High flame-retardant weather-resistant TPO waterproof coiled material and preparation method thereof

Abstract

The present application relates to a kind of high flame-retardant weather-resistant TPO waterproofing membrane, including single TPO waterproof layer, or including upper and lower two layers for TPO waterproof layer and middle for polyester fiber mesh reinforcement layer three-layer structure;The TPO waterproof layer includes by mass fraction: propylene-based elastomer 40-55 parts, polypropylene 15-25 parts, ethylene-based elastomer 4-7 parts, C5 petroleum resin 3-5 parts, compatible agent 1-2 parts, composite flame retardant 15-30 parts, titanium dioxide 2.5-5.0 parts, composite antioxidant 0.3-0.6 parts, light stabilizer 0.5-1.0 parts;The composite flame retardant is the composite of containing P, N and Si element and the composite flame retardant of carbon black simultaneously.By this, the TPO waterproofing membrane prepared in the present application has high mechanical strength, high elongation, high flame retardancy, high weather resistance, easy construction and good high-low temperature stability, etc. Excellent characteristics, waterproof and breathable simultaneously, can be applied to the waterproof layer of a variety of different substrates.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of waterproof materials, in particular to a high-flame-retardant weather-resistant TPO waterproof roll and a preparation method thereof. BACKGROUND

[0002] The thermoplastic polyolefin (TPO) waterproof roll is a new type of polymer waterproof roll, which combines the performance characteristics of the ternary ethylene-propylene waterproof roll and the polyvinyl chloride waterproof roll. Therefore, it has excellent processing performance, mechanical properties and welding performance. At the same time, since the TPO waterproof roll does not contain plasticizers and other harmful substances, it is environmentally friendly and is the preferred waterproof material for large industrial plants, public buildings and other roofs.

[0003] However, since the TPO waterproof roll is a flammable material, a flame retardant needs to be added when designing the TPO waterproof roll formula to meet the requirements of building materials for flame retardation and fire resistance. At present, the flame-retardant modification of domestic TPO waterproof roll is mainly inorganic flame retardant, and a small amount is organic bromine-based flame retardant. However, the addition of a large amount of organic bromine-based flame retardant will reduce the mechanical strength of the TPO waterproof roll and affect the low-temperature properties and hardness of the roll, increasing the difficulty of construction. In addition, organic bromine will produce toxic gases such as brominated dioxin during combustion, which has adverse effects on the human body and the environment, so inorganic flame retardants are still the mainstream. Inorganic flame retardants are used not only as flame-retardant components in TPO waterproof rolls but also as fillers and reinforcing agents. In order to improve the flame-retardant effect, a large amount of inorganic flame retardant is added, which has poor compatibility with the TPO waterproof roll, thereby greatly reducing the mechanical strength of the TPO waterproof roll, increasing the hardness and brittleness of the roll, and causing the waterproofness and use effect of the TPO roll to decrease.

[0004] In addition, due to long-term application in outdoor environments and excessive welding temperature during use, the antioxidants, light stabilizers and other additives in the TPO roll formula system are not durable, resulting in discoloration, color change, loss of surface gloss, microcracks and other phenomena in the product. In addition, due to air pollution, TPO waterproof rolls exposed to the roof have a negative impact on the TPO waterproof roll when they come into contact with contaminated rainwater. These factors can reduce the waterproof performance and service life of the TPO waterproof roll.

[0005] Therefore, it is a technical problem to be solved to improve the flame-retardant performance of the TPO waterproof roll while maintaining or as far as possible not losing its processing performance, mechanical properties, welding performance and excellent weather resistance. SUMMARY

[0006] The technical problem solved by the present application is that the present application provides a high-flame-retardant weather-resistant TPO waterproof roll material and a preparation method thereof, which overcomes the problems of existing TPO waterproof roll materials, i.e., sacrificing the mechanical strength, processing performance and welding performance of the materials to achieve high-efficiency flame retardation, and easily aging and degrading in long-term use.

[0007] To solve the above technical problems, the technical scheme adopted by the present application is as follows:

[0008] The present application provides a high-flame-retardant weather-resistant TPO waterproof roll material, which comprises a single TPO waterproof layer or a three-layer structure comprising upper and lower TPO waterproof layers and a polyester fiber mesh reinforcement layer in the middle.

[0009] The TPO waterproof layer comprises, by mass fraction:

[0010] propylene-based elastomer 40-55 parts, polypropylene 15-25 parts, ethylene-based elastomer 4-7 parts, C5 petroleum resin 3-5 parts, compatibilizer 1-2 parts, composite flame retardant 15-30 parts, titanium white 2.5-5.0 parts, composite antioxidant 0.3-0.6 parts, light stabilizer 0.5-1.0 parts.

