Weather-resistant waterproof coiled material based on modified polyolefin and manufacturing process

Abstract

The invention discloses a weather-resistant waterproof coiled material based on modified polyolefin and a manufacturing process, and relates to the technical field of high polymer material preparation. The waterproof coiled material is obtained by compounding an upper surface layer, a polyester layer, a polyester grid layer and a lower surface layer, the upper surface layer and the lower surface layer are both modified polyolefin coiled material layers. The preparation method has the beneficial effects that by modifying the ethylene propylene diene monomer and the ethylene-octylene copolymer, the ethylene propylene diene monomer and the ethylene-octylene copolymer are grafted with flame-retardant chain segments, so that the flame-retardant property of the waterproof coiled material is effectively improved; meanwhile, through dehydration condensation, the surface of the nano silicon dioxide has similar chain segments of ethylene propylene diene monomer and ethylene-octene copolymer, so that the compatibility of the nano silicon dioxide and matrix resin is improved, and the weather resistance of the whole material is enhanced.

Description

Technical Field

[0001] The 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 waterproof membrane is a high-performance building material, mainly used in waterproof 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 waterproof materials are getting higher and higher, especially in terms of weather resistance. Polyolefin materials, such as polyethylene (PE) and polypropylene (PP), are widely used in the field of waterproof membranes due to their advantages such as light weight, corrosion resistance, and easy processing. However, ordinary polyolefin materials have the problems of insufficient weather resistance and poor aging resistance. They are easily affected by ultraviolet rays, temperature changes, chemical media, and other factors when exposed to outdoor environments for a long time, resulting in a decrease in material performance, which in turn affects the waterproof effect and service life.

[0003] At present, in order to improve the weather resistance of polyolefin waterproof membranes, modification technologies are usually used, such as adding stabilizers, antioxidants, UV absorbers, light stabilizers, etc. These additives can effectively absorb ultraviolet rays to prevent photodegradation of materials, while inhibiting oxidation reactions and improving the thermal and chemical stability of materials. In addition, polyolefin materials themselves are flammable. In order to meet building safety regulations, polyolefins are usually modified by chemical or physical methods to improve their flame retardant properties.

[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: More optimally: the waterproof coiled material is composited by 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 coiled material layers.

[0007] More optimally: the preparation process of the modified polyolefin coil layer is: co-extruding modified EPDM rubber, chlorinated polyethylene, modified ethylene-octene copolymer, antioxidant, light stabilizer, and granulated filler to obtain the modified polyolefin coil layer.

[0008] 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.

[0009] More optimally: the preparation process of the modified EPDM rubber is: 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 diisopropylbenzene peroxide, and reacting for 1-2h to obtain carboxylated EPDM rubber; S2: Tris(hydroxymethyl)aminomethane hydrochloride, triethylamine and N,N-dimethylformamide were mixed and stirred for 30-40 minutes, and then phosphorus oxychloride was slowly added dropwise, and the temperature was controlled not to exceed 20°C during the addition. After the addition was completed, the temperature was raised to 95-100°C and kept for reaction for 8-10 hours to obtain intermediate A; 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.

[0010] More optimally: the carboxylated EPDM rubber comprises the following components: by weight, 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 diisopropylbenzene peroxide; the intermediate A comprises the following components: by weight, 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; the modified EPDM rubber comprises the following components: by weight, 50-60 parts of carboxylated EPDM rubber, 20-25 parts of intermediate A, and 2-3 parts of triethylamine.

[0011] More optimally: the preparation process of the modified ethylene-octene copolymer: S1: premix maleic anhydride, ethylene-octene copolymer, 2,5-bis(tert-butyl)-2,5-dimethylhexane, styrene and antioxidant 1010, heat to 180-200° C., react for 20-30 min, and obtain carboxylated ethylene-octene copolymer; S2: Carboxylated ethylene-octene copolymer, intermediate A, 4-dimethylaminopyridine and dihydroxymethyl acetone were premixed uniformly, placed in a multifunctional torque rheometer, and fully melt-mixed at 180° C. and 50 rpm for 30-40 minutes to obtain a modified ethylene-octene copolymer.

[0012] 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.

[0013] 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 rubber, heating to 150-180°C, and reacting for 30-40 minutes to obtain modified nano-silica.

[0014] More optimally, 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 γ-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 rubber.

[0015] More optimally, 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.

[0016] The present invention modifies EPDM rubber and ethylene-octene copolymer to graft flame retardant segments, thereby effectively improving the flame retardant properties of the waterproof coiled material; at the same time, through dehydration condensation, the surface of the nano-silicon dioxide has similar segments of EPDM rubber and ethylene-octene copolymer, thereby improving its compatibility with the matrix resin and enhancing the weather resistance of the overall material. The details are as follows: First, tris(hydroxymethyl)aminomethane hydrochloride and phosphorus oxychloride are reacted through phosphorylation to obtain a caged phosphonate structure, which is then grafted into carboxylated EPDM rubber and ethylene-octene copolymer through amino groups. The caged phosphonate structure is a green and environmentally friendly flame retardant with strong stability. It promotes the formation of a carbon layer and inhibits smoke release during combustion, which can effectively improve the overall flame retardant and smoke suppression properties of the material. Second: Nano-silica is connected with carboxylated EPDM rubber and ethylene-octene copolymer through silane coupling agent, so that the compatibility of nano-silica with the matrix resin is improved. In addition, nano-silica, as a reinforcement material, can effectively improve the overall weather resistance of the material. DETAILED DESCRIPTION

[0017] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0018] 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 exemplified without any special restrictions: 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.

[0019] Example 1: A manufacturing process of a weather-resistant waterproof membrane based on modified polyolefin: The preparation process of modified EPDM rubber is: S1: 80 parts of EPDM rubber were added to an internal mixer and melted at 100°C, and then 0.5 parts of 2,6-di-tert-butyl-4-methylphenol, 10 parts of maleic anhydride and 1 part of diisopropylbenzene peroxide were added in sequence, and the mixture was reacted for 1 hour to obtain carboxylated EPDM rubber; S2: 16 parts of tris(hydroxymethyl)aminomethane hydrochloride, 10 parts of triethylamine, and 50 parts of N,N-dimethylformamide were mixed, stirred for 30 minutes, and then 8 parts of phosphorus oxychloride were slowly added dropwise, and the temperature was controlled not to exceed 20°C during the addition. After the addition was completed, the temperature was raised to 95°C and kept for reaction for 8 hours to obtain intermediate A; 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.

[0020] Preparation process of modified ethylene-octene copolymer: S1: 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 were premixed uniformly, heated to 180° C., and reacted for 20 minutes to obtain a carboxylated ethylene-octene copolymer; S2: 60 parts of carboxylated ethylene-octene copolymer, 20 parts of intermediate A, 5 parts of 4-dimethylaminopyridine and 5 parts of dihydroxymethylacetone were premixed uniformly, placed in a multifunctional torque rheometer, and fully melt-mixed at 180° C. and 50 rpm for 30 minutes to obtain a modified ethylene-octene copolymer.

[0021] 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 rubber, heat to 150°C, and react for 30 minutes to obtain modified nano-silica.

[0022] 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: 170°C in the feeding section, 190°C in the plasticizing section, 200°C in the metering section, and 180°C in the die temperature; during the compounding process, the hot pressing is 170°C and the cold pressing is 5°C.

[0023] Example 2: A manufacturing process of a weather-resistant waterproof membrane based on modified polyolefin: The preparation process of modified EPDM rubber is: S1: 100 parts of EPDM rubber were added to an internal mixer and melted at 200°C, and then 0.8 parts of 2,6-di-tert-butyl-4-methylphenol, 15 parts of maleic anhydride and 2 parts of diisopropylbenzene peroxide were added in sequence, and the mixture was reacted for 2 hours to obtain carboxylated EPDM rubber; S2: 18 parts of tris(hydroxymethyl)aminomethane hydrochloride, 12 parts of triethylamine and 60 parts of N,N-dimethylformamide were mixed and stirred for 40 minutes, and then 10 parts of phosphorus oxychloride were slowly added dropwise, and the temperature was controlled not to exceed 20°C during the addition. After the addition was completed, the temperature was raised to 100°C and kept for reaction for 10 hours to obtain intermediate A; 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.

[0024] Preparation process of modified ethylene-octene copolymer: 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 uniformly, heated to 200° C., and reacted for 30 minutes to obtain a carboxylated ethylene-octene copolymer; 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 uniformly, placed in a multifunctional torque rheometer, and fully melt-mixed at 180° C. and 50 rpm for 40 minutes to obtain a modified ethylene-octene copolymer.

[0025] 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 rubber, heat to 180°C, and react for 40 minutes to obtain modified nano-silica.

[0026] 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: 170°C in the feeding section, 190°C in the plasticizing section, 200°C in the metering section, and 180°C in the die temperature; during the compounding process, the hot pressing is 170°C and the cold pressing is 5°C.

