CN103755954A - Thermosensitive type organic/inorganic hybrid dendrimers and preparation method thereof - Google Patents
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Abstract
The invention relates to thermosensitive type organic/inorganic hybrid dendrimers and a preparation method thereof. The hybrid dendrimers are prepared through chemical reaction between multifunctional polyhedral oligomeric silsesquioxane (POSS) with reaction activity and alcoxyl ether dendronized elements with reactive functional groups in nuclei. Compared with dendrimers of other types, the dendrimers have the beneficial effects that spherical polymers with plenty of peripheral groups can be obtained under the condition of low algebra, thus greatly reducing the synthesis difficulty of the dendrimers; meanwhile, the dendrimers endow materials with good thermosensitivity and biocompatibility; therefore, the dendrimers are expected to be applied to the fields such as drug controlled release, catalysis, intelligent materials and the like.
Description
Technical field
The present invention relates to a kind of hybrid dendritic macromole and preparation method thereof, particularly a kind of temperature sensitive type hybrid dendritic macromole and preparation method thereof.
Background technology
Dendritic macromole be a class from polyfunctional group kernel, by branch primitive repeated growth progressively, form the three-dimensional macromole of dendroid with highly branched structure.Compare dendritic macromole with traditional linear macromolecule and have following distinguishing feature: (1) dendritic macromole has clear and definite molecular weight and molecular dimension, compound with regular structure, molecular volume, shape and function base all can accurately be controlled on molecular level; (2) intramolecule has wide cavity, and molecular surface has high functional group densities; (3) unit molecule yardstick is at Nano grade.The constructional feature of dendritic macromole uniqueness makes it have good solubility, low melt viscosity and soltion viscosity, unique hydrodynamic performance and easy modified, thereby has a wide range of applications in the fields such as biological medicine, catalysis and photoelectric material.The route of synthesis of dendritic macromole has following two kinds conventionally: a kind of is the method for dispersing (Tomalia, D. A.; Baker, H.; Dewald, J.; Hall, M.; Kallos, G.; Martin, S.; Roeck, J.; Ryder, J.; Smith, P.
polym. J. (Tokyo, Jpn.) 1985,17,117), by epipole, set out, progressively introduce monomer, this kind of method can obtain the dendritic macromole that algebraically is high, molecular weight is large, and shortcoming is easily to produce defect, and is difficult for separating-purifying; Another kind is convergence method (Hawker, C. J.; Frechet, J. M. J.
j. Am. Chem. Soc. 1990,112,7638), first construct peripheral branch, then by epipole, connected, the advantage of the method is that defect is few, and it is separated that product and reactant are easy to, but progressively increases due to sterically hindered, and speed of reaction is slower.The people such as Zhang Afang are successfully designed and have been prepared a class alkyloxy-ethers branch primitive by simple and effectively synthesis path, and take that it has prepared serial branch fluidized polymer and dendritic macromole (Li, W. as unit; Zhang, A.; Schl ü ter, A. D.
chem. Commun. 2008, 5523; Li, W.; Zhang, A.; Chen, Y.; Feldman, K.; Wud, H.; Schl ü ter, A. D.
chem. Commun. 2008, 5948; Li, W.; Zhang, A.; Feldman, K.; Walde, P.; Schl ü ter, A. D.
macromolecules 2008,
41, 3659; Li, W.; Zhang, A.; Schl ü ter, A. D.
macromolecules 2008,
41, 43), research finds that this base polymer has good biocompatibility and temperature sensitive performance, by changing the hydrophilic and hydrophobic of the peripheral group of branch primitive algebraic sum, can realize regulation and control flexibly to its minimum critical gathering temperature range.This class alcoxyl ethers tree shaped polymer all has good solubility and outstanding biocompatibility in water and organic solvent, in fields such as medicine controlled releasing, organizational project and molecular switches, is with a wide range of applications.Although rich and varied dendritic macromole is reported (Duan, R. G. successively; Miller, L. L.; Tomalia, D. A.
j. Am. Chem. Soc. 1995, 117 10783; Furuta, P.; Fr é chet, J. M. J.
j. Am. Chem. Soc. 2003, 125,13173; Fern á ndez, G.; P é rez, E. M.; S á nchez, L.; Mart í n, N.
j. Am. Chem. Soc. 2008, 130 2410; Cheng, Y.; Zhao, L.; Li, Y.; Xu, T.
chem. Soc. Rev. 2011, 40,2673), the research field of dendritic macromole also exists synthetic difficult, synthetic cost high, be difficult to obtain the dendritic macromole of high molecular and high algebraically, and lack the problems such as functional, greatly restricted the development in this field and in the applied research of different directions.
