CN114149605A - Preparation method of porous hydrogel coating on surface of polypropylene patch - Google Patents
Preparation method of porous hydrogel coating on surface of polypropylene patch Download PDFInfo
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- CN114149605A CN114149605A CN202111442446.6A CN202111442446A CN114149605A CN 114149605 A CN114149605 A CN 114149605A CN 202111442446 A CN202111442446 A CN 202111442446A CN 114149605 A CN114149605 A CN 114149605A
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 120
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 117
- -1 polypropylene Polymers 0.000 title claims abstract description 59
- 239000011248 coating agent Substances 0.000 title claims abstract description 51
- 238000000576 coating method Methods 0.000 title claims abstract description 51
- 239000000017 hydrogel Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 76
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 57
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 57
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 50
- 239000000243 solution Substances 0.000 claims abstract description 37
- 230000008014 freezing Effects 0.000 claims abstract description 31
- 238000007710 freezing Methods 0.000 claims abstract description 31
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 25
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 16
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920005606 polypropylene copolymer Polymers 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 206010061218 Inflammation Diseases 0.000 abstract description 3
- 238000002715 modification method Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 17
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 238000004140 cleaning Methods 0.000 description 12
- 229940032296 ferric chloride Drugs 0.000 description 10
- 238000012876 topography Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000010257 thawing Methods 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 206010019909 Hernia Diseases 0.000 description 2
- 206010060932 Postoperative adhesion Diseases 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 210000000056 organ Anatomy 0.000 description 2
- ZAHRKKWIAAJSAO-UHFFFAOYSA-N rapamycin Natural products COCC(O)C(=C/C(C)C(=O)CC(OC(=O)C1CCCCN1C(=O)C(=O)C2(O)OC(CC(OC)C(=CC=CC=CC(C)CC(C)C(=O)C)C)CCC2C)C(C)CC3CCC(O)C(C3)OC)C ZAHRKKWIAAJSAO-UHFFFAOYSA-N 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- QFJCIRLUMZQUOT-HPLJOQBZSA-N sirolimus Chemical compound C1C[C@@H](O)[C@H](OC)C[C@@H]1C[C@@H](C)[C@H]1OC(=O)[C@@H]2CCCCN2C(=O)C(=O)[C@](O)(O2)[C@H](C)CC[C@H]2C[C@H](OC)/C(C)=C/C=C/C=C/[C@@H](C)C[C@@H](C)C(=O)[C@H](OC)[C@H](O)/C(C)=C/[C@@H](C)C(=O)C1 QFJCIRLUMZQUOT-HPLJOQBZSA-N 0.000 description 2
- 229960002930 sirolimus Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001356 surgical procedure Methods 0.000 description 2
- 210000003815 abdominal wall Anatomy 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229940124599 anti-inflammatory drug Drugs 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000003102 growth factor Substances 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Images
Classifications
-
- 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
- C08J7/04—Coating
- C08J7/056—Forming hydrophilic coatings
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- 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
- C08J2429/00—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 at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
Abstract
The invention discloses a preparation method of a porous hydrogel coating on the surface of a polypropylene patch, which comprises the following steps of carrying out ultrasonic cleaning and drying on a polypropylene material; then, sodium bicarbonate is taken and placed in the polyvinyl alcohol solution, and the mixture is slowly stirred until the sodium bicarbonate is completely dissolved; preparing a ferric chloride solution, mixing with the solution, and fully and uniformly stirring to prepare a mixed solution; coating the prepared mixed solution on the surface of the dried polypropylene material, and freezing the polypropylene material at a low temperature; and finally, taking out the frozen polypropylene material, unfreezing at room temperature, and soaking in deionized water to obtain the polypropylene material with the porous hydrogel coating on the surface. The modification method is simple, mild in condition and easy to control. The modified material can keep the mechanical property of the polypropylene body from being reduced, and can improve the surface hydrophilicity and the anti-inflammation of the PP.
