Title of the invention: plasticizer composition and resin composition comprising the same
Technical field
[One]
Mutual citation with related applications
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0144959 filed on November 1, 2017, and all contents disclosed in the documents of the Korean patent application are included as part of this specification.
[3]
[4]
Technical field
[5]
The present invention relates to a plasticizer composition and a resin composition comprising the same.
[6]
Background
[7]
Typically plasticizers react with alcohols with polycarboxylic acids such as phthalic acid and adipic acid to form corresponding esters. In addition, in consideration of domestic and overseas regulations of phthalate plasticizers that are harmful to the human body, studies on plasticizer compositions that can replace phthalate plasticizers such as terephthalate, adipate, and other polymers are continuing.
[8]
On the other hand, in the compound industry whose main properties are high heat resistance and low heating loss, appropriate plasticizers should be used in consideration of the required properties. In the case of PVC compounds for wires and cables, additives such as plasticizers, stabilizers, and pigments are mixed with the PVC resin according to the properties required by the standard, such as tensile strength, elongation, plasticizing efficiency, heating loss, and residual tensile and elongation.
[9]
Currently, diisodecylphthalate (DIDP), which is representatively used in the industry for electric wire compounds and automobile fabrics, is an environmental hormone observation material, and its use is regulated according to environmental issues, so there is a demand for the development of eco-friendly products to replace it. It is increasing.
[10]
Accordingly, research is underway to secure a vinyl chloride resin composition that is free from environmental issues and is excellent in quality by developing a product of a new plasticizer composition that has better physical properties than the diisodecylphthalate (DIDP) and is environmentally friendly. to be.
[11]
Detailed description of the invention
Technical challenge
[12]
In the present invention, as a plasticizer applied to a resin composition, it is intended to provide a plasticizer with improved physical properties such as plasticization efficiency, tensile residual and elongation residual, migration resistance and heating loss, and cold resistance, and a resin composition comprising the same.
[13]
Means of solving the task
[14]
In order to solve the above problems, according to an embodiment of the present invention, cyclohexane 1 containing at least one cyclohexane 1,4-diester having 8 to 12 carbon atoms each independently of the two alkyl groups bonded to the diester group, 4-diester-based material; And there is provided a plasticizer composition comprising a; trimellitate-based material containing the compound represented by the formula (1).
[15]
[Formula 1]
[16]

[17]
In Formula 1, R 1 to R 3 are each independently an alkyl group having 8 to 12 carbon atoms.
[18]
According to an embodiment of the present invention in order to solve the above problem, 100 parts by weight of a resin; And 5 to 150 parts by weight of the plasticizer composition described above; is provided a resin composition comprising.
[19]
Effects of the Invention
[20]
The plasticizer composition according to an embodiment of the present invention, when used in a resin composition, provides excellent plasticization efficiency, tensile strength and elongation, as well as excellent physical properties such as tensile and elongation residual ratio and cold resistance, and further transfer and heating loss. I can.
[21]
Mode for carrying out the invention
[22]
Definition of Terms
[23]
The term "composition" as used herein includes reaction products and decomposition products formed from the materials of the composition, as well as mixtures of materials comprising the composition.
[24]
The prefix "iso-" as used herein refers to an alkyl group in which a methyl group having 1 carbon number is bonded in a branched chain to the main chain of the alkyl group, and generally refers to a methyl branch is bonded to the end of the alkyl group. In the above, it may be used as a generic term for an alkyl group in which a methyl group is bonded to the main chain in a branched chain, including those bonded to the terminal as long as there is no alkyl group otherwise referred to as separately.
[25]
The term "isononyl group" as used herein may mean an alkyl group having a total carbon number of 9 in which one or more of 1 or 2 methyl groups, 1 ethyl group, and 1 propyl group are branched in the main chain, for example , 2-methyloctyl group, 3-methyloctyl group, 4-methyloctyl group, 5-methyloctyl group, 6-methyloctyl group, 3-ethylheptyl group, 2-ethylheptyl group, 2,5-dimethylheptyl group , 2,3-dimethylheptyl group, 4,5-dimethylheptyl group, 3-ethyl-4-methylhexyl group, 2-ethyl-4-methylhexyl group, or 2-propylhexyl group, etc. Isononyl alcohol (CAS No.: 68526-84-1, 27458-94-2) used commercially may mean a composition of isomers having a degree of branching of 1.2 to 1.9, and in the case of the commercial alcohol It may also contain some n-nonyl groups.
[26]
The term "straight vinyl chloride polymer" as used herein, as one of the types of vinyl chloride polymer, may mean polymerization through suspension polymerization or bulk polymerization, and having a size of tens to hundreds of micrometers. It has the form of porous particles in which a large amount of pores are distributed, has no cohesiveness, and has excellent flowability.
[27]
The term "paste vinyl chloride polymer" as used herein, as one of the types of vinyl chloride polymers, may mean polymerized through microsuspension polymerization, microseed polymerization, or emulsion polymerization, and from tens to It refers to a polymer with poor flowability and cohesiveness as particles without fine and dense pores having a size of several thousand nanometers.
[28]
The terms'comprising','having' and their derivatives, whether or not specifically disclosed, are not intended to exclude the presence of any additional components, steps or procedures. For the avoidance of any uncertainty, all compositions claimed through the use of the term'comprising', whether polymer or otherwise, may contain any additional additives, adjuvants, or compounds, unless stated to the contrary. Can include. In contrast, the term'consisting essentially of' excludes from the scope of any subsequent description any other component, step or procedure, except that it is not essential to operability. The term'consisting of' excludes any component, step or procedure not specifically described or listed.
[29]
[30]
How to measure
[31]
In the present specification, analysis of the content of the 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, final value: 280℃/7.8min, program rate: 15℃/min).
[32]
In this specification,'hardness' refers to Shore hardness at 25°C (Shore "A" and/or Shore "D") using ASTM D2240, and is measured under the conditions of 3T 10s, and plasticized It can be an index to evaluate the efficiency, and the lower it means the plasticization efficiency is excellent.
