Cable material and preparation method thereof

Abstract

The invention provides a cable material and a preparation method thereof. The cable material comprises the following components in parts by weight: 200 parts of polyolefin resin, 2-5 parts of a silane crosslinking agent, 0.1-0.2 part of an initiator, 2-5 parts of a catalyst, 160-200 parts of a flame retardant, 2-5 parts of an antioxidant, 5-10 parts of a mildew-resistant agent and 2-5 parts of a lubricant, wherein the mildew-resistant agent comprises an organic mildew-resistant agent, and the organic mildew-resistant auxiliary agent is an isothiazolinone mildew-resistant agent and / or a quaternary ammonium salt mildew-resistant agent. The cable material disclosed by the invention has good flame retardance, high temperature resistance and mildew resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of cable materials, and in particular to a cable material and a preparation method thereof. Background Art

[0002] Currently, photovoltaic cable materials are placing higher demands on safety, environmental friendliness, and durability. Photovoltaic cables are often used in harsh environmental conditions, such as high and low temperatures, strong ultraviolet radiation, high ozone concentrations, and chemical corrosion. Long-term exposure to humid environments can degrade the insulation performance of photovoltaic cables and increase the risk of short circuits.

[0003] Currently, the primary method for cross-linking cables is radiation cross-linking. This involves irradiating polyolefins with high-energy radiation generated by an electron beam. This disrupts the molecular chains, generating free radicals. Two or more linear macromolecular radicals then cross-link to form a network structure. Electron beam cross-linking and cable core extrusion are completely independent processes, allowing for a wide temperature range. This allows for a wide range of materials to be processed. However, radiation cross-linking also presents challenges such as significant equipment investment costs and difficult maintenance. Summary of the Invention

[0004] The main purpose of the present invention is to provide a cable material and a preparation method thereof, so as to solve the problems of poor flame retardancy, mildew resistance and high temperature resistance of cable materials in the prior art.

[0005] In order to achieve the above-mentioned purpose, according to one aspect of the present invention, a cable material is provided, which comprises, in parts by weight: 200 parts of polyolefin resin, 2 to 5 parts of silane crosslinking agent, 0.1 to 0.2 parts of initiator, 2 to 5 parts of catalyst, 160 to 200 parts of flame retardant, 2 to 5 parts of antioxidant, 5 to 10 parts of antifungal agent and 2 to 5 parts of lubricant; wherein the antifungal agent comprises an organic antifungal agent, and the organic antifungal auxiliary agent is an isothiazolinone antifungal agent and / or a quaternary ammonium salt antifungal agent.

[0006] Furthermore, the above-mentioned cable material includes cable material A and cable material B; in parts by weight, cable material A includes: 100 parts of a first polyolefin resin, 2 to 5 parts of a silane crosslinking agent and 0.1 to 0.2 parts of an initiator; in parts by weight, cable material B includes: 100 parts of a second polyolefin resin, 160 to 200 parts of a flame retardant, 2 to 5 parts of a catalyst, 5 to 10 parts of a mildew-resistant agent, 2 to 5 parts of a lubricant, 2 to 5 parts of an antioxidant and 2 to 5 parts of an auxiliary agent; the auxiliary agent is a masterbatch and / or a plasticizer.

[0007] Furthermore, the above-mentioned cable material includes cable material A and cable material B; in parts by weight, cable material A includes: 100 parts of a first polyolefin resin, 160 to 180 parts of a flame retardant, 2 to 3 parts of a silane crosslinker, 0.1 to 0.2 parts of an initiator, 7 to 10 parts of a mildew-resistant agent, 1 to 2 parts of a first lubricant, 2 to 5 parts of an antioxidant and 2 to 4 parts of an auxiliary agent; the auxiliary agent is a masterbatch and / or a plasticizer; in parts by weight, cable material B includes: 100 parts of a second polyolefin resin, 2 to 4 parts of a catalyst and 1 to 2 parts of a second lubricant.

[0008] Furthermore, the above-mentioned cable material includes cable material A and cable material B; in parts by weight, cable material A includes: 100 parts of a first polyolefin resin, 160 to 180 parts of a first flame retardant, 2 to 3 parts of a silane crosslinker, 0.1 to 0.2 parts of an initiator, 7 to 10 parts of a mildew-resistant agent, 1 to 2 parts of a first lubricant, 2 to 5 parts of an antioxidant and 2 to 4 parts of an auxiliary agent; the auxiliary agent is a masterbatch and / or a plasticizer; in parts by weight, cable material B includes: 100 parts of a second polyolefin resin, 5 to 20 parts of a second flame retardant, 2 to 4 parts of a catalyst and 1 to 2 parts of a second lubricant.

[0009] Furthermore, the mass ratio of the flame retardant to the antifungal agent is 20 to 40:1; and / or the flame retardant, the first flame retardant and the second flame retardant are each independently selected from any one or more of an inorganic flame retardant, an organic phosphorus-nitrogen flame retardant and a synergist, wherein the inorganic flame retardant is aluminum hydroxide and / or magnesium hydroxide, the organic phosphorus-nitrogen flame retardant is selected from any one or more of ammonium polyphosphate, melamine, melamine cyanurate, melamine polyphosphate, triphenyl phosphate and tricresyl phosphate, and the synergist is selected from any one or more of red phosphorus, nano-montmorillonite, expanded graphite, nano-zinc borate and nitrogen-phosphorus synergistic flame retardants.

[0010] Furthermore, the isothiazolinone antifungal agent is 2-octyl-4-isothiazolinone-3-one and / or butylisothiazolinone; the quaternary ammonium salt antifungal agent is selected from any one or more of 3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride, KH550 grafted quaternary ammonium salt, pyridine quaternary ammonium salt-acrylic amine copolymer, chitosan quaternary ammonium salt and Gemini-type diquaternary ammonium salt; and / or, the antifungal agent also includes an inorganic antifungal agent, and the inorganic antifungal agent is nano zinc oxide and / or nano titanium dioxide.

[0011] Furthermore, the polyolefin resin, the first polyolefin resin and the second polyolefin resin are each independently selected from any one or more of polyethylene, ethylene-vinyl acetate copolymer and polyolefin elastomer; and / or the silane crosslinker is vinyltrimethoxysilane and / or vinyltrihexyloxysilane; and / or the initiator is selected from any one or more of dicumyl peroxide, di-tert-butyl peroxide and dilauroyl peroxide; and / or the catalyst is selected from any one or more of dibutyltin dilaurate, stannous octoate and organic titanium chelate; and / or the antioxidant is selected from any one or more of hindered phenol antioxidants, thio antioxidants, anti-copper agents and phosphite antioxidants; and / or the lubricant, the first lubricant and the second lubricant are each independently selected from any one or more of polyethylene wax, silicone powder, EVA wax and ethylene bisstearamide.

[0012] According to another aspect of the present invention, a method for preparing the above-mentioned cable material is provided, which comprises: performing sequential mixing, granulation and cross-linking of the raw materials corresponding to the cable material to obtain the cable material; wherein the cross-linking method is selected from any one or more of warm water cross-linking, steam cross-linking and natural cross-linking, the warm water cross-linking process comprises cross-linking in water at a temperature of 70 to 90°C for 4 to 12 hours, the steam cross-linking process comprises cross-linking in steam at a temperature of 70 to 90°C and a pressure of 0.08 to 0.1 MPa for 4 to 12 hours, and the natural cross-linking process comprises cross-linking in a natural environment at a temperature of 25 to 40°C for 3 to 14 days.

[0013] Furthermore, the above preparation method also includes: step S11, separately mixing the raw materials corresponding to the cable material to obtain raw material A and raw material B; step S12, sequentially performing a first drying, mixing, a first granulation, cooling and a second drying on raw material A to obtain cable material A; step S13, sequentially performing banburying, a second granulation, cooling and a third drying on raw material B to obtain cable material B; step S14, cross-linking cable material A and cable material B to obtain cable material; wherein, the mass ratio of cable material A to cable material B is 1 to 3:20 to 25; the mixing speed is 400 to 1000 rpm; and the temperature of the first drying is 50 to 70°C.

[0014] Furthermore, the above-mentioned preparation method also includes: step S21, separately mixing the raw materials corresponding to the cable material to obtain raw material A and raw material B; step S22, successively performing banburying and first granulation on raw material A to obtain a mixture; silane grafting the mixture, and then successively performing second granulation, cooling and drying to obtain cable material A; step S23, successively mixing, third granulation, cooling and drying raw material B to obtain cable material B; step S24, cross-linking cable material A and cable material B to obtain cable material; wherein, the mass ratio of cable material A to cable material B is 20-25:1-3; and the mixing speed is 400-1000rpm.

[0015] By applying the technical solution of the present invention, the beneficial effects of the present application are as follows: the cable material of the present application preferably controls its raw material combination and weight proportion within the above range, which not only reduces the raw material cost, but also improves the flame retardant performance and high temperature resistance of the cable material. More importantly, the cable material of the present application reaches level 0 through a 28-day mold test, proving that it is not prone to mildew when used in a hot and humid environment for a long time, thereby greatly extending the service life of the cable material in a hot and humid environment, and thus better applied to fields such as photovoltaic cables. Specifically, the added anti-fungal agent and flame retardant can synergistically enhance, further enhancing the flame retardant performance of the cable material while reducing the smoke density. The addition of a silane crosslinker can form a three-dimensional network structure through silane grafting hydrolysis crosslinking, thereby increasing the heat deformation temperature of the cable material to above 120°C, and the long-term working temperature reaches above 105°C, thereby better applicable to high temperature environments (such as photovoltaic cables). In addition, the cable material of the present application can be cross-linked by warm water cross-linking, steam cross-linking and natural cross-linking, and the performance and quality of the cable material after cross-linking are stable, while also reducing the cross-linking cost. DETAILED DESCRIPTION

[0016] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below with reference to the embodiments.

[0017] As analyzed in the background technology of this application, cable materials in the prior art have problems such as poor flame retardancy, mildew resistance and high temperature resistance. In order to solve the above problems, this application provides a cable material and a preparation method thereof.

[0018] In a typical embodiment of the present application, a cable material is provided, which includes, by weight: 200 parts of polyolefin resin, 2 to 5 parts of silane crosslinking agent, 0.1 to 0.2 parts of initiator, 2 to 5 parts of catalyst, 160 to 200 parts of flame retardant, 2 to 5 parts of antioxidant, 5 to 10 parts of antifungal agent and 2 to 5 parts of lubricant; wherein the antifungal agent includes an organic antifungal agent, and the organic antifungal agent is an isothiazolinone antifungal agent and / or a quaternary ammonium salt antifungal agent.

[0019] The cable material of the present application preferably controls its raw material combination and weight proportion within the above range, which not only reduces the raw material cost, but also improves the flame retardant performance and high temperature resistance of the cable material. More importantly, the cable material of the present application reaches level 0 through a 28-day mold test, proving that it is used in a hot and humid environment for a long time and is not prone to mildew, thereby greatly extending the service life of the cable material in a hot and humid environment, and thus better applied to fields such as photovoltaic cables. Specifically, the added anti-fungal agent and flame retardant can synergistically strengthen, further enhancing the flame retardant performance of the cable material, while reducing the smoke density. The addition of a silane cross-linking agent can form a three-dimensional network structure through silane grafting hydrolysis cross-linking, thereby increasing the heat deformation temperature of the cable material to above 120°C, and the long-term working temperature reaches above 105°C, thereby better applicable to high temperature environments (such as photovoltaic cables). In addition, the cable material of the present application can be cross-linked by natural cross-linking, warm water cross-linking and steam cross-linking, and the performance and quality of the cable material after cross-linking are stable, while also being able to reduce the cross-linking cost.

[0020] Polyolefin resin is the primary component of cable materials, providing essential physical and mechanical properties such as tensile strength, flexibility, and abrasion resistance. Silane crosslinkers, by crosslinking with polyolefins, enhance the thermal stability, strength, and environmental stress cracking resistance of cable materials. Initiators promote the grafting reaction between the silane crosslinker and the polyolefin resin, accelerating the crosslinking rate and thus improving crosslinking efficiency. Catalysts accelerate hydrolysis and condensation reactions, allowing the silane crosslinker to form a crosslinked network more quickly, thereby shortening the crosslinking cycle and improving crosslinking uniformity and stability. Flame retardants absorb heat released during combustion, generating flame-retardant gases or forming a protective charred layer to prevent flame spread and reduce smoke density, thereby enhancing the flame retardancy of cable materials. Antioxidants inhibit oxidative degradation during processing and use, protecting cable materials from ultraviolet rays, thermal oxygen, and other factors, thereby extending the service life of the cable materials. Antifungal agents inhibit mold and mildew, preventing mildew growth in hot and humid environments, ensuring the insulation performance and appearance quality of the cable, and extending the service life of the cable. Lubricants can improve the processing performance of materials, while also improving the surface smoothness of cable materials and promoting filler dispersion.

[0021] In one embodiment of the present application, the cable material includes cable material A and cable material B; in parts by weight, cable material A includes: 100 parts of a first polyolefin resin, 2 to 5 parts of a silane crosslinker and 0.1 to 0.2 parts of an initiator; in parts by weight, cable material B includes: 100 parts of a second polyolefin resin, 160 to 200 parts of a flame retardant, 2 to 5 parts of a catalyst, 5 to 10 parts of a mildew-resistant agent, 2 to 5 parts of a lubricant, 2 to 5 parts of an antioxidant and 2 to 5 parts of an auxiliary agent; the auxiliary agent is a masterbatch and / or a plasticizer.

[0022] The components and weight percentages of Cable Material A and Cable Material B are preferably controlled within the above ranges, which facilitates the production of the cable material using a single-shot granulation process, thereby improving production efficiency. Furthermore, dispersing the silane crosslinker and catalyst in Cable Material A and Cable Material B separately prevents premature crosslinking between the two, facilitating the production of the cable material. Otherwise, a cable cannot be obtained by extrusion molding. This cable material formula is referred to as Cable Material Formula 1.

[0023] In one embodiment of the present application, the cable material includes cable material A and cable material B; in parts by weight, cable material A includes: 100 parts of a first polyolefin resin, 160 to 180 parts of a flame retardant, 2 to 3 parts of a silane crosslinker, 0.1 to 0.2 parts of an initiator, 7 to 10 parts of a mildew-resistant agent, 1 to 2 parts of a first lubricant, 2 to 5 parts of an antioxidant, and 2 to 4 parts of an auxiliary agent; the auxiliary agent is a masterbatch and / or a plasticizer; in parts by weight, cable material B includes: 100 parts of a second polyolefin resin, 2 to 4 parts of a catalyst, and 1 to 2 parts of a second lubricant.

[0024] The components and weight percentages of cable material A and cable material B are preferably controlled within the above ranges. This formulation concentrates the flame retardant in cable material A, which facilitates more uniform dispersion through high-temperature melting during the silane grafting process, thereby reducing agglomeration. Furthermore, the flame retardant is more tightly bound to the silane grafted segments, further enhancing the synergistic effect between the flame retardant and the polyolefin resin, and achieving higher flame retardant efficiency. This cable material formulation is referred to as Cable Material Formula 2.

[0025] In one embodiment of the present application, the cable material includes cable material A and cable material B; in parts by weight, cable material A includes: 100 parts of a first polyolefin resin, 160 to 180 parts of a first flame retardant, 2 to 3 parts of a silane crosslinker, 0.1 to 0.2 parts of an initiator, 7 to 10 parts of a mildew-resistant agent, 1 to 2 parts of a first lubricant, 2 to 5 parts of an antioxidant, and 2 to 4 parts of an auxiliary agent; the auxiliary agent is a masterbatch and / or a plasticizer; in parts by weight, cable material B includes: 100 parts of a second polyolefin resin, 5 to 20 parts of a second flame retardant, 2 to 4 parts of a catalyst, and 1 to 2 parts of a second lubricant.

[0026] The components and weight fractions of cable material A and cable material B are preferably controlled within the above ranges. The first flame retardant and the second flame retardant are dispersed in cable material A and cable material B, respectively. This helps reduce the filling pressure when the flame retardant is processed alone in cable material A, thereby improving the uniformity of raw material mixing. At the same time, adding some flame retardant to cable material B helps reduce direct interference with the silane grafting reaction, thereby reducing the negative impact on the crosslinking process. This cable material formula is recorded as cable material formula three. In addition, compared with cable material formulas one and two, the cable material obtained by cable material formula three has higher mechanical properties and storage stability.

[0027] In one embodiment of the present application, the mass ratio of the flame retardant to the antifungal agent is 20 to 40:1; and / or the flame retardant, the first flame retardant and the second flame retardant are each independently selected from any one or more of an inorganic flame retardant, an organic phosphorus-nitrogen flame retardant and a synergist, wherein the inorganic flame retardant is aluminum hydroxide and / or magnesium hydroxide, the organic phosphorus-nitrogen flame retardant is selected from any one or more of ammonium polyphosphate (APP), melamine (MCA), melamine cyanurate (MPP), melamine polyphosphate, triphenyl phosphate (TPP) and tricresyl phosphate (TCP), and the synergist is selected from any one or more of red phosphorus, nano-montmorillonite, expanded graphite, nano-zinc borate (ZB) and nitrogen-phosphorus synergistic flame retardant (NPR).

[0028] It is preferred to control the mass ratio of the flame retardant and the antifungal agent within the above range, which helps to improve the synergistic effect of the two and further enhance the flame retardant properties of the cable material while maintaining the antifungal properties. When the cable material is heated or burned, the active ingredients of the flame retardant (such as phosphorus and nitrogen, etc.) help accelerate the activation process of the antifungal agent molecules. Especially in the formula containing phosphorus-based flame retardants, the phosphorus element forms a more stable composite structure with the metal ions or organic functional groups in the antifungal agent, thereby maintaining the activity of the antifungal agent under high temperature conditions and alleviating its premature decomposition and failure. Some components in the antifungal agent, such as organic salts, produce non-combustible gases during the combustion process, which helps to reduce the oxygen concentration on the surface of the cable material and play an auxiliary flame retardant effect.

[0029] In order to further improve the flame retardant properties of the cable material, in one embodiment of the present application, the isothiazolinone anti-fungal agent is N-octyl-isothiazolinone (OIT) and / or butylisothiazolinone (BBIT); the quaternary ammonium salt anti-fungal agent is selected from any one or more of 3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride (code: DC5700), KH550 grafted quaternary ammonium salt, pyridine quaternary ammonium salt-acrylic acid amine copolymer (QVCA), chitosan quaternary ammonium salt (HTCC) and Gemini-type diquaternary ammonium salt; and / or, the anti-fungal agent also includes an inorganic anti-fungal agent, and the inorganic anti-fungal agent is nano-zinc oxide and / or nano-titanium dioxide.

[0030] Optionally, the antifungal agent is a combination of an organic antifungal agent and an inorganic antifungal agent, with the mass ratio of the organic antifungal agent to the inorganic antifungal agent being 1:3-4. This helps improve the antifungal properties of the cable material, and achieves a long-term antifungal performance of over 95% and a thermal weight loss rate of less than 5%. The organic antifungal agent is an isothiazolinone antifungal agent.

[0031] In order to further improve the comprehensive performance of the cable material, in one embodiment of the present application, the polyolefin resin, the first polyolefin resin and the second polyolefin resin are each independently selected from any one or more of polyethylene, ethylene-vinyl acetate copolymer and polyolefin elastomer; and / or the silane crosslinker is vinyltrimethoxysilane and / or vinyltrihexyloxysilane; and / or the initiator is selected from any one or more of dicumyl peroxide (DCP), di-tert-butyl peroxide (DTBP) and dilauroyl peroxide (LPO); and / or the catalyst is selected from any one of dibutyltin dilaurate (DBTL), stannous octoate and organic titanium chelate. or more; and / or, the antioxidant is selected from any one or more of hindered phenol antioxidants, thio antioxidants, anti-copper agents and phosphite antioxidants; optionally, the hindered phenol antioxidant is selected from any one or more of antioxidant 1010, antioxidant 1076 and antioxidant BHT, the thio antioxidant is antioxidant 300 and / or antioxidant 1035, and the phosphite antioxidant is selected from any one or more of antioxidant 168, antioxidant TNPP and antioxidant 622; and / or, the lubricant, the first lubricant and the second lubricant are each independently selected from any one or more of polyethylene wax, silicone powder, EVA wax and ethylene bisstearamide.

[0032] In another typical embodiment of the present application, a preparation method of the above-mentioned cable material is provided, which comprises: sequentially performing banburying, granulation and cross-linking on the raw materials corresponding to the cable material to obtain the cable material; wherein the cross-linking method is selected from any one or more of warm water cross-linking, steam cross-linking and natural cross-linking, the warm water cross-linking process comprises cross-linking in water at a temperature of 70 to 90°C for 4 to 12 hours, the steam cross-linking process comprises cross-linking in steam at a temperature of 70 to 90°C and a pressure of 0.08 to 0.1 MPa for 4 to 12 hours, and the natural cross-linking process comprises cross-linking in a natural environment at a temperature of 25 to 40°C for 3 to 14 days.

[0033] In view of the problems of high equipment investment cost, difficult later maintenance and easy discoloration of products after radiation cross-linking in radiation cross-linking, the cable material of the present application can achieve cross-linking without the above-mentioned warm water cross-linking, steam cross-linking and natural cross-linking, thereby reducing the cross-linking cost and the complexity of operation, and at the same time, a cable material with stable performance and good mildew resistance can be obtained. The use of the above-mentioned warm water cross-linking or steam cross-linking can improve the cross-linking efficiency, make the cross-linking inside the cable material more uniform, thereby improving the strength, heat resistance and mildew resistance of the cable material, and at the same time, reduce the risk of discoloration and be environmentally safe. The use of the above-mentioned natural cross-linking does not require special cross-linking equipment and is simple to operate, thereby greatly reducing production costs and energy consumption, and also has the advantages of high cross-linking stability and environmental friendliness. In addition, the above-mentioned cross-linking method can better maintain the mildew resistance of the cable material, thereby extending the service life of the cable under various environmental conditions.

[0034] The mixing temperature is preferably controlled to be 150-155° C., which helps the components to fully react, thereby maintaining the effectiveness and consistency of the components in the cable material.

[0035] In one embodiment of the present application, the above-mentioned preparation method also includes: step S11, separately mixing the raw materials corresponding to the cable material to obtain raw material A and raw material B; step S12, sequentially performing a first drying, mixing, a first granulation, cooling and a second drying on raw material A to obtain cable material A; step S13, sequentially performing banburying, a second granulation, cooling and a third drying on raw material B to obtain cable material B; step S14, cross-linking cable material A and cable material B to obtain cable material; wherein, the mass ratio of cable material A to cable material B is 1 to 3:20 to 25; the mixing speed is 400 to 1000 rpm; and the temperature of the first drying is 50 to 70°C.

[0036] The above preparation method (one-time granulation) is used to prepare cable material A and cable material B respectively, which helps to improve production efficiency. Controlling the cross-linking of cable material A and cable material B in the mass ratio within the above range helps to improve the synergistic effect between the two. Compared with the secondary granulation method, when cable material formula 1 is adopted, the above preparation method helps to obtain cable material using a one-time molding granulation process, thereby improving production efficiency. Its production efficiency is 1.5 times higher than that of secondary granulation.

[0037] In one embodiment of the present application, the above-mentioned preparation method also includes: step S21, separately mixing the raw materials corresponding to the cable material to obtain raw material A and raw material B; step S22, successively performing banburying and first granulation on raw material A to obtain a mixture; silane grafting the mixture and then successively performing second granulation, cooling and drying to obtain cable material A; step S23, successively mixing, third granulation, cooling and drying raw material B to obtain cable material B; step S24, cross-linking cable material A and cable material B to obtain cable material; wherein, the mass ratio of cable material A to cable material B is 20~25:1~3; and the mixing speed is 400~1000rpm.

