Heat-conducting graphene floor heating pipe

Abstract

The invention discloses a heat-conducting graphene floor heating pipe, and belongs to the technical field of high polymer materials, the heat-conducting graphene floor heating pipe comprises an outer layer, a bonding layer and an inner layer, the outer layer comprises the following components in parts by weight: 100-189 parts of a supporting heat-conducting material, 150-270 parts of matrix resin, 10-16 parts of a toughening agent and 8-19 parts of an antioxidant; the polyethylene resin, the graphene, the supporting material and the hydrophobic material are included; the mass ratio of the graphene to the supporting material to the hydrophobic material is 5: (0.8-1.2): (0.2-1): (0.1-0.8); the supporting material comprises at least one of potassium titanate whiskers and aluminum borate whiskers. The floor heating pipe has excellent heat conduction performance and mechanical performance, the heat dissipation rate is greatly improved, the heating efficiency of a floor heating system is effectively improved, and the overall efficient energy-saving effect is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a heat-conducting graphene floor heating pipe. Background Art

[0002] Due to the large differences in climate and environment in different places, suitable heating equipment is particularly important in the cold winter. The weather in the north remains in a relatively cold environment for a long time, so it is not enough to use air conditioning for heating like most people in the south. In the past, the heating equipment used in the north was generally kang. With the development, floor heating is gradually replacing kang and becoming the main heating method in the north. In modern construction, house heating generally uses floor radiation heating, which is often called floor heating. Floor heating is a heat storage and heat transfer technology based on the ground. At present, new communities in the south are also equipped with floor heating facilities to solve the heating needs of winter residence. Compared with air conditioning heating, floor radiation heating has many advantages, such as uniform indoor surface temperature, no effect on indoor humidity, and comfortable feeling, which is recognized by people.

[0003] Floor heating pipes are important heat dissipation components for floor radiant heating. The thermal conductivity of floor heating pipes affects the effect of floor heating and is an extremely critical performance parameter. At present, floor heating pipes are mainly polyethylene pipes. The thermal conductivity of polyethylene pipes is in the range of 0.2~0.4W / (m·k). Its thermal conductivity is poor and cannot meet the requirements of rapid indoor temperature rise. At the same time, due to the large heat loss of heat conduction, the thermal efficiency is low, which affects the overall heating efficiency of floor heating. Therefore, the market demand for ultra-high thermal conductivity floor heating pipe products is growing.

[0004] The existing floor heating pipes have a relatively slow heat dissipation speed and low working efficiency. When transmitting heat, they tend to waste some heat and waste resources.

[0005] In view of this, this application is filed. Summary of the invention

[0006] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a heat-conducting graphene floor heating pipe with excellent thermal conductivity and mechanical properties.

[0007] To achieve the above object, the technical solution adopted by the present invention is: A heat-conducting graphene floor heating pipe comprises an outer layer, a bonding layer and an inner layer, wherein the outer layer comprises the following components in parts by weight: 100-189 parts of a supporting heat-conducting material, 150-270 parts of a base resin, 10-16 parts of a toughening agent, and 8-19 parts of an antioxidant; The supporting thermal conductive material comprises polyethylene resin, graphene, supporting material and hydrophobic material; the mass ratio of the polyethylene resin, graphene, supporting material and hydrophobic material is 5: (0.8-1.2): (0.2-1): (0.1-0.8); The support material includes at least one of potassium titanate whiskers and aluminum borate whiskers; The hydrophobic material comprises the following components in parts by weight: 1 to 5 parts of titanium dioxide, 1 to 3 parts of epoxidized soybean oil, and 10 to 17 parts of polybutene.