[33]
In this specification,'tensile strength' is a cross head speed of 200 mm/min (1T) using UTM (manufacturer; Instron, model name; 4466) as a test device according to ASTM D638 method. ), and then the point at which the specimen is cut is measured and calculated by Equation 1 below.
[34]
[Equation 1]
[35]
Tensile strength (kgf/cm 2 ) = load value (kgf) / thickness (cm) x width (cm)
[36]
In the present specification, the'elongation rate' is measured at the point where 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 the following equation (2).
[37]
[Equation 2]
[38]
Elongation (%) = length after elongation / initial length x 100
[39]
In this specification, the'migration loss' is obtained by obtaining a test piece with a thickness of 2 mm or more according to KSM-3156, attaching a glass plate to both sides of the test piece, and 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, and calculate the transition loss amount by the following equation.
[40]
[Equation 3]
[41]
Transition loss (%) = {(initial weight of test piece at room temperature-weight of test piece after leaving the oven) / initial weight of test piece at room temperature} x 100
[42]
In the present specification,'volatile loss' refers to the weight of the specimen after working at 80°C for 72 hours.
[43]
[Equation 4]
[44]
Heating loss (% by weight) = {(Initial specimen weight-specimen weight after work) / Initial specimen weight} x 100
[45]
In the case of the various measurement conditions, detailed conditions such as temperature, rotational speed, and time may be slightly different depending on the case, and when different, the measurement method and conditions are separately specified.
[46]
[47]
Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.
[48]
The terms or words used in the description and claims of the present invention should not be construed as being limited to their usual or dictionary meanings, and the inventors appropriately explain the concept of terms in order to explain their own invention in the best way. Based on the principle that it can be defined, it should be interpreted as a meaning and concept consistent with the technical idea of ​​the present invention.
[49]
[50]
Plasticizer composition comprising two or three plasticizers
[51]
According to an embodiment of the present invention, the plasticizer composition includes two or more plasticizers, and the two or more plasticizers are cyclohexane 1,4- each independently having 8 to 12 carbon atoms of the two alkyl groups bonded to the diester group. Cyclohexane 1,4-diester-based material containing at least one diester; And a trimellitate-based material containing a compound represented by the following formula (1).
[52]
[Formula 1]
[53]

[54]
In Formula 1, R 1 to R 3 are each independently an alkyl group having 8 to 12 carbon atoms.
[55]
In addition, when the cyclohexane 1,4-diester-based material and trimellitate-based material are included, the upper limit of the weight ratio of the two materials is 99:1, 95:5, 90:10, 85:15, 80:20, It may be 70:30 or 60:40, and the lower limit may be 1:99, 5:95, 10:90, 15:85, 20:80, 30:70 or 40:60. Preferably it may be 90:10 to 10:90, or 80:20 to 10:90, more preferably 80:20 to 20:80, and when the above preferred range is satisfied, transition characteristics and heating In terms of weight loss characteristics, more improved characteristics may be shown.
[56]
The plasticizer composition may include three types of plasticizers, and in this case, an epoxidized oil may be further included.
[57]
When the plasticizer composition consists of three plasticizers, the weight ratio of the cyclohexane 1,4-diester-based material and the trimellitate-based material may be the same as when two types are selected, and the epoxidized oil As a weight ratio of the total weight of the cyclohexane 1,4-diester-based material and the trimellitate-based material, the weight ratio of the total weight of the two mixtures to the epoxidized oil may be 90:10 to 10:90, preferably 90 :10 to 50:50, more preferably may be 80:20 to 50:50.
[58]
[59]
Cyclohexane 1,4-diester-based material
[60]
The cyclohexane 1,4-diester contained in the cyclohexane 1,4-diester-based material according to an embodiment of the present invention may have 8 to 12 carbon atoms of the two alkyl groups bonded to the diester group, respectively. Preferably it may be 8 to 11, or it may be 8 to 10. Cyclohexane 1,4-diester-based materials are the most useful plasticizers that can replace phthalate-based plasticizers as hydrogenated substances of terephthalate-based materials. , It can be applied as an eco-friendly plasticizer, and has advantages such as that the plasticization efficiency can be significantly improved compared to the terephthalate plasticizer.
[61]
In addition, the two alkyl groups bonded to the diester group of the cyclohexane 1,4-diester-based material, for example, 2-ethylhexyl group, isononyl group, 2-propylheptyl group, isodecyl group, undecyl group , Or a dodecyl group, and preferably a 2-ethylhexyl group, an isononyl group, a 2-propylheptyl group, or an isodecyl group.
[62]
Specifically, when the cyclohexane 1,4-diester is a single compound, diisononyl cyclohexane 1,4-diester (1,4-DINCH), di(2-ethylhexyl) cyclohexane 1,4-diester (1,4-DEHCH), di(2-propylheptyl) cyclohexane 1,4-diester (1,4-DPHCH) and diisodecyl cyclohexane 1,4-diester (1,4-DIDCH) It may be selected from the group consisting of, and preferably di(2-ethylhexyl) cyclohexane 1,4-diester, diisononyl cyclohexane 1,4-diester, or di(2-propylheptyl) cyclohexane 1, It may be a 4-diester.
[63]
In addition, when the cyclohexane 1,4-diester-based material is a mixture, three types of cyclohexane 1,4-diester-based material may be mixed, and among these three, the alkyl bonded to the diester group At least one of those having 8 to 12 carbon atoms may be included, and additionally, two types of cyclohexane 1,4-diester may be further included. In this case, in the case of an additional cyclohexane 1,4-diester, the alkyl group bonded to the diester may have 4 to 12 carbon atoms, but this carbon number is an additional cyclohexane applied when forming a mixture of three types. It is limited to the alkyl group of 1,4-diester.
