CN105820354A - Method capable of achieving hydrophilic/hydrophobic reversible transformation on thermosensitive polymer nanoparticle - Google Patents
Method capable of achieving hydrophilic/hydrophobic reversible transformation on thermosensitive polymer nanoparticle Download PDFInfo
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Abstract
The invention discloses a method capable of achieving reversible transformation of hydrophilicity/hydrophobicity of a thermosensitive polymer nanoparticle. The method is characterized by regulating the thermosensitive polymer nanoparticle once or many times to achieve reversible transformation of hydrophilicity/hydrophobicity, wherein in the process of regulation each time, the thermosensitive polymer nanoparticle is firstly dissolved in a good solvent, then water or ethanol-water mixed liquor as a selective solvent is added and then any one of the following three ways is adopted for desolvation: a) desolvation below 0 DEG C; b) desolvation below the lower critical solution temperature of the thermosensitive polymer nanoparticle and above 0 DEG C; c) desolvation above lower critical solution temperature of the thermosensitive polymer nanoparticle and below the polymer decomposition temperature. The method can achieve reversible transformation of hydrophilicity/hydrophobicity on the same polymer nanoparticle, is simple in preparation process and is green and environment-friendly.
Description
Technical field
The invention belongs to the application of polymer nano material, be specifically related to one and can realize same
The method of temperature sensing polymer nanoparticle hydrophilic/hydrophobic reversible transition.
Background technology
Polymer nano-particle has extensively at aspects such as drug controllable release, gene delivery and bio-chemistry separation
Purposes.But, in order to make it effectively be applied, need polymer nano-particle is controlled
And functional modification.Pharmaceutical carrier distribution in vivo and circulation are had a significant impact by the particle diameter of particle,
It has been generally acknowledged that the micelle of below 200nm could pass through mucosa or through body circulation, medicine is transported to target group
Knit and it needs to certain irritant reaction realizes the release of the fixed point to target tissue；In order to avoid carrier quilt
Protein adsorption and being caught by reticuloendothelial cell, particle surface needs hydrophilic modification, by hydrophilic
The adhesion that also can increase tissue is modified on surface, extends the time of staying in vivo；Polymer micelle
Thermodynamic stability to be had and dynamic stability, to tackle the actual feelings such as high dilution or physiological environment
Condition (Ma S, Xiao M, Wang R.Langmuir, 2013,29 (51): 16010-16017).
Temperature sensing polymer, its construction unit comprises hydrophobic and hydrophilic group simultaneously, there is minimum facing
Boundary's solution temperature (LCST), along with the change of temperature will occur a reversible ball of string-spherical morphology to change.
The aqueous solution performance of this uniqueness, can be used for the regulatable intellectual material of preparation function；In conjunction with nanoparticle
The structure of son uniqueness and surface characteristic, the temperature sensing polymer nanoparticle formed is at medicine realizing controlled-release
Put, the aspect such as bio-chemistry separation, transmission carrier and phase-change material has extensive use (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, the NF membrane of high-hydrophilic
Can improve water permeability of infiltration evaporation in counter osmosis, and too high hydrophilic polymeric material
Material can cause uncomfortable (Maldonado C C, the Efron N. of eyes in contact lens
Ophthalmic and Physiological Optics,2006,26(4):408-418).Surface hydrophilicity pair
Also important impact is had, such as in nanoparticle stability under different physiological environments and release behavior
Polymer nano-particle adhesion in biological tissues and molten can be increased by increasing surface hydrophilicity
Xie Xing, increases surface hydrophobic and then can increase the amalgamation of nanoparticle and liposoluble substance.In order to
Make polymer nano-particle effectively be applied in terms of biological medicine, need the parent to nanoparticle
Water, hydrophobicity are controlled or modify.At present, the hydrophilic/hydrophobic of polymer nano-particle is main
Regulated and controled or late phase reaction modification further by selecting different polymerization monomers to carry out, need to change polymerization
System, adding new trim to regulate and control hydrophilic/hydrophobic, operating process is complicated, the time is long, and
Irreversible.
