CN101864061B - Microwave irradiation method for preparing star polycaprolactone-polylactic acid block copolymer - Google Patents
Microwave irradiation method for preparing star polycaprolactone-polylactic acid block copolymer Download PDFInfo
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- CN101864061B CN101864061B CN2010101864239A CN201010186423A CN101864061B CN 101864061 B CN101864061 B CN 101864061B CN 2010101864239 A CN2010101864239 A CN 2010101864239A CN 201010186423 A CN201010186423 A CN 201010186423A CN 101864061 B CN101864061 B CN 101864061B
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Abstract
The invention relates to a microwave irradiation method for preparing a star polycaprolactone-polylactic acid block copolymer, which comprises the following specific steps of: putting caprolactone and di-penta in a certain proportion into a dry one-neck flask with a stirrer, after melting and mixing in nitrogen atmosphere, adding a catalyst, vacuumizing and introducing nitrogen for three times, and putting the flask into a microwave reactor to perform reaction to obtain a polymer; and melting and mixing the polymer and lactide in a certain proportion in the nitrogen atmosphere, adding the catalyst, vacuumizing and introducing the nitrogen for three times, and putting the flask into the microwave reactor to perform reaction to obtain the star polycaprolactone-polylactic acid block copolymer. The method can shorten the reaction time on the premise of ensuring that the performance of a product is not influenced, and has the characteristics of low cost, environmental protection, simple process and the like.
Description
Technical field
The present invention relates to the method that a kind of microwave exposure prepares star-like polycaprolactone-polylactic-acid block copolymer.
Background technology
POLYACTIC ACID is that a kind of biocompatibility is good, the natural polyester of degradable, no cytotoxicity, and the researchist deepens continuously to the understanding of POLYACTIC ACID materialization and biological property in decades.1966, proposition PLA such as Kulkarni can degrade in vivo, and final meta-bolites is CO
2And H
2O, intermediate product lactic acid also are normal glycometabolic products in the body, can not accumulate in vivo.From then on, the application of PLA orthopaedic surgical operations and medical aspect has obtained extensive studies, like bone fracture internal fixation material, operating suture, drug carrier material, tissue engineering bracket etc.But lactic acid homopolymer character is more crisp, and along with the continuous expansion of POLYACTIC ACID Application Areas, simple lactic acid homopolymer can not satisfy people's requirement.Therefore, the modification for POLYACTIC ACID becomes present research focus.Polycaprolactone is a kind of widely used degradable natural polyester equally, through the copolymerization of POLYACTIC ACID and polycaprolactone, can obtain a kind of excellent permeability of polycaprolactone and long advantage multipolymer of degradation time of POLYACTIC ACID of combining.Yu Muhuo etc. are raw material with end group POLYACTIC ACID prepolymer and isocyanate terminated basic polycaprolactone prepolymer, extrude in the twin screw extruder reaction, obtain POLYACTIC ACID-polycaprolactone block polymer (publication number CN1769317A).This is actually a kind of polyester-polyurethane, contains nondegradable ammonia ester bond.Wu Linbo etc. are raw material with lactic acid and caprolactone, the polylactic acid and caprolactone alloy of system (publication number CN101121814A), and the reaction times is 4-16 hour.
Microwave chemical is as an emerging technology, and microwave exposure can promote chemical reaction, quickens chemical reaction course.Because microwave heating has selectivity, and can inside and outside heating simultaneously.Thereby be superior to traditional type of heating greatly, and reaction efficiency is improved greatly, energy consumption reduces.Microwave exposure prepares star-like polycaprolactone-polylactic-acid block copolymer and does not appear in the newspapers as yet.
Summary of the invention
The object of the present invention is to provide a kind of microwave exposure of green high-efficient to prepare the method for star-like polycaprolactone-polylactic-acid block copolymer.
