High-temperature-resistant polyolefin waterproof coiled material and preparation method thereof

Abstract

The invention relates to the technical field of waterproof coiled materials, and particularly discloses a high-temperature-resistant polyolefin waterproof coiled material and a preparation method thereof. The high-temperature-resistant polyolefin waterproof coiled material is prepared from polypropylene, linear low-density polyethylene, low-density polyethylene, an ethylene-octene copolymer, polyimide cyclosiloxane-ammonium polyphosphate, maleic anhydride grafted polypropylene and an auxiliary agent through melt blending, extrusion granulation and hot press molding. Compared with a common polyolefin waterproof coiled material, the polyolefin waterproof coiled material has more excellent mechanical performance and high temperature resistance, and meets higher industrial requirements.

Description

Technical Field

[0001] The invention relates to the technical field of waterproof coiled materials, in particular to a high temperature resistant polyolefin waterproof coiled material and a preparation method thereof. Background Art

[0002] Waterproofing membrane is a flexible waterproofing product for buildings that can be bent and formed into a roll. It can resist the penetration of rainwater and moisture in the air into the wall. It is widely used in building roofs, bridges, tunnels, viaducts and other places. Polyolefin waterproofing membrane is a polymer waterproofing membrane with good comprehensive performance. It is obtained by organic copolymerization. The atomic distribution is relatively uniform. It has the advantages of good sealing, good waterproofing, low density, and the ability to maintain toughness and waterproofing at low temperatures. Polyolefin waterproofing membrane has excellent performance and brings a lot of convenience to people. However, it belongs to polyolefin polymers, has thermoplasticity, is not resistant to high temperatures, is easy to melt at high temperatures, produces molten droplets, and is flammable. Once a fire occurs, the fire is very easy to spread, causing losses to people. Therefore, it is imperative to enhance the high temperature resistance of polyolefin waterproofing membrane. Summary of the invention

[0003] The purpose of the present invention is to provide a high temperature resistant polyolefin waterproofing membrane and a preparation method thereof, so as to solve the problem that the high temperature resistance of common polyolefin waterproofing membrane is not good enough.

[0004] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0005] A method for preparing a high temperature resistant polyolefin waterproof coiled material, characterized in that the preparation method comprises:

[0006] Polypropylene, linear low-density polyethylene, low-density polyethylene, ethylene-octene copolymer, polyimide cyclosiloxane-ammonium polyphosphate, maleic anhydride grafted polypropylene and additives are dried at 65-75°C for 3-5 hours, melt-blended at 160-200°C, extruded into granules, dried at 70-90°C for 3-5 hours, and hot-pressed at 150-170°C and 4-6MPa to obtain a high-temperature resistant polyolefin waterproof membrane.

[0007] As a limitation of the present invention, the amount of each raw material used in the preparation process of the high-temperature resistant polyolefin waterproof membrane is: by mass, 46-50 parts of polypropylene, 70-74 parts of low-density polyethylene, 40-44 parts of low-density polyethylene, 25-27 parts of ethylene-octene copolymer, 20-24 parts of polyimide cyclosiloxane-ammonium polyphosphate, 9-11 parts of maleic anhydride grafted polypropylene, and 6-10 parts of additives.

[0008] As a limitation of the present invention, the preparation method of polyimide cyclosiloxane-ammonium polyphosphate is:

[0009] Mix 2.9-3.1 parts of bisphenol A diether dianhydride and 105-106 parts of glacial acetic acid by mass to obtain a bisphenol A diether dianhydride solution, slowly add allylamine to the bisphenol A diether dianhydride solution at -5-0°C and 50-70rpm, heat to 25-30°C, react for 1-2h, heat to 98-102°C, react for 11-13h, cool after the reaction, add 180-220 parts of deionized water, filter, wash with deionized water, and vacuum dry to obtain bisphenol A diether diene;

[0010] By weight, under nitrogen as a protective gas, bisphenol A type diether diene, tetrahydrofuran and chloroplatinic acid are mixed, the temperature is raised to 55-65° C., reacted for 25-35 minutes, tetramethyl disiloxane is added, reacted for 7-9 hours, cooled, tetrahydrofuran is removed by vacuum distillation, filtered, and the filter residue is dissolved in 98-102 parts of ethanol, stirred evenly, to obtain a polyimide cyclosiloxane ethanol solution;

[0011] By mass, 9 to 11 parts of ammonium polyphosphate are dissolved in 19 to 20 parts of ethanol to obtain an ammonium polyphosphate solution, the polyimide cyclosiloxane ethanol solution and the ammonium polyphosphate solution are evenly mixed, reacted at 35 to 45° C. and 25 to 35 rpm for 2 to 4 hours, filtered under reduced pressure, and dried to obtain polyimide cyclosiloxane-ammonium polyphosphate.