Summary of the invention
The present invention provides one can realize same temperature sensing polymer nanoparticle hydrophilic/hydrophobic
The method of reversible transition, simple to operate, environmental protection.
A kind of method of temperature sensing polymer nanoparticle hydrophilic/hydrophobic reversible transition, its feature exists
In, temperature sensing polymer nanoparticle is total to by Thermo-sensitive hydrophilic monomer and vinyl hydrophobic monomer block
Poly-prepared, described temperature sensing polymer nanoparticle is carried out one or many regulation and control, hydrophilic to realize
Property/hydrophobic reversible transition；Every time in regulation process, first by described temperature sensing polymer nanoparticle
Son dissolves in good solvent, then adds the water as selective solvent or ethanol-water mixture, then
Any one precipitation of three kinds of modes below using:
A): with cryodesiccated mode precipitation below 0 DEG C, by described temperature sensing polymer nanometer
Particle regulates and controls into hydrophilic nanoparticle；
B): de-under the lowest critical solution temperature of temperature sensing polymer nanoparticle, on 0 DEG C
Molten, described temperature sensing polymer nanoparticle is regulated and controled into hydrophilic nanoparticle；
C): on the lowest critical solution temperature of temperature sensing polymer nanoparticle, Thermo-sensitive polymerization
Precipitation under thing nanoparticle decomposition temperature, regulates and controls into thin by described temperature sensing polymer nanoparticle
The nanoparticle of aqueous.
The present invention utilizes temperature sensing polymer change of configuration under different temperatures and solvent environment
Regulate and control the hydrophilic/hydrophobic of same temperature sensing polymer nanoparticle.In minimum Critical Solution temperature
Below, Thermo-sensitive segment is extended position by hydration to degree (LCST), is wrapped in hydrophobic cores,
Fix the segment unfolded now by lyophilization, nanoparticle presents preferable hydrophilic；It is warming up to
Time on LCST, segment is by unfolding to the sudden change rolled up, due in the rolling up and cause of Thermo-sensitive segment
In core, hydrophobic chain segment part comes out, and makes nanoparticle (temperature sensing polymer nanoparticle) show
For hydrophobicity.By different precipitation conditions and selective solvent coordinated, reach to convert as required
The purpose of nanoparticle hydrophilic/hydrophobic.
This method, specifically includes following steps:
Step (1): temperature sensing polymer nanoparticle dissolution is obtained in good solvent solution A, subsequently
Add solvent orange 2 A (selective solvent), mix to obtain dispersion liquid B；
Step (2): dispersion liquid B carries out the carrying out precipitation treatment of following either type:
A): below 0 DEG C, remove the solvent in dispersion liquid B, obtain hydrophilic nanoparticle A；
B): de-under the lowest critical solution temperature of temperature sensing polymer nanoparticle, on 0 DEG C
Except the solvent in dispersion liquid B, obtain hydrophilic nanoparticle B；
C): on the lowest critical solution temperature of temperature sensing polymer nanoparticle, Thermo-sensitive polymerization
Remove the solvent in dispersion liquid B under thing nanoparticle decomposition temperature, obtain hydrophobic nanoparticle
C；
Step (3): selectivity repeatedly circulates and carries out step (1) and step (2), it is achieved described
The hydrophilic of temperature sensing polymer nanoparticle or hydrophobic inverible transform.
In mode a), cryodesiccated mode can be used to carry out precipitation, e.g., by described dispersion liquid
B pours into liquid nitrogen quick-freezing, is subsequently placed in freezer dryer and is dried, desolvation.
In the present invention, step (1) and step (2) are in a regulation process.
By the inventive method, hydrophilic or oil loving temperature sensing polymer nanoparticle can be will be provided with
Son is transformed into relative temperature sensitive of polarity (hydrophilic or lipophile) in the regulation process of one or many
Property polymer nano-particle, or the polarity recovered to initial temperature sensing polymer nanoparticle.
In the present invention, it is possible under same precipitation mode, ensureing temperature sensing polymer nanoparticle pole
Property constant in the case of, by regulation and control precipitation temperature, it is achieved regulation and control temperature sensing polymer nanoparticle
Hydrophilic or the purpose of hydrophobicity intensity.As, will have hydrophobic sensitive polymer nanoparticle weight
The carrying out precipitation treatment of multiple ways of carrying out c), but the temperature of each carrying out precipitation treatment process is different, and regulation and control obtain
Nanoparticle all possesses hydrophobicity, but hydrophobic intensity is different.
Desolvation process removing good solvent and selective solvent.
Described temperature sensing polymer nanoparticle is by Thermo-sensitive hydrophilic monomer and vinyl hydrophobicity list
The Amphipathilic block polymer that body block copolymerization prepares, wherein, described 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、R2Time different
For H；R3For H or CH3；
In formula 2: R4For C1～C5Aliphatic chain, R5、R6Independently selected from H or CH3。
Described vinyl hydrophobic comonomer has a 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 is C4～C18Aliphatic chain or the C of hydroxyl4～C18
Aliphatic chain.
Temperature sensing polymer nanoparticle can directly be buied, or described each monomer is used existing copolymerization
Method prepares.
As preferably, in temperature sensing polymer nanoparticle polymerization process, Thermo-sensitive hydrophilic monomer and second
The mol ratio of thiazolinyl hydrophobic monomer is 75:25～20:80.
As preferably, Thermo-sensitive hydrophilic monomer is NIPA (NIPAM), described
Vinyl hydrophobic comonomer is octadecyl methacrylate (SMA), styrene (St), acrylic acid
At least one in the tert-butyl ester (tBA).
The lowest critical solution temperature of the temperature sensing polymer nanoparticle that preferred monomers polymerization obtains is
It it is 30～45 DEG C.Wherein, the LCST of poly-N-isopropyl acrylamide is 32～34 DEG C.N-isopropyl
The Thermo-sensitive block copolymer formed after acrylamide and octadecyl methacrylate block polymerization is
Lower critical solution temperature is 37～40 DEG C.
The decomposition temperature of temperature sensing polymer nanoparticle of the present invention is more than 120 DEG C.
After being polymerized, the good solvent of described temperature sensing polymer nanoparticle is used to carry out molten to it
Solve.The solvent of the temperature sensing polymer nanoparticle described in solubilized is used as of the present invention good
Solvent, wherein, every milligram of temperature sensing polymer nanoparticle uses 1～1.5mL good solvent to dissolve.
Dissolved by good solvent, disperse, selective solvent induction self assembly, make polymer be formed and have
Temperature sensitive hydrophilic shell and the core-shell structure nanometer particle of hydrophobic core, nano particle diameter is 50～500
nm。
As preferably, described good solvent is oxolane or acetone.
Further preferably, every milligram of temperature sensing polymer nanoparticle use 1～5mL oxolane or
Acetone fully dissolves.Every milligram of temperature sensing polymer nanoparticle preferably employs 1～1.5mL tetrahydrochysene
Furan or acetone dissolve.
The volume ratio of good solvent and selective solvent is 1:3～20.
As preferably, the volume ratio of good solvent and selective solvent is 1:3～5.
Under described selective solvent, temperature sensing polymer self-assembly, formed and there is parent
Aqueous shell and the stable nanoparticle of hydrophobic cores, in removing system the most at different temperatures
Solvent, the hydrophilic or hydrophobic performance of regulation and control nanoparticle.
In the present invention, each nanoparticle film that precipitation is obtained, measure the water contact on this film surface
Angle judges to be regulated and controled the hydrophilic or hydrophobic performance of each nanoparticle obtained.
In desolvation process, under relatively low temperature, precipitation is conducive to preparing the nanoparticle of good hydrophilic performance
(water contact angle on face is less), along with the rising of precipitation temperature, water contact on face
Angle is gradually increased.
In the present invention, water regulates and controls the contact angle side on the face of the nanoparticle obtained at mode a)
Contact angle mode c) on the face of the nanoparticle that formula b) regulation and control obtain regulates and controls the nanometer obtained
Contact angle on the face of particle.Wherein, mode a) and mode b) shows hydrophilic.Mode c)
Show hydrophobicity.
Compared with prior art, present invention have the advantage that
The present invention utilizes Thermo-sensitive hydrophilic monomer, and unique solubility property can realize block polymer nanometer
The reversible transition of particle hydrophilic/hydrophobic, preparation process is simple, mild condition, and environmental protection can
Obtain stable polymer nano-particle.The technology of the present invention realizes on same polymer nano-particle
The reversible transition of hydrophilic/hydrophobic, according to different environmental applications demands, can be simply and effectively
The hydrophilic/hydrophobic of regulation nanoparticle, can be applicable at drug controllable release, catalyst, sewage
The aspects such as reason and bio-chemistry separation.
Accompanying drawing explanation
Fig. 1 is that the hydrophilic/hydrophobic of temperature sensing polymer nanoparticle changes schematic diagram；
The PNIPAM-b-PSMA nanoparticle that Fig. 2 provides for embodiment 1 is under different samplings
The water contact angle of (at a temperature of precipitation)；
The NIPAM:St nanoparticle that Fig. 3 provides for embodiment 2 TEM under different samplings
Photo.
Detailed description of the invention
As it is shown in figure 1, utilize temperature sensing polymer configuration under different temperatures and solvent environment
Change regulates and controls the hydrophilic/hydrophobic of same temperature sensing polymer nanoparticle.(a) such as Fig. 1
Part, under freezing processing (less than 0 DEG C precipitation), Thermo-sensitive segment is extended position by hydration,
Fixed the segment unfolded by lyophilization, nanoparticle presents preferable hydrophilic；(b) such as Fig. 1
Part, precipitation temperature is increased to lowest critical solution temperature (LCST) below, and Thermo-sensitive segment passes through water
Cooperation, with in extended position, still can be wrapped in hydrophobic cores, and nanoparticle still presents certain hydrophilic
Property；As shown in (c) part of Fig. 1, when being warming up on LCST, segment is prominent by unfolding to roll up
Become, owing to rolling up of Thermo-sensitive segment causes hydrophobic chain segment part in kernel to come out, make nanometer
Particle (temperature sensing polymer nanoparticle) shows as hydrophobicity.
Embodiment 1
Weigh 10mg poly-(NIPA-b-octadecyl methacrylate) block copolymer
(PNIPAM-b-PSMA) in 50mL beaker, wherein polymer monomer mol ratio is
The LCST of NIPAM:SMA=1:2, PNIPAM-b-PSMA is 38.5 DEG C.
In PNIPAM-b-PSMA, add 10mL acetone (good solvent), obtain molten after stirring and dissolving
Liquid A, is added dropwise over after dissolving in 50mL water (selective solvent), and ultrasonic being allowed to is uniformly dispersed,
To stable polymer nano-particle dispersion liquid B.
Take part dispersion liquid B every time, carry out the precipitation of following four kinds of modes respectively:
Mode a): by freezing in fast transfer after part dispersion liquid B liquid nitrogen freezing to freezer dryer
It is dried 12h, removes solvent (good solvent and selective solvent), as shown in (a) part of Fig. 2, will
Recording water contact angle after polymer nano-particle film forming is 41 °, shows as hydrophilic.
Mode b): part dispersion liquid B oven drying at 20 DEG C, to constant weight, is removed solvent, as
Shown in (b) part of Fig. 2, it it is 63 ° by recording water contact angle after polymer nano-particle masking, still
Show as hydrophilic.
Mode c): part dispersion liquid B oven drying at 50 DEG C, to constant weight, is removed solvent, as
Shown in (c) part of Fig. 2, it is 102 ° by recording water contact angle after polymer nano-particle masking,
Show as hydrophobicity.
Mode d): part dispersion liquid B oven drying at 80 DEG C, to constant weight, is removed solvent, as
Shown in (d) part of Fig. 2, it is 109 ° by recording water contact angle after polymer nano-particle masking,
Show as hydrophobicity.
Embodiment 2
Weigh 10mg PNIPAM-b-PSMA in 50mL beaker, wherein polymer monomer mole
It it is 35 DEG C than the LCST for NIPAM:SMA=2:1, PNIPAM-b-PSMA.
In PNIPAM-b-PSMA, add 10mL oxolane, after stirring and dissolving, obtain solution A,
Being added dropwise over after dissolving in 50mL water, ultrasonic being allowed to is uniformly dispersed, and obtains stable polymer nanocomposite
Particle dispersion B.
Take part dispersion liquid B every time, carry out the precipitation of the following two kinds mode respectively:
Mode a): by freezing in fast transfer after part dispersion liquid B liquid nitrogen freezing to freezer dryer
It is dried 12h, removes solvent, be 34 ° by recording water contact angle after polymer nano-particle film forming, table
Being now hydrophilic, (a) of Fig. 3 partly schemes for the TEM of nanoparticle after lyophilization, can see
The state unfolded is presented to shell.
Mode b): part dispersion liquid B is placed in 50 DEG C of oven dryings to constant weight, removal solvent, general
Recording water contact angle after polymer nano-particle masking is 96 °, shows as hydrophobicity, (b) of Fig. 3
Part is the TEM figure of dried nanoparticle on LCST, it can be seen that shell is rolled up, grain
Sub-volume diminishes.
Nanoparticle (the hydrophilic nanoparticle that mode a) precipitation prepares) after lyophilization is placed in
Being added dropwise over after stirring and dissolving in oxolane in 30mL water, ultrasonic disperse obtains stable polymer
Nanoparticle dispersion liquid, is placed in 80 DEG C of oven dryings to constant weight, removal solvent, general's polymerization by dispersion liquid
Recording water contact angle after thing nanoparticle masking is 105 °, shows as hydrophobicity.Realize nanoparticle
Changed to hydrophobicity by hydrophilic.
Embodiment 3
Weigh 10mg poly-(NIPA-b-styrene) block copolymer (NIPAM:St) in
In 50mL beaker, wherein polymer monomer mol ratio is NIPAM:St=1:1, NIPAM:St's
LCST is 37 DEG C.
In NIPAM:St, add 10mL oxolane, after stirring and dissolving, obtain solution A, dissolve
After be added dropwise in 30mL water, ultrasonic being allowed to is uniformly dispersed, and obtains stable polymer nano-particle
Dispersion liquid B.
Take part dispersion liquid B every time, carry out the precipitation of following four kinds of modes respectively:
Mode a): by freezing in fast transfer after part dispersion liquid B liquid nitrogen freezing to freezer dryer
It is dried 12h, removes solvent, be 52 ° by recording water contact angle after polymer nano-particle film forming, table
It it is now hydrophilic.
Mode b): to constant weight, part dispersion liquid B oven drying at 20 DEG C is removed solvent, will
Recording water contact angle after polymer nano-particle masking is 74 °, still shows as hydrophilic.
Mode c): to constant weight, part dispersion liquid B oven drying at 50 DEG C is removed solvent, will
Recording water contact angle after polymer nano-particle masking is 121 °, shows as hydrophobicity.
Mode d): to constant weight, part dispersion liquid B oven drying at 80 DEG C is removed solvent, will
Recording water contact angle after polymer nano-particle masking is 152 °, shows as hydrophobicity.
By the nanoparticle (the hydrophobic nano particle that mode c) is converted to) of oven drying at 50 DEG C
Being placed in oxolane and be added dropwise over after stirring and dissolving in 30mL water, ultrasonic disperse obtains stable gathering
Compound nanoparticle dispersion liquid, by fast transfer after dispersion liquid liquid nitrogen freezing to cold in freezer dryer
The dry 12h of lyophilizing, removes solvent, is 53 ° by recording water contact angle after polymer nano-particle film forming,
Show as hydrophilic；Achieve and hydrophobic nano particle is changed to hydrophilic.
