CN113861485B - Hydrophilic lubricating coating forming interpenetrating network structure with surface of high polymer material and preparation method thereof - Google Patents
Hydrophilic lubricating coating forming interpenetrating network structure with surface of high polymer material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydrophilic lubricating coating forming an interpenetrating network structure with the surface of a high polymer material and a preparation method thereof. The preparation method comprises the following steps: (1) Soaking a high polymer material into an organic solution containing a photoinitiator, so that the photoinitiator enters the surface of the high polymer material under the action of swelling and diffusion, transferring the high polymer material into a cleaning solvent to remove the photoinitiator attached to the outer side of the surface of the high polymer material, taking out the high polymer material, and drying the high polymer material by using inert gas to obtain the high polymer material containing the photoinitiator, wherein the photoinitiator is trapped below the surface of the high polymer material; (2) And (2) placing the high polymer material containing the photoinitiator obtained in the step (1) in a monomer solution, initiating in-situ polymerization of a monomer under ultraviolet illumination, taking out the high polymer material after polymerization is completed, and cleaning to obtain the hydrophilic lubricating coating which forms an interpenetrating network structure with the surface of the high polymer material.
Description
Technical Field
The invention relates to the field of surface coatings of medical polymer materials for implant intervention, in particular to a hydrophilic lubricating coating forming an interpenetrating network structure with the surface of a polymer material and a preparation method thereof.
Background
With the development of medical technology, interventional medical devices (such as guide wires, PICC catheters, endoscopes and the like) have been widely used in clinical treatment. The surface of the medical appliance with the lubricating coating has a low friction coefficient, so that the friction between the appliance and human tissues can be reduced, the pain of a patient can be relieved, the biocompatibility of materials can be improved, particles generated by friction can be reduced, and the long-term use of the medical appliance can be maintained.
Methods of applying lubricating oils (e.g., silicone oils, glycerin) have been used to reduce the coefficient of friction of medical devices, but such methods are difficult to handle, and the resulting lubricity is poor and difficult to last. Researches show that the surface lubricity of the implant intervention medical appliance in the tissue environment can be effectively improved by grafting a hydrophilic polymer chain coating or coating a hydrogel layer on the surface. The hydrophilic polymer has high hydration capacity, and the hydration layer on the surface of the hydrophilic polymer can provide effective lubricity and good biocompatibility. However, the single polymer chain is easily abraded and peeled off in a frictional environment, thereby exposing the surface and losing lubricity. The hydrogel layer with a three-dimensional network structure often generates wear particles in the friction process due to poor mechanical properties of the hydrogel layer, and further causes more serious problems. Moreover, the chemical processes of the methods are complex and cumbersome, and the requirements of mass and rapid production are difficult to meet. Therefore, the long-term lubricity and wear resistance of the coating are solved, the coating is prevented from being worn and falling off, the production process is simplified, and the production speed is improved, so that the method has great significance for practical application.
Generally, the existing hydrophilic coating and the preparation method thereof cannot ensure long-term stable lubricity, improve the wear resistance of the coating and reduce the wear of the coating. In addition, the preparation process has a difficulty in meeting the requirement of batch and rapid production. Therefore, there is a need to provide a new method for preparing hydrophilic lubricating coatings to meet the demand.
Patent specification CN105732848A discloses a preparation method of a hydrophilic lubricating coating, which comprises immersing a medical catheter in a coating solution composed of a photo-curing resin and an alcohol/water mixed solvent for 1-2 minutes, taking out and airing, and curing the catheter surface under the irradiation of ultraviolet light to form the hydrophilic lubricating coating. The hydrophilic lubricating coating is characterized in that the hydrophilic lubricating coating is completely and compactly coated on the outer surface of the catheter.
Erythrocarb et al (chemical propellant and polymer material, 3 rd volume 1, 2005, pages 43-46) studied benzophenone to initiate the grafting of acrylic acid onto polyurethane surface by dropping acrylamide and benzophenone on polyurethane film, pressing quartz glass to form liquid film, and mercury lamp irradiation grafting. The hydrophilic layer formed by grafting is also characterized in that the hydrophilic layer completely and compactly covers the outer surface of the polyurethane film.
