CN104877130A - Synthetic method of polylactic acid-gamma aminobutyric acid copolymerization material - Google Patents
Synthetic method of polylactic acid-gamma aminobutyric acid copolymerization material Download PDFInfo
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- CN104877130A CN104877130A CN201510107468.5A CN201510107468A CN104877130A CN 104877130 A CN104877130 A CN 104877130A CN 201510107468 A CN201510107468 A CN 201510107468A CN 104877130 A CN104877130 A CN 104877130A
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- lactic acid
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- acid
- amino butyric
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Abstract
The invention relates to a synthetic method of a polylactic acid-gamma aminobutyric acid copolymerization material and belongs to the technical field of polymer synthesis. According to the invention, polylactic acid and gamma aminobutyric acid are used as raw materials to prepare a novel binary amino acid copolymer material by a melt polymerization method. The method has advantages of easily-available raw material and stable technological condition, and is suitable for large-scale industrial production. Through the above technology, the preparation technology is simple, and used raw materials are simple and easily available and have low toxicity. The obtained polylactic acid-gamma aminobutyric acid copolymerization material has high yield and good product purity, has low requirements on equipment, is suitable for industrial production, and is convenient for popularization and application.
Description
Technical field
The present invention relates to synthesis of polymer material field, particularly the synthetic method of a kind of poly(lactic acid)-gamma amino butyric acid copolymeric material.
Background technology
Poly(lactic acid) is polylactide again, and be a kind of thermoplastic linear's macromolecular material, the production process of poly(lactic acid) is pollution-free, and product can biological degradation, and realizing the circulation at occurring in nature, is therefore desirable Green Polymer Material.It has good degradation property, biocompatibility, the advantage of workability and production process save energy, but enbrittles simultaneously, and the shortcomings such as snappiness is poor, its application has certain limitation, can not meet the demands.By introducing second component in material, to prepare multipolymer be one of important channel of improving macromolecular material performance, controlled degradation speed and the cycle of polymer materials by molecular weight of copolymer, comonomer type and proportioning etc.The multipolymer of different structure gets up the advantages of differing materials, can give the character that novel material is special.
Poly(lactic acid) involved in the present invention-gamma amino butyric acid copolymeric material is a kind of novel copolymer of poly lactic acid material.This bill of material reveals good degradation property and snappiness, may be used for the bio-medical materials such as suture.
Summary of the invention
Object of the present invention be exactly in order to overcome above-mentioned prior art exist defect and provide a kind of snappiness good, the synthetic method of polymerization technique simple poly(lactic acid)-gamma amino butyric acid copolymeric material.
Object of the present invention can be achieved through the following technical solutions: the synthetic method of a kind of poly(lactic acid)-gamma amino butyric acid copolymeric material, it is characterized in that, the method adopts melt phase polycondensation to synthesize degradable poly(lactic acid)-gamma amino butyric acid copolymeric material, specifically comprises the following steps:
1) lactic acid solution is placed in reactor, is warmed up to 150 ~ 200 DEG C, dewater 1 ~ 3h at ambient pressure, then be progressively evacuated down to 6000 ~ 10000Pa, keep 1 ~ 3h, then regulation system vacuum tightness to 80 ~ 120Pa, continue the 3 ~ 5h that dewaters, obtained poly(lactic acid) prepolymer;
2) getting γ-aminobutyric acid powder is dissolved in poly(lactic acid) prepolymer, abundant stirring and dissolving;
3) add catalyst mix, stirring reaction, controlling reactive system vacuum tightness is 80 ~ 120Pa, and stops at 160 ~ 200 DEG C of reaction 2 ~ 3h;
4) polymkeric substance that upper step is obtained is dissolved in cleaning solvent, after filtering, then is the petroleum ether precipitation of 30 DEG C ~ 60 DEG C by boiling range and filters, the vacuum drying oven be placed in by throw out takes out after dry 24 hours and obtains product at 50 DEG C.
Lactic acid solution described in step (1) is Pfansteihl or DL-LACTIC ACID solution.
γ-aminobutyric acid powder described in step (2) and the molar ratio of poly(lactic acid) prepolymer are 9 ~ 7:1 ~ 3.
γ-aminobutyric acid powder described in step (2) and the molar ratio of poly(lactic acid) prepolymer are 9:1,8:2,7:3 tri-kinds.
Catalyzer described in step (3) is any one in two hydrated stannous chlorides, tosic acid, dibutyl zinc, and its quality that feeds intake is the 10-15% of the quality of poly(lactic acid)-gamma amino butyric acid.