[0012] As a limitation of the present invention, the preparation method of the maleic anhydride grafted polypropylene is:

[0013] Polypropylene, maleic anhydride, styrene and high-density polyethylene are uniformly mixed and extruded through a twin-screw extruder at an extrusion temperature of 140-190° C. and a screw speed of 140-160 rpm to obtain maleic anhydride grafted polypropylene.

[0014] As a limitation of the present invention, the preparation method of the auxiliary agent is:

[0015] By weight, 14 to 16 parts of dicumyl peroxide, 3 to 5 parts of pentaerythritol stearate, 6 to 8 parts of antioxidant, 27 to 29 parts of plasticizer and 9 to 11 parts of calcium stearate are uniformly mixed to obtain an auxiliary agent.

[0016] As a limitation of the present invention, the mass ratio of the allylamine to the bisphenol A diether dianhydride solution is (0.72-0.73):(108-109).

[0017] As a limitation of the present invention, the mass ratio of the bisphenol A type diether diene to tetrahydrofuran, chloroplatinic acid and tetramethyldisiloxane is (4.9-5.1):(88-90):(1.8-2.0):(0.98-0.99).

[0018] As a limitation of the present invention, the mass ratio of the polyimide cyclosiloxane ethanol solution to the ammonium polyphosphate solution is (0.9-1.1):(0.7-0.8).

[0019] As a limitation of the present invention, the amounts of the various substances required in the preparation process of maleic anhydride grafted polypropylene are: 38-42 parts of polypropylene, 0.7-0.9 parts of maleic anhydride, 4-6 parts of styrene, and 0.1-0.3 parts of high-density polyethylene, by mass.

[0020] The beneficial effects achieved by the present invention are:

[0021] Ammonium polyphosphate is an inorganic flame retardant and also an intumescent flame retardant. It has both acid and carbon sources, and a high content of N and P elements. It also has the advantages of good thermal stability, less smoke and dust, and non-toxicity. However, when APP is directly added to polymers as an inorganic substance, it has poor compatibility and is easy to absorb moisture in the air, which then migrates to the surface of the material and causes loss, thereby reducing the mechanical properties and flame retardant efficiency of the polymer.

[0022] Ordinary polyolefins have poor heat resistance and cannot meet industrial needs. Polyolefins can be cross-linked and modified. Cross-linking and modification with polysiloxane can not only greatly improve the heat resistance of polyolefins, but also improve mechanical properties, electrical properties and other properties to a certain extent. The bond length of the silicon-oxygen bond in polysiloxane is long and the bond angle is large. Therefore, the bond energy of the silicon-oxygen bond of polysiloxane is much greater than the bond energy of the carbon-oxygen bond and the bond energy of the carbon-carbon bond in the polymer, showing good flame retardancy, hydrophobicity and thermal stability, and when used in combination with traditional flame retardants, it shows significant synergistic effects. After ammonium polyphosphate is microencapsulated by polysiloxane, the silicon-oxygen-silicon bond in polysiloxane can be grafted to the surface of ammonium polyphosphate to improve the hydrophobicity, thermal stability and compatibility of ammonium polyphosphate with the polymer matrix, which also plays an important role in improving the flame retardant properties of composite materials.

[0023] Polyimide is a polymer with excellent high and low temperature resistance, radiation resistance, and mechanical properties due to its unique imide ring structure. By adding the imide ring structure to the polysiloxane system, an imide ring-containing polysiloxane with the structural advantages of the two compounds can be obtained. Using bisphenol A diether dianhydride and allylamine to prepare a polysiloxane containing an imide ring structure through a series of reactions and adding it to the polymer can further improve the mechanical properties, high temperature resistance and other properties of the polymer.