[0027] Example 3: A manufacturing process of a weather-resistant waterproof membrane based on modified polyolefin: The preparation process of modified EPDM rubber is: S1: 90 parts of EPDM rubber were added to an internal mixer and melted at 150° C., and then 0.6 parts of 2,6-di-tert-butyl-4-methylphenol, 12 parts of maleic anhydride, and 1.5 parts of diisopropylbenzene peroxide were added in sequence, and the mixture was reacted for 1.5 hours to obtain carboxylated EPDM rubber; S2: 17 parts of tris(hydroxymethyl)aminomethane hydrochloride, 11 parts of triethylamine, and 55 parts of N,N-dimethylformamide were mixed, stirred for 35 minutes, and then 9 parts of phosphorus oxychloride were slowly added dropwise, and the temperature was controlled not to exceed 20°C during the addition. After the addition was completed, the temperature was raised to 100°C and kept for 9 hours to obtain intermediate A; 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.

[0028] Preparation process of modified ethylene-octene copolymer: 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 uniformly, heated to 200° C., and reacted for 25 minutes to obtain a carboxylated ethylene-octene copolymer; S2: 70 parts of carboxylated ethylene-octene copolymer, 25 parts of intermediate A, 5.5 parts of 4-dimethylaminopyridine and 5.5 parts of dihydroxymethylacetone were premixed uniformly, placed in a multifunctional torque rheometer, and fully melt-mixed at 180° C. and 50 rpm for 35 minutes to obtain a modified ethylene-octene copolymer.

[0029] 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 rubber, heat to 160°C, and react for 35 minutes to obtain modified nano-silica.

[0030] 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: 170°C in the feeding section, 190°C in the plasticizing section, 200°C in the metering section, and 180°C in the die temperature; during the compounding process, the hot pressing is 170°C and the cold pressing is 5°C.

[0031] Comparative Example 1: No modified nano-silicon dioxide was added, and the rest was the same as Example 3, specifically as follows: The preparation process of modified EPDM rubber is: S1: 90 parts of EPDM rubber were added to an internal mixer and melted at 150° C., and then 0.6 parts of 2,6-di-tert-butyl-4-methylphenol, 12 parts of maleic anhydride, and 1.5 parts of diisopropylbenzene peroxide were added in sequence, and the mixture was reacted for 1.5 hours to obtain carboxylated EPDM rubber; S2: 17 parts of tris(hydroxymethyl)aminomethane hydrochloride, 11 parts of triethylamine, and 55 parts of N,N-dimethylformamide were mixed, stirred for 35 minutes, and then 9 parts of phosphorus oxychloride were slowly added dropwise, and the temperature was controlled not to exceed 20°C during the addition. After the addition was completed, the temperature was raised to 100°C and kept for 9 hours to obtain intermediate A; 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.

[0032] Preparation process of modified ethylene-octene copolymer: 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 uniformly, heated to 200° C., and reacted for 25 minutes to obtain a carboxylated ethylene-octene copolymer; S2: 70 parts of carboxylated ethylene-octene copolymer, 25 parts of intermediate A, 5.5 parts of 4-dimethylaminopyridine and 5.5 parts of dihydroxymethylacetone were premixed uniformly, placed in a multifunctional torque rheometer, and fully melt-mixed at 180° C. and 50 rpm for 35 minutes to obtain a modified ethylene-octene copolymer.

[0033] 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 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: 170°C in the feeding section, 190°C in the plasticizing section, 200°C in the metering section, and 180°C in the die temperature; during the compounding process, the hot pressing is 170°C and the cold pressing is 5°C.

[0034] Comparative Example 2: The EPDM rubber and the ethylene-octene copolymer were not modified, and the rest was the same as Example 3, as follows: 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 rubber, heat to 160°C, and react for 35 minutes to obtain modified nano-silica.

[0035] 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: 170°C in the feeding section, 190°C in the plasticizing section, 200°C in the metering section, and 180°C in the die temperature; during the compounding process, the hot pressing is 170°C and the cold pressing is 5°C.

[0036] Comparative Example 3: No modification was performed on the nano-silicon dioxide, and the rest was the same as in Example 3, as follows: The preparation process of modified EPDM rubber is: S1: 90 parts of EPDM rubber were added to an internal mixer and melted at 150° C., and then 0.6 parts of 2,6-di-tert-butyl-4-methylphenol, 12 parts of maleic anhydride, and 1.5 parts of diisopropylbenzene peroxide were added in sequence, and the mixture was reacted for 1.5 hours to obtain carboxylated EPDM rubber; S2: 17 parts of tris(hydroxymethyl)aminomethane hydrochloride, 11 parts of triethylamine, and 55 parts of N,N-dimethylformamide were mixed, stirred for 35 minutes, and then 9 parts of phosphorus oxychloride were slowly added dropwise, and the temperature was controlled not to exceed 20°C during the addition. After the addition was completed, the temperature was raised to 100°C and kept for 9 hours to obtain intermediate A; 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.

