number of carbon atoms is 4 It may be butanol alone, if it has 7 carbon atoms, it may be n-heptanol or isoheptanol alone, if it has 4 carbon atoms, it is a mixture of n-butanol and isobutanol, or if it has 7 carbon atoms, n-heptanol and branched type It may be a mixture of heptanols.
[79]
[80]
As described above, the plasticizer composition according to an embodiment of the present invention includes a total of four types of citrate, so that an excellent effect can be realized according to a combination of alkyl groups bonded to each type.
[81]
Specifically, the balance of the alkyl group between the higher non-hybridized citrate and the lower non-hybridized citrate, and the coexistence of the hybrid types in the composition, furthermore, what proportion of the lower alkyl group and the higher alkyl group in the total alkyl radical is controlled, furthermore When any one alkyl group is derived from a mixed alcohol, due to characteristics such as the ratio of specific branched alkyl radicals among the branched alkyl groups, it is possible to balance the physical properties of plasticization efficiency and transferability / weight loss characteristics, Due to the interaction of the four types of citrates included in the composition, it is possible to achieve a remarkable improvement in mechanical properties, stress resistance, and also residual ratio characteristics.
[82]
Through this, it is possible to implement a product with improved weight loss characteristics while removing the environmental issues of existing phthalate products, and it is possible to significantly improve the transferability and weight loss characteristics of existing terephthalate products, and compared to existing commercial products. Therefore, it may be possible to realize a product with significantly improved mechanical properties and stress resistance.
[83]
In order to more optimally and preferably implement the above effects, it may be important to match the conditions of R L and R H defined in Chemical Formulas 1-1 to 1-6.
[84]
R L and R H may each be an n-butyl group or an isobutyl group, and an n-heptyl group or a branched heptyl group as defined. These alkyl radicals are factors that can determine the interaction between each type of citrate included in the citrate-based plasticizer composition and the weight of the entire composition, and can play a major role in achieving the effect.
[85]
Preferably, R L is an alkyl group having 4 carbon atoms, and may be an n-butyl group or an isobutyl group. In addition, R H is an alkyl group having 7 carbon atoms, and may be an n-heptyl group or a branched heptyl group, and the branched heptyl group is 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2 -ethylpentyl, 3-ethylpentyl, 4-ethylpentyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3,4-dimethylpentyl and 4 , may be one selected from the group consisting of dimethylpentyl, preferably R H is n-heptyl group, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl group, 2,2- dimethylpentyl, 2,3-dimethylpentyl, or 2,4-dimethylpentyl.
[86]
According to an embodiment of the present invention, the C7 alcohol may essentially include n-heptanol. There are various isomers of C7 alcohol. Among them, it may be preferable to include n-heptanol as C7 alcohol. As n-heptanol is a linear alcohol, the performance of the plasticizer can be improved due to the proper control of intermolecular interactions and steric hindrance effects, which is a synergistic effect associated with the fact that the lower alcohol, 2-ethylhexanol, is a branched alcohol. may be caused by
[87]
In addition, the C7 alcohol includes n-heptanol, but may include one or more branched alcohols selected from 4-methylhexanol and 5-methylhexanol, and the n-heptanol is based on the total weight of the C7 alcohol. It may be included in an amount of 50% by weight or more. C7 alcohol may be used in the form of a mixture of isomers, and in this case, when n-heptanol is included in 50 wt% or more in the mixture, the plasticizer performance may be improved.
[88]
[89]
In the plasticizer composition according to an embodiment of the present invention, in order to further optimize the effect implementation according to the present invention, the ratio of each alkyl group can be adjusted. The weight ratio may be controlled from 80:20 to 1:99, preferably from 80:20 to 5:95, or from 80:20 to 10:90, more preferably from 70:30 to 20:80. By using the lower alkyl-based citrate, which are the citrates represented by Chemical Formulas 1 to 3, in excess of the higher alkyl-based citrate (Formulas 4 to 6), it is possible to control the weight of the entire plasticizer composition, and thus You can expect great performance improvement.
