CN100417651C - Method for catalytic synthesis of lactide from lactic acid - Google Patents
Method for catalytic synthesis of lactide from lactic acid Download PDFInfo
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- CN100417651C CN100417651C CNB2005100428602A CN200510042860A CN100417651C CN 100417651 C CN100417651 C CN 100417651C CN B2005100428602 A CNB2005100428602 A CN B2005100428602A CN 200510042860 A CN200510042860 A CN 200510042860A CN 100417651 C CN100417651 C CN 100417651C
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- lactide
- lactic acid
- muriate
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- trichloride
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Abstract
The present invention provides a depressurizing nitrogen gas flow method which takes lactic acid as raw material and takes acidified montmorillonite, hydrotalcite, palygorskite, montmorillonite-bearing chloride, hydrotalcite-bearing chloride, palygorskite-bearing chloride and silica gel-bearing chloride as catalyst for catalytically synthesizing lactide. The catalyst has the advantages of low cost, less dosage, simple preparation process, short time of depolymerization and high yield of lactide. The highest yield of purified lactide can reach 60%.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of raw material of synthesizing polylactic acid---the preparation method of rac-Lactide relates in particular to a kind of method of using the catalyst synthesis of lactide from lactic acid.
Background technology
Poly(lactic acid) is widely used in medical field, biotechnology and other field because to have good Bc, degradability and an intermediate product nontoxic.But because poly(lactic acid) production cost height, the flow process complexity is greatly limited its application.Synthetic macromolecule amount poly(lactic acid) mainly adopts rac-Lactide ring-opening polymerization method at present.Therefore, can the height of lactide production cost have directly determined poly(lactic acid) be widely used.Up to the present, the preparation rac-Lactide has adopted several different methods, for example: adopt decompression air-flow method, add tin, zinc class Preparation of Catalyst rac-Lactide in lactic acid; Under normal pressure, in nitrogen, lactic acid oligomer is continued synthesis of lactide from; Zinc oxide, tin protochloride, stannous sulfate, stannous octoate and their mixture are catalyzer, adopt decompression air-flow method synthesis of lactide from; With the lanthanum titanium composite oxide is catalyzer, on the traditional synthesis basis, and the D of decompression condensation earlier, L-type lactic acid oligomer, and then to be cracked into dimer be rac-Lactide etc., but these methods respectively have relative merits.Up to the present, also do not find a kind of method of efficient especially synthesis of lactide from.Can finding more effectively, the catalyst synthesis of lactide from becomes the problem that numerous investigators are worth exploration.
Summary of the invention
The purpose of this invention is to provide a kind of is raw material with lactic acid, adopt decompression nitrogen gas stream method, selecting acidifying polynite, hydrotalcite, polygorskite, montmorillonite load muriate, hydrotalcite load muriate, palygorskite load muriate, silica gel load muriate for use is the method for catalyst synthesis of lactide from.
The method of catalysis synthesis of lactide from of the present invention comprises following processing step:
A kind of method of catalytic synthesis of lactide from lactic acid may further comprise the steps successively:
1. distill moisture:, under the vacuum tightness 0.002-0.02MPa, steam the moisture in the lactic acid 25 ℃-120 ℃ of temperature.
2. catalytic oligomerization: with acid montmorillonite, hydrotalcite, polygorskite, montmorillonite load muriate, hydrotalcite load muriate, palygorskite load muriate or silica gel load muriate is catalyzer, in 50 ℃-170 ℃ of temperature, vacuum tightness 1.5 * 10
-4-5.0 * 10
-3Under the MPa, decompression dehydration 1-5 hour, aggregate into low-molecular-weight poly(lactic acid), and steam the water of generation.
3. the nitrogen gas stream that reduces pressure method catalytic degradation: with the low molecular weight that generates, with acidifying polynite, hydrotalcite, polygorskite, montmorillonite load muriate, hydrotalcite load muriate, palygorskite load muriate or silica gel load muriate is catalyzer, at temperature 170-260 ℃, vacuum tightness 8.0 * 10
-5-0.01MPa, nitrogen flow are depolymerization 3-7 hour of reducing pressure under the 0.1-5L/min, form crude lactide;
4. recrystallization: with ethyl acetate the crude lactide that depolymerizes to is carried out recrystallization and get rac-Lactide.
5. it is dry more than 20 hours rac-Lactide to be put into 30 ℃ of-50 ℃ of vacuum drying ovens.
Described lactic acid is D, L-lactic acid.
Described catalyst consumption is D, the 0.001%-10% of L-lactic acid.
Described load muriate is any in butter of antimony, tin protochloride, zinc chloride, Lanthanum trichloride, Cerium II Chloride, chlorination polonium, uranium chloride, Dysprosium trichloride, Neodymium trichloride, Holmium trichloride, praseodymium chloride, Erbium trichloride, samarium trichloride, thulium chloride, the Yttrium trichloride.
Before recrystallization, use the distilled water wash crude lactide.
The present invention compared with prior art has the following advantages:
1, the present invention is a catalyzer with acidifying polynite, hydrotalcite, polygorskite, montmorillonite load muriate, hydrotalcite load muriate, palygorskite load muriate, silica gel load muriate, and cost is low, and consumption is few, the depolymerization time short, the efficient height.
2, preparation technology of the present invention is simple, the yield height of rac-Lactide, and the productive rate of rac-Lactide can reach 60% behind the purifying.
Embodiment
Embodiment 1: 1. with a certain amount of D, L-lactic acid joins in the three neck round-bottomed flasks, and 25 ℃ of temperature, vacuum tightness 0.002MPa decompression earlier sloughs free water; 2. add D, the acid montmorillonite of L-lactic acid production 0.001%, elevated temperature, at 50 ℃, vacuum tightness 1.5 * 10
-4MPa continues dehydration 5 hours down, aggregates into low-molecular-weight poly(lactic acid), and steams the water of generation; 3. change receiving trap, and temperature is risen to 170 ℃, pressure is transferred to 8.0 * 10
-5MPa, nitrogen flow are that depolymerization formed crude lactide in 7 hours under the 0.1L/min; 4. the crude lactide product is used distilled water wash 2-3 time earlier, get rac-Lactide with re-crystallizing in ethyl acetate again, will put into 40 ℃ of dry 24h of vacuum drying oven through recrystallizing lactide then, yield: 58.2%.
Embodiment 2: 1. with a certain amount of D, L-lactic acid joins in the three neck round-bottomed flasks, and 50 ℃ of temperature, vacuum tightness 0.005MPa decompression earlier sloughs free water; 2. add D, the acidified water talcum of L-lactic acid production 0.01%, elevated temperature, at 70 ℃, vacuum tightness 3.0 * 10
-4MPa continues dehydration 5 hours down, aggregates into low-molecular-weight poly(lactic acid), and steams the water of generation; 3. change receiving trap, and temperature is risen to 180 ℃, pressure is transferred to 2.0 * 10
-4MPa, nitrogen flow are that depolymerization formed crude lactide in 7 hours under the 0.5L/min; 4. the crude lactide product is used distilled water wash 2-3 time earlier, get rac-Lactide with re-crystallizing in ethyl acetate again, will put into 50 ℃ of dry 24h of vacuum drying oven through recrystallizing lactide then, yield: 39.6%.
Embodiment 3: 1. with a certain amount of D, L-lactic acid joins in the three neck round-bottomed flasks, and 60 ℃ of temperature, vacuum tightness 0.008MPa decompression earlier sloughs free water; 2. add D, the acidifying polygorskite of L-lactic acid production 0.05%, elevated temperature, at 90 ℃, vacuum tightness 5.0 * 10
-4MPa continues dehydration 4.5 hours down, aggregates into low-molecular-weight poly(lactic acid), and steams the water of generation; 3. change receiving trap, and temperature is risen to 180 ℃, pressure is transferred to 1.0 * 10
-3MPa, nitrogen flow are that depolymerization formed crude lactide in 7 hours under the 1L/min; 4. the crude lactide product is used distilled water wash 2-3 time earlier, get rac-Lactide with re-crystallizing in ethyl acetate again, will put into 45 ℃ of dry 24h of vacuum drying oven through recrystallizing lactide then, yield: 48.5%.
Embodiment 4: 1. with a certain amount of D, L-lactic acid joins in the three neck round-bottomed flasks, and 70 ℃ of temperature, vacuum tightness 0.010MPa decompression earlier sloughs free water; 2. add D, the tin protochloride of the silica gel load of L-lactic acid production 0.1%, elevated temperature, at 110 ℃, vacuum tightness 1.0 * 10
-3MPa continues dehydration 4.5 hours down, aggregates into low-molecular-weight poly(lactic acid), and steams the water of generation; 3. change receiving trap, and temperature is risen to 180 ℃, pressure is transferred to 0.001MPa, and nitrogen flow is that depolymerization formed crude lactide in 7 hours under the 2L/min; 4. the crude lactide product is used distilled water wash 2-3 time earlier, get rac-Lactide with re-crystallizing in ethyl acetate again, will put into 40 ℃ of dry 24h of vacuum drying oven through recrystallizing lactide then, yield: 69.7%.
Embodiment 5: 1. with a certain amount of D, L-lactic acid joins in the three neck round-bottomed flasks, and 80 ℃ of temperature, vacuum tightness 0.012MPa decompression earlier sloughs free water; 2. add D, the montmorillonite load butter of antimony of L-lactic acid production 0.5%, elevated temperature, at 130 ℃, vacuum tightness 2.0 * 10
-3MPa continues dehydration 4 hours down, aggregates into low-molecular-weight poly(lactic acid), and steams the water of generation; 3. change receiving trap, and temperature is risen to 190 ℃, pressure is transferred to 0.004MPa, and nitrogen flow is that depolymerization formed crude lactide in 7 hours under the 3L/min; 4. the crude lactide product is used distilled water wash 2-3 time earlier, get rac-Lactide with re-crystallizing in ethyl acetate again, will put into 40 ℃ of dry 24h yields of vacuum drying oven through recrystallizing lactide then: 58.2%.
Embodiment 6: 1. with a certain amount of D, L-lactic acid joins in the three neck round-bottomed flasks, and 90 ℃ of temperature, vacuum tightness 0.014MPa decompression earlier sloughs free water; 2. add D, the hydrotalcite load zinc chloride of L-lactic acid production 1%, elevated temperature, at 150 ℃, vacuum tightness 3.0 * 10
-3MPa continues dehydration 3.5 hours down, aggregates into low-molecular-weight poly(lactic acid), and steams the water of generation; 3. change receiving trap, and temperature is risen to 200 ℃, pressure is transferred to 0.008MPa, and nitrogen flow is that depolymerization formed crude lactide in 5 hours under the 3.5L/min; 4. the crude lactide product is used distilled water wash 2-3 time earlier, get rac-Lactide with re-crystallizing in ethyl acetate again, will put into 40 ℃ of dry 24h of vacuum drying oven through recrystallizing lactide then, yield: 52.3%.
Embodiment 7: 1. with a certain amount of D, L-lactic acid joins in the three neck round-bottomed flasks, and 100 ℃ of temperature, vacuum tightness 0.016MPa decompression earlier sloughs free water; 2. add D, the palygorskite load Lanthanum trichloride of L-lactic acid production 5%, elevated temperature, at 160 ℃, vacuum tightness 4.0 * 10
-3MPa continues dehydration 2 hours down, aggregates into low-molecular-weight poly(lactic acid), and steams the water of generation; 3. change receiving trap, and temperature is risen to 220 ℃, pressure is transferred to 0.001MPa, and nitrogen flow is that depolymerization formed crude lactide in 4 hours under the 4L/min; 4. the crude lactide product is used distilled water wash 2-3 time earlier, get rac-Lactide with re-crystallizing in ethyl acetate again, will put into 35 ℃ of dry 24h of vacuum drying oven through recrystallizing lactide then, yield: 58.2%.
Embodiment 8: 1. with a certain amount of D, L-lactic acid joins in the three neck round-bottomed flasks, and 120 ℃ of temperature, vacuum tightness 0.018MPa decompression earlier sloughs free water; 2. add D, the Cerium II Chloride of the silica gel load of L-lactic acid production 10%, elevated temperature, at 170 ℃, vacuum tightness 5.0 * 10
-3MPa continues dehydration 1 hour down, aggregates into low-molecular-weight poly(lactic acid), and steams the water of generation; 3. change receiving trap, and temperature is risen to 260 ℃, pressure is transferred to 0.01MPa, and nitrogen flow is that depolymerization formed crude lactide in 3 hours under the 5L/min; 4. the crude lactide product is used distilled water wash 2-3 time earlier, get rac-Lactide with re-crystallizing in ethyl acetate again, will put into 30 ℃ of dry 24h yields of vacuum drying oven through recrystallizing lactide then: 40.0%.
Be the method for catalyzer synthesis of lactide from other montmorillonite load muriate, hydrotalcite load muriate, palygorskite load muriate, silica gel load muriate, same as the previously described embodiments, repeat no more here.
Claims (5)
1. the method for a catalytic synthesis of lactide from lactic acid may further comprise the steps successively:
1. distill moisture:, under the vacuum tightness 0.002-0.02MPa, steam the moisture in the lactic acid 25 ℃-120 ℃ of temperature;
2. catalytic oligomerization: with acid montmorillonite, hydrotalcite, polygorskite, montmorillonite load muriate, hydrotalcite load muriate, palygorskite load muriate or silica gel load muriate is catalyzer, in 50 ℃-170 ℃ of temperature, vacuum tightness 1.5 * 10
-4-5.0 * 10
-3Under the MPa, decompression dehydration 1-5 hour, aggregate into low-molecular-weight poly(lactic acid), and steam the water of generation;
3. the nitrogen gas stream that reduces pressure method catalytic degradation: with the low molecular weight that generates, with acidifying polynite, hydrotalcite, polygorskite, montmorillonite load muriate, hydrotalcite load muriate, palygorskite load muriate or silica gel load muriate is catalyzer, at temperature 170-260 ℃, vacuum tightness 8.0 * 10
-5-0.01MPa, nitrogen flow are depolymerization 3-7 hour of reducing pressure under the 0.1-5L/min, form crude lactide;
4. recrystallization: with ethyl acetate the crude lactide that depolymerizes to is carried out recrystallization and get rac-Lactide;
5. it is dry more than 20 hours rac-Lactide to be put into 30-50 ℃ of vacuum drying oven.
2. the method for catalytic synthesis of lactide from lactic acid according to claim 1, it is characterized in that: described lactic acid is D, L-lactic acid.
3. as the method for catalytic synthesis of lactide from lactic acid as described in the claim 2, it is characterized in that: described catalyst consumption is D, and L seeks the 0.001%-10% of acid.
4. the method for catalytic synthesis of lactide from lactic acid according to claim 1 is characterized in that: described load muriate is any in butter of antimony, tin protochloride, zinc chloride, Lanthanum trichloride, Cerium II Chloride, chlorination polonium, uranium chloride, Dysprosium trichloride, Neodymium trichloride, Holmium trichloride, praseodymium chloride, Erbium trichloride, samarium trichloride, thulium chloride, the Yttrium trichloride.
5. the method for catalytic synthesis of lactide from lactic acid according to claim 1 is characterized in that: use the distilled water wash crude lactide before recrystallization.
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| CNB2005100428602A CN100417651C (en) | 2005-06-22 | 2005-06-22 | Method for catalytic synthesis of lactide from lactic acid |
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| CNB2005100428602A CN100417651C (en) | 2005-06-22 | 2005-06-22 | Method for catalytic synthesis of lactide from lactic acid |
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| CN1721418A CN1721418A (en) | 2006-01-18 |
| CN100417651C true CN100417651C (en) | 2008-09-10 |
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| CN104558543B (en) * | 2013-10-29 | 2016-11-02 | 中国石油天然气股份有限公司 | A kind of method of modifying of silica gel |
| CN112745293B (en) * | 2019-10-31 | 2023-01-10 | 中国石油化工股份有限公司 | Process method for synthesizing lactide from lactic acid convenient for catalyst recycling |
| CN113651794B (en) * | 2021-09-15 | 2022-08-02 | 珠海格力新材料有限公司 | Lactide synthesis method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5521278A (en) * | 1994-08-18 | 1996-05-28 | Ecological Chemical Products | Integrated process for the manufacture of lactide |
| CN1616450A (en) * | 2003-11-11 | 2005-05-18 | 王鹏 | Catalytic synthetic method for lactide |
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- 2005-06-22 CN CNB2005100428602A patent/CN100417651C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5521278A (en) * | 1994-08-18 | 1996-05-28 | Ecological Chemical Products | Integrated process for the manufacture of lactide |
| CN1616450A (en) * | 2003-11-11 | 2005-05-18 | 王鹏 | Catalytic synthetic method for lactide |
Non-Patent Citations (6)
| Title |
|---|
| 三氧化铝催化合成丙交酯. 魏金枝等.东北林业大学学报，第33卷第1期. 2005 |
| 三氧化铝催化合成丙交酯. 魏金枝等.东北林业大学学报，第33卷第1期. 2005 * |
| 丙交酯单体的制备及纯化. 张子勇等.高分子材料科学与工程，第19卷第2期. 2003 |
| 丙交酯单体的制备及纯化. 张子勇等.高分子材料科学与工程，第19卷第2期. 2003 * |
| 催化合成丙交酯研究. 黄晓琴.西北师范大学硕士学位. 2007 |
| 催化合成丙交酯研究. 黄晓琴.西北师范大学硕士学位. 2007 * |
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