CN102775380A - Process for preparing lactide through fixed acid method - Google Patents
Process for preparing lactide through fixed acid method Download PDFInfo
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- CN102775380A CN102775380A CN2012102894438A CN201210289443A CN102775380A CN 102775380 A CN102775380 A CN 102775380A CN 2012102894438 A CN2012102894438 A CN 2012102894438A CN 201210289443 A CN201210289443 A CN 201210289443A CN 102775380 A CN102775380 A CN 102775380A
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Abstract
The invention discloses a process for preparing lactide through a fixed acid method, which comprises the following steps: (1) gradually heating a hydroxy or polyhydroxy or polyamino compound with a boiling point of 250-550 DEG C and lactic acid from 90 DEG C to 160 DEG C within 1.5-3 hours in the presence of a catalyst at a pressure controlled to be 2-3.0 KPa, then regulating the pressure to 0.5-0.8 KPa and the temperature to 170-180 DEG C, and continuing to react for 5-10.0 hours to obtain a hydroxy or polyhydroxy or polyamino lactic acid low polymer with a high boiling point; and (2) at the temperature of 180-230 DEG C and the pressure of 0.4-0.8 KPa, performing cracking reaction on the hydroxy or polyhydroxy or polyamino lactic acid low polymer with a high boiling point, which is obtained in the step (1), to obtain lactide. Compared with the lactide preparation method reported in public, the process disclosed by the invention achieves higher purity and better yield.
Description
Technical field
The present invention relates to a kind of preparation method of rac-Lactide, be specifically related to the technology that the fixed acid legal system is equipped with rac-Lactide.
Background technology
POLYACTIC ACID has higher physical strength because of it and good biocompatibility, biological degradability and Bioabsorbable is widely used in many key areas.Often be used as surgical sutures, controlled drug delivery system, the fixing tissue engineering bracket material that reaches of orthopaedics at the medical field POLYACTIC ACID; It often is used as the added ingredients of makeup in daily field; At its wrapping material and agricultural mulching done commonly used of agriculture field.In addition, have chemical research quite a lot exploitation mechanism POLYACTIC ACID to be used for the degradative plastics field in the world in research, with this as one of outlet that solves the plastic waste pollution problem.
Rac-Lactide is preparation POLYACTIC ACID (Polylactic acid, important source material PLA).The POLYACTIC ACID of synthetic macromolecule quality needs the very high rac-Lactide of chemical purity.The method for preparing at present the high purity rac-Lactide is at first to prepare crude lactide, and then the refining high purity rac-Lactide that obtains.Concrete grammar is: the fs in reaction is the oligomeric stage, and lactic acid esterification dehydration is generated lactic acid oligomer, then the subordinate phase of reaction be the depolymerization stage with lactic acid oligomer catalytic degradation under comparatively high temps, obtain crude lactide.The crude lactide that makes obtains highly purified rac-Lactide because of containing after impurity such as lactic acid, lactic acid dimer, lactic acid tripolymer need pass through 3-5 recrystallization purifying.Patent US5053522, CN101585827, CN101157680 etc. describe in detail this.In addition, patent WO2005056509 has reported a kind of technology that adopts the rectificating method refined lactide.
The existing ubiquitous problem of method that prepare rac-Lactide is to be difficult to obtain simultaneously higher yield and purity preferably, is embodied in following three aspects:
First; In the oligomeric stage; The molecular mass of lactic acid oligomer need just be adapted at next stage cracking generation rac-Lactide in suitable scope (patent US4983745 thinks that lactic acid oligomer relative molecular mass optimum range is 400-2000, and that more suitable is 600-800; Patent US5801255 think suitable depolymerization be the lactic acid oligomer relative molecular mass of rac-Lactide at 400-2000, that more suitable is 1000-2000), be higher or lower than the yield that suitable scope all can influence cracking generation rac-Lactide in various degree.At present viewpoint is thought the lactic acid oligomer that will seek out suitable molecular weight, temperature of reaction and reaction times that must the oligomeric stage of control.Temperature of reaction will be controlled at 120-150 ℃ specifically, and the time in reaction times generally is controlled to be 2-3 hour.Too high temperature of reaction and longer reaction times all can promote the polymerization of lactic acid oligomer, form the bigger polymkeric substance of relative molecular mass.That is to say in oligomerization stage; In order to obtain the lactic acid oligomer of suitable molecular weight; People can't remove the water that the lactic acid esterification generates through rising temperature of reaction, the method in prolongation reaction times; Thereby can't improve the transformation efficiency of lactic acid in the oligomerization, also just can't reduce the content of water and free lactic acid in the reaction system.Can together leave reaction system with the rac-Lactide that generates at depolymerization stage water and lactic acid, become the impurity that remains in the rac-Lactide.
