Low-temperature-resistant corrosion-resistant flexible robot cable and preparation method thereof
By preparing polyester hybrids and modified oligomers, the problems of traditional cable aging in brittle and corrosive environments at low temperatures are solved, and the flexibility and corrosion resistance of robot cables are improved in extreme environments.
Patent Information
- Application Number
- CN202510918772.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-04
- Publication Date
- 2025-08-15
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
Traditional cable materials are prone to brittleness at low temperatures, have reduced mechanical properties, and age in corrosive environments, resulting in a shorter service life and cannot meet the robot's flexibility and corrosion resistance needs in extreme environments.
Tris(2-hydroxyethyl)phosphite is prepared by exchanging reaction of triphenyl phosphite with ethylene glycol ester, and combined with 2-methyl-2-hydroxyethyl phosphate free radical polymerization, functionalized sulfonic acid group modification and cross-linking reaction, polyester hybrids are prepared, low-density polyethylene, polyolefin elastomer and modified materials are combined, and the sheath layer is prepared by a twin-screw extrusion process, which is coated on the surface of the wire.
It improves the flexibility and toughness of the cable at low temperatures, enhances corrosion resistance, ensures structural integrity in acid-base salt spray environments, and improves the mechanical strength and chemical stability of the material.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of cable preparation, and relates to a low-temperature-resistant and corrosion-resistant flexible robot cable and a preparation method thereof. Background Art
[0002] With the rapid development of robotics technology, robots are increasingly being used in industry, healthcare, services, and other fields. In practical applications, robots need to operate for long periods of time in complex and harsh environments, such as low temperatures, high humidity, and highly corrosive gases or chemicals. These extreme operating conditions place higher demands on the performance of robot cables. As a key connecting component in robotic systems, cables must not only have excellent electrical properties but also maintain stable physical and chemical properties in low temperatures, high mechanical stress, and corrosive environments. However, traditional cable materials tend to become brittle at low temperatures, with mechanical properties degrading and even breaking. In addition, prolonged exposure to corrosive environments can cause the cable sheath to chemically degrade or age, shortening its service life and affecting the normal operation and safety of the equipment.
[0003] Currently, common cable sheath materials, including standard polyolefins, offer considerable mechanical strength but are susceptible to brittleness at low temperatures, making them inadequate for the flexibility required in extreme environments. Furthermore, these materials have limited corrosion resistance and are susceptible to degradation in strong acid, alkali, or salt spray environments. Therefore, the design of high-performance flexible cables with both low-temperature toughness and corrosion resistance remains a pressing technical challenge in the polymer composites and cable manufacturing industries. Summary of the Invention
[0004] In response to the shortcomings of the prior art, the present invention aims to provide a low-temperature, corrosion-resistant flexible robot cable and a method for preparing the same. The present invention first prepares tris(2-hydroxyethyl)phosphite through an ester exchange reaction between triphenyl phosphite and ethylene glycol, and then combines this with free radical polymerization of 2-hydroxyethyl 2-methyl-2-acrylate phosphate, functionalized sulfonic acid group modification, and cross-linking reactions. Subsequently, tris(2-hydroxyethyl)phosphite is polyesterified with adipic acid, polytetrahydrofuran diol, and other materials, and silanized with trifluoropropylsilane to prepare a polyester hybrid with corrosion resistance. Low-density polyethylene, a polyolefin elastomer, the modified materials, and additives are compounded, and a sheath masterbatch is prepared using a twin-screw extrusion process. This masterbatch is then coated on the conductor surface, thereby meeting the needs of actual production.
[0005] To achieve this object, the present invention adopts the following technical solutions: In a first aspect, the present invention provides a method for preparing a low-temperature resistant and corrosion-resistant flexible robot cable, the method comprising: S1, in a nitrogen atmosphere, 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate, hydroxyethyl pyrrolidone, and toluene are mixed, and a first portion of azobisisobutyronitrile is added to react to obtain a phosphorus-nitrogen precursor, and then the phosphorus-nitrogen precursor, 2-acrylamido-2-methylpropanesulfonic acid, and deionized water are mixed and stirred uniformly to obtain a sulfonate-modified precursor, and then the sulfonate-modified precursor, divinylbenzene, and toluene are mixed, and a second portion of azobisisobutyronitrile is added to continue the reaction to obtain a modified oligomer; S2, mixing adipic acid, polytetramethylene glycol, polypropylene glycol and tris(2-hydroxyethyl)phosphite to obtain a polyester prepolymer, mixing the polyester prepolymer, trifluoropropyltrimethoxysilane and tetraisopropyl titanate to obtain a fluorocarbon-modified prepolymer, and mixing the fluorocarbon-modified prepolymer with polyethylene glycol 600 to obtain a polyester hybrid; S3, low-density polyethylene, polyolefin elastomer, modified oligomer, polyester hybrid, flame retardant, antioxidant, maleic anhydride grafted polyethylene, light stabilizer and calcium stearate are mixed, extruded into granules to obtain sheath layer masterbatch, the wire core is sequentially coated with a linear low-density polyethylene insulation layer and a polypropylene mesh tape filling layer and twisted into a conductor, the sheath layer masterbatch is added into a twin-screw extruder and extruded and coated on the surface of the conductor to obtain a low-temperature resistant and corrosion-resistant flexible robot cable.