[90]
In more detail, the factors determining the structural properties of the plasticizer composition according to an embodiment of the present invention include non-hybrid citrates of Formulas 1-1 and 1-6 and hybrid citrates of Formulas 1-2 to 1-6. As to control the weight ratio, these weight ratios may be from 80:20 to 5:95, preferably from 70:30 to 10:90, more preferably from 60:40 to 20:80, non-hybrid to hybrid. can In the ester reaction process for preparing the composition, by controlling the reaction, it is possible to control the amount of the product to which the mixed alkyl group is bound, and through this, it can play a large role in achieving the effect.
[91]
Likewise, in the higher alkyl-based citrate, the weight ratio of the higher unhybridized formula (6) to the higher hybrid formula (4) and (5) in the higher alkyl citrate is 80:20 to 20:80, preferably 70:30 to 30:70, more preferably 60: Controlling 40 to 30:70 can also play a similar role, so it is necessary to pay attention to improving the effect of the resulting plasticizer composition by controlling the weight ratio between citrates contained in the higher alkyl-based citrate through appropriate control during the reaction. there is
[92]
When the components of the plasticizer composition according to the present invention are configured within the above range, productivity in the manufacturing process can be increased, as well as productivity in the manufacturing process, in consideration of the equivalent ratio of the materials used as reactants or the actual yield and conversion rate of the reaction. It is possible to prevent deterioration of mechanical properties such as tensile strength and elongation, and significant improvement in light resistance can be exhibited.
[93]
On the other hand, in the case of the substituent defined as R a of the citrate, a hydrogen or an acetyl group may be bonded, but improvement and optimization of mechanical properties such as physical properties of the plasticizer, particularly processability, melting properties, and elongation due to deterioration of plasticization efficiency For this, it may be more preferable that hydrogen is bonded. In addition, when the acetyl group is bonded, it is necessary to consider that it may be difficult to exclude the problem of economic degradation such as cost increase due to production problems such as the addition of a manufacturing process and treatment facility due to the generation of spent acetic acid.
[94]
[95]
The method for preparing a plasticizer composition according to an embodiment of the present invention is a method known in the art, and may be applied without particular limitation if it can prepare the above-described plasticizer composition.
[96]
For example, the composition may be prepared by directly esterifying citric acid or anhydride thereof with two or more alcohols, or the composition may be prepared by transesterifying citrate and one alcohol by transesterification.
[97]
The plasticizer composition according to an embodiment of the present invention is a material prepared by appropriately performing the esterification reaction, and if it meets the above conditions, in particular, if the ratio of the branched alcohol in the isomer mixed alcohol is controlled, the manufacturing method is not particularly limited.
[98]
As an example, the direct esterification reaction comprises the steps of adding citric acid and two or more alcohols, then adding a catalyst and reacting in a nitrogen atmosphere; removing unreacted alcohol and neutralizing unreacted acid; and dehydration and filtration by vacuum distillation.
[99]
The alcohol may be a mono-alcohol having an alkyl group corresponding to R H and R L in Formulas 1-1 to 1-6, and a mono-alcohol having an alkyl group of R L and a mono-alcohol having an alkyl group of R H The weight ratio of the liver may act as a major factor in determining the component ratio in the prepared composition. For example, the C4 alcohol and the C7 alcohol may have a weight ratio of 90:10 to 10:90, preferably 80:20 to 10:90, more preferably 75:25 to 10:90, or 70:30 to 10:90, even more preferably 60:40 to 10:90.
[100]
The alcohol is, based on 100 mol% of the acid, 150 mol% to 500 mol%, 200 mol% to 400 mol%, 200 mol% to 350 mol%, 250 mol% to 400 mol%, or 270 mol% to 330 mol% It can be used within the range, and by controlling the content of this alcohol, it is possible to control the component ratio in the final composition.
