CN108948231B - Water-soluble polyrotaxane crosslinking agent and preparation method thereof - Google Patents
Water-soluble polyrotaxane crosslinking agent and preparation method thereof Download PDFInfo
- Publication number
- CN108948231B CN108948231B CN201810874130.6A CN201810874130A CN108948231B CN 108948231 B CN108948231 B CN 108948231B CN 201810874130 A CN201810874130 A CN 201810874130A CN 108948231 B CN108948231 B CN 108948231B
- Authority
- CN
- China
- Prior art keywords
- water
- polyethylene glycol
- cyclodextrin
- modified
- alpha
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- 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
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
- C08B37/0015—Inclusion compounds, i.e. host-guest compounds, e.g. polyrotaxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- 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
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/338—Polymers modified by chemical after-treatment with inorganic and organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/007—Polyrotaxanes; Polycatenanes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Medicinal Preparation (AREA)
Abstract
The invention discloses a preparation method of a water-soluble polyrotaxane cross-linking agent, which comprises the following steps: 1): carrying out itaconic acid modification on alpha-cyclodextrin to introduce a double bond and a carboxylic acid structure to obtain modified alpha-cyclodextrin; 2): oxidizing hydroxyl groups at two ends of the polyethylene glycol into carboxylic acid to obtain a modified polyethylene glycol chain; 3): and penetrating the modified alpha-cyclodextrin on the modified polyethylene glycol chain prepared in the second step, and then sealing the two ends of the modified polyethylene glycol chain to prepare the water-soluble polyrotaxane crosslinking agent. According to the invention, carboxylic acid groups are introduced through alpha-cyclodextrin modification, and the prepared polyrotaxane cross-linking agent has obvious water solubility, so that the polyrotaxane cross-linking agent can be cross-linked and polymerized with water-soluble monomers such as acrylamide and acrylic acid to prepare hydrogel, and the deformation capability of the hydrogel is improved.
Description
Technical Field
The invention belongs to the technical field of cross-linking agent preparation, and particularly relates to a water-soluble polyrotaxane cross-linking agent and a preparation method thereof.
Background
The hydrogel is a polymer material with a three-dimensional network structure after being appropriately crosslinked, and is widely applied to the fields of industry, agriculture, medicine, bioengineering materials and the like due to unique water absorption, water retention and bionic characteristics.
At present, the synthesis of hydrogel is mostly carried out by crosslinking with a traditional chemical crosslinking agent, the traditional chemical crosslinking agent refers to a molecular formula with two or more than two double bonds, the double bonds participate in polymerization in the process of forming a network structure, and the crosslinking process has randomness, so that the crosslinking points are inevitably unevenly distributed in a gel space, and the polymer chain segments among the crosslinking points are different in length. And the chemical cross-linking points are fixed, so that the polymer chain segments are stressed unevenly under the action of external force, and the short chain segments are stressed greatly and are easy to break first, so that the whole network structure is damaged. This results in a gel which is highly brittle and has poor deformability.
ZL201710929543.5 discloses a universal gel polyrotaxane cross-linking agent and a preparation method thereof, the cross-linking agent can be cross-linked with polymerizable monomers to prepare gel, the cross-linking point is not fixed, the cross-linking point can slide along a polymer chain, and a 'sliding effect' is generated, so that external force is uniformly dispersed to each chain segment and then to the whole network, and the problem that the chemical cross-linking points are not uniformly distributed in space is better solved. The polyrotaxane cross-linking agent is easy to dissolve in an organic solvent, is more suitable for preparing oil gel, but has limited solubility in water, only 0.6713g/100g of water (20 ℃) is detected by tests, and the polyrotaxane cross-linking agent belongs to a slightly soluble substance, and limits the application of the polyrotaxane cross-linking agent in water-soluble monomer cross-linking preparation of hydrogel in an aqueous solution.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a water-soluble polyrotaxane cross-linking agent and a preparation method thereof.
