Art
[1]
Mutual citations and related applications
[2]
This application claims the benefit of priority based on the February 10th issue of Korea Patent Application No. 10-2017-0018590 2017, and all information disclosed in the literature of the Korea patent application are included as part of the specification.
[3]
[4]
Art
[5]
The present invention relates to a plasticizer composition and a resin composition comprising the same.
[6]
BACKGROUND
[7]
Typically the plasticizer to form an alcohol and the phthalic acid and adipic acid and poly-carboxylic esters, such as reaction with an equivalent. Further research has continued on the plasticizer composition, which can be substituted for the phthalate-based plasticizers, such as consideration of the national and international regulations on harmful phthalate-based plasticizer in the human body, terephthalate-based, adipate-based, or other high molecular weight.
[8]
[9]
On the other hand, in the sector of the high-melting compound, low heat loss in the main physical properties required in consideration of the required properties to be used an appropriate plasticizer. And mixing additives such as a wire and, if PVC compound of cable uses the tensile strength properties required in the specification, the elongation, plasticizing efficiency, and heating loss, plasticizers in PVC resins according to the tensile and elongation survival rate, fillers, stabilizers and flame retardants .
[10]
[11]
The current wire compound and typically use and diisodecyl phthalate (DIDP), which are endocrine disruptors observed substances in industry for automotive fabrics, because the regulations used in accordance with the environmental issues is underway, the development needs of eco-friendly products to replace them but is increased, that is the majority of products and many alternative products are yeoksido products that contain any part of the material still contains the phthalate environmental issues.
[12]
[13]
In the diisopropyl has excellent physical properties than decyl phthalate (DIDP), by developing environment-friendly products of the novel plasticizer composition, the study out to secure the free, high vinyl-based resin composition chloride in quality aspects in environmental issues is in progress .
[14]
[15]
[Prior art document]
[16]
[Patent Document]
[17]
[Patent Document 1] Patent No. 10-0957134 No.
[18]
Detailed Description of the Invention
SUMMARY
[19]
Present as a plasticizer applied to the resin composition in the invention, plasticizing efficiency and the inner planets are excellent and improved tensile strength and elongation, tensile survival rate and renal survival rate and to provide a resin composition comprising the plasticizer composition, and this, the cold resistance is improved.
[20]
Problem solving means
[21]
According to one embodiment of the present invention to solve the above problems, the carbon atoms in the two alkyl groups bound to the diester independently 4-10, each terephthalate-based plasticizer; And to trimellitate-based plasticizer represented by Formula 1; include and is provided with a plasticizer composition characterized in that it does not contain an epoxidized oil.
[22]
Formula 1
[23]
[24]
In Formula 1, R 1 to R 3 is an alkyl group having 4 to 10 carbon atoms independently.
[25]
According to one embodiment of the present invention to solve the above problems, the resin 100 parts by weight; And the aforementioned plasticizer composition 5 to 150 parts by weight of a resin composition containing a is provided.
[26]
Effects of the Invention
[27]
Plasticizer The compositions of the present invention, when used in the resin composition, excellent plasticizing efficiency, and the inner ear and the planet can be improved, improved tensile strength and elongation, tensile survival rate and renal survival rate, and, as well as expect the improvement of the cooking loss and cold resistance can.
[28]
Mode for the Invention
[29]
Hereinafter, the present invention will be described in more detail to aid the understanding of the present invention.
[30]
The terms or words used in the description and claims of the present invention is general and not be construed as limited to the dictionary meanings are not, the inventor accordingly the concept of a term to describe his own invention in the best way on the basis of the principle that can be defined, which must be interpreted based on the meanings and concepts corresponding to technical aspects of the present invention.
[31]
[32]
Two kinds or three kinds of a plasticizer composition containing a plasticizer
[33]
According to one embodiment of the present invention, a plasticizer composition comprising two kinds or more of a plasticizer, wherein the two or more kinds of plasticizers each having the carbon number of the two alkyl groups independently selected from 4 to 10 of the terephthalate-based plasticizer is bound to diester; And to trimellitate-based plasticizer represented by formula (1); and the essentially characterized by not containing epoxidized oils.
[34]
Formula 1
[35]
[36]
In Formula 1, R 1 to R 3 is an alkyl group having 4 to 10 carbon atoms independently.
[37]
The plasticizer composition wherein the terephthalate-based plasticizers, and trimellitate-based plasticizers include the case where the weight ratio of the two materials is an upper limit of 99: 1, 95: 5, 90:10, 85:15, 80:20, 70:30, or It may be 60: 40, and may be a lower limit of 1: 99, 5:95, 10:90, 15:85, 20:80, 30:70 or 40:60. Preferably it may be 90: 10 to 10: 90, more preferably from 70:30 to 10:90.
[38]
The plasticizer composition may include three types of plasticizer, in this case to the can further include a citrate-based plasticizer represented by the following formula (2).
[39]
[Formula 2]
[40]
[41]
In Formula 2, R 4 to R 6 are, each independently, an alkyl group of a carbon number of 5-9, R 7 is hydrogen.
[42]
When the plasticizer composition consisting of three kinds of plasticizers, the terephthalate-based plasticizers, and trimellitate-based ratio by weight of the plasticizer is the same weight ratio to the case where two or more kinds selected can be applied, the citrate-based plasticizer terephthalate-based plasticizer, and trimellitate-based total based on 100 parts by weight of the weight of a plasticizer, and may contain 5 to 150 parts by weight, may be included and preferably 10 to 100 parts by weight.
[43]
The plasticizer composition containing the three kinds of plasticizers as described above, when the mixing ratio in this case satisfies the above range, it is possible to improve the inner planet can be expected to improve the tensile survival rate and elongation, and plasticizing efficiency .
[44]
Plasticizer composition according to an embodiment of the present invention is characterized in that it does not include the epoxidized oil. At this time, meaning the epoxidation five days is not input is the content also plasticizers within Also, the resin composition in the case as that avoiding the application of an epoxidized oil as a component of the plasticizer composition, which plasticizer composition is mixed with the resin during processing composition 100 parts by weight of the preparation, 5 parts by weight, preferably less than 3 parts by weight or less, may mean that more preferably is an amount of less than 1 part by weight.
