CN108341908B - A kind of shape memory high molecule material and preparation method thereof of feux rouges response - Google Patents
A kind of shape memory high molecule material and preparation method thereof of feux rouges response Download PDFInfo
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Abstract
The invention discloses a kind of shape memory high molecule materials and preparation method thereof of feux rouges response, belong to technical field of function materials.Obtained by the micella crosslinking film forming containing reactive group of high molecular material of the invention by package porphyrin, the parts by weight of the raw material and each raw material are as follows: 20-40 parts of the vinyl monomer containing hydrophobic group, 1-5 parts of vinyl monomer containing hydrophilic radical, 1-5 parts of vinyl monomer containing reactive group, 2-5 parts of organic solvent, 0.5-1 parts of radical initiator, 1-5 parts of crosslinking agent, 0.0005-0.005 parts of porphyrin.The present invention has the shape memory function of the porphyrin imparting material red light response of photothermal conversion by wrapping up in micella, avoids traditional contact-type triggering response, it can be achieved that the remotely manipulation to material shape memory behavior；Meanwhile porphyrin will not generate harmful side effect to organism as the organic compound having in itself in organism, and feux rouges will not damage skin when penetrating organism, energy loss is smaller, is expected to be applied to the intracorporal photo-thermal therapy of biology.
Description
Technical field
The present invention relates to a kind of shape memory high molecule materials and preparation method thereof of feux rouges response, belong to functional material skill
Art field.
Background technique
Shape-memory material is ubiquitous in our life as a kind of novel intelligent macromolecule material, especially exists
Field of biomedicine has very big application space, and the development of related industry will bring huge economy and society to imitate to the mankind
Benefit.Common shape-memory material has marmem, shape memory ceramics and shape-memory polymer.Wherein, shape
Memory polymer refers to the product with original shape, after changing its original shape under certain conditions and fixing, by outer
The stimulation of boundary's condition (such as heat, light, electricity, chemical co-ordination), and the high molecular material of its original shape can be restored.With shape memory
Alloy and ceramic phase ratio, shape-memory polymer is due to the diversification of its stimulation mode, superior elastic deformation, potential biology
The advantages such as compatibility and biodegradability become a kind of novel shape-memory material greatly developed.
Wherein, thermal shape memory polymer material refers to makes polymer material reach glass by directly or indirectly heating
More than glass transition temperature shape is caused to be restored.And directly heat polymer material and receive limitation in many application fields, such as
Biological vivo applications and underwater operation etc., so indirect heating thermal shape memory, which makes it restore original-shape, becomes hot research
Topic.
Turn currently, indirect heating thermal shape memory typically refers to introduce in shape-memory polymer matrix with photo-thermal
Change effect nanofiller, under light radiation the heat production of filler extinction and propagate to matrix make the temperature of material be increased to vitrifying turn
More than temperature restore to which shape occur, therefore also referred to as photoinduction shape memory.Sichuan University Zhao Yue professor et al. has report
The gold nanoparticle that polycaprolactone is modified is served as Nano-heaters as filler and is introduced into polyurethane matrix material by road, is utilized
Material after the light thermal property induction figuration of gold nanoparticle is returned to its original-shape.But including gold nanoparticle
The most nanofillers discussed so far have a common problem, their biocompatibility and biology can drop
Solution property it is poor, which has limited the photoinduction shape memory high molecule based on photo-thermal effect field of biomedicine application.
Summary of the invention
To solve the above-mentioned problems, the present invention provides it is a kind of with feux rouges response shape memory high molecule material and its
Preparation method.The present invention loads to porphyrin on thermal shape memory polymer material, using the photothermal conversion performance of porphyrin, leads to
Crossing red light irradiation light stimulus indirect heating polymer material makes it restore original-shape, to realize thermally sensitive shape memory materials more
The application in wide field.Specifically, the present invention prepares amphiphilic polymer material (MBDA) by free radical polymerization, and certainly with solution
Assemble method entrains into porphyrin inside micella, is then crosslinked micella, prepares the optical Response shape-memory material.
The first purpose of the invention is to provide a kind of photoresponse shape memory high molecule materials, are that porphyrin is loaded to heat
It is obtained on cause shape memory polymer material.