In order to achieve the above purpose, the following technical solutions are specifically provided:
1. a preparation method of a water-soluble polyrotaxane cross-linking agent comprises the following steps:
1): carrying out itaconic acid modification on alpha-cyclodextrin to introduce a double bond and a carboxylic acid structure to obtain modified alpha-cyclodextrin;
2): oxidizing hydroxyl groups at two ends of the polyethylene glycol into carboxylic acid to obtain a modified polyethylene glycol chain;
3): and penetrating the modified alpha-cyclodextrin on the modified polyethylene glycol chain prepared in the second step, and then sealing the two ends of the modified polyethylene glycol chain to prepare the water-soluble polyrotaxane crosslinking agent.
Further, the modified alpha-cyclodextrin in the step 1) is prepared by the following method:
step A: dissolving alpha-cyclodextrin and itaconic acid in a reactor filled with absolute ethyl alcohol, and then placing the reactor in a drying oven for drying;
and B: taking out the reactor, heating until the reactant is a little viscous yellow liquid, and then placing the reactor in a dryer to evaporate the liquid to dryness;
and C: and further adding absolute ethyl alcohol into the reactor, uniformly stirring, performing suction filtration by using a 0.45um microporous filter membrane to obtain a solid, and drying the solid after suction filtration to obtain a light yellow powdery solid.
Further, the modified alpha-cyclodextrin in the step 1) is prepared by the following method:
step A: dissolving 1.9-2 g of alpha-cyclodextrin and 0.1-0.2 g of itaconic acid in a reactor filled with 250ml of absolute ethyl alcohol, and then placing the reactor in a drying oven to dry for 130min at the temperature of 110 ℃;
and B: taking out the reactor, heating to boil, boiling for 30min, adding a little viscous yellow liquid into the reactor, and drying the liquid in a dryer;
and C: and further adding 50ml of absolute ethyl alcohol into the reactor, uniformly stirring, performing suction filtration by using a 0.45um microporous filter membrane to obtain a solid, washing by using the absolute ethyl alcohol, and drying the solid subjected to suction filtration for 9 hours at the temperature of 100 ℃ to obtain a light yellow powdery solid.
Further, the oxidation method in the step 2) is that polyethylene glycol, tetramethylpiperidine oxynitride, NaBr and NaClO are sequentially added into distilled water, the pH value is adjusted to 10-11, the reaction is carried out for 10-15min at normal temperature, then ethanol is added to stop oxidation, and CH is used after the pH value is adjusted to be less than 22Cl2Extracting, collecting the lower clear liquid, and vacuum drying the lower clear liquidThus obtaining the modified polyethylene glycol chain.
Further, the step 2) also comprises recrystallization, the modified polyethylene glycol chain obtained after vacuum drying is dissolved in ethanol with the temperature of 50-60 ℃ for recrystallization, and vacuum drying is carried out again.
Preferably, the mass ratio of the polyethylene glycol to the tetramethylpiperidine nitroxide to the NaBr is 100:1: 1; the mass-to-volume ratio (g/ml) of NaBr to NaClO is 10: 1.
Further, the penetrating and end-capping step in step 3) is: weighing modified alpha-cyclodextrin and a modified polyethylene glycol chain, dissolving the modified alpha-cyclodextrin and the modified polyethylene glycol chain in distilled water, refrigerating the solution overnight to obtain a white complex, adding the white complex, 1-amantadine, a kat condensation agent and N, N-diisopropylethylamine into N, N-dimethyl amide, uniformly mixing the mixture to obtain white slurry, allowing the white slurry to stand overnight at 0-10 ℃ to obtain milky white slurry, mixing the milky white slurry with methanol, centrifuging and washing the mixture twice, repeatedly washing the milky white slurry with distilled water, performing suction filtration, and performing vacuum drying to obtain the water-soluble polyrotaxane cross-linking agent.
