[go: up one dir, main page]

CN116731607B - (TiZnCe)O2-XPDMS coating and preparation and application thereof - Google Patents

(TiZnCe)O2-XPDMS coating and preparation and application thereof Download PDF

Info

Publication number
CN116731607B
CN116731607B CN202310702365.8A CN202310702365A CN116731607B CN 116731607 B CN116731607 B CN 116731607B CN 202310702365 A CN202310702365 A CN 202310702365A CN 116731607 B CN116731607 B CN 116731607B
Authority
CN
China
Prior art keywords
tiznce
pdms
coating
cerium
metal salt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202310702365.8A
Other languages
Chinese (zh)
Other versions
CN116731607A (en
Inventor
郭芳威
胡艳平
郝旭龙
刘晓依
邓丹
张文琛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Childrens Medical Center Affiliated to Shanghai Jiaotong University School of Medicine
Shanghai Jiao Tong University
Original Assignee
Shanghai Childrens Medical Center Affiliated to Shanghai Jiaotong University School of Medicine
Shanghai Jiao Tong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Childrens Medical Center Affiliated to Shanghai Jiaotong University School of Medicine, Shanghai Jiao Tong University filed Critical Shanghai Childrens Medical Center Affiliated to Shanghai Jiaotong University School of Medicine
Priority to CN202310702365.8A priority Critical patent/CN116731607B/en
Publication of CN116731607A publication Critical patent/CN116731607A/en
Application granted granted Critical
Publication of CN116731607B publication Critical patent/CN116731607B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08—Materials for coatings
    • A61L31/082—Inorganic materials
    • A61L31/088—Other specific inorganic materials not covered by A61L31/084 or A61L31/086
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/10—Bandages or dressings; Absorbent pads specially adapted for fingers, hands or arms; Finger-stalls; Nail-protectors
    • A61F13/104—Bandages or dressings; Absorbent pads specially adapted for fingers, hands or arms; Finger-stalls; Nail-protectors for the hands or fingers
    • 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
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04—Macromolecular materials
    • A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated 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
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08—Materials for coatings
    • A61L31/10—Macromolecular 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
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/16—Biologically active materials, e.g. therapeutic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/606—Coatings
    • 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
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/04—Coatings containing a composite material such as inorganic/organic, i.e. material comprising different phases
    • 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
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/06—Coatings containing a mixture of two or more compounds

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Vascular Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Surgery (AREA)
  • Epidemiology (AREA)
  • Inorganic Chemistry (AREA)
  • Biomedical Technology (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Molecular Biology (AREA)
  • Paints Or Removers (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

本发明涉及表面涂层技术领域，尤其是涉及(TiZnCe)O2‑X/PDMS涂层及其制备与应用。本发明首先将钛金属盐、锌金属盐、铈金属盐与苯甲醇混匀后反应，反应后后处理得到氧化物前驱体；然后将氧化物前驱体进行热处理，得到(TiZnCe)O2‑X粉体；进一步将(TiZnCe)O2‑X粉体与、PDMS和固化剂混匀，得到(TiZnCe)O2‑X/PDMS粉体涂层；最后通过压缩空气喷涂方法在基体上喷涂上述粉体涂层，后处理得到(TiZnCe)O2‑X/PDMS涂层；其中，X为0～2，且X不为2。本发明的(TiZnCe)O2‑X/PDMS涂层可进一步应用于硅酮橡胶手套，得到压力修复手套，并用于患者创面愈合压力治疗。

The present invention relates to the technical field of surface coatings, and in particular to (TiZnCe)O 2-X /PDMS coatings and preparation and application thereof. The present invention firstly mixes titanium metal salt, zinc metal salt, cerium metal salt and benzyl alcohol and then reacts, and then post-processes to obtain an oxide precursor; then the oxide precursor is heat-treated to obtain (TiZnCe)O 2-X powder; further, the (TiZnCe)O 2-X powder is mixed with PDMS and a curing agent to obtain a (TiZnCe)O 2-X /PDMS powder coating; finally, the above-mentioned powder coating is sprayed on a substrate by a compressed air spraying method, and post-processed to obtain a (TiZnCe)O 2-X /PDMS coating; wherein X is 0 to 2, and X is not 2. The (TiZnCe)O 2-X /PDMS coating of the present invention can be further applied to silicone rubber gloves to obtain pressure repair gloves, and used for pressure treatment of wound healing in patients.