In one embodiment, the photoresponse shape memory high molecule material is crosslinked preparation by the micella of package porphyrin
It forms, mesoporphyrin weight is the 0.03%-0.3% of thermal shape memory polymer weight.
In one embodiment, the photoresponse shape memory high molecule material, according to parts by weight, containing following former
Material: 20-40 parts of the vinyl monomer containing hydrophobic group, 1-5 parts of vinyl monomer, the alkene containing reactive group containing hydrophilic radical
1-5 parts of class monomer, 0.5-1 parts of radical initiator, 1-5 parts of crosslinking agent, porphyrin；Its mesoporphyrin is the alkenes containing hydrophobic group
Monomer, the vinyl monomer containing hydrophilic radical, the vinyl monomer containing reactive group, radical initiator, crosslinking agent total weight
0.03%-0.3%.
In one embodiment, the vinyl monomer containing hydrophobic group is esters of acrylic acid, methacrylate
One of class is a variety of.
In one embodiment, the vinyl monomer containing hydrophobic group is methyl acrylate, butyl acrylate, first
Base methyl acrylate, one of ethyl methacrylate or a variety of.
In one embodiment, the vinyl monomer containing hydrophilic radical is acrylic acid, methacrylic acid, acryloyl
One of amine is a variety of.
In one embodiment, the vinyl monomer containing reactive group is Diacetone Acrylamide, N- vinyl
One of pyrrolidones, hydroxy-ethyl acrylate, hydroxypropyl acrylate are a variety of.
In one embodiment, the radical initiator is peroxide type initiators (such as perbenzoic acid uncle
Butyl ester, dibenzoyl peroxide, ammonium persulfate), one of azo-initiator (such as azodiisobutyronitrile).
In one embodiment, the crosslinking agent is one of adipic dihydrazide, glutaraldehyde or a variety of.
A second object of the present invention is to provide the preparation method of the photoresponse shape memory high molecule material, the sides
Method includes preparing amphiphilic polymer material by free radical polymerization, and porphyrin is entrained into micella with solution self-assembling method
Then micella is crosslinked by inside, prepare the optical Response shape-memory material.
In one embodiment, the method, comprising the following steps:
(1) by the vinyl monomer containing hydrophobic group, the vinyl monomer containing hydrophilic radical, the alkenes containing reactive group
Monomer, organic solvent, radical initiator, which are put into container, to be reacted, and amphiphilic polymer MBDA is obtained；
(2) a certain amount of step (1) resulting polymers MBDA and porphyrin is taken to be codissolved in solvent, dispersing and dissolving, then by water
It is slowly dropped into above-mentioned solution, agitation and dropping, to completion of dropwise addition and then the micelle emulsion of solvent flashing preparation package porphyrin；
(3) crosslinking agent, drying and forming-film after mixing is uniformly dispersed are added in the micelle emulsion obtained by step (2).
In one embodiment, the organic solvent of the step (1) is gylcol ether, propylene glycol ethers, dimethyl
One of sulfoxide, N,N-dimethylformamide, tetrahydrofuran are a variety of.
In one embodiment, the solvent of the step (2) is four close furans (THF).
In one embodiment, control crosslinking agent and the vinyl monomer mole containing reactive group in the step (3)
Than for 1:1.
In one embodiment, the step (3) is substituted for: in the aqueous solution of the micella containing porphyrin obtained by step (2)
Crosslinking agent is added, a certain amount of thixotropic agent is then added, is uniformly mixed, is injected into the shape of design, dry fixed shape.
In one embodiment, the thixotropoic agent present is 0.5-1 parts.
