Thermoplastic polyarylene sulfide-based composite cable and preparation method thereof

Abstract

The invention relates to a thermoplastic polyarylene sulfide-based composite cable and a preparation method thereof, and belongs to the technical field of cables. The invention provides a thermoplastic polyarylene sulfide-based composite cable. The thermoplastic polyarylene sulfide-based composite cable is prepared from the following raw materials: maleic anhydride modified polyvinyl chloride, polyarylene sulfide, silane modified nano zinc borate, phenyl silicone resin microcapsules coated with ammonium polyphosphate, an anti-aging compound, an ethylene-acrylate copolymer and a lubricant. Modified polyethylene and polyarylene sulfide synergistically enhance interface bonding and thermal stability, nano zinc borate and phenyl silicone resin microcapsules coated with ammonium polyphosphate are combined to construct a dual flame retardant mechanism, and meanwhile, surface hydrophobic treatment and an anti-aging compound synergistically realize flame retardance and aging resistance, so that the flame retardant has a good application prospect.

Description

Technical Field

[0001] The present invention belongs to the technical field of cables and relates to a thermoplastic polyarylene sulfide-based composite cable and a preparation method thereof. Background Art

[0002] PVC composite cables are cable materials made of polyvinyl chloride (PVC) as the main base material, which are modified by adding a variety of functional additives. This type of cable is widely used due to its low cost and good processing performance. At present, the improvement direction of PVC composite cables is mainly focused on improving the flame retardancy, aging resistance, environmental protection and balanced optimization of mechanical properties. In terms of flame retardancy, halogen-free flame retardants are mainly used to reduce the production of toxic smoke during combustion; in terms of aging resistance, ultraviolet absorbers and antioxidants are added to extend the outdoor service life. However, the improvement of flame retardancy usually relies on a high proportion of inorganic fillers, but these fillers will accelerate the thermal oxidation degradation of PVC molecular chains, and weaken the aging resistance; and anti-aging agents (such as carbon black) may interfere with the synergistic effect of the flame retardant system, and in actual application, it is impossible to effectively take into account both properties at the same time. Summary of the Invention

[0003] The object of the present invention is to provide a thermoplastic polyarylene sulfide-based composite cable and a preparation method. The present invention synergistically enhances interfacial bonding and thermal stability through modified polyethylene and polyarylene sulfide, combines nano zinc borate and phenyl silicone resin microcapsules coated with ammonium polyphosphate to construct a dual flame retardant mechanism, and simultaneously synergistically achieves flame retardancy and aging resistance through surface hydrophobic treatment and anti-aging composites, and has good application prospects.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A thermoplastic polyarylene sulfide-based composite cable comprises, by weight, 43-47 parts of polyvinyl chloride modified with maleic anhydride, 31-33 parts of polyarylene sulfide, 4.5-5.5 parts of silane-modified nano zinc borate, 7.1-7.5 parts of phenyl silicone resin microcapsules coated with ammonium polyphosphate, 3-3.2 parts of an anti-aging compound, 4.8-5.2 parts of an ethylene-acrylate copolymer, and 1.4-1.6 parts of a lubricant.

[0006] Furthermore, the preparation method of the maleic anhydride-modified polyvinyl chloride comprises the following steps:

[0007] Step A1: After heating 10-12 parts by weight of dried polyvinyl chloride resin to 78-82° C., add 0.06-0.1 parts by weight of maleic anhydride and 0.01-0.03 parts by weight of dicumyl peroxide, mix, and stir at 1200-1400 rpm for 30-40 minutes. After cooling to room temperature, wash with acetone to remove unreacted dicumyl peroxide, and dry in vacuo at 60° C. for 12-14 hours to obtain the product.

[0008] Furthermore, the preparation method of the silane-modified nano zinc borate comprises the following steps:

[0009] Step B1, 4-5 parts by weight of nano zinc borate with an average particle size of 25-35 nm and 21-25 parts by weight of anhydrous ethanol, set the ultrasonic frequency to 35-45 kHz, the ultrasonic power to 250-350 W, and ultrasonicate for 25-35 minutes, then add 0.4-0.8 parts by weight of γ-aminopropyltriethoxysilane, stir at 60-120 rpm at 60°C for 2-3 hours, and finally centrifuge at 8000-12000 rpm for 8-12 minutes, remove the supernatant, and dry at 80°C for 4-6 hours to obtain.

[0010] Furthermore, the preparation method of the phenyl silicone resin microcapsules coated with ammonium polyphosphate comprises the following steps:

[0011] Step C1, immersing 5.5-6.5 parts by weight of ammonium polyphosphate in 50-60 parts by weight of sodium hydroxide solution, ultrasonicating at 60° C., centrifuging and washing until neutral, and drying at 80° C. to obtain hydroxylated ammonium polyphosphate;

[0012] Step C2: After mixing 30-40 parts by weight of acetone and 5-7 parts by weight of deionized water, add 2.8-3.8 parts by weight of phenyl silicone resin, 0.25-0.35 parts by weight of nano-silica with an average particle size of 10-20 nm, and 0.12-0.18 parts by weight of γ-aminopropyltriethoxysilane, and stir at 8000-12000 rpm for 10-20 minutes to obtain an emulsion;

[0013] Step C3, mixing the hydroxylated ammonium polyphosphate and the emulsion in a mass ratio of 1:1.4-1.6, ultrasonicating at 50° C., adding 0.04-0.06 parts by weight of a platinum catalyst, heating and stirring, cooling to room temperature in an ice bath, collecting the suspension by filtration, and spray drying to obtain a microcapsule powder;

[0014] Step C4: mixing the microcapsule powder and the treatment liquid in a mass ratio of 1:1, stirring at 60° C. and 180-220 rpm for 30-40 min, and then drying at 80° C. to obtain the product.