(Polyhedral oligomeric silsesquioxane is called for short POSS, R to cage modle multiaspect oligomeric silsesquioxane
nsi
no
1.5n) size approximately 1 ~ 3 nanometer of molecule, its cagelike structure (Si: O=1: 1.5) similar to silicon-dioxide.Eight (or ten, or 12) individual summit of POSS cagelike structure can the organic active organic group of keyed jointing, becomes POSS organic functional monomer, forms multi-functional hybrid molecule.This unique texture has been given POSS can carry out hydridization with organism on molecular level; What is more important, the POSS of take prepares the globular macromolecule that dendritic macromole can just obtain having a large amount of peripheral groups when the low algebraically as core, thereby reduces the synthetic difficulty of dendritic macromole.Therefore, POSS base dendritic macromole arouses great concern.RuLu seminar (Kaneshiro, T. L.; Wang, X.; Lu, Z.-R.
mol. Pharm. 2007,4,759) prepared using PLL dendritic macromole that eight (3-aminopropyl) siloxanes is core and by it as gene delivery vector; Sichuan University turns round and look at loyal big teach problem group (Yuan, H.; Luo, K.; Lai, Y.; Pu, Y.; He, B.; Wang, G.; Wu, Y.; Gu, Z.
mol. Pharm. 2010,7,953) reported the POSS base PLGA dendritic macromole with pH response and target function; (Wang, the X. such as Wang; Ervithayasuporn, V.; Zhang, Y.; Kawakami, Y.
chem. Commun. 2011,47,1282) reported the reversible self-assembly behavior of POSS base crown ether dendritic macromole.Although increasing POSS base hydridization dendritic macromole is produced, up to now, the POSS base hydridization dendritic macromole with temperature-responsive also rarely has report.
Summary of the invention
The object of the present invention is to provide a kind of temperature sensitive type hybrid dendritic macromole.
Two of object of the present invention is to provide this macromolecular preparation method.
For achieving the above object, the present invention adopts following technical scheme:
A kind of temperature sensitive type hybrid dendritic macromole, it is characterized in that this dendritic macromole is that to take the oligomeric cage-type silsesquioxane of multiaspect (POSS) that periphery has a reactive functionality be kernel, with the shell of the alcoxyl ethers branch primitive of reactive functionality, react the hud typed dendritic macromole of generation with epipole, the mol ratio of its center and shell is: 1:8～12.
It is above-mentioned that to take the general formula that periphery has an oligomeric cage-type silsesquioxane POSS of multiaspect of reactive functionality be R '
n(SiO
1.5)
n, n=8～12, R ' is hydrogen, halogen, hydroxyl, vinyl, allyl group or amine propyl group.
Above-mentioned is that structural formula with the alcoxyl ethers branch primitive of reactive functionality is: RG
m, R=Me, Et, m=1,2; G
mrepresent that algebraically is the branch primitive of m.
One of the structural formula of the above-mentioned alcoxyl ethers branch primitive with reactive functionality is following, and wherein Z is COOPfP, and PfP is pentafluranol, CH
2cOOCH=CH
2or COOH.
a.
b.
A kind of method of preparing above-mentioned temperature sensitive type hybrid dendritic macromole, the concrete steps that it is characterized in that the method are: periphery is had to the oligomeric cage-type silsesquioxane of multiaspect of reactive functionality and with the alcoxyl ethers branch primitive of reactive functionality ,-30
oc～90
oC, in solution system, after addition, replacement, amidation coupling, esterification or click reaction 0.5～48 h, obtain POSS base hydridization dendritic macromole; The POSS wherein with reactive behavior is 1: 1.2～2.0 with the ratio of active function groups with the alkyloxy-ethers branch primitive of reactive behavior.
According to POSS base hydridization method for preparing dendritic macromolecule claimed in claim 1, it is characterized in that: solvent for use is methyl alcohol, ethanol, normal hexane, benzene,toluene,xylene, 1,4-dioxane, one or more in DMF, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), methylene dichloride, chloroform.
By epipole, with the alkyloxy-ethers branch primitive of reactive functionality and the oligomeric silsesquioxane containing active group, in solution system, there is chemical reaction in the present invention, the temperature sensitive type hybrid dendritic macromole obtaining is by peripheral alcoxyl ethers branch primitive and the oligomeric cage-type silsesquioxane of multiaspect (Polyhedral oligomeric silsesquioxane, be called for short POSS) kernel formation, resulting materials has good temperature sensitive performance, and can regulate and control its minimum critical solution temperature (LCST).Such material can be widely used in medicine and control the fields such as release, catalysis and intelligent material.
POSS base hydridization dendritic macromole of the present invention has temperature response behavior, and its minimum critical solution temperature (LCST) is at 30-70
oc.This type of hydridization dendritic macromole has structure and the performance characteristics of POSS and dendritic macromole uniqueness concurrently, also has temperature sensitive intelligent characteristic simultaneously, and there is important using value in the fields such as release, catalysis and intelligent material of controlling at medicine.
Beneficial effect:
(1) the present invention can obtain a series of POSS base hybrid dendritic macromoles with temperature sensitive performance by the method for chemical reaction.
(2) by the introducing of polyfunctional group POSS, take it as epipole, convergence method and the method for dispersing combine and prepare dendritic macromole, can when low algebraically, just obtain having the globular macromolecule of a large amount of peripheral groups, thereby greatly reduce the synthetic difficulty of dendritic macromole.
Accompanying drawing explanation
Fig. 1. the epipole in the embodiment of the present invention is the structural representation of the branch primitive of pentafluranol active ester
Fig. 2. the peripheral functional group in the embodiment of the present invention is the synthetic route schematic diagram that amino cage modle is doubly done siloxanes
Fig. 3. the POSS in the embodiment of the present invention
8-EtG
1and POSS
8-EtG
2synthetic route schematic diagram
Fig. 4. POSS
8-EtG
1's
1h NMR spectrogram (CDCl
3, 500MHz)
Fig. 5. POSS
8-EtG
2's
1h NMR spectrogram (CDCl
3, 500MHz)
Fig. 6. POSS
8-EtG
1and POSS
8-EtG
2at aqueous medium solution transmittance, vary with temperature curve (c=0.25%, 500 nm, heating and cooling speed 0.2
oc/min)
Fig. 7. POSS
8-EtG
1and POSS
8-EtG
2the LCST of the aqueous solution is with the change curve of concentration
Fig. 8. 0.05% POSS
8-EtG
1and POSS
8-EtG
2the aggregate size variation with temperature curve of the aqueous solution
Fig. 9. the synthetic route schematic diagram of the embodiment of the present invention three.
Embodiment
Below in conjunction with specific examples, the present invention is further elaborated, but these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's elaboration, these equivalent form of values fall within the application's appended claims limited range equally.
All peripheries have the oligomeric cage-type silsesquioxane of multiaspect of reactive functionality and epipole to be had commercially available with the alcoxyl ethers branch primitive of reactive functionality? or prepare according to reference? or homemade? if according to reference.Please provide reference.If homemade, please provide step.(reference provides in experimental procedure)
Very little, every kind of product should have corresponding embodiment to provide to the embodiment below providing.(supplementing an embodiment, is that the functional group of POSS and the epipole of branch primitive can be reacted in fact again, can prepare hydridization dendritic macromole, has multiple combination mode, and Tong Guo the esterification of namely saying above, amidation or click chemistry reaction realize)
embodiment 1:
The present invention relates to POSS
8-EtG
1preparation synthetic.Synthetic route is with reference to figure 1-3.
1.1 epipoles be pentafluranol active ester generation ethoxy ether branch primitive (
1b) synthetic
The generation ethoxy ether branch primitive that is carboxyl by epipole
1a(2.30 g, 3.50 mmol, reference literature Li, W.; Zhang, A.; Schl ü ter, A. D.
chem. Commun. 2008, 5523 and Yan J T; Li W; Liu K; Wu D L; Chen F; WuP Y; Zhang A. Chem. Asian J. 2011,6,3260 is synthetic) and pentafluranol (0.97 g, 5.3 mmol) be dissolved in the methylene dichloride that 30 mL are dry and in-15
oc stirs 10 minutes, then in solution, adds 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (0.81 g, 4.23 mmol).Mixing solutions is used respectively saturated sodium bicarbonate solution and saturated common salt water washing after at room temperature stirring 12 h, and organic phase anhydrous magnesium sulfate drying filters.Filtrate obtains colourless oil liquid (2.75 g, 74%) through concentrating under reduced pressure by silica gel chromatographic column separated (eluent DCM/MeOH, v/v=30:1).