[45]
For the epoxidation five days, but can see the specific effect on properties such as heat resistance, oil resistance, low temperature, for example, it can cause the symptoms to be about -5 ℃ the slurry liquid plasticizer at a temperature below the screen in the storage and transport of the product It may give rise to a big problem, so that there is a case that the epoxidized oil processing the resin with the plasticizer include the possibility that the cold properties of the transfer of the plasticizer composition, handling, and processing the resin composition deteriorates.
[46]
In addition, to the extent that the problems in addition to containing the epoxidized oil to the plasticizer when applied to products that require insulation, volume resistivity can cause the symptoms to be lowered compared with the eco-plasticizer composition that does not use conventional phthalate products and epoxidized five days have.
[47]
Thus, but a plasticizer the composition according to the invention in order to solve the above problems include the terephthalate-based material and trimellitate-based material as described above as necessary, do not include an epoxidized oil, based Alternatively citrate It may include additional materials. If you do not include this manner an epoxidized oils may be significantly improved low-temperature storage properties, can be expected to improve insulation performance by improving cold resistance of the resulting resin products and the volume resistivity improved.
[48]
[49]
Terephthalate-based plasticizer
[50]
Terephthalate-based plasticizer, in accordance with an embodiment of the present invention may be that the number of carbon atoms of two alkyl groups bonded to the diester of 4 to 10, respectively. Preferably within 6 to 9 days, or it may be 7 to 9. Terephthalate-based plasticizer as the most useful plasticizer that can replace phthalate plasticizers, in the basic mechanical properties compared with traditional phthalate plasticizers could appear in the same level, it may be possible to apply an eco-friendly plasticizer.
[51]
Also, the two groups of bonded to the diester of the terephthalate-based plasticizer, for example, n-butyl group, an isobutyl group, a n-pentyl group, isopentyl group, n-hexyl group, n heptyl group, iso-heptyl, nomalok group, yisook group, a 2-ethylhexyl group, n nonyl, iso-nonyl group, 2-propyl may be a heptyl or iso-decyl group, preferably a n-butyl group, isopentyl group, iso-heptyl group, 2- ethyl may be a hexyl, iso nonyl, 2-propyl-heptyl group, a decyl group or isobutyl.
[52]
Specifically, for example, the terephthalate-based plasticizer is dibutyl terephthalate (DBTP), di-isopentyl terephthalate (DIPTP), dihexyl terephthalate (DHxTP), di-iso-heptyl terephthalate (DIHTP), di (2 ethylhexyl) terephthalate (DEHTP), diisononyl terephthalate (DINTP), di (2-propyl-heptyl) terephthalate (DPHTP), diisodecyl terephthalate (DIDTP), (2-ethylhexyl) terephthalate, isononyl (EHINTP), (2-ethylhexyl) (2-propyl-heptyl) terephthalate, isononyl (2-propyl-heptyl) terephthalate, (isodecyl) (iso-nonyl) terephthalate, (2-ethylhexyl) terephthalate isodecyl phthalate, isodecyl (2-propyl-heptyl) terephthalate, butyl (2-ethylhexyl) terephthalate, iso-heptyl (2-ethylhexyl) terephthalate, iso-pentyl isononyl terephthalate, iso-pentyl (2-ethylhexyl) terephthalate , iso-pentyl (2-propyl Heptyl) terephthalate, and the like, or iso-butyl heptyl terephthalate.
[53]
In connection method, the terephthalate-based plasticizer may be made of terephthalic acid and may be prepared by the direct esterification reaction of one or more alcohols, or a dialkyl terephthalate and a transesterification reaction of alcohol.
[54]
That is, the alcohol is a primary alcohol, n-butyl group is an alkyl group described above, an isobutyl group, a n-pentyl group, isopentyl group, n-hexyl group, n heptyl group, iso-heptyl group, nomalok group, yisook group, 2 ethylhexyl, n nonyl, iso-nonyl group, and may be selected from the group consisting of 2-propyl-heptyl or iso-decyl group. The one kind of alcohol is applied to a direct esterification reaction can be applied, a single terephthalate, at least two mixed alcohols are applied directly to the esterification reaction or transesterification reaction are at least two terephthalate could be applied mixed mixture perform have.
[55]
Specifically, when the transesterification reaction is performed it is a mixed terephthalate-based plasticizer applied, and a mixed terephthalate-based plasticizer may have a particular composition ratio between each terephthalate, for example, having an alkyl A with an alkyl group di (alkyl a) and a terephthalate as the (B-alkyl) alcohol having an alkyl group with reactant B, when the transesterification reaction is carried out, di (alkyl a) terephthalate 3.0 to 99.0 mole%; (Alkyl A) (alkyl B) terephthalate 0.5 to 96.5% by mole and di (alkyl B) terephthalate 0.5 to 96.5 mol%; a mixture of terephthalate can be formed.
[56]
The composition ratio may be a mixture composition ratio that is generated in the esterification reaction, it may be a composition ratio intended by further mixing a specific compound additionally can be appropriately adjust the mixing ratio of the composition to meet the desired physical properties.
[57]
[58]
Trimellitate-based plasticizer
[59]
According to one embodiment of the invention, the plasticizer composition may include a trimellitate-based plasticizers, and trimellitate-based plasticizers may be Tate is represented by the following general formula (1).
[60]
Formula 1
[61]
[62]
In Formula 1, R 1 to R 3 is an alkyl group having 4 to 10 carbon atoms independently.
[63]
As the trimellitate-based plasticizers terephthalate-based as a substance capable of complementing a plasticizer, terephthalate-based effect plasticizer that can not be achieved as compared with phthalate-based plasticizer as described above, not only to complement the inner planet or reduction characteristics rather, it may be possible to improve the overall properties.
[64]
In the trimellitate-based plasticizers, the general formula (I) of R 1 to R 3 may be a carbon number of 4 to 10, each of which may be the same with each other, a different case, R each other 1 to R 3 2 of which are the same will, may be a different one is the alkyl group. For example, the alkyl group is n-butyl group, an isobutyl group, a n-pentyl group, isopentyl group, n-hexyl group, n heptyl group, iso-heptyl group, nomalok group, yisook group, a 2-ethylhexyl group, nonyl group n , iso-nonyl group, an alkyl group such as 2-propyl-heptyl or iso-decyl group may be selected.