Disclosure of Invention
The invention provides a hydrophilic lubricating coating which forms an interpenetrating network structure with the surface of a high polymer material and a preparation method thereof, which can meet the requirements of long-term lubricity and wear resistance of the hydrophilic lubricating coating prepared on the surface of the high polymer material, and an interpenetrating network structure is formed between the obtained coating and the surface layer of the high polymer material, thereby ensuring the combination stability of the coating and the surface, and the wear resistance and lubricity of the coating.
A hydrophilic lubricating coating which forms an interpenetrating network structure with the surface of a high polymer material comprises the following steps:
(1) Soaking a high polymer material into an organic solution containing a photoinitiator, so that the photoinitiator enters the surface of the high polymer material under the action of swelling and diffusion, transferring the high polymer material into a cleaning solvent to remove the photoinitiator attached to the outer side of the surface of the high polymer material, taking out the high polymer material, and drying the high polymer material by using inert gas to obtain the high polymer material containing the photoinitiator, wherein the photoinitiator is trapped below the surface of the high polymer material;
(2) And (2) placing the high molecular material containing the photoinitiator obtained in the step (1) in a monomer solution, initiating in-situ polymerization of the monomer under ultraviolet illumination, taking out the high molecular material after the polymerization is finished, and cleaning to obtain the hydrophilic lubricating coating which forms an interpenetrating network structure with the surface of the high molecular material.
The invention selects a mode of trapping the photoinitiator on the surface and loads the photoinitiator in the high polymer material, so that the photopolymerization is carried out in the surface layer of the high polymer material, and the preparation of the interpenetrating network of the coating and the high polymer material is realized.
The invention washes off the photoinitiator attached to the outer side of the surface of the high polymer material, the photoinitiator is trapped below the surface of the high polymer material, the photoinitiator captures hydrogen on the high polymer material on the surface layer of the high polymer material to initiate polymerization, and a hydrophilic lubricating coating is generated in situ on the surface of the high polymer material to reduce the friction coefficient of the surface of the material.
The preparation method provided by the invention can be carried out by simply immersing the material into the monomer solution, and the coating thickness is uniform and controllable. Inert gas is not needed to be introduced in the ultraviolet polymerization process, the polymerization time is extremely short, the coating preparation process is simplified, the preparation time is shortened, and the preparation cost is reduced. The method provided by the invention has simple process and is used for industrial batch production.
In the step (1), the time for immersing the polymer material in the organic solution containing the photoinitiator is 1 to 20min, for example, 2min,4min,6min,8min,10min,15min,18min, etc.
In the step (1), the polymer material is any one selected from polyurethane, polyvinyl chloride, polyethylene, polyether block polyamide and nylon.
In the step (1), the photoinitiator is one or a mixture of two or more of substituted or unsubstituted thioxanthone, benzophenone, alkyl substituted benzophenone, coumarin ketone, benzoin acetate and anthraquinone, and the concentration of the photoinitiator in the organic solution containing the photoinitiator is 1-20wt%, such as 1.5wt%,3wt%,5wt%,7.5wt%,10wt%,12.5wt%,15wt%,17.5wt%,19wt% and the like.
In step (1), the solvent in the organic solution containing the photoinitiator includes, but is not limited to, ethanol, acetone, N-dimethylformamide, and may be any one of ethanol, acetone, N-dimethylformamide or a combination of at least two thereof.
In the step (1), the high polymer material is transferred into a cleaning solvent, and the time for washing away the photoinitiator attached to the outer side of the surface of the high polymer material is 1-120s.
In the step (1), the cleaning solvent is ethanol.
In the step (1), the inert gas may be nitrogen, a rare gas, or the like.
The invention selects a mode of trapping the photoinitiator on the surface, and loads the photoinitiator in the high polymer material, so that photopolymerization is carried out in the surface layer of the high polymer material, and the preparation of the interpenetrating network of the coating and the high polymer material is realized.
In the step (2), the monomer is selected from one or a mixture of two or more of acrylamide, acrylic acid, isopropyl acrylamide, 2-methacryloxyphosphocholine, hydroxyethyl methacrylate, polyethylene glycol dimethacrylate, 2-acrylamide-2-methylpropanesulfonic acid, sulfobetaine methacrylate and N, N-dimethylacrylamide, and the concentration of the monomer in the monomer solution is 1-70wt%, for example, 3wt%,5wt%, 10wt%, 15wt%, 20wt%, 23wt%, 28wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%,65wt%, etc.