[0015] Furthermore, the sodium hydroxide content of the sodium hydroxide solution in step C1 is 5-6 wt %; the ultrasonic parameters are: ultrasonic frequency of 30-50 kHz, ultrasonic power of 150-250 W, and ultrasonic duration of 25-35 min.

[0016] Furthermore, the heating and stirring in step C3 refers to heating to 85-95° C. and then stirring at a speed of 250-350 rpm for 2.5-3.5 hours.

[0017] Furthermore, the treatment liquid in step C4 is obtained by mixing 2-3 parts by weight of heptadecafluorodecyltrimethoxysilane, 100-102 parts by weight of anhydrous ethanol and 0.2-0.3 parts of glacial acetic acid.

[0018] Furthermore, the anti-aging compound is composed of 5-7 parts by weight of dilauryl thiodipropionate, 2-4 parts by weight of antioxidant 1010, and 1.5-2.5 parts by weight of UV-328.

[0019] Furthermore, the lubricant is oxidized polyethylene wax.

[0020] Furthermore, the preparation method comprises the following steps:

[0021] Step D1, setting the speed to 1000-1200 rpm, adding maleic anhydride-modified polyvinyl chloride and polyarylene sulfide, mixing for 3-5 minutes, adding silane-modified nano zinc borate and phenyl silicone resin microcapsules coated with ammonium polyphosphate, mixing for 5-7 minutes, then adding the anti-aging compound and mixing for 3-5 minutes, and finally adding ethylene-acrylate copolymer and lubricant, mixing for 4-6 minutes and then melting, extruding on the surface of the armored wire core, cooling and forming, to obtain a thermoplastic polyarylene sulfide-based composite cable.

[0022] Beneficial effects of the present invention:

[0023] (1) The present invention promotes the interface bonding between polyvinyl chloride and nano zinc borate by modifying polyvinyl chloride, thereby improving the density of the carbon layer. Nano zinc borate decomposes at high temperature to generate a B2O3 glass layer, which blocks oxygen and heat. Polyarylene sulfide forms a thioaromatic ring structure at high temperature, releasing SO2 gas to dilute combustibles. On this basis, phenyl silicone resin microcapsules coated with ammonium polyphosphate are introduced to achieve a dual flame retardant mechanism, and the thermal stability, moisture barrier and dispersibility are improved through modification. The ammonium polyphosphate releases NH3 and H2O at medium and low temperatures to dilute the combustible gas. At high temperature, the phenyl silicone resin burns to form a residue with SiO2 as the main component, which reduces the carbon content of the residue and thereby suppresses molten droplets and smoke. Finally, heptadecafluorodecyltrimethoxysilane is used for surface treatment to block the penetration of water molecules and protect the performance of the microcapsules in a hot and humid environment.

[0024] (2) The present invention reduces the thermal oxidation degradation of the molecular chain and inhibits aging by modifying polyvinyl chloride; polyarylene sulfide has excellent temperature resistance, which helps to inhibit the breakage of the molecular chain caused by ultraviolet rays and assists in anti-aging; on this basis, phenyl silicone resin microcapsules coated with ammonium polyphosphate are introduced to assist in reflecting ultraviolet rays by forming SiO2-containing residues at high temperatures, thereby delaying photooxidation; at the same time, the auxiliary anti-aging composite synergistically inhibits thermal oxidation and exerts an anti-aging effect. DETAILED DESCRIPTION

[0025] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined purpose of the invention, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0026] The polyvinyl chloride and ethylene-acrylate copolymer in all the embodiments and comparative examples of the present invention were purchased directly from the market and were purchased from Dongguan Yingxiang Plastic Raw Materials Co., Ltd.; maleic anhydride, nano-silica, sodium hydroxide, anhydrous ethanol, glacial acetic acid, and dilauryl thiodipropionate were purchased directly from the market and were purchased from Sigma-Aldrich (Shanghai) Trading Co., Ltd.; dicumyl peroxide was purchased directly from the market and was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; polyarylene sulfide was purchased directly from the market and was purchased from Sichuan Zhongke Xingye High-tech Materials Co., Ltd.; nano-zinc borate was purchased directly from the market and was purchased from Zhongshan Xingrui Chemical Co., Ltd. γ-Aminopropyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, antioxidant 1010, and UV-328 were all purchased directly from the market and were purchased from Wuhan Smack Biotechnology Co., Ltd.; ammonium polyphosphate was all purchased directly from the market and were purchased from Shandong Lida Chemical Co., Ltd.; phenyl silicone resin was all purchased directly from the market and were purchased from Jinan Huijinchuan Trading Co., Ltd.; platinum catalysts were all purchased directly from the market and were purchased from Shanghai Jieyu Electronic Technology Co., Ltd.; acetone was all purchased directly from the market and were purchased from Foshan Zhengyuan Chemical Technology Co., Ltd.; oxidized polyethylene wax was all purchased directly from the market and were purchased from Wengkaier (Shanghai) International Trade Co., Ltd.

[0027] Example 1

[0028] A thermoplastic polyarylene sulfide-based composite cable, wherein the raw materials of the thermoplastic polyarylene sulfide-based composite cable include, by weight, 43 parts of polyvinyl chloride modified with maleic anhydride, 31 parts of polyarylene sulfide, 4.5 parts of nano zinc borate modified with silane, 7.1 parts of phenyl silicone resin microcapsules coated with ammonium polyphosphate, 3 parts of anti-aging compound, 4.8 parts of ethylene-acrylate copolymer, and 1.4 parts of lubricant.