[65]
Further, when a normal alkyl group that is, linear alkyl groups include, but applied in the alkyl group known to be excellent in properties such as cold resistance and is excellent in a commercially iso branched alkyl group of from an economic point of view. For such trimellitate-based plasticizers, when applied by satisfying the number of carbon atoms, it can be expected to plasticizing efficiency, inner planet, cooking loss, kidney survival rate and stress transitivity improvement of the effect.
[66]
[67]
Citrate-based plasticizers
[68]
According to one embodiment of the invention, the plasticizer composition is said terephthalate-based plasticizers and trimellitate-based, containing a plasticizer, a mixture of claim 3, may further include a citrate-based plasticizer, a citrate-based plasticizer is to be represented by the formula (2).
[69]
[Formula 2]
[70]
[71]
In Formula 2, R 4 to R 6 are, each independently, an alkyl group of a carbon number of 5-9, R 7 is hydrogen.
[72]
The citrate-based plasticizer R of formula (II) 4 to R 6 are each independently, a pentyl group, an isopentyl group, a hexyl group, iso-hexyl, heptyl, iso-heptyl group, nomalok group, a 2-ethylhexyl group, n and no group or isononyl group, wherein R 4 to R 6 each may be the same as each other or may be different from each other.
[73]
Wherein R 4 to R 6 is yet an alkyl group having a carbon number of 5 to 9, are different from each other citrate is an alkyl group, for example, isononyl group and 2-propyl heptyl citrate having a combination of substituent groups, a 2-ethylhexyl group and a 2 - can be a profile, such as citrate with a combination of substituent heptyl group, iso-decyl and 2-ethylhexyl citrate having a combination of substituents, the addition is selected from among a carbon number of 5 to 9, the two different carbon atoms the citrate or the like can be applied with a combination of substituent groups, and the alkyl group may be straight linear or branched.
[74]
Wherein R 4 to R 6 is yet an alkyl group having a carbon number of 5 to 9, the citrate is an alkyl group different from each other, for example, isopentyl group and isocitrate having the combination of substituents nonyl group, a 2-ethylhexyl group and isopropyl group cattle having a combination of substituents may be such as citrate, isopentyl group and 2-ethyl-sheet having a combination of substituents hexyl acrylate, the addition is selected from among a carbon number of 5 to 9, the combination of the substituent of the alkyl group having the carbon number of two different the citrate or the like can be applied with, and the alkyl group may be straight linear or branched.
[75]
Wherein R 4 to R 6 is yet an alkyl group having a carbon number of 5 to 9, together with the same citrate alkyl group is, for example, tri-isopentyl citrate (TIPC), trihexyl citrate (THxC), tri-heptyl citrate (THpC ), tri-iso-heptyl citrate (TIHpC), tri (2-ethylhexyl) can be applied, such as the citrate (TEHC), teuriyi Sono carbonyl citrate (TINC), the addition may be applied if an alkyl group having a carbon number of 5 to 9 .
[76]
Preferably may be applied to not less than the number of carbon atoms is 5, in the case of using an alcohol having a carbon number of 5 to 9, more in comparison with the number of carbon atoms is relatively small amount of use as can be seen the equivalent to good effect, etc. plasticizing efficiency and the absorption rate have. In addition, the carbon number of the upper limit of the alkyl group is preferably can be applied to nine individual, when the carbon number exceeds 9, due to the excessive increase in molecular weight can cause a characteristic degradation such as absorption rate, plasticizing efficiency.
[77]
On the other hand, the sheet When an acetyl group is present in rate-based plasticizer, that is, R 7 lungs that occurs in even a by-product in the acetylation if caused, the properties of a plasticizer, in particular can be accompanied by physical properties deterioration such as plasticizing efficiency, and also, the manufacturing process It can be added to the economic, enemy equipment costs for handling acid. When so introduced into the acetyl group, there may result in locations, such as production costs increase due to the processing of the additional process steps and by-products of consideration.
[78]
In other words, citrate-based plasticizer that R in the general formula (2) 7 If the acetyl group, the decrease in the plasticizing efficiency compared to the case of hydrogen, a problem such as increase of the plasticizer added and the product price increases through this associated to overcome this it may be, R 7 is an acetyl group citrate-based plasticizer can not be better than that in which R7 is hydrogen in various aspects such as market, cost-effectiveness and properties.
[79]
[80]
The method
[81]
Preparing a composition by the process of to be able to apply the method for producing the plasticizer composition, the blending method, mixed after preparing a terephthalate-based plasticizer, a citrate-based plasticizers, and trimellitate-based plasticizers, each in the present invention can do.
[82]
The terephthalate-based case of producing the plasticizer directly to the furnace ester, butyl alcohol, isopentyl alcohol, hexyl alcohol, iso-heptyl alcohol, 2-ethylhexyl alcohol, iso-nonyl alcohol, 2-propyl heptyl least one alcohol in an alcohol and terephthalic acid the process of the reaction can be carried out.
[83]
The step of adding the above-mentioned direct esterification reaction, terephthalic acid added to the alcohol and then the catalyst and react under a nitrogen atmosphere; Step of removing unreacted alcohol and neutralizing the unreacted acid; And the step of dehydration, and filtration by vacuum distillation; may be prepared by.
[84]
In addition, the alcohol, 1.5 mol% to 500 mol% of terephthalic acid 100 mol% based on 200 mol% to 400 mol%, 200 mol% to 350 mol%, 250 mol% to 400 mol%, or 270 mol% to 330 mol It may be used within the% range.
[85]
On the other hand, wherein the catalyst is one example of the esterification, sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, p-toluenesulfonic acid, methanesulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid, an acid catalyst such as alkyl sulfate, lactic aluminum, lithium fluoride, potassium chloride , cesium chloride, calcium chloride, iron chloride, aluminum phosphate, such as a metal salt, heteropolyacid, etc. of a metal oxide, a natural / synthetic zeolites, cation and anion exchange resins, tetraalkyl titanate (tetra alkyl titanate) and selected from the group consisting of organic metals of the polymers 1 species may be higher. As specific examples, the catalyst may be a tetra-alkyl titanate.
[86]
The amount of the catalyst used may be different according to the type, in the case of a homogeneous catalyst in one example is 0.01% to 5% by weight relative to the reaction a total of 100% by weight, 0.01% by weight to 3% by weight, 1% to 5% by weight or 2 for in, and the heterogeneous catalyst wt.% to 4 wt.% range of 5% to 200% by weight of the reaction product the total amount, 5% to 100 wt%, 20 wt% to 200 wt%, or 20 wt% to 150 wt. % range can be tomorrow.
