阅读说明：本技术 一种b1级紫外光交联低烟无卤阻燃电缆料及其制备方法 (B1-grade ultraviolet light crosslinking low-smoke halogen-free flame-retardant cable material and preparation method thereof ) 是由 吕伟 董启殿 李广富 刘鹏辉 王宏 杨帮 于 2021-10-09 设计创作，主要内容包括：本发明公开了一种B1级紫外光交联低烟无卤阻燃电缆料及其制备方法。电缆料由以下质量份数计的组分组成：6～40份乙烯-醋酸乙烯共聚物、8～18份聚乙烯、1～5份交联剂、1～5份光引发剂、40～65份无机阻燃剂、5～10份抑烟成碳剂、5～15份协效阻燃剂、0.3～2份抗氧剂、0.5～2份润滑剂。本发明的电缆料挤出速度快,交联效率高,力学性能优越；火焰蔓延、热释放总量、热释放速率峰值、产烟总量、产烟速率峰值、燃烧增长速率指数等性能参数达到B1耐燃级别。(The invention discloses a B1-grade ultraviolet crosslinking low-smoke halogen-free flame-retardant cable material and a preparation method thereof. The cable material comprises the following components in parts by mass: 6-40 parts of ethylene-vinyl acetate copolymer, 8-18 parts of polyethylene, 1-5 parts of crosslinking agent, 1-5 parts of photoinitiator, 40-65 parts of inorganic flame retardant, 5-10 parts of smoke-inhibiting and carbon-forming agent, 5-15 parts of synergistic flame retardant, 0.3-2 parts of antioxidant and 0.5-2 parts of lubricant. The cable material has the advantages of high extrusion speed, high crosslinking efficiency and excellent mechanical property; the flame spread, the total heat release amount, the peak value of the heat release rate, the total smoke production amount, the peak value of the smoke production rate, the combustion growth rate index and other performance parameters reach the B1 flame-resistant level.)

1. A B1-grade ultraviolet light crosslinking low-smoke halogen-free flame-retardant cable material is characterized by comprising the following components in parts by mass: 6-40 parts of ethylene-vinyl acetate copolymer, 8-18 parts of polyethylene, 1-5 parts of crosslinking agent, 1-5 parts of photoinitiator, 40-65 parts of inorganic flame retardant, 5-10 parts of smoke-inhibiting and carbon-forming agent, 5-15 parts of synergistic flame retardant, 0.3-2 parts of antioxidant and 0.5-2 parts of lubricant.

2. The B1-grade ultraviolet crosslinking low-smoke halogen-free flame-retardant cable material as claimed in claim 1, which is characterized by comprising the following components in parts by mass: 20-30 parts of ethylene-vinyl acetate copolymer, 12-18 parts of polyethylene, 2-3 parts of cross-linking agent, 3-4 parts of photoinitiator, 50-55 parts of inorganic flame retardant, 6-8 parts of smoke-inhibiting and carbon-forming agent, 8-12 parts of synergistic flame retardant, 0.5-1 part of antioxidant and 0.5-1 part of lubricant.

3. The B1-grade ultraviolet light crosslinking low-smoke zero-halogen flame-retardant cable material as claimed in claim 1 or 2,

the vinyl acetate content in the ethylene-vinyl acetate copolymer is less than or equal to 40 percent;

the cross-linking agent is at least one of triallyl isocyanurate, trimethylolpropane trimethacrylate, 1, 2-polybutadiene, trimethylolpropane diallyl ether and triallyl cyanurate;

the synergistic flame retardant is at least one of aluminum hypophosphite, diethyl aluminum hypophosphite, ammonium polyphosphate and red phosphorus;

the lubricant is at least one of silicone master batch, zinc stearate, polyethylene wax and ethylene bisstearamide.

4. The B1-grade ultraviolet light crosslinking low-smoke zero-halogen flame-retardant cable material as claimed in claim 3,

the vinyl acetate content in the ethylene-vinyl acetate copolymer is 25-30 percent;

the crosslinking agent is at least one of triallyl isocyanurate and trimethylolpropane trimethacrylate;

the synergistic flame retardant is at least one of aluminum hypophosphite and ammonium polyphosphate;

the lubricant is polyethylene wax.

5. The B1-grade ultraviolet light crosslinking low-smoke zero-halogen flame-retardant cable material as claimed in claim 1 or 2,

the photoinitiator is at least one of benzoin dimethyl ether, 2-hydroxy-2-methyl 1-phenyl acetone, alpha-hydroxyalkyl benzophenone, benzophenone and 2, 4-dihydroxy benzophenone;

the inorganic flame retardant is at least one of aluminum hydroxide and magnesium hydroxide;

the smoke-suppressing carbon-forming agent is at least one of zinc borate hydrate, zinc oxide, molybdenum oxide and montmorillonite;

the antioxidant is at least one of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, dilauryl thiodipropionate, 4' -thiobis (6-tert-butyl-3-methylphenol), diisopropylphenyl diphenylamine and tris [2, 4-di-tert-butylphenyl ] phosphite.

6. The B1-grade ultraviolet light crosslinking low-smoke zero-halogen flame-retardant cable material as claimed in claim 5,

the photoinitiator is at least one of benzoin dimethyl ether, benzophenone and 2, 4-dihydroxy benzophenone;

the inorganic flame retardant is aluminum hydroxide and magnesium hydroxide;

the smoke-inhibiting carbon-forming agent is at least one of zinc oxide and molybdenum oxide;

the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and diisopropylphenyl diphenylamine.

7. The B1-grade ultraviolet light crosslinking low-smoke zero-halogen flame-retardant cable material as claimed in claim 6,

the photoinitiator is benzoin dimethyl ether, benzophenone and 2, 4-dihydroxy benzophenone;

in the inorganic flame retardant, the mass ratio of aluminum hydroxide to magnesium hydroxide is 2: 1;

the smoke-inhibiting carbon-forming agent is zinc oxide and molybdenum oxide;

in the antioxidant, the mass ratio of the tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester to the diisopropylphenyl diphenylamine is 1: 2.

8. the B1-grade ultraviolet crosslinking low-smoke halogen-free flame-retardant cable material as claimed in claim 1 or 2, wherein the polyethylene has a melt index of 1-5 g/10min at 190 ℃ under a 2.16kg test condition.

9. The preparation method of the B1-grade ultraviolet light crosslinking low-smoke zero-halogen flame-retardant cable material as claimed in any one of claims 1-8, characterized by comprising the following steps: mixing the components, banburying the obtained mixture, extruding and granulating to obtain the B1-grade ultraviolet light crosslinking low-smoke halogen-free flame-retardant cable material.

10. The preparation method of the B1-grade ultraviolet light crosslinking low-smoke halogen-free flame-retardant cable material according to claim 9,

the banburying temperature is 110-120 ℃;

the extrusion temperature is 110-130 ℃.

Technical Field

The invention relates to the technical field of low-smoke halogen-free flame-retardant cable materials, in particular to a B1-grade ultraviolet light crosslinking low-smoke halogen-free flame-retardant cable material and a preparation method thereof.

Background

The crosslinked cable has excellent high-temperature resistance, higher long-term service temperature and longer service life, and is widely popularized and applied in the cable industry. The ultraviolet crosslinking technology has been greatly developed in the wire and cable industry in recent years due to the advantages of small equipment investment, low energy consumption, convenient processing, high crosslinking speed and the like.

In the field of cables, many safety-related standards are enforced, wherein the electrical design standard for civil buildings GB 51348-. Most crosslinked cable materials on the market today do not meet this standard in their entirety.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a B1-grade ultraviolet crosslinking low-smoke halogen-free flame-retardant cable material.

The invention also aims to provide a preparation method of the B1-grade ultraviolet crosslinking low-smoke halogen-free flame-retardant cable material.

The purpose of the invention is realized by the following technical scheme: a B1-grade ultraviolet light crosslinking low-smoke halogen-free flame-retardant cable material comprises the following components in parts by weight: 6-40 parts of ethylene-vinyl acetate copolymer, 8-18 parts of polyethylene, 1-5 parts of crosslinking agent, 1-5 parts of photoinitiator, 40-65 parts of inorganic flame retardant, 5-10 parts of smoke-inhibiting and carbon-forming agent, 5-15 parts of synergistic flame retardant, 0.3-2 parts of antioxidant and 0.5-2 parts of lubricant; more preferably, the composition comprises the following components in parts by mass: 20-30 parts of ethylene-vinyl acetate copolymer, 12-18 parts of polyethylene, 2-3 parts of cross-linking agent, 3-4 parts of photoinitiator, 50-55 parts of inorganic flame retardant, 6-8 parts of smoke-inhibiting and carbon-forming agent, 8-12 parts of synergistic flame retardant, 0.5-1 part of antioxidant and 0.5-1 part of lubricant.

Preferably, the content of Vinyl Acetate (VA) in the ethylene-vinyl acetate copolymer (EVA resin) is less than or equal to 40 percent; more preferably, the ethylene-vinyl acetate copolymer (EVA) has a Vinyl Acetate (VA) content of 25% to 30%.

Preferably, the polyethylene (PE resin) has a melt index of 1-5 g/10min at 190 ℃ under a test condition of 2.16 kg.

Preferably, the crosslinking agent is at least one of triallyl isocyanurate, trimethylolpropane trimethacrylate, 1, 2-polybutadiene, trimethylolpropane diallyl ether and triallyl cyanurate; more preferably, the crosslinking agent is at least one of triallyl isocyanurate and trimethylolpropane trimethacrylate.

Preferably, the photoinitiator is at least one of benzoin dimethyl ether, 2-hydroxy-2-methyl 1-phenyl acetone, alpha-hydroxyalkyl benzophenone, benzophenone and 2, 4-dihydroxy benzophenone; more preferably, the photoinitiator is at least one of benzoin dimethyl ether, benzophenone and 2, 4-dihydroxy benzophenone; most preferably, the photoinitiator is benzoin dimethyl ether, benzophenone, and 2, 4-dihydroxybenzophenone.

Preferably, the inorganic flame retardant is at least one of aluminum hydroxide and magnesium hydroxide; more preferably, the inorganic flame retardant is aluminum hydroxide and magnesium hydroxide; most preferably, the mass ratio of the aluminum hydroxide to the magnesium hydroxide is 2: 1.

preferably, the smoke-suppressing and carbon-forming agent is at least one of zinc borate hydrate, zinc oxide, molybdenum oxide and montmorillonite; more preferably, the smoke-inhibiting and carbon-forming agent is at least one of zinc oxide and molybdenum oxide; most preferably, the smoke suppressant and carbon suppressant are zinc oxide and molybdenum oxide.

Preferably, the synergistic flame retardant is at least one of aluminum hypophosphite, diethyl aluminum hypophosphite, ammonium polyphosphate and red phosphorus; more preferably, the synergistic flame retardant is at least one of aluminum hypophosphite and ammonium polyphosphate.

Preferably, the antioxidant is at least one of pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), dilauryl thiodipropionate (antioxidant DLTP), 4' -thiobis (6-tert-butyl-3-methylphenol) (antioxidant 300), diisopropylphenyl diphenylamine (antioxidant KY405) and tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168); more preferably, the antioxidant is pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and diisopropylphenyl diphenylamine; most preferably, the mass ratio of the pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] to the diisopropylphenyl diphenylamine is 1: 2.

preferably, the lubricant is at least one of silicone master batch, zinc stearate, polyethylene wax and ethylene bis-stearic acid amide; more preferably, the lubricant is polyethylene wax.

The preparation method of the B1-grade ultraviolet crosslinking low-smoke halogen-free flame-retardant cable material comprises the following steps: mixing the components, banburying the obtained mixture, extruding and granulating to obtain the B1-grade ultraviolet light crosslinking low-smoke halogen-free flame-retardant cable material.

Preferably, the banburying temperature is 110-120 ℃.

Preferably, the temperature of the extrusion is 110 ℃ to 130 ℃.

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

the B1-grade ultraviolet crosslinking low-smoke halogen-free flame-retardant cable material has the advantages of high extrusion speed, high crosslinking efficiency and excellent mechanical property; the flame spread, the total heat release amount, the peak value of the heat release rate, the total smoke generation amount, the peak value of the smoke generation rate, the combustion growth rate index and other performance parameters reach the B1 flame-resistant level (the detection standard GB 31247-.

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 raw materials used in the examples of the invention and the comparative examples were as follows:

EVA resin with VA content of 28 percent, and moulding;

PE resin with the melt index of 2g/10min under the test condition of 190 ℃ and 2.16kg is named as petrochemical;

crosslinking agents, triallyl isocyanurate, trimethylolpropane trimethacrylate, Rundard in the south of the lake;

photoinitiator (2): benzophenone, benzoin dimethyl ether, 2, 4-dihydroxy benzophenone, Nanjing Wali;

inorganic flame retardant: aluminum hydroxide, medium aluminum; magnesium hydroxide, sodium sulfite;

smoke-suppressing and carbon-forming agent: zinc oxide, Shanghai Yangjiang chemical industry; molybdenum oxide, gold-molybdenum-tungsten;

synergistic flame retardant: aluminum hypophosphite, ammonium polyphosphate, praseofuran;

antioxidant: pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), basf; diisopropylphenyl diphenylamine (antioxidant KY405), Changzhou Jiatong chemical;

lubricant: polyethylene wax, run Jiaze in Ningxia.

Examples and comparative examples

The parts by mass of the components of the cable material in examples 1 to 5 and comparative examples 1 to 2 are shown in table 1.

TABLE 1 parts by mass of the components of the cable materials of examples 1 to 5 and comparative examples 1 to 2

The preparation method of the cable materials of examples 1 to 5 and comparative examples 1 to 2 comprises the following steps:

(1) weighing the raw materials according to the mass parts of the components of the cable materials in the examples 1-5 and the comparative examples 1-2 in the table 1, adding the raw materials into a high-speed stirrer (600r/min), and mixing for 4min to obtain a mixture;

(2) respectively adding the mixture into an internal mixer for internal mixing, wherein the internal mixing temperature is 120 ℃;

(3) and respectively adding the internally mixed mixture into a single-screw extruder for melt extrusion, wherein the extrusion temperature is 130 ℃, and granulating to obtain the cable materials of examples 1-5 and comparative examples 1-2.

The cable materials of examples 1-5 and comparative examples 1-2 were subjected to performance testing, and the testing results are shown in table 2.

TABLE 2 test results of the properties of the cable materials of examples 1 to 5 and comparative examples 1 to 2

And (4) analyzing results: as can be seen from Table 2, compared with comparative examples 1 and 2, the performance of examples 1-5 is very superior, the tensile strength, the elongation at break, the thermal elongation and the oxygen index are obviously better than those of comparative examples 1 and 2, and the performance data such as flame spread, peak heat release rate, burn growth rate index and the like reach the B1 flame resistance grade standard, so that the advantages are obvious. Examples 1-5 all pass the test of GB 31247-2014B 1 burning grade, and the fire-retardant cable material has small heat release and low smoke production. In contrast, example 1 has the best crosslinking effect, higher char formation efficiency, and better flame retardant effect.

It can be seen by analyzing comparative examples 1,2 and example 5 that the smoke suppressant and the synergistic flame retardant play a very important role in the system. Comparative example 1 has no smoke suppressant and no synergistic flame retardant, and the performance data such as flame spread, peak heat release rate, burn growth rate index and the like are very poor and can not reach the B1 flame resistance grade standard. In the comparative example 2 with a small amount of smoke-inhibiting carbon-forming agent and the synergistic flame retardant, the standard test data of the flame resistance level of B1 is obviously better than that of the comparative example 1, and the effect is obvious. Compared with comparative examples 1 and 2, the test data of the B1 project of example 5 are more superior and the effect is obvious with the increase of the parts of the smoke-inhibiting carbon-forming agent and the synergistic flame retardant.

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.