CN105820354B - A kind of method of temperature sensing polymer nano-particle hydrophilic/hydrophobic reversible transition - Google Patents
A kind of method of temperature sensing polymer nano-particle hydrophilic/hydrophobic reversible transition Download PDFInfo
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- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
Abstract
The invention discloses a kind of methods of temperature sensing polymer nano-particle hydrophilic/hydrophobic reversible transition, one or many regulation and control are carried out to the temperature sensing polymer nano-particle, to realize the reversible transition of hydrophilic/hydrophobic；In each regulation process, first the temperature sensing polymer nano-particle is dissolved, then add the water or ethyl alcohol water mixed liquid of alternatively property solvent in good solvent, then uses any one precipitation of following three kinds of modes：a)：In 0 DEG C or less precipitation；b)：Under the lowest critical solution temperature of temperature sensing polymer nano-particle, precipitation on 0 DEG C；c)：On the lowest critical solution temperature of temperature sensing polymer nano-particle, precipitation under polymer decomposition temperature.Present invention can be implemented in the reversible transitions that hydrophilic/hydrophobic is realized on same polymer nano-particle, and preparation process is simple, environmentally protective.
Description
Technical field
The invention belongs to the application fields of polymer nano material, and in particular to same Thermo-sensitive polymerization can be achieved in one kind
The method of object nano-particle hydrophilic/hydrophobic reversible transition.
Background technology
Polymer nano-particle has extensive use in drug controlled release, gene delivery and bio-chemistry separation etc..However,
In order to make it effectively be applied, need to carry out control and functional modification to polymer nano-particle.The grain size pair of particle
Pharmaceutical carrier distribution in vivo and cycle have a significant impact, it is generally recognized that 200nm micelles below could penetrate mucous membrane or warp
Drug is transported to target tissue by body circulation, and needs certain stimulate the reaction to realize the fixed point release to target tissue；In order to keep away
Exempt from carrier to be adsorbed and captured by reticuloendothelial cell by protein, particle surface needs hydrophilic modification, repaiies by water-wetted surface
Decorations can also increase the adhesion strength to tissue, extend the residence time in vivo；Polymer micelle will have thermodynamic stability and move
Mechanical stability, with cope with the actual conditions such as high dilution or physiological environment (Ma S, Xiao M, Wang R.Langmuir,
2013,29(51):16010-16017)。
Temperature sensing polymer includes simultaneously hydrophobic and hydrophilic radical on structural unit, and there are lowest critical solution temperatures
(LCST), change as a reversible ball of string-spherical morphology will occur for the variation of temperature.This unique water soluble energy, can use
In the preparation regulatable intellectual material of function；In conjunction with the unique structure of nano-particle and surface characteristic, it is poly- to be formed by Thermo-sensitive
Close object nano-particle has extensive use in drug controlled release, bio-chemistry separation, transmission carrier and phase-change material etc.
(Petrusic S,Jovancic P,Lewandowski M,et al.Journal of Materials Science,2013,
48(22):7935-7948)。
The application of the polymer on polymer of different hydrophilic plays an important role, and the NF membrane of high-hydrophilic can improve water
The permeability of infiltration evaporation in counter osmosis, and excessively high hydrophilic polymer material in contact lenses for that can cause eye
Eyeball it is uncomfortable (Maldonado C C, Efron N.Ophthalmic and Physiological Optics, 2006,26
(4):408-418).Surface hydrophilicity also has stability of the nano-particle under different physiological environments and release behavior important
Influence, such as can increase polymer nano-particle adhesion strength in biological tissues and dissolving by increasing surface hydrophilicity
Property, the amalgamation of nano-particle and liposoluble substance can then be increased by increasing surface hydrophobic.In order to make polymer nano-particle
It is effectively applied in terms of biological medicine, needs that hydrophilic, the hydrophobicity of nano-particle are controlled or modified.Currently,
Mainly by selecting, different polymerized monomers carries out regulation and control to the hydrophilic/hydrophobic of polymer nano-particle or further the later stage is anti-
It should modify, need to change polymerization system, add new trim to regulate and control hydrophilic/hydrophobic, operating process complexity, time
It is long and irreversible.
