CN112552531A - High-strength medical gel material and preparation method thereof - Google Patents
High-strength medical gel material and preparation method thereof Download PDFInfo
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- CN112552531A CN112552531A CN201910918910.0A CN201910918910A CN112552531A CN 112552531 A CN112552531 A CN 112552531A CN 201910918910 A CN201910918910 A CN 201910918910A CN 112552531 A CN112552531 A CN 112552531A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/14—Chemical modification with acids, their salts or anhydrides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
Abstract
The invention discloses a high-strength medical gel material and a preparation method thereof, wherein the high-strength medical gel material is prepared from 98.0-99.3 parts of methacrylic acid-2-hydroxyethyl ester, 0.5-1.5 parts of hyaluronic acid and 0.2-0.5 part of CaCl2 The traditional Chinese medicine is prepared according to parts by weight. By modifying PHEMA, the problems of poor PHEMA strength and poor water absorption capacity in the prior art are solved, and Hyaluronic Acid (HA) and CaCl are used in the invention2The gel material obtained by modifying the PHEMA gel material has higher strength and higher viscosityWater content.
Description
Technical Field
The invention belongs to the field of modification of gel materials, and particularly relates to a high-strength medical gel material and a preparation method thereof.
Background
2-hydroxyethyl methacrylate (abbreviated as HEMA in English) is a functional monomer synthesized by researchers of DU PONT company in 1936. As a traditional biological base material, HEMA monomers and polymers thereof have good biocompatibility and are widely applied to the aspects of tooth repair, drug slow release, burn coating, organ transplantation, contact lens manufacture, cell culture, biomolecule and enzyme immobilization and the like.
The poly (2-hydroxyethyl methacrylate) (PHEMA) gel material is copolymer hydrogel mainly composed of 2-hydroxyethyl methacrylate monomers, but has the disadvantages of poor mechanical strength, insufficient permeability, weak water absorption capacity and the like, so that the application of the poly (2-hydroxyethyl methacrylate) (PHEMA) gel material is limited to a certain extent. The conventional method for reinforcing the gel material is chemical crosslinking, but the preparation process is complex, the process requirement is high, and industrial production is difficult.
Disclosure of Invention
In view of the above, the present invention needs to provide a high-strength medical gel material and a preparation method thereof, which solves the problems of poor strength and poor water absorption capability of PHEMA in the prior art by modifying PHEMA.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-strength medical gel material is prepared from 98.0-99.3 portions of poly (2-hydroxyethyl methacrylate), 0.5-1.5 portions of hyaluronic acid and 0.2-0.5 portion of CaCl2The traditional Chinese medicine is prepared according to parts by weight.
Further, the molecular weight of the poly (2-hydroxyethyl methacrylate) is 20000-100000.
Further, the molecular weight of the hyaluronic acid is 400000-1000000.
The invention also provides a preparation method of the high-strength medical gel material, which comprises the following steps:
s1, dissolving hyaluronic acid in deionized water to obtain a colloidal solution;
s2, adding poly (2-hydroxyethyl methacrylate) into the colloidal solution, and stirring for 4-8 hours at 70-95 ℃ to obtain polymer mucus;
s3, removing bubbles from the polymer mucus, and then performing freezing-unfreezing circulation reaction to obtain gel;
s4, calcining the gel and then immersing the gel into CaCl2Soaking in the solution, and cleaning to obtain PHEMA/HA-Ca2+A material;
s5, mixing PHEMA/HA-Ca2+After the material is subjected to freezing-unfreezing circulating reaction, the high-strength medical gel material is obtained by calcining.
Further, in step S3, the bubble removal is ultrasonic bubble removal.
Further, the freeze-thaw cycle in step S3 and the freeze-thaw cycle in step S5 are the same, and both are first frozen at a low temperature and then thawed at a high temperature.
Preferably, the low temperature is-30 to-15 ℃, the high temperature is 30 to 40 ℃, and the low temperature and the high temperature are respectively kept for 0.5 to 2 hours.
