CN121086378A - A weather-resistant waterproof membrane for metal protection and its manufacturing process - Google Patents
A weather-resistant waterproof membrane for metal protection and its manufacturing processInfo
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- CN121086378A CN121086378A CN202511449071.4A CN202511449071A CN121086378A CN 121086378 A CN121086378 A CN 121086378A CN 202511449071 A CN202511449071 A CN 202511449071A CN 121086378 A CN121086378 A CN 121086378A
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Abstract
本发明涉及高分子防水领域，具体涉及一种用于金属防护的耐候型防水卷材及其制备工艺。一种用于金属防护的耐候型防水卷材的制备工艺，包括：制备阻燃添加剂；制备改性二硫化钼纳米片；制备抗紫外添加剂；制备防水卷材。本发明通过先向四氯化钛溶液中加入氢氧化钠溶液，生成氢氧化钛前驱体，再加入埃洛石纳米管分散液，加热搅拌进行反应，制成纳米复合材料，然后将脱碱木质素制成纳米片状结构，再与纳米复合材料在水热条件下紧密结合，形成稳定的抗紫外添加剂，将其与聚乙烯等原料熔融混炼制成防水卷材后，能够形成连续的紫外防护网络，减少迁移，显著提升防水卷材的抗紫外线老化性能。
This invention relates to the field of polymer waterproofing, specifically to a weather-resistant waterproof membrane for metal protection and its preparation process. The preparation process of a weather-resistant waterproof membrane for metal protection includes: preparing a flame-retardant additive; preparing modified molybdenum disulfide nanosheets; preparing an anti-UV additive; and preparing the waterproof membrane. This invention first adds sodium hydroxide solution to titanium tetrachloride solution to generate a titanium hydroxide precursor, then adds halloysite nanotube dispersion, heats and stirs to react, and prepares a nanocomposite material. Then, dealkalized lignin is made into a nanosheet structure, which is then tightly bonded with the nanocomposite material under hydrothermal conditions to form a stable anti-UV additive. After being melt-blended with raw materials such as polyethylene to form a waterproof membrane, a continuous UV protection network is formed, reducing migration and significantly improving the waterproof membrane's resistance to UV aging.
Description
Technical Field
The invention relates to the field of macromolecule water prevention, in particular to a weather-proof waterproof coiled material for metal protection and a preparation process thereof.
Background
In industrial buildings, storage facilities and large public buildings, metal roofs and structures are widely applied due to the advantages of convenience in construction, high strength and the like, however, metal base materials are exposed to outdoor environments for a long time and are easy to corrode due to rain erosion, joints and joints of the metal base materials are waterproof weak links, and therefore high-performance waterproof coiled materials become key materials in metal protection systems.
At present, the waterproof coiled materials commonly used for metal protection mainly comprise asphalt-based coiled materials, polyvinyl chloride (PVC) coiled materials and common Polyethylene (PE) coiled materials. The common polyethylene coiled material has good chemical stability, low temperature resistance and processability, is gradually increased in the waterproof field, but has weak ultraviolet aging resistance, is easy to degrade by photo-oxygen after long-term outdoor use, and is low in mechanical property and waterproof and airtight property, meanwhile, the polyethylene coiled material is inflammable, has low limiting oxygen index, and when the traditional flame retardant (such as halogen system and inorganic hydroxide) is added, the problems of uneven dispersion and poor compatibility with a base material are easy to occur, so that the mechanical elasticity and waterproof performance of the coiled material are influenced, and the flame retardant requirement of a metal component in a specific scene is difficult to meet.
Therefore, it is necessary to provide a weather-resistant waterproof roll for metal protection with anti-ultraviolet aging and flame retardant properties and a preparation process thereof, so as to prolong the service life of the waterproof roll.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a weather-resistant waterproof coiled material for metal protection and a preparation process thereof.
