CN113429495A - Gamma-cyclodextrin type pseudopolyrotaxane cross-linking agent, gel particles and preparation method - Google Patents
Gamma-cyclodextrin type pseudopolyrotaxane cross-linking agent, gel particles and preparation method Download PDFInfo
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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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Abstract
The invention provides a gamma-cyclodextrin type pseudopolyrotaxane cross-linking agent, gel particles and a preparation method thereof. The preparation method of the gamma-cyclodextrin type pseudopolyrotaxane cross-linking agent is simple and can be completed by only one step, and gel particles prepared from the pseudopolyrotaxane cross-linking agent prepared according to the invention have higher water absorption rate and more excellent deformation recovery performance.
Description
Technical Field
The invention belongs to the technical field of preparation of cross-linking agents, and particularly relates to a gamma-cyclodextrin type pseudopolyrotaxane cross-linking agent, gel particles and a preparation method.
Background
The cross-linking agent acts as a chemical agent to link the linear polymer chains to each other to form a three-dimensional network structure. The traditional chemical cross-linking agent has fixed cross-linking points, random cross-linking process and uneven distribution in gel space. The gel particle type plugging agent which is one of the profile control and flooding agents with wider application is synthesized by crosslinking with the traditional chemical crosslinking agent, and the prepared gel particles have the problems of high brittleness, breakage under certain pressure and the like.
ZL201910742154.0 discloses a simple preparation method for preparing a water-soluble pseudopolyrotaxane cross-linking agent based on alpha-cyclodextrin, which simplifies the preparation process and needs two steps, and the specific steps are as follows: firstly, preparing polyethylene glycol/alpha-cyclodextrin pseudopolyrotaxane by using a polyethylene glycol solution and an alpha-cyclodextrin solution, and then reacting the polyethylene glycol/alpha-cyclodextrin pseudopolyrotaxane with itaconic anhydride to finally obtain the pseudopolyrotaxane cross-linking agent. ZL201911028720.8 discloses a method for preparing a pseudopolyrotaxane crosslinking agent based on beta-cyclodextrin, which also needs two steps, and comprises the following specific steps: firstly, preparing polyether amine/beta-cyclodextrin quasi-polyrotaxane by using beta-cyclodextrin and polyether amine, and then further preparing polyether amine/beta-cyclodextrin quasi-polyrotaxane and maleic anhydride to obtain the polyether amine/beta-cyclodextrin/maleic anhydride quasi-polyrotaxane cross-linking agent.
Disclosure of Invention
The invention aims to reduce operation steps, produce gel particles with higher water absorption rate and more excellent deformation recovery performance compared with the existing gel particles, and provide a gamma-cyclodextrin type pseudopolyrotaxane cross-linking agent, gel particles and a preparation method.
The invention aims to realize the aim, and provides a preparation method of a gamma-cyclodextrin quasi-polyrotaxane cross-linking agent.
Preferably, the concentration of the gamma-cyclodextrin aqueous solution is 6-10%, and the concentration of the polyethylene glycol diacrylate aqueous solution is 5-50%.
Preferably, the polyethylene glycol diacrylate has an average molecular weight of 400-1000.
Preferably, the stirring time is 3-24 h.
In addition, the present invention provides a gamma-cyclodextrin type pseudopolyrotaxane crosslinking agent prepared by the preparation method according to any of claims 1 to 4.
In addition, the invention also provides a preparation method of the gel particles, distilled water, acrylamide, ammonium persulfate and the gamma-cyclodextrin type pseudopolyrotaxane cross-linking agent prepared according to the method of claim 5 are added into a reaction vessel, and after reaction and drying, the product is cut into pieces to obtain the gel particles.
Preferably, the mass ratio of the gamma-cyclodextrin type pseudopolyrotaxane cross-linking agent to the distilled water, the acrylamide and the ammonium persulfate is 5: 5000: 1000: 2.
preferably, the temperature of the reaction is 55-60 ℃ and the temperature of drying is 75-80 ℃.
In addition, the present invention provides a gel particle produced by the production method according to any of claims 6 to 8.
The invention has the beneficial effects that:
the preparation method of the gamma-cyclodextrin type pseudopolyrotaxane cross-linking agent is simple, the polyethylene glycol diacrylate aqueous solution is creatively introduced, the preparation can be completed only by one step, and gel particles prepared from the pseudopolyrotaxane cross-linking agent prepared according to the invention have higher water absorption rate and more excellent deformation recovery performance.
