WO2018218970A1 - Medical conductive hydrogel, preparation method therefor and use thereof - Google Patents

Medical conductive hydrogel, preparation method therefor and use thereof Download PDF

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Publication number
WO2018218970A1
WO2018218970A1 PCT/CN2018/072343 CN2018072343W WO2018218970A1 WO 2018218970 A1 WO2018218970 A1 WO 2018218970A1 CN 2018072343 W CN2018072343 W CN 2018072343W WO 2018218970 A1 WO2018218970 A1 WO 2018218970A1
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Prior art keywords
conductive hydrogel
water
medical conductive
hydrogen phosphate
medical
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PCT/CN2018/072343
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French (fr)
Chinese (zh)
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包磊
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深圳市前海未来无限投资管理有限公司
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Publication of WO2018218970A1 publication Critical patent/WO2018218970A1/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/0002Galenical forms characterised by the drug release technique; Application systems commanded by energy
    • A61K9/0009Galenical forms characterised by the drug release technique; Application systems commanded by energy involving or responsive to electricity, magnetism or acoustic waves; Galenical aspects of sonophoresis, iontophoresis, electroporation or electroosmosis
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02Electrically-conducting adhesives

Definitions

  • the invention belongs to the technical field of hydrogels, and in particular relates to a medical conductive hydrogel and a preparation method and application thereof.
  • Conductive hydrogel is a kind of smart hydrogel, which forms electro-active molecules in the internal network structure of highly hydrophilic gel by copolymerization, crosslinking, grafting, doping, etc., which combines gel properties and electrical activity. characteristic.
  • the gel component imparts high hydrophilicity, swellability, good biocompatibility, and high diffusivity of small molecules in a three-dimensional network structure.
  • Electroactive molecules make the composite possess high conductivity, electrochemical redox, electromechanical conversion, and the like. The combination of the two breaks through the bottleneck that many electroactive materials can not be used in bio-matrix, and has important application value in the field of medical devices.
  • conductive hydrogels in the prior art, usually based on a gel material, and conductive polymers, carbon nanotubes, graphene, graphene oxide, metal nanoparticles, etc. are prepared by blending, doping, etc. .
  • a biocompatible photothermally responsive self-healing conductive hydrogel as disclosed herein, which is an N,N-dimethylacrylamide monomer, an initiator potassium persulfate, and an accelerator N, N, N ', N'-tetramethylethylenediamine is formulated into a monomer solution, and then the graphene hydrogel is immersed in the above monomer solution for solution replacement, allowed to stand, and finally, polymerization is initiated at room temperature.
  • the disclosed conductive hydrogel uses graphene as a three-dimensional network skeleton, and the graphene has high degree of reduction, good chemical stability, high electrical conductivity, high mechanical strength, good photothermal conversion effect, and imparts a hydrogel in the body temperature range and It exhibits good self-healing properties under near-infrared light.
  • the conductive agent is prone to agglomeration and the like, and the dispersion is uneven, thereby causing the hydrogel to be electrically conductive, mechanically unstable, and the biocompatibility is not ideal.
  • it is generally not directly usable in the medical field. If it is used in the medical field, it is necessary to additionally add an antibacterial component, and the existing conductive hydrogel has uncontrollable color and high price of the conductive material.
  • the object of the present invention is to overcome the deficiencies of the prior art and to provide a method for preparing a medical conductive hydrogel, which solves the technical problem that the current conductive hydrogel has poor biocompatibility and unstable electrical conductivity.
  • a medical conductive hydrogel comprises the following mass percentage components:
  • a method of making a medically conductive hydrogel comprises the following basic steps:
  • the component and the proportion thereof contained in the medical conductive hydrogel according to the present invention are respectively measured to comprise a water-soluble polymer material, a zirconium hydrogen phosphate and a salt electrolyte raw material, and water;
  • the temperature of the water-soluble polymer material suspension is lowered to below 50 ° C, and the ⁇ -zirconium hydrogen phosphate dispersion liquid and a salt electrolyte are added for mixing treatment to form a mixture system;
  • the mixture system was added to a sizing container for a cyclic freeze-thaw treatment.
  • an application of the medical conductive hydrogel of the present invention in the field of electrocardiogram, electroencephalogram, and myoelectric electrodes.
  • the medical conductive hydrogel of the present invention introduces nano-material ⁇ -zirconium hydrogen phosphate into the water-soluble polymer material, and the ⁇ -hydrogen phosphate zirconium and the water-soluble polymer material pass hydrogen bonding to achieve physical interaction.
  • the easily soluble salt electrolyte is doped to play an ion conductive role in the water-soluble polymer material.
  • the medical conductive hydrogel of the present invention has excellent biocompatibility and electrical conductivity by the synergistic action of the water-soluble polymer material of zirconium hydrogen phosphate and the easily soluble salt electrolyte, and can be applied to the medical field.
  • the method for preparing a medical conductive hydrogel of the present invention adopts a cyclic freeze-thaw treatment to form a mixed solution of a water-soluble polymer material containing ⁇ -zirconium hydrogen phosphate and a salt electrolyte to form a conductive hydrogel which can be used for medical treatment, and
  • the medical conductive hydrogel of the invention has excellent biocompatibility and electrical conductivity and is low in economic cost.
  • the preparation method of the invention does not require hot press forming, which simplifies the preparation process thereof, reduces the production cost, and is safe and environmentally friendly.
  • the medical conductive hydrogel of the invention has excellent biocompatibility and electrical conductivity, and has low economic cost, effectively expanding its application in the medical field and improving the biocompatibility of its contact with the human body, and Increased sensitivity to signal collection.
  • the quality of the relevant components mentioned in the description of the embodiments of the present invention may not only refer to the proportional relationship of the components, but also the specific content of the mass between the components. Therefore, the proportions of the relevant components in the specification according to the embodiments of the present invention are enlarged or reduced in proportion to the extent disclosed in the specification of the embodiments of the present invention.
  • the mass described in the specification of the embodiment of the present invention may be a mass unit well known in the chemical industry such as ⁇ g, mg, g, kg, and the like.
  • Embodiments of the present invention provide a medical conductive hydrogel having excellent biocompatibility and electrical conductivity.
  • the medical conductive hydrogel of the present invention comprises the following mass percentage components:
  • the water-soluble polymer material contained in the medical conductive hydrogel is a gel matrix.
  • the water soluble polymeric material is chitosan and chitosan derivatives, hydroxyethyl cellulose, hydroxymethyl cellulose, carbomer, polyvinyl alcohol, polyacrylic acid, gelatin, sodium alginate.
  • the water-soluble polymer materials are selected as monomers for synthesizing hydrogels, which are non-toxic, safe, inexpensive, have good biocompatibility, and are in contact with the skin, and are ideal raw materials for preparing traditional hydrogels. After the nano material is reinforced and introduced into the conductive ions, the application requirements of the medical conductive hydrogel can be met.
  • the ⁇ -zirconium hydrogen phosphate contained in the medical conductive hydrogel is a regular hexagonal sheet-like structure, and the surface contains a large amount of -OH, and forms a hydrogen bond with a hydroxyl group in the water-soluble polymer material to physically crosslink. Cyclic freezing-thawing plays a role in enhancing hydrogen bonding, so that the prepared nanocomposite hydrogel has excellent mechanical properties and can meet medical requirements.
  • the ⁇ -zirconium hydrogen phosphate has a particle diameter of 100 to 500 nm.
  • the ⁇ -zisium hydrogen phosphate having the particle diameter can be uniformly dispersed in the above-mentioned medical conductive hydrogel to improve the mechanical properties and mechanical strength of the medical conductive hydrogel.
  • the salt-based electrolyte contained in the above-mentioned medical conductive hydrogel can be dispersed in the form of ions in the gel due to its electrolyte property, and the above-mentioned medical treatment is excellent in the antibacterial effect and excellent electrical conductivity imparted to the medical conductive hydrogel.
  • the conductive hydrogel is electrically conductive and particularly stable.
  • the salt electrolyte is one or more of NaCl, Na2SO4, NaNO3, KCl, K2SO4, KNO3, and AgNO3.
  • the water contained in the above medical conductive hydrogel may be selected from medical water such as deionized water.
  • the medical conductive hydrogel further contains a pigment.
  • the amount of the pigment to be added may be adjusted according to the application requirements of the above-mentioned medical conductive hydrogel.
  • the pigment has a content of 0.01 to 0.5 Torr in the medical conductive hydrogel.
  • the pigment is one or more of methylene blue, amaranth, and carmine.
  • the above-mentioned medical conductive hydrogel has a synergistic effect of zirconium a-hydrogen phosphate and a dissolved salt electrolyte and a water-soluble polymer material by dispersing ⁇ -zirconium hydrogen phosphate and a soluble salt electrolyte in a water-soluble polymer material.
  • the medical conductive hydrogel of the invention has excellent biocompatibility and electrical conductivity, improves the application value thereof in the medical field, and is economical, safe and environmentally friendly.
  • an embodiment of the present invention further provides a preparation method of the medical conductive hydrogel of the embodiment of the present invention.
  • the method for preparing the medical conductive hydrogel comprises the following steps:
  • step S02 dispersing ⁇ -zirconium hydrogen phosphate measured in step S01 into water to form a zirconium a-hydrogen phosphate dispersion;
  • step S03 dispersing the water-soluble polymer material taken in step S01 at 80 to 120 ° C to prepare a water-soluble polymer material suspension;
  • step S04 reducing the temperature of the water-soluble polymer material suspension prepared in step S03 to below 50 ° C, and adding the ⁇ -zirconium hydrogen phosphate dispersion prepared in step S02 and the salt electrolyte to perform a mixture treatment to form a mixture system;
  • the components and contents of the components of the medical conductive hydrogel are as referred to in the above-mentioned medical conductive hydrogel, and the details are not described herein.
  • the ⁇ -zirconium hydrogen phosphate dispersion can be prepared according to a conventional method.
