CN111620988A - Long-acting antibacterial dressing and preparation method thereof - Google Patents
Long-acting antibacterial dressing and preparation method thereof Download PDFInfo
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- 238000010438 heat treatment Methods 0.000 claims description 9
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 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 7
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
-
- 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
-
- 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
- A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- Chemical Kinetics & Catalysis (AREA)
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Hematology (AREA)
- Materials Engineering (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention discloses a long-acting antibacterial dressing and a preparation method thereof, wherein the preparation method comprises the following steps: preparing vinyl-terminated polysiloxane reaction monomer and quaternary ammonium salt reaction monomer, and carrying out free radical polymerization with acrylic acid and hydroxyethyl methacrylate to prepare polysiloxane elastomer dressing with a cross-linked structure; the system contains a large number of polar groups (amide, carboxyl, hydroxyl and substituted carbamido), so that the elastomer dressing has good skin viscosity and exudate absorbability, quaternary ammonium salt molecules are connected into the elastomer in a chemical crosslinking mode, the material is endowed with a good and lasting antibacterial effect, and the material has potential application in wet dressings.
Description
Technical Field
The invention belongs to the technical field of synthetic macromolecular biomaterials, and particularly relates to a skin wound dressing with a long-acting antibacterial effect and a preparation method thereof.
Technical Field
According to the 'wet wound healing theory', various cells, enzymes and growth factors on the wound have low activity under dry conditions, and the biological activity is greatly increased under the wet environment, so that the growth of granulation tissues can be promoted, the wound healing is facilitated, but the wet environment is also a hotbed for bacteria and fungi, and therefore, the development of the wet dressing with the antibacterial effect is urgent.
Polysiloxane has good biocompatibility and is widely applied to preparation of medical products, particularly skin wound dressings. CN106038065B discloses a silicone elastomer dressing with a two-layer structure, the cross-linking density of the elastic layer is higher, and the dressing strength is provided; the adhesive layer has a large number of hydrogen bonding groups and a low crosslinking density, and is adhesive. The double-layer dressing has good air permeability, water absorption and transparency, but does not have an antibacterial effect, and the preparation process of the double-layer dressing is too complicated. Because the skin viscosity and the mechanical property of the polysiloxane material can not be simultaneously met, the polysiloxane is mostly applied to the field of hydrogel dressing or liquid bandages, and CN1668345A discloses an antibacterial liquid bandage material based on polysiloxane, which is applied to the surface of a wound by adding a small-molecule medicinal active agent to be mixed with a dressing substrate and adopting a spraying or coating mode to achieve the effect of protecting and resisting bacteria. The antibacterial agent is combined with the dressing substrate in a physical blending mode, is easy to lose in the using process and cannot achieve the long-acting antibacterial effect. And the liquid dressing has short use time, and the frequent dressing change is easy to cause secondary injury of the wound due to failure.
Disclosure of Invention
In order to improve the technical current situation, the invention provides the antibacterial dressing with the polysiloxane elastomer with the single-layer structure, the dressing material has a covalent crosslinking structure, but has good skin adhesion, and the quaternary ammonium salt with the antibacterial effect is chemically grafted in the elastomer, so that long-acting antibacterial effect can be realized, and the antibacterial dressing has good application value in skin wound dressings.
The invention aims to provide a long-acting antibacterial dressing.
The invention also aims to provide a preparation method of the long-acting antibacterial dressing.
The above purpose of the invention is realized by the following technical scheme:
a long-acting antimicrobial dressing having the formula:
wherein m, n, r, t, x, 10-25, 10-20, 20-40, 10-20, 6-16;
the reaction process and the preparation method of the long-acting antibacterial dressing are as follows:
1. preparation of Quaternary ammonium salt reactive monomer (QA)
Adding dodecyl dimethyl tertiary amine (12-DMA) and acetone with twice volume into a three-neck flask provided with a condensation reflux device, a constant-pressure dropping funnel, a nitrogen protection device and a stirring paddle, fully stirring and dissolving, heating to 50-60 ℃, then starting to dropwise add p-chloromethyl styrene (p-CMS), and after dropwise adding, keeping the temperature and reacting for 2 hours. After the reaction is finished, precipitating and separating out the product by using n-heptane, washing the product for 3 times by using acetone, and drying the product for 5 hours in a vacuum oven at the temperature of 50-60 ℃ to obtain QA.
The molar ratio of the p-CMS to the 12-DMA is 3: 1.
