A fluorine-containing rubber polymer material for waterproofing membrane

Abstract

This invention relates to the field of polymer materials technology, and proposes a fluorinated rubber polymer material for waterproof membranes, comprising the following components by weight: 100 parts EPDM rubber, 20-30 parts carbon black, 15-25 parts softener, 12-16 parts silica-supported kaempferol, 6-8 parts hydrotalcite, 6-8 parts fluoride, 1-2 parts lubricant, 3-6 parts zinc oxide, and 3-4 parts vulcanizing agent. This technical solution solves the problem of insufficient aging resistance in existing rubber polymer materials for waterproof membranes.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a fluorinated rubber polymer material for waterproof membranes. Background Technology

[0002] Waterproof membranes primarily use styrene-butadiene rubber (SBR), neoprene rubber (NBR), and ethylene propylene diene monomer (EPDM) rubber as base materials, and are applied in waterproofing projects such as building roofs, underground engineering, tunnels, and bridges. As a core waterproofing component, waterproof membranes are exposed to outdoor natural environments or damp underground environments for extended periods, continuously enduring sunlight exposure, temperature fluctuations, rain and snow erosion, acid and alkali corrosion, and structural deformation and stretching. Therefore, the materials require stringent requirements for aging resistance, waterproofing, and mechanical stability. Among these, aging resistance is a core prerequisite for ensuring long-term effective waterproofing and extending the service life of the project.

[0003] When the polymer materials used in waterproof membranes have insufficient anti-aging properties, they cannot effectively resist the synergistic aging effects of ultraviolet rays, heat and oxygen, humidity and heat and corrosive media. After long-term service, the materials are prone to cracking, stickiness, embrittlement and decreased tensile strength, which in turn leads to membrane damage and leakage, shortens the service life of waterproof projects, increases later maintenance costs, and makes it difficult to meet the actual needs of long-term waterproof projects. Summary of the Invention

[0004] This invention proposes a fluorinated rubber polymer material for waterproof membranes, which solves the problem of insufficient aging resistance of rubber polymer materials for waterproof membranes in related technologies.

[0005] The technical solution of the present invention is as follows: This invention proposes a fluorinated rubber polymer material for waterproof membranes, comprising the following components by weight: 100 parts EPDM rubber, 20-30 parts carbon black, 15-25 parts softener, 12-16 parts silica-supported kaempferol, 6-8 parts hydrotalcite, 6-8 parts fluoride, 1-2 parts lubricant, 3-6 parts zinc oxide, and 3-4 parts vulcanizing agent.

[0006] As a further technical solution, the method for preparing kaempferol-supported silica includes the following steps: Add water to silica to obtain a silica suspension; dissolve kaempferol in dimethyl sulfoxide to obtain a kaempferol solution; The kaempferol solution was added to the silica suspension under stirring, a catalyst was added, and the mixture was reacted, washed, and dried to obtain silica-supported kaempferol.

[0007] As a further technical solution, the mass-to-volume ratio of the silica to water is 1g:18~20mL.

[0008] As a further technical solution, the mass-to-volume ratio of kaempferol to dimethyl sulfoxide is 12-15 g: 200 mL.

[0009] As a further technical solution, the stirring speed is 200~300 rpm.

[0010] As a further technical solution, the volume ratio of the kaempferol solution to the silica suspension is 1:0.9~1.

[0011] As a further technical solution, the catalyst is dibutyltin dilaurate.

[0012] As a further technical solution, the droplet acceleration rate of the catalyst is 0.05 mol / drop.

[0013] As a further technical solution, the volume ratio of the catalyst to the kaempferol solution is 0.15~0.25:200.

[0014] As a further technical solution, the reaction temperature is 75~85℃ and the time is 9~11h.

[0015] As a further technical solution, the washing is performed with anhydrous ethanol.

[0016] As a further technical solution, the softener includes one or both of naphthenic oil and paraffin oil.

[0017] As a further technical solution, the fluoride includes one or more of calcium fluoride, magnesium fluoride, sodium fluorosilicate, and sodium fluoroaluminate.