1.2 8 (2-amino ethylmercapto group) ethyl) silsesquioxane hydrochloride (
3)synthetic
Eight vinyl silsesquioxanes (1.27 g, 2 mmol) and 2-aminoothyl mercaptan hydrochloride (9.0 g, 79.2 mmol) are dissolved in DMF/tetrahydrofuran (THF) (6:1) mixing solutions, under catalytic amount AIBN exists in 65
oc reaction 4 hours.After reaction finishes, by sedimentation and filtration, gained precipitation is dissolved in a small amount of methyl alcohol, and dropwise splashes in tetrahydrofuran (THF) and precipitate, and so precipitation-dissolving obtains white solid three times
3(2.40 g, 80%).
1H?NMR?(DMSO):?δ?=?8.29?(s,?24H,?N
H 2.
HCl),?3.01?(t,?16H,?C
H 2NH
2·HCl),?2.88?(t,?16H,?C
H 2?CH
2NH
2·HCl),?2.69?(t,?16H,?SiCH
2C
H 2S),?1.09?(t,?16H,?SiC
H 2).
1.3 POSS
8-EtG
1synthetic
-30
ounder C condition in 15 minutes by compound
3after being dissolved in methyl alcohol (2 mL), (0.10 g, 0.07 mmol) and triethylamine (0.68 g, 6.77 mmol) dropwise add
1bin methylene dichloride (5 mL) solution of (0.80 g, 0.98 mmol).Mixing solutions continues at room temperature to stir 12 hours.After stopped reaction, use successively saturated sodium bicarbonate and saturated common salt water washing, organic phase anhydrous magnesium sulfate drying, filters.Filtrate obtains colourless oil liquid (0.25 g, 57%) through concentrating under reduced pressure by silica gel chromatographic column separated (eluent DCM/MeOH, v/v=30:1).
1H?NMR?(500?MHz,?DMSO):?δ?=?8.18(s,?1H,?NH),?7.17?(s,?2H,?Ar-H),?4.14?~4.10?(m,?6H,?CH
2),?3.76~3.70?(m,?6H,?CH
2),?3.60~3.42?(m,?32H,?CH
2),?2.72?(br,?4H,?CH
2),?1.11~1.07?(m,?11H,?CH
2?+CH
3)
embodiment 2:
The present invention relates to POSS
8-EtG
2preparation synthetic.Synthetic route is with reference to figure 1-3.
2.1 epipoles be pentafluranol active ester two generation ethoxy ether branch primitive (
2b) synthetic
By epipole, be carboxyl two generation ethoxy ether branch primitive
2a(2 g, 0.84 mmol, reference literature Li, W.; Zhang, A.; Schl ü ter, A. D.
chem. Commun. 2008, 5523 and Yan J T; Li W; Liu K; Wu D L; Chen F; WuP Y; Zhang A. Chem. Asian J. 2011,6,3260 is synthetic) and pentafluranol (0.24 g, 1.30 mmol) be dissolved in the methylene dichloride that 20 mL are dry and in-15
oc stirs 10 minutes, then in solution, adds 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (0.20 g, 0.98 mmol).Mixing solutions is used respectively saturated sodium bicarbonate solution and saturated common salt water washing after at room temperature stirring 12 h, and organic phase anhydrous magnesium sulfate drying filters.Filtrate obtains colourless oil liquid (2.00 g, 70%) through concentrating under reduced pressure by silica gel chromatographic column separated (eluent DCM/MeOH, v/v=30:1).
2.2 POSS
8-EtG
2synthetic
-30
ounder C condition in 15 minutes by compound
3after being dissolved in methyl alcohol (1 mL), (0.05 g, 0.033 mmol) and triethylamine (0.34 g, 3.38 mmol) dropwise add
2bin methylene dichloride (5 mL) solution of (1.26 g, 0.49 mmol).Mixing solutions continues at room temperature to stir 12 hours.After stopped reaction, use successively saturated sodium bicarbonate and saturated common salt water washing, organic phase anhydrous magnesium sulfate drying, filters.Filtrate obtains colourless oil liquid (0.2 g, 30%) through concentrating under reduced pressure by silica gel chromatographic column separated (eluent DCM/MeOH, v/v=30:1).
1H?NMR?(500?MHz,?DMSO):?δ?=?8.20?(s,?1H,?NH),?7.16?(s,?2H,?Ar-H),?6.60?(s,?6H,?Ar-H),?4.37?(s,?6H,?CH
2),?4.11~4.02?(m,?24H,?CH
2),?3.74~3.68?(m,?24H,?CH
2),?3.60~3.52?(m,?118,?CH
2),?2.73?(br,?4H,?CH
2),?1.11~1.07?(m,?29?H,?CH
2?+CH
3)。
POSS
8-EtG1 and POSS
8-EtG2 is in room temperature or lower than all water-soluble under room temperature condition, but the aqueous solution of clarifying when being heated to a certain specified temp becomes muddy, shows POSS
8-EtG1 and POSS
8-EtG2 all has temperature sensitive performance.Use alternating temperature ultraviolet-visible spectrum to characterize its temperature response behavior, the results are shown in accordingly Fig. 6.As can be seen from the figure, POSS
8-EtG1 and POSS
8the minimum critical solution temperature (LCST) of-EtG2 is respectively 37 and 40
oC, with document (Li W.; Zhang A.; Chen Y.; Feldman K., Wud H. and Schl ü ter A. D.,
chem. Commun. 2008, 5948) and the dendritic macromole of the corresponding algebraically that is core with 1,1,1-trihydroxy-phenyl ethane of report compares, and exceeds respectively 10
oc and 1
oc.The ratio that this difference derives from the close and distant water base unit in molecular structure is different, and the ratio of the peripheral alkyloxy-ethers of the POSS base hydridization dendritic macromole of same algebraically is much higher, and the wetting ability of molecule increases, so LCST raises.Meanwhile, the LCST of hydridization dendritic macromole obviously reduces algebraically dependency.In addition, from figure, curve it can also be seen that, below LCST, the transmitance of solution approaches 100%, and more than LCST, transmitance is almost 0, and after showing to heat phase transformation and assembling, can be large enough to can be to scattering of light for the size of aggregate; The phase transition process of two kinds of hydridization dendritic macromoles is very fast, and the temperature range of whole process is respectively 0.4 and 0.8
oc, and the very little (<0.9 of lag-effect
oc), show that temperature sensitive process has good reversibility.To different concns POSS
8-EtG1 and POSS
8the LCST of-EtG2 investigates, and result as shown in Figure 7.Along with POSS
8-EtG1 and POSS
8the concentration of-EtG2 is increased to 2% from 0.025% gradually, and their LCST is respectively from 39 and 42
oc drops to 35 and 38
oc, temperature variation interval is only 4
oc, shows that the LCST of both aqueous solution is less to the dependency of concentration.The change procedure that utilizes dynamic light scattering method detection molecules size, the results are shown in Fig. 8.Can find out, in temperature-rise period, when temperature is lower than 39
oCtime, POSS
8the dimensional stabilizing of-EtG1 is in 3 nm effects, when temperature rises to 39
oCtime, molecular dimension sharply increases to 2000 nm, shows intermolecular dehydration, subsides and cause to assemble.Further rising temperature, aggregate size is finally stabilized in 1700 nm left and right.POSS
8the characterization result of-EtG2 is similar, with POSS
8-EtG1 is different is that the size of its aggregate is relatively little, and this is mainly due to POSS
8the wetting ability of-EtG2 molecule causes more by force.
Synthetic route of the present invention is with reference to figure 9.
The branch primitive of the two keys of epipole band synthetic: will be dissolved with dry methylene chloride (10 mL) solution of 1 ~ 1.5mmol acrylate chloride, drop to be dissolved with the generation that 1mmol epipole is benzylalcohol (
1a) or two generations (
2a) ethoxy ether branch primitive, in dry DCM (100 mL) solution of triethylamine (3 ~ 4.5 mmol) and DMAP (0.3 ~ 0.45 mmol), in dropping process, keeping ice bath temperature is 0
oC, after half an hour, remove ice bath, more at room temperature continue to stir 4 h, rear dropping methyl alcohol termination reaction.Reaction solution is used saturated NaHCO successively
3solution and saturated NaCl solution washing, use anhydrous MgSO after separatory
4dry organic phase, filters.Recycle silicon plastic column chromatography is purified, and developping agent is DCM/MeOH (30:1, v/v), obtain colorless oil (
1b or
2b).