[0024] Since polypropylene is a non-polar material, it has poor compatibility with inorganic materials and polar materials, resulting in deterioration of the performance of the modified polymer. Therefore, it is usually necessary to add a compatibilizer such as maleic anhydride grafted polypropylene to improve the compatibility between them. The preparation of maleic anhydride grafted polypropylene usually adopts the melt extrusion grafting method. During the preparation process, if the second monomer is not added, the grafting rate of the product is generally low, and PP is prone to excessive degradation. However, the polyethylene structure is stable, not easy to degrade, and has a certain grafting activity. After adding high-density polyethylene, the side reactions of the grafting reaction are suppressed, the crystallization peak of polypropylene grafted maleic anhydride is increased, the formation of polypropylene β crystals is promoted, and the grafting rate of polypropylene grafted maleic anhydride products is improved. DETAILED DESCRIPTION

[0025] The following is a preferred implementation of the embodiment of the present invention. Obviously, the described embodiment is only a part of the embodiment of the present invention, not all of the embodiments. For ordinary technicians in this technical field, all other embodiments obtained by ordinary technicians in this field without creative work without departing from the principle of the embodiment of the present invention are within the scope of protection of the present invention.

[0026] Linear low-density polyethylene (DFDA7042), low-density polyethylene (2426H), high-density polyethylene (TR580M) and polypropylene (M700) were provided by Sinopec Maoming, ethylene-octene copolymer (8150) was provided by Dow Chemical, USA, ammonium polyphosphate (n=1000) was provided by Jinan Jinyingtai, antioxidant 1010 (R150166) and plasticizer DOP (R004097) were provided by Shanghai Yien.

[0027] Embodiment 1: A method for preparing a high temperature resistant polyolefin waterproofing membrane, specifically:

[0028] Step 1: Preparation of bisphenol A diether diene

[0029] By mass, 3.0 parts of bisphenol A diether dianhydride and 105.5 parts of glacial acetic acid were mixed to obtain a bisphenol A diether dianhydride solution, 0.725 parts of allylamine were slowly added to 108.5 parts of bisphenol A diether dianhydride solution at -2°C and 60rpm, the temperature was raised to 27°C, the reaction was carried out for 1.5h, the temperature was raised to 100°C, the reaction was carried out for 12h, the reaction was completed, and the reaction was cooled, 200 parts of deionized water were added, the mixture was filtered, the mixture was washed with deionized water, and the mixture was dried in vacuo to obtain bisphenol A diether diene.

[0030] Step 2: Preparation of polyimide cyclosiloxane ethanol solution

[0031] By mass, under nitrogen as a protective gas, 5.0 parts of bisphenol A type diether diene, 89 parts of tetrahydrofuran and 1.9 parts of chloroplatinic acid were mixed, the temperature was raised to 55-65°C, and after reacting for 30 minutes, 0.985 parts of tetramethyldisiloxane were added, and the reaction was carried out for 8 hours. The mixture was cooled, and the tetrahydrofuran was removed by distillation under reduced pressure. The mixture was filtered, and the filter residue was dissolved with 100 parts of ethanol and stirred evenly to obtain a polyimide cyclosiloxane ethanol solution.

[0032] Step 3: Preparation of polyimide cyclosiloxane-ammonium polyphosphate

[0033] By mass, 10 parts of ammonium polyphosphate were dissolved in 19.5 parts of ethanol to obtain an ammonium polyphosphate solution, 1.0 parts of polyimide cyclosiloxane ethanol solution and 0.75 parts of ammonium polyphosphate solution were mixed evenly, reacted at 35-45° C. and 25-35 rpm for 2-4 hours, filtered under reduced pressure, and dried to obtain polyimide cyclosiloxane-ammonium polyphosphate.

[0034] Step 4: Preparation of maleic anhydride grafted polypropylene

[0035] 40 parts of polypropylene, 0.8 parts of maleic anhydride, 5 parts of styrene and 0.2 parts of high-density polyethylene were uniformly mixed and extruded by a twin-screw extruder at an extrusion temperature of 170° C. and a screw speed of 150 rpm to obtain maleic anhydride grafted polypropylene.

[0036] Step 5: Prepare the additive

[0037] By weight, 15 parts of dicumyl peroxide, 4 parts of pentaerythritol stearate, 7 parts of antioxidant 1010, 28 parts of plasticizer, and 10 parts of calcium stearate were uniformly mixed to obtain an auxiliary agent.

[0038] Step 6: Prepare high temperature resistant polyolefin waterproof membrane

[0039] 48 parts of polypropylene, 72 parts of linear low-density polyethylene, 42 parts of low-density polyethylene, 26 parts of ethylene-octene copolymer, 22 parts of polyimide cyclosiloxane-ammonium polyphosphate, 10 parts of maleic anhydride grafted polypropylene, and 8 parts of additives were dried at 70°C for 4 hours, melt-blended at 180°C, extruded into granules, dried at 80°C for 4 hours, and hot-pressed at 160°C and 5MPa to obtain a high-temperature resistant polyolefin waterproof membrane.

[0040] Embodiment 2: A method for preparing a high temperature resistant polyolefin waterproofing membrane, specifically:

[0041] Step 1: Preparation of bisphenol A diether diene

[0042] By mass, 3.0 parts of bisphenol A diether dianhydride and 105.5 parts of glacial acetic acid were mixed to obtain a bisphenol A diether dianhydride solution, 0.725 parts of allylamine were slowly added to 108.5 parts of bisphenol A diether dianhydride solution at -2°C and 60rpm, the temperature was raised to 27°C, the reaction was carried out for 1.5h, the temperature was raised to 100°C, the reaction was carried out for 12h, the reaction was completed, and the reaction was cooled, 200 parts of deionized water were added, the mixture was filtered, the mixture was washed with deionized water, and the mixture was dried in vacuo to obtain bisphenol A diether diene.

[0043] Step 2: Preparation of polyimide cyclosiloxane ethanol solution

[0044] By mass, under nitrogen as a protective gas, 5.0 parts of bisphenol A type diether diene, 89 parts of tetrahydrofuran and 1.9 parts of chloroplatinic acid were mixed, the temperature was raised to 55-65°C, and after reacting for 30 minutes, 0.985 parts of tetramethyldisiloxane were added, and the reaction was carried out for 8 hours. The mixture was cooled, and the tetrahydrofuran was removed by distillation under reduced pressure. The mixture was filtered, and the filter residue was dissolved with 100 parts of ethanol and stirred evenly to obtain a polyimide cyclosiloxane ethanol solution.

[0045] Step 3: Preparation of polyimide cyclosiloxane-ammonium polyphosphate

[0046] By mass, 10 parts of ammonium polyphosphate were dissolved in 19.5 parts of ethanol to obtain an ammonium polyphosphate solution, 1.0 parts of polyimide cyclosiloxane ethanol solution and 0.75 parts of ammonium polyphosphate solution were mixed evenly, reacted at 35-45° C. and 25-35 rpm for 2-4 hours, filtered under reduced pressure, and dried to obtain polyimide cyclosiloxane-ammonium polyphosphate.

[0047] Step 4: Preparation of maleic anhydride grafted polypropylene

[0048] 40 parts of polypropylene, 0.8 parts of maleic anhydride, 5 parts of styrene and 0.2 parts of high-density polyethylene were uniformly mixed and extruded by a twin-screw extruder at an extrusion temperature of 170° C. and a screw speed of 150 rpm to obtain maleic anhydride grafted polypropylene.

[0049] Step 5: Prepare the additive

[0050] By weight, 15 parts of dicumyl peroxide, 4 parts of pentaerythritol stearate, 7 parts of antioxidant 1010, 28 parts of plasticizer, and 10 parts of calcium stearate were uniformly mixed to obtain an auxiliary agent.

[0051] Step 6: Prepare high temperature resistant polyolefin waterproof membrane

[0052] 46 parts of polypropylene, 70 parts of linear low-density polyethylene, 40 parts of low-density polyethylene, 25 parts of ethylene-octene copolymer, 9 parts of polyimide cyclosiloxane-ammonium polyphosphate, 20 parts of maleic anhydride grafted polypropylene, and 6 parts of additives were dried at 70°C for 4 hours, melt-blended at 180°C, extruded into granules, dried at 80°C for 4 hours, and hot-pressed at 160°C and 5MPa to obtain a high-temperature resistant polyolefin waterproof membrane.

[0053] Embodiment 3: A method for preparing a high temperature resistant polyolefin waterproofing membrane, specifically:

[0054] Step 1: Preparation of bisphenol A diether diene

[0055] By mass, 3.0 parts of bisphenol A diether dianhydride and 105.5 parts of glacial acetic acid were mixed to obtain a bisphenol A diether dianhydride solution, 0.725 parts of allylamine were slowly added to 108.5 parts of bisphenol A diether dianhydride solution at -2°C and 60rpm, the temperature was raised to 27°C, the reaction was carried out for 1.5h, the temperature was raised to 100°C, the reaction was carried out for 12h, the reaction was completed, and the reaction was cooled, 200 parts of deionized water were added, the mixture was filtered, the mixture was washed with deionized water, and the mixture was dried in vacuo to obtain bisphenol A diether diene.

