CN1073999C - Method for preparing poly-lactic-acid - Google Patents
Method for preparing poly-lactic-acid Download PDFInfo
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- CN1073999C CN1073999C CN97107074A CN97107074A CN1073999C CN 1073999 C CN1073999 C CN 1073999C CN 97107074 A CN97107074 A CN 97107074A CN 97107074 A CN97107074 A CN 97107074A CN 1073999 C CN1073999 C CN 1073999C
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- China
- Prior art keywords
- lactic acid
- stannic oxide
- poly
- oxide
- dialkyltin
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Abstract
The present invention discloses a preparation method for polylactic acid. The prior art uses a two-step method to synthesize polylactic acid. In the preparation method, lactic acid is used as the raw material, dialkyl tin oxide or a monobutyl tin trioxide is used as a catalyst, and the raw material and the catalyst are synthesized to prepare polylactic acid by the methods of pressure reduction and dehydration. The preparation method for polylactic acid shortens the reaction process, and the product yield is improved to more than 90%.
Description
The invention belongs to a kind of preparation of compound, the manufacture method of a kind of poly(lactic acid) of more specifically saying so.
About the manufacture method of poly(lactic acid), people know, and lactic acid and catalyzer are heated jointly, and decompression dehydration can make molecular weight and be lower than 10,000 poly(lactic acid).
Early stage catalyzer has sulfuric acid, boric acid and tosic acid etc.This class is reported among USP2396994, USP2438208 and the USP2174491 and can sees.
Because low-molecular-weight poly(lactic acid) does not have practical value, in order to prepare more high molecular weight polylactic acid, people have adopted two-step approach to make high molecular weight polylactic acid.The first step uses the oxide compound of tellurium as catalyzer, for example: zinc oxide, stannic oxide, weisspiessglanz and plumbous oxide etc., perhaps the halogenide of tellurium is as catalyzer, for example: zinc chloride, tin chloride, Tin tetrabromide, antimonic fluoride becomes the low oligopolymer of molecular weight with lactic acid polymerizes, under high temperature, high vacuum, oligopolymer is cracked into propionic ester then, this class report is found in chem, Werke BYK, DRP267826, DD53074, DE1083275, DE37513 etc.The organic compound that second step was used tellurium again under suitable temperature, makes the propionic ester ring-opening polymerization become molecular weight greater than 10,000 poly(lactic acid) as catalyzer.As the alkyl metal cpd that has of catalyzer, for example hard ester acid tin, Zinc Stearate or arylide compound, tin tetraphenyl for example, perhaps metal salts of organic acids, for example stannous octoate etc.Report about the second step polymerizing catalyst can be at Brit1007347, Fr142533, and DD36499 sees among MaRromol, chem, 87,90-102 (1965) Brit932382, the DE112293.
Because above-mentioned two-step approach flow process is longer, middle lossy, the catalyzer of use has various shortcoming.For example, the metal oxide of the first step system propionic ester easily precipitates, and is poor with the lactic acid mutual solubility, produces a large amount of foams under heating condition, liquid fluctuating, and operational stability is poor.Tin tetraphenyl has severe toxicity, if directly the second step polymerizing catalyst is used for the first step, the water in the raw material easily makes it hydrolysis, organic group comes off, stannous octoate for example, therefore, with regard to the simplicity of enterprise's production and the yield of the finished product, aforesaid method can not make the people satisfied.
The manufacture method that the purpose of this invention is to provide a kind of poly(lactic acid) can improve product yield greatly, shortens reaction process.
The objective of the invention is to be achieved through the following technical solutions.
A kind of manufacture method of poly(lactic acid) is characterized in that with dialkyltin or Monobutyltin trioxide be catalyzer, heating lactic acid, and normal pressure or decompression dehydration obtain poly(lactic acid).Dialkyltin is meant diethyl stannic oxide or dipropyl stannic oxide, Dibutyltin oxide, diamyl stannic oxide, dihexyl stannic oxide, diheptyl stannic oxide, dioctyl tin oxide, dinonyl stannic oxide, didecyl stannic oxide, two undecyl stannic oxide, two dodecyl stannic oxide, two tetradecyl stannic oxide.
Dialkyltin or Monobutyltin trioxide consumption are 0.02～0.2% of lactic acid mole number, and 150～220 ℃ of temperature of reaction, reaction pressure are-0.08～0.098MPa.
Dialkyltin or Monobutyltin trioxide consumption are 0.05～0.1% of lactic acid mole number, and temperature of reaction is 180～200 ℃.
It is catalyzer that the present invention adopts dialkyltin or Monobutyltin trioxide.Because this class material structurally has oxide compound and organic chain group concurrently.Therefore,, exist a large amount of unreacting materials to be wetting ability in the system and when acid in the first step initial reaction stage, the oxide structure of catalyzer can be with it affinity preferably.In the second polymerization later stage in step, when forming the polymer long-chain in the system and being lipophilicity and acid basic the disappearance, the organic chain of catalyzer can make catalyzer continue to keep consistency with system again.In entire reaction and the polymerization process, catalyzer keeps the consistency of higher activity and the whole reaction system that has changed always, therefore, two-step reaction can be combined into a step, and reaction yield can reach more than 90%.
By the following examples, the invention will be further described.
Embodiment 1:
In the 500ml there-necked flask that is equipped with agitator, distillation column, condenser, thermometer and vacuum distillation apparatus, drop into 300g lactic acid (purity 85.0%), 0.5g Dibutyltin oxide.Stir, slowly be warming up to 180 ℃, kept 6 hours, the reaction dehydration.Then, slowly be decompressed to-0.098MPa, temperature is increased to 200 ℃, keep this state after 2 hours, material is poured on the polytetrafluoroethylene film, after the cooling, can obtain light yellow arborescens poly(lactic acid) 188.5g, be 92.4% of theoretical yield, molecular weight 31501/GPC.
Embodiment 2:
Experimental installation is identical with embodiment one with condition, only replaces Dibutyltin oxide with 0.7g dihexyl stannic oxide.Get poly(lactic acid) 184.8g, be 90.6% of theoretical yield, molecular weight 26433/GPC.
Embodiment 3:
Experimental installation is identical with embodiment one with condition, only replaces Dibutyltin oxide with the two dodecyl stannic oxide of 0.7g.Get poly(lactic acid) 187.2g, be 91.8% of theoretical yield, molecular weight 20115/GPC.
Embodiment 4:
Experimental installation is identical with embodiment one with condition, only replaces Dibutyltin oxide with 0.4g Monobutyltin trioxide.Get poly(lactic acid) 191.8g, be 94.0% of theoretical yield, molecular weight 27218/GPC.
Claims (4)
1. the manufacture method of a poly(lactic acid), it is characterized in that with dialkyltin or Monobutyltin trioxide be catalyzer, heating lactic acid, normal pressure or decompression dehydration obtain poly(lactic acid), and dialkyltin or Monobutyltin trioxide consumption are 0.02～0.2% of lactic acid mole number.
2. the manufacture method of a kind of poly(lactic acid) according to claim 1 is characterized in that dialkyltin is meant diethyl stannic oxide or dipropyl stannic oxide, Dibutyltin oxide, diamyl stannic oxide, dihexyl stannic oxide, diheptyl stannic oxide, dioctyl tin oxide, dinonyl stannic oxide, didecyl stannic oxide, two undecyl stannic oxide, two dodecyl stannic oxide, two tetradecyl stannic oxide.
3. the manufacture method of a kind of poly(lactic acid) according to claim 1 is characterized in that temperature of reaction is 150～220 ℃, and reaction pressure is-0.08～0.098Mpa.
4. the manufacture method of a kind of poly(lactic acid) according to claim 1 is characterized in that dialkyltin or Monobutyltin trioxide consumption are 0.05～0.1% of lactic acid mole number, and temperature of reaction is 180～200 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97107074A CN1073999C (en) | 1997-08-15 | 1997-08-15 | Method for preparing poly-lactic-acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97107074A CN1073999C (en) | 1997-08-15 | 1997-08-15 | Method for preparing poly-lactic-acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1208740A CN1208740A (en) | 1999-02-24 |
| CN1073999C true CN1073999C (en) | 2001-10-31 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97107074A Expired - Fee Related CN1073999C (en) | 1997-08-15 | 1997-08-15 | Method for preparing poly-lactic-acid |
Country Status (1)
| Country | Link |
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| CN (1) | CN1073999C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300136C (en) * | 2003-11-11 | 2007-02-14 | 王鹏 | Catalytic synthetic method for lactide |
| CN101463124B (en) * | 2007-12-21 | 2011-08-17 | 东丽纤维研究所（中国）有限公司 | Method for preparing polylactic acid with metal sulphonate as catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62212423A (en) * | 1986-03-12 | 1987-09-18 | Fuso Kagaku Kogyo Kk | Production of polymer or copolymer of hydroxypolycarboxylic ester |
| US5053522A (en) * | 1987-03-19 | 1991-10-01 | Boehringer Ingelheim Kg | Process for the preparation of lactide |
| EP0603889A2 (en) * | 1992-12-25 | 1994-06-29 | MITSUI TOATSU CHEMICALS, Inc. | Process for the preparation of lactic acid polyesters |
-
1997
- 1997-08-15 CN CN97107074A patent/CN1073999C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62212423A (en) * | 1986-03-12 | 1987-09-18 | Fuso Kagaku Kogyo Kk | Production of polymer or copolymer of hydroxypolycarboxylic ester |
| US5053522A (en) * | 1987-03-19 | 1991-10-01 | Boehringer Ingelheim Kg | Process for the preparation of lactide |
| EP0603889A2 (en) * | 1992-12-25 | 1994-06-29 | MITSUI TOATSU CHEMICALS, Inc. | Process for the preparation of lactic acid polyesters |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1208740A (en) | 1999-02-24 |
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Assignee: Wuhu Zhong Ren Pharmaceutical Co., Ltd. Assignor: Zhongren Science and Technology Co., Ltd., Anhui Prov. Contract fulfillment period: 2008.8.8 to 2017.8.14 Contract record no.: 2008320000121 Denomination of invention: Method for preparing poly-lactic-acid Granted publication date: 20011031 License type: exclusive license Record date: 20080909 |
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Free format text: EXCLUSIVE LICENCE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.8.8 TO 2017.8.14 Name of requester: WU HU ZHONGREN PHARMACEUTICAL CO., LTD. Effective date: 20080909 |
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| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Wuhu Simcere Zhongren Pharmaceutical Co., Ltd. Assignor: Zhongren Science and Technology Co., Ltd., Anhui Prov. Contract fulfillment period: 2008.11.20 to 2017.8.14 Contract record no.: 2008320001129 Denomination of invention: Method for preparing poly-lactic-acid Granted publication date: 20011031 License type: exclusive license Record date: 20081211 |
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| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.11.20 TO 2017.8.14; CHANGE OF CONTRACT Name of requester: WUHU XIANSHENGZHONGREN PHARMACEUTICAL CO., LTD. Effective date: 20081211 |