[101]
The catalyst is, for example, an acid catalyst such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, para-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, alkyl sulfuric acid, aluminum lactate, lithium fluoride, potassium chloride, cesium chloride, calcium chloride, It may be at least one selected from metal salts such as iron chloride and aluminum phosphate, metal oxides such as heteropolyacids, natural/synthetic zeolites, cation and anion exchange resins, tetraalkyl titanate and organometallics such as polymers thereof. As a specific example, the catalyst may be tetraalkyl titanate. Preferably, para-toluenesulfonic acid, methanesulfonic acid, etc. may be suitable as an acid catalyst having a low activation temperature.
[102]
The amount of catalyst used may vary depending on the type, for example, in the case of a homogeneous catalyst, 0.01 wt% to 5.0 wt%, 0.01 wt% to 3.0 wt%, 1.0 wt% to 5.0 wt% or within the range of 2.0 wt% to 4.0 wt%, and in the case of a heterogeneous catalyst from 5 wt% to 200 wt%, from 5 wt% to 100 wt%, from 20 wt% to 200 wt%, or from 20 wt% to 150 wt% % can be within the range.
[103]
In this case, the reaction temperature may be in the range of 180 °C to 280 °C, 200 °C to 250 °C, or 210 °C to 230 °C.
[104]
[105]
In another example, the transesterification reaction is performed with citrate and an alcohol having an alkyl radical having a different carbon number from the alkyl radical of the citrate (in the case of citrate to which a higher alkyl group is bonded, a lower alkyl alcohol or a sheet to which a lower alkyl group is bonded) In the case of a rate, a higher alkyl alcohol) may be reacted. Here, the alkyl groups of the citrate and the alcohol may cross each other.
[106]
As used herein, "transesterification reaction" refers to a reaction in which an alcohol and an ester are reacted to exchange an alkyl of the ester and an alkyl of the alcohol:
[107]
In the case of citrate included in the plasticizer composition according to the present invention, when two ester groups are exchanged and when one ester group is exchanged depending on the ester group bonding position, three types may be formed, respectively, and accordingly, in the final composition may contain a mixture of up to 8 compounds (including structural isomers and optical isomers).
[108]
In addition, the transesterification reaction has the advantage of not causing a wastewater problem compared to the acid-alcohol esterification reaction.
[109]
In the mixture prepared by the transesterification reaction, the composition ratio of the mixture may be controlled according to the amount of alcohol added. The amount of the alcohol added may be 10 parts by weight to 200 parts by weight, specifically 20 parts by weight to 150 parts by weight, and more specifically 30 parts by weight to 120 parts by weight based on 100 parts by weight of the citrate compound. For reference, determining the component ratio in the final composition may be the amount of alcohol added as in the direct esterification reaction.
[110]
That is, as the amount of alcohol added to the citrate-based composition increases, the mole fraction of citrate participating in the transesterification reaction will increase. Therefore, the content of citrate as a product in the mixture may increase, Correspondingly, the content of unreacted citrate may tend to decrease.
[111]
According to an embodiment of the present invention, the molar ratio of the reactant citrate to the alcohol is, for example, 1:0.005 to 1:10, 1:0.05 to 1:8, or 1:0.1 to 1:6, within this range Fairness and economic efficiency may be excellent, and there is an effect of obtaining a plasticizer composition that can implement the above-described effects.
[112]
According to an embodiment of the present invention, the transesterification 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 Preferably, it is carried out in 30 minutes to 8 hours, more preferably in 1 hour to 6 hours. Within the above temperature and time range, it is possible to efficiently control the component ratio of the final plasticizer composition. In this case, the reaction time may be calculated from the point at which the reaction temperature is reached after the reactant is heated.
[113]
The transesterification reaction may be carried out under an acid catalyst or a metal catalyst, and in this case, the reaction time is shortened.
[114]
The acid catalyst may be, for example, sulfuric acid, methanesulfonic acid or p-toluenesulfonic acid, and the metal catalyst may be, for example, an organometallic catalyst, a metal oxide catalyst, a metal salt catalyst, or a metal itself.
[115]
The metal component may be, for example, any one selected from the group consisting of tin, titanium, and zirconium, or a mixture of two or more thereof.