[0056] Step 2: Preparation of polyimide cyclosiloxane ethanol solution

[0057] By mass, under nitrogen as a protective gas, 5.0 parts of bisphenol A type diether diene, 89 parts of tetrahydrofuran and 1.9 parts of chloroplatinic acid were mixed, the temperature was raised to 55-65°C, and after reacting for 30 minutes, 0.985 parts of tetramethyldisiloxane were added, and the reaction was carried out for 8 hours. The mixture was cooled, and the tetrahydrofuran was removed by distillation under reduced pressure. The mixture was filtered, and the filter residue was dissolved with 100 parts of ethanol and stirred evenly to obtain a polyimide cyclosiloxane ethanol solution.

[0058] Step 3: Preparation of polyimide cyclosiloxane-ammonium polyphosphate

[0059] By mass, 10 parts of ammonium polyphosphate were dissolved in 19.5 parts of ethanol to obtain an ammonium polyphosphate solution, 1.0 parts of polyimide cyclosiloxane ethanol solution and 0.75 parts of ammonium polyphosphate solution were mixed evenly, reacted at 35-45° C. and 25-35 rpm for 2-4 hours, filtered under reduced pressure, and dried to obtain polyimide cyclosiloxane-ammonium polyphosphate.

[0060] Step 4: Preparation of maleic anhydride grafted polypropylene

[0061] 40 parts of polypropylene, 0.8 parts of maleic anhydride, 5 parts of styrene and 0.2 parts of high-density polyethylene were uniformly mixed and extruded by a twin-screw extruder at an extrusion temperature of 170° C. and a screw speed of 150 rpm to obtain maleic anhydride grafted polypropylene.

[0062] Step 5: Prepare the additive

[0063] By weight, 15 parts of dicumyl peroxide, 4 parts of pentaerythritol stearate, 7 parts of antioxidant 1010, 28 parts of plasticizer, and 10 parts of calcium stearate were uniformly mixed to obtain an auxiliary agent.

[0064] Step 6: Prepare high temperature resistant polyolefin waterproof membrane

[0065] 50 parts of polypropylene, 74 parts of linear low-density polyethylene, 44 parts of low-density polyethylene, 27 parts of ethylene-octene copolymer, 24 parts of polyimide cyclosiloxane-ammonium polyphosphate, 11 parts of maleic anhydride grafted polypropylene, and 10 parts of additives were dried at 70°C for 4 hours, melt-blended at 180°C, extruded into granules, dried at 80°C for 4 hours, and hot-pressed at 160°C and 5MPa to obtain a high-temperature resistant polyolefin waterproof membrane.

[0066] Based on Example 1, control experiments were carried out, specifically Comparative Example 1, Comparative Example 2 and Comparative Example 3, as described below:

[0067] Comparative Example 1: No polyimide cyclosiloxane-ammonium polyphosphate was added, and the other conditions were the same as those in Example 1.

[0068] A method for preparing a high temperature resistant polyolefin waterproofing membrane, specifically comprising:

[0069] Step 1: Preparation of maleic anhydride grafted polypropylene

[0070] 40 parts of polypropylene, 0.8 parts of maleic anhydride, 5 parts of styrene and 0.2 parts of high-density polyethylene were uniformly mixed and extruded by a twin-screw extruder at an extrusion temperature of 170° C. and a screw speed of 150 rpm to obtain maleic anhydride grafted polypropylene.

[0071] Step 2: Prepare the additive

[0072] By weight, 15 parts of dicumyl peroxide, 4 parts of pentaerythritol stearate, 7 parts of antioxidant 1010, 28 parts of plasticizer, and 10 parts of calcium stearate were uniformly mixed to obtain an auxiliary agent.

[0073] Step 3: Preparation of high temperature resistant polyolefin waterproof membrane

[0074] 48 parts of polypropylene, 72 parts of linear low-density polyethylene, 42 parts of low-density polyethylene, 26 parts of ethylene-octene copolymer, 10 parts of maleic anhydride grafted polypropylene, and 8 parts of additives were dried at 70°C for 4 hours, melt-blended at 180°C, extruded into granules, dried at 80°C for 4 hours, and hot-pressed at 160°C and 5MPa to obtain a high-temperature resistant polyolefin waterproof membrane.

[0075] Comparative Example 2: No ammonium polyphosphate was added, and the remaining conditions were the same as those in Example 1.

[0076] A method for preparing a high temperature resistant polyolefin waterproofing membrane, specifically comprising:

[0077] Step 1: Preparation of bisphenol A diether diene

[0078] By mass, 3.0 parts of bisphenol A diether dianhydride and 105.5 parts of glacial acetic acid were mixed to obtain a bisphenol A diether dianhydride solution, 0.725 parts of allylamine were slowly added to 108.5 parts of bisphenol A diether dianhydride solution at -2°C and 60rpm, the temperature was raised to 27°C, the reaction was carried out for 1.5h, the temperature was raised to 100°C, the reaction was carried out for 12h, the reaction was completed, and the reaction was cooled, 200 parts of deionized water were added, the mixture was filtered, the mixture was washed with deionized water, and the mixture was dried in vacuo to obtain bisphenol A diether diene.

[0079] Step 2: Preparation of polyimide cyclosiloxane ethanol solution

[0080] By mass, under nitrogen as a protective gas, 5.0 parts of bisphenol A type diether diene, 89 parts of tetrahydrofuran and 1.9 parts of chloroplatinic acid were mixed, the temperature was raised to 55-65°C, and after reacting for 30 minutes, 0.985 parts of tetramethyldisiloxane were added, and the reaction was carried out for 8 hours. The mixture was cooled, and the tetrahydrofuran was removed by distillation under reduced pressure. The mixture was filtered, and the filter residue was rinsed with ethanol and dried to obtain polyimide cyclosiloxane.

[0081] Step 3: Preparation of maleic anhydride grafted polypropylene

[0082] 40 parts of polypropylene, 0.8 parts of maleic anhydride, 5 parts of styrene and 0.2 parts of high-density polyethylene were uniformly mixed and extruded by a twin-screw extruder at an extrusion temperature of 170° C. and a screw speed of 150 rpm to obtain maleic anhydride grafted polypropylene.

[0083] Step 4: Prepare the additive

[0084] By weight, 15 parts of dicumyl peroxide, 4 parts of pentaerythritol stearate, 7 parts of antioxidant 1010, 28 parts of plasticizer, and 10 parts of calcium stearate were uniformly mixed to obtain an auxiliary agent.

[0085] Step 5: Prepare high temperature resistant polyolefin waterproof membrane

[0086] 48 parts of polypropylene, 72 parts of linear low-density polyethylene, 42 parts of low-density polyethylene, 26 parts of ethylene-octene copolymer, 10 parts of polyimide cyclosiloxane, 10 parts of maleic anhydride grafted polypropylene, and 8 parts of additives were dried at 70°C for 4 hours, melt-blended at 180°C, extruded into granules, dried at 80°C for 4 hours, and hot-pressed at 160°C and 5MPa to obtain a high-temperature resistant polyolefin waterproof membrane.

[0087] Comparative Example 3: No maleic anhydride grafted polypropylene was added, and the other conditions were the same as those in Example 1.

[0088] A method for preparing a high temperature resistant polyolefin waterproofing membrane, specifically comprising:

[0089] Step 1: Preparation of bisphenol A diether diene

[0090] By mass, 3.0 parts of bisphenol A diether dianhydride and 105.5 parts of glacial acetic acid were mixed to obtain a bisphenol A diether dianhydride solution, 0.725 parts of allylamine were slowly added to 108.5 parts of bisphenol A diether dianhydride solution at -2°C and 60rpm, the temperature was raised to 27°C, the reaction was carried out for 1.5h, the temperature was raised to 100°C, the reaction was carried out for 12h, the reaction was completed, and the reaction was cooled, 200 parts of deionized water were added, the mixture was filtered, the mixture was washed with deionized water, and the mixture was dried in vacuo to obtain bisphenol A diether diene.

[0091] Step 2: Preparation of polyimide cyclosiloxane ethanol solution

[0092] By mass, under nitrogen as a protective gas, 5.0 parts of bisphenol A type diether diene, 89 parts of tetrahydrofuran and 1.9 parts of chloroplatinic acid were mixed, the temperature was raised to 55-65°C, and after reacting for 30 minutes, 0.985 parts of tetramethyldisiloxane were added, and the reaction was carried out for 8 hours. The mixture was cooled, and the tetrahydrofuran was removed by distillation under reduced pressure. The mixture was filtered, and the filter residue was dissolved with 100 parts of ethanol and stirred evenly to obtain a polyimide cyclosiloxane ethanol solution.

[0093] Step 3: Preparation of polyimide cyclosiloxane-ammonium polyphosphate

[0094] By mass, 10 parts of ammonium polyphosphate were dissolved in 19.5 parts of ethanol to obtain an ammonium polyphosphate solution, 1.0 parts of polyimide cyclosiloxane ethanol solution and 0.75 parts of ammonium polyphosphate solution were mixed evenly, reacted at 35-45° C. and 25-35 rpm for 2-4 hours, filtered under reduced pressure, and dried to obtain polyimide cyclosiloxane-ammonium polyphosphate.