2. Amino silicone oil (PDMS-amino)2) Preparation of
Reacting octamethylcyclotetrasiloxane (D)4) Adding 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (BAPTMDS) and tetramethylammonium hydroxide (TMAH) into a reaction kettle, heating to 80-100 ℃, reacting for 9 hours, heating to 110-130 ℃, and reacting for 1 hour to obtain the PDMS-amino2。
Said D4The feeding molar ratio of BAPTMDS is 2.5-10: 1, and the feeding amount of TMAH is D40.2% of the mass.
3. Polysiloxane reactive monomer (PDMS-vinyl)2) Preparation of
Mixing PDMS-amino2Dissolving in dichloromethane with twice volume, adding Hexamethylene Diisocyanate (HDI) once under the nitrogen environment at room temperature, stirring for reaction for 1h, adding a mixed dichloromethane solution of hydroxyethyl methacrylate (HEMA) and dibutyltin dilaurate, continuing to react for 1h, and evaporating the solvent to obtain PDMS-vinyl2。
The PDMS-amino2The feeding molar ratio of HDI to HEMA is 1:2:2, and the feeding amount of dibutyltin dilaurate is 2% of the mass of HDI.
Preparation of P (PDMS-co-HEMA-co-QA-co-AA) elastomer dressing
PDMS-vinyl2Putting hydroxyethyl methacrylate (HEMA), QA and Acrylic Acid (AA) into a reaction kettle, adding N' N-Dimethylformamide (DMF) with the same volume, fully stirring and dissolving, adding Azobisisobutyronitrile (AIBN) after 10min, heating to 60-80 ℃ under the protection of nitrogen, reacting for 4h, drying the obtained crosslinked gel in a vacuum oven at 100-120 ℃ for 20h, cooling, carrying out hot press molding at 90-100 ℃ for 20min, carrying out cold press molding for 10min, wherein the thickness of a mold cavity is 0.8mm, and obtaining the P (PDMS-co-HEMA-co-QA-co-AA) elastomer dressing.
Said PDMS-vinyl2The feeding molar ratio of HEMA, QA and AA is 10-25: 10-20: 20-40: 10-20, and AIBN is 0.1-0.3% of the total mass of the monomers.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the surface of the traditional covalent cross-linked polysiloxane material is not self-adhesive and is difficult to be directly applied in wound dressing. The invention leads the elastomer dressing to have good skin viscosity by introducing various hydrogen bond acting groups (amide, carboxyl, hydroxyl and substituted carbamido) into a covalent crosslinking system.
(2) The surface of the traditional covalent cross-linked polysiloxane material has stronger hydrophobicity, and the traditional covalent cross-linked polysiloxane material does not have the capability of absorbing wound exudate when being used as an elastomer dressing.
(3) The quaternary ammonium salt side group is introduced into the crosslinking system of the elastomer dressing, so that the material has a good and lasting antibacterial effect.
Drawings
FIG. 1 shows the FT-IR spectrum of example 1P (PDMS-co-HEMA-co-QA-co-AA).
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
The following performance tests were performed on examples 1-6 and comparative example 1, and the results are shown in Table 1:
(1) water absorption test: soaking the dried sample in distilled water at 37 deg.C and relative humidity of 80%, taking out after 24 hr, removing excessive water on the surface of the film by using filter paper, and weighing. Water absorption (A)W) The calculation formula is as follows:
wherein, WeAnd WdRespectively representing the water absorption equilibrium mass and the dry mass of the film.
(2) And (3) testing air permeability: 10mL of distilled water is filled in a glass bottle with the inner diameter of 18mm of the bottle mouth, an elastomer dressing film is covered on the bottle mouth, a sealing glue is used for sealing the interface, and the glass bottle is placed in an environment with the temperature of 37 ℃ and the relative humidity of 30%. And taking out and weighing after 24h, and calculating the weight loss. The vapor transmission of the film was characterized by the Water Vapor Transmission Rate (WVTR), which is calculated as follows:
wherein Δ G is the change in mass in G; t is time in units of d; a is the area of the bottle mouth and the unit is m2. WVTR units are: g/(m)2·d)。
(3) And (3) viscosity test: the force required for peeling the glass sheet of the elastomer dressing film was measured by a KJ-1065A electronic tensile machine (available from Dongguan Co., Ltd.) as an evaluation of the adhesiveness of the dressing film. The specimen size was 10mm X60 mm, and the peeling rate was 50 mm/min.
