CN109602941B - A kind of high oxygen permeability hydrogel dressing and preparation method thereof - Google Patents
A kind of high oxygen permeability hydrogel dressing and preparation method thereof Download PDFInfo
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- CN109602941B CN109602941B CN201811420837.6A CN201811420837A CN109602941B CN 109602941 B CN109602941 B CN 109602941B CN 201811420837 A CN201811420837 A CN 201811420837A CN 109602941 B CN109602941 B CN 109602941B
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 49
- 239000001301 oxygen Substances 0.000 title claims abstract description 49
- 239000000017 hydrogel Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 230000035699 permeability Effects 0.000 title abstract description 4
- 230000005540 biological transmission Effects 0.000 claims abstract description 40
- 239000000499 gel Substances 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 7
- -1 polydimethylsiloxane Polymers 0.000 claims description 31
- 229920001296 polysiloxane Polymers 0.000 claims description 14
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 239000007983 Tris buffer Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
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- 239000002504 physiological saline solution Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
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- BESKSSIEODQWBP-UHFFFAOYSA-N 3-tris(trimethylsilyloxy)silylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](C)(C)C BESKSSIEODQWBP-UHFFFAOYSA-N 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- ISZBQKWGMCIBCO-UHFFFAOYSA-N 2,2-diethoxy-1-phenylpropan-1-one Chemical compound CCOC(C)(OCC)C(=O)C1=CC=CC=C1 ISZBQKWGMCIBCO-UHFFFAOYSA-N 0.000 claims description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 2
- VPASWAQPISSKJP-UHFFFAOYSA-N ethyl prop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C=C VPASWAQPISSKJP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 230000008961 swelling Effects 0.000 abstract description 7
- 238000002834 transmittance Methods 0.000 abstract description 4
- 210000002950 fibroblast Anatomy 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 2
- 239000003292 glue Substances 0.000 abstract 1
- 208000027418 Wounds and injury Diseases 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 206010052428 Wound Diseases 0.000 description 10
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- 230000004663 cell proliferation Effects 0.000 description 4
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000029663 wound healing Effects 0.000 description 4
- 239000004971 Cross linker Substances 0.000 description 3
- 206010021143 Hypoxia Diseases 0.000 description 3
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- 230000007547 defect Effects 0.000 description 3
- 230000035876 healing Effects 0.000 description 3
- 230000007954 hypoxia Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- 108010087230 Sincalide Proteins 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000008081 blood perfusion Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000010609 cell counting kit-8 assay Methods 0.000 description 1
- 239000006285 cell suspension Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
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- 239000012894 fetal calf serum Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
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- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/20—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing organic materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Epidemiology (AREA)
- Hematology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
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- Materials For Medical Uses (AREA)
Abstract
一种高氧气透过率水凝胶敷料及其制备方法，属于医用敷料技术领域。本发明通过在凝胶网络中引入高氧气透过率、高机械性能的含硅氧烷乙烯基单体(其在凝胶网络中充当交联剂和增容剂)，同时调节其与水凝胶单体的配比，最后在紫外光下引发单体聚合形成凝胶，由此来解决现有水凝胶敷料低氧气透过率、机械性能差、透光率低等问题。实验结果表明，敷料内部为多孔网络结构，溶胀率达到54.6％，氧气透过率达到442.12OTR(mL/m2.day)，断裂伸长率达到的400.1％，拉伸应力达到了1.2704Mpa，且与小鼠胚胎成纤维细胞具有良好的生物相容性。
A high oxygen permeability hydrogel dressing and a preparation method thereof belong to the technical field of medical dressings. The present invention modulates its interaction with hydrogel by introducing a high oxygen transmission rate, high mechanical property siloxane-containing vinyl monomer (which acts as a cross-linking agent and compatibilizer in the gel network) into the gel network. The ratio of the glue monomers, and finally the monomers are polymerized to form a gel under ultraviolet light, thereby solving the problems of low oxygen transmission rate, poor mechanical properties, and low light transmittance of the existing hydrogel dressings. The experimental results show that the inside of the dressing has a porous network structure, the swelling rate reaches 54.6%, the oxygen transmission rate reaches 442.12 OTR (mL/m 2 .day), the elongation at break reaches 400.1%, and the tensile stress reaches 1.2704Mpa, And it has good biocompatibility with mouse embryonic fibroblasts.
Description
Technical Field
The invention belongs to the technical field of medical dressings, and particularly relates to a hydrogel dressing with high oxygen transmission rate and a preparation method thereof.