The POSS that the peripheral functional group of getting 0.424 g (1 mmol) is hydrogen, i.e. T
8h
8(commercially available), the branch primitive of the two keys of epipole band of 10 mmol (
1b or
2b), a little Pt(dcp) catalyzer is placed in Schlenk pipe, takes out inflated with nitrogen three times, and each 15 min, complete after above operation, keep nitrogen atmosphere, and Xiang Guanzhong injects dry Isosorbide-5-Nitrae-dioxane 20 mL, in 80
oc reacts 10 h.After having reacted, reaction solution is concentrated, through silica gel chromatographic column separation obtain colourless viscous liquid (
pOSS 8 -RG n).
Claims (6)
1. a temperature sensitive type hybrid dendritic macromole, it is characterized in that this dendritic macromole is that to take the oligomeric cage-type silsesquioxane of multiaspect (POSS) that periphery has a reactive functionality be kernel, with the shell of the alcoxyl ethers branch primitive of reactive functionality, react the hud typed dendritic macromole of generation with epipole, the mol ratio of its center and shell is: 1:8～12.
2. temperature sensitive type hybrid dendritic macromole according to claim 1, is characterized in that described to take the general formula that periphery has an oligomeric cage-type silsesquioxane POSS of multiaspect of reactive functionality be R '
n(SiO
1.5)
n, n=8～12, R ' is hydrogen, halogen, hydroxyl, vinyl, allyl group or amine propyl group.
3. temperature sensitive type hybrid dendritic macromole according to claim 1 is that the structural formula with the alcoxyl ethers branch primitive of reactive functionality is described in it is characterized in that: RG
m, R=Me, Et, m=1,2; G
mrepresent that algebraically is the branch primitive of m.
4. temperature sensitive type hybrid dendritic macromole according to claim 3, is characterized in that the structural formula of the described alcoxyl ethers branch primitive with reactive functionality is one of following, and wherein Z is COOPfP, and PfP is pentafluranol, CH
2cOOCH=CH
2or COOH;
a.
b.
。
5. prepare according to the method for the temperature sensitive type hybrid dendritic macromole described in claim 1-4 for one kind, the concrete steps that it is characterized in that the method are: periphery is had to the oligomeric cage-type silsesquioxane of multiaspect of reactive functionality and with the alcoxyl ethers branch primitive of reactive functionality ,-30
oc～90
oC, in solution system, after addition, replacement, amidation coupling, esterification or click reaction 0.5～48 h, obtain POSS base hydridization dendritic macromole; The POSS wherein with reactive behavior is 1: 1.2～2.0 with the ratio of active function groups with the alkyloxy-ethers branch primitive of reactive behavior.
6. according to POSS base hydridization method for preparing dendritic macromolecule claimed in claim 1, it is characterized in that: solvent for use is methyl alcohol, ethanol, normal hexane, benzene,toluene,xylene, 1,4-dioxane, one or more in DMF, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), methylene dichloride, chloroform.
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| CN108484797A (en) * | 2018-06-18 | 2018-09-04 | 上海大学 | Alkyloxy-ethers poplar bundles chitosan, its hydrogel material and preparation method thereof |
| CN111826153A (en) * | 2020-06-08 | 2020-10-27 | 上海大学 | Temperature-sensitive amphiphilic dendritic macromolecule based on tetraphenylethylene and preparation method thereof |
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| CN105131303B (en) * | 2015-05-05 | 2018-03-06 | 上海大学 | Intelligent poplar bundles polyalcohol hydrogel and preparation method thereof |
| CN105906765A (en) * | 2016-07-02 | 2016-08-31 | 上海大学 | Alkoxy ether thermosensitive chiral polymer nano-microspheres and preparation method thereof |
| CN105906765B (en) * | 2016-07-02 | 2018-06-01 | 上海大学 | Temperature sensitive chiral polymer nanoparticle of alcoxyl ethers and preparation method thereof |
| CN108484797A (en) * | 2018-06-18 | 2018-09-04 | 上海大学 | Alkyloxy-ethers poplar bundles chitosan, its hydrogel material and preparation method thereof |
| CN108484797B (en) * | 2018-06-18 | 2020-12-15 | 上海大学 | Alkoxy ether branched chitosan, hydrogel material thereof and preparation method thereof |
| CN111826153A (en) * | 2020-06-08 | 2020-10-27 | 上海大学 | Temperature-sensitive amphiphilic dendritic macromolecule based on tetraphenylethylene and preparation method thereof |
| CN111826153B (en) * | 2020-06-08 | 2022-11-22 | 上海大学 | Temperature-sensitive amphiphilic dendritic macromolecule based on tetraphenylethylene and preparation method thereof |
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