CN101891881B - Biodegradable high-polymer additive, preparation method and application thereof - Google Patents
Biodegradable high-polymer additive, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a biodegradable high-polymer additive with a branching structure, a preparation method and application thereof. A branched polymer provided by the invention is formed by combining sequential ring opening polymerization and coordination ring opening polymerization of negative ions, polycaprolactone (PCL) and poly l-lactic acid (PLLA) or poly d-lactic acid (PDLA) and propanol polyepoxide are prepared into a graft polymer with a controllable structure. The length of each inlay section of a main chain of the branched polymer and the length of a grafted chain can be regulated and controlled by changing a monomer feeding rate. The branched polymer not only has good volume increasing effect for a polylactic acid/polycaprolactone blend system, but also can reduce the melt viscosity and improve the processability of blends.
Description
Technical field
The present invention relates to the polymer materials technical field, particularly Biodegradable high-polymer additive of a kind of branched structure with capacity increasing modifying function and preparation method thereof and application.
Background technology
Poly(lactic acid) (Poly lactic acid, PLA) is a kind of biodegradable synthesized polymer material with excellent biocompatibility.This biodegradable aliphatic polyester of PLA is normally take some reproducible natural phant as raw material, and the method for process chemosynthesis obtains.Under the effect of microorganism, water, bronsted lowry acids and bases bronsted lowry, PLA finally is degraded to carbonic acid gas and water, and its degraded product can participate in body metabolism.Because the good biocompatibility of poly(lactic acid) by FDA (FDA) approval, can be used as medical operation suture thread, injection capsule, microballoon and implants etc.In addition, PLA has good mechanical property, is easy to machine-shaping.The poor toughness yet PLA matter is hard, shortage flexibility and elasticity, shock resistance is poor, low, the very easily flexural deformation of heat-drawn wire.The qualitative shortcoming of these of poly(lactic acid) has limited its practical application area greatly.
Blend is as one of important channel of polymer modification, and is not only simple, with low cost, and the co-mixing system comprehensive performance of each component often, thereby satisfies preferably each side ground requirement.Polycaprolactone (PCL)/PLA co-mixing system is one of common PLA co-mixing system.At first, PCL has long-the CH2-segment, and kindliness is better, so sneak into the fragility that can improve PLA among the PLA; Secondly, the introducing of segment of different nature can destroy the order of molecular chain in the poly(lactic acid), affect its crystal property, this also can partly reduce the fragility of PLA material, but the consistency of PCL/PLA co-mixing system is bad, causes the raising of intermingling material mechanical property obvious not.If in the PCL/PLA co-mixing system, add a small amount of corresponding graft copolymer, allow them be dispersed on the inconsistent homopolymer interface, can reduce interfacial tension, phenomenon of phase separation is improved, thereby improve the mechanical property of intermingling material.In addition, because graft copolymer has branched structure, therefore can reduce the viscosity of melt, improve the processing characteristics of co-mixing system.Thisly can play compatibilization, the graft copolymer that can reduce again melt viscosity has potential application prospect in the PCL/PLA co-mixing system.But have no at present correlative study report and patent.
Summary of the invention
The purpose of this invention is to provide a kind of Biodegradable high-polymer additive and preparation method thereof and application.
Biodegradable additive with branched structure provided by the invention is shown in VI;
(formula VI)
Among the formula VI, when A was the poly(lactic acid) repeating unit, B was polycaprolactone repeating unit or poly(lactic acid) repeating unit; When A was the polycaprolactone repeating unit, B was the poly(lactic acid) repeating unit; Described polycaprolactone repeating unit is obtained by the ring-opening polymerization of ring-type esters monomer; Described ring-type esters monomer is lactides or lactone cyclic monomer; X, y and z are 1-7000.
The number-average molecular weight of this multipolymer is 2,000～100,000, and molecular weight distribution is less than 2.
The above-mentioned method with Biodegradable high-polymer additive of branched structure of preparation provided by the invention comprises the steps:
1) contain the preparation of the macromole evocating agent of pendant hydroxyl group:
Take ethoxyethyl group glycidyl ether shown in the formula V (EEGE) and ring-type esters monomer as raw material, under the initiation of potassium alcoholate, in organic solvent, carry out the ring-opening polymerization of negatively charged ion order, obtain containing the segmented copolymer of pendant hydroxyl group blocking group, after removing again the pendant hydroxyl group blocking group in the described segmented copolymer that contains the pendant hydroxyl group blocking group, obtain containing the segmented copolymer of pendant hydroxyl group;
2) have the preparation of the polymkeric substance of branched structure:
Under the condition that catalyzer exists, take described step 1) segmented copolymer that contains pendant hydroxyl group that obtains is initiator, the ring-type esters monomer carries out ring-opening polymerization, obtains having the biodegradable additive of branched structure.
The step 1 of the method) in, the ring-type esters monomer is lactides or lactone cyclic monomer; Wherein, the lactides cyclic monomer is selected from any one in the racemization rac-Lactide (D, LLA) shown in dextrorotation rac-Lactide (DLA) shown in levorotatory lactide shown in the formula I (LLA), the formula II and the formula III;
(formula I:LLA) (formula II:DLA) (formula III: D, LLA)
(formula IV:CL)
(formula V:EEGE)
Described lactone cyclic monomer is caprolactone shown in the formula IV (CL);
Described potassium alcoholate is selected from any one in potassium tert.-butoxide, tertiary amyl alcohol potassium and the hexanol potassium;
The mol ratio of described ethoxyethyl group glycidyl ether, ring-type esters monomer and potassium alcoholate is 1: 1: 0.01-1: 1000: 10, and preferred 1: 1: 0.1-1: 100: 1;
The temperature of described negatively charged ion order ring-opening polymerization is 0-80 ℃, preferred 20-60 ℃; The time of reaction is 16-168h, preferred 24-72h;
The ring-opening polymerization of described negatively charged ion order is carried out in organic solvent; Described organic solvent is selected from least a in toluene, tetrahydrofuran (THF) and the chloroform;
The mass percent concentration of described ethoxyethyl group glycidyl ether in organic solvent is 1%-95%;
The described method that removes the pendant hydroxyl group blocking group in the described segmented copolymer that contains the pendant hydroxyl group blocking group is as follows: in the pH value for removing the pendant hydroxyl group blocking group in the described segmented copolymer that contains the pendant hydroxyl group blocking group under the condition of 2-7;
Step 2) in, the ring-type esters monomer is lactides or lactone cyclic monomer, and wherein, the lactides cyclic monomer is selected from any one in the racemization rac-Lactide shown in dextrorotation rac-Lactide shown in levorotatory lactide, the formula II shown in the formula I and the formula III; Described lactone cyclic monomer is caprolactone shown in the formula IV (CL); Described catalyzer is selected from any one in potassium hydroxide, stannous octoate and the potassium tert.-butoxide.Described catalyzer is selected from any one in carboxylate salt, metal alcoholate and the metal alkylide of metal hydroxides, metal.
