WO2017183877A1 - Composition de plastifiant et composition de résine la comprenant - Google Patents

Composition de plastifiant et composition de résine la comprenant Download PDF

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WO2017183877A1
WO2017183877A1 PCT/KR2017/004118 KR2017004118W WO2017183877A1 WO 2017183877 A1 WO2017183877 A1 WO 2017183877A1 KR 2017004118 W KR2017004118 W KR 2017004118W WO 2017183877 A1 WO2017183877 A1 WO 2017183877A1
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Prior art keywords
diester
cyclohexane
based material
citrate
weight
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PCT/KR2017/004118
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English (en)
Korean (ko)
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김현규
이미연
조윤기
문정주
김주호
정석호
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020170047832A external-priority patent/KR102090295B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US15/580,993 priority Critical patent/US11186702B2/en
Priority to CN201780002231.8A priority patent/CN107709429B/zh
Priority to EP17786145.7A priority patent/EP3293226B1/fr
Publication of WO2017183877A1 publication Critical patent/WO2017183877A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/62—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/75—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a six-membered ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/18—Plasticising macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids

Definitions

  • the present invention relates to a plasticizer composition and a resin composition comprising the same.
  • plasticizers react with alcohols to polycarboxylic acids such as phthalic acid and adipic acid to form the corresponding esters.
  • polycarboxylic acids such as phthalic acid and adipic acid
  • plasticizer compositions that can replace phthalate-based plasticizers such as terephthalate-based, adipate-based, and other polymer-based plastics is being continued.
  • plasticizers should be used in consideration of discoloration, transferability, and mechanical properties.
  • plasticizers, fillers, stabilizers, viscosity-reducing agents, dispersants, antifoaming agents, foaming agents, etc. are blended with PVC resins according to the characteristics required for different industries such as tensile strength, elongation, light resistance, transition, gelling or absorption rate. Done.
  • the plasticizer compositions applicable to PVC when the most widely used di (2-ethylhexyl) terephthalate is applied, the hardness or sol viscosity is high and the absorption rate of the plasticizer is relatively high. It was slow, and the performance and stress performance were not good.
  • the hydrogenated material of di (2-ethylhexyl) terephthalate can be considered as an improvement, the plasticization efficiency is improved, while the migration efficiency and thermal stability are poor, and the production cost is increased due to the hydrogenation reaction. Having difficulty with
  • the present invention is a plasticizer which can improve the physical properties such as plasticization efficiency, transferability, gelling properties, etc. required for the prescription of calendering sheet, plastisol and extrusion / injection compound as a plasticizer used in the resin composition and a manufacturing method thereof. And to provide a resin composition comprising them.
  • the present invention can improve the performance by mixing a certain amount of citrate plasticizers in order to solve the problems of the migration and plasticization efficiency and economical efficiency of the hydrogenated di (2-ethylhexyl) terephthalate,
  • a mixed hydrogenation composition having two or more compositions is superior to a single hydrogenated material
  • two or more kinds of 1,4- are superior in terms of plasticizing efficiency and transferability, plasticizer absorption rate and stress transferability.
  • a plasticizer composition comprising a cyclohexane diester-based material and a citrate-based material is provided.
  • two or more cyclohexane 1,4-diester material and citrate-based material, wherein the weight ratio of the cyclohexane 1,4-diester-based material and the citrate-based material is 99: 1 to 1:99.
  • the citrate-based material may include any one selected from the group consisting of a hybrid alkyl substituted citrate-based material having 4 to 10 carbon atoms and a non-hybrid alkyl substituted citrate-based material having 4 to 10 carbon atoms.
  • the plasticizer composition may further comprise an epoxidized material.
  • the epoxidized material may further include 1 to 100 parts by weight based on 100 parts by weight of the mixed weight of the cyclohexane 1,4-diester-based material and the citrate-based material.
  • a method of preparing a plasticizer composition is provided.
  • the resin may be at least one member selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomers.
  • the plasticizer composition according to an embodiment of the present invention may provide excellent physical properties such as migration resistance and volatility, as well as excellent plasticization efficiency and tensile strength and elongation.
  • 1 is an image showing the improvement of heat resistance according to the addition of the epoxidized material.
  • butyl refers to an alkyl group having 4 carbon atoms, and may be used as a term including both straight and branched chains, and may be, for example, n-butyl, isobutyl, or t-butyl. But preferably n-butyl or isobutyl.
  • octyl and “2-ethylhexyl” are alkyl groups having 8 carbon atoms, and may be used in combination with octyl as an abbreviation of 2-ethylhexyl, and in some cases, may refer to octyl which is a linear alkyl group. However, it can be interpreted to mean a branched alkyl group, 2-ethylhexyl.
  • a plasticizer composition including two or more cyclohexane 1,4-diester-based materials.
  • the cyclohexane 1,4-diester material is 1 to 99% by weight, 20 to 99% by weight, 40 to 99% by weight, 50 to 95% by weight or 60 to 90% by weight based on the total weight of the composition
  • the content selected in the range of the like may be applied.
  • the cyclohexane 1,4-diester material may be a compound represented by the following Chemical Formula 1.
  • R 1 and R 2 may be the same or different and may be selected from alkyl groups having 1 to 12 carbon atoms, respectively.
  • the cyclohexane 1,4-diester-based material may be named, for example, dialkyl cyclohexane-1,4-diester when R1 and R2 are the same, and alkyl (if R1 and R2 are different).
  • the cyclohexane 1,4-diester-based material is butyl (2-ethylhexyl) cyclohexane-1,4-diester (1,4-BOCH), (2-ethylhexyl) isononyl cyclohexane- 1,4-diester (1,4-OINCH), butylisononyl cyclohexane-1,4-diester (1,4-BINCH), pentylisononyl cyclohexane-1,4-diester (1,4-PINCH), isononyl (2-propylheptyl) cyclohexane-1,4-diester (1,4-IPHCH), dibutyl cyclohexane-1,4-diester (1,4 -DBCH), dipentyl cyclohexane-1,4-diester (1,4-DPCH), diisononyl cyclohexane-1,4-diester (1,4
  • the cyclohexane 1,4-diester-based material may be a mixture of three cyclohexane 1,4-diester-based material, for example, di (2-ethylhexyl) cyclohex First mixture, diisononyl cyclo, hexane-1,4-diester, butyl (2-ethylhexyl) cyclohexane-1,4-diester and dibutyl cyclohexane-1,4-diester Second mixture of hexane-1,4-diester, butylisononyl cyclohexane-1,4-diester and dibutyl cyclohexane-1,4-diester, di (2-ethylhexyl 3) a mixture of cyclohexane-1,4-diester, (2-ethylhexyl) isononyl cyclohexane-1,4-diester and diisononyl
  • the first mixture is di (2-ethylhexyl) cyclohexane-1,4-diester 3.0 to 99.0 mol%; Butyl (2-ethylhexyl) cyclohexane-1,4-diester 0.5 to 96.5 mol% and dibutyl cyclohexane-1,4-diester 0.5 to 96.5 mol%; wherein the second mixture is Diisononyl cyclohexane-1,4-diester 3.0 to 99.0 mol%; 0.5 to 96.5 mol% of butyl isononyl cyclohexane-1,4-diester and 0.5 to 96.5 mol% of dibutyl cyclohexane-1,4-diester; wherein the third mixture is di (2- Ethylhexyl) cyclohexane-1,4-diester 3.0 to 99.0 mol%;
  • the composition ratio may be a mixture composition ratio produced by the esterification reaction, and may be an intended composition ratio by additionally mixing a specific compound, and the mixture composition ratio may be appropriately adjusted to suit desired physical properties.
  • the transition characteristics may be improved, the mechanical properties may be considerably excellent, and the plasticization efficiency may be increased.
  • the plasticizer composition comprises a citrate-based material
  • the citrate-based material is a mixed alkyl substituted citrate-based material having 4 to 10 carbon atoms and a non-hybridized alkyl substitution having 4 to 10 carbon atoms It may include one or more compounds selected from the group consisting of citrate-based materials.
  • the mixed alkyl substituted citrate-based material having 4 to 10 carbon atoms may be, for example, 1,2-dibutyl 3- (2-ethylhexyl) 2-hydroxypropane-1,2,3-tricarboxylate, 1,3-dibutyl 2- (2-ethylhexyl) 2-hydroxypropane-1,2,3-tricarboxylate, 1-butyl 2,3-di (2-ethylhexyl) 2-hydroxypropane 4 and 8 carbon atoms, such as -1,2,3-tricarboxylate or 2-butyl 1,3-di (2-ethylhexyl) 2-hydroxypropane-1,2,3-tricarboxylate Citrate having a combination substituent of an alkyl group; 1,2-dipentyl 3-heptyl 2-hydroxypropane-1,2,3-tricarboxylate, 1,3-dipentyl 2-heptyl 2-hydroxypropane-1,2,3-tricarboxyl Rate, 1-penty
  • the alkyl group having 4 to 10 carbon atoms may be linear or branched.
  • Trihexyl citrate THC
  • THPC triheptyl citrate
  • TOC tri (2-ethylhexyl) citrate
  • THC trinonyl citrate
  • TPHC tri (2-propylheptyl) citrate
  • the butyl group to nonyl group may be applied to each of the structural isomers such as isobutyl group for butyl group, 2-ethylhexyl group for octyl group, isononyl group for 2-nonheptyl group, and 2-propylheptyl group. In this case, all of isodecyl may be included.
  • non-hybrid alkyl substituted citrate materials having 4 to 10 carbon atoms may be preferred, compared to hybrid alkyl substituted citrate materials, and tributyl citrate and / or tri (2-ethylhexyl) sheets.
  • the rate may be used at a slightly more frequent frequency.
  • trialkyl citrate, or dinalkyl-malkyl citrate, such as the hybrid or non-hybrid alkyl substituted citrate compound may be applied.
  • the acetyl group is present in the citrate-based material, the physical properties of the plasticizer, particularly There exists a possibility that workability and gelling property may deteriorate with the fall of plasticization efficiency.
  • the citrate-based material is an acetyl citrate compound in which an acetyl group is substituted for hydrogen of the remaining hydroxy group in addition to the three ester groups, the plasticization efficiency is lowered, the amount of plasticizer to be overcome is increased, and the product price is increased. Due to such problems, deterioration in various aspects such as marketability, economic feasibility and physical properties may be a problem.
  • the cyclohexane 1,4-diester-based material and the citrate-based material in the plasticizer composition the upper limit is 99: 1, 95: 5, 90:10, 85:15, 80:20, 70 by weight ratio : 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.
  • the plasticizer composition may include a cyclohexane 1,4-diester-based material and a citrate-based material, and may further include an epoxidized material.
  • the heat resistance may not be excellent, and the heat resistance may further include the epoxidized material. This can be supplemented.
  • the addition amount of the epoxidized material for supplementing the heat resistance property may be 1 to 100 parts by weight based on 100 parts by weight of the mixed weight of cyclohexane 1,4-diester-based material and citrate-based material, preferably 5 to 80 parts by weight Can be.
  • the heat resistance property can be compensated for.
  • the amount of the epoxidized material is added in excess, the cyclohexane 1,4-diester material and the citrate material are relatively low. There is a fear that the physical properties of the basic plasticizer is included, it is necessary to adjust the content.
  • the epoxidized material is, for example, epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized palm oil (epoxidized stearate), epoxidized oleate, epoxidized tallate and epoxidized linoleate or mixtures thereof.
  • epoxidized soybean oil (ESO), epoxidized linseed oil (ELO) and epoxidized ester derivatives thereof may be applied, but are not limited thereto.
  • the terephthalate-based material is a direct esterification reaction of at least two alcohols selected from the group consisting of 2-ethylhexyl alcohol, isononyl alcohol, 2-propylheptyl alcohol, butyl alcohol and isobutyl alcohol and terephthalic acid; Phthalate based materials can be prepared.
  • the direct esterification may include adding terephthalic acid to an alcohol, then adding a catalyst and reacting under a nitrogen atmosphere; Removing unreacted alcohol and neutralizing unreacted acid; And dehydration and filtration by distillation under reduced pressure.
  • the alcohol may be used in the range of 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 terephthalic acid.
  • the catalyst is, for example, acid catalysts such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, paratoluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, alkyl sulfuric acid, aluminum lactic acid, lithium fluoride, potassium chloride, cesium chloride, Metal salts such as calcium chloride, iron chloride, aluminum phosphate, metal oxides such as heteropolyacids, natural / synthetic zeolites, cation and anion exchange resins, tetraalkyl titanate and organic metals such as polymers thereof. .
  • the catalyst may use tetraalkyl titanate.
  • the amount of the catalyst used may vary depending on the type, for example, in the case of a homogeneous catalyst, 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 100% by weight of the total reactants. And, in the case of heterogeneous catalysts, it may be in the range of 5 to 200%, 5 to 100%, 20 to 200%, or 20 to 150% by weight of the total amount of reactants.
  • the direct esterification reaction is 10 minutes to 10 hours, preferably 30 minutes to 8 hours, more preferably 1 to 6 hours in the temperature range of 80 °C to 270 °C, preferably 150 °C to 250 °C It is preferably carried out in, it is possible to effectively obtain a terephthalate-based material in the appropriate temperature, catalyst and time range in consideration of the boiling point of alcohol and the like.
  • cyclohexane 1,4-diester-based material is also a mixture, for example, trans esterification of di (2-ethylhexyl) terephthalate and butyl alcohol; Trans esterification of diisononyl terephthalate and butyl alcohol; Or trans esterification of di (2-ethylhexyl) terephthalate and diisononyl alcohol, trans esterification of diisononyl terephthalate and 2-propylheptyl; It may be to prepare a terephthalate-based material through such.
  • the mixture may produce the same mixture even when the alkyl groups of the terephthalate and the alcohol are interchanged.
  • the product of the trans esterification reaction of di (2-ethylhexyl) terephthalate and diisononyl alcohol may be the same as the product of the trans esterification reaction of diisononyl terephthalate and 2-ethylhexyl alcohol.
  • trans esterification reaction refers to a reaction in which an alcohol and an ester react with each other, as shown in Scheme 1 below, so that R of the ester is interchanged with R 'of an alcohol.
  • the trans-esterification reaction has the advantage that does not cause a waste water problem compared to the acid-alcohol esterification reaction, and can proceed under a non-catalyst, it can solve the problem when using an acid catalyst.
  • di (2-ethylhexyl) terephthalate and butyl alcohol may be prepared by the trans-esterification reaction, such as di (2-ethylhexyl) terephthalate, butyl (2-ethylhexyl) terephthalate and dibutyl terephthalate.
  • And may be specifically formed in amounts of 10% to 50%, 0.5% to 50%, and 35% to 80% by weight.
  • terephthalate-based material mixture having high process efficiency and excellent processability and absorption rate.
  • the mixture prepared by the trans-esterification reaction can control the composition ratio of the mixture according to the amount of alcohol added.
  • the addition amount of the alcohol 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 the terephthalate-based material.
  • the molar fraction of the terephthalate compound participating in the trans-esterification reaction will increase as the terephthalate compound contains more alcohol, the content of the two terephthalate compounds as a product in the mixture may increase. And, correspondingly, the content of the unreacted terephthalate compound may show a tendency to decrease.
  • the molar ratio of the reactant terephthalate compound 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, high process efficiency and processability There is an effect of obtaining an ester plasticizer composition excellent in an improvement effect.
  • composition ratio of the mixture of the three terephthalates is not limited to the above range, and may be added to any one of the three terephthalates to change the composition ratio, and possible mixed composition ratios are as described above. .
  • the ester composition prepared by the trans esterification step may include all of the single attack ester compound, the double attack ester compound, and the reaction residual ester compound, and control the composition ratio of the ester composition according to the amount of the alcohol added. can do.
  • the addition amount of the alcohol 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 the terephthalate.
  • the content of phthalates and terephthalates attacked by two ester groups may increase.
  • the content of residual terephthalate present in the unreacted correspondingly may tend to decrease.
  • the molar ratio of the terephthalate and alcohol may be, for example, 1: 0.005 to 5.0, 1: 0.05 to 2.5, or 1: 0.1 to 1.0, and may provide a plasticizer composition having high process efficiency and excellent processability improvement effect within this range. Terephthalate-based materials can be obtained.
  • the trans esterification reaction is carried out at a reaction temperature of 120 ° C to 190 ° C, preferably 135 ° C to 180 ° C, more preferably 141 ° C to 179 ° C, for 10 minutes to 10 hours, preferably 30 minutes to 8 hours, more Preferably it is carried out in 1 to 6 hours. It is possible to effectively obtain a mixture that is a terephthalate-based material of a desired composition ratio within the temperature and time range. In this case, the reaction time may be calculated from the time point at which the reaction temperature is reached after the reaction temperature is raised.
  • the trans esterification reaction may be performed under a non-catalyst, but in some cases, may be performed under an acid catalyst or a metal catalyst, in which case the reaction time may be shortened.
  • the acid catalyst may be, for example, sulfuric acid, methanesulfonic acid or p-toluenesulfonic acid, and the like, and the metal catalyst may be, for example, an organometallic catalyst, a metal oxide catalyst, a metal salt catalyst, or the metal itself.
  • the metal component may be any one selected from the group consisting of tin, titanium and zirconium, or a mixture of two or more thereof.
  • the method may further include distilling off the unreacted alcohol and reaction by-products, for example, an ester compound after the trans-esterification reaction.
  • the distillation may be, for example, two-stage distillation separately using the boiling point difference of the alcohol and the reaction by-product.
  • the distillation may be mixed distillation.
  • the mixed distillation means distilling butanol and reaction by-products simultaneously.
  • the hydrogenation step may be a step of converting a terephthalate-based material into a cyclohexane 1,4-diester-based material by hydrogenating a terephthalate-based material, which is a single compound or a mixture, in the presence of a metal catalyst.
  • the hydrogenation step is a reaction for removing the aromaticity of the benzene ring of the terephthalate-based materials by adding hydrogen in the presence of a metal catalyst, may be a kind of reduction reaction.
  • the hydrogenation reaction is a reaction of the terephthalate-based material with hydrogen under a metal catalyst to synthesize a cyclohexane 1,4-diester-based material, the reaction conditions of the benzene without affecting the carbonyl group substituted in the benzene It may include all conventional reaction conditions capable of hydrogenating only the ring.
  • the hydrogenation reaction may be performed by further including an organic solvent such as ethanol, but is not limited thereto.
  • an organic solvent such as ethanol
  • a Rh / C catalyst, a Pt catalyst, a Pd catalyst, and the like which are generally used to hydrogenate a benzene ring, may be used.
  • the metal catalyst is not limited thereto.
  • the pressure during hydrogenation in the hydrogenation reaction may be about 3 to 15 MPa, the reaction may be carried out for about 2 to 10 hours, it may be carried out at a temperature of about 80 °C to 200 °C.
  • the above-described reaction step may be an example, and the final hydrogenated cyclohexane 1,4-diester-based material may be hydrogenated with a terephthalate of a single material first to produce a hydrogenated cyclohexane 1,4-diester-based material of the single material.
  • a mixed cyclohexane 1,4-diester-based composition may be prepared by hydrogenation by trans esterification with alcohol.
  • the final product may be prepared by performing a direct ester reaction using terephthalic acid and / or terephthalate and / or a trans ester reaction followed by hydrogenation, or after the hydrogenation of the terephthalate prepared through the ester reaction, followed by trans esterification. Any method for producing a hydrogenated mixture through the oxidization reaction can be applied.
  • the three hydrogenated final mixed compositions prepared through the trans esterification reaction may generally include two substances having the same alkyl group of the diester and one substance having different alkyl groups of the diester.
  • one substance having different alkyl groups from the diester may serve as a main factor affecting the physical properties of the plasticizer, but it may be impossible to commercially and technically separate it as a single substance.
  • the same alkyl groups bonded to the diesters at the 1,4 positions may be prepared as a single substance through direct esterification, respectively, but the alkyl groups bonded to the diesters at the 1,4 positions of the cyclohexane may be different from each other.
  • Different things can only be prepared through trans esterification reaction, in which case it is impossible to separate only one material from which the alkyl group of the diester differs from each other, and even if only a small amount can be separated through excessive iteration at the laboratory level.
  • the blending may be performed by blending the cyclohexane 1,4-diester-based material and the citrate-based material in which the terephthalate-based material is converted through a hydrogenation reaction in a ratio of 1:99 to 99: 1 by weight.
  • a plasticizer composition may be prepared, and the cyclohexane 1,4-diester-based material may be dependent on whether the terephthalate-based material is a single compound or a mixture, and is characterized in that each is a single compound or a mixture.
  • the method may further include adding an epoxidized material. Since the content in the case of adding the said epoxidation material further, and the kind of epoxidation material were mentioned above, the description is abbreviate
  • the aforementioned direct esterification and trans esterification reactions can also be used to prepare the above-mentioned hybrid or non-hybrid citrate compounds.
  • the citrate-based material may also be prepared in a mixed ratio in a predetermined ratio, and the composition ratio of the resulting mixture may be controlled by controlling the content of alcohol as a reaction raw material. have.
  • the citrate compound when the citrate compound is prepared through a direct esterification reaction or a trans esterification reaction, the contents thereof may be applied in the same manner as the contents applied to preparing the terephthalate-based material.
  • a resin composition comprising the plasticizer composition and the resin described above.
  • the resin may be a resin known in the art.
  • one or more mixtures selected from ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, thermoplastic elastomer, and polylactic acid may be used, but is not limited thereto.
  • the plasticizer composition may be included in 5 to 150 parts by weight based on 100 parts by weight of the resin.
  • the content of the plasticizer may be changed according to the method of processing the resin composition.
  • the plasticizer is preferably 5 to 100 parts by weight of the resin. 100 parts by weight, 5 to 60 parts by weight, or 5 to 50 parts by weight.
  • a plasticizer may be included as 30 to 150 parts by weight, 40 to 130 parts by weight, and 60 to 120 parts by weight.
  • the resin composition may further include a filler.
  • the filler may be 0 to 300 parts by weight, preferably 50 to 200 parts by weight, more preferably 100 to 200 parts by weight based on 100 parts by weight of the resin.
  • the filler may be a filler known in the art, it is not particularly limited.
  • it may be at least one mixture selected from silica, magnesium carbonate, calcium carbonate, hard coal, talc, magnesium hydroxide, titanium dioxide, magnesium oxide, calcium hydroxide, aluminum hydroxide, aluminum silicate, magnesium silicate and barium sulfate.
  • the resin composition may further include other additives such as stabilizers, if necessary.
  • additives such as the stabilizer may be, for example, 0 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the resin.
  • the stabilizer may be, for example, a calcium-zinc-based (Ca-Zn-based) stabilizer such as calcium stearate salts, but is not particularly limited thereto.
  • Ca-Zn-based stabilizer such as calcium stearate salts
  • the resin composition may be applied to all resins used for melt processing and plastisol processing, and may be applied to compound industries such as extrusion or injection, calendering and plastisol, for example.
  • Examples of the product may include various electric wires, flooring materials, automotive interior materials, films, sheets, wallpaper, toys, and the like.
  • reaction product was mixed and distilled to remove butanol and 2-ethylhexyl alcohol and finally a mixed composition was prepared.
  • distillation is performed under reduced pressure for 0.5 to 4 hours to remove unreacted raw materials.
  • steam extraction is performed under reduced pressure using steam for 0.5 to 3 hours, the reaction solution temperature is cooled to about 90 ° C., and neutralization is performed using an alkaline solution. .
  • washing with water may be performed, and then the reaction solution is dehydrated to remove moisture.
  • the filtrate was added to the reaction solution from which the water was removed, the mixture was stirred for a predetermined time, and then filtered to obtain a mixed composition.
  • the mixed composition was hydrogenated to prepare a hydrogenated mixed composition.
  • Transesterification was performed using 1,000 g of TOC prepared in Preparation Example 6 and 300 g of n-butanol as reaction raw materials, and finally 840 g of butyloctyl citrate was obtained.
  • the product is a composition, the main components are divided into alkyl groups bonded to the three ester groups of the citrate compound, BOC two butyl groups, BOC one butyl group and TOC unbutylated, respectively The ratio of was about 20%, 50% and 30% by weight.
  • Example 11 and Example 12 were configured as shown in Table 2 below.
  • the specimen is prepared by referring to ASTM D638, 40 parts by weight of the plasticizer composition of Examples 1 to 10 and Comparative Examples 1 to 5, 3 parts by weight of a stabilizer (BZ-153T) in 100 parts by weight of PVC (LS100S) 3L super mixer ( after mixing at 98 and 700 rpm in a super mixer, and then working with a roll mill for 4 minutes at 160 ° C. to produce 5 mm sheets, press work at 180 ° C. for 2.5 minutes at low pressure and 2 minutes at high pressure, and then make 1T and 3T sheets. Specimen was produced. Each specimen was used to evaluate physical properties according to the test items below, and the results are summarized in Tables 3 and 4 below.
  • Tensile Strength (kgf / mm2) Load Value (kgf) / Thickness (mm) ⁇ Width (mm)
  • Elongation (%) [length after extension / initial length] x 100 was calculated.
  • Specimens with a thickness of 2 mm or more were obtained according to KSM-3156.
  • a PS plate was attached to both sides of the specimen and a load of 1 kgf / cm 2 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 attached to both sides of the test piece, the weight before and after leaving in the oven was measured and the transfer loss was calculated by the following equation.
  • Transfer loss (%) [(Initial weight of specimen at room temperature-weight of specimen after leaving the oven) / Initial weight of specimen at room temperature] ⁇ 100
  • Heating loss (%) [(initial specimen weight-specimen weight after operation) / initial specimen weight] x 100.
  • the specimen was bent at room temperature for a period of time, and then observed the degree of transition (the degree of bleeding), and the degree was expressed as a numerical value, the closer to 0, the better and the closer to 3, the worse. It is a characteristic.
  • the thermal stability of the specimen against high temperature contact was tested by moving 0.5T specimen prepared by roll-mill operation using Mathis Oven at a speed of 10mm / 25sec at 220 °C.
  • Example 1 82.5 211.7 296.2 1.56 3.10 0
  • Example 2 78.5 215.2 287.1 1.89 3.51 0
  • Example 3 85.0 221.6 292.8 1.31 1.84 0
  • Example 4 85.0 232.2 307.7 1.60 1.95 0
  • Example 5 88.0 228.5 283.1 0.50 0.54
  • Example 6 86.0 221.1 296.7 1.87 0.87 1.0
  • Example 7 86.0 235.1 301.5 1.55 0.35
  • Example 8 84.0 217.0 284.6 1.90 2.14
  • Example 9 85.5 229.7 288.5 1.62 0.39
  • Example 10 82.0 220.4 278.1 1.45 2.02
  • Comparative Example 1 85.5 204.5 256.4 2.28 3.05
  • Comparative Example 2 88.0 207.1 223.1 1.50 1.32
  • Comparative Example 3 85.0 210.8 266.7 2.40 1.66 1.0 Comparative Example 4 87.0 201.3 221.0 2.86 1.56 2.0 Comparative Example 5 92.0 189.5 201.3 0.47 0.47 1.5
  • Comparative Examples 1 to 3 using the cyclohexane 1,4-diester-based material as a single material it can be seen that the elongation characteristics are significantly poor compared to the examples, the tensile strength is also It can be confirmed that it is not superior to the embodiments.
  • Comparative Examples 4 and 5 that do not contain any one of the citrate-based material or cyclohexane 1,4-diester-based material the hardness is slightly higher, which may adversely affect the plasticization efficiency, It can be seen that the tensile strength and elongation characteristics are poorly shown.
  • Examples 11 and 12 were added to the epoxidized soybean oil in Examples 1 and 4, respectively, it can be confirmed that the heating loss and transition loss is lowered, mechanical strength such as tensile strength, elongation It can be confirmed that even physical properties can be improved.
  • Example 11 in Examples 1 and 4 without adding the epoxidation material, it was confirmed that the specimen was burned and burned to a degree close to black, but in Example 11, discoloration was hardly achieved. It can be seen that the naked eye, and accordingly it can be seen that the thermal stability can be improved through the addition of the epoxidized material.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne une composition de plastifiant et une composition de résine, et un procédé pour les préparer, et peut fournir un plastifiant et une composition de résine le comprenant, le plastifiant pouvant améliorer les propriétés physiques, telles que l'efficacité de plastification, la migration, la résistance à la traction, le taux d'allongement, la migration sous contrainte et la stabilité à la lumière, qui sont requises par les consignes d'obtention d'une feuille lorsque le plastifiant est utilisé en tant que plastifiant d'une composition de résine, en améliorant les médiocres propriétés physiques observées en raison des limites structurales.
PCT/KR2017/004118 2016-04-22 2017-04-17 Composition de plastifiant et composition de résine la comprenant WO2017183877A1 (fr)

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US15/580,993 US11186702B2 (en) 2016-04-22 2017-04-17 Plasticizer composition and resin composition including the same
CN201780002231.8A CN107709429B (zh) 2016-04-22 2017-04-17 增塑剂组合物和包含该增塑剂组合物的树脂组合物
EP17786145.7A EP3293226B1 (fr) 2016-04-22 2017-04-17 Composition de plastifiant et composition de résine la comprenant

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CN112041383A (zh) * 2018-06-12 2020-12-04 株式会社Lg化学 增塑剂组合物和包含该增塑剂组合物的树脂组合物
CN112566891A (zh) * 2018-11-28 2021-03-26 株式会社Lg化学 包括加压的对苯二甲酸酯类组合物的制造方法
US11767420B2 (en) * 2017-11-01 2023-09-26 Lg Chem, Ltd. Plasticizer composition and resin composition including the same

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KR20090038514A (ko) * 2007-10-16 2009-04-21 주식회사 엘지화학 고분자 수지용 1,4-시클로헥산디카복실레이트 조성물 및그의 제조 방법
US8283411B2 (en) * 2001-09-25 2012-10-09 Exxonmobil Chemical Patents Inc. Plasticised polyvinyl chloride
WO2013004265A1 (fr) * 2011-07-01 2013-01-10 Tarkett Gdl Revêtement de surface comprenant un plastifiant à base de citrates
CN103965564A (zh) * 2013-01-25 2014-08-06 北京化工大学 增塑聚氯乙烯材料及其制备
WO2015101569A1 (fr) * 2014-01-03 2015-07-09 Tarkett Gdl Compositions améliorées à base de plastisol de poly(chlorure de vinyle) sans phtalate

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JP2009062394A (ja) * 1999-06-18 2009-03-26 Basf Se シクロヘキサン−１，４−ジカルボン酸ジ（２−エチルヘキシル）エステルおよびその製造方法、シクロヘキサン−１，４−ジカルボン酸ジ（２−エチルヘキシル）エステルを含有する可塑剤
US8283411B2 (en) * 2001-09-25 2012-10-09 Exxonmobil Chemical Patents Inc. Plasticised polyvinyl chloride
KR20090038514A (ko) * 2007-10-16 2009-04-21 주식회사 엘지화학 고분자 수지용 1,4-시클로헥산디카복실레이트 조성물 및그의 제조 방법
WO2013004265A1 (fr) * 2011-07-01 2013-01-10 Tarkett Gdl Revêtement de surface comprenant un plastifiant à base de citrates
CN103965564A (zh) * 2013-01-25 2014-08-06 北京化工大学 增塑聚氯乙烯材料及其制备
WO2015101569A1 (fr) * 2014-01-03 2015-07-09 Tarkett Gdl Compositions améliorées à base de plastisol de poly(chlorure de vinyle) sans phtalate

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11767420B2 (en) * 2017-11-01 2023-09-26 Lg Chem, Ltd. Plasticizer composition and resin composition including the same
CN112041383A (zh) * 2018-06-12 2020-12-04 株式会社Lg化学 增塑剂组合物和包含该增塑剂组合物的树脂组合物
US11629116B2 (en) 2018-06-12 2023-04-18 Lg Chem, Ltd. Plasticizer composition and resin composition including the same
CN112566891A (zh) * 2018-11-28 2021-03-26 株式会社Lg化学 包括加压的对苯二甲酸酯类组合物的制造方法
CN112566891B (zh) * 2018-11-28 2023-06-30 株式会社Lg化学 包括加压的对苯二甲酸酯类组合物的制造方法

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