WO2015119442A1 - 에스테르계 화합물, 이를 포함하는 가소제 조성물, 이의 제조방법, 및 이를 포함하는 수지 조성물 - Google Patents
에스테르계 화합물, 이를 포함하는 가소제 조성물, 이의 제조방법, 및 이를 포함하는 수지 조성물 Download PDFInfo
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- WO2015119442A1 WO2015119442A1 PCT/KR2015/001202 KR2015001202W WO2015119442A1 WO 2015119442 A1 WO2015119442 A1 WO 2015119442A1 KR 2015001202 W KR2015001202 W KR 2015001202W WO 2015119442 A1 WO2015119442 A1 WO 2015119442A1
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- plasticizer composition
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- 0 *OC(c1cccc(C(O*)=O)c1)=O Chemical compound *OC(c1cccc(C(O*)=O)c1)=O 0.000 description 3
- OEAGXMLUZJZNGX-UHFFFAOYSA-N CC(C)CCCCCCCOC(c1cc(C(OCc2ccccc2)=O)ccc1)=O Chemical compound CC(C)CCCCCCCOC(c1cc(C(OCc2ccccc2)=O)ccc1)=O OEAGXMLUZJZNGX-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/80—Phthalic acid 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
Definitions
- the present invention relates to an isophthalate ester compound, and a plasticizer composition comprising the same, a method for preparing the plasticizer composition, and a resin composition comprising the plasticizer composition.
- Polymer resins have been used in various fields, such as living and home appliances, clothing, automobiles, construction materials or packaging materials according to their characteristics.
- plastic resins such as polyethylene (PE), polypropylene (PP), polystyrene (PS), polyurethane (PU), and polyvinyl chloride (PVC) are widely used.
- PVC resin is hard, soft properties and various molding is possible, and excellent price competitiveness has been applied to a variety of applications from household goods to industrial materials with a universal utility.
- plasticizers are added to implement various physical properties.
- the plasticizer serves to impart flexibility of the PVC resin to improve processability and applicability.
- the role of plasticizers has been diversified, and not only flexibility but also the characteristics required by the application fields such as volatility, migration resistance, aging resistance, cold resistance, oil resistance, water resistance, heat resistance, etc.
- Ester compounds currently used as plasticizers include di- (2-ethylhexyl) phthalate (DEHP), diisononylphthalate (DINP), di-2-propylheptyl phthalate (DPHP), or diisodecyl phthalate (DIDP).
- DEHP di- (2-ethylhexyl) phthalate
- DINP diisononylphthalate
- DPHP di-2-propylheptyl phthalate
- DIDP diisodecyl phthalate
- ester compound and its manufacturing method which are environmentally friendly and can be sufficiently improved in all physical properties such as workability of resin, absorption rate with resin, hardness, tensile strength, elongation, as well as volatile loss, transition loss degree and thermal stability. Development is needed.
- the first technical problem to be solved of the present invention is a novel compound for plasticizers, when used in a resin composition, it is environmentally friendly and has a absorption rate and a short melting time for the resin to improve the processability of the resin, as well as tensile strength and elongation, It is to provide a novel ester compound for plasticizers that can provide excellent physical properties such as migration resistance and volatility.
- the second technical problem to be solved by the present invention is to provide a plasticizer composition comprising the ester compound.
- the third technical problem to be solved by the present invention is to provide a method for producing the plasticizer composition.
- the fourth technical problem to be solved by the present invention is to provide a resin composition comprising the ester compound.
- the present invention provides an ester compound of formula 1 according to one embodiment:
- R 1 and R 2 are different from each other, and each independently, a group consisting of C 3 -C 10 alkyl including unbranched or one or more branched chains, and substituted or unsubstituted alkyl aryl, substituted or unsubstituted aryl Any one selected from
- the present invention provides a plasticizer composition comprising the ester compound of Formula 1.
- the present invention comprises the step of esterifying the isophthalic acid of the formula (2) in the presence of a catalyst with at least one alcohol of the formula (3) or a mixture of the alcohol and one or more isomers thereof, the preparation of the plasticizer composition Provide the method:
- R ′ is any one selected from the group consisting of unbranched or C 3 -C 10 alkyl comprising one or more branched chains, and substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl.
- the present invention provides a polyvinyl chloride resin composition comprising the plasticizer composition.
- the present invention provides a resin composition comprising the plasticizer composition.
- the ester compound according to an embodiment of the present invention is a novel isophthalate-based ester compound for plasticizers, and when used in a resin composition, it has excellent plasticization efficiency and excellent physical properties such as tensile strength and elongation as well as resistance to migration and volatility. Can be provided.
- hybrid type refers to a structure where the alkyl group substituted at the symmetric position of the phenyl group is different, unless otherwise specified.
- the term "immiscible type" used in the present invention refers to a structure in which an alkyl group substituted at a symmetric position of a phenyl group is the same unless otherwise specified.
- R 1 and R 2 are different from each other and independently from each other a group of C 3 -C 10 alkyl which includes an unbranched or one or more branched chains, and substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl It may be any one selected.
- the branched chain may be C 1 -C 6 alkyl, C 2 -C 6 alkenyl or C 2 -C 6 alkynyl.