[64]
For example, di(2-ethylhexyl) cyclohexane 1,4-diester, butyl (2-ethylhexyl) cyclohexane 1,4-diester and dibutyl cyclohexane 1,4-diester are mixed Mixture 1, diisononyl cyclohexane 1,4-diester, butylisononyl cyclohexane 1,4-diester and dibutyl cyclohexane 1,4-diester are mixed in the second mixture, bis (2-ethyl Hexyl) cyclohexane-1,4-diester, (2-ethylhexyl)isononyl cyclohexane 1,4-diester and diisononyl cyclohexane 1,4-diester may be a mixed third mixture, In addition to these mixtures, various mixtures may be formed according to a combination of two alkyl groups among the alkyl groups that may be bonded to the diester group.
[65]
Specifically, in the case of the first to third mixtures, it may have a specific composition ratio, and the first mixture is di(2-ethylhexyl) cyclohexane 1,4-diester 3.0 to 99.0 mol%; 0.5 to 96.5 mol% of butyl (2-ethylhexyl) cyclohexane 1,4-diester and 0.5 to 96.5 mol% of dibutyl cyclohexane 1,4-diester; and the second mixture may be diisononyl cyclo Hexane 1,4-diester 3.0 to 99.0 mol%; Butylisononyl cyclohexane 1,4-diester 0.5 to 96.5 mol% and dibutyl cyclohexane 1,4-diester 0.5 to 96.5 mol%; may be, and the third mixture is di(2-ethylhexyl) Cyclohexane 1,4-diester 3.0 to 99.0 mol%; (2-ethylhexyl) isononyl cyclohexane 1,4-diester 0.5 to 96.5 mol% and diisononyl cyclohexane-1,4-diester 0.5 to 96.5 mol%; may be.
[66]
The composition ratio may be a mixed composition ratio generated by an esterification reaction, a specific compound may be additionally mixed to be an intended composition ratio, and the mixed composition ratio may be appropriately adjusted to suit desired physical properties.
[67]
Regarding the manufacturing method, the cyclohexane 1,4-diester-based material may be prepared by direct esterification of 1,4-cyclohexane dicarboxylic acid and at least one alcohol, or dialkyl cyclohexane 1,4- It can be prepared by transesterification reaction of a diester (or dialkyl 1,4-cyclohexanoate) with an alcohol.
[68]
Alternatively, dialkyl terephthalate prepared through an ester reaction using terephthalic acid as a raw material may be prepared through a hydrogenation reaction, and a method for producing a cyclohexane 1,4-diester-based material as a hydrogenation material of a terephthalate-based material If so, there is no particular limitation on the manufacturing method.
[69]
The alcohol is a primary alcohol, and the alkyl group may be selected from the group consisting of the aforementioned 2-ethylhexyl group, isononyl group, 2-propylheptyl group, isodecyl group, undecyl group, or dodecyl group. One type of alcohol may be directly applied to the esterification reaction and a single terephthalate may be applied, and two or more mixed alcohols may be directly applied to the esterification reaction, or a transesterification reaction may be performed to apply a mixture of two or more terephthalates. have.
[70]
Specifically, when the transesterification reaction is performed and a mixed cyclohexane 1,4-diester-based material is applied, the mixed cyclohexane 1,4-diester-based material has a specific composition ratio between each mixture. It may have, and di(alkylA) cyclohexane 1,4-diester 3.0 to 99.0 mol%; (Alkyl A) (alkyl B) 0.5 to 96.5 mol% of cyclohexane 1,4-diester and 0.5 to 96.5 mol% of di(alkyl B) cyclohexane 1,4-diester; wherein alkyl A is a reactant It may be derived from cyclohexane 1,4-diester, and alkyl B may be derived from alcohol.
[71]
The composition ratio may be a mixed composition ratio generated by an esterification reaction, a specific compound may be additionally mixed to be an intended composition ratio, and the mixed composition ratio may be appropriately adjusted to suit desired physical properties.
[72]
As described above, when 1,4-cyclohexanoate having 8 to 12 carbon atoms of the alkyl in the diester group is used as a plasticizer, the plasticization efficiency, transferability, and heating loss characteristics and mechanical properties are obtained through appropriate carbon number control. Physical property balance can be achieved.
[73]
[74]
Trimellitate substance
[75]
According to an embodiment of the present invention, the plasticizer composition may include a trimellitate-based material, and the trimellitate-based material may be represented by Formula 1 below.
[76]
[Formula 1]
[77]

[78]
In Formula 1, R 1 to R 3 are each independently an alkyl group having 8 to 12 carbon atoms.
[79]
The trimellitate-based material is a material capable of supplementing the cyclohexane 1,4-diester-based material as described above, and as an effect that the cyclohexane 1,4-diester-based material cannot be achieved compared to the phthalate plasticizer. , It can complement the migration resistance or weight loss characteristics.
[80]
In the trimellitate-based material, R 1 to R 3 in Formula 1 may have 8 to 12 carbon atoms, each may be the same, and when different from each other, two of R 1 to R 3 are the same And the other one may be a different alkyl group. For example, the alkyl group may be an alkyl group such as octyl group, 2-ethylhexyl group, isononyl group, 2-propylheptyl group, isodecyl group, undecyl group, or dodecyl group. That is, the alkyl group of R 1 to R 3 of Formula 1 may be selected from the same range as the alkyl group of the cyclohexane 1,4-diester-based material described above.
[81]
In addition, in the case of the trimellitate-based material, in particular, control of the number of carbons may be more important, and when the applied alkyl group is changed due to the three ester groups bonded to the benzene ring, the structure or molecular weight of the trimellitate molecule itself is affected. It can be largely reflected, and it may be necessary to select an appropriate alkyl group.
[82]
In addition, the trimellitate-based material may be the most optimal material to be mixed with a cyclohexane 1,4-diester-based material and a plasticizer composition, and compared to other existing products, transferability, heating loss, elongation and elongation residuals, and further Can have a specific effect on improving the tensile residual ratio.
[83]
[84]
Epoxidized oil
[85]
According to an embodiment of the present invention, the plasticizer composition may further include an epoxidized oil as a third mixture, while including the cyclohexane 1,4-diester-based material and the trimellitate-based material.