Description

(TiZnCe) O 2-X/PDMS coating and preparation and application thereof
Technical Field
The invention relates to the technical field of surface coatings, in particular to a (TiZnCe) O 2-X/PDMS coating and preparation and application thereof.
Background
Hereditary epidermolysis bullosa (Epidermolysis bullosa, EB) is a severe hereditary dermatological disease caused by gene defects and characterized by slight abrasion or formation of skin, mucosal blisters or bullae following trauma. Among them, recessive inheritance (RDEB) subtype causes a deficiency of functional type VII collagen (C7) due to mutation of type VII collagen gene (COL 7 A1), resulting in serious systemic symptoms. The hands and feet of the patient repeatedly form blisters, ulcers and heals due to activities and friction in daily life, severe and digital deformity is accompanied by repeated skin injury and scar formation, so that joints are buckled and contracture for a long time, and the activity dysfunction is caused, so that the patient loses the most basic life self-care ability. Fromy et al examined the change in skin blood flow of healthy persons when the finger was subjected to increasing pressure, and found that at low pressure (about 2.67 kPa) the finger skin blood flow increased significantly and when the pressure increased to "capillary closed" (about 4.27 kPa) the finger skin blood flow decreased.
The pressure gloves or pressure socks in the market at present are mainly divided into 3 types according to the pressure range, namely, low-pressure gloves with the pressure of 2.40-2.67 kPa for health care, medium-pressure gloves with the pressure of 2.67-4.00 kPa for treating edema or mild varicose veins, and high-pressure gloves with the pressure of 4.00-5.33 kPa for treating patients suffering from serious venous diseases. The existing finger-separating silica gel pressure glove product gives the scar continuous pressure and the functions of moisturizing and softening so as to delay the contracture of the finger joints and prevent the recurrence of the finger joints, but has the problems of poor comfort level and low patient compliance in clinical use.
Polydimethylsiloxane (PDMS) is a hydrophobic class of linear polymeric silicone materials. Has low surface tension, easy spreading, good biocompatibility, and proper combination of viscosity, which can endow the personal care product with lubrication and low viscosity to endow the skin with dry and comfortable feeling. In particular, the PDMS material has excellent elasticity and rebound resilience, outstanding temperature and weather resistance, light transmission performance and excellent air permeability, which is more than 50 times of the air permeability of the traditional polyester film. The PDMS film series product has good application prospect in medical appliances, flexible electronics, optics and ventilation function type application.
In fact, tiO 2 and ZnO photocatalysts have been widely studied for their broad-spectrum bacteriostasis, but they are often mixed with other substances to optimize their antibacterial action due to uncertainty in antibacterial properties with ZnO films. According to the basic theory of the photocatalytic reaction, tiO 2 and ZnO can play a good role in killing under the condition of illumination. It has been reported and patented that the antibacterial and skin repair of TiO 2 and ZnO materials under low light and no light conditions can be achieved by binary doping with metal ions, but the performance stability is still to be further improved. Regarding research on the biocompatibility of CeO x nanoparticles, the m.sendra team proposed that the amount of charge of the nanoparticles and cell walls could affect cell diversity. The team explores the effect of Zeta potential on cell differentiation by adding positive and negative potential CeO x to seaweed dishes, respectively. the research shows that CeO x nanometer particles with positive Zeta potential can increase cell diversity, ceO x can not cause toxicity when the cell complexity reaches a certain range, and CeO x can increase the generation of active oxygen and toxicity when the complexity reaches a certain degree. martin t. matter team verifies the antibacterial properties of CeO x nanoparticles and demonstrates their effect in inhibiting cell growth on the material surface. The nano particles form a super structure with the similar size and surface charge as bacteria, after CeO x is added into TiO 2, firstly, the ion radius of Ce ions introduced by doping is larger than that of Ti, the doping can promote the lattice expansion of TiO 2, the lattice distortion of titanium dioxide can be caused, a small amount of lattice distortion can generate electron traps, further, the separation and the transfer of holes are facilitated, the catalytic reaction working capacity of the nano particles is improved, secondly, the energy level of residual electrons is introduced, the forbidden bandwidth of the doped TiO 2 is reduced, and the utilization rate of visible light in the whole transition process is improved.
