A weather-resistant waterproof membrane based on modified polyolefin and its manufacturing process

Abstract

The present invention discloses a weather-resistant waterproof roll material based on modified polyolefin and a manufacturing process, and relates to the technical field of polymer material preparation. The waterproof roll material is obtained by compounding an upper surface layer, a polyester layer, a polyester mesh layer, and a lower surface layer; the upper surface layer and the lower surface layer are both modified polyolefin roll material layers. Advantages: The present invention effectively improves the flame retardant properties of the waterproof roll material by modifying EPDM rubber and ethylene-octene copolymer so that the two are grafted with flame retardant segments; at the same time, through dehydration condensation, the surface of the nano-silica has similar segments to EPDM rubber and ethylene-octene copolymer, thereby improving its compatibility with the matrix resin and enhancing the weather resistance of the overall material.

Description

Technical Field

[0001] The present invention relates to the field of polymer material preparation, in particular to a weather-resistant waterproof coiled material based on modified polyolefin and a manufacturing process thereof. Background Art

[0002] Modified polyolefin weather-resistant waterproofing membrane is a high-performance building material primarily used for waterproofing projects such as building roofs, basements, tunnels, and reservoirs. With the acceleration of urbanization and the continuous expansion of infrastructure construction, the performance requirements for building waterproofing materials are becoming increasingly stringent, especially in terms of weather resistance. Polyolefin materials, such as polyethylene (PE) and polypropylene (PP), are widely used in the waterproofing membrane field due to their advantages such as light weight, corrosion resistance, and easy processing. However, conventional polyolefin materials suffer from insufficient weather resistance and poor aging resistance. Prolonged exposure to outdoor environments can easily be affected by factors such as ultraviolet rays, temperature fluctuations, and chemical media, leading to a decline in material performance, which in turn affects the waterproofing effect and service life.

[0003] Currently, modification techniques are commonly used to improve the weather resistance of polyolefin waterproofing membranes, such as adding stabilizers, antioxidants, UV absorbers, and light stabilizers. These additives effectively absorb UV rays, preventing photodegradation of the material while also inhibiting oxidation reactions, thereby improving the thermal and chemical stability of the material. Furthermore, polyolefins are inherently flammable, so to meet building safety regulations, chemical or physical modification is often required to enhance their flame retardancy.

[0004] In summary, the present invention prepares a weather-resistant waterproof membrane based on modified polyolefin. Summary of the Invention

[0005] The object of the present invention is to provide a weather-resistant waterproof membrane based on modified polyolefin and a manufacturing process to solve the problems raised in the above background technology.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] More optimally: the waterproof roll is composited by an upper surface layer, a polyester layer, a polyester mesh layer, and a lower surface layer; and both the upper surface layer and the lower surface layer are modified polyolefin roll layers.

[0008] More optimally, the preparation process of the modified polyolefin coil layer is as follows: modified EPDM rubber, chlorinated polyethylene, modified ethylene-octene copolymer, antioxidant, light stabilizer and granulated filler are co-extruded to obtain the modified polyolefin coil layer.

[0009] More optimally, the raw materials of the modified polyolefin coil layer include the following components: by weight, 30-40 parts of modified EPDM rubber, 5-6 parts of chlorinated polyethylene, 10-12 parts of modified ethylene-octene copolymer, 0.5-0.8 parts of antioxidant, 0.2-0.5 parts of light stabilizer, and 5-6 parts of granulated filler.

[0010] More optimally: the preparation process of the modified EPDM rubber is:

[0011] S1: adding EPDM rubber to an internal mixer and melting it at 100-200°C, then sequentially adding 2,6-di-tert-butyl-4-methylphenol, maleic anhydride, and dicumyl peroxide, and reacting for 1-2 hours to obtain carboxylated EPDM rubber;

[0012] S2: Mix tris(hydroxymethyl)aminomethane hydrochloride, triethylamine, and N,N-dimethylformamide, stir thoroughly for 30-40 minutes, and then slowly add phosphorus oxychloride dropwise, controlling the temperature not to exceed 20°C during the addition. After the addition is complete, heat to 95-100°C and keep the temperature for 8-10 hours to obtain intermediate A;

[0013] S3: Mix the carboxylated EPDM rubber, intermediate A, and triethylamine, raise the temperature to 100-120° C., stir, and react for 4-5 hours to obtain modified EPDM rubber.