Background
Along with improvement of medical conditions and enhancement of health consciousness of patients, the traditional wound dressing is increasingly replaced by novel medical dressings in actual application due to the defects that the traditional wound dressing is easy to adhere to a wound surface, is easy to cause secondary injury during replacement, cannot block bacteria and the like. With the continuous and deep research on the wound healing mechanism, people find that the moist wound environment can promote the migration of wound surface edge cells and accelerate the healing of the wound. Therefore, wet dressings that are more in line with the theory of "wet healing" are rapidly evolving. The hydrogel dressing is a wet dressing which is most widely researched and applied at present, has the advantages of promoting wound healing, relieving pain of patients, improving wound microenvironment, inhibiting bacterial growth, preventing wound adhesion and the like, and is considered to be a novel medical dressing with a very promising prospect.
Hydrogel is a hydrophilic three-dimensional network polymer swelling body containing a large amount of water, has good water absorption (water absorption amount from 10% to thousands times of self dry weight), but is generally poor in mechanical properties because a cross-linked structure is often formed by supermolecular interaction or a single covalent bond, and the application of the material is limited due to the defect.
On the other hand, a number of clinical studies have indicated that the risk of developing chronic non-healing wounds increases rapidly when the tissue oxygen partial pressure (pO2) is below a certain level. Hypoxia (Hypoxia) occurs when oxygen consumption exceeds supply. At the same time, poor blood perfusion is generally considered to be associated with a reduced oxygen supply leading to hypoxia of the wound, and thus oxygen is essential for wound healing. However, the hydrogel material itself has very limited oxygen dissolution and delivery capabilities and does not meet the oxygen requirements of the wound healing process.
Aiming at the problems of low oxygen transmission rate, poor mechanical property and the like of the hydrogel dressing, the hydrogel dressing with high oxygen transmission rate, high mechanical property and high light transmittance is designed and prepared. Firstly, polysiloxane with high oxygen transmission rate, high biocompatibility and high mechanical strength is selected as a core component to carry out end group functionalization on the polysiloxane, the polysiloxane is taken as a macromolecular cross-linking agent, and free radical polymerization of the polysiloxane, a monomer (Tris) with high oxygen transmission rate and a hydrophilic monomer (HEMA) is initiated under the initiation of ultraviolet light, so that the hydrogel dressing material with high oxygen transmission rate, high mechanical strength and high light transmittance is prepared. Relevant reports are not found at home and abroad, and the method has good application prospect.
Disclosure of Invention
In order to overcome the technical defects of the original hydrogel dressing and meet the improvement requirements of the original hydrogel dressing, the invention provides a novel hydrogel dressing with high oxygen transmission rate and a preparation method thereof. The hydrogel dressing is characterized in that siloxane-containing vinyl monomers with high oxygen transmission rate and high mechanical property (serving as a cross-linking agent and a compatibilizer in a gel network) are introduced into the gel network, the proportion of the siloxane-containing vinyl monomers and hydrogel monomers is adjusted, and finally the monomers are initiated to polymerize under ultraviolet light to form gel, so that the problems of low oxygen transmission rate, poor mechanical property, low light transmittance and the like of the conventional hydrogel dressing are solved.
In order to achieve the aim, the invention provides a hydrogel dressing with high oxygen transmission rate, which comprises the following components in percentage by mass based on the mass and 100 percent:
a preparation method of a hydrogel dressing with high oxygen transmission rate comprises the following steps:
1) adding hydroxyl-terminated polydimethylsiloxane into a 100mL bottle with a mouth, mechanically stirring in a water bath at 50-70 ℃ (the rotating speed is 200-400 rmp), and vacuum-drying for 2-4 h;
2) balancing the air pressure of the branch bottle to the normal pressure for 25-35 min, weighing a double-bond end capping agent by using a disposable syringe, injecting the double-bond end capping agent into the branch bottle in the step 1) under the normal pressure, sucking a catalyst by using a 100 mu L microsyringe, dripping the catalyst into the branch bottle, stirring at normal temperature for 18-20 h, dissolving a product in the branch bottle by using n-propanol, performing suction filtration by using a 5 mu m filter membrane, and removing a solvent by rotary evaporation to obtain a polysiloxane macromonomer cross-linking agent;
3) taking 27.5-41.8% of polysiloxane macromonomer cross-linking agent, 16.8-22.9% of hydrophilic monomer, 15.9-22.6% of siloxane-containing vinyl monomer and 1.0-2.5% of photoinitiator prepared in the step 2), dissolving in 17.5-25.0% of diluent, magnetically stirring for 10-20 minutes, and ultrasonically defoaming to obtain a polymerization solution;
4) sucking the polymerization solution obtained in the step 3) by using a dropper, dripping the polymerization solution into a polytetrafluoroethylene mold, covering a glass plate on the mold after the polymerization solution is fully dripped, and polymerizing for 30-60 min under ultraviolet light; and (3) lifting the glass plate, taking out the polymerized gel from the mold, washing the gel with ethanol for 10-20 min, and placing the gel in physiological saline to obtain the complete and transparent hydrogel dressing with high oxygen transmission rate.
