CN108948231A - A kind of water-soluble poly rotaxane crosslinking agent and preparation method thereof - Google Patents
A kind of water-soluble poly rotaxane crosslinking agent and preparation method thereof Download PDFInfo
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- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
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- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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Abstract
The invention discloses a kind of preparation methods of water-soluble poly rotaxane crosslinking agent, include the following steps: 1): alpha-cyclodextrin being carried out the modified introducing double bond of itaconic anhydride and carboxylic acid structure, obtains modified alpha-cyclodextrin；2): the hydroxyl at polyethylene glycol both ends being oxidized to carboxylic acid, obtains modified poly (ethylene glycol) chain；3): on the modified poly (ethylene glycol) chain that modified alpha-cyclodextrin is prepared through second step, then by modified poly (ethylene glycol) chain two ends sealed, preparing water-soluble poly rotaxane crosslinking agent.The present invention is modified to introduce carboxylic acid group by alpha-cyclodextrin, and preparing polyrotaxane crosslinking agent has significant water solubility, therefore can prepare hydrogel with water-soluble monomers cross-linked polymerics such as acrylamide, acrylic acid, improves the deformability of hydrogel.
Description
Technical field
The invention belongs to crosslinking agent preparation technical fields, and in particular to a kind of water-soluble poly rotaxane crosslinking agent and its preparation side
Method.
Background technique
Hydrogel be it is a kind of through it is appropriately crosslinked to three-dimensional net structure high molecular material, because of its unique water suction
Property, water-retaining property and bionical characteristic, be widely used in the fields such as industry, agricultural, medicine and biological engineering material.
The synthesis of hydrogel is crosslinked with traditional chemical cross-linking agent at present, what traditional chemical cross-linking agent referred to
That there are in a molecular formula two or more double bonds, double bond participation is aggregated in form network structure during, by
There is randomness in cross-linking process, inevitably lead to crosslinking points and be unevenly distributed in gel space, so that each crosslinking points
Between polymer segment it is different in size.And chemical crosslinking point is fixed, therefore polymer segment stress under external force
Unevenly, short segment stress is big, is easily first broken, and whole network structure is caused to be destroyed.This results in the gel prepared crisp
Property is big, and deformability is poor.
ZL201710929543.5 discloses a kind of universal gel-like polyrotaxane crosslinking agent and preparation method thereof, the crosslinking
Agent can prepare gel with polymerisable monomer crosslinking, crosslinking points be not it is fixed, crosslinking points can be slided along polymer chain, be generated
" slide effect " makes external force be evenly dispersed each segment and then is dispersed to whole network, hands over to preferably solve chemistry
Connection point is in the non-uniform problem of spatial distribution.This polyrotaxane crosslinking agent is soluble in organic solvent, is relatively suitable for preparing oleogel,
But solubility in water is limited, only has 0.6713g/100g water (20 DEG C) through test measurement, belongs to slightly soluble substance, limit
It implements the application that water-soluble monomer crosslinking prepares hydrogel in aqueous solution.
Summary of the invention
In order to solve the above technical problems, the purpose of the present invention is to provide a kind of water-soluble poly rotaxane crosslinking agent and its preparations
Method.
For achieving the above object, technical solution as described below is specifically provided:
1, a kind of preparation method of water-soluble poly rotaxane crosslinking agent, includes the following steps:
1): alpha-cyclodextrin being subjected to the modified introducing double bond of itaconic anhydride and carboxylic acid structure, obtains modified alpha-cyclodextrin；
2): the hydroxyl at polyethylene glycol both ends being oxidized to carboxylic acid, obtains modified poly (ethylene glycol) chain；
3): on the modified poly (ethylene glycol) chain that modified alpha-cyclodextrin is prepared through second step, then by modified poly (ethylene glycol)
Chain two ends sealed prepares water-soluble poly rotaxane crosslinking agent.
