CN104744922A - Method for preparing magneto type biodegradable shape-memory-polymer nano composite material - Google Patents
Method for preparing magneto type biodegradable shape-memory-polymer nano composite material Download PDFInfo
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Abstract
The invention relates to a method for preparing a magneto type biodegradable shape-memory composite material. According to the shape-memory composite material, isocyanate chain segments are taken as a hard phase, and poly-D,L-lactide and polytetramethylene ether glycol are taken as a soft phase. The method for preparing the shape-memory composite material comprises the steps: initiating the ring-opening polymerization of D,L-lactide with micromolecular glycol, so as to prepare poly-D,L-lactide of a certain molecular weight, of which the two terminals are provided with hydroxyl groups, and then, coupling to polytetramethylene ether glycol through diisocyanate, so as to form a straight-chain block copolymer; then, mixing with surface modified Fe3O4 nanoparticles, thereby preparing the magneto type biodegradable shape-memory composite material. The shape-memory composite material prepared by the method has the characteristics of strong deformation holding ability, high shape recovery rate, good shape memory performance and repeatability, biodegradation and the like; furthermore, the function of initiating shape memory in a non-contact manner is realized, and the material can have a targeting property due to the presence of the Fe3O4 nanoparticles.
Description
Technical field
The invention belongs to biomaterial for medical purpose field, relate to a kind of preparation method of mangneto type biodegradable shape memory polymeric nano composite material.
Background technology
Along with the development of society, intelligentized trend is more and more obvious, and intelligentized development has driven the development of intelligent material.The novel intelligent material that shape-memory material has grown up since being the sixties in last century, its application in life widely, on to the space shuttle in space, under to the biomedicine in our life, the figure of shape-memory material can be found.
While shape-memory material refers to and can change (electric current, magnetic field, heat, light, solvent etc.) at sensing external environment, this change can be responded, and by the adjustment to self mechanics parameter (as shape, position and strain etc.), be returned to the shape preset.First finding that the material of shape memory characteristic is shape memory alloy (Shape Memory Alloy, SMA), is also current most popular shape-memory material.Due to the performance of many excellences such as its amount of bow is large, plasticity is high, multiple fields such as aerospace, mechano-electronic, biologic medical, bridge construction, automotive industry and daily life are widely used in.
Along with the 1980's initial stage shape-memory polymer (Shape Memory Polymer, SMP) discovery, the research of shape-memory polymer is always very popular, this has benefited from the lot of advantages that SMP is better than SMA, and as replied deformation quantity large (can reach 400%), density is low, biodegradability, memory effect are remarkable, machine-shaping is easy, can control the features such as recovery behavior, good insulating, low price.What be therefore widely used in hinge, framework, minute surface and reflective mirror self-deploys the fields such as structure, the collapsible and deformable wing of flyer, intelligent suture line, medicine equipment, automotive brake, weaving and self-healing.
But compared with SMAs, SMPs has obvious shortcoming in some aspects---and physical strength is low, shape recovery stress is little, therefore, in order to overcome these shortcomings of SMPs, expand its Application Areas, conventional method adds to have multi-functional high modulus filler and carry out modification in SMPs.But due to dimensional effect and the rigidity of filler, and during high filler loading capacity filler to the destruction of polymer network structure, add filler while raising polymkeric substance modulus and intensity, often bring the decline of recovery strain rate, this influence degree can be slowed down by the size reducing filler, namely nano combined.
At present, about the research of nano combined shape-memory polymer is very active, the nano particle of filling in particulate-filled composite mainly contains the nano particles such as SiC, carbon black, ceramic particle, Fe3O4, metallic particles.Due to some properties of some filler itself, as electroconductibility, magnetic etc., and Nano filling inherently has the characteristics such as small-size effect, surface effects, quantum size effect, macro quanta tunnel effect and Dielectric confinement effect.Nano filling adds in matrix material, can not only improve shape-memory polymer performance, can also give the mode of excitation that shape-memory polymer is different.Such as carbon nanotube (CNTs) adds in shape-memory polymer, not only plays the effect of enhancing, and can give SMPs and be electrically excited the function with infrared excitation.Fe3O4 and shape-memory polymer compound, can make it have magnetic arousal function.