[86]
The epoxidized oil, for example, epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearate (epoxidized stearate), epoxidized oleate, epoxidized tall oil, epoxidized linoleate, or a mixture thereof may be applied.
[87]
However, preferably, the epoxidized oil may be epoxidized soybean oil (ESO), epoxidized linseed oil (ELO), or a mixture thereof. However, epoxidized soybean oil is epoxidized linseed oil due to market conditions or supply and demand problems May have a higher frequency of use than.
[88]
The plasticizer composition according to an embodiment of the present invention may be appropriately included as a weight ratio of the mixed weight of the cyclohexane 1,4-diester-based material and the trimellitate-based material as described above when the epoxidized oil is included, In the case of containing epoxidized oil, the cyclohexane 1,4-diester-based material and trimellitate-based material are relatively reduced according to the inclusion, but there is no deterioration in physical properties, but rather an improvement effect in physical properties can be seen. In addition, it has the advantage of securing product price competitiveness.
[89]
[90]
Manufacturing method
[91]
In the present invention, the method of preparing the plasticizer composition is a blending method that can be applied, and a process of mixing after each preparing a cyclohexane 1,4-diester-based material, an epoxidized oil, and a trimellitate-based material The composition can be prepared through.
[92]
As a material used in preparing the cyclohexane 1,4-diester-based material, 2-ethylhexyl alcohol, isononyl alcohol when prepared by direct esterification through cyclohexane 1,4-dicarboxylic acid and alcohol Applying one or more alcohols having an alkyl group bonded to the diester group of the aforementioned cyclohexane 1,4-diester-based material such as 2-propylheptyl alcohol, and reacting with cyclohexane 1,4-dicarboxylic acid Can be done.
[93]
In the direct esterification reaction, cyclohexane 1,4-dicarboxylic acid is added to alcohol, and then a catalyst is added and reacted in a nitrogen atmosphere; Removing unreacted alcohol and neutralizing unreacted acid; And dehydration and filtering by distillation under reduced pressure; can be prepared as.
[94]
In addition, the alcohol is 150 to 500 mol%, 200 to 400 mol%, 200 to 350 mol%, 250 to 400 mol%, or 270 to 330 mol% based on 100 mol% of cyclohexane 1,4-dicarboxylic acid Can be used within range.
[95]
On the other hand, the catalyst for the esterification reaction is, for example, sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, paratoluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, an acid catalyst such as alkyl sulfuric acid, aluminum lactate, lithium fluoride, potassium chloride , Metal salts such as cesium chloride, calcium chloride, iron chloride, aluminum phosphate, metal oxides such as heteropoly acids, natural/synthetic zeolites, cation and anion exchange resins, tetraalkyl titanate, and organic metals such as polymers 1 It can be more than a species. As a specific example, the catalyst may be tetraalkyl titanate.
[96]
The amount of catalyst used may vary depending on the type, for example, in the case of a homogeneous catalyst, in the range of 0.01 to 5% by weight, 0.01 to 3% by weight, 1 to 5% by weight, or 2 to 4% by weight based on the total 100% by weight of the reactants. In the case of inner and heterogeneous catalysts, it may be in the range of 5 to 200% by weight, 5 to 100% by weight, 20 to 200% by weight, or 20 to 150% by weight of the total amount of the reactant.
[97]
At this time, the reaction temperature may be in the range of 180 to 280°C, 200 to 250°C, or 210 to 230°C.
[98]
If the cyclohexane 1,4-diester-based material is to be prepared as a mixture, the cyclohexane 1,4-diester may be prepared through the above-described direct esterification reaction and then mixed, or in a direct esterification reaction. A method of applying two or more alcohols may be applied, or cyclohexane 1,4-diesters such as di(2-ethylhexyl) 1,4-cyclohexanoate or diisononyl 1,4-cyclohexanoate And, a transesterification reaction in which alcohols such as 2-propylheptyl alcohol, isodecyl alcohol, and undecyl alcohol react; can be used to prepare a cyclohexane 1,4-diester.
[99]
[100]
The "trans-esterification reaction" used in the present invention refers to a reaction in which an alcohol and an ester react as shown in Scheme 1 below, and R" of an ester is interchanged with R'of an alcohol as shown in Scheme 1 below:
[101]
[Scheme 1]
[102]

[103]
According to an embodiment of the present invention, when the trans-esterification reaction is performed, the alkoxide of the alcohol attacks the carbon of two ester (RCOOR") groups present in the ester compound; as long as it is present in the ester compound. Attacking the carbon of the dog's ester (RCOOR") group; As in the case of unreacted reaction in which no reaction has been made; in three cases, three types of ester compositions may be produced by number.
[104]
In addition, the trans-esterification reaction has the advantage of not causing wastewater problems compared to the acid-alcohol esterification reaction.
[105]
For example, di(2-ethylhexyl) 1,4-cyclohexanoate and isononyl alcohol are obtained by the trans-esterification reaction, di(2-ethylhexyl) 1,4-cyclohexanoate, ( A mixture of 2-ethylhexyl)isononyl 1,4-cyclohexanoate and diisononyl 1,4-cyclohexanoate may be produced, and the three types of cyclohexane 1,4-diester-based material are It may be formed in an amount of 0.5% to 80% by weight, 0.5% to 80% by weight, and 0.5% to 85% by weight, respectively, based on the total weight of the mixture, specifically 1% to 50% by weight, 1% by weight % To 50% by weight, and may be formed in an amount of 10% to 80% by weight.
[106]
In addition, in the mixture prepared by the trans-esterification reaction, the composition ratio of the mixture may be controlled according to the amount of alcohol added.
[107]
The amount of the alcohol added may be 0.1 to 89.9 parts by weight, specifically 3 to 50 parts by weight, and more specifically 5 to 40 parts by weight based on 100 parts by weight of cyclohexane 1,4-diester.