In the step (2), the intensity of the ultraviolet irradiation is 20-500mW/cm 2 E.g. 25mW/cm 2 ，40mW/cm 2 ，100mW/cm 2 ，150mW/cm 2 ，200mW/cm 2 ，250mW/cm 2 ，300mW/cm 2 ，350mW/cm 2 ，400mW/cm 2 ，450mW/cm 2 ，485mW/cm 2 And the like for 1 to 30min, for example, 1.5min,3min,5min,8min,10min,15min,18min,20min,25min,28min and the like.
In the step (2), deionized water is adopted for cleaning, and the cleaning time is 10-30min.
The monomer used in the invention is a water-soluble monomer, has strong hydrophilicity, greatly reduces the surface friction of a high polymer material, simultaneously, the hydrophilic lubricating polymer has certain anticoagulation and anti-protein adhesion effects, can improve biocompatibility, and can be used for improving rejection reaction of the high polymer material used in vivo.
The hydrophilic lubricating coating is polymerized and crosslinked in the surface layer of the high polymer material, and the coating and the surface of the high polymer material form an interpenetrating network structure.
Compared with the prior art, the invention has the main advantages that:
1. different from the existing other preparation methods of hydrophilic lubricating coatings, the surface interception photoinitiator technology adopted by the invention enables the photoinitiation and photopolymerization processes to be carried out on the surface layer of the high polymer material, and the surface layer of the high polymer material and the hydrophilic lubricating coating form an interpenetrating network, so that the coating is firmly combined with the surface of the material, and the coating has high stability. And the interpenetrating network enhances the mechanical strength of the coating and improves the long-term wear resistance of the coating.
2. The preparation method is suitable for preparing the hydrophilic lubricating coating on the planar, tubular, spherical and other polymer materials in any shapes, can meet different application scenes, and has good universality.
3. The preparation process method is easy to operate, the coating thickness is uniform and controllable, the polymerization process is extremely short, oxygen isolation and inert gas introduction are not needed, and the preparation cost is reduced.
4. The process flow can be automatic or semi-automatic, is simple and is used for large-scale batch production.
Drawings
FIG. 1 is a UV absorption spectrum of an initiator in a polymer material having a surface trapped initiator prepared in example 1;
FIG. 2 is a photograph of an interpenetrating network structure of the hydrophilic lubricating coating and the surface of the polymeric material prepared in example 1;
fig. 3 is a graph of coefficient of friction versus number of friction cycles for a hydrophilic lubricious coating prepared in example 1.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
A polyurethane (TPU) material with a hydrophilic lubricating coating is prepared by the following steps:
(1) Ultrasonically cleaning the surface of the TPU by using ethanol and water in sequence, and drying by using nitrogen;
(2) Dissolving benzophenone in acetone to obtain a photoinitiator solution with the mass fraction of 10%;
(3) Dissolving an acrylamide monomer in water to obtain a monomer solution with the mass fraction of 15%;
(4) Soaking the cleaned TPU in a photoinitiator solution for 8min, then cleaning the TPU in ethanol for 10s, removing the initiator attached to the surface, and then drying the TPU by using nitrogen;
(5) Soaking TPU with initiator intercepted on the surface into monomer solution for ultraviolet curing, wherein the ultraviolet light intensity is 116.3mW/cm 2 The ultraviolet polymerization time is 8min;
(6) And carrying out ultrasonic treatment on the obtained coating in deionized water for 10min to obtain the TPU with the hydrophilic lubricating coating.
The TPU with hydrophilic lubricating coating of example 1 was tested for properties by the following method:
1) Surface trapped initiator loading: the polymeric material loaded with the photoinitiator obtained in the step (4) of the example 1 is soaked in an ethanol solution, and the initiator in the polymeric material is extracted overnight. The extracted initiator content was quantitatively determined by uv-vis spectroscopy. The initiator loading was calculated to be 0.155mg/cm according to the standard curve 2 。
2) Interpenetrating network structure of the coating and the high polymer material: the section of the coating obtained in the step (6) in the example 1 is subjected to frozen ultrathin section, and the existence of a phase separation structure in the section of the coating is observed by a transmission electron microscope: respectively a high molecular material and a hydrophilic lubricating coating.