Drawings
FIG. 1 is a schematic view showing the principle of preparation of a gamma-cyclodextrin type pseudopolyrotaxane crosslinking agent;
FIG. 2 is a schematic diagram showing the principle of preparing a gel from a gamma-cyclodextrin type pseudopolyrotaxane cross-linking agent;
FIG. 3 is a one-dimensional NMR spectrum (solvent is heavy water) of gamma-cyclodextrin, polyethylene glycol diacrylate and the gamma-cyclodextrin type pseudopolyrotaxane crosslinking agent prepared in example 1;
FIG. 4 is an XRD spectrum of gamma-cyclodextrin, polyethylene glycol diacrylate and the gamma-cyclodextrin type pseudopolyrotaxane cross-linking agent prepared in example 1 and a physical mixture of gamma-cyclodextrin and polyethylene glycol diacrylate;
FIG. 5 is a TG plot of the gamma-cyclodextrin-type pseudopolyrotaxane crosslinker, gamma-CD and polyethylene glycol diacrylate prepared in example 1;
FIG. 6 is a NOESY two-dimensional NMR spectrum of a gamma-cyclodextrin type pseudopolyrotaxane cross-linking agent prepared in example 1 (the solvent is heavy water);
FIG. 7 is a graph showing water absorption rates of gel particles prepared from the gamma-cyclodextrin type water-soluble pseudopolyrotaxane prepared in example 1 and conventional gel particles prepared from a conventional crosslinking agent;
FIG. 8 is a graph showing deformation properties of gel particles prepared from the gamma-cyclodextrin type water-soluble pseudopolyrotaxane prepared in example 1;
FIG. 9 is a graph showing the deformation behavior of conventional gel particles prepared by a conventional crosslinking agent.
Detailed Description
The present invention will be further described with reference to specific examples, but the present invention is not limited to these examples.
Example 1
Preparation of gamma-cyclodextrin (gamma-CD) type quasi-polyrotaxane crosslinking agent
Firstly, preparing 8% aqueous solution from gamma-CD 4g and 46g H2O; secondly, 2.5g of polyethylene glycol diacrylate (average molecular weight is 1000) and 47.5g of H2O are taken to prepare a 5% aqueous solution; and finally, mixing 20mL of gamma-CD solution and 20mL of polyethylene glycol diacrylate solution, stirring overnight for a long time (24 hours) to separate out a precipitate, and performing suction filtration and drying to obtain the precipitate, namely the gamma-CD type pseudopolyrotaxane cross-linking agent. The preparation process of the pseudopolyrotaxane cross-linking agent is shown in figure 1.
Comparison of gel particles prepared with a gamma-CD type pseudopolyrotaxane crosslinker with gel particles prepared with a conventional crosslinker (N, N-methylenebisacrylamide):
the preparation method of the gel particles comprises the following steps:
50g of distilled water, 10g of acrylamide and 0.02g of ammonium persulfate are respectively added into 2 beakers, then 0.05g of gamma-cyclodextrin type pseudopolyrotaxane cross-linking agent and 0.05g of traditional cross-linking agent (N, N-methylene bisacrylamide) are respectively added, the reaction is carried out for 4 hours at the temperature of 60 ℃, the product is dried for 48 hours at the temperature of 75 ℃, the shearing is carried out, gel particles (novel gel particles) prepared by the gamma-CD type pseudopolyrotaxane cross-linking agent and gel particles (traditional gel particles) prepared by the traditional cross-linking agent (N, N-methylene bisacrylamide) are obtained, and the process for preparing gel by the gamma-cyclodextrin type pseudopolyrotaxane cross-linking agent is shown in figure 2.
Example 2
Preparation of gamma-cyclodextrin (gamma-CD) type quasi-polyrotaxane crosslinking agent
Firstly, preparing 10% aqueous solution from gamma-CD 5g and 45g H2O; secondly, 25g of polyethylene glycol diacrylate (average molecular weight is 400) and 25g of H2O are taken to prepare 25 percent aqueous solution; and finally, mixing 30mL of gamma-CD solution and 10mL of polyethylene glycol diacrylate solution, stirring for 6h to separate out a precipitate, and performing suction filtration and drying to obtain the precipitate, namely the gamma-CD type pseudopolyrotaxane cross-linking agent.
Example 3
Preparation of gamma-cyclodextrin (gamma-CD) type quasi-polyrotaxane crosslinking agent
Firstly, preparing 8% aqueous solution from gamma-CD 4g and 46g H2O; secondly, 15g of polyethylene glycol diacrylate (average molecular weight 800) and 35g of H2O are taken to prepare 30 percent aqueous solution; and finally, mixing 20mL of gamma-CD solution and 20mL of polyethylene glycol diacrylate solution, stirring for 12h to separate out a precipitate, and performing suction filtration and drying to obtain the precipitate, namely the gamma-CD type pseudopolyrotaxane cross-linking agent.
