阅读说明：本技术 一种柔韧耐弯折耐高温低烟低卤阻燃组合物及其制法和应用 (Flexible bending-resistant high-temperature-resistant low-smoke low-halogen flame-retardant composition and preparation method and application thereof ) 是由 王登辉 王志豪 于 2021-11-02 设计创作，主要内容包括：本发明提供了一种柔韧耐弯折耐高温低烟低卤阻燃组合物及其制法和应用。该组合物的原料组成包括：10重量份-15重量份的乙烯醋酸乙烯共聚物,10重量份-15重量份的增韧剂,15重量份-20重量份的超韧性弹性体,20重量份-25重量份的氢氧化镁,15重量份-20重量份的溴系阻燃剂,5重量份-8重量份的三氧化二锑,4重量份-6重量份的硅烷偶联剂表面处理煅烧陶土,0.7重量份-1.5重量份的偶联助剂,3重量份-5重量份的抗氧剂,2重量份-3重量份的交联剂和2重量份-4重量份的润滑剂。本发明还提供了上述组合物的制备方法。由上述组合物制得的低烟低卤阻燃聚烯烃电线电缆。(The invention provides a flexible bending-resistant high-temperature-resistant low-smoke low-halogen flame-retardant composition, and a preparation method and application thereof. The composition comprises the following raw materials: 10-15 parts of ethylene vinyl acetate copolymer, 10-15 parts of toughening agent, 15-20 parts of super-tough elastomer, 20-25 parts of magnesium hydroxide, 15-20 parts of brominated flame retardant, 5-8 parts of antimony trioxide, 4-6 parts of silane coupling agent surface treatment calcined argil, 0.7-1.5 parts of coupling additive, 3-5 parts of antioxidant, 2-3 parts of crosslinking agent and 2-4 parts of lubricant. The invention also provides a preparation method of the composition. The low-smoke low-halogen flame-retardant polyolefin wire and cable prepared from the composition.)

1. A flexible bending-resistant high-temperature-resistant low-smoke low-halogen flame-retardant composition comprises the following raw materials: 10-15 parts of ethylene vinyl acetate copolymer, 10-15 parts of toughening agent, 15-20 parts of super-tough elastomer, 20-25 parts of magnesium hydroxide, 15-20 parts of brominated flame retardant, 5-8 parts of antimony trioxide, 4-6 parts of silane coupling agent surface treatment calcined argil, 0.7-1.5 parts of coupling additive, 3-5 parts of antioxidant, 2-3 parts of crosslinking agent and 2-4 parts of lubricant.

2. The flexible, bend-resistant, high temperature resistant, low smoke, low halogen flame retardant composition of claim 1, wherein the composition comprises the following raw materials: 10-13 parts of ethylene vinyl acetate copolymer, 13-15 parts of toughening agent, 15-18 parts of super-tough elastomer, 20-23 parts of magnesium hydroxide, 15-20 parts of brominated flame retardant, 5-8 parts of antimony trioxide, 4-6 parts of silane coupling agent surface treatment calcined argil, 0.7-1.5 parts of coupling additive, 3-5 parts of antioxidant, 2-3 parts of crosslinking agent and 2-4 parts of lubricant.

3. The flexible, bend-resistant, high temperature resistant, low smoke, low halogen flame retardant composition of claim 1, wherein the ethylene vinyl acetate copolymer has a VA content of 26-28%.

4. The flexible, bend-resistant, high temperature resistant, low smoke, low halogen flame retardant composition of claim 1, wherein the toughening agent is a graft of POE and EPDM.

5. The flexible, bend-resistant, high temperature resistant, low smoke, low halogen flame retardant composition of claim 1, wherein the super tough elastomer is a DF series elastomer;

preferably, the brominated flame retardant is decabromodiphenylethane.

6. The flexible, bend-resistant, high temperature resistant, low smoke, low halogen flame retardant composition of claim 1, wherein the magnesium hydroxide is chemically surface treated magnesium hydroxide, such as S-7 of the jushenjima;

preferably, the coupling assistant is a silane coupling agent FD 570.

7. The flexible, bend-resistant, high temperature resistant, low smoke, low halogen flame retardant composition of claim 1, wherein the antioxidant is a coupling agent treated mixed antioxidant;

preferably, the antioxidant is bisphenol and ammonia antioxidants treated by silane coupling agent and titanate mixture.

8. The flexible, bend-resistant, high temperature resistant, low smoke, low halogen flame retardant composition of claim 1, wherein the cross-linking agent is TAIC or TMATMB;

preferably, the lubricant is silicone and wax.

9. A method of making a flexible, bend-resistant, high temperature resistant, low smoke, low halogen flame retardant composition according to any of claims 1 to 8, comprising the steps of:

mixing materials by a high-order mixing roll, heating and banburying by a banbury mixer, feeding by a double-step cone, shearing and discharging by a double screw, extruding by a single screw, granulating by a granulator, collecting by a fan and a storage bin, cooling materials by a vibrating screen, collecting and subpackaging by a large storage bin, and plastically packaging materials by a vacuum machine to obtain the flexible bending-resistant high-temperature-resistant low-smoke low-halogen flame-retardant composition.

10. An irradiation crosslinking type low-smoke low-halogen flame-retardant polyolefin wire and cable, which is prepared from the flexible bending-resistant high-temperature-resistant low-smoke low-halogen flame-retardant composition according to any one of claims 1 to 8.

Technical Field

The invention relates to a flame-retardant composition, in particular to a flexible bending-resistant high-temperature-resistant low-smoke low-halogen flame-retardant composition, belonging to the technical field of high polymer materials.

Background

With the high-speed development of domestic electric vehicles, related corollary equipment also has developed at a high speed, and high-voltage cables in the electric vehicles also get high attention. The high-voltage cable material in the vehicle mainly considers the following aspects:

1. voltage: the basic difference with conventional automotive cables is that the structure needs to be designed for a nominal voltage of 600V, which can be as high as 1000V if used on commercial vehicles and buses. The cables used in the motor vehicles currently driven by internal combustion engines are designed for a nominal voltage of 60V. The system can reduce the power loss in the transmission system (PLOSS I2 × R) due to the use of lower current, with the generated power (P × I) unchanged.

2. Current: since the cable connects the battery, the inverter and the motor, the high voltage cable needs to transmit a high current. The current may reach 250A to 450A depending on the power requirements of the system components. Such high currents are difficult to find on conventionally driven vehicles.

3. Temperature: the result of the high current transmission is high power consumption and heating of the components. High voltage cables are therefore designed to withstand higher temperatures. It can now be seen that there is a trend towards further increases in the temperature requirements. In contrast, current vehicles typically use a nominal temperature of the cable up to 105 ℃ sufficient as long as the cable is not used in the engine compartment or other areas that are resistant to higher temperatures. The high voltage cable of the electric automobile is usually higher than the temperature, such as 125 ℃ or 150 ℃. If the route passed by the electric automobile is unfavorable, the host factory even puts higher high-temperature resistance requirements. Such as near the exhaust duct, in front of the motor, behind the battery, etc.

4. The service life is as follows: the automotive industry typically designs cables to have a service life of 3000 hours at a specified temperature rating. This value is commonly used for long term aging tests in recognized cable standards (e.g., ISO 6722, ISO 14572). The specific requirements of customers in high-voltage applications may exceed 3000 hours, and the cumulative operating time at the specified temperature may even reach 12000 hours.

5. Flexibility: the challenge in many situations faced by the development of hybrid vehicles is that the existing family of platforms were originally designed to incorporate more electrical components than the space that would house the gasoline engine and its components. Even if the wiring is not taken into consideration, the limitation of the space can be expected. Furthermore, the routing of cables and connectors also requires space. A common consequence is a bend radius that leads to strain. High bending forces are difficult to overcome due to the inherent design of conventional cables. To solve this problem, high flexibility of the high voltage cable is of paramount importance. Routing through the vehicle is only easily possible with a relatively flexible design.

6. Bending resistance: if the motor is located close to the moving part of the vehicle and then causes continuous vibration of the connected high-voltage cable, it is required to be designed to withstand high cyclic bending to ensure good bending resistance.

7. Flame retardance: because the use of the electric automobile is concerned with the life and property safety of people, the good flame-retardant effect of the wires in the automobile can greatly reduce large-area combustion caused by overload or short circuit, and reduce personal and property loss.

In summary, the existing high-voltage cable material in the electric automobile has the following problems:

(1) the rated voltage of a conventional automobile cable is generally below 600V, and the voltage-withstanding requirement of a high-voltage cable in an electric automobile cannot be met; (2) the soft bending-resistant wire and cable material is generally low in temperature resistance; (3) the service life of the conventional automobile cable cannot reach the service life condition of the cable in the electric automobile; (4) the general flame-retardant requirement of the cable in the electric automobile is not high.

Disclosure of Invention

In order to solve the technical problems, the invention aims to provide a cable material with higher temperature resistance level, high-temperature resistance thermal stability and excellent flame retardant property.

In order to achieve the technical purpose, the invention firstly provides a flexible bending-resistant high-temperature-resistant low-smoke low-halogen flame-retardant composition, which comprises the following raw materials: 10-15 parts of ethylene vinyl acetate copolymer, 10-15 parts of toughening agent, 15-20 parts of super-tough elastomer, 20-25 parts of magnesium hydroxide, 15-20 parts of brominated flame retardant, 5-8 parts of antimony trioxide, 4-6 parts of silane coupling agent surface treatment calcined argil, 0.7-1.5 parts of coupling additive, 3-5 parts of antioxidant, 2-3 parts of crosslinking agent and 2-4 parts of lubricant.

In one embodiment of the present invention, the flexible, bending-resistant, high-temperature-resistant, low-smoke, low-halogen flame-retardant composition comprises the following raw materials: 10-13 parts of ethylene vinyl acetate copolymer, 13-15 parts of toughening agent, 15-18 parts of super-tough elastomer, 20-23 parts of magnesium hydroxide, 15-20 parts of brominated flame retardant, 5-8 parts of antimony trioxide, 4-6 parts of silane coupling agent surface treatment calcined argil (the argil after calcination is added with the silane coupling agent and mixed in a high-speed mixer), 0.7-1.5 parts of coupling aid, 3-5 parts of antioxidant, 2-3 parts of crosslinking agent and 2-4 parts of lubricant.

According to the tough bending-resistant high-temperature-resistant low-smoke low-halogen flame-retardant composition, the pressure-resistant grade of a cable material is increased through calcined clay subjected to surface treatment by a coupling agent; the mixed antioxidant treated by the coupling agent improves the long-term aging time of the material and prolongs the service life of the material in the cable; the addition of the brominated flame retardant greatly improves the flame retardant effect of the material, and the flame retardant grade is VW-1; the processing characteristic of irradiation crosslinking increases the temperature resistance grade and the use stability of the material.

In one embodiment of the present invention, the VA content of the ethylene vinyl acetate copolymer used is 26 to 28%.

In a specific embodiment of the invention, the toughening agent used is a graft of POE and EPDM.

In one embodiment of the present invention, the super tough elastomer used is a DF series elastomer.

In one embodiment of the present invention, the brominated flame retardant used is decabromodiphenylethane.

In one embodiment of the present invention, the magnesium hydroxide used is chemically surface treated magnesium hydroxide. Such as S-7 of the japanese god island.

In one embodiment of the present invention, the coupling assistant used is silane coupling agent FD 570.

In one embodiment of the present invention, the antioxidant used is a special coupling agent treatment mixed antioxidant.

In one embodiment of the invention, the antioxidants employed are bisphenol and ammonia antioxidants treated with a mixture of silane coupling agent and titanate.

In one embodiment of the invention, the crosslinker used is TAIC or TMATMB.

In one embodiment of the invention, the lubricants used are silicones and waxes.

The invention also provides a preparation method of the flexible bending-resistant high-temperature-resistant low-smoke low-halogen flame-retardant composition, which comprises the following steps:

mixing materials by a high-order mixing roll, heating and banburying by a banbury mixer, feeding by a double-step cone, shearing and discharging by a double screw, extruding by a single screw, granulating by a granulator, collecting by a fan and a storage bin, cooling materials by a vibrating screen, collecting and subpackaging by a large storage bin, and plastically packaging materials by a vacuum machine to obtain the flexible bending-resistant high-temperature-resistant low-smoke low-halogen flame-retardant composition.

The invention also provides an irradiation crosslinking type low-smoke low-halogen flame-retardant polyolefin wire and cable which are prepared from the flexible bending-resistant high-temperature-resistant low-smoke low-halogen flame-retardant composition. Including but not limited to, the low-smoke low-halogen flame-retardant polyolefin wire cable can be used as a radiation crosslinked cable for a high-voltage wire in an electric automobile. The irradiation crosslinking type low-smoke low-halogen flame-retardant polyolefin wire and cable disclosed by the invention has the advantages that through irradiation crosslinking, the thermal stability of resin in the material is improved, and further, the ageing resistance and the service life of the material are improved.

The flexible bending-resistant high-temperature-resistant low-smoke low-halogen flame-retardant composition is prepared by adding a pressure-resistant material with surface-treated argil, an efficient flame retardant and a mixed antioxidant treated by a coupling agent into a specific elastomer, and increasing the use conditions of the material under the action of irradiation crosslinking, so that the prepared cable has the advantages that:

(1) on the premise of not changing the flexibility of the cable, the voltage-resistant grade of the cable material is improved;

(2) under the condition of not changing the basic performance of the material, the long-term aging time of the cable material is prolonged, and the service life of the cable material is prolonged;

(3) on the premise of not changing the basic performance of the material, the flame retardant grade of the material is improved.

The flexible bending-resistant high-temperature-resistant low-smoke low-halogen flame-retardant composition increases the fluidity in the wire and cable processing and also improves the mechanical strength of the wire and cable electric material to a certain extent through the ethylene-vinyl acetate copolymer and the lubricant; the tensile property of the wire and cable material and the flexibility and corrosion resistance of the material are greatly improved through the super-toughness elastomer; the addition of the toughening agent improves the mechanical and physical properties of the material on one hand and promotes the compatibility of the resin material on the other hand; the magnesium hydroxide and the brominated flame retardant are subjected to surface treatment by a chemical method, so that the flame retardant effect of the material is greatly improved; the pressure-resistant grade of the material is improved by the calcined argil subjected to surface treatment by the silane coupling agent; the dispersion of the powder material in the resin is promoted by adding the coupling agent; a mixed antioxidant treated by a special coupling agent; the heat aging, the service life and the long-term aging time of the material can be improved; by adding the cross-linking agent, various performances of the material can be further improved after irradiation, and the temperature resistance grade of the material can be increased.

The irradiation crosslinking type low-smoke low-halogen flame-retardant polyolefin wire and cable prepared from the flexible bending-resistant high-temperature-resistant low-smoke low-halogen flame-retardant composition improves the temperature-resistant grade of the cable material and enhances the pressure-resistant requirement of the cable material; the stability of the use of the cable material is improved, and the service life of the cable material is prolonged; the flame retardant grade of the material is increased, the wire can meet the flame retardant requirement of VW-1, and the flame retardant effect of the material is improved. It has strong tensile strength: not less than 9 MPa; elongation at break: more than or equal to 300 percent; oxygen index: more than or equal to 30 percent; the specific gravity of the material is as follows: 1.35 plus or minus 0.03; aging conditions are as follows: short-term aging: 150 ℃ 240h or 175 ℃ 240h (mainly depending on the temperature resistant grade of the material), and the performance retention rate is more than or equal to 75 percent. And (3) long-term aging: 150 ℃ 6000h or 125 ℃ 6000h (mainly depending on the temperature resistance grade of the material), no cracking due to normal-temperature winding, and no breakdown due to pressure resistance; pressure resistance: withstand voltage is 1000 after cabling; flame retardant rating: VW-1.

Detailed Description

Examples

Examples and comparative examples are shown in table 1.

TABLE 1

Wherein, the VA content of the ethylene-vinyl acetate copolymer is 26%. The calcined argil is obtained by adding the calcined argil into the silane coupling agent and mixing in a high-speed mixer. The toughening agent is a grafting material of POE and EPDM. The super-tough elastomer is a DF series elastomer. The brominated flame retardant is decabromodiphenylethane. Magnesium hydroxide surface treated chemically. Such as S-7 of the japanese god island. The coupling assistant is silane coupling agent FD 570. The antioxidant is bisphenol and ammonia antioxidant treated with silane coupling agent and titanate mixture. The crosslinking agent is TAIC or TMATMB. The lubricant is silicone and wax.

The preparation method of the flexible bending-resistant high-temperature-resistant low-smoke low-halogen flame-retardant composition comprises the following steps:

mixing materials by a high-order mixing roll, heating and banburying by a banbury mixer, feeding by a double-step cone, shearing and discharging by double screws, extruding by single-screw mixing, granulating by a granulator, collecting by a fan and a storage bin, cooling materials by a vibrating screen, collecting and subpackaging by a large storage bin, and plastically packaging materials by a vacuum machine.

The above examples and comparative examples were tested and the results are shown in table 2.

TABLE 2

The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.