Wear-resistant oil-resistant flame-retardant drag chain cable and production method thereof

Abstract

The invention discloses a wear-resistant oil-resistant flame-retardant drag chain cable and a production method thereof, and relates to the technical field of cables. A wear-resistant oil-resistant flame-retardant drag chain cable is characterized by comprising the following structures: a conductor layer, an insulating layer and a protective sleeve layer, the insulating layer coats the outer surface of the conductor layer; the outer surface of the insulating layer is coated with the protective sleeve layer; the protective sleeve layer comprises modified polypropylene, modified silicon dioxide, a cross-linking agent, a plasticizer and nitrile rubber. The modified polypropylene is obtained by grafting allylphosphoric acid on polypropylene, then carrying out nitrobenzyl alcohol reaction, then carrying out reduction and then carrying out reaction with ethyl malonate; the modified silicon dioxide is obtained by reacting silicon dioxide containing chloropropyl on the surface with 3-cyanopyridine and reacting with dicyandiamide; the wear-resistant, oil-resistant and flame-retardant drag chain cable produced by the invention has good flame-retardant, antibacterial, anti-aging and oil-resistant properties.

Description

Technical Field

[0001] The present invention relates to the technical field of cables, in particular to a wear-resistant, oil-resistant and flame-retardant drag chain cable and a production method thereof. Background Art

[0002] Wear-resistant, oil-resistant and flame-retardant drag chain cables are widely used in industrial automation equipment, robots, CNC machine tools, warehousing systems and heavy machinery, which require frequent movement and complex environments. The core demand comes from the fact that cables in dynamic mechanical systems must withstand the harsh working conditions of repeated bending, mechanical friction, oil erosion and chemical corrosion.

[0003] The typical structure of this type of cable consists of multiple strands of ultra-fine, finely twisted oxygen-free copper wire, a shielding layer, and a wear-resistant sheath. The choice of sheath material is particularly critical. While traditional polypropylene offers certain flexibility and cost advantages, its oil resistance is poor. This makes the cable susceptible to wear, oil penetration, and fire in harsh operating conditions, which in turn affects the cable's service life and safety. Therefore, to overcome these shortcomings of polypropylene, it is particularly important to improve the cable's protective sheath material to impart wear resistance, oil resistance, and flame retardancy to adapt to the various complex working conditions in industrial environments and meet the high performance requirements of equipment.

[0004] At the same time, due to the complex factors that may exist in industrial environments, such as ultraviolet radiation, ozone, high temperature and high humidity, cables also need to have anti-aging properties. Long-term exposure to these harsh conditions can easily cause problems such as material aging and performance degradation in ordinary cables. However, wear-resistant, oil-resistant and flame-retardant drag chain cables with anti-aging properties can effectively slow the rate of material aging, maintain the stability and reliability of the cables, extend their service life, and reduce replacement costs and maintenance frequency.

[0005] Furthermore, in places with strict hygiene requirements, such as food processing and pharmaceutical industries, bacteria can easily grow on cable surfaces, leading to microbial contamination. Therefore, cables must also possess antibacterial properties to prevent bacterial growth and reproduction on the cable surface, ensuring product quality and the sanitation and safety of the production environment. These properties must comply with relevant industry standards and regulations, providing comprehensive protection for industrial production. Summary of the Invention

[0006] The purpose of the present invention is to overcome the deficiencies in the prior art and provide a wear-resistant, oil-resistant and flame-retardant drag chain cable and a production method thereof.

[0007] In order to solve the above technical problems, the present invention provides the following technical solutions: comprising:

[0008] A wear-resistant, oil-resistant and flame-retardant drag chain cable, comprising the following structures: a conductor layer, an insulation layer, and a protective sheath layer;

[0009] The insulating layer is coated on the outer surface of the conductor layer; the protective sleeve layer is coated on the outer surface of the insulating layer;

[0010] The protective cover layer is obtained by mixing modified polypropylene, modified silicon dioxide, a crosslinking agent, a plasticizer and nitrile rubber.

[0011] The preparation of the protective cover layer comprises the following steps:

[0012] (1) Grafting allylphosphonic acid onto pre-irradiated polypropylene to obtain pretreated polypropylene;

[0013] (2) reacting pretreated polypropylene with p-nitrobenzyl alcohol to obtain phosphate polypropylene; and reducing the phosphate polypropylene to obtain pre-modified polypropylene;

[0014] (3) reacting pre-modified polypropylene with ethyl acrylate to obtain modified polypropylene;

[0015] (4) reacting silica, chloropropyltrimethoxysilane, and n-decyltrimethoxysilane to obtain chloropropyl silica; reacting chloropropyl silica and 3-cyanopyridine to obtain pre-modified silica; reacting pre-modified silica and dicyandiamide to obtain modified silica;

[0016] (5) reacting p-hydroxybenzaldehyde and 1,2-bis(2-chloroethoxy)ethane to obtain a crosslinking agent;

[0017] (6) The following components: modified polypropylene, modified silica, crosslinking agent, plasticizer, and nitrile rubber are mixed and then transferred to a twin-screw extruder for extrusion and granulation to obtain a protective sleeve layer.

[0018] Preferably, the production method of the pretreated polypropylene in step (1) is: pre-irradiated polypropylene, an initiator, an emulsifier, and a dispersant are mixed, allylphosphonic acid and pure water are added in sequence, the temperature is raised to 70-80°C, and the reaction is carried out for 8-10 hours to obtain pretreated polypropylene; the mass ratio of pre-irradiated polypropylene, initiator, emulsifier, dispersant, allylphosphonic acid, and pure water is 1:(0.001-0.002):(0.003-0.005):(0.008-0.01):(0.5-1.0):(5-7).