Description
Technical Field
The invention belongs to surface modification of medical polypropylene patch materials, and particularly relates to a preparation method of a porous hydrogel coating on the surface of a polypropylene patch.
Background
Polypropylene (PP) has the advantages of stable chemical properties, high physical strength, good infection resistance, etc., and has been widely used as a material for medical devices, such as a hernia repair material in hernia surgery. However, after surgery, PP patch materials are prone to adhesion to organs and cause associated inflammation. In order to compensate for postoperative adhesion caused by the PP monofilament patch, hydrophilic modification is carried out on the PP monofilament patch to improve hydrophilicity and pollution resistance. Polyvinyl alcohol hydrogel (PVA) has been used in the fields of drug delivery devices, artificial organs, wound dressings, contact lenses, antibacterial, skin care systems, and the like, due to its non-toxicity, high hydrophilicity, good biocompatibility, biodegradability, high mechanical strength, and the like.
Polypropylene materials have poor surface wettability and are not easily combined with hydrophilic materials to improve their surface properties. At present, hydrophilic monomers are grafted on the surface of PP through methods such as chemical modification, initiator initiation, photo initiation, plasma treatment and the like, although the hydrophilicity of the surface of PP can be improved, the method is easy to damage PP to cause reduction of the mechanical property of a body, and the preparation process is complex and is not easy to control. The existing PVA is grafted on the surface of a polypropylene material by a chemical reaction method, so that although the hydrophilicity is improved, the mechanical strength of the PP material is also reduced, and the utilization rate of the material is reduced. Therefore, on the premise of keeping the mechanical property of the polypropylene material body not to be obviously reduced, the hydrophilic modification of the surface of the polypropylene material by adopting a more effective and more economic method is always a hot point of research.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a method for modifying a hydrophilic gel coating on the surface of a polypropylene material by coating.
The technical scheme is as follows: the preparation method of the porous hydrogel coating on the surface of the polypropylene patch comprises the following steps:
(1) carrying out ultrasonic cleaning and drying on a polypropylene material;
(2) placing sodium bicarbonate in polyvinyl alcohol solution, and slowly stirring until the sodium bicarbonate is completely dissolved;
(3) preparing a ferric chloride solution, then mixing the ferric chloride solution with the solution obtained in the step (2), and fully and uniformly stirring to prepare a mixed solution;
(4) coating the mixed solution prepared in the step (3) on the surface of the dried polypropylene material, and then freezing the polypropylene material at low temperature;
(5) and (4) taking out the polypropylene material frozen in the step (4), unfreezing at room temperature, and then soaking in deionized water to obtain the polypropylene material with the porous hydrogel coating on the surface.
Further, the polypropylene material comprises isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene or block copolymer containing ethylene.
Further, the shape of the polypropylene material comprises one or a combination of a plurality of films, nets, particles or microspheres.
Further, in the step (2), the mass ratio of the sodium bicarbonate to the polyvinyl alcohol is 1: 5 to 20.
Further, the polymerization degree of the polyvinyl alcohol is ultrahigh polymerization degree, high polymerization degree, medium polymerization degree and low polymerization degree, and the preferable polymerization degree of the polyvinyl alcohol is 1700-1800.
Further, in the step (3), the volume ratio of the ferric chloride solution to the polyvinyl alcohol solution is 1: 40-400; wherein the concentration of ferric chloride in the ferric chloride solution is 0.01-0.1 mol/L.
Further, in the step (4), the freezing temperature is-5 ℃ to-80 ℃, and the freezing time is 5-24 hours.
Further, in the step (4), the low-temperature freezing mode is non-directional freezing, directional freezing or a combination of the two.
Furthermore, the freezing rate of low-temperature freezing is 0.1-1000 ℃/min. The freezing rate includes a slow rate or a fast rate, the slow rate is 0.1-7 ℃/min, and the fast rate is 7-1000 ℃/min.