Described catalyzer, step 1) segmented copolymer that contains pendant hydroxyl group that obtains and the mol ratio of ring-type esters monomer be 0.001: 1: 1-1: 1: 1000, preferred 0.01: 1: 1-1: 1: 500;
The temperature of described ring-opening polymerization is 40～200 ℃, preferred 80-160 ℃; The time of reaction is 12-168h, preferred 48-144h.
Described ring-opening polymerization carries out in organic solvent; Described organic solvent is selected from least a in toluene, tetrahydrofuran (THF) and the chloroform;
The mass percent concentration of described ring-type esters monomer in organic solvent is 1%-80%.
In addition, the application of biodegradable additive in poly(lactic acid) and polycaprolactone modification with branched structure provided by the invention also belongs to protection scope of the present invention.
The present invention has the following advantages:
(1) adopt the branched copolymers of the method preparation of ring-opening polymerization that the polylactic acid and caprolactone co-mixing system is had good compatibilization effect, and can reduce melt viscosity, effectively improve the consistency of polylactic acid and caprolactone co-mixing system two components, improve the mechanical property of matrix material.
(2) can be by regulating structure, molecular weight and the proportioning etc. of ring-type esters monomer and macromole evocating agent in the branched copolymers preparation process, thus obtain being applicable to the additive of different polylactic acid and caprolactone co-mixing systems.
(3) the polylactic acid and caprolactone co-mixing system is still Biodegradable material, adds the biodegradability that can not affect matrix material in the matrix material as additive.
(4) because the existence of branched structure, so that graft copolymer can improve the processing characteristics of polylactic acid and caprolactone co-mixing system.
Description of drawings
Fig. 1 is by the PCL-b-PG-g-PLLA's of the inventive method preparation
1H NMR spectrogram.
Fig. 2 is by the PLLA-b-PG-g-PCL's of the inventive method preparation
1H NMR spectrogram.
Fig. 3 is by the PDLA-b-PG-g-PLLA's of the inventive method preparation
1H NMR spectrogram.
Fig. 4 is by the PLLA-b-PG-g-PDLA's of the inventive method preparation
1H NMR spectrogram.
Fig. 5 a is the electron scanning micrograph of common polylactic acid and caprolactone co-mixing system, and Fig. 5 b is the electron scanning micrograph of the additive agent modified rear polylactic acid and caprolactone co-mixing system of embodiment 1 preparation.
Fig. 6 is the GPC spectrogram of embodiment 1 preparation resulting polymers.
Embodiment
Below by embodiment the present invention further is illustrated, but the present invention is not limited to following examples.
Concrete steps and the condition of biodegradable additive that preparation provided by the invention has branched structure is as follows:
1) contains the preparation of the macromole evocating agent of pendant hydroxyl group
The R-GLYCIDOL that will contain blocking group in the reaction vessel of drying is dissolved in the tetrahydrofuran (THF); be heated to 30～70 ℃; reaction times＜72h; till reacting completely; under argon shield, the tetrahydrofuran solution of ring-type esters monomer is joined in the reaction system 0～70 ℃ of lower reaction＜24h; remove organic solvent, obtain the segmented copolymer of hydroxyl blocking group.Then, segmented copolymer is dissolved in the mixed solvent of organic solvent/water, under acidic conditions, 0～50 ℃ of lower reaction＜48h removes the side chain of ethyl oxyethyl group group from multipolymer, obtains containing the macromole evocating agent of pendant hydroxyl group.
2) has the preparation of branched structure additive
Under the condition of argon shield, with above-mentioned steps 1) macromole evocating agent and the ring-type esters monomer of preparation join in the dry reaction vessel stannous octoate (SnOct
2) be catalyzer, toluene is solvent, 50～180 ℃ of lower reaction＜200h after monomer reaction is complete, remove organic solvent, obtain product.
With above-mentioned steps 2) branched polymer of preparation is as expanding material or additive, is dissolved in organic solvent with the poly(lactic acid) and/or the polycaprolactone that are used for blend, waters film after the dissolving fully, obtains composition after organic solvent volatilization fully.The parts by weight of preferred each component are: poly(lactic acid): 48～99, polycaprolactone: 1-50, branched polymer: 0.5～30.
This polymeric film is used for machine-shaping, or can be directly above-mentioned steps (2) preparation gained branched polymer and poly(lactic acid) and polycaprolactone be joined in the processing units, carries out machine-shaping and obtains required product.Various machine-shapings are all applicable, such as various machine-shaping modes such as injection molding (injection), blow molding (blowing), extrusion moulding, vacuum forming, pressurized air moulding or spinning mouldings.
Utilize the additive agent modified poly(lactic acid) of branched polymer provided by the invention, its performance test is as follows:
With the poly(lactic acid) of the branched polymer modification of above-mentioned preparation, 180 ℃ of lower meltings dumbbell shape batten that to make thick 0.5mm initial length be 1cm on the vacuum film pressing machine.The disconnected batten of quenching under liquid nitrogen is with the improvement situation that is separated of scanning electron microscope (SEM) observation batten section.The analytical test result of branched polymer polydactyl acid sees accompanying drawing for details.