[0008] The present invention creatively uses polyethylene resin, graphene, supporting materials and hydrophobic materials as supporting thermal conductive materials, which can significantly improve the thermal conductivity of floor heating pipes, greatly improve the heat dissipation rate, effectively improve the heating efficiency of floor heating systems, and achieve overall efficient energy-saving effects. Among them, graphene has a very high thermal conductivity, which can theoretically reach 5300 W / m·K, potassium titanate whiskers have chemical stability and a high melting point, and play an excellent supporting role. Hydrophobic materials can reduce the erosion of water on materials and extend the service life of floor heating pipes. At the same time, reducing the presence of water helps to maintain the thermal conductivity of the material (water may reduce the thermal performance of the material).

[0009] The present invention combines three (graphene, supporting material and hydrophobic material) with polyethylene resin as supporting thermal conductive material, and utilizes the characteristics of the three. Under the synergistic effect of the three, the thermal conductivity and tensile strength of the system are significantly improved. Among them, the two-dimensional sheet of graphene provides an efficient in-plane heat transfer path, and the potassium titanate whisker promotes the formation of a three-dimensional heat conduction network. This combination of two-dimensional and three-dimensional significantly improves the heat transfer efficiency and reduces the heat conduction "dead zone" in the composite material. The potassium titanate whisker provides an additional heat conduction path in the vertical direction through its fiber structure, thereby supplementing the deficiency of graphene in the vertical direction. This complementary effect of anisotropic heat transfer significantly improves the thermal conductivity of the overall material. While reducing moisture, the hydrophobic material fills the microscopic gaps between graphene and potassium titanate whiskers, reducing the thermal resistance between the interfaces, so that heat can be transferred more smoothly between the components. In addition, graphene and potassium titanate whiskers can be bridged by titanium dioxide to form a tighter interface, further reducing the interface thermal resistance.

[0010] As a preferred embodiment of the present invention, the supporting material is potassium titanate whiskers, the diameter of the potassium titanate whiskers is 3-5 μm, and the length is 10-30 μm. In particular, when the length and diameter of the potassium titanate whiskers are within this range, the potassium titanate whiskers can form a denser conductive network structure to make up for the shortcomings of graphene in the vertical direction.

[0011] In the present invention, the length and diameter of potassium titanate whiskers are tested by microscopy: 100 potassium titanate whisker samples are placed under a microscope for observation, the lengths and diameters of all potassium titanate whiskers in the samples are calculated, and the average value is calculated.

[0012] As a preferred embodiment of the present invention, the average particle size of the graphene is 10-14 μm, wherein the average particle size of the graphene is tested according to GB / T 19077-2016.

[0013] As a preferred embodiment of the present invention, the packing density of the graphene is 0.20-0.28 g / ml, wherein the packing density of the graphene is tested according to GB / T 16913.1-1997.

[0014] As a preferred embodiment of the present invention, the mass ratio of the polyethylene resin, graphene, support material and hydrophobic material is 5:1: (0.4-0.7): (0.3-0.6), especially when the mass ratio of the three is within this range, the synergistic effect is more obvious.

[0015] As a preferred embodiment of the present invention, the matrix resin includes polyethylene resin and silicone rubber, and the mass ratio of the polyethylene resin to the silicone rubber is 1: (0.4-0.5). By adopting the matrix resin composed of polyethylene resin and silicone rubber, the dispersion effect of graphene potassium titanate whiskers and titanium dioxide in the system can be improved, and their distribution is uniform and the structure is dense, which promotes the transfer of heat and the improvement of synergistic thermal conductivity, and reduces the interface thermal resistance.

[0016] As a preferred embodiment of the present invention, the silicone rubber is methyl vinyl silicone rubber, the vinyl content of the methyl vinyl silicone rubber is 0.25-0.79%, and the vinyl content of the methyl vinyl silicone rubber is obtained by testing according to the standard of GB / T36691-2018.

[0017] As a preferred embodiment of the present invention, the toughening agent includes at least one of POE resin, CPE resin, and ABS resin; and / or The antioxidant includes at least one of a thioester antioxidant, a hindered phenol antioxidant, a hydroxylamine antioxidant, a phosphite antioxidant, and a phosphate antioxidant.