[0014] More optimally, the carboxylated EPDM rubber comprises the following components: 80-100 parts of EPDM rubber, 0.5-0.8 parts of 2,6-di-tert-butyl-4-methylphenol, 10-15 parts of maleic anhydride, and 1-2 parts of dicumyl peroxide; the intermediate A comprises the following components: 16-18 parts of tris(hydroxymethyl)aminomethane hydrochloride, 10-12 parts of triethylamine, 50-60 parts of N,N-dimethylformamide, and 8-10 parts of phosphorus oxychloride; and the modified EPDM rubber comprises the following components: 50-60 parts of carboxylated EPDM rubber, 20-25 parts of intermediate A, and 2-3 parts of triethylamine.

[0015] More optimally: the preparation process of the modified ethylene-octene copolymer:

[0016] S1: premix maleic anhydride, ethylene-octene copolymer, 2,5-bis(tert-butyl)-2,5-dimethylhexane, styrene, and antioxidant 1010, heat to 180-200°C, and react for 20-30 minutes to obtain a carboxylated ethylene-octene copolymer;

[0017] S2: Carboxylated ethylene-octene copolymer, intermediate A, 4-dimethylaminopyridine, and dihydroxymethyl acetone were premixed uniformly, placed in a multifunctional torque rheometer, and melt-mixed at 180°C and 50 rpm for 30-40 minutes to obtain a modified ethylene-octene copolymer.

[0018] More optimally, the carboxylated ethylene-octene copolymer comprises the following components: by weight, 1-2 parts of maleic anhydride, 80-100 parts of ethylene-octene copolymer, 0.03-0.05 parts of 2,5-bis(tert-butyl)-2,5-dimethylhexane, 2.5-3 parts of styrene, and 0.5-1 parts of antioxidant 1010; the modified ethylene-octene copolymer comprises the following components: by weight, 60-80 parts of carboxylated ethylene-octene copolymer, 20-30 parts of intermediate A, 5-6 parts of 4-dimethylaminopyridine, and 5-6 parts of dihydroxymethylacetone.

[0019] More optimally: the granulated filler is modified nano-silica, and its preparation process is as follows: (1) mixing nano-silica, toluene, and γ-aminopropyltriethoxysilane, heating to 70-80°C, and reacting for 4-5 hours to obtain amino-modified nano-silica; (2) mixing amino-modified nano-silica, carboxylated ethylene-octene copolymer, and carboxylated ethylene propylene diene monomer rubber, heating to 150-180°C, and reacting for 30-40 minutes to obtain modified nano-silica.

[0020] More optimally, the amino-type nano-silica comprises the following components: 20-30 parts of nano-silica, 60-70 parts of toluene, and 1-2 parts of γ-aminopropyltriethoxysilane by weight; the modified nano-silica comprises the following components: 10-12 parts of amino-type nano-silica, 3-4 parts of carboxylated ethylene-octene copolymer, and 5-8 parts of carboxylated ethylene propylene diene monomer rubber by weight.

[0021] More optimally, the co-extrusion process parameters are: feeding section 170-190°C, plasticizing section 190-200°C, metering section 200-210°C, and die temperature 180-200°C.

[0022] The present invention modifies EPDM rubber and ethylene-octene copolymer to graft flame-retardant segments onto them, effectively improving the flame retardancy of the waterproof membrane. Simultaneously, through dehydration condensation, similar segments of EPDM rubber and ethylene-octene copolymer are formed on the surface of the nano-silica, improving its compatibility with the matrix resin and enhancing the weather resistance of the overall material. The details are as follows:

[0023] First, a caged phosphonate structure is formed by phosphorylating tris(hydroxymethyl)aminomethane hydrochloride with phosphorus oxychloride. This structure is then grafted onto carboxylated EPDM rubber and ethylene-octene copolymer via amino groups. The caged phosphonate structure is a green and environmentally friendly flame retardant with high stability. During combustion, it promotes the formation of a char layer and inhibits smoke release, effectively improving the overall flame retardancy and smoke suppression properties of the material.