[108]
In the cyclohexane 1,4-diester-based material, as the amount of alcohol added increases, the mole fraction of cyclohexane 1,4-diester participating in the trans-esterification reaction will increase. The content of two cyclohexane 1,4-diesters may increase, and correspondingly, the content of unreacted cyclohexane 1,4-diester may tend to decrease.
[109]
According to an embodiment of the present invention, the molar ratio of the reactant cyclohexane 1,4-diester and the alcohol is, for example, 1:0.005 to 5.0, 1:0.05 to 2.5, or 1:0.1 to 1.0, within this range There is an effect of obtaining an ester plasticizer composition having high process efficiency and excellent processability improvement effect.
[110]
However, the composition ratio of the mixture of the three types of cyclohexane 1,4-diester-based materials is not limited to the above range, and any one of the three types of cyclohexane 1,4-diester is added to the composition ratio Can be changed, the possible mixing composition ratio is as described above.
[111]
According to an embodiment of the present invention, the trans-esterification reaction is 120 to 190 °C, preferably 135 to 180 °C, more preferably 10 minutes to 10 hours under a reaction temperature of 141 to 179 °C, preferably It is preferable to carry out in 30 minutes to 8 hours, more preferably 1 to 6 hours. Within the above temperature and time range, a mixture of a cyclohexane 1,4-diester-based material having a desired composition ratio can be effectively obtained. In this case, the reaction time may be calculated from the point when the reaction temperature reaches the reaction temperature after heating.
[112]
The trans-esterification reaction may be carried out under an acid catalyst or a metal catalyst, and in this case, the reaction time is shortened.
[113]
The acid catalyst may be sulfuric acid, methanesulfonic acid or p-toluenesulfonic acid, for example, and the metal catalyst may be an organometallic catalyst, a metal oxide catalyst, a metal salt catalyst, or a metal itself.
[114]
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 of them.
[115]
[116]
In addition, alternatively, in the plasticizer composition, the cyclohexane 1,4-diester-based material is prepared through a hydrogenation reaction after performing a direct esterification reaction or a transesterification reaction using terephthalic acid or terephthalate as a reaction raw material. Can be employed.
[117]
The hydrogenation reaction may be a step of converting a terephthalate-based material into a cyclohexane 1,4-diester-based material by hydrogenating a single compound or a mixture of a terephthalate-based material in the presence of a metal catalyst.
[118]
The hydrogenation step is a reaction in which hydrogen is added to remove the aromaticity of the benzene ring of terephthalate-based materials in the presence of a metal catalyst, and may be a kind of reduction reaction.
[119]
The hydrogenation reaction is to synthesize a cyclohexane 1,4-diester-based material by reacting the terephthalate-based material with hydrogen under a metal catalyst, and the reaction conditions are the benzene ring without affecting the carbonyl group substituted in benzene. It may include all of the conventional reaction conditions capable of hydrogenating the bay.
[120]
The hydrogenation reaction may be carried out by further including an organic solvent such as ethanol, but is not limited thereto. As the metal catalyst, an Rh/C catalyst, a Pt catalyst, a Pd catalyst, etc., which are generally used to hydrogenate a benzene ring, may be used, but the hydrogenation reaction as described above is not limited thereto.
[121]
[122]
The direct esterification reaction and transesterification reaction may also be used to prepare the aforementioned trimellitate-based material (trimellitic acid instead of terephthalic acid). In this case, like the cyclohexane 1,4-diester-based material, the trimellitate-based material may also be prepared as a mixture in a predetermined ratio, and the composition ratio of the resulting mixture may be controlled by adjusting the content of alcohol as a reaction raw material. . In addition, when a trimellitate-based material is prepared through a direct esterification reaction or a transesterification reaction, except for the hydrogenation reaction, the same as the contents applied to the production of the cyclohexane 1,4-diester-based material. Contents can be applied.
[123]
In addition, cyclohexane 1,4-dicarboxylic acid, terephthalic acid, citric acid, and trimellitic acid as the reaction raw material may be substituted with an acid anhydride in place of such a carboxylic acid-based material.
[124]
[125]
The plasticizer composition thus prepared is 5 to 150 parts by weight, 10 to 100 parts by weight based on 100 parts by weight of a resin selected from ethylene vinyl acetate, polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomer. Parts, or in the range of 10 to 60 parts by weight, it is possible to provide a resin composition that is effective for extrusion, injection, calendering, and compound formulation.
[126]
In particular, when the polyvinyl chloride resin is applied as a resin, both straight vinyl chloride polymer applied to extrusion, injection, calendering and compound formulation and paste vinyl chloride polymer applied to plastisol formulation can be applied. In the case of the plasticizer composition according to, it may be particularly preferable as a plasticizer for straight vinyl chloride polymers.
[127]
For example, the plasticizer composition may be applied to the manufacture of wires, flooring, automobile interiors, films, sheets, wallpaper or tubes.
[128]
[129]
Example
[130]
Hereinafter, examples will be described in detail to illustrate the present invention in detail. However, the embodiments according to the present invention may be modified in various forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more completely describe the present invention to those with average knowledge in the art.
[131]
[132]
1. Preparation of plasticizer composition
[133]
Preparation Example 1: Preparation of di(2-ethylhexyl) cyclohexane-1,4-diester
[134]
1,4-Cyclohexane dicarboxylic acid (CHDA) 516.0 g, 2-ethylhexyl alcohol in a 4-neck 3-liter reactor equipped with a cooler, condenser, decanter, reflux pump, temperature controller, stirrer, etc. (2-EH) 1170g (CHDA: 2-EH molar ratio (1.0): (3.0)), a titanium-based catalyst (TIPT, tetra isopropyl titanate) as a catalyst 1.55g (0.3 parts by weight per 100 parts by weight of CHDA) Then, the temperature was gradually raised to about 170°C. Generated water started to be generated around 170°C, and the ester reaction was performed for about 4.5 hours while nitrogen gas was continuously added under the conditions of a reaction temperature of about 220°C and atmospheric pressure, and the reaction was terminated when the acid value reached 0.1.
