CN101081925A - Alternating magnetic field driven shape memory biological degradable polymer and preparation method thereof - Google Patents

Alternating magnetic field driven shape memory biological degradable polymer and preparation method thereof Download PDF

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CN101081925A
CN101081925A CN 200710072294 CN200710072294A CN101081925A CN 101081925 A CN101081925 A CN 101081925A CN 200710072294 CN200710072294 CN 200710072294 CN 200710072294 A CN200710072294 A CN 200710072294A CN 101081925 A CN101081925 A CN 101081925A
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caprolactone
lactide
magnetic field
rac
glycollide
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CN100540604C (en
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鲁玺丽
孙志洁
郑玉峰
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Harbin Engineering University
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Harbin Engineering University
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Abstract

The present invention is preparation process of biodegradable alternating magnetic field driven shape memory composite polymer material. The composite polymer material is mixture of copolymer of L-lactide and glycolide and/or epsilon-caprolactone and nanometer Fe3O4 particle coated with poly-L-lactide, polyglycolide or poly-epsilon-caprolactone in the weight ratio of 70-90 to 10-30. Compared with available technology, the present invention has the features of non-contact initiated shape memory function, high restoring ability and mechanical performance suitable for use in medical product, capacity of being used in developing in nuclear magnetic resonance, and targeting function for no-duct conveyance.

Description

The biodegradable polymer of alternating magnetic field driven shape memory and preparation method
(1) technical field
What the present invention relates to is a kind of novel material, specifically a kind of Biodegradable material with shape memory function.
(2) background technology
With poly(lactic acid) and multipolymer thereof is that a class aliphatic polyester of representative is because its good biocompatibility, biological degradability and good mechanical performance and obtain to use widely at medical field, relate to all many-sides such as operating sutures, fracture internal fixing, tissue engineering bracket, medicine controlled release carrier at present, now become the most valued material in the biological degradation field of medical materials.Yet, along with the appearance of new medical skill means of various modern times, the performance of material is also had higher requirement, also increase gradually for the demand of types of functionality material with property.Since people such as Lendlein in 2002 were reporting degradable PCL and PDO segmented copolymer and have excellent shape memory effect on the famous magazine " Science " since, the biodegradable polymer with shape memory effect had caused investigator's extensive interest.The operating sutures that Lendlein makes with the PCL/PDO segmented copolymer with shape memory effect, its original shape is the extended fiber, and has a controlled restorer (1～3MPa), this operating sutures is sewed up a wound with lax state in use, when temperature raises its shape recovery temperature of arrival, because the restorer that presets is tightened up operating sutures, has sewed up wound.People such as king's body state synthesize PLLA/PGA/PCL (PLAGC) segmented copolymer, and its shape memory effect is studied.Studies show that, the mechanical performance that the composition by adjusting copolymer and the length of segment can the regulation and control materials, and copolymer presents good SME, and its shape recovery ratio and shape conservation rate all surpass 90%.
Up to now, the biodegradable shape memory polymers of existing research is the shape-memory polymer of responsive to temperature type mostly, promptly reach the variation of shape with heat, but can not directly heat at some specific position of human body, promptly use traditional method to feed the liquid or the gas of heat, so contactless initiation conditions then is necessary.Existing researcher gives birth to heat by illumination makes the shape-memory polymer generation shape recovery of thermo-responsive type or utilization that the reaction active groups of photosensitive type is introduced in the biodegradable polymers system, realize the light-induced shape-memory effect, but a lot of defectives such as that it also exists is low such as deformation quantity, photoresponse time or recovery time are long.
(3) summary of the invention
The object of the present invention is to provide a kind ofly under the effect of alternating magnetic field, can return to original shape, especially be fit to be applied to the biodegradable polymer of the alternating magnetic field driven shape memory at the medical science position that is difficult to heat.The present invention also aims to provide a kind of preparation method of biodegradable polymer of alternating magnetic field driven shape memory.