  • the preparation method is ⁇ -phosphate.
  • the zirconium hydroxide is dispersed in water and ultrasonically dispersed for 30 to 60 minutes to prepare an ultrasonic dispersion having a mass concentration of not more than 4.00%.
  • the water-soluble polymer material is dispersed in water at 80 to 120 ° C. It is understood that the water-soluble polymer material is sufficiently dispersed. In an embodiment, the water-soluble polymer material is dispersed at 80 to 120 ° C by stirring. Into the water; wherein the stirring rate is 800 to 1200 r / min, stirring for 6 to 10 minutes.
  • the mass concentration of the water-soluble polymer material suspension prepared at the temperature is controlled to be 16% to 40%.
  • the suspension is further subjected to a stirring treatment at 100-200 r/min.
  • the salt electrolyte is preferably added in the form of a solution, such as a salt electrolyte solution having a mass percentage of 2.00 to 8.00%. This allows the salt electrolyte to be sufficiently dispersed in the mixture to ensure high electrical conductivity and electrical stability of the final medical conductive hydrogel.
  • a dye is mixed with the ⁇ -zirconium hydrogen phosphate dispersion and the salt electrolyte to carry out a mixing treatment.
  • the amount of the pigment added is as described above in the medical conductive hydrogel, and can be adjusted according to the application requirements of the medical conductive hydrogel.
  • the pigment is in the above-mentioned medical conductive hydrogel. It is 0.01-0.5 ⁇ .
  • the pigment is one or more of methylene blue, amaranth, and carmine.
  • the above mixture system forms a gel system during the cyclic freeze-thaw treatment.
  • the temperature of the freezing treatment in the cyclic freezing treatment-thawing treatment is -18 to -40 ° C, and the freezing time is 4 to 8 hours.
  • the temperature of the thawing treatment in the circulation freeze-thaw treatment is normal temperature, and the thawing time is 2-4 hours.
  • the freezing treatment and the thawing treatment are repeated for 3-5 times in a cycle.
  • the medical conductive hydrogel prepared by the invention has excellent biocompatibility and electrical conductivity, and has low economic cost, and the preparation method thereof does not require hot press forming, thereby effectively simplifying the preparation process thereof. , safe and environmentally friendly.
  • the medical conductive hydrogel of the embodiment of the invention described above and the preparation method thereof has excellent biocompatibility and electrical conductivity, low economic cost, safety and environmental protection. Therefore, it can be used in the field of electrocardiogram, electroencephalogram, and electromyography electrodes, thereby improving the biocompatibility of its contact with the human body and improving its sensitivity to signal collection.
  • This embodiment provides a medical conductive hydrogel and a preparation method thereof.
  • the medical conductive hydrogel of this embodiment includes polyvinyl alcohol, ⁇ -zirconium hydrogen phosphate, NaCl, and deionized water.
  • Step S11 taking 0.03 g of ⁇ -zirconium hydrogen phosphate dispersed into 10.00 mL of deionized water and ultrasonically dispersing for 60 min to prepare an ultrasonic dispersion of ⁇ -zirconium hydrogen phosphate;
  • Step S12 Disperse 3.00 g of polyvinyl alcohol 1799 into 30.00 mL of deionized water, stir at 90 ° C for 10 min, and stir at a rate of 1000 r / min to obtain a suspension of polyvinyl alcohol 1799, after which the heating was stopped, and the resulting suspension was Stirring at 200 r/min;
  • Step S13 After the temperature of the suspension obtained in the step S12 is lowered to below 50 ° C, the ultrasonic dispersion of ⁇ -zirconium hydrogen phosphate in step S11 and 2.00 g of NaCl are added to the suspension obtained in the step S12, and added dropwise. 1 ⁇ 2 drops of methylene blue dilution to adjust the color, stir until the system is evenly mixed;
  • Step S14 adding the mixture obtained in step S13 to the mold and sealing;
  • Step S15 the mold containing the mixed liquid in step S14 is placed in a -20 ° C freezer for 6 h, then taken out, and placed at room temperature for 3 h to thaw;
  • Step S16 Step S15 is repeated three times, and the mold is taken out to obtain a medical conductive hydrogel.
  • This embodiment provides a medical conductive hydrogel and a preparation method thereof.
  • the medical conductive hydrogel of this embodiment includes polyvinyl alcohol, ⁇ -zirconium hydrogen phosphate, NaCl, and deionized water.
  • Step S21 taking 0.03 g of ⁇ -zirconium hydrogen phosphate dispersed into 10.00 mL of deionized water and ultrasonically dispersing for 60 min to prepare an ultrasonic dispersion of ⁇ -zirconium hydrogen phosphate;
  • Step S22 6.00 g of polyvinyl alcohol 1799 was dispersed in 30.00 mL of deionized water, stirred at 90 ° C for 10 min, and the stirring rate was 1000 r / min to obtain a suspension of polyvinyl alcohol 1799, after which the heating was stopped, and the resulting suspension was Stirring at 200 r/min;
  • Step S23 after the temperature of the suspension obtained in the step S22 is lowered to 50 ° C or lower, the ultrasonic dispersion of ⁇ -zirconium hydrogen phosphate in step S21 and 4.00 g of NaCl are added to the suspension obtained in the step S22, and added dropwise. 1 ⁇ 2 drops of methylene blue dilution to adjust the color, stir until the system is evenly mixed;
  • Step S24 adding the mixture obtained in step S23 to the mold and sealing;
  • Step S25 the mold containing the mixed liquid in step S24 is placed in a -20 ° C freezer for 6 h, then taken out, and placed at room temperature for 3 h to thaw;
  • Step S26 Step S25 is repeated three times, and the mold is taken out to obtain a medical conductive hydrogel.
  • This embodiment provides a medical conductive hydrogel and a preparation method thereof.
  • the medical conductive hydrogel of this embodiment includes chitosan, ⁇ -zirconium hydrogen phosphate, NaCl, and deionized water.
  • Step S31 taking 0.03 g of ⁇ -zirconium hydrogen phosphate dispersed into 10.00 mL of deionized water and ultrasonically dispersing for 60 min to prepare an ultrasonic dispersion of ⁇ -zirconium hydrogen phosphate;
  • Step S32 Disperse 3.00 g of chitosan into 30.00 mL of deionized water, add acetic acid dropwise, adjust the pH to about 5, stir at 120 ° C for 10 min, and stir at a rate of 1000 r / min to obtain a suspension of chitosan. Heating was stopped and the resulting suspension was stirred at 200 r/min;
  • Step S33 After the temperature of the suspension obtained in step S32 is lowered to below 50 ° C, the ultrasonic dispersion of ⁇ -zirconium hydrogen phosphate and 2.00 g of NaCl in step S31 are added to the suspension obtained in step S32, and 1 is added dropwise. ⁇ 2 methylene blue dilution to adjust the color, stir until the system is evenly mixed;
  • Step S34 adding the mixture obtained in step S33 to the mold and sealing;
  • Step S35 the mold containing the mixed liquid in step S34 is placed in a -20 ° C freezer for 6 h, then taken out, and placed at room temperature for 3 h to thaw;
  • Step S36 Step S35 is repeated three times, and the mold is taken out to obtain a medical conductive hydrogel.
  • This embodiment provides a medical conductive hydrogel and a preparation method thereof.
  • the medical conductive water gel of this embodiment includes chitosan, ⁇ -zirconium hydrogen phosphate, NaCl, and deionized water.
  • Step S41 taking 0.03 g of ⁇ -zirconium hydrogen phosphate dispersed into 10.00 mL of deionized water and ultrasonically dispersing for 60 min to prepare an ultrasonic dispersion of ⁇ -zirconium hydrogen phosphate;
  • Step S42 Disperse 6.00 g of chitosan into 30.00 mL of deionized water, add acetic acid dropwise, adjust the pH to about 5, stir at 120 ° C for 10 min, and stir at a rate of 1000 r/min to obtain a suspension of chitosan. Heating was stopped and the resulting suspension was stirred at 200 r/min;
  • Step S43 after the temperature of the suspension obtained in step S42 is lowered to below 50 ° C, the ultrasonic dispersion of ⁇ -zirconium hydrogen phosphate and 4.00 g of NaCl in step S41 are added to the suspension obtained in step S42, and added dropwise. 1 ⁇ 2 methylene blue dilution liquid to adjust the color, stir until the system is evenly mixed;
  • Step S44 adding the mixture obtained in step S43 to the mold and sealing;
  • Step S45 the mold containing the mixed liquid in step S44 is placed in a -20 ° C freezer for 6 h, then taken out, and placed at room temperature for 3 h to thaw;
  • Step S46 Step S45 is repeated three times, and the mold is taken out to obtain a medical conductive hydrogel.
  • the medical conductive hydrogel of this embodiment includes polyvinyl alcohol 1799, polyethylene glycol 6000, ⁇ -zirconium hydrogen phosphate, NaCl, and deionized water.
  • Step S51 taking 0.03 g of ⁇ -zirconium hydrogen phosphate dispersed into 10.00 mL of deionized water and ultrasonically dispersing for 60 min to prepare an ultrasonic dispersion of ⁇ -zirconium hydrogen phosphate;
  • Step S52 Disperse 2.00 g of polyvinyl alcohol 1799 and 1.00 g of polyethylene glycol 6000 into 30.00 mL of deionized water, stir at 90 ° C for 10 min, and stir at a rate of 1000 r / min to obtain polyvinyl alcohol 1799 and polyethylene glycol. a mixed suspension of 6000, after which the heating was stopped, and the resulting suspension was stirred at 200 r/min;
  • Step S53 after the temperature of the suspension obtained in the step S52 is lowered to 50 ° C or lower, the ultrasonic dispersion of ⁇ -zirconium hydrogen phosphate in step S51 and 2.00 g of NaCl are added to the suspension obtained in the step S52, and added dropwise. 1 ⁇ 2 methylene blue dilution liquid to adjust the color, stir until the system is evenly mixed;
  • Step S54 adding the mixture obtained in step S53 to the mold and sealing;
  • Step S55 The mold containing the mixed liquid in step S54 is placed in a -20 ° C freezer for 6 h, then taken out, and placed at room temperature for 3 h to thaw;
  • Step S56 Step S55 is repeated three times, and the mold is taken out to obtain a medical conductive hydrogel.
