Irradiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables

Abstract

The present invention relates to a radiation-crosslinked, oil-resistant, halogen-free, flame-retardant sheathing material for nuclear power plant cables, belonging to the technical field of nuclear cable sheathing materials. To address the existing problems of poor tensile properties and oil resistance, a radiation-crosslinked, oil-resistant, halogen-free, flame-retardant sheathing material for nuclear power plant cables is provided. The material comprises the following components in parts by weight: base material (100 parts); zinc acetate-modified maleic anhydride-grafted SEBS (80-120 parts); high-entropy rare earth zirconate nano-modified polyimide-siloxane block copolymer (100-140 parts); halogen-free flame retardant (80-120 parts); antioxidant (5.0-16 parts); anti-radiation agent (1.0-15 parts); crosslinking sensitizer (1.0-5.0 parts); and mildew inhibitor (2.0-5.0 parts). The base material is a blend of a high-temperature-resistant polyester elastomer, a high-temperature-resistant polyamide elastomer, and a styrene block copolymer. The comprehensive performance of this sheathing material meets the performance requirements of fourth-generation nuclear cable materials.

Description

Technical Field

[0001] The invention relates to a radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power station cables, belonging to the technical field of nuclear cable sheath materials. Background Art

[0002] Cables used in nuclear power plants require cable sheath materials to have excellent physical and mechanical properties, electrical properties, radiation resistance, flame retardancy, and certain oil resistance. At the same time, the thermal life requirements for nuclear power plant cables are getting higher and higher, from 90℃ / 60 years for the third generation nuclear power plants to 90℃ / 80 years for the fourth generation. Radiation resistance requirements under normal working conditions (resistant 60 Co-γ ray cumulative dose 560kGy / room temperature) and accident conditions (DBA and AG, 60 The cumulative Co-γ ray dose reaches 2260 kGy / room temperature) and still maintains a certain level of performance. In existing cable insulation materials, increasing the proportion of polycyclic aromatic hydrocarbon resin modifiers can improve the material's heat resistance and radiation resistance, but this marginal effect is diminishing. Furthermore, excessively high proportions of polycyclic aromatic hydrocarbon resin in the formulation increase smoke production during combustion, resulting in the smoke transmittance in cable combustion tests failing to meet standard requirements. Compared to insulation materials, sheathing materials require higher tensile properties, and some also require certain oil resistance. Compared to the technical requirements for sheathing materials used in fourth-generation nuclear power plant cables, existing sheathing materials have limited tensile strength and poor oil resistance, necessitating new technical solutions.

[0003] The prior art Chinese patent document (authorization announcement number: CN110724324B) discloses a halogen-free, low-smoke flame-retardant sheathing material, which contains at least a high-temperature resistant polyolefin elastomer in the base material and uses a high-temperature resistant and radiation-resistant modified masterbatch containing at least a condensed polycyclic polynuclear aromatic resin. The sheathing material can achieve the requirements of 90°C / 60 years of thermal life and radiation resistance, and has high flame retardant properties, but its oil resistance is poor, which limits its scope of use.

[0004] The prior art Chinese patent document (publication number: CN115353744A) discloses a halogen-free, low-smoke, flame-retardant polyolefin insulation material, comprising 100 parts by weight of a base material, 120-160 parts of a high-entropy rare earth zirconate-modified polyimide-siloxane block copolymer, 60-100 parts of a halogen-free flame retardant, 4.0-12 parts of an antioxidant, and 2-12 parts of an anti-radiation agent. It is used as a nuclear-grade cable insulation material, with a thermal life of 90°C / 84.7 years. Under normal working conditions (resistant to 60 Co-γ ray cumulative dose 412.5kGy / room temperature) and accident conditions (DBA and AG, 60The insulation performance of this material meets the requirements (accumulated Co-γ ray dose of 2064kGy / room temperature). However, its tensile strength is only 10.7MPa, which is insufficient for sheathing materials. It is also not oil-resistant and is therefore not suitable for use as a sheathing material for fourth-generation nuclear power plants.

[0005] Modern research has revealed that marine organisms, such as mussels, can securely connect to the surfaces of various metals, organic matter, and inorganic non-metallic materials in seawater through their byssus threads. This is due to the presence of numerous catechol groups in the byssus protein, which possess extremely strong coordination capabilities. These groups can complex with metal ions to form metal coordination bonds. Metal coordination bonds are also found in strong biopolymers such as spider silk and silkworm silk. These biomaterials possess excellent toughness and strength. Under the influence of external forces, metal coordination bonds continuously dissipate external mechanical energy through dynamic, reversible fracture and reconstruction, releasing hidden lengths and avoiding stress concentration. The metal ions and ligands in metal coordination interactions have a wide range of binding strengths, and the resulting metal coordination bonds can be dynamic or highly stable. Adjusting the number of coordinating ions and ligands in the metal coordination interaction can adjust the mechanical properties of the material. Precisely because the metal coordination bond energy is adjustable, can be dynamically generated, is easy to introduce into polymer materials, and greatly improves the mechanical properties of polymer materials, the metal coordination bond-related mechanisms that simulate biomaterial biomimetic research have been widely used in recent years to improve the strength and toughness of polymer materials. Researchers named this coordination bond and hydrogen bonds and ionic bonds that can play a similar role sacrificial bonds or dynamic bonds. Among them, the metal coordination bond is a strong non-covalent bond with a bond energy close to that of an ionic bond, reaching 50 to 200 kJ / mol, and the bond energy is adjustable. After the sacrificial bond is formed in the material, its tensile strength and toughness will be significantly improved, and some materials also have certain self-healing functions. For example: introducing Zn into polydimethylsiloxane 2+ The metal coordination bonds are formed with carboxyl groups, and the resulting material has strong rigidity and can heal quickly under high temperature environments; by introducing metal coordination bonds into the hydrogel system and preparing a double cross-linked gel system, the material can absorb energy through the metal coordination bond cross-linking network under the action of external stress, preventing stress concentration and greatly improving the mechanical properties of the material. Summary of the Invention

[0006] In view of the above deficiencies in the prior art, the present invention provides an irradiation-crosslinked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables, which solves the problem of how to improve the tensile properties of the sheath material and make the material have a certain oil resistance.

[0007] The object of the present invention is achieved through the following technical solution: a radiation-crosslinked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables, characterized in that the sheath material comprises the following components in parts by weight:

[0008] Base material: 100;

[0009] Zinc acetate modified maleic anhydride grafted SEBS: 80-120;

[0010] High entropy rare earth zirconate nano-modified polyimide-siloxane block copolymer: 100-140;

[0011] Halogen-free flame retardant: 80-120;

[0012] Antioxidant: 5.0~16;

[0013] Anti-radiation agent: 1.0~15;

[0014] Cross-linking sensitizer: 1.0~5.0;

[0015] Antifungal agent: 2.0~5.0;

[0016] The base material is a blend of high temperature resistant polyester elastomer (TPEE), high temperature resistant polyamide elastomer (TPAE) and styrene block copolymer (SEBS).

[0017] By adding zinc acetate-modified maleic anhydride-grafted SEBS containing sacrificial bonds, the tensile properties of the material can be effectively improved, including tensile properties after aging. More specifically, because the sacrificial bonds contained in zinc acetate-modified maleic anhydride-grafted SEBS are dynamic metal coordination bonds with high bond energy, high bond density, flexible bonding, and polarity, new sacrificial bonds are quickly formed at new interfaces when the material deforms or shifts, thereby effectively restoring the tensile strength of the material after deformation. At the same time, when zinc acetate-modified maleic anhydride-grafted SEBS is mixed with high-entropy rare earth zirconate nano-modified polyimide-siloxane block copolymer, a certain coordination synergistic effect is formed with the rare earth metal ions in the modified polyimide-siloxane block copolymer, further increasing the bond density of coordination bonds and sacrificial bonds in the material. This makes it difficult for non-polar substances such as mineral oil to penetrate into the molecular gaps of the material, thereby improving the material's oil resistance. By using zinc acetate modified maleic anhydride grafted SEBS containing sacrificial bonds and the base material, halogen-free flame retardant, antioxidant, anti-radiation agent, cross-linking sensitizer, mildew inhibitor and the like of the present invention to work together, the sheath material can have good tensile properties and certain oil resistance, while also having a thermal life of more than 90°C / 80 years, and achieve a good balance with other properties. Under normal working conditions (resistance 60 Co-γ ray cumulative dose 560kGy / room temperature) and accident conditions (DBA and AG, 60 The performance of the cable reaches the requirements of the fourth generation nuclear power plant cables.

[0018] In the radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables, preferably, the zinc acetate-modified maleic anhydride grafted SEBS is obtained by melt blending maleic anhydride grafted SEBS, 3-amino-1,2,4-triazole (ATA) and zinc acetate as raw materials. Maleic anhydride grafted SEBS, 3-amino-1,2,4-triazole and zinc acetate can react during melt blending, and the amino group in 3-amino-1,2,4-triazole reacts with the maleic anhydride group in maleic anhydride grafted SEBS to form an amide triazole-carboxylic acid group through melt reaction. The amide triazole-carboxylic acid group reacts with Zn 2+ Formation of Zn 2+ -O metal coordination bond can also serve as a ligand for hydrogen bond, thereby successfully constructing Zn in the sheath material of the present invention. 2+ -O metal coordination bonds and hydrogen bonds are sacrificial bonds cross-linking the network, while Zn 2+ The sacrificial bond crosslinking network formed by -O metal coordination bonds and hydrogen bonds can break during stretching to dissipate energy, effectively avoiding stress concentration. Furthermore, the sacrificial bonds continuously reform after breaking, forming a new network. This gives the material excellent tensile toughness, significantly improving its tensile strength and elongation at break. Furthermore, the weight ratio of maleic anhydride-grafted SEBS to 3-amino-1,2,4-triazole is preferably 30-35:1.

[0019] In the above-mentioned radiation-crosslinked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables, preferably, the anti-radiation agent is selected from one or more of ferrocene, 2-amino-5-(p-methoxyphenyl)-1,3,4-thiadiazole lanthanum complex, and 6-benzylaminopurine copper complex.

[0020] In the above-mentioned radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables, preferably, the halogen-free flame retardant is selected from one or a mixture of aluminum hydroxide, aluminum diethylphosphinate and melamine cyanurate.

[0021] In the radiation-crosslinked, oil-resistant, halogen-free, flame-retardant sheathing material for nuclear power plant cables, the antioxidant is preferably selected from a combination of a high-molecular-weight primary antioxidant of an asymmetric hindered phenol-calixarene and a high-molecular-weight secondary antioxidant of a phosphite. The asymmetric hindered phenol-calixarene is selected from asymmetric hindered phenol-calixarene and / or asymmetric hindered phenol-calixarene, and the high-molecular-weight secondary antioxidant of a phosphite is, for example, Antioxidant 168. It is preferred that the antioxidant be selected from a high-molecular-weight primary antioxidant of an asymmetric hindered phenol-calixarene to a high-molecular-weight secondary antioxidant in a mass ratio of 1:0.5 to 0.8.

[0022] In the radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables, preferably, the molecular formula of the high entropy rare earth zirconate in the high entropy rare earth zirconate nano-modified polyimide-siloxane block copolymer is (X 0.2 Y 0.2 Z 0.2 M 0.2 N 0.2 )2Zr2O7, wherein X, Y, Z, M and N are independently selected from lanthanum (La), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), dysprosium (Dy), holmium (Ho), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y) and scandium (Sc), and the X, Y, Z, M and N are all different. It can better enhance the flame retardant and smoke suppression properties of the copolymer, and the material has good crusting performance during combustion, and the transmittance of the combustion smoke can be higher. As a further preference, the mass percentage of siloxane in the high entropy rare earth zirconate nano-modified polyimide-siloxane block copolymer is 50% to 60%. A polyimide-siloxane block copolymer is prepared through a polycondensation reaction using aromatic dianhydride, aromatic diamine, and polysiloxane diamine as raw materials. The copolymer is in the form of a powder or granules and is a thermoplastic elastomer. 2% to 5% high-entropy rare earth zirconate powder is added during the reaction to prepare the block copolymer. The high-entropy rare earth zirconate is a porous granular powder with an outer diameter of 5 to 20 microns. The mixed solvent system used for the polycondensation reaction is relatively viscous. By adding the porous granular powder, a suspension is formed. After the polycondensation reaction is complete and the solvent evaporates, the porous high-entropy rare earth zirconate granular powder is evenly dispersed in the polyimide-siloxane block copolymer, forming the corresponding high-entropy rare earth zirconate nano-modified polyimide-siloxane block copolymer.

[0023] In the radiation-crosslinked, oil-resistant, halogen-free, flame-retardant sheathing material for nuclear power plant cables, the sheathing material preferably further comprises 2.0 to 5.0 parts by weight of a mildewcide. Further preferably, the mildewcide is selected from one or more of 3-iodo-2-propynyl-N-n-butylcarbamate and tributyltin oxide.

[0024] In the above-mentioned radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables, preferably, the cross-linking sensitizer is triallyl isocyanurate.

[0025] In the above-mentioned radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables, preferably, the base material contains at least high-temperature resistant polyester elastomer (TPEE), and the content of high-temperature resistant polyester elastomer (TPEE) in the base material is 45% to 60%.

[0026] In summary, the present invention has the following advantages compared with the prior art:

[0027] 1. By adding zinc acetate-modified maleic anhydride-grafted SEBS containing sacrificial bonds, a synergistic effect with the modified polyimide-siloxane block copolymer is achieved, imparting a degree of mineral oil resistance to the material, meeting the oil resistance requirements of fourth-generation nuclear power plant cables. Furthermore, the sacrificial bonds in the zinc acetate-modified maleic anhydride-grafted SEBS significantly increase the tensile strength of the sheath material, providing better protection against damage from pulling or crushing, thereby enhancing cable safety.

[0028] 2. The comprehensive performance of this sheath material can meet the performance requirements of the fourth generation nuclear cable material, and the thermal life can reach 90℃ / 86 years. 60 Co-γ ray cumulative dose 560kGy / room temperature) and accident conditions (DBA and AG, 60 The performance of the cable reaches the requirements of the fourth generation nuclear power plant cables. DETAILED DESCRIPTION

[0029] The technical solution of the present invention is further specifically described below through specific embodiments, but the present invention is not limited to these embodiments.

[0030] Example 1

[0031] The radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables of this embodiment comprises the following components in parts by weight:

[0032] Base material: 100;

[0033] Zinc acetate modified maleic anhydride grafted SEBS: 100;

[0034] High entropy rare earth zirconate nano-modified polyimide-siloxane block copolymer: 120;

[0035] Halogen-free flame retardant: 80, aluminum diethylphosphinate;

[0036] Antioxidant: 10, a mixture of an asymmetric hindered phenol-type calixarene high molecular weight primary antioxidant and a phosphite high molecular weight auxiliary antioxidant, with the mass ratio of the two being 1:1;

[0037] Anti-radiation agent: 8.0, 6-benzylaminopurine copper complex;

[0038] Crosslinking sensitizer: 2.0, triallyl isocyanurate;

[0039] Antifungal agent: 2,5,3-iodo-2-propynyl-N-butylcarbamate;

[0040] The base material comprises a blend of high temperature resistant polyester elastomer (TPEE), high temperature resistant polyamide elastomer (TPAE) and styrene block copolymer (SEBS), and the content of the high temperature resistant polyester elastomer (TPEE) is 50%.

[0041] The zinc acetate modified maleic anhydride grafted SEBS is prepared by melt blending maleic anhydride grafted SEBS (maleic anhydride grafted SEBS (brand FG1901) from Kraton), 3-amino-1,2,4-triazole (ATA) and zinc acetate as raw materials, wherein the mass ratio of maleic anhydride grafted SEBS to 3-amino-1,2,4-triazole is 33:1.

[0042] The mass percentage of siloxane in the high entropy rare earth zirconate nano-modified polyimide-siloxane block copolymer is 55%, wherein the molecular weight of the high entropy rare earth zirconate (X 0.2 Y 0.2 Z 0.2 M 0.2 N 0.2 )2Zr2O7, wherein X, Y, Z, M and N are each independently selected from lanthanum (La), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), dysprosium (Dy), holmium (Ho), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y) and scandium (Sc), and X, Y, Z, M and N are all different.

[0043] The high-entropy rare earth zirconate nano-modified polyimide-siloxane block copolymer is specifically prepared by using aromatic dianhydride, aromatic diamine and polysiloxane diamine as raw materials through a condensation reaction to obtain a polyimide-siloxane block copolymer, and 5% by mass of high-entropy rare earth zirconate powder is added during the condensation reaction.

[0044] According to the raw material ratios in the above embodiment, the base material, zinc acetate modified maleic anhydride grafted SEBS, high entropy rare earth zirconate nano-modified polyimide-siloxane block copolymer, halogen-free flame retardant, antioxidant, anti-radiation agent, cross-linking sensitizer and mildew inhibitor are mixed evenly, and then put into a two-stage twin-screw extruder, and extrusion granulation is carried out under the conditions of controlling the temperature at 150°C to 200°C and the speed at 200 to 350 rpm to obtain the corresponding radiation cross-linked oil-resistant halogen-free flame retardant sheath material.

[0045] Example 2

[0046] The radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables of this embodiment comprises the following components in parts by weight:

[0047] Base material: 100;

[0048] Zinc acetate modified maleic anhydride grafted SEBS: 120;

[0049] High entropy rare earth zirconate nano-modified polyimide-siloxane block copolymer: 100, the composition of which is the same as that of Example 1;

[0050] Halogen-free flame retardant: 120, aluminum diethylphosphinate and melamine cyanurate mixed in a ratio of 1:1;

[0051] Antioxidant: 12, a mixture of an asymmetric hindered phenol-type calixarene high molecular weight primary antioxidant and a phosphite high molecular weight auxiliary antioxidant, with the mass ratio of the two being 1:1;

[0052] Anti-radiation agent: 10, 2-amino-5-(p-methoxyphenyl)-1,3,4-thiadiazole lanthanum complex;

[0053] Crosslinking sensitizer: 3.0, triallyl isocyanurate;

[0054] Antifungal agent: 3.0, 3-iodo-2-propynyl-N-butylcarbamate;

[0055] The base material includes a blend of high-temperature resistant polyester elastomer (TPEE), high-temperature resistant polyamide elastomer (TPAE) and styrene block copolymer (SEBS), and the content of the high-temperature resistant polyester elastomer (TPEE) is 48%.

[0056] The zinc acetate modified maleic anhydride grafted SEBS is prepared by melt blending maleic anhydride grafted SEBS (maleic anhydride grafted SEBS (brand FG1901) from Kraton), 3-amino-1,2,4-triazole (ATA) and zinc acetate as raw materials, wherein the mass ratio of maleic anhydride grafted SEBS to 3-amino-1,2,4-triazole is 35:1.

[0057] The specific method for making the above-mentioned sheath material is the same as that in Example 1 and will not be repeated here.

[0058] Example 3

[0059] The radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables of this embodiment comprises the following components in parts by weight:

[0060] Base material: 100;

[0061] Zinc acetate modified maleic anhydride grafted SEBS: 120;

[0062] High entropy rare earth zirconate nano-modified polyimide-siloxane block copolymer: 100, the composition of which is the same as that of Example 1;

[0063] Halogen-free flame retardant: 110, aluminum hydroxide;

[0064] Antioxidant: 14, a mixture of an asymmetric hindered phenol-type calixarene high molecular weight primary antioxidant and a phosphite high molecular weight secondary antioxidant, with the mass ratio of the two being 1:1;

[0065] Anti-radiation agent: 12, a 2-amino-5-(p-methoxyphenyl)-1,3,4-thiadiazole lanthanum complex;

[0066] Cross-linking sensitizer: 3.5, triallyl isocyanurate;

[0067] Antifungal agent: 4.0, tributyltin oxide;

[0068] The base material includes a blend of high-temperature resistant polyester elastomer (TPEE), high-temperature resistant polyamide elastomer (TPAE) and styrene block copolymer (SEBS), and the content of the high-temperature resistant polyester elastomer (TPEE) is 55%.

[0069] The zinc acetate modified maleic anhydride grafted SEBS is prepared by melt blending maleic anhydride grafted SEBS (maleic anhydride grafted SEBS (brand FG1901) from Kraton), 3-amino-1,2,4-triazole (ATA) and zinc acetate as raw materials, wherein the mass ratio of maleic anhydride grafted SEBS to 3-amino-1,2,4-triazole (ATA) is 35:1.

[0070] The specific method for making the above-mentioned sheath material is the same as that in Example 1 and will not be repeated here.

[0071] Example 4

[0072] The radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables of this embodiment comprises the following components in parts by weight:

[0073] Base material: 100;

[0074] Zinc acetate modified maleic anhydride grafted SEBS: 90;

[0075] High entropy rare earth zirconate nano-modified polyimide-siloxane block copolymer: 140, the composition of which is the same as that of Example 1;

[0076] Halogen-free flame retardant: 110, aluminum diethylphosphinate;

[0077] Antioxidant: 14, which is a mixture of asymmetric hindered phenol-type calixarene and antioxidant 168, and the mass ratio of the two is 1:0.8;

[0078] Anti-radiation agent: 12, 6-benzylaminopurine copper complex;

[0079] Crosslinking sensitizer: 5.0, triallyl isocyanurate;

[0080] Antifungal agent: 4.5, tributyltin oxide;

[0081] The base material includes a blend of high-temperature resistant polyester elastomer (TPEE), high-temperature resistant polyamide elastomer (TPAE) and styrene block copolymer (SEBS), and the content of the high-temperature resistant polyester elastomer (TPEE) is 60%.

[0082] The zinc acetate modified maleic anhydride grafted SEBS is prepared by melt blending maleic anhydride grafted SEBS (maleic anhydride grafted SEBS (brand FG1901) from Kraton), 3-amino-1,2,4-triazole (ATA) and zinc acetate as raw materials, wherein the mass ratio of maleic anhydride grafted SEBS to 3-amino-1,2,4-triazole is 30:1.

[0083] The specific method for making the above-mentioned sheath material is the same as that in Example 1 and will not be repeated here.

[0084] Example 5

[0085] The radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables of this embodiment comprises the following components in parts by weight:

[0086] Base material: 100;

[0087] Zinc acetate modified maleic anhydride grafted SEBS: 100;

[0088] High entropy rare earth zirconate nano-modified polyimide-siloxane block copolymer: 130, the composition of which is the same as that of Example 1;

[0089] Halogen-free flame retardant: 110, aluminum diethylphosphinate;

[0090] Antioxidant: 14, which is a mixture of asymmetric hindered phenol-type calixarene and antioxidant 168, and the mass ratio of the two is 1:0.5;

[0091] Anti-radiation agent: 12, 6-benzylaminopurine copper complex;

[0092] Cross-linking sensitizer: 1.8, triallyl isocyanurate;

[0093] Antifungal agent: 2,8,3-iodo-2-propynyl-N-butylcarbamate;

[0094] The base material comprises a blend of high temperature resistant polyester elastomer (TPEE), high temperature resistant polyamide elastomer (TPAE) and styrene block copolymer (SEBS), and the content of the high temperature resistant polyester elastomer (TPEE) is 50%.

[0095] The zinc acetate modified maleic anhydride grafted SEBS is prepared by melt blending maleic anhydride grafted SEBS (maleic anhydride grafted SEBS (brand FG1901) from Kraton), 3-amino-1,2,4-triazole (ATA) and zinc acetate as raw materials, wherein the mass ratio of maleic anhydride grafted SEBS to 3-amino-1,2,4-triazole is 32:1.

[0096] The specific method for making the above-mentioned sheath material is the same as that in Example 1 and will not be repeated here.

[0097] Example 6

[0098] The radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables of this embodiment comprises the following components in parts by weight:

[0099] Base material: 100;

[0100] Zinc acetate modified maleic anhydride grafted SEBS: 110;

[0101] High entropy rare earth zirconate nano-modified polyimide-siloxane block copolymer: 110, the composition of which is the same as that of Example 1;

[0102] Halogen-free flame retardant: 110, which is a mixture of aluminum diethylphosphinate and melamine cyanurate in a ratio of 1:1;

[0103] Antioxidant: 14, which is a mixture of asymmetric hindered phenol-type calixarene and antioxidant 168, and the mass ratio of the two is 1:0.6;

[0104] Anti-radiation agent: 12, 6-benzylaminopurine copper complex;

[0105] Cross-linking sensitizer: 3.5, triallyl isocyanurate;

[0106] Antifungal agent: 3.0, tributyltin oxide;

[0107] The base material includes a blend of high-temperature resistant polyester elastomer (TPEE), high-temperature resistant polyamide elastomer (TPAE) and styrene block copolymer (SEBS), and the content of the high-temperature resistant polyester elastomer (TPEE) is 55%.

[0108] The zinc acetate modified maleic anhydride grafted SEBS is prepared by melt blending maleic anhydride grafted SEBS (maleic anhydride grafted SEBS (brand FG1901) from Kraton), 3-amino-1,2,4-triazole (ATA) and zinc acetate as raw materials, wherein the mass ratio of maleic anhydride grafted SEBS to 3-amino-1,2,4-triazole is 33:1.

[0109] The specific method for making the above-mentioned sheath material is the same as that in Example 1 and will not be repeated here.

[0110] Example 7

[0111] The radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables of this embodiment comprises the following components in parts by weight:

[0112] Base material: 100;

[0113] Zinc acetate modified maleic anhydride grafted SEBS: 80;

[0114] High entropy rare earth zirconate nano-modified polyimide-siloxane block copolymer: 120, the composition of which is the same as that of Example 1;

[0115] Halogen-free flame retardant: 80, which is a mixture of aluminum diethylphosphinate and melamine cyanurate in a ratio of 1:1;

[0116] Antioxidant: 16, which is a mixture of asymmetric hindered phenol-type calixarene and antioxidant 168, and the mass ratio of the two is 1:0.4;

[0117] Anti-radiation agent: 12, 6-benzylaminopurine copper complex;

[0118] Cross-linking sensitizer: 1.7, triallyl isocyanurate;

[0119] Antifungal agent: 2.0, 3-iodo-2-propynyl-N-butylcarbamate;

[0120] The base material comprises a blend of high temperature resistant polyester elastomer (TPEE), high temperature resistant polyamide elastomer (TPAE) and styrene block copolymer (SEBS), and the content of the high temperature resistant polyester elastomer (TPEE) is 50%.

[0121] The zinc acetate modified maleic anhydride grafted SEBS is prepared by melt blending maleic anhydride grafted SEBS (maleic anhydride grafted SEBS (brand FG1901) from Kraton), 3-amino-1,2,4-triazole (ATA) and zinc acetate as raw materials, wherein the mass ratio of maleic anhydride grafted SEBS to 3-amino-1,2,4-triazole (ATA) is 30:1.

[0122] The specific method for making the above-mentioned sheath material is the same as that in Example 1 and will not be repeated here.

[0123] Example 8

[0124] The radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables of this embodiment comprises the following components in parts by weight:

[0125] Base material: 100;

[0126] Zinc acetate modified maleic anhydride grafted SEBS: 80;

[0127] High entropy rare earth zirconate nano-modified polyimide-siloxane block copolymer: 120, the composition of which is the same as that of Example 1;

[0128] Halogen-free flame retardant: 80, which is a mixture of aluminum diethylphosphinate and melamine cyanurate in a ratio of 1:1;

[0129] Antioxidant: 16, which is a mixture of asymmetric hindered phenol-type calixarene and antioxidant 168, and the mass ratio of the two is 1:0.4;

[0130] Anti-radiation agent: 12, a 2-amino-5-(p-methoxyphenyl)-1,3,4-thiadiazole lanthanum complex;

[0131] Crosslinking sensitizer: 2.0, triallyl isocyanurate;

[0132] Antifungal agent: 4.5, tributyltin oxide;

[0133] The base material includes a blend of high-temperature resistant polyester elastomer (TPEE), high-temperature resistant polyamide elastomer (TPAE) and styrene block copolymer (SEBS), and the content of the high-temperature resistant polyester elastomer (TPEE) is 60%.

[0134] The zinc acetate modified maleic anhydride grafted SEBS is prepared by melt blending maleic anhydride grafted SEBS (maleic anhydride grafted SEBS (brand FG1901) from Kraton), 3-amino-1,2,4-triazole (ATA) and zinc acetate as raw materials, wherein the mass ratio of maleic anhydride grafted SEBS to 3-amino-1,2,4-triazole is 30:1.

[0135] The specific method for making the above-mentioned sheath material is the same as that in Example 1 and will not be repeated here.

[0136] Comparative Example 1

[0137] In order to illustrate the excellent improvement of the tensile properties and oil resistance of the material by the zinc acetate-modified maleic anhydride-grafted SEBS added in the present invention, this comparative example uses maleic anhydride-grafted SEBS as a substitute for comparison. Taking Example 6 as a comparison, the zinc acetate-modified maleic anhydride-grafted SEBS therein is directly replaced by maleic anhydride-grafted SEBS.

[0138] The radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables in this comparative example comprises the following components in parts by weight:

[0139] Base material: 100;

[0140] Maleic anhydride grafted SEBS: 110;

[0141] High entropy rare earth zirconate nano-modified polyimide-siloxane block copolymer: 110, the composition of which is the same as that of Example 6;

[0142] Halogen-free flame retardant: 110, which is a mixture of aluminum diethylphosphinate and melamine cyanurate in a ratio of 1:1;

[0143] Antioxidant: 14, which is a mixture of asymmetric hindered phenol-type calixarene and antioxidant 168, and the mass ratio of the two is 1:0.6;

[0144] Anti-radiation agent: 12, 6-benzylaminopurine copper complex;

[0145] Cross-linking sensitizer: 3.5, triallyl isocyanurate;

[0146] Antifungal agent: 3.0, tributyltin oxide;

[0147] The base material includes a blend of high-temperature resistant polyester elastomer (TPEE), high-temperature resistant polyamide elastomer (TPAE) and styrene block copolymer (SEBS), and the content of the high-temperature resistant polyester elastomer (TPEE) is 55%.

[0148] The maleic anhydride grafted SEBS is the maleic anhydride grafted SEBS (brand FG1901) produced by Kraton.

[0149] The specific method for making the above-mentioned sheath material is the same as that in Example 1 and will not be repeated here.

[0150] Comparative Example 2

[0151] In order to illustrate that the improvement of the oil resistance of the material by the zinc acetate-modified maleic anhydride grafted SEBS added in the present invention is related to the synergistic effect of the high-entropy rare earth zirconate nano-modified polyimide-siloxane block copolymer, this comparative example compares the two sheath materials after replacing the high-entropy rare earth zirconate nano-modified polyimide-siloxane block copolymer in Example 6 with an equal amount of zinc acetate-modified maleic anhydride grafted SEBS.

[0152] The radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables in this comparative example comprises the following components in parts by weight:

[0153] Base material: 100;

[0154] Zinc acetate modified maleic anhydride grafted SEBS: 220, the composition of which is the same as that of Example 1;

[0155] Halogen-free flame retardant: 110, which is a mixture of aluminum diethylphosphinate and melamine cyanurate in a ratio of 1:1;

[0156] Antioxidant: 14, a mixture of asymmetric hindered phenol-type calixarene and antioxidant 168, with the mass ratio of the two being 1:0.6;

[0157] Anti-radiation agent: 12, 6-benzylaminopurine copper complex;

[0158] Cross-linking sensitizer: 3.5, triallyl isocyanurate;

[0159] Antifungal agent: 3.0, tributyltin oxide; the base material includes a blend of high-temperature resistant polyester elastomer (TPEE), high-temperature resistant polyamide elastomer (TPAE) and styrene block copolymer (SEBS), and the content of high-temperature resistant polyester elastomer (TPEE) is 55%.

[0160] The specific method for making the above-mentioned sheath material is the same as that in Example 1 and will not be repeated here.

[0161] In order to illustrate the performance of the sheath material of the present invention, the cable sheath materials obtained from the above embodiments and comparative examples were randomly selected for performance test analysis, wherein the following partial performance tests are:

[0162] Mechanical and physical properties test: Mechanical and physical properties are tested according to GB / T 2951 method.

[0163] Electrical performance test: Test electrical performance in accordance with GB / T 3048 method.

[0164] Combustion performance test: Combustion performance test according to GB / T 19666 method

[0165] Thermal life test: Thermal life is tested in accordance with GB / T 11026 method.

[0166] Radiation resistance test: Radiation resistance is tested in accordance with IEC 61244 method.

[0167] Table 1 below shows the material properties test of the corresponding sheath materials obtained in Example 2 and Example 4. The results are shown in Table 1 below:

[0168] Table 1:

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175] Table 2 below shows the material properties test of the sheath material obtained in accordance with Example 6. The results are shown in Table 2 below:

[0176] Table 2:

[0177]

[0178]

[0179]

[0180]

[0181]

[0182] Table 3 below shows the material performance test of the corresponding sheath materials obtained in Comparative Example 1 and Comparative Example 2. The results are shown in Table 3 below:

[0183] Table 3:

[0184]

[0185]

[0186]

[0187]

[0188]

[0189] From the performance test data of Example 6, Comparative Example 1, and Comparative Example 2 corresponding to Tables 1 to 3 above, it can be seen that the addition of zinc acetate-modified maleic anhydride-grafted SEBS to the formulation significantly improved the tensile properties of the material. However, relying solely on either zinc acetate-modified maleic anhydride-grafted SEBS or high-entropy rare earth zirconate nano-modified polyimide-siloxane block copolymer resulted in a material with oil resistance that failed to meet the technical requirements. However, the simultaneous addition of both significantly improved oil resistance, achieving the technical requirements for the nuclear power plant cable sheathing of the present invention. This suggests that the two substances create a synergistic effect within this formulation. This may be due to the fact that both materials contain metal ions. During the blending process, the zinc ions in the zinc acetate and the metal ions in the high-entropy rare earth zirconate form more coordination bonds and sacrificial bonds within the material, increasing bond density and cohesive energy. Furthermore, because the metal ion coordination bonds and sacrificial bonds have strong polarity, they enhance resistance to the non-polar IRM902 oil.

[0190] The specific embodiments described herein are merely illustrative of the spirit of the present invention. Persons skilled in the art may make various modifications, additions, or substitutions to the described embodiments without departing from the spirit of the present invention or exceeding the scope of the appended claims.

[0191] Although the present invention has been described in detail and certain specific embodiments have been cited, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

Claims

1. Irradiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables, characterized by: The sheath material comprises the following components in parts by weight: Base material: 100; Zinc acetate-modified maleic anhydride-grafted SEBS: 80-120; the zinc acetate-modified maleic anhydride-grafted SEBS is obtained by melt-blending maleic anhydride-grafted SEBS, 3-amino-1,2,4-triazole, and zinc acetate as raw materials; the weight ratio of maleic anhydride-grafted SEBS to 3-amino-1,2,4-triazole is 30-35:1; High entropy rare earth zirconate nano-modified polyimide-siloxane block copolymer: 100-140; Halogen-free flame retardant: 80-120; Antioxidant: 5.0~16; Anti-radiation agent: 1.0~15; Cross-linking sensitizer: 1.0~5.0; Antifungal agent: 2.0~5.0; The base material is a blend of high-temperature resistant polyester elastomer, high-temperature resistant polyamide elastomer and styrene block copolymer.

2. The radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables according to claim 1, characterized in that: The halogen-free flame retardant is selected from one or a combination of aluminum hydroxide, aluminum diethylphosphinate and melamine cyanurate.

3. The radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables according to claim 1, characterized in that: The antioxidant is selected from a combination of an asymmetric hindered phenol-type calixarene high molecular weight primary antioxidant and a phosphite high molecular weight auxiliary antioxidant.

4. The radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables according to claim 1, characterized in that: The anti-radiation agent is selected from one or more combinations of ferrocene, 2-amino-5-(p-methoxyphenyl)-1,3,4-thiadiazole lanthanum complex, and 6-benzylaminopurine copper complex.

5. The radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables according to claim 4, characterized in that: The sheath material also includes 2.0 to 5.0 parts by weight of a mildew preventer.

6. The radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables according to claim 5, characterized in that: The mildew preventer is selected from one or a combination of 3-iodo-2-propynyl-N-n-butylcarbamate and tributyltin oxide.

7. The radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables according to claim 6, characterized in that: The cross-linking sensitizer is triallyl isocyanurate.

8. The radiation cross-linked oil-resistant halogen-free flame-retardant sheath material for nuclear power plant cables according to claim 1, characterized in that: The base material contains at least high-temperature resistant polyester elastomer, and the content of the high-temperature resistant polyester elastomer in the base material is 45% to 60%.

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