CN108341908A - 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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- CN108341908A CN108341908A CN201810199462.9A CN201810199462A CN108341908A CN 108341908 A CN108341908 A CN 108341908A CN 201810199462 A CN201810199462 A CN 201810199462A CN 108341908 A CN108341908 A CN 108341908A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/16—Materials with shape-memory or superelastic properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/08—Homopolymers or copolymers of acrylic acid esters
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 the high molecular material of the present invention by package porphyrin, the parts by weight of the raw material and each raw material are：20 40 parts of vinyl monomer containing hydrophobic group, 15 parts of the vinyl monomer containing hydrophilic radical, 15 parts of the vinyl monomer containing reactive group, 25 parts of organic solvent, 0.5 1 parts of radical initiator, 15 parts of crosslinking agent, 0.0005 0.005 parts of porphyrin.The shape memory function that the present invention assigns material red light response by wrapping up the porphyrin with photothermal conversion 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, and feux rouges will not damage skin when penetrating organism, energy loss is smaller, is expected to the photo-thermal therapy being applied in organism as the organic compound having in itself in organism to organism.
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 technology
Shape-memory material is ubiquitous in our life as a kind of novel intelligent macromolecule material, especially exists
Biomedical sector has prodigious application space, the development of related industry that will bring huge economic and society's effect 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 for having 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 so that polymer material is reached 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 indirectly heat thermal shape memory, which makes it restore original-shape, becomes hot research
Topic.
Turn with photo-thermal currently, indirectly heat thermal shape memory typically refers to introduce in shape-memory polymer matrix
Change effect Nano filling, 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 professors et al. have report
The gold nanoparticle that polycaprolactone is modified is served as Nano-heaters as filler and is introduced into polyurethane matrix material, utilized by road
Material after the light thermal property induction figuration of gold nanoparticle is returned to its original-shape.But including gold nanoparticle
The most Nano fillings 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 biomedical sector application.
Invention content
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 indirectly heat 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 amphipathic nature polyalcohol material (MBDA) by free radical polymerization, and solution is used in combination certainly
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 by the micella of package porphyrin and is prepared
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, is counted in 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
It is one or more in class.
In one embodiment, the vinyl monomer containing hydrophobic group is methyl acrylate, butyl acrylate, first
Base methyl acrylate, it is one or more in ethyl methacrylate.
In one embodiment, the vinyl monomer containing hydrophilic radical is acrylic acid, methacrylic acid, acryloyl
It is one or more in amine.
In one embodiment, the vinyl monomer containing reactive group is Diacetone Acrylamide, N- vinyl
It is one or more in pyrrolidones, hydroxy-ethyl acrylate, hydroxypropyl acrylate.
In one embodiment, the radical initiator is peroxide type initiators (such as perbenzoic acid uncle
Butyl ester, dibenzoyl peroxide, ammonium persulfate), one kind in azo-initiator (such as azodiisobutyronitrile).
In one embodiment, the crosslinking agent is one or more in adipic dihydrazide, glutaraldehyde.
Second object of the present invention is to provide the preparation method of the photoresponse shape memory high molecule material, the side
Method includes preparing amphipathic nature polyalcohol material by free radical polymerization, being used in combination solution self-assembling method that porphyrin is entrained into micella
Then micella is crosslinked by inside, prepare the optical Response shape-memory material.
In one embodiment, the method includes the following steps：
(1) by the vinyl monomer containing hydrophobic group, the vinyl monomer containing hydrophilic radical, the alkenes containing reactive group
It is reacted in monomer, organic solvent, radical initiator input container, obtains amphipathic nature polyalcohol MBDA；
(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, waits for that completion of dropwise addition and then solvent flashing prepare the micelle emulsion of package porphyrin；
(3) crosslinking agent, drying and forming-film after mixing is uniformly dispersed are added in micelle emulsion obtained by step (2).
In one embodiment, the organic solvent of the step (1) is gylcol ether, propylene glycol ethers, dimethyl
It is one or more in sulfoxide, N,N-dimethylformamide, tetrahydrofuran.
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 being 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 following steps：
(1) by 15-20 parts of the vinyl monomer containing hydrophobic group, 1-5 parts of the vinyl monomer containing hydrophilic radical, containing reaction
Property group 1-5 parts of vinyl monomer, 0.5-1 part of 2-5 parts of organic solvent and radical initiator be put in proportion into container, reaction
Time 3h, 140 DEG C of reaction temperature show that product through ether deposition and purification 3 times, is dried in vacuo to obtain amphipathic nature polyalcohol MBDA；
(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 dissolving, then 40-60 parts of deionized water is slowly dropped into THF solution, agitation and dropping waits for completion of dropwise addition
Later, 50 DEG C or so volatilization THF prepare the micelle emulsion of package porphyrin；
(3) 1-5 parts of crosslinking agent is added in 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) 1-5 parts of crosslinking agent is added in the aqueous solution of the micella containing porphyrin obtained by step (2), is then added a certain amount of
Thixotropic agent HJYM, is uniformly mixed, and is injected into the shape of design, and drying at room temperature fixes shape.
