WO2022260430A1 - 락타이드 라세미체의 분리방법 - Google Patents
락타이드 라세미체의 분리방법 Download PDFInfo
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- WO2022260430A1 WO2022260430A1 PCT/KR2022/008085 KR2022008085W WO2022260430A1 WO 2022260430 A1 WO2022260430 A1 WO 2022260430A1 KR 2022008085 W KR2022008085 W KR 2022008085W WO 2022260430 A1 WO2022260430 A1 WO 2022260430A1
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- Prior art keywords
- lactide
- weight
- mixture
- separation method
- extraction solvent
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- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical class CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002955 isolation Methods 0.000 title abstract 2
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims abstract description 105
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 72
- 238000000605 extraction Methods 0.000 claims description 55
- 239000000203 mixture Substances 0.000 claims description 44
- 239000002904 solvent Substances 0.000 claims description 38
- 238000000926 separation method Methods 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 16
- -1 amine compound Chemical class 0.000 claims description 12
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 150000001408 amides Chemical class 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- BZUDVELGTZDOIG-UHFFFAOYSA-N 2-ethyl-n,n-bis(2-ethylhexyl)hexan-1-amine Chemical compound CCCCC(CC)CN(CC(CC)CCCC)CC(CC)CCCC BZUDVELGTZDOIG-UHFFFAOYSA-N 0.000 claims description 2
- IIFFFBSAXDNJHX-UHFFFAOYSA-N 2-methyl-n,n-bis(2-methylpropyl)propan-1-amine Chemical compound CC(C)CN(CC(C)C)CC(C)C IIFFFBSAXDNJHX-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 claims description 2
- IOKYPACLTOWHCM-UHFFFAOYSA-N n,n-diethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(CC)CC IOKYPACLTOWHCM-UHFFFAOYSA-N 0.000 claims description 2
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 claims description 2
- UQKAOOAFEFCDGT-UHFFFAOYSA-N n,n-dimethyloctan-1-amine Chemical compound CCCCCCCCN(C)C UQKAOOAFEFCDGT-UHFFFAOYSA-N 0.000 claims description 2
- BUHHOHWMNZQMTA-UHFFFAOYSA-N n,n-dioctadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCN(CCCCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCCCC BUHHOHWMNZQMTA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- SWZDQOUHBYYPJD-UHFFFAOYSA-N tridodecylamine Chemical compound CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC SWZDQOUHBYYPJD-UHFFFAOYSA-N 0.000 claims description 2
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 238000007086 side reaction Methods 0.000 abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 32
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 26
- 238000000034 method Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 21
- 238000004817 gas chromatography Methods 0.000 description 17
- 239000012535 impurity Substances 0.000 description 17
- 235000014655 lactic acid Nutrition 0.000 description 12
- 239000004310 lactic acid Substances 0.000 description 12
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 description 10
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 6
- 229920000747 poly(lactic acid) Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000004626 polylactic acid Substances 0.000 description 4
- 230000006340 racemization Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 229930182843 D-Lactic acid Natural products 0.000 description 2
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229940022769 d- lactic acid Drugs 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000066 reactive distillation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OZZQHCBFUVFZGT-UHFFFAOYSA-N 2-(2-hydroxypropanoyloxy)propanoic acid Chemical compound CC(O)C(=O)OC(C)C(O)=O OZZQHCBFUVFZGT-UHFFFAOYSA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
- C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B63/00—Purification; Separation; Stabilisation; Use of additives
Definitions
- the present invention relates to a method for separating lactide racemates in high yield and high efficiency without side reactions.
- Polylactic acid is a material having biodegradable properties and excellent mechanical properties such as tensile strength and modulus of elasticity, and is widely used in various fields. Polylactic acid may have various structures due to homopolymer or stereoregularity. Polylactic acid is generally prepared through ring-opening polymerization of lactide (LT). Since lactide has optical isomers, the properties of polylactic acid may change depending on the arrangement of these optical isomers in a repeating unit.
- LT lactide
- lactide is a lactic acid dimer, which is a cyclic di-ester of lactic acid (2-hydroxyptopionic acid, LA), and is obtained by dehydration condensation of lactic acid to obtain a relatively low molecular weight lactic acid oligomer as an intermediate.
- LA 2-hydroxyptopionic acid
- Lactic acid used in the production of lactide is a chiral molecule having two enantiomers, D-type (or (R)-type) and L-type (or (S)-type). Therefore, the lactide produced from lactic acid is three optical isomers having two stereocenters, specifically, L-lactide (L-LT) formed from two molecules of L-lactic acid. or (S,S)-lactide), D-lactide formed from two molecules of D-lactic acid (D-lactide (D-LT) or (R,R)-lactide), and one molecule of L each -It exists as meso-lactide (meso-LT) or (R,S)-lactide, which is formed from lactic acid and D-lactic acid.
- L-LT L-lactide
- D-LT D-lactide
- R,R R,R
- a lactide mixture having an optical purity of 90% or more that is, containing 90% or more of L-lactide or D-lactide
- a selective synthesis method in the production of lactide but with a high purity of 99% or more. It is difficult to produce.
- meso-lactide included in the product has a faster hydrolysis rate than L-lactide or D-lactide, hydrolysis is promoted as a whole when the content of meso-lactide in the product is high.
- lactic acid or lactic acid oligomers increase acidity and inhibit the formation of high-quality polylactide. Accordingly, there is a demand for a purification method for removing meso-lactide, lactic acid and lactic acid derivatives while containing L-lactide or D-lactide in high purity, depending on the purpose of use.
- lactide changed through racemization is a racemate in which the ratio of L-lactide and D-lactide is 1:1, and it is difficult to separate them because they have the same physical and chemical properties.
- melt-crystallization As a method for isolating the racemate, melt-crystallization, simultaneous crystallization using seed input, use of a chiral solvent, and the like have been proposed.
- melt-crystallization method there is a limitation that it is possible only when the L-lactide ratio is 80% or more.
- L-lactide ratio As a method using the seed input and an ethanol solvent, there is a method in which L-lactide is added as a seed and then L-lactide is separated using an ethanol solvent, but this also requires that the L-lactide ratio is 60% or more. effective when
- An object of the present invention is to provide a method capable of separating racemic lactide in high yield and efficiency without fear of side reactions even when the ratio of L-lactide is low.
- the present invention provides a method for separating racemic lactide comprising the following steps:
- the extraction solvent contains an amine-based compound or an amide-based compound
- step 1 is a step of preparing a mixture by adding and mixing L-lactide to racemic lactide.
- the lactide racemate is a mixture of optical isomers in which L-lactide and D-lactide are mixed in equal amounts, specifically, L-lactide and D-lactide in a weight ratio of 1:1.
- the lactide racemate can be prepared through racemization of meso-lactide produced as a side reaction when lactide is produced using lactic acid. Accordingly, in the present invention, before step 1 of adding and mixing L-lactide to the lactide racemate, racemization of meso-taclide is performed to obtain a lactide racemate containing L-lactide and D-lactide. A step of preparing a sieve may be further included.
- L-lactide introduced for the lactide racemate serves as a crystal seed during the extraction reaction for separation of the lactide racemate.
- the L-lactide may be added in an amount of 10 to 70 parts by weight based on 100 parts by weight of the lactide racemate. More specifically, in the L-lactide, the L-lactide content is greater than 50% by weight and 80% by weight or less with respect to the total weight of the mixture obtained after adding L-lactide to the lactide racemate. , more specifically greater than 50%, or greater than 52%, or greater than 55%, and less than or equal to 80%, or less than or equal to 75%, or less than or equal to 70%, or less than or equal to 65%, or greater than or equal to 60% by weight. or less, or may be added in an amount such that it is less than 60% by weight.
- the L-lactide content is based on the total weight of the mixture obtained after adding L-lactide to the lactide racemate. It may be added in an amount such that it is 65% by weight or more, or 70% by weight or more, and 80% by weight or less, or 75% by weight or less.
- the optimal extraction solvent is used in the subsequent extraction process, separation of L-lactide is possible even when the content of L-lactide in the mixture is as low as 60% by weight or less, or less than 60% by weight. .
- the L-lactide content in the mixture is greater than 50% by weight, or greater than 52% by weight, or greater than 55% by weight, and less than or equal to 60% by weight, based on the total weight of the mixture. Or it may be added in an amount such that less than 60% by weight, or 58% by weight or less.
- step 2 is a step of selectively extracting L-lactide from the racemic lactide by adding an extraction solvent to the mixture prepared in step 1.
- the extraction solvents are non-chiral compounds that do not have chiral characteristics, have polarity, and have a shift of eutectic point on the three-component system of L-lactide, D-lactide, and extraction solvent. eutectic point), it can show excellent extraction effect. Accordingly, the extraction solvents show excellent extraction efficiency compared to alcohols used in the conventional separation of racemic lactide, and in particular, amine compounds such as TEA have high extraction efficiency even when the L-lactide content in the mixture is low. can represent
- the extraction solvent is present in a liquid phase at room temperature (20 ⁇ 5 ° C), and may be a polar solvent having a melting point of 25 ° C or less and a boiling point of 80 ° C or more. More specifically, the extraction solvent has a melting point of 25 ° C or less, or 10 ° C or less, -150 ° C or more, or -120 ° C or more, and a boiling point of 80 ° C or more or 100 ° C or more, 300 ° C or less, or 250 ° C below When the above melting point and boiling point conditions are satisfied, stable and excellent extraction efficiency can be exhibited while minimizing the occurrence of side reactions.
- the amine-based compound may be specifically a tertiary amine represented by Formula 1 below:
- R 11 to R 13 are each independently C 1-20 straight-chain or branched-chain alkyl.
- amine compound examples include trimethylamine, triethylamine, trin-propylamine, trin-butylamine, trin-octylamine, tridodecylamine, trioctadecylamine, triisopropylamine, triiso butylamine, trit-butylamine, tris(2-ethylhexyl)amine, N,N-dimethyloctylamine, N,N-dimethyldodecylamine, N,N-dimethyl-n-octadecylamine, or N, N-diethyldodecylamine and the like, and any one or a mixture of two or more of these may be used.
- the amine-based compound may be a tertiary amine in which R 11 to R 13 in Chemical Formula 1 are each independently C 1-9 straight-chain alkyl. More specifically, the amine-based compound may be triethylamine or trin-octylamine.
- the amide-based compound may be a compound represented by Formula 2 below:
- R 21 to R 23 are each hydrogen, or each independently represents C 1-20 straight-chain or branched-chain alkyl.
- the amide-based compounds represented by Formula 2 may exhibit a better separation effect than dimethylformamide, etc., which do not satisfy the substituent conditions of R 21 to R 23 .
- R 1 to R 3 may each be hydrogen, or each independently represent C 1-8 straight-chain or branched-chain alkyl, and more specifically, each may be hydrogen or each may be methyl.
- amide-based compound examples include formamide or dimethylacetamide, and any one or a mixture of two or more of these may be used.
- the extraction solvent may be used in an amount of 1 to 10 parts by weight based on 1 part by weight of L-lactide present in the mixture. If the amount of the extraction solvent used is too small, the extraction efficiency is not sufficient, and if the amount of the extraction solvent used is too large, fairness may deteriorate, such that a process for removing the extraction solvent should be performed afterwards. When used within the above-mentioned range, the lactide racemate can be separated with excellent extraction efficiency without an additional process for removing the extraction solvent.
- the extraction solvent is present in the mixture in an amount of 1 part by weight or more, or 2 parts by weight or more, or 2.5 parts by weight or more, or 3 parts by weight or more, or 3.1 parts by weight or more, based on 1 part by weight of L-lactide present in the mixture. or 3.2 parts by weight or more, or 10 parts by weight or less, or 8 parts by weight or less, or 6.5 parts by weight or less, or 5 parts by weight or less, or 4 parts by weight or less, or 3.6 parts by weight or less, or 3.5 parts by weight or less. have.
- the mixing process may be performed by a conventional mixing method such as a stirrer or a mixer, and the mixing speed and time may be appropriately selected and performed.
- step 2 may be performed at a temperature of 10 to 40 °C. Specifically, it may be carried out at a temperature of 10 ° C or higher, or 15 ° C or higher, 40 ° C or lower, or 30 ° C or lower, or 25 ° C or lower, and more specifically, it may be carried out at room temperature of 20 ⁇ 5 ° C. . When carried out in the above temperature range, sufficient extraction efficiency can be achieved without fear of side reactions.
- the precipitated solid is D-lactide undissolved in the extraction solvent and the balance is L-lactide. Separation process for these can be carried out by a conventional method, and specifically separated through filtration.
- L-lactide is included in a high content, specifically, 90% by weight or more, or 92% or more, or 93% or more, or 94% or more with respect to the total weight of the filtrate. have.
- the formation of by-products due to side reactions such as hydrolysis was hardly less than 1% by weight or less than 0.95% by weight based on the total weight of the filtrate.
- the method for separating racemic lactide according to the present invention can separate racemic lactide in high yield and efficiency without fear of side reactions even when the ratio of L-lactide is low. Accordingly, the high-purity lactide separated by the above method can be usefully used for the production of high-grade polylactide having a high molecular weight.
- 1 is a graph showing the results of evaluating the L-LT extraction selectivity for each solvent according to the input seed and the L-LT ratio in the experimental example.
- Example 2 is a graph showing the results of gas chromatography analysis for Example 3.
- Example 3 is a graph showing the results of gas chromatography analysis for Example 6.
- samples for gas chromatography (GC) measurement were prepared by taking about 60 ⁇ l of each filtrate obtained in Examples and Comparative Examples and diluting it in 1 ml of acetonitrile (MeCN).
- GC analysis was performed on the prepared sample according to the following conditions.
- the total peak area and the L-LT peak area were respectively obtained from the chromatogram obtained as a result of GC analysis, and the L-LT extraction selectivity (%) was calculated according to Equation 1 below.
- Equation 1 the total peak area and the L-LT peak area were obtained through integration of each peak.
- FIGS. 2 to 4 are Example 3, Example 6 and Comparative Example, respectively. It is a graph showing the gas chromatography analysis result for 3.
- the x-axis starts at 0 min when the analysis starts, but is enlarged from 8 min when the peak is observed so that the results can be clearly identified.
- the areas of peaks corresponding to impurities such as the meso-LT peak and the unknown peak (hereinafter simply referred to as 'impurity peaks') are respectively obtained, and the impurity content (%) according to Equation 2 below was calculated.
- Impurity content (%) (total area of impurity peak / total peak area) X 100
- Equation 2 the total peak area and the impurity peak area are obtained through integration of each peak, and the total impurity peak area means a value obtained by summing the respective impurity peak areas obtained through integration.
- Example 1 70:30 TEA 94.5:5.5 94.491 0
- Example 2 60:40 TEA 93.5:6.5 93.538 0
- Example 3 55:45 TEA 93.9:6.1 93.926 0
- Example 4 70:30 FA 92.0:8.0 92.045 0.643
- Example 5 60:40 FA 84.0:16.0 84 0.884
- Example 6 55:45 FA 66.1:33.9 66.069 0.928
- Example 7 70:30 Tri-n-octylamine 93.5:6.5 93.529 0
- Example 8 60:40 Tri-n-octylamine 92.9:7.1 92.929 0
- Examples 1-9 using TEA, FA or Tri-n-octylamine as the extraction solvent showed excellent L-LT extraction selectivity and significantly reduced impurity content.
- the conventional extraction solvent EtOH has L-LT extraction selectivity lowered to 86.547%, whereas TEA and Tri-n -octylamine still showed high L-LT extraction selectivity, with extraction selectivities of 92.045% and 92.884%, respectively.
- Example 3 using TEA did not have peaks other than L-LT and D-LT in the GC analysis graphs.
- Comparative Example 3 using EtOH solvent unknown peaks were observed in addition to L-LT and D-LT in the GC analysis graph, from which the possibility of side reactions of lactide such as hydrolysis was confirmed.