Preferably, the weight ratio of the modified alpha-cyclodextrin to the modified polyethylene glycol chain is 3.8-4.2: 1.
More preferably, the weight ratio of the white complex to 1-amantadine, the kat-condensing agent, the N, N-diisopropylethylamine and the N, N-dimethyl amide (g: g: g: ml: ml) is as follows: 0.5-0.7: 0.01-0.02: 0.04-0.05: 0.01-0.03: 9-12.
2. The water-soluble polyrotaxane cross-linking agent obtained by the preparation method.
The invention has the beneficial effects that: the invention discloses a preparation method of a water-soluble polyrotaxane cross-linking agent, which comprises the steps of modifying alpha-cyclodextrin by itaconic acid to introduce a double bond and a carboxylic acid structure; oxidizing hydroxyl groups at two ends of the polyethylene glycol into carboxylic acid; and penetrating the prepared modified cyclodextrin on the modified polyethylene glycol chain prepared in the second step, and then sealing the two ends of the modified polyethylene glycol chain to prepare the polyrotaxane crosslinking agent.
Because carboxylic acid groups are introduced in the modification of the alpha-cyclodextrin, the water solubility of the polyrotaxane is enhanced, so that the polyrotaxane can be crosslinked and polymerized with water-soluble monomers such as acrylamide, acrylic acid and the like to prepare hydrogel, and the deformation capacity of the hydrogel is improved.
Drawings
FIG. 1 is a schematic diagram of a process for modifying alpha-cyclodextrin;
FIG. 2 is a schematic diagram of the oxidation process of polyethylene glycol;
FIG. 3 is a schematic diagram of a process for preparing a water-soluble polyrotaxane crosslinking agent;
FIG. 4 is a nuclear magnetic resonance H spectrogram of itaconic acid, alpha-cyclodextrin and modified alpha-cyclodextrin;
FIG. 5 is a nuclear magnetic resonance H spectrogram of polyethylene glycol and oxidized polyethylene glycol;
FIG. 6 is an infrared spectrum of a water-soluble polyrotaxane crosslinking agent;
FIG. 7 is a nuclear magnetic resonance H spectrum of a water-soluble polyrotaxane cross-linking agent;
FIG. 8 is an X-ray diffraction pattern of a water-soluble polyrotaxane crosslinking agent;
FIG. 9 is a photograph showing the morphology of a gel prepared by using a conventional crosslinking agent before and after being subjected to stress;
FIG. 10 is a photograph showing the morphology of a gel prepared with a water-soluble polyrotaxane crosslinking agent before and after being subjected to stress.
Detailed Description
The invention will be explained in more detail below with reference to specific embodiments and the accompanying drawings.
The following examples required raw materials and abbreviations as follows: α -cyclodextrin (α -CD), polyethylene glycol (PEG), sodium hypochlorite (NaClO), acrylamide, dimethyl sulfoxide (DMSO), tetramethylpiperidine nitroxide (TEMPO), 1-amantadine, N-Dimethylamide (DMF), N-diisopropylethylamine (EDIPA), a kat-condensation agent (BOP reagent), and the like.
Examples
Firstly, preparing a test sample
Preparation of a water-soluble polyrotaxane crosslinking agent:
1) preparing modified alpha-cyclodextrin: adding 250ml of absolute ethyl alcohol into a beaker, adding 1.9909g of alpha-CD and 0.1348g of itaconic acid, stirring for 30min, putting the mixture into a drying oven at 110 ℃ for 130min after the mixture is completely dissolved, taking the beaker out, heating the beaker to boil, and boiling for 30min continuously to obtain a little viscous yellow liquid in the beaker. And then putting the beaker into a drying box to evaporate the liquid to dryness. Pouring 50ml of absolute ethyl alcohol, performing suction filtration by using a 0.45um microporous filter membrane, washing by using a small amount of absolute ethyl alcohol, putting the solid after suction filtration into a drying oven at 100 ℃ for drying for 9 hours to obtain light yellow powdery solid, namely modified alpha-cyclodextrin (modified alpha-CD for short), wherein the reaction process is shown in figure 1;
2) oxidation of polyethylene glycol: 0.1002g of TEMPO and 0.1013g of NaBr were added to distilled water and stirred thoroughly until the two substances were completely dissolved, 10.0468g of PEG and 10ml of NaCl were added thereto and stirred to react at room temperature for 15 min. The oxidation was stopped by adding 10mL of ethanol and adjusting the pH to HCl<2, in combination with CH2Cl2Extracting for three times, combining the lower layer clear liquid, dissolving in 125mL hot ethanol, and placing in a refrigerator overnight. Taking out, vacuum drying at 40 deg.C for 20h to obtain white polyethylene glycol chain, wherein the reaction process is shown in FIG. 2;
3) the modified alpha-cyclodextrin penetrates through a polyethylene glycol chain and is blocked: 0.6002g of modified alpha-CD and 0.1503g of oxidized PEG were dissolved in 10mL of distilled water to obtain a white liquid. The dissolved mixture was kept in a refrigerator overnight to obtain 0.6931g of a white complex. The complex was dissolved in 10mL of DMF with 0.0166g of 1-adamantanamine, 0.0482g of Cartesian condensation agent (BOP reagent), 0.02mL of N, N-diisopropylethylamine (EDIPA) and the mixture was observed as a white slurry. And (3) standing the mixed slurry overnight at 0-10 ℃, taking out the refrigerator mixed solution as milky slurry after the overnight, then performing suction filtration and washing twice by using methanol, and performing vacuum drying to obtain 0.1415g of white polyrotaxane cross-linking agent, namely water-soluble polyrotaxane cross-linking agent, wherein the reaction process is shown in figure 3.
Characterization of starting materials, intermediates and products
And (3) performing characterization such as nuclear magnetic resonance H spectrum and infrared spectrum on the alpha-cyclodextrin, the itaconic acid, the modified alpha-cyclodextrin, the polyethylene glycol, the oxidized polyethylene glycol chain and the water-soluble polyrotaxane crosslinking agent prepared by the test example.
1) Characterization of modified alpha-CD
The itaconic acid, alpha-cyclodextrin and modified alpha-cyclodextrin were characterized by using deuterated DMSO as a solvent and using a nuclear magnetic resonance method, and the results are shown in fig. 4.
In FIG. 4, line A is a spectrum of itaconic acid, wherein chemical shifts of methylene hydrogen atoms in itaconic acid are at 3.15ppm and chemical shifts of two hydrogen atoms bonded to a double bond carbon atom of itaconic acid are at 5.63ppm and 6.11ppm, respectively. And the spectral line B is a spectrogram of the alpha-cyclodextrin. And the spectral line C is a spectrogram of the modified alpha-cyclodextrin, and chemical shift peaks of hydrogen atoms also appear at 3.15ppm, 5.63ppm and 6.11ppm of the spectrogram, which indicates that the chemical structure of itaconic acid exists in the structure of the modified alpha-cyclodextrin, namely the modification is successful.
2) Characterization of the oxidized polyethylene glycol chains:
the deuterated DMSO was used as a solvent to characterize the polyethylene glycol, oxidized polyethylene glycol chain using nuclear magnetic resonance means, and the results are shown in fig. 5:
in FIG. 5, the spectrum A is the spectrum of polyethylene glycol, the chemical shift of the hydrogen atom of the alcoholic hydroxyl group in polyethylene glycol is at 2.51ppm, and the chemical shift of the hydrogen atom of the methylene group in polyethylene glycol is at 3.41-3.56 ppm. And the spectral line B is a spectrogram of the oxidized polyethylene glycol chain, a hydrogen atom peak newly appears at the position of 3.98ppm compared with the spectral line A, the peak is the chemical shift of a methylene hydrogen atom directly connected with carboxylic acid groups after oxidation, and the peak at the position of 2.51ppm disappears, which shows that no alcohol hydroxyl hydrogen atoms exist in the oxidized polyethylene glycol chain, namely that all the terminal hydroxyl groups of the polyethylene glycol are oxidized into carboxylic acid.
3) Characterization of Water-soluble Polyrotaxane Cross-linking Agents
And (3) infrared spectrum characterization: the infrared spectrum of the water-soluble polyrotaxane crosslinking agent prepared in the above example is shown in FIG. 6, in which 3400cm is shown-1The broad absorption peak at the position may be a stretching vibration peak of an amino N-H bond or an acid hydroxyl O-H bond, 2931cm-1Position may be the shock absorption peak of the C-H bond attached to the double-bonded carbon, 1638cm-1The position may be the stretching vibration peak of C ═ C double bond, 1148cm-1The positions of the C-O-C bonds are possible to be asymmetric stretching vibration peaks, so that the main characteristic groups in the crosslinking agent have absorption peaks in an infrared spectrum.
Nuclear magnetic resonance H-spectrum characterization: the water-soluble polyrotaxane cross-linking agent is characterized by taking the heavy water as a solvent and using a nuclear magnetic resonance means, as shown in figure 7, chemical shifts of hydrogen atoms from different positions on cyclodextrin molecules are respectively at positions of 3.81-3.89ppm, 3.66-3.80ppm and 3.41-3.52ppm, but the chemical shifts of methylene hydrogen atoms in a polyethylene glycol structure are at positions of 3.54-3.61ppm, and the cross-linking agent has both a cyclodextrin structure and a polyethylene glycol structure. It should be noted that the chemical shifts of the hydrogen atoms in the cyclodextrin molecules and the chemical shifts of the methylene hydrogen atoms in the polyethylene glycol structure in fig. 7 are shifted somewhat from those in fig. 4 and 5 because different solvents are used.
Characterization by X-ray diffraction: the characterization result is shown in fig. 8, and an obvious diffraction signal appears at about 20 degrees, which indicates that the modified cyclodextrin and the modified polyethylene glycol form an inclusion compound, and the crystal stacking type is a tunnel-shaped structure.
Third, Water solubility test
Comparing the water-soluble polyrotaxane crosslinking agent prepared in this example with a general-purpose gel-type polyrotaxane crosslinking agent disclosed in ZL201710929543.5, the results shown in Table 1 were obtained:
table 1 water solubility test data
As is evident from the test data in Table 1, the solubility of the polyrotaxane crosslinking agent prepared by the invention in water is remarkably improved compared with that of the general gel polyrotaxane crosslinking agent.
Fourthly, the application and the performance comparison of the water-soluble polyrotaxane cross-linking agent and the universal polyrotaxane cross-linking agent in preparing the gel are as follows:
70g of distilled water and 14g of acrylamide are respectively added into two beakers, then V50 accounting for 0.2 percent of the mass of the monomer is respectively added, N' -methylene bisacrylamide serving as a traditional cross-linking agent and a novel cross-linking agent accounting for 0.5 percent of the mass of the monomer are respectively added, the reaction is carried out for 4 hours at 70 ℃, and the obtained product is simultaneously dried for 16 hours under vacuum at 70 ℃.