Invention content
The present invention, which provides, a kind of can be achieved same temperature sensing polymer nano-particle hydrophilic/hydrophobic reversible transition
Method, it is easy to operate, environmentally protective.
A kind of method of temperature sensing polymer nano-particle hydrophilic/hydrophobic reversible transition, which is characterized in that Thermo-sensitive
Polymer nano-particle is made by Thermo-sensitive hydrophilic monomer and vinyl hydrophobic monomer block copolymerization, is polymerize to the Thermo-sensitive
Object nano-particle carries out one or many regulation and control, to realize the reversible transition of hydrophilic/hydrophobic；In each regulation process, first
The temperature sensing polymer nano-particle is dissolved in good solvent, then adds the water or alcohol-water of alternatively property solvent
Then mixed liquor uses any one precipitation of following three kinds of modes：
a)：In 0 DEG C or less the precipitation in a manner of freeze-drying, the temperature sensing polymer nano-particle regulation and control are got married
Aqueous nano-particle；
b)：It, will be described under the lowest critical solution temperature of temperature sensing polymer nano-particle, precipitation on 0 DEG C
Temperature sensing polymer nano-particle regulates and controls into hydrophilic nano-particle；
c)：On the lowest critical solution temperature of temperature sensing polymer nano-particle, temperature sensing polymer nano-particle
Precipitation under decomposition temperature regulates and controls the temperature sensing polymer nano-particle at hydrophobic nano-particle.
The present invention is same to regulate and control in the variation of different temperatures and solvent environment lower structure form using temperature sensing polymer
The hydrophilic/hydrophobic of kind temperature sensing polymer nano-particle.In lowest critical solution temperature (LCST) hereinafter, Thermo-sensitive segment
It is in extended position by aquation, is wrapped in hydrophobic cores, at this time by being freeze-dried the fixed segment unfolded, nanoparticle
Preferable hydrophily is presented in son；When being warming up on LCST, segment is by unfolding to the mutation rolled up, due to curling up for Thermo-sensitive segment
Contracting causes hydrophobic chain segment part in kernel to be exposed, and so that nano-particle (temperature sensing polymer nano-particle) is shown as hydrophobic
Property.By different precipitation conditions and selective solvent coordinated, reach transformation nano-particle hydrophilic/hydrophobic as needed
Purpose.
This method specifically comprises the following steps：
Step (1)：Temperature sensing polymer nanoparticle dissolution is obtained into solution A in good solvent, then adds solvent A (choosing
Selecting property solvent), mix to obtain dispersion liquid B；
Step (2)：Dispersion liquid B carries out the carrying out precipitation treatment of following either type：
a)：The solvent in dispersion liquid B is removed at 0 DEG C or less, obtains hydrophilic nano-particle A；
b)：It is removed in dispersion liquid B under the lowest critical solution temperature of temperature sensing polymer nano-particle, on 0 DEG C
Solvent, obtain hydrophilic nano-particle B；
c)：On the lowest critical solution temperature of temperature sensing polymer nano-particle, temperature sensing polymer nano-particle
The solvent in dispersion liquid B is removed under decomposition temperature, obtains hydrophobic nano-particle C；
Step (3)：Repeatedly cycle carries out step (1) and step (2) to selectivity, realizes the temperature sensing polymer nanometer
The hydrophily of particle or hydrophobic inverible transform.
In mode a), the mode that freeze-drying can be used carries out precipitation, and e.g., the dispersion liquid B is poured into liquid nitrogen
It is quick-frozen, dry, removing solvent is subsequently placed in freeze drier.
In the present invention, step (1) and step (2) are in a regulation process.
By the method for the invention, hydrophily or lipophilic temperature sensing polymer nano-particle can have been will be provided with by primary
Or polarity (hydrophily or lipophile) opposite temperature sensing polymer nano-particle is converted in multiple regulation process, or restore
To the polarity of starting temperature sensing polymer nano-particle.
