A TPO composite material for waterproofing coiled material and preparation method thereof

Abstract

The present invention relates to a TPO composite material for waterproof coiled material and a preparation method thereof, and belongs to the technical field of polymer composite materials. The composite material comprises, by weight, 100 parts of polypropylene, 52-58 parts of ethylene propylene diene monomer rubber, 4-5 parts of compatibilizer, 4.5-7 parts of interface reinforcing agent, 2.8-3.6 parts of crosslinking agent, 2.2-3 parts of lubricant, 0.1-0.14 parts of antioxidant and 15-20 parts of filler; the interface reinforcing agent is substituted by the active primary amine of chloroalkane and triethylenetetramine to form a terminal alkyl chain compound, and then dimethyl thiodiacetate is subjected to amine ester exchange with the substituted secondary amine structure to form a chain amide compound, which forms a crosslinked rubber-high toughness β-crystal transition layer at the interface between rubber and polypropylene, improves the interface bonding performance of polypropylene and rubber, improves the overall toughness and puncture resistance of the composite material, and at the same time slows down the aging between the interfaces, and improves the self-aging resistance of the composite material.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer composite materials, and in particular, relates to a TPO composite material for waterproof coiled materials and a preparation method thereof. Background Art

[0002] Waterproof membrane is mainly used for building walls, roofs, tunnels, roads, landfills, etc. It is a flexible building material product that can be rolled into a roll to resist the seepage of external rainwater and groundwater. As a leak-free connection between the project foundation and the building, it is the first barrier to waterproofing the entire project and plays a vital role in the entire project.

[0003] Traditional waterproof materials mainly include asphalt, rubber and synthetic resin materials. Among them, asphalt waterproof membranes have strong permeability, are easy to age and deteriorate, and have poor high temperature resistance. Although rubber materials have certain elasticity and flexibility, they are easy to become brittle under low temperature conditions and also have aging resistance problems. Synthetic resin materials have good weather resistance and chemical resistance, but they are easy to soften under high temperature conditions, affecting the use effect. With the development of waterproof material technology, TPO (thermoplastic polyolefin) waterproof membranes have gradually attracted attention as a new type of thermoplastic waterproof material. Compared with traditional waterproof materials, TPO waterproof membranes have good flexibility, high efficiency and easy construction; however, the overall mechanical properties of the current TPO materials are insufficient. The main reason is that the interface bonding performance between the rubber phase and the polyolefin phase in the TPO material is poor, resulting in mechanical strength that is not as good as a single polyolefin material, and elastic toughness that is not as good as a single rubber. Only the ratio between the various properties can be adjusted, and it is difficult to improve them synergistically. Summary of the invention

[0004] In order to solve the technical problems mentioned in the background technology, the object of the present invention is to provide a TPO composite material for waterproofing coiled material and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A TPO composite material for waterproofing coiled material, comprising the following raw materials in parts by weight:

[0007] 100 parts of polypropylene, 52-58 parts of EPDM rubber, 4-5 parts of compatibilizer, 4.5-7 parts of interface reinforcing agent, 2.8-3.6 parts of crosslinking agent, 2.2-3 parts of lubricant, 0.1-0.14 parts of antioxidant and 15-20 parts of filler;

[0008] The interface strengthener is prepared by the following method:

[0009] Step A1: Add chloroalkane, aluminum chloride, 15-crown ether-5 and dioxane, premix at 40-55°C for 15-30 minutes, then introduce nitrogen protection, add triethylenetetramine, continue to heat to 85-100°C, reflux and stir to react for 1.8-2.6 hours, and after the reaction is completed, remove dioxane by vacuum rotary evaporation to obtain an alkylation intermediate;

[0010] Furthermore, the alkyl chain length of the chloroalkane is C10-C18, which has good affinity and compatibility between the EPDM and PP interfaces.

[0011] Furthermore, the feed ratio of triethylenetetramine, chloroalkane, aluminum chloride, 15-crown ether-5 and dioxane is 10mmol:20mmol:15-20mg:0.5-0.8mL:18-30mL, and the chloroalkane replaces the active primary amine of triethylenetetramine to form a terminal alkyl chain modification.

