Flame-retardant cable material and preparation method thereof

Abstract

The invention discloses a flame-retardant cable material, which is prepared from the following raw materials in parts by weight: 90 to 110 parts of PVC (Polyvinyl Chloride) resin, 45 to 55 parts of plasticizer, 50 to 60 parts of filler, 1 to 10 parts of stabilizer, 0.1 to 1 part of lubricant and 5 to 8 parts of rare earth flame retardant. The rare earth flame retardant with the D50 particle size of 3.97 microns is adopted to replace antimonous oxide, and the weight ratio of the rare earth flame retardant to the PVC resin is 5-7%, so that the flame-retardant effect of the flame-retardant cable material is improved, and the production cost of the flame-retardant cable material is reduced. The flame-retardant cable material disclosed by the invention can be maintained to have a proper specific gravity at relatively low cost, and the use requirements of cables are met. The stability of the flame-retardant cable material is optimized, and the flame-retardant cable material is prevented from being denatured and degraded in a high-temperature environment.

Description

Technical Field

[0001] The invention relates to the field of polymer compounds, and in particular to a flame retardant cable material and a preparation method thereof. Background Art

[0002] Cable materials are used in huge quantities in practical applications. Flame retardant effect is the basic performance of cable materials. Existing cable materials mostly use antimony trioxide as a flame retardant for cable materials. It has good flame retardant effect and can meet the use requirements of PVC cables. However, the cost of antimony trioxide is relatively high, which will significantly increase the cost of cable materials in large-scale industrial production. Using other low-cost flame retardants, the environmental performance and mechanical properties of cable materials cannot achieve a good balance. Therefore, it is very important to develop a low-cost flame retardant cable material.

[0003] Chinese invention patent CN103044802B discloses a water-resistant flame-retardant PVC cable material and its preparation process, wherein the powder is pre-dehydrated and then surface coated to improve the hydrophobicity of the product, so that the product can be used in a humid or submerged environment, and the electrical performance is stable and basically unchanged; the water-resistant agent material uses nano-grade raw materials to improve the compactness of the product, eliminate the micropores of the material, and water vapor cannot invade, but the flame retardant used is expensive, and the cost of industrial production is high. Chinese invention patent CN109096656A discloses a highly flame-retardant and highly thermally conductive PVC composite cable material and its preparation method, wherein polytetrafluoroethylene is dispersed in a perfluoroalkoxy copolymer and an ethylene-chlorotrifluoroethylene copolymer in the form of micropowder, and a suitable proportion of thermal conductive filler, flame retardant and aramid fiber are added to prepare a composite cable material with stable chemical properties, excellent electrical insulation properties and flame retardancy, but the price of tetrafluoroethylene is expensive, and the reactivity with polyvinyl chloride is poor, and the environmental pressure is high.

[0004] Description

[0005] In order to develop a low-cost flame-retardant cable material, the first aspect of the present invention provides a flame-retardant cable material, the raw materials for preparing which include, by weight, 90-110 parts of PVC resin, 45-55 parts of plasticizer, 50-60 parts of filler, 1-10 parts of stabilizer, 0.1-1 parts of lubricant, and 5-8 parts of rare earth flame retardant.

[0006] As a preferred embodiment, the rare earth flame retardant is selected from at least one of a rare earth-nitrogen-phosphorus composite flame retardant, a rare earth-magnesium hydroxide composite flame retardant, a rare earth oxide flame retardant, and a rare earth halogen-containing flame retardant.

[0007] As a preferred implementation, the D50 particle size of the rare earth flame retardant is 1-50 μm, and the oxygen index of the rare earth flame retardant is 30-40%.

[0008] As a preferred implementation, the D50 particle size of the rare earth flame retardant is 1-10 μm, and the oxygen index of the rare earth flame retardant is 30-35%.

[0009] As a preferred implementation, the D50 particle size of the rare earth flame retardant is 3.97 μm, and the oxygen index of the rare earth flame retardant is 32.6%.

[0010] As a preferred embodiment, the usage amount of the rare earth flame retardant accounts for 5-7% of the weight of the PVC resin.

[0011] During the experiment, the inventors found that the use of rare earth flame retardants with a D50 particle size of 3.97 μm instead of traditional antimony trioxide flame retardants can reduce the production cost of flame-retardant cable materials. The reason is that the cost of rare earth flame retardants is relatively low. In this application, adding 5-7% of the rare earth flame retardant by weight to PVC can achieve the flame retardant effect of 4% of antimony trioxide by weight to PVC, meeting the flame retardant requirements. However, the unit ton cost of rare earth flame retardants is still lower than that of antimony trioxide, which is conducive to large-scale factory production.

[0012] As a preferred embodiment, the plasticizer is selected from at least one of epoxy soybean oil, epoxy acetyl linolenic acid methyl ester, trioctyl citrate, epoxy soybean octyl ester, and dioctyl terephthalate.

[0013] As a preferred embodiment, the plasticizer is a combination of epoxidized soybean oil and dioctyl terephthalate, and the weight ratio of the epoxidized soybean oil to dioctyl terephthalate is 1:(5-10);

[0014] As a preferred embodiment, the weight ratio of the epoxidized soybean oil to dioctyl terephthalate is 1:9.

[0015] As a preferred embodiment, the filler is selected from at least one of calcium carbonate, carbon black, graphite, carbon fiber, graphene, talc, and calcium silicate.

[0016] As a preferred embodiment, the filler is calcium carbonate.

[0017] As a preferred embodiment, the weight ratio of the rare earth flame retardant to calcium carbonate is (5-7): (50-60).

[0018] As a preferred embodiment, the weight ratio of the rare earth flame retardant to calcium carbonate is (5-6): (50-55).

[0019] As a preferred implementation, the weight ratio of the rare earth flame retardant to calcium carbonate is 5.6:51.

[0020] The inventors found during the experiment that the weight ratio of rare earth flame retardant to calcium carbonate (5-7): (50-60) can maintain the flame retardant cable material with a suitable specific gravity at a relatively low cost to meet the use requirements of the cable. The possible reason is speculated to be: the density of the rare earth flame retardant is relatively small. By controlling the weight ratio of the rare earth flame retardant to calcium carbonate, a flame retardant cable material with a suitable specific gravity can be obtained. If the preferred weight ratio is exceeded, the size of the cable will increase and will not meet the use requirements of the cable. If the weight ratio is lower than the preferred weight ratio, the mechanical properties of the obtained cable material will decrease, resulting in the cable material being too brittle, affecting the tensile and fracture properties of the cable material.

[0021] As a preferred embodiment, the weight ratio of calcium carbonate to stabilizer is (50-60); (1-5).

[0022] As a preferred embodiment, the weight ratio of calcium carbonate to stabilizer is (50-55); (3-5)

[0023] As a preferred embodiment, the weight ratio of calcium carbonate to stabilizer is 51:5.

[0024] As a preferred embodiment, the stabilizer is a calcium zinc stabilizer.

[0025] The inventors found during the experiment that the performance of PVC cable materials is unstable in a high temperature environment, and the PVC resin molecules are active and easily decomposed. The stability of the PVC resin can be improved by introducing a calcium zinc stabilizer. At the same time, the weight ratio of calcium carbonate to calcium zinc stabilizer is (50-60): (1-5), which can maintain the stability of the performance during cable processing while not reducing the hardness, elongation at break and tensile strength, thereby meeting the actual application requirements of flame retardant cable materials.

[0026] As a preferred embodiment, the lubricant is selected from at least one of stearic acid, oleic acid, paraffin, polyethylene wax, stearic acid amide, ethylene bis stearamide, and butyl stearate.

[0027] As a preferred embodiment, the lubricant is a combination of stearic acid and polyethylene wax.

[0028] As a preferred embodiment, the weight ratio of stearic acid to polyethylene wax is (0.3-0.5): (0.3-0.5).

[0029] As a preferred embodiment, the weight ratio of stearic acid to polyethylene wax is 0.4:0.4.

[0030] A second aspect of the present invention provides a method for preparing a flame retardant cable material, comprising the following steps:

[0031] S1 adds filler, PVC resin, stabilizer, lubricant, rare earth flame retardant and plasticizer in sequence and mixes;

[0032] S2 is mixed by high-speed stirring, heated to 130-140°C, and extruded into granules by a twin-screw extruder.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] (1) The flame retardant cable material of the present invention adopts a rare earth flame retardant with a D50 particle size of 3.97 μm to replace antimony trioxide. The weight ratio of the rare earth flame retardant to the PVC resin is 5-7%, which improves the flame retardant effect of the flame retardant cable material and reduces the production cost of the flame retardant cable material.

[0035] (2) In the flame-retardant cable material of the present invention, the rare earth flame retardant and calcium carbonate are in a weight ratio of (5-7): (50-60), which can maintain the flame-retardant cable material with a suitable specific gravity at a relatively low cost and meet the use requirements of the cable.

[0036] (3) In the flame-retardant cable material of the present invention, the weight ratio of calcium carbonate to calcium zinc stabilizer is (50-60): (1-5), which can improve the stability of the flame-retardant cable material and prevent it from denaturing and degrading in a high temperature environment.

[0037] (4) The flame retardant cable material of the present invention uses a rare earth flame retardant instead of antimony trioxide to increase the amount of calcium carbonate added, further reduce the production cost of the flame retardant cable material, and improve the economic value.

[0038] (5) The flame-retardant cable material of the present invention has good flame-retardant effect at a relatively low price, and its mechanical properties meet the requirements for the use of PVC cable materials. DETAILED DESCRIPTION

[0039] Example 1

[0040] A flame retardant cable material. The raw materials for preparing the material include, by weight, 100 parts of PVC resin, 50 parts of plasticizer, 51 parts of filler, 5 parts of stabilizer, 0.8 parts of lubricant and 5.6 parts of rare earth flame retardant.

[0041] The PVC resin was purchased from Yibin Tianyuan Group Co., Ltd., model number SG-5.

[0042] The plasticizer is a combination of epoxidized soybean oil and dioctyl terephthalate, with a weight ratio of 1:9. The epoxidized soybean oil was purchased from Xinjinlong Bio-based Materials (Hubei) Co., Ltd.

[0043] The filler is calcium carbonate.

[0044] The stabilizer is a calcium zinc stabilizer, which is purchased from Shenzhen Zhihai Industrial Co., Ltd. with a brand number of 6380.

[0045] The lubricant is a combination of stearic acid and polyethylene wax, with a weight ratio of 0.4:0.4. The polyethylene wax is purchased from Sichuan Haosen New Materials Co., Ltd., with a brand name of HS-8310.

[0046] The rare earth flame retardant has a D50 particle size of 3.97 μm and an oxygen index of 32.6%. It is purchased from Northern Rare Earth Ruihong (Baotou) New Materials Technology Co., Ltd. with a brand name of REFR-2312.

[0047] A method for preparing a flame retardant cable material comprises the following steps:

[0048] S1 adds filler, PVC resin, stabilizer, lubricant, rare earth flame retardant and plasticizer in sequence and mixes;

[0049] S2 is mixed by high-speed stirring, heated to 135°C, and extruded into granules by a twin-screw extruder.

[0050] Comparative Example 1

[0051] A flame retardant cable material. The raw materials for preparing the material include, by weight, 100 parts of PVC resin, 50 parts of plasticizer, 48 parts of filler, 5 parts of stabilizer, 0.8 parts of lubricant and 4 parts of antimony trioxide.

[0052] The PVC resin was purchased from Yibin Tianyuan Group Co., Ltd., model number SG-5.

[0053] The plasticizer is a combination of epoxidized soybean oil and dioctyl terephthalate, with a weight ratio of 1:9. The epoxidized soybean oil was purchased from Xinjinlong Bio-based Materials (Hubei) Co., Ltd.

[0054] The filler is calcium carbonate.

[0055] The stabilizer is a calcium zinc stabilizer, which is purchased from Shenzhen Zhihai Industrial Co., Ltd. with a brand number of 6380.

[0056] The lubricant is a combination of stearic acid and polyethylene wax, with a weight ratio of 0.4:0.4.

[0057] The polyethylene wax was purchased from Sichuan Haosen New Materials Co., Ltd. with the brand name HS-8310.

[0058] A method for preparing a flame retardant cable material comprises the following steps:

[0059] S1 adds filler, PVC resin, stabilizer, lubricant, antimony trioxide and plasticizer in sequence and mixes;

[0060] S2 is mixed by high-speed stirring, heated to 135°C, and extruded into granules by a twin-screw extruder.

[0061] Comparative Example 2

[0062] A flame retardant cable material. The raw materials for preparing the material include, by weight, 100 parts of PVC resin, 50 parts of plasticizer, 51 parts of filler, 5 parts of stabilizer, 0.8 parts of lubricant and 4 parts of rare earth flame retardant.

[0063] The PVC resin was purchased from Yibin Tianyuan Group Co., Ltd., model number SG-5.

[0064] The plasticizer is a combination of epoxidized soybean oil and dioctyl terephthalate, with a weight ratio of 1:9. The epoxidized soybean oil was purchased from Xinjinlong Bio-based Materials (Hubei) Co., Ltd.

[0065] The filler is calcium carbonate.

[0066] The stabilizer is a calcium zinc stabilizer, which is purchased from Shenzhen Zhihai Industrial Co., Ltd. with a brand number of 6380.

[0067] The lubricant is a combination of stearic acid and polyethylene wax, with a weight ratio of 0.4:0.4.

[0068] The polyethylene wax was purchased from Sichuan Haosen New Materials Co., Ltd. with the brand name HS-8310.

[0069] The rare earth flame retardant has a D50 particle size of 3.97 μm and an oxygen index of 32.6%. It is purchased from Northern Rare Earth Ruihong (Baotou) New Materials Technology Co., Ltd. with a brand name of REFR-2312.

[0070] A method for preparing a flame retardant cable material comprises the following steps:

[0071] S1 adds filler, PVC resin, stabilizer, lubricant, rare earth flame retardant and plasticizer in sequence and mixes;

[0072] S2 is mixed by high-speed stirring, heated to 135°C, and extruded into granules by a twin-screw extruder.

[0073] Comparative Example 3

[0074] A flame retardant cable material. The raw materials for preparing the material include, by weight, 100 parts of PVC resin, 50 parts of plasticizer, 52 parts of filler, 5 parts of stabilizer, 0.8 parts of lubricant and 2 parts of antimony trioxide.

[0075] The PVC resin was purchased from Yibin Tianyuan Group Co., Ltd., model number SG-5.

[0076] The plasticizer is a combination of epoxidized soybean oil and dioctyl terephthalate, with a weight ratio of 1:9. The epoxidized soybean oil was purchased from Xinjinlong Bio-based Materials (Hubei) Co., Ltd.

[0077] The filler is calcium carbonate.

[0078] The stabilizer is a calcium zinc stabilizer, which is purchased from Shenzhen Zhihai Industrial Co., Ltd. with a brand number of 6380.

[0079] The lubricant is a combination of stearic acid and polyethylene wax, with a weight ratio of 0.4:0.4.

[0080] The polyethylene wax was purchased from Sichuan Haosen New Materials Co., Ltd. with the brand name HS-8310.

[0081] A method for preparing a flame retardant cable material comprises the following steps:

[0082] S1 adds filler, PVC resin, stabilizer, lubricant, antimony trioxide and plasticizer in sequence and mixes;

[0083] S2 is mixed by high-speed stirring, heated to 135°C, and extruded into granules by a twin-screw extruder.

[0084] Comparative Example 4

[0085] A flame retardant cable material. The raw materials for preparing the material include, by weight, 100 parts of PVC resin, 50 parts of plasticizer, 50 parts of filler, 5 parts of stabilizer, 0.8 parts of lubricant and 3 parts of antimony trioxide.

[0086] The PVC resin was purchased from Yibin Tianyuan Group Co., Ltd., model number SG-5.

[0087] The plasticizer is a combination of epoxidized soybean oil and dioctyl terephthalate, with a weight ratio of 1:9. The epoxidized soybean oil was purchased from Xinjinlong Bio-based Materials (Hubei) Co., Ltd.

[0088] The filler is calcium carbonate.

[0089] The stabilizer is a calcium zinc stabilizer, which is purchased from Shenzhen Zhihai Industrial Co., Ltd. with a brand number of 6380.

[0090] The lubricant is a combination of stearic acid and polyethylene wax, with a weight ratio of 0.4:0.4. The polyethylene wax is purchased from Sichuan Haosen New Materials Co., Ltd., with a brand name of HS-8310.

[0091] A method for preparing a flame retardant cable material comprises the following steps:

[0092] S1 adds filler, PVC resin, stabilizer, lubricant, antimony trioxide and plasticizer in sequence and mixes;

[0093] S2 is mixed by high-speed stirring, heated to 135°C, and extruded into granules by a twin-screw extruder.

[0094] Performance Testing

[0095] 1. Cost: Calculate the average cost based on market price.

[0096] 2.Relative density: Refer to GB / T8815-2008 standard to test relative density.

[0097] 3. Hardness: Use a Shore hardness tester to test the hardness of the cable material.

[0098] 4.Tensile strength: Refer to GB / T8815-2008 standard to test tensile strength performance.

[0099] 5. Elongation at break: Test the elongation at break performance in accordance with GB / T8815-2008 standard.

[0100] 6. Flame retardant oxygen index: refer to GB / T 2406-1993 standard to test the flame retardant oxygen index.

[0101] 7. Vertical burning: Refer to the American standard UL1581 to test the flame retardant vertical burning performance.

[0102] The test results are shown in Table 1.

[0103] Table 1

[0104]

Claims

1. A flame retardant cable material, characterized in that: The raw materials for preparation include 90-110 parts of PVC resin, 45-55 parts of plasticizer, 50-60 parts of filler, 1-10 parts of stabilizer, 0.1-1 parts of lubricant and 5-8 parts of rare earth flame retardant in parts by weight.

2. The flame-retardant cable material according to claim 1, characterized in that: The rare earth flame retardant is selected from at least one of a rare earth-nitrogen-phosphorus composite flame retardant, a rare earth-magnesium hydroxide composite flame retardant, a rare earth oxide flame retardant, and a rare earth halogen-containing flame retardant.

3. The flame retardant cable material according to claim 1, characterized in that: The D50 particle size of the rare earth flame retardant is 1-50 μm, and the oxygen index of the rare earth flame retardant is 30-40%.

4. The flame retardant cable material according to claim 1, characterized in that: The usage amount of the rare earth flame retardant accounts for 5-7% of the weight of the PVC resin.

5. The flame retardant cable material according to claim 1, characterized in that: The plasticizer is selected from at least one of epoxy soybean oil, epoxy acetyl linolenic acid methyl ester, trioctyl citrate, epoxy soybean octyl ester, and dioctyl terephthalate.

6. The flame retardant cable material according to claim 1, characterized in that: The filler is selected from at least one of calcium carbonate, carbon black, graphite, carbon fiber, graphene, talc, and calcium silicate.

7. The flame retardant cable material according to claim 6, characterized in that: The weight ratio of the rare earth flame retardant to calcium carbonate is (5-7): (50-60).

8. The flame retardant cable material according to claim 6, characterized in that: The weight ratio of calcium carbonate to stabilizer is (50-60); (1-5).

9. The flame retardant cable material according to claim 1, characterized in that: The lubricant is selected from at least one of stearic acid, oleic acid, paraffin, polyethylene wax, stearic acid amide, ethylene bis stearamide, and butyl stearate.

10. A method for preparing the flame-retardant cable material according to any one of claims 1 to 9, characterized in that: The following steps are involved: S1 adds filler, PVC resin, stabilizer, lubricant, rare earth flame retardant and plasticizer in sequence and mixes; S2 is mixed by high-speed stirring, heated to 130-140°C, and extruded into granules by a twin-screw extruder.

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