The microwave exposure that the present invention proposes prepares the method for star-like polycaprolactone-polylactic-acid block copolymer, and concrete steps are following:
(1) NSC 65881 and caprolactone monomer are placed according to 1: 180 mol ratio has stirrer single port flask, vacuumize, towards nitrogen; Melting mixing under 115-125 ℃ of temperature adds catalyzer again, and catalyzer and monomeric mol ratio are 1: 1000; Vacuumize once more,, place microwave reactor towards nitrogen; The microwave polymerization temperature is 115-125 ℃, and polymerization time is 50min, and obtaining number-average molecular weight is the star-like polycaprolactone of 23460g/mol;
(2) star-like polycaprolactone that step (1) is obtained and rac-Lactide place by different ratios and have stirrer single port flask, vacuumize, towards nitrogen; Melting mixing under 115-125 ℃ of temperature adds catalyzer again, and the mol ratio of catalyzer and lactide monomer is 1: 1000; Vacuumize once more; Towards nitrogen, place microwave reactor, the microwave polymerization temperature is 115-125 ℃; Polymerization time is 20min, and obtaining number-average molecular weight is star-like polycaprolactone-polylactic-acid block copolymer of 39470~54047g/mol.
Among the present invention, step (1) and the said microwave reactor of step (2) can adopt the single mode focused microwave synthesis reactor of U.S. CE M company.
Among the present invention, be that 30: 70~70: 30 ratio is reinforced in the massfraction scope of caprolactone and rac-Lactide in the star-like polycaprolactone in the step (2).
Among the present invention, catalyzer described in step (1) and the step (2) adopts the stannous octoate toluene solution, and stannous octoate is 1/1000mmol/ml with the ratio of toluene.
Beneficial effect of the present invention is: the time of synthetic star-like polycaprolactone-polylactic-acid block copolymer is no more than 1h under microwave exposure; And the reaction times of traditional type of heating is about 24h; In the polymerization process under nitrogen protection; The microwave exposure technology has shortened the reaction times greatly, has reduced energy consumption, and a kind of route of synthesis of high effective green environmentally friendly is provided for synthetic star-like polycaprolactone-polylactic-acid block copolymer.
Description of drawings
Fig. 1 is the infrared spectrogram of product among the embodiment 1, and wherein: curve a is that the 6sPCL macromole evocating agent is at 2943cm
-1About the stretching vibration peak of tangible methylene radical γ-CH is arranged, curve (b) is the infared spectrum of 6sPCL-b-PLLA,
Fig. 2 is the hydrogen spectrum nucleus magnetic resonance figure of product among the embodiment 1, and the peak of the a-d that is indicated among Fig. 2 (a) all is that PCL gets characteristic peak, therefore can prove with the NSC 65881 to be star-like polycaprolactone polymkeric substance synthetic of nuclear.Fig. 2 (b) is the hydrogen spectrum nucleus magnetic resonance figure of 6sPCL-b-PLLA.
Embodiment
For a better understanding of the present invention, further set forth content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.
Embodiment 1:0.038g NSC 65881 places the single port flask that has stirrer of 25ml, adds 3.0g caprolactone (NSC 65881 and caprolactone monomer mol ratio 1: 180), vacuumize-towards nitrogen three times.Stir fusion in 120 ℃ of oil baths, add 26.5 μ l stannous octoate toluene solutions (ratio of stannous octoate and toluene is 1/1000mmol/ml), vacuumize-towards nitrogen three times.Flask is put into microwave reactor, and 120 ℃ of reaction 50min obtain star-like polycaprolactone.The number-average molecular weight of star-like polycaprolactone is 24360g/mol.
The star-like polycaprolactone of 0.4289g (number-average molecular weight is 24360g/mol) and 1.02g rac-Lactide are placed the single port flask that has stirrer of 25ml, vacuumize-towards nitrogen three times.Stir fusion in 120 ℃ of oil baths, add 7.0ul stannous octoate toluene solution (ratio of stannous octoate and toluene is 1/1000mmol/ml), vacuumize-towards nitrogen three times.Flask is put into microwave reactor, and 120 ℃ of reaction 20min obtain star-like polycaprolactone-polylactic-acid block copolymer.The number-average molecular weight of star-like polycaprolactone-polylactic-acid block copolymer is 60355g/mol.