In one embodiment, the method, specifically includes the following steps:
(1) by 15-20 parts of vinyl monomer containing hydrophobic group, 1-5 parts of the vinyl monomer containing hydrophilic radical, containing reaction
Property 1-5 parts of vinyl monomer of group, 2-5 parts and radical initiator 0.5-1 part of organic solvent are put in proportion into container, reaction
Time 3h, show that product through ether deposition and purification 3 times, is dried in vacuo to obtain amphiphilic polymer MBDA by 140 DEG C of reaction temperature；
(2) a certain amount of step (1) resulting polymers and 0.2-1 parts of porphyrin are taken to be codissolved in four close furans (THF), ultrasound
So that it is completely dispersed dissolution, then 40-60 parts of deionized water is slowly dropped into THF solution, agitation and dropping, to completion of dropwise addition
Later, the micelle emulsion of 50 DEG C or so volatilization THF preparation package porphyrins；
(3) it is added crosslinking agent 1-5 parts in the micelle emulsion obtained by step (2), controls crosslinking agent and containing reactive group
Vinyl monomer molar ratio is 1:1, room temperature drying and forming-film after mixing is uniformly dispersed；
(4) it is added crosslinking agent 1-5 parts in the aqueous solution of the micella containing porphyrin obtained by step (2), be then added a certain amount of
Thixotropic agent HJYM, is uniformly mixed, and is injected into the shape of design, the fixed shape of drying at room temperature.
Third object of the present invention is to provide a kind of medical material, the medical material contains photoresponse shape of the invention
Shape remembers high molecular material.
In one embodiment, the medical material is implantation material.
In one embodiment, the medical material application method: first make the photoresponse shape memory high molecule of preparation
Material generates deformation under suitable environment, and cooling fixed shape is implanted to target position, then with after red light irradiation deformation
Photoresponse shape memory high molecule material.
Fourth object of the present invention is to provide the photoresponse shape memory high molecule material and is preparing medical devices side
The application in face.
The beneficial technical effect of the present invention:
(1) present invention is entrained into porphyrin in glue bundle body by the method for solution self assembly；
(2) present invention is cross-linked into film preparation shape memory high molecule material using micella；
(3) feux rouges responsive polymer material prepared by the present invention is can under the red light irradiation of small-power (354mW)
Its shape memory is triggered in a very short period of time, increases about 50~60 DEG C in 40s；
(4) shape of the present invention memory avoids traditional contact-type triggering shape memory, it can be achieved that remotely controlling material
Shape is restored, meanwhile, porphyrin is compound contained by human body and feux rouges will not damage biological while with very strong penetrability
Body skin is expected to be applied to the intracorporal photo-thermal therapy of biology.
Detailed description of the invention
Fig. 1: the schematic diagram of the shape-memory polymer of preparation porphyrin containing infrared optical response.
Fig. 2 is MBDA copolymer in CDCl3In hydrogen nuclear magnetic resonance spectrogram.
Fig. 3 is the infrared spectrum of MBDA copolymer；Wherein illustration represents: unreacted monomer is in 1800-1550cm-1(insatiable hunger
With double bond characteristic peak location) infrared spectroscopy in wave-length coverage.
Fig. 4 is light absorption of the different dispersions between 350~850nm.
Fig. 5 is thermal response of the film of different TPP dosages preparation under IR irradiation；Wherein (a) is without porphyrin shape memory
The blank assay of material, (b), (c), (d) be porphyrin throwing amount 0.5,1.5,5mg shape-memory material.
Fig. 6 is the cumulative exposure time of different samples and the functional relation of film expanded angle.
Specific embodiment
Embodiment and application examples set forth below are for the more specific description present invention, but the present invention is not limited merely at this
Listed embodiment and application examples.
Embodiment 1:
One, the preparation and use of the shape-memory polymer containing infrared optical response
As shown in Figure 1, the schematic diagram of the shape-memory polymer for preparation porphyrin containing infrared optical response.
(1) solvent ethylene glycol butyl ether 10mL；The total 30.06g of vinyl monomer containing hydrophobic group includes: methyl methacrylate
Ester (MMA) 20.77g and butyl acrylate (BA) 9.29g；The total 1.05g of vinyl monomer containing hydrophobic group includes: acrylic acid
(AA)1.05g；The total 2g of vinyl monomer containing reactive group includes: Diacetone Acrylamide (DAAM) 2g；Radical initiator
Peroxidized t-butyl perbenzoate (TBPB) 0.84g.React 3h at 140 DEG C, after add 20mL solvent dilution, obtain product through second
Ether deposition and purification 3 times, it is dried in vacuo to obtain amphiphilic polymer MBDA.