[116]
In addition, the method may further include distilling and removing unreacted alcohol and reaction by-products after the transesterification reaction. The distillation may be, for example, a two-step distillation in which the alcohol and the reaction by-products are separated using a boiling point difference. In another example, the distillation may be mixed distillation. In this case, there is an effect of relatively stably securing the ester-based plasticizer composition in a desired composition ratio. The mixed distillation means simultaneously distilling unreacted alcohol and reaction by-products.
[117]
[118]
According to another embodiment of the present invention, there is provided a resin composition comprising the above-described plasticizer composition and resin.
[119]
As the resin, a resin known in the art may be used. For example, straight vinyl chloride polymer, paste vinyl chloride polymer, ethylene vinyl acetate copolymer, ethylene polymer, propylene polymer, polyketone, polystyrene, polyurethane, at least one mixture selected from the group consisting of natural rubber and synthetic rubber, etc. It can be used, but is not limited thereto.
[120]
The plasticizer composition may be included in an amount of 5 parts by weight to 150 parts by weight, preferably 5 parts by weight to 130 parts by weight, or 10 parts by weight to 120 parts by weight based on 100 parts by weight of the resin.
[121]
In general, the resin in which the plasticizer composition is used may be manufactured into a resin product through melt processing or plastisol processing, and the melt processing resin and the plastisol processing resin may be produced differently according to each polymerization method.
[122]
For example, when a vinyl chloride polymer is melt-processed, solid resin particles with a large average particle diameter are used, which are prepared by suspension polymerization, etc., and this vinyl chloride polymer is a straight vinyl chloride polymer, and when processed with plastisol, emulsion polymerization, etc. A resin in a sol state in which fine resin particles are dispersed is used, and this vinyl chloride polymer is a paste vinyl chloride resin.
[123]
At this time, in the case of the straight vinyl chloride polymer, the plasticizer is preferably included in the range of 5 to 80 parts by weight based on 100 parts by weight of the polymer, and in the case of the paste vinyl chloride polymer, 40 parts by weight to 120 parts by weight based on 100 parts by weight of the polymer. It is preferably included within the range of parts by weight.
[124]
The resin composition may further include a filler. The filler may be 0 parts by weight to 300 parts by weight, preferably 50 parts by weight to 200 parts by weight, more preferably 100 parts by weight to 200 parts by weight based on 100 parts by weight of the resin.
[125]
As the filler, any filler known in the art may be used, and the filler is not particularly limited. For example, it may be a mixture of one or more selected from silica, magnesium carbonate, calcium carbonate, coal, talc, magnesium hydroxide, titanium dioxide, magnesium oxide, calcium hydroxide, aluminum hydroxide, aluminum silicate, magnesium silicate and barium sulfate.
[126]
In addition, the resin composition may further include other additives such as a stabilizer, if necessary. Other additives such as the stabilizer may be, for example, 0 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the resin.
[127]
The stabilizer may be, for example, a calcium-zinc (Ca-Zn-based) stabilizer or a barium-zinc (Ba-Zn-based) stabilizer such as a calcium-zinc complex stearate salt, but is not particularly limited thereto. not.
[128]
The resin composition may be applied to both melt processing and plastisol processing as described above, for example, melt processing may include calendering processing, extrusion processing, or injection processing, and plastisol processing may include coating processing, etc. This can be applied.
[129]
[130]
Example
[131]
Hereinafter, in order to describe the present invention in detail, examples will be described in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described in detail below. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.
[132]
[133]
Example 1
[134]
In a reactor equipped with a stirrer, a condenser and a decanter, 500 g of citric anhydride, 433 g of n-butanol, 600 g of n-heptanol (two alcohols in a molar ratio of 5:5) and 2 g of tetrabutyl titanate (TnBT) were added, and then the ester was added under a nitrogen atmosphere. After the reaction is terminated by chemical reaction, unreacted alcohol is removed, the catalyst and the composition are neutralized and washed with water using a basic aqueous solution, and tri(n-butyl) citrate, di(n-butyl)(n-heptyl) citrate, di(n-heptyl)(n-butyl) citrate and tri(n-heptyl) citrate at 11.5 wt%, 36.4 wt%, 39.2 wt% and To obtain the composition of Example 1 containing 12.9% by weight.