The second, in the depolymerization stage, in order to guarantee the yield of rac-Lactide, reaction vacuum tightness need be less than 1KPa, and temperature of reaction need be controlled at 220-240 ℃, is below or above this TR the yield of rac-Lactide is descended.Therefore in the final stage of lactic acid oligomer depolymerization, the lactic acid dimer that is difficult to further depolymerization, lactic acid tripolymer can together leave reaction system with the rac-Lactide that generates under the depolymerization condition of high temperature, low vacuum, become the impurity that remains in the rac-Lactide.
The 3rd, in the purification phase of rac-Lactide, though use recrystallization method or the rectificating method can the purifying rac-Lactide, all there be deficiency in these two kinds of methods.Use recrystallization method purifying rac-Lactide, crude lactide need pass through recrystallization 3-5 time usually, when improving rac-Lactide purity, significantly reduced the yield of reaction, and the recrystallization of continuous several times has also promoted the cost of industrial-scale production rac-Lactide.Rectification method purifying rac-Lactide is that the steam product stream that generates after the lactic acid oligomer cracking is delivered to rectifying tower, utilizes water, lactic acid, and rac-Lactide, lactic acid dimer, the difference of lactic acid tripolymer boiling point realizes the purifying to rac-Lactide.But this method is very high to the requirement of conversion unit, has increased the production cost of rac-Lactide equally.
Summary of the invention
Technical problem to be solved by this invention provides the technology that a kind of novel fixed acid legal system is equipped with rac-Lactide.
For solving the problems of the technologies described above, thinking of the present invention is following:
(1) for the relative molecular mass with lactic acid oligomer is controlled in the scope of suitable depolymerization, the contriver attempts, and introduces the higher-boiling compound that has hydroxyl or amino in the structure and controls oligomeric stage lactic acid oligomer relative molecular mass.Concrete principle is: in reaction system, add the higher-boiling compound with hydroxyl or amino, utilize the carboxyl of its hydroxyl or amino and lactic acid oligomer molecule to react, form ester bond or peptide bond.So just can fix the carboxyl terminal of lactic acid oligomer molecule, make the molecular weight of lactic acid oligomer can in reaction process, sharply not increase.Next just the molecular mass of lactic acid oligomer is controlled in the scope of suitable depolymerization through the ratio of adjustment higher-boiling compound with the molar weight of lactic acid material.In reaction process, just can make full use of the rising temperature of reaction, prolong the method in reaction times and remove the water that the lactic acid esterification generates; The content of water and free lactic acid in the reduction reaction system; The final content that reduces water and lactic acid in the rac-Lactide has improved the purity of rac-Lactide.
(2) final stage of lactic acid oligomer depolymerization; The lactic acid dimer that is difficult to further depolymerization; The lactic acid tripolymer is because its carboxyl terminal is fixed on the hydroxyl of the higher-boiling compound with hydroxyl or amino, and vacuum tightness and 220-250 ℃ of such cracking condition of being difficult in less than 1KPa leave reaction system with the rac-Lactide that generates down together, thereby have reduced lactic acid dimer in the resultant rac-Lactide; The trimerical content of lactic acid has improved the purity of rac-Lactide.