Polylactide and its copolymer is owing to having unique biological degradability, biocompatibility, thermoplasticity and environment friendly (Middleton JC, Tipton AJ. Synthetic Biodegradable Polymers as Orthopedic Devices [J]. Biomaterial, 2000,21 (23): 2335-2346.).Polytetramethylene ether diol has good biocompatibility, medically can be used to manufacture catheter, bags of blood, gas bushing and all kinds of artificial limb (Xu Zhaoyu. the synthesis of PTMG and application [J]. chemical science and technology market, 2004,03:1-4.).
Summary of the invention
The object of the present invention is to provide a kind of preparation method of mangneto type biodegradable shape memory polymeric nano composite material.
The preparation method of the mangneto type Biodegradable shape-memory matrix material that the present invention proposes, it is characterized in that this composite material of shape memory is straight chain type segmented copolymer, is hard phase with isocyanic ester segment.PDLLA, polytetramethylene ether diol are soft phase; Cause the ring-opening polymerization of D, L-rac-Lactide by small molecules glycol, prepare the straight chain type PDLLA of two ends with hydroxyl, then get up to be formed the segmented copolymer of straight chain type with polytetramethylene ether diol by vulcabond coupling.Then the Fe that surface modification is crossed is mixed into
3o
4nanoparticle obtains mangneto type Biodegradable shape-memory matrix material; Concrete steps are as follows:
(1) ring-opening polymerization: small molecules glycol causes the ring-opening polymerization of DL-rac-Lactide, and polymerization temperature is 125-135 DEG C, and the time is 18-24 hour, nitrogen protection, add dissolution with solvents after polymerization terminates, then it is slowly instilled precipitation agent and polymkeric substance is precipitated, purified product, vacuum-drying, obtain white flock degradable high polymer material, this material is straight chain type PDLLA, the mol ratio controlling small molecules glycol and D, L-rac-Lactide is 1:300-1:400;
(2) chain extension: the straight chain type PDLLA that step (1) obtains is dissolved in dry toluene, 65 DEG C are stirred 20min, add vulcabond and catalyzer, and 65 DEG C ~ 70 DEG C are stirred 10min, add polytetramethylene ether diol, and 70 ~ 75 DEG C are stirred 6h;
(3) film forming: by the Fe crossed through silane coupling agent surface modification
3o
4nanoparticle dispersion is in dry toluene; It is slowly instilled in step (2) the gained solution that stirred, after stirring 2h, pour Teflon mould into; Then 100 ~ 120 DEG C of baking oven solvent flashings are put into; The mangneto type Biodegradable shape-memory matrix material of sheet is obtained after 48 hours.
In the present invention, small molecules glycol described in step (1) is the one in ethylene glycol or butyleneglycol.
In the present invention, catalyzer described in step (2) is the one in stannous octoate or tin protochloride, and catalyst charge is the 0.05-1.0 wt% of D, L-rac-Lactide total amount.
In the present invention, solvent described in step (1) is any one in tetrahydrofuran (THF), chloroform, DMF or methylene dichloride, and described precipitation agent is any one in methyl alcohol, ether or normal hexane.
In the present invention, in step (1), the molecular weight of the straight chain type PDLLA of synthesis is 30000 ~ 60000, and the molecular weight of described polytetramethylene ether diol is 2000.
In the present invention, the vulcabond described in step (2) is 1,6-hexamethylene diisocyanate, Isosorbide-5-Nitrae-phenylene diisocyanate, 4, the one in 4 '-methylene-diphenyl isocyanic ester or 2,4 toluene diisocyanate.
In the present invention, silane coupling agent described in step (3) is (3-(2,3-propylene oxide) in oxypropyl trimethyl silane, 3-aminopropyl triethoxysilane or γ-(methacryloxypropyl) propyl trimethoxy silicane any one, surface modifying method is as follows:
Every 1g Fe
3o
4nanoparticle dispersion, in the solution of 50ml ethanol and deionized water volume ratio 1:1, then adds 0.5ml silane coupling agent, and 40 DEG C are stirred 4h, nitrogen protection, and reaction terminates rear absolute ethanol washing three times, then puts into vacuum drying oven drying.