The present invention prepares the gained biodegradable additive, for having the multipolymer of branched structure, it is the graft copolymer of polycaprolactone (PCL), Poly-L-lactic acid (PLLA) or dextrorotation poly(lactic acid) (PDLA) and poly-R-GLYCIDOL (PG), referred to as PCL-b-PG-g-PLLA (copolymer A), PLLA-b-PG-g-PCL (multipolymer B), PDLA-b-PG-g-PLLA (multipolymer C) and PLLA-b-PG-g-PDLA (multipolymer D).When polyreaction, prepare first PLLA-b-PG, then caprolactone (CL) or dextrorotation rac-Lactide (DLA) are grafted on the polymer chain, obtain multipolymer B or D; When polyreaction, prepare first PCL-b-PG, then levorotatory lactide (LLA) is grafted on the polymer chain, obtain copolymer A; When polyreaction, prepare first PDLA-b-PG, then levorotatory lactide (LLA) is grafted on the polymer chain, obtain multipolymer C.
1g ethoxyethyl group glycidyl ether is joined in the dry reaction vessel, add simultaneously tetrahydrofuran solution (1mol/L) and the 3mL tetrahydrofuran (THF) of 0.5mL potassium tert.-butoxide, 60 ℃ of lower reaction 24h; Under the argon shield condition, the tetrahydrofuran solution (0.333g/mL) with the 5mL caprolactone monomer under the room temperature slowly is added drop-wise in the reaction vessel, 40 ℃ of lower reaction 4h; Reaction mixture is poured into washing of precipitate in the ether, is gathered (6-caprolactone-b-ethoxyethyl group glycidyl ether) after the drying (PCL-b-PEEGE).3g poly-(6-caprolactone-b-ethoxyethyl group glycidyl ether) is dissolved in the 15ml acetone, the aqueous solution with oxalic acid joins in the polymers soln again, after reacting 16h under the room temperature, add calcium hydroxide, the mol ratio of hydroxyl/oxalic acid in the polymkeric substance/calcium hydroxide is 1/0.5/1, under the room temperature reaction 1h after, the centrifugal throw out of removing in the solution, polymers soln is poured in the ether again and precipitates, dried product exhibited is poly-(6-caprolactone-b-R-GLYCIDOL) (PCL-b-PG).
0.2g poly-(6-caprolactone-b-R-GLYCIDOL) is joined in the dry reactor, with the dissolving of 20mL toluene, add again the stannous octoate toluene solution of 1g levorotatory lactide and 0.67mmol, at 100 ℃ of lower reaction 96h.Stopped reaction, reaction mixture are poured into precipitation drying in the ether, obtain white solid and are poly-(6-caprolactone-b-R-GLYCIDOL-g-L-lactic acid) (PCL-b-PG-g-PLLA).This branched polymer is at deuterochloroform (CDCl
3) in
1The H nuclear-magnetism characterizes spectrogram as shown in Figure 1, and this compound structure is correct as can be known.Fig. 6 is the GPC spectrogram of PCL-b-PG and PCL-b-PG-g-PLLA.As can be known, the Mn=11900 of PCL-b-PG, Mw/Mn=1.36; The Mn=28800 of PCL-b-PG-g-PLLA, Mw/Mn=1.59.
1g ethoxyethyl group glycidyl ether is joined in the dry reaction vessel, add simultaneously tetrahydrofuran solution (1mol/L) and the 1mL tetrahydrofuran (THF) of 6.8uL potassium tert.-butoxide, 20 ℃ of lower reaction 168h; Under the argon shield condition, the tetrahydrofuran solution (0.5g/mL) with the 0.75mL caprolactone monomer under the room temperature slowly is added drop-wise in the reaction vessel, 0 ℃ of lower reaction 6h; Reaction mixture is poured into washing of precipitate in the ether, is gathered (6-caprolactone-b-ethoxyethyl group glycidyl ether) after the drying (PCL-b-PEEGE).1g poly-(6-caprolactone-b-ethoxyethyl group glycidyl ether) is dissolved in the 15ml acetone, the aqueous solution with oxalic acid joins in the polymers soln again, after reacting 16h under the room temperature, add calcium hydroxide, the mol ratio of hydroxyl/oxalic acid in the polymkeric substance/calcium hydroxide is 1/0.5/1, under the room temperature reaction 1h after, the centrifugal throw out of removing in the solution, polymers soln is poured in the ether again and precipitates, dried product exhibited is poly-(6-caprolactone-b-R-GLYCIDOL) (PCL-b-PG).
0.2g poly-(6-caprolactone-b-R-GLYCIDOL) is joined in the dry reactor, with the dissolving of 20mL toluene, add again the stannous octoate toluene solution of 0.11g levorotatory lactide and 0.75mmol, at 40 ℃ of lower reaction 12h.Stopped reaction, reaction mixture are poured into precipitation drying in the ether, obtain white solid and are poly-(6-caprolactone-b-R-GLYCIDOL-g-L-lactic acid) (PCL-b-PG-g-PLLA).GPC records: the Mn=140700 of PCL-b-PG, Mw/Mn=1.58; The Mn=310800 of PCL-b-PG-g-PLLA, Mw/Mn=2.
1g ethoxyethyl group glycidyl ether is joined in the dry reaction vessel, add simultaneously tetrahydrofuran solution (1mol/L) and the 3mL tetrahydrofuran (THF) of 0.5ml potassium tert.-butoxide, 60 ℃ of lower reaction 24h; Under the argon shield condition, the tetrahydrofuran solution (0.333g/mL) with 5g levorotatory lactide monomer under the room temperature slowly is added drop-wise in the reaction vessel, 40 ℃ of lower reaction 6h; Reaction mixture is poured into washing of precipitate in the ether, is gathered (Pfansteihl-b-ethoxyethyl group glycidyl ether) after the drying (PLLA-b-PEEGE).3g poly-(Pfansteihl-b-ethoxyethyl group glycidyl ether) is dissolved in the 15ml acetone, the aqueous solution with oxalic acid joins in the polymers soln again, after reacting 16h under the room temperature, add calcium hydroxide, the mol ratio of hydroxyl/oxalic acid in the polymkeric substance/calcium hydroxide is 1/0.5/1, under the room temperature reaction 1h after, the centrifugal throw out of removing in the solution, polymers soln is poured in the ether again and precipitates, dried product exhibited is poly-(Pfansteihl-b-R-GLYCIDOL) (PLLA-b-PG).