(4) And (3) testing the antibacterial effect: placing an elastomer dressing film with the thickness of 10mm multiplied by 10mm after being sterilized by ultraviolet irradiation into a glass culture dish after being sterilized at high temperature, adding 10mL of bacterial liquid of gram-negative bacteria Escherichia Coli (the absorbance OD600 is 4) and 10mL of distilled water, placing the mixture in a shaking table at 37 ℃ for culturing for 3 hours, measuring the absorbance value (OD600) of the mixture at 600nm by adopting an SMA5000 type micro ultraviolet-visible spectrophotometer, and calculating and evaluating the antibacterial effect according to the following formula:
in the formula (I), the compound is shown in the specification,
for OD600 after 3h of cultivation,
is the initial OD 600.
(5) Cytotoxicity test: placing 10mm × 10mm elastomer dressing film sterilized by ultraviolet irradiation into a glass culture dish sterilized at high temperature, adding 10mL RPMI-1640 liquid culture medium, soaking for 24h, taking 100 μ L sample leaching solution, placing into a 96-well plate, adding 100 μ L human renal epithelial cell solution (inoculation density 1.0 × 105/mL) into each well, adding 100 μ L RPMI-1640 liquid culture medium and 100 μ L human renal epithelial cell solution into a blank control group, placing the 96-well plate into a 37 ℃ incubator, culturing for 24h, adding 20 μ L MTT solution (5.0mg/mL) into each well, culturing for 4h at 37 ℃, removing supernatant, adding 150 μ L DMSO, dissolving sufficiently, and measuring the absorbance (OD492) at 492nm by using an MK-III type enzyme marker. Cell viability was calculated according to the following formula:
in the formula (I), the compound is shown in the specification,
for OD492 after 24h of culture,
OD492 after 24h of incubation for the blank control.
Example 1
(1) Preparation of Quaternary ammonium salt reactive monomer (QA)
Adding dodecyl dimethyl tertiary amine (12-DMA) and acetone with twice volume into a three-neck flask provided with a condensation reflux device, a constant-pressure dropping funnel, a nitrogen protection device and a stirring paddle, fully stirring and dissolving, heating to 55 ℃, then beginning to dropwise add p-chloromethyl styrene (p-CMS), and after dropwise adding, keeping the temperature and reacting for 2 hours. After the reaction is finished, precipitating and separating out a product by using n-heptane, washing the product for 3 times by using acetone, and drying the product in a vacuum oven at the temperature of 50 ℃ for 5 hours to obtain QA;
wherein the feeding molar ratio of the p-CMS to the 12-DMA is 3: 1.
(2) Preparation of PDMS500-amino2
Reacting octamethylcyclotetrasiloxane (D)4) 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (BAPTMDS) and tetramethylammonium hydroxide (TMAH) are put into a reaction kettle, heated to 90 ℃ for reaction for 9h and then heated to 110 ℃ for reaction for 1h to obtain PDMS500-amino2。
Wherein D is4The feeding molar ratio of BAPTMDS is 1.7:1, and the feeding amount of TMAH is D40.2% by mass, and mn (gpc) 689 as a product.
(3) Preparation of PDMS500-vinyl2
Mixing PDMS500-amino2Dissolving the mixture in dichloromethane with twice volume, adding HDI once under the nitrogen environment at room temperature, stirring and reacting for 1h, adding a mixed dichloromethane solution dropwise containing HEMA and dibutyltin dilaurate, continuing to react for 1h, and evaporating the solvent to obtain PDMS500-vinyl2。
PDMS500-amino2The molar ratio of HDI to HEMA charged is 1:2:2, the mass of dibutyltin dilaurate charged is 2% of the mass of HDI, and the product Mn (GPC) is 1521.
(4) Preparation of P (
-co-HEMA20-co-QA10-co-AA20) Elastomeric dressing
Mixing PDMS500-vinyl2Putting HEMA, QA and AA into a reaction kettle, adding DMF with the same volume, fully stirring and dissolving, adding AIBN after 10min, heating to 60-80 ℃ for reaction for 4h to obtain crosslinked gel, drying in a vacuum oven at 100 ℃ for 20h, cooling, hot-press molding at 90 ℃ for 20min, cold-press molding for 10min, wherein the thickness of a mold cavity is 0.8mm to obtain P (N), (B), (C), (
-co-HEMA20-co-QA10-co-AA20) An elastomeric dressing film.
Wherein, PDMS500-vinyl2The feeding molar ratio of HEMA, QA and AA is 23:20:10:20, and AIBN is 0.1-0.3% of the total mass of the monomers.
