Hydrophilic lubricating coating solution as well as preparation method and application thereof

Abstract

The invention provides a hydrophilic lubricating coating solution as well as a preparation method and application thereof, and belongs to the technical field of medical instruments. The hydrophilic lubricating coating solution disclosed by the invention is prepared from the following raw materials in parts by mass: 1 to 4 parts of polyurethane prepolymer, 91 to 99 parts of mixed solvent, 2 to 3 parts of 1-methyl-2-pyrrolidone, 1.0 to 1.5 parts of 3-aminopropyltriethoxysilane and 0 to 4 parts of polyvinylpyrrolidone. And immersing the drainage tube into the hydrophilic lubricating coating solution, taking out the drainage tube, airing, and drying to obtain the hydrophilic lubricating coating. The hydrophilic lubricating coating is good in biocompatibility, low in friction coefficient, good in hydrophilic performance and high in adhesiveness, the silicone rubber drainage tube can meet medical clinical application requirements, the service life of the silicone rubber drainage tube can be prolonged, and better use experience is brought to patients.

Description

Technical Field

[0001] The present invention relates to the technical field of medical devices, and in particular to a hydrophilic lubricating coating solution and a preparation method and application thereof. Background Art

[0002] Silicone rubber, as a polymer elastic drainage tube that combines inorganic and organic properties, has a main molecule composed of alternating silicon and oxygen (-Si-O-Si-), and attached to the silicon atom are carbon hydrogen or substituted carbon hydrogen organic groups. These groups are usually methyl or unsaturated vinyl (usually accounting for no more than 0.1%), which gives silicone rubber excellent thermal stability, aging resistance, and resistance to ultraviolet (UV) and ozone erosion. Silicone rubber has been widely used in biology and medicine because of its anti-aging, high transparency, good biocompatibility and excellent temperature resistance. Due to the material of silicone rubber itself, the interface friction between medical silicone rubber and the patient during use can cause pain to the patient and easily tear the wound, causing inflammation and other symptoms. Therefore, improving the lubricity of the silicone rubber surface, reducing the boundary friction of the silicone rubber surface, and reducing the risk of complications, thereby providing patients with a safer and more comfortable use experience, has important application prospects.

[0003] At present, the simplest and most effective method is to apply a layer of lubricating coating on the surface of silicone rubber, and connect hydrophilic groups such as pyrrolidone group, carboxyl group, amide group, etc. on the surface. Thanks to the characteristics of these hydrophilic groups, the surface of the modified drainage tube shows excellent hydrophilicity and lubricity, thereby reducing the boundary friction, and the anti-fouling performance is also greatly improved compared with before. At the same time, the ultra-thin hydrophilic coating will not change the properties of silicone rubber itself. The main drainage tube systems are PEG, polyacrylamide (PAM), hyaluronic acid (HA), etc.

[0004] PEG is a polyether compound with a branched structure. Its molecular structure contains multiple ethylene oxide groups and hydroxyl groups, which make it water-soluble and biocompatible. These groups can form hydrogen bonds with water, making PEG hydrophilic and reducing surface friction. The PEG molecular chain is very soft and can form a uniform lubricating film on the surface of the substrate, making the contact between the friction surfaces smoother, thereby improving the lubrication effect. Studies have found that the PEG coating can block the long-range mutual attraction between bacteria and substrates and introduce a repulsive space effect, thereby changing the hydrophilicity and friction characteristics of the catheter surface, giving it superior lubrication properties. PAM is a highly hydrophilic polymer with strong water absorption. When water molecules interact with the polar groups in the PAM molecules, a "lubricating layer" of water molecules will be formed on the surface of the particles. The presence of this lubricating layer will significantly reduce the friction between the particles and make the surface slippery. HA, also known as hyaluronic acid, is a macromolecular compound of polysaccharides and the main component of the biological extracellular matrix. It has unique physical, chemical and biological properties and exhibits good biocompatibility and biodegradability. At present, although the research on HA lubrication has gradually been applied to the surface modification of medical catheters, there are still unsolved problems in the adhesion and stability between the coating and the catheter surface, which limits its promotion and application in the medical field. Summary of the invention

