CN115850849B - Freely-bendable wear-resistant weather-resistant halogen-free low-smoke cable material, preparation method thereof and application thereof in robot - Google Patents
Freely-bendable wear-resistant weather-resistant halogen-free low-smoke cable material, preparation method thereof and application thereof in robot Download PDFInfo
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Abstract
The invention relates to the technical field of cables and discloses a free-bending wear-resistant weather-resistant halogen-free low-smoke cable material, a preparation method thereof and application thereof in robots.
Description
Technical Field
The invention relates to the technical field of cables, in particular to a free-bending wear-resistant weather-resistant halogen-free low-smoke cable material, a preparation method thereof and application thereof in robots.
Background
In recent years, science and technology in China are rapidly developed, wherein the industrial robot industry in China is rapidly developed and occupies an important position in the global industrial robot market, various industrial robots have wide requirements and applications in numerous fields, robot arms are particularly widely applied in industry, the robot arms mainly comprise cables, the cables are mainly used for transmitting electric power and signals, but due to the complexity and the repeatability of the actions of the robot arms and the difference of the working environment and the temperature in various aspects, the cables used in the robot arms need to be capable of meeting the requirements of repeated bending, stretching, wear resistance and weather resistance.
The cable receives external environment's influence in the use, can generate heat simultaneously, can take place the electric power accident, can cause the conflagration when serious, has certain potential safety hazard, therefore the cable has fire prevention fire behaviour and has important meaning. Chinese patent CN105524368B discloses a polyvinyl chloride sheathing material special for a robot cable, which has excellent flexibility, oil resistance and heat resistance, can be widely applied to the field of robot cables with oil-resistant and flame-retardant requirements, but contains a large amount of chlorine element, and can suffocate people due to a large amount of dense smoke emitted during combustion, thereby affecting visibility, and generating some carcinogens and HCl gas, thereby causing serious harm to the environment. The synthesis method of a bisaminophosphaphenanthrene derivative (namely a nitrogen-containing phosphaphenanthrene monomer) is disclosed before Yun Li, chen Yugong, cai Chunfei, chen Wei, liu Yun and Hu Sai (the synthesis and characterization of a novel nitrogen-phosphorus flame retardant [ J ], the college report of Jianghan university, 2016, 44 (1) and 34-39), and the bisaminophosphaphenanthrene derivative has good flame retardance. With the enhancement of environmental awareness of people, the low-halogen smokeless cable material is more and more, and the development of the halogen-free low-smoke cable material which can be freely bent, is wear-resistant and weather-resistant by using the halogen-free flame retardant has important significance, and accords with the long-term development of the industry.
Disclosure of Invention
In order to solve the technical problems, the invention provides a free-bending wear-resistant weather-resistant halogen-free low-smoke cable material, a preparation method thereof and application thereof in a robot, and solves the problems of poor fire-resistant flame-retardant effect and general wear resistance and weather resistance of a robot cable.
In order to achieve the purpose, the invention discloses a preparation method of a freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material, which comprises the following steps:
(1) Uniformly mixing thionyl chloride and graphene oxide, heating and refluxing at 75-85 ℃ for reaction for 18-36h, filtering after the reaction is finished, washing with tetrahydrofuran, and drying at 60-70 ℃ for 6-12h to obtain graphene chloride acylate;
(2) Uniformly mixing dimethylacetamide, acylchlorinated graphene, lysine and pyridine, reacting, filtering after the reaction is finished, washing by using dimethylacetamide and deionized water, and vacuum-drying at 50-60 ℃ for 12-18h to obtain lysine modified graphene;
(3) Organic solvent, lysine modified graphene and bisaminophosphaphenanthrene derivative (C) 26 H 23 N 2 O 2 Uniformly mixing P), 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride (EDCI), 1-Hydroxybenzotriazole (HOBT) and Triethylamine (TEA), reacting, filtering after the reaction is finished, washing by using dichloromethane, and drying at 60-70 ℃ for 6-12h to obtain the flame retardant modified graphene;
(4) Uniformly mixing ethylene-vinyl acetate copolymer (EVA), polyetherimide (PEI), rubber elastomer, flame retardant modified graphene, an anti-aging agent, an antioxidant and a lubricant, melting, blending and extruding to obtain the freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material.
Preferably, the mass ratio of thionyl chloride to graphene oxide in the step (1) is (4000-6500): 10.
preferably, the mass ratio of the dimethylacetamide, the acylchlorinated graphene, the lysine and the pyridine in the step (2) is (2400-4200): 100: (140-240): (20-40).
Preferably, the temperature of the reaction in the step (2) is 20-35 ℃, and the reaction time is 2-6h.
Preferably, the organic solvent in step (3) includes any one of N, N-dimethylformamide, dichloromethane and tetrahydrofuran.
Preferably, in the step (3), the mass ratio of the organic solvent, the lysine modified graphene, the bisaminophosphaphenanthrene derivative, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, the 1-hydroxybenzotriazole and the triethylamine is (3000-5500): 100: (120-200): (20-35): (10-18): (85-160).