In addition, the titanium dioxide TiO 2 is an inorganic substance, has no toxicity, optimal opacity, optimal whiteness and brightness, and is widely applied to industries such as paint, cosmetics and the like. The nanometer titania can make water drop adhered to the surface of glass diffuse into homogeneous water film, and the surface will not produce fog with light scattering, and the antifogging film with nanometer titania has excellent wear resistance, scratch resistance and solvent resistance. The cerium oxide CeO x rare earth element salt can reduce the content of prothrombin, deactivate the prothrombin, inhibit the generation of thromboplastin, precipitate fibrinogen, catalyze and decompose phosphoric acid compounds, and the cerium oxide also plays an ultraviolet-resistant role in cosmetics.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a (TiZnCe) O 2-X/PDMS coating and preparation and application thereof. The preparation method comprises the steps of firstly uniformly mixing titanium metal salt, zinc metal salt, cerium metal salt and benzyl alcohol, reacting, post-treating to obtain an oxide precursor, then performing heat treatment on the oxide precursor to obtain (TiZnCe) O 2-X powder, further uniformly mixing (TiZnCe) O 2-X powder, PDMS and a curing agent to obtain (TiZnCe) O 2-X/PDMS powder coating, and finally spraying the powder coating on a substrate by a compressed air spraying method, and post-treating to obtain (TiZnCe) O 2-X/PDMS coating, wherein X is 0-2, and X is not 2. The (TiZnCe) O 2-X/PDMS coating of the present invention can be further applied to silicone rubber gloves to obtain pressure repair gloves, and is used for pressure treatment of wound healing of patients.
The aim of the invention can be achieved by the following technical scheme:
The first object of the invention is to provide a preparation method of (TiZnCe) O 2-X/PDMS coating, comprising the following steps:
(S1) uniformly mixing titanium metal salt, zinc metal salt and cerium metal salt with benzyl alcohol, reacting, and post-treating to obtain an oxide precursor;
(S2) performing heat treatment on the oxide precursor prepared in the step (S1) to obtain (TiZnCe) O 2-X powder;
(S3) uniformly mixing the (TiZnCe) O 2-X powder prepared in the step (S2) with PDMS and a curing agent to obtain a (TiZnCe) O 2-X/PDMS powder coating;
(S4) spraying the (TiZnCe) O 2-X/PDMS powder coating prepared in the step (S3) on a substrate by a compressed air spraying method, and performing post-treatment to obtain the (TiZnCe) O 2-X/PDMS coating;
wherein X is 0-2, and X is not 2.
In one embodiment of the present invention, in the step (S1), the titanium metal salt is selected from one of titanium isopropoxide, titanium acetylacetonate, titanium acetate, aromatic titanium, titanium chloride, titanium bromide or titanium iodide;
The zinc metal salt is selected from one of zinc isopropoxide, zinc acetylacetonate, zinc acetate, aromatic zinc, zinc chloride, zinc bromide or zinc iodide;
the cerium metal salt is selected from one of cerium isopropoxide, cerium acetylacetonate, cerium acetate, aromatic cerium, cerium chloride, cerium bromide or cerium iodide.
In one embodiment of the present invention, in step (S1), the titanium metal salt, zinc metal salt, cerium metal salt and benzyl alcohol may be mixed uniformly and heated (below 60 ℃) appropriately to accelerate dissolution.
In one embodiment of the invention, in the step (S1), the temperature rising rate is 5 ℃ per minute, the reaction temperature is 200 ℃ to 300 ℃, and the reaction time is maintained for 40min to 60min in the reaction process.
In one embodiment of the present invention, in the step (S1), the post-treatment is a heat-insulating treatment, followed by centrifugation, washing and drying in sequence;
In the heat preservation process, the temperature is 200-300 ℃ and the time is 24-96 h, and then the furnace is cooled to the room temperature at the cooling rate of 5 ℃ per minute;
centrifuging and washing for more than 3 times;
in the centrifugation process, the rotating speed is more than 10000rpm, and the centrifugation time is 5 min-20 min;
In the washing process, an organic solvent is used for washing, wherein the organic solvent is selected from one of ethanol, isopropanol, diethyl ether or chloroform, and preferably the organic solvent is selected from diethyl ether or chloroform;
In the drying process, the temperature is 60-120 ℃.
In one embodiment of the present invention, in the step (S2), the heat treatment process is performed under an argon atmosphere, and the flow rate of argon is 0.05L/min to 1L/min, preferably, the flow rate of argon is 0.2L/min;
In the heat treatment process, the temperature is 220-350 ℃ and the time is 2-10 h.
In one embodiment of the present invention, the particle size of the (TiZnCe) O 2-X powder is 3nm to 15nm.
In one embodiment of the present invention, in step (S3), one of SYLGARD-84 dimethylsilane or Dow Corning DC-732W is further contained in the (TiZnCe) O 2-X/PDMS powder coating;
