阅读说明：本技术 可瓷化辐照交联低烟无卤阻燃聚烯烃组合物及其制备方法 (Ceramizable irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin composition and preparation method thereof ) 是由 曾昌作 马义生 朱升华 马健鑫 马晓燕 盛大庆 陶恒娟 仝秀秀 赵锦明 陶玲 于 2021-10-12 设计创作，主要内容包括：本发明公开了可瓷化辐照交联低烟无卤阻燃聚烯烃组合物及其制备方法,属于高分子材料制备领域。本发明的材料原料包括聚烯烃类树脂,相容剂,瓷化粉,助熔剂,阻燃剂,润滑剂,抗氧剂,偶联剂,交联敏化剂。将上述原料按照特定的顺序混料并挤出造粒,在制作成最终产品时使用辐照交联技术。本发明的材料除了具有一般陶瓷化聚烯烃组合物的耐火性质外,还具有非常好的阻燃性及耐温性,燃烧时产烟量低、无毒无腐蚀,使用辐照交联技术,进一步提升了其使用温度,拓展了陶瓷化聚烯烃组合物的使用范围。(The invention discloses a low-smoke halogen-free flame-retardant polyolefin composition capable of being subjected to ceramization irradiation crosslinking and a preparation method thereof, belonging to the field of preparation of high polymer materials. The raw materials of the material comprise polyolefin resin, compatilizer, vitrified powder, fluxing agent, flame retardant, lubricant, antioxidant, coupling agent and crosslinking sensitizer. The raw materials are mixed according to a specific sequence and extruded for granulation, and the irradiation crosslinking technology is used when the final product is prepared. The material of the invention has good flame resistance and temperature resistance besides the fire resistance of the common ceramic polyolefin composition, has low smoke yield during combustion, is non-toxic and non-corrosive, uses the irradiation crosslinking technology, further improves the use temperature of the ceramic polyolefin composition, and expands the use range of the ceramic polyolefin composition.)

1. A ceramizable irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin composition is characterized by comprising the following raw materials in parts by weight: 60-100 parts of polyolefin resin, 2-30 parts of a compatilizer, 80-200 parts of vitrified powder, 30-120 parts of a fluxing agent, 20-100 parts of a flame retardant, 1-10 parts of a lubricant, 1-4 parts of an antioxidant and a coupling agent: 1-6 parts of cross-linking sensitizer and 1-5 parts of cross-linking sensitizer.

2. The ceramifiable irradiation-crosslinked low-smoke halogen-free flame-retardant polyolefin composition according to claim 1, wherein the polyolefin resin is: one or more of polyethylene, ethylene-vinyl acetate copolymer, ethylene ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-propylene rubber, ethylene-butene copolymer, ethylene-hexene copolymer and ethylene-octene copolymer.

3. The ceramifiable irradiation-crosslinked low-smoke halogen-free flame-retardant polyolefin composition according to claim 1, wherein the compatibilizer is: one or more of maleic anhydride grafted polyethylene, maleic anhydride grafted ethylene vinyl acetate, maleic anhydride grafted ethylene octene copolymer, maleic anhydride grafted ethylene propylene rubber and ethylene-acrylate-maleic anhydride terpolymer.

4. The ceramifiable irradiation-crosslinked low-smoke halogen-free flame-retardant polyolefin composition according to claim 1, wherein the ceramifiable powder is: one or more of kaolin, wollastonite, montmorillonite, mica powder, white carbon black, antimony trioxide, calcium carbonate and talcum powder.

5. The ceramifiable irradiation-crosslinked low-smoke halogen-free flame-retardant polyolefin composition according to claim 1, wherein the fluxing agent is: one or more of lead-free low-softening-point glass powder, zinc borate, boron trioxide, molybdenum oxide, zinc oxide, magnesium oxide and calcium oxide; the lead-free low-softening-point glass powder comprises the following components: one or more of low-softening-point silicate glass powder, low-softening-point borate glass powder, low-softening-point phosphate glass powder and low-softening-point bismuthate glass powder, wherein the softening point range is 300-700 ℃.

6. The ceramifiable irradiation-crosslinked low-smoke halogen-free flame-retardant polyolefin composition according to claim 1, wherein the flame retardant is: one or more of aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate, triphenyl phosphate, melamine polyphosphate, organic aluminum hypophosphite, inorganic aluminum hypophosphite and red phosphorus; the lubricant is: one or more of zinc stearate, calcium stearate, magnesium stearate, polyethylene wax, ethylene bis stearamide, silicone oil and silicone.

7. The ceramifiable irradiation-crosslinked low-smoke halogen-free flame-retardant polyolefin composition according to claim 1, wherein the antioxidant is: one or more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris [2, 4-di-tert-butylphenyl ] phosphite, dioctadecyl thiodipropionate, dilauryl thiodipropionate, 4 '-bis (alpha, alpha-dimethylbenzyl) diphenylamine and 4, 4' -thiobis (6-tert-butyl-3-methylphenol).

8. The ceramifiable irradiation-crosslinked low-smoke halogen-free flame-retardant polyolefin composition according to claim 1, wherein the coupling agent is: one or more of silane coupling agent, titanate coupling agent, aluminate coupling agent and stearic acid.

9. The ceramifiable irradiation-crosslinked low-smoke halogen-free flame-retardant polyolefin composition according to claim 1, wherein the crosslinking sensitizer is: one or more of triallyl isocyanurate, trimethylolpropane trimethacrylate and 1, 2-polybutadiene.

10. The preparation method of the ceramifiable irradiation crosslinking low-smoke halogen-free flame retardant polyolefin composition according to any one of claims 1 to 9, characterized by comprising the following steps:

(1) pouring polyolefin resin into an internal mixer according to the formula composition, starting the internal mixer under the condition of no pressurization, pouring a coupling agent and a crosslinking sensitizer into the internal mixer to mix with the polyolefin resin for 10-15 seconds, stopping the internal mixer, pouring the rest components according to the formula composition, starting the internal mixer, putting a pressing hammer down to perform pressurization and internal mixing until the temperature is 100-105 ℃, lifting the pressing hammer up, putting the pressing hammer down after the materials in the internal mixer are turned over, lifting the pressing hammer up again when the materials in the internal mixer are subjected to pressurization and internal mixing until the temperature is 120-125 ℃, putting the pressing hammer down after the materials in the internal mixer are turned over, discharging and feeding the materials into a conical feeder when the materials are subjected to internal mixing and internal mixing until the temperature is 135-145 ℃, performing melt extrusion and dispersion at the extrusion temperature of 90-150 ℃, then performing single-screw extrusion granulation at the extrusion temperature of 90-140 ℃, performing hot cutting, air cooling and sieving to obtain the porcelain-like irradiation cross-linking low-smoke halogen-free flame-retardant polyolefin composition granules;

(2) plasticizing granules of the ceramifiable irradiation cross-linked low-smoke halogen-free flame-retardant polyolefin composition on an open mill at 100-140 ℃ to obtain a sheet, placing the obtained sheet in a hydraulic machine at 150-170 ℃ for 10min without pressurization and preheating, then pressurizing for 5min, pressurizing and cooling to room temperature, wherein the pressure of the hydraulic machine is not less than 15MPa, and the thickness of the sheet is 1 mm;

(3) and (3) carrying out irradiation crosslinking on the obtained sheet, wherein the irradiation dose is 6-15 Mrad, and the thermal extension is controlled to be 10-70%, so that the ceramizable irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin composition is obtained.

Technical Field

The invention belongs to the field of preparation of high polymer materials, and particularly relates to a low-smoke halogen-free flame-retardant polyolefin composition capable of being subjected to ceramization irradiation crosslinking and a preparation method thereof.

Background

Polyolefin high molecular material mainly comprises carbon, hydrogen and oxygen elements, most of oxygen indexes are lower than 21, the polyolefin high molecular material belongs to combustible and flammable materials, the heat release rate is high, the heat value is high, the flame propagation speed is high, the polyolefin high molecular material is not easy to extinguish, a large amount of dense smoke and toxic gas are generated even during combustion, and meanwhile, the polyolefin high molecular material is widely used in industrial production and daily life of people, so once a fire disaster occurs, the polyolefin high molecular material can cause great harm to the environment, and great threat to life and property safety of people is formed. Therefore, when the fire-retardant cable is used in many fields, the fire-retardant cable needs to be subjected to low-smoke halogen-free flame-retardant treatment so as to achieve flame retardancy, self-extinguishing property, low smoke property, no toxicity or no corrosiveness, and sometimes needs to have fire resistance, such as an electric wire and a cable used for emergency facilities or equipment, so as to ensure that the equipment can continuously run for a period of time when a fire occurs, and create favorable conditions for escape of fire trapped people and rescue of firefighters.

The porcelainized low-smoke halogen-free flame-retardant polyolefin composition is a novel high polymer material with flame-retardant property and porcelainized property, has the performance of the flame-retardant high polymer material in a common environment, can be rapidly porcelainized under a high-temperature condition (such as fire occurrence), forms a porous ceramic-shaped fire-resistant, heat-insulating and insulating shell with certain strength and self-supporting capacity, and can be applied to the fields of wires, cables, sealing strips and the like.

The published Chinese patent documents relate to a lot of technical information of porcelainized polyolefin high polymer materials, but none of the technical information relates to the research on radiation crosslinking of the porcelainized polyolefin high polymer materials, and most of the porcelainized thermoplastic polyolefin high polymer materials are thermoplastic, while the long-term use temperature of the porcelainized thermoplastic polyolefin high polymer materials in the field of wires and cables does not exceed 90 ℃, but some wires and cables require the long-term use temperature to reach 105 ℃ or above, so that the porcelainized thermoplastic polyolefin high polymer materials also need to be crosslinked to expand the use range of the porcelainized polyolefin high polymer materials.

Disclosure of Invention

Aiming at the problems in the prior art, the invention aims to provide a ceramizable irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin composition. The invention also aims to provide a preparation method of the material, which uses the irradiation crosslinking technology to make the material flame-retardant and fireproof and simultaneously improve the service temperature when preparing a final product.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

a porcelainized irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin composition comprises the following raw materials in parts by weight: 60-100 parts of polyolefin resin, 2-30 parts of a compatilizer, 80-200 parts of vitrified powder, 30-120 parts of a fluxing agent, 20-100 parts of a flame retardant, 1-10 parts of a lubricant, 1-4 parts of an antioxidant and a coupling agent: 1-6 parts of cross-linking sensitizer and 1-5 parts of cross-linking sensitizer.

The polyolefin resin is: one or more of polyethylene, ethylene-vinyl acetate copolymer, ethylene ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-propylene rubber, ethylene-butene copolymer, ethylene-hexene copolymer and ethylene-octene copolymer.

The compatilizer is as follows: one or more of maleic anhydride grafted polyethylene, maleic anhydride grafted ethylene vinyl acetate, maleic anhydride grafted ethylene octene copolymer, maleic anhydride grafted ethylene propylene rubber and ethylene-acrylate-maleic anhydride terpolymer.

The ceramic powder comprises: one or more of kaolin, wollastonite, montmorillonite, mica powder, white carbon black, antimony trioxide, calcium carbonate and talcum powder.

The fluxing agent is: one or more of lead-free low-softening-point glass powder, zinc borate, boron trioxide, molybdenum oxide, zinc oxide, magnesium oxide and calcium oxide.

The lead-free low-softening-point glass powder comprises the following components: one or more of low-softening-point silicate glass powder, low-softening-point borate glass powder, low-softening-point phosphate glass powder and low-softening-point bismuthate glass powder, wherein the softening point range is 300-700 ℃.

The flame retardant is: one or more of aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate (APP), triphenyl phosphate (TPP), melamine polyphosphate (MPP), organic aluminum hypophosphite, inorganic aluminum hypophosphite and red phosphorus.

The lubricant is: one or more of zinc stearate, calcium stearate, magnesium stearate, polyethylene wax, Ethylene Bis Stearamide (EBS), silicone oil and silicone.

The antioxidant is as follows: pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (1010), tris [2, 4-di-tert-butylphenyl ] phosphite (168), dioctadecyl thiodipropionate (DSTP), dilauryl thiodipropionate (DLTP), (4, 4 '-bis (. alpha. alpha. -dimethylbenzyl) diphenylamine) (KY405), and 4, 4' -thiobis (6-tert-butyl-3-methylphenol) (300).

The coupling agent is: one or more of silane coupling agent, titanate coupling agent, aluminate coupling agent and stearic acid.

The crosslinking sensitizer is: one or more of triallyl isocyanurate (TAIC), trimethylolpropane trimethacrylate (TMPTMA) and 1, 2-polybutadiene.

The preparation method of the ceramizable irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin composition comprises the following steps:

(1) pouring 60-100 parts of polyolefin resin into an internal mixer according to the formula composition, starting the internal mixer under the condition of no pressurization, pouring 1-6 parts of coupling agent and 1-5 parts of crosslinking sensitizer into the internal mixer, mixing the polyolefin resin with the internal mixer for 10-15 seconds, stopping the internal mixer, pouring the rest components according to the formula composition, starting the internal mixer, lowering a press hammer to pressurize and mix to 100-105 ℃, lifting the press hammer, lowering the press hammer after the materials in the internal mixer are turned over, lifting the press hammer again when the materials in the internal mixer are pressurized and mixed to 120-125 ℃, lowering the press hammer after the materials in the internal mixer are turned over, discharging and feeding the materials into a conical feeding machine when the materials are subjected to internal mixing to 135-145 ℃, performing melt extrusion and dispersion by a double screw at the extrusion temperature of 90-150 ℃, performing extrusion granulation by a single screw at the extrusion temperature of 90-140 ℃, performing hot cutting, air cooling and sieving to obtain the porcelain-like irradiation cross-linking low-smoke halogen-free flame-retardant polyolefin composition granules;

(2) plasticizing granules of the ceramifiable irradiation cross-linked low-smoke halogen-free flame-retardant polyolefin composition on an open mill at 100-140 ℃ to obtain a sheet, placing the obtained sheet in a hydraulic machine at 150-170 ℃ for 10min without pressurization and preheating, then pressurizing for 5min, pressurizing and cooling to room temperature, wherein the pressure of the hydraulic machine is not less than 15MPa, and the thickness of the sheet is 1 mm;

(3) and carrying out irradiation crosslinking on the obtained sheet, wherein the irradiation dose is 6-15 Mrad, and the thermal extension is controlled to be 10-70%.

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

the invention has the advantages of good flame resistance, low smoke yield during combustion, no toxicity and no corrosion besides the fire resistance of the common ceramic polyolefin material, and the use temperature (the use temperature is 105 ℃ or above) is further improved by adding a crosslinking sensitizer and using an irradiation crosslinking technology, thereby expanding the use range of the ceramic polyolefin material.

Detailed Description

The invention is further described with reference to specific examples.

Example 1:

linear low density polyethylene: 10 parts of ethylene-vinyl acetate copolymer: 30 parts, ethylene-octene copolymer: 39 parts of maleic anhydride grafted ethylene-octene copolymer: 21 parts, kaolin: 20 parts of montmorillonite: 15 parts of white carbon black: 7 parts, talcum powder: 40 parts of wollastonite: 30 parts of low-softening-point silicate glass powder: 30 parts, zinc borate: 40 parts, magnesium hydroxide: 34 parts, organic aluminum hypophosphite: 12 parts, red phosphorus: 8 parts, a silane coupling agent: 2 parts, polyethylene wax: 1 part, silicone: 2 parts, 1010: 0.5 part, DLTP: 0.5 part, TAIC: and 2 parts.

Pouring polyolefin resin into an internal mixer according to the formula composition, starting the internal mixer under the condition of no pressurization, pouring 2 parts of coupling agent and 2 parts of TAIC into the internal mixer to be mixed with the polyolefin resin for 12 seconds, stopping the internal mixer, pouring the rest components according to the formula composition, starting the internal mixer, putting a pressing hammer down to perform pressurization and internal mixing until the temperature is 105 ℃, lifting the pressing hammer up, putting the pressing hammer down after the materials in the internal mixer are turned over, performing pressurization and internal mixing until the temperature is 125 ℃, putting the pressing hammer down after the materials in the internal mixer are turned over, discharging and feeding the materials into a conical feeder when the internal mixer is subjected to internal mixing to 140 ℃, performing melt extrusion and dispersion by a double screw at the extrusion temperature of 90-150 ℃, then performing extrusion granulation by a single screw at the extrusion temperature of 90-140 ℃, and obtaining the granules of the ceramic irradiation crosslinking low-smoke halogen-free flame retardant polyolefin composition after hot cutting, air cooling and sieving.

Plasticizing the granules of the ceramifiable irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin composition on an open mill at 120 ℃ to obtain a sheet, placing the obtained sheet in a hydraulic machine at 170 ℃ to preheat for 10min without pressurization, pressurizing for 5min, pressurizing and cooling to room temperature, wherein the pressure of the hydraulic machine is not less than 15MPa, and the thickness of the sheet is 1 mm.

And carrying out irradiation crosslinking on the obtained sheet, wherein the irradiation dose is 6-15 Mrad, and the thermal extension is controlled to be 10-70%.

Example 2:

ethylene-vinyl acetate copolymer: 40 parts, ethylene-octene copolymer: 39 parts of maleic anhydride grafted ethylene-octene copolymer: 21 parts of mica powder: 13 parts of montmorillonite: 19 parts of white carbon black: 3 parts, talcum powder: 44 parts, wollastonite: 13 parts of antimony trioxide: 12 parts of molybdenum oxide: 5 parts of low-softening-point phosphate glass powder: 33 parts, zinc borate: 33 parts, aluminum hydroxide: 49 parts, red phosphorus: 12 parts, a silane coupling agent: 2 parts, polyethylene wax: 1 part, silicone: 2 parts, 1010: 0.5 part, DLTP: 0.5 part, TAIC: and 2 parts.

The preparation method is the same as example 1.

Example 3:

ethylene propylene rubber: 10 parts of ethylene-vinyl acetate copolymer: 36 parts, ethylene-octene copolymer: 39 parts of maleic anhydride grafted polyethylene: 15 parts of mica powder: 10 parts of montmorillonite: 19 parts of white carbon black: 3 parts, talcum powder: 46 parts, wollastonite: 15 parts, calcium carbonate: 20 parts of low-softening-point bismuthate glass powder: 25 parts, zinc borate: 41 parts, aluminum hydroxide: 40 parts, organic aluminum hypophosphite: 10 parts, ammonium polyphosphate: 7 parts, silane coupling agent: 2 parts, polyethylene wax: 1 part, silicone: 2 parts, 1010: 0.5 part, DLTP: 0.5 part, TAIC: and 2 parts.

The preparation method is the same as example 1.

Example 4:

the performance test data of the ceramifiable irradiation crosslinked low-smoke halogen-free flame retardant polyolefin composition prepared in the embodiments 1 to 3 are shown in the following table 1:

TABLE 1

As can be seen from the data in the table, the ceramifiable irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin composition meets the requirements of 125 ℃ halogen-free low-smoke flame-retardant crosslinking type polyolefin insulating material and sheathing material in the standard GB/T32129, and the oxygen index is far higher than the standard, which shows that the flame retardance is better than that of the common halogen-free low-smoke flame-retardant polyolefin.

At about 2.5mm²The copper core conductor is extruded with the ceramifiable irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin composition with the thickness of 0.8-1 mm, a line integrity fire resistance test is carried out according to the national standard GB/T19216.21-2003 after irradiation crosslinking, and the test results are shown in the following table 2:

TABLE 2

The invention is not limited to the embodiments described above, but within the scope of the inventive concept, obvious modifications will be made by those skilled in the art in light of the above description, all of which are intended to fall within the scope of the appended claims.