[0011] The composite flame retardant is a composite flame retardant containing P, N and Si elements and carbon black.

[0012] The application provides a high-flame-retardant weather-resistant TPO waterproof roll material, which is prepared from a formula for preparing a TPO waterproof layer, and is prepared from a propylene-based elastomer as a base material by adding polypropylene, a vinyl-based elastomer, C5 petroleum resin, a composite flame retardant and the like, and has high mechanical strength, high elongation, high flame retardance, high weather resistance, easy construction, good high and low temperature resistance and the like, and is waterproof and breathable. The composite flame retardant contains multiple effective flame-retardant elements, and the flame-retardant elements have synergistic effects, so that the characteristics of multiple flame retardants can be combined, the amount of the flame retardant can be reduced, and the flame-retardant effect is improved. Specifically, P elements are catalyzed into carbon in the combustion process, and the inner layer of the unburned base material is protected from oxidative decomposition; N elements can generate non-combustible gases such as NH3 in the combustion process, and isolate the contact between oxygen and the base material; Si elements can form a stable SiO2 protective layer in the combustion process, and play a role in enhancing the stability of the carbon layer; and the Si elements can also have the same effect as other substituents, and play a role in improving the waterproofness, mechanical properties and compatibility of the base resin. On the other hand, a certain amount of carbon black is added to the composite flame retardant, which can partially block oxygen in the combustion process, and because an electrically conductive network can be formed, the heat generated during combustion can be quickly transferred, reducing heat accumulation, and further improving the flame retardance of the roll material. Moreover, because the composite flame retardant does not contain halogen, no harmful combustion products are generated, and it is green and environmentally friendly. The introduction of polypropylene reduces the cost of the roll material and improves the mechanical strength and adhesive strength of the roll material; the addition of the vinyl-based elastomer is beneficial to improving the tear resistance and low temperature resistance of the roll material; the use of C5 petroleum resin improves the compatibility between the components, enhances the cohesion of the roll material, and endows the roll material with good high temperature resistance and aging resistance. Through reasonable formula matching, the TPO roll material prepared by the application has high efficient flame retardant capacity, and other physical and chemical properties change little or even higher than the metal hydroxide filling system, and is widely applicable to waterproof layers of various different base materials.

[0013] Optionally, the composite flame retardant is mainly composed of Si-HP / MPP composite and carbon black in a mass ratio of (3-4):1; the Si-HP / MPP composite is prepared by modifying melamine polyphosphate ammonium with hyperbranched polymer and then coating with siloxane oligomer.

[0014] According to the above description, the composite flame retardant of the application is used in combination with Si-HP / MPP composite and carbon black in a certain proportion, and the two components synergize with each other, have good dispersibility, have better flame retardant effect, and improve the mechanical properties and thermal stability of the TPO waterproof roll material.

[0015] Optionally, the preparation method of the Si-HP / MPP composite comprises the following steps:

[0016] A1, add dioxane to melamine polyphosphate, stir until uniform, and heat to 70±10°C while continuing to stir; after the hyperbranched polymer is dissolved in N,N-dimethylacetamide, it is added to the melamine polyphosphate solution, stirred until uniform, then the pH is adjusted to 4-5 using a phosphoric acid solution, and triphenylphosphine is added, and the reaction is continued at 70±10°C for 2h, after which the HP / MPP composite is filtered, washed, and dried;

[0017] A2, the siloxane oligomer is dissolved in anhydrous ethanol, then the HP / MPP composite is added, heated to 50±5°C, and stirred for 2-3h, after which it is filtered under reduced pressure, then solidified at 40±5°C for 1h, and dried at 80°C for 2h, to obtain the Si-HP / MPP composite.

[0018] As can be seen from the above description, the Si-HP / MPP composite prepared by the application has the advantages that, since melamine polyphosphate (MPP) has strong polarity and poor compatibility with other components in the coiled material, which significantly reduces the mechanical properties of the coiled material, and the material is prone to moisture absorption and separation during application, affecting the waterproofness and comprehensive performance of the coiled material, the hyperbranched polymer is used to modify the MPP, improving the dispersibility and compatibility of the MPP with other components, and then the HP / MPP composite is coated with a siloxane resin solution synthesized by the siloxane oligomer in ethanol, which significantly improves the flame retardancy, weather resistance, and waterproofness of the composite flame retardant applied to TPO waterproof coiled material.