The object of the present invention is achieved like this:
The biodegradable polymer of alternating magnetic field driven shape memory of the present invention is by at least a copolymer in L-lactide and glycolide, the 6-caprolactone, with the Fe that coats one deck PLLA, PGA or poly-epsilon-caprolactone rete on the surface 3O 4Nano particle is that 70-90: 30-10 mixes formed polymer composites according to mass percent.
The Fe that coats one deck PLLA, PGA or poly-epsilon-caprolactone rete on the surface described in the polymer of the present invention 3O 4Nano particle is to use NH 3H 2O is as precipitating reagent, is 1: 2 divalent iron salt (FeCl with mol ratio 24H 2O) and trivalent iron salt (FeCl 36H 2O) mixed solution joins in the container, and then with the NH of 28% (mass fraction) 3H 2O joins in the container, vigorous stirring, 60 ℃ of constant temperature water baths, mixed liquor by orange red become black gradually after, continue to be stirred to reaction again and finish, centrifugation uses the distilled water cyclic washing until pH=7.0, remove supernatant liquor, at 60 ℃ of lower vacuum drying 24h, grind resulting nano-magnetic Fe 3O 4Particle; At the inferior tin (Sn (Oct) of octoate catalyst 2) effect under, the Fe of surface engagement hydroxyl 3O 4Nano particle causes the ring-opening polymerisation of L-lactide, glycolide or 6-caprolactone, at Fe 3O 4Nanoparticle surface coats the Fe of the polymer film of one deck PLLA, PGA or poly-epsilon-caprolactone 3O 4Nano particle.
At least two kinds copolymer by in L-lactide, glycolide, the 6-caprolactone described in the polymer of the present invention can be at least two kinds of mixing in L-lactide, glycolide, the 6-caprolactone, by the synthetic random copolymer of random copolymerization; Also can be that the reaction of 6-caprolactone and ethylene glycol or glycerine generates hydroxy-end capped performed polymer, L-lactide or glycolide and succinic acid reaction generate the performed polymer of carboxy blocking, the segmented copolymer that more at least two kinds of mixing in them is synthesized by coupling agent or chain extender.
The biodegradable polymer of alternating magnetic field driven shape memory of the present invention is to adopt such method to prepare:
(1) L-rac-Lactide and glycollide or 6-caprolactone are mixed and made at least a multipolymer in L-rac-Lactide and glycollide, the 6-caprolactone;
(2) use NH 3H 2O is as precipitation agent, with divalent iron salt (FeCl 24H 2O) and trivalent iron salt (FeCl 36H 2O) mixing solutions joins in the container, and then with the NH of 28% (massfraction) 3H 2O joins in the container, vigorous stirring, constant temperature water bath, mixed solution by orange red become black gradually after, continue to be stirred to reaction again and finish, centrifugation uses the distilled water repetitive scrubbing until pH=7.0, remove supernatant liquid,, grind and make nano-magnetic Fe at 60 ℃ of following vacuum-drying 24h 3O 4Particle;
(3) be that 70% glycolic acid is to Fe with concentration 3O 4Nano particle carries out modification, and ultrasonic vibration 30 minutes makes its surface conjunction hydroxyl, at the inferior tin (Sn (Oct) of octoate catalyst 2) effect under (mol ratio of catalyst and monomer consumption is 1: 2000～1: 5000), the Fe of surface engagement hydroxyl 3O 4Nano particle causes the ring-opening polymerisation (polymerization temperature is 130 ℃, and the reaction time is 5～8 hours) of L-lactide, glycolide or 6-caprolactone monomer, makes the Fe that coats one deck PLLA, PGA or poly-epsilon-caprolactone rete on the surface 3O 4Nano particle;
(4) with at least a copolymer in L-lactide and glycolide, the 6-caprolactone, with the Fe that coats one deck PLLA, PGA or poly-epsilon-caprolactone rete on the surface 3O 4Nano particle is that 70-90: 30-10 mixes the formation polymer composites according to mass percent.
Method of the present invention can also comprise some features like this:
(1) described L-rac-Lactide and glycollide or 6-caprolactone are mixed and made at least a multipolymer in L-rac-Lactide and glycollide, the 6-caprolactone, are by the synthetic random copolymers of random copolymerization.