Referring to FIG. 1, the FT-IR spectrum of P (PDMS-co-HEMA-co-QA-co-AA) corresponding to example 1 is shown in FIG. 1.
Example 2
Steps (1) to (3) were the same as in example 1
(4) Preparation of P (
-co-HEMA20-co-QA20-co-AA20) Elastomeric dressing
PDMS500-vinyl2The feeding molar ratio of HEMA, QA and AA is 20:20:20:20, and AIBN is 0.1-0.3% of the total mass of the monomers.
Example 3
Steps (1) to (3) were the same as in example 1
(4) Preparation of P (
-co-HEMA20-co-QA30-co-AA20) Elastomeric dressing
PDMS500-vinyl2Feeding HEMA, QA and AA in a molar ratio of 18:20:30:20, and 0.1-0.3% of AIBN based on the total mass of the monomers.
Example 4
Steps (1) to (3) were the same as in example 1
(4) Preparation of P (
-co-HEMA20-co-QA40-co-AA20) Elastomeric dressing
PDMS500-vinyl2The feeding molar ratio of HEMA, QA and AA is 15:20:40:20, and AIBN is 0.1-0.3% of the total mass of the monomers.
Example 5
Step (1) is the same as in example 1
(2) Preparation of PDMS1000-amino2
D4The feeding molar ratio of BAPTMDS is 3.4:1, and the feeding amount of TMAH is D40.2% by mass, product mn (gpc) 1089.
(3) Preparation of PDMS1000-vinyl2
PDMS1000-amino2The molar ratio of HDI to HEMA charged was 1:2:2, the amount of dibutyltin dilaurate charged was 2% by mass of HDI, and the product mn (gpc) was 1922.
(4) Preparation of P (
-co-HEMA14-co-QA25-co-AA14) Elastomeric dressing
PDMS500-vinyl2The feeding molar ratio of HEMA, QA and AA is 18:14:25:14, and AIBN is 0.1-0.3% of the total mass of the monomers.
Example 6
Steps (1) to (3) were the same as in example 5
(4) Preparation of P (
-co-HEMA5-co-QA25-co-AA5) Elastomeric dressing
PDMS500-vinyl2The feeding molar ratio of HEMA, QA and AA is 21:5:25:5, and AIBN is 0.1-0.3% of the total mass of the monomers.
Comparative example 1
3M TegadermTMFilm(s)
TABLE 1 results of the Performance test of examples 1 to 6 and comparative example 1
Claims (3)
1. A long-acting antibacterial dressing and a preparation method thereof are characterized in that the structural formula is shown as the formula (I):
wherein m, n, r, t, x, is 10-25: 10-20: 20-40: 10-20: 6-16.
2. The long-acting antibacterial dressing and the preparation method thereof are characterized by comprising the following steps:
(1) preparation of Quaternary ammonium salt reactive monomer (QA)
Placing dodecyl dimethyl tertiary amine (12-DMA) and acetone with the volume twice of the volume of the dodecyl dimethyl tertiary amine into a reaction kettle, mixing and dissolving, heating to 50-60 ℃ under the protection of nitrogen, then starting to dropwise add p-chloromethyl styrene (p-CMS), and carrying out heat preservation reaction for 2 hours. After the reaction is finished, precipitating, washing and drying a product to obtain QA;
(2) amino silicone oil (PDMS-amino)2) Preparation of
Reacting octamethylcyclotetrasiloxane (D)4) Adding 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (BAPTMDS) and tetramethylammonium hydroxide (TMAH) into a reaction kettle, heating to 80-100 ℃, reacting for 9 hours, heating to 110-130 ℃, and reacting for 1 hour to obtain the PDMS-amino2；
(3) Polysiloxane reactive monomer (PDMS-vinyl)2) Preparation of
Mixing PDMS-amino2Dissolved in two volumes of dichloromethane in a chamberAdding Hexamethylene Diisocyanate (HDI) under a warm nitrogen environment, stirring and reacting for 1h, adding a mixed dichloromethane solution of hydroxyethyl methacrylate (HEMA) and dibutyltin dilaurate dropwise, continuing to react for 1h, and evaporating the solvent to obtain PDMS-vinyl2；
(4) Preparation of P (PDMS-co-HEMA-co-QA-co-AA) elastomer dressing
Taking Azobisisobutyronitrile (AIBN) as an initiator, N' N-Dimethylformamide (DMF) as a reaction solvent, and PDMS-vinyl2Carrying out free radical polymerization on hydroxyethyl methacrylate (HEMA), QA and Acrylic Acid (AA) serving as monomers, reacting for 4h at 60-80 ℃ under the protection of nitrogen, drying the obtained crosslinked gel in a vacuum oven at 100-120 ℃ for 20h, and carrying out hot pressing and cold pressing molding to obtain the P (PDMS-co-HEMA-co-QA-co-AA) elastomer dressing.