[0018] As a preferred embodiment of the present invention, the inner layer comprises the following components in parts by weight: 40 to 55 parts of hydrophobic material, 20 to 39 parts of antibacterial material, 5 to 17 parts of coupling agent, and 1 to 8 parts of dispersant.

[0019] As a preferred embodiment of the present invention, the coupling agent includes at least one of a titanate coupling agent, a stannate coupling agent, a silane coupling agent, and an aluminate coupling agent; The dispersant includes at least one of zinc stearate, barium stearate and calcium stearate; The antibacterial material is a complex of a triazole compound and silver, and the triazole compound includes at least one of 2-triazole-biphenyl dicarboxylic acid and 1,2,3-triazole.

[0020] As a preferred embodiment of the present invention, the polyethylene resin mentioned in the present invention has a melt flow rate of 0.5-2 g / 10 min at 190° C. / 2.16 kg, and the test method is ISO1133-2011.

[0021] As a preferred embodiment of the present invention, the thickness of the outer layer is 7-14 mm, the thickness of the inner layer is 5-15 mm, and the thickness of the adhesive layer is 50-120 μm.

[0022] The present invention also provides a method for preparing a heat-conducting graphene floor heating pipe, comprising the following steps: (1) preparing the inner layer, weighing the raw materials according to the ratio, mixing the raw materials evenly, melt-blending, extruding the molten blend through an extruder, and cooling to form the inner layer; (2) preparing the outer layer, weighing the raw materials according to the ratio, mixing the raw materials evenly, melt-blending, extruding the molten blend through an extruder, and cooling to form the outer layer; (3) Coating an adhesive between the inner layer and the outer layer, and assembling the inner layer, the adhesive layer, and the outer layer in sequence to obtain a heat-conducting graphene floor heating pipe.

[0023] The beneficial effect of the present invention is that the present invention uses polyethylene resin, graphene, supporting materials and hydrophobic materials as supporting thermal conductive materials, which can significantly improve the thermal conductivity of floor heating pipes, greatly increase the heat dissipation rate, effectively improve the heating efficiency of the floor heating system, and achieve an overall efficient energy-saving effect. DETAILED DESCRIPTION

[0024] In order to make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application are described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present application.

[0025] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0026] In this application, when it comes to numerical ranges, unless otherwise specified, the above numerical ranges are deemed to be continuous and include the minimum and maximum values ​​of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0027] In the present application, there is no particular limitation on the specific dispersion and stirring treatment methods.

[0028] Unless otherwise specified, the components, raw materials or instruments used in the embodiments and comparative examples of the present invention are all commercially available raw materials or instruments, and the components and raw materials used in each parallel experiment are all of the same kind.

[0029] The sources of raw materials for the embodiments and comparative examples are as follows: Polyethylene resin: Dow Chemical, brand: DGDK-3364.

[0030] Methyl vinyl silicone rubber-1: Dongjue silicone, vinyl content 0.25~0.49%, brand 110-4.

[0031] Methyl vinyl silicone rubber-2: Dongjue silicone, vinyl content 0.50~0.79%, brand 110-5.

[0032] Methyl vinyl silicone rubber-3: Dongjue silicone, vinyl content 0.07~0.12%, brand 110-1.

[0033] Methyl vinyl silicone rubber-4: Dongjue silicone, vinyl content 0.8~1.79%, brand 110-6.

[0034] Methyl silicone rubber: Dongjue silicone, brand 110.

[0035] Graphene-1: Xiamen Kaina Graphene Co., Ltd., average particle size 10~14μm, brand KNG-180-3.

[0036] Graphene-2: Xiamen Kaina Graphene Co., Ltd., average particle size 20~45μm, brand KNG-182.

[0037] Graphene-3: Xiamen Kaina Graphene Co., Ltd., average particle size 3~6μm, brand KNG-150.

[0038] Potassium titanate whisker-1: McLean reagent, diameter 3~5μm, length 10~30μm, brand H790559.

