CN1300136C - Catalytic synthetic method for lactide - Google Patents
Catalytic synthetic method for lactide Download PDFInfo
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- CN1300136C CN1300136C CNB2003101076847A CN200310107684A CN1300136C CN 1300136 C CN1300136 C CN 1300136C CN B2003101076847 A CNB2003101076847 A CN B2003101076847A CN 200310107684 A CN200310107684 A CN 200310107684A CN 1300136 C CN1300136 C CN 1300136C
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- lactide
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- zno
- catalytic synthesis
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- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
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- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention discloses a catalytic synthetic method for lactide, which relates to a synthetic technology of lactide. Industry lactic acid of which the content is 85% and a catalyst ZnO are added to a reaction vessel according to the proportion of 135 to 165:1. When the temperature reaches 135 to 155 DEG C, a mixed catalyst made from ZnO and La2O3 is added to the vessel. When the temperature is raised to 170 to 190 DEG C, the vacuum degree is increased to 0.09MPa to 0.10MPa. When the temperature reaches 240 to 260 DEG C, the reaction is finished, and then a receiving bottle is taken off; organic liquid in the receiving bottle immediately generates lactide crystals at room temperature. The present invention adds the catalyst in twice in the synthetic technology, wherein the first time is to add ZnO, and the second time is to add the composite catalyst made from ZnO and La2O3. The method for adding the catalyst in twice is utilized, which obviously increases the synthetic productive rate of the lactide. Compared with the traditional lactide synthetic method, the synthetic productive rate of the lactide of the present invention is increased to 52%. Thereby, the production cost of the polylactic acid is reduced, and the product performance of the polylactic acid is effectively improved.
Description
Technical field: the important source material that the present invention relates to poly(lactic acid)---rac-Lactide is specifically related to the synthesis technique of rac-Lactide.
Background technology: rac-Lactide is the important source material of synthesizing polylactic acid.Poly-lactic acid material has good biodegradability, biocompatibility and excellent mechanical intensity, is the ideal biodegradable material, and it is having broad application prospects aspect sustained release of tissue reparation, wound suture, medicine and agricultural chemicals; In other some Application Areass, poly(lactic acid) replaces traditional polymer materials, can alleviate pollution and harm to environment.Poly(lactic acid) synthetic common method is a rac-Lactide ring-opening polymerization method.From general status, at present the poly(lactic acid) synthetic technology is still immature, and the aspect also has many technical barriers to need to be resolved hurrily improving the poly-lactic acid products performance, reduce production costs etc.
Summary of the invention: the purpose of this invention is to provide a kind of rac-Lactide process for catalytic synthesis, it has the synthetic yield that improves rac-Lactide, reduces the production cost of synthesizing polylactic acid, improves the characteristics of poly-lactic acid products performance.The present invention realizes with following steps: (1) at first be with content 85% industrial lactic acid and catalyzer ZnO in 135~165: 1 ratio joins in the reaction vessel, the mixing heating; (2) begin to vacuumize after the temperature of container contents reaches 100 ℃, in 2~2.5 hours, slowly heat up and increase vacuum tightness; (3) when temperature reaches 135~155 ℃, in container, add ZnO and La again
2O
3Mixed catalyst, press mass ratio ZnO: La
2O
3=3~5: 1, ZnO and La
2O
3The add-on of mixture is industrial lactic acid quality
(4) when vacuum tightness is 0.03~0.04MPa, keep 30~60min, slough moisture that lactic acid Central Plains is contained and that reaction generates; (5) when observe do not have water to distill after, change receiving bottle; When (6) being warmed up to 170~190 ℃, increase vacuum tightness to 0.09~0.10MPa, receive light yellow or the xanchromatic organic liquid; (7) when temperature reaches 240~260 ℃, reaction finishes; (8) take off receiving bottle, the organic liquid of the inside at room temperature produces the rac-Lactide crystallization at once; With rac-Lactide crystallization distilled water wash 2~3 times, suction filtration; (9) purify 2~4 times with re-crystallizing in ethyl acetate; (10) in vacuum drying oven dry 20~24 hours, obtain rac-Lactide.The present invention is a raw material with industrial lactic acid, and catalyzer adds at twice in synthesis technique, only adds ZnO for the first time, adds ZnO and La for the second time
2O
3Composite catalyst, obviously improved the synthetic yield of rac-Lactide with this method that adds catalyzer at twice, compare with traditional rac-Lactide synthetic method, the synthetic yield of rac-Lactide brings up to 52%, thereby reduced the production cost of poly(lactic acid), and improved the product performance of poly(lactic acid) effectively.