In the process of the stirring reaction described in step (3), reactor is equipped with de-watering apparatus.
Cleaning solvent described in step (4) is any one in tetrahydrofuran (THF), trichloromethane, acetone, its quality that feeds intake be the 1-3 of the quality of poly(lactic acid)-gamma amino butyric acid doubly.
Compared with prior art, the present invention has the following advantages:
1 the present invention adopts melt phase polycondensation, reduces the synthesis cost of poly(lactic acid)-Y aminobutyric acid copolymeric material, improves the molecular weight of poly(lactic acid)-Y aminobutyric acid copolymeric material.
2 the present invention are with poly(lactic acid), Y aminobutyric acid for raw material, and adopt four step rule to be obtained by reacting with poly(lactic acid)-Y aminobutyric acid copolymeric material, overall yield is up to more than 90%.
3 operating procedures of the present invention are easy, and raw material is cheap and easy to get, and yield is high, and good product purity is low for equipment requirements, are applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of target compound of the present invention;
Fig. 2 is the nmr spectrum of target compound of the present invention.
Embodiment
The present invention is further illustrated to use embodiment below, but content of the present invention is not limited only to the involved content in the present embodiment.
Embodiment 1
1) get 100ml lactic acid solution (Pfansteihl or DL-LACTIC ACID) and put into 250ml there-necked flask, connect water-and-oil separator and prolong, open magnetic agitation, be warmed up to 180 DEG C, dewater 2h at ambient pressure, is then then progressively evacuated down to about 8000Pa with water pump with water pump, keeps 2h, then use vacuum pump regulation system vacuum tightness to 100Pa, continue the 4h that dewaters.Stop experiment, write down the water yield in water-and-oil separator, obtained poly(lactic acid) prepolymer is taken out for subsequent use.
2) taking 100g γ-aminobutyric acid powder is dissolved in poly(lactic acid) prepolymer, abundant stirring and dissolving, and wherein the molar ratio of γ-aminobutyric acid powder and poly(lactic acid) prepolymer is 8:2.
3) in step (2) gained material, catalyzer two hydrated stannous chloride is added, the catalyzer quality that feeds intake is about 12% of the quality of poly(lactic acid)-gamma amino butyric acid, mixing, keep magnetic agitation, and install the de-watering apparatus that a small amount of hydrolith is housed additional and (hydrolith particle is put into dry water-and-oil separator, amount is about 1/4th of water receiving pipe height) to remove the trace water produced in reaction process, the ridity that maintenance system is higher, controlling reactive system vacuum tightness is 100Pa, and stops 180 DEG C of reaction regular hours.
4) polymkeric substance that upper step obtains is dissolved in the solution that tetrahydrofuran (THF) makes 10wt%, after filtering, then is the petroleum ether precipitation of 30 DEG C to 60 DEG C by boiling range and filters, the vacuum drying oven be placed in by throw out takes out after dry 24 hours and tests at 50 DEG C.
Gained poly(lactic acid)-gamma amino butyric acid infrared spectrum as described in Figure 1, can be found out:
Peak position is at 3494.1cm
-1place is the OH absorption peak of PLA, 2995.7cm
-1and 1454.5cm
-1place is the CH of PLA
3stretch and flexural vibration peak, 1757.9cm
-1the CH that place is PLA stretches and flexural vibration peak.2870-2950cm
-1γ-aminobutyric acid CH2 stretching vibration absorption peak, 1610.60cm
-1it is NH symmetrical stretching vibration absorption peak in amino.
The nmr spectrum of gained poly(lactic acid)-gamma amino butyric acid as described in Figure 2, can be found out:
Be doublet in δ=1.57, strength ratio is 1:1, and peak area is 61.15, it can thus be appreciated that they are the methyl (CH adjoined each other in PLA respectively
3) and methylene radical (CH
2).In figure, peak, δ=3.4 place is CH, δ in γ-aminobutyric acid=2.6 peaks, place is NH
2.
Embodiment 2:
1) get 50ml lactic acid solution (Pfansteihl or DL-LACTIC ACID) and put into 250ml there-necked flask, connect water-and-oil separator and prolong, open magnetic agitation, be warmed up to 180 DEG C, dewater 2h at ambient pressure, is then then progressively evacuated down to about 8 000Pa with water pump with water pump, keeps 2h, then use vacuum pump regulation system vacuum tightness to 100Pa, continue the 4h that dewaters.Stop experiment, write down the water yield in water-and-oil separator, obtained poly(lactic acid) prepolymer is taken out for subsequent use.
2) taking 100g γ-aminobutyric acid powder is dissolved in poly(lactic acid) prepolymer, abundant stirring and dissolving, and wherein the molar ratio of γ-aminobutyric acid powder and poly(lactic acid) prepolymer is 9:3.
3) in step (2) gained material, catalyzer tosic acid is added, the catalyzer quality that feeds intake is about 14% of the quality of poly(lactic acid)-gamma amino butyric acid, mixing, keep magnetic agitation, and install the de-watering apparatus that a small amount of hydrolith is housed additional and (hydrolith particle is put into dry water-and-oil separator, amount is about 1/4th of water receiving pipe height) to remove the trace water produced in reaction process, the ridity that maintenance system is higher, controlling reactive system vacuum tightness is 100Pa, and stops 180 DEG C of reaction regular hours.
4) polymkeric substance that upper step obtains is dissolved in the solution that tetrahydrofuran (THF) makes 10wt%, after filtering, then is the petroleum ether precipitation of 30 DEG C to 60 DEG C by boiling range and filters, the vacuum drying oven be placed in by throw out takes out after dry 24 hours and tests at 50 DEG C.
Embodiment 3:
1) get 100ml lactic acid solution (Pfansteihl or DL-LACTIC ACID) and put into 250ml there-necked flask, connect water-and-oil separator and prolong, open magnetic agitation, be warmed up to 150 DEG C, dewater 3h at ambient pressure, is then then progressively evacuated down to 6000Pa with water pump with water pump, keeps 3h, then use vacuum pump regulation system vacuum tightness to 80Pa, continue the 5h that dewaters.Stop experiment, write down the water yield in water-and-oil separator, obtained poly(lactic acid) prepolymer is taken out for subsequent use.
2) taking 50g γ-aminobutyric acid powder is dissolved in poly(lactic acid) prepolymer, abundant stirring and dissolving, and wherein the molar ratio of γ-aminobutyric acid powder and poly(lactic acid) prepolymer is 9:2.
3) in step (2) gained material, catalyzer dibutyl zinc is added, the catalyzer quality that feeds intake is about 13% of the quality of poly(lactic acid)-gamma amino butyric acid, mixing, keep magnetic agitation, and install the de-watering apparatus that a small amount of hydrolith is housed additional and (hydrolith particle is put into dry water-and-oil separator, amount is about 1/4th of water receiving pipe height) to remove the trace water produced in reaction process, the ridity that maintenance system is higher, controlling reactive system vacuum tightness is 80Pa, and stops in the time of 180 DEG C of reaction 3h.
4) polymkeric substance that upper step is obtained is dissolved in trichloromethane, the trichloromethane quality that feeds intake is about 1 times of the quality of poly(lactic acid)-gamma amino butyric acid, after filtering, be the petroleum ether precipitation of 30 DEG C to 60 DEG C by boiling range again and filter, the vacuum drying oven be placed in by throw out takes out after dry 24 hours and tests at 50 DEG C.
Embodiment 4:
1) get 100ml lactic acid solution (Pfansteihl or DL-LACTIC ACID) and put into 250ml there-necked flask, connect water-and-oil separator and prolong, open magnetic agitation, be warmed up to 200 DEG C, dewater 2h at ambient pressure, is then then progressively evacuated down to about 10000Pa with water pump with water pump, keeps 1h, then use vacuum pump regulation system vacuum tightness to 120Pa, continue the 3h that dewaters.Stop experiment, write down the water yield in water-and-oil separator, obtained poly(lactic acid) prepolymer is taken out for subsequent use.
2) taking 100g γ-aminobutyric acid powder is dissolved in poly(lactic acid) prepolymer, abundant stirring and dissolving, and wherein the molar ratio of γ-aminobutyric acid powder and poly(lactic acid) prepolymer is 8:2.
3) in step (2) gained material, catalyzer tosic acid is added, the catalyzer quality that feeds intake is about 12% of the quality of poly(lactic acid)-gamma amino butyric acid, mixing, keep magnetic agitation, and install the de-watering apparatus that a small amount of hydrolith is housed additional and (hydrolith particle is put into dry water-and-oil separator, amount is about 1/4th of water receiving pipe height) to remove the trace water produced in reaction process, the ridity that maintenance system is higher, controlling reactive system vacuum tightness is 120Pa, and stops in the time of 200 DEG C of reaction 2h.
4) polymkeric substance that upper step is obtained is dissolved in acetone, the acetone quality that feeds intake is about 3 times of the quality of poly(lactic acid)-gamma amino butyric acid, after filtering, be the petroleum ether precipitation of 30 DEG C to 60 DEG C by boiling range again and filter, the vacuum drying oven be placed in by throw out takes out after dry 24 hours and tests at 50 DEG C.
Embodiment 5:
1) get 100ml lactic acid solution (Pfansteihl or DL-LACTIC ACID) and put into 250ml there-necked flask, connect water-and-oil separator and prolong, open magnetic agitation, be warmed up to 180 DEG C, dewater 2h at ambient pressure, is then then progressively evacuated down to about 8 000Pa with water pump with water pump, keeps 2h, then use vacuum pump regulation system vacuum tightness to 50Pa, continue the 4h that dewaters.Stop experiment, write down the water yield in water-and-oil separator, obtained poly(lactic acid) prepolymer is taken out for subsequent use.
2) taking 100g γ-aminobutyric acid powder is dissolved in poly(lactic acid) prepolymer, abundant stirring and dissolving, and wherein the molar ratio of γ-aminobutyric acid powder and poly(lactic acid) prepolymer is 7:3.
3) in step (2) gained material, catalyzer two hydrated stannous chloride is added, the catalyzer quality that feeds intake is about 10% of the quality of poly(lactic acid)-gamma amino butyric acid, mixing, keep magnetic agitation, and install the de-watering apparatus that a small amount of hydrolith is housed additional and (hydrolith particle is put into dry water-and-oil separator, amount is about 1/4th of water receiving pipe height) to remove the trace water produced in reaction process, the ridity that maintenance system is higher, controlling reactive system vacuum tightness is 80Pa, and stops in the time of 160 DEG C of reaction 3h.
4) polymkeric substance that upper step obtains is dissolved in the solution that tetrahydrofuran (THF) makes 10wt%, after filtering, then is the petroleum ether precipitation of 30 DEG C to 60 DEG C by boiling range and filters, the vacuum drying oven be placed in by throw out takes out after dry 24 hours and tests at 50 DEG C.
Embodiment 6:
1) get 100ml lactic acid solution (Pfansteihl or DL-LACTIC ACID) and put into 250ml there-necked flask, connect water-and-oil separator and prolong, open magnetic agitation, be warmed up to 180 DEG C, dewater 2h at ambient pressure, is then then progressively evacuated down to about 8000Pa with water pump with water pump, keeps 2h, then use vacuum pump regulation system vacuum tightness to 100Pa, continue the 4h that dewaters.Stop experiment, write down the water yield in water-and-oil separator, obtained poly(lactic acid) prepolymer is taken out for subsequent use.
2) taking 100g γ-aminobutyric acid powder is dissolved in poly(lactic acid) prepolymer, abundant stirring and dissolving, and wherein the molar ratio of γ-aminobutyric acid powder and poly(lactic acid) prepolymer is 9:1.
3) in step (2) gained material, catalyzer dibutyl zinc is added, the catalyzer quality that feeds intake is about 10% of the quality of poly(lactic acid)-gamma amino butyric acid, mixing, keep magnetic agitation, and install the de-watering apparatus that a small amount of hydrolith is housed additional and (hydrolith particle is put into dry water-and-oil separator, amount is about 1/4th of water receiving pipe height) to remove the trace water produced in reaction process, the ridity that maintenance system is higher, controlling reactive system vacuum tightness is 100Pa, and stops in the time of 180 DEG C of reaction 3h.
4) polymkeric substance that upper step obtains is dissolved in the solution that trichloromethane makes 10wt%, after filtering, then is the petroleum ether precipitation of 30 DEG C to 60 DEG C by boiling range and filters, the vacuum drying oven be placed in by throw out takes out after dry 24 hours and tests at 50 DEG C.
Claims (7)
1. a synthetic method for poly(lactic acid)-gamma amino butyric acid copolymeric material, is characterized in that, the method adopts melt phase polycondensation to synthesize degradable poly(lactic acid)-gamma amino butyric acid copolymeric material, specifically comprises the following steps:
1) lactic acid solution is placed in reactor, is warmed up to 150 ~ 200 DEG C, dewater 1 ~ 3h at ambient pressure, then be progressively evacuated down to 6000 ~ 10000Pa, keep 1 ~ 3h, then regulation system vacuum tightness to 80 ~ 120Pa, continue the 3 ~ 5h that dewaters, obtained poly(lactic acid) prepolymer;
2) getting γ-aminobutyric acid powder is dissolved in poly(lactic acid) prepolymer, abundant stirring and dissolving;
3) add catalyst mix, stirring reaction, controlling reactive system vacuum tightness is 80 ~ 120Pa, and stops at 160 ~ 200 DEG C of reaction 2 ~ 3h;
4) polymkeric substance that upper step is obtained is dissolved in cleaning solvent, after filtering, then is the petroleum ether precipitation of 30 DEG C ~ 60 DEG C by boiling range and filters, the vacuum drying oven be placed in by throw out takes out after dry 24 hours and obtains product at 50 DEG C.
2. the synthetic method of a kind of poly(lactic acid)-gamma amino butyric acid copolymeric material according to claim 1, is characterized in that, the lactic acid solution described in step (1) is Pfansteihl or DL-LACTIC ACID solution.
3. the synthetic method of a kind of poly(lactic acid)-gamma amino butyric acid copolymeric material according to claim 1, is characterized in that, the γ-aminobutyric acid powder described in step (2) and the molar ratio of poly(lactic acid) prepolymer are 9 ~ 7:1 ~ 3.
4. the synthetic method of a kind of poly(lactic acid)-gamma amino butyric acid copolymeric material according to claim 1 or 3, is characterized in that, the γ-aminobutyric acid powder described in step (2) and the molar ratio of poly(lactic acid) prepolymer are 9:1,8:2,7:3 tri-kinds.
5. the synthetic method of a kind of poly(lactic acid)-gamma amino butyric acid copolymeric material according to claim 1, it is characterized in that, catalyzer described in step (3) is any one in two hydrated stannous chlorides, tosic acid, dibutyl zinc, and its quality that feeds intake is the 10-15% of the quality of poly(lactic acid)-gamma amino butyric acid.
6. the synthetic method of a kind of poly(lactic acid)-gamma amino butyric acid copolymeric material according to claim 1, is characterized in that, in the process of the stirring reaction described in step (3), reactor is equipped with de-watering apparatus.
7. the synthetic method of a kind of poly(lactic acid)-gamma amino butyric acid copolymeric material according to claim 1, it is characterized in that, cleaning solvent described in step (4) is any one in tetrahydrofuran (THF), trichloromethane, acetone, its quality that feeds intake be the 1-3 of the quality of poly(lactic acid)-gamma amino butyric acid doubly.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111206301A (en) * | 2020-01-22 | 2020-05-29 | 华东理工大学 | Preparation method of bio-based degradable polymer superfine fiber |
| CN114015032A (en) * | 2021-11-01 | 2022-02-08 | 千芝雅(湖北)卫生用品有限公司 | Preparation method of breathable and antiallergic material for adult paper diaper |
| CN115260478A (en) * | 2022-07-19 | 2022-11-01 | 绍兴文理学院 | Preparation method and application of high-strength high-toughness polylactic acid copolymer |
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| CN1775827A (en) * | 2005-11-23 | 2006-05-24 | 上海氯碱化工股份有限公司 | Method for preparing L-lactic acid and amino acid copolymer by melt-solid phase condensation polymerization |
| CN103172855A (en) * | 2013-04-11 | 2013-06-26 | 常州大学 | Lactic acid-amino acid copolyester amide and preparation method thereof |
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2015
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| CN1775827A (en) * | 2005-11-23 | 2006-05-24 | 上海氯碱化工股份有限公司 | Method for preparing L-lactic acid and amino acid copolymer by melt-solid phase condensation polymerization |
| CN103172855A (en) * | 2013-04-11 | 2013-06-26 | 常州大学 | Lactic acid-amino acid copolyester amide and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111206301A (en) * | 2020-01-22 | 2020-05-29 | 华东理工大学 | Preparation method of bio-based degradable polymer superfine fiber |
| CN111206301B (en) * | 2020-01-22 | 2022-08-12 | 华东理工大学 | Preparation method of bio-based degradable polymer superfine fiber |
| CN114015032A (en) * | 2021-11-01 | 2022-02-08 | 千芝雅(湖北)卫生用品有限公司 | Preparation method of breathable and antiallergic material for adult paper diaper |
| CN115260478A (en) * | 2022-07-19 | 2022-11-01 | 绍兴文理学院 | Preparation method and application of high-strength high-toughness polylactic acid copolymer |
| CN115260478B (en) * | 2022-07-19 | 2024-02-02 | 绍兴文理学院 | Preparation method and application of high-strength high-toughness polylactic acid copolymer |
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