(2) described L-lactide and glycolide or 6-caprolactone are mixed and made at least a copolymer in L-lactide and glycolide, the 6-caprolactone, that 6-caprolactone and ethylene glycol or glycerine reaction are generated hydroxy-end capped performed polymer, L-lactide, glycolide and succinic acid reaction generate the performed polymer of carboxy blocking, the segmented copolymer that more at least two kinds of mixing in them is synthesized by coupling agent or chain extender.
(3) described Fe 3O 4The diameter of particle is between 10nm～50nm.
With the biodegradable polymer based composites of alternating magnetic field driven shape memory at its 20～30 ℃ of molded one-tenth original shapes of temperature range melting model more than fusing point, the material deformation of figuration becomes second kind of shape more than second-order transition temperature, keep deformation with material cooled below second-order transition temperature, solid shape has stable solid shape behind the material deformation.The material that will have second kind of shape places under the action of alternating magnetic field, applies the alternating magnetic field of different frequency and magneticstrength, and material returns to original shape.The mode of texturing of wherein mentioning can be hole enlargement, stretching, compression, bending, reverse any or several mixing uses.
The present invention compared with prior art has following characteristics: (1) has realized the function of contactless initiation shape memory, is conducive to medically manyly be difficult to direct-fired position and use; (2) because Fe 3O 4The existence of nano particle is played the effect that particle strengthens, so that Fe 3O 4Nano particle/poly lactic acid series biodegradable polymers based composites has higher restoring force and mechanical property, is conducive to the application on the medical article higher to mechanical property requirements; (3) Fe 3O 4Nano particle can develop under nuclear magnetic resonance, is conducive to carry out mark in the implant into body, has made things convenient for use procedure; (4) Fe 3O 4The existence of nano particle makes material have targeting, can realize carrying in the ductless body, is conducive to simplify use cost and the operating process of implant devices.
The medical use advantage of material of the present invention:
Compare with existing biodegradable shape memory polymers material, magnetic nanoparticle/degradable polyalcohol group matrix material has many performances that are better than existing Biodegradable shape-memory material:
(1) because Fe 3O 4Nano particle is under the effect of alternating magnetic field, dissipation rf wave energy transform into heat energy, the temperature of surrounding medium is raise, reach the shape recovery temperature of polymeric matrix, be that material can recover in the effect generation shape of alternating magnetic field, be conducive to the medical application at the direct-fired position of many inconveniences; (2) Fe 3O 4Nano particle is dosed in the polymeric matrix, plays the effect that particle strengthens, and can improve to a certain extent the mechanical property of polymeric matrix and improve its restoring force, is conducive to the application on the medical article higher to mechanical property requirements; (3) Fe 3O 4Nano particle has superparamagnetism, and the external source that can serve as magnetic resonance is contrasted the source, can at magnetic resonance imaging (MRI), carry out mark when helping in the material implant into body; (4) Fe 3O 4Nano particle has targeting, can realize the duct free location, is conducive to simplify use cost and the operating process of implant devices, and above-mentioned advantage is used practical medical and had very important significance.
(4) embodiment
For example the present invention is described in more detail below:
Embodiment 1:
(1) with L-rac-Lactide, glycollide and 6-caprolactone is 6: 2: 2 or mixing in 6: 1: 3 in molar ratio, by the synthetic random copolymerss of random copolymerization with different compositions; Or be 400: 1 6-caprolactone and ethylene glycol or glycerol 130 ℃ of reactions 24 hours down with mol ratio, generate hydroxy-end capped performed polymer, (mol ratio is 200: 1 for L-rac-Lactide, glycollide and Succinic Acid reaction, reaction conditions be 110 ℃ following 24 hours) generate the performed polymer of carboxy blocking, be to add diisocyanates coupling agent at 1: 1.1 or chainextender synthesizes segmented copolymer more in molar ratio.
(2) adopt chemical coprecipitation to prepare magnetic Nano Fe 3O 4, use NH 3H 2O is as precipitation agent, is 1: 2 divalent iron salt (FeCl with mol ratio 24H 2O) and trivalent iron salt (FeCl 36H 2O) mixing solutions joins in the container, and then with the NH of 28% (massfraction) 3H 2O joins in the container, vigorous stirring, constant temperature water bath.Mixed liquor by orange red become black gradually after, continue again to be stirred to reaction and finish centrifugation, with the distilled water cyclic washing until pH=7.0, remove supernatant liquor, at 60 ℃ of lower vacuum drying 24h, grind and namely get the nano-magnetic Fe of particle diameter between 10nm～50nm 3O 4Particle.
(3) with glycolic acid to Fe 3O 4Nano particle carries out modification, makes its surface conjunction hydroxyl, at the inferior tin (Sn (Oct) of octoate catalyst 2) effect under (mol ratio of catalyst and monomer consumption is 1: 2000～1: 5000), the Fe of surface engagement hydroxyl 3O 4Nano particle causes the ring-opening polymerisation of L-lactide, glycolide or 6-caprolactone monomer, at Fe 3O 4Nanoparticle surface coats the polymer film of one deck PLLA, PGA or poly-epsilon-caprolactone, is conducive to Fe 3O 4Nano particle is more efficiently dispersion in different polymeric matrixs.
(4) press at least a copolymer in L-lactide and glycolide, the 6-caprolactone, with the Fe that coats one deck PLLA, PGA or poly-epsilon-caprolactone rete on the surface 3O 4Nano particle is that 70-90: 30-10 mixes according to mass percent, and the method for employing blend technique and in-situ polymerization prepares the Biodegradable polymer composite material of alternating magnetic field driven shape memory.
(5) with the biodegradable polymer of above-mentioned alternating magnetic field driven shape memory at its 20～30 ℃ of molded one-tenth original shapes of temperature range melting model more than fusing point, the material deformation of figuration becomes second kind of shape more than second-order transition temperature, keep deformation with material cooled below second-order transition temperature, solid shape has stable solid shape behind the material deformation.The material that will have second kind of shape places under the action of alternating magnetic field, applies the alternating magnetic field of different frequency and magneticstrength, and material returns to original shape.The mode of texturing of wherein mentioning can be hole enlargement, stretching, compression, bending, reverse any or several mixing uses.
Embodiment 2:
Fe 3O 4The SME of nano particle/PLLA-caprolactone based composites.
Molar percentage is that L-rac-Lactide/6-caprolactone ring-opening polymerization generation viscosity-average molecular weight under the effect of stannous octoate of 80: 20 is poly-L-rac-Lactide/6-caprolactone random copolymers of 280,000.Fe with 20nm 3O 4Nano particle makes its fermentation wrap one deck PLLA film with the described method of condition (2), adopts then the method for mechanical blending, is the Fe after 10% the surface modification with percentage by weight 3O 4Nano particle and viscosity average molecular weigh are 280,000 PLLA/compound Fe that is prepared into of 6-caprolactone random copolymer 3O 4Nano particle/PLLA-caprolactone based composites.Material is heated to its more than fusing point 20 ℃, and the 10MPa compression molding of pressurizeing is then adopted on the self-control stretching device and is measured, and stretching device places under the alternating magnetic field and has the transmitter of measuring temperature.The alternating magnetic field frequency is 13MHz, and magnetic field intensity is 540A/m, and shape was recovered in 25 seconds, and the deformation recovery rate is 95%.
Embodiment 3:
Fe 3O 4The SME of nano particle/PLLA-glycolide based composites.