[0039] Potassium titanate whisker-2: McLean reagent, diameter 0.1~0.3μm, length 3~5μm, brand H790559.

[0040] Potassium titanate whisker-3: McLean reagent, diameter 20~100μm, length 1μm, brand H790559.

[0041] Aluminum borate whiskers: McLean reagent, diameter 20~100μm, length 1μm, brand: H790559.

[0042] POE resin: DuPont, molecular weight range is between 2 million and 6 million, brand: Engage 8842.

[0043] Antioxidant: BASF, active ingredient content is more than 98%, brand: Irganox 1010.

[0044] Titanium dioxide: Clariant, brand: Tiona R24.

[0045] Epoxidized soybean oil: Cargill, brand: Edenor SO-300.

[0046] Polybutene: ExxonMobil, melt index is 1.0 g / 10 min (230°C, 2.16 kg), brand: Exact3035.

[0047] Coupling agent: Dow Corning, silane coupling agent, brand: Dynasylan® GLYMO.

[0048] Antibacterial material: Add 2-triazole-biphenyl dicarboxylic acid and silver nitrate in a mass ratio of 1:1 into DMF solution, stir evenly at room temperature, heat treat at 180°C for 2h, and dry at 60°C to obtain a complex of 2-triazole-biphenyl dicarboxylic acid and silver.

[0049] Dispersant: Zinc stearate, commonly available in the market.

[0050] The following examples are provided to facilitate understanding of the present invention. These examples are not provided to limit the scope of the claims.

[0051] Example 1 A heat-conducting graphene floor heating pipe comprises an outer layer, a bonding layer and an inner layer, wherein the thickness of the outer layer is 10 mm, the thickness of the inner layer is 8 mm, and the thickness of the bonding layer is 70 μm.

[0052] Wherein, the outer layer comprises the following components in parts by weight: 150 parts of supporting thermal conductive material, 225 parts of base resin, 15 parts of toughening agent, and 10 parts of antioxidant.

[0053] The supporting thermal conductive material comprises polyethylene resin, graphene-1, potassium titanate whisker-1 and hydrophobic material; The mass ratio of the polyethylene resin, graphene-1, supporting material and hydrophobic material is 5:1:0.6:0.4.

[0054] The hydrophobic material comprises the following components in parts by weight: 4 parts of titanium dioxide, 2 parts of epoxidized soybean oil, and 14 parts of polybutene.

[0055] The matrix resin includes polyethylene resin and methyl vinyl silicone rubber-1, and the mass ratio of the polyethylene resin to the methyl vinyl silicone rubber-1 is 1:0.4.

[0056] The inner layer includes the following components in parts by weight: 52 parts of hydrophobic material (same as the outer layer), 30 parts of antibacterial material, 12 parts of coupling agent, and 6 parts of dispersant.

[0057] The preparation method of the thermally conductive graphene floor heating pipe comprises the following steps: (1) preparing the inner layer, weighing the raw materials according to the ratio, mixing the raw materials evenly, melt-blending, extruding the molten blend through an extruder, and cooling to form the inner layer; (2) preparing the outer layer, weighing the raw materials according to the ratio, mixing the raw materials evenly, melt-blending, extruding the molten blend through an extruder, and cooling to form the outer layer; (3) Coating an adhesive between the inner layer and the outer layer, and assembling the inner layer, the adhesive layer, and the outer layer in sequence to obtain a heat-conducting graphene floor heating pipe.

[0058] Example 2 The difference between Example 2 and Example 1 is that the amount of raw materials used in the outer layer is different, and the other aspects are the same.

[0059] The outer layer comprises the following components in parts by weight: 100 parts of supporting thermal conductive material, 150 parts of base resin, 10 parts of toughening agent, and 8 parts of antioxidant.

[0060] Example 3 The difference between Example 3 and Example 1 is that the amount of raw materials used in the outer layer is different, and the other aspects are the same.

[0061] The outer layer includes the following components in parts by weight: 189 parts of supporting thermal conductive material, 270 parts of base resin, 16 parts of toughening agent, and 19 parts of antioxidant.

[0062] Example 4 The difference between Example 4 and Example 1 is that potassium titanate whisker-2 is used to replace potassium titanate whisker-1, and the other aspects are the same.

[0063] Example 5 The difference between Example 5 and Example 1 is that potassium titanate whisker-3 is used to replace potassium titanate whisker-1, and the other parts are the same.

[0064] Example 6 The difference between Example 6 and Example 1 is that aluminum borate whiskers are used to replace potassium titanate whiskers-1, and the other aspects are the same.

[0065] Example 7 The difference between Example 7 and Example 1 is that the mass ratios of polyethylene resin, graphene, potassium titanate whisker-1 and hydrophobic material are different, and the others are the same.

[0066] In this embodiment, the mass ratio of polyethylene resin, graphene, potassium titanate whisker-1 and hydrophobic material is 5:1:0.4:0.6.

[0067] Example 8 The difference between Example 8 and Example 1 is that the mass ratios of polyethylene resin, graphene-1, potassium titanate whisker-1 and hydrophobic material are different, and the others are the same.

[0068] In this embodiment, the mass ratio of polyethylene resin, graphene-1, potassium titanate whisker-1 and hydrophobic material is 5:1:0.7:0.3.

[0069] Example 9 The difference between Example 9 and Example 1 is that the mass ratios of polyethylene resin, graphene-1, potassium titanate whisker-1 and hydrophobic material are different, and the others are the same.

[0070] In this embodiment, the mass ratio of polyethylene resin, graphene, potassium titanate whisker-1 and hydrophobic material is 5:1:0.2:0.1.

[0071] Example 10 The difference between Example 10 and Example 1 is that the mass ratios of polyethylene resin, graphene-1, potassium titanate whisker-1 and hydrophobic material are different, and the others are the same.

[0072] In this embodiment, the mass ratio of polyethylene resin, graphene-1, potassium titanate whisker-1 and hydrophobic material is 5:1:1:0.8.

[0073] Embodiment 11 The difference between Example 11 and Example 1 is that graphene-2 ​​is used to replace graphene-1, and the other aspects are the same.

[0074] Example 12 The difference between Example 12 and Example 1 is that graphene-3 is used to replace graphene-1, and the other aspects are the same.

[0075] Example 13 The difference between Example 13 and Example 1 is that methyl vinyl silicone rubber-2 is used to replace methyl vinyl silicone rubber-1, and the other parts are the same.

[0076] Embodiment 14 The difference between Example 14 and Example 1 is that methyl vinyl silicone rubber-3 is used to replace methyl vinyl silicone rubber-1, and the other parts are the same.

[0077] Embodiment 15 The difference between Example 15 and Example 1 is that methyl vinyl silicone rubber-4 is used to replace methyl vinyl silicone rubber-1, and the other parts are the same.

[0078] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the base resin of Comparative Example 1 is different from that of Example 1, and the other parts are the same.

[0079] The base resin of this comparative example is a single polyethylene resin.

[0080] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that the base resin of Comparative Example 2 is different from that of Example 1, and the other parts are the same.

[0081] The base resin in this comparative example includes polyethylene resin and methyl silicone rubber, and the mass ratio of the polyethylene resin to the methyl silicone rubber is 1:0.4.

[0082] Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that the supporting thermal conductive material of Comparative Example 3 is different from that of Example 1, and the other parts are the same.

[0083] The supporting thermal conductive material comprises polyethylene resin, potassium titanate whisker-1 and hydrophobic material; the mass ratio of the polyethylene resin, the supporting material and the hydrophobic material is 5:0.6:0.4.

[0084] The hydrophobic material comprises the following components in parts by weight: 4 parts of titanium dioxide, 2 parts of epoxidized soybean oil, and 14 parts of polybutene.

[0085] Comparative Example 4 The difference between Comparative Example 4 and Example 1 is that the supporting thermal conductive material of Comparative Example 4 is different from that of Example 1, and the other parts are the same.