[0006] Specifically include: A1, under a nitrogen atmosphere, triphenyl phosphite, ethylene glycol, and p-toluenesulfonic acid are mixed and the temperature is adjusted to a first temperature for reaction to obtain tris(2-hydroxyethyl)phosphite; S1, under a nitrogen atmosphere, 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate, hydroxyethyl pyrrolidone, and toluene are mixed, the temperature is adjusted to a second temperature, and a first portion of azobisisobutyronitrile is added for reaction to obtain a phosphorus-nitrogen precursor, the phosphorus-nitrogen precursor, 2-acrylamido-2-methylpropanesulfonic acid, and deionized water are mixed and stirred uniformly, potassium carbonate is added to adjust the pH to 7-7.5, and the temperature is adjusted to a third temperature for reaction to obtain a sulfonate-modified precursor, the sulfonate-modified precursor, divinylbenzene, and toluene are mixed, the temperature is adjusted to a second temperature under a nitrogen atmosphere, and a second portion of azobisisobutyronitrile is added for continued reaction to obtain a modified oligomer; S2, mixing adipic acid, polytetrahydrofuran diol, polypropylene glycol and tris(2-hydroxyethyl)phosphite, adjusting the temperature to a fourth temperature to react to obtain a polyester prepolymer, mixing the polyester prepolymer, trifluoropropyltrimethoxysilane and tetraisopropyl titanate, adjusting the temperature to a first temperature under a nitrogen atmosphere to react to obtain a fluorocarbon-modified prepolymer, mixing the fluorocarbon-modified prepolymer with polyethylene glycol 600, adjusting the temperature to a fifth temperature to react to obtain a polyester hybrid; S3, low-density polyethylene, polyolefin elastomer, modified oligomer, polyester hybrid, flame retardant, antioxidant, maleic anhydride grafted polyethylene, light stabilizer and calcium stearate are mixed, and the mixture is added to a twin-screw extruder, extruded into granules to obtain a sheath layer masterbatch, the wire core is sequentially coated with a linear low-density polyethylene insulation layer and a polypropylene mesh tape filling layer and twisted into a conductor, the sheath layer masterbatch is added to a twin-screw extruder and extruded and coated on the surface of the conductor to obtain a low-temperature and corrosion-resistant flexible robot cable.
[0007] 2-Hydroxyethyl 2-methyl-2-acrylate phosphate is a functional monomer. The phosphate group in its molecule imparts polarity and potential flame retardancy, while the unsaturated double bond of the acrylate provides an active site for free radical polymerization. Hydroxyethyl pyrrolidone, a cyclic compound containing an amide structure, exhibits excellent polarity and hydrogen bonding ability. Azobisisobutyronitrile (AIBN) is added as a free radical initiator. AIBN undergoes homolytic cleavage under thermal conditions, generating active free radicals that react with the double bond of the 2-hydroxyethyl 2-methyl-2-acrylate phosphate molecule to form intermediate active free radicals. These active free radicals then undergo chain propagation reactions with other monomers in the system (such as hydroxyethyl pyrrolidone), ultimately forming a polymer precursor containing a phosphate group and a pyrrolidone ring structure, termed a phosphorus-nitrogen precursor. The prepared phosphorus-nitrogen precursor is mixed with 2-acrylamido-2-methylpropanesulfonic acid and deionized water and stirred until uniformly distributed. 2-Acrylamido-2-methylpropanesulfonic acid is a bifunctional monomer. The acrylamide double bond contained in its molecule can participate in free radical polymerization, while the sulfonic acid group provides significant polarity and ionic conductivity. After the addition of potassium carbonate, the pH value of the system is adjusted to a neutral range. Potassium carbonate mainly plays the role of neutralizing the acidic byproducts in the reaction system and simultaneously creates a suitable chemical environment for the introduction of the sulfonic acid group. In this step, the active sites in the phosphorus-nitrogen precursor undergo a free radical addition reaction with the double bonds of 2-acrylamido-2-methylpropanesulfonic acid to form a modified precursor containing a sulfonic acid group. The sulfonate-modified precursor is mixed with divinylbenzene and toluene and reacted under nitrogen protection. Divinylbenzene, as a bifunctional crosslinking agent, contains two vinyl double bonds that can undergo a crosslinking reaction with the active sites in the modified precursor, thereby forming an oligomer with a three-dimensional network structure. This process again uses AIBN as an initiator. The cross-linking reaction initiated by free radicals not only gives the material higher mechanical strength and thermal stability, but also improves the rigidity and chemical resistance of the material through the aromatic ring structure of divinylbenzene.
[0008] Triphenyl phosphite is a phosphorus compound with three ester groups, and its ester groups are prone to transesterification with alcohol compounds under suitable conditions. Ethylene glycol contains two hydroxyl groups, which have a high nucleophilicity. This allows it to undergo a nucleophilic substitution reaction with the ester groups in the triphenyl phosphite molecule. The hydroxyl groups of ethylene glycol attack the phosphorus atom of triphenyl phosphite, causing the phenol group on the ester group to leave as a leaving group, generating a new ester bond. Since ethylene glycol is a diol, its two hydroxyl groups can react with triphenyl phosphite, ultimately generating tris(2-hydroxyethyl)phosphite. Adipic acid, polytetrahydrofuran diol, and polypropylene glycol are mixed with tris(2-hydroxyethyl)phosphite at a relatively high temperature to undergo a polyesterification reaction. Adipic acid is a dicarboxylic acid, while polytetrahydrofuran diol and polypropylene glycol are two diols with different molecular weights. The core mechanism of the polyesterification reaction is the condensation reaction between the carboxyl group and the hydroxyl group. The carboxyl group of adipic acid undergoes a condensation reaction with the hydroxyl group of the polyol, generating an ester bond while releasing water molecules. The hydroxyl group in tris(2-hydroxyethyl)phosphite also participates in this condensation reaction, introducing the phosphate structure into the polyester chain, giving the polyester material flame retardancy and polarity adjustment capabilities.
[0009] After the polyesterification reaction is complete, the resulting polyester prepolymer is mixed with trifluoropropyltrimethoxysilane and tetraisopropyl titanate for a silanization modification reaction. Trifluoropropyltrimethoxysilane is a functionalized silane molecule containing both fluorinated alkyl groups and trimethoxysilyl groups in its structure. The trimethoxysilyl groups can hydrolyze to form silanol groups, which can then undergo condensation reactions with each other or with hydroxyl groups in the prepolymer to form silanol bonds. This process not only introduces fluorinated alkyl groups into the polyester molecule but also enhances the chemical stability and weatherability of the polyester through the formation of silanol bonds. Finally, the resulting fluorocarbon-modified prepolymer is blended and reacted with polyethylene glycol 600 to produce a polyester hybrid. Polyethylene glycol 600 is a short-chain polyether with terminal hydroxyl groups, which can undergo further condensation reactions with the active groups in the fluorocarbon-modified prepolymer to form a polyester-polyether blend system. Through this reaction, the flexibility of the polyester is improved, and the introduction of fluorinated alkyl groups gives the material excellent corrosion resistance and low surface energy. The polyester hybrid combines polyester segments with polyether segments to form a blended structure of soft and hard segments. The polyether segments have a low glass transition temperature and excellent low-temperature flexibility, which reduces the brittle temperature of the entire material system and enhances the material's flexibility and fracture resistance in low-temperature environments. The introduction of fluorinated alkyl groups and silicon-oxygen bonds not only enhances the material's chemical stability but also indirectly improves its flexibility under low-temperature conditions by improving the sliding properties of the polymer segments.
[0010] As a preferred technical solution of the present invention, in A1, the mass ratio of triphenyl phosphite, ethylene glycol and p-toluenesulfonic acid is (100-110): (200-210): 1, for example, it can be (100, 101, 102, 103, 104, 105, 106, 107, 108, 109 or 110): (200, 201, 202, 203, 204, 205, 206, 207, 208, 209 or 210): 1, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0011] In some optional examples, the first temperature is 120-125°C, for example, it can be 120.0°C, 120.5°C, 121.0°C, 121.5°C, 122.0°C, 122.5°C, 123.0°C, 123.5°C, 124.0°C, 124.5°C or 125.0°C, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0012] As a preferred technical solution of the present invention, in S1, the mass ratio of the 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate, hydroxyethyl pyrrolidone, toluene and the first portion of azobisisobutyronitrile is (100-110): (40-45): 50: 1, for example, it can be (100, 101, 102, 103, 104, 105, 106, 107, 108, 109 or 110): (40.0, 40.5, 41.0, 41.5, 42.0, 42.5, 43.0, 43.5, 44.0, 44.5 or 45.0): 50: 1, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.
[0013] In some optional examples, the second temperature range is 70-75°C, for example, it can be 70.0°C, 70.5°C, 71.0°C, 71.5°C, 72.0°C, 72.5°C, 73.0°C, 73.5°C, 74.0°C, 74.5°C or 75.0°C, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0014] In some optional examples, the reaction time for adding the first portion of azobisisobutyronitrile is 6-7h, for example, it can be 6.0h, 6.1h, 6.2h, 6.3h, 6.4h, 6.5h, 6.6h, 6.7h, 6.8h, 6.9h or 7.0h, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0015] The mass ratio of the phosphorus-nitrogen precursor, 2-acrylamido-2-methylpropanesulfonic acid and deionized water is (100-105): (15-18): 30, for example, it can be (100.0, 100.5, 101.0, 101.5, 102.0, 102.5, 103.0, 103.5, 104.0 or 104.5 and 105.0): (15.0, 15.3, 15.6, 15.9, 16.2, 16.5, 16.8, 17.1, 17.4, 17.7 or 18.0): 30, but is not limited to the listed values, and other values not listed within this numerical range are also applicable.
[0016] In some optional examples, the third temperature is 50-55°C, for example, it can be 50.0°C, 50.5°C, 51.0°C, 51.5°C, 52.0°C, 52.5°C, 53.0°C, 53.5°C, 54.0°C, 54.5°C or 55.0°C, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0017] In some optional examples, the time of the third temperature reaction is 2-3h, for example, it can be 2.0h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h or 3.0h, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0018] In some optional examples, the mass ratio of the sulfonate modified precursor, divinylbenzene, toluene and the second portion of azobisisobutyronitrile is (100-110): (1.5-2.0): 20: 0.5, for example, it can be (100, 101, 102, 103, 104, 105, 106, 107, 108, 109 or 110): (1.50, 1.55, 1.60, 1.65, 1.70, 1.75, 1.80, 1.85, 1.90, 1.95 or 2.00): 20: 0.5, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0019] In some optional examples, the time for continuing the reaction after adding the second portion of azobisisobutyronitrile is 1-2 hours, for example, it can be 1.0 hours, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours or 2.0 hours, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0020] As a preferred technical solution of the present invention, in S2, the mass ratio of adipic acid, polytetrahydrofuran diol, polypropylene glycol and tris(2-hydroxyethyl)phosphite is (100-110): (50-55): (30-34): (5-8), for example, it can be (100, 101, 102, 103, 104, 105, 106, 107, 108, 109 or 110): (50.0, 50.5, 51.0, 51.5, 52.0, 52.5, 53.0, 53.5, 54.0, 54.5 or 55.0): (30.0, 30.4, 30.8, 31.2, 31.6, 32.0, 32.4, 32.8, 33.2, 33.6 or 34.0): (5.0, 5.3, 5.6, 5.9, 6.2, 6.5, 6.8, 7.1, 7.4, 7.7 or 8.0), but are not limited to the listed values, other values not listed within the numerical range are also applicable.
[0021] In some optional instances, the average Mn of the polytetrahydrofuran diol is 1000.
[0022] In some optional examples, the average Mn of the polypropylene glycol is 2000.
[0023] In some optional examples, the fourth temperature is 160-165°C, for example, it can be 160.0°C, 160.5°C, 161.0°C, 161.5°C, 162.0°C, 162.5°C, 163.0°C, 163.5°C, 164.0°C, 164.5°C or 165.0°C, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0024] In some optional examples, the fourth temperature reaction time is 5-6h, for example, it can be 5.0h, 5.1h, 5.2h, 5.3h, 5.4h, 5.5h, 5.6h, 5.7h, 5.8h, 5.9h or 6.0h, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0025] In some optional examples, the mass ratio of the polyester prepolymer, trifluoropropyltrimethoxysilane and tetraisopropyl titanate is (100-110): (15-20): 1, for example, it can be (100, 101, 102, 103, 104, 105, 106, 107, 108, 109 or 110): (15.0, 15.5, 16.0, 16.5, 17.0, 17.5, 18.0, 18.5, 19.0, 19.5 or 20.0): 1, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0026] In some optional examples, the time of the first temperature reaction is 6-7h, for example, it can be 6.0h, 6.1h, 6.2h, 6.3h, 6.4h, 6.5h, 6.6h, 6.7h, 6.8h, 6.9h or 7.0h, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0027] In some optional examples, the mass ratio of the fluorocarbon-modified prepolymer to polyethylene glycol 600 is (100-110):10, for example, it can be (100, 101, 102, 103, 104, 105, 106, 107, 108, 109 or 110):10, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0028] In some optional examples, the fifth temperature is 80-85°C, for example, it can be 80.0°C, 80.5°C, 81.0°C, 81.5°C, 82.0°C, 82.5°C, 83.0°C, 83.5°C, 84.0°C, 84.5°C or 85.0°C, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0029] In some optional examples, the time of the fifth temperature reaction is 2-3h, for example, it can be 2.0h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h or 3.0h, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0030] As a preferred technical solution of the present invention, in S3, the mass ratio of the low-density polyethylene, polyolefin elastomer, modified oligomer, polyester hybrid, flame retardant, antioxidant, maleic anhydride grafted polyethylene, light stabilizer and calcium stearate is (80-90): (20-30): (8-12): (6-10): (5-8): 2:6:3:2, for example, it can be (80, 81, 82, 83, 84, 85, 86, 87, 88, 89 or 90): (20, 21, 22, 23, 24, 25, 26, 27, 28 , 29 or 30): (8.0, 8.4, 8.8, 9.2, 9.6, 10.0, 10.4, 10.8, 11.2, 11.6 or 12.0): (6.0, 6.4, 6.8, 7.2, 7.6, 8.0, 8.4, 8.8, 9.2, 9.6 or 10.0): (5.0, 5.3, 5.6, 5.9, 6.2, 6.5, 6.8, 7.1, 7.4, 7.7 or 8.0): 2:6:3:2, but is not limited to the listed values, other values not listed within the numerical range are also applicable.
[0031] In some optional examples, the flame retardant is magnesium hydroxide, D 50 0.5-1μm.
[0032] In some optional examples, the antioxidant is antioxidant 1010.
[0033] In some optional examples, the light stabilizer is one or more of light stabilizer 770, light stabilizer 783, and light stabilizer 791.
[0034] In a second aspect, the present invention provides a low-temperature-resistant and corrosion-resistant flexible robot cable prepared by the preparation method described in the first aspect.
[0035] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) by introducing modified oligomers and polyester hybrids, especially combining the synergistic effect of phosphate groups, flexible chain segments and fluoroalkyl groups, the performance of the material in low temperature environments is optimized from the perspective of molecular structure. The introduction of ester groups and nitrogen heterocyclic structures improves the polarity of the molecular chain of the material, enhances the interaction force between the molecular chains, thereby improving the flexibility and toughness of the material. The flexible chain segments reduce the glass transition temperature of the material, so that the material can still maintain the activity of the molecular chain under low temperature conditions; (2) through the silanization reaction of the polyester hybrid Functional structures such as silicon-oxygen bonds and fluoroalkyl groups are introduced to improve the corrosion resistance of the material. Silicon-oxygen bonds have extremely high bond energy and chemical stability, and can maintain structural integrity in corrosive environments such as acidic, alkaline and salt spray. Fluoroalkyl groups can form a chemical barrier due to their excellent hydrophobicity and low surface energy; (3) The phosphate groups and silicon-oxygen bonds in the modified oligomers and polyester hybrids form a uniformly distributed cross-linked network, which enhances the structural strength of the material and makes it exhibit higher crack resistance under bending and dynamic loads. The synergistic effect of the flexible chain segments and polar groups improves the ductility and flexibility of the material. DETAILED DESCRIPTION
[0036] The technical solutions of the present invention are described in detail below with reference to specific embodiments. The embodiments described herein are specific embodiments of the present invention and are used to illustrate the concept of the present invention; these descriptions are explanatory and exemplary and should not be understood as limiting the embodiments of the present invention and the scope of protection of the present invention. In addition to the embodiments described herein, those skilled in the art can also adopt other obvious technical solutions based on the contents disclosed in the claims of this application and its specification, including technical solutions that adopt any obvious replacements and modifications to the embodiments described herein.
[0037] The chemical reagents used in the examples and comparative examples of the present invention are all commercially available products and have not been subjected to any further purification treatment.
[0038] Example 1 This embodiment provides a low-temperature-resistant and corrosion-resistant flexible robot cable and a preparation method thereof. The preparation method specifically includes the following steps: A1: In a nitrogen atmosphere, 100 parts of triphenyl phosphite, 200 parts of ethylene glycol, and 1 part of p-toluenesulfonic acid were mixed, and the temperature was adjusted to 120°C for 6 hours to obtain tris(2-hydroxyethyl)phosphite; S1, under a nitrogen atmosphere, 100 parts of 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate, 40 parts of hydroxyethyl pyrrolidone and 50 parts of toluene were mixed, the temperature was adjusted to 70°C, 1 part of azobisisobutyronitrile was added and the reaction was continued for 8 hours to obtain a phosphorus-nitrogen precursor, 100 parts of the phosphorus-nitrogen precursor, 15 parts of 2-acrylamido-2-methylpropanesulfonic acid and 30 parts of deionized water were mixed and stirred uniformly, potassium carbonate was added to adjust the pH to 7 and the temperature was adjusted to 50°C and the reaction was continued for 2 hours to obtain a sulfonate-modified precursor, 100 parts of the sulfonate-modified precursor, 1.5 parts of divinylbenzene and 20 parts of toluene were mixed, the temperature was adjusted to 70°C under a nitrogen atmosphere, 0.5 parts of azobisisobutyronitrile was added and the reaction was continued for 1 hour to obtain a modified oligomer; S2, mixing 100 parts of adipic acid, 50 parts of polytetrahydrofuran diol, 30 parts of polypropylene glycol and 5 parts of tris(2-hydroxyethyl)phosphite, adjusting the temperature to 160° C. and reacting for 5 hours to obtain a polyester prepolymer, mixing 100 parts of a polyester prepolymer, 15 parts of trifluoropropyltrimethoxysilane and 1 part of tetraisopropyl titanate, adjusting the temperature to 120° C. under a nitrogen atmosphere and reacting for 6 hours to obtain a fluorocarbon-modified prepolymer, mixing 100 parts of the fluorocarbon-modified prepolymer with 10 parts of polyethylene glycol 600, adjusting the temperature to 80° C. and reacting for 2 hours to obtain a polyester hybrid; S3, 80 parts of low-density polyethylene, 20 parts of polyolefin elastomer, 8 parts of modified oligomer, 6 parts of polyester hybrid, 5 parts of flame retardant, 2 parts of antioxidant, 6 parts of maleic anhydride grafted polyethylene, 3 parts of light stabilizer and 2 parts of calcium stearate are mixed, and the mixture is added to a twin-screw extruder, and granulated by extrusion to obtain a sheath layer masterbatch, and the wire core is sequentially coated with a linear low-density polyethylene insulation layer and a polypropylene mesh tape filling layer and twisted into a conductor, and the sheath layer masterbatch is added to the twin-screw extruder and extruded and coated on the surface of the conductor to obtain a low-temperature and corrosion-resistant flexible robot cable.
[0039] Example 2 This embodiment provides a low-temperature-resistant and corrosion-resistant flexible robot cable and a preparation method thereof. The preparation method specifically includes the following steps: A1: Under nitrogen atmosphere, mix 102 parts of triphenyl phosphite, 204 parts of ethylene glycol, and 1 part of p-toluenesulfonic acid, adjust the temperature to 122°C, and react for 6.3 hours to obtain tris(2-hydroxyethyl)phosphite; S1, under a nitrogen atmosphere, 103 parts of 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate, 42 parts of hydroxyethyl pyrrolidone and 50 parts of toluene were mixed, the temperature was adjusted to 72°C, 1 part of azobisisobutyronitrile was added and the reaction was continued for 8.3 hours to obtain a phosphorus-nitrogen precursor, 105 parts of the phosphorus-nitrogen precursor, 18 parts of 2-acrylamido-2-methylpropanesulfonic acid and 30 parts of deionized water were mixed and stirred uniformly, potassium carbonate was added to adjust the pH to 7.2 and the temperature was adjusted to 51°C and the reaction was continued for 2.3 hours to obtain a sulfonate-modified precursor, 102 parts of the sulfonate-modified precursor, 2.0 parts of divinylbenzene and 20 parts of toluene were mixed, the temperature was adjusted to 71°C under a nitrogen atmosphere, 0.5 parts of azobisisobutyronitrile was added and the reaction was continued for 1.4 hours to obtain a modified oligomer; S2, 110 parts of adipic acid, 55 parts of polytetrahydrofuran diol, 34 parts of polypropylene glycol and 7 parts of tris(2-hydroxyethyl)phosphite were mixed, the temperature was adjusted to 161° C. and the reaction was carried out for 5.4 hours to obtain a polyester prepolymer, 102 parts of a polyester prepolymer, 20 parts of trifluoropropyltrimethoxysilane and 1 part of tetraisopropyl titanate were mixed, the temperature was adjusted to 122° C. under a nitrogen atmosphere and the reaction was carried out for 6.3 hours to obtain a fluorocarbon-modified prepolymer, 103 parts of the fluorocarbon-modified prepolymer were mixed with 10 parts of polyethylene glycol 600, the temperature was adjusted to 81° C. and the reaction was carried out for 2.3 hours to obtain a polyester hybrid; S3, 82 parts of low-density polyethylene, 24 parts of polyolefin elastomer, 10 parts of modified oligomer, 10 parts of polyester hybrid, 6 parts of flame retardant, 2 parts of antioxidant, 6 parts of maleic anhydride grafted polyethylene, 3 parts of light stabilizer and 2 parts of calcium stearate are mixed, and the mixture is added to a twin-screw extruder, and granulated by extrusion to obtain a sheath layer masterbatch, and the wire core is sequentially coated with a linear low-density polyethylene insulation layer and a polypropylene mesh tape filling layer and twisted into a conductor, and the sheath layer masterbatch is added to the twin-screw extruder and extruded and coated on the surface of the conductor to obtain a low-temperature and corrosion-resistant flexible robot cable.
[0040] Example 3 This embodiment provides a low-temperature-resistant and corrosion-resistant flexible robot cable and a preparation method thereof. The preparation method specifically includes the following steps: A1: Under nitrogen atmosphere, mix 110 parts of triphenyl phosphite, 210 parts of ethylene glycol, and 1 part of p-toluenesulfonic acid, adjust the temperature to 125°C, and react for 7 hours to obtain tris(2-hydroxyethyl)phosphite; S1, under a nitrogen atmosphere, 110 parts of 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate, 45 parts of hydroxyethyl pyrrolidone and 50 parts of toluene were mixed, the temperature was adjusted to 75°C, 1 part of azobisisobutyronitrile was added and the reaction was continued for 9 hours to obtain a phosphorus-nitrogen precursor, 102 parts of the phosphorus-nitrogen precursor, 16 parts of 2-acrylamido-2-methylpropanesulfonic acid and 30 parts of deionized water were mixed and stirred uniformly, potassium carbonate was added to adjust the pH to 7.4 and the temperature was adjusted to 55°C and the reaction was continued for 3 hours to obtain a sulfonate-modified precursor, 110 parts of the sulfonate-modified precursor, 1.7 parts of divinylbenzene and 20 parts of toluene were mixed, the temperature was adjusted to 75°C under a nitrogen atmosphere, 0.5 parts of azobisisobutyronitrile was added and the reaction was continued for 2 hours to obtain a modified oligomer; S2, mixing 103 parts of adipic acid, 51 parts of polytetrahydrofuran diol, 31 parts of polypropylene glycol and 6 parts of tris(2-hydroxyethyl)phosphite, adjusting the temperature to 165° C. and reacting for 6 hours to obtain a polyester prepolymer, mixing 110 parts of a polyester prepolymer, 17 parts of trifluoropropyltrimethoxysilane and 1 part of tetraisopropyl titanate, adjusting the temperature to 125° C. under a nitrogen atmosphere and reacting for 7 hours to obtain a fluorocarbon-modified prepolymer, mixing 110 parts of the fluorocarbon-modified prepolymer with 10 parts of polyethylene glycol 600, adjusting the temperature to 85° C. and reacting for 3 hours to obtain a polyester hybrid; S3, 90 parts of low-density polyethylene, 30 parts of polyolefin elastomer, 12 parts of modified oligomer, 8 parts of polyester hybrid, 8 parts of flame retardant, 2 parts of antioxidant, 6 parts of maleic anhydride grafted polyethylene, 3 parts of light stabilizer and 2 parts of calcium stearate are mixed, and the mixture is added to a twin-screw extruder, and granulated by extrusion to obtain a sheath layer masterbatch, and the wire core is sequentially coated with a linear low-density polyethylene insulation layer and a polypropylene mesh tape filling layer and twisted into a conductor, and the sheath layer masterbatch is added to the twin-screw extruder and extruded and coated on the surface of the conductor to obtain a low-temperature and corrosion-resistant flexible robot cable.
[0041] Example 4 This embodiment provides a low-temperature-resistant and corrosion-resistant flexible robot cable and a preparation method thereof. The preparation method specifically includes the following steps: A1: Under nitrogen atmosphere, mix 107 parts of triphenyl phosphite, 208 parts of ethylene glycol, and 1 part of p-toluenesulfonic acid, adjust the temperature to 124°C, and react for 6.8 hours to obtain tris(2-hydroxyethyl)phosphite; S1, under a nitrogen atmosphere, 107 parts of 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate, 44 parts of hydroxyethyl pyrrolidone and 50 parts of toluene were mixed, the temperature was adjusted to 74°C, 1 part of azobisisobutyronitrile was added and the reaction was continued for 8.6 hours to obtain a phosphorus-nitrogen precursor, 104 parts of the phosphorus-nitrogen precursor, 17 parts of 2-acrylamido-2-methylpropanesulfonic acid and 30 parts of deionized water were mixed and stirred uniformly, potassium carbonate was added to adjust the pH to 7.5 and the temperature was adjusted to 54°C and the reaction was continued for 2.7 hours to obtain a sulfonate-modified precursor, 107 parts of the sulfonate-modified precursor, 1.9 parts of divinylbenzene and 20 parts of toluene were mixed, the temperature was adjusted to 73°C under a nitrogen atmosphere, 0.5 parts of azobisisobutyronitrile was added and the reaction was continued for 1.8 hours to obtain a modified oligomer; S2, mixing 107 parts of adipic acid, 53 parts of polytetrahydrofuran diol, 32 parts of polypropylene glycol and 8 parts of tris(2-hydroxyethyl)phosphite, adjusting the temperature to 164° C. and reacting for 5.7 hours to obtain a polyester prepolymer, mixing 108 parts of a polyester prepolymer, 18 parts of trifluoropropyltrimethoxysilane and 1 part of tetraisopropyl titanate, adjusting the temperature to 124° C. under a nitrogen atmosphere and reacting for 6.7 hours to obtain a fluorocarbon-modified prepolymer, mixing 107 parts of the fluorocarbon-modified prepolymer with 10 parts of polyethylene glycol 600, adjusting the temperature to 84° C. and reacting for 2.6 hours to obtain a polyester hybrid; S3, 84 parts of low-density polyethylene, 27 parts of polyolefin elastomer, 9 parts of modified oligomer, 7 parts of polyester hybrid, 7 parts of flame retardant, 2 parts of antioxidant, 6 parts of maleic anhydride grafted polyethylene, 3 parts of light stabilizer and 2 parts of calcium stearate are mixed, and the mixture is added to a twin-screw extruder, and extruded into granules to obtain a sheath layer masterbatch, and the wire core is sequentially coated with a linear low-density polyethylene insulation layer and a polypropylene mesh tape filling layer and twisted into a conductor, and the sheath layer masterbatch is added to the twin-screw extruder and extruded and coated on the surface of the conductor to obtain a low-temperature and corrosion-resistant flexible robot cable.
[0042] Comparative Example 1 This comparative example provides a low-temperature resistant and corrosion-resistant flexible robot cable and a preparation method thereof. The difference between it and Example 1 is that the fluorocarbon-modified prepolymer in S2 is not mixed with polyethylene glycol 600 to react to prepare a polyester hybrid, and an equal mass of the fluorocarbon-modified prepolymer is used to replace the polyester hybrid in the subsequent steps. The other process parameters and operating conditions are exactly the same as those in Example 1.
[0043] Comparative Example 2 This comparative example provides a low-temperature resistant and corrosion-resistant flexible robot cable and a preparation method thereof. The difference between it and Example 1 is that the mass fraction of trifluoropropyltrimethoxysilane in S2 is 5 parts, and the other process parameters and operating conditions are exactly the same as those in Example 1.
[0044] Comparative Example 3 This comparative example provides a low-temperature resistant and corrosion-resistant flexible robot cable and a preparation method thereof. The difference between it and Example 1 is that the mass fraction of the modified oligomer in S4 is 0, and the other process parameters and operating conditions are exactly the same as those in Example 1.
[0045] The low-temperature brittleness test method was ASTM D746. For corrosion resistance testing, the cable sheath was immersed in a 10 wt.% H₂SO₄ solution at 25±2°C for three days. The change in elongation at break after immersion was calculated as (elongation at break after immersion - elongation at break before immersion) / elongation at break before immersion * 100%. The flexural strength test standard was GB / T 9341-2008. The test results are shown in Table 1.
[0046] Table 1 Test results of low temperature and corrosion resistant flexible robot cables of Examples 1 to 4 and Comparative Examples 1 to 3 As shown in Table 1, compared to Example 1, the low-temperature resistance, corrosion resistance, and flexural strength of Comparative Example 1 decreased; the low-temperature resistance, corrosion resistance, and flexural strength of Comparative Example 2 decreased; and the low-temperature resistance, corrosion resistance, and flexural strength of Comparative Example 3 decreased. This is because in Example 1, the fluorocarbon-modified prepolymer was not mixed with polyethylene glycol 600 to prepare the polyester hybrid. An equal amount of fluorocarbon-modified prepolymer was used to replace the polyester hybrid in the subsequent step. Polyethylene glycol 600 contains flexible segments in its molecular structure and has a low glass transition temperature. It can maintain high molecular chain mobility in low-temperature environments, thus giving the material good flexibility and resistance to low-temperature brittleness. In Comparative Example 2, the mass fraction of trifluoropropyltrimethoxysilane is insufficient. Trifluoropropyltrimethoxysilane forms a cross-linked silicon-oxygen bond network in the polyester hybrid through a silanization reaction, providing molecular chain flexibility and structural stability, helping the material maintain molecular chain mobility in low-temperature environments. At the same time, the fluoroalkyl group has ultra-low surface energy and chemical inertness. The reduced number of fluoroalkyl groups weakens the surface barrier effect. The modified oligomer improves the molecular chain flexibility and interface compatibility of the material through the phosphate group and nitrogen heterocyclic structure in its molecular structure. In Comparative Example 3, the mass fraction of the modified oligomer is 0, the polarity of the material is reduced, and the intermolecular interaction is weakened, resulting in insufficient flexible chain segments. The lack of phosphate and sulfonic acid groups reduces the polarity of the material and reduces the chemical barrier ability.
[0047] The above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and disclosure scope of the present invention.
Claims
1. A method for preparing a low-temperature-resistant and corrosion-resistant flexible robot cable, characterized in that: The preparation method comprises: S1, in a nitrogen atmosphere, 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate, hydroxyethyl pyrrolidone, and toluene are mixed, and a first portion of azobisisobutyronitrile is added to react to obtain a phosphorus-nitrogen precursor, and then the phosphorus-nitrogen precursor, 2-acrylamido-2-methylpropanesulfonic acid, and deionized water are mixed and stirred uniformly to obtain a sulfonate-modified precursor, and then the sulfonate-modified precursor, divinylbenzene, and toluene are mixed, and a second portion of azobisisobutyronitrile is added to continue the reaction to obtain a modified oligomer; S2, mixing adipic acid, polytetramethylene glycol, polypropylene glycol and tris(2-hydroxyethyl)phosphite to obtain a polyester prepolymer, mixing the polyester prepolymer, trifluoropropyltrimethoxysilane and tetraisopropyl titanate to obtain a fluorocarbon-modified prepolymer, and mixing the fluorocarbon-modified prepolymer with polyethylene glycol 600 to obtain a polyester hybrid; S3, low-density polyethylene, polyolefin elastomer, modified oligomer, polyester hybrid, flame retardant, antioxidant, maleic anhydride grafted polyethylene, light stabilizer and calcium stearate are mixed, extruded into granules to obtain sheath layer masterbatch, the wire core is sequentially coated with a linear low-density polyethylene insulation layer and a polypropylene mesh tape filling layer and twisted into a conductor, the sheath layer masterbatch is added into a twin-screw extruder and extruded and coated on the surface of the conductor to obtain a low-temperature resistant and corrosion-resistant flexible robot cable.
2. The method for preparing a low-temperature-resistant and corrosion-resistant flexible robot cable according to claim 1, characterized in that: The preparation method of the tris(2-hydroxyethyl)phosphite comprises: A1: Under nitrogen atmosphere, triphenyl phosphite, ethylene glycol, and p-toluenesulfonic acid are mixed and reacted to obtain tris(2-hydroxyethyl)phosphite.
3. The method for preparing a low-temperature-resistant and corrosion-resistant flexible robot cable according to claim 1, characterized in that: In S1, The mass ratio of the 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate, hydroxyethyl pyrrolidone, toluene and the first portion of azobisisobutyronitrile is (100-110): (40-45): 50:
1.
4. The method for preparing a low-temperature-resistant and corrosion-resistant flexible robot cable according to claim 1, characterized in that: In S1, The mass ratio of the phosphorus-nitrogen precursor, 2-acrylamido-2-methylpropanesulfonic acid and deionized water is (100-105): (15-18): 30; The mass ratio of the sulfonate modified precursor, divinylbenzene, toluene and the second portion of azobisisobutyronitrile is (100-110): (1.5-2.0): 20: 0.
5.
5. The method for preparing a low-temperature-resistant and corrosion-resistant flexible robot cable according to claim 1, characterized in that: In S2, The mass ratio of the adipic acid, polytetrahydrofuran diol, polypropylene glycol and tris(2-hydroxyethyl)phosphite is (100-110): (50-55): (30-34): (5-8); The average Mn of the polytetrahydrofuran diol is 1000; The average Mn of the polypropylene glycol is 2000.
6. The method for preparing a low-temperature-resistant and corrosion-resistant flexible robot cable according to claim 1, characterized in that: In S2, The mass ratio of the polyester prepolymer, trifluoropropyltrimethoxysilane and tetraisopropyl titanate is (100-110): (15-20): 1; The mass ratio of the fluorocarbon-modified prepolymer to polyethylene glycol 600 is (100-110):
10.
7. The method for preparing a low-temperature-resistant and corrosion-resistant flexible robot cable according to claim 1, characterized in that: In S3, The mass ratio of the low-density polyethylene, polyolefin elastomer, modified oligomer, polyester hybrid, flame retardant, antioxidant, maleic anhydride grafted polyethylene, light stabilizer and calcium stearate is (80-90): (20-30): (8-12): (6-10): (5-8): 2:6:3:
2.
8. The method for preparing a low-temperature-resistant and corrosion-resistant flexible robot cable according to claim 1, characterized in that: In S3, The flame retardant is magnesium hydroxide, D 50 0.5-1μm; The antioxidant is antioxidant 1010; The light stabilizer is one or more of light stabilizer 770, light stabilizer 783, and light stabilizer 791.
9. The method for preparing tris(2-hydroxyethyl)phosphite according to claim 2, wherein In A1, The mass ratio of triphenyl phosphite, ethylene glycol and p-toluenesulfonic acid is (100-110): (200-210):
1.
10. Low temperature resistant and corrosion resistant flexible robot cable, characterized in that: Obtained according to the preparation method according to any one of claims 1 to 9.