0.2g poly-(Pfansteihl-b-R-GLYCIDOL) is joined in the dry reactor, with the dissolving of 20mL toluene, add again the stannous octoate toluene solution of 1g caprolactone and 0.67mmol, at 100 ℃ of lower reaction 96h.Stopped reaction, reaction mixture are poured into precipitation drying in the ether, obtain white solid and are poly-(Pfansteihl-b-R-GLYCIDOL-g-caprolactone) (PCL-b-PG-g-PLLA).This branched polymer is at deuterochloroform (CDCl
3) in
1H nuclear-magnetism sign spectrogram (
1HNMR) as shown in Figure 2, this compound structure is correct as can be known.GPC records: the Mn=21000 of PLLA-b-PG, Mw/Mn=1.45; The Mn=31800 of PLLA-b-PG-g-PCL, Mw/Mn=1.72.
1g ethoxyethyl group glycidyl ether is joined in the dry reaction vessel, add simultaneously tetrahydrofuran solution (1mol/L) and the 3mL tetrahydrofuran (THF) of 10ml potassium tert.-butoxide, 80 ℃ of lower reaction 16h; Under the argon shield condition, the tetrahydrofuran solution (0.333g/mL) with 6.85g levorotatory lactide monomer under the room temperature slowly is added drop-wise in the reaction vessel, 40 ℃ of lower reaction 6h; Reaction mixture is poured into washing of precipitate in the ether, is gathered (Pfansteihl-b-ethoxyethyl group glycidyl ether) after the drying (PLLA-b-PEEGE).3g poly-(Pfansteihl-b-ethoxyethyl group glycidyl ether) is dissolved in the 15ml acetone, the aqueous solution with oxalic acid joins in the polymers soln again, after reacting 16h under the room temperature, add calcium hydroxide, the mol ratio of hydroxyl/oxalic acid in the polymkeric substance/calcium hydroxide is 1/0.5/1, under the room temperature reaction 1h after, the centrifugal throw out of removing in the solution, polymers soln is poured in the ether again and precipitates, dried product exhibited is poly-(Pfansteihl-b-R-GLYCIDOL) (PLLA-b-PG).
0.2g poly-(Pfansteihl-b-R-GLYCIDOL) is joined in the dry reactor, with the dissolving of 20mL toluene, add again the stannous octoate toluene solution of 28.5g caprolactone and 0.25umol, at 200 ℃ of lower reaction 168h.Stopped reaction, reaction mixture are poured into precipitation drying in the ether, obtain white solid and are poly-(Pfansteihl-b-R-GLYCIDOL-g-caprolactone) (PCL-b-PG-g-PLLA).GPC records: the Mn=3000 of PLLA-b-PG, Mw/Mn=1.35; The Mn=311800 of PLLA-b-PG-g-PCL, Mw/Mn=1.72.
1g ethoxyethyl group glycidyl ether is joined in the dry reaction vessel, add simultaneously tetrahydrofuran solution (1mol/L) and the 3mL tetrahydrofuran (THF) of 0.5ml potassium tert.-butoxide, 60 ℃ of lower reaction 24h; Under the argon shield condition, the tetrahydrofuran solution (0.333g/mL) with 5g dextrorotation lactide monomer under the room temperature slowly is added drop-wise in the reaction vessel, 40 ℃ of lower reaction 6h; Reaction mixture is poured into washing of precipitate in the ether, is gathered (D-ALPHA-Hydroxypropionic acid-b-ethoxyethyl group glycidyl ether) after the drying (PDLA-b-PEEGE).3g poly-(D-ALPHA-Hydroxypropionic acid-b-ethoxyethyl group glycidyl ether) is dissolved in the 15ml acetone, the aqueous solution with oxalic acid joins in the polymers soln again, after reacting 16h under the room temperature, add calcium hydroxide, the mol ratio of hydroxyl/oxalic acid in the polymkeric substance/calcium hydroxide is 1/0.5/1, under the room temperature reaction 1h after, the centrifugal throw out of removing in the solution, polymers soln is poured in the ether again and precipitates, dried product exhibited is poly-(D-ALPHA-Hydroxypropionic acid-b-R-GLYCIDOL) (PDLA-b-PG).
0.2g poly-(D-ALPHA-Hydroxypropionic acid-b-R-GLYCIDOL) is joined in the dry reactor, with the dissolving of 20mL toluene, add again the stannous octoate toluene solution of 1g levorotatory lactide and 0.67mmol, at 100 ℃ of lower reaction 96h.Stopped reaction, reaction mixture are poured into precipitation drying in the ether, obtain white solid and are poly-(D-ALPHA-Hydroxypropionic acid-b-R-GLYCIDOL-g-L-lactic acid) (PDLA-b-PG-g-PLLA).This branched polymer is at deuterochloroform (CDCl
3) in
1H nuclear-magnetism sign spectrogram (
1HNMR) as shown in Figure 3, this compound structure is correct as can be known.GPC records: the Mn=24500 of PDLA-b-PG, Mw/Mn=1.36; The Mn=38100 of PDLA-b-PG-g-PLLA, Mw/Mn=1.63.
1g ethoxyethyl group glycidyl ether is joined in the dry reaction vessel, add simultaneously tetrahydrofuran solution (1mol/L) and the 3mL tetrahydrofuran (THF) of 0.5ml potassium tert.-butoxide, 60 ℃ of lower reaction 24h; Under the argon shield condition, the tetrahydrofuran solution (0.333g/mL) with 5g levorotatory lactide monomer under the room temperature slowly is added drop-wise in the reaction vessel, 40 ℃ of lower reaction 6h; Reaction mixture is poured into washing of precipitate in the ether, is gathered (Pfansteihl-b-ethoxyethyl group glycidyl ether) after the drying (PLLA-b-PEEGE).3g poly-(Pfansteihl-b-ethoxyethyl group glycidyl ether) is dissolved in the 15ml acetone, the aqueous solution with oxalic acid joins in the polymers soln again, after reacting 16h under the room temperature, add calcium hydroxide, the mol ratio of hydroxyl/oxalic acid in the polymkeric substance/calcium hydroxide is 1/0.5/1, under the room temperature reaction 1h after, the centrifugal throw out of removing in the solution, polymers soln is poured in the ether again and precipitates, dried product exhibited is poly-(Pfansteihl-b-R-GLYCIDOL) (PLLA-b-PG).
0.2g poly-(Pfansteihl-b-R-GLYCIDOL) is joined in the dry reactor, with the dissolving of 20mL toluene, add again the stannous octoate toluene solution of 1g dextrorotation rac-Lactide and 0.67mmol, at 100 ℃ of lower reaction 96h.Stopped reaction, reaction mixture are poured into precipitation drying in the ether, obtain white solid and are poly-(Pfansteihl-b-R-GLYCIDOL-g-D-lactic acid) (PLLA-b-PG-g-PDLA).This branched polymer is at deuterochloroform (CDCl
3) in
1H nuclear-magnetism sign spectrogram (
1HNMR) as shown in Figure 4, this compound structure is correct as can be known.GPC records: the Mn=28500 of PLLA-b-PG, Mw/Mn=1.26; The Mn=68100 of PLLA-b-PG-g-PDLA, Mw/Mn=1.52.
Utilize PLLA-b-PG-g-PCL, 0.8g PLLA and the 0.2g PCL of embodiment 2 preparations to be dissolved in the 20m methylene dichloride 0.05g, water film after the dissolving fully.Dried polymeric film is placed on the vacuum film pressing machine 180 ℃ of lower meltings dumbbell shape batten that to make thick 0.5mm initial length be 1cm.The disconnected batten of quenching under liquid nitrogen is with the improvement situation that is separated of scanning electron microscope (SEM) observation batten section
(a) is the electron scanning micrograph of common polylactic acid and caprolactone co-mixing system among Fig. 5, the electron scanning micrograph of the additive agent modified rear polylactic acid and caprolactone co-mixing system with branched structure that (b) prepares by the embodiment of the invention 1.Can find out, add the phenomenon of phase separation that can obviously change the polylactic acid and caprolactone co-mixing system by the additive with branched structure of the inventive method preparation.
Claims (3)
1. the biodegradable additive that has branched structure shown in the formula VI;
(formula VI)
Among the described formula VI, when A was the poly(lactic acid) repeating unit, B was polycaprolactone repeating unit or poly(lactic acid) repeating unit; When A was the polycaprolactone repeating unit, B was the poly(lactic acid) repeating unit;
Described polycaprolactone repeating unit is obtained by the ring-opening polymerization of lactone cyclic monomer;
Described poly(lactic acid) repeating unit is obtained by the ring-opening polymerization of lactides cyclic monomer;
The preparation method who has the biodegradable additive of branched structure shown in the formula VI is following 1)-6) arbitrary shown in:
1) 1g ethoxyethyl group glycidyl ether is joined in the dry reaction vessel, add simultaneously tetrahydrofuran solution and the 3mL tetrahydrofuran (THF) of 0.5mL1mol/L potassium tert.-butoxide, 60 ℃ of lower reaction 24h; Under the argon shield condition, the tetrahydrofuran solution with 5mL 0.333g/mL caprolactone monomer under the room temperature slowly is added drop-wise in the reaction vessel, 40 ℃ of lower reaction 4h; Reaction mixture is poured into washing of precipitate in the ether, is gathered (6-caprolactone-b-ethoxyethyl group glycidyl ether) after the drying; 3g poly-(6-caprolactone-b-ethoxyethyl group glycidyl ether) is dissolved in the 15ml acetone, the aqueous solution with oxalic acid joins in the polymers soln again, after reacting 16h under the room temperature, add calcium hydroxide, the mol ratio of hydroxyl/oxalic acid in the polymkeric substance/calcium hydroxide is 1/0.5/1, under the room temperature reaction 1h after, the centrifugal throw out of removing in the solution, polymers soln is poured in the ether again and precipitates, dried product exhibited is poly-(6-caprolactone-b-R-GLYCIDOL);
0.2g poly-(6-caprolactone-b-R-GLYCIDOL) is joined in the dry reactor, with the dissolving of 20mL toluene, add again the stannous octoate toluene solution of 1g levorotatory lactide and 0.67mmol, at 100 ℃ of lower reaction 96h; Stopped reaction, reaction mixture are poured into precipitation drying in the ether, obtain white solid and are poly-(6-caprolactone-b-R-GLYCIDOL-g-L-lactic acid); The Mn=11900 of PCL-b-PG, Mw/Mn=1.36; The Mn=28800 of PCL-b-PG-g-PLLA, Mw/Mn=1.59;
2) 1g ethoxyethyl group glycidyl ether is joined in the dry reaction vessel, add simultaneously tetrahydrofuran solution and the 1mL tetrahydrofuran (THF) of 6.8uL1mol/L potassium tert.-butoxide, 20 ℃ of lower reaction 168h; Under the argon shield condition, the tetrahydrofuran solution with 0.75mL 0.5g/mL caprolactone monomer under the room temperature slowly is added drop-wise in the reaction vessel, 0 ℃ of lower reaction 6h; Reaction mixture is poured into washing of precipitate in the ether, is gathered (6-caprolactone-b-ethoxyethyl group glycidyl ether) after the drying; 1g poly-(6-caprolactone-b-ethoxyethyl group glycidyl ether) is dissolved in the 15ml acetone, the aqueous solution with oxalic acid joins in the polymers soln again, after reacting 16h under the room temperature, add calcium hydroxide, the mol ratio of hydroxyl/oxalic acid in the polymkeric substance/calcium hydroxide is 1/0.5/1, under the room temperature reaction 1h after, the centrifugal throw out of removing in the solution, polymers soln is poured in the ether again and precipitates, dried product exhibited is poly-(6-caprolactone-b-R-GLYCIDOL); 0.2g poly-(6-caprolactone-b-R-GLYCIDOL) is joined in the dry reactor, with the dissolving of 20mL toluene, add again the stannous octoate toluene solution of 0.11g levorotatory lactide and 0.75mmol, at 40 ℃ of lower reaction 12h; Stopped reaction, reaction mixture are poured into precipitation drying in the ether, obtain white solid and are poly-(6-caprolactone-b-R-GLYCIDOL-g-L-lactic acid); The Mn=140700 of PCL-b-PG, Mw/Mn=1.58; The Mn=310800 of PCL-b-PG-g-PLLA, Mw/Mn=2;