[0019] Optionally, in step A1, the ratio of the melamine polyphosphate to the dioxane is 0.4g / mL, the ratio of the hyperbranched polymer to the N,N-dimethylacetamide is 0.8g / mL, the mass ratio of the melamine polyphosphate to the hyperbranched polymer is (8-10):1, and the mass ratio of the triphenylphosphine to the melamine polyphosphate is (0.02-0.03):1.

[0020] In step A2, the volume ratio of the siloxane oligomer to the anhydrous ethanol is 1:1, and the ratio of the HP / MPP composite to the siloxane oligomer is 0.3g / mL.

[0021] Optionally, the hyperbranched polymer is a double-bond-terminated hyperbranched polyamide ester, and is at least one of a double-bond-terminated second-generation hyperbranched polyamide ester, a double-bond-terminated third-generation hyperbranched polyamide ester, and a double-bond-terminated fourth-generation hyperbranched polyamide ester.

[0022] According to the above description, the application adopts the double bond end-capped hyperbranched polyamide ester, on the one hand, the hyperbranched polyamide ester has a large number of polar groups inside, which can increase the compatibility between MPP and each component of the coiled material when used for MPP modification, and the hyperbranched polyamide ester has the dual effects of carbon source and gas source, and compounding with MPP is beneficial to improve the flame-retardant effect of the coiled material; on the other hand, the end of the hyperbranched polyamide ester is modified by a double bond, reducing the hydrophilic group, which has little effect on the waterproof performance of the coiled material. In addition, the hyperbranched polyamide ester has a high molecular weight, so it is not easy to migrate from the material, which can reduce the harm to the environment and the reduction of the flame-retardant efficiency caused by the migration of small molecular weight components in the composite flame retardant; at the same time, it can also reduce the damage to the mechanical properties of the material caused by the addition of the composite flame retardant.

[0023] The double bond end-capped hyperbranched polyamide ester used in the application is a second-generation double bond end-capped hyperbranched polyamide ester, and its structural formula is as follows:

[0024]

[0025] It is prepared by the following method:

[0026] (1) Synthesis of AB2 type monomer: diisopropanolamine and trimellitic anhydride are reacted to obtain AB2 type monomer;

[0027] (2) Synthesis of hyperbranched polyamide ester: AB2 type monomer and triethanolamine core molecule are reacted to obtain hyperbranched polyamide ester;

[0028] (3) Double bond end-capped hyperbranched polyamide ester: the hyperbranched polyamide ester is end-capped with methyl acrylate to obtain the double bond end-capped hyperbranched polyamide ester.

[0029] Alternatively, the compatibility agent is a maleic anhydride grafted polymer; the titanium white is rutile titanium white; the composite antioxidant is a mixture of antioxidant 1010 and antioxidant 168, and the mass ratio of antioxidant 1010 to antioxidant 168 in the composite antioxidant is (1-2):1; the light stabilizer is at least one of ultraviolet absorber UV-531, light stabilizer AM-101 and light stabilizer 744.

[0030] The application also provides a preparation method of the high-flame-retardant weather-resistant TPO waterproof coiled material.

[0031] Preparation of the homogeneous TPO waterproof coiled material: the raw materials in the TPO waterproof layer are prepared according to the mass ratio, and are mixed uniformly in a vacuum pump suction mixer; then the uniformly mixed raw materials are conveyed into a double screw extruder through a material conveying system, and are extruded, then are formed into a certain thickness by a three-roll thickness forming machine, and then are drawn, cooled, wound and packaged to obtain the finished product.

[0032] or

[0033] Preparation of the enhanced TPO waterproof roll material: two portions of each raw material in the TPO waterproof layer are prepared according to the mass fraction, and are divided into formula materials A and B, which are mixed uniformly in different mixers through vacuum pumping; then the uniformly mixed formula material A is transported into a double-screw extruder A through a material conveying system to extrude a polymer sheet A, and is compounded with a polyester fiber mesh cloth, and then is formed into a predetermined thickness through three rollers, and is compounded with a polymer sheet B (the uniformly mixed formula material B is transported into a double-screw extruder B through a material conveying system to extrude a polymer sheet B), and then is formed into a predetermined thickness through two rollers, is cooled, and then is drawn, cooled, wound, and packaged to obtain a finished product.

[0034] Optionally, the extrusion temperature is 170-230 DEG C.

[0035] The preparation method of the application has simple operation, environment-friendly raw materials, and is easy to popularize and industrialize. DETAILED DESCRIPTION

[0036] In order to better understand the above technical solutions, the specific embodiments of the application are further described below in combination with examples. The following examples are only used to more clearly illustrate the technical solutions of the application, and cannot be used to limit the protection scope of the application.

[0037] The application provides a high-flame-retardant weather-resistant TPO waterproof roll material, which comprises a single TPO waterproof layer, or a three-layer structure comprising upper and lower TPO waterproof layers and a polyester fiber mesh reinforcement layer therebetween.