Concrete technical scheme is following:
A kind of fixed acid legal system is equipped with the technology of rac-Lactide, and it comprises the steps:
(1) be that 250 ~ 550 ℃ hydroxyl or poly-hydroxy or polyamino compound and lactic acid is under the catalyzer existence condition with boiling point; Control pressure is at 2 ~ 3.0KPa; In 1.5 ~ 3h, be warming up to 160 ℃ gradually by 90 ℃; Re-adjustment pressure is 0.5 ~ 0.8KPa, and temperature is that 170 ~ 180 ℃ of continuation reaction 5 ~ 7h obtain high boiling point hydroxyl or poly-hydroxy or polyamino lactic acid oligomer;
(2) high boiling point hydroxyl that step (1) is obtained or poly-hydroxy or polyamino lactic acid oligomer are under 180 ~ 230 ℃, 0.4-0.8KPa condition, and scission reaction obtains rac-Lactide.
In the step (1); Described boiling point is that 250 ~ 550 ℃ hydroxyl or poly-hydroxy or polyamino compound is tetramethylolmethane, nucite, D-sorbyl alcohol, 1,4-anhydrous sorbitol, Xylitol, D-wood sugar, D-pectinose, D-ribose, D-fructose, sucrose, '-bis (hydroxymethyl) biphenyl or N-diphenyl-para-phenylene diamine.
In the step (1), described lactic acid is D, L-lactic acid, L-lactic acid or D-lactic acid.
In the step (1), described catalyzer is stannous octoate, zinc oxide, zinc acetate or tin protochloride.
In the step (1), the mass ratio of catalyzer and lactic acid is 1:20 ~ 500.
In the step (1), described boiling point is that 250 ~ 550 ℃ the hydroxyl or the mol ratio of poly-hydroxy or polyamino compound and lactic acid are 1:10 ~ 150.
In the step (1), the number-average molecular weight scope of high boiling point hydroxyl or poly-hydroxy or polyamino lactic acid oligomer is 1000 ~ 13000.Wherein, each ramose number-average molecular weight scope is 300 ~ 2200.
In the step (1), high boiling point hydroxyl for preparing or poly-hydroxy or polyamino lactic acid oligomer contain following hydroxyl lactic acid oligomer chain end structural unit, and structural formula is following:
In the step (2), the scission reaction time is 40min ~ 80min.
Beneficial effect: innovative point of the present invention is:
(1) through having the higher-boiling compound of hydroxyl or amino and the ratio of the molar weight of lactic acid material, control lactic acid oligomer depolymerization the righttest required molecular weight in the adjustment structure.
(2) in the final stage of depolymerization, fix lactic acid dimer and tripolymer, improved the purity of rac-Lactide through the higher-boiling compound that has hydroxyl or amino in the structure.
Embodiment
According to following embodiment, can understand the present invention better.Yet, those skilled in the art will readily understand that the described content of embodiment only is used to explain the present invention, and the present invention that should also can not limit in claims to be described in detail.
Embodiment 1
, churned mechanically three-necked bottle adds 100.0g 85wt%D in being housed, and the L-lactic acid aqueous solution (contain 85g D, L-lactic acid, 0.944mol), 7.3g (0.0536mol) tetramethylolmethane and 2.0g zinc acetate; Place 90 ℃ of oil baths, be evacuated to 3.0KPa, keep this vacuum state; 2.0 temperature at the uniform velocity is warming up to 160.0 ℃ by 90 ℃ in hour, then vacuum tightness is risen to 0.5KPa, temperature rises to 180.0 ℃; React with this understanding and obtained oligopolymer in 5.0 hours, keep vacuum tightness 0.5KPa, temperature rises to 230.0 ℃ gradually by 180.0 ℃ and carries out scission reaction; Scission reaction total time is 40min, collects to obtain 63.4g rac-Lactide, yield 93.2%.Analyze through the performance liquid chromatography normalization method, purity is 96.9%.