[0086] The supporting thermal conductive material comprises polyethylene resin, graphene-1 and hydrophobic material; the mass ratio of the polyethylene resin, graphene-1 and hydrophobic material is 5:1:0.4.

[0087] The hydrophobic material comprises the following components in parts by weight: 4 parts of titanium dioxide, 2 parts of epoxidized soybean oil, and 14 parts of polybutene.

[0088] Comparative Example 5 The difference between Comparative Example 5 and Example 1 is that the supporting thermal conductive material of Comparative Example 5 is different from that of Example 1, and the other parts are the same.

[0089] The supporting thermal conductive material comprises polyethylene resin, graphene-1 and potassium titanate whisker-1; the ratio of polyethylene resin, graphene-1 and supporting material is 5:1:0.6.

[0090] Comparative Example 6 The difference between Comparative Example 6 and Example 1 is that the supporting thermal conductive material of Comparative Example 6 is different from that of Example 1, and the rest are the same.

[0091] The supporting thermal conductive material comprises polyethylene resin and graphene-1, and the mass ratio of the polyethylene resin to the graphene-1 is 5:1.

[0092] Comparative Example 7 The difference between Comparative Example 7 and Example 1 is that the supporting thermal conductive material of Comparative Example 7 is different from that of Example 1, and the other parts are the same.

[0093] The supporting heat-conducting material comprises polyethylene resin and potassium titanate whisker-1, and the mass ratio of the polyethylene resin to the potassium titanate whisker-1 is 5:0.6.

[0094] Comparative Example 8 The difference between Comparative Example 8 and Example 1 is that the supporting thermal conductive material of Comparative Example 8 is different from that of Example 1, and the other parts are the same.

[0095] The supporting thermal conductive material comprises polyethylene resin and hydrophobic material, and the mass ratio of the polyethylene resin to the hydrophobic material is 5:0.4.

[0096] The hydrophobic material comprises the following components in parts by weight: 4 parts of titanium dioxide, 2 parts of epoxidized soybean oil, and 14 parts of polybutene.

[0097] Comparative Example 9 The difference between Comparative Example 9 and Example 1 is that the supporting thermal conductive material of Comparative Example 9 is different from that of Example 1, and the other parts are the same.

[0098] The supporting thermal conductive material comprises polyethylene resin, graphene-1, potassium titanate whisker-1 and titanium dioxide; the mass ratio of the polyethylene resin, graphene-1, supporting material and titanium dioxide is 5:1:0.6:0.4.

[0099] Comparative Example 10 The difference between Comparative Example 10 and Example 1 is that the supporting thermal conductive material of Comparative Example 10 is different from that of Example 1, and the other parts are the same.

[0100] The supporting thermal conductive material comprises polyethylene resin, graphene-1, potassium titanate whisker-1 and talcum powder; the mass ratio of the polyethylene resin, graphene-1, potassium titanate whisker-1 and talcum powder is 1:0.6:0.4.

[0101] Test Case The tensile strength standard is ASTM D638, the specimen size is 57mm*127mm*3.2mm (effective size), and the tensile speed is 5mm / min.

[0102] Thermal conductivity test standard: ASTMD1461.

[0103] Table 1 It can be seen from Table 1 that the thermally conductive graphene floor heating pipe of the present invention has excellent thermal conductivity and tensile strength, wherein the thermal conductivity of the thermally conductive graphene floor heating pipe is ≥2.8 W / m·K, and the tensile strength is ≥21 MPa.

[0104] By comparing Example 1 with Comparative Examples 3 to 10, it can be seen that the graphene, supporting material and hydrophobic material in the supporting thermal conductive material described in the present invention have a significant synergistic effect, which can significantly improve the thermal conductivity and tensile strength. The lack of any one of them or the use of other raw materials for replacement will lead to a significant decrease in the thermal conductivity and tensile strength.

