HPVC electric power pipe with high impact resistance and processing technology thereof

Abstract

The invention discloses a high-impact-resistance HPVC electric power pipe and a processing technology thereof, belongs to the technical field of HPVC materials, and aims to solve the technical problem that the impact resistance and wear resistance of an HPVC electric power pipe in the prior art need to be further improved. The composite material comprises an anti-electromagnetic interference layer and an anti-impact HPVC layer wrapping the anti-electromagnetic interference layer, a radiation cross-linking agent and HPVC powder are subjected to melt extrusion, modified HPVC with a three-dimensional network structure is obtained through radiation cross-linking, and then the modified HPVC, a modified plasticizer and auxiliary materials are subjected to melt extrusion to hybridize a polyvinyl chloride chain segment space structure. Wherein the three-dimensional siloxane network and the copper grids are matched with each other, so that the electromagnetic shielding capability of the material is improved, the electrical insulating property is improved, the mechanical property and the adaptability are enhanced, and the impact-resistant and anti-interference HPVC electric power pipe which is resistant to high temperature, resistant to stretching, resistant to abrasion, resistant to flame and good in sealing performance is obtained.

Description

Technical Field

[0001] The invention relates to the technical field of HPVC material processing, and in particular to a high-impact resistant HPVC power pipe and a processing technology thereof. Background Art

[0002] The development of impact-resistant power pipes can be traced back to the early 20th century. Metal materials were initially used, but due to their heavy weight and easy corrosion, they were gradually replaced by lightweight plastic materials. In the 21st century, the increase in environmental awareness prompted manufacturers to transform to sustainable materials, and many new synthetic materials were developed to reduce the impact on the environment.

[0003] In addition, the design and production process of impact-resistant power pipes are constantly improved to meet higher safety and performance requirements. Overall, impact-resistant power pipes have evolved from traditional to modern and from heavy to light, continuously adapting to the growing needs of power infrastructure and playing an important role in improving the reliability and safety of power systems.

[0004] Prior art CN105968642A discloses a high-impact and high-strength electric power pipe, wherein the weight proportions of the components are as follows: polyvinyl chloride resin (PVC-U): 10-100 parts, chlorinated polyvinyl chloride (CPVC): 10-100 parts, high-polymerization polyvinyl chloride (HPVC): 20-50 parts, heat-resistant plasticizer: 0-30 parts, polylactic acid (PLA): 0-20 parts, filler: 0-25 parts, heat stabilizer: 2-15 parts, lubricant: 1-2 parts, processing aid: 2-8 parts, plastic modifier: 2-8 parts and molybdenum chrome red: 0.5-2.0 parts. The obtained high-impact and high-strength electric power pipe has the advantages of high impact resistance, high strength and heat resistance, easy processing and reasonable cost.

[0005] Although the above content aims to improve the impact resistance and other properties of the pipes by optimizing the formula of the power pipes, and melt-extrudes a variety of auxiliary materials with a variety of polyvinyl chlorides to obtain the power pipes, the polarity difference between the inorganic and organic materials in the formula is large, which easily leads to poor compatibility between the materials, resulting in poor wear resistance of the materials, and the sealing of the power pipes is reduced after friction. In addition, due to the difference between the components and the pyrolysis of the polyvinyl chloride material under high-temperature processing, the internal structure of the finally prepared power pipe is unstable, which will also lead to the need for further improvement of the impact resistance.

[0006] In view of the technical defects in this aspect, a solution is now proposed. Summary of the invention

[0007] The object of the present invention is to provide a highly impact-resistant HPVC power pipe and a processing technology thereof, so as to solve the technical problem that the impact resistance and wear resistance of the HPVC power pipe in the prior art need to be further improved.

[0008] The object of the present invention can be achieved by the following technical scheme: A highly impact-resistant HPVC power pipe, comprising an anti-electromagnetic interference layer and an impact-resistant HPVC layer wrapped outside the layer;

[0009] The impact-resistant HPVC layer comprises the following raw material components in parts by weight: 80-100 parts of modified HPVC, 10-20 parts of modified plasticizer, 15-20 parts of plasticizer, 10-15 parts of filler, 3-5 parts of stabilizer, 3-5 parts of antioxidant and 3-5 parts of ultraviolet absorber;

[0010] The preparation method of the modified HPVC powder is as follows: adding HPVC powder and a radiation crosslinking agent to a twin-screw extruder for melt blending and granulation to obtain a modified HPVC precursor, placing the prepared mixed material in an irradiation tank, filling the irradiation tank with argon gas and sealing the irradiation tank, placing the irradiation tank in a cobalt source chamber for irradiation at room temperature, and obtaining the modified HPVC after irradiation with an absorbed dose of 20-40 kGy;

[0011] Reaction principle: After being irradiated by a cobalt source, the polyvinyl chloride chain segments in the HPVC precursor are activated by high-energy electrons generated by γ rays, forming a large number of free radicals. The free radicals and the radiation cross-linking agent continuously polymerize to form a complex three-dimensional network structure to obtain modified HPVC.

[0012] The preparation method of the modified plasticizer is:

[0013] B1. Add telomerized silicone oil, benzoic acid, ferric chloride and dimethyl sulfoxide into a reactor and stir. The temperature of the reactor is lowered to 0-5°C. Saturated hydrogen peroxide solution is added dropwise into the reactor under the stirring state. The dropping operation is maintained for 3-4 hours. After the dropping is completed, the reaction mixture is stirred for 1 hour under the stirring state. The epoxidized silicone oil is obtained by post-treatment.

[0014] The synthetic reaction equation of epoxy silicone oil is:

[0015]

[0016] The synthetic reaction principle of epoxy silicone oil is as follows: at low temperature, the added saturated hydrogen peroxide solution reacts with benzoic acid to form peracid, and under the catalysis of Lewis acid ferric chloride, the peracid oxidizes the carbon-carbon double bonds in the silicone oil to form epoxy groups, and finally obtains epoxy silicone oil.

[0017] B2. Add epoxidized silicone oil, maleic anhydride, magnesium chloride and dimethyl sulfoxide into a reactor, raise the temperature of the reactor to 120-160° C., keep the temperature for 2-3 hours, and perform post-treatment to obtain a modified plasticizer.

[0018] The synthetic reaction equation of the modified plasticizer is:

[0019]

[0020] Where:

[0021] The synthetic reaction principle of the modified plasticizer is as follows: under the catalysis of Lewis acid, the epoxy group and amino group inside the epoxidized silicone oil react with maleic anhydride, the maleic anhydride ring opens to form free radicals, and further reacts with the remaining epoxy groups of the epoxidized silicone oil to form a complex spatial structure, and finally a modified plasticizer is obtained.

[0022] Furthermore, the dosage ratio of HPVC powder and radiation cross-linking agent is 60-80g:3-5g, the temperatures of the eight temperature sections of the twin-screw extruder from the feed port to the discharge port are 180°C, 195, 195°C, 210°C, 210°C, 220°C, and 220°C, respectively, and the main engine speed of the twin-screw extruder is 80-120rpm, and the pressure is 100-150bar.

[0023] Furthermore, the filler is one or more of nano-silica particles, titanium dioxide and carbon black; the stabilizer is one or more of diphenyl (2,4-di-tert-butyl) pyran, bis (2,4-di-tert-butylphenyl) benzothiophene and 2,4-dichlorophenyl fluorinated benzophenone; the antioxidant is one or more of tri-tert-butyl hydroxyphenyl acrylate, tetramethyl dihydroxyphenyl acrylate and tri-tert-butyl hydroxyphenyl acrylate; the ultraviolet absorber is one or more of diphenyl triazolyl diphenyl triazoline, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -2H-benzotriazole-4-one) and 2-hydroxy-4-methoxybenzoic acid butyl ester.

[0024] Furthermore, the preparation method of the radiation crosslinking agent comprises the following steps:

[0025] A1. Add 1,3,5-triglycidyl-S-triazinetrione, diethylstilbestrol diphosphate, triethylamine and N,N-dimethylformamide into a reaction kettle, raise the temperature of the reaction kettle to 60-80°C, keep the temperature for 1-3h, and post-treat to obtain a radiation crosslinking agent precursor;

[0026] The synthesis reaction equation of the radiation crosslinker precursor is:

[0027]

[0028] Where:

[0029] The synthesis reaction principle of the radiation crosslinker precursor is as follows: under the catalysis of alkaline conditions, the epoxy group on 1,3,5-triglycidyl-S-triazinetrione and the hydroxyl group on diethylstilbestrol diphosphate undergo a ring-opening reaction, and the multiple hydroxyl groups on diethylstilbestrol diphosphate react with the multiple epoxy groups on 1,3,5-triglycidyl-S-triazinetrione to form a complex spatial network structure, and finally the radiation crosslinker precursor is obtained.

[0030] A2. Add the radiation crosslinking agent precursor, 3-isocyanate propylene, triethylamine and N,N-dimethylformamide into a reaction kettle, keep the reaction at room temperature for 1-3 hours, and post-treat to obtain the radiation crosslinking agent.

[0031] The synthetic reaction equation of the radiation crosslinker is:

[0032]

[0033] The synthetic reaction principle of the radiation crosslinker is as follows: under the catalysis of alkaline conditions, a large number of isocyanate groups on the radiation crosslinker precursor react with 3-isocyanate propylene, and a large number of carbon-carbon double bonds and carbamate bonds are introduced into the spatial network structure of the radiation crosslinker precursor, and finally the radiation crosslinker is prepared.

[0034] Furthermore, in step A1, the amount ratio of 1,3,5-triglycidyl-S-triazinetrione, diethylstilbestrol diphosphate, triethylamine and N,N-dimethylformamide is 3-5g:8-10g:0.5-1g:30-40mL, and the post-treatment includes: after the temperature of the reactor is reduced to room temperature, the reaction liquid is added to a rotary evaporator with a water bath temperature of 80-100°C, and the reduced pressure distillation is performed until no liquid is produced to obtain a radiation crosslinking agent precursor; in step A2, the amount ratio of the radiation crosslinking agent precursor, 3-isocyanate propylene, triethylamine and N,N-dimethylformamide is 8-12g:2-4g:0.5-1g:40-60mL, and the post-treatment includes: after the reaction is completed, the reaction liquid is added to a rotary evaporator with a water bath temperature of 80-100°C, and the reduced pressure distillation is performed until no liquid is produced to obtain a radiation crosslinking agent.

[0035] Further, in step B1, the stirring rate is 120-160rpm, the amount ratio of the polysilicone oil, benzoic acid, ferric chloride, dimethyl sulfoxide and saturated hydrogen peroxide solution is 15-20g:4-6g:0.5-0.8g:60-80mL:10-15mL, and the post-treatment includes: after the temperature of the reactor is raised to room temperature, the reaction solution is added to a rotary evaporator with a water bath temperature of 80-100°C, and the reduced pressure distillation is performed until no liquid is produced to obtain epoxidized silicone oil; in step B2, the amount ratio of the epoxidized silicone oil, maleic anhydride, magnesium chloride and dimethyl sulfoxide is 8-12g:2-4g:0.5-0.8g:50-60mL, and the post-treatment includes: after the temperature of the reactor is cooled to room temperature, the reaction solution is added to a rotary evaporator with a water bath temperature of 80-100°C, and the reduced pressure distillation is performed until no liquid is produced to obtain a modified plasticizer.

[0036] Furthermore, in step B1, the preparation method of the telomerized silicone oil comprises the following steps:

[0037] C1. Add hydrogenated silicone oil, ethylene ammonia, chloroplatinic acid and xylene into a reactor, raise the temperature of the reactor to 50-60°C, keep the temperature for reaction for 2-3h, and perform post-treatment to obtain aminated silicone oil;

[0038] The synthetic reaction equation of ammoniated silicone oil is:

[0039]

[0040] The synthetic reaction principle of ammoniated silicone oil is as follows: under the catalysis of chloroplatinic acid, the silicon-hydrogen bonds on the hydrogen-containing silicone oil react with the double bonds on ethyleneamine to form a stable structure to obtain ammoniated silicone oil.

[0041] C2, adding aminated silicone oil, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane and ether into a reaction kettle and stirring, raising the temperature of the reaction kettle to 30-50° C., keeping the temperature and stirring for 15-20 minutes, to obtain a reaction precursor solution;

[0042] C3. Add the reaction precursor solution and 98.0%wt concentrated sulfuric acid into the reactor and stir. After stirring for 8-10 hours at room temperature, add sodium bicarbonate powder into the reactor to adjust the pH of the system to 8-9, and perform post-treatment to obtain telomerized silicone oil.

[0043] The synthetic reaction equation of telomerized silicone oil is:

[0044]

[0045] The synthetic reaction principle of telomerized silicone oil is as follows: under the catalysis of concentrated sulfuric acid, aminated silicone oil, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane and 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane are telomerized, 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane is used as a telomerizing agent, aminated silicone oil and 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane are used as main chain monomer substances, and the carbon oxygen silicon structure of the side chain is hydrolyzed to finally prepare telomerized silicone oil.

[0046] Further, in step C1, the amount ratio of the hydrogenated silicone oil, ethylene ammonia, chloroplatinic acid and xylene is 8-10g:2-3g:0.3-0.5g:40-50mL, and the post-treatment includes: after the temperature of the reactor is cooled to room temperature, the reaction solution is added to a rotary evaporator with a water bath temperature of 80-100°C, and the reduced pressure distillation is performed until no liquid is produced to obtain ammoniated silicone oil; in step C2, the stirring rate is 120-160rpm, the ammoniated silicone oil, 1,3,5,7-tetravinyl -1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane and ether are used in a ratio of 6-8g:7-9g:2-3g:50-80mL; in step C3, the reaction precursor solution and 98.0%wt concentrated sulfuric acid are used in a ratio of 20-24mL:2-3mL, and the post-treatment includes: adding the reaction solution to a rotary evaporator with a water bath temperature of 80-100°C, and distilling under reduced pressure until no liquid is produced to obtain a telomerized silicone oil.

[0047] The present invention also proposes a processing technology for a high impact resistant HPVC power pipe, comprising the following steps:

[0048] S1. uniformly mixing the modified HPVC, the modified plasticizer, the filler, the stabilizer, the antioxidant, the ultraviolet absorber and the lubricant to obtain a mixture;

[0049] S2. Place the copper mesh in a mold and add the mixed material into a twin-screw extruder. The temperatures of the eight temperature sections of the twin-screw extruder from the feed port to the discharge port are 180°C, 195°C, 195°C, 210°C, 210°C, 220°C, and 220°C, respectively. The main engine speed of the twin-screw extruder is 80-120rpm, and the pressure is 100-150bar. The mixture is melt-extruded and coated on the surface of the copper mesh, and then cooled to obtain the HPVC power pipe.

[0050] The reaction equation that occurs during the production process is:

[0051]

[0052] The reaction principle that occurs during the production process is as follows: during the processing, as the temperature rises, the amide segments in the modified HPVC undergo an imide reaction to produce more high-temperature resistant imide segments. Further, the polyvinyl chloride segments in the modified HPVC undergo pyrolysis to produce free radicals, which react with the epoxy groups and carbon-carbon double bonds in the modified plasticizer to hybridize the polyvinyl chloride segments and melt-blend with the auxiliary materials to obtain the HPVC power pipe.

[0053] The present invention has the following beneficial effects:

[0054] 1. In the process of preparing a high-impact resistant HPVC power pipe, the present invention first prepares a radiation crosslinking agent and a modified plasticizer. In the process of processing the modified HPVC, the HPVC powder and the radiation crosslinking agent are melt-extruded and then activated by radiation, and the polyvinyl chloride chain segments generate free radicals that are crosslinked with the radiation crosslinking agent by radiation, so that the polyvinyl chloride chain segments form a complex spatial network structure, thereby enhancing the wear resistance and impact resistance of the material. The acid source and the carbon source on the radiation crosslinking agent cooperate in combustion to make the modified HPVC have excellent flame retardancy. In the process of processing the HPVC pipe, the polyvinyl chloride chain segments are pyrolyzed at high temperature to generate free radicals that react with the active functional groups in the modified plasticizer. The spatial structure of the hybrid chain segment continues to be further enhanced to further enhance the wear resistance and impact resistance of the pipe. The modified plasticizer further undergoes thermal imide reaction at high temperature to form a high-temperature resistant imide group that cooperates with the siloxane structure in the modified plasticizer to enhance the thermal stability of the material. The density of the material is significantly improved through the secondary hybrid chain segment structure of the radiation cross-linking agent and the modified plasticizer. The silicon cross-linked network provides an excellent electromagnetic shielding effect through its unique chemical structure, which cooperates with the copper grid to increase the electromagnetic shielding ability of the material, improve electrical insulation, enhance mechanical properties and adaptability, and finally prepares a high-temperature resistant, tensile, wear-resistant, flame-retardant, and well-sealed impact-resistant and anti-interference HPVC power pipe.

[0055] 2. In the process of preparing a radiation crosslinking agent of the present invention, 1,3,5-triglycidyl-S-triazinetrione with a triazine-like structure is first selected as a chain segment hub structure, and reacted with ethinyl stilbestrol diphosphate having multiple hydroxyl groups and phosphate groups to obtain a radiation crosslinking agent precursor, wherein the benzene ring as a rigid structure provides support for the generated complex spatial network structure, the generated hydroxyl group further reacts with 3-isocyanate propylene, and a large number of carbamate groups and double bonds are introduced into the radiation crosslinking agent precursor to obtain a radiation crosslinking agent. The excellent toughness of the carbamate makes the spatial structure more stable, the generated double bonds react with the free radicals generated by the radiation of the polyvinyl chloride segment, hybridize the polyvinyl chloride segment, and enhance the wear resistance of the material. In the process of combustion, the decomposition of the phosphate group promotes the carbonization of the triazine-like ring to form a flame-retardant carbon layer, so that the material has excellent flame retardancy.

[0056] 3. In the process of preparing a modified plasticizer, the present invention introduces amino groups into hydrogenated silicone oil through a hydrosilylation reaction, generates a branched long-chain siloxane structure containing a large number of double bonds through a polyol reaction, and obtains a modified lubricating oil having an amide group, an epoxy group and a large number of double bonds through peroxyacid oxidation and reaction with maleic anhydride; the modified lubricating oil uses siloxane as the main chain, and during the processing, the polyvinyl chloride chain segment undergoes pyrolysis to generate free radicals that graft with the epoxy groups therein to form a cross-linked structure, and further undergoes cyclization with the double bond structure therein, further improving the impact resistance of the material, and the main chain siloxane significantly enhances the wear resistance and high temperature resistance of the material, while significantly reducing the polarity of the polyvinyl chloride chain segment and enhancing its compatibility with auxiliary materials, and as the processing temperature rises, the amide group of the modified plasticizer further undergoes a thermal imide reaction, and the chain segment is further optimized on the basis of the hybrid chain segment to form a compact organic structure, and finally the HPVC power pipe is obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0058] Figure 1 It is a structural schematic diagram of the present invention;

[0059] Figure 2 It is a schematic diagram of the internal structure analysis diagram of the present invention;

[0060] In the figure: 100, anti-electromagnetic interference layer; 200, impact-resistant HPVC layer. DETAILED DESCRIPTION

[0061] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than 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.

[0062] The hydrogen-containing silicone oil used in the present invention was purchased from Suzhou Bingsheng New Material Technology Co., Ltd., with the product number MHX-1107;

[0063] The polyethylene wax used in the present invention is purchased from Wuhan Xindongyi Chemical Co., Ltd., and the model is Q-18PE wax.

[0064] Example 1

[0065] This embodiment is used to provide a processing technology for a high-impact resistant HPVC power pipe, comprising the following steps:

[0066] S1. Preparation of modified HPVC

[0067] Weigh: 12.0 g 1,3,5-triglycidyl-S-triazinetrione, 27.0 g diethylstilbestrol diphosphate, 1.8 g triethylamine and 90.0 mL N,N-dimethylformamide and add them into a reactor, raise the temperature of the reactor to 60° C., keep the temperature for 1 hour, lower the temperature of the reactor to room temperature, add the reaction liquid into a rotary evaporator with a water bath temperature of 80° C., and distill under reduced pressure until no liquid is produced to obtain a radiation crosslinking agent precursor;

[0068] Weigh: 27.0 g of radiation crosslinker precursor, 9.0 g of 3-isocyanate propylene, 1.8 g of triethylamine and 120.0 mL of N,N-dimethylformamide, add them into a reactor, keep the reaction at room temperature for 1 hour, after the reaction is completed, add the reaction liquid into a rotary evaporator with a water bath temperature of 80°C, and distill under reduced pressure until no liquid is extracted to obtain a radiation crosslinker;

[0069] Weigh: 60.0g HPVC powder and 4.0g radiation crosslinking agent are added to a twin-screw extruder, the temperatures of the eight temperature sections of the twin-screw extruder from the feed port to the discharge port are 180°C, 195, 195°C, 210°C, 210°C, 220°C, and 220°C, respectively, the main engine speed of the twin-screw extruder is 80rpm, the pressure is 100bar, and the modified HPVC precursor is obtained by melt extrusion. The prepared mixed material is placed in an irradiation tank, the irradiation tank is closed after being filled with argon, and the irradiation tank is placed in a cobalt source chamber for room temperature irradiation. After irradiation with an absorbed dose of 20kGy, the modified HPVC is obtained.

[0070] S2. Preparation of modified plasticizer

[0071] Weigh: 24.0g hydrogenated silicone oil, 6.0g ethylene ammonia, 1.2g chloroplatinic acid and 120.0mL xylene are added to a reactor, the reactor temperature is raised to 50°C, and the reaction is kept warm for 2h. After the reactor temperature is cooled to room temperature, the reaction liquid is added to a rotary evaporator with a water bath temperature of 80°C, and distilled under reduced pressure until no liquid is produced to obtain ammoniated silicone oil;

[0072] Weigh: 21.0 g of ammoniated silicone oil, 24.0 g of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 7.2 g of 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane and 150 mL of ether, add them into a reaction kettle and stir at a stirring rate of 120 rpm. The temperature of the reaction kettle is raised to 30° C. and stirred for 15 minutes to obtain a reaction precursor solution;

[0073] Weigh: 24.0 mL of reaction precursor solution and 3.0 mL of 98.0% wt concentrated sulfuric acid, add them into the reaction kettle and stir, stir for 8 h at room temperature, add sodium bicarbonate powder into the reaction kettle, adjust the system pH to 8, add the reaction solution into a rotary evaporator with a water bath temperature of 80°C, and distill under reduced pressure until no liquid is produced to obtain telomerized silicone oil;

[0074] Weigh: 16.0g of telomerized silicone oil, 5.0g of benzoic acid, 0.6g of ferric chloride and 72.0mL of dimethyl sulfoxide, add them into a reactor and stir, lower the temperature of the reactor to 5°C, add 12.0mL of saturated hydrogen peroxide solution dropwise into the reactor while keeping warm and stirring, and maintain the dropping operation for h. After the dropping is completed, keep warm and stir for 1h. After the temperature of the reactor is raised to room temperature, add the reaction solution into a rotary evaporator with a water bath temperature of 100°C, and distill under reduced pressure until no liquid is produced to obtain epoxidized silicone oil;

[0075] Weigh: 10.0 g of epoxidized silicone oil, 3.0 g of maleic anhydride, 0.6 g of magnesium chloride and 50.0 mL of dimethyl sulfoxide and add them into a reactor. The temperature of the reactor is raised to 120° C. and the reaction is kept warm for 2 hours. After the reactor temperature is cooled to room temperature, the reaction liquid is added to a rotary evaporator with a water bath temperature of 80° C. and distilled under reduced pressure until no liquid is produced to obtain a modified plasticizer.

[0076] S3. Preparation of HPVC power pipe

[0077] Weigh: 80.0 g of modified HPVC, 10.0 g of modified plasticizer, 10.0 g of nano-silicon dioxide particles, 3.0 g of diphenyl (2,4-di-tert-butyl) pyran, 3.0 g of tri-tert-butyl hydroxyphenyl acrylate and 3.0 g of diphenyl triazolyl diphenyl triazoline, and mix them evenly to obtain a mixture;

[0078] Place the copper mesh in the mold and add the mixed material into the twin-screw extruder. The temperatures of the eight temperature sections of the twin-screw extruder from the feed port to the discharge port are 180°C, 195°C, 195°C, 210°C, 210°C, 220°C, and 220°C, respectively. The main engine speed of the twin-screw extruder is 80rpm, and the pressure is 100bar. The mixture is melt-extruded and coated on the surface of the copper mesh, and then cooled to obtain the HPVC power pipe.

[0079] Example 2

[0080] This embodiment is used to provide a processing technology for a high-impact resistant HPVC power pipe, comprising the following steps:

[0081] S1. Preparation of modified HPVC

[0082] Weigh: 12.0 g 1,3,5-triglycidyl-S-triazinetrione, 30.0 g diethylstilbestrol diphosphate, 1.8 g triethylamine and 96.0 mL N,N-dimethylformamide and add them into a reactor, raise the temperature of the reactor to 80° C., keep the temperature for 3 hours, lower the temperature of the reactor to room temperature, add the reaction liquid into a rotary evaporator with a water bath temperature of 100° C., and distill under reduced pressure until no liquid is extracted to obtain a radiation crosslinking agent precursor;

[0083] Weigh: 24.0 g of radiation crosslinker precursor, 6.0 g of 3-isocyanate propylene, 2.1 g of triethylamine and 12.0 mL of N,N-dimethylformamide, add them into a reactor, keep the reaction at room temperature for 3 hours, after the reaction is completed, add the reaction liquid into a rotary evaporator with a water bath temperature of 100° C., and distill under reduced pressure until no liquid is extracted to obtain a radiation crosslinker;

[0084] Weigh: 64.0g HPVC powder and 4.8g radiation crosslinking agent are added to a twin-screw extruder, the temperatures of the eight temperature sections of the twin-screw extruder from the feed port to the discharge port are 180°C, 195, 195°C, 210°C, 210°C, 220°C, and 220°C, respectively, the main engine speed of the twin-screw extruder is 120rpm, the pressure is 150bar, and the modified HPVC precursor is obtained by melt extrusion. The prepared mixed material is placed in an irradiation tank, the irradiation tank is closed after being filled with argon, and the irradiation tank is placed in a cobalt source chamber for room temperature irradiation. After irradiation with an absorbed dose of 40kGy, the modified HPVC is obtained.

[0085] S2. Preparation of modified plasticizer

[0086] Weigh: 25.0g hydrogenated silicone oil, 7.2g ethylene ammonia, 1.5g chloroplatinic acid and 120.0mL xylene are added to a reactor, the reactor temperature is raised to 60°C, and the reaction is kept warm for 3h. After the reactor temperature is cooled to room temperature, the reaction liquid is added to a rotary evaporator with a water bath temperature of 100°C, and distilled under reduced pressure until no liquid is produced to obtain ammoniated silicone oil;

[0087] Weigh: 18.0 g of ammoniated silicone oil, 21.0 g of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 7.2 g of 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane and 150.0 mL of ether, add them into a reaction kettle and stir at a stirring rate of 160 rpm. The temperature of the reaction kettle is raised to 50° C. and stirred for 20 min to obtain a reaction precursor solution.

[0088] Weigh: 24.0 mL of reaction precursor solution and 7.2 mL of 98.0% wt concentrated sulfuric acid, add them into a reaction kettle and stir. After stirring at room temperature for 10 h, add sodium bicarbonate powder into the reaction kettle to adjust the system pH to 9. Add the reaction solution into a rotary evaporator with a water bath temperature of 100° C., and distill under reduced pressure until no liquid is produced to obtain telomerized silicone oil;

[0089] Weigh: 16.0g of telomerized silicone oil, 4.8g of benzoic acid, 0.6g of ferric chloride and 72.0mL of dimethyl sulfoxide, add them into a reactor and stir, lower the temperature of the reactor to 0°C, add 11.0mL of saturated hydrogen peroxide solution dropwise into the reactor while keeping warm and stirring, and maintain the dropping operation for 4h. After the dropwise addition is completed, keep warm and stir for 1h. After the temperature of the reactor is raised to room temperature, add the reaction solution into a rotary evaporator with a water bath temperature of 100°C, and distill under reduced pressure until no liquid is produced to obtain epoxidized silicone oil;

[0090] Weigh: 12.0g of epoxidized silicone oil, 3.6g of maleic anhydride, 0.6g of magnesium chloride and 54.0mL of dimethyl sulfoxide and add them into a reactor, raise the temperature of the reactor to 160°C, and keep the reaction warm for 3h. After the reactor temperature is cooled to room temperature, add the reaction liquid into a rotary evaporator with a water bath temperature of 100°C, and distill under reduced pressure until no liquid is produced to obtain a modified plasticizer.

[0091] S3. Preparation of HPVC power pipe

[0092] Weigh: 100.0 g of modified HPVC, 20.0 g of modified plasticizer, 15.0 g of nano-silicon dioxide particles, 3.0 g of diphenyl (2,4-di-tert-butyl) pyran, 5.0 g of tri-tert-butyl hydroxyphenyl acrylate and 3.0 g of diphenyl triazolyl diphenyl triazoline, and mix them evenly to obtain a mixture;

[0093] Place the copper mesh in the mold and add the mixed material into the twin-screw extruder. The temperatures of the eight temperature sections of the twin-screw extruder from the feed port to the discharge port are 180°C, 195, 195°C, 210°C, 210°C, 220°C, and 220°C respectively. The main engine speed of the twin-screw extruder is 120rpm and the pressure is 150bar. The mixture is melt-extruded and coated on the surface of the copper mesh, and then cooled to obtain the HPVC power pipe.

[0094] Example 3

[0095] This embodiment is used to provide a processing technology for a high-impact resistant HPVC power pipe, comprising the following steps:

[0096] S1. Preparation of modified HPVC

[0097] Weigh: 36.0 g 1,3,5-triglycidyl-S-triazinetrione, 12.0 g diethylstilbestrol diphosphate, 2.4 g triethylamine and 96.0 mL N,N-dimethylformamide and add them into a reactor, raise the temperature of the reactor to 80° C., keep the temperature for 3 hours, lower the temperature of the reactor to room temperature, add the reaction liquid into a rotary evaporator with a water bath temperature of 100° C., and distill under reduced pressure until no liquid is extracted to obtain a radiation crosslinking agent precursor;

[0098] Weigh: 30.0 g of radiation crosslinker precursor, 12.0 g of 3-isocyanate propylene, 1.8 g of triethylamine and 120.0 mL of N,N-dimethylformamide, add them into a reactor, keep the reaction at room temperature for 3 hours, after the reaction is completed, add the reaction solution into a rotary evaporator with a water bath temperature of 100° C., and distill under reduced pressure until no liquid is extracted to obtain a radiation crosslinker;

[0099] Weigh: 80.0g HPVC powder and 4.0g radiation crosslinking agent are added to a twin-screw extruder, the temperatures of the eight temperature sections of the twin-screw extruder from the feed port to the discharge port are 180°C, 195, 195°C, 210°C, 210°C, 220°C, and 220°C, respectively, the main engine speed of the twin-screw extruder is 120rpm, the pressure is 150bar, and the modified HPVC precursor is obtained by melt extrusion. The prepared mixed material is placed in an irradiation tank, the irradiation tank is closed after being filled with argon, and the irradiation tank is placed in a cobalt source chamber for room temperature irradiation. After irradiation with an absorbed dose of 40kGy, the modified HPVC is obtained.

[0100] S2. Preparation of modified plasticizer

[0101] Weigh: 27.0g hydrogenated silicone oil, 7.2g ethylene ammonia, 1.2g chloroplatinic acid and 120.0mL xylene are added to a reactor, the reactor temperature is raised to 60°C, and the reaction is kept warm for 3h. After the reactor temperature is cooled to room temperature, the reaction liquid is added to a rotary evaporator with a water bath temperature of 100°C, and distilled under reduced pressure until no liquid is produced to obtain ammoniated silicone oil;

[0102] Weigh: 21.0 g of ammoniated silicone oil, 27.0 g of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 7.2 g of 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane and 150.0 mL of ether, add them into a reaction kettle and stir at a stirring rate of 160 rpm. The temperature of the reaction kettle is raised to 50° C. and stirred for 20 min to obtain a reaction precursor solution.

[0103] Weigh: 24.0 mL of reaction precursor solution and 2.4 mL of 98.0% wt concentrated sulfuric acid, add them into the reaction kettle and stir, stir at room temperature for 10 h, add sodium bicarbonate powder into the reaction kettle, adjust the system pH to 9, add the reaction solution into a rotary evaporator with a water bath temperature of 100° C., and distill under reduced pressure until no liquid is produced to obtain telomerized silicone oil;

[0104] Weigh: 18.0g of telomerized silicone oil, 5.0g of benzoic acid, 0.6g of ferric chloride and 50.0mL of dimethyl sulfoxide, add them into a reactor and stir, lower the temperature of the reactor to 3°C, add 12.0mL of saturated hydrogen peroxide solution dropwise into the reactor while keeping warm and stirring, and maintain the dropping operation for 4h. After the dropwise addition is completed, keep warm and stir for 1h. After the temperature of the reactor is raised to room temperature, add the reaction solution into a rotary evaporator with a water bath temperature of 90°C, and distill under reduced pressure until no liquid is produced to obtain epoxidized silicone oil;

[0105] Weigh: 12.0g of epoxidized silicone oil, 3.0g of maleic anhydride, 0.6g of magnesium chloride and 54.0mL of dimethyl sulfoxide and add them into a reactor, raise the temperature of the reactor to 140°C, and keep the reaction warm for 3h. After the reactor temperature is cooled to room temperature, add the reaction liquid into a rotary evaporator with a water bath temperature of 100°C, and distill under reduced pressure until no liquid is extracted to obtain a modified plasticizer.

[0106] S3. Preparation of HPVC power pipe

[0107] Weigh: 96.0 g of modified HPVC, 20.0 g of modified plasticizer, 12.0 g of nano-silicon dioxide particles, 3.6 g of diphenyl (2,4-di-tert-butyl) pyran, 4.2 g of tri-tert-butyl hydroxyphenyl acrylate and 3.6 g of diphenyl triazolyl diphenyl triazoline, and mix them evenly to obtain a mixture;

[0108] Place the copper mesh in the mold and add the mixed material into the twin-screw extruder. The temperatures of the eight temperature sections of the twin-screw extruder from the feed port to the discharge port are 180°C, 195, 195°C, 210°C, 210°C, 220°C, and 220°C, respectively. The main engine speed of the twin-screw extruder is 100rpm, and the pressure is 125bar. The mixed material is melt-extruded and coated on the surface of the copper mesh, and then cooled to obtain the HPVC power pipe.

[0109] Comparative Example 1

[0110] The difference between this comparative example and Example 3 is that step S1 is omitted and an equal amount of HPVC powder is used to replace the modified HPVC.

[0111] Comparative Example 2

[0112] The difference between this comparative example and Example 3 is that step S2 is omitted and an equal amount of diisooctyl phthalate is used to replace the modified plasticizer.

[0113] Comparative Example 3

[0114] The difference between this comparative example and Example 3 is that in step S1, an equal amount of triallyl cyanurate is used to replace the radiation cross-linking agent.

[0115] Performance Test:

[0116] The ring stiffness, Vicat softening temperature, tensile strength, flame retardant properties and connection sealing of the HPVC power pipes prepared in Examples 1-3 and Comparative Examples 1-3 were tested with reference to the standard DL / T 802.9-2018 "Technical Conditions for Power Cable Conduits Part 9: High-Strength Polyvinyl Chloride Plastic Cable Conduits";

[0117] The volume wear of the HPVC power pipes prepared in Examples 1-3 and Comparative Examples 1-3 was tested with reference to the standard GB / T 9867-2008 "Determination of wear resistance of vulcanized rubber or thermoplastic rubber (rotating roller abrasion machine method)";

[0118] The vertical combustion rating of the HPVC power pipes prepared in Examples 1-3 and Comparative Examples 1-3 was tested with reference to the standard GB / T26526-2011 "Specification for Thermoplastic Elastomer Low Smoke Halogen-Free Flame Retardant Materials";

[0119] The anti-electromagnetic interference performance of the HPVC power pipes prepared in Examples 1-3 and Comparative Examples 1-3 was tested with reference to the standard GB / T32511-2016 "General Technical Requirements for Electromagnetic Shielding Plastics".

[0120] Table 1-Performance test data of each sample

[0121]

[0122]

[0123] Data Analysis:

[0124] Comparing and analyzing the data in Table 1 above, the ring stiffness (3%) of the HPVC power pipe prepared by the present invention is 28kPa, the Vicat softening temperature is 108°C, the tensile strength is 65MPa, the limiting oxygen index is 35%, the connection sealing is excellent, and the volume wear is 43mm 3 The vertical combustion level is V-1, and the anti-electromagnetic interference level reaches SE-2. All performance test data are better than the control group.

[0125] It is explained that in the present invention, after the HPVC powder is blended with the radiation crosslinking agent and melt extruded, the chain segment structure of the HPVC material is hybridized after radiation crosslinking to obtain modified HPVC, wherein the phosphate group in the radiation crosslinking agent decomposes at high temperature, promotes the carbonization of the triazine-like structure in the radiation crosslinking agent, forms a flame-retardant carbon layer, and enhances the flame retardant properties of the material, and the active functional groups embedded in the complex spatial structure of the radiation crosslinking agent react with the HPVC to form free radicals after radiation, so that the organic segments form a complex spatial network structure, thereby improving the mechanical properties and tensile strength of the material;

[0126] Furthermore, an HPVC power pipe is obtained by blending with a modified plasticizer, wherein the modified plasticizer is a complex siloxane segment with a large number of double bonds and epoxy groups on the segment. In the process of high-temperature processing to generate the HPVC power pipe, the polyvinyl chloride segment undergoes pyrolysis to generate free radicals that react with epoxy groups to hybridize organic segments, or reacts with double bonds to undergo cyclization to enhance the impact resistance of the power pipe. In the process of processing, the modified plasticizer segment further undergoes an imide reaction to generate an imide group to further enhance the high temperature resistance of the power pipe, thereby ensuring the processing temperature resistance of the modified HPVC material. After hybridization of the polyvinyl chloride segment with a radiation crosslinker and a modified plasticizer, the density of the material is enhanced, and the sealing and wear resistance of the power pipe are significantly improved. The three-dimensional siloxane network and the copper grid cooperate with each other to increase the electromagnetic shielding capability of the material, improve electrical insulation, and enhance mechanical properties and adaptability, thereby finally preparing an HPVC power pipe that is resistant to high temperature, tensile, wear-resistant, flame-retardant, and has good sealing properties and is impact-resistant and anti-interference.

[0127] The above contents are merely examples and explanations of the structure of the present invention. The technicians in this technical field 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 structure of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

[0128] In the description of this 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.

[0129] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A high impact resistant HPVC power pipe, characterized in that: It includes an anti-electromagnetic interference layer and an impact-resistant HPVC layer wrapped outside; The impact-resistant HPVC layer comprises the following raw material components in parts by weight: 80-100 parts of modified HPVC, 10-20 parts of modified plasticizer, 15-20 parts of plasticizer, 10-15 parts of filler, 3-5 parts of stabilizer, 3-5 parts of antioxidant and 3-5 parts of ultraviolet absorber; The preparation method of the modified HPVC powder is as follows: adding HPVC powder and a radiation crosslinking agent to a twin-screw extruder for melt blending and granulation to obtain a modified HPVC precursor, placing the prepared mixed material in an irradiation tank, filling the irradiation tank with argon gas and sealing the irradiation tank, placing the irradiation tank in a cobalt source chamber for irradiation at room temperature, and obtaining the modified HPVC after irradiation with an absorbed dose of 20-40 kGy; The preparation method of the modified plasticizer is: B1. Add telomerized silicone oil, benzoic acid, ferric chloride and dimethyl sulfoxide into a reactor and stir. The temperature of the reactor is lowered to 0-5°C. Saturated hydrogen peroxide solution is added dropwise into the reactor under the stirring state. The dropping operation is maintained for 3-4 hours. After the dropping is completed, the reaction mixture is stirred for 1 hour under the stirring state. The epoxidized silicone oil is obtained by post-treatment. B2. Add epoxidized silicone oil, maleic anhydride, magnesium chloride and dimethyl sulfoxide into a reactor, raise the temperature of the reactor to 120-160° C., keep the temperature for 2-3 hours, and perform post-treatment to obtain a modified plasticizer.

2. A high impact resistant HPVC power pipe according to claim 1, characterized in that: The dosage ratio of HPVC powder and radiation cross-linking agent is 60-80g:3-5g. The temperatures of the eight temperature sections of the twin-screw extruder from the feed port to the discharge port are 180°C, 195, 195°C, 210°C, 210°C, 220°C, and 220°C, respectively. The main engine speed of the twin-screw extruder is 80-120rpm, and the pressure is 100-150bar.

3. The high impact resistant HPVC power pipe according to claim 1, characterized in that: The preparation method of the radiation crosslinking agent comprises the following steps: A1. Add 1,3,5-triglycidyl-S-triazinetrione, diethylstilbestrol diphosphate, triethylamine and N,N-dimethylformamide into a reaction kettle, raise the temperature of the reaction kettle to 60-80°C, keep the temperature for 1-3h, and post-treat to obtain a radiation crosslinking agent precursor; A2. Add the radiation crosslinking agent precursor, 3-isocyanate propylene, triethylamine and N,N-dimethylformamide into a reaction kettle, keep the reaction at room temperature for 1-3 hours, and post-treat to obtain the radiation crosslinking agent.

4. The high impact resistant HPVC power pipe according to claim 3, characterized in that: In step A1, the amount ratio of 1,3,5-triglycidyl-S-triazinetrione, diethylstilbestrol diphosphate, triethylamine and N,N-dimethylformamide is 3-5g:8-10g:0.5-1g:30-40mL. In step A2, the amount ratio of radiation crosslinking agent precursor, 3-isocyanate propylene, triethylamine and N,N-dimethylformamide is 8-12g:2-4g:0.5-1g:40-60mL.

5. The high impact resistant HPVC power pipe according to claim 1, characterized in that: In step B1, the stirring rate is 120-160rpm, and the amount ratio of the polysilicone oil, benzoic acid, ferric chloride, dimethyl sulfoxide and saturated hydrogen peroxide solution is 15-20g:4-6g:0.5-0.8g:60-80mL:10-15mL; in step B2, the amount ratio of epoxidized silicone oil, maleic anhydride, magnesium chloride and dimethyl sulfoxide is 8-12g:2-4g:0.5-0.8g:50-60mL.

6. The high impact resistant HPVC power pipe according to claim 1, characterized in that: In step B1, the preparation method of the telomerized silicone oil comprises the following steps: C1. Add hydrogenated silicone oil, ethylene ammonia, chloroplatinic acid and xylene into a reactor, raise the temperature of the reactor to 50-60°C, keep the temperature for reaction for 2-3h, and perform post-treatment to obtain aminated silicone oil; C2, adding aminated silicone oil, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane and ether into a reaction kettle and stirring, raising the temperature of the reaction kettle to 30-50° C., keeping the temperature and stirring for 15-20 minutes, to obtain a reaction precursor solution; C3. Add the reaction precursor solution and 98.0%wt concentrated sulfuric acid into the reactor and stir. After stirring for 8-10 hours at room temperature, add sodium bicarbonate powder into the reactor to adjust the pH of the system to 8-9, and perform post-treatment to obtain telomerized silicone oil.

7. The high impact resistant HPVC power pipe according to claim 6, characterized in that: In step C1, the amount ratio of the hydrogenated silicone oil, ethyleneamine, chloroplatinic acid and xylene is 8-10g:2-3g:0.3-0.5g:40-50mL; in step C2, the stirring rate is 120-160rpm, and the amount ratio of ammoniated silicone oil, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane and ether is 6-8g:7-9g:2-3g:50-80mL; in step C3, the amount ratio of the reaction precursor solution and 98.0%wt concentrated sulfuric acid is 20-24mL:2-3mL.

8. A processing technology for a high impact resistant HPVC power pipe according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1. uniformly mixing the modified HPVC, the modified plasticizer, the filler, the stabilizer, the antioxidant, the ultraviolet absorber and the lubricant to obtain a mixture; S2. Place the copper mesh in a mold, add the mixed material into a twin-screw extruder for melt extrusion to cast the copper mesh, and obtain the HPVC power pipe after the material is cooled.

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