CN110885408B - A method for controlling the mechanical properties of acrylonitrile-based binary copolymerized high-strength hydrogels by molecular weight of cross-linking agent - Google Patents
A method for controlling the mechanical properties of acrylonitrile-based binary copolymerized high-strength hydrogels by molecular weight of cross-linking agent Download PDFInfo
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- CN110885408B CN110885408B CN201811052059.XA CN201811052059A CN110885408B CN 110885408 B CN110885408 B CN 110885408B CN 201811052059 A CN201811052059 A CN 201811052059A CN 110885408 B CN110885408 B CN 110885408B
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 48
- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 38
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000012660 binary copolymerization Methods 0.000 claims abstract description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 17
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 26
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 26
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 26
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 16
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 16
- 239000000499 gel Substances 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 15
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000002953 phosphate buffered saline Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 230000005587 bubbling Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims 4
- 230000006583 body weight regulation Effects 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 abstract description 10
- 230000001276 controlling effect Effects 0.000 abstract description 6
- 230000000977 initiatory effect Effects 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract 1
- 239000008055 phosphate buffer solution Substances 0.000 description 15
- 238000002156 mixing Methods 0.000 description 8
- 239000003755 preservative agent Substances 0.000 description 6
- 230000002335 preservative effect Effects 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a method for regulating and controlling mechanical properties of acrylonitrile-based binary copolymerization high-strength hydrogel by utilizing molecular weight of a cross-linking agent, which can obtain the acrylonitrile-based binary copolymerization high-strength hydrogel with controllable mechanical strength by initiating the cross-linking polymerization of acrylonitrile and polyethylene glycol dimethacrylate with different molecular weights in dimethyl sulfoxide through free radicals. The mechanical strength of the hydrogel is regulated and controlled by regulating the molecular weight of the cross-linking agent, so that the hydrogel has universality in practical application, the performance of the hydrogel can be regulated according to different environments, and meanwhile, the water content of the hydrogel is regulated and controlled by regulating the molecular weight of the cross-linking agent, so that the purposes of controlling the mechanical strength and the water content of the hydrogel are achieved.
Description
Technical Field
The invention relates to the technical field of mechanical strength controllable hydrogel, in particular to a method for regulating and controlling the mechanical property of acrylonitrile-based binary copolymerization high-strength hydrogel by utilizing the molecular weight of a cross-linking agent.
Background
The conventional artificial hydrogel usually has the microscopic defects of low molecular chain density, small acting force between molecular chains, arbitrary cross-linked network structure formed in the gelling process and the like of a molecular-level high-molecular polymer, so that the hydrogel macroscopically has the serious defects of poor mechanical property, poor stability, poor stimulus responsiveness and the like, and the practical application of the hydrogel is greatly hindered.
The traditional high-strength hydrogel is complex in preparation process and relates to multi-step polymerization, and the synthesized hydrogel is single and uncontrollable in mechanical property and even cannot stably exist in a water environment, so that the hydrogel does not have universality in practical application.
Disclosure of Invention
The invention overcomes the defects in the prior art, and provides a method for regulating and controlling the mechanical property of acrylonitrile-based binary copolymerization high-strength hydrogel by using the molecular weight of a cross-linking agent.
The purpose of the invention is realized by the following technical scheme.
The method for regulating and controlling the mechanical property of acrylonitrile-based binary copolymerization high-strength hydrogel by utilizing the molecular weight of a cross-linking agent comprises the following steps:
step 1, adding acrylonitrile and a cross-linking agent polyethylene glycol dimethacrylate (PEGDMA) into dimethyl sulfoxide (DMSO), placing the mixture in a centrifugal tube for dissolving, swirling the mixture in the centrifugal tube until a clear solution is obtained, carrying out nitrogen bubbling on the solution at the room temperature of 20-25 ℃ for 8-12min to remove oxygen, and simultaneously adding an initiator Benzoyl Peroxide (BPO) and a promoter N, N-Dimethylaniline (DMA) for initiating system polymerization, wherein the mass ratio of the acrylonitrile to the cross-linking agent (PEGDMA) is (0.5-1.5) to 1, the total solid content is 25-35 wt% (the total solid content is the ratio of the total mass of all reactants to the total mass of all solvents), the Benzoyl Peroxide (BPO) is 1-3 wt% of the total mass of monomers and the cross-linking agent, and the N, N-Dimethylaniline (DMA) is 40-60 wt% of the mass of the Benzoyl Peroxide (BPO), the molecular weight of polyethylene glycol dimethacrylate (PEGDMA) is 2000-8000;
and 2, placing the reaction solution prepared in the step 1 in a mold consisting of a polymethyl methacrylate (PMMA) plate and a silica gel gasket for polymerization, wherein the reaction temperature is 20-30 ℃, the reaction time is 20-30 hours, taking out the gel after the reaction is finished, and soaking the gel in Phosphate Buffer Solution (PBS) at the temperature of 20-30 ℃ to replace the organic solvent and remove residual monomers and initiators, so as to obtain the strength-controllable binary copolymerization high-strength hydrogel.