[0019] Preferably, the preparation method of the pre-irradiated polypropylene is: polypropylene is spread flat on a circulating material vehicle with a spreading thickness of 0.6 cm, the material vehicle speed is 5 m / min, and pre-irradiated polypropylene is obtained by irradiation with an irradiation source; the irradiation source for pre-irradiation is a medium-energy electron accelerator with an acceleration voltage of 3 MeV, 120 kW, a scanning width of 1.2 m, a beam length of 7.5 cm, and a pre-irradiation dose of 10 kGy.

[0020] Preferably, the production method of the pre-modified polypropylene is as follows: the pretreated polypropylene is swelled in 1,2-dichlorobenzene at 110-120°C for 1-2 hours, p-nitrobenzyl alcohol and 4-dimethylaminopyridine are added, and the reaction is carried out at 100-110°C for 5-6 hours under nitrogen protection to obtain phosphate polypropylene; under nitrogen protection, the phosphate polypropylene is swelled in solvent A at 110-120°C for 1-2 hours, the temperature is lowered to 80°C, sodium sulfide and solvent B are mixed and added, and the reaction is carried out at 80°C for 8-10 hours to obtain pre-modified polypropylene.

[0021] Preferably, the mass ratio of the pretreated polypropylene, 1,2-dichlorobenzene, p-nitrobenzyl alcohol, and 4-dimethylaminopyridine is 1:(15-20):(1-1.2):(0.02-0.03); the mass ratio of the phosphate polypropylene, solvent A, solvent B, and sodium sulfide is 1:(15-20):(10-15):(2-3); the solvent A is obtained by mixing xylene, N-methylpyrrolidone, and dimethyl sulfoxide in a volume ratio of 5:3:2; the solvent B is obtained by mixing ethanol, N-methylpyrrolidone, and tetrabutylammonium bromide in a mass ratio of 4:1:0.2.

[0022] Preferably, the production method of the modified polypropylene in step (3) is: swelling the pre-modified polypropylene in toluene at 100-110° C. for 1-2 hours, adding ethyl acrylate, p-toluenesulfonic acid, acetic anhydride, sodium pyrosulfate, and 10 wt% palladium-carbon catalyst, and reflux reaction for 2-3 hours to obtain the modified polypropylene;

[0023] The mass ratio of pre-modified polypropylene, toluene, ethyl acrylate, p-toluenesulfonic acid, acetic anhydride, sodium pyrosulfate and 10wt% palladium carbon catalyst is 1:(20-30):(0.2-0.3):(0.3-0.4):(0.7-0.9):(1-1.2):(0.005-0.01).

[0024] Preferably, the production method of the modified silica in step (4) is: mixing silica, n-decyltrimethoxysilane, chloropropyltrimethoxysilane, anhydrous ethanol and pure water, adjusting the pH to 4.5-5.5 with hydrochloric acid, heating to 70-80°C and reacting for 7-8h to obtain chloropropyl silica;

[0025] Mix chloropropyl silica, 3-cyanopyridine, acetonitrile, and tetrabutylammonium bromide, heat to 75-85°C, and reflux for 4-6 hours to obtain pre-modified silica;

[0026] Mix pre-modified silica, dicyandiamide, potassium hydroxide and 2-methoxyethanol, heat to 115-125°C, and react for 1-2 hours to obtain modified silica.

[0027] Preferably, the mass ratio of the silicon dioxide, n-decyltrimethoxysilane, chloropropyltrimethoxysilane, anhydrous ethanol and pure water is 1:(0.5-0.7):(0.5-0.7):(10-12):(10-12);

[0028] The mass ratio of the chloropropyl silica, 3-cyanopyridine, acetonitrile and tetrabutylammonium bromide is 1:(0.7-1.0):(20-30):(0.01-0.05);

[0029] The mass ratio of the pre-modified silica, dicyandiamide, potassium hydroxide and 2-methoxyethanol is 1:(0.5-0.7):(1-1.2):(20-30).

[0030] Preferably, the production method of the cross-linking agent in step (5) is: mixing p-hydroxybenzaldehyde, potassium carbonate, and N,N-dimethylformamide, adding 1,2-bis(2-chloroethoxy)ethane-N,N-dimethylformamide solution, heating to 85-90°C and reacting for 6-8h to obtain the cross-linking agent;

[0031] Preferably, the molar ratio of 1,2-bis(2-chloroethoxy)ethane, p-hydroxybenzaldehyde, and potassium carbonate is 1:(2.2-2.4):(4-5); the mass of N,N-dimethylformamide is 10-12 times that of p-hydroxybenzaldehyde; 1,2-bis(2-chloroethoxy)ethane and N,N-dimethylformamide are obtained by mixing 1,2-bis(2-chloroethoxy)ethane and N,N-dimethylformamide in a mass ratio of 1:(5-6).

[0032] Preferably, the amounts of the components in step (6) are: 100 parts by mass of modified polypropylene, 5-7 parts by mass of modified silicon dioxide, 2-3 parts by mass of crosslinking agent, 5-8 parts by mass of plasticizer, and 10-12 parts by mass of nitrile rubber.

[0033] The present invention also provides a production method for a wear-resistant, oil-resistant and flame-retardant drag chain cable according to any one of the above items, the production method comprising the following steps: coating the conductor layer with an insulating layer, mixing modified polypropylene, modified silica, a cross-linking agent, a plasticizer and nitrile rubber, melt-extruding and granulating in a twin-screw extruder to obtain a protective sheath, and melt-extruded the protective sheath on the insulating layer coated with the conductor layer to obtain a wear-resistant, oil-resistant and flame-retardant drag chain cable.