3) And (3) friction test: the hydrophilic lubricating coating obtained in the step (6) of example 1 was subjected to a friction test using a ball-and-disk friction tester, and a TPU having a size of 25mm × 20mm × 5mm and a coating was fixed using a jig, and the friction ball applied a pressure of 20N to the coating to perform a friction test with a frequency of 5Hz and a friction stroke of 5mm with a reciprocating motion of 100000 times. The magnitude of the friction force is recorded by software, and the friction coefficient is calculated by the ratio of the transverse friction force to the longitudinal pressure force.
The ultraviolet absorption spectrum of the polymer material obtained in the step (4) and loaded with the initiator is shown in figure 1.
The interpenetrating network structure of the hydrophilic lubricating coating prepared in the step (6) and the high polymer material is shown in fig. 2.
The friction coefficient during 100000 times of rubbing of the hydrophilic lubricating coating prepared is shown in fig. 3.
The surface of the photoinitiator is trapped inside the surface layer of the high polymer material, and polymerization occurs on the surface layer of the high polymer material, so that the hydrophilic lubricating coating prepared by the method forms an interpenetrating network structure with the surface of the high polymer material, and the stable combination between the coating and the high polymer material, the long-term stability, the wear resistance and the lubricity of the coating are ensured.
The interpenetrating network structure of the coating of the invention determines that the properties of the coating are completely different from the coating which is completely and compactly coated on the surface of the high polymer material in the prior art, and the generated friction lubrication effect has uniqueness compared with the coating which is completely and compactly coated on the surface of the high polymer material in the prior art.
Example 2
A polyurethane material with a hydrophilic lubricating coating is prepared by the following steps:
(1) Ultrasonically cleaning the surface of the TPU by using ethanol and water in sequence, and drying by using nitrogen;
(2) Dissolving benzophenone in acetone to obtain a photoinitiator solution with the mass fraction of 20%;
(3) Dissolving a 2-acrylamide-2-methylpropanesulfonic acid monomer in water to obtain a monomer solution with the mass fraction of 20%;
(4) And soaking the cleaned TPU in a photoinitiator solution for 6min, then cleaning the TPU in ethanol for 20s, and removing the initiator attached to the surface. Then blowing the mixture by using nitrogen;
(5) Soaking TPU with initiator intercepted on the surface into monomer solution for ultraviolet curing, wherein the ultraviolet light intensity is 116.3mW/cm 2 Purple colorThe external polymerization time was 8min.
(6) The resulting coating was sonicated in deionized water for 10min and then placed in 0.9% nacl for one week to give TPU with a hydrophilic lubricious coating.
Example 3
A polyether block polyamide catheter with a hydrophilic lubricating coating is prepared by the following steps:
(1) Sequentially ultrasonically cleaning the surface of the silicon rubber catheter by using isopropanol and water, and drying by using nitrogen;
(2) Dissolving chlorothianthrone in acetone to obtain a photoinitiator solution with the mass fraction of 8%;
(3) Dissolving a 2-methacryloxyphosphocholine monomer in water to obtain a monomer solution with the mass fraction of 5%;
(4) And (3) soaking the cleaned silicon rubber conduit in a photoinitiator solution for 10min, then cleaning the silicone rubber conduit in ethanol for 10s, and removing the initiator attached to the surface. Then blowing the mixture by using nitrogen;
(5) Immersing the silicon rubber catheter with the surface retaining the initiator into a monomer solution for ultraviolet curing, wherein the ultraviolet intensity is 124.6mW/cm 2 The UV polymerization time was 4min.
(6) And washing the obtained coating in deionized water for 10min to obtain the silicone rubber with the hydrophilic lubricating coating.
Example 4
A polyvinyl chloride catheter with a hydrophilic lubricating coating is prepared by the following steps:
(1) Ultrasonically cleaning the surface of a polyvinyl chloride catheter by using ethanol and water in sequence, and drying by using nitrogen;
(2) Dissolving coumarin ketone in ethanol to obtain a photoinitiator solution with the mass fraction of 15%;
(3) Dissolving polyethylene glycol dimethacrylate (Mn = 540) in water to obtain a monomer solution with the mass fraction of 10%;
(4) And soaking the cleaned polyvinyl chloride catheter in a photoinitiator solution for 10min, and then cleaning the catheter in ethanol for 60s to remove the initiator attached to the surface. Then blowing the mixture by using nitrogen;
(5) Immersing the silicon rubber catheter with the surface retaining the initiator into a monomer solution for ultraviolet curing, wherein the ultraviolet intensity is 64.5mW/cm 2 The UV polymerization time was 4min.