The hydroxyl-terminated polydimethylsiloxane of the present invention is any one of hydroxyalkyl-terminated modified organosilicon compounds such as Tech-2120, KF-6001(Mn 2000), KF-6002(Mn 3000), and the like.
The double-bond end-capping reagent is one of Isocyano Ethyl Methacrylate (IEM) or isocyanate ethyl acrylate, and the molar ratio of the usage amount of the double-bond end-capping reagent to the hydroxyl end-capped polydimethylsiloxane is 1: 2.
the catalyst is one of dibutyltin dilaurate or 1, 4-butanediol, and the dosage of the catalyst is 1-1.5% of the mass of the hydroxyl-terminated polydimethylsiloxane.
The hydrophilic monomer is any one of hydroxyethyl methacrylate (HEMA), N-dimethyl methacrylamide (DMMA), N-dimethyl acrylamide (DMA) and N-vinyl-2-pyrrolidone (NVP).
The siloxane-containing vinyl monomer is any one of methacryloxypropyl Tris (trimethylsiloxy) silane (Tris), N- [ Tris (trimethylsiloxy) silylpropyl ] - (meth) acrylamide, N- [ Tris (dimethylpropylsilyloxy) -silylpropyl ] - (meth) acrylamide, and N- [ Tris (dimethylphenylsiloxy) silylpropyl ] - (meth) acrylamide.
The photoinitiator is any one of diethoxypropiophenone, Darocur1173 and Darocur 2959.
The diluent is any one of methanol, isopropanol and n-propanol.
Drawings
FIG. 1 is a photograph of a real object of a hydrogel dressing having a high oxygen transmission rate prepared in example 2 of the present invention;
FIG. 2 is an IR spectrum of a polysiloxane macromer crosslinker prepared in example 1 of the present invention;
FIG. 3 is an FE-SEM photograph of the hydrogel dressing with high oxygen transmission rate prepared in example 2 of the present invention;
FIG. 4 is a swelling ratio curve at 37 ℃ of the high oxygen transmission rate hydrogel dressing prepared in example 2 of the present invention;
fig. 5 is an experimental report of the oxygen transmission rate test at 37 ℃ of the high oxygen transmission rate hydrogel dressing prepared in example 2 of the present invention.
FIG. 6 is a stress-strain curve of a high oxygen transmission rate hydrogel dressing prepared in example 2 of the present invention;
FIG. 7 cell proliferation measured in example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
Example 1
A preparation method of a polysiloxane macromonomer cross-linking agent comprises the following steps:
7.5g KF-6001 was added to a 100mL jar, mechanical stirring was inserted, the vacuum flask was stoppered, the vacuum line connected to the stopcock, the jar was dried in a 55 ℃ water bath at 300rmp under vacuum for 2 h. The air pressure is balanced to the normal pressure for 30 +/-5 min, 1.165g of IEM is weighed by a differential method, injected into a reactor by a syringe, 100 mu L of dibutyltin dilaurate catalyst is absorbed by a 100 mu L microsyringe and dripped into the reactor, and stirred for 16h at normal temperature. And dissolving the product in the reaction bottle by using 35mL of n-propanol, transferring the product into a product bottle, carrying out suction filtration by using a 5-micron filter membrane, and removing the solvent by rotary evaporation to obtain the polysiloxane macromonomer crosslinking agent.
Example 2
A preparation method of a hydrogel dressing with high oxygen transmission rate comprises the following steps:
37.5g of the polysiloxane macromonomer crosslinking agent of example 1, 17.8g of hydroxyethyl methacrylate (HEMA), 20.6g of methacryloxypropyl Tris (trimethylsiloxy) silane (Tris), 1.0g of Darocur1173 were weighed out and dissolved in 23.1g by mass of n-propanol, and the solution was magnetically stirred for 20 minutes and ultrasonically defoamed for 10 minutes to obtain a polymerization solution for later use. 5mL of the polymerization solution was sucked up by a pipette and dropped into a Teflon mold having an internal groove of 5X 0.2cm, and after the dropping was completed, a glass plate of 6X 0.2cm was placed on the mold, and the whole was exposed to ultraviolet light to polymerize for 40 min. And (3) lifting the glass plate, taking off the polymerized solid gel from the mold, washing the gel with ethanol for 15min, and then placing the gel in physiological saline to obtain the complete and transparent hydrogel dressing with high oxygen transmission rate.