3. The long-acting antibacterial dressing and the preparation method thereof according to claim 2, wherein the dressing comprises the following components:
the feeding molar ratio of the p-CMS to the 12-DMA in the step (1) is 3: 1;
d in the step (2)4The feeding molar ratio of BAPTMDS is 2.5-10: 1, and the feeding amount of TMAH is D40.2% of the mass;
the PDMS-amino of the step (3)2The feeding molar ratio of HDI to HEMA is 1:2:2, and the feeding amount of dibutyltin dilaurate is 2% of the mass of HDI;
PDMS-vinyl of the step (4)2The feeding molar ratio of HEMA, QA and AA is 10-25: 10-20: 20-40: 10-20, and AIBN is 0.1-0.3% of the total mass of the monomers.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114103281A (en) * | 2021-11-24 | 2022-03-01 | 四川中烟工业有限责任公司 | Moisturizing three-layer material and preparation method thereof |
| CN114103320A (en) * | 2021-11-24 | 2022-03-01 | 四川中烟工业有限责任公司 | Application of moisturizing three-layer material in regulation and control of microenvironment humidity of cigar |
| CN114732936A (en) * | 2021-01-08 | 2022-07-12 | 陈娜 | High-air-permeability degradable drug-loaded skin wound dressing |
| CN115282320A (en) * | 2022-10-09 | 2022-11-04 | 佳利士江苏新材料科技有限公司 | Bacteria-resistant PU film medical dressing and processing technology thereof |
| CN115948018A (en) * | 2023-03-15 | 2023-04-11 | 山东泰瑞丰新材料有限公司 | Ionomer modified styrene thermoplastic elastomer and preparation method thereof |
| CN116726066A (en) * | 2023-07-27 | 2023-09-12 | 中科万康药业(广州)有限公司 | Sustained-release antibacterial gel composition and preparation method thereof |
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| CN105885054A (en) * | 2016-04-28 | 2016-08-24 | 华南理工大学 | Quaternary ammonium salt group containing polysiloxane block copolymer and preparation method and application |
| CN110184814A (en) * | 2019-06-14 | 2019-08-30 | 吉林大学 | A kind of medical antibacterial dressing and preparation method thereof |
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| CN105885054A (en) * | 2016-04-28 | 2016-08-24 | 华南理工大学 | Quaternary ammonium salt group containing polysiloxane block copolymer and preparation method and application |
| CN110184814A (en) * | 2019-06-14 | 2019-08-30 | 吉林大学 | A kind of medical antibacterial dressing and preparation method thereof |
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| CN114732936A (en) * | 2021-01-08 | 2022-07-12 | 陈娜 | High-air-permeability degradable drug-loaded skin wound dressing |
| CN114103281A (en) * | 2021-11-24 | 2022-03-01 | 四川中烟工业有限责任公司 | Moisturizing three-layer material and preparation method thereof |
| CN114103320A (en) * | 2021-11-24 | 2022-03-01 | 四川中烟工业有限责任公司 | Application of moisturizing three-layer material in regulation and control of microenvironment humidity of cigar |
| CN114103281B (en) * | 2021-11-24 | 2024-01-19 | 四川中烟工业有限责任公司 | Moisturizing three-layer material and preparation method thereof |
| CN114103320B (en) * | 2021-11-24 | 2024-01-19 | 四川中烟工业有限责任公司 | Application of moisturizing three-layer material in aspect of regulating and controlling humidity of cigar microenvironment |
| CN115282320A (en) * | 2022-10-09 | 2022-11-04 | 佳利士江苏新材料科技有限公司 | Bacteria-resistant PU film medical dressing and processing technology thereof |
| CN115948018A (en) * | 2023-03-15 | 2023-04-11 | 山东泰瑞丰新材料有限公司 | Ionomer modified styrene thermoplastic elastomer and preparation method thereof |
| CN116726066A (en) * | 2023-07-27 | 2023-09-12 | 中科万康药业(广州)有限公司 | Sustained-release antibacterial gel composition and preparation method thereof |
| CN116726066B (en) * | 2023-07-27 | 2024-03-26 | 中科万康药业(广州)有限公司 | Antibacterial gel composition and preparation method thereof |
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