[87]
At this time, the reaction temperature is in the range 180 ℃ to 280 ℃, 200 ℃ to 250 ℃, or 210 ℃ to 230 ℃ can tomorrow.
[88]
If you wish to prepare the terephthalate-based plasticizer in the mixture, after being through the esterification reaction described above directly terephthalate compound is prepared it may be mixed, or a method of direct application of two or more of alcohol in the esterification reaction can be applied, and , or di (2-ethylhexyl) terephthalate or diisononyl terephthalate, such as terephthalic lactate compounds and butyl alcohol, isopentyl alcohol, hexyl alcohol, iso-heptyl alcohol, and transesterification of the alcohol, such as 2-propyl heptyl reaction reaction; can be prepared via a terephthalate compound, wherein the order of introduction of the alcohol can rearrange the order according to the production method. For example, di (2-ethylhexyl) terephthalate, and the product produced by the reaction of butyl alcohol is di-butyl terephthalate and 2-ethyl not much different from the product produced by the reaction of the cyclohexyl alcohol, the content ratio of the product was identically produced when controlling the reaction conditions and the conversion may be possible.
[89]
"Transesterification reaction" used in the present invention means a reaction in which alcohol and ester are reacted as shown R "is R 'interchangeably with each other in the alcohol of the ester in the following scheme 1 as shown below in Scheme 1:
[90]
[Reaction Scheme 1]
[91]
[92]
According to one embodiment of the invention, the trans-case to attack the carbon of the two esters (RCOOR ") group, which is the esterification reaction is completed, the alkoxide of the alcohol present in the ester compound, one present in the ester compound of ester (RCOOR ") If the attack of the carbon group; If the unreacted that is not the reaction is performed; such as, a polyester composition of the three can be produced by a number of the three cases.
[93]
In addition, the trans-esterification reaction is acid-as compared to alcohol esterification reaction between the advantage that does not cause a waste water problem, because it can take place under non-catalytic, it is possible to solve the problems of the acid catalyst used.
[94]
For example, di (2-ethylhexyl) terephthalate, and iso-octyl alcohol is the trans-esterification by the reaction, di (2-ethylhexyl) terephthalate, (2-ethylhexyl) terephthalate, and isononyl diimide Sono carbonyl terephthalate this may be generated a mixture of, the amount of terephthalate of the three species respectively 3.0% by weight to 70% by weight relative to the total weight of the mixture, 0.5% to 50% by weight, and 0.5% by weight to 85% by weight It can be formed by, and can be specifically formed in an amount of 10% to 50% by weight, 0.5% to 50% by weight, and 35% by weight to 80% by weight.
[95]
Further, the mixture prepared by the transesterification reaction is able to control the composition ratio of the mixture in accordance with the added amount of the alcohol.
[96]
The amount of the alcohol is in the range of 0.1 part by weight to 89.9 parts by weight based on 100 parts by weight of the terephthalate compound, specifically, it may be 3 parts by weight to 50 parts by weight, more specifically 5 parts by weight to 40 parts by weight.
[97]
The terephthalate compound is more the amount of addition of alcohols, because larger the mole fraction (mole fraction) of the terephthalate compound participating in the transesterification reaction, it is possible to the amount of the two terephthalate compound of the product increase in said mixture , corresponding to the content of the terephthalate compound present as unreacted can be seen a tendency to decrease.
[98]
According to one embodiment of the invention, the reaction of terephthalate compound and the molar ratio of alcohol is one example: 0.005 to 1: 5.0, 1: 0.05 to 1: 2.5 or 1: 0.1 to 1: 1, and within this range highly efficient process is effective for obtaining an excellent ester plasticizer composition processability improving effect on the.
[99]
However, the terephthalate-based composition ratio of the mixture of the plasticizer of the three kinds is not limited to the above range, the input of the three kinds terephthalate adding any one capable of changing the composition ratio, possible mixed composition ratio of the above-described as it described.
[100]
According to one embodiment of the invention, the trans-esterification reaction is 120 ℃ to 190 ℃, preferably from 135 ℃ to 180 ℃, more preferably from 10 minutes to 10 hours in a reaction temperature of 141 ℃ to 179 ℃, preferably carried out from 30 minutes to 8 hours, more preferably from 1 hour to 6 hours. A terephthalate-based plasticizer which is a mixture of the desired composition within the temperature and time range can be obtained effectively. At this time, the reaction time may be calculated from the time the reaction was warmed to reach the reaction temperature.
[101]
The trans-esterification reaction may be carried out the presence of an acid catalyst or a metal catalyst, in this case, there is an effect, the response time is shortened.
[102]
The acid catalyst and the like, methanesulfonic acid or p- toluenesulfonic acid and sulfuric acid as an example, the metal catalyst may be for example an organic metal catalyst, metal oxide catalyst, a metal salt catalyst or the metal itself.
[103]
The metal component may be any one or a mixture of two or more of those selected from the group consisting of tin, titanium, and zirconium, for example.
[104]
[105]
The screen direct esterification reaction and the transesterification reaction can also be used to manufacture the above citrate-based plasticizer (using terephthalic acid instead of citric acid), and trimellitate-based plasticizers (terephthalic acid instead of trimellitic acid used). In this case, the terephthalate-based plasticizer as with citrate-based plasticizer, or trimellitate-based plasticizers also possible to control the composition ratio of the mixture which is generated in accordance with the content of control of the alcohol as the reaction raw material may be made of a mixture of a predetermined ratio. In addition, when manufacturing via a citrate or trimellitate a direct esterification reaction or transesterification reaction, in the same manner as have been applied to the manufacturing of the said terephthalate-based plasticizer can be applied to the contents.
[106]
In addition, terephthalic acid, citric acid and trimellitic acid acid in place of material of this acid anhydride series, such as the reaction raw materials may be used as a substitute material.
[107]
[108]
On the other hand, a method for preparing the plasticizer composition can be applied a method of manufacturing, the mixture at the same time the esterification reaction of a raw material can be applied to a method of preparing a blended after each.