Preferably, the reaction temperature in the step (3) is 15-30 ℃, and the reaction time is 24-36h.
Preferably, the mass ratio of the ethylene-vinyl acetate copolymer, the polyetherimide, the rubber elastomer, the flame retardant modified graphene, the antioxidant and the lubricant in the step (4) is 100: (35-75): (18-30): (3-8): (0.1-0.6): (0.3-1.2): (1-3).
Preferably, the rubber elastomer in the step (4) comprises one of ethylene propylene diene monomer, ethylene propylene diene monomer and nitrile rubber.
Preferably, the temperature of the melt blending in the step (4) is 180-195 ℃, and the time of the melt blending is 8-12min.
Preferably, in the step (4), the anti-aging agent is N, N' -di (beta-naphthyl) p-phenylenediamine, the antioxidant is antioxidant 1010, and the lubricant is polyethylene wax.
Preferably, the halogen-free low-smoke cable material with wear resistance and weather resistance is prepared by the preparation method of the halogen-free low-smoke cable material with wear resistance and weather resistance.
Preferably, the freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material is applied to a robot.
According to the invention, thionyl chloride is firstly used for modifying graphene oxide, acyl chloride groups are introduced to the surface of the graphene oxide to obtain acyl chlorinated graphene, the acyl chloride groups on the surface of the acyl chlorinated graphene and amino groups on lysine react under the action of pyridine, a lysine flexible long chain, carboxyl groups and unreacted amino groups are introduced to the surface of the graphene to obtain lysine modified graphene, in an organic solvent, the carboxyl groups on the surface of the lysine modified graphene and the amino groups on a bisaminophosphaphenanthrene derivative react under the action of 1-ethyl- (3-dimethylaminopropyl) carbonyl diimine hydrochloride, 1-hydroxybenzotriazole and triethylamine to obtain flame retardant modified graphene, and the obtained flame retardant modified graphene, ethylene-vinyl acetate copolymer, polyetherimide, rubber elastomer, anti-aging agent, antioxidant and lubricant are uniformly mixed, melted, blended and extruded to obtain the low-smoke, wear-resistant and weather-resistant halogen-free cable material.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the ethylene-vinyl acetate copolymer is used as a matrix material, the added graphene oxide has excellent mechanical properties and can improve the wear resistance and mechanical properties of the matrix, and meanwhile, the graphene oxide has small size, can effectively reflect and refract ultraviolet rays, has ultraviolet resistance, can cut bacterial cell membranes to kill bacteria, has excellent antibacterial properties, is added into the matrix, and improves the weather resistance of the matrix to a great extent.
The flexibility of a matrix can be further improved by the flexible long chain in the introduced lysine, the flexible long chain has stronger capability of being bent freely, a large amount of non-combustible gas can be generated by the amino on the introduced lysine and the amino on the polyetherimide in the combustion process of the matrix, the concentration of oxygen in a combustion system is effectively diluted, the flame retardant effect is effectively improved, the introduced bisaminophosphaphenanthrene derivative can generate acidic substances such as phosphoric acid, phosphorous acid and the like in the combustion process of the matrix, the matrix is promoted to form carbon, the combustion reaction is prevented from proceeding, PO & free radicals generated in the combustion process can capture OH & H & free radicals in flame, the combustion chain reaction is interrupted, the heat released by combustion is reduced, the nitrogen and phosphorus flame retardant has a synergistic effect, a more compact impermeable carbon layer can be generated on the surface of the matrix during heated combustion, the heat conduction is prevented, meanwhile, no smoke is generated in the combustion process, the used flame retardant component does not contain halogen, and the flame retardant has the characteristics of environmental protection.
The ethylene-vinyl acetate copolymer used in the invention has certain polarity, carbonyl and hydroxyl with stronger polarity can form intramolecular and intermolecular hydrogen bonds, carbonyl and hydroxyl on the ethylene-vinyl acetate copolymer and amino groups on materials such as flame retardant modified graphene and polyetherimide can form hydrogen bonds to form a multi-dimensional interpenetrating network structure, the materials have stronger acting force, the mechanical property and compatibility are better, the added polyetherimide has good flexibility, the rubber elastomer also has good toughness, the freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material obtained after mixing has excellent comprehensive performance, and the bending resistance, wear resistance, weather resistance and flame retardance can all meet the application in robots.
Drawings
FIG. 1 is a flow chart of the present invention for preparing a freely bendable, abrasion-resistant, weather-resistant, halogen-free, low-smoke cable material;
fig. 2 is a schematic diagram of preparation of lysine-modified graphene in the present invention;
fig. 3 is a schematic diagram of preparation of flame retardant modified graphene in the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1
A preparation method of a freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material comprises the following steps:
(1) Mixing the components in a mass ratio of 4000:10, uniformly mixing thionyl chloride and graphene oxide, heating and refluxing at 75 ℃ for reaction for 36 hours, filtering after the reaction is finished, washing with tetrahydrofuran, and drying at 60 ℃ for 12 hours to obtain graphene oxychloride;
(2) Mixing the components in a mass ratio of 2400:100:140: uniformly mixing 20 parts of dimethylacetamide, acylchlorinated graphene, lysine and pyridine, reacting at 20 ℃ for 6 hours, filtering after the reaction is finished, washing with dimethylacetamide and deionized water, and vacuum drying at 50 ℃ for 18 hours to obtain lysine modified graphene;
(3) Mixing 3000:100:120:20:10:85 of N, N-dimethylformamide, lysine modified graphene, a bisaminophosphaphenanthrene derivative, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride, 1-hydroxybenzotriazole and triethylamine are uniformly mixed, reacted at 15 ℃ for 36 hours, filtered after the reaction is finished, washed by dichloromethane and dried at 60 ℃ for 12 hours to obtain flame retardant modified graphene;
(4) Mixing the components in a mass ratio of 100:35:18:3:0.1:0.3:1 ethylene-vinyl acetate copolymer, polyetherimide, rubber elastomer ethylene propylene diene monomer, flame retardant modified graphene, antioxidant N, N' -di (beta-naphthyl) p-phenylenediamine, antioxidant 1010 and lubricant polyethylene wax are uniformly mixed, melted and blended for 12min at 180 ℃, and extruded to obtain the free-bending wear-resistant weather-resistant halogen-free low-smoke cable material.
Example 2
A preparation method of a freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material comprises the following steps:
(1) Mixing 4600:10, uniformly mixing thionyl chloride and graphene oxide, heating and refluxing at 80 ℃ for reaction for 24 hours, filtering after the reaction is finished, washing with tetrahydrofuran, and drying at 65 ℃ for 10 hours to obtain graphene chloride acylate;
(2) Mixing a mixture of 2800:100:170:25, uniformly mixing dimethylacetamide, acylchlorinated graphene, lysine and pyridine, reacting at 25 ℃ for 3 hours, filtering after the reaction is finished, washing with dimethylacetamide and deionized water, and vacuum drying at 55 ℃ for 15 hours to obtain lysine modified graphene;
(3) Mixing the components in a mass ratio of 3400:100:140:24:12: uniformly mixing 105N, N-dimethylformamide, lysine modified graphene, a bisaminophosphaphenanthrene derivative, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride, 1-hydroxybenzotriazole and triethylamine, reacting at 20 ℃ for 28 hours, filtering after the reaction is finished, washing with dichloromethane, and drying at 65 ℃ for 8 hours to obtain flame retardant modified graphene;
(4) And (2) mixing the following components in percentage by mass as 100:45:21:4:0.2:0.5:1.5 evenly mixing ethylene-vinyl acetate copolymer, polyetherimide, rubber elastomer ethylene propylene diene monomer, flame retardant modified graphene, anti-aging agent N, N' -di (beta-naphthyl) p-phenylenediamine, antioxidant 1010 and lubricant polyethylene wax, melting and blending for 9min at 185 ℃, and extruding to obtain the free-bending wear-resistant weather-resistant halogen-free low-smoke cable material.
Example 3
A preparation method of a freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material comprises the following steps:
(1) Mixing 5200:10, uniformly mixing thionyl chloride and graphene oxide, heating and refluxing at 80 ℃ for reaction for 30 hours, filtering after the reaction is finished, washing with tetrahydrofuran, and drying at 65 ℃ for 10 hours to obtain graphene chloride acylate;
(2) Mixing the components in a mass ratio of 3400:100:200: uniformly mixing 30 parts of dimethylacetamide, acylchlorinated graphene, lysine and pyridine, reacting at 30 ℃ for 4 hours, filtering after the reaction is finished, washing with dimethylacetamide and deionized water, and vacuum drying at 55 ℃ for 15 hours to obtain lysine modified graphene;
(3) Mixing the components in a mass ratio of 4000:100:160:28:14: uniformly mixing 125 parts of N, N-dimethylformamide, lysine modified graphene, a bisaminophosphaphenanthrene derivative, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride, 1-hydroxybenzotriazole and triethylamine, reacting at 25 ℃ for 30 hours, filtering after the reaction is finished, washing with dichloromethane, and drying at 65 ℃ for 8 hours to obtain flame retardant modified graphene;
(4) Mixing the components in a mass ratio of 100:55:24:5:0.4:0.8:2, uniformly mixing ethylene-vinyl acetate copolymer, polyetherimide, rubber elastomer ethylene propylene diene monomer, flame retardant modified graphene, antioxidant N, N' -di (beta-naphthyl) p-phenylenediamine, antioxidant 1010 and lubricant polyethylene wax, melting and blending for 9min at 185 ℃, and extruding to obtain the freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material.
Example 4
A preparation method of a freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material comprises the following steps:
(1) Mixing the components in a mass ratio of 6000:10, uniformly mixing thionyl chloride and graphene oxide, heating and refluxing at 80 ℃ for reaction for 32 hours, filtering after the reaction is finished, washing with tetrahydrofuran, and drying at 65 ℃ for 10 hours to obtain graphene chloride acylate;
(2) Mixing materials with mass ratio of 3800:100:225:35, uniformly mixing dimethylacetamide, acylchlorinated graphene, lysine and pyridine, reacting for 5 hours at 30 ℃, filtering after the reaction is finished, washing with dimethylacetamide and deionized water, and vacuum-drying for 15 hours at 55 ℃ to obtain lysine modified graphene;
(3) Mixing the components in a mass ratio of 5000:100:185:32:16:150 of N, N-dimethylformamide, lysine modified graphene, a bisaminophosphaphenanthrene derivative, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride, 1-hydroxybenzotriazole and triethylamine are uniformly mixed, reacted for 32 hours at 25 ℃, filtered after the reaction is finished, washed by dichloromethane and dried for 8 hours at 65 ℃ to obtain flame retardant modified graphene;
(4) And (2) mixing the following components in percentage by mass as 100:65:28:6.5:0.5:1:2.5 uniformly mixing ethylene-vinyl acetate copolymer, polyetherimide, rubber elastomer ethylene propylene diene monomer, flame retardant modified graphene, anti-aging agent N, N' -di (beta-naphthyl) p-phenylenediamine, antioxidant 1010 and lubricant polyethylene wax, melting and blending for 10min at 190 ℃, and extruding to obtain the freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material.
Example 5
A preparation method of a freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material comprises the following steps:
(1) Mixing 6500:10, uniformly mixing thionyl chloride and graphene oxide, heating and refluxing at 85 ℃ for reaction for 18 hours, filtering after the reaction is finished, washing with tetrahydrofuran, and drying at 70 ℃ for 6 hours to obtain graphene chloride acylate;
(2) Mixing the raw materials in a mass ratio of 4200:100:240: uniformly mixing 40 parts of dimethylacetamide, acylchlorinated graphene, lysine and pyridine, reacting for 2 hours at 35 ℃, filtering after the reaction is finished, washing with dimethylacetamide and deionized water, and vacuum-drying for 12 hours at 60 ℃ to obtain lysine modified graphene;
(3) The mass ratio is 5500:100:200:35:18:160 parts of N, N-dimethylformamide, lysine modified graphene, a bisaminophosphaphenanthrene derivative, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride, 1-hydroxybenzotriazole and triethylamine are uniformly mixed, react at 30 ℃ for 24 hours, are filtered after the reaction is finished, are washed by dichloromethane and are dried at 70 ℃ for 6 hours to obtain flame retardant modified graphene;
(4) And (2) mixing the following components in percentage by mass as 100:75:30:8:0.6:1.2:3, uniformly mixing ethylene-vinyl acetate copolymer, polyetherimide, rubber elastomer ethylene propylene diene monomer, flame retardant modified graphene, antioxidant N, N' -di (beta-naphthyl) p-phenylenediamine, antioxidant 1010 and lubricant polyethylene wax, melting and blending for 8min at 195 ℃, and extruding to obtain the freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material.
Example 6
A preparation method of a freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material comprises the following steps:
(1) Mixing the components in a mass ratio of 6000:10, uniformly mixing thionyl chloride and graphene oxide, heating and refluxing at 80 ℃ for reaction for 32 hours, filtering after the reaction is finished, washing with tetrahydrofuran, and drying at 65 ℃ for 10 hours to obtain graphene chloride acylate;
(2) Mixing materials with mass ratio of 3800:100:225:35, uniformly mixing dimethylacetamide, acylchlorinated graphene, lysine and pyridine, reacting for 5 hours at 30 ℃, filtering after the reaction is finished, washing with dimethylacetamide and deionized water, and vacuum-drying for 15 hours at 55 ℃ to obtain lysine modified graphene;
(3) Mixing the components in a mass ratio of 5000:100:185:32:16:150 parts of dichloromethane, lysine modified graphene, a bisaminophosphaphenanthrene derivative, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride, 1-hydroxybenzotriazole and triethylamine are uniformly mixed, reacted for 32 hours at 25 ℃, filtered after the reaction is finished, washed by dichloromethane and dried for 8 hours at 65 ℃ to obtain flame retardant modified graphene;
(4) And (2) mixing the following components in percentage by mass as 100:65:28:6.5:0.5:1:2.5 uniformly mixing ethylene-vinyl acetate copolymer, polyetherimide, rubber elastomer ethylene propylene diene monomer, flame retardant modified graphene, anti-aging agent N, N' -di (beta-naphthyl) p-phenylenediamine, antioxidant 1010 and lubricant polyethylene wax, melting and blending for 10min at 190 ℃, and extruding to obtain the freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material.
Example 7
A preparation method of a free-bending wear-resistant weather-resistant halogen-free low-smoke cable material comprises the following steps:
(1) Mixing the components in a mass ratio of 6000:10, uniformly mixing thionyl chloride and graphene oxide, heating and refluxing at 80 ℃ for reaction for 32 hours, filtering after the reaction is finished, washing with tetrahydrofuran, and drying at 65 ℃ for 10 hours to obtain graphene chloride acylate;
(2) Mixing materials with mass ratio of 3800:100:225:35, uniformly mixing dimethylacetamide, acylchlorinated graphene, lysine and pyridine, reacting for 5 hours at 30 ℃, filtering after the reaction is finished, washing with dimethylacetamide and deionized water, and vacuum-drying for 15 hours at 55 ℃ to obtain lysine modified graphene;
(3) Mixing the components in a mass ratio of 5000:100:185:32:16: uniformly mixing 150 parts of tetrahydrofuran, lysine modified graphene, a bisaminophosphaphenanthrene derivative, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride, 1-hydroxybenzotriazole and triethylamine, reacting at 25 ℃ for 32 hours, filtering after the reaction is finished, washing with dichloromethane, and drying at 65 ℃ for 8 hours to obtain flame retardant modified graphene;
(4) And (2) mixing the following components in percentage by mass as 100:65:28:6.5:0.5:1:2.5 uniformly mixing ethylene-vinyl acetate copolymer, polyetherimide, rubber elastomer ethylene propylene diene monomer, flame retardant modified graphene, anti-aging agent N, N' -di (beta-naphthyl) p-phenylenediamine, antioxidant 1010 and lubricant polyethylene wax, melting and blending for 10min at 190 ℃, and extruding to obtain the freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material.
Example 8
A preparation method of a freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material comprises the following steps:
(1) Mixing the components in a mass ratio of 6000: uniformly mixing 10 parts of thionyl chloride and graphene oxide, heating and refluxing at 80 ℃ for reaction for 32 hours, filtering after the reaction is finished, washing with tetrahydrofuran, and drying at 65 ℃ for 10 hours to obtain graphene oxychloride;
(2) Mixing materials with mass ratio of 3800:100:225:35, uniformly mixing dimethylacetamide, acylchlorinated graphene, lysine and pyridine, reacting for 5 hours at 30 ℃, filtering after the reaction is finished, washing with dimethylacetamide and deionized water, and vacuum drying for 15 hours at 55 ℃ to obtain lysine modified graphene;
(3) Mixing the components in a mass ratio of 5000:100:185:32:16:150 of N, N-dimethylformamide, lysine modified graphene, a bisaminophosphaphenanthrene derivative, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride, 1-hydroxybenzotriazole and triethylamine are uniformly mixed, reacted for 32 hours at 25 ℃, filtered after the reaction is finished, washed by dichloromethane and dried for 8 hours at 65 ℃ to obtain flame retardant modified graphene;
(4) And (2) mixing the following components in percentage by mass as 100:65:28:6.5:0.5:1:2.5 uniformly mixing ethylene-vinyl acetate copolymer, polyetherimide, rubber elastomer ethylene propylene rubber, flame retardant modified graphene, anti-aging agent N, N' -di (beta-naphthyl) p-phenylenediamine, antioxidant 1010 and lubricant polyethylene wax, melting and blending for 10min at 190 ℃, and extruding to obtain the freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material.
Example 9
A preparation method of a free-bending wear-resistant weather-resistant halogen-free low-smoke cable material comprises the following steps:
(1) Mixing the components in a mass ratio of 6000:10, uniformly mixing thionyl chloride and graphene oxide, heating and refluxing at 80 ℃ for reaction for 32 hours, filtering after the reaction is finished, washing with tetrahydrofuran, and drying at 65 ℃ for 10 hours to obtain graphene chloride acylate;
(2) And mixing materials in a mass ratio of 3800:100:225:35, uniformly mixing dimethylacetamide, acylchlorinated graphene, lysine and pyridine, reacting for 5 hours at 30 ℃, filtering after the reaction is finished, washing with dimethylacetamide and deionized water, and vacuum drying for 15 hours at 55 ℃ to obtain lysine modified graphene;
(3) Mixing the components in a mass ratio of 5000:100:185:32:16:150 parts of N, N-dimethylformamide, lysine modified graphene, a bisaminophosphaphenanthrene derivative, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride, 1-hydroxybenzotriazole and triethylamine are uniformly mixed, react for 32 hours at 25 ℃, are filtered after the reaction is finished, are washed by dichloromethane and are dried for 8 hours at 65 ℃ to obtain flame retardant modified graphene;
(4) And (2) mixing the following components in percentage by mass as 100:65:28:6.5:0.5:1:2.5 uniformly mixing ethylene-vinyl acetate copolymer, polyetherimide, rubber elastomer nitrile rubber, flame retardant modified graphene, anti-aging agent N, N' -di (beta-naphthyl) p-phenylenediamine, antioxidant 1010 and lubricant polyethylene wax, melting and blending for 10min at 190 ℃, and extruding to obtain the freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material.
Comparative example 1
A preparation method of a halogen-free low-smoke cable material comprises the following steps:
(1) Mixing the components in a mass ratio of 6000:10, uniformly mixing thionyl chloride and graphene oxide, heating and refluxing at 80 ℃ for reaction for 32 hours, filtering after the reaction is finished, washing with tetrahydrofuran, and drying at 65 ℃ for 10 hours to obtain graphene chloride acylate;
(2) Mixing materials with mass ratio of 3800:100:225:35, uniformly mixing dimethylacetamide, acylchlorinated graphene, lysine and pyridine, reacting for 5 hours at 30 ℃, filtering after the reaction is finished, washing with dimethylacetamide and deionized water, and vacuum drying for 15 hours at 55 ℃ to obtain lysine modified graphene;
(3) Mixing the components in a mass ratio of 100:65:28:6.5:0.5:1:2.5 mixing ethylene-vinyl acetate copolymer, polyetherimide, rubber elastomer ethylene propylene diene monomer, lysine modified graphene, antioxidant N, N' -di (beta-naphthyl) p-phenylenediamine, antioxidant 1010 and lubricant polyethylene wax uniformly, melting and blending for 10min at 190 ℃, and extruding to obtain the halogen-free low-smoke cable material.
Comparative example 2
A preparation method of a halogen-free low-smoke cable material comprises the following steps:
(1) Mixing the components in a mass ratio of 6000: uniformly mixing 10 parts of thionyl chloride and graphene oxide, heating and refluxing at 80 ℃ for reaction for 32 hours, filtering after the reaction is finished, washing with tetrahydrofuran, and drying at 65 ℃ for 10 hours to obtain graphene oxychloride;
(2) Mixing materials with mass ratio of 3800:100:225:35, uniformly mixing dimethylacetamide, acylchlorinated graphene, lysine and pyridine, reacting for 5 hours at 30 ℃, filtering after the reaction is finished, washing with dimethylacetamide and deionized water, and vacuum drying for 15 hours at 55 ℃ to obtain lysine modified graphene;
(3) Mixing the components in a mass ratio of 5000:100:185:32:16:150 of N, N-dimethylformamide, lysine modified graphene, a bisaminophosphaphenanthrene derivative, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride, 1-hydroxybenzotriazole and triethylamine are uniformly mixed, reacted for 32 hours at 25 ℃, filtered after the reaction is finished, washed by dichloromethane and dried for 8 hours at 65 ℃ to obtain flame retardant modified graphene;
(4) Mixing the components in a mass ratio of 100:65:6.5:0.5:1:2.5 mixing the ethylene-vinyl acetate copolymer, the polyetherimide, the flame retardant modified graphene, the anti-aging agent N, N' -di (beta-naphthyl) p-phenylenediamine, the antioxidant 1010 and the lubricant polyethylene wax uniformly, melting and blending for 10min at 190 ℃, and extruding to obtain the halogen-free low-smoke cable material.
Comparative example 3
A preparation method of a halogen-free low-smoke cable material comprises the following steps:
(1) Mixing the components in a mass ratio of 6000: uniformly mixing 10 parts of thionyl chloride and graphene oxide, heating and refluxing at 80 ℃ for reaction for 32 hours, filtering after the reaction is finished, washing with tetrahydrofuran, and drying at 65 ℃ for 10 hours to obtain graphene oxychloride;
(2) Mixing materials with mass ratio of 3800:100:225:35, uniformly mixing dimethylacetamide, acylchlorinated graphene, lysine and pyridine, reacting for 5 hours at 30 ℃, filtering after the reaction is finished, washing with dimethylacetamide and deionized water, and vacuum-drying for 15 hours at 55 ℃ to obtain lysine modified graphene;
(3) Mixing the components in a mass ratio of 5000:100:185:32:16:150 of N, N-dimethylformamide, lysine modified graphene, a bisaminophosphaphenanthrene derivative, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride, 1-hydroxybenzotriazole and triethylamine are uniformly mixed, reacted for 32 hours at 25 ℃, filtered after the reaction is finished, washed by dichloromethane and dried for 8 hours at 65 ℃ to obtain flame retardant modified graphene;
(4) And (2) mixing the following components in percentage by mass as 100:28:6.5:0.5:1:2.5 mixing ethylene-vinyl acetate copolymer, rubber elastomer ethylene propylene diene monomer, flame retardant modified graphene, antioxidant N, N' -di (beta-naphthyl) p-phenylenediamine, antioxidant 1010 and lubricant polyethylene wax uniformly, melting and blending for 10min at 190 ℃, and extruding to obtain the halogen-free low-smoke cable material.
Comparative example 4
A preparation method of a halogen-free low-smoke cable material comprises the following steps:
and (2) mixing the following components in percentage by mass as 100:65:28:2.2:4.3:0.5:1:2.5 mixing ethylene-vinyl acetate copolymer, polyetherimide, rubber elastomer ethylene propylene diene monomer, graphene oxide, bisamino phosphaphenanthrene derivative, anti-aging agent N, N' -di (beta-naphthyl) p-phenylenediamine, antioxidant 1010 and lubricant polyethylene wax uniformly, melting and blending for 10min at 190 ℃, and extruding to obtain the halogen-free low-smoke cable material.
The graphene oxide used in the examples and comparative examples of the present invention was obtained from Hangzhou Zhi titanium purification technology Co., ltd, and was a single layer graphene oxide having an average thickness of 0.5 to 1.2nm and a diameter of 4 to 7 μm; ethylene-vinyl acetate copolymer available from Mitsui chemical corporation as EVA260 having a vinyl acetate mass content of 32% and a density of 0.957g/cm 3 The melt index is 43g/10min under the test condition of 190 ℃/2.16 kg; polyetherimide was purchased from QIADIELI Plastic materials Co., ltd, manufactured by Dongguan city; the ethylene propylene diene monomer is purchased from Shanghai petrochemical three-well chemical company Limited, and has the model of EPDM 3092PM-1; ethylene propylene rubber was purchased from shanghai fuyou international trade ltd; nitrile rubber was purchased from Guangdong Yuebeautification industries, inc.; dimethylacetamide available from Jinxin Shunji chemical Co., ltd, model number XS230; lysine was purchased from Henan Collection of beauty products, inc.; the polyethylene wax is purchased from Reid chemical technology Co., ltd. Of Fujian province; other reagents of the invention are commercially available.
The halogen-free low-smoke cable materials prepared in the examples 1 to 5 and the comparative examples 1 to 4 are selected as samples and respectively marked as samples 1 to 9, and corresponding tests are carried out on the samples.
(1) And (3) testing the bending strength: processing samples 1-9 into strip samples of 80mm × 10mm × 4mm, testing the bending strength performance by referring to GB/T9341-2008, testing the bending strength on a XHW-S2000N electronic digital display tension tester, wherein the testing speed is 2mm/min, the span is 64mm, each sample is tested for 5 times, the average value is calculated, and the test results are shown in Table 1:
TABLE 1 flexural Property test
According to the test results in table 1, it can be seen that the wear-resistant weather-resistant halogen-free low-smoke cable materials corresponding to samples 1-5 have excellent bending strength, the bending strength of sample 5 is as high as 103.1MPa, the added graphene oxide has excellent mechanical properties, the flexibility of the matrix can be further improved by the flexible long chain in the introduced lysine, and the matrix has stronger capability of free bending, the used ethylene-vinyl acetate copolymer has certain polarity, the carbonyl group with stronger polarity and the hydroxyl group can form intramolecular and intermolecular hydrogen bonds, the carbonyl group and the hydroxyl group on the ethylene-vinyl acetate copolymer can form hydrogen bonds with amino groups on the materials such as flame retardant modified graphene, polyetherimide and the like, so as to form a multi-dimensional interpenetrating network structure, the materials have stronger acting force, the mechanical properties and the compatibility are better, the added polyetherimide has good flexibility, the rubber elastomer also has good toughness, the lysine modified graphene in sample 6 is used for replacing the flame retardant modified graphene to be added into the mixed material, the prepared cable material has stronger bending strength, can reach 103.9MPa, the added polyetherimide in the cable elastomer has a larger influence on the bending property of the sample, the bending property of the cable is obviously reduced, the polyether imide added, the sample, the polyether imide modified graphene oxide is easily reduced, and the bending property of the sample is obviously;
(2) And (3) testing the wear resistance: processing samples 1-9 into strip samples of 80mm × 10mm × 4mm, carrying out abrasion loss test on the strip samples, wherein the test standard of the abrasion loss refers to GB/T5478-2008, in the test process, weights on two sides are 1000g and 5000 circles respectively, the rotating speed is 60rpm/min, the length of each round piece is 100mm, the abrasion loss test is carried out on a Leibote LBT-5612 plastic taber linear abrasion resistance tester, each sample is tested for 5 times, the average value is calculated, and the test results are shown in Table 2:
TABLE 2 abrasion resistance test
According to the test results in table 2, it can be seen that the halogen-free low-smoke cable materials corresponding to samples 1-9 all have excellent wear resistance, wherein no rubber elastomer is added to sample 7, the abrasion loss of the corresponding cable material is reduced to 278.1mg, graphene oxide has excellent wear resistance, the abrasion loss is reduced along with the increase of the content of the added graphene oxide in samples 1-5, wherein the abrasion loss of the cable material corresponding to sample 5 is 282.0mg, and the graphene oxide in sample 9 is not modified, and is easy to agglomerate when added to a matrix, so that the dispersion is not uniform, and the abrasion resistance is greatly influenced;
(3) And (3) testing the flame retardant property: the flame retardant performance is tested on samples 1-9 by referring to GB/T2406.2-2009 oxygen index method-plastic combustion performance experimental method, each sample is tested for 5 times, the average value is calculated, and the test result is shown in Table 3:
TABLE 3 flame retardancy Property test
According to the test results in table 3, the wear-resistant weather-resistant halogen-free low-smoke cable materials corresponding to the samples 1-5 have excellent flame retardant performance, the limited oxygen index of the cable material corresponding to the sample 5 can reach 29.8%, the cable material has excellent flame retardant performance, the graphene oxide can promote a substrate to form a compact carbon layer in the combustion process, the heat can be effectively prevented from entering the substrate, the barrier effect is very strong, the escape of small molecules is inhibited, the flame retardant performance of the substrate is effectively improved, the graphene oxide is effectively prevented from agglomerating after being modified, the graphene oxide can be uniformly dispersed in the substrate, the compatibility is improved, a large amount of non-combustible gas can be generated in the combustion process of the substrate by the amino groups on the introduced lysine and the amino groups on the polyetherimide, and the concentration of oxygen in the combustion system is effectively diluted, the flame retardant effect is effectively improved, the introduced bisaminophosphaphenanthrene derivative can generate acidic substances such as phosphoric acid and phosphorous acid in the process of matrix combustion by a phosphacycle, the matrix carbonization is promoted, the combustion reaction is prevented from proceeding, PO & free radicals generated in the combustion process can capture OH & H & free radicals in flame, the combustion chain reaction is interrupted, the heat released by combustion is reduced, a nitrogen and phosphorus flame retardant has synergistic effect, a more compact impermeable carbon layer can be generated on the surface of the matrix during heated combustion, the heat conduction is prevented, meanwhile, no smoke is generated in the combustion process, the flame retardant property of the cable material is further improved, the lysine modified graphene is used for replacing the flame retardant modified graphene in the sample 6 to be added into a mixed material, the flame retardant property of the prepared cable material is greatly reduced, and the cable material is easy to combust, the ethylene propylene diene monomer elastomer is not added in the sample 7, the limit oxygen index of the corresponding cable material can reach 30.1%, the graphene oxide in the sample 9 is not modified, and the graphene oxide and the bisamino phosphaphenanthrene derivative are added into a matrix together as an additive, so that the prepared cable material has general flame retardant property, and the limit oxygen index is 27.5%.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A preparation method of a wear-resistant weather-resistant halogen-free low-smoke cable material capable of being freely bent is characterized by comprising the following steps: the method comprises the following steps:
(1) Modifying graphene oxide by using thionyl chloride to obtain acylchlorinated graphene;
(2) Uniformly mixing dimethylacetamide, acylchlorinated graphene, lysine and pyridine, reacting, filtering after the reaction is finished, washing, and drying to obtain lysine modified graphene;
(3) Uniformly mixing an organic solvent, lysine modified graphene, a bisaminophosphaphenanthrene derivative, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride, 1-hydroxybenzotriazole and triethylamine, reacting, filtering, washing and drying after the reaction is finished to obtain flame retardant modified graphene;
(4) Uniformly mixing ethylene-vinyl acetate copolymer, polyetherimide, rubber elastomer, flame retardant modified graphene, an anti-aging agent, an antioxidant and a lubricant, melting, blending and extruding to obtain the freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material.
2. The preparation method of the freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material according to claim 1, characterized by comprising the following steps: the mass ratio of the dimethylacetamide, the acylchlorinated graphene, the lysine and the pyridine in the step (2) is (2400-4200): 100: (140-240): (20-40), the reaction temperature is 20-35 ℃, and the reaction time is 2-6h.
3. The preparation method of the freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material as claimed in claim 1, is characterized in that: in the step (3), the mass ratio of the organic solvent, the lysine modified graphene, the bisaminophosphaphenanthrene derivative, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, the 1-hydroxybenzotriazole and the triethylamine is (3000-5500): 100: (120-200): (20-35): (10-18): (85-160), the reaction temperature is 15-30 ℃, and the reaction time is 24-36h.
4. The preparation method of the freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material according to claim 1, characterized by comprising the following steps: the organic solvent in the step (3) comprises any one of N, N-dimethylformamide, dichloromethane and tetrahydrofuran.
5. The preparation method of the freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material as claimed in claim 1, is characterized in that: in the step (4), the mass ratio of the ethylene-vinyl acetate copolymer, the polyetherimide, the rubber elastomer, the flame retardant modified graphene, the anti-aging agent, the antioxidant and the lubricant is 100: (35-75): (18-30): (3-8): (0.1-0.6): (0.3-1.2): (1-3).
6. The preparation method of the freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material as claimed in claim 1, is characterized in that: the rubber elastomer in the step (4) comprises one of ethylene propylene diene monomer, ethylene propylene diene monomer and nitrile rubber.
7. The preparation method of the freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material as claimed in claim 1, is characterized in that: the temperature of melt blending in the step (4) is 180-195 ℃, and the time of melt blending is 8-12min.
8. The preparation method of the freely bendable wear-resistant weather-resistant halogen-free low-smoke cable material as claimed in claim 1, is characterized in that: in the step (4), the anti-aging agent is N, N' -di (beta-naphthyl) p-phenylenediamine, the antioxidant is antioxidant 1010, and the lubricant is polyethylene wax.
9. The halogen-free low-smoke cable material with the wear resistance and the weather resistance, which is prepared by the preparation method of the halogen-free low-smoke cable material with the wear resistance and the weather resistance, which can be freely bent, of any one of claims 1 to 8.
10. Use of the freely bendable, abrasion resistant, weather resistant, halogen free low smoke cable material of claim 9 in a robot.
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