阅读说明：本技术 一种无卤阻燃材料及其制备方法与应用 (Halogen-free flame-retardant material and preparation method and application thereof ) 是由 董启殿 李广富 吕伟 张翼翔 刘鹏辉 于 2021-09-14 设计创作，主要内容包括：本发明公开了一种无卤阻燃材料及其制备方法与应用。无卤阻燃材料由以下质量百分比的原料组成：乙烯/丁二烯/苯乙烯共聚物20％～60％、乙烯/辛烯嵌段共聚物10％～40％、聚苯醚10％～40％、相容剂1％～5％、无卤阻燃剂10％～50％、加工助剂1％～5％。本发明的无卤阻燃材料综合性能优异,具有低硬度、拉伸性能好、耐温性能好的特性,并可满足安全标准UL1581和UL94的阻燃要求；材料中阻燃剂分散均匀,无颗粒、杂质等不良表观现象；适合用绝缘芯线外被材料,押出的绝缘芯线表面光滑无颗粒。(The invention discloses a halogen-free flame-retardant material, and a preparation method and application thereof. The halogen-free flame-retardant material comprises the following raw materials in percentage by mass: 20-60% of ethylene/butadiene/styrene copolymer, 10-40% of ethylene/octene block copolymer, 10-40% of polyphenyl ether, 1-5% of compatilizer, 10-50% of halogen-free flame retardant and 1-5% of processing aid. The halogen-free flame retardant material has excellent comprehensive performance, has the characteristics of low hardness, good tensile property and good temperature resistance, and can meet the flame retardant requirements of safety standards UL1581 and UL 94; the flame retardant in the material is uniformly dispersed, and has no bad appearance phenomena such as particles, impurities and the like; the coating material is suitable for the coating material of the insulated core wire, and the surface of the extruded insulated core wire is smooth and has no particles.)

1. The halogen-free flame retardant material is characterized by comprising the following raw materials in percentage by mass: 20-60% of ethylene/butadiene/styrene copolymer, 10-40% of ethylene/octene block copolymer, 10-40% of polyphenyl ether, 1-5% of compatilizer, 10-50% of halogen-free flame retardant and 1-5% of processing aid.

2. The halogen-free flame retardant material according to claim 1, which is characterized by comprising the following raw materials in percentage by mass: 20-40% of ethylene/butadiene/styrene copolymer, 10-30% of ethylene/octene block copolymer, 10-20% of polyphenyl ether, 2-3% of compatilizer, 20-40% of halogen-free flame retardant and 2-3% of processing aid.

3. Halogen free flame retardant material according to claim 1 or 2,

the ethylene/butadiene/styrene copolymer is at least one of SOE elastomer series products of Asahi Kasei corporation;

the compatilizer is at least one of maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene and maleic anhydride grafted SEBS;

the halogen-free flame retardant is at least one of aluminum diethylphosphinate, aluminum hypophosphite, melamine cyanurate, melamine pyrophosphate, melamine polyphosphate, magnesium hydroxide, zinc oxide, zinc borate and piperazine pyrophosphate;

the processing aid is at least one of a lubricant, an antioxidant and a copper resisting agent.

4. Halogen-free flame retardant material according to claim 3,

the ethylene/butadiene/styrene copolymer is an SOE elastomer with the brand number S1605 of Asahi Kasei corporation in Japan;

the grafting rate of the compatilizer is 0.5-1.5%;

the halogen-free flame retardant is at least two of diethyl aluminum hypophosphite, melamine cyanurate and magnesium hydroxide;

the processing aids comprise a lubricant, an antioxidant and a copper resisting agent.

5. Halogen free flame retardant material according to claim 3 or 4,

the lubricant is at least one of polydimethylsiloxane, erucamide, ethylene bis-stearamide, pentaerythritol stearate and polyethylene wax;

the antioxidant is at least one of hindered phenol antioxidant and phosphite antioxidant;

the copper resisting agent is bis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionyl) hydrazine.

6. The halogen-free flame retardant material of claim 5, wherein the antioxidant is a mixture of hindered phenol antioxidant and phosphite antioxidant.

7. The halogen-free flame retardant material of claim 6, wherein the antioxidant is antioxidant B215.

8. Halogen free flame retardant material according to claim 1 or 2,

the melt index of the ethylene/octene block copolymer is 2.16kg, and the melt index is 1-10g/10min at 190 ℃;

the polyphenylene ether has an intrinsic viscosity of 30-50cm³/g。

9. The process for the preparation of halogen-free flame retardant material according to any of claims 1 to 8, characterized in that it comprises the following steps: mixing the raw materials, and pelletizing to obtain the halogen-free flame retardant material;

the grain extraction adopts a double-screw extruder, and the length-diameter ratio of the grain extraction is 48-60: 1, setting the working temperature to be 180-230 ℃.

10. Use of the halogen-free flame retardant material according to any of claims 1 to 8 for the preparation of an insulated core wire.

Technical Field

The invention relates to the technical field of insulating core wires, in particular to a halogen-free flame retardant material and a preparation method and application thereof.

Background

The halogen-free insulating core wire on the market mainly uses materials without flame retardant properties such as polyethylene, polypropylene, polyether ester and the like, and the flame retardant property of a wire rod product is mainly provided by a sheath material. When the insulating core wire in the wire rod is made of a material without flame resistance, the phenomena of overlarge flame, overlong flame delay time, burning distance exceeding the standard and the like are probably caused when the wire rod burns, so that the wire rod cannot meet the corresponding flame-retardant standard.

The insulating core wire has small outer coating thickness and high requirement on material plasticizing uniformity, and the flame retardant is difficult to disperse and generate particles on the surface of the insulating core wire to cause poor insulating property of the core wire when the flame retardant is simply added into materials such as polyethylene, polypropylene, polyether ester and the like for modification. Meanwhile, the insulating core wire material needs low hardness and tensile property, and the flame retardant modification of polyethylene, polypropylene and polyether ester materials can not be met. Therefore, there is a need to develop a halogen-free flame retardant material which has excellent dispersion of flame retardant and can be applied to an insulated core wire.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a halogen-free flame retardant material.

The invention also aims to provide a preparation method of the halogen-free flame retardant material.

The invention also aims to provide application of the halogen-free flame retardant material.

The purpose of the invention is realized by the following technical scheme: a halogen-free flame retardant material is composed of the following raw materials in percentage by mass: 20-60% of ethylene/butadiene/styrene copolymer, 10-40% of ethylene/octene block copolymer, 10-40% of polyphenyl ether, 1-5% of compatilizer, 10-50% of halogen-free flame retardant and 1-5% of processing aid.

Preferably, the halogen-free flame retardant material is composed of the following raw materials in percentage by mass: 20-40% of ethylene/butadiene/styrene copolymer, 10-30% of ethylene/octene block copolymer, 10-20% of polyphenyl ether, 2-3% of compatilizer, 20-40% of halogen-free flame retardant and 2-3% of processing aid.

Preferably, the ethylene/butadiene/styrene copolymer is at least one of SOE elastomer series products of asahi company; more preferably, the SOE elastomer is available from the company under the trade name S1605.

Preferably, the ethylene/octene block copolymer (OBC elastomer) has a melt index of 2.16kg and a melt index of 1-10g/10min at 190 ℃.

Preferably, the polyphenylene ether (poly-2, 6-dimethyl-1, 4-phenylene ether, PPE) has an intrinsic viscosity of 30-50cm³/g。

Preferably, the compatilizer is at least one of maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene and maleic anhydride grafted SEBS (hydrogenated styrene-butadiene block copolymer), and the grafting rate is 0.5-1.5%.

Preferably, the halogen-free flame retardant is at least one of aluminum diethylphosphinate, aluminum hypophosphite, melamine cyanurate, melamine pyrophosphate, melamine polyphosphate, magnesium hydroxide, zinc oxide, zinc borate and piperazine pyrophosphate; more preferably, the halogen-free flame retardant is at least two of diethyl aluminum hypophosphite, melamine cyanurate and magnesium hydroxide.

Preferably, the processing aid is at least one of a lubricant, an antioxidant and a copper resisting agent; more preferably, the processing aid is a lubricant, an antioxidant or a copper inhibitor.

Preferably, the lubricant is at least one of polydimethylsiloxane, erucamide, ethylene bis stearamide, pentaerythritol stearate and polyethylene wax.

Preferably, the antioxidant is at least one of hindered phenol antioxidant and phosphite antioxidant; more preferably, the antioxidant is a compound formed by mixing a hindered phenol antioxidant and a phosphite ester antioxidant; most preferably, the antioxidant is antioxidant B215.

Preferably, the copper inhibitor is bis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionyl) hydrazine.

The preparation method of the halogen-free flame retardant material comprises the following steps: mixing the raw materials, and pelletizing to obtain the halogen-free flame retardant material.

Preferably, the mixing is stirring for 5-10 min.

Preferably, the grain extraction adopts a double-screw extruder, and the length-diameter ratio of the grain extraction is 48-60: 1, setting the working temperature to be 180-230 ℃; more preferably, the working temperatures set in the zones 1 to 14 are 180 ℃, 210 ℃, 230 ℃, 225 ℃, 220 ℃ and 215 ℃, respectively.

The halogen-free flame retardant material is applied to the preparation of an insulating core wire.

In the invention, the ethylene/butadiene/styrene copolymer and the ethylene/octene block copolymer have the characteristics of low hardness, high tensile property, good heat resistance and the like, and the obtained halogen-free flame retardant material has low hardness and tensile property and can be mixed with polyphenyl ether for processing under the condition of higher processing temperature.

In the invention, the polyphenylene ether resin can form a compact carbon layer during combustion, thereby isolating oxygen and effectively preventing the phenomenon of melt dripping. Meanwhile, the polyphenyl ether resin can generate strong friction force when being prepared in a double-screw extruder, and the dispersion of the flame retardant is promoted.

In the invention, the compatilizer can effectively promote the dispersion of the flame retardant in the two copolymers, and can improve the mechanical property of the product.

In the invention, the lubricant plays a role in promoting the dispersion of the components in the double-screw extruder, reduces the friction with machine equipment and can improve the surface hand feeling of products.

In the invention, the antioxidant can prevent the components of the formula from being decomposed during processing in a double-screw extruder, thereby prolonging the service life of the product.

Compared with the prior art, the invention has the following beneficial effects:

the halogen-free flame retardant material has excellent comprehensive performance, has the characteristics of low hardness, good tensile property and good temperature resistance, can meet the flame retardant requirements of safety standards UL1581 and UL94, and has the advantages of uniform dispersion of flame retardant in the material, no adverse appearance phenomena such as particles and impurities; the coating material is suitable for the coating material of the insulated core wire, and the surface of the extruded insulated core wire is smooth and has no particles.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The following raw material information of examples 1 to 3 and comparative examples 1 to 6 is shown in Table 1.

TABLE 1 raw material information of examples 1-3 and comparative examples 1-6

Example 1

Weighing raw materials of the halogen-free flame retardant material according to the table 2, wherein the SOE elastomer is S1605, the OBC elastomer is 9010, the polyphenyl ether is LXR040C, the compatilizer is KT-25, the halogen-free flame retardant is melamine cyanurate MCA-15 and diethyl aluminum phosphinate OP935, the lubricant is PA445200, the antioxidant is B215, and the copper resistant agent is 1024.

Example 2

Example 2 differs from example 1 in the amount of starting materials: the mass percent of the SOE elastomer is 20 percent, and the mass percent of the OBC elastomer is 30 percent. The mass percentages of the raw materials are shown in table 2. The material obtained in this example is a low hardness product.

Example 3

Example 3 differs from example 1 in the amount of starting materials: the mass percent of the SOE elastomer is 40 percent, and the mass percent of the OBC elastomer is 10 percent. The mass percentage of the OBC elastomer is 10 percent. The mass percentages of the raw materials are shown in table 2. The material obtained in this example is a slightly harder product.

Comparative example 1

Comparative example 1 differs from example 1 in that no SOE elastomer, OBC elastomer, polyphenylene ether, 65% by mass of polypropylene K8025 was added. The polypropylene material with flame retardant added is compared with the material in the example 1. The mass percentages of the raw materials are shown in table 2.

Comparative example 2

Comparative example 2 differs from example 1 in that no SOE elastomer, no OBC elastomer, no polyphenylene ether, 65% by mass of polyethylene 7042 was added. The effect of the polyethylene material added with the flame retardant is compared with that of the material in the example 1. The mass percentages of the raw materials are shown in table 2.

Comparative example 3

Comparative example 3 differs from example 1 in that no SOE elastomer, OBC elastomer, polyphenylene ether, 65% by mass of polyether ester G140D were added. The material with polyether ester added with flame retardant is compared with the material in the example 1. The mass percentages of the raw materials are shown in table 2.

Comparative example 4

Comparative example 4 differs from example 1 in that the SOE elastomer is 50% by mass and no OBC elastomer is added. The performance effect of using only the SOE elastomer can be compared. The mass percentages of the raw materials are shown in table 2.

Comparative example 5

Comparative example 5 differs from example 1 in that the OBC elastomer was 50% and no SOE elastomer was added. The effect of the material using only OBC elastomer was compared with example 1. The mass percentages of the raw materials are shown in table 2.

Comparative example 6

Comparative example 6 differs from example 1 in that 20% of POE elastomer was added and no OBC elastomer was added. The properties of the material obtained with the OBC elastomer and the POE elastomer are compared with those of example 1. The mass percentages of the raw materials are shown in table 2.

TABLE 2 feed compositions for examples 1-3 and comparative examples 1-6

The preparation methods of examples 1 to 3 and comparative examples 4 to 6 were as follows:

1) weighing raw materials according to the formula components;

2) stirring and mixing all the components for 8min to obtain a mixed material;

3) and adding the mixed materials into a double-screw extruder for grain extraction to obtain the halogen-free flame retardant material.

During grain extraction, the length-diameter ratio of the double-screw extruder is 56:1, and the working temperatures of 1-14 regions are respectively 180 ℃, 210 ℃, 230 ℃, 230 ℃, 230 ℃, 230 ℃, 230 ℃, 230 ℃, 225 ℃, 220 ℃, 220 ℃, 220 ℃ and 215 ℃.

Comparative examples 1 to 3 were prepared as follows:

1) weighing raw materials according to the formula components;

2) mixing all the raw materials for 8min to obtain a mixture;

3) and pouring the mixture into a double-screw extruder for extrusion and grain extraction to obtain the material.

The length to diameter ratio of the twin screw extruder was 56: 1. The set temperature of each temperature zone of the double-screw extruder is as follows: 160 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃, 195 ℃, 195 ℃, 195 ℃, 190 ℃.

The results of the performance tests of the halogen-free flame retardant materials prepared in examples 1 to 3 and comparative examples 1 to 6 are shown in Table 3.

TABLE 3 results of Performance test of examples 1 to 3 and comparative examples 1 to 6

The detection results in table 3 show that the halogen-free flame retardant materials of embodiments 1-3 of the present invention have good flame retardant dispersibility, good mechanical properties, good aging properties, a hardness of 75-90A, and a significant flame retardant effect, and satisfy the flame retardant requirements of UL94 and UL 1581. And the halogen-free flame-retardant material is used for extruding the insulated core wire for the data wire, and the surface is smooth and has no particles.

Comparative examples 1 to 3 use polypropylene, polyethylene, polyether ester materials for flame retardant modification, when the same amount of flame retardant was added, the tensile, aging, flame retardant properties were poor, and the hardness was within the range of Shore D. After the flame retardant is added, the flame retardant cannot be uniformly dispersed, so that white dots are distributed on the surface of the material, the surface of the extruded insulating core wire is rough, particle impurities exist, and the wire cannot be normally used.

In comparative example 4, using only the SOE elastomer, the material was hard and low in elongation at break, and slight unevenness occurred upon dispersion. In comparative example 5, the OBC elastomer alone was used, but the material hardness was low, but the tensile strength was low, and the aging property and flame retardant property were poor. In comparative example 6, using POE elastomer instead of OBC elastomer, tensile strength was reduced and aging and flame retardant properties were severely degraded. Therefore, the SOE elastomer, the OBC elastomer and other components in the halogen-free flame retardant material are matched for use, and the obtained material can meet the performance requirement.

While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.