(2) 1.6858g amphipathic polymer MBDA and a certain amount of (0,0.5mg, 1.5mg, 5mg) porphyrin (TPP) are taken, is added
After 10mL THF is completely dispersed dissolution, hydramine is added dropwise and adjusts pH to meta-alkalescence, 10mL deionized water is then slowly added dropwise, knot is added dropwise
50 DEG C of evaporation at constant temperature THF after beam, the glue bundle body of preparation package porphyrin.
(3) the crosslinking agent adipic dihydrazide for being 1:1 with Diacetone Acrylamide molar ratio is added in this micellar solution,
Drying at room temperature film-forming.
The membrane material of preparation is set to generate deformation under 70 DEG C of environment, cooling is fixed into temporary shapes at room temperature.To probe into material
Film is placed under the solid-state laser of 635nm (close to the absorption peak of the 650nm of TPP) by the light thermal property of material, and power is
354mW/cm2, the distance of the bending position of light source and film is 20mm.The size of illuminated laser spot is about 3mm, passes through laser edge
Film bending position scanning come realize shape restore.
The light thermal property of material is indicated with the functional relation of cumulative exposure time and film expanded angle, as shown in Figure 6.It can
See, the shape memory polymer material for loading porphyrin obviously has optical Response, by 354mW/cm2635nm feux rouges 50s
After irradiation, expanded angle is about 140 °.Different porphyrin load capacity film deployment rates, that is, recovery of shape rate is different.
Furthermore, it is possible to matter is added in adding the micelle emulsion after adipic dihydrazide than the thixotropic agent HJYM for 1.5%,
Prepare injectable shape memory high molecule material, its photothermal conversion performance of technique study similar to the above.
Two, the characterization of the shape-memory polymer of the porphyrin containing infrared optical response
(1) copolymer MBDA is characterized
Fig. 2 gives CDCl3Middle MBDA copolymer1H-NMR spectrum.In this work,1H-NMR be disclose copolymer at
The useful technology of function synthesis.Figure it is seen that the peak for corresponding to double bond proton completely disappears.Ownership peak is listed in Table 2 below.δ=
Peak at 3.61ppm is attributed to methoxyl group the proton (- OCH of PMMA3), δ=4.00ppm is the ethyoxyl (- OCH on PBA2)
The formant of proton.δ=6.99 are the proton resonance signals in PDAAM on amide N (- NH-).However, at δ=11.0ppm
The corresponding proton peak of AA carboxylate groups is not present, this may be the concentration relatively low due to the AA for participating in copolymerization, Huo Zheyou
It cannot cause magnetic resonance in acid monomers.Peak at δ=0.901ppm belongs to the proton for the methyl not being connected with oxygen in polymer.
According to the inferred from input data of explanation, MMA, BA, DAAM and AA have participated in radical copolymerization, and confirm the successful conjunction of MBDA copolymer
At.
In conjunction with Fourier transform infrared (FTIR) spectrum and gel permeation chromatography (GPC) testing result of Fig. 3, it was demonstrated that
The successful synthesis of macromolecular, and ensure that filming performance to a certain extent.
(2) micella MBDA-TPP-NPs is characterized
Fig. 4 shows light absorption of the different dispersions between 350~850nm.For do not add TPP pure lotion and
TPP in water, is absorbed without obvious.However, the micelle emulsion for introducing TPP generates one strong absorb at about 416nm (Soret band)
There are 4 weak peaks at peak in 500~680nm (Q band) range, respectively 513,546,591,650nm.This and TPP are in THF
Characteristic peak is consistent.The above different dispersions of comparison, it can be deduced that such conclusion: micella package TPP stablizes it in aqueous solution
In, and the presence of TPP makes composite micelle MBDA-TPP-NDs have the ability for absorbing infrared light.In addition, also having carried out DLS
Characterization, UV-vis spectrum and DLS characterization mutually evidence, show to be successfully prepared the load TPP with red light absorption as the result is shown
Micella, and have good dispersibility.
(3) MBDA-TPP-ADH shape memory film characterizes
Due to closely related with driving temperature, glass transition temperature (Tg) is the main of shape-memory polymer (SMP)
One of feature.Differential scanning calorimetry (DSC) carries out the Tg of investigation SMP.Under 20~85 DEG C of nitrogen atmosphere, with 10 DEG C/min
Heating rate carry out second and heat, measure Tg value.Whole DSC curves of the MBDA-TPP-ADH film of various dose TPP are aobvious
Show, the Tg without the film of TPP is 46.88 DEG C.With TPP be 0.5mg, 1.5mg, 5mg when, the Tg of MBDA-TPP-ADH film
Respectively 44.15 DEG C, 44.24 DEG C, 45.44 DEG C.