[0034] Beneficial effects of the present invention:

[0035] The wear-resistant, oil-resistant and flame-retardant drag chain cable produced by the present invention comprises a conductor layer, an insulating layer and a protective sheath layer; the protective sheath layer comprises modified polypropylene, modified silicon dioxide, a crosslinking agent, a plasticizer and nitrile rubber;

[0036] First, vinyl phosphoric acid is grafted onto polypropylene via a suspension grafting method in the presence of an initiator. Then, a flame-retardant phosphate structure is generated through an ester exchange reaction between phosphoric acid and nitrobenzyl alcohol. The nitrobenzene structure is then reduced to an aminophenyl structure under the reducing action of sodium sulfide. The aminophenyl group then undergoes condensation and cyclization with malonic acid to form a quinolinone structure with antioxidant properties, giving the material excellent antioxidant properties.

[0037] Secondly, silica containing chloropropyl groups on its surface reacts with 3-cyanopyridine to produce a quaternary ammonium salt of pyridine with antibacterial properties. The cyano group on 3-cyanopyridine reacts with dicyandiamide to form a diaminotriazine structure. The triazine structure acts as a good carbon-forming agent and can synergistically flame retardant with the phosphate structure, further improving the flame retardancy of the material.

[0038] Finally, hydroxybenzaldehyde and 1,2-bis(2-chloroethoxy)ethane are reacted to form a linear crown ether structure with a benzaldehyde end group. This linear crown ether structure can increase the polarity of polypropylene and enhance its oil resistance. Modified polypropylene, modified silica, and a crosslinking agent are mixed to form a protective sheath material. The aldehyde structures at both ends of the crosslinking agent can react with the remaining aminophenyl groups on the modified polypropylene and the amino groups on the modified silica to form a Schiff base structure, thereby enhancing the crosslinking density. This further improves oil resistance, and the formation of Schiff base covalent bonds can also enhance the compatibility of the crown ether with the polypropylene matrix.

[0039] The presence of silica can act as a wear-resistant filler to enhance the wear resistance of polypropylene and give polypropylene good oil resistance through physical barrier effect. DETAILED DESCRIPTION

[0040] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with the embodiments of the specification.

[0041] The polypropylene described in the following examples and comparative examples is model T30s, purchased from Daqing Petrochemical Co., Ltd.; the silica particle size is 200 nm; the conductor layer is a copper core, and the insulating layer is a polyvinyl chloride insulating layer, model HF-90; the nitrile rubber model is Japanese JSR nitrile rubber N240S; and the remaining raw materials, unless otherwise specified, are all commonly available in the market.

[0042] Example 1:

[0043] A method for producing a wear-resistant, oil-resistant, and flame-retardant drag chain cable comprises: coating a conductor layer with an insulating layer; and melt-extruding a protective sheath on the insulating layer coated with the conductor layer. A twin-screw extruder is used during extrusion at a temperature of 180° C. to obtain a wear-resistant, oil-resistant, and flame-retardant drag chain cable. The protective sheath is prepared as follows:

[0044] (1) Pre-irradiated polypropylene, initiator benzoyl peroxide, emulsifier sodium dodecylbenzene sulfonate, and dispersant calcium hydroxyphosphate were mixed, allylphosphonic acid and pure water were added in sequence, the temperature was raised to 80°C, and the reaction was continued for 10 hours. The mixture was extracted with tetrahydrofuran for 48 hours, washed with pure water, and dried to obtain pretreated polypropylene;

[0045] The preparation method of pre-irradiated polypropylene comprises: laying polypropylene on a circulating material cart with a thickness of 0.6 cm, the material cart speed is 5 m / min, and irradiating the polypropylene with an irradiation source to obtain the pre-irradiated polypropylene; the irradiation source is a medium energy electron accelerator with an acceleration voltage of 3 MeV, 120 kW, a scan width of 1.2 m, a beam length of 7.5 cm, and a pre-irradiation dose of 10 kGy;

[0046] The mass ratio of pre-irradiated polypropylene, initiator, emulsifier, dispersant, allylphosphonic acid and pure water is 1:0.001:0.003:0.008:0.5:5;

[0048] (2) The pretreated polypropylene was swelled in 1,2-dichlorobenzene at 120°C for 2 h, p-nitrobenzyl alcohol and 4-dimethylaminopyridine were added, and the mixture was reacted at 110°C for 6 h under nitrogen protection. After the reaction, the mixture was precipitated with methanol at 5°C, filtered with saturated sodium bicarbonate, washed with ethanol, and dried to obtain phosphate polypropylene;

[0049] The mass ratio of pretreated polypropylene, 1,2-dichlorobenzene, p-nitrobenzyl alcohol, and 4-dimethylaminopyridine is 1:15:1:0.02;

[0050] Under nitrogen protection, phosphate polypropylene was swelled in solvent A at 120°C for 2 hours, cooled to 80°C, sodium sulfide and solvent B were mixed and added, and reacted at 80°C for 10 hours. The product was precipitated with pure water, washed with 0.1M dilute hydrochloric acid, saturated sodium bicarbonate, and dried with ethanol to obtain pre-modified polypropylene.

[0051] The mass ratio of phosphate polypropylene, solvent A, solvent B, and sodium sulfide is 1:15:10:2;

[0052] Solvent A is prepared by mixing xylene, N-methylpyrrolidone, and dimethyl sulfoxide in a volume ratio of 5:3:2; Solvent B is prepared by mixing ethanol, N-methylpyrrolidone, and tetrabutylammonium bromide in a mass ratio of 4:1:0.2;

[0053] (3) The pre-modified polypropylene was swelled in toluene at 110°C for 2 h, and ethyl acrylate, p-toluenesulfonic acid, acetic anhydride, sodium pyrosulfate, and 10 wt% palladium carbon catalyst were added. The mixture was refluxed for 3 h, and the catalyst was removed by filtration. The modified polypropylene was precipitated with methanol at 5°C, filtered, washed, and dried to obtain the modified polypropylene.