[0105] By comparing Example 1 with Comparative Examples 1-2, it can be seen that the present invention uses polyethylene resin and silicone rubber as base resins, which can significantly improve thermal conductivity and tensile strength.

[0106] By comparing Examples 1 and 4 to 6, it can be seen that the present invention uses potassium titanate whiskers with a diameter of 3 to 5 μm and a length of 10 to 30 μm, which can further improve the thermal conductivity and tensile strength.

[0107] By comparing Examples 1, 7 to 10, it can be seen that the present invention further improves thermal conductivity and tensile strength by adopting polyethylene resin, graphene, supporting material and hydrophobic material in a ratio of 5:1:(0.4-0.7):(0.3-0.6).

[0108] By comparing Examples 1, 11 and 12, it can be seen that the present invention uses graphene with an average particle size of 10 to 14 μm, which further improves the thermal conductivity and tensile strength.

[0109] Comparative Examples 1 and 13 to 15 show that the present invention uses methyl vinyl silicone rubber with a vinyl content of 0.25 to 0.79%, which further improves thermal conductivity and tensile strength.

[0110] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A thermally conductive graphene floor heating pipe, characterized in that: It comprises an outer layer, a bonding layer and an inner layer, wherein the outer layer comprises the following components in parts by weight: 100-189 parts of a supporting thermal conductive material, 150-270 parts of a base resin, 10-16 parts of a toughening agent, and 8-19 parts of an antioxidant; The supporting thermal conductive material comprises polyethylene resin, graphene, supporting material and hydrophobic material; the mass ratio of the polyethylene resin, graphene, supporting material and hydrophobic material is 5: (0.8-1.2): (0.2-1): (0.1-0.8); The support material includes at least one of potassium titanate whiskers and aluminum borate whiskers; The hydrophobic material comprises the following components in parts by weight: 1 to 5 parts of titanium dioxide, 1 to 3 parts of epoxidized soybean oil, and 10 to 17 parts of polybutene.

2. The heat-conducting graphene floor heating pipe according to claim 1, characterized in that: The supporting material is potassium titanate whisker, and the diameter of the potassium titanate whisker is 3-5 μm and the length is 10-30 μm.

3. The heat-conducting graphene floor heating pipe according to claim 1, characterized in that: The average particle size of the graphene is 10-14 μm.

4. The heat-conducting graphene floor heating pipe according to claim 1, characterized in that: The mass ratio of the polyethylene resin, graphene, support material and hydrophobic material is 5:1:(0.4-0.7):(0.3-0.6).

5. The heat-conducting graphene floor heating pipe according to claim 1, characterized in that: The matrix resin includes polyethylene resin and silicone rubber, and the mass ratio of the polyethylene resin to the silicone rubber is 1:(0.4-0.5).

6. The heat-conducting graphene floor heating pipe according to claim 5, characterized in that: The silicone rubber is methyl vinyl silicone rubber, and the vinyl content of the methyl vinyl silicone rubber is 0.25-0.79%.

7. The heat-conducting graphene floor heating pipe according to claim 1, characterized in that: The toughening agent comprises at least one of POE resin, CPE resin and ABS resin; and / or The antioxidant includes at least one of a thioester antioxidant, a hindered phenol antioxidant, a hydroxylamine antioxidant, a phosphite antioxidant, and a phosphate antioxidant.

8. The heat-conducting graphene floor heating pipe according to claim 1, characterized in that: The inner layer comprises the following components in parts by weight: 40 to 55 parts of hydrophobic material, 20 to 39 parts of antibacterial material, 5 to 17 parts of coupling agent, and 1 to 8 parts of dispersant.

9. The heat-conducting graphene floor heating pipe according to claim 8, characterized in that: The coupling agent includes at least one of a titanate coupling agent, a stannate coupling agent, a silane coupling agent, and an aluminate coupling agent.

10. The heat-conducting graphene floor heating pipe according to claim 8, characterized in that: The dispersant includes at least one of zinc stearate, barium stearate and calcium stearate.

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