Embodiment one: present embodiment realizes with following steps: (1) at first be with content 85% industrial lactic acid and catalyzer ZnO in 135~165: 1 ratio joins in the reaction vessel, the mixing heating; (2) begin to vacuumize after the temperature of container contents reaches 100 ℃, in 2~2.5 hours, slowly heat up and increase vacuum tightness; (3) when temperature reaches 135~155 ℃, in container, add ZnO and La again
2O
3Mixed catalyst, press mass ratio ZnO: La
2O
3=3~5: 1, ZnO and La
2O
3The add-on of mixture is industrial lactic acid quality
(4) when vacuum tightness is 0.03~0.04MPa, keep 30~60min, slough moisture that lactic acid Central Plains is contained and that reaction generates; (5) when observe do not have water to distill after, change receiving bottle; When (6) being warmed up to 170~190 ℃, increase vacuum tightness to 0.09~0.10MPa, receive light yellow or the xanchromatic organic liquid; (7) when temperature reaches 240~260 ℃, reaction finishes; (8) take off receiving bottle, the organic liquid of the inside at room temperature produces the rac-Lactide crystallization at once; With rac-Lactide crystallization distilled water wash 2~3 times, suction filtration; (9) purify 2~4 times with re-crystallizing in ethyl acetate; (10) in vacuum drying oven dry 20~24 hours, obtain rac-Lactide.
Embodiment two: present embodiment realizes with following steps, and (1) is that 85% industrial lactic acid 150ml and 1g catalyzer ZnO join in the there-necked flask mixing heating with content; (2) begin to vacuumize after a bottle content temperature reaches 100 ℃, slowly heated up in 2 hours and increase vacuum tightness, heat-up rate is every 10min3~5 ℃; (3) when temperature reaches 140 ℃, in there-necked flask, add ZnO and La again
2O
3Mixed catalyst, press mass ratio ZnO: La
2O
3=5: 1, add-on is 0.5g; (4) keep 50min during for 0.035MPa in vacuum tightness, slough moisture that lactic acid Central Plains is contained and that reaction generates; (5) after observing anhydrous distilling, change receiving bottle; Increase vacuum tightness when (6) being warmed up to 180 ℃ to 0.098MPa, receive light yellow or the xanchromatic organic liquid; (7) when temperature reaches 250 ℃, reaction finishes; (8) take off receiving bottle, the organic liquid of the inside at room temperature produces the rac-Lactide crystallization at once, with rac-Lactide crystallization distilled water wash 2 times, suction filtration; (9) purify 3 times with re-crystallizing in ethyl acetate; (10) in vacuum drying oven dry 24 hours, obtain rac-Lactide.
Claims (8)
1, rac-Lactide process for catalytic synthesis is characterized in that it realizes with following steps: (1) at first be with content 85% industrial lactic acid and catalyzer ZnO in 135~165: 1 ratio joins in the reaction vessel, the mixing heating; (2) begin to vacuumize after the temperature of container contents reaches 100 ℃, in 2~2.5 hours, slowly heat up and increase vacuum tightness; (3) when temperature reaches 135~155 ℃, in container, add ZnO and La again
2O
3Mixed catalyst, press mass ratio ZnO: La
2O
3=3~5: 1, ZnO and La
2O
3The add-on of mixture is industrial lactic acid quality
(4) when vacuum tightness is 0.03~0.04MPa, keep 30~60min, slough moisture that lactic acid Central Plains is contained and that reaction generates; (5) when observe do not have water to distill after, change receiving bottle; When (6) being warmed up to 170~190 ℃, increase vacuum tightness to 0.09~0.10MPa, receive light yellow or the xanchromatic organic liquid; (7) when temperature reaches 240~260 ℃, reaction finishes; (8) take off receiving bottle, the organic liquid of the inside at room temperature produces the rac-Lactide crystallization at once; With rac-Lactide crystallization distilled water wash 2~3 times, suction filtration; (9) purify 2~4 times with re-crystallizing in ethyl acetate; (10) in vacuum drying oven dry 20~24 hours, obtain rac-Lactide.
2, rac-Lactide process for catalytic synthesis according to claim 1, the heating-up time that it is characterized in that step (2) is 2 hours, heat-up rate is every 10min3~5 ℃.
3, rac-Lactide process for catalytic synthesis according to claim 1 is characterized in that the temperature that step (3) reaches is 140 ℃, and the mass ratio of mixed catalyst is ZnO: La
2O
3=5: 1.
4, rac-Lactide process for catalytic synthesis according to claim 1, the vacuum tightness that it is characterized in that step (4) is 0.035MPa, the hold-time is 50min.
5, rac-Lactide process for catalytic synthesis according to claim 1 is characterized in that increasing when step (6) is warmed up to 180 ℃ vacuum tightness to 0.098MPa.
6, rac-Lactide process for catalytic synthesis according to claim 1, when the temperature that it is characterized in that step (7) reached 250 ℃, reaction finished.
7, rac-Lactide process for catalytic synthesis according to claim 1 is characterized in that step (8) is with rac-Lactide crystallization distilled water wash 2 times.
8, rac-Lactide process for catalytic synthesis according to claim 1 is characterized in that step (9) purifies 3 times with re-crystallizing in ethyl acetate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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CNB2003101076847A CN1300136C (en) | 2003-11-11 | 2003-11-11 | Catalytic synthetic method for lactide |
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CNB2003101076847A CN1300136C (en) | 2003-11-11 | 2003-11-11 | Catalytic synthetic method for lactide |
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CN1616450A CN1616450A (en) | 2005-05-18 |
CN1300136C true CN1300136C (en) | 2007-02-14 |
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Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100417651C (en) * | 2005-06-22 | 2008-09-10 | 西北师范大学 | Method for catalytic synthesis of lactide from lactic acid |
CN100417652C (en) * | 2005-08-25 | 2008-09-10 | 西北师范大学 | Method for lactide synthesis from lactic acid catalysized by montmorillonite |
KR101326521B1 (en) * | 2011-05-26 | 2013-11-07 | 현대자동차주식회사 | Manufacturing Method of Lactide from Lactic acid |
CN102911347A (en) * | 2012-10-22 | 2013-02-06 | 长沙理工大学 | Method for preparing high molecular weight poly(L-lactide-co-caprolactone) random copolymer |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1112293B (en) * | 1959-05-20 | 1961-08-03 | Wolfen Filmfab Veb | Process for the production of polylactic acid |
CN1208740A (en) * | 1997-08-15 | 1999-02-24 | 安徽中人科技有限责任公司 | Method for preparing poly-lactic-acid |
CN1298892A (en) * | 1999-12-09 | 2001-06-13 | 浙江大学 | Process for preparing biodegradable polylactate material by direct polycondensation of lactic acid |
-
2003
- 2003-11-11 CN CNB2003101076847A patent/CN1300136C/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1112293B (en) * | 1959-05-20 | 1961-08-03 | Wolfen Filmfab Veb | Process for the production of polylactic acid |
CN1208740A (en) * | 1997-08-15 | 1999-02-24 | 安徽中人科技有限责任公司 | Method for preparing poly-lactic-acid |
CN1298892A (en) * | 1999-12-09 | 2001-06-13 | 浙江大学 | Process for preparing biodegradable polylactate material by direct polycondensation of lactic acid |
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