(TiZnCe) O 2-X powder, PDMS, SYLGARD-84 dimethyl silane or Dow Corning DC-732W, and the mass percentage of the chemical agent is 1% -9%, 0.5% -1%, 89% -98%.
In one embodiment of the present invention, in the compressed air spraying process in the step (S4), the spraying pressure is 0.1mpa to 0.25mpa, and the coating thickness is 10 μm to 50 μm.
In one embodiment of the present invention, in step (S4), the post-treatment is a curing drying treatment;
the curing and drying process is in an ultraviolet state, the temperature is 10-30 ℃, the humidity is 40-70%, and the time is 30-90 min.
A second object of the present invention is to provide a (TiZnCe) O 2-X/PDMS coating prepared by the above method.
It is a third object of the present invention to provide a glove containing a brush-like (TiZnCe) O 2-X/PDMS coating.
A fourth object of the present invention is to provide a glove comprising a brush-like (TiZnCe) O 2-X/PDMS coating for use in pressure therapy for wound healing in patients.
Compared with the prior art, the invention has the following beneficial effects:
The invention provides a (TiZnCe) O 2-X/PDMS coating and a preparation method thereof, wherein X is 0-2, and X is not 2, and the (TiZnCe) O 2-X/PDMS coating obtained by the preparation method can be applied to silicone rubber gloves by combining with a micrometer stamping technology to obtain gloves containing brush-shaped (TiZnCe) O 1.98/PDMS coatings, and is further used as pressure repairing gloves for healing pressure treatment of wound surfaces of patients.
Drawings
FIG. 1 is a schematic diagram of the structure of a single finger containing a brush-like (TiZnCe) O 1.98/PDMS coating in example 2;
The reference numbers in the figure are 1, a single finger of a silicone rubber glove, 2, brush-shaped bulges, 3, (TiZnCe) O 1.98/PDMS coating.
Detailed Description
The invention provides a preparation method of a (TiZnCe) O 2-X/PDMS coating, which comprises the following steps:
(S1) uniformly mixing titanium metal salt, zinc metal salt and cerium metal salt with benzyl alcohol, reacting, and post-treating to obtain an oxide precursor;
(S2) performing heat treatment on the oxide precursor prepared in the step (S1) to obtain (TiZnCe) O 2-X powder;
(S3) uniformly mixing the (TiZnCe) O 2-X powder prepared in the step (S2) with PDMS and a curing agent to obtain a (TiZnCe) O 2-X/PDMS powder coating;
(S4) spraying the (TiZnCe) O 2-X/PDMS powder coating prepared in the step (S3) on a substrate by a compressed air spraying method, and performing post-treatment to obtain the (TiZnCe) O 2-X/PDMS coating;
wherein X is 0-2, and X is not 2.
In one embodiment of the present invention, in the step (S1), the titanium metal salt is selected from one of titanium isopropoxide, titanium acetylacetonate, titanium acetate, aromatic titanium, titanium chloride, titanium bromide or titanium iodide;
The zinc metal salt is selected from one of zinc isopropoxide, zinc acetylacetonate, zinc acetate, aromatic zinc, zinc chloride, zinc bromide or zinc iodide;
the cerium metal salt is selected from one of cerium isopropoxide, cerium acetylacetonate, cerium acetate, aromatic cerium, cerium chloride, cerium bromide or cerium iodide.
In one embodiment of the present invention, in step (S1), the titanium metal salt, zinc metal salt, cerium metal salt and benzyl alcohol may be mixed uniformly and heated (below 60 ℃) appropriately to accelerate dissolution.
In one embodiment of the invention, in the step (S1), the temperature rising rate is 5 ℃ per minute, the reaction temperature is 200 ℃ to 300 ℃, and the reaction time is maintained for 40min to 60min in the reaction process.
In one embodiment of the present invention, in the step (S1), the post-treatment is a heat-insulating treatment, followed by centrifugation, washing and drying in sequence;
In the heat preservation process, the temperature is 200-300 ℃ and the time is 24-96 h, and then the furnace is cooled to the room temperature at the cooling rate of 5 ℃ per minute;
centrifuging and washing for more than 3 times;
in the centrifugation process, the rotating speed is more than 10000rpm, and the centrifugation time is 5 min-20 min;
In the washing process, an organic solvent is used for washing, wherein the organic solvent is selected from one of ethanol, isopropanol, diethyl ether or chloroform, and preferably the organic solvent is selected from diethyl ether or chloroform;
In the drying process, the temperature is 60-120 ℃.
In one embodiment of the present invention, in the step (S2), the heat treatment process is performed under an argon atmosphere, and the flow rate of argon is 0.05L/min to 1L/min, preferably, the flow rate of argon is 0.2L/min;
In the heat treatment process, the temperature is 220-350 ℃ and the time is 2-10 h.
In one embodiment of the present invention, the particle size of the (TiZnCe) O 2-X powder is 3nm to 15nm.