[0038] The TPO waterproof layer comprises, by mass fraction:

[0039] 40-55 parts of propylene-based elastomer, 15-25 parts of polypropylene, 4-7 parts of ethylene-based elastomer, 3-5 parts of C5 petroleum resin, 1-2 parts of compatibilizer, 15-30 parts of composite flame retardant, 2.5-5.0 parts of titanium white, 0.3-0.6 parts of composite antioxidant, and 0.5-1.0 parts of light stabilizer.

[0040] The composite flame retardant is a composite flame retardant containing P, N and Si elements and carbon black.

[0041] The composite flame retardant is mainly composed of Si-HP / MPP composite and carbon black in a mass ratio of (3-4):1; the Si-HP / MPP composite is prepared by modifying melamine polyphosphate ammonium with hyperbranched polymer, and then coating with siloxane oligomer.

[0042] The preparation method of the Si-HP / MPP composite comprises the following steps:

[0043] A1, add dioxane to melamine polyphosphate, stir until uniform, and heat to 70±10°C while continuing to stir; dissolve the hyperbranched polymer in N,N-dimethylacetamide, then add to the melamine polyphosphate solution, stir until uniform, then adjust the pH to 4-5 using a phosphoric acid solution, then add triphenylphosphine, continue to react at 70±10°C for 2h, filter, wash, and dry to obtain the HP / MPP composite;

[0044] The ratio of the melamine polyphosphate to the dioxane is 0.4g / mL, the ratio of the hyperbranched polymer to the N,N-dimethylacetamide is 0.8g / mL, and the mass ratio of the melamine polyphosphate to the hyperbranched polymer is (8-10):1, and the mass ratio of the triphenylphosphine to the melamine polyphosphate is (0.02-0.03):1.

[0045] A2, dissolve the siloxane oligomer in anhydrous ethanol, then add the HP / MPP composite described above, heat to 50±5°C, stir to react for 2-3h, filter under reduced pressure, then solidify at 40±5°C for 1h, and then dry at 80°C for 2h to obtain the Si-HP / MPP composite;

[0046] The volume ratio of the siloxane oligomer to the anhydrous ethanol is 1:1, and the ratio of the HP / MPP composite to the siloxane oligomer is 0.3g / mL.

[0047] The hyperbranched polymer is a double bond-terminated hyperbranched polyamide ester, and is at least one of a double bond-terminated second-generation hyperbranched polyamide ester, a double bond-terminated third-generation hyperbranched polyamide ester, and a double bond-terminated fourth-generation hyperbranched polyamide ester.

[0048] Preferably, the double bond-terminated hyperbranched polyamide ester used is a double bond-terminated second-generation hyperbranched polyamide ester, and has the following structure:

[0049]

[0050] It is prepared by the following method:

[0051] (1) Synthesis of AB2 monomer: dissolve 192g (1.0mol) of trimellitic anhydride in 900mL of N,N-dimethylacetamide; add 133g (1.0mol) of diisopropanolamine to the reactor, then add 700mL of N,N-dimethylacetamide to dissolve it, stir and use nitrogen to remove air from the reactor, then add the dissolved trimellitic anhydride solution to the reactor dropwise, and react at room temperature for 5h to obtain the monomer, which has the following structure:

[0052]

[0053] (2) Synthesis of hyperbranched polyamide ester: 16.6 g (0.11 mol) of triethanolamine is added to the above monomer as a core molecule, 1.2 g of p-toluenesulfonic acid is added as a catalyst, 1200 mL of toluene is added as a water-carrying agent, and the reaction is carried out at 135 DEG C until no water is generated, to obtain a second-generation hyperbranched polyamide ester, the structural formula of which is as follows:

[0054]

[0055] (3) Double bond terminated hyperbranched polyamide ester: 115 g of methyl acrylate is added to the above second-generation hyperbranched polyamide ester, 2.29 g of p-toluenesulfonic acid is added as a catalyst, 1.38 g of hydroquinone is added as a polymerization inhibitor, and the condensation reflux is carried out at 95 DEG C for 12 h, and the solvent is removed by distillation under reduced pressure, to obtain the double bond terminated second-generation hyperbranched polyamide ester.

[0056] The compatilizer is a maleic anhydride grafted polymer; the titanium white is a rutile titanium white; the composite antioxidant is a mixture of antioxidant 1010 and antioxidant 168, the mass ratio of antioxidant 1010 and antioxidant 168 in the composite antioxidant is (1-2):1; and the light stabilizer is at least one of ultraviolet absorber UV-531, light stabilizer AM-101 and light stabilizer 744.

[0057] The application further provides a preparation method of the high-flame-retardant weather-resistant TPO waterproof coiled material.

[0058] Preparation of the homogeneous TPO waterproof coiled material: the raw materials in the TPO waterproof layer are prepared according to the mass ratio, and are mixed uniformly in a mixing machine through a vacuum pump; then the uniformly mixed raw materials are conveyed into a double-screw extruder through a material conveying system to be extruded at a temperature of 170 DEG C-230 DEG C, and are then formed into a sheet through a three-roller thickness forming machine, and are subsequently drawn, cooled, wound and packaged to obtain a finished product.

[0059] Or

[0060] Preparation of the reinforced TPO waterproof coiled material: the raw materials in the TPO waterproof layer are prepared according to the mass ratio in two portions, and are divided into formula A and B; the formula A is mixed uniformly in a mixing machine through a vacuum pump; then the uniformly mixed formula A is conveyed into a double-screw extruder A through a material conveying system to be extruded at a temperature of 170 DEG C-230 DEG C to obtain a polymer sheet A, and is then compounded with a polyester fiber mesh cloth, and is then formed into a sheet through a three-roller thickness forming machine, and is then compounded with a polymer sheet B (the uniformly mixed formula B is conveyed into a double-screw extruder B through a material conveying system to be extruded at a temperature of 170 DEG C-230 DEG C to obtain the polymer sheet B), and is then formed into a sheet through a two-roller thickness forming machine, and is then cooled, drawn, wound and packaged to obtain a finished product.

[0061] In the following examples, the propylene-based elastomer uses Dow Chemical versify 2300 or Mobil Vistamaxx 6102; the polypropylene uses K8003; the ethylene-based elastomer uses Dow Engage 8150; the C5 petroleum resin uses Kravitz Wingtack 98; the compatibilizer uses Basell HDPE Plexar PX2246; the titanium white powder uses Chun Tai R-105; the composite antioxidant uses BASF B225; the light stabilizer uses BASF light stabilizer 2020; the siloxane oligomer uses SHINETSU silicone oligomer KR-513.

[0062] Example 1

[0063] A high-flame-retardant weather-resistant TPO waterproof roll material, the roll material structure is a three-layer structure with two TPO waterproof layers on the top and bottom and a polyester fiber mesh reinforcement layer in the middle;

[0064] The TPO waterproof layer comprises, by mass fraction:

[0065] 40 parts of propylene-based elastomer (Dow Chemical versify 2300), 25 parts of polypropylene, 6 parts of ethylene-based elastomer, 5 parts of C5 petroleum resin, 1 part of compatibilizer (maleic anhydride grafted polymer), 23 parts of composite flame retardant, 2.5 parts of rutile titanium white powder, 0.5 parts of composite antioxidant, and 0.5 parts of light stabilizer;

[0066] The composite flame retardant is a composite flame retardant containing P, N and Si elements and carbon black.

[0067] The composite flame retardant is mainly composed of Si-HP / MPP composite and carbon black in a mass ratio of 4:1; the Si-HP / MPP composite is prepared by modifying melamine polyphosphate with a double bond-terminated second-generation hyperbranched polyamide ester and then coating with a siloxane oligomer.

[0068] The preparation method of the Si-HP / MPP composite comprises the following steps:

[0069] A1, 200 mL of dioxane is added to 80 g of melamine polyphosphate, stirred uniformly, and heated to 70°C for continuous stirring; 10 g of double bond-terminated second-generation hyperbranched polyamide ester is dissolved in 12.5 mL of N,N-dimethylacetamide, then added to the melamine polyphosphate solution, stirred uniformly, and then the pH value is adjusted to 5 using a phosphoric acid solution, and 1.6 g of triphenylphosphine is added, and the reaction is continued at 70°C for 2 h, and then filtered, washed and dried to obtain the HP / MPP composite.

[0070] A2, 100 mL of silicone oligomer was added to 100 mL of anhydrous ethanol for dissolution, then 30 g of the HP / MPP composite described above was added, heated to 50°C, and stirred for 3 h, then filtered under reduced pressure, and then solidified at 40°C for 1 h, and then dried at 80°C for 2 h to obtain a Si-HP / MPP composite.

[0071] The preparation method of the enhanced TPO waterproof roll material comprises the following steps:

[0072] S1, raw material premixing: the raw materials in the TPO waterproof layer were prepared in two parts according to the mass fraction ratio, and were divided into formula A and B. They were respectively sucked into different mixers by vacuum pump, and were respectively high-mixed for 5 min, and then were respectively preheated to 50°C for 3 min, and then were respectively low-mixed for 3 min, and were uniformly mixed.