Example 3
Biocompatibility evaluation was performed on the material of example 2 using mouse embryonic fibroblasts (3T3), and a cell suspension was prepared and seeded in a 24-well plate containing the dressing material of example 2; the control group was cells seeded in 96-well plates without the dressing material of example 2. 10000 cells per well. Culturing at 37 deg.C in 5% carbon dioxide incubator, changing fresh 10% fetal calf serum culture medium every 24 hr, and performing CCK-8 cell proliferation detection. The OD value at a wavelength of 450nm was measured, and the higher the OD value, the larger the number of cells.
The polysiloxane macromonomer cross-linking agent and the hydrogel dressing with high oxygen transmission rate synthesized by the invention are subjected to detailed performance characterization, and the specific characterization mode is as follows:
infrared spectroscopic analysis
The prepared macromonomer crosslinker was characterized by infrared spectroscopy (Spectrum FTIR 8400S spectrometer, Shimadzu). And (3) dropwise adding the prepared macromonomer onto the pressed potassium bromide tablet, drying and testing.
Topography analysis
The morphology of the lyophilized gel was observed by using FE-SEM (Hitachi FE-SEM S-4800 instrument).
Swelling property test:
cutting the freeze-dried gel into small blocks, accurately weighing the mass Wq, soaking the cut small blocks in 500mL of physiological saline at 37 ℃, taking out the small blocks at intervals, wiping off surface water, weighing the small blocks until the weight is unchanged, and recording the mass as Ws, wherein the Swelling Rate (SR) can be calculated by the following formula:
oxygen transmission rate:
oxygen transmission rate measurement the gel material we prepared in example 2 was measured using a Guangzhou international standard Y310 oxygen transmission rate determinator in compliance with the national standard for oxygen transmission rates for thin film materials (GB/T19789-.
And (3) testing mechanical properties:
the prepared hydrogel film sample with high oxygen permeability is cut into standard sample strips (length multiplied by width multiplied by thickness-14 mm multiplied by lOmm multiplied by 1mm), the sample is placed in the center of a flat plate of a universal material tensile testing machine to keep the sample white and vertical, then a clamp is used for clamping, load is slowly applied at a constant speed (20mm/min) until the sample strips break, the maximum tensile stress strength and the elongation at break are measured, and corresponding stress and strain data are calculated according to the maximum tensile stress strength and the elongation at break.
And (3) analyzing an experimental result:
FIG. 2 is an infrared analysis of the polysiloxane macromer crosslinker obtained in example 1: in the figure, 2930 shows a stretching vibration peak of-CH 3. The amide bond absorption peak at 1658 indicates that isocyanic acid does react successfully with the hydroxyl group on KF-6001. While peaks around 1600 are from double bonds on the IEM. In conclusion, the IEM successfully seals the KF-6001.
The FE-SEM photograph of fig. 3 clearly shows the porous network structure inside the high oxygen transmission rate hydrogel dressing prepared in example 2.
Fig. 4 is a swelling curve of the hydrogel dressing with high oxygen transmission rate prepared in example 2 at 37 c, and it can be seen that swelling equilibrium is reached after 90 minutes, and the swelling rate is 54.6%.
FIG. 5 is an experimental report of oxygen transmission rate of the hydrogel dressing with high oxygen transmission rate prepared in example 2, and it can be seen from the graph that the oxygen transmission rate of the material reaches 442.12OTR (mL/m)2.day)。
FIG. 6 is a stress-strain curve of the hydrogel dressing with high oxygen permeability prepared in example 2, from which it can be seen that the elongation at break of the material reaches 400.1% and the tensile stress reaches 1.2704 MPa. Compared with the traditional hydrogel, the mechanical property is obviously improved.
FIG. 7 cell proliferation measured in example 3, the higher OD value indicates the greater number of cells, the good cell proliferation in the first three days, and the good biocompatibility of the gel dressing prepared in example 2 with mouse embryonic fibroblasts.