[0054] The mass ratio of pre-modified polypropylene, toluene, ethyl acrylate, p-toluenesulfonic acid, acetic anhydride, sodium pyrosulfate, and 10 wt% palladium-carbon catalyst is 1:20:0.2:0.3:0.7:1:0.005;

[0055] (4) Silica, n-decyltrimethoxysilane, chloropropyltrimethoxysilane, anhydrous ethanol, and pure water were mixed in a mass ratio of 1:0.5:0.5:10:10, the pH was adjusted to 5.5 with hydrochloric acid, the temperature was raised to 80°C, the reaction was carried out for 8 hours, and the chloropropyl silica was obtained by filtering, washing, and drying;

[0056] Chloropropyl silica, 3-cyanopyridine, acetonitrile, and tetrabutylammonium bromide were mixed in a mass ratio of 1:0.7:20:0.01, heated to 85°C and refluxed for 6 hours, and filtered, washed, and dried to obtain pre-modified silica;

[0057] Pre-modified silica, dicyandiamide, potassium hydroxide, and 2-methoxyethanol were mixed in a mass ratio of 1:0.5:1:20, heated to 125°C, reacted for 2 hours, and filtered, washed, and dried to obtain modified silica;

[0058] (5) p-Hydroxybenzaldehyde, potassium carbonate, and N,N-dimethylformamide were mixed, and 1,2-bis(2-chloroethoxy)ethane-N,N-dimethylformamide solution was added dropwise at a rate of 0.4 mL / min. The mixture was heated to 90°C and reacted for 8 h. The mixture was subjected to vacuum rotary evaporation, washed with pure water, decolorized with ethanol and activated carbon, and recrystallized to obtain a crosslinking agent.

[0059] The molar ratio of 1,2-bis(2-chloroethoxy)ethane, p-hydroxybenzaldehyde, and potassium carbonate is 1:2.2:4; the mass of N,N-dimethylformamide is 10 times that of p-hydroxybenzaldehyde; 1,2-bis(2-chloroethoxy)ethane and N,N-dimethylformamide are obtained by mixing 1,2-bis(2-chloroethoxy)ethane and N,N-dimethylformamide in a mass ratio of 1:5;

[0060] (6) The following components, calculated by mass, are added into an internal mixer: 100 parts of modified polypropylene, 5 parts of modified silica, 2 parts of a crosslinking agent, 5 parts of a plasticizer, paraffin oil, and 10 parts of a nitrile rubber, and mixed evenly. The mixture is then transferred to a twin-screw extruder to extrude a protective sleeve. The screw speed of the twin-screw extruder is 160 r / min and the temperature is 180°C.

[0061] Example 2:

[0062] A method for producing a wear-resistant, oil-resistant, and flame-retardant drag chain cable comprises: coating a conductor layer with an insulating layer; and melt-extruding a protective sheath on the insulating layer coated with the conductor layer. A twin-screw extruder is used during extrusion at a temperature of 180° C. to obtain a wear-resistant, oil-resistant, and flame-retardant drag chain cable. The protective sheath is prepared as follows:

[0063] (1) Pre-irradiated polypropylene, initiator benzoyl peroxide, emulsifier sodium dodecylbenzene sulfonate, and dispersant calcium hydroxyphosphate were mixed, allylphosphonic acid and pure water were added in sequence, the temperature was raised to 75°C, and the reaction was continued for 9 hours. The mixture was extracted with tetrahydrofuran for 48 hours, washed with pure water, and dried to obtain pretreated polypropylene;

[0064] The preparation method of pre-irradiated polypropylene comprises: laying polypropylene on a circulating material cart with a thickness of 0.6 cm, the material cart speed is 5 m / min, and irradiating the polypropylene with an irradiation source to obtain the pre-irradiated polypropylene; the irradiation source is a medium energy electron accelerator with an acceleration voltage of 3 MeV, 120 kW, a scan width of 1.2 m, a beam length of 7.5 cm, and a pre-irradiation dose of 10 kGy;

[0065] The mass ratio of pre-irradiated polypropylene, initiator, emulsifier, dispersant, allylphosphonic acid and pure water is 1:0.001:0.004:0.009:0.7:6;

[0067] (2) The pretreated polypropylene was swelled in 1,2-dichlorobenzene at 115°C for 1.5 h, p-nitrobenzyl alcohol and 4-dimethylaminopyridine were added, and the mixture was reacted at 105°C for 5.5 h under nitrogen protection. After the reaction, the mixture was precipitated with methanol at 4°C, filtered with saturated sodium bicarbonate, washed with ethanol, and dried to obtain phosphate polypropylene;

[0068] The mass ratio of pretreated polypropylene, 1,2-dichlorobenzene, p-nitrobenzyl alcohol, and 4-dimethylaminopyridine is 1:17:1.1:0.025;

[0069] Under nitrogen protection, phosphate polypropylene was swelled in solvent A at 115°C for 1.5 hours, cooled to 80°C, sodium sulfide and solvent B were mixed and added, and reacted at 80°C for 9 hours. The product was precipitated with pure water, washed with 0.1M dilute hydrochloric acid, saturated sodium bicarbonate, and dried with ethanol to obtain pre-modified polypropylene.

[0070] The mass ratio of phosphate polypropylene, solvent A, solvent B, and sodium sulfide is 1:17:13:2.5;

[0071] Solvent A is prepared by mixing xylene, N-methylpyrrolidone, and dimethyl sulfoxide in a volume ratio of 5:3:2; Solvent B is prepared by mixing ethanol, N-methylpyrrolidone, and tetrabutylammonium bromide in a mass ratio of 4:1:0.2;

[0072] (3) The pre-modified polypropylene was swelled in toluene at 105°C for 1.5 h, and ethyl acrylate, p-toluenesulfonic acid, acetic anhydride, sodium pyrosulfate, and 10 wt% palladium carbon catalyst were added. The mixture was refluxed for 2.5 h, and the catalyst was removed by filtration. The modified polypropylene was precipitated with methanol at 3°C, filtered, washed, and dried to obtain the modified polypropylene.

[0073] The mass ratio of pre-modified polypropylene, toluene, ethyl acrylate, p-toluenesulfonic acid, acetic anhydride, sodium pyrosulfate, and 10wt% palladium carbon catalyst is 1:25:0.25:0.35:0.8:1.1:0.007;

[0075] (4) Silica, n-decyltrimethoxysilane, chloropropyltrimethoxysilane, anhydrous ethanol, and pure water were mixed in a mass ratio of 1:0.6:0.6:11:11, the pH was adjusted to 5 with hydrochloric acid, the temperature was raised to 75°C, the reaction was continued for 7.5 hours, and the chloropropyl silica was obtained by filtering, washing, and drying.

[0076] Chloropropyl silica, 3-cyanopyridine, acetonitrile, and tetrabutylammonium bromide were mixed in a mass ratio of 1:0.9:25:0.03, heated to 80°C and refluxed for 5 hours, and filtered, washed, and dried to obtain pre-modified silica;

[0077] Pre-modified silica, dicyandiamide, potassium hydroxide, and 2-methoxyethanol were mixed in a mass ratio of 1:0.6:1.1:25, heated to 120°C, reacted for 1.5 hours, and filtered, washed, and dried to obtain modified silica;

[0078] (5) p-Hydroxybenzaldehyde, potassium carbonate, and N,N-dimethylformamide were mixed, and 1,2-bis(2-chloroethoxy)ethane-N,N-dimethylformamide solution was added dropwise at a rate of 0.4 mL / min. The mixture was heated to 87°C and reacted for 7 h. The mixture was evaporated under reduced pressure, washed with pure water, decolorized with ethanol and activated carbon, and recrystallized to obtain a crosslinking agent.

[0079] The molar ratio of 1,2-bis(2-chloroethoxy)ethane, p-hydroxybenzaldehyde, and potassium carbonate is 1:2.3:4.5; the mass of N,N-dimethylformamide is 11 times that of p-hydroxybenzaldehyde; 1,2-bis(2-chloroethoxy)ethane and N,N-dimethylformamide are obtained by mixing 1,2-bis(2-chloroethoxy)ethane and N,N-dimethylformamide in a mass ratio of 1:5.5;

[0080] (6) The following components, calculated by mass, are added into an internal mixer: 100 parts of modified polypropylene, 6 parts of modified silica, 2.5 parts of a crosslinking agent, 6 parts of a plasticizer, paraffin oil, and 11 parts of a nitrile rubber, and mixed evenly. The mixture is then transferred to a twin-screw extruder and extruded to obtain a protective sleeve layer. The screw speed of the twin-screw extruder is 160 r / min and the temperature is 175°C.

[0081] Example 3:

[0082] A method for producing a wear-resistant, oil-resistant, and flame-retardant drag chain cable comprises: coating a conductor layer with an insulating layer; and melt-extruding a protective sheath on the insulating layer coated with the conductor layer. A twin-screw extruder is used during extrusion at a temperature of 180° C. to obtain a wear-resistant, oil-resistant, and flame-retardant drag chain cable. The protective sheath is prepared as follows:

[0083] (1) Pre-irradiated polypropylene, initiator benzoyl peroxide, emulsifier sodium dodecylbenzene sulfonate, and dispersant calcium hydroxyphosphate were mixed, allylphosphonic acid and pure water were added in sequence, the temperature was raised to 70°C, and the reaction was continued for 8 hours. The mixture was extracted with tetrahydrofuran for 48 hours, washed with pure water, and dried to obtain pretreated polypropylene;

[0084] The preparation method of pre-irradiated polypropylene comprises: laying polypropylene on a circulating material cart with a thickness of 0.6 cm, the material cart speed is 5 m / min, and irradiating the polypropylene with an irradiation source to obtain the pre-irradiated polypropylene; the irradiation source is a medium energy electron accelerator with an acceleration voltage of 3 MeV, 120 kW, a scan width of 1.2 m, a beam length of 7.5 cm, and a pre-irradiation dose of 10 kGy;

[0085] The mass ratio of pre-irradiated polypropylene, initiator, emulsifier, dispersant, allylphosphonic acid and pure water is 1:0.002:0.005:0.01:1.0:7;

[0087] (2) The pretreated polypropylene was swelled in 1,2-dichlorobenzene at 110°C for 1 hour, and p-nitrobenzyl alcohol and 4-dimethylaminopyridine were added. The mixture was reacted at 100°C for 5 hours under nitrogen protection. After the reaction, the mixture was precipitated with methanol at 0°C, filtered with saturated sodium bicarbonate, washed with ethanol, and dried to obtain phosphate polypropylene.

[0088] The mass ratio of pretreated polypropylene, 1,2-dichlorobenzene, p-nitrobenzyl alcohol, and 4-dimethylaminopyridine is 1:20:1.2:0.03;

[0089] Under nitrogen protection, phosphate polypropylene was swollen in solvent A at 110°C for 1 hour, cooled to 80°C, sodium sulfide and solvent B were mixed and added, and reacted at 80°C for 8 hours. The product was precipitated with pure water, washed with 0.1M dilute hydrochloric acid, saturated sodium bicarbonate, and dried with ethanol to obtain pre-modified polypropylene.

[0090] The mass ratio of phosphate polypropylene, solvent A, solvent B, and sodium sulfide is 1:15:10:2;

[0091] Solvent A is prepared by mixing xylene, N-methylpyrrolidone, and dimethyl sulfoxide in a volume ratio of 5:3:2; Solvent B is prepared by mixing ethanol, N-methylpyrrolidone, and tetrabutylammonium bromide in a mass ratio of 4:1:0.2;

[0092] (3) The pre-modified polypropylene was swelled in toluene at 100°C for 1 hour, and ethyl acrylate, p-toluenesulfonic acid, acetic anhydride, sodium pyrosulfate, and 10 wt% palladium carbon catalyst were added. The mixture was refluxed for 2 hours. After filtering to remove the catalyst, the modified polypropylene was precipitated with methanol at 0°C, filtered, washed, and dried to obtain the modified polypropylene.