[109]
Specifically, the terephthalate-based plasticizer, a citrate-based plasticizers, and trimellitate-based To apply to all carbon atoms of the alkyl group the same according to the plasticizer, the alcohol having an acid mixture, such as terephthalic acid, citric acid, trimellitic acid, certain groups It can be directly prepared by the esterification reaction and, in which case there is a terephthalate, citrate, and all of the carbon atoms of the alkyl group of the same trimellitate plasticizer composition can be obtained.
[110]
That is, in case of using the same alcohol, it may be a commercially economical method of reacting two or more acid or anhydride with an alcohol in the manufacturing process at the same time.
[111]
[112]
According to another embodiment of the present invention, on the other a plasticizer composition prepared as the resin 100 parts by weight of the preparation, 5 parts by weight to 150 parts by weight, 20 parts by weight to 100 parts by weight, 30 to 80 parts by weight or 40 parts by weight to 70 parts by weight It is mixed with the resin portion is provided to the resin composition.
[113]
The resin may be selected from ethylene-vinyl acetate, polyethylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomers.
[114]
Further, the resin composition may be mixed with various additives such as heat stabilizers, stabilizers, lubricants and fillers, the kind and content can be applied, as is known in the art.
[115]
The resin composition prepared as described above, e.g., in calendering or compound formulation may provide for both effective resin composition or the like, for example, through the resin composition, electric wire, flooring, vehicle interior materials, film, sheet, or tube It can be applied to manufacturing.
[116]
[117]
Example
[118]
Hereinafter, the embodiment example in detail to illustrate the present invention in detail will be described. However, embodiments according to the present invention can be modified in many different forms and the scope of the invention is not to be construed as limited to the embodiments set forth herein. Embodiments of the present invention are provided to more fully illustrate the present invention to those having ordinary skill in the art.
[119]
[120]

[121]
Preparation of di (2-ethylhexyl) terephthalate (DEHTP): Preparation 1
[122]
Condenser, a condenser, a decanter, a reflux pump, a temperature controller, a stirrer such as a purified terephthalic acid with 4 of the sphere 3 liter reactor (purified terephthalic acid; PTA) 498.0 g, 2- ethylhexyl alcohol (2-EH) 1170 g (TPA: 2 the molar ratio (1.0) of -EH: in (3.0)), 0.31 parts by weight of the titanium-containing catalyst (TIPT, tetra isopropyl titanate), a 1.54 g (100 parts by weight for the TPA as a catalyst), and up to about 170 ℃ was gradually elevated . Was the generation number generated in the vicinity of about 170 ℃ started, reaction temperature of about 220 ℃, performs an ester to react for about 4.5 hours while continuing to inject the nitrogen gas from atmospheric pressure to terminate the reaction when the acid value reached 0.01.
[123]
After the reaction was completed, the distillation extract under reduced pressure to remove the unreacted raw material is performed for 0.5 to 4 hours. Below a predetermined content level using steam in order to remove the unreacted raw material to enforce for 0.5 to 3 hours under reduced pressure, steam extraction, and after cooling the reaction mixture temperature at about 90 ℃, using an alkaline solution is subjected to neutralization treatment . In addition, the may be subjected to washing with water, after the reaction liquid was dehydrated to remove water. By incorporating a filter material to the moisture is removed the reaction mixture stirred for a while, filtered and finally di (2-ethylhexyl) terephthalate 1326.7 g (Yield: 99.0%) was obtained.
[124]
[125]
Preparation 2: Preparation of diisononyl terephthalate (DINTP)
[126]
An esterification reaction of 2-ethylhexyl, instead of using the alcohol except for using isononyl alcohol 1,296g, and the diimide in the same manner as in Preparation Example 1 sono carbonyl terephthalate was prepared.
[127]
[128]
Preparation Example 3: Preparation of di (2-propyl-heptyl) terephthalate (DPHTP)
[129]
When the esterification reaction, except that the 2-propyl-heptyl alcohol 1,422g, instead of using the di-2-ethylhexyl alcohol in the same manner as in Preparation Example 1 (2-propyl-heptyl) was prepared terephthalate.
[130]
[131]
Preparation of di-butyl terephthalate (DBTP): Preparation 4
[132]
By esterification during the same manner as in Preparation Example 1, except that the low-temperature reaction carried out using the methane sulfonic acid (Methanesulfonic aicd) 5g as n-butyl alcohol 670g, the catalyst, instead of using the 2-ethylhexyl alcohol, dibutyl It was prepared terephthalate.
[133]
At this time, the reaction end point was carried out by setting the GC and any acid (Acid value).
[134]
[135]
Preparation Example 5: Preparation of di-isopentyl terephthalate (DIPTP)
[136]
An esterification reaction of 2-ethyl in the same manner as Preparation Example 1 except for using isopentyl alcohol 792g instead of using the alcohol-hexyl di-isopentyl terephthalate was prepared.
[137]
[138]
Preparation Example 6: Preparation of dihexyl terephthalate (DHxTP)
[139]
When the esterification reaction was prepared dihexyl terephthalate in the same manner as in Preparation Example 1 except for using n-hexyl alcohol 918g instead of using the 2-ethylhexyl alcohol.
[140]
[141]

[142]
Preparation 7: Preparation of tributyl tree trimellitate (TBTM)
[143]
As a reaction raw material by using trimellitic anhydride and 576.3g 866g n- butyl alcohol, finally tributyl trimellitate 1,112g product (yield: 98%) was obtained.
[144]
[145]
Preparation Example 8: Preparation of isopentyl tree trimellitate (TIPTM)
[146]
As a reaction raw material by using trimellitic anhydride and 576.3g isopentyl alcohol 1,030g, finally tree isopentyl trimellitate 1,236g product (yield: 98%) was obtained.
[147]
[148]
Preparation 9: Preparation of trihexyl tree trimellitate (THxTM)
[149]
As a reaction raw material by using trimellitic anhydride and 576.3g hexyl alcohol 1,196g, finally trihexyl trimellitate 1,360g product (yield: 98%) was obtained.
[150]
[151]
Preparation of tri (2-ethylhexyl) trimellitate (TEHTM): Preparation 10
[152]
As a reaction raw material by using trimellitic anhydride and 576.3g of 2-ethylhexyl alcohol 1,521g, finally tri (2-ethylhexyl) trimellitate 1,607g product (yield: 98%) was obtained.