Embodiment 2
, churned mechanically three-necked bottle adds 100.0g 85wt%D in being housed, and the L-lactic acid aqueous solution (contain 85g D, L-lactic acid, 0.944mol), 1.4g (0.00777mol) nucite and 0.50g zinc acetate; Place 90 ℃ of oil baths, be evacuated to 3.0KPa, keep this vacuum state; 3.0 temperature at the uniform velocity is warming up to 160.0 ℃ by 90 ℃ in hour, then vacuum tightness is risen to 0.5KPa, temperature rises to 180.0 ℃; React with this understanding and obtained oligopolymer in 5.0 hours, keep vacuum tightness 0.5KPa, temperature rises to 230.0 ℃ gradually by 180.0 ℃ and carries out scission reaction; Scission reaction total time is 60min, collects to obtain 63.54g rac-Lactide, yield 93.4%.Analyze through the performance liquid chromatography normalization method, purity is 97.3%.
Embodiment 3
, churned mechanically three-necked bottle adds 100.0g 85wt%D in being housed, and the L-lactic acid aqueous solution (contain 85g D, L-lactic acid, 0.944mol), 4.8g (0.0292mol) 1; 4-anhydrate sorbyl alcohol and 2.2g zinc acetate place 90 ℃ of oil baths, are evacuated to 3.0KPa, keep this vacuum state; 2.0 temperature at the uniform velocity is warming up to 160.0 ℃ by 90 ℃ in hour, then vacuum tightness is risen to 0.5KPa, temperature rises to 180.0 ℃; React with this understanding and obtained oligopolymer in 5.0 hours, keep vacuum tightness 0.5KPa, temperature rises to 230.0 ℃ gradually by 180.0 ℃ and carries out scission reaction; Scission reaction total time is 80min, collects to obtain 65.6g rac-Lactide, yield 96.4%.Analyze through the performance liquid chromatography normalization method, purity is 97.7%.
Embodiment 4
, churned mechanically three-necked bottle adds 100.0g 85wt%D in being housed, and the L-lactic acid aqueous solution (contain 85g D, L-lactic acid, 0.944mol), 17.3g (0.0939mol) N-diphenyl-para-phenylene diamine and 2.0g zinc oxide; Place 90 ℃ of oil baths, be evacuated to 3.0KPa, keep this vacuum state; 3.0 temperature at the uniform velocity is warming up to 160.0 ℃ by 90 ℃ in hour, then vacuum tightness is risen to 0.5KPa, temperature rises to 180.0 ℃; React with this understanding and obtained oligopolymer in 6.0 hours, keep vacuum tightness 0.5KPa, temperature rises to 230.0 ℃ gradually by 180.0 ℃ and carries out scission reaction; Scission reaction total time is 80min, collects to obtain 63.06g rac-Lactide, yield 92.7%.Analyze through the performance liquid chromatography normalization method, purity is 96.1%.
Embodiment 5
, churned mechanically three-necked bottle adds 100.0g 85wt%D in being housed, and the L-lactic acid aqueous solution (contain 85g D, L-lactic acid, 0.944mol), 5.7g (0.0313mol) D-sorbyl alcohol and 2.0g tin protochloride; Place 90 ℃ of oil baths, be evacuated to 3.0KPa, keep this vacuum state; 2.0 temperature at the uniform velocity is warming up to 160.0 ℃ by 90 ℃ in hour, then vacuum tightness is risen to 0.5KPa, temperature rises to 180.0 ℃; React with this understanding and obtained oligopolymer in 5.0 hours, keep vacuum tightness 0.5KPa, temperature rises to 230.0 ℃ gradually by 180.0 ℃ and carries out scission reaction; Scission reaction total time is 80min, collects to obtain 64.5g rac-Lactide, yield 94.8%.Analyze through the performance liquid chromatography normalization method, purity is 93.5%.
Embodiment 6
, churned mechanically three-necked bottle adds 100.0g 85wt%D in being housed, and the L-lactic acid aqueous solution (contain 85g D, L-lactic acid, 0.944mol), 6.0g (0.0394mol) Xylitol and 2.0g tin protochloride; Place 90 ℃ of oil baths, be evacuated to 3.0KPa, keep this vacuum state; 2.0 temperature at the uniform velocity is warming up to 160.0 ℃ by 90 ℃ in hour, then vacuum tightness is risen to 0.5KPa, temperature rises to 180.0 ℃; React with this understanding and obtained oligopolymer in 6.0 hours, keep vacuum tightness 0.5KPa, temperature rises to 230.0 ℃ gradually by 180.0 ℃ and carries out scission reaction; Scission reaction total time is 80min, collects to obtain 63.8g rac-Lactide, yield 93.9%.Analyze through the performance liquid chromatography normalization method, purity is 98.6%.
Embodiment 7
, churned mechanically three-necked bottle adds 100.0g 85wt%D in being housed, and the L-lactic acid aqueous solution (contain 85g D, L-lactic acid, 0.944mol), 5.5g (0.0366mol) D-wood sugar and 2.0g tin protochloride; Place 90 ℃ of oil baths, be evacuated to 3.0KPa, keep this vacuum state; 2.0 temperature at the uniform velocity is warming up to 160.0 ℃ by 90 ℃ in hour, then vacuum tightness is risen to 0.5KPa, temperature rises to 180.0 ℃; React with this understanding and obtained oligopolymer in 5.0 hours, keep vacuum tightness 0.5KPa, temperature rises to 230.0 ℃ gradually by 180.0 ℃ and carries out scission reaction; Scission reaction total time is 80min, collects to obtain 62.9g rac-Lactide, yield 92.5%.Analyze through the performance liquid chromatography normalization method, purity is 93.8%.
Embodiment 8
, churned mechanically three-necked bottle adds 100.0g 85wt%D in being housed, and the L-lactic acid aqueous solution (contain 85g D, L-lactic acid, 0.944mol), 5.5g (0.0366mol) D-pectinose and 2.0g tin protochloride; Place 90 ℃ of oil baths, be evacuated to 3.0KPa, keep this vacuum state; 2.0 temperature at the uniform velocity is warming up to 160.0 ℃ by 90 ℃ in hour, then vacuum tightness is risen to 0.5KPa, temperature rises to 180.0 ℃; React with this understanding and obtained oligopolymer in 5.0 hours, keep vacuum tightness 0.5KPa, temperature rises to 230.0 ℃ gradually by 180.0 ℃ and carries out scission reaction; Scission reaction total time is 80min, collects to obtain 64.9g rac-Lactide, yield 95.5%.Analyze through the performance liquid chromatography normalization method, purity is 95.1%.
Embodiment 9
, churned mechanically three-necked bottle adds 100.0g 85wt%D in being housed, and the L-lactic acid aqueous solution (contain 85g D, L-lactic acid, 0.944mol), 5.5g (0.0366mol) D-ribose and 2.0g tin protochloride; Place 90 ℃ of oil baths, be evacuated to 3.0KPa, keep this vacuum state; 2.0 temperature at the uniform velocity is warming up to 160.0 ℃ by 90 ℃ in hour, then vacuum tightness is risen to 0.5KPa, temperature rises to 180.0 ℃; React with this understanding and obtained oligopolymer in 5.0 hours, keep vacuum tightness 0.5KPa, temperature rises to 230.0 ℃ gradually by 180.0 ℃ and carries out scission reaction; Scission reaction total time is 80min, collects to obtain 61.9g rac-Lactide, yield 91.0%.Analyze through the performance liquid chromatography normalization method, purity is 92.7%.
Embodiment 10
, churned mechanically three-necked bottle adds 100.0g 85wt%D in being housed, and the L-lactic acid aqueous solution (contain 85g D, L-lactic acid, 0.944mol), 7.0g (0.0388mol) D-fructose and 2.0g tin protochloride; Place 90 ℃ of oil baths, be evacuated to 3.0KPa, keep this vacuum state; 2.0 temperature at the uniform velocity is warming up to 160.0 ℃ by 90 ℃ in hour, then vacuum tightness is risen to 0.5KPa, temperature rises to 180.0 ℃; React with this understanding and obtained oligopolymer in 5.0 hours, keep vacuum tightness 0.5KPa, temperature rises to 230.0 ℃ gradually by 180.0 ℃ and carries out scission reaction; Scission reaction total time is 60min, collects to obtain 64.08g rac-Lactide, yield 94.2%.Analyze through the performance liquid chromatography normalization method, purity is 93.1%.
Embodiment 11
, churned mechanically three-necked bottle adds 100.0g 85wt%D in being housed, and the L-lactic acid aqueous solution (contain 85g D, L-lactic acid, 0.944mol), 6.5g (0.019mol) sucrose and 2.0g tin protochloride; Place 90 ℃ of oil baths, be evacuated to 3.0KPa, keep this vacuum state; 2.0 temperature at the uniform velocity is warming up to 160.0 ℃ by 90 ℃ in hour, then vacuum tightness is risen to 0.5KPa, temperature rises to 180.0 ℃; React with this understanding and obtained oligopolymer in 5.0 hours, keep vacuum tightness 0.5KPa, temperature rises to 230.0 ℃ gradually by 180.0 ℃ and carries out scission reaction; Scission reaction total time is 60min, collects to obtain 64.63g rac-Lactide, yield 95.0%.Analyze through the performance liquid chromatography normalization method, purity is 93.3%.
Embodiment 12
, churned mechanically three-necked bottle adds 100.0g 85wt%D in being housed, and the L-lactic acid aqueous solution (contain 85g D, L-lactic acid, 0.944mol), 16.8g '-bis (hydroxymethyl) biphenyl (0.0784mol) and 1.5g stannous octoate; Place 90 ℃ of oil baths, be evacuated to 3.0KPa, keep this vacuum state; 1.5 temperature at the uniform velocity is warming up to 160.0 ℃ by 90 ℃ in hour, then vacuum tightness is risen to 0.5KPa, temperature rises to 180.0 ℃; React with this understanding and obtained oligopolymer in 5.0 hours, keep vacuum tightness 0.5KPa, temperature rises to 230.0 ℃ gradually by 180.0 ℃ and carries out scission reaction; Scission reaction total time is 60min, collects to obtain 64.42g rac-Lactide, yield 94.7%.Analyze through the performance liquid chromatography normalization method, purity is 98.4%.
Claims (7)
1. a fixed acid legal system is equipped with the technology of rac-Lactide, it is characterized in that it comprises the steps:
(1) be that 250 ~ 550 ℃ hydroxyl or poly-hydroxy or polyamino compound and lactic acid is under the catalyzer existence condition with boiling point; Control pressure is at 2 ~ 3.0KPa; In 1.5 ~ 3h, be warming up to 160 ℃ gradually by 90 ℃; Re-adjustment pressure is 0.5 ~ 0.8KPa, and temperature is that 170 ~ 180 ℃ of continuation reaction 5 ~ 7h obtain high boiling point hydroxyl or poly-hydroxy or polyamino lactic acid oligomer;
(2) high boiling point hydroxyl that step (1) is obtained or poly-hydroxy or polyamino lactic acid oligomer are under 180 ~ 230 ℃, 0.4-0.8KPa condition, and scission reaction obtains rac-Lactide.
2. fixed acid legal system according to claim 1 is equipped with the technology of rac-Lactide; It is characterized in that; In the step (1); Described boiling point is that 250 ~ 550 ℃ hydroxyl or poly-hydroxy or polyamino compound is tetramethylolmethane, nucite, D-sorbyl alcohol, 1,4-anhydrous sorbitol, Xylitol, D-wood sugar, D-pectinose, D-ribose, D-fructose, sucrose, '-bis (hydroxymethyl) biphenyl or N-diphenyl-para-phenylene diamine.
3. fixed acid legal system according to claim 1 is equipped with the technology of rac-Lactide, it is characterized in that, in the step (1), described lactic acid is D, L-lactic acid, L-lactic acid or D-lactic acid.
4. fixed acid legal system according to claim 1 is equipped with the technology of rac-Lactide, it is characterized in that, in the step (1), described catalyzer is stannous octoate, zinc oxide, zinc acetate or tin protochloride.
5. be equipped with the technology of rac-Lactide according to claim 1 or 4 described fixed acid legal systems, it is characterized in that in the step (1), the mass ratio of catalyzer and lactic acid is 1:20 ~ 500.