[0018] As a further technical solution, when the fluoride is calcium fluoride, magnesium fluoride and sodium fluoroaluminate, the mass ratio of calcium fluoride, magnesium fluoride and sodium fluoroaluminate is 1:1:0.8~1.2.

[0019] In this invention, when the fluorides are calcium fluoride, magnesium fluoride, and sodium fluoroaluminate, sodium fluoroaluminate has better chemical stability than sodium fluorosilicate. The physical barrier layer formed between the sodium fluoroaluminate, calcium fluoride, and magnesium fluoride particles provides better protection in corrosive media, effectively improving the corrosion resistance of fluoride-containing rubber polymer materials, thereby enhancing the corrosion and aging resistance of waterproof membranes. The mass ratio of calcium fluoride, magnesium fluoride, and sodium fluoroaluminate is 1:1:0.8~1.2, and can be selected from 1:1:0.8, 1:1:0.9, 1:1:1, 1:1:1.1, and 1:1:1.2. Preferably, the mass ratio of calcium fluoride, magnesium fluoride, and sodium fluoroaluminate is 1:1:1.

[0020] As a further technical solution, the lubricant includes stearic acid.

[0021] As a further technical solution, the vulcanizing agent includes vulcanizing agent DCP.

[0022] The working principle and beneficial effects of this invention are as follows: In this invention, the addition of kaempferol loaded onto silica can improve the aging resistance of rubber polymer materials. Kaempferol is a flavonoid compound with certain antioxidant properties, which can effectively inhibit the oxidation reaction of rubber molecular chains. At the same time, silica itself has certain UV aging resistance properties. When kaempferol is loaded onto silica, the migration of kaempferol is also inhibited, and it is not easy to migrate in the matrix, so it can play its role better and more uniformly. When applied to waterproof membranes, the waterproof membranes have excellent aging resistance. Detailed Implementation

[0023] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0024] In the following examples and comparative examples, carbon black: type N550; silica: particle size 20nm; hydrotalcite: particle size 5000 mesh.

[0025] Example 1 A fluorinated rubber polymer material for waterproof membranes comprises the following components in parts by weight: 100 parts EPDM rubber, 30 parts carbon black, 25 parts naphthenic oil, 16 parts silica-loaded kaempferol, 8 parts hydrotalcite, 8 parts fluoride, 2 parts stearic acid, 6 parts zinc oxide, and 4 parts vulcanizing agent DCP. The fluorides are calcium fluoride and magnesium fluoride in a mass ratio of 1:1; The method for preparing kaempferol-supported silica includes the following steps: Add water to silica to obtain silica suspension (mass-volume ratio of 1g:18mL); dissolve kaempferol in dimethyl sulfoxide to obtain kaempferol solution (mass-volume ratio of kaempferol to dimethyl sulfoxide of 12g:200mL). At a rotation speed of 200 rpm, kaempferol solution was added to silica suspension (volume ratio of kaempferol solution to silica suspension was 1:0.9), and dibutyltin dilaurate (volume ratio of dibutyltin dilaurate to kaempferol solution was 0.15:200) was added dropwise at a rate of 0.05 mol / drop. The mixture was reacted at 75 °C for 11 h in a round-bottom three-necked flask, washed with anhydrous ethanol, and dried at 80 °C for 12 h to obtain kaempferol-supported silica.