[135]
[136]
Examples 2 to 9
[137]
In a reactor equipped with a stirrer, condenser and decanter, 500 g of citric anhydride, 1,180 g of n-heptanol, and 2 g of tetrabutyl titanate (TnBT) were added, and then esterified under a nitrogen atmosphere to terminate the reaction, and unreacted alcohol After removing , 253 g of n-butanol was added to carry out a transesterification reaction. After completion of the reaction, the catalyst and composition are neutralized, unreacted alcohol and water are purified to finally tri(n-butyl) citrate, di(n-butyl)(n-heptyl) citrate, and di(n-heptyl) The composition of Example 2 was obtained comprising 0.7 wt%, 8.9 wt%, 38.2 wt% and 52.2 wt% of (n-butyl) citrate and tri(n-heptyl) citrate, respectively.
[138]
In the above reaction, the compositions of Examples 3 to 9 having the compositions shown in Table 1 below were prepared by adjusting the type and input amount of the reactants.
[139]
[140]
Comparative Example 1
[141]
Dioctyl phthalate (DOP, LG Chem) was used as a plasticizer.
[142]
[143]
Comparative Example 2
[144]
Diisononyl phthalate (DINP, LG Chem) was used as a plasticizer.
[145]
[146]
Comparative Example 3
[147]
Di(2-ethylhexyl) terephthalate (GL300, LG Chem) was used as a plasticizer.
[148]
[149]
Comparative Examples 4 to 6
[150]
Tri(2-ethylhexyl) of Comparative Example 4 was reacted in the same manner except that in Example 1, only 2-ethylhexanol was added instead of adding 2-ethylhexanol and n-butanol as alcohol. citrate was obtained.
[151]
Comparative Examples 5 and 6 were changed from Comparative Example 4 to the alcohol shown in Table 1 below.
[152]
[153]
Comparative Examples 7 to 14
[154]
In Example 6, the alcohol used in the direct esterification reaction and the higher and lower alcohols used in the transesterification reaction were reacted in the same manner as described in Table 1 below, respectively, to obtain a citrate composition .
[155]
[156]
[Table 1]
division lower
alcohol high
alcohol alcohol dose product composition
low-level heterosexuality low hybridity advanced mix advanced unmarried
Example 1 nB n-Hp 5:5 11.5 36.4 39.2 12.9
Example 2 nB n-Hp C4 20% of TnHpC 0.7 8.9 38.2 52.2
Example 3 nB 5-MHx C4 19% of TiHpC 1.4 13.6 41.9 43.1
Example 4 nB n-Hp C4 30% of TnHpC 2.7 22.5 40.7 34.1
Example 5 nB n-Hp C4 40% of TnHpC 5.3 30.2 38.5 26.0
Example 6 n:i=9:1 n-Hp C4 30% of TnHpC 2.5 21.0 41.2 35.3
Example 7 n:i=7:3 n:5=9:1 C4 30% of TnHpC 2.0 20.3 40.8 36.9
Example 8 iB n-Hp C4 20% of TnHpC 1.0 8.5 39.8 50.7
Example 9 nB n-Hp C7 50% of TnBC 18.5 38.5 36.2 6.8
Comparative Example 4 2-EH - - - - -
Comparative Example 5 nP - - - - -
Comparative Example 6 n-Hp - - - - -
Comparative Example 7 nB 2-EH C4 20% of TEHC 3.2 19.7 42.8 34.3
Comparative Example 8 nB 2-EH C8 30% of TBC 26.7 42.5 24.3 6.5
Comparative Example 9 nB 2-EH C4 40% of TEHC 11.0 32.2 42.3 14.5
Comparative Example 10 nB IN C4 20% of TINC 2.8 18.2 44.0 35.0
Comparative Example 11 nP IN C5 20% of TINC 3.0 18.5 44.1 34.4
Comparative Example 12 n-Hx 2-EH C6 30% of TEHC 5.2 27.0 44.7 23.1
Comparative Example 13 nP n-Hp C5 20% of THpC 2.4 17.5 43.2 36.9
[157]
- nB: n-butanol
[158]
- iB: isobutanol
[159]
- n-Hp: n-heptanol
[160]
- 5-MHx: 5-methylhexanol
[161]
- n-Hx: n-hexanol
[162]
- 2-EH: 2-ethylhexanol
[163]
- IN: isononanol
[164]
- In Table 1 above, "C4 20% of TnHpC" means 20 parts by weight of C4 alcohol based on 100 parts by weight of TnHpC, and similar descriptions may be interpreted in the same way.