[0029] The preparation method of the maleic anhydride-modified polyvinyl chloride comprises the following steps:

[0030] Step A1: After heating 10 parts by weight of dried polyvinyl chloride resin to 78° C., 0.06 parts by weight of maleic anhydride and 0.01 parts by weight of dicumyl peroxide were added and mixed. The mixture was stirred at 1200 rpm for 30 minutes. After cooling to room temperature, the unreacted dicumyl peroxide was removed by washing with acetone and vacuum drying at 60° C. for 12 hours to obtain the product.

[0031] The preparation method of the silane-modified nano zinc borate comprises the following steps:

[0032] Step B1, 4 parts by weight of nano zinc borate with an average particle size of 25 nm and 21 parts by weight of anhydrous ethanol, set the ultrasonic frequency to 35 kHz, the ultrasonic power to 250 W, and ultrasonicate for 25 minutes, then add 0.4 parts by weight of γ-aminopropyltriethoxysilane, stir at 60 rpm at 60 ° C for 2 hours, and finally centrifuge at 8000 rpm for 8 minutes, remove the supernatant, and dry at 80 ° C for 4 hours.

[0033] The preparation method of the phenyl silicone resin microcapsules coated with ammonium polyphosphate comprises the following steps:

[0034] Step C1, immersing 5.5 parts by weight of ammonium polyphosphate in 50 parts by weight of sodium hydroxide solution, ultrasonicating at 60° C., centrifuging and washing until neutral, and drying at 80° C. to obtain hydroxylated ammonium polyphosphate;

[0035] Step C2: 30 parts by weight of acetone and 5 parts by weight of deionized water were mixed, and then 2.8 parts by weight of phenyl silicone resin, 0.25 parts by weight of nano-silica with an average particle size of 10 nm, and 0.12 parts by weight of γ-aminopropyltriethoxysilane were added. The mixture was stirred at 8000 rpm for 10 minutes to obtain an emulsion.

[0036] Step C3, mixing the hydroxylated ammonium polyphosphate and the emulsion in a mass ratio of 1:1.4, ultrasonicating at 50° C., adding 0.04 parts by weight of a platinum catalyst, heating and stirring, cooling to room temperature in an ice bath, collecting the suspension by filtration, and spray drying to obtain a microcapsule powder;

[0037] Step C4: The microcapsule powder and the treatment liquid are mixed in a mass ratio of 1:1, stirred at 180 rpm and 60° C. for 30 min, and then dried at 80° C. to obtain the product.

[0038] The sodium hydroxide content of the sodium hydroxide solution in step C1 is 5 wt %; the ultrasonic parameters are: ultrasonic frequency of 30 kHz, ultrasonic power of 150 W, and ultrasonication for 25 min.

[0039] The heating and stirring in step C3 refers to heating to 85° C. and stirring at 250 rpm for 2.5 hours.

[0040] The treatment liquid in step C4 is obtained by mixing 2 parts by weight of heptadecafluorodecyltrimethoxysilane, 100 parts by weight of anhydrous ethanol and 0.2 parts of glacial acetic acid.

[0041] The anti-aging compound consists of 5 parts by weight of dilauryl thiodipropionate, 2 parts by weight of antioxidant 1010 and 1.5 parts by weight of UV-328.

[0042] The lubricant is oxidized polyethylene wax.

[0043] The preparation method comprises the following steps:

[0044] Step D1, setting the speed to 1000 rpm, adding maleic anhydride-modified polyvinyl chloride and polyarylene sulfide, mixing for 3 minutes, adding silane-modified nano zinc borate and phenyl silicone resin microcapsules coated with ammonium polyphosphate, mixing for 5 minutes, then adding the anti-aging compound and mixing for 3 minutes, and finally adding ethylene-acrylate copolymer and lubricant, mixing for 4 minutes and then melting, extruding on the surface of the armored wire core, cooling and forming, to obtain a thermoplastic polyarylene sulfide-based composite cable.

[0045] Example 2

[0046] A thermoplastic polyarylene sulfide-based composite cable, wherein the raw materials of the thermoplastic polyarylene sulfide-based composite cable include, by weight, 44 parts of polyvinyl chloride modified with maleic anhydride, 31.6 parts of polyarylene sulfide, 4.8 parts of silane-modified nano zinc borate, 7.2 parts of phenyl silicone resin microcapsules coated with ammonium polyphosphate, 3.05 parts of an anti-aging compound, 4.9 parts of an ethylene-acrylate copolymer, and 1.47 parts of a lubricant.

[0047] The preparation method of the maleic anhydride-modified polyvinyl chloride comprises the following steps:

[0048] Step A1: After heating 10.2 parts by weight of dried polyvinyl chloride resin to 79° C., 0.07 parts by weight of maleic anhydride and 0.01 parts by weight of dicumyl peroxide were added and mixed. The mixture was stirred at 1250 rpm for 32 minutes. After cooling to room temperature, the mixture was washed with acetone to remove unreacted dicumyl peroxide and dried in vacuo at 60° C. for 12 hours to obtain the product.

[0049] The preparation method of the silane-modified nano zinc borate comprises the following steps:

[0050] Step B1, 4.3 parts by weight of nano zinc borate with an average particle size of 28 nm and 22 parts by weight of anhydrous ethanol, set the ultrasonic frequency to 38 kHz, the ultrasonic power to 260 W, and ultrasonicate for 28 minutes, then add 0.5 parts by weight of γ-aminopropyltriethoxysilane, stir at 80 rpm at 60°C for 2.2 hours, and finally centrifuge at 9000 rpm for 9 minutes, remove the supernatant, and dry at 80°C for 4 hours to obtain.

[0051] The preparation method of the phenyl silicone resin microcapsules coated with ammonium polyphosphate comprises the following steps:

[0052] Step C1, immersing 5.7 parts by weight of ammonium polyphosphate in 53 parts by weight of sodium hydroxide solution, ultrasonicating at 60° C., centrifuging and washing until neutral, and drying at 80° C. to obtain hydroxylated ammonium polyphosphate;

[0053] Step C2: 32 parts by weight of acetone and 5.5 parts by weight of deionized water were mixed, and then 3 parts by weight of phenyl silicone resin, 0.27 parts by weight of nano-silica with an average particle size of 12 nm, and 0.14 parts by weight of γ-aminopropyltriethoxysilane were added. The mixture was stirred at 9000 rpm for 13 minutes to obtain an emulsion.

[0054] Step C3, mixing the hydroxylated ammonium polyphosphate and the emulsion in a mass ratio of 1:1.45, ultrasonicating at 50° C., adding 0.04 parts by weight of a platinum catalyst, heating and stirring, cooling to room temperature in an ice bath, collecting the suspension by filtration, and spray drying to obtain a microcapsule powder;

[0055] Step C4: The microcapsule powder and the treatment liquid were mixed in a mass ratio of 1:1, stirred at 60° C. and 190 rpm for 33 min, and then dried at 80° C. to obtain the product.

[0056] The sodium hydroxide content of the sodium hydroxide solution in step C1 is 5.2 wt %; the ultrasonic parameters are: ultrasonic frequency of 35 kHz, ultrasonic power of 180 W, and ultrasonication for 28 min.

[0057] The heating and stirring in step C3 refers to heating to 87° C. and stirring at 260 rpm for 2.7 hours.

[0058] The treatment liquid in step C4 is obtained by mixing 2.2 parts by weight of heptadecafluorodecyltrimethoxysilane, 100.8 parts by weight of anhydrous ethanol and 0.23 parts of glacial acetic acid.

[0059] The anti-aging compound consists of 5.6 parts by weight of dilauryl thiodipropionate, 2.7 parts by weight of antioxidant 1010 and 1.8 parts by weight of UV-328.

[0060] The lubricant is oxidized polyethylene wax.

[0061] The preparation method comprises the following steps:

[0062] Step D1, setting the speed to 1050 rpm, adding maleic anhydride-modified polyvinyl chloride and polyarylene sulfide, mixing for 3.5 minutes, adding silane-modified nano zinc borate and phenyl silicone resin microcapsules coated with ammonium polyphosphate, mixing for 5.5 minutes, then adding the anti-aging compound and mixing for 3.5 minutes, finally adding ethylene-acrylate copolymer and lubricant, mixing for 4.5 minutes, then melting, extruding on the surface of the armored wire core, cooling and forming, to obtain a thermoplastic polyarylene sulfide-based composite cable.

[0063] Example 3

[0064] A thermoplastic polyarylene sulfide-based composite cable, wherein the raw materials of the thermoplastic polyarylene sulfide-based composite cable include, by weight, 45 parts of polyvinyl chloride modified with maleic anhydride, 32 parts of polyarylene sulfide, 5 parts of nano zinc borate modified with silane, 7.3 parts of phenyl silicone resin microcapsules coated with ammonium polyphosphate, 3.1 parts of anti-aging compound, 5 parts of ethylene-acrylate copolymer, and 1.5 parts of lubricant.

[0065] The preparation method of the maleic anhydride-modified polyvinyl chloride comprises the following steps:

[0066] Step A1: After heating 11 parts by weight of dried polyvinyl chloride resin to 80° C., 0.08 parts by weight of maleic anhydride and 0.02 parts by weight of dicumyl peroxide were added and mixed. The mixture was stirred at 1300 rpm for 35 minutes. After cooling to room temperature, the unreacted dicumyl peroxide was removed by washing with acetone and vacuum drying at 60° C. for 13 hours to obtain the product.

[0067] The preparation method of the silane-modified nano zinc borate comprises the following steps:

[0068] Step B1, 4.5 parts by weight of nano zinc borate with an average particle size of 30 nm and 23 parts by weight of anhydrous ethanol were ultrasonically treated at a frequency of 40 kHz and a power of 300 W for 30 minutes, and then 0.6 parts by weight of γ-aminopropyltriethoxysilane were added. The mixture was stirred at 90 rpm for 2.5 hours at 60°C, and finally centrifuged at 10,000 rpm for 10 minutes. The supernatant was removed and the mixture was dried at 80°C for 5 hours.

[0069] The preparation method of the phenyl silicone resin microcapsules coated with ammonium polyphosphate comprises the following steps:

[0070] Step C1, immersing 6 parts by weight of ammonium polyphosphate in 55 parts by weight of sodium hydroxide solution, ultrasonicating at 60° C., centrifuging and washing until neutral, and drying at 80° C. to obtain hydroxylated ammonium polyphosphate;

[0071] Step C2: 35 parts by weight of acetone and 6 parts by weight of deionized water were mixed, and then 3.3 parts by weight of phenyl silicone resin, 0.3 parts by weight of nano-silica with an average particle size of 15 nm, and 0.15 parts by weight of γ-aminopropyltriethoxysilane were added, and the mixture was stirred at 10,000 rpm for 15 minutes to obtain an emulsion;

[0072] Step C3, mixing the hydroxylated ammonium polyphosphate and the emulsion in a mass ratio of 1:1.5, ultrasonicating at 50° C., adding 0.05 parts by weight of a platinum catalyst, heating and stirring, cooling to room temperature in an ice bath, collecting the suspension by filtration, and spray drying to obtain a microcapsule powder;

[0073] Step C4: The microcapsule powder and the treatment liquid are mixed in a mass ratio of 1:1, stirred at 200 rpm at 60° C. for 35 min, and then dried at 80° C. to obtain the product.

[0074] The sodium hydroxide content of the sodium hydroxide solution in step C1 is 5.5 wt %; the ultrasonic parameters are: ultrasonic frequency of 40 kHz, ultrasonic power of 200 W, and ultrasonication for 30 min.

[0075] The heating and stirring in step C3 refers to heating to 90° C. and stirring at 300 rpm for 3 hours.

[0076] The treatment liquid in step C4 is obtained by mixing 2.5 parts by weight of heptadecafluorodecyltrimethoxysilane, 101 parts by weight of anhydrous ethanol and 0.25 parts of glacial acetic acid.

[0077] The anti-aging compound consists of 6 parts by weight of dilauryl thiodipropionate, 3 parts by weight of antioxidant 1010 and 2 parts by weight of UV-328.

[0078] The lubricant is oxidized polyethylene wax.

[0079] The preparation method comprises the following steps:

[0080] Step D1, setting the speed to 1100 rpm, adding maleic anhydride-modified polyvinyl chloride and polyarylene sulfide, mixing for 4 minutes, adding silane-modified nano zinc borate and phenyl silicone resin microcapsules coated with ammonium polyphosphate, mixing for 6 minutes, then adding the anti-aging compound and mixing for 4 minutes, and finally adding ethylene-acrylate copolymer and lubricant, mixing for 5 minutes and then melting, extruding on the surface of the armored wire core, cooling and forming, to obtain a thermoplastic polyarylene sulfide-based composite cable.

[0081] Example 4

[0082] A thermoplastic polyarylene sulfide-based composite cable, wherein the raw materials of the thermoplastic polyarylene sulfide-based composite cable include, by weight, 46 parts of polyvinyl chloride modified with maleic anhydride, 32.5 parts of polyarylene sulfide, 5.2 parts of silane-modified nano zinc borate, 7.4 parts of phenyl silicone resin microcapsules coated with ammonium polyphosphate, 3.14 parts of an anti-aging compound, 5.1 parts of an ethylene-acrylate copolymer, and 1.55 parts of a lubricant.

[0083] The preparation method of the maleic anhydride-modified polyvinyl chloride comprises the following steps:

[0084] Step A1: After heating 11.4 parts by weight of dried polyvinyl chloride resin to 81° C., 0.09 parts by weight of maleic anhydride and 0.03 parts by weight of dicumyl peroxide were added and mixed. The mixture was stirred at 1350 rpm for 38 minutes. After cooling to room temperature, the unreacted dicumyl peroxide was removed by washing with acetone and vacuum drying at 60° C. for 14 hours to obtain the product.

[0085] The preparation method of the silane-modified nano zinc borate comprises the following steps:

[0086] Step B1, 4.6 parts by weight of nano zinc borate with an average particle size of 32 nm and 24 parts by weight of anhydrous ethanol were added, the ultrasonic frequency was set to 42 kHz, the ultrasonic power was set to 320 W, and the ultrasonic was performed for 34 minutes. Then, 0.7 parts by weight of γ-aminopropyltriethoxysilane was added, and the mixture was stirred at 100 rpm at 60°C for 2.7 hours. Finally, the mixture was centrifuged at 11000 rpm for 11 minutes, the supernatant was removed, and the mixture was dried at 80°C for 6 hours.

[0087] The preparation method of the phenyl silicone resin microcapsules coated with ammonium polyphosphate comprises the following steps:

[0088] Step C1, immersing 6.2 parts by weight of ammonium polyphosphate in 57 parts by weight of sodium hydroxide solution, ultrasonicating at 60° C., centrifuging and washing until neutral, and drying at 80° C. to obtain hydroxylated ammonium polyphosphate;

[0089] Step C2: 36 parts by weight of acetone and 6.3 parts by weight of deionized water were mixed, and then 3.5 parts by weight of phenyl silicone resin, 0.31 parts by weight of nano-silica with an average particle size of 16 nm, and 0.17 parts by weight of γ-aminopropyltriethoxysilane were added, and the mixture was stirred at 11,000 rpm for 16 minutes to obtain an emulsion;

[0090] Step C3, mixing the hydroxylated ammonium polyphosphate and the emulsion in a mass ratio of 1:1.55, ultrasonicating at 50° C., adding 0.06 parts by weight of a platinum catalyst, heating and stirring, cooling to room temperature in an ice bath, collecting the suspension by filtration, and spray drying to obtain a microcapsule powder;

[0091] Step C4: The microcapsule powder and the treatment liquid were mixed in a mass ratio of 1:1, stirred at 60° C. and 210 rpm for 37 min, and then dried at 80° C. to obtain the product.

[0092] The sodium hydroxide content of the sodium hydroxide solution in step C1 is 5.8 wt %; the ultrasonic parameters are: ultrasonic frequency of 45 kHz, ultrasonic power of 220 W, and ultrasonication for 32 min.

[0093] The heating and stirring in step C3 refers to heating to 93° C. and stirring at 310 rpm for 3.2 hours.

[0094] The treatment liquid in step C4 is obtained by mixing 2.6 parts by weight of heptadecafluorodecyltrimethoxysilane, 101.5 parts by weight of anhydrous ethanol and 0.27 parts of glacial acetic acid.

[0095] The anti-aging compound consists of 6.4 parts by weight of dilauryl thiodipropionate, 3.5 parts by weight of antioxidant 1010 and 2.3 parts by weight of UV-328.

[0096] The lubricant is oxidized polyethylene wax.

[0097] The preparation method comprises the following steps:

[0098] Step D1, setting the speed to 1150 rpm, adding maleic anhydride-modified polyvinyl chloride and polyarylene sulfide, mixing for 4.5 minutes, adding silane-modified nano zinc borate and phenyl silicone resin microcapsules coated with ammonium polyphosphate, mixing for 6.5 minutes, then adding the anti-aging compound and mixing for 4.5 minutes, and finally adding ethylene-acrylate copolymer and lubricant, mixing for 5.5 minutes and then melting, extruding on the surface of the armored core, cooling and forming to obtain a thermoplastic polyarylene sulfide-based composite cable.

[0099] Example 5

[0100] A thermoplastic polyarylene sulfide-based composite cable, wherein the raw materials of the thermoplastic polyarylene sulfide-based composite cable include, by weight, 47 parts of polyvinyl chloride modified with maleic anhydride, 33 parts of polyarylene sulfide, 5.5 parts of nano zinc borate modified with silane, 7.5 parts of phenyl silicone resin microcapsules coated with ammonium polyphosphate, 3.2 parts of anti-aging compound, 5.2 parts of ethylene-acrylate copolymer, and 1.6 parts of lubricant.

[0101] The preparation method of the maleic anhydride-modified polyvinyl chloride comprises the following steps:

[0102] Step A1: After heating 12 parts by weight of dried polyvinyl chloride resin to 82° C., 0.1 parts by weight of maleic anhydride and 0.03 parts by weight of dicumyl peroxide were added and mixed. The mixture was stirred at 1400 rpm for 40 minutes. After cooling to room temperature, the unreacted dicumyl peroxide was removed by washing with acetone and vacuum drying at 60° C. for 14 hours to obtain the product.

[0103] The preparation method of the silane-modified nano zinc borate comprises the following steps:

[0104] Step B1, 5 parts by weight of nano zinc borate with an average particle size of 35 nm and 25 parts by weight of anhydrous ethanol, set the ultrasonic frequency to 45 kHz, the ultrasonic power to 350 W, and ultrasonicate for 35 minutes, then add 0.8 parts by weight of γ-aminopropyltriethoxysilane, stir at 120 rpm at 60°C for 3 hours, and finally centrifuge at 12000 rpm for 12 minutes, remove the supernatant, and dry at 80°C for 6 hours to obtain.

[0105] The preparation method of the phenyl silicone resin microcapsules coated with ammonium polyphosphate comprises the following steps:

[0106] Step C1, immersing 6.5 parts by weight of ammonium polyphosphate in 60 parts by weight of sodium hydroxide solution, ultrasonicating at 60° C., centrifuging and washing until neutral, and drying at 80° C. to obtain hydroxylated ammonium polyphosphate;

[0107] Step C2: After mixing 40 parts by weight of acetone and 7 parts by weight of deionized water, 3.8 parts by weight of phenyl silicone resin, 0.35 parts by weight of nano-silica with an average particle size of 20 nm, and 0.18 parts by weight of γ-aminopropyltriethoxysilane were added, and the mixture was stirred at 12,000 rpm for 20 minutes to obtain an emulsion;

[0108] Step C3, mixing the hydroxylated ammonium polyphosphate and the emulsion in a mass ratio of 1:1.6, ultrasonicating at 50° C., adding 0.06 parts by weight of a platinum catalyst, heating and stirring, cooling to room temperature in an ice bath, collecting the suspension by filtration, and spray drying to obtain a microcapsule powder;

[0109] Step C4: The microcapsule powder and the treatment liquid are mixed in a mass ratio of 1:1, stirred at 220 rpm at 60° C. for 40 min, and then dried at 80° C. to obtain the product.

[0110] The sodium hydroxide content of the sodium hydroxide solution in step C1 is 6 wt %; the ultrasonic parameters are: ultrasonic frequency of 50 kHz, ultrasonic power of 250 W, and ultrasonication for 35 min.

[0111] The heating and stirring in step C3 refers to heating to 95° C. and stirring at 350 rpm for 3.5 hours.

[0112] The treatment liquid in step C4 is obtained by mixing 3 parts by weight of heptadecafluorodecyltrimethoxysilane, 102 parts by weight of anhydrous ethanol and 0.3 parts of glacial acetic acid.

[0113] The anti-aging compound consists of 7 parts by weight of dilauryl thiodipropionate, 4 parts by weight of antioxidant 1010 and 2.5 parts by weight of UV-328.

[0114] The lubricant is oxidized polyethylene wax.

[0115] The preparation method comprises the following steps:

[0116] Step D1, setting the speed to 1200 rpm, adding maleic anhydride-modified polyvinyl chloride and polyarylene sulfide, mixing for 5 minutes, adding silane-modified nano zinc borate and phenyl silicone resin microcapsules coated with ammonium polyphosphate, mixing for 7 minutes, then adding the anti-aging compound and mixing for 5 minutes, and finally adding ethylene-acrylate copolymer and lubricant, mixing for 6 minutes and then melting, extruding on the surface of the armored wire core, cooling and forming, to obtain a thermoplastic polyarylene sulfide-based composite cable.

[0117] Example 6

[0118] On the basis of Example 3, the polyvinyl chloride modified with maleic anhydride was removed and replaced with polyvinyl chloride of equal weight, and other conditions remained the same as in Example 3.

[0119] Example 7

[0120] On the basis of Example 3, the silane-modified nano zinc borate was removed and replaced with an equal weight of nano zinc borate, and other conditions remained the same as in Example 3.

[0121] Example 8

[0122] On the basis of Example 3, the phenyl silicone resin microcapsules coating the ammonium polyphosphate were removed and replaced with an equal weight of ammonium polyphosphate. Other conditions remained the same as in Example 3.

[0123] Example 9

[0124] On the basis of Example 3, the silane-modified nano zinc borate was removed and replaced with an equal weight of phenyl silicone resin microcapsules coated with ammonium polyphosphate, and other conditions remained the same as in Example 3.

[0125] Example 10

[0126] On the basis of Example 3, the phenyl silicone resin microcapsules coated with ammonium polyphosphate were removed and replaced with an equal weight of silane-modified nano zinc borate. Other conditions remained the same as in Example 3.

[0127] Comparative Example 1

[0128] On the basis of Example 3, keeping other conditions unchanged, the preparation method of phenyl silicone resin microcapsules coated with ammonium polyphosphate was changed to the following steps:

[0129] Step C1: After mixing 35 parts by weight of acetone and 6 parts by weight of deionized water, 3.3 parts by weight of phenyl silicone resin, 0.3 parts by weight of nano-silica with an average particle size of 15 nm, and 0.15 parts by weight of γ-aminopropyltriethoxysilane were added, and the mixture was stirred at 10,000 rpm for 15 minutes to obtain an emulsion;

[0130] Step C2, ammonium polyphosphate and the emulsion were mixed in a mass ratio of 1:1.5, and ultrasonicated at 50° C., and then 0.05 parts by weight of a platinum catalyst was added. The mixture was heated and stirred, and cooled to room temperature in an ice bath. The suspension was collected by filtration and spray-dried to obtain a microcapsule powder;

[0131] Step C3: The microcapsule powder and the treatment liquid are mixed in a mass ratio of 1:1, stirred at 200 rpm at 60° C. for 35 min, and then dried at 80° C. to obtain the product.

[0132] Comparative Example 2

[0133] On the basis of Example 3, keeping other conditions unchanged, the preparation method of phenyl silicone resin microcapsules coated with ammonium polyphosphate was changed to the following steps:

[0134] Step C1, immersing 6 parts by weight of ammonium polyphosphate in 55 parts by weight of sodium hydroxide solution, ultrasonicating at 60° C., centrifuging and washing until neutral, and drying at 80° C. to obtain hydroxylated ammonium polyphosphate;

[0135] Step C2: 35 parts by weight of acetone and 6 parts by weight of deionized water were mixed, and then 3.3 parts by weight of phenyl silicone resin, 0.3 parts by weight of nano-silica with an average particle size of 15 nm, and 0.15 parts by weight of γ-aminopropyltriethoxysilane were added, and the mixture was stirred at 10,000 rpm for 15 minutes to obtain an emulsion;

[0136] Step C3, after mixing the hydroxylated ammonium polyphosphate and the emulsion in a mass ratio of 1:1.5, ultrasonically mix at 50° C., add 0.05 parts by weight of a platinum catalyst, heat and stir, cool to room temperature in an ice bath, collect the suspension by filtration, and spray dry to obtain the product.

[0137] Comparative Example 3

[0138] On the basis of Example 3, keeping other conditions unchanged, the preparation method of phenyl silicone resin microcapsules coated with ammonium polyphosphate was changed to the following steps:

[0139] Step C1, immersing 6 parts by weight of ammonium polyphosphate in 55 parts by weight of sodium hydroxide solution, ultrasonicating at 60° C., centrifuging and washing until neutral, and drying at 80° C. to obtain hydroxylated ammonium polyphosphate;

[0140] Step C2: 35 parts by weight of acetone and 6 parts by weight of deionized water were mixed, 3.3 parts by weight of phenyl silicone resin and 0.3 parts by weight of nano-silicon dioxide with an average particle size of 15 nm were added, and the mixture was stirred at 10,000 rpm for 15 minutes to obtain an emulsion;

[0141] Step C3, mixing the hydroxylated ammonium polyphosphate and the emulsion in a mass ratio of 1:1.5, ultrasonicating at 50° C., adding 0.05 parts by weight of a platinum catalyst, heating and stirring, cooling to room temperature in an ice bath, collecting the suspension by filtration, and spray drying to obtain a microcapsule powder;

[0142] Step C4: The microcapsule powder and the treatment liquid are mixed in a mass ratio of 1:1, stirred at 200 rpm at 60° C. for 35 min, and then dried at 80° C. to obtain the product.

[0143] The composite cables prepared in Examples 1-10 and Comparative Examples 1-3 were used as samples, and their flame retardant properties were tested according to GB / T18380.32-2022, as shown in Table 1 below. According to GB / T16422.3-1997 and GB / T 1040-1992, 6 specimens with a length of 10 cm were cut from each group of samples, 3 of which were subjected to tensile testing and the initial tensile strength, i.e., the tensile strength before aging, was recorded. The other 3 were placed in a UV aging box for aging treatment for 6 days at a UV intensity of 210 W / m 2 The aging temperature is 80°C. After the aging is completed, a tensile test is performed and the tensile strength after aging is recorded. The anti-aging performance of the composite cable is evaluated according to the aging tensile strength retention rate = tensile strength after aging / tensile strength before aging * 100%. The results are averaged and recorded as shown in Table 1 below.

[0144] Table 1

[0145]

[0146]

[0147] As can be seen from Table 1, the thermoplastic polyarylene sulfide-based composite cable prepared in the present invention has good flame retardant properties and anti-aging properties.

[0148] The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Although the present invention has been disclosed as a preferred embodiment as above, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to equivalent embodiments using the technical contents disclosed above without departing from the scope of the technical solution of the present invention. However, any indirect modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A thermoplastic polyarylene sulfide-based composite cable, characterized in that: The raw materials of the thermoplastic polyarylene sulfide-based composite cable include, by weight, 43-47 parts of polyvinyl chloride modified with maleic anhydride, 31-33 parts of polyarylene sulfide, 4.5-5.5 parts of nano zinc borate modified with silane, 7.1-7.5 parts of phenyl silicone resin microcapsules coated with ammonium polyphosphate, 3-3.2 parts of anti-aging compound, 4.8-5.2 parts of ethylene-acrylate copolymer, and 1.4-1.6 parts of lubricant.

2. A thermoplastic polyarylene sulfide-based composite cable according to claim 1, characterized in that: The preparation method of the maleic anhydride-modified polyvinyl chloride comprises the following steps: Step A1: After heating 10-12 parts by weight of dried polyvinyl chloride resin to 78-82° C., add 0.06-0.1 parts by weight of maleic anhydride and 0.01-0.03 parts by weight of dicumyl peroxide, mix, and stir at 1200-1400 rpm for 30-40 minutes. After cooling to room temperature, wash with acetone to remove unreacted dicumyl peroxide, and dry in vacuo at 60° C. for 12-14 hours to obtain the product.

3. The thermoplastic polyarylene sulfide-based composite cable according to claim 1, characterized in that: The preparation method of the silane-modified nano zinc borate comprises the following steps: Step B1, 4-5 parts by weight of nano zinc borate with an average particle size of 25-35 nm and 21-25 parts by weight of anhydrous ethanol, set the ultrasonic frequency to 35-45 kHz, the ultrasonic power to 250-350 W, and ultrasonicate for 25-35 minutes, then add 0.4-0.8 parts by weight of γ-aminopropyltriethoxysilane, stir at 60-120 rpm at 60°C for 2-3 hours, and finally centrifuge at 8000-12000 rpm for 8-12 minutes, remove the supernatant, and dry at 80°C for 4-6 hours to obtain.

4. The thermoplastic polyarylene sulfide-based composite cable according to claim 1, characterized in that: The preparation method of the phenyl silicone resin microcapsules coated with ammonium polyphosphate comprises the following steps: Step C1, immersing 5.5-6.5 parts by weight of ammonium polyphosphate in 50-60 parts by weight of sodium hydroxide solution, ultrasonicating at 60° C., centrifuging and washing until neutral, and drying at 80° C. to obtain hydroxylated ammonium polyphosphate; Step C2: After mixing 30-40 parts by weight of acetone and 5-7 parts by weight of deionized water, add 2.8-3.8 parts by weight of phenyl silicone resin, 0.25-0.35 parts by weight of nano-silica with an average particle size of 10-20 nm, and 0.12-0.18 parts by weight of γ-aminopropyltriethoxysilane, and stir at 8000-12000 rpm for 10-20 minutes to obtain an emulsion; Step C3, mixing the hydroxylated ammonium polyphosphate and the emulsion in a mass ratio of 1:1.4-1.6, ultrasonicating at 50° C., adding 0.04-0.06 parts by weight of a platinum catalyst, heating and stirring, cooling to room temperature in an ice bath, collecting the suspension by filtration, and spray drying to obtain a microcapsule powder; Step C4: mixing the microcapsule powder and the treatment liquid in a mass ratio of 1:1, stirring at 60° C. and 180-220 rpm for 30-40 min, and then drying at 80° C. to obtain the product.

5. The thermoplastic polyarylene sulfide-based composite cable according to claim 4, characterized in that: The sodium hydroxide content of the sodium hydroxide solution in step C1 is 5-6wt%; the ultrasonic parameters are: ultrasonic frequency of 30-50kHz, ultrasonic power of 150-250W, and ultrasonication for 25-35min.

6. The thermoplastic polyarylene sulfide-based composite cable according to claim 4, characterized in that: The heating and stirring in step C3 refers to heating to 85-95° C. and then stirring at 250-350 rpm for 2.5-3.5 hours.

7. The thermoplastic polyarylene sulfide-based composite cable according to claim 4, characterized in that: The treatment liquid in step C4 is obtained by mixing 2-3 parts by weight of heptadecafluorodecyltrimethoxysilane, 100-102 parts by weight of anhydrous ethanol and 0.2-0.3 parts of glacial acetic acid.

8. The thermoplastic polyarylene sulfide-based composite cable according to claim 1, characterized in that: The anti-aging compound consists of 5-7 parts by weight of dilauryl thiodipropionate, 2-4 parts by weight of antioxidant 1010 and 1.5-2.5 parts by weight of UV-328.

9. The thermoplastic polyarylene sulfide-based composite cable according to claim 1, characterized in that: The lubricant is oxidized polyethylene wax.

10. A method for preparing a thermoplastic polyarylene sulfide-based composite cable according to claims 1 to 9, characterized in that: The preparation method comprises the following steps: Step D1, setting the speed to 1000-1200 rpm, adding maleic anhydride-modified polyvinyl chloride and polyarylene sulfide, mixing for 3-5 minutes, adding silane-modified nano zinc borate and phenyl silicone resin microcapsules coated with ammonium polyphosphate, mixing for 5-7 minutes, then adding the anti-aging compound and mixing for 3-5 minutes, and finally adding ethylene-acrylate copolymer and lubricant, mixing for 4-6 minutes and then melting, extruding on the surface of the armored wire core, cooling and forming, to obtain a thermoplastic polyarylene sulfide-based composite cable.

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