The ring-opening polymerization under the effect of stannous octoate of 80: 20 in molar ratio ratio of L-rac-Lactide and glycollide obtains poly-L-poly (lactide-co-glycolide), and surveying its viscosity-average molecular weight is 180,000.Fe with 30nm 3O 4Nano particle makes its fermentation wrap one deck PLLA film with the described method of condition (2), adopts then the method for mechanical blending, is the Fe after 15% the surface modification with percentage by weight 3O 4Nano particle and viscosity average molecular weigh are 180,000 the compound Fe that is prepared into of PLLA-glycolide copolymer 3O 4Nano particle/PLLA-glycolide based composites.Material is heated to its more than fusing point 20 ℃, and the 10MPa compression molding of pressurizeing is then adopted on the self-control stretching device and is measured, and stretching device places under the alternating magnetic field and has the transmitter of measuring temperature.The alternating magnetic field frequency is 13MHz, and magnetic field intensity is 320A/m, and shape was recovered in 20 seconds, and the deformation recovery rate is 92.3%.

Claims (8)

1, a kind of biodegradable polymer of alternating magnetic field driven shape memory, it is characterized in that: it is by at least a copolymer in L-lactide and glycolide, the 6-caprolactone, with the Fe that coats one deck PLLA, PGA or poly-epsilon-caprolactone rete on the surface 3O 4Nano particle is that 70-90: 30-10 mixes formed polymer composites according to mass percent.
2, the biodegradable polymer of alternating magnetic field driven shape memory according to claim 1, it is characterized in that: described can be at least two kinds of mixing in L-rac-Lactide, glycollide, the 6-caprolactone by at least two kinds multipolymer in L-rac-Lactide, glycollide, the 6-caprolactone, by the synthetic random copolymers of random copolymerization.
3, the biodegradable polymer of alternating magnetic field driven shape memory according to claim 1, it is characterized in that: described can be 6-caprolactone and ethylene glycol or the hydroxy-end capped performed polymer of glycerol reaction generation by at least two kinds multipolymer in L-rac-Lactide, glycollide, the 6-caprolactone, L-rac-Lactide or glycollide and Succinic Acid reaction generate the performed polymer of carboxy blocking, the segmented copolymer that at least two kinds of mixing in them are synthesized by coupling agent or chainextender again.
4, according to the biodegradable polymer of claim 1,2 or 3 described alternating magnetic field driven shape memories, it is characterized in that: the described Fe that coats one deck PLLA, PGA or poly-epsilon-caprolactone rete on the surface 3O 4Nano particle is to use NH 3H 2O is as precipitating reagent, with FeCl 24H 2O and FeCl 36H 2The mixed solution of O joins in the container, and then with the NH of mass fraction 28% 3H 2O joins in the container, vigorous stirring, constant temperature water bath, mixed liquor by orange red become black gradually after, continue to be stirred to reaction again and finish, centrifugation uses the distilled water cyclic washing until pH=7.0, remove supernatant liquor, at 60 ℃ of lower vacuum drying 24 h, grind resulting nano-magnetic Fe 3O 4Particle; At catalyst S n (Oct) 2Effect under, the Fe of surface engagement hydroxyl 3O 4Nano particle causes the ring-opening polymerisation of L-lactide, glycolide or 6-caprolactone, at Fe 3O 4Nanoparticle surface coats the Fe of the polymer film of one deck PLLA, PGA or poly-epsilon-caprolactone 3O 4Nano particle.
5, a kind of preparation method of biodegradable polymer of alternating magnetic field driven shape memory is characterized in that:
(1) L-rac-Lactide and glycollide or 6-caprolactone copolymerization are made at least a multipolymer in L-rac-Lactide and glycollide, the 6-caprolactone;
(2) use NH 3H 2O is as precipitation agent, with FeCl 24H 2O and FeCl 36H 2The mixing solutions of O joins in the container, and then with the NH of massfraction 28% 3H 2O joins in the container, vigorous stirring, constant temperature water bath, mixed solution by orange red become black gradually after, continue to be stirred to reaction again and finish, centrifugation uses the distilled water repetitive scrubbing until pH=7.0, remove supernatant liquid,, grind and make nano-magnetic Fe at 60 ℃ of following vacuum-drying 24h 3O 4Particle;
(3) with glycolic acid to Fe 3O 4Nano particle carries out modification, makes its surface conjunction hydroxyl, at catalyst S n (Oct) 2Effect under, the Fe of surface engagement hydroxyl 3O 4Nano particle causes the ring-opening polymerisation of L-lactide, glycolide or 6-caprolactone, makes the Fe that coats one deck PLLA, PGA or poly-epsilon-caprolactone rete on the surface 3O 4Nano particle;
(4) with at least a copolymer in L-lactide and glycolide, the 6-caprolactone, with the Fe that coats one deck PLLA, PGA or poly-epsilon-caprolactone rete on the surface 3O 4Nano particle is that 70-90: 30-10 mixes the formation polymer composites according to mass percent.