Claims (5)
1. A preparation method of a hydrogel dressing with high oxygen transmission rate comprises the following steps:
1) adding hydroxyl-terminated polydimethylsiloxane into a 100mL bottle with a branch mouth, mechanically stirring in a water bath at 50-70 ℃, and vacuum-drying for 2-4 h; wherein the rotation speed of the mechanical stirring is 200-400 rmp;
2) balancing the air pressure of the branch bottle to the normal pressure for 25-35 min, weighing a double-bond end capping agent by using a disposable syringe, injecting the double-bond end capping agent into the branch bottle in the step 1) under the normal pressure, sucking a catalyst by using a 100 mu L microsyringe, dripping the catalyst into the branch bottle, stirring at normal temperature for 18-20 h, dissolving a product in the branch bottle by using n-propanol, performing suction filtration by using a 5 mu m filter membrane, and removing a solvent by rotary evaporation to obtain a polysiloxane macromonomer cross-linking agent;
3) taking 27.5-41.8% of polysiloxane macromonomer cross-linking agent, 16.8-22.9% of hydrophilic monomer, 15.9-22.6% of siloxane-containing vinyl monomer and 1.0-2.5% of photoinitiator prepared in the step 2), dissolving in 17.5-25.0% of diluent, magnetically stirring for 10-20 minutes, and ultrasonically defoaming to obtain a polymerization solution;
4) sucking the polymerization solution obtained in the step 3) by using a dropper, dripping the polymerization solution into a polytetrafluoroethylene mold, covering a glass plate on the mold after the polymerization solution is fully dripped, and polymerizing for 30-60 min under ultraviolet light; lifting the glass plate, taking out the polymerized gel from the mold, washing the gel with ethanol for 10-20 min, and placing the gel in physiological saline to obtain the hydrogel dressing with high oxygen transmission rate;
wherein, the hydroxyl-terminated polydimethylsiloxane is any one of Tech-2120, KF-6001 with Mn =2000 or KF-6002 with Mn = 3000; the hydrophilic monomer is any one of hydroxyethyl methacrylate, N-dimethyl methacrylamide, N-dimethyl acrylamide and N-vinyl-2-pyrrolidone; the siloxane-containing vinyl monomer is any one of methacryloxypropyltris (trimethylsiloxy) silane, N- [ tris (trimethylsiloxy) silylpropyl ] - (meth) acrylamide, N- [ tris (dimethylpropylsilyloxy) -silylpropyl ] - (meth) acrylamide, N- [ tris (dimethylphenylsilyloxy) silylpropyl ] - (meth) acrylamide; the diluent is any one of methanol, isopropanol and n-propanol.
2. The method of preparing a hydrogel dressing having a high oxygen transmission rate according to claim 1, wherein: the double-bond end capping agent is one of isocyano ethyl methacrylate or isocyanate ethyl acrylate, and the molar ratio of the using amount of the double-bond end capping agent to the hydroxyl end capping polydimethylsiloxane is 1: 2.
3. the method of preparing a hydrogel dressing having a high oxygen transmission rate according to claim 1, wherein: the catalyst is one of dibutyltin dilaurate or 1, 4-butanediol, and the dosage of the catalyst is 1-1.5% of the mass of the hydroxyl-terminated polydimethylsiloxane.
4. The method of preparing a hydrogel dressing having a high oxygen transmission rate according to claim 1, wherein: the photoinitiator is any one of diethoxypropiophenone, Darocur1173 and Darocur 2959.
5. A hydrogel dressing with high oxygen transmission rate is characterized in that: is prepared by the method of any one of claims 1 to 4.
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| CN105399954A (en) * | 2015-12-23 | 2016-03-16 | 江苏海伦隐形眼镜有限公司 | Hydrophilic siloxane oligomer, silicon hydrogel, corneal contact lens and preparation method |
| CN107057035A (en) * | 2016-09-18 | 2017-08-18 | 爱生华(苏州)光学有限公司 | Double end-blocking dimethyl silicone polymers of a kind of pair of methacryloxypropyl ethylamino methanoyl ethoxycarbonyl propyl and its preparation method and application |
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| CN105399954A (en) * | 2015-12-23 | 2016-03-16 | 江苏海伦隐形眼镜有限公司 | Hydrophilic siloxane oligomer, silicon hydrogel, corneal contact lens and preparation method |
| CN107057035A (en) * | 2016-09-18 | 2017-08-18 | 爱生华(苏州)光学有限公司 | Double end-blocking dimethyl silicone polymers of a kind of pair of methacryloxypropyl ethylamino methanoyl ethoxycarbonyl propyl and its preparation method and application |
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