In step 1, the mass ratio of acrylonitrile to the crosslinking agent is 1:1, and the total solid content is 28 to 32 wt%.
In step 1, Benzoyl Peroxide (BPO) accounts for 1-2 wt% of the total mass of the monomer and the cross-linking agent, and N, N-Dimethylaniline (DMA) accounts for 48-52 wt% of the mass of the Benzoyl Peroxide (BPO).
In the step 2, the temperature of the polymerization reaction is 24-28 ℃, and the time of the polymerization reaction is 22-26 h.
In the step 2, the length and width of the polymethyl methacrylate (PMMA) plate are 8-12cm, the thickness is 1-3mm, the thickness of the silica gel gasket is 0.5-2.5mm, and the soaking process is to replace Phosphate Buffer Solution (PBS) every 10-12h for 5-10 days.
As shown in FIG. 1, after cutting the gel into dumbbell type test pieces (effective length 10mm, width 2mm, thickness 0.5mm), the gel was stretched using a strain rate of 100mm/min to obtain a hydrogel having Young's modulus of 0.5 to 2.1MPa and tensile strength of 1.7 to 3.0MPa, indicating that the tensile properties of the hydrogel can be changed according to the change in molecular weight of the crosslinking agent.
As shown in FIG. 2, after the gel was prepared into a cylindrical sample (effective diameter 4.7mm, height 4mm), it was compressed at a strain rate of 10mm/min to obtain a hydrogel having a compression modulus of 1.4-3.5MPa and a compressive strength of 9.0-14.5MPa, indicating that the compression properties of the hydrogel could be changed according to the change in molecular weight of the crosslinking agent.
As shown in FIG. 3, the prepared columnar gel was soaked in PBS, and the water content of the hydrogel after equilibration was 65-85%, indicating that the water content of the hydrogel can be changed according to the change of the molecular weight of the cross-linking agent.
The invention has the beneficial effects that: the preparation method is simple, the mechanical property of the hydrogel can be changed by the simple method, and the controllability of the performance is realized; the hydrogel has high modulus and strength, and can stably exist in a water environment.
Drawings
FIG. 1 is a tensile stress-strain test chart of the hydrogel prepared by the present invention, wherein a is the molecular weight of the cross-linking agent 2000, b is the molecular weight of the cross-linking agent 4000, c is the molecular weight of the cross-linking agent 6000, and d is the molecular weight of the cross-linking agent 8000;
FIG. 2 is a graph of the compressive stress-strain test of the hydrogel prepared by the present invention, wherein a is the molecular weight of the cross-linking agent 2000, b is the molecular weight of the cross-linking agent 4000, c is the molecular weight of the cross-linking agent 6000, and d is the molecular weight of the cross-linking agent 8000;
FIG. 3 is a graph showing the equilibrium water content of the hydrogel prepared according to the present invention.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
Step 1, weighing 0.15g of polyethylene glycol dimethacrylate (PEGDMA, molecular weight 2000) by using an analytical balance, putting the weighed polyethylene glycol dimethacrylate into a 5ml centrifuge tube, measuring 0.7ml of DMSO by using a pipette gun to completely dissolve the polyethylene glycol dimethacrylate, adding 0.15ml of acrylonitrile, adding 0.006g of BPO, uniformly mixing the mixture again, and introducing nitrogen for 10min to remove oxygen.
And 2, adding 3 mu L of DMA (direct memory access) into the mixture, uniformly mixing, immediately adding the solution in the centrifugal tube into a mold consisting of a PMMA (polymethyl methacrylate) plate and a silica gel gasket by using a plastic dropper, sealing the opening by using a preservative film, placing the opening in a thermostat at 25 ℃ for 24 hours, and taking out the opening.
And 3, uncovering the mold, taking out the gel sheet, and soaking the gel sheet in Phosphate Buffered Saline (PBS) at 25 ℃. In the soaking process, PBS is replaced every 12h, and the soaking is carried out for 7 days so as to replace the organic solvent and remove residual monomers and the initiator.
Example 2
Step 1, weighing 0.2g of polyethylene glycol dimethacrylate (PEGDMA, molecular weight 4000) by using an analytical balance, putting the weighed polyethylene glycol dimethacrylate into a 5ml centrifuge tube, measuring 0.7ml of DMSO by using a pipette gun to completely dissolve the polyethylene glycol dimethacrylate, adding 0.1ml of acrylonitrile, adding 0.006g of BPO, uniformly mixing the mixture again, and introducing nitrogen for 12min to remove oxygen.
And 2, adding 3 mu L of DMA (direct memory access) into the mixture, uniformly mixing, immediately adding the solution in the centrifugal tube into a mold consisting of a PMMA (polymethyl methacrylate) plate and a silica gel gasket by using a plastic dropper, sealing the opening by using a preservative film, placing the opening in a thermostat at 20 ℃ for 30 hours, and taking out the opening.
And 3, uncovering the mold, taking out the gel sheet, and soaking the gel sheet in Phosphate Buffer Solution (PBS) at the temperature of 20 ℃. In the soaking process, PBS is required to be replaced every 11 hours, and the soaking is carried out for 5 days so as to replace the organic solvent and remove residual monomers and initiators.
Example 3
Step 1, weighing 0.13g of polyethylene glycol dimethacrylate (PEGDMA, molecular weight of 6000) by using an analytical balance, putting the weighed polyethylene glycol dimethacrylate into a 5ml centrifuge tube, measuring 0.7ml of DMSO by using a pipette gun to completely dissolve the polyethylene glycol dimethacrylate, adding 0.17ml of acrylonitrile, adding 0.006g of BPO, uniformly mixing the mixture again, and introducing nitrogen for 11min to remove oxygen.
And 2, adding 3 mu L of DMA (direct memory access) into the mixture, uniformly mixing, immediately adding the solution in the centrifugal tube into a mold consisting of a PMMA (polymethyl methacrylate) plate and a silica gel gasket by using a plastic dropper, sealing the opening by using a preservative film, placing the preservative film in a thermostat at 28 ℃ for 24 hours, and taking out the preservative film.
And 3, uncovering the mold, taking out the gel sheet, and soaking the gel sheet in Phosphate Buffered Saline (PBS) at 28 ℃. In the soaking process, PBS is replaced every 12h, and the soaking is carried out for 10 days so as to replace the organic solvent and remove residual monomers and the initiator.
Example 4
Step 1, weighing 0.15g of polyethylene glycol dimethacrylate (PEGDMA, molecular weight of 8000) by using an analytical balance, putting the weighed polyethylene glycol dimethacrylate into a 5ml centrifuge tube, measuring 0.7ml of DMSO by using a pipette gun to completely dissolve the polyethylene glycol dimethacrylate, adding 0.15ml of acrylonitrile, adding 0.006g of BPO, uniformly mixing the mixture again, and introducing nitrogen for 8min to remove oxygen.
And 2, adding 3 mu L of DMA (direct memory access) into the mixture, uniformly mixing, immediately adding the solution in the centrifugal tube into a mold consisting of a PMMA (polymethyl methacrylate) plate and a silica gel gasket by using a plastic dropper, sealing the opening by using a preservative film, placing the opening in a 30-DEG C incubator for 30 hours, and taking out.
And 3, uncovering the mold, taking out the gel sheet, and soaking the gel sheet in Phosphate Buffer Solution (PBS) at the temperature of 30 ℃. In the soaking process, PBS is required to be replaced every 11 hours, and the soaking is carried out for 6 days so as to replace the organic solvent and remove residual monomers and initiators.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
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| US6621685B1 (en) * | 2002-04-03 | 2003-09-16 | Korea Institute Of Science And Technology | Electric double-layered capacitor using UV-curing gel type polymer electrolyte |
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| CN101475663A (en) * | 2009-01-21 | 2009-07-08 | 中国科学院长春应用化学研究所 | Method for preparing ion liquid type gel polymer electrolyte and battery by in situ polymerization |
| CN101588790A (en) * | 2006-07-06 | 2009-11-25 | 艾博特呼吸有限责任公司 | Superporous hydrogels |
| CN105098233A (en) * | 2014-05-22 | 2015-11-25 | 上海交通大学 | Preparation method of semi-interpenetrating network polymer gel electrolyte membrane |
| CN106750377A (en) * | 2015-11-20 | 2017-05-31 | 温州医科大学 | Hydrogel, the composition for preparing hydrogel and hydrogel preparation method |
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| WO2007016371A2 (en) * | 2005-07-28 | 2007-02-08 | Akina, Inc. | Readily shapeable xerogels having controllably delayed swelling properties |
| US20070212419A1 (en) * | 2006-02-18 | 2007-09-13 | Jozsef Bako | Synthesis of biocompatible nanocomposite hydrogels as a local drug delivery system |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6621685B1 (en) * | 2002-04-03 | 2003-09-16 | Korea Institute Of Science And Technology | Electric double-layered capacitor using UV-curing gel type polymer electrolyte |
| CN101588790A (en) * | 2006-07-06 | 2009-11-25 | 艾博特呼吸有限责任公司 | Superporous hydrogels |
| CN101127408A (en) * | 2007-08-23 | 2008-02-20 | 广州市天赐高新材料科技有限公司 | Polymer electrolyte membrane of micro-crosslinked gel-state lithium ion battery and preparation method thereof |
| CN101475663A (en) * | 2009-01-21 | 2009-07-08 | 中国科学院长春应用化学研究所 | Method for preparing ion liquid type gel polymer electrolyte and battery by in situ polymerization |
| CN105098233A (en) * | 2014-05-22 | 2015-11-25 | 上海交通大学 | Preparation method of semi-interpenetrating network polymer gel electrolyte membrane |
| CN106750377A (en) * | 2015-11-20 | 2017-05-31 | 温州医科大学 | Hydrogel, the composition for preparing hydrogel and hydrogel preparation method |
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