[0024] Second: Nano-silica is connected to carboxylated EPDM rubber and ethylene-octene copolymer through silane coupling agent, so that the compatibility of nano-silica with the matrix resin is improved. Moreover, nano-silica, as a reinforcement material, can effectively improve the overall weather resistance of the material. DETAILED DESCRIPTION

[0025] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0026] It should be noted that the following parts are parts by weight, and the purchase manufacturers of all raw materials involved in the present invention are not subject to any special restrictions and are exemplified as follows: in the following embodiments, tris(hydroxymethyl)aminomethane hydrochloride CAS is 1185-53-1, and the purchase manufacturer is Wuhan Difu Biotechnology Co., Ltd.; 2,6-di-tert-butyl-4-methylphenol CAS is 128-37-0, and the purchase manufacturer is Aladdin; ethylene propylene diene monomer rubber CAS is 9010-79-1, and the brand is Wuhan Adama; ethylene-octene copolymer CAS is 26221-73-8, and the manufacturer is Hangzhou Jieheng Chemical Co., Ltd.

[0027] Example 1: A manufacturing process for a weather-resistant waterproof membrane based on modified polyolefin:

[0028] The preparation process of modified EPDM rubber is:

[0029] S1: 80 parts of EPDM rubber were added to an internal mixer and melted at 100°C. Then, 0.5 parts of 2,6-di-tert-butyl-4-methylphenol, 10 parts of maleic anhydride, and 1 part of dicumyl peroxide were added in sequence and reacted for 1 hour to obtain carboxylated EPDM rubber;

[0030] S2: 16 parts of tris(hydroxymethyl)aminomethane hydrochloride, 10 parts of triethylamine, and 50 parts of N,N-dimethylformamide were mixed and stirred thoroughly for 30 minutes. Then, 8 parts of phosphorus oxychloride were slowly added dropwise while controlling the temperature not to exceed 20°C during the addition. After the addition was complete, the temperature was raised to 95°C and kept for 8 hours to obtain intermediate A.

[0031] S3: 50 parts of carboxylated EPDM rubber, 20 parts of intermediate A, and 2 parts of triethylamine were mixed, heated to 100° C., stirred, and reacted for 4 hours to obtain modified EPDM rubber.

[0032] Preparation process of modified ethylene-octene copolymer:

[0033] S1: Premix 1 part of maleic anhydride, 80 parts of ethylene-octene copolymer, 0.03 parts of 2,5-bis(tert-butyl)-2,5-dimethylhexane, 2.5 parts of styrene, and 0.5 parts of antioxidant 1010, heat to 180°C, and react for 20 minutes to obtain a carboxylated ethylene-octene copolymer;

[0034] S2: 60 parts of carboxylated ethylene-octene copolymer, 20 parts of intermediate A, 5 parts of 4-dimethylaminopyridine, and 5 parts of dihydroxymethyl acetone were premixed and placed in a multifunctional torque rheometer. The mixture was melt-mixed at 180°C and 50 rpm for 30 minutes to obtain a modified ethylene-octene copolymer.

[0035] Preparation process of modified nano-silica: (1) Mix 20 parts of nano-silica, 60 parts of toluene, and 1 part of γ-aminopropyltriethoxysilane, heat to 70°C, and react for 4 hours to obtain amino-modified nano-silica; (2) Mix 10 parts of amino-modified nano-silica, 3 parts of carboxylated ethylene-octene copolymer, and 5 parts of carboxylated ethylene-propylene diene monomer rubber, heat to 150°C, and react for 30 minutes to obtain modified nano-silica.

[0036] 30 parts of modified EPDM rubber, 5 parts of chlorinated polyethylene, 10 parts of modified ethylene-octene copolymer, 0.5 parts of antioxidant 1010, 0.2 parts of light stabilizer 2020, and 5 parts of modified nano-silica are co-extruded to obtain a modified polyolefin coil layer, which serves as the upper surface layer and the lower surface layer, and is compounded with the polyester layer and the polyester mesh layer to obtain a waterproof coil; the co-extrusion process parameters are: feeding section 170°C, plasticizing section 190°C, metering section 200°C, die mouth temperature 180°C, hot pressing at 170°C, and cold pressing at 5°C during the compounding process.