[165]
[166]
Experimental Example 1: Evaluation of sheet performance
[167]
Using the plasticizers of Examples and Comparative Examples, specimens were manufactured under the following prescription and manufacturing conditions according to ASTM D638.
[168]
(1) Prescription : 100 parts by weight of straight vinyl chloride polymer (LS100), 50 parts by weight of plasticizer and 3 parts by weight of stabilizer (BZ-153T)
[169]
(2) Mixing : Mixing at 700 rpm at 98℃
[170]
(3) Specimen production : 1T, 2T and 3T sheets were produced by working at 160°C for 4 minutes with a roll mill and 2.5 minutes (low pressure) and 2 minutes (high pressure) at 180°C with a press
[171]
(4) Evaluation items
[172]
1) Hardness : Using ASTM D2240, the shore hardness (Shore "A" and "D") at 25 ℃ was measured for 10 seconds with a 3T specimen. It is evaluated that the plasticizing efficiency is excellent, so that a numerical value is small.
[173]
2) Tensile strength : After pulling the crosshead speed to 200 mm/min using a test device, UTM (manufacturer; Instron, model name; 4466), according to ASTM D638 method, 1T specimen The cut point was measured. Tensile strength was calculated as follows:
[174]
Tensile strength (kgf/cm 2 ) = load value (kgf) / thickness (cm) x width (cm)
[175]
3) Measurement of elongation rate : According to the ASTM D638 method, after pulling the cross head speed to 200 mm/min using the UTM, measuring the point at which the 1T specimen is cut, the elongation is measured Calculated as follows:
[176]
Elongation (%) = length after stretching / was calculated as initial length x 100.
[177]
4) Measurement of migration loss : A test piece with a thickness of 2 mm or more was obtained according to KSM-3156, and after attaching a glass plate to both sides of the 1T specimen, a load of 1 kgf/cm 2 was applied. The specimens were left in a hot air circulation oven (80° C.) for 72 hours, then taken out and cooled at room temperature for 4 hours. Then, after removing the glass plate attached to both sides of the test piece, the weight before and after leaving the glass plate and the specimen plate in the oven was measured to calculate the transfer loss by the following formula.
[178]
Transition loss (%) = {[(initial weight of specimen at room temperature) - (weight of specimen after leaving in oven)] / (weight of initial specimen at room temperature)} x 100
[179]
5) Measurement of volatile loss : After working the prepared specimen at 80° C. and 100° C. for 72 hours, the weight of the specimen was measured.
[180]
Loss on heating (wt%) = {[(initial specimen weight) - (test specimen weight after work)] / (initial specimen weight)} x 100.
[181]
6) Stress test (stress resistance) : After leaving a specimen with a thickness of 2 mm in a bent state at 23° C. for 168 hours, the degree of transition (the degree of seepage) was observed, and the result was written as a numerical value, at 0 The closer it was, the better the properties were.
[182]
7) Measurement of residual elongation (%): Measurement of elongation residual is to measure the elongation remaining in the specimen after heating at 100° C. for 168 hours, and the measuring method is the same as the elongation measuring method.
[183]
(5) Evaluation results
[184]
The evaluation results of the above items are shown in Tables 2 and 3 below.
[185]
[Table 2]
Hardness (Shore "A") Hardness
(Shore "D") Performance loss
(%) Heat loss
(%) Tensile strength (kgf/㎠) Elongation
(%) Kidney Residual Rate
(%)
80℃ 100℃
Example 1 83.0 36.2 0.67 1.14 1.85 183.7 325.6 91.2
Example 2 85.7 38.5 1.23 0.70 1.27 187.7 299.4 92.1
Example 3 86.1 39.0 1.13 0.80 1.44 186.3 303.5 92.8
Example 4 84.6 37.5 1.02 0.89 1.42 188.0 305.6 92.4
Example 5 83.9 37.0 0.96 0.95 1.50 186.4 310.4 91.3
Example 6 84.7 37.5 1.00 0.76 1.30 190.5 309.7 93.6
Example 7 84.6 37.3 0.95 0.70 1.20 192.3 308.6 95.7
Example 8 85.5 38.5 0.82 0.52 0.88 186.9 305.5 98.6
Example 9 80.1 34.1 0.68 1.35 1.86 183.5 326.1 92.6
Comparative Example 1 84.6 38.3 1.31 1.26 3.10 180.0 285.6 90.5
Comparative Example 2 86.9 40.6 2.08 0.71 1.29 197.8 290.3 93.6
Comparative Example 3 88.4 41.7 5.91 0.81 1.47 197.5 310.8 92.7
Comparative Example 4 90.5 43.6 1.92 0.21 0.56 205.6 301.2 95.8
Comparative Example 5 82.8 36.0 1.10 1.84 3.02 175.8 287.5 93.1
Comparative Example 6 88.7 41.7 1.45 1.24 2.35 187.6 295.3 93.5
Comparative Example 7 85.5 39.2 1.75 1.65 3.47 175.3 284.3 84.2
Comparative Example 8 81.2 34.6 1.46 3.58 6.28 165.2 265.8 78.5
Comparative Example 9 83.8 37.0 1.60 2.74 5.82 172.1 280.0 81.0
Comparative Example 10 88.9 41.6 2.48 1.58 2.66 180.2 288.3 95.2
Comparative Example 11 91.3 43.9 2.33 0.84 1.25 182.6 295.1 96.1
Comparative Example 12 87.9 41.1 2.08 0.90 1.33 191.2 274.0 93.4
Comparative Example 13 86.2 40.2 1.56 1.84 3.66 169.4 270.8 82.4
[186]
[Table 3]
stress resistance
1 day elapsed 2 days passed 3 days passed
Example 1 0 0 0
Example 2 0.5 0.5 0.5
Example 3 0.5 1.5 1.0
Example 4 0.5 0.5 0.5
Example 5 0 0.5 0.5
Example 6 0.5 0.5 0.5
Example 7 0.5 0.5 0.5
Example 8 0 0.5 0.5
Example 9 0 0 0
Comparative Example 1 0.5 1.0 0
Comparative Example 2 1.0 1.5 1.0
Comparative Example 3 1.5 3.0 3.0
Comparative Example 4 1.0 1.5 2.5
Comparative Example 5 0.5 1.0 1.0
Comparative Example 6 1.0 2.0 2.0
Comparative Example 7 0.5 0.5 1.0
Comparative Example 8 0.5 0.5 0.5
Comparative Example 9 0.5 0.5 0.5
Comparative Example 10 1.0 2.0 2.5
Comparative Example 11 1.5 2.5 3.0
Comparative Example 12 1.0 1.5 2.0
Comparative Example 13 0.5 0.5 1.0
[187]
Referring to Tables 2 and 3, in the case of Examples 1 to 9 to which the plasticizer composition according to an embodiment of the present invention is applied, the plasticization efficiency and transition loss are large compared to Comparative Examples 1 to 3 used as existing products. It can be confirmed that the improvement was improved, and the elongation residual rate also exhibited an excellent effect, and it can be confirmed that the stress resistance is also excellent.
[188]
In addition, Comparative Examples 4 to 6 apply citrate prepared with one alcohol without hybridizing the alkyl group of citrate with two or more alcohols, and it is confirmed that the citrate is inferior in all physical properties compared to Examples 1 to 9, It can be seen that there is a problem in that there is a large variation in physical properties depending on the number of carbon atoms.
[189]
On the other hand, in Comparative Examples 7 to 13, as in the example according to the present invention, two types of alcohols were used to hybridize the alkyl group, but the carbon number was compared without adjusting the carbon number to C4 for the lower alcohol and C7 for the higher alcohol.
[190]
Looking at these results, in Comparative Examples 7 to 9 and 13, the poor tensile strength and elongation were conspicuously shown, and it was confirmed that the elongation residual rate was very poor and the flexibility was greatly lost in a high-temperature environment, and the heating loss deteriorated. It can also be checked.
[191]
And, it can be seen that Comparative Examples 11 and 12 have poor migration resistance and stress resistance despite poor plasticization efficiency due to high hardness.
[192]
Through this, when applying citrate as a plasticizer as in the embodiments of the present invention, it is necessary to hybridize the alkyl group of citrate by using two or more alcohols, but by using a combination of C4 and C7 alcohols, in this case excellent It was confirmed that it was possible to implement a plasticizer of performance.
Claims
[Claim 1]
A citrate-based composition containing three or more citrates of Formula 1 is included, wherein the alkyl group of the citrate is derived from C4 alcohol and C7 alcohol, and the C4 alcohol includes one or more selected from n-butanol and isobutanol. And, the C7 alcohol is a plasticizer composition comprising at least one selected from an n-heptyl group and a branched heptyl group: [Formula 1] In Formula 1, R 1 to R 3 are each independently, having 4 or 7 is an alkyl group, and R 4 is hydrogen or an acetyl group.
[Claim 2]
According to claim 1, wherein the citrate-based composition comprises a lower non-hybridized citrate having a C4 alcohol-derived alkyl group, and a lower hybrid citrate having a C4 alcohol-derived alkyl group and a C7 alcohol-derived alkyl group, but having more C4 alcohol-derived alkyl groups. lower alkyl-based citrates; and higher alkyl-based citrates, including higher hybrid citrates having C4 alcohol-derived alkyl groups and C7 alcohol-derived alkyl groups, but having more C7 alcohol-derived alkyl groups, and higher non-hybridizing citrates having C7 alcohol-derived alkyl groups; Phosphorus plasticizer composition.
[Claim 3]
The plasticizer composition according to claim 1, wherein the C4 alcohol and the C7 alcohol have a molar ratio of 90:10 to 10:90.
[Claim 4]
The plasticizer composition according to claim 1, wherein the C4 alcohol and the C7 alcohol have a molar ratio of 60:40 to 10:90.
[Claim 5]
The plasticizer composition of claim 1 , wherein the C7 alcohol comprises n-heptanol.
[Claim 6]
The method according to claim 1, wherein the C7 alcohol comprises n-heptanol and at least one branched alcohol selected from 4-methylhexanol and 5-methylhexanol, and wherein the n-heptanol is based on the total weight of the C7 alcohol. A plasticizer composition that is included in an amount of 50% by weight or more.
[Claim 7]
The plasticizer composition according to claim 2, wherein the lower alkyl-based citrate and the higher alkyl-based citrate have a weight ratio of 80:20 to 1:99.
[Claim 8]
The plasticizer composition according to claim 2, wherein the weight ratio of the sum of the immiscible citrates and the sum of the hybrid citrates is 80:20 to 5:95.
[Claim 9]
100 parts by weight of resin; And 5 to 150 parts by weight of the plasticizer composition of claim 1; A resin composition comprising a.
[Claim 10]
10. The method of claim 9, wherein the resin is selected from the group consisting of straight vinyl chloride polymer, paste vinyl chloride polymer, ethylene vinyl acetate copolymer, ethylene polymer, propylene polymer, polyketone, polystyrene, polyurethane, natural rubber and synthetic rubber. A resin composition that is more than a species.