The invention provides a preparation process of a weather-proof waterproof coiled material for metal protection, which comprises the following steps:
S1, preparing a flame retardant additive
S1.1, adding 2, 4-diamino-6-phenyl-1, 3,5 triazine and vanillin into absolute ethanol according to 1g (1.6-1.7 g) (25-35) mL, and heating and stirring for reaction for 5-6h at 65-75 ℃ to obtain an intermediate solution;
S1.2, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into the intermediate solution, heating and stirring at 75-85 ℃ for reaction for 20-24 hours, naturally cooling to room temperature, filtering, respectively washing for 2-3 times by 70-80 ℃ hot water and toluene, and vacuum drying to obtain a flame retardant additive;
s2, preparing modified molybdenum disulfide nanosheets
Preparing molybdenum disulfide nanosheet suspension liquid from massive molybdenum disulfide, preparing (4-carboxybutyl) triphenylphosphine bromide aqueous solution, then mixing the molybdenum disulfide nanosheet suspension liquid with the (4-carboxybutyl) triphenylphosphine bromide aqueous solution, stirring, centrifuging, washing and drying to obtain modified molybdenum disulfide nanosheets;
s3, preparing an anti-ultraviolet additive
Adding a sodium hydroxide solution into a titanium tetrachloride solution, stirring and mixing, adding halloysite nanotube dispersion liquid, preparing a nanocomposite, dispersing in deionized water, and adding nano sheet lignin for hydrothermal reaction to obtain an ultraviolet-resistant additive;
S4, preparing the waterproof coiled material
Adding the linear high-density polyethylene, the linear low-density polyethylene, the metallocene polyethylene, the polyethylene octene co-elastomer, the anti-ultraviolet additive, the flame retardant additive, the modified molybdenum disulfide nanosheets and the antioxidant 1010 into a mixer for full mixing, then feeding into a double screw extruder for melt mixing, and then extruding, calendaring and freeze shaping to obtain the waterproof coiled material.
Further, S2 specifically includes the following steps:
S2.1, adding blocky molybdenum disulfide into N-methylpyrrolidone according to 1g (180-200) mL, carrying out ultrasonic treatment for 6-8h, centrifuging at 4000-5000rpm for 20-30min, and taking supernatant to obtain molybdenum disulfide nanosheet suspension;
S2.2, adding (4-carboxybutyl) triphenylphosphine bromide into deionized water, and fully stirring and dissolving to obtain (4-carboxybutyl) triphenylphosphine bromide aqueous solution with the concentration of 1.6-1.8 mg/mL;
S2.3, adding the molybdenum disulfide nanosheet suspension into the (4-carboxybutyl) triphenylphosphine bromide aqueous solution, stirring for 2-3h at 200-300rpm, centrifuging for 20-30min at 7000-8000rpm, discarding the supernatant, washing for 2-3 times by deionized water, and vacuum drying to obtain the modified molybdenum disulfide nanosheets.
Further, S3 specifically includes the following steps:
s3.1, dispersing halloysite nanotubes in deionized water according to 1g (45-55) mL, and carrying out ultrasonic treatment for 30-40min to obtain halloysite nanotube dispersion;
S3.2, heating a titanium tetrachloride solution with the concentration of 2mol/L to 40-50 ℃, adding a sodium hydroxide solution with the concentration of 2mol/L while stirring, continuously stirring for 20-30min, adding the halloysite nanotube dispersion liquid, stirring for 2-3h at 80-90 ℃, regulating the pH to 5 with a hydrochloric acid solution with the concentration of 1mol/L, continuously stirring for 20-30min, filtering, washing and drying to obtain a nanocomposite;
S3.3, dissolving the dealkalized lignin in deionized water according to 1g (30-40) mL, carrying out ultrasonic treatment for 2-3h, and then carrying out freeze drying and grinding to obtain nano flaky lignin;
S3.4, adding the nano composite material into deionized water according to 1g (30-40) mL, performing ultrasonic dispersion for 20-30min, adding the nano platy lignin, stirring for 30-40min, performing hydrothermal reaction for 2-3h at 125-135 ℃, and washing and drying to obtain the ultraviolet resistant additive.
Further, the mass ratio of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to 2, 4-diamino-6-phenyl-1, 3, 5-triazine is (2.2-2.3): 1.
Further, the mass ratio of the (4-carboxybutyl) triphenylphosphine bromide to the molybdenum disulfide nanosheets is (1-3): 1.
Further, the addition amount of the sodium hydroxide solution was 2 times the volume of the titanium tetrachloride solution.
Further, the halloysite nanotube dispersion was added in an amount of 4 times the volume of the titanium tetrachloride solution.
Further, the mass ratio of the nano-sheet lignin to the nano-composite material is 1 (5-6).
Further, the waterproof coiled material comprises, by mass, 30-50 parts of linear high-density polyethylene, 20-40 parts of linear low-density polyethylene, 10-20 parts of metallocene polyethylene, 5-15 parts of polyethylene octene co-elastomer, 6-8 parts of anti-ultraviolet additive, 10-15 parts of flame retardant additive, 3-5 parts of modified molybdenum disulfide nano-sheet and 0.5-1 part of antioxidant 1010.