Furthermore, the calcination process in the step S4 is the same as the calcination process in the step S5, and the calcination process is performed at the temperature of 120-140 ℃ for 1-3 h.
Further, in step S4, the soaking time is 24-72 hours, and the cleaning is performed by using deionized water.
Further, in step S4, the CaCl is2The concentration of the solution is 0.05-0.2 mol/L.
Compared with the prior art, the Hyaluronic Acid (HA) and CaCl are used in the invention2The PHEMA gel material is modified to obtain the gel material with higher strength and higher water content. Firstly, the HA material HAs extremely high water absorption performance, the modified gel material can have higher water content by adding the HA material, and molecular chains of the PHEMA gel material become softer due to the existence of water molecules, so that the toughness is improved.
In CaCl2During the soaking of the solution, Ca2+Ions and carboxyl on PHEMA generate electrostatic interaction to obtain a gel material with a two-dimensional network structure, so that the material has higher strength.
Meanwhile, the preparation method is optimized, and the calcination process is carried out after the freezing-unfreezing circulating reaction, so that the crystallinity of the PHEMA is further improved, and the strength of the modified material is further improved. The invention adopts a pure physical modification means to prepare the two-dimensional reinforced medical gel material, and greatly expands the application field of the poly (2-hydroxyethyl methacrylate) gel material.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
Dissolving 1 part of hyaluronic acid in deionized water according to parts by weight to obtain a colloidal solution; adding 98.7 parts of poly (2-hydroxyethyl methacrylate) into the colloidal solution, and stirring at 85 ℃ for 6 hours to obtain polymer mucus; removing bubbles from the polymer mucus under the ultrasonic condition, and pouring the polymer mucus into a Teflon reaction kettle for freezing (-20 ℃) to unfreezing (35 ℃) to circularly react for 1 hour (0.5 hour for each freezing and unfreezing); putting the reacted gel into an oven, heating to 125 ℃, and preserving heat for 1.5 hours; taking 0.3 part of CaCl2Preparing CaCl with the concentration of 0.08mol/L2Solution, immersing the dried gel in CaCl2Soaking in the solution for 40 hr, and washing with deionized water to obtain PHEMA/HA-Ca2+A material; mixing PHEMA/HA-Ca2+The material is frozen at (-20 ℃) to unfreeze at (35 ℃) for cyclic reaction in a Teflon reaction kettle, and then is put into an oven to be heated to 125 ℃ and then is kept warm for 2 hours, so that the high-strength medical gel material is prepared.
Example 2
Dissolving 1.2 parts by weight of hyaluronic acid in deionized water to obtain a colloidal solution; 98.4 parts of polymethacrylic acid-2-hydroxyAdding ethyl ester into the colloidal solution, and stirring at 80 deg.C for 5 hr to obtain polymer mucus; removing bubbles from the polymer mucus under the ultrasonic condition, and pouring the polymer mucus into a Teflon reaction kettle for freezing (-25 ℃) to unfreezing (32 ℃) to circularly react for 1 hour (0.5 hour for each freezing and unfreezing); putting the reacted gel into an oven, heating to 130 ℃, and preserving heat for 2 hours; taking 0.4 part of CaCl2Prepared into CaCl with the concentration of 0.1mol/L2Solution, immersing the dried gel in CaCl2Soaking in the solution for 48 hr, and washing with deionized water to obtain PHEMA/HA-Ca2+A material; mixing PHEMA/HA-Ca2+The material is frozen at (-25 ℃) to unfreeze at (32 ℃) for cyclic reaction in a Teflon reaction kettle, and then the material is put into an oven to be heated to 130 ℃ and then is kept warm for 2 hours, so that the high-strength medical gel material is prepared.
