WO2017018741A1 - Composition de plastifiant, composition de résine, et leurs procédés de préparation - Google Patents

Composition de plastifiant, composition de résine, et leurs procédés de préparation Download PDF

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WO2017018741A1
WO2017018741A1 PCT/KR2016/008046 KR2016008046W WO2017018741A1 WO 2017018741 A1 WO2017018741 A1 WO 2017018741A1 KR 2016008046 W KR2016008046 W KR 2016008046W WO 2017018741 A1 WO2017018741 A1 WO 2017018741A1
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Prior art keywords
epoxidized
epoxy
oil
alcohol
alkyl ester
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English (en)
Korean (ko)
Inventor
김현규
이미연
문정주
김주호
정석호
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020160092874A external-priority patent/KR102019938B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to US15/558,448 priority Critical patent/US11560460B2/en
Priority to CN201680017113.XA priority patent/CN107406621B/zh
Priority to EP16830774.2A priority patent/EP3327075B1/fr
Priority to ES16830774T priority patent/ES3041078T3/es
Publication of WO2017018741A1 publication Critical patent/WO2017018741A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates to a plasticizer composition, a resin composition and a method for producing 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 in order to manufacture products such as flooring, wallpaper, sheets, interior and exterior materials of automobiles, films, and wires, appropriate plasticizers should be used in consideration of transferability, heating loss, tensile strength, elongation, and plasticization efficiency.
  • Plasticizers, fillers, stabilizers, viscosity-reducing agents, dispersants, antifoaming agents, foaming agents, etc. may be blended with PVC resins according to the tensile strength, elongation, light resistance, transferability, gelling properties, etc., which are required for various types of industries.
  • the plasticizer efficiency is low, the plasticizer absorption rate is relatively slow, and the light resistance and the transferability are not good.
  • the inventors have identified a plasticizer composition that can improve the poor physical properties caused by structural limitations while continuing to study the plasticizer, and have completed the present invention.
  • an object of the present invention is to provide a plasticizer capable of improving the physical properties such as plasticization efficiency, transferability, gelling property, light resistance, etc. required in the prescription of a sheet, etc., when used as a plasticizer of the resin composition, a method for producing the same, and a resin composition comprising the same I'm trying to provide.
  • isophthalate-based material and an epoxy-based alkyl ester compound represented by Formula 1; wherein the weight ratio of the isophthalate-based material to the epoxy-based alkyl ester compound is 99: 1 to 1:99, and the epoxy-based alkyl ester compound is a single compound or A plasticizer composition is provided that is a mixture containing two or more species.
  • R1 is an alkyl group having 8 to 20 carbon atoms or an alkyl group containing at least one epoxy group
  • R2 is an alkyl group having 4 or 8 carbon atoms.
  • the weight ratio of the isophthalate-based material to the epoxy-based alkyl ester compound may be 95: 5 to 5:95.
  • the isophthalate-based material may be di (2-ethylhexyl) isophthalate (DEHIP), diisononylisophthalate (DINIP), or a mixture thereof.
  • DEHIP di (2-ethylhexyl) isophthalate
  • DIIP diisononylisophthalate
  • the epoxy alkyl ester compounds may be iodine value of less than 4 g I 2/100 g.
  • the epoxidation alkyl ester compound may have an epoxidation index (E.I.) of 1.5 or more.
  • the plasticizer composition may further comprise an epoxidized oil.
  • the epoxidized oil may include 1 to 100 parts by weight based on 100 parts by weight of the mixed weight of the isophthalate-based material and the epoxy-based alkyl ester compound.
  • the epoxidized oil is epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearic acid acid), epoxidized oleic acid, epoxidized tall oil, and epoxidized linoleic acid.
  • an isophthalate-based material Esterifying a epoxidized oil with a primary alkyl alcohol having 4 or 8 carbon atoms to obtain an epoxy-based alkyl ester compound represented by Formula 1 below; And mixing the isophthalate-based material and the epoxy-based alkyl ester compound in a weight ratio of 99: 1 to 1:99, wherein the epoxy-based alkyl ester compound is a single compound or a mixture of two or more thereof.
  • a method for preparing is provided.
  • R1 is an alkyl group containing 8 to 20 carbon atoms or an alkyl group containing at least one epoxy group
  • R2 is an alkyl group having 4 or 8 carbon atoms.
  • the primary alkyl alcohol may be one or more selected from the group consisting of butyl alcohol, isobutyl alcohol, 2-ethylhexyl alcohol and octyl alcohol.