(6) And (3) washing the obtained coating in deionized water for 30min to obtain the polyvinyl chloride catheter with the hydrophilic lubricating coating.
Example 5
A nylon guide wire with a hydrophilic lubricating coating is prepared by the following steps:
(1) Ultrasonically cleaning the surface of a nylon guide wire by using ethanol and water in sequence, drying by using nitrogen, and vacuumizing for 20min;
(2) Dissolving 2-isopropyl thioxanthone in N, N-dimethylformamide to obtain a photoinitiator solution with the mass fraction of 5%;
(3) Dissolving hydroxyethyl methacrylate monomers and acrylic acid monomers in water to obtain a monomer solution with the mass fraction of 15% of hydroxyethyl methacrylate and 5% of acrylic acid;
(4) And soaking the cleaned nylon guide wire in a photoinitiator solution for 2min, then cleaning the nylon guide wire in ethanol for 20s, and removing the initiator attached to the surface. Then blowing the mixture by using nitrogen;
(5) Soaking the nylon guide wire with the initiator intercepted on the surface into a monomer solution for ultraviolet curing, wherein the ultraviolet intensity is 73.6mW/cm 2 The ultraviolet polymerization time is 10min.
(6) And carrying out ultrasonic treatment on the obtained coating in deionized water for 20min to obtain the nylon guide wire with the hydrophilic lubricating coating.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (1)
1. The TPU material with the hydrophilic lubricating coating is characterized by comprising the following preparation methods:
(1) Ultrasonically cleaning the surface of the TPU by using ethanol and water in sequence, and drying by using nitrogen;
(2) Dissolving benzophenone in acetone to obtain a photoinitiator solution with the mass fraction of 10%;
(3) Dissolving an acrylamide monomer in water to obtain a monomer solution with the mass fraction of 15%;
(4) Soaking the cleaned TPU in a photoinitiator solution for 8min, then cleaning the TPU in ethanol for 10s, removing the initiator attached to the surface, and then drying the TPU by using nitrogen;
(5) Soaking TPU with initiator intercepted on the surface into monomer solution for ultraviolet curing, wherein the ultraviolet intensity is 116.3mW/cm 2 The ultraviolet polymerization time is 8min;
(6) And carrying out ultrasonic treatment on the obtained coating in deionized water for 10min to obtain the TPU with the hydrophilic lubricating coating.
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| CN110841170A (en) * | 2019-11-13 | 2020-02-28 | 中国科学院兰州化学物理研究所 | Layered lubricating catheter and preparation method thereof |
| CN111621240A (en) * | 2020-06-05 | 2020-09-04 | 中国科学院兰州化学物理研究所 | Polymer brush modified transparent anti-fog patch and preparation method thereof |
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| US6936399B2 (en) * | 2001-10-22 | 2005-08-30 | Fuji Photo Film Co., Ltd. | Hydrophilic member, hydrophilic graft polymer, and support of planographic printing plate |
| CN104857571B (en) * | 2014-12-03 | 2017-10-24 | 美昕医疗器械（上海）有限公司 | The preparation method of hydrophilic lubrication silica fubber cathete and its hydrophilic lubrication coating |
| CN108676193B (en) * | 2018-04-17 | 2021-07-30 | 上海艾瑞德生物科技有限公司 | Plastic surface modification method |
| CN113350579B (en) * | 2021-06-04 | 2022-11-01 | 上海交通大学医学院附属第九人民医院 | Preparation method of anti-sputum-thrombus tracheal catheter loaded with hydrogel coating |
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| CN110841170A (en) * | 2019-11-13 | 2020-02-28 | 中国科学院兰州化学物理研究所 | Layered lubricating catheter and preparation method thereof |
| CN111621240A (en) * | 2020-06-05 | 2020-09-04 | 中国科学院兰州化学物理研究所 | Polymer brush modified transparent anti-fog patch and preparation method thereof |
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