In the present invention, also it can ensure the constant feelings of temperature sensing polymer nano-particle polarity under same precipitation mode
Under condition, by regulating and controlling precipitation temperature, the hydrophily of regulation and control temperature sensing polymer nano-particle or the purpose of hydrophobicity intensity are realized.
Such as, the carrying out precipitation treatment of mode c), but each carrying out precipitation treatment process will be repeated with hydrophobic sensitive polymer nano-particle
Temperature it is different, the nano-particle regulated and controled all has hydrophobicity, but hydrophobic intensity is different.
Desolvation process removes good solvent and selective solvent.
The temperature sensing polymer nano-particle is by Thermo-sensitive hydrophilic monomer and vinyl hydrophobic monomer block copolymerization
Amphipathilic block polymer obtained, wherein the Thermo-sensitive hydrophilic monomer has structural formula shown in formula 1 or formula 2：
In formula 1：R1、R2Independently selected from H or C2~C5Aliphatic chain, and R1、R2It is asynchronously H；R3For H or CH3；
In formula 2：R4For C1~C5Aliphatic chain, R5、R6Independently selected from H or CH3。
The vinyl hydrophobic comonomer has structural formula shown in formula 3 or formula 4：
In formula 3：R7For H, CH3Or C2H5；R8For phenyl, substituted-phenyl, CN or alkyl ether；
In formula 4：R9For H, CH3Or C2H5, X C4~C18Aliphatic chain or hydroxyl C4~C18Aliphatic chain.
Temperature sensing polymer nano-particle can directly be bought, or each monomer is made using existing copolymerization process.
Preferably, in temperature sensing polymer nano-particle polymerization process, Thermo-sensitive hydrophilic monomer and the hydrophobic list of vinyl
The molar ratio of body is 75:25~20:80.
Preferably, Thermo-sensitive hydrophilic monomer is n-isopropyl acrylamide (NIPAM), the vinyl hydrophobic copolymer
Monomer is at least one of octadecyl methacrylate (SMA), styrene (St), tert-butyl acrylate (tBA).
The lowest critical solution temperature for the temperature sensing polymer nano-particle that preferred monomers polymerize is 30~45 DEG C.
Wherein, the LCST of poly-N-isopropyl acrylamide is 32~34 DEG C.N-isopropyl acrylamide is embedding with octadecyl methacrylate
The lowest critical solution temperature of the Thermo-sensitive block copolymer formed after Duan Juhe is 37~40 DEG C.
The decomposition temperature of temperature sensing polymer nano-particle of the present invention is more than 120 DEG C.
After the completion of polymerization, it is dissolved using the good solvent of the temperature sensing polymer nano-particle.It can dissolve institute
The solvent for the temperature sensing polymer nano-particle stated is used as good solvent of the present invention, wherein every milligram of Thermo-sensitive is poly-
Object nano-particle is closed to be dissolved using 1~1.5mL good solvents.
By good solvent dissolving, dispersion, selective solvent induces self assembly, and so that polymer is formed has temperature sensitive hydrophily
The core-shell structure nanometer particle of shell and hydrophobic core, nano particle diameter is in 50~500nm.
Preferably, the good solvent is tetrahydrofuran or acetone.
Further preferably, every milligram of temperature sensing polymer nano-particle is carried out abundant using 1~5mL tetrahydrofurans or acetone
Dissolving.Every milligram of temperature sensing polymer nano-particle preferably uses 1~1.5mL tetrahydrofurans or acetone to be dissolved.
The volume ratio of good solvent and selective solvent is 1:3~20.
Preferably, the volume ratio of good solvent and selective solvent is 1:3~5.
Under the selective solvent, temperature sensing polymer self-assembly, formed have hydrophily shell and
The stabilization nano-particle of hydrophobic cores, then the solvent in removing system at different temperatures, regulates and controls the hydrophilic of nano-particle
Or hydrophobic performance.
