CN103613742A - Method for preparing cyclic polyester by utilizing Lewis acid-base pair - Google Patents
Method for preparing cyclic polyester by utilizing Lewis acid-base pair Download PDFInfo
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- CN103613742A CN103613742A CN201310586157.2A CN201310586157A CN103613742A CN 103613742 A CN103613742 A CN 103613742A CN 201310586157 A CN201310586157 A CN 201310586157A CN 103613742 A CN103613742 A CN 103613742A
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- lactic acid
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Abstract
The invention relates to a method for preparing cyclic polyester by utilizing Lewis acid-base pair. The method is characterized in that a Lewis acid-base pair catalyst is successfully applied to the open-loop polymerization reaction, and a twin-system integrating Zn(C6F5) and organic alkali (amine or phosphine) can promote the controllable open-loop polymerization of lactide and epsilon-caprolactone. The monomer is activated through the synergistic effect of the Lewis acid-base pair, so that the cyclic polyester with high molecular weight can be obtained. By adopting the method, a novel way is provided for the synthesis of the cyclic polyester, and the effective molecular chain extension provides a way for synthesizing the cyclic embedded copolymer.
Description
Technical field
The present invention relates to a kind of method of preparing annular polyester, relate in particular to a kind of utilization based on Zn (C
6f
5)
2the preparation method of annular polyester is prepared in the right ring-opening polymerization of Lewis Acids and Bases.
Background technology
Phosphoric acid hydrogen/borine to can be under gentle condition can traitor's property hydrogen, a variety of Lewis Acids and Bases are to being produced out, be not phosphoric acid hydrogen, also have amine and nitrogen heterocyclic ring Cabbeen (NHC) to be used for being combined with perfluor aryl borine, other based on aluminium, carbon, Louis's acid solution of silicon or transition metal also is produced out.These Lewis Acids and Bases are to a lot of small molecules are had to synergistic activation ability, and Lewis Acids and Bases is to also having played effect to collaborative nonmetal catalysis.At present Lewis Acids and Bases to can synergistic activation monomer and generation there are the both sexes species of high activity.
Ring-opening polymerization (ROP) is a kind of very powerful and widely used polymerization technique, it provides very effective path for utilizing lactone and relevant monomer to prepare valuable biodegradability polymkeric substance, in ring-opening polymerization, if preparation has the polymkeric substance of controlled architecture under mild conditions, catalyzer plays a part very crucial.In prior art, B (C
6f
6)
3/ Lewis base acid base pair just can be observed in some specific stoichiometric reaction (the contracting ring reaction of the ring-opening polymerization of δ-valerolactone and rac-Lactide), both sexes phosphorus/ammonium borate the alkoxide producing in these reactions to the coordination of lactone and insertion be do not have activated, under the existence of the contrary derivative at boron, the alkoxide of zinc can promote the ring-opening polymerization of annular ester and lactone effectively, and prior art has limitation to Lewis Acids and Bases to the application for ring-opening polymerization.
Annular polymeric is the very attractive macromole of a class, the pattern of annular give ring molecule some special have the very performance of big difference with linear molecule.Especially ring molecule and linear molecule have different degradeds and bio distribution characteristic, but its composition problem has very seriously limited the research and development of the annular polyester with property.The method of the polyfunctional ring molecule for the preparation of high controlled molecular weight just seems and is necessary very much effectively.
Summary of the invention
In the present invention, in conjunction with Zn (C
6f
5) and the dual system of organic bases (amine or phosphuret-(t)ed hydrogen) can promote the controlled ring-opening polymerization of rac-Lactide and 6-caprolactone, Lewis Acids and Bases activates monomer to synergy, thereby obtains high molecular annular polyester.Concrete steps are as follows:
(1) polymerization of rac-Lactide: in a glove-box, first by Zn (C
6f
5)
2pack in a Shu Lunke bottle with lactic acid lactide, add 5mL methyltetrahydrofuran (Me-THF) dissolved monomer/Zn (C
6f
5)
2mixture, at 70 ℃, stir 20～60min after adding 4.5 μ L (0.025mmol) pentamethyl-piperidines (PMP), add HCl/Et
2o (2.0mol/L, 0.05mmol) solution stops polyreaction; Toluene joins precipitation and complexation thing and ammonium salt in starting materials, salt is removed by the method for filtering, solvent is removed by vacuum drying method, and original polymer is dissolved in methylene dichloride and then in cold ether or pentane, after precipitation, with pentane or ether, washs then vacuum-drying.