[135]
After completion of the reaction, distillation extraction was performed for 0.5 to 4 hours under reduced pressure in order to remove unreacted raw materials. In order to remove unreacted raw materials below a certain content level, steam extraction is performed for 0.5 to 3 hours under reduced pressure using steam, the temperature of the reaction solution is cooled to about 90°C, and neutralization is performed using an alkali solution. . In addition, water washing may be performed, after which the reaction solution is dehydrated to remove moisture. A filter medium was added to the reaction solution from which moisture was removed, stirred for a certain period of time, and filtered to finally obtain 1167 g of di(2-ethylhexyl) 1,4-cyclohexanoate (yield: 98.0%).
[136]
[137]
Preparation Example 2: Preparation of diisononyl cyclohexane-1,4-diester
[138]
In the esterification reaction in Preparation Example 1, instead of using 2-ethylhexyl alcohol, isononyl alcohol was used to obtain a hydrogenated material in the same manner as in Preparation Example 1.
[139]
[140]
Preparation Example 3: Preparation of di(2-propylheptyl) cyclohexane-1,4-diester
[141]
In the esterification reaction in Preparation Example 1, instead of using 2-ethylhexyl alcohol, 2-propylheptyl alcohol was used to obtain a hydrogenated material in the same manner as in Preparation Example 1.
[142]
[143]
Preparation Example 4: Preparation of a hydrogenation mixture of DEHCH/ EHINCH/ DINCH
[144]
In a reactor equipped with a stirrer, condenser and decanter, 2000 g of di(2-ethylhexyl) 1,4-cyclohexanoate and 440 g of isononyl alcohol (100 parts by weight of di(2-ethylhexyl) 1,4-cyclohexanoate) 22 parts by weight) was added, followed by trans-esterification reaction for 2 hours at a reaction temperature of 160° C. in a nitrogen atmosphere, and di(2-ethylhexyl) 1,4-cyclohexanoate (1,4- DEHCH), octylisononyl 1,4-cyclohexanoate (1,4-EHINCH) and diisononyl 1,4-cyclohexanoate (1,4-DINCH) in 48% by weight and 42% by weight, respectively And a plasticizer composition comprising in the range of 10 wt%.
[145]
The reaction product was mixed and distilled to remove isononyl alcohol and 2-ethylhexyl alcohol, and finally a mixed composition was prepared.
[146]
[147]
Preparation Example 5: Preparation of tri(2-ethylhexyl) trimellitate
[148]
Using 576.3 g of trimellitic acid and 1,755 g of 2-ethylhexyl alcohol as reaction raw materials, 1,606 g (yield: 98%) of tri(2-ethylhexyl) trimellitate product was finally obtained.
[149]
[150]
Preparation Example 6: Preparation of triisononyl trimellitate
[151]
Using 576.3 g of trimellitic acid and 1,948 g of isononyl alcohol as reaction raw materials, 1,731 g of triisononyl trimellitate product (yield: 98%) was finally obtained.
[152]
[153]
2. Plasticizer properties evaluation items and measurement method
[154]
Hardness measurement
[155]
Using ASTM D2240, the shore (shore “A”) hardness at 25° C., 3T 10s was measured.
[156]
[157]
Measurement of tensile strength
[158]
According to the ASTM D638 method, the cross head speed was pulled at 200 mm/min (1T) using a test instrument UTM (manufacturer; Instron, model name; 4466), and then the point at which the specimen was cut was measured. . Tensile strength was calculated as follows:
[159]
Tensile strength (kgf/㎟) = load value (kgf) / thickness (mm) x width (mm)
[160]
[161]
Elongation rate measurement
[162]
According to the ASTM D638 method, after pulling the cross head speed at 200 mm/min (1T) using the UTM, the point at which the specimen was cut was measured, and the elongation was calculated as follows:
[163]
It was calculated as elongation (%) = [length after elongation / initial length] x 100.
[164]
[165]
Measurement of migration loss
[166]
According to KSM-3156, a specimen having a thickness of 2 mm or more was obtained, and a PS plate was attached to both sides of the specimen, and a load of 2 kgf/cm2 was applied. The specimen was left in a hot air circulation oven (80°C) for 72 hours and then taken out and cooled at room temperature for 4 hours. Then, after removing the PS adhered to both sides of the test piece, the weight before and after leaving it in the oven was measured, and the transfer loss was calculated by the following equation.
[167]
Transition loss (%) = [(initial weight of specimen at room temperature-weight of specimen after leaving the oven) / initial weight of specimen at room temperature] x 100
[168]
[169]
Measurement of volatile loss
[170]
After the fabricated specimen was worked at 100° C. for 168 hours, the weight of the specimen was measured.
[171]
Heating loss (%) = [(initial specimen weight-specimen weight after work) / initial specimen weight] x 100.
[172]
[173]
Tensile and elongation residual measurement
[174]
The measurement of the tensile and elongation residual rate is to measure the tensile and elongation properties remaining in the specimen after heating at 100°C for 168 hours, and the measurement method is the same as that of the above measurement of tensile strength and elongation.
[175]
[176]
Cold resistance
[177]
Five prepared specimens were allowed to stand at a specific temperature for 3 minutes and then hit to measure the temperature when three of the five were damaged.
[178]
[179]
3. Results of evaluation of plasticizer properties
[180]
1) Configuration of Examples and Comparative Examples
[181]
Examples and comparative examples were configured together as shown in Tables 1 and 2 below using the materials prepared in the above Preparation Example. In the case of the plasticizer materials used in the following Examples and Comparative Examples, materials not described in the above Preparation Examples can be easily obtained commercially, and a product made by LG Chem was used.