Characterization of the product:
the gamma-CD, the polyethylene glycol diacrylate and the gamma-CD type pseudopolyrotaxane cross-linking agent are respectively used as solvents by using deuterium oxide, and a one-dimensional nuclear magnetic resonance hydrogen spectrum is tested, and the test result is shown in figure 3.
Line A in FIG. 3 is the 1H-NMR spectrum of γ -CD, and the chemical shift of H1 in γ -CD is at δ 5.07. The spectral line C is a 1H-NMR spectrogram of the polyethylene glycol diacrylate, chemical shifts of H on double bond carbon in the polyethylene glycol diacrylate are at delta 5.94-6.44, and chemical shifts of H on methylene in the polyethylene glycol diacrylate are at delta 3.62. And a spectral line B is a 1H NMR spectrogram of the pseudopolyrotaxane cross-linking agent formed by the gamma-CD and the polyethylene glycol diacrylate, wherein the B delta 5.07 part is the chemical shift of H1 in the gamma-CD, the delta 5.94-6.44 parts are the chemical shift of H on the carbon of a double bond in the polyethylene glycol diacrylate, and the delta 3.62 part is the chemical shift of H on a methylene in the polyethylene glycol diacrylate. From the results of 1H-NMR, it was concluded that γ -CD had undergone an inclusion reaction with polyethylene glycol diacrylate.
FIG. 4 is an X-ray diffraction pattern of γ -CD (line A), polyethylene glycol diacrylate (line B), γ -CD type pseudopolyrotaxane crosslinker (line C), a physical mixture of γ -CD and polyethylene glycol diacrylate (line D). As can be seen from the spectrum of FIG. 4, the spectrum of the physical mixture is a simple superposition of the spectra of both gamma-CD and polyethylene glycol diacrylate. In line C of fig. 4, a new diffraction peak appears at 7.5 ° 2 θ, indicating that γ -CD and polyethylene glycol diacrylate form an inclusion structure with double strand penetration, rather than a simple physical mixture of γ -CD and polyethylene glycol diacrylate, and the diffraction characteristic peak position of double strand inclusion is 7.5 ° 2 θ.
FIG. 5 shows the thermal weight loss process of gamma-CD type poly (pseudo) rotaxane crosslinker (spectrum line A), gamma-CD (spectrum line B) and polyethylene glycol diacrylate (spectrum line C), wherein the scanning range of thermogravimetric analysis test is from room temperature to 600 ℃, the heating rate is 10 ℃/min, and the atmosphere is protected by nitrogen. As can be seen from line C of fig. 5, the thermal decomposition temperature of the polyethylene glycol diacrylate is 350 ℃, and as can be seen from line B, the thermal decomposition temperature of the crystalline γ -CD is 300 ℃. In line A, 210 ℃ may correspond to the decomposition of a single or a few γ -CD molecules, indicating that γ -CD is randomly distributed in the copolymer backbone and thus does not form a complete crystalline structure, so the decomposition temperature is lower than that of crystalline γ -CD (300 ℃) and at 397 ℃ may correspond to the decomposition of polyethylene glycol diacrylate in the crosslinking agent, and the thermal decomposition temperature is higher than that of pure polyethylene glycol diacrylate (350 ℃), indicating that the inclusion of γ -CD increases the decomposition temperature of polyethylene glycol diacrylate to some extent. At 600 ℃, the residual mass percentage of the gamma-CD type pseudopolyrotaxane cross-linking agent is 31.15 percent, the residual mass percentages of the gamma-CD and the polyethylene glycol diacrylate are 7.03 percent and 0.05 percent respectively, and the residual mass percentage of the gamma-CD type pseudopolyrotaxane cross-linking agent is far higher than that of the gamma-CD and the polyethylene glycol diacrylate, which shows that the inclusion of the gamma-CD has a certain improvement effect on the thermal stability of a polymer chain. Therefore, according to the results of thermogravimetric analysis, the gamma-CD can be proved to have undergone the inclusion reaction with the polyethylene glycol diacrylate to generate the gamma-CD type pseudopolyrotaxane crosslinking agent.
FIG. 6 shows the NOESY two-dimensional NMR spectrum of a gamma-CD type pseudopolyrotaxane cross-linking agent. As can be seen from FIG. 6, H3 (delta 3.87) and H5 (delta 3.78) in the lumen of γ -CD generate interference peaks with H (delta 3.62) on the methylene group of the polyethylene glycol diacrylate, respectively, indicating that an inclusion phenomenon occurs, i.e., γ -CD has penetrated through the molecular chain of the polyethylene glycol diacrylate to form a γ -CD type pseudopolyrotaxane cross-linking agent.