Further, in the step (1), the solvent for ultrasonic cleaning is ethanol or dichloromethane, and the drying temperature is 25-40 ℃.
The preparation principle of the invention is as follows: the invention adopts PVA as the surface hydrophilic coating, because the PVA is easy to form glue and film, the PVA is coated on the polypropylene material, after low-temperature freezing, microcrystals are formed among PVA molecular chains to become physical cross-linking points, and meanwhile, the PVA molecular chains pass through the net of the PP materialThe pores are overlapped with each other, and after thawing, a stable hydrophilic hydrogel coating is formed on the surface of the polypropylene material. Meanwhile, a pore-foaming agent sodium bicarbonate is added into the gel, and the obtained pore structure is effectively regulated and controlled by adjusting the addition amount, so that a series of pore structures with different sizes are prepared, and the loading of other substances is facilitated. In addition, ferric chloride solution, Fe, was added to the PVA solution in different proportions3+As a biological metal ion cross-linking agent, the strength of the hydrogel coating can be improved, and the invention adopts PVA, sodium bicarbonate and Fe3+The combination of the components ensures the basic strength of the PP material, improves the hydrophilic property of the surface of the PP material, can also load anti-inflammatory drugs, growth factors and the like, and promotes abdominal wall repair while preventing postoperative adhesion.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: the surface modification method used in the invention is simple, mild in condition and easy to control. The modified material can keep the mechanical property of the polypropylene body from being reduced, and can improve the surface hydrophilicity and the anti-inflammation of the PP. According to the polymerization degree and different addition amounts of the used polyvinyl alcohol, the surface hydrophilicity of the polypropylene material can be effectively controlled, and the method is simple and easy to implement and easy to apply in a large scale.
Drawings
FIG. 1 is a pure PP surface topography;
FIG. 2 is a surface topography of the PP prepared in example 1;
FIG. 3 is a surface topography plot of the PP prepared in comparative example 1;
FIG. 4 is a surface topography plot of the PP prepared in comparative example 2;
FIG. 5 is a surface topography plot of the PP prepared in comparative example 3;
FIG. 6 is a graph of water contact angle for pure PP, example 1 and comparative example 1.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the accompanying drawings and examples.
Example 1
(1) Placing the PP material net in ethanol, stirring and cleaning for three times, wherein each time is 20mL, the cleaning time is three hours, and drying is carried out for 24 hours at the temperature of 40 ℃;
(2) adding 4g of polyvinyl alcohol and 1750 of polymerization degree into 40mL of deionized water, and stirring and dissolving at 80 ℃;
(3) dissolving 0.8g of sodium bicarbonate into the polyvinyl alcohol solution in the step (2), and slowly stirring until the sodium bicarbonate is dissolved;
(4) adding 0.027g of ferric chloride hexahydrate into 10mL of deionized water, and dissolving at room temperature to obtain 0.01mol/L ferric chloride solution;
(5) adding 0.9mL of the ferric chloride hexahydrate solution obtained in the step (4) into the polyvinyl alcohol solution obtained in the step (3), and uniformly mixing;
(6) coating the surface of the PP material net treated in the step (1) with the mixed solution of polyvinyl alcohol and ferric chloride hexahydrate dissolved in the step (5);
(7) freezing the treated PP material net obtained in the step (6) for 12 hours at-20 ℃ by adopting non-directional freezing, wherein the freezing rate is 0.5 ℃/min;
(8) and (4) taking out the PP material net frozen in the step (7), thawing for 12 hours at room temperature, and soaking in deionized water for 72 hours to obtain the polypropylene material with the porous hydrogel coating on the surface. After the PP material net processed by the method is frozen and dried, the PP material net is soaked in PBS, and the hydrogel coating still exists completely.