6, the preparation method of the biodegradable polymer of alternating magnetic field driven shape memory according to claim 5, it is characterized in that: described L-rac-Lactide and glycollide or 6-caprolactone are mixed and made at least a multipolymer in L-rac-Lactide and glycollide, the 6-caprolactone, are by the synthetic random copolymers of random copolymerization.
7, the preparation method of the biodegradable polymer of alternating magnetic field driven shape memory according to claim 5, it is characterized in that: described L-rac-Lactide and glycollide or 6-caprolactone are mixed and made at least a multipolymer in L-rac-Lactide and glycollide, the 6-caprolactone, be with 6-caprolactone and ethylene glycol or the hydroxy-end capped performed polymer of glycerol reaction generation, L-rac-Lactide, glycollide and Succinic Acid reaction generate the performed polymer of carboxy blocking, the segmented copolymer that at least two kinds of mixing in them are synthesized by coupling agent or chainextender again.
8, the preparation method of the biodegradable polymer of alternating magnetic field driven shape memory according to claim 5 is characterized in that: described Fe 3O 4The diameter of particle is between 10nm～50nm.
CNB2007100722949A 2007-06-01 2007-06-01 The biodegradable polymer of alternating magnetic field driven shape memory and preparation method Expired - Fee Related CN100540604C (en)

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CN102344655A (en) * 2010-07-30 2012-02-08 华东师范大学 Nano composite material with magnetic-field-induced shape memory function and its production method
CN105002658A (en) * 2015-08-19 2015-10-28 哈尔滨工业大学 Preparation method and driving method of remotely controllable multiple shape memory polymer composite fibrous membrane
CN110828656A (en) * 2019-11-04 2020-02-21 西安交通大学 Rapid reversible shape memory method based on magnetic response
CN112625292A (en) * 2020-12-17 2021-04-09 青岛博远高分子材料研究院有限公司 Preparation method of degradable shape memory polymer medical splint
CN114891328A (en) * 2022-03-24 2022-08-12 哈尔滨工程大学 Preparation method and application of polymer blend with water-induced two-way shape memory effect

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102344655A (en) * 2010-07-30 2012-02-08 华东师范大学 Nano composite material with magnetic-field-induced shape memory function and its production method
CN102344655B (en) * 2010-07-30 2013-10-30 华东师范大学 Nano composite material with magnetic-field-induced shape memory function and its production method
CN105002658A (en) * 2015-08-19 2015-10-28 哈尔滨工业大学 Preparation method and driving method of remotely controllable multiple shape memory polymer composite fibrous membrane
CN105002658B (en) * 2015-08-19 2017-11-03 哈尔滨工业大学 The preparation method and driving method of remote-controllable Multiple Shape memory polymer composite cellulosic membrane
CN110828656A (en) * 2019-11-04 2020-02-21 西安交通大学 Rapid reversible shape memory method based on magnetic response
CN110828656B (en) * 2019-11-04 2021-07-09 西安交通大学 Rapid reversible shape memory method based on magnetic response
CN112625292A (en) * 2020-12-17 2021-04-09 青岛博远高分子材料研究院有限公司 Preparation method of degradable shape memory polymer medical splint
CN114891328A (en) * 2022-03-24 2022-08-12 哈尔滨工程大学 Preparation method and application of polymer blend with water-induced two-way shape memory effect
CN114891328B (en) * 2022-03-24 2023-08-01 哈尔滨工程大学 Preparation method and application of polymer blend with water-induced double-way shape memory effect

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