[182]
[Table 1]
Primary plasticizer 1st plasticizer weight ratio
Example 1-1 1,4-DINCH TEHTM 9:1
Example 1-2 1,4-DINCH TEHTM 7:3
Example 1-3 1,4-DINCH TEHTM 5:5
Example 1-4 1,4-DINCH TEHTM 3:7
Example 1-5 1,4-DINCH TEHTM 1:9
Example 1-6 1,4-DPHCH TEHTM 7:3
Example 1-7 1,4-DPHCH TINTM 5:5
Example 1-8 1,4-DEHCH TINTM 5:5
Example 1-9 1,4-DEHCH TPHTM 3:7
Example 1-10 DEHCH/EHINCH/DINCH TPHTM 7:3
Example 1-11 DEHCH/EHINCH/DINCH TEHTM 1:9
Comparative Example 1-1 DIDP - -
Comparative Example 1-2 DPHP - -
Comparative Example 1-3 1,4-DINCH - -
Comparative Example 1-4 - TPHTM -
Comparative Example 1-5 DEHTP TEHTM 7:3
Comparative Example 1-6 1,4-DEHCH ATEHC 5:5
Comparative Example 1-7 1,4-DEHCH ESO 5:5
Comparative Example 1-8 1,4-DBCH TEHTM 5:5
Comparative Example 1-9 1,4-DEHCH TBTM 5:5
[183]
[Table 2]
Primary plasticizer 1st plasticizer weight ratio Secondary plasticizer 1st: 2nd weight ratio
Example 2-1 1,4-DEHCH TEHTM 2:8 ESO 5:5
Example 2-2 1,4-DEHCH TINTM 6:4 ESO 7:3
Example 2-3 1,4-DEHCH TPHTM 8:2 ESO 8:2
Example 2-4 1,4-DEHCH TINTM 4:6 ESO 6:4
Example 2-5 1,4-DINCH TEHTM 7:3 ESO 9:1
Example 2-6 1,4-DPHCH TEHTM 5:5 ESO 7:3
Example 2-7 DBCH/EHINCH/DINCH TEHTM 3:7 ESO 9:1
Comparative Example 2-1 DIDP - - -
Comparative Example 2-2 DPHP - - -
Comparative Example 2-3 - TEHTM - ESO 5:5
[184]
2) Experimental Example: Evaluation of compound properties
[185]
Specimens were prepared using the mixed plasticizer compositions of Examples and Comparative Examples described in Tables 1 and 2.
[186]
For the preparation of the specimen, referring to ASTM D638, based on 100 parts by weight of a polyvinyl chloride resin (PVC (LS100)), 50 parts by weight of the plasticizer composition prepared in the Examples and Comparative Examples, and RUP-144 (Adeka Korea) 5 parts by weight, 40 parts by weight of Omya 1T (Omiya) as a filler, and 0.3 parts by weight of St-A (Isu Chemical) as a lubricant were mixed at 700 rpm at 98°C. A specimen was prepared by working at 160° C. for 4 minutes using a roll mill, and working at 180° C. for 3 minutes (low pressure) and 2.5 minutes (high pressure) using a press.
[187]
The fabricated specimen was evaluated for each set according to the measurement method of the above-described evaluation items, and the results are shown in Tables 3 and 4 below.
[188]
[Table 3]
　 Hardness (Shore A) Tensile strength (kgf/cm 2 ) Tensile residual (%) Elongation (%) Elongation residual rate (%) Performance loss (%) Heating loss (%) Cold resistance (℃)
Example 1-1 91.2 171.0 104.5 314.8 92.7 1.23 1.44 -27.5
Example 1-2 91.7 172.5 103.4 310.5 93.0 1.02 0.90 -28
Example 1-3 92.0 172.3 102 308.7 93.4 0.64 0.78 -28
Example 1-4 92.3 173.2 101.2 306.9 94.3 0.30 0.67 -28.5
Example 1-5 92.8 176.4 98.7 305.2 96.7 0.21 0.40 -32.5
Example 1-6 92.1 175.8 101.7 306.1 96.5 0.73 0.72 -28.5
Example 1-7 92.7 182.6 99.8 302.4 98.7 0.70 0.34 -30
Example 1-8 91.6 176.8 100.3 303.2 95.5 0.58 0.45 -30.5
Example 1-9 93.4 188.9 98.4 302.7 99.7 0.34 0.30 -34
Example 1-10 91.8 175.0 102.5 305.8 93.7 1.00 0.92 -29
Example 1-11 92.4 174.6 100.6 305.4 94.5 0.35 0.70 -29.5
Comparative Example 1-1 92.7 170.6 93.4 297.5 92.1 1.54 0.88 -28.5
Comparative Example 1-2 93.2 169.7 91.5 278.6 88.4 1.74 1.24 -27.5
Comparative Example 1-3 90.7 168.0 106.7 314.2 86.3 2.03 2.11 -26
Comparative Example 1-4 97.8 183.0 97.8 288.6 98.7 0.30 0.28 -34
Comparative Example 1-5 93.0 172.3 96.4 298.2 95.6 2.30 0.95 -28
Comparative Example 1-6 93.6 170.5 88.6 301.4 87.4 1.86 1.92 -30.5
Comparative Example 1-7 93.9 164.0 92.3 286.4 93.8 1.67 1.68 -22.5
Comparative Example 1-8 90.3 154.0 72.0 286.9 65.7 4.58 8.77 -29.5
Comparative Example 1-9 90.8 170.1 79.8 288.2 81.3 1.78 2.54 -30
[189]
Referring to Table 3, it is confirmed that in Examples 1-1 to 1-11, all physical properties are improved compared to Comparative Examples 1-1 to 1-9. Specifically, Comparative Examples 1-1 and 1-2, which are conventional phthalate-based products, show inferiority to the examples in elongation and elongation residual rate, and in tensile residual rate, and in Comparative Example 1-3 using only hydrogenated products, poor environment It can be seen that the deterioration of the physical properties in the (elongation residual rate and cold resistance) is at a serious level, and it can be seen that the transition loss and heating loss are also about 50% or more inferior to the examples.
[190]
In addition, it can be confirmed that Comparative Example 1-4 using only trimellitate-based products has a significant disadvantage in plasticization efficiency and is not suitable as a material for imparting a plasticizing effect due to low elongation itself, and terephthalate-based materials and In the case of Comparative Examples 1-5 in which a trimellitate-based material was mixed, all physical properties were noticeably poor compared to the examples in which the terephthalate-based material was hydrogenated, and in particular, the transferability and elongation residual rate were significantly lowered. I can confirm.
[191]
In addition, in the case of Comparative Example 1-8 which does not satisfy the carbon number as cyclohexane 1,4-diester or Comparative Example 1-9 that does not satisfy the carbon number as a trimellitate-based material, transfer loss, heating loss, tensile and elongation residuals , And it was confirmed that most of the physical properties, such as elongation, deteriorated rapidly.
[192]
And, in the case of using acetyl citrate or epoxidized oil other than a trimellitate material as a mixed plasticizer of cyclohexane 1,4-diester (Comparative Examples 1-6 and 1-7), the improvement effect is Compared to the use of trimellitate-based materials, it is remarkably poor. Specifically, epoxidized oil cannot improve cold resistance, tensile strength, and elongation, and acetyl citrate has the effect of It is confirmed that there is no significant effect on improvement.
[193]
[194]
[Table 4]
　 Hardness (Shore A) Tensile strength (kgf/cm 2 ) Tensile residual (%) Elongation (%) Elongation residual rate (%) Performance loss (%) Heating loss (%) Cold resistance (%)
Example 2-1 91 173.5 98.6 297.6 94.8 0.2 0.3 -26.5
Example 2-2 91.8 179.6 95.8 306.6 98.7 0.27 0.45 -29
Example 2-3 92 185.4 96.7 310.4 96.7 0.58 0.98 -29.5
Example 2-4 92.1 190.4 98.4 312 99.1 0.2 0.31 -27
Example 2-5 91.5 184.2 92.4 311.7 94.2 0.98 1.02 -30.5
Example 2-6 91.2 188.4 95.6 308.6 96.5 0.44 0.68 -29
Example 2-7 91.6 184.6 96.8 302.7 93.4 0.35 0.41 -31
Comparative Example 2-1 92.7 170.6 93.4 297.5 92.1 1.54 0.88 -28.5
Comparative Example 2-2 93.2 169.7 91.5 278.6 88.4 1.74 1.24 -27.5
Comparative Example 2-3 95 170.3 99.7 288.7 95.1 0.34 0.31 -23.5
[195]
Referring to Table 4, in mixing the cyclohexane 1,4-diester-based material and the trimellitate-based material, an excellent effect can be confirmed in the case of using as a plasticizer by additionally adding epoxidized oil. When a hexane 1,4-diester-based material is used as a plasticizer, it can be seen that mixing with the epoxidized oil should be used as a third material.
[196]
In particular, in the case of using only trimellitate-based materials and epoxidized oil without using cyclohexane 1,4-diester-based materials (Comparative Example 2-3), it is not possible to improve the cold resistance and the elongation is significantly less than expected. It is confirmed that there is a problem.
[197]
[198]
That is, in the case of using a cyclohexane 1,4-diester-based material, it can be seen that the trimellitate-based material is the most suitable material as a mixing partner, and further improvement in physical properties is achieved when additional epoxidized oil is added. can confirm. Even if several substances are mixed, if different substances are added to one plasticizer composition, the content of the original plasticizer substance is relatively reduced, and therefore, considering that'improvement' is not a matter of course, the above and It can be seen that the improvement of the effect by selective mixing of the same plasticizer composition is quite significant.
Claims
[Claim 1]
A cyclohexane 1,4-diester-based material containing at least one cyclohexane 1,4-diester having 8 to 12 carbon atoms each independently of the two alkyl groups bonded to the diester group; And a trimellitate-based material containing a compound represented by the following Formula 1; Plasticizer composition comprising: [Formula 1] In Formula 1, R 1 to R 3 are each independently an alkyl group having 8 to 12 carbon atoms.
[Claim 2]
The plasticizer composition of claim 1, wherein the cyclohexane 1,4-diester-based material and trimellitate-based material have a weight ratio of 90:10 to 10:90.
[Claim 3]
The plasticizer composition of claim 1, wherein the cyclohexane 1,4-diester-based material and the trimellitate-based material have a weight ratio of 80:20 to 10:90.
[Claim 4]
The method of claim 1, wherein the two alkyl groups bonded to the diester group of the cyclohexane 1,4-diester-based material are each independently selected from the group consisting of 2-ethylhexyl group, isononyl group, and 2-propylheptyl group. Plasticizer composition.
[Claim 5]
The plasticizer composition of claim 1, wherein R 1 to R 3 in Formula 1 are each independently selected from the group consisting of a 2-ethylhexyl group, an isononyl group, and a 2-propylheptyl group.
[Claim 6]
The method of claim 1, wherein the cyclohexane 1,4-diester-based material is a mixed composition of three types, and the mixed composition is a cyclone having 8 to 12 carbon atoms each independently of the two alkyl groups bonded to the diester group. A plasticizer composition comprising hexane 1,4-diester, and further comprising two types of cyclohexane 1,4-diester.
[Claim 7]
The plasticizer composition of claim 1, wherein the plasticizer composition further comprises an epoxidized oil as a secondary plasticizer:
[Claim 8]
The plasticizer composition of claim 7, wherein the epoxidized oil has a ratio of the mixed weight of the cyclohexane 1,4-diester-based material and the trimellitate-based material and the weight of the epoxidized oil of 90:10 to 50:50. .
[Claim 9]
The method of claim 7, wherein the epoxidized oil is epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxy Plasticizer composition comprising at least one selected from the group consisting of epoxidized stearate, epoxidized oleate, epoxidized tall oil, and epoxidized linoleate.
[Claim 10]
100 parts by weight of resin; And 5 to 150 parts by weight of the plasticizer composition of claim 1.
[Claim 11]
The resin composition of claim 10, wherein the resin is at least one selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomer.