CN101456812B - Purification method of lactic acid ester - Google Patents
Purification method of lactic acid ester Download PDFInfo
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- CN101456812B CN101456812B CN 200910028648 CN200910028648A CN101456812B CN 101456812 B CN101456812 B CN 101456812B CN 200910028648 CN200910028648 CN 200910028648 CN 200910028648 A CN200910028648 A CN 200910028648A CN 101456812 B CN101456812 B CN 101456812B
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- alkali
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- 238000000746 purification Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title abstract description 27
- 150000003903 lactic acid esters Chemical class 0.000 title 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims abstract description 51
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 238000004821 distillation Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 150000001768 cations Chemical class 0.000 claims abstract description 5
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 5
- 239000011347 resin Substances 0.000 claims abstract description 5
- 229920005989 resin Polymers 0.000 claims abstract description 5
- 238000005342 ion exchange Methods 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- -1 menthanol lactic acid ester Chemical class 0.000 claims description 10
- 238000005809 transesterification reaction Methods 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 235000011054 acetic acid Nutrition 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 claims 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims 2
- NDVWOBYBJYUSMF-UHFFFAOYSA-N 2-methylcyclohexan-1-ol Chemical compound CC1CCCCC1O NDVWOBYBJYUSMF-UHFFFAOYSA-N 0.000 claims 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims 1
- SFBIZPBTKROSDE-UHFFFAOYSA-N octyl 2-hydroxypropanoate Chemical compound CCCCCCCCOC(=O)C(C)O SFBIZPBTKROSDE-UHFFFAOYSA-N 0.000 claims 1
- 239000000539 dimer Substances 0.000 abstract description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000001953 recrystallisation Methods 0.000 abstract description 3
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 abstract description 2
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 abstract description 2
- 229940116333 ethyl lactate Drugs 0.000 abstract description 2
- 229940057867 methyl lactate Drugs 0.000 abstract description 2
- 150000002148 esters Chemical group 0.000 abstract 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 16
- 238000006471 dimerization reaction Methods 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 10
- 238000005886 esterification reaction Methods 0.000 description 9
- 239000004310 lactic acid Substances 0.000 description 8
- 235000014655 lactic acid Nutrition 0.000 description 8
- 230000032050 esterification Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229940041616 menthol Drugs 0.000 description 6
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005815 base catalysis Methods 0.000 description 2
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NOOLISFMXDJSKH-KXUCPTDWSA-N (-)-Menthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@H]1O NOOLISFMXDJSKH-KXUCPTDWSA-N 0.000 description 1
- 235000016257 Mentha pulegium Nutrition 0.000 description 1
- 244000246386 Mentha pulegium Species 0.000 description 1
- 235000004357 Mentha x piperita Nutrition 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- UJNOLBSYLSYIBM-WISYIIOYSA-N [(1r,2s,5r)-5-methyl-2-propan-2-ylcyclohexyl] (2r)-2-hydroxypropanoate Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@H]1OC(=O)[C@@H](C)O UJNOLBSYLSYIBM-WISYIIOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- KDPXOGYCOOUWOS-UHFFFAOYSA-N hexyl 2-hydroxypropanoate Chemical compound CCCCCCOC(=O)C(C)O KDPXOGYCOOUWOS-UHFFFAOYSA-N 0.000 description 1
- 235000001050 hortel pimenta Nutrition 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229940001447 lactate Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- NGSFWBMYFKHRBD-UHFFFAOYSA-N sodium;2-hydroxypropanoic acid Chemical compound [Na+].CC(O)C(O)=O NGSFWBMYFKHRBD-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for purifying lactate. The method comprises: dissolving the lactate containing dimer and polymer in a solvent of lower alcohol, adding a catalytic amount of alkali, carrying out the ester exchange reaction at a temperature of between 0 and 80 DEG C, converting the dimer or polymer into lactate products and methyl lactate or ethyl lactate, and adding acid for neutralization or adopting cation resin for ion exchange so as to neutralize the reaction product; and recovering the solvent, and obtaining the finished product by recrystallization or reduced pressure distillation. The method has the advantages that the method can effectively lower hydrolysis of the lactate simultaneously carried out during depolymerization of the dimer or polymer in the purification process, the reaction can be carried out at normal temperature, and the production cost can be effectively lowered, along with simple operation, safety and high efficiency; moreover, the purity of the obtained target product reaches more than 98 percent, so that the method has industrial application values.
Description
Technical field
The present invention relates to a kind of purification process of lactate, relate to especially especially a kind of in the esterification process of lactic acid and alcohol the depolymerization method of the poly-lactic acid ester that produces.
Background technology
The common preparation method of lactate be by lactic acid and alcohol under the effect of catalyzer, occur esterification and, in esterification reaction process, easily generate dipolymer or the polymer of by product one lactate, shown in I, this brings very large difficulty for the separating-purifying of lactate.There is a small amount of reported in literature when disclosing the lactate preparation method, to provide the degradation method of its dipolymer or polymer, but method wherein is mostly in dipolymer or polymer degraded, can again the lactate product be converted into raw material, this production to lactate is unfavorable.
Such as, MENTHOL lactate (L-Menthyllactate) is a kind of peppermint derivative of synthetic, because its cooling effect is light and long, therefore replace natural menthol as freshener.The people such as Mark B.Erman synthetic have done detailed disclosure to it in US7173146, be with menthol, lactic acid under suitable solvent and catalyst action, carry out esterification and must menthanol lactic acid ester and dimerization, trimerization compound.Be degraded dipolymer and polymer wherein, the mixture of gained is hydrolyzed under the highly basic such as sodium hydroxide, the hydrolysis of dimerization and polymer is converted into menthanol lactic acid ester, but in its hydrolytic process, to there be a large amount of menthanol lactic acid esters to continue to be hydrolyzed and again to be converted into menthol and Sodium.alpha.-hydroxypropionate (as shown in the formula II), this purification process is uneconomical, effect
Menthanol lactic acid ester
Rate is also very low.
The purifying of the prepared lactate of esterification of lactic acid and alcohol mainly is the depolymerization method of poly-lactic acid ester, and people are seeking a kind of more economic method always.
Summary of the invention
The invention provides a kind of purification process of lactate, can overcome the existing purification process problem that lactate is hydrolyzed simultaneously when dimerization or polymer depolymerization, by the transesterification reaction under the normal temperature, make dipolymer or polymer be converted into lactate, more effectively carry out the purifying of lactate.
The present invention studies the esterification of aliphatic alcohols lactate, utilize base catalysis to carry out transesterify and remove dimerization or polymer in the lactate, namely take dehydrated alcohol or anhydrous methanol as solvent, suitable alkali is for making catalyzer, carry out transesterify under the normal temperature, make dipolymer or polymer finally be converted into target product lactate and methyl lactate or ethyl lactate, be isolated again highly purified lactate.
The technical solution used in the present invention is as follows:
A kind of purification process of lactate may further comprise the steps:
The lactate that 1) will contain dipolymer and polymer is dissolved in the solvent lower alcohol, adds the alkali of catalytic amount, carries out transesterification reaction under 0～80 ℃;
2) solids removed by filtration alkali, and acid neutralization to reaction product is neutral, or carries out ion-exchange with resin cation (R.C.), is neutral to reaction product;
3) reclaim solvent after, through underpressure distillation or crystallisation by cooling and the target product lactate.
Depolymerization method of the present invention can following chemical formulation:
Among the present invention, described lactate can be prepared with the esterification of alcohol by lactic acid, is the mixture of lactate, its dipolymer and polymer.Esterification reaction process is with being dissolved in the solvent by certain amount ratio of lactic acid and alcohol, adds catalyzer and refluxes a few hours, and excessive lactic acid is removed in the diluted alkaline washing, reclaims solvent and can make described lactate mixture.Solvent can be selected band aqua commonly used such as benzene, toluene, hexanaphthene, normal heptane, normal hexane, sherwood oil or methyl tertiary butyl ether etc., catalyzer can be the vitriol oil, tosic acid, methylsulfonic acid commonly used, or solid acid such as sodium pyrosulfate, tin protochloride etc. and with loaded article, molecular sieve, resin cation (R.C.) or the heteropolyacid etc. of diatomite or silicon-dioxide.
Described solvent is selected lower alcohol commonly used, such as anhydrous methanol, dehydrated alcohol or its mixture.
Described alkali can be anhydrous sodium carbonate, Anhydrous potassium carbonate or its mixture.
Transesterification reaction temperature can be 0～80 ℃, preferred 20～30 ℃.
The present invention is to lactate, and particularly the esterification of fat (ring) pure lactate and transesterification reaction are done further research, propose more effective purification process.Make the mixture of corresponding lactate, its dipolymer and trimer (GC detects separately content) by above-mentioned known method, again above mixture is dissolved in the lower alcohol (anhydrous methanol or dehydrated alcohol), the alkali (yellow soda ash or salt of wormwood) that adds catalytic amount carries out transesterification reaction, stirring at room is GC detection lactate, its dipolymer and trimeric content after a few hours, the results are shown in Table 1.
The transesterification reaction result of table 1 lactate
By as seen from Table 1, carry out transesterify with base catalysis and remove dipolymer or polymer in the lactate, pure content does not increase in the product behind the purifying, dipolymer or polymer are effectively degraded, the total content of polymkeric substance can fall too low, generally all below 0.5%, have efficient, temperature condition is gentle, the alkali that uses is the advantages such as catalytic amount, product purity is higher.
Among the present invention, step 2) purpose of the alkali in the neutralization reaction product, for avoiding in the still-process, there is the decomposition of the product lactate that may cause in alkali, being neutralized to reaction product pH value reaches neutral and gets final product, can select acid neutralization, mineral acid commonly used such as sulfuric acid, hydrochloric acid or nitric acid, organic acid such as formic acid, acetic acid or propionic acid etc.; Or adopt resin cation (R.C.) to carry out ion-exchange, be neutral to reaction product.
By above as seen, according to purification process of the present invention, through the lactate of gained after the transesterification reaction degraded, wherein the content of alcohol can not raise, and the total content of polymkeric substance can be down to below 0.5%, behind distillating recovering solvent, can obtain target product again.Through underpressure distillation or recrystallization, can obtain the very high product of purity, purity is more than 98%; For some lactate products, even need not underpressure distillation or recrystallization, can directly obtain high purity product.
Purification process according to lactate of the present invention, compare with existing method, the simultaneous hydrolysis of lactate in the time of can effectively reducing in the purifying products process dimerization or polymer depolymerization, pass through transesterification reaction, efficient realization dimerization or polymer depolymerization, and reaction is carried out at normal temperatures, and simple to operate, safety, efficient are high, can effectively reduce production costs.The purity of gained target product has more industrial value in being applied to produce more than 98%.
Describe the present invention below in conjunction with embodiment.Scope of the present invention is not limited with embodiment, but is limited by the scope of claim.
Embodiment
Embodiment 1
By method preparation of the present invention and purifying menthanol lactic acid ester, may further comprise the steps:
(1) preparation of menthanol lactic acid ester, dimerization and polymer mixture:
In four-hole boiling flask, drop into respectively quantitative 50g menthol and 50g lactic acid (85%wt) and 50mL toluene, slowly splash into the 0.35g vitriol oil under the whipped state, oil bath reflux 2h, water trap is collected 15mL water, GC detects menthol content＜8%wt, reactant is cooled to room temperature, regulating the pH value with saturated aqueous common salt 10mL washing, 10% aqueous sodium hydroxide solution respectively washs again to 6.5-7.5, saturated aqueous common salt 10mL, reclaim solvent, residue is menthanol lactic acid ester, dimerization and polymer mixture.
(2) degraded of polymkeric substance:
Under the room temperature, above-mentioned steps gained mixture is dissolved in the 70mL anhydrous methanol, adds 0.6g solid carbonic acid potassium, stir 2h, GC detects wherein dimer content＜0.5%wt, suction filtration, and filtrate is with the acetic acid pH=7.0 that neutralizes, reclaim solvent and get oily matter, be cooled to room temperature, standing over night, suction filtration, get column menthanol lactic acid ester crystal 6 5.0g, it is 99.1% that GC detects its menthanol lactic acid ester purity.
Embodiment 2
By method preparation of the present invention and purity ring hexanol lactate, may further comprise the steps:
(1) preparation of hexalin lactate, dimerization and poly mixture:
Working method is pressed embodiment 1, adds the 33g hexalin, and solvent is 50mL benzene, and catalyzer is the 0.8g tosic acid, and backflow 3.5h is remaining with embodiment 1.
(2) degraded of polymkeric substance:
Under the room temperature, above gained mixture is dissolved in the 50mL dehydrated alcohol, add the 1.0g solid sodium carbonate, stir 2.5h, GC detects dipolymer＜0.5%, suction filtration, filtrate is reclaimed solvent and is got oily matter, underpressure distillation with the acetic acid pH=7.0 that neutralizes, get oily matter 45.3g, it is 98.8% that GC detects its hexalin lactate purity.
Embodiment 3
By method preparation of the present invention and purifying LA, may further comprise the steps:
(1) preparation of LA, dimerization and poly mixture:
Working method is pressed embodiment 1, adds the 60g lauryl alcohol, and solvent is 50mL sherwood oil (60-90 ℃), and catalyzer is the 5g sodium pyrosulfate, and backflow 5.0h is remaining with embodiment 1.
(2) degraded of polymkeric substance:
Under the room temperature, above gained mixture is dissolved in the 75mL anhydrous methanol, add 0.6g solid carbonic acid potassium, stir 2.5h, GC detects dipolymer＜0.5%, suction filtration, filtrate is with the acetic acid pH=7.0 that neutralizes, reclaim solvent and get oily matter, underpressure distillation gets oily matter 75.2g, and it is 99.2% that GC detects its LA purity.
Embodiment 4
By method preparation of the present invention and purifying 3,3,5-cyclonol lactate may further comprise the steps:
(1) 3, the preparation of 3,5-cyclonol lactate, dimerization and poly mixture:
Working method is pressed embodiment 1, adds 46g 3,3, and 5-cyclonol, solvent are the 50mL hexanaphthene, and catalyzer is the 0.5g vitriol oil, and backflow 4.0h is remaining with embodiment 1.
(2) degraded of polymkeric substance:
Under the room temperature, above gained mixture is dissolved in the 75mL dehydrated alcohol, adds the 1.0g solid sodium carbonate, stir 2.5h, GC detects dipolymer＜0.5%, suction filtration, filtrate is reclaimed solvent and is got oily matter with the acetic acid pH=7.0 that neutralizes, underpressure distillation gets oily liquids 51.0g, GC detects wherein 3,3, and 5-cyclonol lactate purity is 98.5%.
Claims (3)
1. the purification process of a lactate may further comprise the steps:
The lactate that 1) will contain dipolymer and polymer is dissolved in solvent anhydrous methanol, dehydrated alcohol or its mixture, the alkali that adds catalytic amount, carry out transesterification reaction under 0～30 ℃, described lactate is menthanol lactic acid ester, hexalin lactate, 2 methyl cyclohexanol lactate, 4 methyl cyclohexanol lactate, 3,3,5-cyclonol lactate, 1-octanol lactate, LA or stearyl alcohol lactate;
2) solids removed by filtration alkali, and acid neutralization to reaction product is neutral, or carries out ion-exchange with resin cation (R.C.), is neutral to reaction product;
3) reclaim solvent after, through underpressure distillation or crystallisation by cooling and described lactate product.
2. purification process according to claim 1, it is characterized in that: described alkali is anhydrous sodium carbonate, Anhydrous potassium carbonate or its mixture.
3. purification process according to claim 1, it is characterized in that: described acid is hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid or propionic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910028648 CN101456812B (en) | 2009-01-07 | 2009-01-07 | Purification method of lactic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910028648 CN101456812B (en) | 2009-01-07 | 2009-01-07 | Purification method of lactic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101456812A CN101456812A (en) | 2009-06-17 |
| CN101456812B true CN101456812B (en) | 2013-01-02 |
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| CN112521264A (en) * | 2020-11-23 | 2021-03-19 | 安徽丰原福泰来聚乳酸有限公司 | Method and device for recovering lactic acid from polylactic acid synthetic substrate |
| CN115073280A (en) * | 2022-08-02 | 2022-09-20 | 马鞍山同杰良生物材料有限公司 | Method for recovering high-optical-purity lactic acid from polylactic acid synthetic substrate |
| CN115850065A (en) * | 2022-10-14 | 2023-03-28 | 东莞理工学院 | Method for preparing R-3-hydroxybutyrate by catalyzing degradation of poly-3-hydroxybutyrate with sodium bisulfate as catalyst |
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