From Fig. 1 (a), we can find out that the 6sPCL macromole evocating agent is at 2943cm
-1About the stretching vibration peak of tangible methylene radical γ-CH is arranged; Polymkeric substance is at 1722cm
-1About strong C=O stretching vibration absorption peak is arranged, these all are the synthetic of proof PCL polymkeric substance.Fig. 1 (b) is the infared spectrum of 6sPCL-b-PLLA, from the infared spectrum of 6sPCL and 6sPCL-b-PLLA, can see, both maximum differences are the position at carbonyl peak place.In Fig. 1 (b), it is wideer that carbonyl peak becomes, and split into two peaks.At 1751cm
-1About the carbonylic stretching vibration peak located corresponding be the carbonyl in the polylactic acid chain segment in the segmented copolymer, and 1722cm
-1About the carbonylic stretching vibration peak located corresponding be the carbonyl peak in the polycaprolactone segment in the segmented copolymer.This has proved and in polymkeric substance, has connected the PLLA segment really.
From the contrast of Fig. 2 (a) and Fig. 2 (b), we can see that the end group methylene peak (d ') at 3.65ppm place among (a) figure has disappeared, and the substitute is the PLLA end group characteristic peak at 4.36ppm (e ') and 1.50ppm (f ') two places.The CH characteristic peak at e place and the CH3 characteristic peak at f place also all are the characteristic peaks of PLLA, and these have proved that all the hydroxyl 6sPCL macromole evocating agent of end group has successfully caused the ring-opening polymerization of L-rac-Lactide, and the 6sPCL-b-PLLA segmented copolymer has been synthesized in preparation.
Embodiment 2:0.038g NSC 65881 places the single port flask that has stirrer of 25ml, adds the 3.0g caprolactone, vacuumize-towards nitrogen three times.Stir fusion in 120 ℃ of oil baths, add 26.5 μ l stannous octoate toluene solutions (ratio of stannous octoate and toluene is 1/1000mmol/ml), vacuumize-towards nitrogen three times.Flask is put into microwave reactor, and 120 ℃ of reaction 50min obtain star-like polycaprolactone.The number-average molecular weight of star-like polycaprolactone is 24360g/mol.
The star-like polycaprolactone of 0.6678g (number-average molecular weight is 24360g/mol) and 1.05g rac-Lactide are placed the single port flask that has stirrer of 25ml, vacuumize-towards nitrogen three times.Stir fusion in 120 ℃ of oil baths, add 7.0ul stannous octoate toluene solution (ratio of stannous octoate and toluene is 1/1000mmol/ml), vacuumize-towards nitrogen three times.Flask is put into microwave reactor, and 120 ℃ of reaction 20min obtain star-like polycaprolactone-polylactic-acid block copolymer.The number-average molecular weight of star-like polycaprolactone-polylactic-acid block copolymer is 52388g/mol.
Embodiment 3:0.038g NSC 65881 places the single port flask that has stirrer of 25ml, adds the 3.0g caprolactone, vacuumize-towards nitrogen three times.Stir fusion in 120 ℃ of oil baths, add 26.5 μ l stannous octoate toluene solutions (ratio of stannous octoate and toluene is 1/1000mmol/ml), vacuumize-towards nitrogen three times.Flask is put into microwave reactor, and 120 ℃ of reaction 50min obtain star-like polycaprolactone.The number-average molecular weight of star-like polycaprolactone is 24360g/mol.
The star-like polycaprolactone of 1.0223g (number-average molecular weight is 24360g/mol) and 1.00g rac-Lactide are placed the single port flask that has stirrer of 25ml, vacuumize-towards nitrogen three times.Stir fusion in 120 ℃ of oil baths, add 7.0ul stannous octoate toluene solution (ratio of stannous octoate and toluene is 1/1000mmol/ml), vacuumize-towards nitrogen three times.Flask is put into microwave reactor, and 120 ℃ of reaction 20min obtain star-like polycaprolactone-polylactic-acid block copolymer.The number-average molecular weight of star-like polycaprolactone-polylactic-acid block copolymer is 42054g/mol.
Embodiment 4:0.038g NSC 65881 places the single port flask that has stirrer of 25ml, adds the 3.0g caprolactone, vacuumize-towards nitrogen three times.Stir fusion in 120 ℃ of oil baths, add 26.5 μ l stannous octoate toluene solutions (ratio of stannous octoate and toluene is 1/1000mmol/ml), vacuumize-towards nitrogen three times.Flask is put into microwave reactor, and 120 ℃ of reaction 50min obtain star-like polycaprolactone.The number-average molecular weight of star-like polycaprolactone is 24360g/mol.