Embodiment 4
Weigh 10mg poly-(NIPA-b-tert-butyl acrylate) block copolymer
(NIPAM:tBA) in 50mL beaker, wherein polymer monomer mol ratio is NIPAM:tBA=3:1,
LCST42 DEG C of NIPAM:tBA.
In NIPAM:tBA, add 10mL oxolane, after stirring and dissolving, obtain solution A, molten
Being added dropwise over after solution in 30mL water, ultrasonic being allowed to is uniformly dispersed, and obtains stable polymer nanoparticle
Sub-dispersion liquid B.
Take part dispersion liquid B every time, carry out the precipitation of following four kinds of modes respectively:
Mode a): by freezing in fast transfer after part dispersion liquid B liquid nitrogen freezing to freezer dryer
It is dried 12h, removes solvent, be 25 ° by recording water contact angle after polymer nano-particle film forming, table
It it is now hydrophilic.
Mode b): to constant weight, part dispersion liquid B oven drying at 20 DEG C is removed solvent, will
Recording water contact angle after polymer nano-particle masking is 57 °, still shows as hydrophilic.
Mode c): to constant weight, part dispersion liquid B oven drying at 50 DEG C is removed solvent, will
Recording water contact angle after polymer nano-particle masking is 98 °, shows as hydrophobicity.
Mode d): to constant weight, part dispersion liquid B oven drying at 80 DEG C is removed solvent, will
Recording water contact angle after polymer nano-particle masking is 106 °, shows as hydrophobicity.
Embodiment 5
Weigh 10mg poly-(NIPA-b-styrene/acrylic tert-butyl ester) block copolymerization
Thing (NIPAM:St:tBA) is in 50mL beaker, and wherein polymer monomer mol ratio is
The LCST of NIPAM:St:tBA=1:2:2, NIPAM:St:tBA is 34 DEG C.
Take part dispersion liquid B every time, carry out the precipitation of following four kinds of modes respectively:
Mode a): add 10mL oxolane in NIPAM:St:tBA, obtain after stirring and dissolving
Solution A, is added dropwise over after dissolving in 30mL water-ethanol (volume ratio 3:1), and ultrasonic being allowed to is disperseed
Uniformly, stable polymer nano-particle dispersion liquid B is obtained.
Mode b): by freezing in fast transfer after part dispersion liquid B liquid nitrogen freezing to freezer dryer
It is dried 12h, removes solvent, be 56 ° by recording water contact angle after polymer nano-particle film forming, table
It it is now hydrophilic.
Mode c): to constant weight, part dispersion liquid B oven drying at 20 DEG C is removed solvent, will
Recording water contact angle after polymer nano-particle masking is 77 °, still shows as hydrophilic.
Mode d): to constant weight, part dispersion liquid B oven drying at 80 DEG C is removed solvent, will
Recording water contact angle after polymer nano-particle masking is 134 °, shows as hydrophobicity.
Embodiment 6
By stirring and dissolving in hydrophobic nanoparticle oxolane prepared for embodiment 5 mode d)
After, it being added dropwise in 30mL water, ultrasonic disperse obtains dispersion liquid, by dispersion liquid baking oven at 30 DEG C
It is dried to constant weight, removes solvent, be 81 ° by recording water contact angle after polymer nano-particle masking,
Show as hydrophilic.After stirring and dissolving in this prepared hydrophilic nanoparticle oxolane,
Being added dropwise in 30mL water, after ultrasonic disperse, at 80 DEG C, oven drying, to constant weight, is removed molten again
Agent, is 144 ° by recording water contact angle after polymer nano-particle masking, the Polarity restoration of nanoparticle
To hydrophobicity.Regulated and controled by repeatedly precipitation, recover the hydrophobic performance of nanoparticle.
Claims (8)
1. a method for temperature sensing polymer nanoparticle hydrophilic/hydrophobic reversible transition, it is special
Levying and be, temperature sensing polymer nanoparticle is embedding by Thermo-sensitive hydrophilic monomer and vinyl hydrophobic monomer
Duan Gongju prepares, and described temperature sensing polymer nanoparticle is carried out one or many regulation and control, to realize
The reversible transition of hydrophilic/hydrophobic；Every time in regulation process, first described temperature sensing polymer is received
Rice corpuscles dissolves in good solvent, then adds the water as selective solvent or ethanol-water mixture,
Then any one precipitation of three kinds of modes below using:
A): with cryodesiccated mode precipitation below 0 DEG C, by described temperature sensing polymer nanometer
Particle regulates and controls into hydrophilic nanoparticle；
B): de-under the lowest critical solution temperature of temperature sensing polymer nanoparticle, on 0 DEG C
Molten, described temperature sensing polymer nanoparticle is regulated and controled into hydrophilic nanoparticle；
C): on the lowest critical solution temperature of temperature sensing polymer nanoparticle, Thermo-sensitive polymerization
Precipitation under thing nanoparticle decomposition temperature, regulates and controls into thin by described temperature sensing polymer nanoparticle
The nanoparticle of aqueous.
Temperature sensing polymer nanoparticle hydrophilic/hydrophobic the most according to claim 1 is reversible
The method changed, it is characterised in that described Thermo-sensitive hydrophilic monomer has shown in formula 1 or formula 2
Structural formula:
In formula 1: R1、R2Independently selected from H or C2～C5Aliphatic chain, and R1、R2Time different
For H；R3For H or CH3；
In formula 2: R4For C1～C5Aliphatic chain, R5、R6Independently selected from H or CH3。
Temperature sensing polymer nanoparticle hydrophilic/hydrophobic the most according to claim 2 is reversible
The method changed, it is characterised in that described vinyl hydrophobic comonomer has formula 3 or formula 4 institute
The structural formula shown:
In formula 3: R7For H, CH3Or C2H5；R8For phenyl, substituted-phenyl, CN or alkyl ether；
In formula 4: R9For H, CH3Or C2H5, X is C4～C18Aliphatic chain or the C of hydroxyl4～C18
Aliphatic chain.
Temperature sensing polymer nanoparticle hydrophilic/hydrophobic the most according to claim 3 is reversible
The method changed, it is characterised in that described Thermo-sensitive hydrophilic monomer is NIPA,
Described vinyl hydrophobic comonomer is octadecyl methacrylate, styrene, tert-butyl acrylate
In at least one.
Temperature sensing polymer nanoparticle hydrophilic/hydrophobic the most according to claim 4 is reversible
The method changed, it is characterised in that in temperature sensing polymer nanoparticle polymerization process, Thermo-sensitive parent
Aqueous monomer is 75:25～20:80 with the mol ratio of vinyl hydrophobic monomer.
Temperature sensing polymer nanoparticle hydrophilic/hydrophobic the most according to claim 5 is reversible
The method changed, it is characterised in that described good solvent is oxolane or acetone.
Temperature sensing polymer nanoparticle hydrophilic/hydrophobic the most according to claim 6 is reversible
The method changed, it is characterised in that the volume ratio of good solvent and selective solvent is 1:3～20.
Temperature sensing polymer nanoparticle hydrophilic/hydrophobic the most according to claim 7 is reversible
The method changed, it is characterised in that NIPA gathers with octadecyl methacrylate block
The lowest critical solution temperature of the Thermo-sensitive block copolymer formed after conjunction is 37～40 DEG C.
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| CN110465271A (en) * | 2019-08-22 | 2019-11-19 | 四川轻化工大学 | A kind of synthetic method and application of temperature control targeted capture material |
| CN114539494A (en) * | 2022-03-15 | 2022-05-27 | 阜阳师范大学 | Temperature-sensitive polymer-based temperature-sensitive plaster and preparation method thereof |
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| CN114539494A (en) * | 2022-03-15 | 2022-05-27 | 阜阳师范大学 | Temperature-sensitive polymer-based temperature-sensitive plaster and preparation method thereof |
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| CN105820354B (en) | 2018-07-31 |
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