A weather-proof waterproof roll for metal protection, which is prepared by the preparation process of the weather-proof waterproof roll for metal protection.
The invention has the following advantages:
1. According to the invention, a sodium hydroxide solution is firstly added into a titanium tetrachloride solution to generate a titanium hydroxide precursor, then a halloysite nanotube dispersion is added, heating and stirring are carried out to react to form a covalent bond, so that titanium dioxide nano particles are uniformly loaded on the surface of the halloysite nanotube, nano titanium dioxide aggregation is inhibited to prepare a nano composite material, dealkalized lignin is prepared into a nano sheet-shaped structure, then the nano sheet-shaped structure is tightly combined with the nano composite material under a hydrothermal condition to form a stable ultraviolet-resistant additive, and the stable ultraviolet-resistant additive and raw materials such as polyethylene are fused and mixed to prepare a waterproof coiled material.
2. According to the invention, 2, 4-diamino-6-phenyl-1, 3,5 triazine and vanillin are mixed for reaction to generate an intermediate containing two imine bonds, then 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added for reaction, phosphorus is introduced to form a phosphorus-nitrogen synergistic flame retardant additive, the phosphorus and polyethylene and other raw materials are melted and mixed to prepare the waterproof coiled material, and then the phosphorus in the flame retardant additive is heated and decomposed to generate phosphoric acid, polyphosphoric acid and other acidic substances to catalyze the waterproof coiled material matrix to carry out dehydration and carbonization reaction, a continuous and compact carbon layer is formed on the surface of the waterproof coiled material, so that flame heat can be effectively prevented from being transferred to the polyethylene, the continuous temperature rising decomposition of the matrix is avoided, the flame retardant property of the waterproof coiled material is improved, meanwhile, alkaline gas generated by the decomposition of triazine ring in the flame retardant can react with the acidic substances generated by the decomposition of phosphorus component to generate stable phosphorus nitrogen compounds (such as phosphoric acid ammonium salt), the volatilization loss of the phosphorus component is reduced, carbon can be further catalyzed, the flame retardant efficiency is improved, and the flame retardant can be greatly improved, and excellent flame retardant efficiency is achieved.
3. According to the invention, after the blocky molybdenum disulfide is prepared into the molybdenum disulfide nanosheets, the blocky molybdenum disulfide is added into the (4-carboxybutyl) triphenylphosphine bromide aqueous solution, the (4-carboxybutyl) triphenylphosphine bromide molecules are adsorbed on the surfaces of the molybdenum disulfide nanosheets through electrostatic interaction, after the modified molybdenum disulfide nanosheets are obtained, the compatibility of the modified molybdenum disulfide nanosheets with a polyethylene matrix is improved, after the modified molybdenum disulfide nanosheets and raw materials such as polyethylene are melt mixed and prepared into a waterproof coiled material, the layered nanosheets migrate towards the surfaces of the materials, are stacked to form a compact 'lamellar barrier', oxygen is blocked from diffusing into the matrix, meanwhile, phosphorus element in quaternary phosphine cations introduced into the surfaces of the layered nanosheets can catalyze the polyethylene matrix to carry out dehydration and crosslinking reaction at high temperature, the formation of a carbon layer is promoted, and further the flame retardant property of the waterproof coiled material is improved.
Drawings
Fig. 1 is a flowchart of a preparation process of a weather-proof waterproof roll for metal protection according to an embodiment of the present invention.