[0037] Preparation process of modified ethylene-octene copolymer: 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 uniformly, heated to 200° C., and reacted for 25 minutes to obtain a carboxylated ethylene-octene copolymer; S2: 70 parts of carboxylated ethylene-octene copolymer, 25 parts of intermediate A, 5.5 parts of 4-dimethylaminopyridine and 5.5 parts of dihydroxymethylacetone were premixed uniformly, placed in a multifunctional torque rheometer, and fully melt-mixed at 180° C. and 50 rpm for 35 minutes to obtain a modified ethylene-octene copolymer.

[0038] 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: 170°C in the feeding section, 190°C in the plasticizing section, 200°C in the metering section, and 180°C in the die temperature; during the compounding process, the hot pressing is 170°C and the cold pressing is 5°C.

[0039] Testing experiment: (1) According to the test method specified in GB27789-2011 "Thermoplastic polyolefin (TPO) waterproofing membrane", the weather resistance of the waterproofing membranes of Examples 1-3 and Comparative Examples 1-3 was tested (heat aging at 115°C); (2) The limiting oxygen index of the waterproofing 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: Table 1

[0040] Conclusion: Examples 1-3 modify EPDM rubber and ethylene-octene copolymer to graft flame retardant segments, effectively improving the flame retardant properties of waterproof membranes; at the same time, through dehydration condensation, the surface of nano-silica has similar segments of EPDM rubber and ethylene-octene copolymer, which improves its compatibility with the matrix resin and enhances the weather resistance of the overall material. Comparative Example 1 does not add modified nano-silica, and the performance is reduced; Comparative Example 2 does not modify EPDM rubber and ethylene-octene copolymer, and the performance is reduced; Comparative Example 3 does not modify nano-silica, and the performance is reduced.

[0041] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is 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 can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A manufacturing process for a weather-resistant waterproof membrane based on modified polyolefin, characterized in that: The waterproof coiled material is composited by 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 coiled material layers.

2. 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 polyolefin coiled material 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 coiled material layer.

3. The manufacturing process of a weather-resistant waterproof membrane based on modified polyolefin according to claim 2, 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 granulated filler.

4. The manufacturing process of a weather-resistant waterproof membrane based on modified polyolefin according to claim 2, characterized in that: The preparation process of the modified EPDM rubber is: 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 diisopropylbenzene peroxide, and reacting for 1-2h to obtain carboxylated EPDM rubber; S2: Tris(hydroxymethyl)aminomethane hydrochloride, triethylamine and N,N-dimethylformamide were mixed and stirred for 30-40 minutes, and then phosphorus oxychloride was slowly added dropwise, and the temperature was controlled not to exceed 20°C during the addition. After the addition was completed, the temperature was raised to 95-100°C and kept for reaction for 8-10 hours to obtain intermediate A; 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.

5. The manufacturing process of a weather-resistant waterproof membrane based on modified polyolefin according to claim 4, characterized in that: The carboxylated EPDM rubber comprises the following components: by weight, 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 diisopropylbenzene peroxide; the intermediate A comprises the following components: by weight, 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; the modified EPDM rubber comprises the following components: by weight, 50-60 parts of carboxylated EPDM rubber, 20-25 parts of intermediate A, and 2-3 parts of triethylamine.

6. The manufacturing process of a weather-resistant waterproof membrane based on modified polyolefin according to claim 2, characterized in that: The preparation process of the modified ethylene-octene copolymer: S1: premix maleic anhydride, ethylene-octene copolymer, 2,5-bis(tert-butyl)-2,5-dimethylhexane, styrene and antioxidant 1010, heat to 180-200° C., react for 20-30 min, and obtain carboxylated ethylene-octene copolymer; S2: Carboxylated ethylene-octene copolymer, intermediate A, 4-dimethylaminopyridine and dihydroxymethyl acetone were premixed uniformly, placed in a multifunctional torque rheometer, and fully melt-mixed at 180° C. and 50 rpm for 30-40 minutes to obtain a modified ethylene-octene copolymer.

7. The manufacturing process of a weather-resistant waterproof membrane based on modified polyolefin according to claim 6, 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 dihydroxymethylacetone.

8. The manufacturing process of a weather-resistant waterproof membrane based on modified polyolefin according to claim 2, 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 rubber, heating to 150-180°C, and reacting for 30-40 minutes to obtain modified nano-silica.

9. The manufacturing process of a weather-resistant waterproof membrane based on modified polyolefin according to claim 8, 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 rubber.

10. The manufacturing process of a weather-resistant waterproof membrane based on modified polyolefin according to claim 2, characterized in that: The process parameters of the co-extrusion are: 170-190°C in the feeding section, 190-200°C in the plasticizing section, 200-210°C in the metering section, and 180-200°C in the die opening temperature.

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