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
L-LT 투입 후, 혼합물 내 L-LT:D-LT의 중량비 | 추출 용매 | 최종 수득된 여액 중 L-LT:D-LT의 중량비 | L-LT 추출 선택도(%) | 불순물 함량 (%) |
|
실시예 1 | 70:30 | TEA | 94.5:5.5 | 94.491 | 0 |
실시예 2 | 60:40 | TEA | 93.5:6.5 | 93.538 | 0 |
실시예 3 | 55:45 | TEA | 93.9:6.1 | 93.926 | 0 |
실시예 4 | 70:30 | FA | 92.0:8.0 | 92.045 | 0.643 |
실시예 5 | 60:40 | FA | 84.0:16.0 | 84 | 0.884 |
실시예 6 | 55:45 | FA | 66.1:33.9 | 66.069 | 0.928 |
실시예 7 | 70:30 | Tri-n-octylamine | 93.5:6.5 | 93.529 | 0 |
실시예 8 | 60:40 | Tri-n-octylamine | 92.9:7.1 | 92.929 | 0 |
실시예 9 | 55:45 | Tri-n-octylamine | 93.2:6.8 | 92.884 | 0 |
비교예 1 | 70:30 | EtOH | 94.0:6.0 | 93.963 | 11.782 |
비교예 2 | 60:40 | EtOH | 94.3:5.7 | 94.266 | 6.940 |
비교예 3 | 55:45 | EtOH | 86.5:13.5 | 86.547 | 5.227 |
비교예 4 | 70:30 | 1,4-dioxane | 79.2:20.8 | 79.252 | 0 |
비교예 5 | 60:40 | 1,4-dioxane | 66.3:33.7 | 66.274 | 0 |
비교예 6 | 55:45 | 1,4-dioxane | 57.9:42.1 | 57.898 | 0 |
Claims (11)
- 락타이드 라세미체에 L-락타이드를 투입하고 혼합하여 혼합물을 준비하는 단계; 및상기 혼합물에 추출 용매를 투입하여, 상기 락타이드 라세미체로부터 L-락타이드를 선택 추출하는 단계;를 포함하며,상기 추출 용매는 아민계 화합물 또는 아미드계 화합물을 포함하는,락타이드 라세미체의 분리방법.
- 제1항에 있어서,상기 추출 용매는 액상이며, 융점이 25℃ 이하이고, 비점이 80℃ 이상인 극성 용매인,분리방법.
- 제1항에 있어서,상기 추출 용매는 비키랄성 화합물인,분리방법.
- 제1항에 있어서,상기 아민계 화합물은 트리메틸아민, 트리에틸아민, 트리n-프로필아민, 트리n-부틸아민, 트리n-옥틸아민, 트리도데실아민, 트리옥타데실아민, 트리이소프로필아민, 트리이소부틸아민, 트리t-부틸아민, 트리스(2-에틸헥실)아민, N,N-디메틸옥틸아민, N,N-디메틸도데실아민, N,N-디메틸-n-옥타데실아민, 또는 N,N-디에틸도데실아민인,분리 방법.
- 제1항에 있어서,상기 아민계 화합물은 트리에틸아민, 또는 트리n-옥틸아민인,분리방법.
- 제1항에 있어서,상기 아미드계 화합물은 포름아미드, 또는 디메틸아세트아미드인,분리방법.
- 제1항에 있어서,상기 추출 용매는 상기 혼합물내 존재하는 L-락타이드 1중량부에 대하여 1 내지 10중량부로 사용되는,분리방법.
- 제1항에 있어서,상기 L-락타이드는 락타이드 라세미체 100 중량부에 대하여 10 내지 70 중량부의 양으로 투입되는,분리방법.
- 제1항에 있어서,상기 L-락타이드는, 상기 혼합물 내 L-락타이드의 함량이 혼합물 총 중량에 대하여 50중량% 초과이고, 80중량% 이하가 되도록 하는 양으로 투입되는,분리방법.
- 제1항에 있어서,상기 L-락타이드는, 상기 혼합물 내 L-락타이드의 함량이 혼합물 총 중량에 대하여 50중량% 초과이고, 60중량% 미만이 되도록 하는 양으로 투입되는,분리방법.
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