[0012] Step A2: dimethyl thiodiacetate, alkylated intermediate, tetrabutylammonium hydroxide and anhydrous tetrahydrofuran are mixed, the temperature of the water bath is controlled at 10-20°C, sodium hydride is slowly added and stirred for reaction for 4-6 hours, and then the temperature is continuously raised to 55-65°C and refluxed and stirred for reaction for 2-3.5 hours. After the reaction is completed, tetrahydrofuran is removed by rotary evaporation, the substrate is washed with water, the aqueous phase is removed and vacuum dried to obtain an interfacial strengthener;

[0013] Furthermore, the feed ratio of dimethyl thiodiacetate, the alkylation intermediate, tetrabutylammonium hydroxide, sodium hydride and anhydrous tetrahydrofuran is 10mmol:10mmol:10-20mg:25-40mg:45-60mL, and the secondary amine structure of the alkylation intermediate undergoes amine ester exchange with dimethyl thiodiacetate to form a chain amide compound.

[0014] Preferably, the compatibilizer is maleic anhydride grafted polypropylene.

[0015] Preferably, the crosslinking agent is triallyl isocyanate.

[0016] Preferably, the lubricant is a composite of polypropylene wax and calcium stearate.

[0017] A method for preparing a TPO composite material for waterproofing coiled material comprises the following steps:

[0018] Step S1: adding EPDM rubber, an interfacial strengthening agent, a cross-linking agent and a lubricant, refining at 80-90° C. and thinning for 3-4 times, cutting and crushing the material to obtain a premixed raw rubber material;

[0019] Step S2: adding the premixed raw rubber material, polypropylene, compatibilizer and filler, mixing at 220° C. under nitrogen protection until the torque is stable, adding an antioxidant, mixing, extruding and granulating, and obtaining a TPO composite material.

[0020] Beneficial effects of the present invention:

[0021] The invention is based on the existing TPO composite system and introduces a self-developed interface strengthening agent for blending modification; the interface strengthening agent is substituted by chloroalkane and the active primary amine of triethylenetetramine to form an alkyl terminal chain compound, i.e., an alkylation intermediate; and then dimethyl thiodiacetate and the secondary amine structure of the alkylation intermediate are subjected to amine ester exchange to form a chain amide compound, i.e., the interface strengthening agent is a macromolecular chain, which is not easy to migrate and segregate during the blending process and can be stably dispersed at the interface between rubber and polypropylene; during high-temperature plastic molding, the disulfide bonds in the molecular chain are easy to break, and the exposed sulfur free radicals are cross-linked with the rubber; the alkyl chain segments in the molecules have high affinity with the polypropylene phase and play a modification role; a large number of amide structures are introduced into the polypropylene phase, and a large number of high-toughness β-phase crystals are promoted to be generated in the polypropylene during the molding process; a cross-linked rubber-high-toughness β-crystal transition layer is formed at the interface between the rubber and the polypropylene, the interface bonding performance of the polypropylene and the rubber is improved, the overall toughness and puncture resistance of the composite material are effectively improved, and the aging between the interfaces is slowed down, and the self-aging resistance of the composite material is improved. DETAILED DESCRIPTION

[0022] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0023] Example 1, preparation of TPO composite material for waterproofing membrane, the specific implementation process is as follows:

[0024] (1) Preparation of interface strengthener

[0025] Step A1: Take chloroalkane, aluminum chloride, 15-crown ether-5 and dioxane as feed materials, premix at 40°C for 15 minutes, then introduce nitrogen protection, add triethylenetetramine, continue to heat to 85°C, reflux and stir to react for 1.8 hours, wherein the chloroalkane is selected from chlorodecane with an alkyl chain length of C10, and the feed ratio of triethylenetetramine, chlorodecane, aluminum chloride, 15-crown ether-5 and dioxane is 10mmol:20mmol:15mg:0.5mL:18mL. After the reaction is completed, the dioxane is quickly removed by reduced pressure rotary evaporation to obtain an alkylated intermediate.

[0026] Step A2: dimethyl thiodiacetate, alkylated intermediate, tetrabutylammonium hydroxide and anhydrous tetrahydrofuran are mixed, the temperature of the water bath is controlled at 10°C, sodium hydride is slowly added and stirred for reaction for 6 hours, and then the temperature is continued to be raised to 55°C and refluxed and stirred for reaction for 3.5 hours, wherein the feed ratio of dimethyl thiodiacetate, alkylated intermediate, tetrabutylammonium hydroxide, sodium hydride and anhydrous tetrahydrofuran is 10mmol:10mmol:10mg:25mg:45mL. After the reaction is completed, tetrahydrofuran is removed by rotary evaporation, the substrate is washed with water, the aqueous phase is removed and vacuum dried to obtain an interfacial enhancer.