In the present invention, each nano-particle film that precipitation is obtained measures water in the contact angle of the film surface to judge
Regulate and control the hydrophilic or hydrophobic performance of obtained each nano-particle.
In desolvation process, in the nano-particle for being conducive to obtained good hydrophilic performance compared with precipitation under low temperature, (water is in film surface
On contact angle it is smaller), with the raising of precipitation temperature, contact angle of the water on film surface gradually increases.
In the present invention, Jie Chu Jiao≤mode b) regulation and control of the water on the film surface for the nano-particle that mode a) regulation and control obtain obtain
Nano-particle film surface on the obtained film surface of nano-particle of Jie Chu Jiao≤mode c) regulation and control on contact angle.Wherein, side
Formula a) and mode b) show hydrophily.Mode c) shows hydrophobicity.
Compared with prior art, the invention has the advantages that：
The present invention using the unique solubility property of Thermo-sensitive hydrophilic monomer can realize block polymer nano-particle hydrophily/
Hydrophobic reversible transition, preparation process is simple, mild condition, environmentally protective, can obtain stable polymer nano-particle.This
Inventive technique realizes the reversible transition of hydrophilic/hydrophobic on same polymer nano-particle, according to different environment
Application demand can simply and effectively adjust the hydrophilic/hydrophobic of nano-particle, can be applied to drug controlled release, catalysis
Agent, sewage disposal and bio-chemistry separation etc..
Description of the drawings
Fig. 1 is that the hydrophilic/hydrophobic of temperature sensing polymer nano-particle changes schematic diagram；
Fig. 2 is the PNIPAM-b-PSMA nano-particles that provide of embodiment 1 under different samplings (at a temperature of precipitation)
Water contact angle；
Fig. 3 is the NIPAM that embodiment 2 provides:TEM photo of the St nano-particles under different samplings.
Specific implementation mode
As shown in Figure 1, being regulated and controled in the variation of different temperatures and solvent environment lower structure form using temperature sensing polymer
The hydrophilic/hydrophobic of same temperature sensing polymer nano-particle.Such as part (a) of Fig. 1, (0 DEG C or less under freezing processing
Precipitation), Thermo-sensitive segment is in extended position by aquation, and by being freeze-dried the fixed segment unfolded, nano-particle is in
Now preferable hydrophily；Such as part (b) of Fig. 1, precipitation temperature is increased to lowest critical solution temperature (LCST) hereinafter, Thermo-sensitive
Segment is in extended position by aquation, can still be wrapped in hydrophobic cores, certain hydrophily is still presented in nano-particle；Such as
Shown in part (c) of Fig. 1, when being warming up on LCST, segment is by unfolding to the mutation rolled up, due to rolling up for Thermo-sensitive segment
Cause hydrophobic chain segment part in kernel to be exposed, so that nano-particle (temperature sensing polymer nano-particle) is shown as hydrophobic
Property.
Embodiment 1
Weigh poly- (n-isopropyl acrylamide-b- octadecyl methacrylates) block copolymer (PNIPAM-b- of 10mg
PSMA) in 50mL beakers, wherein polymer monomer molar ratio is NIPAM:SMA=1:2, PNIPAM-b-PSMA LCST is
38.5℃。
10mL acetone (good solvent) is added into PNIPAM-b-PSMA, obtains solution A after stirring and dissolving, after dissolving dropwise
It is added in 50mL water (selective solvent), ultrasound is allowed to be uniformly dispersed, and obtains stable polymer nano-particle dispersion liquid B.
Part dispersion liquid B is taken every time, carries out the precipitation of following four kinds of modes respectively：
Mode a)：It will be freeze-dried 12h in fast transfer to freeze drier after the dispersion liquid B liquid nitrogen frozens of part, gone
Except solvent (good solvent and selective solvent), as shown in part (a) of Fig. 2, after polymer nano-particle is formed a film measuring water connects
Feeler is 41 °, shows as hydrophily.