[153]
[154]
Preparation 11: Preparation of teuriyi Sono carbonyl trimellitate (TINTM)
[155]
As a reaction raw material by using trimellitic anhydride and 576.3g isononyl alcohol 1,685g, finally teuriyi Sono carbonyl trimellitate 1,731g product (yield: 98%) was obtained.
[156]
[157]
Preparation of tri (2-propyl-heptyl) trimellitate (TPHTM): Preparation 12
[158]
As a reaction raw material by using 576.3g of trimellitic anhydride and 2-propyl-heptyl alcohol 1,852g, finally tri (2-propyl-heptyl) trimellitate 1,855g product (yield: 98%) was obtained.
[159]
[160]

[161]
Preparation 13: Preparation of tree isopentyl citrate (TIPC)
[162]
And as a reaction raw material using citric acid 576 g and 1,030 g isopentyl alcohol, and finally the tree isopentyl citrate 1,183g (yield: 98%) was obtained.
[163]
[164]
Preparation 14: Preparation of a tree-hexyl citrate (THxC)
[165]
As a reaction raw material by using the citric acid 576 g and 1,196 g hexyl alcohol, finally trihexyl citrate 1,307g (yield: 98%) was obtained.
[166]
[167]
Preparation of tri (2-ethylhexyl) citrate (TEHC): Preparation 15
[168]
And as a reaction raw material using citric acid 576 g and 1,521 g 2-ethylhexyl alcohol, finally tri (2-ethylhexyl) citrate 1,554g (yield: 98%) was obtained.
[169]
[170]
Preparation 16: Preparation of teuriyi Sono carbonyl citrate (TINC)
[171]
As a reaction raw material by using the citric acid 576 g and 1,685 g isononyl alcohol, finally teuriyi Sono carbonyl citrate 1,679 g (yield: 98%) was obtained.
[172]
[173]
Preparative Examples 1 was prepared by a plasticizer composition of an embodiment by mixing a material prepared at 16, showed summarized in the Examples and Comparative an example plasticizer composition Tables 1 and 2 with respect to this, property evaluation of the plasticizer composition is It was carried out in accordance with the test item. A substance other than the material prepared in Preparative Example are all products that can be purchased commercially or ㈜LG chemicals.
[174]
TABLE 1
A plasticizer Plasticizer B Plasticizer C
Examples 1-1 DEHTP 50 TINTM 50 -
Example 1-2 DEHTP 90 TPHTM 10 -
Examples 1-3 DINTP 60 THxTM 40 -
Example 1-4 DPHTP 30 THxTM 70 -
Example 1-5 DHxTP 40 TEHTM 60 -
Example 1-6 DIPTP 80 TINTM 20 -
Example 1-7 DINTP 20 TIPTM 80 -
Example 1-8 DPHTP 10 THxTM 90 -
Example 1-9 DBTP 10 TINTM 90 -
Example 1-10 GL1001) 70 THxTM 30 -
Example 1-11 GL5202) 40 TINTM 60 -
Comparative Examples 1-1 DIDP3) 100 - -
Comparative Examples 1-2 DEHTP 100 - -
Comparative Examples 1-3 - TPHTM 100 -
Comparative Examples 1-4 DEHTP 50 TINTM 50 ESO 4)
Comparative Example 1-5 DINTP 60 THxTM 40 ESO 4)

[175]
1) GL100 (㈜LG Chemicals): diisononyl terephthalate, isononyl (2-ethylhexyl) terephthalate, and di (2-ethylhexyl the terephthalate composition) is from about 10:50:40 weight ratio of terephthalate
[176]
2) GL520 (㈜LG Chemicals): dibutyl terephthalate, butyl (2-ethylhexyl) terephthalate, and di (2-ethylhexyl the terephthalate composition) of about 5:25:70 by weight of terephthalate
[177]
3) DIDP: diisodecyl terephthalate
[178]
4) Plasticizer A and B total sum 100 parts by weight of 20 parts by weight of epoxidized soybean oil (ESO) In contrast
[179]
[180]
TABLE 2
A plasticizer Plasticizer B Plasticizer C (parts by weight) 1)
Examples 2-1 DEHTP 62.5 TEHTM 37.5 TEHC 25
Example 2-2 DEHTP 37.5 TEHTM 62.5 THxC 25
Example 2-3 DEHTP 66.7 TINTM 33.3 THxC 67
Examples 2-4 DEHTP 50 THxTM 50 TEHC 67
Example 2-5 DINTP 77.8 TBTM 22.2 TIPC 11
Example 2-6 DINTP 40 TIPTM 60 TIPC 100
Example 2-7 DPHTP 11.1 THTM 88.9 I'M 11
Example 2-8 GL520 85.7 TPHTM 14.3 TEHC 43
Comparative Examples 2-1 DIDP 100 - -
Comparative Example 2-2 DINTP 100 - TINC 25
Comparative Examples 2-3 DPHTP 100 - TEHC 43
Comparative Examples 2-4 DEHTP 66.7 TINTM 33.3 ATHxC2) 67

[181]
1) 100 parts by weight of the mixture compared to the content of the total weight of the plasticizer A and the plasticizer B
[182]
2) ATHxC: acetyl trihexyl citrate
[183]
[184]

[185]
Hardness (hardness) measurement
[186]
Using the ASTM D2240, it was measured Shore (shore "A") hardness, 3T 10s at 25 ℃.
[187]
[188]
The tensile strength (tensile strength) measurement
[189]
ASTM by D638 method, a test device, the UTM after using (manufacturer;; Instron, Model 3345) pulls the crosshead speed (cross head speed) of 200 ㎜ / min (1T), to measure the point at which the specimen is cut . Tensile strength was calculated as follows:
[190]
Tensile strength (kgf / cm 2 ) = Load (load) value (kgf) / thickness (cm) x width (cm)
[191]
[192]
Measure elongation (elongation rate)
[193]
ASTM D638 method by using the UTM, pulls the crosshead speed (cross head speed) of 200 ㎜ / min (1T), and then measuring the point at which the specimen is cut, the elongation at break was calculated as follows:
[194]
Elongation at break (%) = length after elongation / initial length] x 100 was calculated.