  • the isophthalate-based material may be prepared through a direct esterification reaction of isophthalic acid and at least one alcohol selected from primary alkyl alcohols having 4 to 12 carbon atoms.
  • the primary alkyl alcohol having 4 to 12 carbon atoms may be one or more selected from the group consisting of 2-ethylhexyl alcohol, octyl alcohol and isononyl alcohol.
  • the epoxidized oil is epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearic acid acid), epoxidized oleic acid, epoxidized tall oil, and epoxidized linoleic acid.
  • 100 parts by weight of resin; And 5 to 150 parts by weight of the above-described plasticizer composition is provided.
  • the resin may be one or more 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 can provide excellent physical properties such as migration resistance and volatility, as well as excellent plasticization efficiency and tensile strength and elongation. It can be suitably used for resin products that have excellent absorption rate and require eco-friendly plasticizers using vegetable raw materials.
  • Figure 1 is an image of the results of the thermal stability test for the samples of the Examples and Comparative Examples.
  • IPA isophthalic acid
  • 2-EH 2-ethylhexyl alcohol
  • IPA The molar ratio of 2-EH (1.0): (3.0)
  • 1.54 g (0.31 parts by weight based on 100 parts by weight of TPA) of a titanium catalyst (TIPT, tetra isopropyl titanate) was added as a catalyst, and the temperature was gradually raised to about 170 ° C. I was.
  • the production of water was started at about 170 ° C., and the reaction was carried out for about 4.5 hours while nitrogen gas was continuously added at a reaction temperature of about 220 ° C. and atmospheric pressure. The reaction was terminated when the acid value reached 0.01.
  • 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 had been removed, followed by stirring for some time, and then filtered to obtain 1326.7 g (yield: 99.0%) of di (2-ethylhexyl) isophthalate.
  • the transesterification reaction was carried out using 500 g of epoxidized soybean oil and 490 g of butanol as a reaction raw material, and finally 510 g (yield: 95%) of epoxidized butyl soyate was obtained.
  • IP material eFAAE substance Mixing weight ratio Article 3 Example 2-1 DEHIP eFAEHE 7: 3 ESO (70 parts by weight)
  • Experimental specimens were prepared using the plasticizer compositions of Examples and Comparative Examples above.
  • the specimen is prepared by referring to ASTM D638, 40 parts by weight of plasticizer and 3 parts by weight of plasticizer (BZ-153T) in 100 parts of PVC, blended at 700 rpm at 98 ° C. in a mixer, followed by a roll mill at 160 ° C. for 4 minutes. After working and working at 180 ° C. for 2.5 minutes at low pressure and 2 minutes at high pressure, 1-3 sheets were produced. Using each specimen, the following physical properties were tested.
  • Shore (shore “A) hardness at 25 ° C. was measured using ASTM D2240.
  • Elongation (%) calculated after elongation / initial length x 100.
  • Test specimens having a thickness of 2 mm or more were obtained according to KSM-3156, and a PS plate was attached to both sides of the specimens, and a load of 1 kgf / cm 2 was applied thereto.
  • the test piece 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.
  • % Of transfer 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
  • Absorption rate was evaluated by measuring the time required for the resin and the ester compound to be mixed to stabilize the torque of the mixer by using a Planatary mixer (Brabender, P600) under the conditions of 77 °C, 60rpm.
  • the prepared specimen was heated to 230 ° C. in a Mathis oven to check the burned degree of the specimen.
  • Example 1-1 84.1 237.2 326.6 4.02 3.32 4:35
  • Example 1-2 83.0 233.4 334.5 3.88 3.70 3:52
  • Example 1-3 81.5 229.7 324.9 3.76 4.31 3:27
  • Example 1-4 84.7 240.8 321.5 3.88 3.25 4:40
  • Example 1-5 85.2 245.0 317.1 3.68 3.23 4:55
  • Example 1-6 84.9 244.1 323.7 3.94 3.30 4:53
  • Example 2-1 84.0 256.7 324.0 1.21 1.52 5:08
  • Example 2-2 84.5 250.4 321.6 1.45 1.88 4:50
  • Comparative Examples 1 to 3 in which the epoxy-based alkyl ester compound is not added, are materials that have been conventionally used as general-purpose products, which have excellent basic physical properties but are competitive in price, limited use, or environment. It is a material having a problem such as a problem, and compared with the examples, the specimens of the examples have almost the same mechanical properties (tensile strength and elongation) of these, and in terms of absorption rate or plasticization efficiency Significant improvements have been made and improvements have been found in the case of transition losses and heating losses.