(2) linear poly(lactic acid) (PLA) analogue is synthetic: first compound concentration is respectively the original solution of zinc cation complex compound, amylalcohol and the pentamethyl-piperidines of 0.3mol/L, 2.0mol/L and 0.8mol/L; Concrete compound method is as follows: at gloves, be in operation box, first by lactic acid lactide (0.169g, 1.17mol) and methylene dichloride (2.3mL) pack in a Shu Lunke bottle, be then dissolved in zinc complex (22.5 μ L, 4.5 * 10 in methylene dichloride
-3mmol) join in monomer solution stirring at room 1～5min, amyl alcohol solution (9 μ L, 9.0 * 10
-3mmol) join in above-mentioned solution, then add pentamethyl-piperidine solution (22.5 μ L, 4.5 * 10
-3mmol).Stir 20～60min, after polyreaction completes, polymkeric substance is in cold methyl alcohol or ether after Precipitation, and filtration and vacuum-drying obtain sample.
(3) polymerization of 6-caprolactone: in a glove-box, first by Zn (C
6f
5)
2(10mg, 0.025mmol) is encased in a Shu Lunke bottle.Methyl-tetrahydrofuran (THF) (1.5mL) adds and in bottle, dissolves Zn (C
6f
5)
2.6-caprolactone (83.2 μ L, 0.75mmol) and pentamethyl-piperidines (4.5 μ L, 0.025mmol) join in solution and then at 70 ℃, stir 3～4h, add HCl/Et
2o (2.0mol/L, 0.05mmol) solution termination reaction, by product Precipitation in cold ether, obtains sample with pentane (1.5～6.0mL) washing and vacuum-drying.
(4) Zn (C
6f
5)
2the preparation of/Lewis base adducts: by Zn (C
6f
5)
2join C
6d
6in reagent, be mixed with solution, by DMAP, P
nbu
3or pentamethyl-piperidines joins in above-mentioned solution, and reaction is passed through
19f and/or
31the nuclear magnetic resonance spectrum monitoring of P.
(5) 6-caprolactone/lactic acid lactide is at Zn (C
6f
5)
2sequential co-polymerization under/PMP exists: by 10.0mg (0.025mmol) Zn (C
6f
5)
2join in the methyl-tetrahydrofuran solution of 111 μ L 6-caprolactones, with a microsyringe, dropwise add PMP (4.53 μ L, 0.025mmol) in above-mentioned mixing solutions again, stirring reaction 5～8h at 70 ℃, add 144.3mg (1mmol) lactic acid lactide, reaction 12h; After reaction finishes, use HCl/Et
2o terminator (2.0mol/L, 0.05mmol) termination reaction is filtered to remove salts solution and is isolated multipolymer in toluene and cold ether, and it is dry that polymkeric substance is washed twice final vacuum with pentane.
In the present invention with the right Zn (C of Lewis Acids and Bases
6f
6)
2replace B (C
6f
6)
2/ Zn (C
6f
6)
2with the combination of organic bases (amine or phosphoric acid hydrogen) can control the ring-opening polymerization of rac-Lactide and 6-caprolactone really, thereby give the structure of polymkeric substance annular, effectively the synthetic approach that provides of Cyclic block copolymer is provided molecular chain.
In the present invention in conjunction with Zn (C
6f
5) and the dual system of organic bases (amine or phosphuret-(t)ed hydrogen) can promote the controlled ring-opening polymerization of rac-Lactide and 6-caprolactone, Lewis Acids and Bases activates monomer to synergy, thereby obtains high molecular annular polyester.
Embodiment
In order to deepen the understanding of the present invention, below in conjunction with specific embodiment, the present invention is described in further detail.
(1) polymerization of rac-Lactide: in a glove-box, first by Zn (C
6f
5)
2(10mg, 0.025mmol) and lactic acid lactide (360.8mg, 2.25mmol) pack in a Shu Lunke bottle, then add 5mL methyltetrahydrofuran (Me-THF) dissolved monomer/Zn (C
6f
5)
2mixture, at 70 ℃, stir 20～60min after then adding the pentamethyl-piperidines (PMP) of 4.5 μ L (0.025mmol), add HCl/Et
2o (2.0mol/L, 0.05mmol) solution stops polyreaction.Toluene joins precipitation and complexation thing and ammonium salt in starting materials, salt is removed by the method for filtering, solvent is removed by vacuum drying method, and original polymer is dissolved in methylene dichloride and then in cold ether or pentane, after precipitation, with pentane or ether, washs then vacuum-drying.