[0026] Example 2 A fluorinated rubber polymer material for waterproof membranes comprises the following components in parts by weight: 100 parts EPDM rubber, 20 parts carbon black, 15 parts paraffin oil, 12 parts silica-loaded kaempferol, 6 parts hydrotalcite, 6 parts fluoride, 1 part stearic acid, 3 parts zinc oxide, and 3 parts vulcanizing agent DCP. The fluorides are calcium fluoride and magnesium fluoride in a mass ratio of 1:1; The method for preparing kaempferol-supported silica includes the following steps: Add water to silica to obtain silica suspension (mass-volume ratio of 1g:20mL); dissolve kaempferol in dimethyl sulfoxide to obtain kaempferol solution (mass-volume ratio of kaempferol to dimethyl sulfoxide of 12g:200mL). At a rotation speed of 300 rpm, kaempferol solution was added to silica suspension (volume ratio of kaempferol solution to silica suspension was 1:1), and dibutyltin dilaurate (volume ratio of dibutyltin dilaurate to kaempferol solution was 0.25:200) was added dropwise at a rate of 0.05 mol / drop. The mixture was reacted at 85 °C for 9 h in a round-bottom three-necked flask, washed with anhydrous ethanol, and dried at 80 °C for 12 h to obtain kaempferol-supported silica.

[0027] Example 3 A fluorinated rubber polymer material for waterproof membranes comprises the following components in parts by weight: 100 parts EPDM rubber, 25 parts carbon black, 20 parts naphthenic oil, 14 parts silica-supported kaempferol, 7 parts hydrotalcite, 7 parts fluoride, 1.5 parts lubricant, 4.5 parts zinc oxide, and 3.5 parts vulcanizing agent DCP; The fluorides are calcium fluoride and magnesium fluoride in a mass ratio of 1:1; The method for preparing kaempferol-supported silica includes the following steps: Add water to silica to obtain silica suspension (mass-volume ratio of 1g:20mL); dissolve kaempferol in dimethyl sulfoxide to obtain kaempferol solution (mass-volume ratio of kaempferol to dimethyl sulfoxide of 14g:200mL). At a rotation speed of 250 rpm, kaempferol solution was added to silica suspension (volume ratio of kaempferol solution to silica suspension was 1:1), and dibutyltin dilaurate (volume ratio of dibutyltin dilaurate to kaempferol solution was 0.2:200) was added dropwise at a rate of 0.05 mol / drop. The mixture was reacted at 70 °C for 10 h in a round-bottom three-necked flask, washed with anhydrous ethanol, and dried at 80 °C for 12 h to obtain kaempferol-supported silica.

[0028] Example 4 A fluorinated rubber polymer material for waterproof membranes comprises the following components in parts by weight: 100 parts EPDM rubber, 25 parts carbon black, 20 parts naphthenic oil, 14 parts silica-supported kaempferol, 7 parts hydrotalcite, 7 parts fluoride, 1.5 parts lubricant, 4.5 parts zinc oxide, and 3.5 parts vulcanizing agent DCP; The fluoride is calcium fluoride, magnesium fluoride and sodium fluorosilicate in a mass ratio of 1:1:0.8; The method for preparing kaempferol-supported silica includes the following steps: Add water to silica to obtain silica suspension (mass-volume ratio of 1g:20mL); dissolve kaempferol in dimethyl sulfoxide to obtain kaempferol solution (mass-volume ratio of kaempferol to dimethyl sulfoxide of 14g:200mL). At a rotation speed of 250 rpm, kaempferol solution was added to silica suspension (volume ratio of kaempferol solution to silica suspension was 1:1), and dibutyltin dilaurate (volume ratio of dibutyltin dilaurate to kaempferol solution was 0.2:200) was added dropwise at a rate of 0.05 mol / drop. The mixture was reacted at 70 °C for 10 h in a round-bottom three-necked flask, washed with anhydrous ethanol, and dried at 80 °C for 12 h to obtain kaempferol-supported silica.