[0073] S2, extrusion molding: the power of the double-screw extruder A and the double-screw extruder B was turned on, the extruder temperature was set to 190-220°C, the screen changer and flow channel temperature was set to 210-230°C, the die head temperature was set to 190-220°C, and the three-roll temperature was set to 30-60°C. After the temperature reached the set temperature, it was continuously maintained for 90-120 min.

[0074] Then the uniformly mixed formula A was transported into the double-screw extruder A through the material conveying system to extrude the polymer sheet A (which was the upper TPO waterproof layer after subsequent processing), and then the polymer sheet B (the uniformly mixed formula B was transported into the double-screw extruder B through the material conveying system to extrude the polymer sheet B (which was the lower TPO waterproof layer after subsequent processing) at a temperature of 190-220°C) was calendered and compounded, and then was two-roll thickness forming and cooling.

[0075] S3, internal stress treatment: the molded waterproof roll material was pulled by the traction roller, and was pulled to the internal stress treatment section, and was cross-pulled 4 times by 4 groups of 80°C high-temperature rollers and 4 groups of 10°C low-temperature rollers for sheet treatment, shaping, and eliminating internal stress in the sheet.

[0076] S4, roll winding: the treated waterproof roll material was dried and cooled, and was pulled and wound.

[0077] Among them, the upper and lower TPO waterproof layers were according to the provisions of GB 27789-2011, and the product specification was 1.2 mm, so as to facilitate the detection of various properties.

[0078] Example 2

[0079] The main difference between this example and Example 1 is that the addition amount of each component is different.

[0080] A kind of high flame-retardant weather-resistant TPO waterproof roll material, roll material structure is the three-layer structure of upper and lower two layers being TPO waterproof layer and middle being polyester fiber mesh reinforcement layer;

[0081] The TPO waterproof layer includes, by mass parts:

[0082] Propylene-based elastomer (mobil vistamaxx6102) 46 parts, polypropylene 15 parts, ethylene-based elastomer 4 parts, C5 petroleum resin 3 parts, compatible agent (maleic anhydride graft polymer) 2 parts, composite flame retardant 30 parts, rutile titanium dioxide 5 parts, composite antioxidant 0.3 parts, light stabilizer 0.5 parts;

[0083] The composite flame retardant is a composite containing P, N and Si elements and carbon black.

[0084] The composite flame retardant is mainly composed of Si-HP / MPP composite and carbon black in a mass ratio of 3:1;The Si-HP / MPP composite is prepared by modifying melamine polyphosphate with double bond terminated second generation hyperbranched polyamide ester and then coating with siloxane oligomer.

[0085] The preparation method of the Si-HP / MPP composite includes the following steps:

[0086] A1, 250mL dioxane is added to 100g melamine polyphosphate, stirred uniformly, heated to 70℃ and continued to stir;10g double bond terminated second generation hyperbranched polyamide ester is added to 12.5mL N, N-dimethylacetamide, dissolved, then added to the melamine polyphosphate solution, stirred uniformly, then the pH value is adjusted to 5 using phosphoric acid solution, and then 3g triphenylphosphine is added, and the reaction is continued at 70℃ for 2h, filtered, washed and dried to obtain HP / MPP composite.

[0087] A2, 100mL siloxane oligomer is added to 100mL anhydrous ethanol to dissolve, then 30g HP / MPP composite is added, heated to 50℃, stirred for 3h, reduced pressure filtration, then solidified at 40℃ for 1h, and then dried at 80℃ for 2h to obtain Si-HP / MPP composite.

[0088] Example 3

[0089] The main difference between this embodiment and example 1 is that the addition amount of each component is different.

[0090] A kind of high flame-retardant weather-resistant TPO waterproof roll material, roll material structure is the three-layer structure of upper and lower two layers being TPO waterproof layer and middle being polyester fiber mesh reinforcement layer;

[0091] The TPO waterproof layer includes, by mass parts:

[0092] propylene-based elastomer (mobil vistamaxx 6102) 55 parts, polypropylene 18 parts, ethylene-based elastomer 7 parts, C5 petroleum resin 4 parts, compatibilizer (maleic anhydride grafted polymer) 1 part, composite flame retardant 15 parts, rutile titanium dioxide 3 parts, composite antioxidant 0.6 parts, light stabilizer 0.6 parts;

[0093] The composite flame retardant is a composite flame retardant containing P, N and Si elements and carbon black.

[0094] The composite flame retardant is mainly composed of Si-HP / MPP composite and carbon black in a mass ratio of 4:1; the Si-HP / MPP composite is prepared by modifying melamine polyphosphate with a second-generation hyperbranched polyamide ester capped with double bonds, and then coated with a siloxane oligomer.

[0095] The preparation method of the Si-HP / MPP composite is the same as that in Example 2.

[0096] Example 4

[0097] The main difference between this embodiment and Example 1 is that the addition amount of each component is different.

[0098] A high-flame-retardant weather-resistant TPO waterproof roll material, the roll material structure is a three-layer structure with TPO waterproof layers on the upper and lower layers and a polyester fiber mesh reinforcement layer in the middle;

[0099] The TPO waterproof layer comprises, by mass fraction:

[0100] propylene-based elastomer (mobil vistamaxx 6102) 48.5 parts, polypropylene 16.7 parts, ethylene-based elastomer 5.4 parts, C5 petroleum resin 4.3 parts, compatibilizer (maleic anhydride grafted polymer) 1.7 parts, composite flame retardant 23.4 parts, rutile titanium dioxide 4.5 parts, composite antioxidant 0.3 parts, light stabilizer 0.5 parts;

[0101] The composite flame retardant is a composite flame retardant containing P, N and Si elements and carbon black.

[0102] The composite flame retardant is mainly composed of Si-HP / MPP composite and carbon black in a mass ratio of 4:1; the Si-HP / MPP composite is prepared by modifying melamine polyphosphate with a second-generation hyperbranched polyamide ester capped with double bonds, and then coated with a siloxane oligomer.

[0103] The preparation method of the Si-HP / MPP composite is the same as that in Example 2.

[0104] Comparative Example 1

[0105] The main difference between this comparative example and Example 4 is that the composite flame retardant is replaced by 40 parts of 3000 mesh magnesium hydroxide.

[0106] Comparative Example 2

[0107] The main difference between this comparative example and Example 4 is that the Si-HP / MPP composite in this comparative example is used as the flame retardant alone (i.e. without carbon black).

[0108] Comparative Example 3

[0109] The main difference between this comparative example and Example 4 is that the flame retardant in this comparative example is directly mixed from melamine polyphosphate, second generation hyperbranched polyamide ester capped with double bonds, siloxane oligomer and carbon black in a mass ratio of 10:1:1:3.

[0110] Comparative Example 4

[0111] The main difference between this comparative example and Example 4 is that the composite flame retardant in this comparative example is composed of Si-MPP composite and carbon black in a mass ratio of 4:1 (i.e. without modification by hyperbranched polyamide ester capped with double bonds).

[0112] The Si-MPP composite is prepared by dissolving 100 mL of siloxane oligomer in 100 mL of anhydrous ethanol, then adding 30 g of melamine polyphosphate, heating to 50°C, stirring for 3 h, vacuum filtration, then solidifying at 40°C for 1 h, and then drying at 80°C for 2 h.

[0113] Comparative Example 5

[0114] The main difference between this comparative example and Example 4 is that the C5 petroleum resin is not included in this comparative example, and the amount of vinyl elastomer is modified to 9.7 parts.

[0115] The TPO waterproofing membranes prepared in Examples 1-4 and Comparative Examples 1-5 above are tested for performance according to GB 27789-2011, and the results are recorded in Table 1 and Table 2.

[0116] Table 1 Performance test results of TPO waterproofing membranes prepared in Examples

[0117]

[0118] Table 2 Performance test results of TPO waterproofing membranes prepared in Comparative Examples

[0119]

[0120]

[0121] As can be seen from Table 1, the weather-resistant TPO waterproofing membrane prepared in Examples 1-4 of the present application has high tensile strength, elasticity, high and low temperature stability, excellent aging resistance, waterproofness and flame retardancy, low water absorption, and is environmentally friendly. As can be seen from the data in Table 2, compared with Comparative Example 1, the TPO waterproofing membrane prepared by using the composite flame retardant of the present application has significantly better comprehensive performance than the metal oxide flame retardant system; compared with Comparative Example 2, the use of carbon black can further improve the thermal stability, mechanical strength and flame retardancy of the present application; compared with Comparative Example 3, the flame retardant prepared by directly mixing raw materials has lower mechanical strength, weather resistance and flame retardancy than Example 4; compared with Comparative Example 4, the modification of melamine ammonium polyphosphate by introducing double bond-terminated hyperbranched polyamide ester can improve the flame retardancy and aging resistance of the membrane, and can also enhance the bonding force between the components of the membrane, improve the mechanical strength and toughness of the membrane; as can be seen from the comparison between Example 4 and Comparative Example 5, C5 petroleum resin can further improve the comprehensive performance of the TPO waterproofing membrane.