(2) linear poly(lactic acid) (PLA) analogue is synthetic: first compound concentration is respectively the original solution of zinc cation complex compound, amylalcohol and the pentamethyl-piperidines of 0.3mol/L, 2.0mol/L and 0.8mol/L, concrete compound method is as follows: at gloves, be in operation box, first by lactic acid lactide (0.169g, 1.17mol) and methylene dichloride (2.3mL) pack in a Shu Lunke bottle, then be dissolved in zinc complex (22.5 μ L, 4.5 * 10 in methylene dichloride
-3mmol) join in monomer solution stirring at room 1～5min; Amyl alcohol solution (9 μ L, 9.0 * 10
-3mmol) join in above-mentioned solution, then add pentamethyl-piperidine solution (22.5 μ L, 4.5 * 10
-3mmol), stir 20～60min, polyreaction just can complete after 3h, and after completing, polymkeric substance is in cold methyl alcohol or ether after Precipitation, and filtration and vacuum-drying obtain sample.
(3) polymerization of 6-caprolactone: in a glove-box, first by Zn (C
6f
5)
2(10mg, 0.025mmol) is encased in a Shu Lunke bottle, and methyl-tetrahydrofuran (THF) (1.5mL) adds and in bottle, dissolves Zn (C
6f
5)
2, 6-caprolactone (83.2 μ L, 0.75mmol) and pentamethyl-piperidines (4.5 μ L, 0.025mmol) join in solution and then at 70 ℃, stir 3h, add HCl/Et
2o solution (2.0mol/L, 0.05mmol) termination reaction, then by product Precipitation in cold ether, obtains sample with pentane (2 * 1.5mL) washing and vacuum-drying.
(4) Zn (C
6f
5)
2the preparation of/Lewis base adducts: by 10.0mg Zn (C
6f
5)
2join C
6d
6in reagent, then 2.4mgDMAP, 6.20 μ LPnBu3 or 4.53 μ L pentamethyl-piperidines join in above-mentioned solution, and reaction is passed through
19f and/or
31the nuclear magnetic resonance spectrum monitoring of P.
(5) 6-caprolactone/lactic acid lactide is at Zn (C
6f
5)
2sequential co-polymerization under/PMP exists: first by 10.0mg (0.025mmol) Zn (C
6f
5)
2join in the methyl-tetrahydrofuran solution of 111 μ L 6-caprolactones, then with a microsyringe, dropwise add PMP (4.53 μ L, 0.025mmol) in above-mentioned mixing solutions, stirring reaction 6h at 70 ℃, then add 144.3mg (1mmol) lactic acid lactide, reaction 12h; After reaction finishes, use HCl/Et
2o terminator (2.0mol/L, 0.05mmol) termination reaction is filtered to remove salts solution and is isolated multipolymer in toluene and cold ether, and it is dry that polymkeric substance is washed twice (2 * 1.5mL) final vacuum with pentane.
Claims (2)
1. Lewis Acids and Bases is to the method for the preparation of annular polyester, and its step is as follows:
(1) polymerization of rac-Lactide:
In a glove-box, first by Zn (C
6f
5)
2pack in a Shu Lunke bottle with lactic acid lactide, add 5mL methyltetrahydrofuran (Me-THF) dissolved monomer/Zn (C
6f
5)
2mixture, at 70 ℃, stir 20～60min after adding 4.5 μ L (0.025mmol) pentamethyl-piperidines (PMP), add HCl/Et
2o (2.0mol/L, 0.05mmol) solution stops polyreaction; Toluene joins precipitation and complexation thing and ammonium salt in starting materials, salt is removed by the method for filtering, solvent is removed by vacuum drying method, and original polymer is dissolved in methylene dichloride and then in cold ether or pentane, after precipitation, with pentane or ether, washs then vacuum-drying;
(2) linear poly(lactic acid) (PLA) analogue is synthetic:
First compound concentration is respectively the original solution of zinc cation complex compound, amylalcohol and the pentamethyl-piperidines of 0.3mol/L, 2.0mol/L and 0.8mol/L; Concrete compound method is as follows: at gloves, be in operation box, first by lactic acid lactide (0.169g, 1.17mol) and methylene dichloride (2.3mL) pack in a Shu Lunke bottle, be then dissolved in zinc complex (22.5 μ L, 4.5 * 10 in methylene dichloride
-3mmol) join in monomer solution stirring at room 1～5min, amyl alcohol solution (9 μ L, 9.0 * 10
-3mmol) join in above-mentioned solution, then add pentamethyl-piperidine solution (22.5 μ L, 4.5 * 10
-3mmol), stir 20～60min, after polyreaction completes, polymkeric substance is in cold methyl alcohol or ether after Precipitation, and filtration and vacuum-drying obtain sample;