  • This embodiment provides a medical conductive hydrogel and a preparation method thereof.
  • the medical conductive hydrogel of this embodiment includes Carbomer 940, ⁇ -zirconium hydrogen phosphate, NaCl, and deionized water.
  • Step S61 taking 0.03 g of ⁇ -zirconium hydrogen phosphate dispersed into 10.00 mL of deionized water and ultrasonically dispersing for 60 min to prepare an ultrasonic dispersion of ⁇ -zirconium hydrogen phosphate;
  • Step S62 Disperse 3.00 g of carbomer 940 into 30.00 mL of deionized water, stir at 90 ° C for 10 min, and stir at a rate of 1000 r / min to obtain a suspension of carbomer 940, and then stop heating, and the resulting suspension is Stirring at 200 r/min;
  • Step S63 after the temperature of the suspension obtained in the step S62 is lowered to 50 ° C or lower, the ultrasonic dispersion of ⁇ -zirconium hydrogen phosphate in step S61 and 2.00 g of NaCl are added to the suspension obtained in the step S62, and added dropwise. 1 ⁇ 2 methylene blue dilution liquid to adjust the color, stir until the system is evenly mixed;
  • Step S64 adding the mixture obtained in step S63 to the mold and sealing;
  • Step S65 the mold containing the mixed liquid in step S64 is placed in a -20 ° C freezer for 6 h, then taken out, and placed at room temperature for 3 h to thaw;
  • Step S66 Step S65 is repeated three times, and the mold is taken out to obtain a medical conductive hydrogel.
  • This embodiment provides a medical conductive hydrogel and a preparation method thereof.
  • the medical conductive hydrogel of this example comprises polyvinyl alcohol 1799, carbomer 940, NaCl, and deionized water.
  • Step S71 taking 0.03 g of ⁇ -zirconium hydrogen phosphate dispersed into 10.00 mL of deionized water and ultrasonically dispersing for 60 min to prepare an ultrasonic dispersion of ⁇ -zirconium hydrogen phosphate;
  • Step S72 2.00 g of polyvinyl alcohol 1799 and 1.00 g of carbomer 940 were dispersed into 30.00 mL of deionized water, stirred at 90 ° C for 10 min, and the stirring rate was 1000 r / min to obtain polyvinyl alcohol 1799 and carbomer 940. Suspension, then heating was stopped, and the resulting suspension was stirred at 200 r/min;
  • Step S73 after the temperature of the suspension obtained in the step S72 is lowered to 50 ° C or lower, the ultrasonic dispersion of ⁇ -zirconium hydrogen phosphate in step S71 and 2.00 g of NaCl are added to the suspension obtained in the step S72, and added dropwise. 1 ⁇ 2 methylene blue dilution liquid to adjust the color, stir until the system is evenly mixed;
  • Step S74 adding the mixture obtained in step S73 to the mold and sealing;
  • Step S75 the mold containing the mixed liquid in step S74 is placed in a -20 ° C freezer for 6 h, then taken out, and placed at room temperature for 3 h to thaw;
  • Step S76 Step S75 is repeated three times, and the mold is taken out to obtain a medical conductive hydrogel.
  • This embodiment provides a medical conductive hydrogel and a preparation method thereof.
  • the medical conductive hydrogel of this example comprises polyvinyl alcohol 1799, gelatin, NaCl, and deionized water.
  • Step S81 taking 0.03 g of ⁇ -zirconium hydrogen phosphate dispersed into 10.00 mL of deionized water and ultrasonically dispersing for 60 min to prepare an ultrasonic dispersion of ⁇ -zirconium hydrogen phosphate;
  • Step S82 Disperse 2.00 g of polyvinyl alcohol 1799 and 1.00 g of gelatin into 30.00 mL of deionized water, stir at 90 ° C for 10 min, and stir at a rate of 1000 r / min to obtain a suspension of polyvinyl alcohol 1799 and gelatin, and then stop heating. The resulting suspension was stirred at 200 r/min;
  • Step S83 After the temperature of the suspension obtained in the step S82 is lowered to 50 ° C or lower, the ultrasonic dispersion of ⁇ -zirconium hydrogen phosphate in step S81 and 2.00 g of NaCl are added to the suspension obtained in the step S82, and added dropwise. 1 ⁇ 2 methylene blue dilution liquid to adjust the color, stir until the system is evenly mixed;
  • Step S84 adding the mixture obtained in step S83 to the mold and sealing;
  • Step S85 the mold containing the mixed liquid in step S84 is placed in a -20 ° C freezer for 6 h, then taken out, and placed at room temperature for 3 h to thaw;
  • Step S86 Step S85 is repeated three times, and the mold is taken out to obtain a medical conductive hydrogel.
  • the medical conductive hydrogels prepared in the above Examples 1-8 were subjected to the relevant performance tests in Table 1 below, and the test results are shown in Table 1. Among them, conductivity, biocompatibility, and ECG signal acquisition applications are in accordance with commonly used test methods in the industry.
  • the medical conductive hydrogel of the embodiment of the invention has excellent biocompatibility and electrical conductivity, and can ensure the sensitivity and stability of ECG signal acquisition.

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Abstract

Disclosed are a medical conductive hydrogel, a preparation method therefor and the use thereof. The hydrogel comprises 8.00-20.00% of a water-soluble macromolecular material, 0.05-2.00% of -zirconium hydrogen phosphate, 0.20-10.00% of a salt electrolyte and 68-91% of water. In the hydrogel, the -zirconium hydrogen phosphate and the dissolved salt electrolyte are dispersed in the water-soluble macromolecular material. By means of the synergistic effect of the -zirconium hydrogen phosphate and the dissolved salt electrolyte with the water-soluble macromolecular material, the hydrogel has excellent biocompatibility and conductivity, and can be used in the medical field. No hot press moulding is required during preparation, thereby simplifying the preparation process, reducing production costs, and being safety and environmentally friendly.

Description

医用导电水凝胶及其制备方法与应用Medical conductive hydrogel and preparation method and application thereof 技术领域Technical field
本发明属于水凝胶技术领域,具体涉及一种医用导电水凝胶及其制备方法与应用。The invention belongs to the technical field of hydrogels, and in particular relates to a medical conductive hydrogel and a preparation method and application thereof.
背景技术Background technique
导电水凝胶是一种智能水凝胶,其通过共聚、交联、接枝、掺杂等方式使电活性分子在高亲水性凝胶内部网络结构形成,集合了凝胶特性和电活性特性。凝胶成分赋予复合材料高亲水性、溶胀性、良好的生物相容性以及小分子在三维网络结构中的高扩散性。电活性分子使得复合材料拥有高导电性、电化学氧化还原性、电机械转换性等。二者相结合突破了许多电活性材料不能用于生物基体的瓶颈,在医疗器械领域具有重要的应用价值。Conductive hydrogel is a kind of smart hydrogel, which forms electro-active molecules in the internal network structure of highly hydrophilic gel by copolymerization, crosslinking, grafting, doping, etc., which combines gel properties and electrical activity. characteristic. The gel component imparts high hydrophilicity, swellability, good biocompatibility, and high diffusivity of small molecules in a three-dimensional network structure. Electroactive molecules make the composite possess high conductivity, electrochemical redox, electromechanical conversion, and the like. The combination of the two breaks through the bottleneck that many electroactive materials can not be used in bio-matrix, and has important application value in the field of medical devices.
然而,现有技术中的导电水凝胶品种很多,通常以凝胶材料为基底,导电高分子、碳纳米管、石墨烯、氧化石墨烯、金属纳米颗粒等通过共混、掺杂等方法制备。如在当前公开的一种生物相容的光热响应自愈合导电水凝胶,其是将N,N-二甲基丙烯酰胺单体、引发剂过硫酸钾和加速剂N,N,N',N'-四甲基乙二胺的配制成单体溶液,然后将石墨烯水凝胶浸泡于上述单体溶液中进行溶液置换,静置,最后在室温下引发聚合反应制得。该公开的导电水凝胶以石墨烯作为三维网络骨架,石墨烯还原程度高,化学稳定性好,电导率高,机械强度高,光热转换效果好,并赋予水凝胶在体温范围内及近红外光照射下表现出良好的自愈合性能。但是现有导电水凝胶存在导电剂易发生团聚等现象而分散不均,从而导致水凝胶导电、机械等性能不稳定,生物兼容性不理想。而且一般不能够直接被用于医用领域,如果用于医用领域,则需要另外添加抗菌成分,而且 现有导电水凝胶颜色不可控以及导电材料价格高昂等缺陷。However, there are many varieties of conductive hydrogels in the prior art, usually based on a gel material, and conductive polymers, carbon nanotubes, graphene, graphene oxide, metal nanoparticles, etc. are prepared by blending, doping, etc. . A biocompatible photothermally responsive self-healing conductive hydrogel as disclosed herein, which is an N,N-dimethylacrylamide monomer, an initiator potassium persulfate, and an accelerator N, N, N ', N'-tetramethylethylenediamine is formulated into a monomer solution, and then the graphene hydrogel is immersed in the above monomer solution for solution replacement, allowed to stand, and finally, polymerization is initiated at room temperature. The disclosed conductive hydrogel uses graphene as a three-dimensional network skeleton, and the graphene has high degree of reduction, good chemical stability, high electrical conductivity, high mechanical strength, good photothermal conversion effect, and imparts a hydrogel in the body temperature range and It exhibits good self-healing properties under near-infrared light. However, in the existing conductive hydrogel, the conductive agent is prone to agglomeration and the like, and the dispersion is uneven, thereby causing the hydrogel to be electrically conductive, mechanically unstable, and the biocompatibility is not ideal. Moreover, it is generally not directly usable in the medical field. If it is used in the medical field, it is necessary to additionally add an antibacterial component, and the existing conductive hydrogel has uncontrollable color and high price of the conductive material.