[0093] The mass ratio of pre-modified polypropylene, toluene, ethyl acrylate, p-toluenesulfonic acid, acetic anhydride, sodium pyrosulfate, and 10wt% palladium carbon catalyst is 1:30:0.3:0.4:0.9:1.2:0.01;

[0095] (4) Silica, n-decyltrimethoxysilane, chloropropyltrimethoxysilane, anhydrous ethanol, and pure water were mixed in a mass ratio of 1:0.7:0.7:12:12, and the pH was adjusted to 4.5 with hydrochloric acid. The mixture was heated to 70°C and reacted for 7 hours. The mixture was filtered, washed, and dried to obtain chloropropyl silica.

[0096] Chloropropyl silica, 3-cyanopyridine, acetonitrile, and tetrabutylammonium bromide were mixed in a mass ratio of 1:1.0:30:0.05, heated to 75°C and refluxed for 4 hours, and filtered, washed, and dried to obtain pre-modified silica;

[0097] Pre-modified silica, dicyandiamide, potassium hydroxide, and 2-methoxyethanol were mixed in a mass ratio of 1:0.7:1.2:30, heated to 115°C, reacted for 1 hour, and filtered, washed, and dried to obtain modified silica;

[0098] (5) p-Hydroxybenzaldehyde, potassium carbonate, and N,N-dimethylformamide were mixed, and 1,2-bis(2-chloroethoxy)ethane-N,N-dimethylformamide solution was added dropwise at a rate of 0.4 mL / min. The mixture was heated to 85°C and reacted for 6 h. The mixture was subjected to vacuum rotary evaporation, washed with pure water, decolorized with ethanol and activated carbon, and recrystallized to obtain a crosslinking agent.

[0099] The molar ratio of 1,2-bis(2-chloroethoxy)ethane, p-hydroxybenzaldehyde, and potassium carbonate is 1:2.4:5; the mass of N,N-dimethylformamide is 12 times that of p-hydroxybenzaldehyde; 1,2-bis(2-chloroethoxy)ethane and N,N-dimethylformamide are obtained by mixing 1,2-bis(2-chloroethoxy)ethane and N,N-dimethylformamide in a mass ratio of 1:6;

[0100] (6) The following components, calculated by mass, are added into an internal mixer: 100 parts of modified polypropylene, 7 parts of modified silica, 3 parts of a crosslinking agent, 8 parts of a plasticizer, paraffin oil, and 12 parts of a nitrile rubber. The mixture is then transferred to a twin-screw extruder to extrude a protective sleeve. The screw speed of the twin-screw extruder is 160 r / min and the temperature is 180°C.

[0101] Comparative Example 1:

[0102] The wear-resistant, oil-resistant and flame-retardant drag chain cable of Comparative Example 1 differs from that of Example 2 in that the polypropylene is not modified, specifically, steps (1) to (3) are not included, and step (6) is modified as follows: the following components, calculated by mass, 100 parts of polypropylene, 6 parts of modified silica, 2.5 parts of a cross-linking agent, 6 parts of a plasticizer, paraffin oil, and 11 parts of a nitrile rubber are added to an internal mixer and mixed uniformly, and then transferred to a twin-screw extruder for extrusion to obtain a protective sheath; the screw speed of the twin-screw extruder is 160 r / min and the temperature is 175°C. The remaining steps are the same as those of Example 2.

[0103] Comparative Example 2:

[0104] The production method of the wear-resistant, oil-resistant and flame-retardant drag chain cable of Comparative Example 2 differs from that of Example 2 in that the silica is not modified. Specifically, step (4) is not included, and step (6) is modified as follows: the following components, calculated by mass, 100 parts of modified polypropylene, 6 parts of silica, 2.5 parts of a cross-linking agent, 6 parts of a plasticizer, paraffin oil, and 11 parts of a nitrile rubber are added to an internal mixer and mixed uniformly, and then transferred to a twin-screw extruder for extrusion to obtain a protective sheath; the screw speed of the twin-screw extruder is 160 r / min and the temperature is 175°C. The remaining steps are the same as those of Example 2.

[0105] Comparative Example 3:

[0106] The production method of the wear-resistant, oil-resistant and flame-retardant drag chain cable of Comparative Example 3 differs from that of Example 2 in that no crosslinking agent is added, specifically, step (5) is not included, and step (6) is modified as follows: the following components: 100 parts by mass of modified polypropylene, 6 parts of modified silica, 6 parts of plasticizer paraffin oil, and 11 parts of nitrile rubber are added to an internal mixer and mixed uniformly, and then transferred to a twin-screw extruder for extrusion to obtain a protective sheath; the screw speed of the twin-screw extruder is 160 r / min and the temperature is 175°C. The remaining steps are the same as those of Example 2.

[0107] The protective cover materials prepared in the examples and comparative examples were subjected to the following performance tests:

[0108] Test Example 1: Flame Retardancy Testing: The protective cover materials prepared in the Examples and Comparative Examples were pressed into sheets using a flat-plate vulcanizer at a pressure of 14.5 MPa, a temperature of 160°C, and a time of 10 minutes. The sheets were then tested for flame retardancy, with oxygen index measured according to standard GB / T 2406.2-2009. The specimens had a size of 80 mm * 10 mm * 4 mm. The results are shown in Table 1.

[0109] Table 1 Flame retardant performance test

[0110]

[0111] From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-3 in Table 1, it can be found that the material prepared by the present invention has good flame retardant properties.