[0122] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application, and not to limit them; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A high flame resistant weatherable TPO waterproofing membrane characterized in that, The TPO waterproof layer comprises, by mass fraction: The TPO waterproof layer comprises, by mass fraction: propylene-based elastomer 40-55 parts, polypropylene 15-25 parts, vinyl-based elastomer 4-7 parts, C5 petroleum resin 3-5 parts, compatibilizer 1-2 parts, composite flame retardant 15-30 parts, titanium white 2.5-5.0 parts, composite antioxidant 0.3-0.6 parts, light stabilizer 0.5-1.0 parts; The composite flame retardant is a composite flame retardant containing P, N and Si elements and carbon black. The composite flame retardant is mainly composed of Si-HP / MPP composite and carbon black in a mass ratio of (3-4):1; the Si-HP / MPP composite is prepared by modifying melamine polyphosphate with hyperbranched polymer and then coating with siloxane oligomer.

2. The high flame retardant weatherable TPO waterproofing membrane of claim 1, wherein, The preparation method of the Si-HP / MPP composite comprises the following steps: A1, add dioxane to melamine polyphosphate, stir uniformly, and continue to stir at 70±10℃; dissolve the hyperbranched polymer in N,N-dimethylacetamide, then add to the melamine polyphosphate solution, stir uniformly, then adjust the pH value to 4-5 with phosphoric acid solution, then add triphenylphosphine, continue to react at 70±10℃ for 2h, filter, wash and dry to obtain HP / MPP composite; A2, dissolve siloxane oligomer in anhydrous ethanol, then add the HP / MPP composite, heat to 50±5℃, stir for 2-3h, reduce pressure and filter, then solidify at 40±5℃ for 1h, and then dry at 80℃ for 2h to obtain Si-HP / MPP composite.

3. The high flame retardant weatherable TPO waterproofing membrane of claim 2, wherein, In step A1, the ratio of the melamine polyphosphate to the dioxane is 0.4g / mL, the ratio of the hyperbranched polymer to the N,N-dimethylacetamide is 0.8g / mL, the mass ratio of the melamine polyphosphate to the hyperbranched polymer is (8-10):1, and the mass ratio of the triphenylphosphine to the melamine polyphosphate is (0.02-0.03):1; In step A2, the volume ratio of the siloxane oligomer to the anhydrous ethanol is 1:1, and the ratio of the HP / MPP composite to the siloxane oligomer is 0.3g / mL.

4. The high flame retardant weatherable TPO waterproofing membrane of any one of claims 1-3, wherein, The hyperbranched polymer is a double bond terminated hyperbranched polyamide ester, which is at least one of a second generation double bond terminated hyperbranched polyamide ester, a third generation double bond terminated hyperbranched polyamide ester and a fourth generation double bond terminated hyperbranched polyamide ester.

5. The high flame retardant weatherable TPO waterproofing membrane of claim 1, wherein, The compatibilizer is a maleic anhydride grafted polymer; the titanium white is rutile titanium white; the composite antioxidant is a mixture of antioxidant 1010 and antioxidant 168, and the mass ratio of antioxidant 1010 to antioxidant 168 in the composite antioxidant is (1-2):1; and the light stabilizer is at least one of ultraviolet absorber UV-531, light stabilizer AM-101 and light stabilizer 744.

6. A method for preparing the high-flame-retardant weather-resistant TPO waterproof roll material according to claim 1, comprising the following steps: Preparation of the homogeneous TPO waterproof roll material: the raw materials in the TPO waterproof layer are prepared in mass parts, and are mixed uniformly in a mixing machine through vacuum pumping; then the uniformly mixed raw materials are transported into a double-screw extruder through a material conveying system for extrusion, and are then subjected to three-roller thickness forming, followed by traction, cooling, winding, and packaging to obtain the finished product. Or Preparation of the reinforced TPO waterproof roll material: the raw materials in the TPO waterproof layer are prepared in two mass parts, and are divided into formula A and B; the formula A and B are mixed uniformly in different mixing machines through vacuum pumping; then the uniformly mixed formula A is transported into a double-screw extruder A through a material conveying system for extruding a polymer sheet A, and is then compounded with a polyester fiber mesh cloth; after three-roller thickness forming, the polymer sheet A is compounded with a polymer sheet B (the uniformly mixed formula B is transported into a double-screw extruder B through a material conveying system for extruding a polymer sheet B); then the polymer sheet B is subjected to two-roller thickness forming, cooling, traction, cooling, winding, and packaging to obtain the finished product.

7. The method for preparing the high flame-retardant and weather-resistant TPO waterproof membrane as described in claim 6, characterized in that, The extrusion temperature is 170-230°C.

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