[0038] The above-mentioned preparation method (secondary granulation) is adopted to prepare cable material A and cable material B respectively. Cable material A is subjected to secondary granulation (first granulation and second granulation) to remove the moisture in the material as much as possible, thereby reducing the risk of pre-crosslinking of the material. At the same time, the basic grafting is completed by a twin-screw extruder for the first time in the second granulation process. When the twin-screw extruder sprays silane for the second time, the flame retardant is evenly distributed during the first granulation, thereby reducing the side reaction caused by direct contact of the silane cross-linking agent and the flame retardant at high temperature, thereby improving the grafting rate of silane. Controlling cable material A and cable material B to be cross-linked with a mass ratio within the above-mentioned range helps to improve the synergistic effect of the two. When cable material formula two or cable material formula three is adopted, the above-mentioned preparation method is adopted to help improve the compatibility of the flame retardant with the polyolefin resin as much as possible, improve the dispersion effect and silane grafting efficiency of the flame retardant, enhance the synergistic efficiency of the antifungal agent and the flame retardant, thereby further improving the flame retardant performance and mechanical properties of the cable material, and further optimizing the antifungal performance. In addition, the twin-screw extruder is used for the grafting reaction of silane. This is because the mixing shear force and temperature control provided by the twin-screw extruder help promote the grafting reaction between silane and polyolefin molecules, forming a more stable structure, thereby improving the heat resistance and mechanical properties of the cable material.

[0039] The present application is further described in detail below with reference to specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in this application.

[0040] Example 1

[0041] The raw materials for the cable material are divided into raw material A and raw material B. Raw material A is composed, by weight, of 100 parts of a first polyolefin resin (polyethylene), 3 parts of a silane crosslinker (vinyltrimethoxysilane), and 0.15 parts of an initiator (dicumyl peroxide). Raw material B is composed, by weight, of 100 parts of a second polyolefin resin (polyethylene), 180 parts of a flame retardant (magnesium hydroxide), 3 parts of a catalyst (dibutyltin dilaurate), 7 parts of a fungicide (2-octyl-4-isothiazolin-3-one), 3 parts of a lubricant (polyethylene wax), 1 part of a hindered phenolic antioxidant (1010), 2 parts of an anti-copper agent (1024), and 3 parts of an additive (masterbatch).

[0042] Preparation of Cable Material A: Raw Materials A were dried at 60°C and then mixed at a second speed of 600 rpm to obtain a mixture. The mixture was extruded through a twin-screw extruder and then transferred to a single-screw extruder. The mixture was then extruded from the single-screw extruder and transferred to a pelletizer for primary pelletization. Finally, the mixture was cooled and then dried to obtain Cable Material A.

[0043] Preparation of cable material B: The above raw materials B are put into an internal mixer in the order of flame retardant, polyolefin resin, catalyst, anti-fungal agent, lubricant, hindered phenol antioxidant, anti-copper agent and auxiliary agent, and are mixed at 152°C. Then, they are sent to a twin-screw extruder through an elevator for extrusion and pushed to a single-screw extruder. The single-screw extruder then extrudes and pushes them to a pelletizer for a second granulation. Finally, after cooling and a third drying, cable material B is obtained.

[0044] Preparation of cable material: Cable material A and cable material B were mixed in a mass ratio of 2:23 and cross-linked in water at a temperature of 80° C. for 8 h to obtain a cable material.

[0045] Example 2

[0046] The raw materials for the cable material are divided into raw material A and raw material B. Raw material A is composed, by weight, of 100 parts of a first polyolefin resin (polyethylene), 2 parts of a silane crosslinker (vinyltrimethoxysilane), and 0.2 parts of an initiator (dicumyl peroxide). Raw material B is composed, by weight, of 100 parts of a second polyolefin resin (polyethylene), 160 parts of a flame retardant (magnesium hydroxide), 5 parts of a catalyst (dibutyltin dilaurate), 5 parts of a fungicide (2-octyl-4-isothiazolin-3-one), 5 parts of a lubricant (polyethylene wax), 1 part of a hindered phenolic antioxidant (1010), 1 part of an anti-copper agent (1024), and 5 parts of an additive (masterbatch).

[0047] Preparation of Cable Material A: Raw Materials A were dried at 50°C and then mixed at a second speed of 400 rpm to obtain a mixture. The mixture was extruded through a twin-screw extruder and then transferred to a single-screw extruder. The mixture was then extruded from the single-screw extruder and transferred to a pelletizer for primary pelletization. Finally, the mixture was cooled and then dried to obtain Cable Material A.

[0048] Preparation of cable material B: The above raw materials B are put into an internal mixer in the order of flame retardant, polyolefin resin, catalyst, anti-fungal agent, lubricant, hindered phenol antioxidant, anti-copper agent and auxiliary agent, and are mixed at 150°C. Then, they are sent to a single-screw extruder for extrusion through an elevator, and then extruded and pushed to a pelletizer by the single-screw extruder for the second granulation. Finally, after cooling and the third drying, cable material B is obtained.

[0049] Preparation of cable material: Cable material A and cable material B were mixed in a mass ratio of 1:25 and cross-linked in water at a temperature of 70° C. for 12 hours to obtain a cable material.

[0050] Example 3

[0051] The raw materials for the cable material are divided into raw material A and raw material B. Raw material A is composed, by weight, of 100 parts of a first polyolefin resin (polyethylene), 5 parts of a silane crosslinker (vinyltrimethoxysilane), and 0.1 parts of an initiator (dicumyl peroxide). Raw material B is composed, by weight, of 100 parts of a second polyolefin resin (polyethylene), 200 parts of a flame retardant (magnesium hydroxide), 2 parts of a catalyst (dibutyltin dilaurate), 10 parts of a fungicide (2-octyl-4-isothiazolin-3-one), 2 parts of a lubricant (polyethylene wax), 2 parts of a hindered phenolic antioxidant (1010), 3 parts of an anti-copper agent (1024), and 2 parts of an additive (masterbatch).

[0052] Preparation of Cable Material A: Raw Materials A were dried at 70°C and then mixed at a second speed of 1000 rpm to obtain a mixture. The mixture was extruded through a twin-screw extruder and then transferred to a single-screw extruder. The mixture was then extruded from the single-screw extruder and transferred to a pelletizer for primary pelletization. Finally, the mixture was cooled and then dried to obtain Cable Material A.

[0053] Preparation of cable material B: The above raw materials B are put into an internal mixer in the order of flame retardant, polyolefin resin, catalyst, anti-fungal agent, lubricant, hindered phenol antioxidant, anti-copper agent and auxiliary agent, and are mixed at 155°C. Then, the raw materials are sent to a single-screw extruder for extrusion through an elevator, and then extruded and pushed to a pelletizer by the single-screw extruder for the second granulation. Finally, after cooling and the third drying, the cable material B is obtained.

[0054] Preparation of cable material: Cable material A and cable material B were mixed in a mass ratio of 3:20 and cross-linked in water at a temperature of 90° C. for 4 hours to obtain a cable material.

[0055] Example 4

[0056] The raw materials for the cable material are divided into raw material A and raw material B. Raw material A is composed, by weight, of 100 parts of a first polyolefin resin (polyethylene), 170 parts of a flame retardant (magnesium hydroxide), 2.5 parts of a silane crosslinker (vinyl trihexyloxysilane), 0.14 parts of an initiator (dicumyl peroxide), 8 parts of a mildew-resistant agent (3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride), 1.5 parts of a first lubricant (EVA wax), 2 parts of a thio-antioxidant (300), 1 part of an anti-copper agent (1024), and 3 parts of an auxiliary masterbatch. Raw material B is composed, by weight, of 100 parts of a second polyolefin resin (polyethylene), 3 parts of a catalyst (stannous octoate), and 1.5 parts of a second lubricant (EVA wax).

[0057] Preparation of Cable Material A: The above raw materials A are added to an internal mixer in the order of flame retardant, first polyolefin resin, silane crosslinker, initiator, antifungal agent, first lubricant, thio-type antioxidant, anti-copper agent, and auxiliary agent, and mixed at 153°C. The raw materials are then fed into a twin-screw extruder via an elevator for extrusion and pushed to a single-screw extruder. From the single-screw extruder, the raw materials are extruded and pushed to a pelletizer for a first pelletization to produce semi-finished material A. The semi-finished material A is returned to the twin-screw extruder and the single-screw extruder, and the silane crosslinker is intermittently sprayed into the screw between the first to eighth sections of the twin-screw extruder through an automatic quantitative spraying device for silane grafting. The raw materials are then subjected to a second pelletization in a single-screw extruder. Finally, the semi-finished material A is cooled and dried to produce Cable Material A.

[0058] Preparation of cable material B: The above raw materials B were mixed at a speed of 400 rpm, added to a twin-screw extruder for extrusion and pushed to a single-screw extruder, and then extruded from the single-screw extruder to a pelletizer for third granulation, and finally cooled and dried to obtain cable material B.

[0059] Preparation of cable material: Cable material A and cable material B were mixed in a mass ratio of 20:1, and then cross-linked in steam at a temperature of 70° C. and a pressure of 0.08 MPa for 12 hours to obtain a cable material.

[0060] Example 5

[0061] The raw materials for the cable material are divided into raw material A and raw material B. Raw material A is composed, by weight, of 100 parts of a first polyolefin resin (polyethylene), 180 parts of a first flame retardant (red phosphorus), 2 parts of a silane crosslinker (vinyl trihexyloxysilane), 0.2 parts of an initiator (dicumyl peroxide), 7 parts of a mildew-resistant agent (3-(trimethoxysilyl)propyl dimethyl octadecyl ammonium chloride), 2 parts of a first lubricant (EVA wax), 2 parts of a thio-antioxidant (300), 3 parts of an anti-copper agent (1024), and 2 parts of an auxiliary masterbatch. Raw material B is composed, by weight, of 100 parts of a second polyolefin resin (polyethylene), 5 parts of a second flame retardant (red phosphorus), 4 parts of a catalyst (stannous octoate), and 1 part of a second lubricant (EVA wax).

[0062] Preparation of Cable Material A: The above raw materials A are added to an internal mixer in the order of the first flame retardant, the first polyolefin resin, the silane crosslinker, the initiator, the antifungal agent, the first lubricant, the thio-type antioxidant, the anti-copper agent, and the auxiliary agent, and mixed at 153°C. The raw materials are then fed into a twin-screw extruder via an elevator for extrusion and pushed to a single-screw extruder. From the single-screw extruder, the raw materials are extruded and pushed to a pelletizer for a first pelletization to produce semi-finished material A. The semi-finished material A is returned to the twin-screw extruder and the single-screw extruder, and the silane crosslinker is intermittently sprayed into the screw between the first to eighth sections of the twin-screw extruder through an automatic quantitative spraying device for silane grafting. The raw materials are then subjected to a second pelletization in a single-screw extruder. Finally, the semi-finished material A is cooled and dried to produce Cable Material A.

[0063] Preparation of cable material B: The above raw materials B were mixed at a speed of 1000 rpm, added to a twin-screw extruder for extrusion and pushed to a single-screw extruder, and then extruded from the single-screw extruder to a pelletizer for third granulation, and finally cooled and dried to obtain cable material B.

[0064] Preparation of cable material: Cable material A and cable material B were mixed in a mass ratio of 25:3, and then cross-linked in steam at a temperature of 90° C. and a pressure of 0.1 MPa for 4 hours to obtain a cable material.

[0065] Example 6

[0066] The difference from Example 1 is that the total weight of the flame retardant magnesium hydroxide and the antifungal agent 2-octyl-4-isothiazolinone-3-one is 187 parts, the mass ratio of the flame retardant to the antifungal agent is 20:1, and a cable material is finally obtained.

[0067] Example 7

[0068] The difference from Example 1 is that the total weight of the flame retardant magnesium hydroxide and the antifungal agent 2-octyl-4-isothiazolinone-3-one is 187 parts, the mass ratio of the flame retardant to the antifungal agent is 18:1, and a cable material is finally obtained.

[0069] Example 8

[0070] The difference from Example 1 is that the antifungal agent is a combination of an organic antifungal agent N-octyl-isothiazolinone and an inorganic antifungal agent nano zinc oxide, and the mass ratio of the organic antifungal agent to the inorganic antifungal agent is 1:3, and a cable material is finally obtained.

[0071] Example 9

[0072] The difference from Example 1 is that the antifungal agent is a combination of an organic antifungal agent N-octyl-isothiazolinone and an inorganic antifungal agent nano zinc oxide, and the mass ratio of the organic antifungal agent to the inorganic antifungal agent is 1:5, and a cable material is finally obtained.

[0073] Example 10

[0074] The difference from Example 1 is that, in the preparation of the cable material, cable material A and cable material B are mixed in a mass ratio of 25:3 and cross-linked in a natural environment at a temperature of 25° C. for 14 days to obtain the cable material.

[0075] Example 11

[0076] The difference from Example 1 is that, in the preparation of the cable material, cable material A and cable material B are mixed in a mass ratio of 25:3 and then cross-linked in a natural environment at a temperature of 35° C. for 3 days to obtain the cable material.

[0077] Example 12

[0078] The difference from Example 4 is that the mass ratio of cable material A to cable material B is 23:2, and the cable material is finally obtained.

[0079] Example 13

[0080] The difference from Example 4 is that the mass ratio of cable material A to cable material B is 15:1, and the cable material is finally obtained.

[0081] Comparative Example 1

[0082] The cable material consists of 60 parts of base resin polyethylene, 30 parts of silane grafting material, 120 parts of flame retardant magnesium hydroxide, 1.5 parts of surface modifier vinyl silane, 1 part of lubricant polyethylene wax, 2 parts of antioxidant 1010, 2 parts of anti-copper agent benzotriazole, 0.3 parts of benzophenone-based UV absorber, and 2 parts of crosslinking sensitizer triallyl isocyanurate (TAIC). The raw materials were placed in an internal mixer at 152°C for mixing, then fed via an elevator into a twin-screw extruder and pushed onto a single-screw extruder for granulation. The cable material was then cooled and dried to produce the material. Crosslinking was achieved by irradiation at 15 Mrad.

[0083] Comparative Example 2

[0084] The difference from Example 1 is that the raw materials of the cable material are divided into raw material A and raw material B. Raw material A is composed, by weight, of 100 parts of a first polyolefin resin, polyethylene; 1 part of a silane crosslinking agent, vinyltrimethoxysilane; and 0.3 parts of an initiator, dicumyl peroxide. Raw material B is composed, by weight, of 100 parts of a second polyolefin resin, polyethylene; 210 parts of a flame retardant, magnesium hydroxide; 6 parts of a catalyst, dibutyltin dilaurate; 2 parts of a fungicide, 2-octyl-4-isothiazolin-3-one; 1 part of a lubricant, polyethylene wax; 1 part of a hindered phenolic antioxidant, 1010; and 6 parts of an additive, a masterbatch.

[0085] Comparative Example 3

[0086] The difference from Example 1 is that the difference from Example 1 is that the cable material is prepared as follows: cable material A and cable material B are mixed in a mass ratio of 25:3, and the mixture is cross-linked in steam at a temperature of 60°C and a pressure of 0.2 MPa for 3 hours to obtain the cable material.

[0087] Test method:

[0088] The cable materials of the above embodiments and comparative examples were subjected to performance tests. The test standard requirements were implemented according to 2PfG 2962 / 12.23. The test results are shown in Tables 1 to 3.

[0089] Table 1

[0090]

[0091]

[0092] Table 2

[0093]

[0094]

[0095] Table 3

[0096]

[0097] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0098] The cable material of the present application preferably controls its raw material combination and weight proportion within the above range, which not only reduces the raw material cost, but also improves the flame retardant performance and high temperature resistance of the cable material. More importantly, the cable material of the present application reaches level 0 through a 28-day mold test, proving that it is used in a hot and humid environment for a long time and is not prone to mildew, thereby greatly extending the service life of the cable material in a hot and humid environment, and thus better applied to fields such as sea photovoltaic cables. Specifically, the added anti-fungal agent and flame retardant can synergistically enhance, further enhancing the flame retardant performance of the cable material, while reducing the smoke density. The addition of a silane cross-linking agent can form a three-dimensional network structure through silane grafting hydrolysis cross-linking, thereby increasing the thermal deformation temperature of the cable material to above 120°C, and the long-term working temperature reaches above 105°C, thereby better applicable to high temperature environments (such as photovoltaic cables). In addition, the cable material of the present application can be cross-linked by natural cross-linking, warm water cross-linking and steam cross-linking, and the performance and quality of the cable material after cross-linking are stable, while also reducing the cross-linking cost.

[0099] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A cable material, characterized in that: In parts by weight, the cable material comprises: 200 parts of polyolefin resin; 2 to 5 parts of a silane crosslinking agent; 0.1-0.2 parts of initiator; 2 to 5 parts of catalyst; 160-200 parts of flame retardant; 2-5 parts of antioxidant; 5-10 parts of antifungal agent; and 2 to 5 parts of lubricant; Wherein, the antifungal agent includes an organic antifungal agent, and the organic antifungal auxiliary agent is an isothiazolinone antifungal agent and / or a quaternary ammonium salt antifungal agent.

2. The cable material according to claim 1, characterized in that The cable material includes cable material A and cable material B; In parts by weight, the cable material A comprises: 100 parts of a first polyolefin resin; 2 to 5 parts of the silane crosslinking agent; and 0.1 to 0.2 parts of the initiator; In parts by weight, the cable material B comprises: 100 parts of a second polyolefin resin; 160 to 200 parts of the flame retardant; 2 to 5 parts of the catalyst; 5 to 10 parts of the antifungal agent; 2 to 5 parts of the lubricant; 2 to 5 parts of the antioxidant; and 2 to 5 parts of additives; The auxiliary agent is a color masterbatch and / or a plasticizer.

3. The cable material according to claim 1, characterized in that The cable material includes cable material A and cable material B; In parts by weight, the cable material A comprises: 100 parts of a first polyolefin resin; 160-180 parts of the flame retardant; 2 to 3 parts of the silane crosslinking agent; 0.1 to 0.2 parts of the initiator; 7 to 10 parts of the antifungal agent; 1-2 parts of the first lubricant; 2 to 5 parts of the antioxidant; and 2 to 4 parts of additives; The auxiliary agent is a color masterbatch and / or a plasticizer; In parts by weight, the cable material B comprises: 100 parts of a second polyolefin resin; 2 to 4 parts of the catalyst; and 1-2 parts of the second lubricant.

4. The cable material according to claim 1, characterized in that The cable material includes cable material A and cable material B; In parts by weight, the cable material A comprises: 100 parts of a first polyolefin resin; 160-180 parts of a first flame retardant; 2 to 3 parts of the silane crosslinking agent; 0.1 to 0.2 parts of the initiator; 7 to 10 parts of the antifungal agent; 1-2 parts of the first lubricant; 2 to 5 parts of the antioxidant; and 2 to 4 parts of additives; The auxiliary agent is a color masterbatch and / or a plasticizer; In parts by weight, the cable material B comprises: 100 parts of a second polyolefin resin; 5 to 20 parts of a second flame retardant; 2 to 4 parts of the catalyst; and 1-2 parts of the second lubricant.

5. The cable material according to any one of claims 1 to 4, characterized in that The mass ratio of the flame retardant to the antifungal agent is 20 to 40:1; and / or the flame retardant, the first flame retardant and the second flame retardant are each independently selected from any one or more of an inorganic flame retardant, an organic phosphorus-nitrogen flame retardant and a synergist, wherein the inorganic flame retardant is aluminum hydroxide and / or magnesium hydroxide, the organic phosphorus-nitrogen flame retardant is selected from any one or more of ammonium polyphosphate, melamine, melamine cyanurate, melamine polyphosphate, triphenyl phosphate and tricresyl phosphate, and the synergist is selected from any one or more of red phosphorus, nano-montmorillonite, expanded graphite, nano-zinc borate and nitrogen-phosphorus synergistic flame retardants.

6. The cable material according to any one of claims 1 to 4, characterized in that The isothiazolinone antifungal agent is 2-octyl-4-isothiazolinone-3-one and / or butylisothiazolinone; the quaternary ammonium salt antifungal agent is selected from any one or more of 3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride, KH550 grafted quaternary ammonium salt, pyridinium quaternary ammonium salt-acrylic amine copolymer, chitosan quaternary ammonium salt and Gemini type diquaternary ammonium salt; And / or, the antifungal agent further includes an inorganic antifungal agent, and the inorganic antifungal agent is nano zinc oxide and / or nano titanium dioxide.

7. The cable material according to any one of claims 1 to 4, characterized in that The polyolefin resin, the first polyolefin resin and the second polyolefin resin are each independently selected from any one or more of polyethylene, ethylene-vinyl acetate copolymer and polyolefin elastomer; and / or the silane crosslinker is vinyltrimethoxysilane and / or vinyltrihexyloxysilane; and / or the initiator is selected from any one or more of dicumyl peroxide, di-tert-butyl peroxide and dilauroyl peroxide; and / or the catalyst is selected from any one or more of dibutyltin dilaurate, stannous octoate and organic titanium chelate; and / or the antioxidant is selected from any one or more of hindered phenol antioxidants, thio antioxidants, anti-copper agents and phosphite antioxidants; and / or the lubricant, the first lubricant and the second lubricant are each independently selected from any one or more of polyethylene wax, silicone powder, EVA wax and ethylene bisstearamide.

8. A method for preparing the cable material according to any one of claims 1 to 7, characterized in that: The preparation method comprises: sequentially performing banburying, granulation and cross-linking on raw materials corresponding to the cable material to obtain the cable material; Wherein, the crosslinking method is selected from any one or more of warm water crosslinking, steam crosslinking and natural crosslinking. The warm water crosslinking process includes crosslinking in water at a temperature of 70 to 90°C for 4 to 12 hours, the steam crosslinking process includes crosslinking in steam at a temperature of 70 to 90°C and a pressure of 0.08 to 0.1 MPa for 4 to 12 hours, and the natural crosslinking process includes crosslinking in a natural environment at a temperature of 25 to 40°C for 3 to 14 days.

9. The preparation method according to claim 8, characterized in that The preparation method further comprises: Step S11, respectively mixing the raw materials corresponding to the cable material to obtain raw material A and raw material B; Step S12, sequentially subjecting the raw material A to a first drying, mixing, first granulation, cooling, and second drying to obtain cable material A; Step S13, subjecting the raw material B to the aforementioned mixing, second granulation, cooling, and third drying in sequence to obtain cable material B; Step S14, cross-linking the cable material A and the cable material B to obtain the cable material; The mass ratio of the cable material A to the cable material B is 1-3:20-25; the mixing speed is 400-1000 rpm; and the first drying temperature is 50-70°C.

10. The preparation method according to claim 8, characterized in that The preparation method further comprises: Step S21, respectively mixing the raw materials corresponding to the cable material to obtain raw material A and raw material B; Step S22, subjecting the raw material A to the banburying and first granulation in sequence to obtain a mixture; subjecting the mixture to silane grafting and then to second granulation, cooling and drying in sequence to obtain cable material A; Step S23, mixing, third granulation, cooling and drying the raw material B in sequence to obtain cable material B; Step S24, cross-linking the cable material A and the cable material B to obtain the cable material; Wherein, the mass ratio of the cable material A to the cable material B is 20-25:1-3; and the mixing rotation speed is 400-1000 rpm.

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