3) 1g ethoxyethyl group glycidyl ether is joined in the dry reaction vessel, add simultaneously tetrahydrofuran solution and the 3mL tetrahydrofuran (THF) of 0.5ml1mol/L potassium tert.-butoxide, 60 ℃ of lower reaction 24h; Under the argon shield condition, the tetrahydrofuran solution with 5g 0.333g/mL levorotatory lactide monomer under the room temperature slowly is added drop-wise in the reaction vessel, 40 ℃ of lower reaction 6h; Reaction mixture is poured into washing of precipitate in the ether, is gathered (Pfansteihl-b-ethoxyethyl group glycidyl ether) after the drying; 3g poly-(Pfansteihl-b-ethoxyethyl group glycidyl ether) is dissolved in the 15ml acetone, the aqueous solution with oxalic acid joins in the polymers soln again, after reacting 16h under the room temperature, add calcium hydroxide, the mol ratio of hydroxyl/oxalic acid in the polymkeric substance/calcium hydroxide is 1/0.5/1, under the room temperature reaction 1h after, the centrifugal throw out of removing in the solution, polymers soln is poured in the ether again and precipitates, dried product exhibited is poly-(Pfansteihl-b-R-GLYCIDOL); 0.2g poly-(Pfansteihl-b-R-GLYCIDOL) is joined in the dry reactor, with the dissolving of 20mL toluene, add again the stannous octoate toluene solution of 1g caprolactone and 0.67mmol, at 100 ℃ of lower reaction 96h; Stopped reaction, reaction mixture are poured into precipitation drying in the ether, obtain white solid and are poly-(Pfansteihl-b-R-GLYCIDOL-g-caprolactone); The Mn=21000 of PLLA-b-PG, Mw/Mn=1.45; The Mn=31800 of PLLA-b-PG-g-PCL, Mw/Mn=1.72;
4) 1g ethoxyethyl group glycidyl ether is joined in the dry reaction vessel, add simultaneously tetrahydrofuran solution and the 3mL tetrahydrofuran (THF) of 10ml1mol/L potassium tert.-butoxide, 80 ℃ of lower reaction 16h; Under the argon shield condition, the tetrahydrofuran solution with 6.85g 0.333g/mL levorotatory lactide monomer under the room temperature slowly is added drop-wise in the reaction vessel, 40 ℃ of lower reaction 6h; Reaction mixture is poured into washing of precipitate in the ether, is gathered (Pfansteihl-b-ethoxyethyl group glycidyl ether) after the drying; 3g poly-(Pfansteihl-b-ethoxyethyl group glycidyl ether) is dissolved in the 15ml acetone, the aqueous solution with oxalic acid joins in the polymers soln again, after reacting 16h under the room temperature, add calcium hydroxide, the mol ratio of hydroxyl/oxalic acid in the polymkeric substance/calcium hydroxide is 1/0.5/1, under the room temperature reaction 1h after, the centrifugal throw out of removing in the solution, polymers soln is poured in the ether again and precipitates, dried product exhibited is poly-(Pfansteihl-b-R-GLYCIDOL); 0.2g poly-(Pfansteihl-b-R-GLYCIDOL) is joined in the dry reactor, with the dissolving of 20mL toluene, add again the stannous octoate toluene solution of 28.5g caprolactone and 0.25umol, at 200 ℃ of lower reaction 168h; Stopped reaction, reaction mixture are poured into precipitation drying in the ether, obtain white solid and are poly-(Pfansteihl-b-R-GLYCIDOL-g-caprolactone); The Mn=3000 of PLLA-b-PG, Mw/Mn=1.35; The Mn=311800 of PLLA-b-PG-g-PCL, Mw/Mn=1.72;
5) 1g ethoxyethyl group glycidyl ether is joined in the dry reaction vessel, add simultaneously tetrahydrofuran solution and the 3mL tetrahydrofuran (THF) of 0.5ml1mol/L potassium tert.-butoxide, 60 ℃ of lower reaction 24h; Under the argon shield condition, the tetrahydrofuran solution with 5g 0.333g/mL dextrorotation lactide monomer under the room temperature slowly is added drop-wise in the reaction vessel, 40 ℃ of lower reaction 6h; Reaction mixture is poured into washing of precipitate in the ether, is gathered (D-ALPHA-Hydroxypropionic acid-b-ethoxyethyl group glycidyl ether) after the drying; 3g poly-(D-ALPHA-Hydroxypropionic acid-b-ethoxyethyl group glycidyl ether) is dissolved in the 15ml acetone, the aqueous solution with oxalic acid joins in the polymers soln again, after reacting 16h under the room temperature, add calcium hydroxide, the mol ratio of hydroxyl/oxalic acid in the polymkeric substance/calcium hydroxide is 1/0.5/1, under the room temperature reaction 1h after, the centrifugal throw out of removing in the solution, polymers soln is poured in the ether again and precipitates, dried product exhibited is poly-(D-ALPHA-Hydroxypropionic acid-b-R-GLYCIDOL); 0.2g poly-(D-ALPHA-Hydroxypropionic acid-b-R-GLYCIDOL) is joined in the dry reactor, with the dissolving of 20mL toluene, add again the stannous octoate toluene solution of 1g levorotatory lactide and 0.67mmol, at 100 ℃ of lower reaction 96h; Stopped reaction, reaction mixture are poured into precipitation drying in the ether, obtain white solid and are poly-(D-ALPHA-Hydroxypropionic acid-b-R-GLYCIDOL-g-L-lactic acid); The Mn=24500 of PDLA-b-PG, Mw/Mn=1.36; The Mn=38100 of PDLA-b-PG-g-PLLA, Mw/Mn=1.63;
6) 1g ethoxyethyl group glycidyl ether is joined in the dry reaction vessel, add simultaneously tetrahydrofuran solution and the 3mL tetrahydrofuran (THF) of 0.5ml1mol/L potassium tert.-butoxide, 60 ℃ of lower reaction 24h; Under the argon shield condition, the tetrahydrofuran solution with 5g 0.333g/mL levorotatory lactide monomer under the room temperature slowly is added drop-wise in the reaction vessel, 40 ℃ of lower reaction 6h; Reaction mixture is poured into washing of precipitate in the ether, is gathered (Pfansteihl-b-ethoxyethyl group glycidyl ether) after the drying; 3g poly-(Pfansteihl-b-ethoxyethyl group glycidyl ether) is dissolved in the 15ml acetone, the aqueous solution with oxalic acid joins in the polymers soln again, after reacting 16h under the room temperature, add calcium hydroxide, the mol ratio of hydroxyl/oxalic acid in the polymkeric substance/calcium hydroxide is 1/0.5/1, under the room temperature reaction 1h after, the centrifugal throw out of removing in the solution, polymers soln is poured in the ether again and precipitates, dried product exhibited is poly-(Pfansteihl-b-R-GLYCIDOL);
0.2g poly-(Pfansteihl-b-R-GLYCIDOL) is joined in the dry reactor, with the dissolving of 20mL toluene, add again the stannous octoate toluene solution of 1g dextrorotation rac-Lactide and 0.67mmol, at 100 ℃ of lower reaction 96h; Stopped reaction, reaction mixture are poured into precipitation drying in the ether, obtain white solid and are poly-(Pfansteihl-b-R-GLYCIDOL-g-D-lactic acid); The Mn=28500 of PLLA-b-PG, Mw/Mn=1.26; The Mn=68100 of PLLA-b-PG-g-PDLA, Mw/Mn=1.52.