[0095] Step 4: Prepare the additive

[0096] By weight, 15 parts of dicumyl peroxide, 4 parts of pentaerythritol stearate, 7 parts of antioxidant 1010, 28 parts of plasticizer, and 10 parts of calcium stearate were uniformly mixed to obtain an auxiliary agent.

[0097] Step 5: Prepare high temperature resistant polyolefin waterproof membrane

[0098] 48 parts of polypropylene, 72 parts of linear low-density polyethylene, 42 parts of low-density polyethylene, 26 parts of ethylene-octene copolymer, 22 parts of polyimide cyclosiloxane-ammonium polyphosphate, and 8 parts of additives were dried at 70°C for 4 hours, melt-blended at 180°C, extruded into granules, dried at 80°C for 4 hours, and hot-pressed at 160°C and 5MPa to obtain a high-temperature resistant polyolefin waterproof membrane.

[0099] Detection experiment:

[0100] The high temperature resistant polyolefin waterproof membrane required for the test was prepared according to the preparation methods in Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, and Comparative Example 3, respectively, and placed in an environment with a temperature of 23° C. and a relative humidity of 60% for 24 hours.

[0101] Mechanical properties test: The test was carried out in accordance with "Thermoplastic Polyolefin (TPO) Waterproof Membrane" (GB / T 27789-2011). 150mm×50mm×1.5mm specimens were cut out from the waterproof membrane prepared above, and the specimens were fixed on the fixture of the tensile testing machine. The tensile testing machine was used to test each specimen in turn, and the tensile strength and elongation at break of each specimen were measured.

[0102] Water absorption test: the test was conducted in accordance with Thermoplastic Polyolefin (TPO) Waterproofing Membrane (GB / T 27789-2011). Samples of 100 mm × 100 mm × 1.5 mm were cut out from the waterproof membrane prepared above, and each sample was weighed after being dried for 24 hours. Each sample was then soaked in 70°C distilled water for 168 hours, taken out, and then put into 23°C distilled water for 15 minutes. The water marks on the surface of the sample were immediately wiped dry, and the weight of each sample was weighed again to calculate the water absorption of each sample.

[0103] Heat aging resistance test: The test was carried out in accordance with "Thermoplastic Polyolefin (TPO) Waterproof Membrane" (GB / T 27789-2011). 300mm×200mm×1.5mm specimens were cut out from the above-prepared waterproof membrane, and each specimen was placed in a hot air aging test box for aging at a temperature of 80°C and an aging time of 672h. After aging, the specimens were placed in an environment with a temperature of 23°C and a relative humidity of 60% for 24h, and then the elongation at break of each specimen was tested according to the mechanical properties test method.

[0104] Heat resistance test: The test was conducted in accordance with Thermoplastic Polyolefin (TPO) Waterproof Membrane (GB / T 27789-2011). Samples of 100mm×100mm×1.5mm were cut from the waterproof membrane prepared above, and the samples were placed on a heating plate in an oven with the upper surface of the membrane facing upward. The samples were heated at 80°C for 24h, and the samples were taken out and restored in an environment with a temperature of 23°C and a relative humidity of 60% for 24h. The size of the samples was measured and the rate of change was calculated.

[0105]

[0106] Conclusion: It can be seen from the experiment that the sample of Example 1 is superior to Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4 in all aspects. The high temperature resistant polyolefin waterproof membrane of the present invention is superior to the general thermoplastic polyolefin waterproof membrane in terms of mechanical properties, water resistance, heat aging resistance and heat resistance, and achieves the purpose of high temperature resistance of the prepared waterproof membrane.

[0107] Finally, it should be noted that the above is only a preferred embodiment of the present invention, but the protection scope of this application is not limited thereto. Any changes or substitutions that can be easily thought of by any technician familiar with the technical field within the spirit and principle of the present invention and within the technical scope disclosed in this application should be included in the protection scope of this application; in the absence of conflict, the embodiments of this application and the features in the embodiments can be combined with each other. Therefore, the protection scope of this application shall be based on the protection scope of the claims.

Claims

1. A method for preparing a high temperature resistant polyolefin waterproof coiled material, characterized in that: The preparation method is: Polypropylene, linear low-density polyethylene, low-density polyethylene, ethylene-octene copolymer, polyimide cyclosiloxane-ammonium polyphosphate, maleic anhydride grafted polypropylene and additives are dried at 65-75°C for 3-5 hours, melt-blended at 180-220°C, extruded into granules, dried at 70-90°C for 3-5 hours, and hot-pressed at 150-170°C and 4-6MPa to obtain a high-temperature resistant polyolefin waterproof membrane.

2. The method for preparing a high temperature resistant polyolefin waterproofing coiled material according to claim 1, characterized in that: The amount of each raw material used in the preparation process of high-temperature resistant polyolefin waterproof membrane is: by mass, 46-50 parts of polypropylene, 70-74 parts of low-density polyethylene, 40-44 parts of low-density polyethylene, 25-27 parts of ethylene-octene copolymer, 20-24 parts of polyimide cyclosiloxane-ammonium polyphosphate, 9-11 parts of maleic anhydride grafted polypropylene, and 6-10 parts of additives.

3. A method for preparing a high temperature resistant polyolefin waterproofing membrane according to claim 1 and claim 2, characterized in that: The preparation method of polyimide cyclosiloxane-ammonium polyphosphate is: Mix bisphenol A diether dianhydride and glacial acetic acid to obtain a bisphenol A diether dianhydride solution, slowly add allylamine to the bisphenol A diether dianhydride solution at -5 to 0°C and 50 to 70 rpm, heat to 25 to 30°C, react for 1 to 2 hours, heat to 98 to 102°C, react for 11 to 13 hours, cool after the reaction, add 180 to 220 parts of deionized water, filter, wash with deionized water, and vacuum dry to obtain bisphenol A diether diene; Under nitrogen as protective gas, bisphenol A type diether diene, tetrahydrofuran and chloroplatinic acid are mixed, heated to 55-65°C, reacted for 25-35 minutes, tetramethyl disiloxane is added, reacted for 7-9 hours, cooled, tetrahydrofuran is removed by vacuum distillation, filtered, the filter residue is dissolved in ethanol, stirred evenly, and a polyimide cyclosiloxane ethanol solution is obtained; Dissolve ammonium polyphosphate in ethanol to obtain an ammonium polyphosphate solution, mix the polyimide cyclosiloxane ethanol solution and the ammonium polyphosphate solution evenly, react at 35-45° C. and 25-35 rpm for 2-4 hours, filter under reduced pressure, and dry to obtain polyimide cyclosiloxane-ammonium polyphosphate.

4. A method for preparing a high temperature resistant polyolefin waterproofing membrane according to claim 1 and claim 2, characterized in that: The preparation method of maleic anhydride grafted polypropylene is: Polypropylene, maleic anhydride, styrene and high-density polyethylene are uniformly mixed and extruded through a twin-screw extruder at an extrusion temperature of 140-190° C. and a screw speed of 140-160 rpm to obtain maleic anhydride grafted polypropylene.

5. The method for preparing a high temperature resistant polyolefin waterproofing membrane according to claim 1 and claim 2, characterized in that: The preparation method of the auxiliary agent is: By weight, 14 to 16 parts of dicumyl peroxide, 3 to 5 parts of pentaerythritol stearate, 6 to 8 parts of antioxidant, 27 to 29 parts of plasticizer and 9 to 11 parts of calcium stearate are uniformly mixed to obtain an auxiliary agent.

6. The method for preparing a high temperature resistant polyolefin waterproofing coiled material according to claim 3, characterized in that: The mass ratio of allylamine to bisphenol A diether dianhydride solution is (0.72-0.73):(108-109).

7. The method for preparing a high temperature resistant polyolefin waterproofing coiled material according to claim 3, characterized in that: The mass ratio of bisphenol A type diether diene to tetrahydrofuran, chloroplatinic acid and tetramethyldisiloxane is (4.9-5.1):(88-90):(1.8-2.0):(0.98-0.99).

8. The method for preparing a high temperature resistant polyolefin waterproofing coiled material according to claim 3, characterized in that: The mass ratio of the polyimide cyclosiloxane ethanol solution to the ammonium polyphosphate solution is (0.9-1.1):(0.7-0.8).

9. The method for preparing a high temperature resistant polyolefin waterproofing coiled material according to claim 4, characterized in that: The amounts of various substances required in the preparation process of maleic anhydride grafted polypropylene are: by mass, 38-42 parts of polypropylene, 0.7-0.9 parts of maleic anhydride, 4-6 parts of styrene, and 0.1-0.3 parts of high-density polyethylene.

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