[0005] The purpose of the present invention is to provide a hydrophilic lubricating coating solution and a preparation method and application thereof, so as to solve the problems of high friction coefficient and low adhesion of the lubricating coating in the prior art.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides a hydrophilic lubricating coating solution, wherein the hydrophilic lubricating coating solution comprises the following raw materials in parts by weight:

[0008]

[0009] Preferably, the mixed solvent comprises acetone, ethyl lactate and tetrahydrofuran, wherein the mass ratio of acetone, ethyl lactate and tetrahydrofuran is 56-59:24-27:11-13.

[0010] Preferably, the hydrophilic lubricating coating solution comprises the following raw materials in parts by weight:

[0011]

[0012] Preferably, the hydrophilic lubricating coating solution comprises the following raw materials in parts by weight:

[0013]

[0014]

[0015] The present invention also provides a method for preparing the above-mentioned hydrophilic lubricating coating solution, comprising the following steps:

[0016] (1) mixing a polyurethane prepolymer and a mixed solvent to obtain a mixed solution A;

[0017] (2) mixing 1-methyl-2-pyrrolidone and 3-aminopropyltriethoxysilane to obtain a mixed solution B;

[0018] (3) Mixing the mixed solution A and the mixed solution B, and adding polyvinyl pyrrolidone to prepare a hydrophilic lubricating coating solution.

[0019] The present invention also provides an application of the hydrophilic lubricating coating solution described above in preparing a hydrophilic lubricating coating, comprising the following steps: immersing the drainage tube in the hydrophilic lubricating coating solution, taking it out, air-drying it, and baking it to obtain a hydrophilic lubricating coating.

[0020] Preferably, the drainage tube is cleaned with heptane and then immersed in the hydrophilic lubricating coating solution.

[0021] Preferably, the immersion time is 4 to 6 minutes.

[0022] Preferably, the drying is carried out in air, and the drying time is 20 to 40 minutes.

[0023] Preferably, the drying temperature is 60-80° C. and the drying time is 0.5-1.5 h; after the drying, the drainage tube is placed in the air for 24 h before use.

[0024] Beneficial effects of the present invention:

[0025] The polyurethane prepolymer in the present invention is used as a binder, and after being cured with the silane coupling agent 3-aminopropyltriethoxysilane, an interpenetrating network structure is formed, which can modify the interface of the silicone rubber drainage tube and enhance the adhesion and durability of the coating. 1-methyl-2-pyrrolidone and 3-aminopropyltriethoxysilane are used as additives. The strong solubility and bonding properties of 1-methyl-2-pyrrolidone and 3-aminopropyltriethoxysilane make the coating more stable. Polyvinyl pyrrolidone is used as a hydrophilic lubricant, so that the coating has hydrophilic lubrication properties.

[0026] The present invention utilizes polyurethane prepolymer, mixed solvent, 1-methyl-2-pyrrolidone, 3-aminopropyltriethoxysilane, and polyvinylpyrrolidone to prepare a hydrophilic lubricating coating solution, places a silicone rubber drainage tube in the hydrophilic lubricating coating solution, and prepares a hydrophilic lubricating coating on the drainage tube. The hydrophilic lubricating coating has good biocompatibility, low friction coefficient, good hydrophilic performance, and strong adhesion, so that the silicone rubber drainage tube can meet medical clinical application requirements, and can extend the service life of the silicone rubber drainage tube, bringing a better use experience to patients. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 : is a curve diagram of the change of friction coefficient of an uncoated silicone rubber drainage tube and a silicone rubber drainage tube coated with a hydrophilic lubricating coating, wherein PDMS is an uncoated silicone rubber drainage tube, 1 is a silicone rubber drainage tube coated with the hydrophilic lubricating coating solution of Example 1, 2 is a silicone rubber drainage tube coated with the hydrophilic lubricating coating solution of Example 2, 3 is a silicone rubber drainage tube coated with the hydrophilic lubricating coating solution of Example 3, 4 is a silicone rubber drainage tube coated with the hydrophilic lubricating coating solution of Example 4, and 5 is a silicone rubber drainage tube coated with the hydrophilic lubricating coating solution of Example 5;

[0028] Figure 2 This is a comparison chart of the average friction coefficient of the silicone rubber drainage tube with a hydrophilic lubricating coating in Application Example 1;

[0029] Figure 3 A comparison diagram of water contact angles of an uncoated silicone rubber drainage tube and a silicone rubber drainage tube with a hydrophilic lubricating coating in Application Example 1;

[0030] Figure 4 This is a comparison chart of adhesion test results of the silicone rubber drainage tube with a hydrophilic lubricating coating in Application Example 1;

[0031] Figure 5 The friction coefficient variation curves of the silicone rubber drainage tube which is not coated with PDMS and the silicone rubber drainage tube which is coated with the coating solutions of Comparative Example 2 and Comparative Example 3;

[0032] Figure 6 This is a comparison diagram of the water contact angles of a silicone rubber drainage tube that is not coated with PDMS and a silicone rubber drainage tube that is coated with the coating solutions of Comparative Examples 2 and 3. DETAILED DESCRIPTION

[0033] The present invention provides a hydrophilic lubricating coating solution, wherein the hydrophilic lubricating coating solution comprises the following raw materials in parts by weight:

[0034]

[0035] In the present invention, the mixed solvent comprises acetone, ethyl lactate and tetrahydrofuran, wherein the mass ratio of acetone, ethyl lactate and tetrahydrofuran is 56-59:24-27:11-13.

[0036] The present invention adopts acetone, ethyl lactate and tetrahydrofuran as solvents, which have good dissolving and volatilizing properties, can effectively dissolve the polyurethane prepolymer and volatilize quickly after the coating is formed.

[0037] In the present invention, the hydrophilic lubricating coating solution comprises the following raw materials in parts by weight:

[0038]

[0039] In the present invention, the hydrophilic lubricating coating solution comprises the following raw materials in parts by weight:

[0040]

[0041] The present invention also provides a method for preparing the above-mentioned hydrophilic lubricating coating solution, comprising the following steps:

[0042] (1) mixing a polyurethane prepolymer and a mixed solvent to obtain a mixed solution A;

[0043] (2) mixing 1-methyl-2-pyrrolidone and 3-aminopropyltriethoxysilane to obtain a mixed solution B;

[0044] (3) Mixing the mixed solution A and the mixed solution B, and adding polyvinyl pyrrolidone to prepare a hydrophilic lubricating coating solution.

[0045] The present invention also provides an application of the hydrophilic lubricating coating solution described above in preparing a hydrophilic lubricating coating, comprising the following steps: immersing the drainage tube in the hydrophilic lubricating coating solution, taking it out, air-drying it, and baking it to obtain a hydrophilic lubricating coating.

[0046] In the present invention, the drainage tube is cleaned with heptane and then immersed in the hydrophilic lubricating coating solution.

[0047] In the present invention, the heptane is used to clean the surface of the drainage tube. It has excellent cleaning performance and volatility, can effectively clean the surface of the drainage tube and avoid the presence of residues, and can expand the drainage tube to a certain extent. During coating, the hydrophilic lubricating coating solution enters the surface of the silicone rubber drainage tube, making the bonding stronger.

[0048] In the present invention, the immersion time is 4 to 6 minutes, preferably 5 minutes.

[0049] In the present invention, the drying is carried out in air, and the drying time is 20 to 40 minutes, preferably 25 to 35 minutes, and more preferably 30 minutes.

[0050] In the present invention, the drying temperature is 60-80° C. and the drying time is 0.5-1.5 h. After the drying, the drainage tube is placed in the air for 24 h before use.

[0051] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0052] The detailed information of each raw material used in the embodiments of the present invention is as follows:

[0053] Polyurethane prepolymer (Xinyuhong, 99%), polyvinylpyrrolidone K30 (AR, Zhonglian Reagent), 3-aminopropyltriethoxysilane (aladdin, 221.37MW), ethyl lactate (lnnochem, 98%), tetrahydrofuran (AR, Tianjin Beichen Fangzheng Reagent Factory), 1-methyl-2-pyrrolidone (aladdin, AR), acetone (AR, Laiyang Economic and Technological Development Zone Fine Chemical Factory), heptane (aladdin, AR).

[0054] Example 1

[0055] 1 part of polyurethane prepolymer, 56 parts of acetone, 24 parts of ethyl lactate and 11 parts of tetrahydrofuran were mixed evenly until completely dissolved to obtain a mixed solution A; 2.6 parts of 1-methyl-2-pyrrolidone and 1.2 parts of 3-aminopropyltriethoxysilane (APTES) were mixed evenly and allowed to stand for 5 minutes to obtain a mixed solution B; mixed solution A and mixed solution B were combined and stirred for 24 hours. As the stirring time increased, white particles or flocculent precipitation appeared in the solution, and a hydrophilic lubricating coating solution was obtained.

[0056] Example 2

[0057] 2 parts of polyurethane prepolymer, 57 parts of acetone, 25 parts of ethyl lactate and 12 parts of tetrahydrofuran are mixed evenly until they are completely dissolved to obtain a mixed solution A; 2.6 parts of 1-methyl-2-pyrrolidone and 1.2 parts of 3-aminopropyltriethoxysilane are mixed evenly and allowed to stand for 5 minutes to obtain a mixed solution B; mixed solution A and mixed solution B are combined and stirred for 24 hours. As the stirring time increases, white particles or flocculent precipitation appears in the solution. Finally, 1 part of polyvinylpyrrolidone K30 is added and mixed evenly to obtain a hydrophilic lubricating coating solution.

[0058] Example 3

[0059] 3 parts of polyurethane prepolymer, 58 parts of acetone, 26 parts of ethyl lactate and 13 parts of tetrahydrofuran are mixed evenly until completely dissolved to obtain a mixed solution A; 2.6 parts of 1-methyl-2-pyrrolidone and 1.2 parts of 3-aminopropyltriethoxysilane are mixed evenly and allowed to stand for 5 minutes to obtain a mixed solution B; mixed solution A and mixed solution B are combined and stirred for 24 hours. As the stirring time increases, white particles or flocculent precipitation appears in the solution. Finally, 2 parts of polyvinylpyrrolidone K30 are added and mixed evenly to obtain a hydrophilic lubricating coating solution.

[0060] Example 4

[0061] 3.8 parts of polyurethane prepolymer, 56 parts of acetone, 24 parts of ethyl lactate and 11 parts of tetrahydrofuran were mixed evenly until completely dissolved to obtain a mixed solution A; 2.6 parts of 1-methyl-2-pyrrolidone and 1.2 parts of 3-aminopropyltriethoxysilane were mixed evenly and allowed to stand for 5 minutes to obtain a mixed solution B; mixed solution A and mixed solution B were combined and stirred for 24 hours. As the stirring time increased, white particles or flocculent precipitation appeared in the solution. Finally, 3 parts of polyvinylpyrrolidone K30 were added and mixed evenly to obtain a hydrophilic lubricating coating solution.

[0062] Example 5

[0063] 4 parts of polyurethane prepolymer, 56 parts of acetone, 24 parts of ethyl lactate and 11 parts of tetrahydrofuran are mixed evenly until completely dissolved to obtain a mixed solution A; 2.6 parts of 1-methyl-2-pyrrolidone and 1.2 parts of 3-aminopropyltriethoxysilane are mixed evenly and allowed to stand for 5 minutes to obtain a mixed solution B; the mixed solution A and the mixed solution B are combined and stirred for 24 hours. As the stirring time increases, white particles or flocculent precipitation appears in the solution. Finally, 4 parts of polyvinylpyrrolidone K30 are added and mixed evenly to obtain a hydrophilic lubricating coating solution.

[0064] Comparative Example 1

[0065] The difference from Example 3 is that 3-aminopropyltriethoxysilane is not added, and other conditions are the same.

[0066] Comparative Example 2

[0067] The difference from Example 4 is that 1-methyl-2-pyrrolidone is not added, and other conditions are the same.

[0068] Comparative Example 3

[0069] The difference from Example 5 is that polyacrylic acid (AR, Kermelo's reagent) is used to replace polyvinyl pyrrolidone K30, and other conditions are the same.

[0070] Application Example 1

[0071] The medical silicone rubber drainage tube was immersed in heptane, wiped dry after 10 seconds, and air-dried in the air for 5 minutes, and then immersed in the hydrophilic lubricating coating solutions of Examples 1 to 5 and the lubricating coating solutions of Comparative Examples 1 to 3, respectively. The tube was taken out after being immersed in the hydrophilic lubricating coating solutions of Examples 1 to 5 and the lubricating coating solutions of Comparative Examples 1 to 2 for 5 minutes, and immersed in the lubricating coating solution of Comparative Example 3 for 30 minutes, and then air-dried in the air for 30 minutes. Finally, the silicone rubber drainage tube was placed in an oven and dried at 71°C for 1 hour. After drying, it was taken out and placed in the air for 24 hours before use. The silicone rubber drainage tubes with hydrophilic lubricating coatings were numbered 1, 2, 3, 4, and 5, respectively, wherein 1, 2, 3, 4, and 5 correspond to the hydrophilic lubricating coating solutions of Examples 1 to 5, respectively.

[0072] Performance Testing:

[0073] (1) Friction performance test: The friction performance of the medical silicone rubber drainage tube with lubricating coating in water environment was tested by high-speed reciprocating friction and wear tester (MDW-02A, Jinan Yihua Tribology Testing Technology Co., Ltd.). The friction coefficient of the silicone rubber drainage tube and the stainless steel ball was tested under the conditions of 5N and 1Hz. 50mL of deionized water was added to the sample tank, and the loading pressure was 5N. Each group of samples was tested 3 times, and the test results were averaged. The friction coefficient test results are shown in Figure 2. Figure 1 , 2 shown.

[0074] (2) Surface wettability test: The surface wettability of different samples was measured using a dynamic / static contact angle meter (JCW-1, Shanghai Fangrui Instrument Co., Ltd.). The droplet for each measurement was 5 μL of deionized water. Six points were randomly tested for each sample. After the water droplet stabilized, its contact angle (WCA) was measured and the results were averaged.

[0075] (3) Adhesion test: The bonding strength of the coating was tested using the ISO2409-2007 grid method. First, a grid of 10 × 10 mm was drawn on the surface of the coated PDMS sample using a grid knife with uniform pressure, and 3M tape was attached to the sample surface and quickly torn off to observe the delamination position of the coating and the grid.

[0076] Result analysis:

[0077] Comparative Example 1 did not add 3-aminopropyltriethoxysilane, so the prepared solution did not form a coating on the PDMS sample. The experimental results of Comparative Examples 2 and 3 are as follows: Figure 5 , 6As shown, in Comparative Example 2, without adding 1-methyl-2-pyrrolidone, the water contact angle of the coating formed is lower than that of the original PDMS, but the friction coefficient is higher than that of the unmodified PDMS, and there is no meaning of modification. Comparative Example 3 uses polyacrylic acid to prepare a lubricating coating solution, and the lubricating coating formed has a smaller water contact glue and a lower friction coefficient, but the coating process takes too long, and can only be deposited on a flat surface, so it has no practical application significance.

[0078] pass Figure 1 and Figure 3 It can be seen that the silicone rubber drainage tube coated with the hydrophilic lubricating coating of the present invention has good friction performance and hydrophilicity. Figure 2 The average friction coefficient comparison diagram of the silicone rubber drainage tube with hydrophilic lubricating coating in Application Example 1 is shown in FIG. Figure 2 and Figure 3 It can be seen that in Example 4, when the polyurethane prepolymer is 3.8 parts, acetone is 56 parts, ethyl lactate is 24 parts, tetrahydrofuran is 11 parts, 1-methyl-2-pyrrolidone is 2.6 parts, APTES is 1.2 parts, and polyvinyl pyrrolidone K30 is 3 parts, the friction coefficient of the hydrophilic lubricating coating obtained is the lowest average of 0.13, and its water contact angle is 62.5, which is higher than that of Example 5. However, it can be seen from the adhesion performance test that the adhesion of the hydrophilic lubricating coating decreases when polyvinyl pyrrolidone K30 is 4 parts (see Figure 4 ), which will cause the hydrophilic lubricating coating to be worn during the friction process, resulting in an increase in the friction coefficient. Therefore, the ratio of the hydrophilic lubricating coating solution in Example 4 is optimal.

[0079] from Figure 4 It can be seen that when no polyvinyl pyrrolidone is added, the coating has the best adhesion performance, and no coating is observed to be adhered to the tape. As the content of polyvinyl pyrrolidone increases, the bonding performance of the coating gradually decreases. When the content of polyvinyl pyrrolidone is 4 parts, it can be observed that the coating is fully adhered to the tape. Combining the friction coefficient and contact angle data, it can be obtained that when three parts of polyvinyl pyrrolidone are added, the coating has good adhesion and lubrication properties.

[0080] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A hydrophilic lubricating coating solution, characterized in that: The hydrophilic lubricating coating solution comprises the following raw materials in parts by weight:

2. The hydrophilic lubricating coating solution according to claim 1, characterized in that: The mixed solvent comprises acetone, ethyl lactate and tetrahydrofuran, wherein the mass ratio of acetone, ethyl lactate and tetrahydrofuran is 56-59:24-27:11-13.

3. The hydrophilic lubricating coating solution according to claim 1 or 2, characterized in that: The hydrophilic lubricating coating solution comprises the following raw materials in parts by weight:

4. The hydrophilic lubricating coating solution according to claim 3, characterized in that: The hydrophilic lubricating coating solution comprises the following raw materials in parts by weight:

5. The method for preparing the hydrophilic lubricating coating solution according to any one of claims 1 to 4, characterized in that: The steps include: (1) mixing a polyurethane prepolymer and a mixed solvent to obtain a mixed solution A; (2) mixing 1-methyl-2-pyrrolidone and 3-aminopropyltriethoxysilane to obtain a mixed solution B; (3) Mixing the mixed solution A and the mixed solution B, and adding polyvinyl pyrrolidone to prepare a hydrophilic lubricating coating solution.

6. Use of the hydrophilic lubricating coating solution according to any one of claims 1 to 4 in preparing a hydrophilic lubricating coating, characterized in that: The method comprises the following steps: immersing the drainage tube into a hydrophilic lubricating coating solution, taking the tube out, air-drying it, and baking it to obtain the hydrophilic lubricating coating.

7. Use of the hydrophilic lubricating coating solution according to claim 6 in preparing a hydrophilic lubricating coating, characterized in that: The drainage tube is cleaned with heptane and then immersed in the hydrophilic lubricating coating solution.

8. Use of the hydrophilic lubricating coating solution according to claim 6 or 7 in preparing a hydrophilic lubricating coating, characterized in that: The immersion time is 4 to 6 minutes.

9. Use of the hydrophilic lubricating coating solution according to claim 8 in preparing a hydrophilic lubricating coating, characterized in that: The drying is carried out in the air, and the drying time is 20 to 40 minutes.

10. Use of the hydrophilic lubricating coating solution according to claim 7 or 9 in preparing a hydrophilic lubricating coating, characterized in that: The drying temperature is 60-80° C. and the drying time is 0.5-1.5 h. After the drying, the drainage tube is placed in the air for 24 h before use.

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