6. fixed acid legal system according to claim 1 is equipped with the technology of rac-Lactide, it is characterized in that, in the step (1), described boiling point is that 250 ~ 550 ℃ the hydroxyl or the mol ratio of poly-hydroxy or polyamino compound and lactic acid are 1:10 ~ 150.
7. fixed acid legal system according to claim 1 is equipped with the technology of rac-Lactide, it is characterized in that, in the step (2), the scission reaction time is 40min～80min.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105324A (en) * | 2019-06-10 | 2019-08-09 | 南京大学 | The method that zinc Isoocatanoate catalyzes and synthesizes lactide |
| CN110563695A (en) * | 2019-09-22 | 2019-12-13 | 苏州格里克莱新材料有限公司 | Preparation method of mixture of glycolide and lactide |
| CN110951065A (en) * | 2014-12-19 | 2020-04-03 | 三菱化学株式会社 | Polycarbonate resin |
| CN111892571A (en) * | 2020-08-28 | 2020-11-06 | 浙江海正生物材料股份有限公司 | Method for preparing lactide |
| CN113416134A (en) * | 2021-07-27 | 2021-09-21 | 重庆大学 | Lactic acid oligomer and preparation method and application thereof |
| CN114315788A (en) * | 2021-12-29 | 2022-04-12 | 普立思生物科技有限公司 | Preparation method of lactide |
| CN114773310A (en) * | 2022-04-20 | 2022-07-22 | 长兴电子（苏州）有限公司 | Method for synthesizing optically pure lactide by composite catalysis method |
| CN115745947A (en) * | 2022-11-23 | 2023-03-07 | 华东理工大学 | Preparation method of L-lactide |
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| CN101108844A (en) * | 2007-07-10 | 2008-01-23 | 南京工业大学 | Method for manufacturing lactide with polyhydroxy lactic acid oligomer |
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| US5053522A (en) * | 1987-03-19 | 1991-10-01 | Boehringer Ingelheim Kg | Process for the preparation of lactide |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110951065A (en) * | 2014-12-19 | 2020-04-03 | 三菱化学株式会社 | Polycarbonate resin |
| CN110105324A (en) * | 2019-06-10 | 2019-08-09 | 南京大学 | The method that zinc Isoocatanoate catalyzes and synthesizes lactide |
| CN110563695A (en) * | 2019-09-22 | 2019-12-13 | 苏州格里克莱新材料有限公司 | Preparation method of mixture of glycolide and lactide |
| CN111892571A (en) * | 2020-08-28 | 2020-11-06 | 浙江海正生物材料股份有限公司 | Method for preparing lactide |
| CN113416134A (en) * | 2021-07-27 | 2021-09-21 | 重庆大学 | Lactic acid oligomer and preparation method and application thereof |
| CN114315788A (en) * | 2021-12-29 | 2022-04-12 | 普立思生物科技有限公司 | Preparation method of lactide |
| CN114773310A (en) * | 2022-04-20 | 2022-07-22 | 长兴电子（苏州）有限公司 | Method for synthesizing optically pure lactide by composite catalysis method |
| CN115745947A (en) * | 2022-11-23 | 2023-03-07 | 华东理工大学 | Preparation method of L-lactide |
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| CN102775380B (en) | 2014-12-31 |
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Inventor after: Tang Shigui Inventor after: Guo Kai Inventor after: Jiang Yunchen Inventor after: Gan Haifeng Inventor after: Wei Ping Inventor after: Sun Yanlong Inventor before: Tang Shigui Inventor before: Guo Kai Inventor before: Gan Haifeng Inventor before: Wei Ping Inventor before: Jiang Yunchen Inventor before: Sun Yanlong |
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Effective date of registration: 20160922 Address after: Spark Road high tech Development Zone Nanjing city Jiangsu province 210032 No. 10 Dingye gestos biological building block A room 1014 Patentee after: Nanjing Hi Tech Institute of Biotechnology Research Co Ltd Address before: 210009 Nanjing City, Jiangsu Province, the new model road No. 5 Patentee before: Nanjing University of Technology |