Detailed Description
In order to enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
Embodiment 1, a preparation process of a weather-proof waterproof roll for metal protection, as shown in fig. 1, comprises the following steps:
S1, preparing a flame retardant additive
S1.1, adding 2, 4-diamino-6-phenyl-1, 3,5 triazine and vanillin into absolute ethanol according to a ratio of 1g to 1.6g to 25mL, and heating and stirring at 65 ℃ for reaction for 5 hours to obtain an intermediate solution;
S1.2, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into the intermediate solution, heating and stirring for reaction for 20 hours at 75 ℃, naturally cooling to room temperature, filtering, washing for 2 times respectively by 70 ℃ hot water and toluene, and vacuum drying to obtain a flame retardant additive, wherein the mass ratio of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the 2, 4-diamino-6-phenyl-1, 3,5 triazine is 2.2:1;
s2, preparing modified molybdenum disulfide nanosheets
S2.1, adding blocky molybdenum disulfide into N-methylpyrrolidone according to a ratio of 1g to 180mL, carrying out ultrasonic treatment for 6h, centrifuging at 4000rpm for 20min, and taking supernatant to obtain molybdenum disulfide nanosheet suspension;
S2.2, adding (4-carboxybutyl) triphenylphosphine bromide into deionized water, and fully stirring and dissolving to obtain a (4-carboxybutyl) triphenylphosphine bromide aqueous solution with the concentration of 1.6 mg/mL;
S2.3, adding the molybdenum disulfide nanosheet suspension into the (4-carboxybutyl) triphenylphosphine bromide aqueous solution, stirring for 2 hours at 200rpm, centrifuging for 20 minutes at 7000rpm, discarding the supernatant, washing for 2 times by deionized water, and drying in vacuum to obtain modified molybdenum disulfide nanosheets, wherein the mass ratio of the (4-carboxybutyl) triphenylphosphine bromide to the molybdenum disulfide nanosheets is 1:1;
s3, preparing an anti-ultraviolet additive
S3.1, dispersing halloysite nanotubes in deionized water according to a ratio of 1g to 45mL, and carrying out ultrasonic treatment for 30min to obtain halloysite nanotube dispersion;
s3.2, heating a titanium tetrachloride solution with the concentration of 2mol/L to 40 ℃, adding 2mol/L sodium hydroxide solution while stirring, continuously stirring for 20min, adding the halloysite nanotube dispersion liquid, stirring for 2h at 80 ℃, then adjusting the pH to 5 by using 1mol/L hydrochloric acid solution, continuously stirring for 20min, filtering, washing and drying to obtain a nanocomposite, wherein the adding amount of the sodium hydroxide solution is 2 times of the volume of the titanium tetrachloride solution, and the adding amount of the halloysite nanotube dispersion liquid is 4 times of the volume of the titanium tetrachloride solution;
s3.3, dissolving the dealkalized lignin in deionized water according to a ratio of 1g to 30mL, performing ultrasonic treatment for 2 hours, and performing freeze drying and grinding to obtain nano sheet lignin;
S3.4, adding the nano composite material into deionized water according to a mass ratio of 1g to 30mL, performing ultrasonic dispersion for 20min, adding the nano sheet lignin, stirring for 30min, performing hydrothermal reaction at 125 ℃ for 2h, and washing and drying to obtain an ultraviolet-resistant additive, wherein the mass ratio of the nano sheet lignin to the nano composite material is 1:5;
S4, preparing the waterproof coiled material
Adding 30 parts by mass of linear high-density polyethylene, 20 parts by mass of linear low-density polyethylene, 10 parts by mass of metallocene polyethylene, 5 parts by mass of polyethylene octene co-elastomer, 6 parts by mass of the anti-ultraviolet additive, 10 parts by mass of the flame retardant additive, 3 parts by mass of the modified molybdenum disulfide nanosheets and 0.5 part by mass of the antioxidant 1010 into a mixer for full mixing, then feeding into a double screw extruder for melt mixing, and extruding, calendaring and freeze shaping to obtain the waterproof coiled material.
Embodiment 2, a process for preparing a weather-proof waterproof roll for metal protection, as shown in fig. 1, comprises the following steps:
S1, preparing a flame retardant additive
S1.1, adding 2, 4-diamino-6-phenyl-1, 3,5 triazine and vanillin into absolute ethanol according to a ratio of 1g to 1.65g to 30mL, and heating and stirring at 70 ℃ for reaction for 5.5h to obtain an intermediate solution;
s1.2, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into the intermediate solution, heating and stirring for reaction for 22h at 80 ℃, naturally cooling to room temperature, filtering, washing for 2 times respectively by 75 ℃ hot water and toluene, and vacuum drying to obtain a flame retardant additive, wherein the mass ratio of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the 2, 4-diamino-6-phenyl-1, 3,5 triazine is 2.25:1;
s2, preparing modified molybdenum disulfide nanosheets
S2.1, adding blocky molybdenum disulfide into N-methylpyrrolidone according to a ratio of 1g to 190mL, carrying out ultrasonic treatment for 7h, centrifuging at 4500rpm for 25min, and taking supernatant to obtain molybdenum disulfide nanosheet suspension;
s2.2, adding (4-carboxybutyl) triphenylphosphine bromide into deionized water, and fully stirring and dissolving to obtain a (4-carboxybutyl) triphenylphosphine bromide aqueous solution with the concentration of 1.7 mg/mL;
S2.3, adding the molybdenum disulfide nanosheet suspension into the (4-carboxybutyl) triphenylphosphine bromide aqueous solution, stirring for 2.5h at 250rpm, centrifuging for 25min at 7500rpm, discarding the supernatant, washing for 2 times by deionized water, and vacuum drying to obtain modified molybdenum disulfide nanosheets, wherein the mass ratio of the (4-carboxybutyl) triphenylphosphine bromide to the molybdenum disulfide nanosheets is 2:1;
s3, preparing an anti-ultraviolet additive
S3.1, dispersing halloysite nanotubes in deionized water according to a ratio of 1g to 50mL, and carrying out ultrasonic treatment for 35min to obtain halloysite nanotube dispersion;
S3.2, heating a titanium tetrachloride solution with the concentration of 2mol/L to 45 ℃, adding 2mol/L sodium hydroxide solution while stirring, continuously stirring for 25min, adding the halloysite nanotube dispersion liquid, stirring for 2.5h at 85 ℃, then adjusting the pH value to 5 by using 1mol/L hydrochloric acid solution, continuously stirring for 25min, filtering, washing and drying to obtain a nanocomposite, wherein the adding amount of the sodium hydroxide solution is 2 times of the volume of the titanium tetrachloride solution, and the adding amount of the halloysite nanotube dispersion liquid is 4 times of the volume of the titanium tetrachloride solution;
s3.3, dissolving the dealkalized lignin in deionized water according to the ratio of 1g to 35mL, carrying out ultrasonic treatment for 2.5 hours, and then carrying out freeze drying and grinding to obtain nano flaky lignin;
s3.4, adding the nano composite material into deionized water according to a ratio of 1g to 35mL, performing ultrasonic dispersion for 25min, adding the nano platy lignin, stirring for 35min, performing hydrothermal reaction at 130 ℃ for 2.5h, and washing and drying to obtain an ultraviolet resistant additive, wherein the mass ratio of the nano platy lignin to the nano composite material is 1:5.5;
S4, preparing the waterproof coiled material
Adding 40 parts by mass of linear high-density polyethylene, 30 parts by mass of linear low-density polyethylene, 15 parts by mass of metallocene polyethylene, 10 parts by mass of polyethylene octene co-elastomer, 7 parts by mass of the anti-ultraviolet additive, 12.5 parts by mass of the flame retardant additive, 4 parts by mass of the modified molybdenum disulfide nano-sheet and 0.75 part by mass of the antioxidant 1010 into a mixer for fully mixing, then feeding into a double-screw extruder for melt mixing, and extruding, calendaring and freeze shaping to obtain the waterproof coiled material.
Embodiment 3, a preparation process of a weather-proof waterproof roll for metal protection, as shown in fig. 1, comprises the following steps:
S1, preparing a flame retardant additive
S1.1, adding 2, 4-diamino-6-phenyl-1, 3,5 triazine and vanillin into absolute ethanol according to a ratio of 1g to 1.7g to 35mL, and heating and stirring at 75 ℃ for reaction for 6 hours to obtain an intermediate solution;
S1.2, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into the intermediate solution, heating and stirring for reaction for 24 hours at 85 ℃, naturally cooling to room temperature, filtering, washing for 3 times respectively by 80 ℃ hot water and toluene, and vacuum drying to obtain a flame retardant additive, wherein the mass ratio of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the 2, 4-diamino-6-phenyl-1, 3,5 triazine is 2.3:1;
s2, preparing modified molybdenum disulfide nanosheets
S2.1, adding blocky molybdenum disulfide into N-methylpyrrolidone according to a ratio of 1g to 200mL, carrying out ultrasonic treatment for 8 hours, centrifuging at 5000rpm for 30 minutes, and taking supernatant to obtain molybdenum disulfide nanosheet suspension;
S2.2, adding (4-carboxybutyl) triphenylphosphine bromide into deionized water, and fully stirring and dissolving to obtain a (4-carboxybutyl) triphenylphosphine bromide aqueous solution with the concentration of 1.8 mg/mL;
S2.3, adding the molybdenum disulfide nanosheet suspension into the (4-carboxybutyl) triphenylphosphine bromide aqueous solution, stirring for 3 hours at 300rpm, centrifuging for 30 minutes at 8000rpm, discarding the supernatant, washing for 3 times by deionized water, and drying in vacuum to obtain modified molybdenum disulfide nanosheets, wherein the mass ratio of the (4-carboxybutyl) triphenylphosphine bromide to the molybdenum disulfide nanosheets is 3:1;
s3, preparing an anti-ultraviolet additive
S3.1, dispersing halloysite nanotubes in deionized water according to a ratio of 1g to 55mL, and carrying out ultrasonic treatment for 40min to obtain halloysite nanotube dispersion;
S3.2, heating a titanium tetrachloride solution with the concentration of 2mol/L to 50 ℃, adding 2mol/L sodium hydroxide solution while stirring, continuously stirring for 30min, adding the halloysite nanotube dispersion liquid, stirring for 3h at 90 ℃, then adjusting the pH to 5 by using 1mol/L hydrochloric acid solution, continuously stirring for 30min, filtering, washing and drying to obtain a nanocomposite, wherein the adding amount of the sodium hydroxide solution is 2 times of the volume of the titanium tetrachloride solution, and the adding amount of the halloysite nanotube dispersion liquid is 4 times of the volume of the titanium tetrachloride solution;
s3.3, dissolving the dealkalized lignin in deionized water according to the ratio of 1g to 40mL, carrying out ultrasonic treatment for 3 hours, and then carrying out freeze drying and grinding to obtain nano sheet lignin;
S3.4, adding the nano composite material into deionized water according to a mass ratio of 1g to 40mL, performing ultrasonic dispersion for 30min, adding the nano sheet lignin, stirring for 40min, performing hydrothermal reaction at 135 ℃ for 3h, and washing and drying to obtain an ultraviolet resistant additive, wherein the mass ratio of the nano sheet lignin to the nano composite material is 1:6;
S4, preparing the waterproof coiled material
50 Parts by mass of linear high-density polyethylene, 40 parts by mass of linear low-density polyethylene, 20 parts by mass of metallocene polyethylene, 15 parts by mass of polyethylene octene co-elastomer, 8 parts by mass of the anti-ultraviolet additive, 15 parts by mass of the flame retardant additive, 5 parts by mass of the modified molybdenum disulfide nanosheets and 1 part by mass of the antioxidant 1010 are added into a mixer to be fully mixed, and then the mixture is sent into a double screw extruder to be melted and mixed, and then extruded, calendered and frozen to be shaped to obtain the waterproof coiled material.
Comparative example 1 this comparative example 1 differs from example 1 in that the uv-resistant additive in step S4 was removed.
Comparative example 2 this comparative example 2 differs from example 1 in that the uv-resistant additive in step S4 was replaced by an equivalent amount of nanocomposite.
Comparative example 3 this comparative example 3 differs from example 1 in that the flame retardant additive in step S4 was removed.
Comparative example 4 this comparative example 4 differs from example 1 in that the flame retardant additive in step S4 was replaced with an equivalent amount of aluminium hydroxide.
Comparative example 5 this comparative example 5 differs from example 1 in that the modified molybdenum disulfide nanosheets in step S4 were replaced with equivalent amounts of molybdenum disulfide nanosheets.
Comparative example 6 this comparative example 6 differs from example 1 in that the modified molybdenum disulfide nanoplatelets in step S4 were replaced with an equivalent amount of flame retardant additive.
Comparative example 7 this comparative example 7 differs from example 1 in that the flame retardant additive in step S4 was replaced with an equivalent amount of modified molybdenum disulfide nanoplatelets.
Test example:
Test 1. The waterproof rolls prepared in examples 1 to 3 and comparative examples 1 to 2 were tested for their ultraviolet aging resistance, respectively, and were tested three times in parallel, and the average value was taken, and the results are shown in Table 1.
TABLE 1 ultraviolet aging resistance test results of waterproof coiled materials
From table 1 above, it can be seen that when the anti-ultraviolet additive is not added in comparative example 1, the tensile retention and elongation retention of the obtained waterproof coiled material after ultraviolet aging for 200 hours are far lower than those of example 1, and when the anti-ultraviolet additive is replaced by an equivalent nanocomposite in comparative example 2, the tensile retention and elongation retention of the obtained waterproof coiled material after ultraviolet aging for 200 hours are both higher than those of comparative example 1, but lower than those of example 1, therefore, by adding sodium hydroxide solution into titanium tetrachloride solution to generate titanium hydroxide precursor, adding halloysite nanotube dispersion, heating and stirring to react, a nanocomposite is prepared, dealkalized lignin is prepared into a nano sheet structure, and then the nano sheet structure is tightly combined with raw materials such as polyethylene under hydrothermal condition, so that after the nano sheet lignin is melt-mixed with the raw materials such as polyethylene to prepare the waterproof coiled material, the dispersion of the nano sheet lignin in a polyethylene matrix can be further improved, the uniform distribution of the anti-ultraviolet additive is ensured, a continuous ultraviolet protection network is formed, the waterproof coiled material can be remarkably improved, and the waterproof aging performance is remarkably improved.
Test 2 limiting oxygen indexes of the waterproof rolls prepared in examples 1 to 3 and comparative examples 3 to 7 were measured in parallel three times using an oxygen index measuring instrument, and the average value was taken, and the results are shown in Table 2.
TABLE 2 limiting oxygen index test results of waterproof rolls
From the above table 2, it can be seen that when the flame retardant additive is not added in the comparative example 3, the limiting oxygen index of the obtained waterproof coiled material is significantly lower than that of the example 1, and thus, by mixing 2, 4-diamino-6-phenyl-1, 3,5 triazine with vanillin to react to generate an intermediate containing two imine bonds, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to react, introducing phosphorus element, forming a phosphorus-nitrogen synergistic flame retardant additive, and melting and mixing the phosphorus-nitrogen synergistic flame retardant additive with raw materials such as polyethylene to prepare the waterproof coiled material, the flame retardant performance of the waterproof coiled material can be effectively improved, and when the flame retardant additive is replaced by an equivalent amount of a common inorganic hydroxide flame retardant (aluminum hydroxide) in the comparative example 4, the limiting oxygen index of the obtained waterproof coiled material is also lower than that of the example 1, and thus, the flame retardant additive has a higher flame retardant efficiency per unit mass compared with aluminum hydroxide, and can achieve an excellent flame retardant effect without high addition amount.
In addition, in comparative example 5, after molybdenum disulfide nanosheets are not modified, the limiting oxygen index of the prepared waterproof coiled material is lower than that of example 1, so that after the molybdenum disulfide nanosheets are prepared from massive molybdenum disulfide, the waterproof coiled material is added into (4-carboxybutyl) triphenylphosphine bromide aqueous solution, and (4-carboxybutyl) triphenylphosphine bromide molecules are adsorbed on the surfaces of the molybdenum disulfide nanosheets through electrostatic interaction, so that after the modified molybdenum disulfide nanosheets are obtained, the compatibility of the modified molybdenum disulfide nanosheets with a polyethylene matrix is improved, and after the modified molybdenum disulfide nanosheets and raw materials such as polyethylene are fused and mixed to prepare the waterproof coiled material, the flame retardant property of the waterproof coiled material can be improved;
when only one of the flame retardant additive or the modified molybdenum disulfide nanosheets is added in comparative examples 6 and 7, the limiting oxygen index of the prepared waterproof coiled material is lower than that of example 1, and therefore, the modified molybdenum disulfide and the flame retardant additive can synergistically improve the flame retardant property of the waterproof coiled material.
It will be understood that modifications and variations will be apparent to those skilled in the art from the foregoing description, and it is intended that all such modifications and variations be included within the scope of the following claims. Parts of the specification not described in detail belong to the prior art known to those skilled in the art.
Claims (10)
1. The preparation process of the weather-proof waterproof coiled material for metal protection is characterized by comprising the following steps of:
S1, preparing a flame retardant additive
S1.1, adding 2, 4-diamino-6-phenyl-1, 3,5 triazine and vanillin into absolute ethanol according to 1g (1.6-1.7 g) (25-35) mL, and heating and stirring for reaction for 5-6h at 65-75 ℃ to obtain an intermediate solution;
S1.2, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into the intermediate solution, heating and stirring at 75-85 ℃ for reaction for 20-24 hours, naturally cooling to room temperature, filtering, respectively washing for 2-3 times by 70-80 ℃ hot water and toluene, and vacuum drying to obtain a flame retardant additive;
s2, preparing modified molybdenum disulfide nanosheets
Preparing molybdenum disulfide nanosheet suspension liquid from massive molybdenum disulfide, preparing (4-carboxybutyl) triphenylphosphine bromide aqueous solution, then mixing the molybdenum disulfide nanosheet suspension liquid with the (4-carboxybutyl) triphenylphosphine bromide aqueous solution, stirring, centrifuging, washing and drying to obtain modified molybdenum disulfide nanosheets;
s3, preparing an anti-ultraviolet additive
Adding a sodium hydroxide solution into a titanium tetrachloride solution, stirring and mixing, adding halloysite nanotube dispersion liquid, preparing a nanocomposite, dispersing in deionized water, and adding nano sheet lignin for hydrothermal reaction to obtain an ultraviolet-resistant additive;
S4, preparing the waterproof coiled material
Adding the linear high-density polyethylene, the linear low-density polyethylene, the metallocene polyethylene, the polyethylene octene co-elastomer, the anti-ultraviolet additive, the flame retardant additive, the modified molybdenum disulfide nanosheets and the antioxidant 1010 into a mixer for full mixing, then feeding into a double screw extruder for melt mixing, and then extruding, calendaring and freeze shaping to obtain the waterproof coiled material.
2. The preparation process of the weather-resistant waterproof coiled material for metal protection as claimed in claim 1, wherein the step S2 specifically comprises the following steps:
S2.1, adding blocky molybdenum disulfide into N-methylpyrrolidone according to 1g (180-200) mL, carrying out ultrasonic treatment for 6-8h, centrifuging at 4000-5000rpm for 20-30min, and taking supernatant to obtain molybdenum disulfide nanosheet suspension;
S2.2, adding (4-carboxybutyl) triphenylphosphine bromide into deionized water, and fully stirring and dissolving to obtain (4-carboxybutyl) triphenylphosphine bromide aqueous solution with the concentration of 1.6-1.8 mg/mL;
S2.3, adding the molybdenum disulfide nanosheet suspension into the (4-carboxybutyl) triphenylphosphine bromide aqueous solution, stirring for 2-3h at 200-300rpm, centrifuging for 20-30min at 7000-8000rpm, discarding the supernatant, washing for 2-3 times by deionized water, and vacuum drying to obtain the modified molybdenum disulfide nanosheets.
3. The preparation process of the weather-resistant waterproof coiled material for metal protection according to claim 2, wherein the step S3 specifically comprises the following steps:
s3.1, dispersing halloysite nanotubes in deionized water according to 1g (45-55) mL, and carrying out ultrasonic treatment for 30-40min to obtain halloysite nanotube dispersion;
S3.2, heating a titanium tetrachloride solution with the concentration of 2mol/L to 40-50 ℃, adding a sodium hydroxide solution with the concentration of 2mol/L while stirring, continuously stirring for 20-30min, adding the halloysite nanotube dispersion liquid, stirring for 2-3h at 80-90 ℃, regulating the pH to 5 with a hydrochloric acid solution with the concentration of 1mol/L, continuously stirring for 20-30min, filtering, washing and drying to obtain a nanocomposite;
S3.3, dissolving the dealkalized lignin in deionized water according to 1g (30-40) mL, carrying out ultrasonic treatment for 2-3h, and then carrying out freeze drying and grinding to obtain nano flaky lignin;
S3.4, adding the nano composite material into deionized water according to 1g (30-40) mL, performing ultrasonic dispersion for 20-30min, adding the nano platy lignin, stirring for 30-40min, performing hydrothermal reaction for 2-3h at 125-135 ℃, and washing and drying to obtain the ultraviolet resistant additive.
4. The process for preparing a weather-resistant waterproof roll for metal protection according to claim 1, wherein the mass ratio of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to 2, 4-diamino-6-phenyl-1, 3, 5-triazine is (2.2-2.3): 1.
5. The preparation process of the weather-resistant waterproof coiled material for metal protection according to claim 2, wherein the mass ratio of the (4-carboxybutyl) triphenylphosphine bromide to the molybdenum disulfide nanosheets is (1-3): 1.
6. The process for producing a weather-resistant waterproof roll for metal protection according to claim 3, wherein the addition amount of the sodium hydroxide solution is 2 times the volume of the titanium tetrachloride solution.
7. The process for producing a weather-resistant waterproof roll for metal protection according to claim 3, wherein the halloysite nanotube dispersion is added in an amount of 4 times the volume of the titanium tetrachloride solution.
8. The process for preparing the weather-resistant waterproof coiled material for metal protection according to claim 3, wherein the mass ratio of the nano sheet lignin to the nano composite material is 1 (5-6).
9. The preparation process of the weather-resistant waterproof coiled material for metal protection according to claim 1 is characterized in that the waterproof coiled material comprises, by mass, 30-50 parts of linear high-density polyethylene, 20-40 parts of linear low-density polyethylene, 10-20 parts of metallocene polyethylene, 5-15 parts of polyethylene octene co-elastomer, 6-8 parts of anti-ultraviolet additive, 10-15 parts of flame retardant additive, 3-5 parts of modified molybdenum disulfide nano-sheets and 0.5-1 part of antioxidant 1010.
10. A weather-resistant waterproof roll for metal protection, characterized in that the waterproof roll is prepared by the preparation process of the weather-resistant waterproof roll for metal protection according to any one of claims 1 to 9.
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