In one embodiment of the present invention, in step (S3), one of SYLGARD-84 dimethylsilane or Dow Corning DC-732W is further contained in the (TiZnCe) O 2-X/PDMS powder coating;
(TiZnCe) O 2-X powder, PDMS, SYLGARD-84 dimethyl silane or Dow Corning DC-732W, and the mass percentage of the chemical agent is 1% -9%, 0.5% -1%, 89% -98%.
In one embodiment of the present invention, in the compressed air spraying process in the step (S4), the spraying pressure is 0.1mpa to 0.25mpa, and the coating thickness is 10 μm to 50 μm.
In one embodiment of the present invention, in step (S4), the post-treatment is a curing drying treatment;
the curing and drying process is in an ultraviolet state, the temperature is 10-30 ℃, the humidity is 40-70%, and the time is 30-90 min.
The invention provides the (TiZnCe) O 2-X/PDMS coating prepared by the method.
The present invention provides a glove containing a brush-like (TiZnCe) O 2-X/PDMS coating.
The invention provides an application of a glove containing a brush-shaped (TiZnCe) O 2-X/PDMS coating in pressure treatment of wound healing of patients.
The invention will now be described in detail with reference to the drawings and specific examples.
In the examples below, unless otherwise specified, all reagents used were commercially available, and all detection means and methods used were conventional in the art.
Example 1
The embodiment provides a (TiZnCe) O 1.98/PDMS coating and a preparation method thereof.
(S1) mixing titanium acetylacetonate (0.26 g), zinc chloride (0.14 g), cerium acetate (0.32 g) and 25mL benzyl alcohol in a polytetrafluoroethylene reaction kettle, heating at 45 ℃ to accelerate uniform mixing, sealing the polytetrafluoroethylene reaction kettle, placing in a high-temperature drying box, reacting at 250 ℃ for 50min (the heating rate is 5 ℃ per min), preserving heat for 48h, cooling to room temperature along with a furnace at the cooling rate of 5 ℃ per min to obtain a sol-gel product, taking out the sol-gel product, placing in a 50mL centrifuge tube, adding diethyl ether for washing operation, placing in a centrifuge for 10000rpm centrifugation for 20min, pouring washing waste liquid after centrifugation is finished, repeating the washing centrifugation process for 4 times, and then placing the final product in the 80 ℃ drying box for drying to obtain an oxide precursor;
(S2) placing the oxide precursor obtained in the step (S1) in a non-oxygen furnace for heat treatment, wherein the flow rate of argon in the furnace is 0.2L/min, and the temperature is kept at 300 ℃ for 6 hours to obtain (TiZnCe) O 1.98 powder with the particle size of 3 nm;
(S3) uniformly mixing (TiZnCe) O 1.98 powder (4.5 wt%) obtained in the step (S2) with PDMS (0.5 wt%), dow Corning DC-732W (0.8 wt%) and tetraethoxysilane (94.2 wt%) to obtain (TiZnCe) O 1.98/PDMS powder coating;
And (S4) spraying the (TiZnCe) O 1.98/PDMS powder coating obtained in the step (S3) on polycarbonate by a compressed air spraying method, controlling the spraying pressure to be 0.2MPa and the spraying thickness to be 35 mu m, placing the polycarbonate/PDMS powder coating in a sterile operation box after the spraying is finished, performing curing and drying treatment, starting a 200W ultraviolet lamp in the sterile operation phase, controlling the temperature to be 20 ℃, controlling the humidity to be 50%, and curing and drying for 60min to obtain the (TiZnCe) O 1.98/PDMS coating.
Example 2
This example provides a coating containing brush-like (TiZnCe) O 1.98/PDMS and a method for preparing the same.
Steps (S1), (S2) and (S3) of this example are the same as those of example 1;
(S4) preparing a silicone rubber glove using a micro-stamping technique comprising the steps of:
Using soft sand mud to make a flat mold, putting hands of a tester into the mold, extruding the mold to form a mold, then scanning the mold by using a handheld optical 3D scanner (Sense) to generate a palm mold, selecting an FDM (fused extrusion molding) printer to print the palm mold by using a resin material, covering a glove support material (polyurethane fiber) and a silk screen (copper mesh with the aperture of 1 mm) outside the palm mold after printing, finally coating PDMS on the surface of the palm mold, controlling the thickness to be 5mm, placing the whole body in an aseptic operation box to be cured and dried, starting a 200W ultraviolet lamp in the aseptic operation box, controlling the temperature to be 20 ℃ and the humidity to be 50%, and curing and drying for 60min to obtain the silicone rubber glove;
(S5) removing palm impression and glove support materials, spraying the (TiZnCe) O 1.98/PDMS powder coating obtained in the step (S3) on the inner side of the silicone rubber glove by using a compressed air spraying method, controlling the spraying thickness to be 35 mu m, placing the silicone rubber glove in a sterile operation box after the spraying is finished, curing and drying the silicone rubber glove, starting a 200W ultraviolet lamp in the sterile operation box, controlling the temperature to be 20 ℃ and the humidity to be 50%, curing and drying for 60 minutes, and taking out a silk screen to obtain the glove containing brush-shaped (TiZnCe) O 1.98/PDMS coating (the glove can also be called as a 'pressure repairing glove'), wherein the structure schematic diagram of a single finger containing brush-shaped (TiZnCe) O 1.98/PDMS coating is shown as shown in figure 1, and the inner side of a single finger 1 of the silicone rubber glove contains brush-shaped protrusions 2, and the (TiZnCe) O 1.98/PDMS coating 3 is coated on the outer surface of the brush-shaped protrusions 2.
The glove containing the brush-shaped (TiZnCe) O 1.98/PDMS coating prepared in the embodiment can be further applied to pressure treatment of wound healing of patients.
Example 3
The embodiment provides a (TiZnCe) O 1.97/PDMS coating and a preparation method thereof.
(S1) mixing titanium isopropoxide (0.28 g), zinc acetate (0.18 g) and cerium chloride (0.35 g) with 30mL of benzyl alcohol in a polytetrafluoroethylene reaction kettle, heating at 50 ℃ to accelerate uniform mixing, sealing the polytetrafluoroethylene reaction kettle, placing in a high-temperature drying box, reacting at 300 ℃ for 40min (the heating rate is 5 ℃ per min), preserving heat for 24h, cooling to room temperature along with a furnace at the cooling rate of 5 ℃ per min to obtain a sol-gel product, taking out the sol-gel product, placing in a 50mL centrifuge tube, adding chloroform for washing operation, placing in a centrifuge for 12000rpm centrifugation for 10min, pouring washing waste liquid after centrifugation is finished, repeating the washing centrifugation process for 5 times, and then placing the final product in the 1200 ℃ drying box for drying to obtain an oxide precursor;
(S2) placing the oxide precursor obtained in the step (S1) in a non-oxygen furnace for heat treatment, wherein the flow rate of argon in the furnace is 1L/min, and the temperature is kept at 350 ℃ for 2 hours to obtain (TiZnCe) O 1.97 powder with the particle size of 10 nm;
(S3) uniformly mixing the (TiZnCe) O 1.97 powder (9 wt%) obtained in the step (S2) with PDMS (1 wt%), SYLGARD-84 dimethyl silane (1 wt%), tetramethyl orthosilicate (89 wt%) to obtain (TiZnCe) O 1.97/PDMS powder coating;
And (S4) spraying the (TiZnCe) O 1.97/PDMS powder coating obtained in the step (S3) on a glass plate by using a compressed air spraying method, controlling the spraying pressure to be 0.1MPa and the spraying thickness to be 10 mu m, placing the glass plate in a sterile operation box for curing and drying after the spraying is finished, starting a 200W ultraviolet lamp in the sterile operation phase, controlling the temperature to be 30 ℃ and the humidity to be 70%, and curing and drying for 90 minutes to obtain the (TiZnCe) O 1.97/PDMS coating.
Example 4
The embodiment provides a (TiZnCe) O 1.99/PDMS coating and a preparation method thereof.
(S1) mixing titanium chloride (0.38 g), zinc acetylacetonate (0.53 g) and cerium acetylacetonate (0.87 g) with 50mL benzyl alcohol in a polytetrafluoroethylene reaction kettle, heating at 55 ℃ to accelerate uniform mixing, sealing the polytetrafluoroethylene reaction kettle, placing in a high-temperature drying box, reacting at 200 ℃ for 60min (the temperature rising rate is 5 ℃ per min), preserving heat for 96h, finally cooling to room temperature along with the furnace at the temperature falling rate of 5 ℃ per min to obtain a sol-gel product, taking out the sol-gel product, placing in a 50mL centrifuge tube, adding ethanol for washing operation, placing in a centrifuge for 15000rpm centrifugation for 5min, pouring washing waste liquid after centrifugation is finished, repeating the washing centrifugation process for 3 times, and then placing the final product in the 60 ℃ drying box for drying to obtain an oxide precursor;
(S2) placing the oxide precursor obtained in the step (S1) in a non-oxygen furnace for heat treatment, wherein the flow rate of argon in the furnace is 0.05L/min, and the temperature is kept at 220 ℃ for 10 hours to obtain (TiZnCe) O 1.99 powder with the particle size of 15 nm;
(S3) uniformly mixing (TiZnCe) O 1.99 powder (1 wt%) obtained in the step (S2) with PDMS (0.5 wt%), SYLGARD-84 dimethyl silane (0.5 wt%) and tetrabutyl orthosilicate (98 wt%) to obtain (TiZnCe) O 1.99/PDMS powder coating;
And (S4) spraying the (TiZnCe) O 1.99/PDMS powder coating obtained in the step (S3) on polycarbonate by a compressed air spraying method, controlling the spraying pressure to be 0.25MPa and the spraying thickness to be 50 mu m, placing the polycarbonate/PDMS powder coating in a sterile operation box for curing and drying after the spraying is finished, starting a 200W ultraviolet lamp in the sterile operation phase, controlling the temperature to be 10 ℃ and the humidity to be 40%, and curing and drying for 30min to obtain the (TiZnCe) O 1.99/PDMS coating.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the explanation of the present invention, should make improvements and modifications without departing from the scope of the present invention.