In the present invention, in step (3), Fe
3o
4nanoparticle and dry toluene blending ratio are: every 0.1g Fe
3o
4nanoparticle dispersion is in 20 ~ 25ml dry toluene.
beneficial effect of the present invention is:
Biodegradable shape-memory nano composite material described in the present invention, has temperature and alternating magnetic field dual sense type shape memory function.Thermo-responsive: there is certain transition temperature T
0.When temperature is higher than T
0time, polymkeric substance can random variation.Temperature drops to T
0lower shape is fixed.When temperature is elevated to T again
0time above, return to original shape.Alternating magnetic field induction type: there is certain transition temperature T
0.When temperature is higher than T
0time, polymkeric substance can random variation.Temperature drops to T
0lower shape is fixed, and puts it in alternating magnetic field, returns to original shape.This shape memory nano composite material has that deformation hold facility is strong, shape recovery rate is high, shape-memory properties is reproducible and the various features such as biodegradable.And achieve the function of contactless initiation shape memory, Fe
3o
4the existence of nanoparticle, makes material have targeting.
Accompanying drawing explanation
The nuclear magnetic spectrogram of Fig. 1: PDLLA prepared by embodiment 1.
Fig. 2: the relation in mangneto type biodegradable shape memory polymeric nano composite material shape-memory properties test prepared by embodiment 1 between temperature, stress, strain.
Embodiment
the present invention is further illustrated below by embodiment.
embodiment 1
The solution (volume ratio 1:1) of 500ml ethanol and deionized water is put into, 10g Fe in the round-bottomed flask of 1L
3o
4nanoparticle dispersion is in wherein; add 5ml (3-(2,3-propylene oxide) oxypropyl trimethyl silane, under nitrogen protection 40 DEG C of stirring 4h; after having reacted, after washing three times respectively with the magnet rear deionized water of separation and dehydrated alcohol, put into vacuum drying oven drying.
7.5ml dry toluene is put into, by the Fe that 0.03g surface modification is crossed in sample bottle
3o
4nanoparticle dispersion wherein.Ultrasonic disperse 30 ~ 45min.For subsequent use.
Will through vinyl acetate recrystallization three times, dried D, L-rac-Lactide 8.064g(0.056 mol) add in the round-bottomed flask of 50ml drying, add 0.0126g(1.4 × 10
-4mol) butyleneglycol, 15 μ l stannous octoates (0.001mol/L).Under 130 DEG C and nitrogen protection, be polymerized 24 hours.After reaction terminates, add methylene dichloride and dissolve, then instill precipitation purification product in the normal hexane of ice, vacuum-drying obtains white flock shaped polymer.Molecular weight is 50,000.Be dissolved in 2ml dry toluene by the white flocculent polymer 1.28g obtained, 65 DEG C are stirred 30min.Add 0.024g 1,6-hexamethylene diisocyanate and the sub-tin of 20 μ l chain extension octoate catalysts.65 DEG C are stirred 10min.Add 0.191g polytetramethylene ether diol, at 75 DEG C, stir 6h.Use mechanical stirring instead, instill scattered Fe while stirring
3o
4nanoparticle toluene solution.Teflon mould is poured into after stirring 2h.Then 100 ~ 120 DEG C of baking oven solvent flashings are put into.The shape-memory polymer nano composite material of sheet is obtained after 48 hours.
As shown in Figure 1, this figure is the nuclear magnetic spectrogram of the PDLLA of preparation, and the characteristic peak on figure and the characteristic peak of poly(lactic acid) match.
As shown in Figure 2, this figure is the relation in the mangneto type biodegradable shape memory polymeric nano composite material shape-memory properties test of preparation between temperature, stress, strain.From figure, curve can calculate, and the shape memory response rate of twice circulation is respectively 85.50% and 87.4%.Shape fixed rate is all higher than 99%.
embodiment 2
Fe
3o
4nano particle surface modifying method is as embodiment 1.
15ml dry toluene is put into, by the Fe that 0.06g surface modification is crossed in sample bottle
3o
4nanoparticle dispersion wherein.Ultrasonic disperse 30 ~ 45min.For subsequent use.
Will through vinyl acetate recrystallization three times, dried D, L-rac-Lactide 8.064g(0.056 mol) add in the round-bottomed flask of 50ml drying, add 0.0126g(1.4 × 10
-4mol) butyleneglycol, 15 μ l stannous octoates (0.001mol/L).Under 130 DEG C and nitrogen protection, be polymerized 24 hours.After reaction terminates, add methylene dichloride and dissolve, then instill precipitation purification product in the normal hexane of ice, vacuum-drying obtains white flock shaped polymer.Molecular weight is 50,000.Be dissolved in 2ml dry toluene by the white flocculent polymer 1.28g obtained, 65 DEG C are stirred 30min.Add 0.024g 1,6-hexamethylene diisocyanate and the sub-tin of 20 μ l chain extension octoate catalysts.65 DEG C are stirred 10min.Add 0.191g polytetramethylene ether diol, at 75 DEG C, stir 6h.Use mechanical stirring instead, instill scattered Fe while stirring
3o
4nanoparticle toluene solution.Teflon mould is poured into after stirring 2h.Then 100 ~ 120 DEG C of baking oven solvent flashings are put into.The shape-memory polymer nano composite material of sheet is obtained after 48 hours.
embodiment 3
Fe
3o
4nano particle surface modifying method is as embodiment 1.
22.5ml dry toluene is put into, by the Fe that 0.09g surface modification is crossed in sample bottle
3o
4nanoparticle dispersion wherein.Ultrasonic disperse 30 ~ 45min.For subsequent use.
Will through vinyl acetate recrystallization three times, dried D, L-rac-Lactide 8.064g(0.056 mol) add in the round-bottomed flask of 50ml drying, add 0.0126g(1.4 × 10
-4mol) butyleneglycol, 15 μ l stannous octoates (0.001mol/L).Under 130 DEG C and nitrogen protection, be polymerized 24 hours.After reaction terminates, add methylene dichloride and dissolve, then instill precipitation purification product in the normal hexane of ice, vacuum-drying obtains white flock shaped polymer.Molecular weight is 50,000.Be dissolved in 2ml dry toluene by the white flocculent polymer 1.28g obtained, 65 DEG C are stirred 30min.Add 0.024g 1,6-hexamethylene diisocyanate and the sub-tin of 20 μ l chain extension octoate catalysts.65 DEG C are stirred 10min.Add 0.191g polytetramethylene ether diol, at 75 DEG C, stir 6h.Use mechanical stirring instead, instill scattered Fe while stirring
3o
4nanoparticle toluene solution.Teflon mould is poured into after stirring 2h.Then 100 ~ 120 DEG C of baking oven solvent flashings are put into.The shape-memory polymer nano composite material of sheet is obtained after 48 hours.
embodiment 4
Fe
3o
4nano particle surface modifying method is as embodiment 1.
30ml dry toluene is put into, by the Fe that 0.12g surface modification is crossed in sample bottle
3o
4nanoparticle dispersion wherein.Ultrasonic disperse 30 ~ 45min.For subsequent use.
Will through vinyl acetate recrystallization three times, dried D, L-rac-Lactide 8.064g(0.056 mol) add in the round-bottomed flask of 50ml drying, add 0.0126g(1.4 × 10
-4mol) butyleneglycol, 15 μ l stannous octoates (0.001mol/L).Under 130 DEG C and nitrogen protection, be polymerized 24 hours.After reaction terminates, add methylene dichloride and dissolve, then instill precipitation purification product in the normal hexane of ice, vacuum-drying obtains white flock shaped polymer.Molecular weight is 50,000.Be dissolved in 2ml dry toluene by the white flocculent polymer 1.28g obtained, 65 DEG C are stirred 30min.Add 0.024g 1,6-hexamethylene diisocyanate and the sub-tin of 20 μ l chain extension octoate catalysts.65 DEG C are stirred 10min.Add 0.191g polytetramethylene ether diol, at 75 DEG C, stir 6h.Use mechanical stirring instead, instill scattered Fe while stirring
3o
4nanoparticle toluene solution.Teflon mould is poured into after stirring 2h.Then 100 ~ 120 DEG C of baking oven solvent flashings are put into.The shape-memory polymer nano composite material of sheet is obtained after 48 hours.
embodiment 5
Fe
3o
4nano particle surface modifying method is as embodiment 1.
37.5ml dry toluene is put into, by the Fe that 0.15g surface modification is crossed in sample bottle
3o
4nanoparticle dispersion wherein.Ultrasonic disperse 30 ~ 45min.For subsequent use.
Will through vinyl acetate recrystallization three times, dried D, L-rac-Lactide 8.064g(0.056 mol) add in the round-bottomed flask of 50ml drying, add 0.0126g(1.4 × 10
-4mol) butyleneglycol, 15 μ l stannous octoates (0.001mol/L).Under 130 DEG C and nitrogen protection, be polymerized 24 hours.After reaction terminates, add methylene dichloride and dissolve, then instill precipitation purification product in the normal hexane of ice, vacuum-drying obtains white flock shaped polymer.Molecular weight is 50,000.Be dissolved in 2ml dry toluene by the white flocculent polymer 1.28g obtained, 65 DEG C are stirred 30min.Add 0.024g 1,6-hexamethylene diisocyanate and the sub-tin of 20 μ l chain extension octoate catalysts.65 DEG C are stirred 10min.Add 0.191g polytetramethylene ether diol, at 75 DEG C, stir 6h.Use mechanical stirring instead, instill scattered Fe while stirring
3o
4nanoparticle toluene solution.Teflon mould is poured into after stirring 2h.Then 100 ~ 120 DEG C of baking oven solvent flashings are put into.The shape-memory polymer nano composite material of sheet is obtained after 48 hours.
Claims (8)
1. a preparation method for mangneto type Biodegradable shape-memory matrix material, it is characterized in that this composite material of shape memory is straight chain type segmented copolymer, is hard phase with isocyanic ester segment, and PDLLA, polytetramethylene ether diol are soft phase; D is caused by small molecules glycol, the ring-opening polymerization of L-rac-Lactide, prepares the straight chain type PDLLA of two ends with hydroxyl, then get up to be formed the segmented copolymer of straight chain type with polytetramethylene ether diol by vulcabond coupling, be then mixed into the Fe that surface modification is crossed
3o
4nanoparticle obtains mangneto type Biodegradable shape-memory matrix material; Concrete steps are as follows:
(1) ring-opening polymerization: small molecules glycol causes the ring-opening polymerization of D, L-rac-Lactide, and polymerization temperature is 125-135 DEG C, time is 18-24 hour, nitrogen protection, adds dissolution with solvents after polymerization terminates, then it is slowly instilled precipitation agent polymkeric substance is precipitated, purified product, vacuum-drying, obtains white flock degradable high polymer material, this material is that straight chain type gathers D, L-rac-Lactide, the mol ratio controlling small molecules glycol and D, L-rac-Lactide is 1:300-1:400;
(2) chain extension: the straight chain type PDLLA that step (1) obtains is dissolved in dry toluene, 65 DEG C are stirred 20min, add vulcabond and catalyzer, and 65 DEG C ~ 70 DEG C are stirred 10min, add polytetramethylene ether diol, and 70 ~ 75 DEG C are stirred 6h;
(3) film forming: by the Fe crossed through silane coupling agent surface modification
3o
4nanoparticle dispersion is in dry toluene; It is slowly instilled in step (2) the gained solution that stirred, after stirring 2h, pour Teflon mould into; Then 100 ~ 120 DEG C of baking oven solvent flashings are put into; The mangneto type Biodegradable shape-memory matrix material of sheet is obtained after 48 hours.
2., according to the preparation method of the mangneto type Biodegradable shape-memory matrix material described in claim 1, it is characterized in that small molecules glycol described in step (1) is the one in ethylene glycol or butyleneglycol.
3. the preparation method of mangneto type Biodegradable shape-memory matrix material according to claim 1, it is characterized in that catalyzer described in step (2) is the one in stannous octoate or tin protochloride, catalyst charge is the 0.05-1.0 wt% of D, L-rac-Lactide total amount.
4. the preparation method of mangneto type Biodegradable shape-memory matrix material according to claim 1, it is characterized in that described in step (1), solvent is tetrahydrofuran (THF), chloroform, N, in dinethylformamide or methylene dichloride any one, described precipitation agent is any one in methyl alcohol, ether or normal hexane.
5. the preparation method of mangneto type Biodegradable shape-memory matrix material according to claim 1, it is characterized in that the straight chain type of synthesis in step (1) gathers D, the molecular weight of L-rac-Lactide is 30000 ~ 60000, and the molecular weight of described polytetramethylene ether diol is 2000.
6. the preparation method of mangneto type Biodegradable shape-memory matrix material according to claim 1, it is characterized in that the vulcabond described in step (2) is 1,6-hexamethylene diisocyanate, 1,4-phenylene diisocyanate, 4, one in 4 '-methylene-diphenyl isocyanic ester or 2,4 toluene diisocyanate.
7. the preparation method of mangneto type Biodegradable shape-memory matrix material according to claim 1, it is characterized in that the silane coupling agent described in step (3) is (3-(2,3-propylene oxide) in oxypropyl trimethyl silane, 3-aminopropyl triethoxysilane or γ-(methacryloxypropyl) propyl trimethoxy silicane any one, surface modifying method is as follows:
Every 1g Fe
3o
4nanoparticle dispersion, in the solution of 50ml ethanol and deionized water volume ratio 1:1, then adds 0.5ml silane coupling agent, and 40 DEG C are stirred 4h, nitrogen protection, and reaction terminates rear absolute ethanol washing three times, then puts into vacuum drying oven drying.
8. the preparation method of mangneto type Biodegradable shape-memory matrix material according to claim 1, is characterized in that in step (3), Fe
3o
4nanoparticle and dry toluene blending ratio are: every 0.1g Fe
3o
4nanoparticle dispersion is in 20 ~ 25ml dry toluene.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112980144A (en) * | 2021-02-24 | 2021-06-18 | 中国工程物理研究院化工材料研究所 | Photoelectromagnetic response epoxy glass polymer |
| CN114015225A (en) * | 2021-09-30 | 2022-02-08 | 河北大学 | Magnetic-drive shape memory material and preparation method and application thereof |
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| CN102675858A (en) * | 2012-05-22 | 2012-09-19 | 同济大学 | Method for preparing degradable tear duct embolisms having shape memory function |
| CN102863750A (en) * | 2012-09-28 | 2013-01-09 | 哈尔滨工程大学 | Biodegradable polymer composite material having multistep shape memory effect, preparation method thereof and molded part manufacturing and shape recovery method |
| CN103254595A (en) * | 2013-04-17 | 2013-08-21 | 同济大学 | Preparation method of degradable lacrimal passage bracket with shape memory function |
| CN103772962A (en) * | 2012-10-18 | 2014-05-07 | 徐州金创科技有限公司 | New-type shape memory composite material Fe3O4 / PLAU (polylactic acid based polyurethane) |
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| CN102675858A (en) * | 2012-05-22 | 2012-09-19 | 同济大学 | Method for preparing degradable tear duct embolisms having shape memory function |
| CN102863750A (en) * | 2012-09-28 | 2013-01-09 | 哈尔滨工程大学 | Biodegradable polymer composite material having multistep shape memory effect, preparation method thereof and molded part manufacturing and shape recovery method |
| CN103772962A (en) * | 2012-10-18 | 2014-05-07 | 徐州金创科技有限公司 | New-type shape memory composite material Fe3O4 / PLAU (polylactic acid based polyurethane) |
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| CN112980144A (en) * | 2021-02-24 | 2021-06-18 | 中国工程物理研究院化工材料研究所 | Photoelectromagnetic response epoxy glass polymer |
| CN114015225A (en) * | 2021-09-30 | 2022-02-08 | 河北大学 | Magnetic-drive shape memory material and preparation method and application thereof |
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