Example 2
(1) Placing the PP material net in dichloromethane, stirring and cleaning for three times, wherein each time is 20mL, the cleaning time is three hours, and drying is carried out for 30 hours at the temperature of 25 ℃;
(2) adding 16g of polyvinyl alcohol with the polymerization degree of 1700 into 360mL of deionized water, and stirring and dissolving at 80 ℃;
(3) dissolving 0.8g of sodium bicarbonate into the polyvinyl alcohol solution in the step (2), and slowly stirring until the sodium bicarbonate is dissolved;
(4) adding 0.27g of ferric chloride hexahydrate into 10mL of deionized water, and dissolving at room temperature to obtain 0.1mol/L ferric chloride solution;
(5) adding 0.9mL of the ferric chloride hexahydrate solution obtained in the step (4) into the polyvinyl alcohol solution obtained in the step (3), and uniformly mixing;
(6) coating the surface of the PP material net treated in the step (1) with the mixed solution of polyvinyl alcohol and ferric chloride hexahydrate dissolved in the step (5);
(7) freezing the treated PP material net obtained in the step (6) for 5 hours at-80 ℃ by adopting non-directional freezing, wherein the freezing rate is 500 ℃/min;
(8) and (4) taking out the PP material net frozen in the step (7), thawing for 12 hours at room temperature, and soaking in deionized water for 72 hours to obtain the polypropylene material with the porous hydrogel coating on the surface. After the PP material net processed by the method is frozen and dried, the PP material net is soaked in PBS, and the hydrogel coating still exists completely.
Example 3:
(1) placing the PP material net in dichloromethane, stirring and cleaning for three times, wherein each time is 20mL, the cleaning time is three hours, and drying is carried out for 25 hours at the temperature of 30 ℃;
(2) adding 8g of polyvinyl alcohol and 1800 g of polymer into 180mL of deionized water, and stirring and dissolving at 80 ℃;
(3) dissolving 0.8g of sodium bicarbonate into the polyvinyl alcohol solution in the step (2), and slowly stirring until the sodium bicarbonate is dissolved;
(4) adding 0.135g of ferric chloride hexahydrate into 10mL of deionized water, and dissolving at room temperature to obtain 0.05mol/L ferric chloride solution;
(5) adding 0.9mL of the ferric chloride hexahydrate solution obtained in the step (4) into the polyvinyl alcohol solution obtained in the step (3), and uniformly mixing;
(6) coating the surface of the PP material net treated in the step (1) with the mixed solution of polyvinyl alcohol and ferric chloride hexahydrate dissolved in the step (5);
(7) freezing the treated PP material net obtained in the step (6) for 15 hours at-5 ℃ by adopting non-directional freezing, wherein the freezing rate is 7 ℃/min;
(7) and (4) taking out the PP material net frozen in the step (7), thawing for 12 hours at room temperature, and soaking in deionized water for 72 hours to obtain the polypropylene material with the porous hydrogel coating on the surface. After the PP material net processed by the method is frozen and dried, the PP material net is soaked in PBS, and the hydrogel coating still exists completely.
Comparative example 1
Coating PVA only
(1) Placing the polypropylene material net in ethanol, stirring and cleaning for three times, wherein each time is 20mL, the cleaning time is three hours, and drying is carried out for 24 hours at the temperature of 40 ℃;
(2) adding 1g of polyvinyl alcohol and 1750 of polymerization degree into 10mL of deionized water, and stirring and dissolving at 80 ℃;
(3) coating the surface of the PP material net processed in the step (1) with the polyvinyl alcohol solution dissolved in the step (2) to obtain PVA/PP;
(4) freezing the PVA/PP obtained in the step (3) for 12 hours at the temperature of minus 20 ℃;
(5) and (4) taking out the PVA/PP frozen in the step (4), unfreezing at room temperature, and obtaining the polypropylene material with the polyvinyl alcohol hydrogel coating on the surface after 12 hours.