Example 3
Dissolving 0.8 part of hyaluronic acid in deionized water according to parts by weight to obtain a colloidal solution; adding 98.9 parts of poly (2-hydroxyethyl methacrylate) into the colloidal solution, and stirring at 90 ℃ for 7 hours to obtain polymer mucus; removing bubbles from the polymer mucus under the ultrasonic condition, and pouring the polymer mucus into a Teflon reaction kettle for freezing (-18 ℃) to unfreezing (38 ℃) to circularly react for 1.5 hours (0.75 hour for each freezing and unfreezing); putting the reacted gel into an oven, heating to 135 ℃, and preserving heat for 2.5 hours; taking 0.3 part of CaCl2Prepared into CaCl with the concentration of 0.15mol/L2Solution, immersing the dried gel in CaCl2Soaking in the solution for 60 hr, and washing with deionized water to obtain PHEMA/HA-Ca2+A material; mixing PHEMA/HA-Ca2+The material is frozen at (-18 ℃) to unfreeze at 38 ℃ for cyclic reaction in a Teflon reaction kettle, and then is put into an oven to be heated to 135 ℃ and then is kept warm for 2.5 hours, so that the high-strength medical gel material is prepared.
Example 4
Dissolving 0.5 part of hyaluronic acid in deionized water according to parts by weight to obtain a colloidal solution; adding 98.3 parts of poly (2-hydroxyethyl methacrylate) into the colloidal solution, and stirring at 70 ℃ for 4 hours to obtain polymer mucus; removing bubbles from polymer mucus under ultrasonic condition, and freezing in Teflon reaction kettle (-15 deg.C)Thawing (30 ℃) cycle reaction for 0.5 hours (0.25 h each for freezing and thawing); putting the reacted gel into an oven, heating to 120 ℃, and preserving heat for 1 hour; taking 0.2 part of CaCl2Prepared into CaCl with the concentration of 0.05mol/L2Solution, immersing the dried gel in CaCl2Soaking in the solution for 24 hr, and washing with deionized water to obtain PHEMA/HA-Ca2+A material; mixing PHEMA/HA-Ca2+The material is frozen at (-15 ℃) to unfreeze at (30 ℃) for cyclic reaction in a Teflon reaction kettle, and then the material is put into an oven to be heated to 120 ℃ and then is kept warm for 1 hour, so that the high-strength medical gel material is prepared.
Example 5
Dissolving 1.5 parts by weight of hyaluronic acid in deionized water to obtain a colloidal solution; adding 98 parts of poly (2-hydroxyethyl methacrylate) -into the colloidal solution, and stirring at 95 ℃ for 8 hours to obtain polymer mucus; removing bubbles from the polymer mucus under the ultrasonic condition, and pouring the polymer mucus into a Teflon reaction kettle for freezing (-30 ℃) to unfreezing (40 ℃) to circularly react for 2 hours (1 hour for each freezing and unfreezing); putting the reacted gel into an oven, heating to 140 ℃, and preserving heat for 3 hours; taking 0.5 part of CaCl2Preparing CaCl with the concentration of 0.2mol/L2Solution, immersing the dried gel in CaCl2Soaking in the solution for 72 hr, and washing with deionized water to obtain PHEMA/HA-Ca2+A material; the PHEMA/HA-Ca2+ material is frozen (-30 ℃) to unfreeze (40 ℃) in a Teflon reaction kettle for circular reaction, and then the PHEMA/HA-Ca2+ material is placed in an oven to be heated to 140 ℃ and then is kept warm for 3 hours, so that the high-strength medical gel material is prepared.
After the high-strength medical gel materials prepared in examples 1 to 5 and the same poly (2-hydroxyethyl methacrylate) used in examples 1 to 5 were immersed in water for 24 hours as a comparison, the hydrogel materials swollen in equilibrium were weighed, dried to weight, and the equilibrium water content EWC of the sample was calculated, wherein,
ww is the mass of the hydrogel with balanced swelling, and Wd is the mass of the dried hydrogel;
preparing a sample into a dumbbell-shaped tensile sample strip with the length of 12mm and the width of 2mm, loading 100N force on a tensile strength tester HY-0580, and testing the tensile strength at the tensile speed of 100 mm/min;
the hardness H of the hydrogel was measured by lowering it at a rate of 15mm/min using a cylindrical probe (diameter 6mm) on a QTS-25Texture Analyser, when the hydrogel surface was pressed 6mm down. The results of the above tests are shown in Table 1.
TABLE 1 results of Performance testing of examples 1-5 and comparative samples
As can be seen from Table 1, the strength, softness and water content of the high-strength medical gel material prepared by the invention are all obviously improved, so that the application field of the material is greatly expanded.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The high-strength medical gel material is characterized by comprising 98.0-99.3 parts of methacrylic acid-2-hydroxyethyl ester, 0.5-1.5 parts of hyaluronic acid and 0.2-0.5 part of CaCl2 The traditional Chinese medicine is prepared according to parts by weight.
2. The high-strength medical gel material as claimed in claim 1, wherein the molecular weight of the poly-2-hydroxyethyl methacrylate is 20000-100000.
3. The high strength medical gel material of claim 1, wherein the molecular weight of the hyaluronic acid is 400000-1000000.
4. The method for preparing a high strength medical gel material according to any one of claims 1 to 3, comprising the steps of:
s1, dissolving hyaluronic acid in deionized water to obtain a colloidal solution;
s2, adding poly (2-hydroxyethyl methacrylate) into the colloidal solution, and stirring for 4-8 hours at 70-95 ℃ to obtain polymer mucus;
s3, removing bubbles from the polymer mucus, and then performing freezing-unfreezing circulation reaction to obtain gel;
s4, calcining the gel and then immersing the gel into CaCl2Soaking in the solution, and cleaning to obtain PHEMA/HA-Ca2+A material;
s5, mixing PHEMA/HA-Ca2+After the material is subjected to freezing-unfreezing circulating reaction, the high-strength medical gel material is obtained by calcining.
5. The method of claim 4, wherein the step S3, the bubble removal is ultrasonic bubble removal.
6. The method of claim 4, wherein the freeze-thaw cycle of step S3 and the freeze-thaw cycle of step S5 are identical and are performed by first freezing at a low temperature and then thawing at a high temperature.
7. The method according to claim 6, wherein the low temperature is-30 to-15 ℃, the high temperature is 30 to 40 ℃, and the low temperature and the high temperature are respectively maintained for 0.5 to 2 hours.
8. The method according to claim 4, wherein the calcination in step S4 is the same as the calcination in step S5, and the calcination is performed at 120-140 ℃ for 1-3 h.
9. The method according to claim 4, wherein in step S4, the soaking time is 24-72h, and the cleaning is deionized water cleaning.
10. The method of claim 4, wherein in step S4, the CaCl is2The concentration of the solution is 0.05-0.2 mol/L.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101588790A (en) * | 2006-07-06 | 2009-11-25 | 艾博特呼吸有限责任公司 | Superporous hydrogels |
| CN103254447A (en) * | 2012-08-08 | 2013-08-21 | 上海交通大学 | Hyaluronic acid physical hydrogel containing multi-carboxyl micromolecules and preparation method thereof |
| CN106619488A (en) * | 2016-11-29 | 2017-05-10 | 广州新诚生物科技有限公司 | Preparation method and application of microsphere-loaded PHEMA hydrogel drug carrying body |
| CN107189079A (en) * | 2017-04-29 | 2017-09-22 | 成都博美实润科技有限公司 | A kind of preparation method of high intensity double-network hydrogel |
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- 2019-09-26 CN CN201910918910.0A patent/CN112552531A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101588790A (en) * | 2006-07-06 | 2009-11-25 | 艾博特呼吸有限责任公司 | Superporous hydrogels |
| CN103254447A (en) * | 2012-08-08 | 2013-08-21 | 上海交通大学 | Hyaluronic acid physical hydrogel containing multi-carboxyl micromolecules and preparation method thereof |
| CN106619488A (en) * | 2016-11-29 | 2017-05-10 | 广州新诚生物科技有限公司 | Preparation method and application of microsphere-loaded PHEMA hydrogel drug carrying body |
| CN107189079A (en) * | 2017-04-29 | 2017-09-22 | 成都博美实润科技有限公司 | A kind of preparation method of high intensity double-network hydrogel |
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