The star-like polycaprolactone of 0.7757g (number-average molecular weight is 24360g/mol) and 0.50g rac-Lactide are placed the single port flask that has stirrer of 25ml, vacuumize-towards nitrogen three times.Stir fusion in 120 ℃ of oil baths, add 7.0ul stannous octoate toluene solution (ratio of stannous octoate and toluene is 1/1000mmol/ml), vacuumize-towards nitrogen three times.Flask is put into microwave reactor, and 120 ℃ of reaction 20min obtain star-like polycaprolactone-polylactic-acid block copolymer.The number-average molecular weight of star-like polycaprolactone-polylactic-acid block copolymer is 33440g/mol.
Embodiment 5:0.038g NSC 65881 places the single port flask that has stirrer of 25ml, adds the 3.0g caprolactone, vacuumize-towards nitrogen three times.Stir fusion in 120 ℃ of oil baths, add 26.5 μ l stannous octoate toluene solutions (ratio of stannous octoate and toluene is 1/1000mmol/ml), vacuumize-towards nitrogen three times.Flask is put into microwave reactor, and 120 ℃ of reaction 50min obtain star-like polycaprolactone.The number-average molecular weight of star-like polycaprolactone is 24360g/mol.
The star-like polycaprolactone of 1.0260g (number-average molecular weight is 24360g/mol) and 0.44g rac-Lactide are placed the single port flask that has stirrer of 25ml, vacuumize-towards nitrogen three times.Stir fusion in 120 ℃ of oil baths, add 7.0ul stannous octoate toluene solution (ratio of stannous octoate and toluene is 1/1000mmol/ml), vacuumize-towards nitrogen three times.Flask is put into microwave reactor, and 120 ℃ of reaction 20min obtain star-like polycaprolactone-polylactic-acid block copolymer.The number-average molecular weight of star-like polycaprolactone-polylactic-acid block copolymer is 29256g/mol.
Claims (4)
1. a microwave exposure prepares the method for star-like polycaprolactone-polylactic-acid block copolymer, it is characterized in that concrete steps are following:
(1) NSC 65881 and caprolactone monomer are placed according to 1: 180 mol ratio has stirrer single port flask, vacuumize inflated with nitrogen; Melting mixing under 115-125 ℃ of temperature adds catalyzer again, and the mol ratio of catalyzer and caprolactone is 1: 1000; Vacuumize once more, inflated with nitrogen places microwave reactor; The microwave polymerization temperature is 115-125 ℃, and polymerization time is 50min, and obtaining number-average molecular weight is the star-like polycaprolactone of 23460g/mol;
(2) star-like polycaprolactone that step (1) is obtained and rac-Lactide place in proportion and have stirrer single port flask, vacuumize inflated with nitrogen; Melting mixing under 115-125 ℃ of temperature adds catalyzer again, and the mol ratio of catalyzer and lactide monomer is 1: 1000; Vacuumize once more, inflated with nitrogen places microwave reactor; The microwave polymerization temperature is 115-125 ℃, and polymerization time is 20min, and obtaining number-average molecular weight is star-like polycaprolactone-polylactic-acid block copolymer of 39470~54047g/mol.
2. microwave exposure according to claim 1 prepares the method for star-like polycaprolactone-polylactic-acid block copolymer, it is characterized in that microwave reactor described in step (1) and the step (2) adopts the single mode focused microwave synthesis reactor of U.S. CE M company.
3. microwave exposure according to claim 1 prepares the method for star-like polycaprolactone-polylactic-acid block copolymer, it is characterized in that the ratio of star-like polycaprolactone and rac-Lactide in the step (2) be massfraction scope by caprolactone and rac-Lactide in the star-like polycaprolactone be 30: 70~70: 30 reinforced.
4. microwave exposure according to claim 1 prepares the method for star-like polycaprolactone-polylactic-acid block copolymer, it is characterized in that catalyzer adopts the stannous octoate toluene solution in step (1) and the step (2), and stannous octoate is 1/1000mmol/ml with the ratio of toluene.
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CN112851917B (en) * | 2021-01-28 | 2023-03-24 | 山东采采医疗科技有限公司 | Preparation method of polylactide caprolactone |
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