[0112] The flame retardant properties of Examples 1-3 are better than those of the comparative example, indicating that, first, in the presence of an initiator, vinyl phosphoric acid is grafted onto polypropylene by a suspension grafting method, and then a phosphate structure with flame retardant properties is generated by an ester exchange reaction between phosphoric acid and nitrobenzyl alcohol; secondly, silica containing chloropropyl groups on the surface is reacted with 3-cyanopyridine, and the cyano group on 3-cyanopyridine reacts with dicyandiamide to generate a diaminotriazine structure. The triazine structure, as a good carbon-forming agent, can synergistically flame retard with the phosphate structure, further improving the flame retardant properties of the material.

[0113] Test Example 2, test of mechanical properties, the protective cover materials prepared in the examples and comparative examples were prepared into 1BA dumbbell-shaped specimens according to the standard GB / T1040-2006, with a specimen thickness of 2 mm, a narrow width of 5 mm, and a gauge length of 25 mm. The tensile strength of the material was then tested according to the standard at a tensile rate of 500 mm / min.

[0114] To test aging resistance, the protective cover materials prepared in the Examples and Comparative Examples were prepared into 1BA dumbbell-shaped specimens according to GB / T 1040-2006. The specimens had a thickness of 2 mm, a narrow width of 5 mm, and a gauge length of 25 mm. The specimens were then aged for 600 h at 60°C according to GB / T 2951.12-2008. The tensile strength after aging was measured according to the mechanical properties test method, and the tensile strength retention was calculated. The results are shown in Table 2.

[0115] Oil resistance testing was performed on the protective cover materials prepared in the Examples and Comparative Examples. The materials were subjected to an IRM903 fuel resistance test according to the GB / T1690-2010 standard. The tensile strength after the oil resistance test was measured according to the mechanical properties test method, and the tensile strength retention was calculated. The results are shown in Table 2.

[0116] Table 2 Tests of mechanical properties, anti-aging properties and oil resistance

[0117]

[0118] From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-3 in Table 2, it can be found that the material prepared by the present invention has good mechanical properties, anti-aging properties, and oil resistance.

[0119] The mechanical, aging-resistant and oil-resistant properties of Examples 1-3 are better than those of the comparative example, indicating that, first, in the presence of an initiator, vinyl phosphoric acid is grafted onto polypropylene by a suspension grafting method, and then a phosphate structure is generated by an ester exchange reaction between phosphoric acid and nitrobenzyl alcohol. Then, under the reducing action of sodium sulfide, the nitrobenzene structure is reduced to an aminophenyl structure, and the aminophenyl group and malonic acid are condensed and cyclized to generate a quinolinone structure with antioxidant properties, thereby giving the material good antioxidant properties; hydroxybenzaldehyde and 1,2-bis(2-chloroethoxy)ethane are reacted to generate a linear crown ether structure with a benzaldehyde end group, and the linear crown ether structure can increase the polarity of polypropylene and enhance its oil resistance; modified polypropylene, modified silica and a crosslinking agent are mixed to obtain a protective sheath material, and the aldehyde structures at both ends of the crosslinking agent can generate a Schiff base structure with the amino group to enhance the crosslinking density, thereby further improving the oil resistance.

[0120] Test Example 3: Antibacterial performance test: Antibacterial performance was tested according to QB / T 2591-2003A, and the test bacteria was Escherichia coli ATcc 25922. The results are shown in Table 3.

[0121] Table 3 Test of antibacterial performance

[0122]

[0123] From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-3 in Table 3, it can be found that the material prepared by the present invention has good antibacterial properties.

[0124] The antibacterial properties of Examples 1-3 are better than those of the comparative example, indicating that reacting silicon dioxide containing chloropropyl groups on its surface with 3-cyanopyridine to generate quaternary pyridine ammonium salt with antibacterial properties can impart certain antibacterial properties to the material.

[0125] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.

Claims

1. A wear-resistant, oil-resistant and flame-retardant drag chain cable, characterized in that: It includes the following structures: conductor layer, insulation layer, and protective sheath layer; The insulating layer is coated on the outer surface of the conductor layer; The protective sleeve layer is coated on the outer surface of the insulating layer; The protective cover layer is obtained by mixing modified polypropylene, modified silicon dioxide, a cross-linking agent, a plasticizer, and nitrile rubber; The preparation of the protective cover layer comprises the following steps: (1) Grafting allylphosphonic acid onto pre-irradiated polypropylene to obtain pretreated polypropylene; (2) reacting pretreated polypropylene with p-nitrobenzyl alcohol to obtain phosphate polypropylene; and reducing the phosphate polypropylene to obtain pre-modified polypropylene; (3) reacting pre-modified polypropylene with ethyl acrylate to obtain modified polypropylene; (4) reacting silica, chloropropyltrimethoxysilane, and n-decyltrimethoxysilane to obtain chloropropyl silica; reacting chloropropyl silica and 3-cyanopyridine to obtain pre-modified silica; reacting pre-modified silica and dicyandiamide to obtain modified silica; (5) reacting p-hydroxybenzaldehyde and 1,2-bis(2-chloroethoxy)ethane to obtain a crosslinking agent; (6) The following components: modified polypropylene, modified silica, crosslinking agent, plasticizer, and nitrile rubber are mixed and then transferred to a twin-screw extruder for extrusion and granulation to obtain a protective sleeve layer.

2. The wear-resistant, oil-resistant and flame-retardant drag chain cable according to claim 1, characterized in that: The production method of the pretreated polypropylene in step (1) is as follows: pre-irradiated polypropylene, an initiator, an emulsifier, and a dispersant are mixed, allylphosphonic acid and pure water are added in sequence, the mixture is mixed, the temperature is raised to 70-80° C., and the mixture is reacted for 8-10 hours to obtain pretreated polypropylene; The mass ratio of pre-irradiated polypropylene, initiator, emulsifier, dispersant, allylphosphonic acid and pure water is 1:(0.001-0.002):(0.003-0.005):(0.008-0.01):(0.5-1.0):(5-7).

3. The wear-resistant, oil-resistant and flame-retardant drag chain cable according to claim 1, characterized in that: The production method of the pre-modified polypropylene comprises the following steps: swelling the pretreated polypropylene in 1,2-dichlorobenzene at 110-120° C. for 1-2 hours, adding p-nitrobenzyl alcohol and 4-dimethylaminopyridine, and reacting at 100-110° C. for 5-6 hours to obtain phosphate polypropylene; swelling the phosphate polypropylene in solvent A at 110-120° C. for 1-2 hours, cooling to 80° C., mixing sodium sulfide and solvent B, adding the resulting mixture, and reacting at 80° C. for 8-10 hours to obtain the pre-modified polypropylene.

4. The wear-resistant, oil-resistant and flame-retardant drag chain cable according to claim 3, characterized in that: The mass ratio of the pretreated polypropylene, 1,2-dichlorobenzene, p-nitrobenzyl alcohol, and 4-dimethylaminopyridine is 1:(15-20):(1-1.2):(0.02-0.03); The mass ratio of the phosphate polypropylene, solvent A, solvent B, and sodium sulfide is 1:(15-20):(10-15):(2-3); The solvent A is prepared by mixing xylene, N-methylpyrrolidone, and dimethyl sulfoxide in a volume ratio of 5:3:2; The solvent B is prepared by mixing ethanol, N-methylpyrrolidone, and tetrabutylammonium bromide in a mass ratio of 4:1:0.

2.

5. The wear-resistant, oil-resistant and flame-retardant drag chain cable according to claim 1, characterized in that: The production method of the modified polypropylene in step (3) is as follows: pre-modified polypropylene is swelled in toluene at 100-110° C. for 1-2 hours, ethyl acrylate, p-toluenesulfonic acid, acetic anhydride, sodium pyrosulfate, and 10 wt% palladium-carbon catalyst are added, and reflux reaction is carried out for 2-3 hours to obtain modified polypropylene; The mass ratio of pre-modified polypropylene, toluene, ethyl acrylate, p-toluenesulfonic acid, acetic anhydride, sodium pyrosulfate and 10wt% palladium carbon catalyst is 1:(20-30):(0.2-0.3):(0.3-0.4):(0.7-0.9):(1-1.2):(0.005-0.01).

6. The wear-resistant, oil-resistant and flame-retardant drag chain cable according to claim 1, characterized in that: The production method of the modified silica in step (4) is as follows: silica, n-decyltrimethoxysilane, chloropropyltrimethoxysilane, anhydrous ethanol, and pure water are mixed, the pH is adjusted to 4.5-5.5 with hydrochloric acid, and the temperature is raised to 70-80° C. and reacted for 7-8 hours to obtain chloropropyl silica; Mix chloropropyl silica, 3-cyanopyridine, acetonitrile, and tetrabutylammonium bromide, heat to 75-85°C, and reflux for 4-6 hours to obtain pre-modified silica; Mix pre-modified silica, dicyandiamide, potassium hydroxide and 2-methoxyethanol, heat to 115-125°C, and react for 1-2 hours to obtain modified silica.

7. The wear-resistant, oil-resistant and flame-retardant drag chain cable according to claim 6, characterized in that: The mass ratio of the silicon dioxide, n-decyltrimethoxysilane, chloropropyltrimethoxysilane, anhydrous ethanol and pure water is 1:(0.5-0.7):(0.5-0.7):(10-12):(10-12); The mass ratio of the chloropropyl silica, 3-cyanopyridine, acetonitrile and tetrabutylammonium bromide is 1:(0.7-1.0):(20-30):(0.01-0.05); The mass ratio of the pre-modified silica, dicyandiamide, potassium hydroxide and 2-methoxyethanol is 1:(0.5-0.7):(1-1.2):(20-30).

8. The wear-resistant, oil-resistant and flame-retardant drag chain cable according to claim 1, characterized in that: The production method of the cross-linking agent in step (5) is as follows: p-hydroxybenzaldehyde, potassium carbonate, and N,N-dimethylformamide are mixed, 1,2-bis(2-chloroethoxy)ethane-N,N-dimethylformamide solution is added, and the mixture is heated to 85-90° C. and reacted for 6-8 hours to obtain the cross-linking agent; The molar ratio of 1,2-bis(2-chloroethoxy)ethane, p-hydroxybenzaldehyde and potassium carbonate is 1:(2.2-2.4):(4-5); the mass of N,N-dimethylformamide is 10-12 times that of p-hydroxybenzaldehyde; 1,2-bis(2-chloroethoxy)ethane and N,N-dimethylformamide are obtained by mixing 1,2-bis(2-chloroethoxy)ethane and N,N-dimethylformamide in a mass ratio of 1:(5-6).

9. The wear-resistant, oil-resistant and flame-retardant drag chain cable according to claim 1, characterized in that: The amounts of the components in step (6) are as follows: 100 parts by mass of modified polypropylene, 5-7 parts by mass of modified silicon dioxide, 2-3 parts by mass of crosslinking agent, 5-8 parts by mass of plasticizer, and 10-12 parts by mass of nitrile rubber.

10. The method for producing the wear-resistant, oil-resistant and flame-retardant drag chain cable according to any one of claims 1 to 9, characterized in that: The production method comprises the following steps: coating a conductor layer with an insulating layer, uniformly mixing modified polypropylene, modified silica, a crosslinking agent, a plasticizer, and nitrile rubber, melt-extruding and granulating the mixture in a twin-screw extruder to obtain a protective sheath layer, and melt-extruding the protective sheath layer on the insulating layer coated with the conductor layer to obtain a wear-resistant, oil-resistant, and flame-retardant drag chain cable.

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