The PVA/PP treated above was freeze-dried and then soaked in PBS, and the hydrogel coating remained intact.
Comparative example 2
Coating of PVA containing sodium bicarbonate
(1) Placing the polypropylene material net in ethanol or dichloromethane, stirring and cleaning for three times, wherein each time is 20mL, the cleaning time is three hours, and drying is carried out for 24 hours at the temperature of 40 ℃;
(2) adding 1g of polyvinyl alcohol and 1750 of polymerization degree into 20mL of deionized water, and stirring and dissolving at 80 ℃;
(3) dissolving 0.05g of sodium bicarbonate into the polyvinyl alcohol solution in the step (2), and slowly stirring until the sodium bicarbonate is dissolved;
(4) coating the surface of the PP material net processed in the step (1) with the mixed solution of polyvinyl alcohol and sodium bicarbonate dissolved in the step (3);
(5) freezing the treated PP material net obtained in the step (4) for 12 hours at the temperature of minus 20 ℃;
(6) and (4) taking out the PP material net frozen in the step (6), thawing for 12 hours at room temperature, and soaking in deionized water for 72 hours to obtain the polypropylene material with the porous hydrogel coating on the surface.
After the PP material net processed by the method is frozen and dried, the PP material net is soaked in PBS, and the hydrogel coating still exists completely.
Comparative example 3
Coating with PVA and Fe only3+Free of sodium bicarbonate
(1) Placing the polypropylene material net in ethanol, stirring and cleaning for three times, wherein each time is 20mL, the cleaning time is three hours, and drying is carried out for 24 hours at the temperature of 40 ℃;
(2) adding 1g of polyvinyl alcohol and 1750 of polymerization degree into 10mL of deionized water, and stirring and dissolving at 80 ℃;
(3) adding 0.027g of ferric chloride hexahydrate into 10mL of deionized water, and dissolving at room temperature to obtain 0.01mol/L ferric chloride solution;
(4) adding 0.25mL of the ferric chloride hexahydrate solution obtained in the step (4) into the polyvinyl alcohol solution obtained in the step (3), and uniformly mixing;
(5) coating the surface of the PP material net treated in the step (1) with the mixed solution of polyvinyl alcohol and ferric chloride hexahydrate dissolved in the step (5);
(6) freezing the treated PP material net obtained in the step (5) for 12 hours at the temperature of minus 20 ℃;
(7) and (4) taking out the PP material net frozen in the step (6), unfreezing at room temperature, and obtaining the polypropylene material with the surface provided with the polyvinyl alcohol hydrogel coating after 12 hours.
The PVA/PP treated above was freeze-dried and then soaked in PBS, and the hydrogel coating remained intact.
Referring to fig. 1-5, surface topography maps of materials prepared from a plain PP surface, example 1, comparative example 2, and comparative example 3, respectively, are shown. FIG. 2 is a comparison of FIG. 1, illustrating the addition of PVA, sodium bicarbonate and ferric chloride hexahydrate to form a coating with a uniform pore structure on the surface of PP; FIG. 3 is a smooth surface coating without a significant void structure, illustrating the presence of only the PVA coating; in fig. 4, only PVA and sodium bicarbonate were added, resulting in a micro-porous structure, but layer cross-linking was not evident; in fig. 5, with the addition of PVA and ferric chloride hexahydrate only, a non-uniform pore structure appeared, illustrating that the coating was not as crosslinked as in example 1.
Referring to fig. 6, the hydrophilicity of example 1 is compared with that of comparative example 1 for pure PP, and it can be seen that the surface hydrophilicity of comparative example 1 is increased and the water contact angle is decreased from 112.25 ° to 47.07 ° compared with unmodified PP. With the addition of sodium bicarbonate and ferric chloride hexahydrate, surface crosslinking is obvious, a network structure is formed, and the water contact angle is 48.80 degrees. Compared with the comparative example 1, the water contact angle of the example 1 is only raised by 1.73 degrees, and the surface structure of the example 1 which simultaneously adopts PVA, sodium bicarbonate and ferric chloride hexahydrate is the best, which indicates that the method not only can improve the surface appearance of PP, but also can increase the hydrophilicity of the PP surface.