  • FIGS. 1 and 2 it can be seen that the thermal stability can be improved in the case of the specimens using the examples compared to the plasticizers of the comparative examples.
  • the specimens It can be confirmed that all burned and burned black, and in Examples 1-1 to 1-3 and Examples 1-5, 1-6, and 2-2, the degree of combustion is considerably smaller than that of the comparative example. have.
  • 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 mixed with octyl as an abbreviation of 2-ethylhexyl, and in some cases, may mean octyl which is a linear alkyl group. However, it can be interpreted to mean 2-ethylhexyl, which is a branched alkyl group.
  • the present invention isophthalate-based material; And an epoxy-based alkyl ester compound, wherein the weight ratio of the isophthalate-based material to the epoxy-based alkyl ester compound is 99: 1 to 1:99, and the epoxy-based alkyl ester compound includes a single compound or two or more kinds thereof.
  • a plasticizer composition is provided that is a mixture.
  • the isophthalate-based material has a content selected from the range of 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. Can be applied.
  • the isophthalate-based material may be di (2-ethylhexyl) isophthalate (DEHIP), diisononylisophthalate (DINIP) or a mixture thereof, preferably di (2-ethylhexyl) isophthalate. .
  • 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 plasticizer composition includes an isophthalate-based material and includes an epoxy-based alkyl ester compound.
  • the epoxy alkyl ester compound may be represented by the following general formula (1), the iodine value may be less than (Iodine Value, IV) a 4 g I 2/100 g.
  • R1 is an alkyl group having 8 to 20 carbon atoms or an alkyl group having at least one epoxy group
  • R2 is an alkyl group having 4 or 8 carbon atoms.
  • the epoxy-based alkyl ester compound may have an oxirane value (Oxirane Value, O.V.) of 6.0% or more, 6.3% or more, and preferably 6.5% or more.
  • O.V. oxirane Value
  • the oxirane can be changed according to the number of epoxy groups contained in the substituent represented by R1 in the formula (1), can be measured by a titration method, the method of ASTM D1562-04 using a sample and an acid solution It may be measured by.
  • the epoxy alkyl ester compound but the iodine can be less than 4 g I 2/100 g, can be not more than preferably 3.8 I 2/100 g.
  • the iodine number represents the content of the double bond present in the molecule, and may be derived from a value measured by a titration method through iodization of the double bond.
  • the epoxy-based alkyl ester compound may be an important element when the measured iodine and oxirane are applied to the plasticizer composition.
  • the iodine value is 4 g I 2/100 g, if more than this out, the compatibility with the resin is significantly reduced, and can not be used in the plasticizer purpose, incidentally it is iodine value is 4 g I 2
  • the mechanical and physical properties such as tensile strength, elongation and absorption rate may also be improved.
  • oxiraga can also have similar technical significance and similar effects as iodine number.
  • the iodine number may represent the content of the double bond, and the content of the double bond may be the content of the double bond remaining after the epoxidation reaction such as epoxidation of vegetable oil or epoxidation of fatty acid alkyl ester is performed. That is, the oxirags and iodines may be indicative of how much epoxidation has been performed, and thus may be partially related to each other, and in theory, may be inversely related to each other.
  • the double bonds of vegetable oils or fatty acid alkyl esters may vary from material to material, so the two parameters do not form an exact inverse relationship or trade off relationship, and a higher iodine value between the two materials.
  • the material may be higher in oxirane at the same time. Therefore, it may be preferable to apply to the plasticizer composition that the iodine number and the oxirane value of an epoxy-type alkyl ester compound satisfy the above-mentioned range.
  • the epoxidation index (E.I.) of the epoxy-based alkyl ester compound may be 1.5 or more.
  • the 'epoxidation index' is a ratio of oxirane to iodine number of the epoxy-based alkyl ester compound, and may be a ratio of remaining double bonds that do not react with the double bonds epoxidized by the epoxidation reaction.
  • the hardness may increase and the plasticization efficiency may be greatly deteriorated. And heat loss characteristics may be greatly deteriorated.
  • the epoxidation index may be 1.5 or more as the ratio of oxiraga to iodine number (oxiraga / iodine number). That is, when the oxirane value of the epoxy-based alkyl ester divided by iodine number is 1.5 or more, a more optimized plasticizer composition can be obtained, and in particular, the compatibility with the resin may be improved.
  • the epoxy-based alkyl ester compound may be an epoxidized Fatty Acid Alkyl Ester (eFAAE), specifically, may be represented by Formula 1, 'alkyl' of the epoxy-based alkyl ester compound has 4 carbon atoms Or eight.
  • eFAAE epoxidized Fatty Acid Alkyl Ester
  • R 2 may have 4 to 8 carbon atoms, and preferably, a butyl group or a 2-ethylhexyl group.
  • the epoxy-based alkyl ester compound represented by the formula (1) may include two or more kinds to form a mixed composition, when two or more kinds are included is a mixture of 4 and 8 carbon atoms It may be preferable, when the carbon number of R2 of Formula 1 is 4 or 8, the absorption characteristics are excellent to reduce the gelling phenomenon, the processability can be improved, and the mechanical properties such as basic tensile strength and elongation is also excellent In particular, excellent performance can be exhibited in transitional performance and heat loss characteristics.
  • the isophthalate-based material and the epoxy-based alkyl ester compound in the plasticizer composition may be included in a weight ratio of 99: 1 to 1:99, 99: 1 to 20:80, or 99: 1 to 40:60 days It may be, preferably contained in a ratio of 95: 5 to 50:50, or 90:10 to 60:40.
  • the tensile strength and elongation may be excellent, and an improved effect may be observed in the transition and heating loss, and the absorption rate It can be controlled so that the workability can be improved together.
  • an isophthalate-based material Esterifying a epoxidized oil with a primary alkyl alcohol having 4 or 8 carbon atoms to obtain an epoxy-based alkyl ester compound represented by Formula 1 below; And mixing the isophthalate-based material and the epoxy-based alkyl ester compound in a weight ratio of 99: 1 to 1:99, wherein the epoxy-based alkyl ester compound is a single compound or a mixture of two or more thereof.
  • a method for preparing is provided.
  • isophthalate-based material and the epoxy-based alkyl ester compound may be carried out respectively, and the materials may be prepared through direct esterification reaction and / or trans esterification reaction.
  • the isophthalate-based material may be prepared through a direct esterification reaction in which isophthalic acid and an alcohol selected from primary alkyl alcohols having 8 to 10 carbon atoms react.
  • the epoxy-based alkyl ester compound may be prepared by the trans esterification reaction of the epoxidized oil and the primary alkyl alcohol having 4 or 8 carbon atoms.
  • the primary alkyl alcohol having 8 to 10 carbon atoms may be selected from the group consisting of 2-ethylhexyl alcohol, octyl alcohol and isononyl alcohol.
  • the primary alkyl alcohol having 4 or 8 carbon atoms used as a raw material for producing the epoxy-based alkyl ester compound may be one or more selected from the group consisting of butyl alcohol, isobutyl alcohol, 2-ethylhexyl alcohol and octyl alcohol. have.
  • the alkyl group of the alcohol may correspond to R2 of Formula 1 in the epoxy-based alkyl ester compound represented by Formula 1 after the reaction is completed.
  • the epoxidized oil for example, epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized palm oil, epoxidized palm oil Stearic acid (epoxidized stearic acid), epoxidized oleic acid, epoxidized tall oil, epoxidized linoleic acid, or mixtures thereof.
  • the compound may be introduced into a certain amount of epoxy group.
  • the epoxidized oil may be represented by the following Chemical Formula 2, and may include three ester groups in one molecule, and may contain a certain amount of epoxy groups.
  • the epoxidized oil represented by Formula 2 corresponds to one example.
  • the epoxidized oil can be a iodine value is 4 g I 2/100 g is less than can there, iodine value and substantially the same level of iodine transesterification reaction varied potential is lowered product of epoxy alkyl esters for compound The characteristics thereof are the same as those of the iodine number of the above-mentioned epoxy-based alkyl ester compound.
  • trans-esterification reaction refers to a reaction in which an alcohol reacts with an ester as shown in Scheme 1, where R " of the ester is interchanged with R ′ of the alcohol as shown in Scheme 1 below:
  • the alkoxide of the alcohol is substituted with an ester (RCOOR ′′) group present in the ester compound to generate R ′′ alcohol.
  • RCOOR ′′ an ester
  • the trans esterification reaction has an advantage that the reaction rate is faster than the acid and alcohol esterification reaction without causing a waste water problem.
  • the trans esterification reaction for preparing an epoxy-based alkyl ester compound may be performed, for example, under the following conditions.
  • the trans esterification reaction is 10 minutes to 10 hours, preferably 30 minutes to 8 hours, more preferably 1 to 4 under a reaction temperature of 40 to 230, preferably 50 to 200, more preferably 70 to 200. May be performed in time. It is possible to effectively obtain the desired epoxy-based alkyl ester compound within the above 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.
  • polyhydric alcohol and the reaction by-products and the unreacted alcohol produced after the trans-esterification reaction may further comprise the step of separating, washing and distilling the reaction by-products.
  • the purification process may be performed after the trans esterification reaction for a certain period of time to cool and settle at a temperature of 80 to 100 °C, in which case layer separation occurs, the upper layer includes an epoxy-based alkyl ester and alcohol
  • the lower layer may contain glycerin and other byproducts.
  • neutralization and water washing can be induced by adding a catalyst neutralization aqueous solution to neutralize the catalyst.
  • the neutralization and washing process may be performed after first separating the lower layer containing mainly by-products, and may be discharged by dissolving the by-products of the lower layer in water during the neutralization and washing process, and then unreacted after the repeated washing process Alcohol and water can be recovered and removed.
  • 2-ethylhexyl alcohol having 8 carbon atoms when 2-ethylhexyl alcohol having 8 carbon atoms is used, 2-ethylhexyl alcohol has low solubility in water, and there is no problem of waste water generation. Therefore, in this case, the alcohol is removed after neutralization and washing with water. In the case of the removal, the neutralization and washing with water after removing the byproduct layer of the lower layer may be advantageous without proceeding with a fatal problem.
  • the physical properties of the epoxy-based alkyl ester compound to be produced may vary depending on the type and content of the catalyst to be used, the reaction time or 1 to react with the epoxidized oil Depending on the content of the primary alkyl alcohol, the physical properties, yield or quality of the product may also be modified.
  • NaOMe is preferably used as a catalyst in the process of preparing the epoxy-based alkyl ester compound, and the color of the prepared epoxy-based alkyl ester compound does not meet the standard compared to a catalyst such as sodium hydroxide or potassium hydroxide.
  • a catalyst such as sodium hydroxide or potassium hydroxide.
  • the epoxidation index, oxirane content, etc. of an epoxy-type alkyl ester compound may not produce the target numerical value.
  • the catalyst may be the most effective in terms of reaction rate of 0.1 to 2.0% by weight, preferably 0.1 to 1.0% by weight relative to the total weight of the epoxidized oil as a reaction raw material, the content of the catalyst when out of this range Failure to control may not meet the quality standards of epoxy-based alkyl ester compounds such as epoxidation indexes.
  • the addition amount of the epoxidized oil and the primary alkyl alcohol may also be an important factor.
  • the primary alkyl alcohol it is preferable to add 30 to 100 parts by weight relative to the epoxidized oil, and 30 parts by weight.
  • impurities such as residual epoxidized oil or dimerized material of epoxidized oil may remain excessively. There are many concerns about energy and process efficiency issues during the process.
  • mixing may be performed.
  • the mixing ratio may be suitably selected within the range of 99: 1 to 1:99, and may be mixed by applying the above-described mixing weight ratio.
  • plasticizer composition according to the present invention may further include an epoxidized oil in addition to the isophthalate-based material and the epoxy-based alkyl ester compound.
  • the heat resistance may not be excellent, and the heat resistance may be compensated by further including the epoxidized oil.
  • the epoxidized oil is, for example, epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized palm oil, epoxidized stearic acid (epoxidized stearic acid), epoxidized oleic acid, epoxidized tall oil, epoxidized linoleic acid, or mixtures thereof.
  • epoxidized soybean oil (ESO), or epoxidized linseed oil (ELO) may be applied, but is not limited thereto.
  • the epoxidized oil may include 1 to 100 parts by weight, preferably 10 to 100 parts by weight, preferably 20 to 100 parts by weight of the mixed weight of the isophthalate-based material and the epoxy-based alkyl ester compound. To 100 parts by weight may be included. When included within the above range, a plasticizer composition having suitably superior physical properties between mechanical properties and heat resistance properties can be obtained.
  • the overall freezing point of the plasticizer composition can be further lowered, and thus the freezing point is lower than that of the epoxy-based plasticizer composition.
  • a composition can be provided.
  • 100 parts by weight of the resin 100 parts by weight of the resin; And 5 to 150 parts by weight of the above-described plasticizer composition.