Claims (8)

1. A method for preparing (TiZnCe) O 2-X/PDMS coating, comprising the steps of:
(S1) uniformly mixing titanium metal salt, zinc metal salt and cerium metal salt with benzyl alcohol, reacting, and post-treating to obtain an oxide precursor;
(S2) performing heat treatment on the oxide precursor prepared in the step (S1) to obtain (TiZnCe) O 2-X powder;
(S3) uniformly mixing the (TiZnCe) O 2-X powder prepared in the step (S2) with PDMS and a curing agent to obtain a (TiZnCe) O 2-X/PDMS powder coating;
(S4) spraying the (TiZnCe) O 2-X/PDMS powder coating prepared in the step (S3) on a substrate by a compressed air spraying method, and performing post-treatment to obtain the (TiZnCe) O 2-X/PDMS coating;
Wherein X is 0-2, and X is not 2;
In the step (S1), the temperature is 200-300 ℃ and the time is 40-60 min in the reaction process;
In the step (S2), the heat treatment process is carried out in an argon atmosphere, the temperature is 220-350 ℃, and the time is 2-10 hours.
2. The method of claim 1, wherein in step (S1), the titanium metal salt is selected from one of titanium isopropoxide, titanium acetylacetonate, titanium acetate, titanium chloride, titanium bromide, and titanium iodide;
the zinc metal salt is selected from one of zinc isopropoxide, zinc acetylacetonate, zinc acetate, zinc chloride, zinc bromide or zinc iodide;
The cerium metal salt is selected from one of cerium isopropoxide, cerium acetylacetonate, cerium acetate, cerium chloride, cerium bromide or cerium iodide.
3. The method for preparing the (TiZnCe) O 2-X/PDMS coating according to claim 1 wherein in the step (S1), the post-treatment is a heat-preserving treatment followed by centrifugation, washing and drying in sequence.
4. The method of claim 1, wherein in the step (S3), one of SYLGARD-84 dimethylsilane and doucorning DC-732W is further contained in the (TiZnCe) O 2-X/PDMS powder coating;
(TiZnCe) O 2-X powder, PDMS, SYLGARD-84 dimethyl silane or Dow Corning DC-732W, and the mass percentage of the curing agent is 1% -9%, 0.5% -1% and 89% -98%.
5. The method for preparing the (TiZnCe) O 2-X/PDMS coating according to claim 1, wherein in the step (S4), the spraying pressure is 0.1MPa to 0.25MPa and the thickness of the coating is 10 μm to 50 μm in the compressed air spraying process.
6. The method of claim 1, wherein in step (S4), the post-treatment is a curing and drying treatment;
the curing and drying process is in an ultraviolet state, the temperature is 10-30 ℃, the humidity is 40-70%, and the time is 30-90 min.
7. A (TiZnCe) O 2-X/PDMS coating prepared by the method of any one of claims 1-6.
8. A glove comprising a brush-like (TiZnCe) O 2-X/PDMS coating according to claim 7.
CN202310702365.8A 2023-06-14 2023-06-14 (TiZnCe)O2-XPDMS coating and preparation and application thereof Active CN116731607B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310702365.8A CN116731607B (en) 2023-06-14 2023-06-14 (TiZnCe)O2-XPDMS coating and preparation and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310702365.8A CN116731607B (en) 2023-06-14 2023-06-14 (TiZnCe)O2-XPDMS coating and preparation and application thereof