Further, step 1) the modified alpha-cyclodextrin is prepared as follows:
Step A: alpha-cyclodextrin, itaconic acid are dissolved in the reactor equipped with dehydrated alcohol, are then placed in reactor
It is dried in drying box；
Step B: reactor is taken out and it is a little in thick yellow liquid to be heated to reactant, then reactor is placed in dry
Liquid is evaporated in dry device；
Step C: dehydrated alcohol is further added into reactor and stirs evenly, is taken out using 0.45um miillpore filter
Consider to obtain solid, light yellow powder solid is dried to obtain in filtered solid.
Further, step 1) the modified alpha-cyclodextrin is prepared as follows:
Step A: 1.9~2g alpha-cyclodextrin, 0.1~0.2g itaconic acid are dissolved in the reaction equipped with 250ml dehydrated alcohol
In device, reactor is then placed in drying box dry 130min under the conditions of 110 DEG C；
Step B: reactor is taken out and is heated to boiling, and after constantly boiling 30min, reactant is in thick Huang in reactor
Color liquid is a little, then reactor is placed in drier and is evaporated liquid；
Step C: being further added into reactor and 50ml dehydrated alcohol and stir evenly, using 0.45um miillpore filter into
Row filters to obtain solid, then is washed with dehydrated alcohol, and 9h is dried under the conditions of 100 DEG C of temperature in filtered solid, is obtained shallowly
Yellow powdery solid.
Further, the step 2) method for oxidation are as follows: by polyethylene glycol, tetramethyl piperidine nitrogen oxides, NaBr and NaClO
It sequentially adds in distilled water, adjusting pH value is 10-11, reacts 10-15min under room temperature, and ethyl alcohol is then added and stops oxidation, and adjusts
CH is used after section pH < 22Cl2Extraction, takes subnatant, which is dried in vacuo up to the modified poly (ethylene glycol) chain.
Further, step 2) further includes recrystallization, and resulting modified poly (ethylene glycol) chain is dissolved in 50- after vacuum drying
It recrystallizes in 60 DEG C of ethyl alcohol, is dried in vacuo again.
Preferably, the mass ratio of the polyethylene glycol, tetramethyl piperidine nitrogen oxides and NaBr is 100:1:1；It is described
The mass volume ratio (g/ml) of NaBr and NaClO is 10:1.
Further, step 3) described the step of running through and blocking are as follows: weigh modified alpha-cyclodextrin and modified poly (ethylene glycol) chain
It being dissolved in distilled water, refrigerated overnight obtains white complex compound, by the white complex compound and 1- amantadine, block special condensing agent, N,
N- diisopropylethylamine adds to N together, in N- dimethylformamide and is uniformly mixed white slurries, by the white slurries 0~
Milky slurries are obtained at 10 DEG C overnight, then by milky slurries and methanol mixing centrifuge washing twice after, then it is anti-with distilled water
After backwashing is washed, and is filtered and is dried in vacuo to obtain water-soluble poly rotaxane crosslinking agent.
Preferably, it is 3.8~4.2:1 that modified alpha-cyclodextrin and modified poly (ethylene glycol) chain, which weigh mass ratio,.
It is further preferred that the white complex compound and 1- amantadine, block special condensing agent, n,N-diisopropylethylamine,
The addition mass ratio (g:g:g:ml:ml) of N, N- dimethylformamide are as follows: 0.5~0.7:0.01~0.02:0.04~0.05:
0.01~0.03:9~12.
2, the water-soluble poly rotaxane crosslinking agent obtained by the preparation method.
The beneficial effects of the present invention are: the invention discloses a kind of preparation methods of water-soluble poly rotaxane crosslinking agent, lead to
It crosses and alpha-cyclodextrin is subjected to the modified introducing double bond of itaconic anhydride and carboxylic acid structure structure；The hydroxyl at polyethylene glycol both ends is oxidized to
Carboxylic acid；On the modified poly (ethylene glycol) chain that the modified cyclodextrin of preparation is prepared through second step, then by modified poly (ethylene glycol) chain
Two ends sealed prepares polyrotaxane crosslinking agent.
Due to alpha-cyclodextrin it is modified in introduce carboxylic acid group, enhance the water solubility of polyrotaxane, thus can and propylene
The water-soluble monomers cross-linked polymeric such as amide, acrylic acid prepares hydrogel, improves the deformability of hydrogel.