The MBDA-TPP-NDs of load various concentration TPP is prepared for the MBDA- with different light absorptives by cross-linking reaction
TPP-ADH film.The results show that SMP material wider absorption band at 650nm shows that it has optics to turn at feux rouges (635nm)
Become, to select the light of 635nm to provide data supporting as the radiating light source of excitation shape memory.In addition, the absorbance increased
The stronger smooth capturing ability of film is disclosed, and then leads to the raising of photothermal conversion rate, this is conducive to the recovery of shape of material.
Three, the light of the shape-memory polymer containing infrared optical response excites shape memory effect
In order to check the heating properties of composite material, film is placed on 635nm's (close to the absorption peak of the 650nm of TPP)
Under solid-state laser, power 354mW/cm2, the distance of the bending position of light source and film is 20mm.Illuminated laser spot it is big
Small about 3mm realizes that shape is restored along the bending position scanning of film by laser.Due to real in the form of electromagnetic radiation
Existing infrared heating, so actuating method is contactless.
Fig. 5 shows thermal response of the film of different TPP loading capacity preparations under IR irradiation, and all films are opened at room temperature
Begin.The light of time control from 0 to 50s triggers recovery process, the accumulation of expanded angle and laser explosure of the figure based on film
Relationship between time.Expanded angle be restore when instantaneous " angle ", by measurement bending film straight end between angle come
It determines.The results show that there is no for the film of not TPP when being exposed to laser and observe variation.Loading TPP's
It observes that significant and quick shape is restored in film, and depends on the dosage of TPP.
Shape resume speed is used to assessment shape memory effect, because it is the important feature of SMP material application, such as schemes
Shown in 6.The results show that when TPP dosage is 0.5 and 1.5mg, since the temperature of film not yet rises to Tg, so being opened up before irradiation 10s
Angle of release is 0 °.When TPP dosage increases to 1.5mg from 0.5mg, MBDA-TPP 1.5-ADH film is in the identical cumulative exposure time
Under have obvious recovery, show that resume speed is very fast, and the rule is maintained at entire recovery process within the scope of 0~50s.From
From the point of view of photo-thermal effect, MBDA-TPP1.5-ADH film absorption radianting capacity with higher at 635nm is conducive to improve back
Multiple efficiency.However, the property of TPP is crucial for the reduction of the response rate of film when the dosage of TPP is further increased to 5mg
's.Compared with other fillers, TPP has many intermolecular interactions.Basically, TPP once increases to a certain concentration
Shape recovery rate may be influenced, because hindering the relaxation of strand for restoring force decrease caused by by interacting.These realities
Test further demonstrate TPP addition cause and improve SMP film optical drive shape memory effect viewpoint.In addition, the use of TPP
Amount needs to control can be only achieved optimal shape recovery effects in a certain range.
Embodiment 2:
Solvent dimethyl sulfoxide 10mL, monomer methyl acrylate 0.32mol, ethyl methacrylate 0.08mol, N- ethylene
Base pyrrolidones 0.016mol, methacrylic acid 0.016mol, initiator peroxidized t-butyl perbenzoate 0.08mol, at 140 DEG C
React 3h, after add 20mL solvent dilution, show that product through ether deposition and purification 3 times, is dried in vacuo to obtain amphiphilic polymer.
After taking 4g amphipathic polymer and 3mg porphyrin, addition 10mL THF to be completely dispersed dissolution, dropwise addition hydramine adjusting pH to meta-alkalescence, so
After 10mL deionized water is slowly added dropwise, 50 DEG C of evaporation at constant temperature THF after completion of dropwise addition, preparation package porphyrin glue bundle body.In this glue
The crosslinking agent glutaraldehyde for being 1:1 with n-vinyl pyrrolidone molar ratio, drying at room temperature film-forming are added in beam solution.
The membrane material of preparation is set to generate deformation under 70 DEG C of environment, cooling is fixed into temporary shapes at room temperature.To probe into material
Film is placed under the solid-state laser of 635nm (close to the absorption peak of the 650nm of TPP) by the light thermal property of material, and power is
354mW/cm2, the distance of the bending position of light source and film is 20mm.The size of illuminated laser spot is about 3mm, passes through laser edge
Film bending position scanning come realize shape restore.
Furthermore, it is possible to which matter is added in adding the micelle emulsion after glutaraldehyde than the thixotropic agent HJYM for 1.5%, preparation can
Inject shape memory high molecule material, its photothermal conversion performance of technique study similar to the above.
Above description has been very full on a specific embodiment of the invention.It should be pointed out that being familiar with the field
Range of any change that technical staff does a specific embodiment of the invention all without departing from claims of the present invention.
Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.
Claims (8)
1. a kind of photoresponse shape memory high molecule material, which is characterized in that the photoresponse shape memory high molecule material is
Porphyrin loaded to and is obtained on thermal shape memory polymer material；
The photoresponse shape memory high molecule material is prepared by the micella crosslinking of package porphyrin；
The photoresponse shape memory high molecule material contains the following raw material according to parts by weight: the alkenes containing hydrophobic group
20-40 parts of monomer, 1-5 parts of the vinyl monomer containing hydrophilic radical, 1-5 parts of vinyl monomer, free radical containing reactive group draw
Send out agent 0.5-1 parts, 1-5 parts of crosslinking agent, porphyrin；Its mesoporphyrin is vinyl monomer containing hydrophobic group, containing hydrophilic radical
Vinyl monomer, the vinyl monomer containing reactive group, radical initiator, crosslinking agent total weight 0.03%-0.3%；
The preparation method of the photoresponse shape memory high molecule material includes preparing amphiphilic polymer by free radical polymerization
Material, and entrained into porphyrin inside micella with solution self-assembling method, then micella is crosslinked, prepares the optical Response shape
Memory material；
The porphyrin is tetraphenylporphyrin.
2. photoresponse shape memory high molecule material according to claim 1, which is characterized in that described to contain hydrophobic group
Vinyl monomer be methyl acrylate, butyl acrylate, methyl methacrylate, one of ethyl methacrylate or more
Kind；The vinyl monomer containing hydrophilic radical is acrylic acid, methacrylic acid, one of acrylamide or a variety of.
3. photoresponse shape memory high molecule material according to claim 1, which is characterized in that described to contain reactive group
Vinyl monomer be one of Diacetone Acrylamide, n-vinyl pyrrolidone, hydroxy-ethyl acrylate, hydroxypropyl acrylate
Or it is a variety of.
4. the preparation method of photoresponse shape memory high molecule material described in claim 1, which is characterized in that the method packet
It includes, amphiphilic polymer material is prepared by free radical polymerization, and entrained into porphyrin inside micella with solution self-assembling method,
Then micella is crosslinked, prepares the optical Response shape-memory material.
5. according to the method described in claim 4, the following steps are included:
(1) by the vinyl monomer containing hydrophobic group, the vinyl monomer containing hydrophilic radical, containing the alkenes list of reactive group
Body, organic solvent, radical initiator, which are put into container, to be reacted, and amphiphilic polymer is obtained；
(2) a certain amount of step (1) resulting polymers and porphyrin are taken to be codissolved in solvent, then water is slowly dropped by dispersing and dissolving
In above-mentioned solution, agitation and dropping, to completion of dropwise addition and then the micelle emulsion of solvent flashing preparation package porphyrin；
(3) crosslinking agent, drying and forming-film after mixing is uniformly dispersed are added in the micelle emulsion obtained by step (2).
6. according to the method described in claim 5, it is characterized in that, the step (3) is substituted for: containing porphin in step (2) gained
Crosslinking agent is added in the aqueous solution of quinoline micella, a certain amount of thixotropic agent is then added, is uniformly mixed, is injected into the shape of design
Shape, dry fixed shape.
7. a kind of medical material, which is characterized in that it is high that the medical material contains photoresponse shape memory described in claim 1
Molecular material.
8. application of any photoresponse shape memory high molecule material of claims 1 to 3 in terms of preparing medical devices.
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