Mode b)：By part dispersion liquid B, oven drying removes solvent, such as the part (b) institute of Fig. 2 to constant weight at 20 DEG C
Show, it is 63 ° that water contact angle is measured after polymer nano-particle is film-made, and still shows as hydrophily.
Mode c)：By part dispersion liquid B, oven drying removes solvent, such as the part (c) institute of Fig. 2 to constant weight at 50 DEG C
Show, it is 102 ° that water contact angle is measured after polymer nano-particle is film-made, and shows as hydrophobicity.
Mode d)：By part dispersion liquid B, oven drying removes solvent, such as the part (d) institute of Fig. 2 to constant weight at 80 DEG C
Show, it is 109 ° that water contact angle is measured after polymer nano-particle is film-made, and shows as hydrophobicity.
Embodiment 2
10mg PNIPAM-b-PSMA are weighed in 50mL beakers, wherein polymer monomer molar ratio is NIPAM:SMA=
2:1, PNIPAM-b-PSMA LCST is 35 DEG C.
10mL tetrahydrofurans are added into PNIPAM-b-PSMA, obtains solution A after stirring and dissolving, is added dropwise after dissolving
In 50mL water, ultrasound is allowed to be uniformly dispersed, and obtains stable polymer nano-particle dispersion liquid B.
Part dispersion liquid B is taken every time, carries out the precipitation of the following two kinds mode respectively：
Mode a)：It will be freeze-dried 12h in fast transfer to freeze drier after the dispersion liquid B liquid nitrogen frozens of part, gone
Except solvent, it is 34 ° that water contact angle is measured after polymer nano-particle is formed a film, and shows as hydrophily, (a) of Fig. 3 is partly cold
The TEM figures of dry rear nano-particle are lyophilized, it can be seen that the state unfolded is presented in shell.
Mode b)：Part dispersion liquid B is placed in 50 DEG C of oven dryings to constant weight, solvent is removed, by polymer nano-particle
It is 96 ° that water contact angle is measured after film, shows as hydrophobicity, (b) of Fig. 3 is partly nano-particle after the drying on LCST
TEM schemes, it can be seen that shell is rolled up, and particle volume becomes smaller.
Nano-particle (hydrophilic nano-particle made from mode a) precipitations) after freeze-drying is placed in tetrahydrofuran
It is added dropwise after middle stirring and dissolving in 30mL water, ultrasonic disperse obtains stable polymer nano-particle dispersion liquid, by dispersion liquid
80 DEG C of oven dryings are placed in constant weight, remove solvent, it is 105 ° that water contact angle is measured after polymer nano-particle is film-made, performance
For hydrophobicity.It realizes nano-particle from hydrophily to hydrophobic sex reversal.
Embodiment 3
Weigh poly- (n-isopropyl acrylamide-b- styrene) block copolymer (NIPAM of 10mg:St) in 50mL beakers
In, wherein polymer monomer molar ratio is NIPAM:St=1:1, NIPAM:The LCST of St is 37 DEG C.
To NIPAM:10mL tetrahydrofurans are added in St, obtains solution A after stirring and dissolving, 30mL water is added dropwise after dissolving
In, ultrasound is allowed to be uniformly dispersed, and obtains stable polymer nano-particle dispersion liquid B.
Part dispersion liquid B is taken every time, carries out the precipitation of following four kinds of modes respectively：
Mode a)：It will be freeze-dried 12h in fast transfer to freeze drier after the dispersion liquid B liquid nitrogen frozens of part, gone
Except solvent, it is 52 ° that water contact angle is measured after polymer nano-particle is formed a film, and shows as hydrophily.
Mode b)：By part dispersion liquid B, oven drying removes solvent, by polymer nano-particle to constant weight at 20 DEG C
It is 74 ° that water contact angle is measured after film, still shows as hydrophily.
Mode c)：By part dispersion liquid B, oven drying removes solvent, by polymer nano-particle to constant weight at 50 DEG C
It is 121 ° that water contact angle is measured after film, shows as hydrophobicity.
Mode d)：By part dispersion liquid B, oven drying removes solvent, by polymer nano-particle to constant weight at 80 DEG C
It is 152 ° that water contact angle is measured after film, shows as hydrophobicity.
The nano-particle (the hydrophobic nano particle that mode c) is converted to) of oven drying at 50 DEG C is placed in tetrahydrochysene furan
It is added dropwise after stirring and dissolving of muttering in 30mL water, ultrasonic disperse obtains stable polymer nano-particle dispersion liquid, will disperse
12h is freeze-dried after liquid liquid nitrogen frozen in fast transfer to freeze drier, solvent is removed, polymer nano-particle is formed a film
After measure water contact angle be 53 °, show as hydrophily；It realizes and converts hydrophobic nano particle to hydrophily.
Embodiment 4
Weigh poly- (n-isopropyl acrylamide-b- tert-butyl acrylates) block copolymer (NIPAM of 10mg:TBA) in
In 50mL beakers, wherein polymer monomer molar ratio is NIPAM:TBA=3:1, NIPAM:LCST42 DEG C of tBA.
To NIPAM:10mL tetrahydrofurans are added in tBA, obtains solution A after stirring and dissolving, 30mL is added dropwise after dissolving
In water, ultrasound is allowed to be uniformly dispersed, and obtains stable polymer nano-particle dispersion liquid B.
Part dispersion liquid B is taken every time, carries out the precipitation of following four kinds of modes respectively：
Mode a)：It will be freeze-dried 12h in fast transfer to freeze drier after the dispersion liquid B liquid nitrogen frozens of part, gone
Except solvent, it is 25 ° that water contact angle is measured after polymer nano-particle is formed a film, and shows as hydrophily.
Mode b)：By part dispersion liquid B, oven drying removes solvent, by polymer nano-particle to constant weight at 20 DEG C
It is 57 ° that water contact angle is measured after film, still shows as hydrophily.
Mode c)：By part dispersion liquid B, oven drying removes solvent, by polymer nano-particle to constant weight at 50 DEG C
It is 98 ° that water contact angle is measured after film, shows as hydrophobicity.
Mode d)：By part dispersion liquid B, oven drying removes solvent, by polymer nano-particle to constant weight at 80 DEG C
It is 106 ° that water contact angle is measured after film, shows as hydrophobicity.
Embodiment 5
Weigh poly- (n-isopropyl acrylamide-b- styrene/acrylics tert-butyl ester) block copolymer (NIPAM of 10mg:
St:TBA) in 50mL beakers, wherein polymer monomer molar ratio is NIPAM:St:TBA=1:2:2, NIPAM:St:TBA's
LCST is 34 DEG C.
Part dispersion liquid B is taken every time, carries out the precipitation of following four kinds of modes respectively：
Mode a)：To NIPAM:St:10mL tetrahydrofurans are added in tBA, obtain solution A after stirring and dissolving, after dissolving by
It is added dropwise to 30mL water-ethanols (volume ratio 3:1) in, ultrasound is allowed to be uniformly dispersed, and obtains stable polymer nano-particle dispersion
Liquid B.
Mode b)：It will be freeze-dried 12h in fast transfer to freeze drier after the dispersion liquid B liquid nitrogen frozens of part, gone
Except solvent, it is 56 ° that water contact angle is measured after polymer nano-particle is formed a film, and shows as hydrophily.
Mode c)：By part dispersion liquid B, oven drying removes solvent, by polymer nano-particle to constant weight at 20 DEG C
It is 77 ° that water contact angle is measured after film, still shows as hydrophily.
Mode d)：By part dispersion liquid B, oven drying removes solvent, by polymer nano-particle to constant weight at 80 DEG C
It is 134 ° that water contact angle is measured after film, shows as hydrophobicity.