发明内容Summary of the invention
本发明的目的在于克服上述现有技术存在的不足,提供一种医用导电水凝胶其制备方法,以解决现有导电水凝胶生物相容性不理想,导电性不稳定的技术问题。The object of the present invention is to overcome the deficiencies of the prior art and to provide a method for preparing a medical conductive hydrogel, which solves the technical problem that the current conductive hydrogel has poor biocompatibility and unstable electrical conductivity.
为了实现上述发明目的,本发明的一方面,提供了一种医用导电水凝胶。所述医用导电水凝胶包括如下质量百分比的组分:In order to achieve the above object, in an aspect of the invention, a medical conductive hydrogel is provided. The medical conductive hydrogel comprises the following mass percentage components:
Figure PCTCN2018072343-appb-000001
Figure PCTCN2018072343-appb-000001
本发明的另一方面,提供一种医用导电水凝胶的制备方法。所述医用导电水凝胶的制备方法包括以下基本步骤:In another aspect of the invention, a method of making a medically conductive hydrogel is provided. The method for preparing the medical conductive hydrogel comprises the following basic steps:
按照本发明医用导电水凝胶所含的组分及其比例分别量取包含水溶性高分子材料、α-磷酸氢锆和盐类电解质原料以及水;The component and the proportion thereof contained in the medical conductive hydrogel according to the present invention are respectively measured to comprise a water-soluble polymer material, a zirconium hydrogen phosphate and a salt electrolyte raw material, and water;
将α-磷酸氢锆分散到水中,形成α-磷酸氢锆分散液;Dispersing α-zirconium hydrogen phosphate into water to form an α-zirconium hydrogen phosphate dispersion;
将水溶性高分子材料在80-120℃下分散到水,配制水溶性高分子材料悬浮液;Dissolving the water-soluble polymer material in water at 80-120 ° C to prepare a suspension of water-soluble polymer material;
将所述水溶性高分子材料悬浮液温度降至50℃以下,并加入所述α-磷酸氢锆分散液和盐类电解质进行混料处理,形成混合物体系;The temperature of the water-soluble polymer material suspension is lowered to below 50 ° C, and the α-zirconium hydrogen phosphate dispersion liquid and a salt electrolyte are added for mixing treatment to form a mixture system;
将所述混合物体系加入至定型容器中进行循环冷冻处理-解冻处理。The mixture system was added to a sizing container for a cyclic freeze-thaw treatment.
本发明的又一方面,提供了一种本发明医用导电水凝胶心电、脑电、肌电电极领域中的应用。In still another aspect of the present invention, there is provided an application of the medical conductive hydrogel of the present invention in the field of electrocardiogram, electroencephalogram, and myoelectric electrodes.
与现有技术相比,本发明医用导电水凝胶通过在水溶性高分子材料中引入纳米材料α-磷酸氢锆,α-磷酸氢锆与水溶性高分子材料通过氢键作用,达到 物理交联,以增强水凝胶力学性能。易溶性盐类电解质掺杂在水溶性高分子材料中起到离子导电的作用。通过α-磷酸氢锆和易溶性盐类电解质的水溶性高分子材料的协同作用,使得本发明医用导电水凝胶具有优异的生物相容性和导电性,能够应用于医用领域。Compared with the prior art, the medical conductive hydrogel of the present invention introduces nano-material α-zirconium hydrogen phosphate into the water-soluble polymer material, and the α-hydrogen phosphate zirconium and the water-soluble polymer material pass hydrogen bonding to achieve physical interaction. Union to enhance the mechanical properties of hydrogels. The easily soluble salt electrolyte is doped to play an ion conductive role in the water-soluble polymer material. The medical conductive hydrogel of the present invention has excellent biocompatibility and electrical conductivity by the synergistic action of the water-soluble polymer material of zirconium hydrogen phosphate and the easily soluble salt electrolyte, and can be applied to the medical field.
本发明医用导电水凝胶制备方法采用循环冷冻-解冻处理,使得含有α-磷酸氢锆和盐类电解质的水溶性高分子材料混合溶液形成合成出可用于医用的导电水凝胶,并使得本发明医用导电水凝胶具有优异的生物相容性和导电性,而且经济成本低。另外,本发明制备方法不需热压成型,有效简化了其制备工艺,降低了生产成本,安全环保。The method for preparing a medical conductive hydrogel of the present invention adopts a cyclic freeze-thaw treatment to form a mixed solution of a water-soluble polymer material containing α-zirconium hydrogen phosphate and a salt electrolyte to form a conductive hydrogel which can be used for medical treatment, and The medical conductive hydrogel of the invention has excellent biocompatibility and electrical conductivity and is low in economic cost. In addition, the preparation method of the invention does not require hot press forming, which simplifies the preparation process thereof, reduces the production cost, and is safe and environmentally friendly.
正是由于本发明医用导电水凝胶具有优异的生物相容性和导电性,且经济成本低,有效扩展了其在医用领域中的应用,提高了其与人体接触的生物相容性,而且提高了其对信号收集的灵敏度。It is because the medical conductive hydrogel of the invention has excellent biocompatibility and electrical conductivity, and has low economic cost, effectively expanding its application in the medical field and improving the biocompatibility of its contact with the human body, and Increased sensitivity to signal collection.
具体实施方式detailed description
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。In order to make the objects, technical solutions and advantages of the present invention more comprehensible, the present invention will be further described in detail below with reference to the embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
本发明实施例说明书中所提到的相关成分的质量不仅仅可以指代各组分的比例关系,也可以表示各组分间质量的具体含量。因此,只要是按照本发明实施例说明书相关组分的含量按比例放大或缩小均在本发明实施例说明书公开的范围之内。具体地,本发明实施例说明书中所述的质量可以是μg、mg、g、kg等化工领域公知的质量单位。The quality of the relevant components mentioned in the description of the embodiments of the present invention may not only refer to the proportional relationship of the components, but also the specific content of the mass between the components. Therefore, the proportions of the relevant components in the specification according to the embodiments of the present invention are enlarged or reduced in proportion to the extent disclosed in the specification of the embodiments of the present invention. Specifically, the mass described in the specification of the embodiment of the present invention may be a mass unit well known in the chemical industry such as μg, mg, g, kg, and the like.
本发明实施例提供一种具有优异生物相容性和导电性的医用导电水凝胶。本发明医用导电水凝胶包括如下质量百分比的组分:Embodiments of the present invention provide a medical conductive hydrogel having excellent biocompatibility and electrical conductivity. The medical conductive hydrogel of the present invention comprises the following mass percentage components:
Figure PCTCN2018072343-appb-000002
Figure PCTCN2018072343-appb-000002
Figure PCTCN2018072343-appb-000003
Figure PCTCN2018072343-appb-000003
其中,上述医用导电水凝胶所含的水溶性高分子材料为凝胶基质。在一实施例中,水溶性高分子材料为壳聚糖及壳聚糖衍生物、羟乙基纤维素、羟甲基纤维素、卡波姆、聚乙烯醇、聚丙烯酸、明胶、海藻酸钠、聚乙二醇中的一种或两种以上。选用该些水溶性高分子材料作为合成水凝胶的单体,其无毒安全,价格低廉,具良好的生物相容性,与皮肤具有可接触性,是制备传统水凝胶的理想原料,经纳米材料增强和引入导电离子后能够满足医用导电水凝胶的应用要求。The water-soluble polymer material contained in the medical conductive hydrogel is a gel matrix. In one embodiment, the water soluble polymeric material is chitosan and chitosan derivatives, hydroxyethyl cellulose, hydroxymethyl cellulose, carbomer, polyvinyl alcohol, polyacrylic acid, gelatin, sodium alginate. One or more of polyethylene glycols. The water-soluble polymer materials are selected as monomers for synthesizing hydrogels, which are non-toxic, safe, inexpensive, have good biocompatibility, and are in contact with the skin, and are ideal raw materials for preparing traditional hydrogels. After the nano material is reinforced and introduced into the conductive ions, the application requirements of the medical conductive hydrogel can be met.
上述医用导电水凝胶所含的α-磷酸氢锆是规整的六边形片状结构,表面含有大量-OH,与水溶性高分子材料中的羟基形成氢键起到物理交联的效果,循环冷冻-解冻起到了增强氢键的作用,使得所制备的纳米复合水凝胶具有优异的力学性能,能够满足医用要求。在一实施例中,所述α-磷酸氢锆的粒径为100~500nm。该粒径的α-磷酸氢锆能够在上述医用导电水凝胶中均匀分散,提高上述医用导电水凝胶的力学性能和机械强度。The α-zirconium hydrogen phosphate contained in the medical conductive hydrogel is a regular hexagonal sheet-like structure, and the surface contains a large amount of -OH, and forms a hydrogen bond with a hydroxyl group in the water-soluble polymer material to physically crosslink. Cyclic freezing-thawing plays a role in enhancing hydrogen bonding, so that the prepared nanocomposite hydrogel has excellent mechanical properties and can meet medical requirements. In one embodiment, the α-zirconium hydrogen phosphate has a particle diameter of 100 to 500 nm. The α-zisium hydrogen phosphate having the particle diameter can be uniformly dispersed in the above-mentioned medical conductive hydrogel to improve the mechanical properties and mechanical strength of the medical conductive hydrogel.