2. one kind prepares the described method with biodegradable additive of branched structure of claim 1, is following 1)-6) arbitrary shown in:
1) 1g ethoxyethyl group glycidyl ether is joined in the dry reaction vessel, add simultaneously tetrahydrofuran solution and the 3mL tetrahydrofuran (THF) of 0.5mL1mol/L potassium tert.-butoxide, 60 ℃ of lower reaction 24h; Under the argon shield condition, the tetrahydrofuran solution with 5mL 0.333g/mL caprolactone monomer under the room temperature slowly is added drop-wise in the reaction vessel, 40 ℃ of lower reaction 4h; Reaction mixture is poured into washing of precipitate in the ether, is gathered (6-caprolactone-b-ethoxyethyl group glycidyl ether) after the drying; 3g poly-(6-caprolactone-b-ethoxyethyl group glycidyl ether) is dissolved in the 15ml acetone, the aqueous solution with oxalic acid joins in the polymers soln again, after reacting 16h under the room temperature, add calcium hydroxide, the mol ratio of hydroxyl/oxalic acid in the polymkeric substance/calcium hydroxide is 1/0.5/1, under the room temperature reaction 1h after, the centrifugal throw out of removing in the solution, polymers soln is poured in the ether again and precipitates, dried product exhibited is poly-(6-caprolactone-b-R-GLYCIDOL);
0.2g poly-(6-caprolactone-b-R-GLYCIDOL) is joined in the dry reactor, with the dissolving of 20mL toluene, add again the stannous octoate toluene solution of 1g levorotatory lactide and 0.67mmol, at 100 ℃ of lower reaction 96h; Stopped reaction, reaction mixture are poured into precipitation drying in the ether, obtain white solid and are poly-(6-caprolactone-b-R-GLYCIDOL-g-L-lactic acid); The Mn=11900 of PCL-b-PG, Mw/Mn=1.36; The Mn=28800 of PCL-b-PG-g-PLLA, Mw/Mn=1.59;
2) 1g ethoxyethyl group glycidyl ether is joined in the dry reaction vessel, add simultaneously tetrahydrofuran solution and the 1mL tetrahydrofuran (THF) of 6.8uL1mol/L potassium tert.-butoxide, 20 ℃ of lower reaction 168h; Under the argon shield condition, the tetrahydrofuran solution with 0.75mL 0.5g/mL caprolactone monomer under the room temperature slowly is added drop-wise in the reaction vessel, 0 ℃ of lower reaction 6h; Reaction mixture is poured into washing of precipitate in the ether, is gathered (6-caprolactone-b-ethoxyethyl group glycidyl ether) after the drying; 1g poly-(6-caprolactone-b-ethoxyethyl group glycidyl ether) is dissolved in the 15ml acetone, the aqueous solution with oxalic acid joins in the polymers soln again, after reacting 16h under the room temperature, add calcium hydroxide, the mol ratio of hydroxyl/oxalic acid in the polymkeric substance/calcium hydroxide is 1/0.5/1, under the room temperature reaction 1h after, the centrifugal throw out of removing in the solution, polymers soln is poured in the ether again and precipitates, dried product exhibited is poly-(6-caprolactone-b-R-GLYCIDOL);
0.2g poly-(6-caprolactone-b-R-GLYCIDOL) is joined in the dry reactor, with the dissolving of 20mL toluene, add again the stannous octoate toluene solution of 0.11g levorotatory lactide and 0.75mmol, at 40 ℃ of lower reaction 12h; Stopped reaction, reaction mixture are poured into precipitation drying in the ether, obtain white solid and are poly-(6-caprolactone-b-R-GLYCIDOL-g-L-lactic acid); The Mn=140700 of PCL-b-PG, Mw/Mn=1.58; The Mn=310800 of PCL-b-PG-g-PLLA, Mw/Mn=2;
3) 1g ethoxyethyl group glycidyl ether is joined in the dry reaction vessel, add simultaneously tetrahydrofuran solution and the 3mL tetrahydrofuran (THF) of 0.5ml1mol/L potassium tert.-butoxide, 60 ℃ of lower reaction 24h; Under the argon shield condition, the tetrahydrofuran solution with 5g 0.333g/mL levorotatory lactide monomer under the room temperature slowly is added drop-wise in the reaction vessel, 40 ℃ of lower reaction 6h; Reaction mixture is poured into washing of precipitate in the ether, is gathered (Pfansteihl-b-ethoxyethyl group glycidyl ether) after the drying; 3g poly-(Pfansteihl-b-ethoxyethyl group glycidyl ether) is dissolved in the 15ml acetone, the aqueous solution with oxalic acid joins in the polymers soln again, after reacting 16h under the room temperature, add calcium hydroxide, the mol ratio of hydroxyl/oxalic acid in the polymkeric substance/calcium hydroxide is 1/0.5/1, under the room temperature reaction 1h after, the centrifugal throw out of removing in the solution, polymers soln is poured in the ether again and precipitates, dried product exhibited is poly-(Pfansteihl-b-R-GLYCIDOL);
0.2g poly-(Pfansteihl-b-R-GLYCIDOL) is joined in the dry reactor, with the dissolving of 20mL toluene, add again the stannous octoate toluene solution of 1g caprolactone and 0.67mmol, at 100 ℃ of lower reaction 96h; Stopped reaction, reaction mixture are poured into precipitation drying in the ether, obtain white solid and are poly-(Pfansteihl-b-R-GLYCIDOL-g-caprolactone); The Mn=21000 of PLLA-b-PG, Mw/Mn=1.45; The Mn=31800 of PLLA-b-PG-g-PCL, Mw/Mn=1.72;