[0027] (2) Preparation of TPO composite materials

[0028] Step S1: taking raw materials according to weight parts, 52 parts of EPDM rubber, 4045 type raw materials are used in the implementation process; 4.5 parts of interface strengthener, which is self-made in this embodiment; 2.8 parts of cross-linking agent, industrial grade triallyl isocyanate is used in the implementation process; 2.2 parts of lubricant, PP-200 type polypropylene wax and industrial grade calcium stearate are compounded in equal mass ratio in the implementation process; mixing the raw materials, refining at 80°C and thinning 3 times, cutting and crushing the discharged material to obtain a premixed raw rubber material.

[0029] Step S2: Take raw materials according to weight parts, 100 parts of polypropylene, T30S type raw material is used in the implementation process; 4 parts of compatibilizer, CMG9801 type raw material is used in the implementation process; 0.1 parts of antioxidant, antioxidant 1010 and antioxidant 168 are compounded in equal weight ratio in the implementation process; 15 parts of filler, LP-600 rubber and plastic type nano calcium carbonate is used in the implementation process; the premixed raw rubber, polypropylene, compatibilizer and filler prepared as above are added, mixed at 220°C under nitrogen protection until the torque is stable, the antioxidant is added to mix, and extruded and granulated to obtain a TPO composite material.

[0030] Example 2, preparing TPO composite material for waterproofing membrane, the specific implementation process is as follows:

[0031] (1) Preparation of interface strengthener

[0032] Step A1: Take chloroalkane, aluminum chloride, 15-crown ether-5 and dioxane as feed materials, premix at 55°C for 30 minutes, then introduce nitrogen protection, add triethylenetetramine, continue to heat to 100°C, reflux and stir to react for 2.6 hours, wherein the chloroalkane is selected from chlorooctadecane with an alkyl chain length of C18, and the feed ratio of triethylenetetramine, chlorooctadecane, aluminum chloride, 15-crown ether-5 and dioxane is 10mmol:20mmol:20mg:0.8mL:30mL. After the reaction is completed, the dioxane is quickly removed by reduced pressure rotary evaporation to obtain an alkylated intermediate.

[0033] Step A2: dimethyl thiodiacetate, alkylated intermediate, tetrabutylammonium hydroxide and anhydrous tetrahydrofuran are mixed, the temperature of the water bath is controlled at 20°C, sodium hydride is slowly added and stirred for reaction for 4 hours, and then the temperature is continued to be raised to 65°C and refluxed and stirred for reaction for 2 hours, wherein the feed ratio of dimethyl thiodiacetate, alkylated intermediate, tetrabutylammonium hydroxide, sodium hydride and anhydrous tetrahydrofuran is 10mmol:10mmol:20mg:40mg:60mL. After the reaction is completed, tetrahydrofuran is removed by rotary evaporation, the substrate is washed with water, the aqueous phase is removed and vacuum dried to obtain an interfacial enhancer.

[0034] (2) Preparation of TPO composite materials

[0035] Step S1: taking raw materials according to weight parts, 58 parts of EPDM rubber, 4045 type raw material is used in the implementation process; 7 parts of interface strengthener, which is self-made in this embodiment; 3.6 parts of cross-linking agent, industrial grade triallyl isocyanate is used in the implementation process; 3 parts of lubricant, PP-200 type polypropylene wax and industrial grade calcium stearate are compounded in equal mass ratio in the implementation process; mixing the raw materials, refining at 90°C and thinning 4 times, cutting and crushing the discharged material to obtain a premixed raw rubber material.

[0036] Step S2: Take raw materials according to weight parts, 100 parts of polypropylene, T30S type raw material is used in the implementation process; 5 parts of compatibilizer, CMG9801 type raw material is used in the implementation process; 0.14 parts of antioxidant, antioxidant 1010 and antioxidant 168 are compounded in equal weight ratio in the implementation process; 20 parts of filler, LP-600 rubber and plastic type nano calcium carbonate is used in the implementation process; the premixed raw rubber, polypropylene, compatibilizer and filler prepared as above are added, mixed at 220°C under nitrogen protection until the torque is stable, the antioxidant is added to mix, and extruded into granules to obtain a TPO composite material.

[0037] Example 3, preparing TPO composite material for waterproofing membrane, the specific implementation process is as follows:

[0038] (1) Preparation of interface strengthener

[0039] Step A1: Take chloroalkane, aluminum chloride, 15-crown ether-5 and dioxane as feed materials, premix at 50°C for 25 minutes, then introduce nitrogen protection, add triethylenetetramine, continue to heat to 90°C, reflux and stir to react for 2.2 hours, wherein the chloroalkane is selected from chlorotetradecane with an alkyl chain length of C14, and the feed ratio of triethylenetetramine, chlorotetradecane, aluminum chloride, 15-crown ether-5 and dioxane is 10mmol:20mmol:17mg:0.7mL:25mL. After the reaction is completed, the dioxane is quickly removed by reduced pressure rotary evaporation to obtain an alkylated intermediate.

[0040] Step A2: dimethyl thiodiacetate, alkylated intermediate, tetrabutylammonium hydroxide and anhydrous tetrahydrofuran are mixed, the temperature of the water bath is controlled at 20°C, sodium hydride is slowly added and stirred for reaction for 5 hours, and then the temperature is continued to be raised to 60°C and refluxed and stirred for reaction for 2.5 hours, wherein the feed ratio of dimethyl thiodiacetate, alkylated intermediate, tetrabutylammonium hydroxide, sodium hydride and anhydrous tetrahydrofuran is 10mmol:10mmol:15mg:35mg:55mL. After the reaction is completed, tetrahydrofuran is removed by rotary evaporation, the substrate is washed with water, the aqueous phase is removed and vacuum dried to obtain an interfacial enhancer.

[0041] (2) Preparation of TPO composite materials

[0042] Step S1: Take raw materials according to weight parts, 55 parts of EPDM rubber, 4045 type raw materials are used in the implementation process; 6.2 parts of interface strengthener, which is self-made in this embodiment; 3.2 parts of cross-linking agent, industrial grade triallyl isocyanate is used in the implementation process; 2.5 parts of lubricant, PP-200 type polypropylene wax and industrial grade calcium stearate are compounded in equal mass ratio in the implementation process; mix the raw materials, start refining at 85°C and thin pass 3 times, cut and crush the discharged material to obtain a premixed raw rubber material.

[0043] Step S2: Take raw materials according to weight parts, 100 parts of polypropylene, T30S type raw material is used in the implementation process; 4 parts of compatibilizer, CMG9801 type raw material is used in the implementation process; 0.12 parts of antioxidant, antioxidant 1010 and antioxidant 168 are compounded in equal weight ratio in the implementation process; 17 parts of filler, LP-600 rubber and plastic type nano calcium carbonate is used in the implementation process; the premixed raw rubber, polypropylene, compatibilizer and filler prepared as above are added, mixed at 220°C under nitrogen protection until the torque is stable, the antioxidant is added to mix, and extruded and granulated to obtain a TPO composite material.

[0044] Example 4, preparing TPO composite material for waterproofing membrane, the specific implementation process is as follows:

[0045] (1) Preparation of interface strengthener

[0046] Step A1: Take chloroalkane, aluminum chloride, 15-crown ether-5 and dioxane as feed materials, premix at 48°C for 30 minutes, then introduce nitrogen protection, add triethylenetetramine, continue to heat to 95°C, reflux and stir to react for 2 hours, wherein the chloroalkane is selected from tetradecane chloride with an alkyl chain length of C14, and the feed ratio of triethylenetetramine, tetradecane chloride, aluminum chloride, 15-crown ether-5 and dioxane is 10mmol:20mmol:18mg:0.6mL:25mL. After the reaction is completed, dioxane is quickly removed by reduced pressure rotary evaporation to obtain an alkylated intermediate.

[0047] Step A2: dimethyl thiodiacetate, alkylated intermediate, tetrabutylammonium hydroxide and anhydrous tetrahydrofuran are mixed, the temperature of the water bath is controlled at 15°C, sodium hydride is slowly added and stirred to react for 5.5 hours, and then the temperature is continued to be raised to 60°C and refluxed and stirred to react for 3 hours, wherein the feed ratio of dimethyl thiodiacetate, alkylated intermediate, tetrabutylammonium hydroxide, sodium hydride and anhydrous tetrahydrofuran is 10mmol:10mmol:18mg:30mg:60mL. After the reaction is completed, tetrahydrofuran is removed by rotary evaporation, the substrate is washed with water, the aqueous phase is removed and vacuum dried to obtain an interfacial enhancer.

[0048] (2) Preparation of TPO composite materials

[0049] Step S1: taking raw materials according to weight parts, 55 parts of EPDM rubber, 4045 type raw materials are used in the implementation process; 6.5 parts of interface strengthener, which is self-made in this embodiment; 3 parts of cross-linking agent, industrial grade triallyl isocyanate is used in the implementation process; 2.8 parts of lubricant, PP-200 type polypropylene wax and industrial grade calcium stearate are compounded in equal mass ratio in the implementation process; mixing the raw materials, refining at 85°C and thinning 4 times, cutting and crushing the discharged material to obtain a premixed raw rubber material.