[195]
[196]
Implementation losses (migration loss) measured
[197]
KSM-3156 was obtained according to the above 2 mm thick specimen, after both sides of the specimen attached to Glass Plate with wax paper on both sides of the specimen kgf 2 / cm 2 was added to the weight of the. Taken out after leaving the test piece in a hot air circulation oven (80 ℃) for 72 hours and cooled for 4 hours at room temperature. Then the test piece after removing the PS attached to both surfaces to measure the weight before and after left in the oven was calculated according to an expression such as the implementation of the loss below.
[198]
Implementation loss (%) = [(initial weight of the sample at room temperature - the weight of the oven and then left to stand sample) / initial weight of the specimen at room temperature] x 100
[199]
[200]
The tensile and elongation measurements survival rate
[201]
Was added to the column is measured for 121 ℃, 168 hours of tensile and elongation survival rate, intended to measure the tensile and elongation properties which remain in the specimen, the measurement method is the same as the method above, the tensile strength and elongation measured.
[202]
[203]
Hardy
[204]
After the fabricated five samples was allowed to stand for 3 minutes at a specific temperature to measure the temperature at the time of hitting damage than three out of five dogs.
[205]
[206]
Experimental Example 1: evaluation of physical properties 1
[207]
A specimen using the above Tables 1 and 2 and Comparative Example of the mixed plasticizer composition was prepared as described in Example.
[208]
The sample produced was ASTM reference to D638, polyvinyl resins (PVC (LS100)) RUP-144 a plasticizer composition prepared based on 100 parts by weight, in the Examples and Comparative Examples to 50 parts by weight of a stabilizer chloride (ADEKA Korea) were mixed in 5 parts by weight, Omya 1T (Omiya), 40 parts by weight of the St-a (Isu Chemical) 0.3 parts by weight blended with a lubricant 98 ℃ to 700 rpm as the filler. Was working at 160 ℃ for 4 minutes by using a roll mill (Roll mill), a specimen was prepared by working in 3 minutes (the low pressure) and 2.5 minutes (high pressure) at 180 ℃ using a press (press).
[209]
Respectively evaluating the tests with respect to the sample the results are shown in Table 3 below.
[210]
TABLE 3
경도(Shore "A") Tensile strength (kg / cm 2 ) Tensile survival rate (%) Elongation at break (%) Renal survival rate (%) Cold Resistance (℃)
Examples 1-1 92.0 164.3 111.6 301.3 78.5 -29
Example 1-2 90.3 170.2 102.4 306.8 86.4 -32
Examples 1-3 89.2 172.6 105.0 314.5 96.4 -32
Example 1-4 89.3 170.1 102.0 300.2 93.4 -31
Example 1-5 90.6 165.9 98.2 295.6 92.3 -33
Example 1-6 88.5 167.5 96.7 290.3 80.6 -35
Example 1-7 89.2 170.3 102.0 304.6 94.2 -32
Example 1-8 89.0 172.0 98.8 310.5 92.6 -33
Example 1-9 92.8 162.4 105.6 298.5 83.6 -29
Example 1-10 89.0 177.5 97.8 295.7 95.8 -36
Example 1-11 90.7 198.7 98.7 314.8 88.5 -29
Comparative Examples 1-1 91.3 158.7 95.6 280.1 74.3 -28
Comparative Examples 1-2 91.6 143.6 78.5 270.3 65.3 -30
Comparative Examples 1-3 96.8 170.3 98.3 255.6 92.3 -25

[211]
[212]
Referring to Table 3, since in selecting the terephthalate-based plasticizers and trimellitate-based plasticizers controlling a carbon number of 4 to 10 and suitably control the respective content ratios, Comparative Example 1 and Comparative Example 1-1, existing products 2 compared to can confirm the performance is that the significantly improved, in case of the comparative example 1-2 to be used as environmentally friendly products universally DEHTP (Comparative example 1-2), a plasticizer, it is possible to see that the physical properties are improved as superior , to check that all plasticizers exhibit superior performance plasticizer DIDP (Comparative example 1-1) due to environmental concerns, it was confirmed that this product can completely replace the DIDP.
[213]
Further, the terephthalate-based if the comparison has not been used at all the plasticizer has plasticizing efficiency of Examples 1-3 (hardness) The embodiments from about 5% or more, and elongation characteristics compared to the present example, the drop in contrast of at least about 10% of the width and and it may also determine that it is by nature a fairly poor tribal doegie a substitute for existing products as compared to conventional products.
[214]
[215]
Experimental Example 2: Property Evaluation 2
[216]
The embodiment described in Table 1 Examples and Comparative Examples of the plasticizer composition were produced by using the mixture of the specimen as shown in Experimental Example 1 to respectively evaluate the tests with respect to the sample are shown in the following Table 4 as a result.
[217]
TABLE 4
경도(Shore "A") Tensile strength (kg / cm 2 ) Tensile survival rate (%) Elongation at break (%) Renal survival rate (%) Cold Resistance (℃)
Examples 1-1 92.0 164.3 111.6 301.3 78.5 -29
Comparative Examples 1-4 91.6 160.2 95.6 287.3 75.1 -23
Examples 1-3 89.2 172.6 105.0 314.5 96.4 -32
Comparative Example 1-5 89.5 170.0 92.5 295.8 89.3 -27

[218]
[219]
The Comparative Examples 1-4 and 1-5 will be further added in addition to epoxidized soybean oil in Examples 1-1 and 1-3 respectively, as a plasticizer. Referring to Table 4, the epoxidation When mixed with the oil as a plasticizer, may determine the physical properties significantly decreased in the eye, in Example 1-1 compared to the epoxidation case of the comparative examples 1-4 mixed soybean oil, the tensile strength , elongation, kidney survival rate was decreased performance, tensile and cold survival rate is available to the poor haejyeoteum considerable width.
[220]
Which as can be found under the same change in the Comparative Example 1-5 and Example 1-3, a plasticizer composition can be said to show that it is preferable that none of the epoxidized oil.
[221]
[222]
Experimental Example 3: Property Evaluation 3
[223]
Table 2 described in the embodiment examples and the comparison using the plasticizer composition blend of Example was produced specimens as Experimental Example 1 to assess the respective test items with respect to the specimen and the results are shown in Table 5.