上述医用导电水凝胶所含的盐类电解质由于其电解质特性,其能够在凝胶中以离子形式分散,从提赋予上述医用导电水凝胶良好的抗菌效果,优异的导电性能,使得上述医用导电水凝胶导电特定稳定。在一实施例中,该盐类电解质为NaCl、Na2SO4、NaNO3、KCl、K2SO4、KNO3、AgNO3中的一种或两种以上。The salt-based electrolyte contained in the above-mentioned medical conductive hydrogel can be dispersed in the form of ions in the gel due to its electrolyte property, and the above-mentioned medical treatment is excellent in the antibacterial effect and excellent electrical conductivity imparted to the medical conductive hydrogel. The conductive hydrogel is electrically conductive and particularly stable. In one embodiment, the salt electrolyte is one or more of NaCl, Na2SO4, NaNO3, KCl, K2SO4, KNO3, and AgNO3.
上述医用导电水凝胶所含的水可以选用医用的水,如去离子水。The water contained in the above medical conductive hydrogel may be selected from medical water such as deionized water.
在上述各实施例的基础上,上述医用导电水凝胶还包含色素。该色素的添加量可以根据上述医用导电水凝胶的应用需求进行调节,如在一实施例中,所述色素在上述医用导电水凝胶的含量为0.01-0.5‰。在具体实施例中,所述色素为亚甲基蓝、苋菜红、胭脂红中的一种或两种以上。In addition to the above embodiments, the medical conductive hydrogel further contains a pigment. The amount of the pigment to be added may be adjusted according to the application requirements of the above-mentioned medical conductive hydrogel. For example, in one embodiment, the pigment has a content of 0.01 to 0.5 Torr in the medical conductive hydrogel. In a specific embodiment, the pigment is one or more of methylene blue, amaranth, and carmine.
因此,上述医用导电水凝胶通过在水溶性高分子材料中分散α-磷酸氢锆 和易溶性盐类电解质,通过α-磷酸氢锆和溶解盐类电解质与水溶性高分子材料的协同作用,使得本发明医用导电水凝胶具有优异的生物相容性和导电性,提高了其在医学界的应用价值,而且经济成本,安全环保。Therefore, the above-mentioned medical conductive hydrogel has a synergistic effect of zirconium a-hydrogen phosphate and a dissolved salt electrolyte and a water-soluble polymer material by dispersing α-zirconium hydrogen phosphate and a soluble salt electrolyte in a water-soluble polymer material. The medical conductive hydrogel of the invention has excellent biocompatibility and electrical conductivity, improves the application value thereof in the medical field, and is economical, safe and environmentally friendly.
相应地,本发明实施例还提供了本发明实施例医用导电水凝胶的一种制备方法。所述医用导电水凝胶的制备方法包括如下步骤:Correspondingly, an embodiment of the present invention further provides a preparation method of the medical conductive hydrogel of the embodiment of the present invention. The method for preparing the medical conductive hydrogel comprises the following steps:
S01:按照上文本发明医用导电水凝胶所含的组分及其比例分别量取包含水溶性高分子材料、α-磷酸氢锆和盐类电解质原料以及水;S01: according to the composition and proportion of the medical conductive hydrogel according to the above invention, the water-soluble polymer material, α-hydrogen phosphate zirconium and salt electrolyte raw materials and water are respectively measured;
S02:将步骤S01量取的α-磷酸氢锆分散到水中,形成α-磷酸氢锆分散液;S02: dispersing α-zirconium hydrogen phosphate measured in step S01 into water to form a zirconium a-hydrogen phosphate dispersion;
S03:将步骤S01量取的水溶性高分子材料在80~120℃下分散到水,配制水溶性高分子材料悬浮液;S03: dispersing the water-soluble polymer material taken in step S01 at 80 to 120 ° C to prepare a water-soluble polymer material suspension;
S04:将步骤S03配制的水溶性高分子材料悬浮液温度降至50℃以下,并加入步骤S02配制的α-磷酸氢锆分散液和盐类电解质进行混料处理,形成混合物体系;S04: reducing the temperature of the water-soluble polymer material suspension prepared in step S03 to below 50 ° C, and adding the α-zirconium hydrogen phosphate dispersion prepared in step S02 and the salt electrolyte to perform a mixture treatment to form a mixture system;
S05:将步骤S04配制的混合物体系加入至定型容器中进行循环冷冻处理-解冻处理。S05: The mixture system prepared in the step S04 is added to a sizing container for cyclic freezing treatment-thawing treatment.
具体地,上述步骤S01中称取各组分原料均如上文医用导电水凝胶中所含的组分和含量,为了节约篇幅,在此不再赘述。Specifically, in the above step S01, the components and contents of the components of the medical conductive hydrogel are as referred to in the above-mentioned medical conductive hydrogel, and the details are not described herein.
上述步骤S02中,α-磷酸氢锆分散液配制可以按照常规方法进行配制,为了提高α-磷酸氢锆的分散度和分散液的稳定性,在一实施例中,配制方法是将α-磷酸氢锆分散到水中,超声分散30~60min,制成质量浓度不大于4.00%的超声分散液。In the above step S02, the α-zirconium hydrogen phosphate dispersion can be prepared according to a conventional method. In order to improve the dispersion of α-hydrogen zirconium phosphate and the stability of the dispersion, in one embodiment, the preparation method is α-phosphate. The zirconium hydroxide is dispersed in water and ultrasonically dispersed for 30 to 60 minutes to prepare an ultrasonic dispersion having a mass concentration of not more than 4.00%.
上述步骤S03中,水溶性高分子材料在80~120℃下分散到水应该理解的是充分分散,如在一实施例中,采用搅拌的方式将水溶性高分子材料在80~120℃下分散到水中;其中,搅拌的速率为800~1200r/min下搅拌6~10min。In the above step S03, the water-soluble polymer material is dispersed in water at 80 to 120 ° C. It is understood that the water-soluble polymer material is sufficiently dispersed. In an embodiment, the water-soluble polymer material is dispersed at 80 to 120 ° C by stirring. Into the water; wherein the stirring rate is 800 to 1200 r / min, stirring for 6 to 10 minutes.
在一实施例中,在该温度下配制的水溶性高分子材料悬浮液的质量浓度控 制为16%-40%。在进一步实施例中,待配制成水溶性高分子材料悬浮液之后,还对该悬浮液以100-200r/min继续进行搅拌处理。通过对水溶性高分子材料悬浮液浓度控制和后续处理,使得水溶性高分子材料悬浮液分散度高,分散体系稳定。In one embodiment, the mass concentration of the water-soluble polymer material suspension prepared at the temperature is controlled to be 16% to 40%. In a further embodiment, after the suspension of the water-soluble polymer material is to be formulated, the suspension is further subjected to a stirring treatment at 100-200 r/min. By controlling the concentration of the water-soluble polymer material suspension and subsequent treatment, the dispersion of the water-soluble polymer material suspension is high, and the dispersion system is stable.
上述步骤S04中,盐类电解质优选以溶液的形式加入,如将其配制质量百分比为2.00~8.00%的盐类电解质溶液。这样使得盐类电解质能够在混合液中充分分散,从而保证最终的医用导电水凝胶高的导电性和导电的稳定性。In the above step S04, the salt electrolyte is preferably added in the form of a solution, such as a salt electrolyte solution having a mass percentage of 2.00 to 8.00%. This allows the salt electrolyte to be sufficiently dispersed in the mixture to ensure high electrical conductivity and electrical stability of the final medical conductive hydrogel.
在上述各实施例的基础上,在该步骤S04中,还加入有色素与α-磷酸氢锆分散液和盐类电解质进行混料处理。该色素的添加量如上文在医用导电水凝胶中所述的,可以根据医用导电水凝胶的应用需求进行调节,如在一实施例中,所述色素在上述医用导电水凝胶的含量为0.01-0.5‰。在具体实施例中,所述色素为亚甲基蓝、苋菜红、胭脂红中的一种或两种以上。In addition to the above respective embodiments, in the step S04, a dye is mixed with the α-zirconium hydrogen phosphate dispersion and the salt electrolyte to carry out a mixing treatment. The amount of the pigment added is as described above in the medical conductive hydrogel, and can be adjusted according to the application requirements of the medical conductive hydrogel. For example, in one embodiment, the pigment is in the above-mentioned medical conductive hydrogel. It is 0.01-0.5 ‰. In a specific embodiment, the pigment is one or more of methylene blue, amaranth, and carmine.
上述步骤S05中,上述混合物体系在循环冷冻处理-解冻处理过程中,形成凝胶体系。一实施例中,所述循环冷冻处理-解冻处理中的冷冻处理的温度为-18~-40℃,冷冻时间为4-8h。在另一实施例中,所述循环冷冻处理-解冻处理中的解冻处理的温度为常温,解冻时间为2-4h。在具体实施例中,以所述冷冻处理和解冻处理为周期进行重复处理3-5次。通过对凝胶形成的条件进行控制,在其所含组分的基础上,使得上述混合物体系形成结构优异且稳定的导电水凝胶,并赋予其的生物相容性,提高其在医学领域中的应用价值。In the above step S05, the above mixture system forms a gel system during the cyclic freeze-thaw treatment. In one embodiment, the temperature of the freezing treatment in the cyclic freezing treatment-thawing treatment is -18 to -40 ° C, and the freezing time is 4 to 8 hours. In another embodiment, the temperature of the thawing treatment in the circulation freeze-thaw treatment is normal temperature, and the thawing time is 2-4 hours. In a specific embodiment, the freezing treatment and the thawing treatment are repeated for 3-5 times in a cycle. By controlling the conditions of gel formation, based on the components contained therein, the above mixture system is formed into an excellent and stable conductive hydrogel, and imparts biocompatibility to the medical field. Application value.
由上述医用导电水凝胶制备方法可知,其制备的医用导电水凝胶具有优异的生物相容性和导电性,而且经济成本低,其制备方法不需热压成型,有效简化了其制备工艺,安全环保。According to the preparation method of the above medical conductive hydrogel, the medical conductive hydrogel prepared by the invention has excellent biocompatibility and electrical conductivity, and has low economic cost, and the preparation method thereof does not require hot press forming, thereby effectively simplifying the preparation process thereof. , safe and environmentally friendly.
另一方面,由上文所述的本发明实施例医用导电水凝胶及其制备方法中上述的,上述医用导电水凝胶具有优异的生物相容性和导电性,经济成本低,安全环保,因此,其可以在心电、脑电、肌电电极领域中的应用,从而提高了其与人体接触的生物相容性,而且提高了其对信号收集的灵敏度。On the other hand, in the medical conductive hydrogel of the embodiment of the invention described above and the preparation method thereof, the medical conductive hydrogel has excellent biocompatibility and electrical conductivity, low economic cost, safety and environmental protection. Therefore, it can be used in the field of electrocardiogram, electroencephalogram, and electromyography electrodes, thereby improving the biocompatibility of its contact with the human body and improving its sensitivity to signal collection.
以下结合具体优选实施例对本发明医用导电水凝胶及其制备方法进行详细阐述。The medical conductive hydrogel of the present invention and a preparation method thereof will be described in detail below in conjunction with specific preferred embodiments.
实施例1Example 1
本实施例提供一种医用导电水凝胶及其制备方法。本实施例医用导电水凝胶包括聚乙烯醇、α-磷酸氢锆、NaCl和去离子水。This embodiment provides a medical conductive hydrogel and a preparation method thereof. The medical conductive hydrogel of this embodiment includes polyvinyl alcohol, α-zirconium hydrogen phosphate, NaCl, and deionized water.
本实施例医用导电水凝胶制备方法如下:The preparation method of the medical conductive hydrogel of this embodiment is as follows:
步骤S11:取0.03g α-磷酸氢锆分散到10.00mL去离子水中,超声分散60min,制成α-磷酸氢锆的超声分散液;Step S11: taking 0.03 g of α-zirconium hydrogen phosphate dispersed into 10.00 mL of deionized water and ultrasonically dispersing for 60 min to prepare an ultrasonic dispersion of α-zirconium hydrogen phosphate;
步骤S12:将3.00g聚乙烯醇1799分散到30.00mL去离子水中,在90℃下搅拌10min,搅拌速率为1000r/min,得到聚乙烯醇1799的悬浮液,之后停止加热,所得的悬浮液以200r/min进行搅拌;Step S12: Disperse 3.00 g of polyvinyl alcohol 1799 into 30.00 mL of deionized water, stir at 90 ° C for 10 min, and stir at a rate of 1000 r / min to obtain a suspension of polyvinyl alcohol 1799, after which the heating was stopped, and the resulting suspension was Stirring at 200 r/min;
步骤S13:待步骤S12所得的悬浮液温度降至50℃以下之后,将步骤S11中的α-磷酸氢锆的超声分散液以及2.00g的NaCl加入到步骤S12所得的悬浮液中,并滴加1~2滴亚甲基蓝稀释液调节颜色,搅拌至体系混合均匀;Step S13: After the temperature of the suspension obtained in the step S12 is lowered to below 50 ° C, the ultrasonic dispersion of α-zirconium hydrogen phosphate in step S11 and 2.00 g of NaCl are added to the suspension obtained in the step S12, and added dropwise. 1~2 drops of methylene blue dilution to adjust the color, stir until the system is evenly mixed;
步骤S14:将步骤S13所得的混合液加入到模具中密封好;Step S14: adding the mixture obtained in step S13 to the mold and sealing;
步骤S15:将步骤S14中装有混合液的模具放入-20℃冷柜中冷冻6h,然后取出,常温下放置3h解冻;Step S15: the mold containing the mixed liquid in step S14 is placed in a -20 ° C freezer for 6 h, then taken out, and placed at room temperature for 3 h to thaw;
步骤S16:重复步骤S15 3次,取出模具,即得一种医用导电水凝胶。Step S16: Step S15 is repeated three times, and the mold is taken out to obtain a medical conductive hydrogel.
实施例2Example 2
本实施例提供一种医用导电水凝胶及其制备方法。本实施例医用导电水凝胶包括聚乙烯醇、α-磷酸氢锆、NaCl和去离子水。This embodiment provides a medical conductive hydrogel and a preparation method thereof. The medical conductive hydrogel of this embodiment includes polyvinyl alcohol, α-zirconium hydrogen phosphate, NaCl, and deionized water.
本实施例医用导电水凝胶制备方法如下:The preparation method of the medical conductive hydrogel of this embodiment is as follows:
步骤S21:取0.03g α-磷酸氢锆分散到10.00mL去离子水中,超声分散60min,制成α-磷酸氢锆的超声分散液;Step S21: taking 0.03 g of α-zirconium hydrogen phosphate dispersed into 10.00 mL of deionized water and ultrasonically dispersing for 60 min to prepare an ultrasonic dispersion of α-zirconium hydrogen phosphate;
步骤S22:将6.00g聚乙烯醇1799分散到30.00mL去离子水中,在90℃下搅拌10min,搅拌速率为1000r/min,得到聚乙烯醇1799的悬浮液,之后停 止加热,所得的悬浮液以200r/min进行搅拌;Step S22: 6.00 g of polyvinyl alcohol 1799 was dispersed in 30.00 mL of deionized water, stirred at 90 ° C for 10 min, and the stirring rate was 1000 r / min to obtain a suspension of polyvinyl alcohol 1799, after which the heating was stopped, and the resulting suspension was Stirring at 200 r/min;
步骤S23:待步骤S22所得的悬浮液温度降至50℃以下之后,将步骤S21中的α-磷酸氢锆的超声分散液以及4.00g的NaCl加入到步骤S22所得的悬浮液中,并滴加1~2滴亚甲基蓝稀释液调节颜色,搅拌至体系混合均匀;Step S23: after the temperature of the suspension obtained in the step S22 is lowered to 50 ° C or lower, the ultrasonic dispersion of α-zirconium hydrogen phosphate in step S21 and 4.00 g of NaCl are added to the suspension obtained in the step S22, and added dropwise. 1~2 drops of methylene blue dilution to adjust the color, stir until the system is evenly mixed;
步骤S24:将步骤S23所得的混合液加入到模具中密封好;Step S24: adding the mixture obtained in step S23 to the mold and sealing;
步骤S25:将步骤S24中装有混合液的模具放入-20℃冷柜中冷冻6h,然后取出,常温下放置3h解冻;Step S25: the mold containing the mixed liquid in step S24 is placed in a -20 ° C freezer for 6 h, then taken out, and placed at room temperature for 3 h to thaw;
步骤S26:重复步骤S25 3次,取出模具,即得一种医用导电水凝胶。Step S26: Step S25 is repeated three times, and the mold is taken out to obtain a medical conductive hydrogel.
实施例3Example 3
本实施例提供一种医用导电水凝胶及其制备方法。本实施例医用导电水凝胶包括壳聚糖、α-磷酸氢锆、NaCl和去离子水。This embodiment provides a medical conductive hydrogel and a preparation method thereof. The medical conductive hydrogel of this embodiment includes chitosan, α-zirconium hydrogen phosphate, NaCl, and deionized water.
本实施例医用导电水凝胶制备方法如下:The preparation method of the medical conductive hydrogel of this embodiment is as follows:
步骤S31:取0.03g α-磷酸氢锆分散到10.00mL去离子水中,超声分散60min,制成α-磷酸氢锆的超声分散液;Step S31: taking 0.03 g of α-zirconium hydrogen phosphate dispersed into 10.00 mL of deionized water and ultrasonically dispersing for 60 min to prepare an ultrasonic dispersion of α-zirconium hydrogen phosphate;
步骤S32:将3.00g壳聚糖分散到30.00mL去离子水中,滴加醋酸,调节pH为5左右,在120℃下搅拌10min,搅拌速率为1000r/min,得到壳聚糖的悬浮液,之后停止加热,所得的悬浮液以200r/min进行搅拌;Step S32: Disperse 3.00 g of chitosan into 30.00 mL of deionized water, add acetic acid dropwise, adjust the pH to about 5, stir at 120 ° C for 10 min, and stir at a rate of 1000 r / min to obtain a suspension of chitosan. Heating was stopped and the resulting suspension was stirred at 200 r/min;
步骤S33:待步骤S32所得的悬浮液温度降至50℃以下之后,将步骤S31中α-磷酸氢锆的超声分散液以及2.00g的NaCl加入到步骤S32所得的悬浮液中,并滴加1~2亚甲基蓝稀释液调节颜色,搅拌至体系混合均匀;Step S33: After the temperature of the suspension obtained in step S32 is lowered to below 50 ° C, the ultrasonic dispersion of α-zirconium hydrogen phosphate and 2.00 g of NaCl in step S31 are added to the suspension obtained in step S32, and 1 is added dropwise. ~2 methylene blue dilution to adjust the color, stir until the system is evenly mixed;
步骤S34:将步骤S33所得的混合液加入到模具中密封好;Step S34: adding the mixture obtained in step S33 to the mold and sealing;
步骤S35:将步骤S34中装有混合液的模具放入-20℃冷柜中冷冻6h,然后取出,常温下放置3h解冻;Step S35: the mold containing the mixed liquid in step S34 is placed in a -20 ° C freezer for 6 h, then taken out, and placed at room temperature for 3 h to thaw;
步骤S36:重复步骤S35 3次,取出模具,即得一种医用导电水凝胶。Step S36: Step S35 is repeated three times, and the mold is taken out to obtain a medical conductive hydrogel.
实施例4Example 4
本实施例提供一种医用导电水凝胶及其制备方法。本实施例医用导电水凝 胶包括壳聚糖、α-磷酸氢锆、NaCl和去离子水。This embodiment provides a medical conductive hydrogel and a preparation method thereof. The medical conductive water gel of this embodiment includes chitosan, α-zirconium hydrogen phosphate, NaCl, and deionized water.
本实施例医用导电水凝胶制备方法如下:The preparation method of the medical conductive hydrogel of this embodiment is as follows:
步骤S41:取0.03g α-磷酸氢锆分散到10.00mL去离子水中,超声分散60min,制成α-磷酸氢锆的超声分散液;Step S41: taking 0.03 g of α-zirconium hydrogen phosphate dispersed into 10.00 mL of deionized water and ultrasonically dispersing for 60 min to prepare an ultrasonic dispersion of α-zirconium hydrogen phosphate;
步骤S42:将6.00g壳聚糖分散到30.00mL去离子水中,滴加醋酸,调节pH为5左右,在120℃下搅拌10min,搅拌速率为1000r/min,得到壳聚糖的悬浮液,之后停止加热,所得的悬浮液以200r/min进行搅拌;Step S42: Disperse 6.00 g of chitosan into 30.00 mL of deionized water, add acetic acid dropwise, adjust the pH to about 5, stir at 120 ° C for 10 min, and stir at a rate of 1000 r/min to obtain a suspension of chitosan. Heating was stopped and the resulting suspension was stirred at 200 r/min;
步骤S43:待步骤S42所得的悬浮液温度降至50℃以下之后,将步骤步骤S41中α-磷酸氢锆的超声分散液以及4.00g的NaCl加入到步骤S42所得的悬浮液中,并滴加1~2亚甲基蓝稀释液调节颜色,搅拌至体系混合均匀;Step S43: after the temperature of the suspension obtained in step S42 is lowered to below 50 ° C, the ultrasonic dispersion of α-zirconium hydrogen phosphate and 4.00 g of NaCl in step S41 are added to the suspension obtained in step S42, and added dropwise. 1~2 methylene blue dilution liquid to adjust the color, stir until the system is evenly mixed;
步骤S44:将步骤S43所得的混合液加入到模具中密封好;Step S44: adding the mixture obtained in step S43 to the mold and sealing;
步骤S45:将步骤S44中装有混合液的模具放入-20℃冷柜中冷冻6h,然后取出,常温下放置3h解冻;Step S45: the mold containing the mixed liquid in step S44 is placed in a -20 ° C freezer for 6 h, then taken out, and placed at room temperature for 3 h to thaw;
步骤S46:重复步骤S45 3次,取出模具,即得一种医用导电水凝胶。Step S46: Step S45 is repeated three times, and the mold is taken out to obtain a medical conductive hydrogel.
实施例5Example 5
本实施例提供一种医用导电水凝胶及其制备方法。本实施例医用导电水凝胶包括聚乙烯醇1799、聚乙二醇6000、α-磷酸氢锆、NaCl和去离子水。This embodiment provides a medical conductive hydrogel and a preparation method thereof. The medical conductive hydrogel of this embodiment includes polyvinyl alcohol 1799, polyethylene glycol 6000, α-zirconium hydrogen phosphate, NaCl, and deionized water.
本实施例医用导电水凝胶制备方法如下:The preparation method of the medical conductive hydrogel of this embodiment is as follows:
步骤S51:取0.03g α-磷酸氢锆分散到10.00mL去离子水中,超声分散60min,制成α-磷酸氢锆的超声分散液;Step S51: taking 0.03 g of α-zirconium hydrogen phosphate dispersed into 10.00 mL of deionized water and ultrasonically dispersing for 60 min to prepare an ultrasonic dispersion of α-zirconium hydrogen phosphate;
步骤S52:将2.00g聚乙烯醇1799和1.00g聚乙二醇6000分散到30.00mL去离子水中,在90℃下搅拌10min,搅拌速率为1000r/min,得到聚乙烯醇1799和聚乙二醇6000的混合悬浮液,之后停止加热,所得的悬浮液以200r/min进行搅拌;Step S52: Disperse 2.00 g of polyvinyl alcohol 1799 and 1.00 g of polyethylene glycol 6000 into 30.00 mL of deionized water, stir at 90 ° C for 10 min, and stir at a rate of 1000 r / min to obtain polyvinyl alcohol 1799 and polyethylene glycol. a mixed suspension of 6000, after which the heating was stopped, and the resulting suspension was stirred at 200 r/min;
步骤S53:待步骤S52所得的悬浮液温度降至50℃以下之后,将步骤S51中的α-磷酸氢锆的超声分散液以及2.00g的NaCl加入到步骤S52所得的悬浮 液中,并滴加1~2亚甲基蓝稀释液调节颜色,搅拌至体系混合均匀;Step S53: after the temperature of the suspension obtained in the step S52 is lowered to 50 ° C or lower, the ultrasonic dispersion of α-zirconium hydrogen phosphate in step S51 and 2.00 g of NaCl are added to the suspension obtained in the step S52, and added dropwise. 1~2 methylene blue dilution liquid to adjust the color, stir until the system is evenly mixed;
步骤S54:将步骤S53所得的混合液加入到模具中密封好;Step S54: adding the mixture obtained in step S53 to the mold and sealing;
步骤S55:将步骤S54中装有混合液的模具放入-20℃冷柜中冷冻6h,然后取出,常温下放置3h解冻;Step S55: The mold containing the mixed liquid in step S54 is placed in a -20 ° C freezer for 6 h, then taken out, and placed at room temperature for 3 h to thaw;
步骤S56:重复步骤S55 3次,取出模具,即得一种医用导电水凝胶。Step S56: Step S55 is repeated three times, and the mold is taken out to obtain a medical conductive hydrogel.
实施例6Example 6
本实施例提供一种医用导电水凝胶及其制备方法。本实施例医用导电水凝胶包括卡波姆940、α-磷酸氢锆、NaCl和去离子水。This embodiment provides a medical conductive hydrogel and a preparation method thereof. The medical conductive hydrogel of this embodiment includes Carbomer 940, α-zirconium hydrogen phosphate, NaCl, and deionized water.
本实施例医用导电水凝胶制备方法如下:The preparation method of the medical conductive hydrogel of this embodiment is as follows:
步骤S61:取0.03g α-磷酸氢锆分散到10.00mL去离子水中,超声分散60min,制成α-磷酸氢锆的超声分散液;Step S61: taking 0.03 g of α-zirconium hydrogen phosphate dispersed into 10.00 mL of deionized water and ultrasonically dispersing for 60 min to prepare an ultrasonic dispersion of α-zirconium hydrogen phosphate;
步骤S62:将3.00g卡波姆940分散到30.00mL去离子水中,在90℃下搅拌10min,搅拌速率为1000r/min,得到卡波姆940的悬浮液,之后停止加热,所得的悬浮液以200r/min进行搅拌;Step S62: Disperse 3.00 g of carbomer 940 into 30.00 mL of deionized water, stir at 90 ° C for 10 min, and stir at a rate of 1000 r / min to obtain a suspension of carbomer 940, and then stop heating, and the resulting suspension is Stirring at 200 r/min;
步骤S63:待步骤S62所得的悬浮液温度降至50℃以下之后,将步骤S61中的α-磷酸氢锆的超声分散液以及2.00g的NaCl加入到步骤S62所得的悬浮液中,并滴加1~2亚甲基蓝稀释液调节颜色,搅拌至体系混合均匀;Step S63: after the temperature of the suspension obtained in the step S62 is lowered to 50 ° C or lower, the ultrasonic dispersion of α-zirconium hydrogen phosphate in step S61 and 2.00 g of NaCl are added to the suspension obtained in the step S62, and added dropwise. 1~2 methylene blue dilution liquid to adjust the color, stir until the system is evenly mixed;
步骤S64:将步骤S63所得的混合液加入到模具中密封好;Step S64: adding the mixture obtained in step S63 to the mold and sealing;
步骤S65:将步骤S64中装有混合液的模具放入-20℃冷柜中冷冻6h,然后取出,常温下放置3h解冻;Step S65: the mold containing the mixed liquid in step S64 is placed in a -20 ° C freezer for 6 h, then taken out, and placed at room temperature for 3 h to thaw;
步骤S66:重复步骤S65 3次,取出模具,即得一种医用导电水凝胶。Step S66: Step S65 is repeated three times, and the mold is taken out to obtain a medical conductive hydrogel.
实施例7Example 7
本实施例提供一种医用导电水凝胶及其制备方法。本实施例医用导电水凝胶包括聚乙烯醇1799、卡波姆940、NaCl和去离子水。This embodiment provides a medical conductive hydrogel and a preparation method thereof. The medical conductive hydrogel of this example comprises polyvinyl alcohol 1799, carbomer 940, NaCl, and deionized water.
本实施例医用导电水凝胶制备方法如下:The preparation method of the medical conductive hydrogel of this embodiment is as follows:
步骤S71:取0.03g α-磷酸氢锆分散到10.00mL去离子水中,超声分散 60min,制成α-磷酸氢锆的超声分散液;Step S71: taking 0.03 g of α-zirconium hydrogen phosphate dispersed into 10.00 mL of deionized water and ultrasonically dispersing for 60 min to prepare an ultrasonic dispersion of α-zirconium hydrogen phosphate;
步骤S72:将2.00g聚乙烯醇1799和1.00g卡波姆940分散到30.00mL去离子水中,在90℃下搅拌10min,搅拌速率为1000r/min,得到聚乙烯醇1799和卡波姆940的悬浮液,之后停止加热,所得的悬浮液以200r/min进行搅拌;Step S72: 2.00 g of polyvinyl alcohol 1799 and 1.00 g of carbomer 940 were dispersed into 30.00 mL of deionized water, stirred at 90 ° C for 10 min, and the stirring rate was 1000 r / min to obtain polyvinyl alcohol 1799 and carbomer 940. Suspension, then heating was stopped, and the resulting suspension was stirred at 200 r/min;
步骤S73:待步骤S72所得的悬浮液温度降至50℃以下之后,将步骤S71中的α-磷酸氢锆的超声分散液以及2.00g的NaCl加入到步骤S72所得的悬浮液中,并滴加1~2亚甲基蓝稀释液调节颜色,搅拌至体系混合均匀;Step S73: after the temperature of the suspension obtained in the step S72 is lowered to 50 ° C or lower, the ultrasonic dispersion of α-zirconium hydrogen phosphate in step S71 and 2.00 g of NaCl are added to the suspension obtained in the step S72, and added dropwise. 1~2 methylene blue dilution liquid to adjust the color, stir until the system is evenly mixed;
步骤S74:将步骤S73所得的混合液加入到模具中密封好;Step S74: adding the mixture obtained in step S73 to the mold and sealing;
步骤S75:将步骤S74中装有混合液的模具放入-20℃冷柜中冷冻6h,然后取出,常温下放置3h解冻;Step S75: the mold containing the mixed liquid in step S74 is placed in a -20 ° C freezer for 6 h, then taken out, and placed at room temperature for 3 h to thaw;
步骤S76:重复步骤S75 3次,取出模具,即得一种医用导电水凝胶。Step S76: Step S75 is repeated three times, and the mold is taken out to obtain a medical conductive hydrogel.
实施例8Example 8
本实施例提供一种医用导电水凝胶及其制备方法。本实施例医用导电水凝胶包括聚乙烯醇1799、明胶、NaCl和去离子水。This embodiment provides a medical conductive hydrogel and a preparation method thereof. The medical conductive hydrogel of this example comprises polyvinyl alcohol 1799, gelatin, NaCl, and deionized water.
本实施例医用导电水凝胶制备方法如下:The preparation method of the medical conductive hydrogel of this embodiment is as follows:
步骤S81:取0.03g α-磷酸氢锆分散到10.00mL去离子水中,超声分散60min,制成α-磷酸氢锆的超声分散液;Step S81: taking 0.03 g of α-zirconium hydrogen phosphate dispersed into 10.00 mL of deionized water and ultrasonically dispersing for 60 min to prepare an ultrasonic dispersion of α-zirconium hydrogen phosphate;
步骤S82:将2.00g聚乙烯醇1799和1.00g明胶分散到30.00mL去离子水中,在90℃下搅拌10min,搅拌速率为1000r/min,得到聚乙烯醇1799和明胶的悬浮液,之后停止加热,所得的悬浮液以200r/min进行搅拌;Step S82: Disperse 2.00 g of polyvinyl alcohol 1799 and 1.00 g of gelatin into 30.00 mL of deionized water, stir at 90 ° C for 10 min, and stir at a rate of 1000 r / min to obtain a suspension of polyvinyl alcohol 1799 and gelatin, and then stop heating. The resulting suspension was stirred at 200 r/min;
步骤S83:待步骤S82所得的悬浮液温度降至50℃以下之后,将步骤S81中的α-磷酸氢锆的超声分散液以及2.00g的NaCl加入到步骤S82所得的悬浮液中,并滴加1~2亚甲基蓝稀释液调节颜色,搅拌至体系混合均匀;Step S83: After the temperature of the suspension obtained in the step S82 is lowered to 50 ° C or lower, the ultrasonic dispersion of α-zirconium hydrogen phosphate in step S81 and 2.00 g of NaCl are added to the suspension obtained in the step S82, and added dropwise. 1~2 methylene blue dilution liquid to adjust the color, stir until the system is evenly mixed;
步骤S84:将步骤S83所得的混合液加入到模具中密封好;Step S84: adding the mixture obtained in step S83 to the mold and sealing;
步骤S85:将步骤S84中装有混合液的模具放入-20℃冷柜中冷冻6h,然后取出,常温下放置3h解冻;Step S85: the mold containing the mixed liquid in step S84 is placed in a -20 ° C freezer for 6 h, then taken out, and placed at room temperature for 3 h to thaw;
步骤S86:重复步骤S85 3次,取出模具,即得一种医用导电水凝胶。Step S86: Step S85 is repeated three times, and the mold is taken out to obtain a medical conductive hydrogel.
相关性能测试:Related performance tests:
将上述实施例1-8制备的医用导电水凝胶进行如下表1中的相关性能测试,测试结果如表1中所示。其中,导电性、生物相容性、心电信号采集应用均按照行业常用的试验方法。The medical conductive hydrogels prepared in the above Examples 1-8 were subjected to the relevant performance tests in Table 1 below, and the test results are shown in Table 1. Among them, conductivity, biocompatibility, and ECG signal acquisition applications are in accordance with commonly used test methods in the industry.
表1Table 1
Figure PCTCN2018072343-appb-000004
Figure PCTCN2018072343-appb-000004
由表1可知,本发明实施例医用导电水凝胶具有优异的生物相容性和导电性,并能够保证心电信号采集的灵敏性和稳定。It can be seen from Table 1 that the medical conductive hydrogel of the embodiment of the invention has excellent biocompatibility and electrical conductivity, and can ensure the sensitivity and stability of ECG signal acquisition.
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。The above is only the preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. Within the scope.

Claims (10)

  1. 一种医用导电水凝胶,包括如下质量百分比的组分:A medical conductive hydrogel comprising the following mass percentage components:
    Figure PCTCN2018072343-appb-100001
    Figure PCTCN2018072343-appb-100001
  2. 根据权利要求1所述的医用导电水凝胶,其特征在于:所述α-磷酸氢锆的粒径为100nm-500nm。The medical conductive hydrogel according to claim 1, wherein the α-zirconium hydrogen phosphate has a particle diameter of from 100 nm to 500 nm.
  3. 根据权利要求1所述的医用导电水凝胶,其特征在于:所述水溶性高分子材料为壳聚糖及壳聚糖衍生物、羟乙基纤维素、羟甲基纤维素、卡波姆、聚乙烯醇、聚丙烯酸、明胶、海藻酸钠、聚乙二醇中的一种或两种以上;和/或The medical conductive hydrogel according to claim 1, wherein the water-soluble polymer material is chitosan and chitosan derivatives, hydroxyethyl cellulose, hydroxymethyl cellulose, and carbomer. , one or more of polyvinyl alcohol, polyacrylic acid, gelatin, sodium alginate, polyethylene glycol; and/or
    所述盐类电解质为NaCl、Na2SO4、NaNO3、KCl、K2SO4、KNO3、AgNO3中的一种或两种以上。The salt electrolyte is one or more of NaCl, Na2SO4, NaNO3, KCl, K2SO4, KNO3, and AgNO3.
  4. 根据权利要求1-3任一所述的医用导电水凝胶,其特征在于:所述医用导电水凝胶还包含色素。The medical conductive hydrogel according to any one of claims 1 to 3, wherein the medical conductive hydrogel further comprises a pigment.
  5. 根据权利要求4所述的医用导电水凝胶,其特征在于:所述色素的含量为0.01-0.5‰;和/或The medical conductive hydrogel according to claim 4, wherein the pigment is contained in an amount of from 0.01 to 0.5 Å; and/or
    所述色素为亚甲基蓝、苋菜红、胭脂红中的一种或两种以上。The pigment is one or more of methylene blue, amaranth, and carmine.
  6. 一种医用导电水凝胶的制备方法,包括如下步骤:A method for preparing a medical conductive hydrogel comprises the following steps:
    按照权利要求1-5任一所述的医用导电水凝胶所含的组分及其比例分别量取包含水溶性高分子材料、α-磷酸氢锆和盐类电解质原料以及水;The composition and ratio of the medical conductive hydrogel according to any one of claims 1 to 5, respectively, comprising a water-soluble polymer material, a-hydrogen zirconium hydrogen phosphate and a salt electrolyte material, and water;
    将α-磷酸氢锆分散到水中,形成α-磷酸氢锆分散液;Dispersing α-zirconium hydrogen phosphate into water to form an α-zirconium hydrogen phosphate dispersion;
    将水溶性高分子材料在80-120℃下分散到水,配制水溶性高分子材料悬浮液;Dissolving the water-soluble polymer material in water at 80-120 ° C to prepare a suspension of water-soluble polymer material;
    将所述水溶性高分子材料悬浮液温度降至50℃以下,并加入所述α-磷酸 氢锆分散液和盐类电解质进行混料处理,形成混合物体系;The temperature of the water-soluble polymer material suspension is lowered to below 50 ° C, and the α-hydrogen zirconium phosphate dispersion liquid and a salt electrolyte are added for mixing treatment to form a mixture system;
    将所述混合物体系加入至定性容器中进行循环冷冻处理-解冻处理。The mixture system is added to a qualitative container for cyclic freeze-thaw treatment.
  7. 根据权利要求6所述的制备方法,其特征在于:所述循环冷冻处理-解冻处理中的冷冻处理温度为-18~-40℃,冷冻时间为4-8h;和/或The preparation method according to claim 6, wherein the freezing treatment temperature in the cyclic freezing treatment-thawing treatment is -18 to -40 ° C, and the freezing time is 4 to 8 hours; and/or
    所述循环冷冻处理-解冻处理中的解冻处理温度为常温,解冻时间为2-4h。The thawing treatment temperature in the circulation freezing treatment-thawing treatment is normal temperature, and the thawing time is 2-4 hours.
  8. 根据权利要求7所述的制备方法,其特征在于:所述循环冷冻处理-解冻处理的循环次数为3-5次。The preparation method according to claim 7, wherein the number of cycles of the circulation freezing treatment-thawing treatment is 3-5 times.
  9. 根据权利要求6-8任一所述的制备方法,其特征在于:所述α-磷酸氢锆分散液的质量浓度不大于4%;和/或The preparation method according to any one of claims 6 to 8, characterized in that the mass concentration of the α-zirconium hydrogen phosphate dispersion is not more than 4%; and/or
    所述水溶性高分子材料悬浮液质量浓度为16%-40%。The water-soluble polymer material suspension has a mass concentration of 16% to 40%.
  10. 根据权利要求1-5任一所述的医用导电水凝胶或权利要求6-9任一所述的制备方法制备的医用导电水凝胶在心电、脑电、肌电电极领域中的应用。The medical conductive hydrogel according to any one of claims 1 to 5 or the medical conductive hydrogel prepared by the preparation method according to any one of claims 6 to 9 in the field of electrocardiogram, electroencephalogram, and electromyography electrode.
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