- Ester compound of Formula 1 preferably, R 1 and R 2 are different from each other and each independently, an unbranched or at least one C 1 -C 4 alkyl branched chain It may be an ester compound comprising any one selected from the group consisting of alkyl of C 4 -C 9 , and phenyl or benzyl including unbranched or at least one C 1 -C 4 alkyl branched chain.
- the ester compound of Formula 1 may be more preferably at least one ester compound selected from the group consisting of:
- the hybrid type ester compound according to an embodiment of the present invention is a novel compound for plasticizer, and has excellent purity, low residual alcohol and water content, and is environmentally friendly when used in a resin composition, and has a short absorption rate to the resin. It can have a short melting time to improve the processability of the resin and provide excellent physical properties.
- An ester compound according to an embodiment of the present invention is an isophthalate ester compound having an ester (-COO-) group at 1,3, ie, a meta-position in a benzene ring, and an ester (-COO-) group. It is more environmentally friendly than phthalate ester compounds having ester groups in other positions, such as the Ortho-position (position 1,2 and benzene) or the Para-position (position 1 and 4). In addition to tensile strength and elongation, it can provide excellent physical properties such as migration resistance and volatility.
- the ortho-positioned benzenedicarboxylic acid used as a raw material to prepare a phthalate ester compound having an ester group in the ortho-position is a phthalate issue, specifically a problem of environmental pollution and harmful to humans. There is a limit that cannot be free from problems.
- the phthalate-based ester compound having an ester group in the para-position has a relatively poor compatibility and bonding stability with the resin due to the linear structure, which may act as an adverse effect on the workability and workability of the product.
- the ester compound according to an embodiment of the present invention secures an equivalent level of tensile strength and elongation as compared to a phthalate compound mainly used as a plasticizer.
- the transition loss (%) and heating loss (%) are significantly reduced by more than 1/2 compared to DIDP, which may mean a reduction in the loss of ester compound (plasticizer) present inside the specimen.
- the overall physical properties can be equivalent to or more than the conventional phthalate system.
- the present invention may provide a plasticizer composition further comprising at least one compound selected from the group consisting of the following formulas.
- the plasticizer compound of the non-hybrid type such as Chemical Formulas 1-16 to 21, may be included in the final product during the esterification reaction process of the hybrid type compound.
- the plasticizer composition is a hybrid type isophthalate compound, at least one selected from the group consisting of compounds of Formulas 1-1 to 1-15, non-hybrid type isophthalate compounds, and compounds of Formulas 1-16 to 21. It may be a configuration including a.
- the total content of the hybrid type isophthalate compound and the non-hybrid type isophthalate compound of the plasticizer composition is 5 to 80% by weight of the hybrid type isophthalate compound and the total content of the non-hybrid type isophthalate compounds based on the total weight of the plasticizer composition. 20 to 95% by weight, preferably 10 to 60% by weight of the hybrid type isophthalate compound and 40 to 90% by weight of the total content of the hybrid type isophthalate compounds.
- the content of the hybrid type isophthalate compound is less than 5% by weight of the total content of the plasticizer composition, physical properties such as hardness, tensile strength, elongation and viscosity stability may be insufficient, and the content of the hybrid type isophthalate compound When more than 80% by weight of the total content of the plasticizer composition, it is possible to reduce the migration resistance, volatile loss and workability.
- a plasticizer composition comprising a compound of the formula.
- plasticizer composition may include compounds of the following formula.
- the ester compound or the plasticizer composition according to one embodiment of the present invention is a step of esterifying the isophthalic acid of Formula 2 in the presence of a catalyst with at least one alcohol of Formula 3 or a mixture of the alcohol and at least one isomer thereof: May include:
- R ′ may be any one selected from the group consisting of unbranched or C 3 -C 10 alkyl comprising one or more branched chains, and substituted or unsubstituted alkyl aryl, substituted or unsubstituted aryl.
- the branched chain which R ' may include may be C 1 -C 6 alkyl, C 2 -C 6 alkenyl, or C 2 -C 6 alkynyl.
- the alcohol of Formula 2 is preferably C 4 -C 9 alkyl, and unbranched, wherein R ′ is unbranched or comprises at least one C 1 -C 4 alkyl branched chain. Or an alcohol including any one selected from the group consisting of phenyl or benzyl including one or more C 1 -C 4 alkyl branched chains.
- the esterification reaction may be an ester bond by dehydration condensation reaction of a carboxyl group (-COOH) substituted with a phenyl group in isophthalic acid of Formula 2 with at least one alcohol, preferably 1 to 3 alcohols.
- the esterification reaction is preferably carried out for 1 to 15 hours in the temperature range of 80 °C to 270 °C.
- the reaction time may be calculated from the point of time when the reaction temperature is reached after the reaction temperature is reached.
- the isophthalic acid of Formula 2 and the alcohol of Formula 3 may be used in an amount of 1: 0.01-5 molar ratio.
- it when using two different alcohols of the formula (3), it can be used in an amount of 1: 0.1 to 4.9: 0.1 to 4.9 molar ratio.
- the isophthalic acid of Formula 2 is 2-ethylhexanol (2-EH) and 2-propylheptanol of Formula 6 (2-PH ) (Or a mixture of 2-propylheptanol and one or more alcohol isomers thereof) may be used in an amount of 1: 0.1 to 4.9: 0.1 to 4.9.
- the alcohol of Formula 3 may be prepared and used in a conventional manner, or may be purchased and used commercially.
- the alcohol of Formula 3 may be mixed with one or more alcohol isomers thereof, and the alcohol of Formula 3 may be, for example, 50 parts by weight to 100 parts by weight: 0 parts by weight. It may be included in an amount of from 50 to 30 parts by weight, preferably 70 to 100 parts by weight: 0 to 30 parts by weight.
- the esterification temperature is increased to a maximum of 270 ° C after the input of the raw materials and the catalyst, and maintained for 1 to 15 hours, and the unreacted alcohol evaporated during the reaction can be continuously recycled by condensation using a condenser and then reinserted. have.
- nitrogen gas which is an inert gas, may be directly added to the reaction liquid until the reaction is completed. In this way, a reaction product having a conversion rate of 99% or more can be effectively obtained at an acid value of 0.01 after the reaction.
- the method may further include removing unreacted raw materials by maintaining the vacuum for about 0.5 to 6 hours.
- the catalyst added to the reaction may be an organometallic catalyst such as Sn-based or Ti-based, an acid catalyst such as sulfonic acid-based or sulfuric acid-based, or a mixed catalyst thereof.
- the organometallic catalyst is selected from, for example, titanium tetraalkoxide [Ti (OR) 4 ] such as tetraisobutyl titanate and tetraisopropyl titanate, tin dialkoxide [Sn (OR) 2 ] such as dibutyl tin oxide, and the like. It may include one or more.
- the acid catalyst may include one or more selected from, for example, paratoluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, sulfuric acid, and the like.
- the reaction catalyst may be in the range of 0.01 to 5.0 parts by weight based on 100 parts by weight of isophthalic acid as a reaction raw material. If the catalyst is used in less than the above range the reaction efficiency may be lowered, the product may discolor when exceeded.
- the present invention can provide a plasticizer composition comprising the ester compound of Formula 1, and a polyvinyl chloride (PVC) resin composition comprising a polyvinyl chloride resin.
- PVC polyvinyl chloride
- the ester compound is added as a plasticizer.
- the plasticizer composition may be included in an amount of 10 parts by weight to 150 parts by weight, preferably 20 parts by weight to 100 parts by weight, based on 100 parts by weight of polyvinyl chloride.
- the weight part range within the weight part range, as well as workability with a resin such as short absorption rate and melting time, it is possible to improve the hardness (hardness), tensile strength (tensile strength), elongation rate (elongation rate) In particular, it is possible to minimize migration loss and sheet volatiles loss rate.
- the present invention can provide a resin composition comprising the plasticizer composition, and a resin, in addition to the PVC resin composition, the resin may be a resin known in the art.
- the resin may be a resin known in the art.
- synthetic rubbers such as ethylene vinyl acetate, polyethylene, polypropylene, polystyrene, polyurethane, thermoplastic elastomer, polylactic acid, SBR, NBR, BR, but is not limited thereto.
- 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.
- Stabilizers that may be used in accordance with one embodiment of the present invention may be used, for example, calcium-zinc-based (Ca-Zn-based) stabilizers such as calcium stearate salts, but is not particularly limited thereto.
- Ca-Zn-based stabilizers such as calcium stearate salts
- the resin composition is dioctyl terephthalate (DOTP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), dipropylheptyl phthalate (DPHP), triox Tyl trimellitate (TOTM), di- (2-ethylhexyl) terephthalate (DEHTP), dioctyl adipate (DOA), butyloctyl terephthalate (BOTP), dioctylsuccinate (DOSx), neopentyl glycol type
- It may further comprise a plasticizer composition selected from at least one of trimethylolpropane-based, diethylene glycol-based, triethylene glycol-based products.
- the plasticizer composition may be in the range of 0 to 150 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the resin.
- the resin composition has an absorption rate of 3 minutes to 10 minutes, 3 minutes to 8 minutes, more preferably 4 minutes to 7 minutes, and has excellent workability and workability within this range.
- the absorption rate may be evaluated by measuring the time until the resin and the ester compound is mixed with each other and the torque of the mixer is stabilized using a mixer (product name: Brabender, P600) under a condition of 77 ° C. and 60 rpm.
- the ester compound according to an embodiment of the present invention has an absorption rate and a short melting time for the resin to improve the processability of the resin, and the sheet formulation of wires, automobile interior materials, films, sheets, tubes, wallpaper, toys, flooring materials, and the like. It can provide excellent physical properties when formulating compounds.
- Obtained isophthalic plasticizer composition comprising 17% by weight of ethylhexyl) isophthalate (DEHIP) and 34% by weight of di- (2-propylheptyl) isophthalate (DPIP) of formula 1-21 .
- LG Chem's LGflex DPHP (trade name) was used.
- diisodecyl phthalate (DIDP; LGfex DIDP, LG Chemical) was used.
- dioundesyl isophthalate was manufactured by the manufacturing method similar to Example 1.
- EHPIP 2-ethylhexyl 2-propylheptyl isophthalate
- PVC polyvinyl chloride resin
- isophthalic plasticizer composition comprising 17 weight% of di- (2-ethylhexyl) isophthalate (DEHIP), and 36 weight% of di- (2-propylheptyl) isophthalate (DPIP) 5 parts by weight of RUP stabilizer (RUP 144, Adeka Korea), 40 parts by weight of calcium carbonate (Omya 1T, BSH), 0.3 phr of stearic acid (ST / A) as a stabilizer (hand mixing).
- the roll mill was used for 4 minutes at 160 ° C, and the press was used at 180 ° C for 2.5 minutes (low pressure) and 2 minutes (high pressure) to produce sheets with a thickness of 1 to 3 mm. It was.
- a sheet was manufactured in the same manner as in Example 14, except that the compositions of Examples 2 to 13 were used as the plasticizer.
- a sheet was prepared in the same manner as in Example 14, except that DPHP of Comparative Example 1 was used as a plasticizer.
- a sheet was produced in the same manner as in Example 14, except that diisodecylphthalate (DIDP; LGfex DIDP, LG Chemical), which was Comparative Example 2, was used as a plasticizer.
- DIDP diisodecylphthalate
- LGfex DIDP LG Chemical
- a sheet was prepared in the same manner as in Example 14 except that Dioundesylisophthalate of Comparative Example 3 was used as the plasticizer.
- Example 14 Same as Example 14, except that 50% by weight of undecyl-isotridecylisophthalate, 24% by weight of diundecylisophthalate, and 26% by weight of diisotridecylisophthalate as a plasticizer were used The sheet was produced by the method.
- Elongation (%) calculated after elongation / initial length ⁇ 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
- Example 14 90.7 183.4 227.8 0.11 2.09
- Example 15 87.6 181.5 285.1 0.48 2.35
- Example 16 86.7 179.5 282.6 0.56 3.20
- Example 17 88.5 182.6 286.9 0.39 1.02
- Example 18 87.2 175.6 259.4 0.55 0.88
- Example 19 93.5 195.6 288.6 0.08 0.85
- Example 20 91.4 194.7 268.9 0.10 0.90
- Example 21 93.3 207.9 291.5 0.03 0.35
- Example 22 90.3 201.7 268.5 0.15 0.55
- Example 23 92.5 208.5 284.6 0.05 0.30
- Example 24 91.4 201.3 251.3 0.14 0.56
- Example 25 91.5 204.6 260.5 0.15 0.48
- Example 26 87.6 182.4 232.5 0.14 2.53
- Comparative Example 6 89.5 185.6 231.7 0.89 1.89
- Comparative Example 7 90.0 183.5 241.2 0.18 1.07
- Comparative Example 8 92.2 210.3 221.5 0.04 0.35
- Examples 14 to 26 using the plasticizer composition (Examples 1 to 13) according to one embodiment of the present invention as a plasticizer, it could be confirmed that it can be used for a suitable use for the resin physical properties.
- the isophthalate series using mainly alcohols with small molecular weight was able to confirm relatively superior hardness and elongation characteristics compared to the comparative examples, and when using high molecular weight alcohols, the transition loss and heating loss were equal to or higher than those of the comparative examples. Showed physical properties. If the new compound containing such a mixed alcohol is properly utilized according to the intended use, it is expected that excellent workability and physical effects that meet the required properties can be expected.
- PIA isophthalic acid
- 2-EH 2-ethyl hexanol
- distillation was performed under reduced pressure for 0.5 to 2 hours to remove unreacted raw materials.
- steam extraction was performed under reduced pressure using steam for 0.5 to 3 hours, the reaction solution temperature was cooled to about 90 ° C, and neutralization treatment was performed using an alkali solution. .
- washing with water may be performed, and then the reaction solution is dehydrated to remove moisture.
- PIA isophthalic acid
- 2-EH 2-ethyl hexanol
- the generation of generated water began at about 170 ° C., and the reaction temperature was about 220 ° C., and nitrogen gas was continuously added at about 3 hours for about 3 hours.
- the esterification reaction was carried out and the reaction was terminated when the acid value reached 0.3.
- Example 27 After completion of the reaction, post-treatment methods such as removal of unreacted raw materials, neutralization, water washing, and dehydration were performed in the same manner as in Example 27. Finally 41 wt% of 2-ethylhexyl 2-propylheptyl isophthalate (EHPIP) of Formula 1, 46 wt% of di- (2-ethylhexyl) isophthalate (DEHIP) of Formula 2, and di- ( An isophthalic plasticizer composition comprising 13% by weight of 2-propylheptyl) isophthalate (DPIP) was obtained.
- EHPIP 2-ethylhexyl 2-propylheptyl isophthalate
- DEHIP di- (2-ethylhexyl) isophthalate
- DPIP 2-propylheptyl isophthalate
- the generation of generated water began at about 170 ° C., and the reaction temperature was about 220 ° C., and nitrogen gas was continuously added at about 3 hours for about 3 hours.
- the esterification reaction was carried out and the reaction was terminated when the acid value reached 0.3.
- EHPIP 2-ethylhexyl 2-propylheptyl isophthalate
- DEHIP di- (2-ethylhexyl) isophthalate
- DPIP 2-propylheptyl isophthalate
- EHPIP 2-ethylhexyl 2-propylheptyl isophthalate
- DEHIP di- (2-ethylhexyl) isophthalate
- DPIP 2-propylheptyl isophthalate
- the generation of generated water began at about 170 ° C., and the reaction temperature was about 220 ° C., and nitrogen gas was continuously added at about 3 hours for about 3 hours.
- the esterification reaction was carried out and the reaction was terminated when the acid value reached 0.3.
- EHPIP 2-ethylhexyl 2-propylheptyl isophthalate
- DEHIP di- (2-ethylhexyl) isophthalate
- DPIP 2-propylheptyl isophthalate
- DIDP Diisodecyl phthalate Exxonmobil
- the plasticizer composition or compound prepared in Examples 27 to 31 and Comparative Example 10 as a plasticizer with respect to 100 parts by weight of polyvinyl chloride resin (PVC (LS 130s)), an additive as a RUP stabilizer (RUP 144, Adeka Korea ) 5 parts by weight, 40 parts by weight of calcium carbonate (Omya 1T, BSH), 0.3 phr of stearic acid (ST / A) as a stabilizer, and work for 4 minutes at 160 °C using a roll mill Using a press, the sheet was manufactured to a thickness of 1.3 mm by working at 180 ° C. for 2.5 minutes (low pressure) and 2 minutes (high pressure).
- the sheets produced using the plasticizer compositions of Examples 27 to 31, respectively, were used as Comparative Examples 11, in which the sheets using the plasticizers of Examples 32 to 46 and Comparative Example 10 were sequentially used.
- Example 32 Example 33
- Example 34 Example 35
- Example 36 Comparative Example 11
- Shore "A” 89.5 88.5 87.7 90.2 90.5 89.8
- Tensile strength (kgf / cm 2 ) 196.8 193.9 191.9 190.2 187.0 171.5 % Elongation
- 302.8 303.0 309.1 300.1
- Performance loss (%) 0.08 0.10 0.04 0.05 0.06 0.11 Heating loss (%) 1.1 1.6 2.5 0.5 0.3 1.4
- Examples 35 to 36 were measured to decrease to an excellent level compared to the sheet of Comparative Example 11 using the plasticizer of Comparative Example 10, and the sheets of Examples 32 to 34 also showed an equivalent level to Comparative Example 11. I could confirm that. As a result, it could be confirmed that the sheets of Examples 32 to 36 using the plasticizers of Examples 27 to 31 according to the examples of the present invention exhibited better physical properties than the sheets of Comparative Example 11 using Comparative Example 10, which is a conventional plasticizer. .
- PIA isophthalic acid
- PIA isophthalic acid
- TIPT tetra isopropyl titanate
- DIDP Diisodecyl phthalate, Exxonmobil
- the plasticizer composition or compound prepared in Examples 37 to 40 and Comparative Example 12 50 parts by weight of the plasticizer composition or compound prepared in Examples 37 to 40 and Comparative Example 12, respectively, as a plasticizer with respect to 100 parts by weight of polyvinyl chloride resin (PVC (LS 130s)), and an RUP stabilizer (RUP 144, Deca Korea) 5 parts by weight, 40 parts by weight of calcium carbonate (Omya 1T, BSH), 0.3 phr of stearic acid (ST / A) as a stabilizer, 4 minutes at 160 °C using a roll mill (Roll mill)
- the sheet was manufactured in a thickness of 1 mm and 3 mm using a press for 2.5 minutes (low pressure) and 2 minutes (high pressure) at 180 ° C.
- seat using the plasticizer of Examples 41-44 and the comparative example 12 are made into the comparative example 13 sequentially.
- PIA isophthalic acid
- 2-EH 2-ethyl hexanol
- INA isononyl alcohol
- TIPT titanium based catalyst
- the production of water was started at about 170 ° C., and the esterification 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 0.2.
- distillation was performed under reduced pressure for 0.5 to 4 hours to remove unreacted raw materials.
- steam extraction was performed under reduced pressure using steam for 0.5 to 3 hours, the reaction solution temperature was cooled to about 90 ° C, and neutralization treatment was performed using an alkali solution. .
- washing with water may be performed, and then the reaction solution is dehydrated to remove moisture.
- the filter medium was added to the reaction solution from which the water was removed, the mixture was stirred for a predetermined time, and then filtered and finally, 16% by weight of 2-ethylhexyl isononyl isophthalate (EHINIP) of Chemical Formula 1, di- (2-ethylhexyl) of Chemical Formula 2
- EHINIP 2-ethylhexyl isononyl isophthalate
- An isophthalic plasticizer composition was obtained comprising 1% by weight of isophthalate (DEHIP) and 83% by weight of di-isononyl isophthalate (DINIP).
- Example 45 except that 351.6 g of 2-ethyl hexanol (2-EH) and 908.8 g of isononyl alcohol (INA) (molar ratio of PIA: 2-PH to INA 1.0: 0.9: 2.1) were used. Similarly, the filtrate was finally 44% by weight of 2-ethylhexyl isononyl isophthalate (EHINIP) of Formula 1, 7% by weight of di- (2-ethylhexyl) isophthalate (DEHIP) of Formula 2, and An isophthalic plasticizer composition comprising 49% by weight of diisononyl isophthalate (DINIP) was obtained.
- EHINIP 2-ethylhexyl isononyl isophthalate
- DEHIP di- (2-ethylhexyl) isophthalate
- DINIP diisononyl isophthalate
- Example 45 except that 586.0 g of 2-ethyl hexanol (2-EH) and 649.1 g of isononyl alcohol (INA) (molar ratio of PIA: 2-PH to INA of 1.0: 1.5: 1.5) were used. Similarly, the filtrate was finally 55% by weight of 2-ethylhexyl isononyl isophthalate (EHINIP) of Formula 1, 20% by weight of di- (2-ethylhexyl) isophthalate (DEHIP) of Formula 2, and An isophthalic plasticizer composition comprising 25% by weight of diisononyl isophthalate (DINIP) was obtained.
- EHINIP 2-ethylhexyl isononyl isophthalate
- DEHIP di- (2-ethylhexyl) isophthalate
- DINIP diisononyl isophthalate
- Example 45 except that 820.5 g of 2-ethyl hexanol (2-EH) and 389.5 g of isononyl alcohol (INA) (molar ratio of PIA: 2-PH to INA of 1.0: 2.1: 0.9) were used. Similarly, the filtrate was finally 46% by weight of 2-ethylhexyl isononyl isophthalate (EHINIP) of Formula 1, 44% by weight of di- (2-ethylhexyl) isophthalate (DEHIP) of Formula 2, and An isophthalic plasticizer composition comprising 10% by weight of diisononyl isophthalate (DINIP) was obtained.
- EHINIP 2-ethylhexyl isononyl isophthalate
- DEHIP di- (2-ethylhexyl) isophthalate
- DINIP diisononyl isophthalate
- Example 45 except that 1054.9 g of 2-ethyl hexanol (2-EH) and 129.8 g of isononyl alcohol (INA) (molar ratio of PIA: 2-PH to INA 1.0: 2.7: 0.3) were used. Similarly, the resultant was filtered and finally 20% by weight of 2-ethylhexyl isononyl isophthalate (EHINIP) of Formula 1, 79% by weight of di- (2-ethylhexyl) isophthalate (DEHIP) of Formula 2, and The isophthalic plasticizer composition containing 1 weight% of diisononyl isophthalates (DINIP) was obtained.
- EHINIP 2-ethylhexyl isononyl isophthalate
- DEHIP di- (2-ethylhexyl) isophthalate
- DIDP Diisodecyl phthalate Exxonmobil
- plasticizer composition or compound prepared in Examples 45 to 49 and Comparative Example 14 as a plasticizer with respect to 100 parts by weight of polyvinyl chloride resin (PVC (LS 100s)) as an additive, RUP stabilizer (RUP 144, Adeka Korea) 5 parts by weight, calcium carbonate (Omya 1T, BSH) 40 parts by weight, 2 minutes at 200rpm using a 3L super mixer (EM) incorporating 0.3 phr of stearic acid (ST / A; stearic acid) as a stabilizer, After blending at 500 rpm for 3 minutes, the mixture was raised to 700 rpm until it reached 100 ° C to obtain a final blend.
- PVC polyvinyl chloride resin
- RUP stabilizer RUP stabilizer
- calcium carbonate Omya 1T, BSH
- Example 50 (1: 9)
- Example 51 (3: 7)
- Example 52 (5: 5)
- Example 53 (7: 3)
- Example 54 (9: 1) Comparative Example 15 Shore "A” 89.2 88.7 88.5 88.0 87.7 90.0
- Tensile strength (kgf / cm 2 )
- 188.7 189.9 194.2 192.5 190.2 183.5
- Elongation 298.2 294.9 297.0 303.5 295.5
- Performance loss (%) 0.12 0.12 0.14 0.15 0.17 0.18 Heating loss (%) 1.03 1.34 1.97 2.40 2.70 1.07
- the 2-EH: INA is a molar ratio of (2-EH (2-ethylhexyl alcohol): INA (isononyl alcohol) introduced in the preparation of the plasticizer.
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Abstract
Description
에스테르계조성물(중량%) | |||
실시예1 | 화학식 1-1(47%) | 화학식 1-20(17%) | 화학식 1-21(36%) |
실시예2 | 화학식 1-4(53%) | 화학식 1-16(15%) | 화학식 1-21(32%) |
실시예3 | 화학식 1-5(50 %) | 화학식 1-16(20%) | 화학식 1-17(30%) |
실시예4 | 화학식 1-6(48%) | 화학식 1-16(16%) | 화학식 1-18(36%) |
실시예5 | 화학식 1-7(47%) | 화학식 1-19(35%) | 화학식 1-16(18%) |
실시예6 | 화학식 1-8(44%) | 화학식 1-20(24%) | 화학식 1-18(32%) |
실시예7 | 화학식 1-9(47%) | 화학식 1-19(28%) | 화학식 1-20(25%) |
실시예8 | 화학식 1-10(49%) | 화학식 1-21(26%) | 화학식 1-18(25%) |
실시예9 | 화학식 1-11(50%) | 화학식 1-21(30%) | 화학식 1-19(20%) |
실시예10 | 화학식 1-12(47%) | 화학식 1-17(25%) | 화학식 1-18(38%) |
실시예11 | 화학식 1-13(49%) | 화학식 1-19(19%) | 화학식 1-17(32%) |
실시예12 | 화학식 1-14(46%) | 화학식 1-19(17%) | 화학식 1-18(37%) |
실시예 13 | 화학식 1-15(45%) | 화학식 1-16(21%) | 화학식 1-20(34%) |
비교예 1 | DPHP(100%) | ||
비교예 2 | DIDP(100%) | ||
비교예 3 | 디운데실이소프탈레이트(100%) | ||
비교예 4 | 운데실, 이소트리데실이소프탈레이트( 50%) | 디운데실이소프탈레이트(24%) | 디이소트리데실이소프탈레이트(26%) |
경도(Shore “A”) | 인장강도(kg/cm2) | 신율(%) | 이행손실(%) | 가열감량(%) | |
실시예 14 | 90.7 | 183.4 | 227.8 | 0.11 | 2.09 |
실시예 15 | 87.6 | 181.5 | 285.1 | 0.48 | 2.35 |
실시예 16 | 86.7 | 179.5 | 282.6 | 0.56 | 3.20 |
실시예 17 | 88.5 | 182.6 | 286.9 | 0.39 | 1.02 |
실시예 18 | 87.2 | 175.6 | 259.4 | 0.55 | 0.88 |
실시예 19 | 93.5 | 195.6 | 288.6 | 0.08 | 0.85 |
실시예 20 | 91.4 | 194.7 | 268.9 | 0.10 | 0.90 |
실시예 21 | 93.3 | 207.9 | 291.5 | 0.03 | 0.35 |
실시예 22 | 90.3 | 201.7 | 268.5 | 0.15 | 0.55 |
실시예 23 | 92.5 | 208.5 | 284.6 | 0.05 | 0.30 |
실시예 24 | 91.4 | 201.3 | 251.3 | 0.14 | 0.56 |
실시예 25 | 91.5 | 204.6 | 260.5 | 0.15 | 0.48 |
실시예 26 | 87.6 | 182.4 | 232.5 | 0.14 | 2.53 |
비교예 6 | 89.5 | 185.6 | 231.7 | 0.89 | 1.89 |
비교예 7 | 90.0 | 183.5 | 241.2 | 0.18 | 1.07 |
비교예 8 | 92.2 | 210.3 | 221.5 | 0.04 | 0.35 |
비교예 9 | 93.8 | 214.9 | 216.5 | 0.02 | 0.25 |
실시예32 | 실시예33 | 실시예34 | 실시예35 | 실시예36 | 비교예 11 | |
경도(Shore "A") | 89.5 | 88.5 | 87.7 | 90.2 | 90.5 | 89.8 |
인장강도(kgf/cm2) | 196.8 | 193.9 | 191.9 | 190.2 | 187.0 | 171.5 |
신율(%) | 302.8 | 303.0 | 309.1 | 300.1 | 300.1 | 282.6 |
이행손실(%) | 0.08 | 0.10 | 0.04 | 0.05 | 0.06 | 0.11 |
가열감량(%) | 1.1 | 1.6 | 2.5 | 0.5 | 0.3 | 1.4 |
실시예 41 | 실시예 42 | 실시예43 | 실시예44 | 비교예13 | |
경도(Shore "A") | 91 | 91.5 | 90 | 91.5 | 91 |
인장강도(kgf/cm2) | 194.1 | 189.4 | 173.8 | 198.9 | 193.3 |
신율(%) | 293.8 | 295.2 | 289.8 | 300.2 | 278.2 |
이행손실(%) | 0.04 | 0.08 | 0.07 | 0.02 | 0.10 |
가열감량(%) | 1.03 | 1.06 | 1.08 | 0.97 | 1.2 |
(2-EH : INA) | 실시예 50(1:9) | 실시예 51(3:7) | 실시예52(5:5) | 실시예53(7:3) | 실시예54(9:1) | 비교예15 |
경도(Shore "A") | 89.2 | 88.7 | 88.5 | 88.0 | 87.7 | 90.0 |
인장강도(kgf/cm2) | 188.7 | 189.9 | 194.2 | 192.5 | 190.2 | 183.5 |
신율(%) | 298.2 | 294.9 | 297.0 | 303.5 | 295.5 | 281.2 |
이행손실(%) | 0.12 | 0.12 | 0.14 | 0.15 | 0.17 | 0.18 |
가열감량(%) | 1.03 | 1.34 | 1.97 | 2.40 | 2.70 | 1.07 |
Claims (19)
- 청구항 1에 있어서,상기 분지쇄는 C1-C6의 알킬, C2-C6의 알케닐, 또는 C2-C6의 알키닐인 것을 특징으로 하는 에스테르 화합물.
- 청구항 2에 있어서,R1 및 R2는서로 상이하고 각각 독립적으로, 비분지 또는 1 이상의 C1-C4의알킬분지쇄를 포함하는 C4-C9의 알킬, 및 비분지 또는 1 이상의 C1-C4의 알킬 분지쇄를 포함하는 페닐 또는 벤질로 이루어진 군에서 선택되는 어느 하나인 것을 특징으로 하는 에스테르 화합물.
- 청구항 1의 에스테르 화합물을 포함하는 가소제 조성물.
- 청구항10에 있어서,상기 분지쇄는 C1-C6의 알킬, C2-C6의 알케닐 또는 C2-C6의 알키닐인 것을 특징으로 하는 가소제 조성물의 제조방법.
- 청구항10에 있어서,상기 에스테르화 반응은 80℃ 내지 270℃ 에서 수행되는 것을 특징으로 하는 가소제 조성물의 제조방법.
- 청구항10에 있어서,상기 촉매는 Sn계 또는 Ti계를 포함하는 유기금속 촉매, 술폰산계 또는 황산계를 포함하는 산 촉매, 또는 이들의 혼합 촉매인 것을 특징으로 하는 가소제 조성물의 제조방법.
- 청구항10에 있어서,상기 화학식 2의 이소프탈산, 및 상기 화학식 3의 알코올 또는 상기 알코올과 이의 1종 이상의 이성질체의 혼합물은 1 : 0.01 내지 5 몰비의 양으로 사용되는 것을 특징으로 하는 가소제 조성물의 제조방법.
- 청구항 5의 가소제 조성물, 및 폴리염화비닐 수지를 포함하는 폴리염화비닐 수지 조성물.
- 청구항 15에 있어서,상기 가소제 조성물은 폴리염화비닐 수지 100 중량부에 대하여 10 내지 150 중량부의 양으로 포함되는 것을 특징으로 하는 폴리염화비닐 수지 조성물.
- 청구항 5의 가소제 조성물, 및 수지를 포함하는 수지 조성물.
- 청구항 17에 있어서,상기 수지는 에틸렌 초산 비닐, 폴리에틸렌, 폴리프로필렌, 폴리스타이렌, 폴리우레탄, 열가소성 엘라스토머, 폴리유산, SBR, NBR, BR 중에서 선택된 1종 이상을 포함하는 것을 특징으로 하는 수지 조성물.
- 청구항 17에 있어서,상기 가소제 조성물은 수지 100 중량부에 대하여 10 내지 150 중량부의 양으로 포함되는 것을 특징으로 하는 수지 조성물.
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CN201580006359.2A CN105939991B (zh) | 2014-02-07 | 2015-02-05 | 酯化合物,包含其的增塑剂组合物,该组合物的制备方法和包含该增塑剂组合物的树脂组合物 |
US15/038,989 US10208185B2 (en) | 2014-02-07 | 2015-02-05 | Ester-based compound, plasticizer composition including the same, preparation method of the composition and resin composition including the plasticizer composition |
JP2016545859A JP6481984B2 (ja) | 2014-02-07 | 2015-02-05 | エステル系化合物、これを含む可塑剤組成物、この製造方法、及びこれを含む樹脂組成物 |
RU2016126233A RU2670764C2 (ru) | 2014-02-07 | 2015-02-05 | Соединение на основе сложного эфира, пластифицирующая композиция, включающая это соединение, способ получения композиции и смоляная композиция, включающая пластифицирующую композицию |
ES15746629T ES2788702T3 (es) | 2014-02-07 | 2015-02-05 | Composición plastificante, procedimiento para fabricar una composición plastificante y composición de resina que comprende una composición plastificante |
EP15746629.3A EP3103788B1 (en) | 2014-02-07 | 2015-02-05 | Plasticizer composition, method for manufacturing plasticizer composition, and resin composition comprising plasticizer composition |
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KR10-2014-0021597 | 2014-02-24 | ||
KR1020150017577A KR101758447B1 (ko) | 2014-02-07 | 2015-02-04 | 이소프탈레이트계 에스테르 화합물 및 이를 포함하는 가소제 조성물 |
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KR10-2015-0017576 | 2015-02-04 | ||
KR1020150017574A KR101720852B1 (ko) | 2014-02-07 | 2015-02-04 | 이소프탈레이트계 에스테르 화합물 및 이를 포함하는 가소제 조성물 |
KR1020150017573A KR101712718B1 (ko) | 2014-02-07 | 2015-02-04 | 이소프탈레이트계 에스테르 화합물, 이의 제조방법, 및 이를 포함하는 수지 조성물 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3293172A4 (en) * | 2016-04-22 | 2019-01-23 | LG Chem, Ltd. | SOFTMAKER COMPOSITION AND METHOD FOR THE PRODUCTION THEREOF |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3096364A (en) * | 1958-12-08 | 1963-07-02 | Monsanto Chemicals | Production of benzyl alkyl phthalates by ester interchange |
US3324040A (en) * | 1965-09-17 | 1967-06-06 | Wallace & Tiernan Inc | Homogeneous benzoyl peroxide paste |
JP2012089287A (ja) * | 2010-10-18 | 2012-05-10 | Yamazol Co Ltd | 電線・ケーブル被覆用塩化ビニル樹脂組成物 |
KR20130035493A (ko) * | 2011-09-30 | 2013-04-09 | 주식회사 엘지화학 | 에스터 가소제 조성물 |
-
2015
- 2015-02-05 WO PCT/KR2015/001202 patent/WO2015119442A1/ko active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3096364A (en) * | 1958-12-08 | 1963-07-02 | Monsanto Chemicals | Production of benzyl alkyl phthalates by ester interchange |
US3324040A (en) * | 1965-09-17 | 1967-06-06 | Wallace & Tiernan Inc | Homogeneous benzoyl peroxide paste |
JP2012089287A (ja) * | 2010-10-18 | 2012-05-10 | Yamazol Co Ltd | 電線・ケーブル被覆用塩化ビニル樹脂組成物 |
KR20130035493A (ko) * | 2011-09-30 | 2013-04-09 | 주식회사 엘지화학 | 에스터 가소제 조성물 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3293172A4 (en) * | 2016-04-22 | 2019-01-23 | LG Chem, Ltd. | SOFTMAKER COMPOSITION AND METHOD FOR THE PRODUCTION THEREOF |
US10633511B2 (en) | 2016-04-22 | 2020-04-28 | Lg Chem Ltd. | Plasticizer composition and method of preparing the same |
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