[0050] Step S2: Take raw materials according to weight parts, 100 parts of polypropylene, T30S type raw material is used in the implementation process; 5 parts of compatibilizer, CMG9801 type raw material is used in the implementation process; 0.1 parts of antioxidant, antioxidant 1010 and antioxidant 168 are compounded in equal weight ratio in the implementation process; 18 parts of filler, LP-600 rubber and plastic type nano calcium carbonate is used in the implementation process; the premixed raw rubber, polypropylene, compatibilizer and filler prepared as above are added, mixed at 220°C under nitrogen protection until the torque is stable, the antioxidant is added to mix, and extruded and granulated to obtain a TPO composite material.

[0051] Comparative Example 1 refers to Example 4, except that no interface strengthener is added, and the rest of the implementation process is exactly the same.

[0052] Comparative Example 2: This comparative example is a commercially available homogeneous Polyeco TM NS TPO waterproof membrane, with a thickness of 1.5mm, comes from Saint-Gobain Group.

[0053] The composite materials prepared in Examples 1-4 and Comparative Example 1 were taken and hot-pressed at 230° C. using a flat vulcanizer to form a sheet with a thickness of 1.5 mm. The obtained sheet was sampled, and the tensile properties and right-angle tear properties of the samples were tested with reference to the contents specified in GB 27789-2011, and an artificial climate accelerated aging test was performed to detect the tensile property retention rate. The puncture resistance of the samples was tested with reference to the contents specified in CJ / T 234-2006, and the specific test results are shown in Table 1:

[0054] Table 1

[0055]

[0056] It can be seen from the test results in Table 1 that the coiled material sample prepared in the embodiment has excellent strength, toughness and puncture resistance, and has a high strength and toughness retention rate after artificial aging, and has more excellent stability.

[0057] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0058] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A TPO composite material for waterproof coiled material, characterized in that: The following raw materials are included in parts by weight: 100 parts of polypropylene, 52-58 parts of EPDM rubber, 4-5 parts of compatibilizer, 4.5-7 parts of interface strengthener, 2.8-3.6 parts of crosslinking agent, 2.2-3 parts of lubricant, 0.1-0.14 parts of antioxidant and 15-20 parts of filler; The interface strengthener is prepared by the following method: Step A1: alkane chloride, aluminum chloride, 15-crown ether-5 and dioxane are added, premixed at 40-55° C. for 15-30 minutes, and then nitrogen is introduced for protection, triethylenetetramine is added, and the temperature is continued to rise to 85-100° C. and refluxed with stirring for reaction for 1.8-2.6 hours. After the reaction is completed, dioxane is removed to obtain an alkylated intermediate, wherein the feed ratio of triethylenetetramine, alkane chloride, aluminum chloride, 15-crown ether-5 and dioxane is 10mmol:20mmol:15-20mg:0.5-0.8mL:18-30mL; Step A2: dimethyl thiodiacetate, an alkylated intermediate, tetrabutylammonium hydroxide and anhydrous tetrahydrofuran are mixed, the temperature of a water bath is controlled at 10-20°C, sodium hydride is slowly added and stirred for reaction for 4-6 hours, and then the temperature is continued to be raised to 55-65°C and refluxed and stirred for reaction for 2-3.5 hours. After the reaction is completed, tetrahydrofuran is removed, the substrate is washed with water, the aqueous phase is removed and vacuum dried to obtain an interface enhancer, wherein the feed ratio of dimethyl thiodiacetate, the alkylated intermediate, tetrabutylammonium hydroxide, sodium hydride and anhydrous tetrahydrofuran is 10mmol:10mmol:10-20mg:25-40mg:45-60mL.

2. The TPO composite material for waterproof coiled material according to claim 1, characterized in that: The alkyl chain length of chlorinated alkanes is C10-C18.

3. The TPO composite material for waterproof coiled material according to claim 1, characterized in that: The compatibilizer is maleic anhydride grafted polypropylene.

4. The TPO composite material for waterproof coiled material according to claim 1, characterized in that: The crosslinking agent is triallyl isocyanate.

5. The TPO composite material for waterproof coiled material according to claim 1, characterized in that: The lubricant is a compound of polypropylene wax and calcium stearate.

6. A method for preparing the TPO composite material for waterproofing roll according to any one of claims 1 to 5, characterized in that: The steps include: Step S1: adding EPDM rubber, an interfacial strengthening agent, a cross-linking agent and a lubricant, refining at 80-90° C. and thinning for 3-4 times, cutting and crushing the material to obtain a premixed raw rubber material; Step S2: adding the premixed raw rubber material, polypropylene, compatibilizer and filler, mixing at 220° C. under nitrogen protection until the torque is stable, adding an antioxidant, mixing, extruding and granulating, and obtaining a TPO composite material.

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