Thermoplastic polyolefin waterproof coiled material and preparation method thereof
By introducing a collaborative flame retardant system of phosphorus, nitrogen and sulfur into the thermoplastic polyolefin waterproof coil, the problems of flammability and mechanical properties of the material are solved, and efficient preparation of waterproof coils with flame retardant, heat-resistant and environmentally friendly is achieved.
Patent Information
- Application Number
- CN202510731953.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-03
- Publication Date
- 2025-08-01
AI Technical Summary
The existing thermoplastic polyolefin waterproof coils have shortcomings in flame retardant properties, especially in fire conditions that are prone to flammable and release toxic fumes, and traditional flame retardants will affect the mechanical properties and processing properties of the materials.
A new flame retardant additive is used. This additive forms a collaborative flame retardant system by integrating three elements of phosphorus, nitrogen and sulfur into the same molecular structure, and is prepared through specific chemical reactions, including the reaction of DOPO and 2-aminobenzothiazole to form a phosphorothioate flame retardant with P=S bond, and combines benzothiazole groups and benzene ring structure to improve the flame retardant, heat resistance and mechanical properties of the material.
It significantly improves the flame retardant and heat resistance of the waterproof coil material, while maintaining the mechanical properties and processing stability of the material, avoiding the release of toxic gases, and complying with environmental protection requirements.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of waterproof coiled materials, and specifically, to a thermoplastic polyolefin waterproof coiled material and a preparation method thereof. Background Art
[0002] In the field of building waterproofing, waterproof coiled materials are key materials to ensure the waterproof performance of buildings, and their quality and performance directly affect the service life and service functions of buildings. Thermoplastic polyolefin (TPO) waterproof coiled materials are sheet-shaped thermoplastic rubber elastic waterproof materials made with ethylene resin as the base material, using advanced polymerization technologies and specific formulas. They are a new type of material that has been popular in the United States and Europe in recent years. The ingredients do not contain plasticizers, so there is no embrittlement due to plasticizer migration. They have comprehensive characteristics such as large tensile strength, good puncture resistance, strong ultraviolet resistance, smooth surface, high reflectivity, and pollution resistance. They are easy to process, can be welded, are convenient for construction, can be fully recycled, and are green and environmentally friendly. They are excellent waterproof materials. Due to their excellent performance, they have become important alternatives to traditional waterproof materials such as asphalt-based coiled materials and PVC coiled materials.
[0003] With the continuous improvement of building safety standards, especially the increasingly strict requirements for fire resistance performance, the main components of ordinary TPO waterproof coiled materials include polyolefin materials such as polypropylene (PP), polyethylene (PE), and ethylene propylene diene monomer (EPDM). These materials themselves are flammable or combustible substances with a low limiting oxygen index (LOI). Under fire conditions, they are prone to burning and releasing a large amount of heat and toxic smoke, which not only accelerates the spread of the fire but also may seriously impede the escape of personnel and fire fighting and rescue. The deficiency of TPO waterproof coiled materials in flame retardancy has become one of the key factors restricting their application in high-risk places.
[0004] Currently, the main method to improve the flame retardancy of TPO waterproof coiled materials is to add flame retardants, but this technical route faces many challenges. First, although traditional halogen-based flame retardants have high flame retardancy efficiency, they produce a large amount of toxic and corrosive gases when burning, which poses a significant hazard to the environment and human health. With the worldwide restriction on the use of halogen-based flame retardants, the development of environmentally friendly halogen-free flame retardant systems is extremely urgent. Second, although inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide are environmentally friendly, a high addition amount (usually exceeding 50%) is required to achieve an ideal flame retardant effect. This will significantly reduce the mechanical properties and processing properties of the material, resulting in a decrease in the flexibility of the coiled material and a reduction in the tensile strength, affecting its basic functions as a waterproof material. Therefore, it is urgent to solve the above problems and invent a thermoplastic polyolefin waterproof coiled material with both mechanical properties and flame retardancy to meet the higher requirements in the technical field of waterproof coiled materials. Summary of the Invention
[0005] The present invention provides a thermoplastic polyolefin waterproof coil and a preparation method thereof, which solves the problem of poor flame retardancy of thermoplastic polyolefin waterproof coils in the related art.
[0006] The technical solution of the present invention is as follows: The present invention provides a thermoplastic polyolefin waterproof coil, comprising the following raw materials in parts by mass: 51 - 63 parts of polypropylene, 43 - 55 parts of ethylene propylene diene monomer rubber, 2 - 4 parts of antioxidant aid, 3 - 5 parts of light stabilizer aid, 4 - 12 parts of flame retardant aid, and 3 - 6 parts of processing aid.
[0007] As a further technical solution, the antioxidant aid is a hindered phenol antioxidant.
[0008] As a further technical solution, the light stabilizer aid is a hindered amine light stabilizer.
[0009] As a further technical solution, the processing aid is one of polyethylene wax, stearic acid, and oleamide.
[0010] As a further technical solution, the flame retardant aid is prepared through the following steps: Step 1: Place 9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide (DOPO) in a three - necked flask, then add N,N - dimethylformamide as a solvent, and then put it into an ultrasonic machine for ultrasonic treatment to accelerate the dissolution of DOPO. After dissolution, add phosphorus pentasulfide to the flask. Under a nitrogen atmosphere, heat it to 70 °C and maintain stirring for 4 h. After the reaction is completed, filter while it is hot, transfer the liquid to a rotary evaporator, perform rotary evaporation, and then purify it by silica gel column chromatography (eluent: the volume ratio of petroleum ether / ethyl acetate is 10:1) to obtain product A; In Step 1, 9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide reacts with phosphorus pentasulfide; the reaction formula is as follows:
[0011] Step 2: Place 2 - aminobenzothiazole in a three - necked flask, then add ethanol as a solvent, and then perform magnetic stirring to fully disperse 2 - aminobenzothiazole in the ethanol solvent. During the stirring process, continuously add n - octanal to the three - necked flask. When the n - octanal is completely added, heat the device to 80 °C, continue stirring, and reflux for 6 h. After the reaction is completed, cool it naturally at room temperature, filter and separate the product, and place the product in an oven for drying to obtain product B; In Step 2, 2 - aminobenzothiazole reacts with n - octanal to form a C=N bond; the reaction formula is as follows:
[0012] Step 3: Place product A in a three-necked flask, then add N,N-dimethylformamide as a solvent, and then put it into an ultrasonic machine for ultrasonic treatment to dissolve product A. Then place the three-necked flask in an oil bath preheated to 85°C for magnetic stirring, and slowly add product B during the stirring process. After the addition is complete, continuously stir at this temperature for 12 h. After the reaction is completed, perform rotary evaporation, and then filter, wash, and separate the obtained product to remove unreacted product A and product B. Finally, place the product in an oven for drying to obtain a flame retardant additive; In Step 3, product A reacts with product B to obtain a flame retardant additive; the reaction formula is as follows:
[0013] The flame retardant additive of the present invention contains a variety of flame retardant components. Among them, the P=O bond in DOPO is converted into a P=S bond through the reaction, belonging to a thiophosphate ester flame retardant. The P and S in the structure can play a synergistic role in gas-phase flame retardancy and condensed-phase flame retardancy, and can improve the flame retardant performance of the matrix; in addition, the flame retardant additive molecule also contains a benzothiazole group, and the thiazole in the group is a five-membered heterocyclic compound containing sulfur and nitrogen, which has excellent heat resistance and can improve the heat resistance of the matrix; moreover, the flame retardant additive molecule also contains multiple benzene ring structures, which can not only further improve the heat resistance of the matrix, but also, as a rigid group, improve the mechanical properties of the matrix; finally, one end of the flame retardant additive is a carbon chain structure, which can be inserted into the macromolecular chain of the matrix, improve the migration resistance of the flame retardant additive, and make the flame retardant performance more stable.
[0014] It should be added that the flame retardant additive contains P, N, and S elements at the same time, forming a P-N-S synergistic flame retardant system, which significantly improves the flame retardant performance of the matrix.
[0015] As a further technical solution, the dosage ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, N,N-dimethylformamide, and diphosphorus pentasulfide in Step 1 is 21.6 g:100 mL:6.6 g.
[0016] As a further technical solution, the dosage ratio of 2-aminobenzothiazole, ethanol, and n-octanal in Step 2 is 14.9 g:100 mL:12.8 g.
[0017] As a further technical solution, the dosage ratio of product A, N,N-dimethylformamide, and product B in Step 3 is 25.9 g:150 mL:23.2 g.
[0018] The present invention also provides a preparation method of a thermoplastic polyolefin waterproof coil, including the following steps: After drying polypropylene and ethylene propylene diene monomer (EPDM) in a drying oven, they are stirred and mixed evenly with antioxidant additives, light stabilizer additives, flame retardant additives and processing additives, and then added to a Banbury mixer. After Banbury mixing, extrusion and pelletizing are carried out to obtain masterbatch. The masterbatch is extruded, calendered, shaped and wound up to obtain a thermoplastic polyolefin waterproof coil.
[0019] As a further technical solution, the drying temperature is 80 - 100 °C and the time is 12 - 24 h.
[0020] As a further technical solution, the Banbury mixing temperature is 170 - 190 °C and the time is 6 - 8 h.
[0021] The working principle and beneficial effects of the present invention are as follows: 1. By integrating three flame retardant elements of phosphorus, nitrogen and sulfur into the same molecular structure, the present invention forms an efficient synergistic flame retardant system, greatly improving the flame retardant performance of the waterproof coil. 2. The benzothiazole structure and benzene ring introduced in the flame retardant additive enhance both the heat resistance of the material and the mechanical strength, while the long carbon chain structure improves the stability of the coil. 3. The present invention adopts a halogen-free flame retardant system, which conforms to the trend of increasingly strict current environmental protection regulations from the perspective of environmental protection. Compared with traditional halogen-based flame retardants, it avoids the problem of release of toxic gases, reflecting the development direction of green chemistry. In summary, the thermoplastic polyolefin waterproof coil prepared by the present invention has stable and efficient flame retardant, heat resistance and mechanical properties, and has important application value in the technical field of waterproof coils. Specific embodiments
[0022] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the scope of protection of the present invention.
[0023] Example 1 Prepare the flame retardant additive: Step 1: Place 21.6 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in a three-necked flask, then add 100 mL of N,N-dimethylformamide as a solvent, and then put it into an ultrasonic machine for ultrasonic treatment to accelerate the dissolution of DOPO. After dissolution, add 6.6 g of phosphorus pentasulfide to the flask. Under a nitrogen atmosphere, heat to 70 °C and maintain stirring for 4 h. After the reaction is completed, filter while it is hot, transfer the liquid to a rotary evaporator, and after rotary evaporation, purify it by silica gel column chromatography (eluent: the volume ratio of petroleum ether / ethyl acetate is 10:1) to obtain product A; Step 2: Place 14.9 g of 2-aminobenzothiazole in a three-necked flask, then add 100 mL of ethanol as a solvent, and then carry out magnetic stirring to make 2-aminobenzothiazole fully dispersed in the ethanol solvent. During the stirring process, continuously add 12.8 g of n-octanal to the three-necked flask. When the addition of n-octanal is complete, heat the device to 80 °C, continue stirring, and reflux for 6 h. After the reaction is completed, cool naturally at room temperature, filter and separate the product, and place the product in an oven for drying to obtain product B; Step 3: Place 25.9 g of product A in a three-necked flask, then add 150 mL of N,N-dimethylformamide as a solvent, and then put it into an ultrasonic machine for ultrasonic treatment to dissolve product A. Then place the three-necked flask in an oil bath preheated to 85 °C for magnetic stirring, and slowly add 23.2 g of product B during the stirring process. After the addition is complete, continuously stir at this temperature for 12 h. After the reaction is completed, carry out rotary evaporation, and then filter, wash and separate the obtained product to remove unreacted product A and product B. Finally, place the product in an oven for drying to obtain the flame retardant additive.
[0024] Example 2 A preparation method of a thermoplastic polyolefin waterproof coil, comprising the following steps: After drying 51 g of polypropylene (model M800E) and 43 g of ethylene-propylene-diene rubber (model 3092PM) in an oven at 80 °C for 12 h, then stir and mix evenly with 2 g of antioxidant 3114, 3 g of light stabilizer 944, 4 g of the flame retardant additive prepared in Example 1, and 3 g of polyethylene wax, and add them to a mixer. At 170 °C, mix for 6 h. After mixing, extrude and pelletize to obtain masterbatch, and extrude, calender, shape, and wind up the masterbatch to obtain the thermoplastic polyolefin waterproof coil.
[0025] Example 3 A preparation method of a thermoplastic polyolefin waterproof coil, comprising the following steps: After drying 57 g of polypropylene (model M800E) and 49 g of ethylene propylene diene monomer rubber (model 3092PM) in a drying oven at 90 °C for 24 h, they were then stirred and mixed evenly with 3 g of antioxidant 3114, 4 g of light stabilizer 944, 8 g of the flame retardant aid prepared in Example 1, and 4.5 g of stearic acid, and then added to an internal mixer. At 180 °C, they were internally mixed for 7 h. After internal mixing, they were extruded and pelletized to obtain masterbatch. The masterbatch was extruded, calendered, shaped, and wound up to obtain a thermoplastic polyolefin waterproof coil.
[0026] Example 4 A preparation method of a thermoplastic polyolefin waterproof coil, comprising the following steps: After drying 63 g of polypropylene (model M800E) and 55 g of ethylene propylene diene monomer rubber (model 3092PM) in a drying oven at 80 - 100 °C for 24 h, they were then stirred and mixed evenly with 4 g of antioxidant 3114, 5 g of light stabilizer 944, 12 g of the flame retardant aid prepared in Example 1, and 6 g of oleamide, and then added to an internal mixer. At 190 °C, they were internally mixed for 8 h. After internal mixing, they were extruded and pelletized to obtain masterbatch. The masterbatch was extruded, calendered, shaped, and wound up to obtain a thermoplastic polyolefin waterproof coil.
[0027] Comparative Example 1 The flame retardant aid in Example 4 was replaced with a commercially available phosphorus-based flame retardant, and the remaining steps were the same as those in Example 4 to prepare a waterproof coil.
[0028] Comparative Example 2 Use the TPO waterproof coil produced by Shandong Yaorong Waterproof Technology Co., Ltd.
[0029] The following performance tests were carried out on Examples 2, 3, 4 and Comparative Examples 1, 2: The tensile strength and heat aging resistance of the specimens were measured according to the national standard GB27789-2011 "Thermoplastic polyolefin (TPO) waterproof coil"; The oxygen index was measured according to the national standard GB / T 2406.2-2009 "Plastics - Determination of burning behavior by the oxygen index method - Part 2: Room temperature test"; After storing Examples 2, 3, 4 and Comparative Example 1 at room temperature for 300 days, the oxygen index was measured according to the national standard GB / T 2406.2-2009; The measurement results are shown in the following table:
[0030] As can be seen from the above table, for the thermoplastic polyolefin waterproof coiled material prepared in the embodiment of the present invention, due to the addition of the flame retardant aid prepared in Embodiment 1 of the present invention, its flame retardancy, mechanical properties and heat resistance are all higher than those of the comparative example, and after 90 days of storage, good flame retardant performance can still be ensured. Therefore, the present invention has important application value in the technical field of waterproof coiled materials.
[0031] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
Claims
1. A thermoplastic polyolefin waterproof coiled material, characterized in that, It comprises raw materials in the following parts by mass: 51 - 63 parts of polypropylene, 43 - 55 parts of ethylene propylene diene monomer rubber, 2 - 4 parts of antioxidant additive, 3 - 5 parts of light stabilizer additive, 4 - 12 parts of flame retardant additive, and 3 - 6 parts of processing additive.
2. The thermoplastic polyolefin waterproof coiled material according to claim 1, wherein The flame retardant additive is prepared through the following steps: Step 1: Place 9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide in a flask, then add N,N - dimethylformamide. After ultrasonic treatment, add phosphorus pentasulfide. Under a nitrogen atmosphere, heat to 70 °C and stir for 4 h. After the reaction is completed, product A is obtained; Step 2: Place 2 - aminobenzothiazole in a flask, then add ethanol and stir magnetically. During the stirring process, add n - octanal, and then heat to 80 °C and continuously stir for reflux reaction for 6 h. After the reaction is completed, product B is obtained; Step 3: Place product A in a flask, then add N,N - dimethylformamide. After ultrasonic treatment, place the flask in an oil bath at 85 °C and stir. During the stirring process, add product B. After the addition is completed, continuously stir at this temperature for 12 h. After the reaction is completed, the flame retardant additive is obtained.
3. The thermoplastic polyolefin waterproof coiled material according to claim 2, characterized in that, In Step 1, the dosage ratio of 9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide, N,N - dimethylformamide, and phosphorus pentasulfide is 21.6 g:100 mL:6.6 g.
4. A thermoplastic polyolefin waterproof coiled material according to claim 2, characterized in that, In Step 2, the dosage ratio of 2 - aminobenzothiazole, ethanol, and n - octanal is 14.9 g:100 mL:12.8 g.
5. A thermoplastic polyolefin waterproof coiled material according to claim 2, characterized in that, In Step 3, the dosage ratio of product A, N,N - dimethylformamide, and product B is 25.9 g:150 mL:23.2 g.
6. The thermoplastic polyolefin waterproof coiled material according to claim 1, characterized in that, The antioxidant additive is a hindered phenol antioxidant.
7. The thermoplastic polyolefin waterproof coiled material according to claim 1, characterized in that, The light stabilizer additive is a hindered amine light stabilizer.
8. The thermoplastic polyolefin waterproof coiled material according to claim 1, characterized in that, The processing additive is one of polyethylene wax, stearic acid, and oleamide.
9. The preparation method of a thermoplastic polyolefin waterproof coiled material according to any one of claims 1-8, characterized in that, It comprises the following steps: After drying the polypropylene and ethylene propylene diene monomer rubber, stir - mix them evenly with the antioxidant additive, light stabilizer additive, flame retardant additive, and processing additive, then add them to a mixer. After mixing, extrude and pelletize to obtain masterbatch. Extrude, calender, shape, and wind up the masterbatch to obtain a thermoplastic polyolefin waterproof coil.
10. The preparation method of a thermoplastic polyolefin waterproof coil according to claim 9, characterized in that, The drying temperature is 80 - 100 °C and the time is 12 - 24 h; the mixing temperature is 170 - 190 °C and the time is 6 - 8 h.