(3) polymerization of 6-caprolactone:
In a glove-box, first by Zn (C
6f
5)
2(10mg, 0.025mmol) is encased in a Shu Lunke bottle, and methyl-tetrahydrofuran (THF) (1.5mL) adds and in bottle, dissolves Zn (C
6f
5)
2, 6-caprolactone (83.2 μ L, 0.75mmol) and pentamethyl-piperidines (4.5 μ L, 0.025mmol) join in solution and then at 70 ℃, stir 3～4h, add HCl/Et
2o (2.0mol/L, 0.05mmol) solution termination reaction, by product Precipitation in cold ether, obtains sample with pentane (1.5～6.0mL) washing and vacuum-drying;
(4) Zn (C
6f
5)
2the preparation of/Lewis base adducts:
By Zn (C
6f
5)
2join C
6d
6in reagent, be mixed with solution, by DMAP, P
nbu
3or pentamethyl-piperidines joins in above-mentioned solution, and reaction is passed through
19f and/or
31the nuclear magnetic resonance spectrum monitoring of P;
(5) 6-caprolactone/lactic acid lactide is at Zn (C
6f
5)
2sequential co-polymerization under/PMP exists:
By 10.0mg (0.025mmol) Zn (C
6f
5)
2join in the methyl-tetrahydrofuran solution of 111 μ L 6-caprolactones, with a microsyringe, dropwise add PMP (4.53 μ L, 0.025mmol) in above-mentioned mixing solutions again, stirring reaction 5～8h at 70 ℃, add 144.3mg (1mmol) lactic acid lactide, reaction 12h; After reaction finishes, use HCl/Et
2o terminator (2.0mol/L, 0.05mmol) termination reaction is filtered to remove salts solution and is isolated multipolymer in toluene and cold ether, and it is dry that polymkeric substance is washed twice final vacuum with pentane.
2. the method for the annular polyester of preparation as claimed in claim 1, is characterized in that: Zn (C in step (1)
6f
5)
2with the mol ratio of lactic acid lactide be 1:100.
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| CN201310586157.2A CN103613742A (en) | 2013-11-15 | 2013-11-15 | Method for preparing cyclic polyester by utilizing Lewis acid-base pair |
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061501A (en) * | 2015-08-07 | 2015-11-18 | 江苏红太阳新材料有限公司 | Metal complex for catalyzing cycloate polymerization and application of metal complex for catalyzing cycloate polymerization |
| CN106496538A (en) * | 2016-10-19 | 2017-03-15 | 安徽红太阳新材料有限公司 | A kind of synthetic method of high molecular polycaprolactone |
| CN106633006A (en) * | 2016-10-19 | 2017-05-10 | 安徽红太阳新材料有限公司 | Synthesis method for ring-like polylactone-type polymer |
| CN113896875A (en) * | 2021-10-11 | 2022-01-07 | 吉林大学 | Intramolecular trifunctional Lewis acid-base pair catalyst, annular topological structure PMMBL polymer, preparation method and application |
| CN114106299A (en) * | 2021-12-31 | 2022-03-01 | 深圳市鑫元素新材料科技有限公司 | Preparation method of lactone and lactide block copolymer |
-
2013
- 2013-11-15 CN CN201310586157.2A patent/CN103613742A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| ESTEFANIA PIEDRA-ARRONI等: "Ring-opening polymerization with Zn(C6F5)2-based Lewis pairs: original and efficient approach to cyclic polyesters", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061501A (en) * | 2015-08-07 | 2015-11-18 | 江苏红太阳新材料有限公司 | Metal complex for catalyzing cycloate polymerization and application of metal complex for catalyzing cycloate polymerization |
| CN106496538A (en) * | 2016-10-19 | 2017-03-15 | 安徽红太阳新材料有限公司 | A kind of synthetic method of high molecular polycaprolactone |
| CN106633006A (en) * | 2016-10-19 | 2017-05-10 | 安徽红太阳新材料有限公司 | Synthesis method for ring-like polylactone-type polymer |
| CN106633006B (en) * | 2016-10-19 | 2021-12-03 | 安徽红太阳新材料有限公司 | Synthesis method of cyclic polylactone polymer |
| CN113896875A (en) * | 2021-10-11 | 2022-01-07 | 吉林大学 | Intramolecular trifunctional Lewis acid-base pair catalyst, annular topological structure PMMBL polymer, preparation method and application |
| CN113896875B (en) * | 2021-10-11 | 2022-05-31 | 吉林大学 | Intramolecular trifunctional Lewis acid-base pair catalyst, annular topological structure PMMBL polymer, preparation method and application |
| CN114106299A (en) * | 2021-12-31 | 2022-03-01 | 深圳市鑫元素新材料科技有限公司 | Preparation method of lactone and lactide block copolymer |
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Application publication date: 20140305 |