  • the resin may be at least one resin selected from ethylene vinyl acetate, polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomer, wherein the plasticizer composition is based on 100 parts by weight of the resin, 5 It may be included in the range of from 150 to 150 parts by weight, 40 to 100 parts by weight, or 40 to 50 parts by weight to provide a resin composition effective for all of the compound formulation, sheet formulation and plastisol formulation.
  • the resin composition includes the plasticizer composition as described above, and can be applied to various applications such as flooring, wallpaper, automobile interior, sheet, film, hose, or electric wire, and has tensile strength and elongation, plasticization efficiency and heating loss.
  • the same basic mechanical properties may also exhibit physical properties equivalent to those of conventional plasticizers.
  • 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 as 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.
  • Stabilizers that can be used can be used, for example, calcium-zinc-based (Ca-Zn-based) stabilizers, such as calcium-zinc complex stearic acid salt, but is not particularly limited thereto.
  • Ca-Zn-based stabilizers such as calcium-zinc complex stearic acid salt

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Abstract

La présente invention concerne une composition de plastifiant, un procédé pour la préparer, et une composition de résine comprenant la composition de plastifiant, la composition de plastifiant comprenant : un matériau à base d'isophtalate; et un composé ester d'alkyle à base d'époxy représenté par la formule chimique 1 ci-dessous, le rapport en poids du matériau à base d'isophtalate au composé ester d'alkyle à base d'époxy étant de 99:1 à 1:99, et le composé ester d'alkyle à base d'époxy comprenant un composé unique ou un mélange comprenant au moins deux types de composés. (Dans la formule chimique 1, R1 est un groupe alkyle ayant de huit à 20 atomes de carbone ou un groupe alkyle contenant au moins un groupe époxy, et R2 est un groupe alkyle ayant quatre ou huit atomes de carbone.) La présente invention peut fournir : un agent plastifiant permettant d'améliorer les propriétés physiques requises lorsqu'il est utilisé comme plastifiant pour une composition de résine, telles que la résistance à la traction, la résistance à la migration, et la perte au chauffage, en améliorant les moins bonnes propriétés physiques provoquées par les restrictions structurelles; et une composition de résine comprenant l'agent plastifiant.
PCT/KR2016/008046 2015-07-24 2016-07-22 Composition de plastifiant, composition de résine, et leurs procédés de préparation Ceased WO2017018741A1 (fr)

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US15/558,448 US11560460B2 (en) 2015-07-24 2016-07-22 Plasticizer composition, resin composition and method of preparing the same
CN201680017113.XA CN107406621B (zh) 2015-07-24 2016-07-22 增塑剂组合物，树脂组合物及其制备方法
EP16830774.2A EP3327075B1 (fr) 2015-07-24 2016-07-22 Composition de plastifiant, composition de résine, et leurs procédés de préparation
ES16830774T ES3041078T3 (en) 2015-07-24 2016-07-22 Plasticizer composition, resin composition, and preparation methods therefor

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CN113121877A (zh) * 2019-12-31 2021-07-16 中国石油化工股份有限公司 一种增塑剂及其制备方法
US11702529B2 (en) * 2017-10-13 2023-07-18 Lg Chem, Ltd. Plasticizer composition and resin composition including the same

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US20120085568A1 (en) * 2008-02-15 2012-04-12 Union Carbide Chemicals & Plastics Technology Llc Replacement plasticizer system for phthalate-plasticized formulations
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US20080318042A1 (en) * 2001-01-31 2008-12-25 Kusek Walter W Method of making reinforced pvc plastisol resin and products prepared therewith
US20120085568A1 (en) * 2008-02-15 2012-04-12 Union Carbide Chemicals & Plastics Technology Llc Replacement plasticizer system for phthalate-plasticized formulations
US20150112008A1 (en) * 2010-12-14 2015-04-23 Exxonmobil Chemical Patents Inc. Glycol Ether-Based Cyclohexanoate Ester Plasticizers and Blends Therefrom
KR20140116371A (ko) * 2011-10-14 2014-10-02 갈라타 케미컬스, 엘엘씨 재생가능한 원료로부터 유도된 가소제

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US11702529B2 (en) * 2017-10-13 2023-07-18 Lg Chem, Ltd. Plasticizer composition and resin composition including the same
CN113121877A (zh) * 2019-12-31 2021-07-16 中国石油化工股份有限公司 一种增塑剂及其制备方法
CN113121877B (zh) * 2019-12-31 2022-08-12 中国石油化工股份有限公司 一种增塑剂及其制备方法

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