The PP material webs prepared in example 1, comparative example 1 and comparative example 3 were used for rapamycin encapsulation and loading, and the test results are shown in table 1.
TABLE 1 rapamycin Loading
| Sample (I) | Encapsulation efficiency% | Load ratio% |
| Example 1 | 30.74 | 15.02 |
| Comparative example 1 | 0 | 0 |
| Comparative example 3 | 0 | 0 |
As can be seen from the table above, the modified PP net has a drug loading rate as high as 15.02% and an encapsulation rate as high as 30.74%, and has no loading effect when only PVA and ferric chloride hexahydrate are added.
Claims (10)
1. A preparation method of a porous hydrogel coating on the surface of a polypropylene patch is characterized by comprising the following steps:
(1) carrying out ultrasonic cleaning and drying on a polypropylene material;
(2) placing sodium bicarbonate in polyvinyl alcohol solution, and slowly stirring until the sodium bicarbonate is completely dissolved;
(3) preparing a ferric chloride solution, then mixing the ferric chloride solution with the solution obtained in the step (2), and fully and uniformly stirring to prepare a mixed solution;
(4) coating the mixed solution prepared in the step (3) on the surface of the dried polypropylene material, and then freezing the polypropylene material at low temperature;
(5) and (4) taking out the polypropylene material frozen in the step (4), unfreezing at room temperature, and then soaking in deionized water to obtain the polypropylene material with the porous hydrogel coating on the surface.
2. The method for preparing the porous hydrogel coating on the surface of the polypropylene patch according to claim 1, wherein the method comprises the following steps: the polypropylene material comprises isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene or block copolymer containing ethylene.
3. The method for preparing the porous hydrogel coating on the surface of the polypropylene patch for use according to claim 2, wherein the method comprises the following steps: the shape of the polypropylene material comprises one or a combination of a plurality of films, nets, particles or microspheres.
4. The method for preparing the porous hydrogel coating on the surface of the polypropylene patch, according to claim 1, wherein the method comprises the following steps: in the step (2), the mass ratio of the sodium bicarbonate to the polyvinyl alcohol is 1: 5 to 20.
5. The method for preparing the porous hydrogel coating on the surface of the polypropylene patch for use according to claim 4, wherein the method comprises the following steps: the polymerization degree of the polyvinyl alcohol is 1700-1800.
6. The method for preparing the porous hydrogel coating on the surface of the polypropylene patch, according to claim 1, wherein the method comprises the following steps: in the step (3), the volume ratio of the ferric chloride solution to the polyvinyl alcohol solution is 1: 40-400; wherein the concentration of ferric chloride in the ferric chloride solution is 0.01-0.1 mol/L.
7. The method for preparing the porous hydrogel coating on the surface of the polypropylene patch, according to claim 1, wherein the method comprises the following steps: in the step (4), the freezing temperature is-5 ℃ to-80 ℃, and the freezing time is 5-24 hours.
8. The method for preparing the porous hydrogel coating on the surface of the polypropylene patch, according to claim 1, wherein the method comprises the following steps: in the step (4), the low-temperature freezing mode is non-directional freezing, directional freezing or a combination of the two.
9. The method for preparing the porous hydrogel coating on the surface of the polypropylene patch for use according to claim 8, wherein the method comprises the following steps: the freezing rate of the low-temperature freezing is 0.1-1000 ℃/min.
10. The method for preparing the porous hydrogel coating on the surface of the polypropylene patch, according to claim 1, wherein the method comprises the following steps: in the step (1), the solvent for ultrasonic cleaning is ethanol or dichloromethane, and the drying temperature is 25-40 ℃.
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