4) 1g ethoxyethyl group glycidyl ether is joined in the dry reaction vessel, add simultaneously tetrahydrofuran solution and the 3mL tetrahydrofuran (THF) of 10ml1mol/L potassium tert.-butoxide, 80 ℃ of lower reaction 16h; Under the argon shield condition, the tetrahydrofuran solution with 6.85g 0.333g/mL levorotatory lactide monomer under the room temperature slowly is added drop-wise in the reaction vessel, 40 ℃ of lower reaction 6h; Reaction mixture is poured into washing of precipitate in the ether, is gathered (Pfansteihl-b-ethoxyethyl group glycidyl ether) after the drying; 3g poly-(Pfansteihl-b-ethoxyethyl group glycidyl ether) is dissolved in the 15ml acetone, the aqueous solution with oxalic acid joins in the polymers soln again, after reacting 16h under the room temperature, add calcium hydroxide, the mol ratio of hydroxyl/oxalic acid in the polymkeric substance/calcium hydroxide is 1/0.5/1, under the room temperature reaction 1h after, the centrifugal throw out of removing in the solution, polymers soln is poured in the ether again and precipitates, dried product exhibited is poly-(Pfansteihl-b-R-GLYCIDOL);
0.2g poly-(Pfansteihl-b-R-GLYCIDOL) is joined in the dry reactor, with the dissolving of 20mL toluene, add again the stannous octoate toluene solution of 28.5g caprolactone and 0.25umol, at 200 ℃ of lower reaction 168h; Stopped reaction, reaction mixture are poured into precipitation drying in the ether, obtain white solid and are poly-(Pfansteihl-b-R-GLYCIDOL-g-caprolactone); The Mn=3000 of PLLA-b-PG, Mw/Mn=1.35; The Mn=311800 of PLLA-b-PG-g-PCL, Mw/Mn=1.72;
5) 1g ethoxyethyl group glycidyl ether is joined in the dry reaction vessel, add simultaneously tetrahydrofuran solution and the 3mL tetrahydrofuran (THF) of 0.5ml1mol/L potassium tert.-butoxide, 60 ℃ of lower reaction 24h; Under the argon shield condition, the tetrahydrofuran solution with 5g 0.333g/mL dextrorotation lactide monomer under the room temperature slowly is added drop-wise in the reaction vessel, 40 ℃ of lower reaction 6h; Reaction mixture is poured into washing of precipitate in the ether, is gathered (D-ALPHA-Hydroxypropionic acid-b-ethoxyethyl group glycidyl ether) after the drying; 3g poly-(D-ALPHA-Hydroxypropionic acid-b-ethoxyethyl group glycidyl ether) is dissolved in the 15ml acetone, the aqueous solution with oxalic acid joins in the polymers soln again, after reacting 16h under the room temperature, add calcium hydroxide, the mol ratio of hydroxyl/oxalic acid in the polymkeric substance/calcium hydroxide is 1/0.5/1, under the room temperature reaction 1h after, the centrifugal throw out of removing in the solution, polymers soln is poured in the ether again and precipitates, dried product exhibited is poly-(D-ALPHA-Hydroxypropionic acid-b-R-GLYCIDOL);
0.2g poly-(D-ALPHA-Hydroxypropionic acid-b-R-GLYCIDOL) is joined in the dry reactor, with the dissolving of 20mL toluene, add again the stannous octoate toluene solution of 1g levorotatory lactide and 0.67mmol, at 100 ℃ of lower reaction 96h; Stopped reaction, reaction mixture are poured into precipitation drying in the ether, obtain white solid and are poly-(D-ALPHA-Hydroxypropionic acid-b-R-GLYCIDOL-g-L-lactic acid); The Mn=24500 of PDLA-b-PG, Mw/Mn=1.36; The Mn=38100 of PDLA-b-PG-g-PLLA, Mw/Mn=1.63;
6) 1g ethoxyethyl group glycidyl ether is joined in the dry reaction vessel, add simultaneously tetrahydrofuran solution and the 3mL tetrahydrofuran (THF) of 0.5ml1mol/L potassium tert.-butoxide, 60 ℃ of lower reaction 24h; Under the argon shield condition, the tetrahydrofuran solution with 5g 0.333g/mL levorotatory lactide monomer under the room temperature slowly is added drop-wise in the reaction vessel, 40 ℃ of lower reaction 6h; Reaction mixture is poured into washing of precipitate in the ether, is gathered (Pfansteihl-b-ethoxyethyl group glycidyl ether) after the drying; 3g poly-(Pfansteihl-b-ethoxyethyl group glycidyl ether) is dissolved in the 15ml acetone, the aqueous solution with oxalic acid joins in the polymers soln again, after reacting 16h under the room temperature, add calcium hydroxide, the mol ratio of hydroxyl/oxalic acid in the polymkeric substance/calcium hydroxide is 1/0.5/1, under the room temperature reaction 1h after, the centrifugal throw out of removing in the solution, polymers soln is poured in the ether again and precipitates, dried product exhibited is poly-(Pfansteihl-b-R-GLYCIDOL);
0.2g poly-(Pfansteihl-b-R-GLYCIDOL) is joined in the dry reactor, with the dissolving of 20mL toluene, add again the stannous octoate toluene solution of 1g dextrorotation rac-Lactide and 0.67mmol, at 100 ℃ of lower reaction 96h; Stopped reaction, reaction mixture are poured into precipitation drying in the ether, obtain white solid and are poly-(Pfansteihl-b-R-GLYCIDOL-g-D-lactic acid); The Mn=28500 of PLLA-b-PG, Mw/Mn=1.26; The Mn=68100 of PLLA-b-PG-g-PDLA, Mw/Mn=1.52.
3. the described application of biodegradable additive in poly(lactic acid) and the modification of polycaprolactone co-mixing system with branched structure of claim 1.
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