Fig. 7 shows water absorption rates of the novel gel particles and the conventional gel particles, a certain mass (m0) of the gel particles prepared above was put into 500mL of distilled water, and the gel particles were respectively taken out and weighed (mt) at different times t, and the swelling water absorption rate (Q) was calculated: q ═ mt-m0)/m 0. The relationship of the water absorption capacity of the gel prepared by different crosslinking agents along with the swelling time is shown in fig. 7, the water absorption capacity of the novel gel particle (fig. 7A) prepared by the gamma-CD type pseudopolyrotaxane crosslinking agent is always higher than that of the traditional gel particle (fig. 7B) prepared by the traditional crosslinking agent, the novel gel particle basically achieves swelling balance after 315 hours of swelling, the water absorption capacity when the swelling balance is achieved is 99.14 times, the gel particle prepared by the traditional crosslinking agent basically achieves swelling balance after 246 hours of swelling, and the water absorption capacity when the swelling balance is achieved is 10.76 times, which shows that compared with the gel particle prepared by the traditional crosslinking agent, the gel particle prepared by the pseudopolyrotaxane crosslinking agent has higher water absorption capacity in a certain range.
The 2 kinds of gel particles were added to a beaker containing 500mL of distilled water, and after absorbing water for the same time, the gel particles of the same size were taken out to measure the deformation recovery properties as shown in FIGS. 8 to 9. Aligning the center of gel particles prepared by the gamma-CD type pseudopolyrotaxane cross-linking agent to the central shaft of an NK (natural killer) series tension meter, adjusting zero, rotating a knob above the tension meter anticlockwise to enable the central shaft to be extruded downwards, stressing the gel particles, recording dial readings, canceling external force and observing gel deformation recovery capacity. The above procedure was repeated under the same conditions to measure the deformation recovery ability of the gel particles prepared by the conventional crosslinking agent.
As can be seen from FIG. 8, when the gel particles synthesized by the gamma-CD type pseudopolyrotaxane cross-linking agent are subjected to a force of 24.0N of an NK series push-pull dynamometer, the gel particles deform, and the gel can still recover the original state after the pull dynamometer knob is rotated to remove the external force, which shows that the deformation recovery capability is excellent. As can be seen from FIG. 9, the gel particles synthesized by the conventional crosslinking agent are subjected to a force of 11.0N by an NK series push-pull dynamometer and then the external force is removed, and the gel particles are broken, which indicates that the deformation recovery capability is poor.
The experimental results show that compared with the cross-linking agent prepared by other methods, the gamma-CD type gamma-CD quasi-polyrotaxane cross-linking agent prepared by the invention has the advantages that the preparation steps are greatly simplified, only one step is needed, and in a certain range, gel particles prepared by the quasi-polyrotaxane cross-linking agent provided by the invention have higher water absorption multiplying power and more excellent deformation recovery capability than gel particles prepared by the traditional cross-linking agent.
Claims (9)
1. A preparation method of a gamma-cyclodextrin type pseudopolyrotaxane cross-linking agent is characterized by mixing a gamma-cyclodextrin aqueous solution and a polyethylene glycol diacrylate aqueous solution, stirring until a precipitate is separated out, and performing suction filtration and drying on the precipitate to obtain the gamma-cyclodextrin type pseudopolyrotaxane cross-linking agent.
2. The method for preparing a gamma-cyclodextrin-type pseudopolyrotaxane cross-linking agent according to claim 1, wherein the concentration of the aqueous solution of gamma-cyclodextrin is 6 to 10%, and the concentration of the aqueous solution of polyethylene glycol diacrylate is 5 to 50%.
3. The method for preparing a gamma-cyclodextrin-type pseudopolyrotaxane crosslinking agent according to claim 2, wherein the polyethylene glycol diacrylate has an average molecular weight of 400-1000.
4. The method for preparing a gamma-cyclodextrin-type pseudopolyrotaxane crosslinking agent according to claim 3, wherein the stirring time is 3 to 24 hours.
5. A gamma-cyclodextrin type pseudopolyrotaxane crosslinking agent which is obtained by the production method according to any of claims 1 to 4.
6. A method for preparing gel particles, adding distilled water, acrylamide, ammonium persulfate and the gamma-cyclodextrin type pseudopolyrotaxane cross-linking agent prepared according to the method of claim 5 into a reaction vessel, reacting and drying, and shearing the product to obtain the gel particles.