[224]
Table 5
경도(Shore "A") Tensile strength (kg / cm 2 ) Tensile survival rate (%) Elongation at break (%) Renal survival rate (%) Implementation loss (%) Cold Resistance (℃)
Examples 2-1 91.3 164.6 100.9 293.3 83.0 1.98 -31
Example 2-2 90.7 166.2 102.6 297.3 85.2 1.73 -30
Example 2-3 89.4 159.6 112.8 309.3 82.3 1.66 -31
Examples 2-4 89.9 168.5 102.5 303.3 82.7 1.80 -30
Example 2-5 91.0 168.9 102.0 305.7 88.5 1.88 -31
Example 2-6 87.2 162.8 98.0 325.4 86.4 0.88 -35
Example 2-7 87.5 169.8 103.5 308.4 88.0 0.73 -35
Example 2-8 91.0 173.4 102.3 310.0 92.5 1.32 -33
Comparative Examples 2-1 91.3 158.7 95.6 280.1 74.3 1.79 -28
Comparative Example 2-2 94.5 167.0 96.5 281.0 85.1 5.65 -28
Comparative Examples 2-3 95.0 150.2 88.2 275.3 80.6 6.50 -27

[225]
[226]
Referring to Table 5, Examples 2-1 to 2-8 the same or more level of physical properties in all aspects than the conventional product of Comparative Example 2-1 was viewed for securing, whereby terephthalate and trimellitate-based plasticizers when using the additional citrate-based plasticizer with a mix of the plasticizer-based plasticizer, there can be seen that to take advantage as an alternative to existing products without degradation of certain properties can be achieved also with good quality improved physical properties.
[227]
Also, without using a trimellitate-based plasticizers, in the case of Comparative Examples 2-2 and 2-3 used in addition only the citrate-based plasticizer has plasticizing efficiency (hardness) is poor become larger, the implementation loss characteristics also greatly degraded that the to check, the examples 2-1 to 2-8 compared with the survival rate tensile elongation, and reduced cold resistance can also be checked.
[228]
[229]
Example 4: Physical property evaluation 4
[230]
Table 2 described in the embodiment examples and the comparison using the plasticizer composition blend of Example was produced specimens as Experimental Example 1 to assess the respective test items with respect to the specimens shown in Table 6. The results are.
[231]
TABLE 6
경도(Shore "A") Tensile strength (kg / cm 2 ) Tensile survival rate (%) Elongation at break (%) Renal survival rate (%) Implementation loss (%) Cold Resistance (℃)
Example 2-3 89.4 159.6 112.8 309.3 82.3 1.66 -31
Comparative Examples 2-1 91.3 158.7 95.6 280.1 74.3 1.79 -28
Comparative Examples 2-4 90.2 149.3 98.6 300.2 78.2 1.90 -30

[232]
[233]
Comparative Example 2-4 geotinde to replace the citrate-based plasticizer applied in Example 2-3 as the acetyl group is bonded, with reference to Table 6, the physical properties are viewed degraded. That is, was the tensile strength and elongation decreases plasticizing efficiency decline (hardness increase), and has a tensile elongation survival rate survival rate and to determine the dropped. Furthermore, because by applying the acetyl group is bonded to obtain a result not all existing products in poor physical properties further implementation loss and tensile strength side. That is, it was confirmed that the case of the citrate, the combination of acetyl group to view the damage as well as in the damage side of the physical properties in the economic and environmental aspects, as described above.
[234]
[235]
A preferred embodiment but will be described in detail for example the scope of the present invention of the present invention in the above is not rather various changes and modifications in the form of one of ordinary skill in the art using the basic concept of the invention as defined in the following claims is not limited thereto Furthermore, the present invention It belongs to the scope.
[236]

Claims
[Claim 1]
The carbon number of the two alkyl groups bound to a diester each independently 4-10 terephthalate-based plasticizer; And to trimellitate type plasticizer represented by formula (1); plasticizer composition, characterized in that including, and not containing an epoxidized oil: [Formula 1] In Chemical Formula 1, R 1 to R 3 are carbon atoms are each independently an alkyl group of 4 to 10.
[Claim 2]
The method of claim 1 wherein said terephthalate-based plasticizers, and trimellitic plasticizers in the composition lactate-based plasticizer will in a weight ratio of 90: 10 to 10: 90.
[Claim 3]
According to claim 1, wherein said plasticizer composition to a plasticizer composition further comprises a citrate-based plasticizer represented by the following formula 2: [Formula 2] In Formula 2, R 4 to R 6 are, each independently, a carbon number of 5 to 9, and an alkyl group, R 7 is hydrogen.
[Claim 4]
4. The method of claim 3 wherein the citrate-based plasticizer terephthalate-based plasticizers, and trimellitate-based mixtures the total weight 100 parts by weight of the preparation, 5 parts by weight to 150 parts by weight of a plasticizer; the plasticizer, the composition is included in.
[Claim 5]
The method of claim 1, wherein the two alkyl groups bonded to the diester of the terephthalate-based plasticizers are, each independently, a n-butyl group, an isobutyl group, a n-pentyl group, isopentyl group, n-hexyl group, n heptyl group, iso the plasticizer composition heptyl, nomalok group, yisook group, a 2-ethylhexyl group, n nonyl, iso-nonyl group, to 2-propyl heptyl group or is selected from the group consisting of iso-decyl group.
[Claim 6]
The method of claim 1 wherein the general formula (I) of R 1 to R 3 are, each independently, a n-butyl group, an isobutyl group, a n-pentyl group, isopentyl group, n-hexyl group, n heptyl group, iso-heptyl group, nomalok group the plasticizer composition, yisook group, a 2-ethylhexyl group, n nonyl, iso-nonyl group, to 2-propyl heptyl group or is selected from the group consisting of iso-decyl group.
[Claim 7]
4. The method of claim 3 wherein the formula (2) of the R 4 to R 6 are, each independently, a pentyl group, an isopentyl group, a hexyl group, iso-hexyl, heptyl, iso-heptyl group, nomalok group, a 2-ethylhexyl group, the plasticizer composition n nonyl or isononyl group is selected from the group consisting of.
[Claim 8]
100 parts by weight of the resin; And a plasticizer composition of claim 1 5 to 150 parts by weight of a resin composition comprising a.
[Claim 9]
The method of claim 8 wherein the resin is a resin composition is at least one member selected from the group consisting of ethylene-vinyl acetate, polyethylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomer.