Special cable protective sleeve material for truck and preparation method of special cable protective sleeve material

Abstract

The invention relates to a special cable sheath material for trucks and a preparation method thereof, and belongs to the technical field of cable sheath materials, the special cable sheath material comprises the following raw materials: 40-55 parts of polyvinyl chloride, 15-20 parts of high vinyl polybutadiene rubber, 12-16 parts of a modified reinforcing material, 0.5-1.5 parts of a stabilizer, 1-3 parts of an anti-aging agent, 2-4 parts of a compatilizer and 4-8 parts of a filler; according to the technical scheme, the plant-based compound is combined with caffeic acid, epoxidation is performed, and the composite plasticizer is obtained; the composite plasticizer is combined with the silanized graphene oxide to obtain a reinforcing material; combining the reinforcing material with an amino compound to obtain a modified reinforcing material; mixing polyvinyl chloride, high vinyl polybutadiene rubber, the modified reinforcing material, a stabilizer, an anti-aging agent, a compatilizer and a filler, and performing extrusion granulation to obtain the special cable protective sleeve material for the truck. The mechanical property, the corrosion resistance and the aging resistance of the protective sleeve are integrally improved, and the environmental protection property is good.

Description

Technical Field

[0001] The present invention belongs to the technical field of cable sheath materials, and in particular, relates to a special cable sheath material for trucks and a preparation method thereof. Background Art

[0002] Cable is a general term for items such as optical cables and electrical cables. Cables have many uses, mainly used for multiple functions such as control installation, connecting equipment, and transmitting electricity. They are an indispensable infrastructure for the daily operation of modern society. With the popularization and application of cables, especially in heavy-duty transportation equipment such as trucks, the demand for high performance of cables is also growing. In order to ensure that the cables can still work normally under complex and changeable working conditions, insulating sheaths are often added to the cables to protect them. Polyvinyl chloride sheath material is a widely used polymer sheath material for cables. It is mainly made of polyvinyl chloride resin, fillers, plasticizers, stabilizers, additives, etc., which are evenly mixed by a high mixer and then plasticized, extruded and granulated on a twin-screw extruder to form a polymer material. Polyvinyl chloride sheath material is widely used in cable sheath layers because of its excellent physical and mechanical properties, flexibility, low price, and excellent processing performance.

[0003] At present, traditional PVC sheath materials usually use petroleum-based phthalates as their plasticizers, but this type of plasticizer is carcinogenic and easily migrates from the PVC matrix, posing a threat to people's health and environmental safety; protective sheath materials exposed to harsh outdoor environments for a long time are easily affected by environmental factors such as ultraviolet rays, acid rain, and salt spray, causing aging and decreased corrosion resistance, resulting in the cable being unable to work normally; and the interface compatibility between the components of the PVC sheath material needs to be further improved to enhance the mechanical properties and durability of the cable. Summary of the invention

[0004] The purpose of the present invention is to provide a special cable protective sheath material for trucks and a preparation method thereof. A composite plasticizer is obtained by combining a plant-based compound with caffeic acid and then performing epoxidation. The plasticizing effect of the plasticizer in polyvinyl chloride resin can be further improved, and the aging resistance of the cable protective sheath can be enhanced. The epoxidation reaction is performed to make the plasticizer have good anti-volatility and migration resistance, and can provide reaction sites for subsequent reactions. The composite plasticizer is combined with silanized graphene oxide to obtain a reinforced material. The interface compatibility between the silanized graphene oxide and the composite plasticizer is improved, and the silanized graphene oxide is increased. The dispersibility of graphene oxide in polyvinyl chloride resin further improves the mechanical properties and corrosion resistance of the cable protective sheath; by combining the reinforcing material with the amino compound, a modified reinforcing material is obtained; the aging resistance, corrosion resistance and mechanical properties of the cable protective sheath are further improved; polyvinyl chloride, high vinyl polybutadiene rubber, modified reinforcing material, stabilizer, antioxidant, compatibilizer and filler are mixed, and extrusion granulation is performed to obtain a special cable protective sheath material for trucks; high vinyl polybutadiene rubber also improves the aging resistance of the cable protective sheath, and overall improves the comprehensive performance of the cable protective sheath material, and has good environmental protection.

[0005] The technical problem to be solved by the present invention is as follows: Traditional polyvinyl chloride protective sheath materials usually use petroleum-based phthalates as their plasticizers, but such plasticizers are carcinogenic and easily migrate from the polyvinyl chloride matrix, posing a threat to people's health and environmental safety; protective sheath materials exposed to harsh outdoor environments for a long time are easily affected by environmental factors such as ultraviolet rays, acid rain, and salt spray, causing aging and decreased corrosion resistance, resulting in the cable being unable to work normally; and the interface compatibility between the components of the polyvinyl chloride sheath material needs to be further improved to enhance the mechanical properties and durability of the cable.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A special cable protective sheath material for trucks, comprising the following raw materials in parts by weight: 40-55 parts of polyvinyl chloride, 15-20 parts of high vinyl polybutadiene rubber, 12-16 parts of modified reinforcing material, 0.5-1.5 parts of stabilizer, 1-3 parts of antioxidant, 2-4 parts of compatibilizer and 4-8 parts of filler;

[0008] The preparation method of the modified reinforced material comprises the following steps:

[0009] S1: The composite plasticizer is obtained by combining plant-based compounds with caffeic acid and then epoxidizing them;

[0010] S2: A reinforced material is obtained by combining a composite plasticizer with silanized graphene oxide;

[0011] S3: combining the reinforcing material with the amino compound to obtain a modified reinforcing material.

[0012] Furthermore, step S1 is specifically as follows:

[0013] A1: Mix caffeic acid and plant-based compounds, put them into an oil bath, and stir them evenly under a nitrogen atmosphere. When the system temperature rises to 125-135°C, add a catalyst, continue to heat to 145-155°C, and react for 7-9 hours. Cool the system temperature to 50-60°C, add sodium hydroxide solution, stir for 25-35 minutes, centrifuge for 5-10 minutes, extract with ethyl acetate, remove ethyl acetate by rotary evaporation, and dry at 55-65°C to obtain an intermediate product.

[0014] A2: The intermediate product is dissolved in dichloromethane to obtain solution A, which is then placed in an ice-water bath. The oxidant is dissolved in dichloromethane to obtain solution B, and solution B is added to solution A. The mixture is stirred at room temperature for 22-24 hours, and then washed with sodium bicarbonate and saturated sodium chloride, dried with anhydrous sodium sulfate, and dichloromethane is removed by rotary evaporation to obtain a composite plasticizer.

[0015] In the above reaction process, in step A1, caffeic acid has a hydroxyl group, a carboxyl group and a carbon-carbon double bond, and the plant-based compound includes eleostearic acid and vanillic acid. The eleostearic acid has a carbon-carbon double bond and a carboxyl group, and the vanillic acid has a carboxyl group and a hydroxyl group. The carboxyl groups on the eleostearic acid and the vanillic acid can be combined with the hydroxyl group in the caffeic acid through an esterification reaction, and the plant-based compound and the caffeic acid are combined to obtain an intermediate product; in step A2, the carbon-carbon double bonds on the eleostearic acid and the caffeic acid can undergo an epoxidation reaction under the action of an oxidant, and the carbon-carbon double bonds are oxidized into epoxy groups, and finally a composite plasticizer is obtained.

[0016] Furthermore, in step A1, the mass ratio of caffeic acid to plant-based compounds is 3-3.5:5-6.

[0017] Furthermore, in step A1, the plant-based compound is composed of eleostearic acid and vanillic acid mixed in a mass ratio of 0.9-1.1:0.8-1.2.

[0018] Furthermore, in step A1, the catalyst is p-toluenesulfonic acid.

[0019] Furthermore, in step A2, the mass ratio of the intermediate product to dichloromethane is 2-3:20-30.

[0020] Furthermore, in step A2, the mass ratio of the oxidant to dichloromethane is 0.8-1.2:13-17.

[0021] Furthermore, in step A2, the oxidant is meta-chloroperbenzoic acid.

[0022] Furthermore, step S2 is specifically as follows:

[0023] B1: Disperse graphene oxide in dimethylformamide and stir for 1-2 hours, then add aminosilane at 85-95°C and stir under reflux for 7-9 hours. After the reaction is completed, wash with deionized water and freeze-dry to obtain silanized graphene oxide;

[0024] B2: Add silanized graphene oxide to tetrahydrofuran and ultrasonically disperse for 25-35 minutes, then add the composite plasticizer in step S1, stir and reflux for 20-24 hours at 110-120° C. in a nitrogen atmosphere, then wash with deionized water and freeze-dry to obtain a reinforced material.

[0025] In the above reaction process, in step B1, the graphene oxide has hydroxyl groups and carboxyl groups, and the hydroxyl groups on the graphene oxide can be combined with the silanol groups generated after the hydrolysis of aminosilane, and the aminosilane is grafted onto the graphene oxide to obtain silylated graphene oxide; in step B2, the silylated graphene oxide has amino groups, and the composite plasticizer has epoxy groups. The amino groups on the silylated graphene oxide can be combined with the epoxy groups in the composite plasticizer through a ring-opening reaction, and the silylated graphene oxide and the composite plasticizer are combined together to obtain a reinforced material.

[0026] Furthermore, in step B1, the mass ratio of graphene oxide to dimethylformamide is 0.4-0.6:80-100.

[0027] Furthermore, in step B1, the aminosilane is a mixture of γ-aminopropyltriethoxysilane and γ-glycidyloxypropyltrimethoxysilane in a mass ratio of 0.7-0.9:0.1-0.3.

[0028] Furthermore, in step B2, the mass ratio of the silanized graphene oxide to tetrahydrofuran is 0.8-1.2:50-60.

[0029] Furthermore, step S3 is specifically as follows:

[0030] The amino compound is dissolved in deionized water and stirred for 10-15 minutes, then the reinforcing material in step S2 is added, and stirred and refluxed at 75-85° C. for 8-10 hours, centrifuged for 10-15 minutes, washed with deionized water, and vacuum dried at 50-60° C. to obtain a modified reinforcing material.

[0031] In the above reaction process, the amino compound has an amino group, and the graphene oxide in the reinforcing material has a carboxyl group. The amino group in the amino compound can combine with the carboxyl group in the reinforcing material, and the amino compound is grafted onto the surface of the reinforcing material to finally obtain a modified reinforcing material.

[0032] Furthermore, the mass ratio of the amino compound to deionized water is 0.1-0.2:40-50.

[0033] Furthermore, the amino compound is composed of 3-amino methyl acrylate and 2,3,3,3-tetrafluoropropionamide mixed in a mass ratio of 0.5-0.7:0.3-0.5.

[0034] A method for preparing a special cable protective sheath material for trucks comprises the following steps:

[0035] Weigh the raw materials by mass, mix polyvinyl chloride, high vinyl polybutadiene rubber, modified reinforcing material, stabilizer, antioxidant, compatibilizer and filler, stir at 95-105° C. for 25-35 minutes to obtain a mixture, add the mixture into a twin-screw extruder for extrusion granulation, and finally obtain a special cable protective cover material for trucks.

[0036] Furthermore, the stabilizer is a calcium-zinc composite stabilizer.

[0037] Furthermore, the antioxidant is at least one of antioxidant 4020, antioxidant 1010, antioxidant 445 and antioxidant 4010.

[0038] Furthermore, the compatibilizer is maleic anhydride grafted polyethylene or maleic anhydride grafted ethylene-vinyl acetate copolymer.

[0039] Furthermore, the filler is at least one of white carbon black, nano titanium dioxide, talcum powder and kaolin.

[0040] Furthermore, the operating temperature of the twin-screw extruder is 135-155° C., and the main engine speed is 300-400 r / min.

[0041] Beneficial effects of the present invention:

[0042] (1) In the technical scheme of the present invention, a composite plasticizer is obtained by combining a plant-based compound with caffeic acid and then performing epoxidation. The plant-based compound is composed of a mixture of eleostearic acid and vanillic acid. Both eleostearic acid and vanillic acid have the advantages of low cost, non-toxicity and environmental sustainability, and can be used as a substitute for phthalate plasticizers. Caffeic acid also has the characteristics of non-toxicity, low cost, antioxidant and anti-aging. Combining caffeic acid with the plant-based compound can not only further improve the plasticizing effect of the plasticizer in polyvinyl chloride resin, but also enhance the aging resistance of the cable protective sheath. At the same time, the carbon-carbon double bonds in caffeic acid can also participate in the subsequent epoxidation reaction. After caffeic acid is combined with the plant-based compound, an epoxidation reaction is performed to oxidize the carbon-carbon double bonds therein into epoxy groups, which not only makes the plasticizer have better anti-volatility and migration resistance, but also provides reaction sites for subsequent reactions, further improving the bonding between the composite plasticizer and silanized graphene oxide. Combined force; a reinforcing material is obtained by combining a composite plasticizer with silanized graphene oxide; silanized graphene oxide is obtained by grafting aminosilane onto the surface of graphene oxide, wherein the aminosilane is a mixture of γ-aminopropyltriethoxysilane and γ-glycidyloxypropyltrimethoxysilane, and both silane coupling agents can be combined with the hydroxyl groups on the surface of graphene oxide, thereby improving the grafting efficiency of the aminosilane. In addition, the amino groups on the γ-aminopropyltriethoxysilane can be combined with the epoxy groups on the composite plasticizer, thereby improving the interface compatibility between the silanized graphene oxide and the composite plasticizer, and increasing the dispersibility of the silanized graphene oxide in the polyvinyl chloride resin, thereby further improving the mechanical properties and corrosion resistance of the cable protective sheath, and at the same time, the epoxy groups in the γ-glycidyloxypropyltrimethoxysilane can also interact with the functional groups in the polyvinyl chloride molecules, thereby improving the compatibility between the reinforcing material and the polyvinyl chloride resin.

[0043] (2) In the technical scheme of the present invention, a modified reinforcing material is obtained by combining a reinforcing material with an amino compound; the amino compound is composed of a mixture of 3-aminomethyl acrylate and 2,3,3,3-tetrafluoropropionamide, and the amino groups in 3-aminomethyl acrylate and 2,3,3,3-tetrafluoropropionamide can be combined with the carboxyl groups in the reinforcing material, thereby improving the binding force between the amino compound and the reinforcing material, and the fluorine group in 2,3,3,3-tetrafluoropropionamide can enhance the hydrophobicity of the cable protective sheath. The amino compound is combined with the reinforcing material to further improve the aging resistance, corrosion resistance and mechanical properties of the cable protective sheath, and increase the compatibility between the modified reinforcing material and polyvinyl chloride; polyvinyl chloride, high vinyl polybutadiene rubber, modified reinforcing material, stabilizer, antioxidant, compatibilizer and filler are mixed and extruded and granulated to obtain a special cable protective sheath material for trucks; high vinyl polybutadiene rubber has excellent aging resistance, which can further improve the aging resistance of the cable protective sheath.

[0044] (3) In the technical scheme of the present invention, a plant-based compound is combined with caffeic acid and then epoxidized to obtain a composite plasticizer, which is then combined with silanized graphene oxide and finally combined with an amino compound to obtain a modified reinforcing material. Polyvinyl chloride, high vinyl polybutadiene rubber, modified reinforcing material, stabilizer, antioxidant, compatibilizer and filler are mixed and extruded and granulated to obtain a special cable protective sheath material for trucks. The mechanical properties, corrosion resistance and aging resistance of the cable protective sheath material are improved as a whole. The prepared cable protective sheath material has good environmental protection, long service life and good comprehensive performance. DETAILED DESCRIPTION

[0045] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0046] The specific parameters of the raw materials used in the present invention are as follows:

[0047] Polyvinyl chloride, number average molecular weight of 83,000, weight average molecular weight of 210,000 g / mol, K value of 72-73, provided by Shanghai Aladdin Biochemical Technology Co., Ltd.; high vinyl polybutadiene rubber (HVPB, Mn = 203,400, PDI = 3.62), provided by Sinopec Qilu Branch; caffeic acid, CAS No.: 501-16-6, provided by Shanghai MacLean Biochemical Technology Co., Ltd.; eleostearic acid, CAS No.: 463-40-1, provided by Shanghai Provided by Haitai Technology Co., Ltd.; vanillic acid, CAS No.: 121-34-6, provided by Shanghai Aladdin Biochemical Technology Co., Ltd.; graphene oxide, thickness 1-3nm, provided by Jiangsu Xianfeng Nanomaterial Technology Co., Ltd.; 3-aminoacrylate methyl ester, CAS No.: 124703-69-1, provided by Shanghai Aladdin Biochemical Technology Co., Ltd.; 2,3,3,3-tetrafluoropropionamide, CAS No.: 45102-52-1, provided by Shanghai Titan Technology Co., Ltd.

[0048] Example 1

[0049] The modified reinforced material is prepared by the following specific steps:

[0050] S1: The preparation method of the composite plasticizer comprises the following steps:

[0051] A1: According to the mass ratio of caffeic acid to plant-based compound of 3:5, caffeic acid and plant-based compound are mixed, and then put into an oil bath and stirred evenly under nitrogen atmosphere. When the system temperature rises to 125°C, p-toluenesulfonic acid is added (the mass of p-toluenesulfonic acid is 0.5wt% of the plant-based compound), and the temperature is continued to rise to 145°C and react for 7h. The system temperature is cooled to 50°C, and then 10wt% sodium hydroxide solution is added (the mass of sodium hydroxide solution is equal to the mass of plant-based compound), and stirred for 25min to remove the residual plant-based compound, and centrifuged at 2000rpm for 10min, and then extracted with ethyl acetate at 30°C for 3 times (the mass of ethyl acetate each time is 3 times the mass of plant-based compound), and the ethyl acetate is removed by rotary evaporation, and dried at 55°C to obtain an intermediate product, wherein the plant-based compound is composed of eleostearic acid and vanillic acid mixed in a mass ratio of 0.9:0.8;

[0052] A2: The intermediate product was dissolved in dichloromethane at a mass ratio of 2:20 to obtain solution A, which was then placed in an ice-water bath. Meta-chloroperbenzoic acid was dissolved in dichloromethane at a mass ratio of 0.8:13 to obtain solution B. Solution B was added to solution A, and the mixture was stirred at room temperature for 22 hours. The mixture was then washed with sodium bicarbonate and saturated sodium chloride three times each (the mass of sodium bicarbonate and saturated sodium chloride each time was 8 times the mass of the intermediate product), dried with anhydrous sodium sulfate for 4 hours, and dichloromethane was removed by rotary evaporation at 25°C to obtain a composite plasticizer;

[0053] S2: The method for preparing the reinforcing material comprises the following steps:

[0054] B1: According to the mass ratio of graphene oxide to dimethylformamide of 0.4:80, graphene oxide is dispersed in dimethylformamide and stirred for 1 hour, then aminosilane (the mass of aminosilane is twice the mass of graphene oxide) is added at 85°C, stirred and refluxed for 7 hours, and after the reaction is completed, it is washed with deionized water 3 times (the mass of deionized water each time is 30wt% of dimethylformamide), and freeze-dried at minus 30°C to obtain silylated graphene oxide, wherein the aminosilane is composed of γ-aminopropyltriethoxysilane and γ-glycidyloxypropyltrimethoxysilane mixed in a mass ratio of 0.7:0.1;

[0055] B2: According to the mass ratio of silanized graphene oxide to tetrahydrofuran being 0.8:50, silanized graphene oxide is added to tetrahydrofuran, and ultrasonically dispersed for 25 minutes, and then the composite plasticizer in step S1 is added (the mass of the composite plasticizer is 80wt% of the silanized graphene oxide), stirred and refluxed for 20 hours at a nitrogen atmosphere and 110°C, and then washed with deionized water for 3 times (the mass of the deionized water each time is 40wt% of tetrahydrofuran), and freeze-dried at minus 30°C to obtain a reinforced material;

[0056] S3: dissolving the amino compound in deionized water at a mass ratio of 0.1:40, stirring for 10 minutes, then adding the reinforcing material in step S2 (the mass of the reinforcing material is 60wt% of the amino compound), stirring and refluxing at 75°C for 8 hours, centrifuging at a speed of 5000rpm for 15 minutes, washing with deionized water 3 times (the mass of deionized water each time is 15 times the mass of the amino compound), and vacuum drying at 50°C for 12 hours to obtain a modified reinforcing material, wherein the amino compound is composed of 3-amino methyl acrylate and 2,3,3,3-tetrafluoropropionamide mixed at a mass ratio of 0.5:0.3;

[0057] A special cable protective sheath material for trucks, comprising the following raw materials in parts by weight: 40 parts of polyvinyl chloride, 15 parts of high vinyl polybutadiene rubber, 12 parts of modified reinforcing material, 0.5 parts of calcium zinc composite stabilizer, 1 part of antioxidant 4020, 2 parts of maleic anhydride grafted polyethylene and 4 parts of white carbon black;

[0058] The preparation method comprises the following steps:

[0059] Weigh the raw materials by mass, mix polyvinyl chloride, high vinyl polybutadiene rubber, modified reinforcing material, calcium zinc composite stabilizer, antioxidant 4020, maleic anhydride grafted polyethylene and white carbon black, stir at 95°C and 300 r / min for 35 min to obtain a mixture, add the mixture into a twin-screw extruder for extrusion granulation, the operating temperature of the twin-screw extruder is 135°C, and the main engine speed is 300 r / min, finally obtaining a special cable protective cover material for trucks.

[0060] Example 2

[0061] The modified reinforced material is prepared by the following specific steps:

[0062] S1: The preparation method of the composite plasticizer comprises the following steps:

[0063] A1: According to the mass ratio of caffeic acid to plant-based compound of 3.3:5.5, caffeic acid and plant-based compound are mixed, then put into an oil bath, and stirred evenly under nitrogen atmosphere. When the system temperature rises to 130°C, p-toluenesulfonic acid is added (the mass of p-toluenesulfonic acid is 0.5wt% of the plant-based compound), and the temperature is continued to rise to 150°C and react for 8h. The system temperature is cooled to 55°C, and then 15wt% sodium hydroxide solution is added (the mass of sodium hydroxide solution is equal to the mass of plant-based compound), and stirred for 30min to remove the residual plant-based compound, and centrifuged at 2500rpm for 8min, and then extracted with ethyl acetate at 35°C for 3 times (the mass of ethyl acetate each time is 3 times the mass of plant-based compound), and the ethyl acetate is removed by rotary evaporation, and dried at 60°C to obtain an intermediate product, wherein the plant-based compound is composed of eleostearic acid and vanillic acid mixed in a mass ratio of 1:1;

[0064] A2: The intermediate product was dissolved in dichloromethane at a mass ratio of 2.5:25 to dichloromethane to obtain solution A, which was then placed in an ice-water bath. Meta-chloroperbenzoic acid was dissolved in dichloromethane at a mass ratio of 1:15 to obtain solution B. Solution B was added to solution A, and the mixture was stirred at room temperature for 23 hours. The mixture was then washed with sodium bicarbonate and saturated sodium chloride three times each (the mass of sodium bicarbonate and saturated sodium chloride each time was 8 times the mass of the intermediate product), dried with anhydrous sodium sulfate for 5 hours, and dichloromethane was removed by rotary evaporation at 28°C to obtain a composite plasticizer;

[0065] S2: The method for preparing the reinforcing material comprises the following steps:

[0066] B1: According to the mass ratio of graphene oxide to dimethylformamide of 0.5:90, graphene oxide is dispersed in dimethylformamide and stirred for 1.5 hours, and then aminosilane (the mass of aminosilane is twice the mass of graphene oxide) is added at 90°C, stirred and refluxed for 8 hours. After the reaction is completed, it is washed with deionized water for 3 times (the mass of deionized water each time is 30wt% of dimethylformamide), and freeze-dried at minus 25°C to obtain silylated graphene oxide, wherein the aminosilane is composed of γ-aminopropyltriethoxysilane and γ-glycidyloxypropyltrimethoxysilane mixed in a mass ratio of 0.8:0.2;

[0067] B2: According to the mass ratio of silanized graphene oxide to tetrahydrofuran being 1:55, silanized graphene oxide is added to tetrahydrofuran, and ultrasonically dispersed for 30 minutes, and then the composite plasticizer in step S1 is added (the mass of the composite plasticizer is 80wt% of the silanized graphene oxide), stirred and refluxed for 22 hours at a nitrogen atmosphere and 115°C, and then washed with deionized water for 3 times (the mass of the deionized water each time is 40wt% of tetrahydrofuran), and freeze-dried at -25°C to obtain a reinforced material;

[0068] S3: dissolving the amino compound in deionized water at a mass ratio of 0.15:45 between the amino compound and deionized water, stirring for 13 minutes, then adding the reinforcing material in step S2 (the mass of the reinforcing material is 60wt% of the amino compound), stirring and refluxing at 80°C for 9 hours, centrifuging at a speed of 5500rpm for 13 minutes, washing with deionized water 3 times (the mass of the deionized water each time is 15 times the mass of the amino compound), and vacuum drying at 55°C for 13 hours to obtain a modified reinforcing material, wherein the amino compound is composed of 3-amino methyl acrylate and 2,3,3,3-tetrafluoropropionamide mixed at a mass ratio of 0.6:0.4;

[0069] A special cable protective sheath material for trucks, comprising the following raw materials in parts by weight: 48 parts of polyvinyl chloride, 17 parts of high-vinyl polybutadiene rubber, 14 parts of modified reinforcing material, 1 part of calcium-zinc composite stabilizer, 2 parts of antioxidant 1010, 3 parts of maleic anhydride grafted ethylene-vinyl acetate copolymer and 6 parts of nano titanium dioxide;

[0070] The preparation method comprises the following steps:

[0071] Weigh the raw materials by mass, mix polyvinyl chloride, high vinyl polybutadiene rubber, modified reinforcing material, calcium zinc composite stabilizer, antioxidant 1010, maleic anhydride grafted ethylene-vinyl acetate copolymer and nano titanium dioxide, stir at 100°C and 350 r / min for 30 min to obtain a mixture, add the mixture into a twin-screw extruder for extrusion granulation, the operating temperature of the twin-screw extruder is 145°C, the main engine speed is 350 r / min, and finally obtain a special cable protective cover material for trucks.

[0072] Example 3

[0073] The modified reinforced material is prepared by the following specific steps:

[0074] S1: The preparation method of the composite plasticizer comprises the following steps:

[0075] A1: According to the mass ratio of caffeic acid to plant-based compound of 3.5:6, caffeic acid and plant-based compound are mixed, then put into an oil bath, and stirred evenly under nitrogen atmosphere. When the system temperature rises to 135°C, p-toluenesulfonic acid is added (the mass of p-toluenesulfonic acid is 0.5wt% of the plant-based compound), and the temperature is continued to rise to 155°C, and the reaction is carried out for 9 hours. The system temperature is cooled to 60°C, and then 20wt% sodium hydroxide solution (the mass of sodium hydroxide solution is equal to the mass of plant-based compound) is added, and stirred for 35 minutes to remove the residual plant-based compound, and centrifuged at 3000rpm for 5 minutes, and then extracted with ethyl acetate at 40°C for 3 times (the mass of ethyl acetate each time is 3 times the mass of plant-based compound), and the ethyl acetate is removed by rotary evaporation, and dried at 65°C to obtain an intermediate product, wherein the plant-based compound is composed of eleostearic acid and vanillic acid mixed in a mass ratio of 1.1:1.2;

[0076] A2: The intermediate product was dissolved in dichloromethane at a mass ratio of 3:30 to dichloromethane to obtain solution A, which was then placed in an ice-water bath, and m-chloroperbenzoic acid was dissolved in dichloromethane at a mass ratio of 1.2:17 to obtain solution B, which was added to solution A, stirred at room temperature for 24 hours, and then washed with sodium bicarbonate and saturated sodium chloride three times each (the mass of each sodium bicarbonate and saturated sodium chloride was 8 times the mass of the intermediate product), dried with anhydrous sodium sulfate for 6 hours, and dichloromethane was removed by rotary evaporation at 30°C to obtain a composite plasticizer;

[0077] S2: The method for preparing the reinforcing material comprises the following steps:

[0078] B1: According to the mass ratio of graphene oxide to dimethylformamide of 0.6:100, graphene oxide is dispersed in dimethylformamide and stirred for 2 hours, then aminosilane (the mass of aminosilane is twice the mass of graphene oxide) is added at 95°C, stirred and refluxed for 9 hours, and after the reaction is completed, it is washed with deionized water for 3 times (the mass of deionized water each time is 30wt% of dimethylformamide), and freeze-dried at minus 20°C to obtain silylated graphene oxide, wherein the aminosilane is composed of γ-aminopropyltriethoxysilane and γ-glycidyloxypropyltrimethoxysilane mixed in a mass ratio of 0.9:0.3;

[0079] B2: According to the mass ratio of silanized graphene oxide to tetrahydrofuran being 1.2:60, silanized graphene oxide is added to tetrahydrofuran, and ultrasonically dispersed for 35 minutes, and then the composite plasticizer in step S1 is added (the mass of the composite plasticizer is 80wt% of the silanized graphene oxide), stirred and refluxed for 24 hours at a nitrogen atmosphere and 120°C, and then washed with deionized water for 3 times (the mass of the deionized water each time is 40wt% of tetrahydrofuran), and freeze-dried at -20°C to obtain a reinforced material;

[0080] S3: dissolving the amino compound in deionized water at a mass ratio of 0.2:50, stirring for 15 minutes, then adding the reinforcing material in step S2 (the mass of the reinforcing material is 60wt% of the amino compound), stirring and refluxing at 85°C for 10 hours, centrifuging at 6000rpm for 10 minutes, washing with deionized water 3 times (the mass of the deionized water each time is 15 times the mass of the amino compound), and vacuum drying at 60°C for 14 hours to obtain a modified reinforcing material, wherein the amino compound is composed of 3-amino methyl acrylate and 2,3,3,3-tetrafluoropropionamide mixed at a mass ratio of 0.7:0.5;

[0081] A special cable protective sheath material for trucks, comprising the following raw materials in parts by weight: 55 parts of polyvinyl chloride, 20 parts of high vinyl polybutadiene rubber, 16 parts of modified reinforcing material, 1.5 parts of calcium zinc composite stabilizer, 3 parts of antioxidant 445, 4 parts of maleic anhydride grafted polyethylene and 8 parts of talcum powder;

[0082] The preparation method comprises the following steps:

[0083] Weigh the raw materials by mass, mix polyvinyl chloride, high vinyl polybutadiene rubber, modified reinforcing material, calcium zinc composite stabilizer, antioxidant 445, maleic anhydride grafted polyethylene and talcum powder, stir at 105°C and 400 r / min for 25 min to obtain a mixture, add the mixture into a twin-screw extruder for extrusion granulation, the operating temperature of the twin-screw extruder is 155°C, and the main engine speed is 400 r / min, finally obtaining a special cable protective cover material for trucks.

[0084] Comparative Example 1

[0085] The difference between this comparative example and Example 3 is that when preparing the composite plasticizer, the mass of the plant-based compound in step A1 is replaced by eleostearic acid, and the remaining steps and raw materials are the same as those in Example 3;

[0086] A1: Caffeic acid and eleostearic acid are mixed in a mass ratio of 3.5:6, and then put into an oil bath and stirred evenly under a nitrogen atmosphere. When the system temperature rises to 135°C, p-toluenesulfonic acid is added (the mass of p-toluenesulfonic acid is 0.5wt% of eleostearic acid), and the temperature is continued to rise to 155°C and reacted for 9h. The system temperature is cooled to 60°C, and 20wt% sodium hydroxide solution (the mass of sodium hydroxide solution is equal to that of eleostearic acid) is added and stirred for 35min to remove residual plant-based compounds. The mixture is centrifuged at 3000rpm for 5min, and then extracted with ethyl acetate at 40°C for 3 times (the mass of ethyl acetate each time is 3 times the mass of eleostearic acid). The ethyl acetate is removed by rotary evaporation and dried at 65°C to obtain an intermediate product.

[0087] Comparative Example 2

[0088] The difference between this comparative example and Example 3 is that, when preparing the composite plasticizer, after combining the caffeic acid and the plant-based compound in step S1, epoxidation is not performed, and the remaining steps and raw materials are the same as those in Example 3;

[0089] The specific operations of step S1 are:

[0090] According to the mass ratio of caffeic acid to plant-based compounds of 3.5:6, caffeic acid and plant-based compounds are mixed, then put into an oil bath and stirred evenly under a nitrogen atmosphere. When the system temperature rises to 135°C, p-toluenesulfonic acid is added (the mass of p-toluenesulfonic acid is 0.5wt% of the plant-based compound), the temperature is continued to rise to 155°C, and the reaction is carried out for 9 hours. The system temperature is cooled to 60°C, and 20wt% sodium hydroxide solution (the mass of the sodium hydroxide solution is equal to the mass of the plant-based compound) is added, and stirred for 35 minutes to remove the residual plant-based compound, centrifuged at 3000rpm for 5 minutes, and then extracted with ethyl acetate at 40°C for 3 times (the mass of ethyl acetate each time is 3 times the mass of the plant-based compound), the ethyl acetate is removed by rotary evaporation, and dried at 65°C to obtain a composite plasticizer, wherein the plant-based compound is composed of eleostearic acid and vanillic acid mixed in a mass ratio of 1.1:1.2.

[0091] Comparative Example 3

[0092] The difference between this comparative example and Example 3 is that when preparing the reinforcing material, the aminosilane in step B1 is replaced by γ-aminopropyltriethoxysilane, and the remaining steps and raw materials are the same as those in Example 3;

[0093] The specific operations of step B1 are:

[0094] According to the mass ratio of graphene oxide to dimethylformamide of 0.6:100, graphene oxide was dispersed in dimethylformamide and stirred for 2 hours, and then γ-aminopropyltriethoxysilane (the mass of γ-aminopropyltriethoxysilane is twice the mass of graphene oxide) was added at 95°C, stirred and refluxed for 9 hours. After the reaction, it was washed with deionized water for 3 times (the mass of deionized water each time was 30wt% of dimethylformamide), and freeze-dried at minus 20°C to obtain silanized graphene oxide.

[0095] Comparative Example 4

[0096] The difference between this comparative example and Example 3 is that when preparing the modified reinforcing material, the amino compound in step S3 is replaced by 3-amino methyl acrylate, and the remaining steps and raw materials are the same as those in Example 3;

[0097] The specific operations of step S3 are:

[0098] According to the mass ratio of 3-amino methyl acrylate to deionized water being 0.2:50, 3-amino methyl acrylate was dissolved in deionized water and stirred for 15 minutes, and then the reinforcing material in step S2 (the mass of the reinforcing material was 60wt% of 3-amino methyl acrylate) was added, and the mixture was stirred and refluxed at 85°C for 10 hours, centrifuged at a speed of 6000rpm for 10 minutes, washed with deionized water 3 times (the mass of deionized water each time was 15 times the mass of 3-amino methyl acrylate), and vacuum dried at 60°C for 14 hours to obtain a modified reinforcing material.

[0099] Comparative Example 5

[0100] The difference between this comparative example and Example 3 is that when preparing the special cable protective cover material for trucks, the high vinyl polybutadiene rubber is replaced with low vinyl polybutadiene rubber, and the remaining steps and raw materials are synchronized with Example 3;

[0101] A special cable protective sheath material for trucks, comprising the following raw materials in parts by weight: 55 parts of polyvinyl chloride, 20 parts of low-vinyl polybutadiene rubber, 16 parts of modified reinforcing material, 1.5 parts of calcium-zinc composite stabilizer, 3 parts of antioxidant 445, 4 parts of maleic anhydride grafted polyethylene and 8 parts of talc;

[0102] The preparation method comprises the following steps:

[0103] Weigh the raw materials by mass, mix polyvinyl chloride, low vinyl polybutadiene rubber, modified reinforcing material, calcium zinc composite stabilizer, antioxidant 445, maleic anhydride grafted polyethylene and talcum powder, stir at 105°C and 400 r / min for 25 min to obtain a mixture, add the mixture into a twin-screw extruder for extrusion granulation, the operating temperature of the twin-screw extruder is 155°C, and the main engine speed is 400 r / min, finally obtaining a special cable protective cover material for trucks.

[0104] The special cable protective sheath materials for trucks prepared in Examples 1-3 and Comparative Examples 1-5 are now tested for tensile strength, elongation at break, corrosion resistance and aging resistance; tensile strength and elongation at break are tested according to GB / T2951.11-2008; aging resistance is tested according to GB / T 2951.2-1997; Corrosion resistance test: the special cable protective sheath materials for trucks prepared in Examples 1-3 and Comparative Examples 1-5 are soaked in 45g / L oxalic acid solution and 40g / L sodium hydroxide solution respectively according to IEC 60811, and soaked at 23±2°C for 3 days, and acid and alkali corrosion resistance tests are performed, and the change rate of tensile strength and the change rate of elongation at break are calculated. The test results are shown in Tables 1 and 2 below:

[0105] Table 1 Mechanical properties and aging resistance of special cable protective sheath materials for trucks prepared in Examples 1-3 and Comparative Examples 1-5

[0106]

[0107] Table 2 Corrosion resistance of special cable protective sheath materials for trucks prepared in Examples 1-3 and Comparative Examples 1-5

[0108]

[0109] It can be seen from the data in Table 1 and Table 2 above that, by comparing Comparative Examples 1-2 and Example 3, it can be seen that the special cable protective sheath material for trucks is prepared by replacing the mass of the plant-based compound in step A1 with eleostearic acid or combining the caffeic acid and the plant-based compound in step S1 without epoxidation. The test results are worse than those in Example 3, indicating that the plant-based compound composed of a mixture of eleostearic acid and vanillic acid is combined with caffeic acid and then epoxidized. The prepared composite plasticizer has a good plasticizing effect on polyvinyl chloride, and the interface compatibility between the composite plasticizer and the polyvinyl chloride resin is good, which can further improve the mechanical properties of the cable protective sheath material, and also has a good effect on its corrosion resistance and aging resistance;

[0110] From the comparison between Comparative Example 3 and Example 3, it can be seen that the aminosilane in step B1 is replaced with γ-aminopropyltriethoxysilane to prepare the special cable protective sheath material for trucks. The test result is worse than that of Example 3, indicating that the aminosilane composed of γ-aminopropyltriethoxysilane and γ-glycidyloxypropyltrimethoxysilane can not only enhance the dispersibility of graphene oxide and improve the bonding force between silanized graphene oxide and the composite plasticizer, but also improve the interface compatibility between the reinforcing material and the polyvinyl chloride resin, thereby further improving the mechanical properties, corrosion resistance and aging resistance of the cable protective sheath material;

[0111] From the comparison between Comparative Example 4 and Example 3, it can be seen that the quality of the amino compound in step S3 is replaced by 3-amino methyl acrylate, and finally the special cable protective cover material for trucks is prepared. The test result is worse than that of Example 3, indicating that the amino compound composed of 3-amino methyl acrylate and 2,3,3,3-tetrafluoropropionamide is mixed to form the amino compound, and the amino compound is combined with the reinforcing material to prepare the modified reinforcing material, which can not only improve the interface compatibility between the reinforcing material and the polyvinyl chloride resin, but also enhance the hydrophobicity of the cable protective cover, thereby further improving the corrosion resistance and mechanical properties of the cable protective cover, and also has a good effect on its aging resistance;

[0112] From the comparison between Comparative Example 5 and Example 3, it can be seen that the test results of the special cable protective sheath material for trucks prepared by replacing high vinyl polybutadiene rubber with low vinyl polybutadiene rubber are worse than those of Example 3, indicating that the addition of high vinyl polybutadiene rubber can improve its interface compatibility with polyvinyl chloride resin, thereby further improving the aging resistance and mechanical properties of the cable protective sheath material, and also has a good effect on its corrosion resistance.

[0113] It can be seen from Table 1 and Table 2 above that the special cable protective sheath material for trucks prepared in Examples 1-3 is compared with the special cable protective sheath material for trucks prepared in Comparative Examples 1-5. The plant-based compound is combined with caffeic acid, and then epoxidized to obtain a composite plasticizer, which is then combined with silanized graphene oxide, and finally combined with an amino compound to obtain a modified reinforced material. Polyvinyl chloride, high vinyl polybutadiene rubber, modified reinforcing material, stabilizer, antioxidant, compatibilizer and filler are mixed, and extrusion granulation is performed to obtain a special cable protective sheath material for trucks, which meets the test performance requirements, while the special cable protective sheath material for trucks prepared in Comparative Examples 1-5 does not meet the performance requirements. The special cable protective sheath material for trucks prepared by the present invention not only has good corrosion resistance, aging resistance and mechanical properties, but also has good environmental protection and a long service life.

[0114] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0115] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A special cable protective sheath material for trucks, characterized in that: The invention comprises the following raw materials in parts by weight: 40-55 parts of polyvinyl chloride, 15-20 parts of high vinyl polybutadiene rubber, 12-16 parts of modified reinforcing material, 0.5-1.5 parts of stabilizer, 1-3 parts of antioxidant, 2-4 parts of compatibilizer and 4-8 parts of filler; The preparation method of the modified reinforced material comprises the following steps: S1: The composite plasticizer is obtained by combining plant-based compounds with caffeic acid and then epoxidizing them; S2: A reinforced material is obtained by combining a composite plasticizer with silanized graphene oxide; S3: combining the reinforcing material with the amino compound to obtain a modified reinforcing material.

2. The special cable protective sheath material for trucks according to claim 1, characterized in that: Step S1 is specifically as follows: A1: Mix caffeic acid and plant-based compounds, put them into an oil bath, and stir them evenly under a nitrogen atmosphere. When the system temperature rises to 125-135°C, add a catalyst, continue to heat to 145-155°C, and react for 7-9 hours. Cool the system temperature to 50-60°C, add sodium hydroxide solution, stir for 25-35 minutes, centrifuge for 5-10 minutes, extract with ethyl acetate, remove ethyl acetate by rotary evaporation, and dry at 55-65°C to obtain an intermediate product. A2: The intermediate product is dissolved in dichloromethane to obtain solution A, which is then placed in an ice-water bath. The oxidant is dissolved in dichloromethane to obtain solution B, and solution B is added to solution A. The mixture is stirred at room temperature for 22-24 hours, and then washed with sodium bicarbonate and saturated sodium chloride, dried with anhydrous sodium sulfate, and dichloromethane is removed by rotary evaporation to obtain a composite plasticizer.

3. The special cable protective sheath material for trucks according to claim 2, characterized in that: In step A1, the plant-based compound is composed of eleostearic acid and vanillic acid mixed in a mass ratio of 0.9-1.1:0.8-1.

2.

4. The special cable protective sheath material for trucks according to claim 2, characterized in that: In step A2, the oxidant is m-chloroperbenzoic acid.

5. The special cable protective sheath material for trucks according to claim 1, characterized in that: Step S2 is specifically as follows: B1: Disperse graphene oxide in dimethylformamide and stir for 1-2 hours, then add aminosilane at 85-95°C and stir under reflux for 7-9 hours. After the reaction is completed, wash with deionized water and freeze-dry to obtain silanized graphene oxide; B2: Add silanized graphene oxide to tetrahydrofuran and ultrasonically disperse for 25-35 minutes, then add the composite plasticizer in step S1, stir and reflux for 20-24 hours at 110-120° C. in a nitrogen atmosphere, then wash with deionized water and freeze-dry to obtain a reinforced material.

6. The special cable protective sheath material for trucks according to claim 5, characterized in that: In step B1, the aminosilane is a mixture of γ-aminopropyltriethoxysilane and γ-glycidyloxypropyltrimethoxysilane in a mass ratio of 0.7-0.9:0.1-0.

3.

7. The special cable protective sheath material for trucks according to claim 1, characterized in that: Step S3 is specifically as follows: The amino compound is dissolved in deionized water and stirred for 10-15 minutes, then the reinforcing material in step S2 is added, and stirred and refluxed at 75-85° C. for 8-10 hours, centrifuged for 10-15 minutes, washed with deionized water, and vacuum dried at 50-60° C. to obtain a modified reinforcing material.

8. The special cable protective sheath material for trucks according to claim 7, characterized in that: The amino compound is composed of 3-amino methyl acrylate and 2,3,3,3-tetrafluoropropionamide mixed in a mass ratio of 0.5-0.7:0.3-0.

5.

9. The special cable protective sheath material for trucks according to claim 1, characterized in that: The filler is at least one of white carbon black, nano titanium dioxide, talcum powder and kaolin.

10. A method for preparing a special cable protective sheath material for trucks according to any one of claims 1 to 9, characterized in that: The following steps are involved: Weigh the raw materials by mass, mix polyvinyl chloride, high vinyl polybutadiene rubber, modified reinforcing material, stabilizer, antioxidant, compatibilizer and filler, stir at 95-105° C. for 25-35 minutes to obtain a mixture, add the mixture into a twin-screw extruder for extrusion granulation, and finally obtain a special cable protective cover material for trucks.

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