7. The method for preparing gel particles according to claim 6, wherein the mass ratio of the gamma-cyclodextrin type pseudopolyrotaxane cross-linking agent to the distilled water, the acrylamide and the ammonium persulfate is 5: 5000: 1000: 2.
8. the method of claim 6, wherein the reaction temperature is 55-60 ℃ and the drying temperature is 75-80 ℃.
9. A gel particle produced by the production method according to any one of claims 6 to 8.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN115417999A (en) * | 2022-08-24 | 2022-12-02 | 浙江大学杭州国际科创中心 | One-dimensional polyrotaxane constructed based on coordinated boron-nitrogen bond and preparation method and application thereof |
| CN116239708A (en) * | 2023-03-20 | 2023-06-09 | 山东滨州智源生物科技有限公司 | End-capped polyrotaxane and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006115255A1 (en) * | 2005-04-25 | 2006-11-02 | The University Of Tokyo | Gel composition and method for producing same |
| JP2008184583A (en) * | 2007-01-31 | 2008-08-14 | Lintec Corp | Pseudo-polyrotaxane, polyrotaxane and method for producing them |
| CA2686789A1 (en) * | 2007-05-07 | 2008-11-20 | Japan Science And Technology Agency | Molecule-responsive gel fine particles, process for production of the same and use thereof |
| CN102391445A (en) * | 2011-08-28 | 2012-03-28 | 山东理工大学 | Polyacrylate polymer terminated cyclodextrin polyrotaxane and preparation method thereof |
| WO2018021267A1 (en) * | 2016-07-25 | 2018-02-01 | 国立大学法人 東京大学 | Pseudopolyrotaxane, polyrotaxane, and methods for producing pseudopolyrotaxane and polyrotaxane |
| 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 |
-
2021
- 2021-05-21 CN CN202110558621.1A patent/CN113429495A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006115255A1 (en) * | 2005-04-25 | 2006-11-02 | The University Of Tokyo | Gel composition and method for producing same |
| JP2008184583A (en) * | 2007-01-31 | 2008-08-14 | Lintec Corp | Pseudo-polyrotaxane, polyrotaxane and method for producing them |
| CA2686789A1 (en) * | 2007-05-07 | 2008-11-20 | Japan Science And Technology Agency | Molecule-responsive gel fine particles, process for production of the same and use thereof |
| CN102391445A (en) * | 2011-08-28 | 2012-03-28 | 山东理工大学 | Polyacrylate polymer terminated cyclodextrin polyrotaxane and preparation method thereof |
| WO2018021267A1 (en) * | 2016-07-25 | 2018-02-01 | 国立大学法人 東京大学 | Pseudopolyrotaxane, polyrotaxane, and methods for producing pseudopolyrotaxane and polyrotaxane |
| 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 |
Non-Patent Citations (5)
| Title |
|---|
| BEIBEI WANG 等: "High strength dual-crosslinked hydrogels with photo-switchable color changing behavior", 《EUROPEAN POLYMER JOURNAL》 * |
| JIE LIU 等: "Chiral pH responsive hydrogels constructed by N-Acryloyl-alanine and PEGDA/α-CD inclusion complex: preparation and chiral release ability", 《POLYM. ADV. TECHNOL.》 * |
| JUAN WU等: "Effect of interfacial properties of a surface modified surface plasmon resonance chip on protein immobilization performance", 《CHANGING BEHAVIOR》 * |
| KEUMHEE JANG 等: "Synthesis and properties of rotaxane-cross-linked polymers using a double-stranded γ-CD-based inclusion complex as a supramolecular cross-linker", 《POLYMER》 * |
| PENG ZHANG 等: "A Simple Synthesis Method of Water-Soluble Pseudo-Polyrotaxane Cross-Linkers Based on Cyclodextrin", 《MACROMOL. CHEM. PHYS》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN115417999A (en) * | 2022-08-24 | 2022-12-02 | 浙江大学杭州国际科创中心 | One-dimensional polyrotaxane constructed based on coordinated boron-nitrogen bond and preparation method and application thereof |
| CN115417999B (en) * | 2022-08-24 | 2023-07-07 | 浙江大学杭州国际科创中心 | One-dimensional polyrotaxane constructed based on coordination boron-nitrogen bond, and preparation method and application thereof |
| CN116239708A (en) * | 2023-03-20 | 2023-06-09 | 山东滨州智源生物科技有限公司 | End-capped polyrotaxane and preparation method and application thereof |
| CN116239708B (en) * | 2023-03-20 | 2024-08-06 | 山东滨州智源生物科技有限公司 | End-capped polyrotaxane and preparation method and application thereof |
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