Publications (2)

Publication Number Publication Date
CN116731607A CN116731607A (en) 2023-09-12
CN116731607B true CN116731607B (en) 2025-03-07

Family

ID=87909217

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310702365.8A Active CN116731607B (en) 2023-06-14 2023-06-14 (TiZnCe)O2-XPDMS coating and preparation and application thereof

Country Status (1)

Country Link
CN (1) CN116731607B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102260410A (en) * 2011-07-13 2011-11-30 大连海洋大学 Long-acting antibacterial organic silicon rubber material and preparation method thereof
KR101373663B1 (en) * 2013-11-12 2014-03-13 임석민 Coated rubber gloves manufacturing method and the manufacturing unit, electrode mold

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002085989A1 (en) * 2001-04-25 2002-10-31 Nanopac Ltd. Photocatalytic coating material having photocatalytic activity and adsorption property and method for preparing the same
GB2462883A (en) * 2008-08-29 2010-03-03 Univ Sheffield Hallam Antimicrobial sol-gel coating
CN102618109B (en) * 2012-02-27 2013-12-04 浙江吉利汽车研究院有限公司 A kind of preparation method and application of ZnO/TiO2 composite powder
CN108864459B (en) * 2018-06-12 2021-08-17 福建师范大学 A kind of hydrophobic photocatalytic self-cleaning hybrid film applicable to the surface of silicone rubber and preparation method thereof
CN113444407A (en) * 2021-03-23 2021-09-28 上海涂固安高科技有限公司 Anti-fouling and anti-virus fluorocarbon coating and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102260410A (en) * 2011-07-13 2011-11-30 大连海洋大学 Long-acting antibacterial organic silicon rubber material and preparation method thereof
KR101373663B1 (en) * 2013-11-12 2014-03-13 임석민 Coated rubber gloves manufacturing method and the manufacturing unit, electrode mold

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Microstructure and antibacterial activity of ions (Ce, Y, or B)-doped Zn-TiO2: a comparative study;Wang, YZ等;《MATERIALS TECHNOLOGY》;20171231;第32卷(第5期);第310–320页 *

Also Published As

Publication number Publication date
CN116731607A (en) 2023-09-12

Similar Documents

Publication Publication Date Title
CN105311668B (en) A kind of cuprous antiseptic dressing of bacteria cellulose combined oxidation and preparation method thereof
Wang et al. Bioceramic materials with ion‐mediated multifunctionality for wound healing
CN103768700B (en) Antibacterial catheter of albumen and preparation method thereof
CA2397614A1 (en) Honey based wound dressing
CN109200334B (en) A composite hydrogel dressing for photodynamic therapy of wound infection and preparation method thereof
CN102657893A (en) Medical nano-fiber sponge material and preparation method and application thereof
CN102352051A (en) Method for preparing collagen-modified bacteria cellulose compound film
Liu et al. Research progress on the use of micro/nano carbon materials for antibacterial dressings
Xia et al. Metal–phenolic network-based polydopamine@ Cu within a polyvinyl alcohol hydrogel film for improved infected wound healing through antibacterial and pro-angiogenesis activity
CN101301487A (en) Gelatine/biological activity glass composite sponge dressing and preparation thereof
CN102357265A (en) Surface modification polyurethane central venous catheter and preparation method thereof
CN106110383A (en) A kind of chitosan alginate dressing and freeze-drying process thereof
CN201242632Y (en) Nanometer self-cleaning light modulation glass
CN116731607B (en) (TiZnCe)O2-XPDMS coating and preparation and application thereof
CN113244178B (en) Gellan gum composite drug-loaded microspheres with remote controllable drug release and preparation method and application thereof
CN106983907A (en) A kind of preparation method of the Ag/Ag AgCl/ZnO composite aquogel dressing of optical dynamic therapy skin trauma
CN1308231C (en) Active carbon loading silver and its preparing method and use
CN102430145B (en) Asymmetric polyurethane/nano TiO2 film wound dressing and preparation method thereof
CN1837270B (en) Modified polymethyl methacrylate material and preparation method thereof
Liu et al. Fabrication of a bionic asymmetric wettable Cu-doped chitosan-laponite-PCL wound dressing with rapid healing and antibacterial effect
CN116421768A (en) A kind of antibacterial hydrogel dressing for the treatment of infected chronic wounds and its preparation method
CN103989269B (en) A kind of preparation method of photocatalytic self-cleaning mouth mask
CN204033031U (en) Antibacterial curtain
CN108498859B (en) Antibacterial bioactive glass nanofiber scaffold and preparation method thereof
CN207785367U (en) A device for humidity regulation and antibacterial care of the skin and an antibacterial skin care film

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant