Preparation method of anti-skid particle glass beads in anti-skid coating for rail transit and anti-skid coating
By modifying glass beads with silane coupling agent, fluorosilane and ZIF-8, the problem of insufficient performance of glass beads in traditional anti-slip coatings is solved, significantly improving the anti-slip performance, wear resistance and adhesion of anti-slip coatings, and extending the service life.
Patent Information
- Application Number
- CN202510253585.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-05
- Publication Date
- 2025-05-06
AI Technical Summary
Unmodified glass beads in traditional anti-slip coatings have problems such as degraded anti-slip performance, poor wear resistance, and insufficient adhesion during use, resulting in a shortening of the service life of the paint.
By modifying the glass beads with silane coupling agent, fluorosilane and ZIF-8, the interface bonding force, wear resistance and hydrophobicity with the resin are improved, thereby improving the performance of anti-slip coatings.
It significantly improves the anti-slip performance, wear resistance and adhesion of glass beads in anti-slip coatings, extends the service life of the coating, simplifies the modification processing process, and is easy to industrially produce.
Smart Images
Figure BDA0005297674680000091
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of rail transit material preparation, and in particular to a method for preparing anti-skid granular glass beads in an anti-skid coating for rail transit and the anti-skid coating. Background Art
[0002] As an important part of modern urban transportation, rail transit has attracted much attention for its safety and comfort. The application of anti-skid coatings on rail transit vehicles and tracks is of great significance for improving driving safety and passenger comfort. However, traditional anti-skid coatings are prone to problems such as decreased anti-skid performance and poor wear resistance during long-term use. As one of the main fillers of anti-skid coatings, the performance of anti-skid granular glass beads directly affects the anti-skid effect of the coating. However, unmodified glass beads have deficiencies in dispersibility, adhesion and wear resistance in coatings. The surface energy of unmodified glass beads is relatively high, and they are easy to absorb dust, resulting in decreased anti-skid performance of the coating; ordinary glass beads also have low-temperature brittleness, which makes the coating prone to cracking; the fracture toughness of glass beads is relatively poor, and they are easy to break during use, and the wear resistance is poor, thereby accelerating the wear rate and shortening the life of the coating. Therefore, modifying the glass beads and improving their performance has become the key to improving the quality of anti-skid coatings. Summary of the invention
[0003] In view of this, the purpose of the present invention is to provide a method for preparing anti-skid granular glass beads in anti-skid coatings for rail transit and an anti-skid coating. The present invention adopts silane coupling agent modification to improve the interfacial bonding force between glass beads and resin through chemical bonding; or adopts fluorosilane to modify glass beads to build a hydrophobic barrier while enhancing its wear resistance; or uses ZIF-8 to coat glass beads, and utilizes the high specific surface area and rigid structure of MOF to fill the micro cracks of the coating, improve the hardness and wear resistance of the coating, and extend the service life of the anti-skid coating.
[0004] In order to achieve the above object, the technical solution of the present invention is as follows:
[0005] A method for preparing anti-skid granular glass beads in an anti-skid coating for rail transit comprises the following steps:
[0006] Step 1: Glass bead pretreatment
[0007] Cleaning and activating the glass beads to obtain pretreated glass beads;
[0008] Step 2: using a modifier to modify the pretreated glass beads;
[0009] The modifier is one or more of a silane coupling agent, a fluorosilane and ZIF-8.
[0010] In the above technical solution, preferably, in step 1, the step of cleaning the glass beads is as follows:
[0011] The glass beads were ultrasonically cleaned with deionized water for 30 minutes to remove surface impurities, then ultrasonically cleaned with ethanol for 15 minutes, and finally dried at 100-120°C for 2 hours.
[0012] In the above technical solution, preferably, in step 1, the step of activating the glass beads is as follows:
[0013] The cleaned glass beads are immersed in a hydrofluoric acid solution with a mass fraction of 5% for 10 to 15 minutes, then rinsed with deionized water until neutral, and dried at 100 to 120° C. for 2 hours.
[0014] In the above technical solution, preferably, in step 2, when the modifier is a silane coupling agent, the steps of modifying the glass beads are as follows:
[0015] The pretreated glass beads are immersed in an ethanol solution of a silane coupling agent, wherein the mass ratio of the silane coupling agent to the ethanol is 1:0.05-0.1, refluxed at 60-80° C. for 2-3 hours, and centrifuged to dry.
[0016] In the above technical solution, it is further preferred that the silane coupling agent is γ-aminopropyltriethoxysilane KH-550.
[0017] In the above technical solution, preferably, in step 2, when the modifier is fluorosilane, the steps of modifying the glass beads are as follows:
[0018] (1) Preparation of fluorosilane solution:
[0019] Add fluorosilane to anhydrous ethanol, the mass volume ratio of fluorosilane to anhydrous ethanol is 1g:10mL, and stir at a speed of 300-500rpm on a magnetic stirrer for 30min;
[0020] (2) Glass bead impregnation:
[0021] Adding the pretreated glass beads to the fluorosilane solution prepared in step (1), wherein the mass volume ratio of the glass beads to the fluorosilane solution is between 1:5 and 1:20, reacting at 30 to 60° C. for 2 to 4 hours to cause a hydrolysis reaction to generate active silanol groups, and then reacting at 80 to 150° C. for 2 to 6 hours to cause a condensation reaction between the silanol groups to form a three-dimensional network structure;
[0022] (3) Post-processing:
[0023] The glass beads obtained in step (2) are taken out and dried at 100 to 120° C. for 4 to 6 hours to remove the residual solvent and unreacted fluorosilane, thereby obtaining fluorosilane-modified glass beads.
[0024] In the above technical solution, it is further preferred that the fluorosilane is perfluorooctyltrimethoxysilane.
[0025] In the above technical solution, preferably, in step 2, when the modifier is ZIF-8, the steps of modifying the glass beads are as follows:
[0026] (1) Functional modification:
[0027] First, the pretreated glass beads were immersed in an ethanol solution of a silane coupling agent for 30 minutes, wherein the silane coupling agent was γ-aminopropyltriethoxysilane KH-550 with a mass concentration of 5%, and dried at 60° C. to form silanol groups on the surface of the glass beads;
[0028] (2) dispersing the glass beads obtained in step (1) in a 2-methylimidazole solution of Zn(NO3)2, so that ZIF-8 grows in situ on the surface of the modified glass beads to form a ZIF-8 coating layer, the molar ratio of Zn(NO3)2 to 2-methylimidazole is 1:1, stirring at 60°C for 6 hours, followed by solvent thermal reaction at 120°C for 6 hours, to obtain ZIF-8 coated glass beads;
[0029] (3) After centrifugal drying, ZIF-8 modified glass beads were obtained.
[0030] An anti-skid coating for rail transit, comprising the following components:
[0031] By mass, the glass beads prepared by the present invention are 10-20 parts, the alkyd resin matrix is 30-50 parts, the silicon micropowder is 10-25 parts, the diluent is 5-20 parts, the defoamer is 0.5-1 part, the dispersant is 0.3-1 part, and the anti-settling agent is 0.2-1 part.
[0032] The beneficial effects of the present invention are:
[0033] The method for preparing anti-skid granular glass beads in an anti-skid coating for rail transit of the present invention has the following advantages:
[0034] 1. Modification with silane coupling agent is carried out by evenly coating the surface of glass beads. Chemical bonding between glass beads and coating matrix is achieved through siloxane bonding to form chemical bonds, thus solving the problem of easy shedding of traditional physically modified particles.
[0035] 2. Alternatively, fluorosilane is used to modify glass beads to form a fluorosilane hydrophobic coating on the surface of the glass beads. The hydrophobicity and self-lubricating properties of fluorosilane are utilized to construct a super-hydrophobic surface while enhancing the wear resistance and hydrophobicity of the glass beads.
[0036] 3. Or use ZIF-8 to coat glass beads. The nano-multilevel pore structure of ZIF-8 can fill the micro-cracks on the surface of the glass beads, forming a dense protective layer, blocking external abrasives from invading the coating substrate, and forming an effective physical barrier. The pores of ZIF-8 can adsorb fillers in the coating, reducing their migration and agglomeration during friction. In addition, the hexagonal honeycomb skeleton of ZIF-8 undergoes elastic deformation when subjected to friction stress, absorbs energy through sacrificial wear, and reduces the direct contact stress between the glass beads and the substrate. The surface of ZIF-8 is rich in amino (-NH2) and carboxyl (-COOH), which can undergo condensation reactions with glass beads with silanol groups after functional modification to form siloxane amine bonds, achieve chemical bonding, and enhance interfacial bonding. The high specific surface area and rigid structure of MOF can be used to fill the micro-cracks of the coating and improve the hardness and wear resistance of the coating.
[0037] The invention significantly improves the anti-skid performance, wear resistance and adhesion of the glass beads in the anti-skid coating through modification treatment.
[0038] The invention discloses a method for preparing anti-skid granular glass beads in an anti-skid coating for rail transit, and the modification method is simple and feasible, and is easy for industrial production.
[0039] The anti-skid coating for rail transit of the present invention is prepared by uniformly mixing the modified glass beads with other components of the anti-skid coating (such as resin, filler, diluent, additive, etc.). The prepared anti-skid coating has excellent anti-skid performance, friction coefficient and adhesion, and provides a high-performance anti-skid coating for the rail transit field. DETAILED DESCRIPTION
[0040] The technical scheme of the present invention is clearly and completely described below through examples, but it should be understood that the following examples do not limit the protection scope of the present invention.
[0041] The alkyd resin, defoamer, anti-settling agent, dispersant, silane coupling agent and other reagents used in the following examples were purchased from the following manufacturers or product models, and the remaining reagents not given are also commercially available products.
[0042] Alkyd resin: 1363, Jiangsu Sanmu Group Co., Ltd.;
[0043] Defoaming agent: AKN-3801, Foshan Qianyou Chemical Co., Ltd.
[0044] Anti-settling agent: AKN-7010, Foshan Qianyou Chemical Co., Ltd.
[0045] Dispersant: BYK163, BYK Chemical, Germany;
[0046] Silane coupling agent: KH550, KH560, Shandong Shuntai New Materials Co., Ltd.;
[0047] Xylene: Sinopec Shijiazhuang Refining and Chemical Company;
[0048] Ethanol: Anhui Zesheng Technology Co., Ltd.;
[0049] Hydrofluoric acid: Laiyang Kangte New Materials Co., Ltd.;
[0050] Silica powder: Xuzhou Yingtuo New Materials Co., Ltd.
[0051] Glass beads: Jiangsu Haimen Glass Bead Factory;
[0052] Zinc nitrate: Hunan Huihong Reagent Co., Ltd.;
[0053] 2-Methylimidazole: Changzhou Yongtaifeng Chemical Co., Ltd.
[0054] Example 1: Silane coupling agent modified glass bead anti-slip coating
[0055] 1. Glass bead pretreatment:
[0056] (1) Cleaning: The glass beads were ultrasonically cleaned with deionized water for 30 minutes to remove surface dust and other impurities, then ultrasonically cleaned with ethanol for 15 minutes, and finally dried at 110°C for 2 hours.
[0057] (2) Activation: The cleaned glass beads were immersed in a 5% by mass hydrofluoric acid solution for 15 minutes, then rinsed with deionized water until neutral, and dried at 100° C. for 2 hours.
[0058] 2. Prepare a silane solution according to the mass ratio of silane coupling agent γ-aminopropyltriethoxysilane (KH-550) to ethanol of 1:0.1, stir until completely dissolved, then add the pretreated glass beads to the above silane solution, reflux at 80°C for 2 hours, and centrifuge and dry to obtain silane coupling agent modified glass beads;
[0059] 3. According to the mass percentage, 35 parts of commercially available alkyd resin, 5 parts of diluent xylene, 0.5 parts of defoaming agent, 0.3 parts of dispersant and 0.3 parts of anti-settling agent are added to the dispersion kettle, and stirred at high speed at room temperature. After mixing evenly, 20 parts of silicon micropowder and 15 parts of glass beads modified by silane coupling agent are added to the dispersion kettle. The stirring speed is 50 rpm. After stirring and mixing evenly, an anti-slip coating is obtained.
[0060] Example 2: Fluorosilane-modified glass bead anti-slip coating
[0061] 1. Glass bead pretreatment: same as Example 1.
[0062] 2. Preparation of fluorosilane solution: Add fluorosilane to anhydrous ethanol (prepared by adding 1 g of perfluorooctyltrimethoxysilane to 10 mL of anhydrous ethanol), and stir on a magnetic stirrer at 400 rpm for 30 min.
[0063] 3. Glass bead impregnation
[0064] Slowly add the pretreated glass beads to the prepared fluorosilane solution to ensure that the glass beads are completely immersed. The mass volume ratio of glass beads to fluorosilane solution is 1:5. React at 40°C for 3 hours to hydrolyze fluorosilane to generate active silanol groups. Then react at 120°C for 4 hours to cause condensation reaction between silanol groups to form a three-dimensional network structure.
[0065] 4. Post-processing
[0066] After the reaction is completed, the glass beads are taken out and dried at 110° C. for 5 hours to remove the residual solvent and unreacted fluorosilane, thereby obtaining fluorosilane-modified glass beads.
[0067] 5. According to the mass percentage, 35 parts of commercially available alkyd resin, 5 parts of diluent xylene, 0.5 parts of defoaming agent, 0.3 parts of dispersant and 0.3 parts of anti-settling agent are added to the dispersion kettle, and stirred at high speed at room temperature. After mixing evenly, 20 parts of silicon micropowder and 15 parts of fluorosilane-modified glass beads are added to the dispersion kettle at a stirring speed of 50 rpm. After stirring and mixing evenly, an anti-slip coating is obtained.
[0068] Example 3: ZIF-8 coated glass beads anti-slip coating
[0069] 1. Glass bead pretreatment: same as Example 1.
[0070] 2. Functional modification: (1) Preparation of silane solution: Add silane coupling agent γ-aminopropyltriethoxysilane KH550 to ethanol solution (the concentration of γ-aminopropyltriethoxysilane is 5%) and stir until completely dissolved. (2) Impregnation reaction: Add the pretreated glass beads to the above silane solution, place the solution in a 60°C constant temperature water bath and stir for 30 minutes to allow the silanol groups on the hydrolyzed silane coupling agent and the glass beads with silanol groups to further dehydrate and condense to form Si-O-Si covalent bonds, separate the solid by centrifugation, and dry in vacuum at 60°C.
[0071] The above-mentioned Si-O-Si covalent bond formation principle is: the glass beads are first subjected to ultrasound to promote the formation of surface microporous structures to increase the specific surface area, and HF corrodes the surface of the glass beads to generate hydrolyzable fluorosilicic acid intermediates, which are then hydrolyzed into Si-OH, which is the reaction site of the silane coupling agent. The structure of KH550 is: NH2-CH2-CH2-Si(OEt)3, in which the three ethoxy groups (-OEt) are leaving groups. Under acidic conditions, H + Protonate the ethoxy group, enhance its leaving ability, and promote the nucleophilic substitution of the hydroxyl group (-OH). Each ethoxy group is replaced by the hydroxyl group of the ethanol molecule to generate a silanol group (-SiOH), while releasing ether as a byproduct. The silanol group (-SiOH) dehydrates and condenses with the Si-OH on the surface of the glass beads to form a Si-O-Si covalent bond, and the amino group of KH550 further reacts with the silanol group on the surface of the glass beads.
[0072] 3. The functionalized glass beads were dispersed in a Zn(NO3)2 / 2-methylimidazole mixture (the molar ratio of Zn(NO3)2 to 2-methylimidazole was 1:1) and stirred at 60°C for 6 hours. Then, the ZIF-8 was subjected to solvent thermal reaction at 120°C for 6 hours, and ZIF-8 grew in situ on the surface of the glass beads to form a uniform coating layer. After centrifugation, the ZIF-8-coated glass beads were obtained by drying at 60°C.
[0073] 4. According to the mass percentage, 35 parts of commercially available alkyd resin, 5 parts of diluent xylene, 0.5 parts of defoaming agent, 0.3 parts of dispersant and 0.3 parts of anti-settling agent are added to the dispersion kettle, and stirred at high speed at room temperature. After mixing evenly, 20 parts of silicon micropowder and 15 parts of ZIF-8 coated glass beads are added to the dispersion kettle at a stirring speed of 50 rpm. After stirring and mixing evenly, an anti-slip coating is obtained.
[0074] Example 4: Silane coupling agent KH-560 modified glass bead anti-slip coating
[0075] 1. Glass bead pretreatment: same as Example 1.
[0076] 2. Silane coupling agent modification: The pretreated glass beads were immersed in an ethanol solution of silane coupling agent γ-glycidyloxypropyltrimethoxysilane (KH-560) (mass ratio of KH-560 to ethanol was 1:0.2), refluxed at 70° C. for 1.5 hours, and centrifuged to obtain silane coupling agent KH-560 modified glass beads.
[0077] 3. By mass, add 35 parts of alkyd resin, 5 parts of diluent xylene, 0.5 parts of defoaming agent, 0.3 parts of dispersant and 0.3 parts of anti-settling agent into a dispersion kettle, and stir at high speed at room temperature. After mixing evenly, add 20 parts of silicon micropowder and 12 parts of KH-560 modified glass beads into the dispersion kettle at a stirring speed of 50 rpm. After stirring and mixing evenly, an anti-slip coating is obtained.
[0078] Example 5: Dual modified (KH-550 / ZIF-8) glass bead anti-slip coating
[0079] 1. Glass bead pretreatment: same as Example 1.
[0080] 2. Silane coupling agent modification: The glass beads were treated with KH-550 according to the steps of Example 1.
[0081] 3. ZIF-8 coating: The glass beads modified with KH-550 were coated with ZIF-8 according to the steps of Example 3, but the solvent thermal reaction was extended to 8 hours to enhance the density of the coating layer.
[0082] 4. By mass, add 35 parts of alkyd resin, 5 parts of diluent xylene, 0.5 parts of defoaming agent, 0.3 parts of dispersant and 0.3 parts of anti-settling agent into a dispersion kettle, and stir at high speed at room temperature. After mixing evenly, add 20 parts of silica powder and 18 parts of double-modified glass beads into the dispersion kettle, stir and mix evenly at 50 rpm to obtain an anti-slip coating.
[0083] Comparative Example 1: Unmodified glass beads
[0084] According to the mass percentage, 35 parts of commercially available alkyd resin, 5 parts of diluent xylene, 0.5 parts of defoaming agent, 0.3 parts of dispersant and 0.3 parts of anti-settling agent are added to a dispersion kettle and stirred at high speed at room temperature. After mixing evenly, 20 parts of silicon micropowder and 15 parts of unmodified glass beads are added to the dispersion kettle at a stirring speed of 50 rpm. After stirring and mixing evenly, an anti-slip coating is obtained.
[0085] Comparative Example 2: No glass beads
[0086] According to the mass percentage, 35 parts of commercially available alkyd resin, 5 parts of diluent xylene, 0.5 parts of defoaming agent, 0.3 parts of dispersant and 0.3 parts of anti-settling agent are added to a dispersion kettle and stirred at high speed at room temperature. After mixing evenly, 20 parts of silicon micropowder are added to the dispersion kettle at a stirring speed of 50 rpm. After stirring and mixing evenly, an anti-slip coating is obtained.
[0087] Comparative Example 3: Traditional anti-slip coating (commercially available product)
[0088] A traditional anti-slip coating was selected as a control group, and the brand number of the traditional anti-slip coating was German Henkel2760.
[0089] The performance of Examples 1-3 and Comparative Examples 1-3 of the present invention is characterized as shown in the following table:
[0090] Performance data comparison:
[0091]
[0092] Note: The evaluation standards for anti-slip performance, adhesion, impact resistance and flexibility are set by ourselves, where "excellent" means the best performance, "good" means better performance, "medium" means average performance, and "poor" means poor performance. The friction coefficient and wear resistance data are actual test results.
[0093] The above data show that the anti-slip coating provided by the present invention containing the modified glass beads prepared by the present invention shows significant advantages in anti-slip performance, friction coefficient, adhesion, impact resistance and flexibility, and has broad application prospects.
[0094] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the present invention.
Claims
1. A method for preparing anti-skid granular glass beads in anti-skid coating for rail transit, characterized in that: The following steps are involved: Step 1: Glass bead pretreatment Cleaning and activating the glass beads to obtain pretreated glass beads; Step 2: using a modifier to modify the pretreated glass beads; The modifier is one or more of a silane coupling agent, a fluorosilane and ZIF-8.
2. The preparation method according to claim 1, characterized in that: In step 1, the steps for cleaning the glass beads are as follows: The glass beads were ultrasonically cleaned with deionized water for 30 minutes to remove surface impurities, then ultrasonically cleaned with ethanol for 15 minutes, and finally dried at 100-120°C for 2 hours.
3. The preparation method according to claim 1, characterized in that: In step 1, the steps for activating the glass beads are as follows: The cleaned glass beads are immersed in a hydrofluoric acid solution with a mass fraction of 5% for 10 to 15 minutes, then rinsed with deionized water until neutral, and dried at 100 to 120° C. for 2 hours.
4. The preparation method according to claim 1, characterized in that: In step 2, when the modifier is a silane coupling agent, the steps of modifying the glass beads are as follows: The pretreated glass beads are immersed in an ethanol solution of a silane coupling agent, wherein the mass ratio of the silane coupling agent to the ethanol is 1:0.05-0.1, refluxed at 60-80° C. for 2-3 hours, and centrifuged to dry.
5. The preparation method according to claim 4, characterized in that: The silane coupling agent is γ-aminopropyltriethoxysilane KH-550.
6. The preparation method according to claim 1, characterized in that: In step 2, when the modifier is fluorosilane, the steps of modifying the glass beads are as follows: (1) Preparation of fluorosilane solution: Add fluorosilane to anhydrous ethanol, the mass volume ratio of fluorosilane to anhydrous ethanol is 1g:10mL, and stir at a speed of 300-500rpm on a magnetic stirrer for 30min; (2) Glass bead impregnation: Adding the pretreated glass beads to the fluorosilane solution prepared in step (1), wherein the mass volume ratio of the glass beads to the fluorosilane solution is between 1:5 and 1:20, reacting at 30 to 60° C. for 2 to 4 hours to cause a hydrolysis reaction to generate active silanol groups, and then reacting at 80 to 150° C. for 2 to 6 hours to cause a condensation reaction between the silanol groups to form a three-dimensional network structure; (3) Post-processing: The glass beads obtained in step (2) are taken out and dried at 100 to 120° C. for 4 to 6 hours to remove the residual solvent and unreacted fluorosilane, thereby obtaining fluorosilane-modified glass beads.
7. The preparation method according to claim 6, characterized in that: The fluorosilane is perfluorooctyltrimethoxysilane.
8. The preparation method according to claim 1, characterized in that: In step 2, when the modifier is ZIF-8, the steps of modifying the glass beads are as follows: (1) Functional modification: First, the pretreated glass beads were immersed in an ethanol solution of a silane coupling agent for 30 minutes, wherein the silane coupling agent was γ-aminopropyltriethoxysilane KH-550 with a mass concentration of 5%, and dried at 60° C. to form silanol groups on the surface of the glass beads; (2) dispersing the glass beads obtained in step (1) in a 2-methylimidazole solution of Zn(NO3)2, so that ZIF-8 grows in situ on the surface of the modified glass beads to form a ZIF-8 coating layer, the molar ratio of Zn(NO3)2 to 2-methylimidazole is 1:1, stirring at 60°C for 6 hours, followed by solvent thermal reaction at 120°C for 6 hours, to obtain ZIF-8 coated glass beads; (3) After centrifugal drying, ZIF-8 modified glass beads were obtained.
9. An anti-skid coating for rail transit, characterized in that: Contains the following ingredients: In parts by mass, the glass beads prepared by the preparation method according to any one of claims 1 to 8 are 10 to 20 parts, the alkyd resin matrix is 30 to 50 parts, the silicon powder is 10 to 25 parts, the diluent is 5 to 20 parts, the defoaming agent is 0.5 to 1 part, the dispersant is 0.3 to 1 part, and the anti-settling agent is 0.2 to 1 part.