[0037] Example 2: A manufacturing process for a weather-resistant waterproof membrane based on modified polyolefin:

[0038] The preparation process of modified EPDM rubber is:

[0039] S1: 100 parts of EPDM rubber were added to an internal mixer and melted at 200°C. Then, 0.8 parts of 2,6-di-tert-butyl-4-methylphenol, 15 parts of maleic anhydride, and 2 parts of dicumyl peroxide were added in sequence and reacted for 2 hours to obtain carboxylated EPDM rubber;

[0040] S2: 18 parts of tris(hydroxymethyl)aminomethane hydrochloride, 12 parts of triethylamine, and 60 parts of N,N-dimethylformamide were mixed and stirred thoroughly for 40 minutes. Then, 10 parts of phosphorus oxychloride were slowly added dropwise while controlling the temperature not to exceed 20°C during the addition. After the addition was complete, the temperature was raised to 100°C and the reaction was maintained for 10 hours to obtain intermediate A.

[0041] S3: 60 parts of carboxylated EPDM rubber, 25 parts of intermediate A, and 3 parts of triethylamine were mixed, heated to 120° C., stirred, and reacted for 5 hours to obtain modified EPDM rubber.

[0042] Preparation process of modified ethylene-octene copolymer:

[0043] S1: 2 parts of maleic anhydride, 100 parts of ethylene-octene copolymer, 0.05 parts of 2,5-bis(tert-butyl)-2,5-dimethylhexane, 3 parts of styrene, and 1 part of antioxidant 1010 were premixed, heated to 200°C, and reacted for 30 minutes to obtain a carboxylated ethylene-octene copolymer;

[0044] S2: 80 parts of carboxylated ethylene-octene copolymer, 30 parts of intermediate A, 6 parts of 4-dimethylaminopyridine, and 6 parts of dihydroxymethyl acetone were premixed and placed in a multifunctional torque rheometer. The mixture was melt-mixed at 180°C and 50 rpm for 40 minutes to obtain a modified ethylene-octene copolymer.

[0045] Preparation process of modified nano-silica: (1) Mix 30 parts of nano-silica, 70 parts of toluene, and 2 parts of γ-aminopropyltriethoxysilane, heat to 80°C, and react for 5 hours to obtain amino-modified nano-silica; (2) Mix 12 parts of amino-modified nano-silica, 4 parts of carboxylated ethylene-octene copolymer, and 8 parts of carboxylated ethylene propylene diene monomer rubber, heat to 180°C, and react for 40 minutes to obtain modified nano-silica.

[0046] 40 parts of modified EPDM rubber, 6 parts of chlorinated polyethylene, 12 parts of modified ethylene-octene copolymer, 0.8 parts of antioxidant 1010, 0.5 parts of light stabilizer 2020, and 6 parts of modified nano-silica are co-extruded to obtain a modified polyolefin coil layer, which serves as the upper surface layer and the lower surface layer, and is compounded with the polyester layer and the polyester mesh layer to obtain a waterproof coil; the co-extrusion process parameters are: feeding section 170°C, plasticizing section 190°C, metering section 200°C, die mouth temperature 180°C, hot pressing at 170°C, and cold pressing at 5°C during the compounding process.

[0047] Example 3: A manufacturing process for a weather-resistant waterproof membrane based on modified polyolefin:

[0048] The preparation process of modified EPDM rubber is:

[0049] S1: 90 parts of EPDM rubber were added to an internal mixer and melted at 150°C. Then, 0.6 parts of 2,6-di-tert-butyl-4-methylphenol, 12 parts of maleic anhydride, and 1.5 parts of dicumyl peroxide were added in sequence and reacted for 1.5 hours to obtain carboxylated EPDM rubber;

[0050] S2: 17 parts of tris(hydroxymethyl)aminomethane hydrochloride, 11 parts of triethylamine, and 55 parts of N,N-dimethylformamide were mixed and stirred thoroughly for 35 minutes. Then, 9 parts of phosphorus oxychloride were slowly added dropwise while controlling the temperature not to exceed 20°C during the addition. After the addition was complete, the temperature was raised to 100°C and the reaction was maintained for 9 hours to obtain intermediate A.

[0051] S3: 55 parts of carboxylated EPDM rubber, 22 parts of intermediate A, and 2.5 parts of triethylamine were mixed, heated to 110° C., stirred, and reacted for 4.5 hours to obtain modified EPDM rubber.

[0052] Preparation process of modified ethylene-octene copolymer:

[0053] S1: 1.5 parts of maleic anhydride, 90 parts of ethylene-octene copolymer, 0.04 parts of 2,5-bis(tert-butyl)-2,5-dimethylhexane, 2.8 parts of styrene, and 0.8 parts of antioxidant 1010 were premixed, heated to 200° C., and reacted for 25 minutes to obtain a carboxylated ethylene-octene copolymer;

[0054] S2: 70 parts of carboxylated ethylene-octene copolymer, 25 parts of intermediate A, 5.5 parts of 4-dimethylaminopyridine, and 5.5 parts of dihydroxymethyl acetone were premixed and placed in a multifunctional torque rheometer. The mixture was melt-mixed at 180°C and 50 rpm for 35 minutes to obtain a modified ethylene-octene copolymer.

[0055] Preparation process of modified nano-silica: (1) Mix 25 parts of nano-silica, 65 parts of toluene, and 1.5 parts of γ-aminopropyltriethoxysilane, heat to 75°C, and react for 4.5 hours to obtain amino-modified nano-silica; (2) Mix 11 parts of amino-modified nano-silica, 3.5 parts of carboxylated ethylene-octene copolymer, and 7 parts of carboxylated ethylene propylene diene monomer rubber, heat to 160°C, and react for 35 minutes to obtain modified nano-silica.

[0056] 35 parts of modified EPDM rubber, 5.5 parts of chlorinated polyethylene, 11 parts of modified ethylene-octene copolymer, 0.6 parts of antioxidant 1010, 0.3 parts of light stabilizer 2020, and 5.5 parts of modified nano-silica are co-extruded to obtain a modified polyolefin coil layer, which serves as the upper surface layer and the lower surface layer, and is compounded with the polyester layer and the polyester mesh layer to obtain a waterproof coil; the co-extrusion process parameters are: feeding section 170°C, plasticizing section 190°C, metering section 200°C, die mouth temperature 180°C, hot pressing at 170°C, and cold pressing at 5°C during the compounding process.

[0057] Comparative Example 1: No modified nano-silica was added, and the rest was the same as Example 3, specifically as follows:

[0058] The preparation process of modified EPDM rubber is:

[0059] S1: 90 parts of EPDM rubber were added to an internal mixer and melted at 150°C. Then, 0.6 parts of 2,6-di-tert-butyl-4-methylphenol, 12 parts of maleic anhydride, and 1.5 parts of dicumyl peroxide were added in sequence and reacted for 1.5 hours to obtain carboxylated EPDM rubber;

[0060] S2: 17 parts of tris(hydroxymethyl)aminomethane hydrochloride, 11 parts of triethylamine, and 55 parts of N,N-dimethylformamide were mixed and stirred thoroughly for 35 minutes. Then, 9 parts of phosphorus oxychloride were slowly added dropwise while controlling the temperature not to exceed 20°C during the addition. After the addition was complete, the temperature was raised to 100°C and the reaction was maintained for 9 hours to obtain intermediate A.

[0061] S3: 55 parts of carboxylated EPDM rubber, 22 parts of intermediate A, and 2.5 parts of triethylamine were mixed, heated to 110° C., stirred, and reacted for 4.5 hours to obtain modified EPDM rubber.

[0062] Preparation process of modified ethylene-octene copolymer:

[0063] S1: 1.5 parts of maleic anhydride, 90 parts of ethylene-octene copolymer, 0.04 parts of 2,5-bis(tert-butyl)-2,5-dimethylhexane, 2.8 parts of styrene, and 0.8 parts of antioxidant 1010 were premixed, heated to 200° C., and reacted for 25 minutes to obtain a carboxylated ethylene-octene copolymer;

[0064] S2: 70 parts of carboxylated ethylene-octene copolymer, 25 parts of intermediate A, 5.5 parts of 4-dimethylaminopyridine, and 5.5 parts of dihydroxymethyl acetone were premixed and placed in a multifunctional torque rheometer. The mixture was melt-mixed at 180°C and 50 rpm for 35 minutes to obtain a modified ethylene-octene copolymer.

[0065] 35 parts of modified EPDM rubber, 5.5 parts of chlorinated polyethylene, 11 parts of modified ethylene-octene copolymer, 0.6 parts of antioxidant 1010, and 0.3 parts of light stabilizer 2020 are co-extruded to obtain a modified polyolefin roll layer, which serves as the upper surface layer and the lower surface layer, and is compounded with the polyester layer and the polyester mesh layer to obtain a waterproof roll; the co-extrusion process parameters are: feeding section 170°C, plasticizing section 190°C, metering section 200°C, die mouth temperature 180°C, hot pressing at 170°C, and cold pressing at 5°C during the compounding process.

[0066] Comparative Example 2: The EPDM rubber and ethylene-octene copolymer were not modified, and the rest was the same as in Example 3, specifically as follows:

[0067] Preparation process of modified nano-silica: (1) Mix 25 parts of nano-silica, 65 parts of toluene, and 1.5 parts of γ-aminopropyltriethoxysilane, heat to 75°C, and react for 4.5 hours to obtain amino-modified nano-silica; (2) Mix 11 parts of amino-modified nano-silica, 3.5 parts of carboxylated ethylene-octene copolymer, and 7 parts of carboxylated ethylene propylene diene monomer rubber, heat to 160°C, and react for 35 minutes to obtain modified nano-silica.

[0068] 35 parts of modified EPDM rubber, 5.5 parts of chlorinated polyethylene, 11 parts of modified ethylene-octene copolymer, 0.6 parts of antioxidant 1010, 0.3 parts of light stabilizer 2020, and 5.5 parts of modified nano-silica are co-extruded to obtain a modified polyolefin coil layer, which serves as the upper surface layer and the lower surface layer, and is compounded with the polyester layer and the polyester mesh layer to obtain a waterproof coil; the co-extrusion process parameters are: feeding section 170°C, plasticizing section 190°C, metering section 200°C, die mouth temperature 180°C, hot pressing at 170°C, and cold pressing at 5°C during the compounding process.

[0069] Comparative Example 3: No modification was performed on the nano-silica, and the rest was the same as in Example 3, as follows:

[0070] The preparation process of modified EPDM rubber is:

[0071] S1: 90 parts of EPDM rubber were added to an internal mixer and melted at 150°C. Then, 0.6 parts of 2,6-di-tert-butyl-4-methylphenol, 12 parts of maleic anhydride, and 1.5 parts of dicumyl peroxide were added in sequence and reacted for 1.5 hours to obtain carboxylated EPDM rubber;

[0072] S2: 17 parts of tris(hydroxymethyl)aminomethane hydrochloride, 11 parts of triethylamine, and 55 parts of N,N-dimethylformamide were mixed and stirred thoroughly for 35 minutes. Then, 9 parts of phosphorus oxychloride were slowly added dropwise while controlling the temperature not to exceed 20°C during the addition. After the addition was complete, the temperature was raised to 100°C and the reaction was maintained for 9 hours to obtain intermediate A.

[0073] S3: 55 parts of carboxylated EPDM rubber, 22 parts of intermediate A, and 2.5 parts of triethylamine were mixed, heated to 110° C., stirred, and reacted for 4.5 hours to obtain modified EPDM rubber.

[0074] Preparation process of modified ethylene-octene copolymer:

[0075] S1: 1.5 parts of maleic anhydride, 90 parts of ethylene-octene copolymer, 0.04 parts of 2,5-bis(tert-butyl)-2,5-dimethylhexane, 2.8 parts of styrene, and 0.8 parts of antioxidant 1010 were premixed, heated to 200° C., and reacted for 25 minutes to obtain a carboxylated ethylene-octene copolymer;

[0076] S2: 70 parts of carboxylated ethylene-octene copolymer, 25 parts of intermediate A, 5.5 parts of 4-dimethylaminopyridine, and 5.5 parts of dihydroxymethyl acetone were premixed and placed in a multifunctional torque rheometer. The mixture was melt-mixed at 180°C and 50 rpm for 35 minutes to obtain a modified ethylene-octene copolymer.

[0077] 35 parts of modified EPDM rubber, 5.5 parts of chlorinated polyethylene, 11 parts of modified ethylene-octene copolymer, 0.6 parts of antioxidant 1010, 0.3 parts of light stabilizer 2020, and 5.5 parts of nano-silica are co-extruded to obtain a modified polyolefin coil layer, which serves as the upper surface layer and the lower surface layer, and is compounded with the polyester layer and the polyester mesh layer to obtain a waterproof coil; the co-extrusion process parameters are: feeding section 170°C, plasticizing section 190°C, metering section 200°C, die mouth temperature 180°C, hot pressing at 170°C, and cold pressing at 5°C during the compounding process.

[0078] Testing experiment: (1) According to the test method specified in GB27789-2011 "Thermoplastic polyolefin (TPO) waterproof membrane", the weather resistance of the waterproof membranes of Examples 1-3 and Comparative Examples 1-3 was tested (heat aging at 115°C); (2) The limiting oxygen index of the waterproof membranes of Examples 1-3 and Comparative Examples 1-3 was measured according to the provisions of GB / T2406-2009. The obtained data are shown in the following table:

[0079] Table 1

[0080]

[0081] Conclusion: Examples 1-3 effectively enhance the flame retardancy of the waterproof membrane by modifying EPDM rubber and ethylene-octene copolymer, grafting flame-retardant segments onto them. Furthermore, through dehydration condensation, the nanosilica surface possesses segments similar to those of EPDM rubber and ethylene-octene copolymer, improving its compatibility with the matrix resin and enhancing the overall weather resistance of the material. Comparative Example 1, which does not incorporate modified nanosilica, exhibits reduced performance; Comparative Example 2, which does not modify the EPDM rubber and ethylene-octene copolymer, also exhibits reduced performance; and Comparative Example 3, which does not modify the nanosilica, also exhibits reduced performance.

[0082] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art will be able to modify the technical solutions described in the aforementioned embodiments or substitute equivalents for some of the technical features. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A process for manufacturing a weather-resistant waterproof membrane based on modified polyolefin, characterized by: The waterproof roll is composited by an upper surface layer, a polyester layer, a polyester mesh layer, and a lower surface layer; both the upper surface layer and the lower surface layer are modified polyolefin roll layers; The preparation process of the modified polyolefin coil layer is as follows: co-extruding modified EPDM rubber, chlorinated polyethylene, modified ethylene-octene copolymer, antioxidant, light stabilizer and granulated filler to obtain the modified polyolefin coil layer; The preparation process of the modified EPDM rubber is as follows: S1: adding the EPDM rubber to an internal mixer and melting it at 100-200°C, then adding 2,6-di-tert-butyl-4-methylphenol, maleic anhydride, and diisopropylbenzene peroxide in sequence, and reacting for 1-2 hours to obtain the carboxylated EPDM rubber; S2: mixing tris(hydroxymethyl)aminomethane hydrochloride, triethylamine, and N,N-dimethylformamide, stirring them thoroughly for 30-40 minutes, and then slowly adding phosphorus oxychloride dropwise, controlling the temperature not to exceed 20°C during the addition process. After the addition is completed, the temperature is raised to 95-100°C and kept warm for reaction for 8-10 hours to obtain intermediate A; S3: mixing the carboxylated EPDM rubber, intermediate A, and triethylamine, heating them to 100-120°C, stirring, and reacting for 4-5 hours to obtain the modified EPDM rubber.

2. The manufacturing process of a weather-resistant waterproof membrane based on modified polyolefin according to claim 1, characterized in that: The raw materials of the modified polyolefin coil layer include the following components: by weight, 30-40 parts of modified EPDM rubber, 5-6 parts of chlorinated polyethylene, 10-12 parts of modified ethylene-octene copolymer, 0.5-0.8 parts of antioxidant, 0.2-0.5 parts of light stabilizer, and 5-6 parts of granular filler.

3. The manufacturing process of a weather-resistant waterproof membrane based on modified polyolefin according to claim 1, characterized in that: The carboxylated EPDM rubber comprises the following components: 80-100 parts by weight of EPDM rubber, 0.5-0.8 parts of 2,6-di-tert-butyl-4-methylphenol, 10-15 parts of maleic anhydride, and 1-2 parts of dicumyl peroxide; the intermediate A comprises the following components: 16-18 parts by weight of tris(hydroxymethyl)aminomethane hydrochloride, 10-12 parts of triethylamine, 50-60 parts of N,N-dimethylformamide, and 8-10 parts of phosphorus oxychloride; and the modified EPDM rubber comprises the following components: 50-60 parts by weight of carboxylated EPDM rubber, 20-25 parts of intermediate A, and 2-3 parts of triethylamine.

4. The manufacturing process of a weather-resistant waterproof membrane based on modified polyolefin according to claim 1, characterized in that: The preparation process of the modified ethylene-octene copolymer includes the following steps: S1: uniformly premixing maleic anhydride, ethylene-octene copolymer, 2,5-bis(tert-butyl)-2,5-dimethylhexane, styrene, and antioxidant 1010, heating the mixture to 180-200° C., and reacting the mixture for 20-30 minutes to obtain a carboxylated ethylene-octene copolymer; and S2: uniformly premixing the carboxylated ethylene-octene copolymer, intermediate A, 4-dimethylaminopyridine, and dihydroxymethyl acetone, placing the mixture in a multifunctional torque rheometer, and thoroughly melt-mixing the mixture at 180° C. and 50 rpm for 30-40 minutes to obtain a modified ethylene-octene copolymer.

5. The manufacturing process of a weather-resistant waterproof membrane based on modified polyolefin according to claim 4, characterized in that: The carboxylated ethylene-octene copolymer comprises the following components: by weight, 1-2 parts of maleic anhydride, 80-100 parts of ethylene-octene copolymer, 0.03-0.05 parts of 2,5-bis(tert-butyl)-2,5-dimethylhexane, 2.5-3 parts of styrene, and 0.5-1 parts of antioxidant 1010; the modified ethylene-octene copolymer comprises the following components: by weight, 60-80 parts of carboxylated ethylene-octene copolymer, 20-30 parts of intermediate A, 5-6 parts of 4-dimethylaminopyridine, and 5-6 parts of dihydroxymethyl acetone.

6. The manufacturing process of a weather-resistant waterproof membrane based on modified polyolefin according to claim 1, characterized in that: The granulated filler is modified nano-silica, and its preparation process is as follows: (1) mixing nano-silica, toluene, and γ-aminopropyltriethoxysilane, heating to 70-80°C, and reacting for 4-5 hours to obtain amino-modified nano-silica; (2) mixing amino-modified nano-silica, carboxylated ethylene-octene copolymer, and carboxylated ethylene propylene diene monomer rubber, heating to 150-180°C, and reacting for 30-40 minutes to obtain modified nano-silica.

7. The manufacturing process of a weather-resistant waterproof membrane based on modified polyolefin according to claim 6, characterized in that: The amino-type nano-silica comprises the following components: by weight, 20-30 parts of nano-silica, 60-70 parts of toluene, and 1-2 parts of gamma-aminopropyltriethoxysilane; the modified nano-silica comprises the following components: by weight, 10-12 parts of amino-type nano-silica, 3-4 parts of carboxylated ethylene-octene copolymer, and 5-8 parts of carboxylated ethylene propylene diene monomer rubber.

8. The manufacturing process of a weather-resistant waterproof membrane based on modified polyolefin according to claim 1, characterized in that: The process parameters of the co-extrusion are: feeding section 170-190°C, plasticizing section 190-200°C, metering section 200-210°C, and die temperature 180-200°C.

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