Detailed description of the invention
Fig. 1 is the modifying process schematic diagram of alpha-cyclodextrin；
Fig. 2 is the oxidation process schematic diagram of polyethylene glycol；
Fig. 3 is the preparation process schematic diagram of water-soluble poly rotaxane crosslinking agent；
Fig. 4 is the nuclear magnetic resonance H spectrogram of itaconic acid, alpha-cyclodextrin, modified alpha-cyclodextrin；
Fig. 5 is polyethylene glycol, the nuclear magnetic resonance H spectrogram for aoxidizing polyethylene glycol；
Fig. 6 is the infrared spectrogram of water-soluble poly rotaxane crosslinking agent；
Fig. 7 is that the nuclear magnetic resonance H of water-soluble poly rotaxane crosslinking agent is composed；
Fig. 8 is the X-ray diffraction spectrogram of water-soluble poly rotaxane crosslinking agent；
Fig. 9 is that conventional cross-linking agent prepares form photo before and after gel stress；
Figure 10 is that water-soluble poly rotaxane crosslinking agent prepares form photo before and after gel stress.
Specific embodiment
More detailed elaboration is carried out to the present invention below in conjunction with specific embodiments and drawings.
Raw material needed for following embodiment and abbreviation are as follows: alpha-cyclodextrin (α-CD), polyethylene glycol (PEG), sodium hypochlorite
(NaClO), acrylamide, dimethyl sulfoxide (DMSO), tetramethyl piperidine nitrogen oxides (TEMPO), 1- amantadine, N, N- bis-
Methyl nitrosourea (DMF), n,N-diisopropylethylamine (EDIPA) block special condensing agent (bop reagent) etc..
Embodiment
One, test specimen is prepared
A kind of preparation of water-soluble poly rotaxane crosslinking agent:
1) preparation of modified alpha-cyclodextrin: being added 250ml dehydrated alcohol in beaker, add 1.9909g α-CD and
0.1348g itaconic acid stirs 30min, 130min in 110 DEG C of drying box is put into after being completely dissolved, then beaker is taken out, and uses
It is heated to boiling, it is a little in thick yellow liquid in beaker after constantly boiling 30min.Beaker is put into liquid in drying box again
Body is evaporated.50ml dehydrated alcohol is poured into, is filtered using 0.45um miillpore filter, then is washed with a small amount of dehydrated alcohol, will be taken out
Solid after filter is put into 100 DEG C of drying box dry 9h, obtains light yellow powder solid, as modified alpha-cyclodextrin (letter
Claim modified alpha-CD), reaction process is as shown in Figure 1；
2) oxidation of polyethylene glycol: 0.1002gTEMPO, 0.1013gNaBr is added in distilled water and is stirred well to two kinds
Substance is completely dissolved, and 10.0468gPEG is added thereto, and 15min is reacted in 10mLNaClO stirring at room temperature.Add 10mL second
Alcohol stops oxidation, is adjusted to pH < 2 with HCl, and use CH2Cl2Extraction three times, is dissolved in the hot second of 125mL after taking subnatant to merge
In alcohol, it is put into refrigerator overnight.40 DEG C of vacuum drying 20h are taken out, the polyglycol chain of white, reaction process such as Fig. 2 institute are obtained
Show；
3) modified alpha-cyclodextrin is through polyglycol chain, and blocks: 0.6002g modified alpha-CD and 0.1503g being taken to aoxidize
PEG is dissolved in 10mL distilled water, is white liquid after dissolution.The mixed liquor of dissolution is put into refrigerator and keeps overnight, obtaining
0.6931g white complex compound.By complex compound and 0.0166g 1- amantadine, 0.0482g card spy's condensing agent (bop reagent),
0.02mL n,N-diisopropylethylamine (EDIPA) is dissolved in 10mL DMF, observes mixed liquor for white slurries.Mixing slurry
At 0~10 DEG C of liquid overnight, it is milky slurries that refrigerator mixed liquor is taken out after staying overnight, then twice with methanol filtering and washing, vacuum
It is dried to obtain the white polyrotaxane crosslinking agent of 0.1415g, i.e. water-soluble poly rotaxane crosslinking agent, the process that reacts is as shown in Figure 3.
Two, the characterization of raw material, intermediary and product
Polyglycol chain and process after taking alpha-cyclodextrin, itaconic acid, modification alpha-cyclodextrin, polyethylene glycol, oxidation is upper
The water-soluble poly rotaxane crosslinking agent for stating test example preparation carries out the characterization such as nuclear magnetic resonance H spectrum, infrared spectroscopy.
1) characterization of modified alpha-CD
Solvent, which is made, using deuterated DMSO uses nuclear magnetic resonance means characterization itaconic acid, alpha-cyclodextrin, modified alpha-cyclodextrin, knot
Fruit is as shown in Figure 4.
Spectral line A is the spectrogram of itaconic acid in Fig. 4, is the chemical shift of itaconic acid methylene hydrogen atom at 3.15ppm,
5.63ppm be respectively the chemical shift of two hydrogen atoms that itaconic acid double-linked carbon is connected at 6.11ppm.Spectral line B is α-
The spectrogram of cyclodextrin.Spectral line C is the spectrogram of modified alpha-cyclodextrin, which hydrogen also occurs at 3.15,5.63 and 6.11ppm
The chemical shift peak of atom shows the chemical structure in modified alpha-cyclodextrin structure there are itaconic acid, that is, is modified successfully.
2) characterization of the polyglycol chain after aoxidizing:
Solvent, which is made, using deuterated DMSO uses the polyglycol chain after nuclear magnetic resonance means characterization polyethylene glycol, oxidation, knot
Fruit is as shown in Figure 5:
Spectral line A is the spectrogram of polyethylene glycol in Fig. 5, is the chemical potential of alcoholic extract hydroxyl group hydrogen atom in polyethylene glycol at 2.51ppm
It moves, the chemical shift of polyethylene glycol methylene hydrogen atom at 3.41-3.56ppm.Spectral line B is the polyglycol chain after oxidation
Spectrogram compares spectral line A, newly hydrogen atom peak occurs at 3.98ppm, for the methylene hydrogen being connected directly after oxidation with carboxylic acid group
The chemical shift of atom, and the peak at 2.51ppm disappears, and shows that alcoholic extract hydroxyl group hydrogen atom is not present in oxidation polyglycol chain,
That is the terminal hydroxy group of polyethylene glycol is all oxidized to carboxylic acid.
3) characterization of water-soluble poly rotaxane crosslinking agent
Infrared spectrum characterization: the infrared spectrogram of gained water-soluble poly rotaxane crosslinking agent, such as Fig. 6 are prepared by above-described embodiment
It is shown, 3400cm in figure-1Wide absorption peak at position may be the stretching vibration peak of amido N-H key or sour hydroxyl O-H key,
2931cm-1It may be the vibration absorption peak for the c h bond being connected with double key carbon, 1638cm at position-1It may be bis- for C=C at position
The stretching vibration peak of key, 1148cm-1It may be the asymmetric stretching vibration peak of C-O-C key at position, it can be seen that in crosslinking agent
There is absorption peak in infrared spectrum in main characteristic group.
Nuclear magnetic resonance H stave sign: solvent is done with heavy water and characterizes water-soluble poly rotaxane crosslinking agent using nuclear magnetic resonance means, such as
It is on cyclodextrin molecular shown in Fig. 7, at 3.81-3.89ppm, 3.66-3.80ppm and 3.41-3.52ppm from different location
Hydrogen atom chemical shift, but should be the chemical shift of polyethylene glycol structures methylene hydrogen atom at 3.54-3.61ppm,
Not only there is cyclodextrin structure in the crosslinking agent but also there are polyethylene glycol structures.It should be noted that hydrogen in Fig. 7 cyclodextrin molecule
Atom chemistry displacement and the chemical shift of polyethylene glycol structures methylene hydrogen atom have some offsets compared with Fig. 4, Fig. 5,
Because having used different solvents.
X-ray diffraction characterization: characterization result shows as shown in figure 8, there is apparent diffracted signal at 20 ° or so
Modified cyclodextrin and modified poly (ethylene glycol) form inclusion compound, and it is tunnel-like structures that crystal, which piles up type,.
Three, water-soluble test
By universal gel disclosed in water-soluble poly rotaxane crosslinking agent manufactured in the present embodiment and ZL201710929543.5
Class polyrotaxane crosslinking agent carries out water-soluble test and comparison, obtains result as shown in Table 1:
The water-soluble testing experiment data of table 1
Can significantly be illustrated by 1 test data of table, the solubility of polyrotaxane crosslinking agent prepared by the present invention in water compared to
Universal gel-like polyrotaxane crosslinking agent has the raising of highly significant.
Four, water-soluble poly rotaxane crosslinking agent, universal polyrotaxane crosslinking agent are used to prepare application and the performance test of gel:
70g distilled water and 14g acrylamide are separately added into two beakers, then each be added accounts for monomer mass 0.2%
V50, is separately added into conventional cross-linking agent N, and N '-methylene-bisacrylamide and novel crosslinker respectively account for the 0.5% of monomer mass, 70
4h is reacted at DEG C, obtained product is dried in vacuo 16h at 70 DEG C simultaneously.
Taking the identical length of size is respectively two kinds of volume expansion grains of 2.1cm, 1.5cm, 0.6cm, is respectively put into dress
Have in 500mL distilled water beaker, absorbs water after 10h, take the gel of same size respectively.Conventional gel center alignment NK series is pushed away
The central axis of tensiometer, zeroing, rotating knob above tensiometer counterclockwise is pressed down against central axis, and gel stress is to be passed
Recording meter panel registration after gel of uniting is broken.It repeats the above steps under the same conditions and measures the deformation nature of new type gel.Such as Fig. 9
Shown, when power of the gel by 174.2N of conventional cross-linking agent synthesis, gel is broken.As shown in Figure 10, novel crosslinker synthesizes
Gel after the power by 286.4N, then after removing external force, gel is simultaneously unbroken and can restore to reset condition, can say above
Bright water-soluble poly rotaxane crosslinking agent has slide effect, therefore deformability and recovery capability are strong, conventional cross-linking agent N, N '-methylene
Base bisacrylamide does not have slide effect, therefore deformability and recovery capability are poor.
Finally, it is stated that preferred embodiment above is only used to illustrate the technical scheme of the present invention and not to limit it, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (10)
1. a kind of preparation method of water-soluble poly rotaxane crosslinking agent, which comprises the steps of:
1): alpha-cyclodextrin being subjected to the modified introducing double bond of itaconic anhydride and carboxylic acid structure, obtains modified alpha-cyclodextrin；
2): the hydroxyl at polyethylene glycol both ends being oxidized to carboxylic acid, obtains modified poly (ethylene glycol) chain；
3): on the modified poly (ethylene glycol) chain that modified alpha-cyclodextrin is prepared through second step, then by modified poly (ethylene glycol) chain two
Water-soluble poly rotaxane crosslinking agent is prepared at end seal end.
2. a kind of preparation method of water-soluble poly rotaxane crosslinking agent according to claim 1, which is characterized in that step 1) is described
Modified alpha-cyclodextrin is prepared as follows:
Step A: alpha-cyclodextrin, itaconic acid are dissolved in the reactor equipped with dehydrated alcohol, reactor is then placed in drying
It is dried in case；
Step B: reactor is taken out and it is a little in thick yellow liquid to be heated to reactant, then reactor is placed in drier
It is middle to be evaporated liquid；
Step C: dehydrated alcohol is further added into reactor and stirs evenly, filter using 0.45um miillpore filter
Light yellow powder solid is dried to obtain in filtered solid by solid.
3. a kind of preparation method of water-soluble poly rotaxane crosslinking agent according to claim 1, which is characterized in that step 1) is described
Modified alpha-cyclodextrin is prepared as follows:
Step A: 1.9~2g alpha-cyclodextrin, 0.1~0.2g itaconic acid are dissolved in the reactor equipped with 250ml dehydrated alcohol,
Then reactor is placed in drying box dry 130min under the conditions of 110 DEG C；
Step B: reactor is taken out and is heated to boiling, and after constantly boiling 30min, reactant is in thick yellow liquid in reactor
Body is a little, then reactor is placed in drier and is evaporated liquid；
Step C: 50ml dehydrated alcohol is further added into reactor and stirs evenly, is taken out using 0.45um miillpore filter
Consider to obtain solid, then washed with dehydrated alcohol, 9h is dried under the conditions of 100 DEG C of temperature in filtered solid, is obtained light yellow
Pulverulent solids.
4. a kind of preparation method of water-soluble poly rotaxane crosslinking agent according to claim 1, which is characterized in that step 2) is described
Method for oxidation are as follows: polyethylene glycol, tetramethyl piperidine nitrogen oxides, NaBr and NaClO are sequentially added in distilled water, pH value is adjusted
For 10-11,10-15min is reacted under room temperature, ethyl alcohol is then added and stops oxidation, and uses CH after adjusting pH < 22Cl2Extraction, is removed
Layer clear liquid, which is dried in vacuo up to the modified poly (ethylene glycol) chain.
5. a kind of preparation method of water-soluble poly rotaxane crosslinking agent according to claim 4, which is characterized in that step 2) is also wrapped
Recrystallization is included, resulting modified poly (ethylene glycol) chain, which is dissolved in 50-60 DEG C of ethyl alcohol, after vacuum drying recrystallizes, and vacuum is dry again
It is dry.
6. a kind of preparation method of water-soluble poly rotaxane crosslinking agent according to claim 4, which is characterized in that the poly- second two
The mass ratio of alcohol, tetramethyl piperidine nitrogen oxides and NaBr is 100:1:1；Mass volume ratio (the g/ of the NaBr and NaClO
It ml) is 10:1.
7. a kind of preparation method of water-soluble poly rotaxane crosslinking agent according to claim 1, which is characterized in that step 3) is described
The step of running through and blocking are as follows: weigh modified alpha-cyclodextrin and modified poly (ethylene glycol) chain is dissolved in distilled water, refrigerated overnight obtains
The white complex compound is added to N, N- together with 1- amantadine, the special condensing agent of card, n,N-diisopropylethylamine by white complex compound
In dimethylformamide and white slurries are uniformly mixed, which are stayed overnight into obtain milky slurries at 0~10 DEG C, then
By milky slurries and methanol mixing centrifuge washing twice after, then washed repeatedly with distilled water, filter and be dried in vacuo to obtain water
Dissolubility polyrotaxane crosslinking agent.
8. stating a kind of preparation method of water-soluble poly rotaxane crosslinking agent according to claim 7, which is characterized in that modified alpha-cyclodextrin
Weighing mass ratio with modified poly (ethylene glycol) chain is 3.8~4.2:1.
9. a kind of preparation method of water-soluble poly rotaxane crosslinking agent according to claim 7, which is characterized in that the white network
Close object and 1- amantadine, block special condensing agent, N, N- diisopropylethylamine, N, N- dimethylformamide addition mass ratio (g:
G:g:ml:ml) are as follows: 0.5~0.7:0.01~0.02:0.04~0.05:0.01~0.03:9~12.
10. the water-soluble poly rotaxane crosslinking agent that any one preparation method obtains according to claim 1~9.
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| CN110330667A (en) * | 2019-08-13 | 2019-10-15 | 重庆科技学院 | A kind of simple and convenient process for preparing and products thereof of water-soluble poly rotaxane crosslinking agent |
| CN110746521A (en) * | 2019-10-28 | 2020-02-04 | 重庆科技学院 | Method for preparing polyrotaxane crosslinking agent based on β cyclodextrin and product |
| CN115124662A (en) * | 2022-07-20 | 2022-09-30 | 南方科技大学 | Polyrotaxane quasi-slip ring hydrogel and preparation method and application thereof |
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