CN112028869B - Method for synthesizing lactide in one step - Google Patents
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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Abstract
The invention discloses a method for synthesizing lactide in one step, which is characterized in that lactate ester is taken as a raw material, a tin-containing molecular sieve is taken as a catalyst, the lactide is synthesized by a gas-phase normal-pressure one-step method, the conversion rate of the lactate ester in the reaction can reach more than 98 percent, and the selectivity of the lactide is more than 92 percent. Compared with the traditional synthesis method which takes lactic acid as a raw material and carries out condensation polymerization and depolymerization after dehydration, the method has mild reaction conditions, simple process and continuous operation, does not need high vacuum and high boiling point solvent, and compared with the conventional metal compound catalyst, the tin-containing molecular sieve used in the method is safe, environment-friendly and recyclable, and is more suitable for the industrial production of lactide.
Description
Technical Field
The invention relates to a method for synthesizing lactide in one step, belonging to the field of catalytic reaction.
Background
Polylactic acid (PLA) has excellent biocompatibility and biodegradability. Polylactic acid and its copolymer are widely used in the field of biological materials, especially as tissue engineering scaffold materials, drug release materials and fracture internal fixation members, and are receiving attention from people. At present, the synthesis method of PLA mainly comprises a one-step method and a two-step method: the one-step method is to directly synthesize PLA by taking lactic acid, lactate and derivatives thereof as raw materials, but the synthesized PLA has low molecular weight, poor strength and low practical application value; the two-step method is to carry out polycondensation-depolymerization on the raw materials to obtain lactide, and carry out ring-opening polymerization on the refined and purified monomer to obtain PLA.
Lactide, which is an intermediate in the synthesis of polylactic acid and copolymers thereof, is also gaining attention as a biomedical material. Therefore, an important approach is to solve the problem of large-scale synthesis of lactide. The most common methods for preparing lactide are: firstly, lactic acid is directly polycondensed at low temperature under the action of catalyst to obtain oligolactic acid, then the lactic acid oligomer is depolymerized at higher temperature to produce lactide, and according to the mode of removing small molecular by-product water, the method can be divided into reduced pressure method and normal pressure gas flow method, and the patents CN100417652C, CN101585827A, CN101747314B, CN1951933A and CN104710401A, etc. all adopt said method, but because of the property of lactic acid, the raw material lactic acid must be dewatered before reaction. In order to simplify the reaction steps, the reaction may be carried out by using a lactic acid ester as a starting material.
The lactide synthesis method needs two steps, and in order to further simplify the process steps, the one-step lactide synthesis method has become a research hotspot in recent years. In the patent CN108610323A, lactic acid is used as a raw material, an H-beta molecular sieve is used as a catalyst, and lactide is synthesized by a one-step method under a reduced pressure condition; patents CN111039918A and CN101891733B disclose a one-step method for synthesizing lactide by using lactate as raw material and metal oxide as carrier for co-catalysis, but both use a large flow of nitrogen to vaporize the raw material and perform the reaction under reduced pressure.
In conclusion, the one-step synthesis of lactide by using a catalyst with excellent performance and a relatively simple and easy synthesis process is the target of the large-scale industrial production of lactide.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for synthesizing lactide, which takes a tin-containing molecular sieve as a catalyst and continuously synthesizes the lactide by a gas-phase normal-pressure one-step method, thereby simplifying the lactide synthesis process.
The invention aims to provide a method for preparing lactide with high conversion rate and high selectivity.
The invention discloses a method for synthesizing lactide in one step, which takes lactate as a raw material and a tin-containing molecular sieve as a catalyst, synthesizes the lactide in a gas phase and normal pressure one-step method, and comprises the following specific processes: firstly, heating and vaporizing lactate, and introducing the gaseous lactate into a reactor filled with a tin-containing molecular sieve catalyst for cyclization reaction to obtain the product lactide.
Further, in the technical scheme, the tin-containing molecular sieve is one or a mixture of more of Sn-Beta, Sn-MOR, Sn-ZSM-22, Sn-ZSM-35 and Sn-ZSM-5.
Further, in the above technical solution, the crystallinity of the tin-containing molecular sieve is greater than 95%, and the silica-alumina ratio is 2000-.
Further, in the above technical solution, the grain size of the tin-containing molecular sieve is 3000nm, preferably 1000nm and 100 nm.
Further, in the above technical solution, the content of tin in the tin-containing molecular sieve is 0.2-4%, preferably 1-2%.
Further, in the above embodiment, the lactate ester is methyl lactate, ethyl lactate, propyl lactate, or butyl lactate, and methyl lactate and ethyl lactate are preferable.
Further, in the above technical solution, the lactate may be L-lactate, D-lactate, or D, L-lactate.
Further, in the technical scheme, the vaporization temperature of the lactate is 150-.
Further, in the above technical scheme, the cyclization reaction temperature is 180-.
Further, in the above technical means, the catalyst and the raw material are subjected to a gas phase contact reaction, and a fixed bed, a fluidized bed, a moving bed, a boiling bed or an expanded bed may be used.
The invention provides a method for synthesizing polylactic acid, which takes lactate as a raw material and a tin-containing molecular sieve as a catalyst to synthesize lactide by a gas-phase normal-pressure one-step method, and comprises the following specific processes: firstly heating and vaporizing lactate, feeding the gaseous lactate into a reactor filled with a tin-containing molecular sieve catalyst for cyclization reaction to obtain lactide product, purifying the lactide, and polymerizing the lactide into a product with a relative weight average molecular weight of more than 2 x 10 under the action of a ring-opening polymerization catalyst5The polylactic acid has the polymerization catalyst of stannous octoate, stannous acetate or alkyl aluminum, the polymerization reaction temperature is 130-180 ℃, the reaction pressure is 100-300KPa, the reaction time is 2-6h, and the catalyst dosage is 250-600 mu g/g.
Further, in the technical scheme, the tin-containing molecular sieve is one or a mixture of more of Sn-Beta, Sn-MOR, Sn-ZSM-22, Sn-ZSM-35 and Sn-ZSM-5.
Further, in the above technical solution, the crystallinity of the tin-containing molecular sieve is greater than 95%, and the silica-alumina ratio is 2000-.
Further, in the above technical solution, the grain size of the tin-containing molecular sieve is 3000nm, preferably 1000nm and 100 nm.
Further, in the above technical solution, the content of tin in the tin-containing molecular sieve is 0.2-4%, preferably 1-2%.
Further, in the above embodiment, the lactate ester is methyl lactate, ethyl lactate, propyl lactate, or butyl lactate, and methyl lactate and ethyl lactate are preferable.
Further, in the above technical solution, the lactate may be L-lactate, D-lactate, or D, L-lactate.
Further, in the technical scheme, the vaporization temperature of the lactate is 150-.
Further, in the above technical scheme, the cyclization reaction temperature is 180-.
Further, in the above technical means, the catalyst and the raw material are subjected to a gas phase contact reaction, and a fixed bed, a fluidized bed, a moving bed, a boiling bed or an expanded bed may be used.
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The invention is further described with reference to the following figures and examples.
FIG. 1 is a mass spectrum of lactide synthesized in example 7.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the illustrated examples.
The lactate is selected from any commercially available reagent, requiring a purity of no less than 98%; the tin-containing molecular sieve of the catalyst is self-made or commercially available, and the relative crystallinity of the tin-containing molecular sieve is required to be more than 95 percent.
For the purpose of better illustrating the present invention, the preparation of the tin-containing molecular sieve is set forth, but is not limited to the tin-containing molecular sieve prepared by the following method.
The synthesis method of the tin-containing molecular sieve comprises the following steps: taking a tin-free molecular sieve as a raw material, performing acid treatment and dealumination, taking anhydrous stannic chloride as a tin source, performing gas phase treatment for 6-24h at the temperature of 450-plus-material and 700 ℃, washing, drying and roasting to obtain raw powder of the tin-containing molecular sieve, uniformly mixing the raw powder and sesbania powder, adding a binder, further uniformly mixing, extruding into strips by a strip extruding machine for molding, drying the molded sample at the temperature of 100 ℃ for 12h, and roasting to obtain the strip-shaped tin-containing molecular sieve.
Example 1
The tin-containing molecular sieve Sn-Beta (tin content: 1.7%, silica-alumina ratio: 3000) catalyst is sieved into 20-40 mesh particles, 4g of the catalyst is filled into the middle section of a fixed bed reaction tube, inert quartz sand is filled at two ends of the reaction tube, the vaporization temperature of L-methyl lactate is 220 ℃, the reaction temperature is 240 ℃, the feeding amount of L-methyl lactate is 12g/h, the reaction is carried out under normal pressure, and the reaction result is shown in Table 1.
Example 2
The tin-containing molecular sieve Sn-Beta (tin content: 1.7%, silica-alumina ratio: 3000) catalyst is sieved into 20-40 mesh particles, 4g of the catalyst is filled into the middle section of a fixed bed reaction tube, inert quartz sand is filled at two ends of the reaction tube, the vaporization temperature of L-methyl lactate is 260 ℃, the reaction temperature is 240 ℃, the feeding amount of L-methyl lactate is 12g/h, the reaction is carried out under normal pressure, and the reaction result is shown in Table 1.
Example 3
The tin-containing molecular sieve Sn-Beta (tin content: 1.7%, silica-alumina ratio: 3000) catalyst is sieved into 20-40 mesh particles, 4g of the catalyst is filled into the middle section of a fixed bed reaction tube, inert quartz sand is filled at two ends of the reaction tube, the vaporization temperature of L-methyl lactate is 220 ℃, the reaction temperature is 220 ℃, the feeding amount of L-methyl lactate is 12g/h, the reaction is carried out under normal pressure, and the reaction result is shown in Table 1.
Example 4
The tin-containing molecular sieve Sn-Beta (tin content: 1.7%, silica-alumina ratio: 3000) catalyst is sieved into 20-40 mesh particles, 4g of the catalyst is filled into the middle section of a fixed bed reaction tube, inert quartz sand is filled at two ends of the reaction tube, the vaporization temperature of L-methyl lactate is 220 ℃, the reaction temperature is 280 ℃, the feeding amount of L-methyl lactate is 12g/h, the reaction is carried out under normal pressure, and the reaction result is shown in Table 1.
Example 5
The tin-containing molecular sieve Sn-Beta (tin content: 1.7%, silica-alumina ratio: 3000) catalyst is sieved into 20-40 mesh particles, 4g of the catalyst is filled into the middle section of a fixed bed reaction tube, inert quartz sand is filled at two ends of the reaction tube, the vaporization temperature of L-methyl lactate is 220 ℃, the reaction temperature is 240 ℃, the feeding amount of L-methyl lactate is 6g/h, the reaction is carried out under normal pressure, and the reaction result is shown in Table 1.
Example 6
The tin-containing molecular sieve Sn-Beta (tin content: 1.7%, silica-alumina ratio: 3000) catalyst is sieved into 20-40 mesh particles, 4g of the catalyst is filled into the middle section of a fixed bed reaction tube, inert quartz sand is filled at two ends of the reaction tube, the vaporization temperature of L-methyl lactate is 220 ℃, the reaction temperature is 240 ℃, the feeding amount of L-methyl lactate is 12g/h, the reaction is carried out under normal pressure, and the reaction result is shown in Table 1.
Example 7
The tin-containing molecular sieve Sn-Beta (tin content: 1.7%, silica-alumina ratio: 3000) catalyst is sieved into particles of 20-40 meshes, 4g of the catalyst is filled into the middle section of a fixed bed reaction tube, inert quartz sand is filled at two ends of the reaction tube, the vaporization temperature of D, L-methyl lactate is 220 ℃, the reaction temperature is 240 ℃, the feeding amount of D, L-methyl lactate is 12g/h, the reaction is carried out under normal pressure, and the reaction result is shown in table 1. And (3) separating and purifying the material obtained by the reaction to obtain a product D, L-lactide, wherein the mass spectrum of the product is shown in the attached figure.
Example 8
The tin-containing molecular sieve Sn-Beta (tin content: 1.7%, silica-alumina ratio: 3000) catalyst is sieved into 20-40 mesh particles, 4g of the catalyst is filled into the middle section of a fixed bed reaction tube, inert quartz sand is filled at two ends of the reaction tube, the vaporization temperature of L-ethyl lactate is 220 ℃, the reaction temperature is 240 ℃, the feeding amount of L-ethyl lactate is 12g/h, the reaction is carried out under normal pressure, and the reaction result is shown in Table 1.
Example 9
The tin-containing molecular sieve Sn-Beta (tin content: 2.0%, silica-alumina ratio: 5000) catalyst is sieved into 20-40 mesh particles, 4g of the catalyst is filled into the middle section of a fixed bed reaction tube, inert quartz sand is filled at two ends of the reaction tube, the vaporization temperature of L-methyl lactate is 220 ℃, the reaction temperature is 240 ℃, the feeding amount of L-methyl lactate is 12g/h, the reaction is carried out under normal pressure, and the reaction result is shown in table 1.
Example 10
The tin-containing molecular sieve Sn-MOR (tin content: 1.8%, silica-alumina ratio: 3200) catalyst is sieved into 20-40 mesh particles, 4g of the catalyst is filled into the middle section of a fixed bed reaction tube, inert quartz sand is filled at two ends of the reaction tube, the vaporization temperature of L-methyl lactate is 220 ℃, the reaction temperature is 240 ℃, the feeding amount of L-methyl lactate is 12g/h, the reaction is carried out under normal pressure, and the reaction result is shown in Table 1.
Example 11
The tin-containing molecular sieve Sn-ZSM-35 (tin content: 1.7%, silica alumina ratio: 3000) catalyst was sieved into 20-40 mesh particles, 4g of the catalyst was loaded into the middle section of a fixed bed reaction tube, inert quartz sand was loaded into both ends of the reaction tube, the L-methyl lactate vaporization temperature was 220 ℃, the reaction temperature was 240 ℃, the L-methyl lactate feed amount was 12g/h, the reaction was carried out at normal pressure, and the reaction results are shown in Table 1.
Example 12
Screening Sn-ZSM-5 (with tin content of 2.0% and silica-alumina ratio of 4000) catalyst containing tin molecular sieve into 20-40 mesh particles, filling 4g of catalyst into the middle section of a fixed bed reaction tube, filling inert quartz sand into two ends of the reaction tube, carrying out reaction at normal pressure, wherein the vaporization temperature of L-methyl lactate is 220 ℃, the reaction temperature is 240 ℃, the feeding amount of L-methyl lactate is 12g/h, and the reaction result is shown in Table 1
Example 13
Preparing polylactic acid: dissolving 0.012g stannous octoate in petroleum ether, adding the dissolved stannous octoate and 30g lactide prepared in the embodiment into a stainless steel reaction kettle, evacuating the kettle for at least three times by using nitrogen, vacuumizing for 0.5h under stirring to remove the petroleum ether, raising the temperature to 160 ℃, timing, keeping the reaction pressure at 200KPa, stopping the reaction after 5h to obtain polylactic acid, and measuring the relative weight-average molecular weight of the polylactic acid by a Gel Permeation Chromatograph (GPC) to be 2.77 multiplied by 105。
The above-mentioned embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
TABLE 1 results of the reaction
Claims (13)
1. A method for synthesizing lactide in one step is characterized in that lactate is taken as a raw material, a tin-containing molecular sieve is taken as a catalyst, and the lactide is synthesized in a gas phase normal pressure one-step method, which comprises the following specific steps: firstly, heating and vaporizing lactate, and enabling gaseous lactate to enter a reactor filled with a tin-containing molecular sieve catalyst for cyclization reaction to obtain a product lactide;
the synthesis method of the tin-containing molecular sieve comprises the following steps: taking a tin-free molecular sieve as a raw material, performing acid treatment and dealumination, taking anhydrous stannic chloride as a tin source, performing gas phase treatment for 6-24h at the temperature of 450-plus-material and 700 ℃, washing, drying and roasting to obtain raw powder of the tin-containing molecular sieve, uniformly mixing the raw powder and sesbania powder, adding a binder, further uniformly mixing, extruding the mixture into strips by using a strip extruding machine for molding, drying the molded sample at the temperature of 100 ℃ for 12h, and roasting to obtain the strip-shaped tin-containing molecular sieve;
the tin-containing molecular sieve is one or a mixture of Sn-Beta, Sn-MOR, Sn-ZSM-22, Sn-ZSM-35 and Sn-ZSM-5.
2. The method as claimed in claim 1, wherein the tin-containing molecular sieve has a crystallinity of greater than 95% and a silica to alumina ratio of 2000-.
3. The method as claimed in claim 1, wherein the tin-containing molecular sieve has a grain size of 100-3000 nm.
4. The method as claimed in claim 1, wherein the tin-containing molecular sieve has a grain size of 200-1000 nm.
5. The method of claim 1, wherein the tin content of the tin-containing molecular sieve is from 0.2% to 4%.
6. The method of claim 1, wherein the tin content of the tin-containing molecular sieve is 1-2%.
7. The method according to claim 1, wherein the lactate is methyl lactate, ethyl lactate, propyl lactate, or butyl lactate.
8. The method according to claim 7, wherein the lactate is selected from the group consisting of L-lactate, D-lactate, and D, L-lactate.
9. The method as claimed in claim 1, wherein the vaporization temperature of the lactate is 150-600 ℃.
10. The method as claimed in claim 1, wherein the lactate vaporization temperature is 180-350 ℃.
11. The process as claimed in claim 1, wherein the cyclization reaction temperature is 180-300 ℃, the reaction pressure is normal pressure, and the feed mass space velocity is 1-8g lactate per gram catalyst per hour.
12. The method of claim 1, wherein the catalyst and the raw material are subjected to gas phase contact reaction, and a fixed bed, a fluidized bed, a moving bed, an ebullating bed or an expanded bed can be used.
13. A method of synthesizing polylactic acid, characterized by: the method is characterized in that lactide is synthesized by taking lactate as a raw material and a tin-containing molecular sieve as a catalyst through a gas-phase normal-pressure one-step method, and the specific process is as follows: firstly, lactic acid is first preparedHeating and vaporizing ester, introducing gaseous lactate into a reactor containing tin-containing molecular sieve catalyst, performing cyclization reaction to obtain lactide, purifying lactide, and polymerizing to obtain lactide with relative weight average molecular weight of more than 2 × 10 under the action of ring-opening polymerization catalyst5The polylactic acid of (1) has polymerization catalyst of stannous octoate, stannous acetate or alkyl aluminum, the polymerization reaction temperature is 130-;
the synthesis method of the tin-containing molecular sieve comprises the following steps: taking a tin-free molecular sieve as a raw material, performing acid treatment and dealumination, taking anhydrous stannic chloride as a tin source, performing gas phase treatment for 6-24h at the temperature of 450-plus-material and 700 ℃, washing, drying and roasting to obtain raw powder of the tin-containing molecular sieve, uniformly mixing the raw powder and sesbania powder, adding a binder, further uniformly mixing, extruding the mixture into strips by using a strip extruding machine for molding, drying the molded sample at the temperature of 100 ℃ for 12h, and roasting to obtain the strip-shaped tin-containing molecular sieve;
the tin-containing molecular sieve is one or a mixture of Sn-Beta, Sn-MOR, Sn-ZSM-22, Sn-ZSM-35 and Sn-ZSM-5.
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Families Citing this family (7)
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| CN112175177B (en) * | 2020-10-15 | 2023-01-20 | 贵州省材料技术创新基地 | Catalyst and preparation method thereof, and preparation method of polylactic acid |
| CN115246809B (en) * | 2021-04-26 | 2024-04-09 | 万华化学(四川)有限公司 | Method for preparing lactide by one-step gas phase reaction |
| CN116060088B (en) * | 2021-10-31 | 2024-05-10 | 中国石油化工股份有限公司 | Catalyst for preparing lactide by lactic acid dehydration and synthesis method and application thereof |
| CN116060090B (en) * | 2021-10-31 | 2024-05-07 | 中国石油化工股份有限公司 | Catalyst for preparing lactide from lactic acid and synthetic method and application thereof |
| CN114377720B (en) * | 2022-01-25 | 2024-04-19 | 浙江省林业科学研究院 | Tin-based catalyst and preparation method and application thereof |
| CN115382570A (en) * | 2022-08-02 | 2022-11-25 | 马鞍山同杰良生物材料有限公司 | Nanometer Beta molecular sieve for preparing lactide and preparation method thereof |
| CN115417851A (en) * | 2022-08-30 | 2022-12-02 | 中国科学院长春应用化学研究所 | Method for directly preparing lactide from lactic acid |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863596A (en) * | 2012-10-08 | 2013-01-09 | 中国科学院长春应用化学研究所 | Polylactic acid segmented copolymer and modified polylactic acid preparation method |
| WO2013160485A1 (en) * | 2012-04-28 | 2013-10-31 | Uhde Inventa-Fischer Gmbh | Process for continuous preparation of lactide directly from concentrated lactic acid |
| WO2018055170A1 (en) * | 2016-09-23 | 2018-03-29 | Katholieke Universiteit Leuven | Process for preparing cyclic esters from alpha-hydroxy esters and catalysts used therein |
| CN108610323A (en) * | 2018-06-14 | 2018-10-02 | 中国科学院长春应用化学研究所 | A kind of preparation method of lactide |
| CN110402246A (en) * | 2017-03-15 | 2019-11-01 | 巴斯夫欧洲公司 | The method that cyclic diester or cyclic annular diamides are prepared and reacting hydroxycarboxylic acid or amide with acidity BEA (H- beta-polymorph A) type zeolite |
| WO2020021346A1 (en) * | 2018-07-26 | 2020-01-30 | Cuervo Garces Laura Viviana | Method for obtaining polylactic acid (pla) from cheese whey |
| CN111057040A (en) * | 2019-11-05 | 2020-04-24 | 浙江工业大学 | Method for catalytically synthesizing lactide by using shape-selective zeolite supported catalyst |
| CN111533727A (en) * | 2019-12-24 | 2020-08-14 | 安徽丰原发酵技术工程研究有限公司 | Method for preparing lactide by one-step gas phase reaction |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109833904B (en) * | 2017-11-29 | 2020-08-11 | 中国科学院大连化学物理研究所 | Acid-base bifunctional catalyst, preparation method thereof and application thereof in ethanol conversion reaction |
-
2020
- 2020-09-23 CN CN202011005818.4A patent/CN112028869B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013160485A1 (en) * | 2012-04-28 | 2013-10-31 | Uhde Inventa-Fischer Gmbh | Process for continuous preparation of lactide directly from concentrated lactic acid |
| CN102863596A (en) * | 2012-10-08 | 2013-01-09 | 中国科学院长春应用化学研究所 | Polylactic acid segmented copolymer and modified polylactic acid preparation method |
| WO2018055170A1 (en) * | 2016-09-23 | 2018-03-29 | Katholieke Universiteit Leuven | Process for preparing cyclic esters from alpha-hydroxy esters and catalysts used therein |
| CN110402246A (en) * | 2017-03-15 | 2019-11-01 | 巴斯夫欧洲公司 | The method that cyclic diester or cyclic annular diamides are prepared and reacting hydroxycarboxylic acid or amide with acidity BEA (H- beta-polymorph A) type zeolite |
| CN108610323A (en) * | 2018-06-14 | 2018-10-02 | 中国科学院长春应用化学研究所 | A kind of preparation method of lactide |
| WO2020021346A1 (en) * | 2018-07-26 | 2020-01-30 | Cuervo Garces Laura Viviana | Method for obtaining polylactic acid (pla) from cheese whey |
| CN111057040A (en) * | 2019-11-05 | 2020-04-24 | 浙江工业大学 | Method for catalytically synthesizing lactide by using shape-selective zeolite supported catalyst |
| CN111533727A (en) * | 2019-12-24 | 2020-08-14 | 安徽丰原发酵技术工程研究有限公司 | Method for preparing lactide by one-step gas phase reaction |
Non-Patent Citations (8)
| Title |
|---|
| Breaking the Si/Al Limit of Nanosized β Zeolites: Promoting Catalytic Production of Lactide;Qiang Zhang等;《Chemistry Materials》;20191227;第32卷(第2期);全文 * |
| Catalytic Gas-Phase Production of Lactide from Renewable Alkyl Lactates;De Clercq;《ANGEWANDTE CHEMIE-INTERNATIONAL EDITION》;20180122;第57卷(第12期);全文 * |
| Design of a heterogeneous catalytic process for the continuous and direct synthesis of lactide from lactic acid;Pravin P. Upare等;《Green Chemistry》;20160923;第18卷(第22期);全文 * |
| Economically Efficient Synthesis of Lactide Using a Solid Catalyst;Hyun Woo Park等;《Organic Process Research Development》;20171117;第21卷(第12期);全文 * |
| Morphology and Catalytic Properties of Hierarchical Zeolites with MOR, BEA, MFI, and MTW Topology;O. V. Shvets等;《Theoretical and Experimental Chemistry》;20180609;第54卷(第2期);第144页最后三段 * |
| Qintong Huang等.Size E ects of the Crystallite of ZSM-5 Zeolites on the Direct Catalytic Conversion of L-Lactic Acid to L, L-Lactide.《crystals》.2020,第10卷(第9期), * |
| Shape-selective zeolite catalysis for bioplastics production;Michiel Dusselier等;《Science》;20151231;第349卷(第6243期);全文 * |
| Size effects of the Crystallite of ZSM-5 Zeolites on the Direct Catalytic Conversion of L-Lactic Acid to L, L-Lactide;Qintong Huang等;《crystals》;20200903;第10卷(第9期);全文 * |
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