Embodiment 6
After stirring and dissolving in hydrophobic nano-particle tetrahydrofuran made from 5 mode d) of embodiment, it is added dropwise
In 30mL water, ultrasonic disperse obtains dispersion liquid, and by dispersion liquid, oven drying removes solvent, by polymer nano to constant weight at 30 DEG C
It is 81 ° to measure water contact angle after rice corpuscles film, shows as hydrophily.It will the hydrophilic nano-particle tetrahydrochysene furan obtained
After stirring and dissolving of muttering, it is added dropwise in 30mL water, oven drying removes solvent to constant weight at 80 DEG C again after ultrasonic disperse,
It is 144 ° that water contact angle is measured after polymer nano-particle is film-made, the Polarity restoration of nano-particle to hydrophobicity.By multiple
Precipitation regulates and controls, and restores the hydrophobic performance of nano-particle.
Claims (5)
1. a kind of method of temperature sensing polymer nano-particle hydrophilic/hydrophobic reversible transition, which is characterized in that Thermo-sensitive is poly-
It closes object nano-particle to be made by Thermo-sensitive hydrophilic monomer and vinyl hydrophobic monomer block copolymerization, to the temperature sensing polymer
Nano-particle carries out one or many regulation and control, to realize the reversible transition of hydrophilic/hydrophobic；In each regulation process, first will
The temperature sensing polymer nano-particle dissolves in good solvent, then to add the alternatively water of property solvent or alcohol-water mixed
Liquid is closed, any one precipitation of following three kinds of modes is then used：
a)：In 0 DEG C or less the precipitation in a manner of freeze-drying, the temperature sensing polymer nano-particle is regulated and controled into hydrophily
Nano-particle；
b)：It, will be described temperature sensitive under the lowest critical solution temperature of temperature sensing polymer nano-particle, precipitation on 0 DEG C
Property polymer nano-particle regulation and control at hydrophilic nano-particle；
c)：On the lowest critical solution temperature of temperature sensing polymer nano-particle, the decomposition of temperature sensing polymer nano-particle
Precipitation under temperature regulates and controls the temperature sensing polymer nano-particle at hydrophobic nano-particle；
The Thermo-sensitive hydrophilic monomer has structural formula shown in formula 1 or formula 2：
In formula 1：R1、R2Independently selected from H or C2~C5Aliphatic chain, and R1、R2It is asynchronously H；R3For H or CH3；
In formula 2：R4For C1~C5Aliphatic chain, R5、R6Independently selected from H or CH3；
The vinyl hydrophobic comonomer has structural formula shown in formula 3 or formula 4：
In formula 3：R7For H, CH3Or C2H5；R8For phenyl, substituted-phenyl, CN or alkyl ether；
In formula 4：R9For H, CH3Or C2H5, X C4~C18Aliphatic chain or hydroxyl C4~C18Aliphatic chain；
The volume ratio of the good solvent and selective solvent is 1:3-20.
2. the method for temperature sensing polymer nano-particle hydrophilic/hydrophobic reversible transition according to claim 1, special
Sign is that the Thermo-sensitive hydrophilic monomer is n-isopropyl acrylamide, and the vinyl hydrophobic comonomer is methyl
At least one of octadecyl acrylate, styrene, tert-butyl acrylate.
3. the method for temperature sensing polymer nano-particle hydrophilic/hydrophobic reversible transition according to claim 1, special
Sign is, in temperature sensing polymer nano-particle polymerization process, the molar ratio of Thermo-sensitive hydrophilic monomer and vinyl hydrophobic monomer
It is 75:25~20:80.
4. the method for temperature sensing polymer nano-particle hydrophilic/hydrophobic reversible transition according to claim 1, special
Sign is that the good solvent is tetrahydrofuran or acetone.
5. the method for temperature sensing polymer nano-particle hydrophilic/hydrophobic reversible transition according to claim 2, special
Sign is that the Thermo-sensitive block copolymer formed after n-isopropyl acrylamide and octadecyl methacrylate block polymerization is most
Lower critical solution temperature is 37~40 DEG C.
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