Taking two kinds of bulked particles with the same size, length, width and height of 2.1cm, 1.5cm and 0.6cm respectively, putting the bulked particles into beakers filled with 500mL of distilled water respectively, and taking gel with the same size after absorbing water for 10 hours. Aligning the center of the traditional gel to the central shaft of the NK series push-pull dynamometer, adjusting zero, rotating a knob above the dynamometer anticlockwise to enable the central shaft to be extruded downwards, bearing the gel, and recording dial indication after the traditional gel is crushed. The above procedure was repeated under the same conditions to measure the deformation properties of the novel gel. As shown in FIG. 9, when the gel synthesized by the conventional crosslinking agent is subjected to a force of 174.2N, the gel is broken. As shown in fig. 10, after the gel synthesized by the novel cross-linking agent is subjected to 286.4N force and the external force is removed, the gel is not broken and can be restored to the original state, which indicates that the water-soluble polyrotaxane cross-linking agent has a sliding effect, so the deformation capability and the restoration capability are strong, and the traditional cross-linking agent N, N' -methylene bisacrylamide has no sliding effect, so the deformation capability and the restoration capability are poor.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (9)
1. The preparation method of the water-soluble polyrotaxane cross-linking agent is characterized by comprising the following steps:
1): carrying out itaconic acid modification on alpha-cyclodextrin to introduce a double bond and a carboxylic acid structure to obtain modified alpha-cyclodextrin;
2): oxidizing hydroxyl groups at two ends of the polyethylene glycol into carboxylic acid to obtain a modified polyethylene glycol chain;
3): penetrating the modified alpha-cyclodextrin on the modified polyethylene glycol chain prepared in the second step, and then sealing the two ends of the modified polyethylene glycol chain to prepare the water-soluble polyrotaxane crosslinking agent;
the modified alpha-cyclodextrin in the step 1) is prepared by the following method:
step A: dissolving alpha-cyclodextrin and itaconic acid in a reactor filled with absolute ethyl alcohol, and then placing the reactor in a drying oven for drying;
and B: taking out the reactor, heating until the reactant is a little viscous yellow liquid, and then placing the reactor in a dryer to evaporate the liquid to dryness;
and C: and further adding absolute ethyl alcohol into the reactor, uniformly stirring, performing suction filtration by using a 0.45um microporous filter membrane to obtain a solid, and drying the solid after suction filtration to obtain a light yellow powdery solid.
2. The method for preparing a water-soluble polyrotaxane crosslinking agent according to claim 1, wherein the modified α -cyclodextrin in the step 1) is prepared by the following method:
step A: dissolving 1.9-2 g of alpha-cyclodextrin and 0.1-0.2 g of itaconic acid in a reactor filled with 250ml of absolute ethyl alcohol,
then the reactor is placed in a drying oven to be dried for 130min at the temperature of 110 ℃;
and B: taking out the reactor, heating to boil, boiling for 30min, adding a little viscous yellow liquid into the reactor, and drying the liquid in a dryer;
and C: and further adding 50ml of absolute ethyl alcohol into the reactor, uniformly stirring, performing suction filtration by using a 0.45um microporous filter membrane to obtain a solid, washing by using the absolute ethyl alcohol, and drying the solid subjected to suction filtration for 9 hours at the temperature of 100 ℃ to obtain a light yellow powdery solid.
3. The method for preparing a water-soluble polyrotaxane cross-linking agent according to claim 1, wherein the oxidation method in step 2) comprises sequentially adding polyethylene glycol, tetramethylpiperidine nitroxide, NaBr and NaClO into distilled water, adjusting pH to 10-11, reacting at room temperature for 10-15min, adding ethanol to stop oxidation, adjusting pH to less than 2, and adding CH2Cl2Extracting, taking the lower clear liquid, and drying the lower clear liquid in vacuum to obtain the modified polyethylene glycol chain.
4. The method for preparing a water-soluble polyrotaxane cross-linking agent according to claim 3, wherein the step 2) further comprises recrystallization, the modified polyethylene glycol chain obtained after vacuum drying is dissolved in ethanol at 50-60 ℃ for recrystallization, and vacuum drying is performed again.
5. The method for preparing the water-soluble polyrotaxane crosslinking agent according to claim 3, wherein the mass ratio of the polyethylene glycol to the tetramethylpiperidine nitroxide to the NaBr is 100:1: 1; the mass-to-volume ratio (g/ml) of NaBr to NaClO is 10: 1.
6. The method for preparing a water-soluble polyrotaxane crosslinking agent according to claim 1, wherein the penetrating and end-capping step of step 3) is: weighing modified alpha-cyclodextrin and a modified polyethylene glycol chain, dissolving the modified alpha-cyclodextrin and the modified polyethylene glycol chain in distilled water, refrigerating the solution overnight to obtain a white complex, adding the white complex, 1-amantadine, a kat condensation agent and N, N-diisopropylethylamine into N, N-dimethyl amide, uniformly mixing the mixture to obtain white slurry, allowing the white slurry to stand overnight at 0-10 ℃ to obtain milky white slurry, mixing the milky white slurry with methanol, centrifuging and washing the mixture twice, repeatedly washing the milky white slurry with distilled water, performing suction filtration, and performing vacuum drying to obtain the water-soluble polyrotaxane cross-linking agent.
7. The preparation method of the water-soluble polyrotaxane crosslinking agent according to claim 6, wherein the weight ratio of the modified alpha-cyclodextrin to the modified polyethylene glycol chain is 3.8-4.2: 1.
8. The method for preparing a water-soluble polyrotaxane cross-linking agent according to claim 6, wherein the weight ratio of the white complex to the 1-amantadine, the kat-condensing agent, the N, N-diisopropylethylamine, and the N, N-dimethylformamide (g: g: g: ml: ml) is as follows: 0.5-0.7: 0.01-0.02: 0.04-0.05: 0.01-0.03: 9-12.
9. The water-soluble polyrotaxane crosslinking agent obtained by the preparation method according to any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810874130.6A CN108948231B (en) | 2018-08-03 | 2018-08-03 | Water-soluble polyrotaxane crosslinking agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810874130.6A CN108948231B (en) | 2018-08-03 | 2018-08-03 | Water-soluble polyrotaxane crosslinking agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108948231A CN108948231A (en) | 2018-12-07 |
| CN108948231B true CN108948231B (en) | 2020-11-13 |
Family
ID=64467437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810874130.6A Active CN108948231B (en) | 2018-08-03 | 2018-08-03 | Water-soluble polyrotaxane crosslinking agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108948231B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705372B (en) * | 2018-12-29 | 2021-08-13 | 广东工业大学 | Supramolecular material, hydrogel and preparation method thereof |
| CN110330667B (en) * | 2019-08-13 | 2021-09-24 | 重庆科技学院 | Simple preparation method of water-soluble polyrotaxane crosslinking agent and product thereof |
| 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 |
| CN115212845B (en) * | 2022-07-08 | 2023-09-22 | 重庆科技学院 | Dye wastewater treatment method |
| CN115124662B (en) * | 2022-07-20 | 2023-12-01 | 南方科技大学 | Polyrotaxane quasi-slip ring hydrogel and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106007478A (en) * | 2016-05-19 | 2016-10-12 | 衢州贝蒙文教用品制造有限公司 | Ultralight clay composition and preparation method thereof |
| CN107474162A (en) * | 2017-10-09 | 2017-12-15 | 重庆科技学院 | A kind of universal gel-like polyrotaxane crosslinking agent and preparation method thereof |
| CN107849199A (en) * | 2015-07-23 | 2018-03-27 | 住友化学株式会社 | Resin and surface protection board or materials used in auto manufacturing |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4911474B2 (en) * | 2008-02-26 | 2012-04-04 | 富士フイルム株式会社 | Hard coat film, polarizing plate, and image display device |
-
2018
- 2018-08-03 CN CN201810874130.6A patent/CN108948231B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107849199A (en) * | 2015-07-23 | 2018-03-27 | 住友化学株式会社 | Resin and surface protection board or materials used in auto manufacturing |
| CN106007478A (en) * | 2016-05-19 | 2016-10-12 | 衢州贝蒙文教用品制造有限公司 | Ultralight clay composition and preparation method thereof |
| CN107474162A (en) * | 2017-10-09 | 2017-12-15 | 重庆科技学院 | A kind of universal gel-like polyrotaxane crosslinking agent and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis of two b-cyclodextrin derivatives containing a vinyl group;Yong-Fu Li等;《Carbohydrate Research》;20141129;第404卷;第55-62页 * |
| α- 环糊精/ 聚乙二醇准聚轮烷触变水凝胶的制备及其流变学性质研究;刘松华等;《中国当代医药》;20160518;第23卷(第14期);第7-9页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108948231A (en) | 2018-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108948231B (en) | Water-soluble polyrotaxane crosslinking agent and preparation method thereof | |
| Chujo et al. | Iron (II) bipyridyl-branched polyoxazoline complex as a thermally reversible hydrogel | |
| Haldar et al. | Polyisobutylene-based pH-responsive self-healing polymeric gels | |
| Liu et al. | Thermally reversible cross-linked polyamides and thermo-responsive gels by means of Diels–Alder reaction | |
| Wang et al. | Ultrasonic-assisted synthesis of sodium lignosulfonate-grafted poly (acrylic acid-co-poly (vinyl pyrrolidone)) hydrogel for drug delivery | |
| Arai et al. | Versatile Supramolecular Cross‐Linker: A Rotaxane Cross‐Linker That Directly Endows Vinyl Polymers with Movable Cross‐Links | |
| Vancoillie et al. | Synthesis of novel boronic acid-decorated poly (2-oxazoline) s showing triple-stimuli responsive behavior | |
| Liu et al. | A supramolecular approach for fabrication of photo-responsive block-controllable supramolecular polymers | |
| CN113429495A (en) | Gamma-cyclodextrin type pseudopolyrotaxane cross-linking agent, gel particles and preparation method | |
| Shen et al. | Dual-responsive recurrent self-assembly of a supramolecular polymer based on the host–guest complexation interaction between β-cyclodextrin and azobenzene | |
| Miao et al. | Alkynyl-functionalization of hydroxypropyl cellulose and thermoresponsive hydrogel thereof prepared with P (NIPAAm-co-HEMAPCL) | |
| Pan et al. | Dual thermo‐and pH‐sensitive network‐grafted hydrogels formed by macrocrosslinker as drug delivery system | |
| Ge et al. | Thermo and pH dual responsive polypeptides derived from “clickable” poly (γ-3-methylthiopropyl-l-glutamate) | |
| Coumes et al. | Catechol/boronic acid chemistry for the creation of block copolymers with a multi-stimuli responsive junction | |
| Luo et al. | Preparation and properties of kraft lignin-N-isopropyl acrylamide hydrogel | |
| Dahlke et al. | A New Approach Toward Metal‐Free Self‐Healing Ionomers Based on Phosphate and Methacrylate Containing Copolymers | |
| Giammona et al. | Glycidyl methacrylate derivatization of α, β-poly (N-hydroxyethyl)-dl-aspartamide and α, β-polyasparthydrazide | |
| Özyürek et al. | Thermoresponsive glycopolymers via controlled radical polymerization | |
| Yu et al. | Photo-responsive gels based on cyclic/linear polymers: efficient synthesis and properties | |
| Liu et al. | Synthesis and Characterization of PNIPAm Core Cross‐Linked Star Polymers and Their Functionalization with Cyclodextrin | |
| Feng et al. | Preparation of thermo-sensitive hydrogels from acrylated lignin and N-isopropylacrylamide through photocrosslinking | |
| Araki et al. | Synthesis of a “molecular rope curtain”: Preparation and characterization of a sliding graft copolymer with grafted poly (ethylene glycol) side chains by the “grafting onto” strategy | |
| CN110003390B (en) | Starch or cellulose-based high-molecular porous adsorption resin and preparation method thereof | |
| Fan et al. | Protein–polymer hybrid oil–absorbing gel using hair keratin as macroinitiator by SET-LRP | |
| CN113831706B (en) | High-toughness polycaprolactone remodelable shape memory material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |