A high and low temperature resistant flame retardant cable material and its preparation method and application

Abstract

The present invention provides a high and low temperature resistant flame retardant cable material and its preparation method and application. The raw materials for preparing the high and low temperature resistant flame retardant cable material include, by mass, 30-50 parts of EPDM rubber, 5-20 parts of polyethylene, 1-8 parts of nylon elastomer, 0.5-6 parts of butadiene-based polymer, 0.5-6 parts of compatibilizer, 0.1-3 parts of cross-linking agent, 0.1-4 parts of auxiliary cross-linking agent, and 40-100 parts of flame retardant; the compatibilizer includes a combination of ethylene-acrylic acid copolymer and maleic anhydride graft. The present invention, through the design and compounding of components, enables the high and low temperature resistant flame retardant cable material to have excellent flexibility and mechanical properties while achieving excellent flame retardant and insulation effects, and will not crack under extremely cold conditions, and has good high temperature resistance and low temperature resistance, thereby broadening the use temperature of the cable material, so that it can maintain stable operation in high temperature or severe cold environments.

Description

Technical Field

[0001] The invention belongs to the technical field of cable materials, and in particular relates to a high and low temperature resistant flame retardant cable material and a preparation method and application thereof. Background Art

[0002] Wires and cables play a vital role in power transmission and are the core components of the power transmission system. Their performance directly determines the operating level of electrical equipment and power systems. At present, cable materials are mainly divided into the following categories according to their formula: styrene-butadiene rubber, chloroprene rubber, chlorinated polyethylene, EPDM rubber, etc. Among them, EPDM rubber has good operating reliability, good moisture resistance, and almost no decrease in electrical and mechanical properties after immersion in water. It has good water resistance and heat resistance and is one of the most widely used rubber materials in the cable field.

[0003] CN104592650A discloses a method for preparing a flame-retardant EPDM rubber sheath for cables, comprising the following steps: mixing EPDM rubber, fumed silica, chlorinated paraffin, aluminum hydroxide, hexabromocyclododecane, boehmite and sodium molybdate to form a masterbatch; mixing a vulcanizing agent and the masterbatch to perform a first vulcanization treatment, and then performing a second vulcanization in an oven to prepare a flame-retardant EPDM rubber for cables, and finally extruding to obtain a flame-retardant EPDM rubber sheath for cables. In parts by weight, relative to 100 parts of EPDM rubber, fumed silica is 160-190 parts, chlorinated paraffin is 3-7 parts, aluminum hydroxide is 35-55 parts, hexabromocyclododecane is 4-8 parts, boehmite is 7-10 parts, and sodium molybdate is 0.3-1.2 parts. The EPDM rubber sheath material has a high limiting oxygen index and good flame retardancy.

[0004] CN105086165A discloses a mining EPDM cable sheath material, a substrate composed of EPDM, ethylene-butylene elastomer and chlorinated polyethylene in a mass ratio of 13-15:5-6:1-2, based on the substrate, 2.5-3wt% white carbon black, 10-13wt% nano silicon dioxide, 4.5-5wt% aluminum hydroxide, 1-3wt% zinc oxide, 1-2wt% stearic acid, 1-1.5wt% 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 1.5-2wt% N,N1-m-phenylene bismaleimide, 20-25wt% paraffin oil, and accelerator M, accelerator TMTD and silane coupling agent. The EPDM cable sheath material has good tear strength, plasticity, processing performance and compression deformation resistance.

[0005] CN104448664A discloses a novel EPDM rubber material for wires and cables, comprising the following raw materials: 85-115 parts of EPDM rubber, 2.5-10 parts of acrylic acid, 1.5-7 parts of sodium stearate, 1.5-6 parts of initiator, 2.5-8 parts of antioxidant, 0.5-1.5 parts of inorganic filler, and 1-2 parts of flame retardant; the EPDM rubber material has high strength, good anti-aging and flame retardancy, and stable power supply performance.

[0006] With the rise of new energy, wind power generation, photovoltaic power generation and other equipment have also put forward higher requirements for cable materials. Cable materials need to maintain stable operation in high temperature or severe cold environments, requiring them to have a wide operating temperature range, good flexibility, and no problems such as low temperature cracking and high temperature mechanical property loss. However, existing cable materials cannot meet the use requirements in high and low temperature environments. Therefore, the development of cable materials with excellent high and low temperature resistance is the research focus of this field. Summary of the invention

[0007] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a high and low temperature resistant flame retardant cable material and a preparation method and application thereof. Through the design and mutual compounding of each component, the high and low temperature resistant flame retardant cable material has excellent flexibility and mechanical properties on the basis of achieving excellent insulation and flame retardant effects, good high temperature resistance and low temperature resistance, and will not crack under extremely cold conditions, which greatly broadens the use temperature of the cable material and enables it to maintain stable operation in high temperature or severe cold environments.

[0008] To achieve this object, the present invention adopts the following technical solutions:

[0009] In a first aspect, the present invention provides a high and low temperature resistant flame retardant cable material, wherein the raw materials for preparing the cable material include the following components by weight:

[0010]

[0011]

[0012] The compatibilizer includes a combination of ethylene-acrylic acid copolymer and maleic anhydride graft.

[0013] In the high and low temperature resistant flame retardant cable material provided by the present invention, EPDM rubber and polyethylene are compounded as the matrix material, and nylon elastomer is introduced therein, which can effectively improve the high temperature resistance and flexibility of the cable material; the butadiene-based polymer contains side chain vinyl, which is compounded with EPDM rubber and polyethylene, and undergoes vulcanization cross-linking reaction with a cross-linking agent and a cross-linking aid, so that a dense and stable cross-linked network is formed in the cable material, which significantly improves the flexibility and mechanical properties of the cable material. The compatibilizer adopts a compound of ethylene-acrylic acid copolymer and maleic anhydride grafted product, and the two cooperate with each other to form a good bonding effect between the multi-phases of EPDM rubber, polyethylene, nylon elastomer, and butadiene-based polymer, and improves the compatibility between the organic system and the flame retardant, improves the interface bonding force, and further improves the mechanical properties and high and low temperature resistance of the cable material.

[0014] The present invention designs nylon elastomer, butadiene-based polymer, compatibilizer and compounding with EPDM rubber, polyethylene, cross-linking agent, co-cross-linking agent and flame retardant, so that the high and low temperature resistant flame retardant cable material has excellent flexibility and mechanical properties while achieving excellent flame retardant and insulation effects, will not crack under extremely cold conditions, and has good high temperature resistance and low temperature resistance, thereby broadening the use temperature of the cable material and enabling it to maintain stable operation in high temperature or severe cold environments.

[0015] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0016] In the preparation raw materials of the present invention, the mass parts of the EPDM rubber are 30-50 parts, for example, it can be 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 44 parts, 45 parts, 46 parts or 48 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0017] The mass proportion of the polyethylene is 5-20 parts, for example, it can be 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 15 parts, 16 parts or 18 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0018] The mass proportion of the nylon elastomer is 1-8 parts, for example, it can be 1.5 parts, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts or 7 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0019] The mass fraction of the butadiene-based polymer is 0.5-6 parts, for example, it can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts or 5.5 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0020] The mass fraction of the compatibilizer is 0.5-6 parts, for example, it can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts or 5.5 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0021] The mass fraction of the cross-linking agent is 0.1-3 parts, for example, it can be 0.2 parts, 0.5 parts, 0.8 parts, 1 parts, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts or 2.8 parts, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0022] The weight percentage of the auxiliary cross-linking agent is 0.1-4 parts, for example, it can be 0.2 parts, 0.5 parts, 0.8 parts, 1 parts, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts, 3 parts, 3.2 parts, 3.5 parts or 3.8 parts, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0023] The mass parts of the flame retardant are 40-100 parts, for example, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts or 95 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0024] In the present invention, the EPDM rubber is a copolymer of ethylene, propylene and a third monomer, and the third monomer preferably includes ethylidene norbornene (ENB) and / or dicyclopentadiene (DCPD).

[0025] Preferably, the mass percentage of ethylene-based structural units in the EPDM rubber is 45-75%, for example, it can be 48%, 50%, 52%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, 72% or 74%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0026] Preferably, the mass percentage of the structural unit based on the third monomer in the EPDM rubber is 1-5%, for example, it can be 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.5%, 4% or 4.5%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0027] Preferably, the weight average molecular weight of the EPDM rubber is 50,000-300,000, for example, it can be 60,000, 80,000, 100,000, 120,000, 150,000, 160,000, 180,000, 200,000, 220,000, 240,000, 250,000, 260,000 or 280,000, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0028] Preferably, the Mooney viscosity of the EPDM rubber is 25-85MU, for example, 30MU, 35MU, 40MU, 45MU, 50MU, 55MU, 60MU, 65MU, 70MU, 75MU or 80MU, and specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range. Exemplarily, the Mooney viscosity is tested under ML (1+4) 100°C.

[0029] Preferably, the polyethylene includes any one of linear low-density polyethylene, high-density polyethylene, and metallocene polyethylene, or a combination of at least two thereof, and high-density polyethylene is further preferred.

[0030] Preferably, the molecular structure of the nylon elastomer includes a polyamide hard segment and a polyether polyol soft segment.

[0031] Preferably, the polyamide hard segment comes from any one of polyamide 6, polyamide 11, and polyamide 12, or a combination of at least two of them.

[0032] Preferably, the polyether polyol soft segment is derived from any one of polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and propylene oxide polyether, or a combination of at least two thereof.

[0033] Preferably, the butadiene-based polymer comprises polybutadiene and / or butadiene-styrene copolymer;

[0034] Preferably, the number average molecular weight of the butadiene-based polymer is 1000-10000, for example, it may be 2000, 3000, 4000, 5000, 6000, 7000, 8000 or 9000, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0035] Preferably, the butadiene-based polymer comprises a structural unit represented by formula I:

[0036]

[0037] In the present invention, the butadiene-based polymer contains the 1,2-vinyl structural unit shown in Formula I, and the vinyl in the side chain has high reactivity and can undergo crosslinking reaction with a crosslinking agent, a co-crosslinking agent, EPDM rubber and polyethylene, etc., to form a specific multi-dimensional crosslinked network structure in the cable material, so that the high and low temperature flame-retardant cable material has better flexibility and achieves excellent comprehensive performance in mechanical properties, high temperature resistance and low temperature resistance. If the butadiene-based polymer does not contain the 1,2-vinyl structural unit shown in Formula I, its reactivity is insufficient, resulting in a decrease in the crosslinking degree of the cable material, thereby reducing the mechanical properties and high and low temperature resistance.

[0038] Preferably, the molar percentage of the structural unit represented by formula I in the butadiene-based polymer is 20-90%, for example, it can be 25%, 30%, 35%, 40%, 45%, 50%, 52%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 88%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0039] Preferably, the mass ratio of ethylene-acrylic acid copolymer to maleic anhydride graft in the compatibilizer is 1:(0.8-2), for example, it can be 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8 or 1:1.9, etc.

[0040] Preferably, the maleic anhydride grafted material includes any one of maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene-vinyl acetate copolymer, and maleic anhydride grafted ethylene propylene diene monomer rubber, or a combination of at least two thereof.

[0041] Preferably, the cross-linking agent comprises an organic peroxide, and further preferably any one or a combination of at least two of diisopropylbenzene hydroperoxide, dibenzoyl peroxide, isopropylbenzene hydroperoxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl peracetate, tert-amyl peroxy (2-ethylhexyl) carbonate, di(4-methylbenzoyl) peroxide, 2,5-dimethyl-2,5-di-tert-butyl peroxide ethane, cyclohexanone peroxide, and tert-butyl peroxy-3,5,5-trimethylhexanoate.

[0042] Preferably, the auxiliary cross-linking agent includes any one of pentaerythritol triacrylate, triallyl isocyanurate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, tri(1,2-propylene glycol) diacrylate, tri(2-hydroxyethyl)isocyanuric acid triacrylate, and propoxylated trimethylolpropane triacrylate, or a combination of at least two thereof.

[0043] Preferably, the flame retardant is any one of antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc stannate, or a combination of at least two of them, and more preferably a combination of at least two (or three) of antimony trioxide, aluminum hydroxide, and zinc borate.

[0044] Preferably, the preparation raw materials also include 0.1-5 parts of plasticizer by mass, and the mass parts of the plasticizer can be 0.5 parts, 1 parts, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts or 4.5 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0045] Preferably, the plasticizer includes any one of dioctyl adipate, octyl epoxy stearate, dioctyl phthalate, diisodecyl phthalate, and dioctyl terephthalate, or a combination of at least two of them.

[0046] Preferably, the preparation raw materials further include any one of a lubricant, a stabilizer, a silane coupling agent, an ultraviolet absorber, and an antioxidant, or a combination of at least two of them.

[0047] Preferably, the preparation raw material also includes 0.1-2 parts of lubricant by mass, and the mass proportion of the lubricant can be 0.2 parts, 0.5 parts, 0.8 parts, 1 parts, 1.2 parts, 1.5 parts or 1.8 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0048] Preferably, the lubricant includes any one of silicone powder, silicone masterbatch, microcrystalline wax, polyethylene wax, or a combination of at least two thereof.

[0049] Preferably, the preparation raw materials also include 0.1-2 parts of stabilizer by mass, and the mass parts of the stabilizer can be 0.2 parts, 0.5 parts, 0.8 parts, 1 parts, 1.2 parts, 1.5 parts, 1.6 parts or 1.8 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0050] Preferably, the stabilizer includes any one of zinc stearate, calcium stearate, magnesium stearate, and pentaerythritol tetrakis(β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) or a combination of at least two thereof.

[0051] Preferably, the preparation raw materials further include 0.1-2 parts by mass of a silane coupling agent, and the mass parts of the silane coupling agent can be 0.2 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.8 parts, 1 parts, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts or 1.8 parts, as well as specific points between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0052] Preferably, the silane coupling agent includes any one of an alkenyl silane coupling agent, an epoxy silane coupling agent, an amino silane coupling agent, and a mercapto silane coupling agent, or a combination of at least two thereof.

[0053] Further preferably, the silane coupling agent includes any one of vinyltriethoxysilane, vinyltrimethoxysilane, γ-(methacryloxy)propyltrimethoxysilane, methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-aminoethylaminopropyltrimethoxysilane, or a combination of at least two thereof.

[0054] Preferably, the preparation raw materials further include 0.1-1 parts of antioxidants by mass, and the mass parts of the antioxidants can be 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts or 0.9 parts, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0055] Preferably, the antioxidant includes any one of a hindered phenol antioxidant, a hindered amine antioxidant, and a phosphite antioxidant, or a combination of at least two thereof.

[0056] In a second aspect, the present invention provides a method for preparing the high and low temperature resistant flame retardant cable material as described in the first aspect, the preparation method comprising:

[0057] The prepared raw materials are mixed and extruded to obtain pellets;

[0058] The pellets are made into wires through a wire extruder, and the wires are irradiated and cross-linked through an electron accelerator to obtain the high and low temperature resistant flame-retardant cable material.

[0059] Preferably, the mixing is carried out in an internal mixer.

[0060] Preferably, the mixing temperature is 140-180°C, for example, it can be 145°C, 150°C, 155°C, 160°C, 162°C, 165°C, 168°C, 170°C, 172°C, 175°C or 178°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0061] Preferably, the mixing time is 5-30 min, for example, it can be 6 min, 8 min, 10 min, 12 min, 15 min, 18 min, 20 min, 22 min, 25 min or 28 min, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0062] Preferably, the extrusion granulation is carried out in a screw extruder.

[0063] Preferably, the operating temperature of the screw extruder is 100-150°C, for example, it can be 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C or 148°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0064] Preferably, the temperature of the feeding zone in the screw extruder is 110-125°C, for example, it can be 112°C, 115°C, 118°C, 120°C, 122°C or 124°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0065] Preferably, the temperature of the conveying zone in the screw extruder is 110-125°C, for example, it can be 112°C, 115°C, 118°C, 120°C, 122°C or 124°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0066] Preferably, the temperature of the heating zone in the screw extruder is 120-130°C, for example, it can be 121°C, 122°C, 124°C, 125°C, 126°C, 128°C or 129°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0067] Preferably, the head temperature of the screw extruder is 125-135°C, for example, it can be 126°C, 128°C, 130°C, 132°C or 134°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0068] Preferably, the operating temperature of the wire extruder is 120-190°C, for example, it can be 125°C, 130°C, 140°C, 150°C, 160°C, 170°C, 175°C, 180°C or 185°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0069] Preferably, the wire extruder comprises a zone A, a zone B, a zone C and a zone D connected in sequence, so that the pellets can pass through the zones A, B, C and D in sequence, wherein the operating temperature of the zone A is 130-160°C (e.g., 132°C, 135°C, 138°C, 140°C, 142°C, 145°C, 148°C, 150°C, 152°C, 155°C, 158°C, etc.), and the operating temperature of the zone B is 150-175°C (e.g., 152°C, 155°C, 158°C, etc.). , 158°C, 160°C, 162°C, 165°C, 168°C, 170°C, 172°C, etc.), the operating temperature of zone C is 150-175°C (for example, 152°C, 155°C, 158°C, 160°C, 162°C, 165°C, 168°C, 170°C, 172°C, etc.), and the operating temperature of zone D is 160-180°C (for example, 162°C, 165°C, 168°C, 170°C, 172°C, 175°C, 178°C, etc.).

[0070] Preferably, the dose of the radiation cross-linking is 2-15 Mrad, for example, it can be 3 Mrad, 4 Mrad, 5 Mrad, 6 Mrad, 7 Mrad, 8 Mrad, 9 Mrad, 10 Mrad, 11 Mrad, 12 Mrad, 13 Mrad or 14 Mrad, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0071] In a third aspect, the present invention provides an application of the high and low temperature resistant flame retardant cable material as described in the first aspect in a photovoltaic power generation device, a wind power generation device or an oil production platform.

[0072] Compared with the prior art, the present invention has the following beneficial effects:

[0073] (1) In the high and low temperature resistant flame retardant cable material provided by the present invention, EPDM rubber and polyethylene are compounded as the base material. Through the design of nylon elastomer, butadiene-based polymer, compatibilizer and its compounding with base material, cross-linking agent, auxiliary cross-linking agent and flame retardant, the high and low temperature resistant flame retardant cable material has excellent flexibility and mechanical properties while achieving excellent flame retardant and insulation effects. It will not crack under extremely cold conditions and has good high temperature resistance and low temperature resistance, thereby broadening the use temperature of the cable material so that it can maintain stable operation in high temperature or severe cold environments.

[0074] (2) Through the design and optimization of components, the present invention enables the high and low temperature resistant flame retardant cable material to pass single vertical combustion, with a tensile strength of ≥15MPa, an elongation at break ≥340%, a change rate of elongation at break after aging at 185°C for 240h of ≤6%, no cracks at -40°C, and a cold resistance temperature as low as -60°C, achieving excellent comprehensive performance in mechanical properties, high temperature resistance and low temperature resistance. DETAILED DESCRIPTION

[0075] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0076] As used herein, the terms "comprises," "including," "having," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises the listed elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0077] "Optionally", "optionally" or "either" means that the subsequently described matter or event can or cannot occur, and that the description includes cases where the event occurs and cases where it does not.

[0078] In the following specific embodiments of the present invention, the materials for which the preparation methods are not provided are all commercially available chemicals, and the specific information is as follows:

[0079]

[0080]

[0081] The following will take multiple embodiments as examples to describe in detail the high and low temperature resistant flame retardant cable material and the preparation method thereof of the present invention, but the high and low temperature resistant flame retardant cable material and the preparation method thereof of the present invention are not limited to these embodiments.

[0082] Examples 1-8, Comparative Examples 1-7

[0083] A high and low temperature resistant flame retardant cable material, the raw materials for its preparation are shown in Table 1 and Table 2, and the dosage unit of each component is "part".

[0084] The preparation method of the high and low temperature resistant flame retardant cable material is as follows:

[0085] (1) adding each component into a mixer according to the formula amount, premixing for 5 minutes to obtain a mixture; adding the mixture into an internal mixer, mixing at 165° C. for 25 minutes, and extruding and granulating through a single screw extruder to obtain pellets; the temperatures of the feeding zone, conveying zone, heating zone, and die head of the single screw extruder are 115° C., 120° C., 125° C., and 128° C., respectively.

[0086] (2) adding the pellets obtained in step (1) into a wire extruder and extruding to obtain wires, wherein the operating temperatures of the AD zone in the wire extruder are 150° C., 170° C., 170° C., and 175° C., respectively; irradiating the wires with an electron accelerator for cross-linking, and the irradiation dose is 6 Mrad to obtain the high and low temperature resistant flame-retardant cable material.

[0087] The following performance tests are conducted on high and low temperature resistant flame retardant cable materials:

[0088] (1) Single vertical burning test: The test is conducted in accordance with the method in standard UL 1581.

[0089] (2) Tensile strength and elongation at break: tested according to the method in standard GB / T 2951.11-2008.

[0090] (3) Heat resistance: After the cable material to be tested is aged at 185°C for 240 h, its elongation at break is tested and compared with the elongation at break measured in (2) to obtain the rate of change; rate of change = difference in elongation at break before and after aging / original test value.

[0091] (4) -40℃ cracking: tested according to the method in GB / T 2951.6-97;

[0092] (5) Cold resistance: The test is carried out in accordance with the method in standard Q / HWCCL33-2017 "Cold-resistant wires and cables", where level I is cold-resistant to -60℃, level II is cold-resistant to -55℃, level III is cold-resistant to -50℃, and level IV is cold-resistant to -40℃.

[0093] The test results are shown in Table 1 and Table 2.

[0094] Table 1

[0095]

[0096]

[0097] Table 2

[0098]

[0099]

[0100] According to the formula and effect data in Table 1, the present invention makes the high and low temperature flame retardant cable material have excellent flame retardancy, flexibility and mechanical properties, good high temperature resistance and low temperature resistance, and no cracking phenomenon occurs under extremely cold conditions through the design of nylon elastomer, butadiene polymer, compatibilizer and compounding with EPDM rubber, polyethylene, crosslinking agent, auxiliary crosslinking agent and flame retardant. Among them, the cable material of Examples 1-6 can pass a single vertical combustion, with a tensile strength of 15.1-15.7MPa, an elongation at break of 340-353%, a change rate of elongation at break of 4.5-5.6% after aging at 185°C for 240h, no cracks will be generated at a low temperature of -40°C, and the cold-resistant temperature can be as low as -60°C, thereby broadening the use temperature of the cable material, so that it can maintain stable operation in high temperature or severe cold environments.

[0101] The compatibilizer of the present invention adopts the compound of ethylene-acrylic acid copolymer and maleic anhydride graft, and the two cooperate with each other to form a good combination between the multiphases of each polymer, improve the compatibility and interfacial bonding between the organic system and the flame retardant, and make the cable material have excellent flexibility, mechanical properties and high and low temperature resistance. Further, the mass ratio of the preferred ethylene-acrylic acid copolymer and the maleic anhydride graft of the present invention is 1: (0.8-2), which optimizes the coordination of the two compatibilizers and is more conducive to improving the comprehensive performance of the cable material. The amount of the two compatibilizers in Examples 7-8 exceeds the preferred range of the present invention, resulting in a decrease in the mechanical properties and cold resistance of the cable material. There is only one compatibilizer in Comparative Examples 1-2, respectively, resulting in poor combination between the multiphases, which significantly reduces the flexibility, mechanical properties, high temperature resistance and cold resistance of the cable material.

[0102] The high and low temperature resistant flame retardant cable material provided by the present invention uses EPDM rubber and polyethylene compound as the base material, introduces nylon elastomer and butadiene-based polymer containing side chain vinyl into it, and each component is compounded with each other to form a dense and stable cross-linked network in the cable material, which significantly improves the flexibility and mechanical properties of the cable material. Comparative Example 3 does not contain butadiene-based polymer, and Comparative Example 4 contains hydrogenated SEBS. Since the system does not contain side chain vinyl, the cross-linking degree of the cable material decreases, resulting in a comprehensive deterioration of its mechanical properties, high temperature resistance and cold resistance. In Comparative Example 5, the amount of butadiene-based polymer is too much, resulting in a decrease in the elongation at break of the cable material, a decrease in flexibility, and poor cold resistance. Comparative Examples 6-7 do not contain nylon elastomer, and the mechanical properties, high temperature resistance and low temperature resistance of the cable material are significantly deteriorated.

[0103] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate the high and low temperature resistant flame-retardant cable material and its preparation method and application, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A high and low temperature resistant flame retardant cable material, characterized in that: The raw materials for preparing the high and low temperature resistant flame retardant cable material include the following components by mass: The compatibilizer includes a combination of ethylene-acrylic acid copolymer and maleic anhydride graft.

2. The high and low temperature resistant flame retardant cable material according to claim 1, characterized in that: The weight average molecular weight of the EPDM rubber is 50,000-300,000; Preferably, the polyethylene includes any one of linear low-density polyethylene, high-density polyethylene, and metallocene polyethylene, or a combination of at least two thereof, and high-density polyethylene is further preferred.

3. The high and low temperature resistant flame retardant cable material according to claim 1 or 2, characterized in that: The molecular structure of the nylon elastomer includes a polyamide hard segment and a polyether polyol soft segment; Preferably, the polyamide hard segment is from any one of polyamide 6, polyamide 11, and polyamide 12, or a combination of at least two thereof; Preferably, the polyether polyol soft segment is any one or a combination of at least two of polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and propylene oxide polyether; Preferably, the butadiene-based polymer comprises polybutadiene and / or butadiene-styrene copolymer; Preferably, the number average molecular weight of the butadiene-based polymer is 1000-10000; Preferably, the butadiene-based polymer comprises a structural unit represented by formula I, and the molar percentage of the structural unit represented by formula I in the butadiene-based polymer is 20-90%; 4. The high and low temperature resistant flame retardant cable material according to any one of claims 1 to 3, characterized in that: The mass ratio of ethylene-acrylic acid copolymer to maleic anhydride graft in the compatibilizer is 1:(0.8-2); Preferably, the maleic anhydride grafted material includes any one of maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene-vinyl acetate copolymer, and maleic anhydride grafted ethylene propylene diene monomer rubber, or a combination of at least two thereof.

5. The high and low temperature resistant flame retardant cable material according to any one of claims 1 to 4, characterized in that: The cross-linking agent includes an organic peroxide, preferably any one of diisopropylbenzene hydroperoxide, dibenzoyl peroxide, isopropylbenzene hydroperoxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peracetate, tert-amyl peroxy (2-ethylhexyl) carbonate, di (4-methylbenzoyl) peroxide, 2,5-dimethyl-2,5-di-tert-butyl peroxide ethane, cyclohexanone peroxide, tert-butyl peroxy-3,5,5-trimethylhexanoate or a combination of at least two thereof; Preferably, the auxiliary cross-linking agent includes any one of pentaerythritol triacrylate, triallyl isocyanurate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, tri(1,2-propylene glycol) diacrylate, tri(2-hydroxyethyl)isocyanuric acid triacrylate, and propoxylated trimethylolpropane triacrylate, or a combination of at least two thereof.

6. The high and low temperature resistant flame retardant cable material according to any one of claims 1 to 5, characterized in that: Any one or a combination of at least two of the flame retardants antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc stannate; Preferably, the raw material for preparation further comprises 0.1-5 parts by weight of a plasticizer; Preferably, the plasticizer includes any one of dioctyl adipate, octyl epoxy stearate, dioctyl phthalate, diisodecyl phthalate, and dioctyl terephthalate, or a combination of at least two of them.

7. The high and low temperature resistant flame retardant cable material according to any one of claims 1 to 6, characterized in that: The preparation raw materials also include any one or a combination of at least two of a lubricant, a stabilizer, a silane coupling agent, an ultraviolet absorber, and an antioxidant; Preferably, the raw material for preparation further comprises 0.1-2 parts by mass of lubricant; Preferably, the lubricant comprises any one of silicone powder, silicone masterbatch, microcrystalline wax, polyethylene wax, or a combination of at least two thereof; Preferably, the raw material for preparation further comprises 0.1-2 parts of a stabilizer by weight; Preferably, the stabilizer includes any one of zinc stearate, calcium stearate, magnesium stearate, and pentaerythritol tetrakis(β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate) or a combination of at least two thereof; Preferably, the raw material for preparation further comprises 0.1-2 parts by mass of a silane coupling agent; Preferably, the silane coupling agent includes any one of an alkenyl silane coupling agent, an epoxy silane coupling agent, an amino silane coupling agent, and a mercapto silane coupling agent, or a combination of at least two thereof; Preferably, the raw material for preparation further comprises 0.1-1 parts by mass of an antioxidant.

8. A method for preparing a high and low temperature resistant flame retardant cable material according to any one of claims 1 to 7, characterized in that: The preparation method comprises: The prepared raw materials are mixed and extruded to obtain pellets; The pellets are made into wires through a wire extruder, and the wires are irradiated and cross-linked through an electron accelerator to obtain the high and low temperature resistant flame-retardant cable material.

9. The preparation method according to claim 8, characterized in that: The mixing temperature is 140-180°C; Preferably, the mixing time is 5-30 min; Preferably, the extrusion granulation is carried out in a screw extruder; Preferably, the operating temperature of the screw extruder is 100-150°C; Preferably, the working temperature of the wire extruder is 120-190°C; Preferably, the radiation cross-linking dosage is 2-15 Mrad.

10. Use of the high and low temperature resistant flame retardant cable material according to any one of claims 1 to 7 in a photovoltaic power generation device, a wind power generation device or an oil production platform.

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