[0029] Example 5 A fluorinated rubber polymer material for waterproof membranes comprises the following components in parts by weight: 100 parts EPDM rubber, 25 parts carbon black, 20 parts naphthenic oil, 14 parts silica-supported kaempferol, 7 parts hydrotalcite, 7 parts fluoride, 1.5 parts lubricant, 4.5 parts zinc oxide, and 3.5 parts vulcanizing agent DCP; The fluoride is calcium fluoride, magnesium fluoride and sodium fluoroaluminate in a mass ratio of 1:1:0.8; The method for preparing kaempferol-supported silica includes the following steps: Add water to silica to obtain silica suspension (mass-volume ratio of 1g:20mL); dissolve kaempferol in dimethyl sulfoxide to obtain kaempferol solution (mass-volume ratio of kaempferol to dimethyl sulfoxide of 14g:200mL). At a rotation speed of 250 rpm, kaempferol solution was added to silica suspension (volume ratio of kaempferol solution to silica suspension was 1:1), and dibutyltin dilaurate (volume ratio of dibutyltin dilaurate to kaempferol solution was 0.2:200) was added dropwise at a rate of 0.05 mol / drop. The mixture was reacted at 70 °C for 10 h in a round-bottom three-necked flask, washed with anhydrous ethanol, and dried at 80 °C for 12 h to obtain kaempferol-supported silica.

[0030] Example 6 A fluorinated rubber polymer material for waterproof membranes comprises the following components in parts by weight: 100 parts EPDM rubber, 25 parts carbon black, 20 parts naphthenic oil, 14 parts silica-supported kaempferol, 7 parts hydrotalcite, 7 parts fluoride, 1.5 parts lubricant, 4.5 parts zinc oxide, and 3.5 parts vulcanizing agent DCP; The fluoride is calcium fluoride and sodium fluoroaluminate in a mass ratio of 1:0.8; The method for preparing kaempferol-supported silica includes the following steps: Add water to silica to obtain silica suspension (mass-volume ratio of 1g:20mL); dissolve kaempferol in dimethyl sulfoxide to obtain kaempferol solution (mass-volume ratio of kaempferol to dimethyl sulfoxide of 14g:200mL). At a rotation speed of 250 rpm, kaempferol solution was added to silica suspension (volume ratio of kaempferol solution to silica suspension was 1:1), and dibutyltin dilaurate (volume ratio of dibutyltin dilaurate to kaempferol solution was 0.2:200) was added dropwise at a rate of 0.05 mol / drop. The mixture was reacted at 70 °C for 10 h in a round-bottom three-necked flask, washed with anhydrous ethanol, and dried at 80 °C for 12 h to obtain kaempferol-supported silica.

[0031] Example 7 A fluorinated rubber polymer material for waterproof membranes comprises the following components in parts by weight: 100 parts EPDM rubber, 25 parts carbon black, 20 parts naphthenic oil, 14 parts silica-supported kaempferol, 7 parts hydrotalcite, 7 parts fluoride, 1.5 parts lubricant, 4.5 parts zinc oxide, and 3.5 parts vulcanizing agent DCP; The fluoride is magnesium fluoride and sodium fluoroaluminate in a mass ratio of 1:0.8; The method for preparing kaempferol-supported silica includes the following steps: Add water to silica to obtain silica suspension (mass-volume ratio of 1g:20mL); dissolve kaempferol in dimethyl sulfoxide to obtain kaempferol solution (mass-volume ratio of kaempferol to dimethyl sulfoxide of 14g:200mL). At a rotation speed of 250 rpm, kaempferol solution was added to silica suspension (volume ratio of kaempferol solution to silica suspension was 1:1), and dibutyltin dilaurate (volume ratio of dibutyltin dilaurate to kaempferol solution was 0.2:200) was added dropwise at a rate of 0.05 mol / drop. The mixture was reacted at 70 °C for 10 h in a round-bottom three-necked flask, washed with anhydrous ethanol, and dried at 80 °C for 12 h to obtain kaempferol-supported silica.

[0032] Example 8 A fluorinated rubber polymer material for waterproof membranes comprises the following components in parts by weight: 100 parts EPDM rubber, 25 parts carbon black, 20 parts naphthenic oil, 14 parts silica-supported kaempferol, 7 parts hydrotalcite, 7 parts fluoride, 1.5 parts lubricant, 4.5 parts zinc oxide, and 3.5 parts vulcanizing agent DCP; The fluoride is composed of calcium fluoride, magnesium fluoride, and sodium fluoroaluminate in a mass ratio of 1:1:1. The method for preparing kaempferol-supported silica includes the following steps: Add water to silica to obtain silica suspension (mass-volume ratio of 1g:20mL); dissolve kaempferol in dimethyl sulfoxide to obtain kaempferol solution (mass-volume ratio of kaempferol to dimethyl sulfoxide of 14g:200mL). At a rotation speed of 250 rpm, kaempferol solution was added to silica suspension (volume ratio of kaempferol solution to silica suspension was 1:1), and dibutyltin dilaurate (volume ratio of dibutyltin dilaurate to kaempferol solution was 0.2:200) was added dropwise at a rate of 0.05 mol / drop. The mixture was reacted at 70 °C for 10 h in a round-bottom three-necked flask, washed with anhydrous ethanol, and dried at 80 °C for 12 h to obtain kaempferol-supported silica.

[0033] Example 9 A fluorinated rubber polymer material for waterproof membranes comprises the following components in parts by weight: 100 parts EPDM rubber, 25 parts carbon black, 20 parts naphthenic oil, 14 parts silica-supported kaempferol, 7 parts hydrotalcite, 7 parts fluoride, 1.5 parts lubricant, 4.5 parts zinc oxide, and 3.5 parts vulcanizing agent DCP; The fluoride is calcium fluoride, magnesium fluoride and sodium fluoroaluminate in a mass ratio of 1:1:1.2; The method for preparing kaempferol-supported silica includes the following steps: Add water to silica to obtain silica suspension (mass-volume ratio of 1g:20mL); dissolve kaempferol in dimethyl sulfoxide to obtain kaempferol solution (mass-volume ratio of kaempferol to dimethyl sulfoxide of 14g:200mL). At a rotation speed of 250 rpm, kaempferol solution was added to silica suspension (volume ratio of kaempferol solution to silica suspension was 1:1), and dibutyltin dilaurate (volume ratio of dibutyltin dilaurate to kaempferol solution was 0.2:200) was added dropwise at a rate of 0.05 mol / drop. The mixture was reacted at 70 °C for 10 h in a round-bottom three-necked flask, washed with anhydrous ethanol, and dried at 80 °C for 12 h to obtain kaempferol-supported silica.

[0034] Comparative Example 1 A fluorinated rubber polymer material for waterproof membranes comprises the following components in parts by weight: 100 parts EPDM rubber, 25 parts carbon black, 20 parts naphthenic oil, 14 parts silica, 7 parts hydrotalcite, 7 parts fluoride, 1.5 parts lubricant, 4.5 parts zinc oxide, and 3.5 parts vulcanizing agent DCP. The fluoride is calcium fluoride and magnesium fluoride in a mass ratio of 1:1.

[0035] Comparative Example 2 A fluorinated rubber polymer material for waterproof membranes comprises the following components in parts by weight: 100 parts EPDM rubber, 25 parts carbon black, 20 parts naphthenic oil, 0.8 parts kaempferol, 13.2 parts silica, 7 parts hydrotalcite, 7 parts fluoride, 1.5 parts lubricant, 4.5 parts zinc oxide, and 3.5 parts vulcanizing agent DCP; The fluoride is calcium fluoride and magnesium fluoride in a mass ratio of 1:1.

[0036] Experimental Example 1 The waterproof membrane is prepared according to the components of the fluorinated polymer materials in the various embodiments and comparative examples, including the following steps: Mix all components except for the vulcanizing agent DCP, remove excess adhesive to obtain a rubber compound; add the vulcanizing agent DCP to the rubber compound and mix, then extrude and vulcanize to obtain a waterproof membrane.

[0037] The waterproof membranes prepared in Examples 1-3 and Comparative Examples 1-2 were tested for aging resistance according to the methods specified in GB / T 18173.1-2012 "Polymer Waterproofing Materials Part 1: Sheets". The samples were homogeneous sheets with a thickness of 1.5 mm, a width of 1.0 m, and a length of 20 m. The test results are shown in Table 1. Table 1. Test results of waterproof membranes prepared in Examples 1-3 and Comparative Examples 1-2

[0038] Compared with Comparative Examples 1-2, the waterproof membrane made from the fluorinated rubber polymer materials obtained in Examples 1-3 showed significantly better aging resistance than that made from Comparative Examples 1-2. This indicates that loading kaempferol onto silica can improve the aging resistance of the rubber polymer materials and further enhance the aging resistance of the waterproof membrane.

[0039] Experimental Example 2 The waterproof membranes prepared in Examples 3-9 were tested for aging resistance according to the methods specified in GB / T 18173.1-2012 "Polymer Waterproofing Materials Part 1: Sheets". The samples were homogeneous sheets with a thickness of 1.5 mm, a width of 1.0 m, and a length of 20 m. The test results are shown in Table 2. Table 2 Test results of waterproof membranes prepared in Examples 3-9

[0040] Compared with Examples 3-9, the corrosion resistance of the waterproof membrane made from the fluorinated rubber polymer material obtained in Example 5 is significantly better than that of Examples 3-4, 6-7, and 9. This indicates that the corrosion resistance of the rubber polymer material is improved when calcium fluoride, magnesium fluoride, and sodium fluoroaluminate are used together. The corrosion resistance of the waterproof membrane made from the fluorinated rubber polymer material obtained in Example 8 is significantly higher than that of the other examples. This indicates that when the mass ratio of calcium fluoride, magnesium fluoride, and sodium fluoroaluminate is 1:1:1, the corrosion and aging resistance of the waterproof membrane is further improved.

[0041] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A fluorinated rubber polymer material for waterproof membranes, characterized in that, The product comprises the following components in parts by weight: 100 parts EPDM rubber, 20-30 parts carbon black, 15-25 parts softener, 12-16 parts silica-supported kaempferol, 6-8 parts hydrotalcite, 6-8 parts fluoride, 1-2 parts lubricant, 3-6 parts zinc oxide, and 3-4 parts vulcanizing agent.

2. The fluorinated rubber polymer material for waterproof membranes according to claim 1, characterized in that, The method for preparing kaempferol-supported silica includes the following steps: Add water to silica to obtain a silica suspension; dissolve kaempferol in dimethyl sulfoxide to obtain a kaempferol solution; The kaempferol solution was added to the silica suspension under stirring, a catalyst was added, and the mixture was reacted, washed, and dried to obtain silica-supported kaempferol.

3. The fluorinated rubber polymer material for waterproof membranes according to claim 2, characterized in that, The mass-to-volume ratio of the silica to water is 1g:18~20mL; The mass-to-volume ratio of kaempferol to dimethyl sulfoxide is 12-15 g: 200 mL.

4. The fluorinated rubber polymer material for waterproof membranes according to claim 2, characterized in that, The stirring speed is 200~300 rpm; The volume ratio of the kaempferol solution to the silica suspension is 1:0.9~1.

5. The fluorinated rubber polymer material for waterproof membranes according to claim 2, characterized in that, The catalyst is dibutyltin dilaurate; The volume ratio of the catalyst to the kaempferol solution is 0.15~0.25:200; The reaction is carried out at a temperature of 75-85°C for 9-11 hours.

6. The fluorinated rubber polymer material for waterproof membranes according to claim 1, characterized in that, The softener includes one or both of naphthenic oil and paraffin oil.

7. The fluorinated rubber polymer material for waterproof membranes according to claim 1, characterized in that, The fluoride includes one or more of calcium fluoride, magnesium fluoride, sodium fluorosilicate, and sodium fluoroaluminate.

8. The fluorinated rubber polymer material for waterproof membranes according to claim 7, characterized in that, When the fluoride is calcium fluoride, magnesium fluoride, and sodium fluoroaluminate, the mass ratio of calcium fluoride, magnesium fluoride, and sodium fluoroaluminate is 1:1:0.8~1.

2.

9. The fluorinated rubber polymer material for waterproof membranes according to claim 1, characterized in that, The lubricant includes stearic acid.

10. The fluorinated rubber polymer material for waterproof membranes according to claim 1, characterized in that, The vulcanizing agent includes vulcanizing agent DCP.

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