Third object of the present invention is to provide a kind of medical material, the medical material contains the photoresponse shape of the present 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 location, 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 technique 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) the feux rouges responsive polymer material for preparing of the present invention is can under the red light irradiation of small-power (354mW)
About 50~60 DEG C are increased in extremely short its shape memory of time internal trigger, 40s；
(4) shape of the present invention memory avoids traditional contact-type triggering shape memory, it can be achieved that remote control 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 the photo-thermal therapy being applied in organism.
Description of the drawings
Fig. 1：Prepare the schematic diagram of the shape-memory polymer of the porphyrin containing infrared optical response.
Fig. 2 is MBDA copolymers in CDCl3In hydrogen nuclear magnetic resonance spectrogram.
Fig. 3 is the infrared spectrum of MBDA copolymers；Wherein illustration represents：Unreacted monomer is in 1800-1550cm-1(insatiable hunger
With double bond characteristic peak location) infrared spectrum 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 irradiations；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 functional relation of the cumulative exposure time and film expanded angle of different samples.
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 to prepare the 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 solvents dilution, obtain product through second
Ether deposition and purification 3 times is dried in vacuo to obtain amphipathic nature polyalcohol MBDA.
(2) 1.6858g amphipathic polymers MBDA and a certain amount of (0,0.5mg, 1.5mg, 5mg) porphyrin (TPP) are taken, is added
After 10mL THF are completely dispersed dissolving, hydramine is added dropwise and adjusts pH to meta-alkalescence, 10mL deionized waters are then slowly added dropwise, knot is added dropwise
50 DEG C of evaporation at constant temperature THF after beam prepare the glue bundle body of package porphyrin.
(3) it is 1 to be added in this micellar solution with Diacetone Acrylamide molar ratio：1 crosslinking agent adipic dihydrazide,
Drying at room temperature film-forming.
The membrane material of preparation is set to generate deformation under 70 DEG C of environment, cooling at room temperature is fixed into temporary shapes.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
It is scanned along the bending position of film to realize that shape is restored.
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 the micelle emulsion after adding 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 copolymers1H-NMR is composed.In this work,1H-NMR be disclose copolymer at
The useful technology of work(synthesis.Figure it is seen that the peak 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-)
Proton formant.δ=6.99 are the proton resonance signals on amide N (- NH-) in PDAAM.However, in δ=11.0ppm
The corresponding proton peak of place's AA carboxylate groups is not present, this may be the relatively low concentration of AA due to participating in copolymerization, or
Since acid monomers cannot cause magnetic resonance.Peak at δ=0.901ppm belongs to the matter for the methyl not being connected with oxygen in polymer
Son.According to the inferred from input data of explanation, MMA, BA, DAAM and AA have participated in radical copolymerization, and confirm MBDA copolymers at
Work(synthesizes.
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 apparent.However, the micelle emulsion for introducing TPP generates one strong absorb in about 416nm (Soret bands)
There are 4 weak peaks at peak, respectively 513,546,591,650nm in 500~680nm (Q bands) range.This is with TPP in THF
Characteristic peak is consistent.The above different dispersions of comparison, it can be deduced that such conclusion：Micella package TPP makes it stablize 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
As a result characterization shows UV-vis spectrum and DLS characterizations mutually evidence, shows to be successfully prepared the load TPP with red light absorption
Micella, and have good dispersibility.
(3) MBDA-TPP-ADH shape memories 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/
The heating rate of min carries out second and heats, and measures Tg values.Whole DSC of the MBDA-TPP-ADH films of various dose TPP are bent
Line shows that the Tg without the film of TPP is 46.88 DEG C.With TPP be 0.5mg, 1.5mg, 5mg when, MBDA-TPP-ADH
The Tg of film is respectively 44.15 DEG C, 44.24 DEG C, 45.44 DEG C.
The MBDA- that the MBDA-TPP-NDs of load various concentration TPP is prepared for having different light absorptives by cross-linking reaction
TPP-ADH films.The results show that SMP material absorption band wider 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, increased absorbance
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 is scanned along the bending position of film to realize that shape is restored by laser.Due to real in the form of electromagnetic radiation
Existing infrared heating, so actuating method is contactless.
Fig. 5 shows that thermal response of the film of different TPP loading capacities preparations under IR irradiations, 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 be bent film straight end between angle come
It determines.The results show that when being exposed to laser, the film of not TPP there is no and observe variation.Loading TPP's
Observe that notable and quick shape is restored in film, and depending 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 films are 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 films have higher absorption radianting capacity at 635nm, are conducive to improve back
Multiple efficiency.However, when the dosage of TPP is further increased to 5mg, the property of TPP is crucial for the reduction of the response rate of film
's.Compared with other fillers, TPP has many intermolecular interactions.Basically, TPP once increases to a certain concentration
Shape recovery rate may be influenced, the restoring force caused by for by interacting weakens the relaxation for hindering strand.These realities
Test further demonstrate TPP addition cause and improve SMP films optical drive shape memory effect viewpoint.In addition, the use of TPP
Amount needs to control can be only achieved best shape recovery effects in a certain range.
Embodiment 2：
Solvent dimethyl sulfoxide (DMSO) 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 the dilution of 20mL solvents, show that product through ether deposition and purification 3 times, is dried in vacuo to obtain amphipathic nature polyalcohol.
After taking 4g amphipathic polymers and 3mg porphyrins, addition 10mL THF to be completely dispersed dissolving, hydramine is added dropwise and adjusts pH to meta-alkalescence, so
After 10mL deionized waters are slowly added dropwise, 50 DEG C of evaporation at constant temperature THF after completion of dropwise addition, prepare package porphyrin glue bundle body.In this glue
It is 1 to be added in beam solution with n-vinyl pyrrolidone molar ratio：1 crosslinking agent glutaraldehyde, drying at room temperature film-forming.
The membrane material of preparation is set to generate deformation under 70 DEG C of environment, cooling at room temperature is fixed into temporary shapes.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
It is scanned along the bending position of film to realize that shape is restored.
Furthermore, it is possible to which matter is added in the micelle emulsion after adding 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 the specific implementation mode of the present invention.It should be pointed out that being familiar with the field
Technical staff is to any change for being done of specific implementation mode of the present invention all without departing from the range of claims of the present invention.
Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.
Claims (10)
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.
2. photoresponse shape memory high molecule material according to claim 1, which is characterized in that the photoresponse shape note
Recall high molecular material to be prepared by the micella crosslinking of package porphyrin.
3. photoresponse shape memory high molecule material according to claim 1, which is characterized in that the photoresponse shape note
Recall high molecular material, count in parts by weight, contains the following raw material：20-40 parts of vinyl monomer containing hydrophobic group contains hydrophily
1-5 parts of the vinyl monomer of group, 0.5-1 parts of 1-5 parts of vinyl monomer, radical initiator, crosslinking agent 1-5 containing reactive group
Part, porphyrin；Its mesoporphyrin is the vinyl monomer containing hydrophobic group, the vinyl monomer containing hydrophilic radical, contains reactive group
Vinyl monomer, radical initiator, crosslinking agent total weight 0.03%-0.3%.
4. 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 kind or more in ethyl methacrylate
Kind；The vinyl monomer containing hydrophilic radical is acrylic acid, and methacrylic acid is one or more in acrylamide.
5. photoresponse shape memory high molecule material according to claim 1, which is characterized in that described to contain reactive group
Vinyl monomer be Diacetone Acrylamide, n-vinyl pyrrolidone, hydroxy-ethyl acrylate, one kind in hydroxypropyl acrylate
Or it is a variety of.
6. the preparation method of photoresponse shape memory high molecule material described in claim 1, which is characterized in that the method packet
It includes, amphipathic nature polyalcohol material is prepared by free radical polymerization, solution self-assembling method is used in combination to entrain into porphyrin inside micella,
Then micella is crosslinked, prepares the optical Response shape-memory material.
7. according to the method described in claim 7, including the following steps：
(1) by the vinyl monomer containing hydrophobic group, the vinyl monomer containing hydrophilic radical, containing the alkenes list of reactive group
It is reacted in body, organic solvent, radical initiator input container, obtains amphipathic nature polyalcohol；
(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 waits for that completion of dropwise addition and then solvent flashing prepare the micelle emulsion of package porphyrin；
(3) crosslinking agent, drying and forming-film after mixing is uniformly dispersed are added in micelle emulsion obtained by step (2).
8. the method according to the description of claim 7 is characterized in that the step (3) is substituted for：Contain porphin obtained by step (2)
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.
9. a kind of medical material, which is characterized in that the medical material contains the photoresponse shape memory high molecule material of the present invention
Material.
10. any photoresponse shape memory high molecule material the answering in terms of preparing medical devices of claim 1~6
With.
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| CN110452327A (en) * | 2019-08-27 | 2019-11-15 | 江南大学 | A kind of fluorescence polymer shape-memory material and preparation method thereof |
| CN110669184A (en) * | 2019-10-16 | 2020-01-10 | 临沂大学 | Preparation method of shape memory polymer material with drug release function, obtained product and application |
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| CN105597098A (en) * | 2015-12-28 | 2016-05-25 | 哈尔滨医科大学 | Trastuzumab bond-linking gold nanorod compound, preparation method and application thereof in diagnosis and treatment of HER2 positive breast cancer |
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| CN110669184A (en) * | 2019-10-16 | 2020-01-10 | 临沂大学 | Preparation method of shape memory polymer material with drug release function, obtained product and application |
| CN110669184B (en) * | 2019-10-16 | 2022-05-31 | 临沂大学 | Preparation method of shape memory polymer material with drug release function, obtained product and application |
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