High-strength and high-toughness plastic steel stay wire for replacing steel strand and production process of high-strength and high-toughness plastic steel stay wire

Abstract

The invention relates to the technical field of polyurethane resin for pultrusion, in particular to a high-strength and high-toughness plastic steel stay wire for replacing a steel strand and a production process of the high-strength and high-toughness plastic steel stay wire. The high-strength and high-toughness plastic steel stay wire for replacing the steel strand comprises continuous fibers and polyurethane resin, the mass percentage of the continuous fibers is 76-80w% of the total mass of the high-strength and high-toughness plastic steel stay wire, and the mass percentage of the polyurethane resin is 20-24w% of the total mass of the high-strength and high-toughness plastic steel stay wire; the polyurethane resin is composed of polyisocyanate, polyol, a chain extender, a catalyst, an antibacterial mildew-proof auxiliary agent, a reinforced filler, an antioxidant auxiliary agent, an anti-ultraviolet aging auxiliary agent, a surface modifier and a defoaming agent. The high-strength and high-toughness polyurethane plastic steel stay wire has excellent tensile mechanical property, ultraviolet aging resistance and chemical corrosion resistance, can replace a steel strand of a guyed tower, can effectively improve the service life and safety risk control coefficient of a polyurethane-based composite stay wire, and reduces the maintenance period of the guyed tower stay wire.

Description

Technical Field

[0001] The present invention relates to the technical field of polyurethane resin for pultrusion, and in particular to a high-strength and high-toughness plastic steel wire for replacing steel strands and a production process thereof. Background Art

[0002] Guyed towers are widely used in warehousing and logistics, substations, communication hubs, important public facilities, industrial enterprises, and other locations due to their low investment, fast construction, and wide adaptability. The steel strands of guyed towers are affected by the environment, especially in subtropical monsoon climates. The hot and humid climate severely damages the strands, and after only three to four years of use, the strands can develop rust, pitting, cracks, or even breakage. Furthermore, the strands are subject to extreme tension from external winds, which eliminates stress and increases displacement, exacerbating damage to the anchor points and tower base, creating operational safety risks for the towers. The strands are typically replaced every three years, leading to high maintenance costs and low safety risk control.

[0003] To address the weathering resistance issues of existing steel strands and the high maintenance costs associated with frequent replacement, research institutions have proposed replacing conventional steel strands with pultruded composite materials, which offer superior weathering resistance. Pultruded composite materials are manufactured through a pultrusion process using a matrix resin (such as unsaturated polyester, epoxy, or polyurethane) and high-performance fibers (such as glass fiber, quartz fiber, or basalt fiber).

[0004] Unsaturated polyesters are not suitable as matrix resins in pultruded composite materials due to their poor mechanical properties and the fact that they use peroxide as a curing agent, which poses a processing safety risk. Epoxy resins have a highly cross-linked three-dimensional network structure that gives them good mechanical properties and corrosion resistance, but they are brittle and lack toughness. When the external wind is strong, epoxy-based pultruded composite cables are at risk of breaking, resulting in low safety and wind control. They are only suitable for areas with low winds on inner roads, which limits their scope of application. Furthermore, the high cost of epoxy resins results in a relatively high overall cost for epoxy-based pultruded composite cables. AB-component polyurethane thermoplastic elastomers, as matrix resins in pultruded composite materials, can, on the one hand, give polyurethane-based composite cables good mechanical properties and corrosion resistance, and on the other hand, possess shape memory properties – resilience – which allows them to return to their original shape after the stress disappears, effectively improving the service life and safety and wind control coefficient of polyurethane-based composite cables.

[0005] Existing Chinese patent application number 2012102465038 discloses a polyurethane resin composite for pultrusion, prepared from continuous fibers and polyurethane resin. The continuous fibers are either glass fibers or carbon fibers, accounting for 60-85% by weight of the total composite material, and the polyurethane resin accounts for 15-40% by weight of the total composite material. The raw materials and their weight ratios for preparing the polyurethane resin are as follows: 42-60% isocyanate, 0-58% polymer polyol, 0.1-0.5% catalyst, 1-2% water scavenger, 0-1% defoamer, 0-5% filler, and 0-1% release agent. The isocyanate is one or more of diphenylmethane diisocyanate, liquefied MDI, or polymerized MDI. As disclosed in Examples 3-4 of the patent, the glass fiber / polyurethane-based composite material can achieve a tensile strength of 1138-1186 MPa.

[0006] While the aforementioned glass fiber / polyurethane composite material has application value in tower cable, its synthetic raw materials are primarily aromatic isocyanates. Under the influence of strong ultraviolet radiation and high temperatures in summer, the benzene ring structure in the aromatic isocyanate is easily isomerized, and photooxidation destroys the hard segment benzene ring structure, resulting in a significant decrease in overall mechanical properties and corrosion resistance, limiting the application of this type of polyurethane-based composite cable in the field and outdoors. To this end, the inventors provide a high-strength and high-toughness plastic steel cable and its production process for replacing steel stranded wire. Summary of the Invention

[0007] In order to solve the technical problems that the existing polyurethane-based composite pull wire has weak UV aging resistance and its mechanical properties need to be further improved, the present invention provides a high-strength and high-toughness plastic-steel pull wire and its production process for replacing steel strands, which has excellent tensile strength, UV aging resistance and chemical corrosion resistance.

[0008] The present invention provides a high-strength and high-toughness plastic-steel cable for replacing steel strands, which is achieved through the following technical solutions:

[0009] A high-strength and high-toughness plastic steel cable for replacing steel strands comprises continuous fibers and polyurethane resin, wherein the mass percentage of the continuous fibers is 76-80w% of the total mass of the high-strength and high-toughness plastic steel cable, and the polyurethane resin is 20-24w% of the total mass of the high-strength and high-toughness plastic steel cable; the polyurethane resin is made of the following raw materials in parts by weight: 26-37 parts of polyisocyanate, 42-56 parts of polyol, 5.5-12 parts of chain extender, 0.02-0.04 parts of catalyst, 0 0.6-0.8 parts of antibacterial and antifungal agents, 2-5 parts of reinforcing fillers, 0.4-0.8 parts of antioxidants, 0-0.8 parts of anti-ultraviolet aging agents, 0.1-0.4 parts of surface modifiers, and 0.15-0.30 parts of defoaming agents; the polyisocyanate includes alicyclic diisocyanates, and the alicyclic diisocyanates are at least one of dicyclohexylmethane diisocyanate H12MDI, isophorone diisocyanate IPDI, and norbornane diisocyanate NBDI.

[0010] The high-strength and high-toughness polyurethane plastic-steel cable in the present invention has excellent tensile mechanical properties, UV aging resistance and chemical corrosion resistance. It can replace the steel strands of the cable tower, effectively improve the service life and safety risk control coefficient of the polyurethane-based composite cable, and reduce the maintenance cycle of the cable tower cable.

[0011] Preferably, the continuous fiber is any one of HS2 high-strength glass fiber roving, HS4 high-strength glass fiber roving, and HS6 high-strength glass fiber roving with a tensile strength of ≥4000 MPa.

[0012] The tensile strength of the steel strands of existing guying towers is 1450-1600 MPa. The high-strength and high-toughness plastic-steel guy wire prepared by the present invention using high-strength glass fiber roving combined with a special polyurethane resin through an extrusion process has a tensile strength of 1440-1570 MPa. That is, the high-strength and high-toughness plastic-steel guy wire can meet the mechanical strength requirements of the guy wire for the guying tower, and has good resilience, which can improve the safety and risk control coefficient of the guying tower.

[0013] Preferably, the R value of the polyurethane resin is 1.00-1.03, and the NCO molar amount in the polyisocyanate is 1.00-1.03 times the sum of the active hydrogen molar amount in the polyol and the active hydrogen molar amount in the chain extender.

[0014] By controlling the R value of the urethane resin, the resilience of the prepared polyurethane resin can be guaranteed, and it will return to its original state after the stress disappears, which can effectively improve the service life and safety risk control coefficient of the polyurethane-based composite cable.

[0015] When the R value of the polyurethane resin is greater than 1.00 and less than or equal to 1.03, the polyurethane matrix is lightly cross-linked, has good resilience, and has relatively better mechanical strength, wear resistance, hydrolysis resistance, corrosion resistance, weather resistance, and UV aging resistance.

[0016] When the R value of the polyurethane resin is greater than 1.03, as the cross-linking density increases, the hardness increases but its resilience deteriorates, which will affect the service life and safety risk control coefficient of the polyurethane-based composite cable.

[0017] In the actual production process, considering that the continuous fiber has active hydrogen groups after surface treatment and the antibacterial and antifungal additives and reinforcing fillers have active hydrogen groups after surface treatment, they will consume the NCO groups in the polyisocyanate. When designing the polyurethane formula, the R value of the polyurethane resin should be controlled at 1.01-1.03.

[0018] Preferably, the polyisocyanate further comprises triisocyanate, wherein the NCO molar amount in the triisocyanate accounts for 0-0.5% of the total NCO molar amount in the polyisocyanate; and the triisocyanate is at least one of HDI trimer, IPDI trimer, and L-lysine triisocyanate.

[0019] The triisocyanate in the polyurethane resin formula of the present invention does not contain a benzene ring group, which can make the polyurethane network slightly cross-linked, giving the high-strength and high-toughness plastic steel cable better resilience while having relatively better mechanical strength, wear resistance, hydrolysis resistance, corrosion resistance, weather resistance and UV aging resistance.

[0020] Preferably, the polyol comprises at least one of polytetramethylene glycol having a hydroxyl value of 110-170 mg KOH / g and polycarbonate diol, or at least one of polytetramethylene glycol having a hydroxyl value of 110-170 mg KOH / g and polycarbonate diol, in combination with at least one of polyolefin diol having a hydroxyl value of 70-130 mg KOH / g and polyether triol having a hydroxyl value of 200-550 mg KOH / g; and the polyolefin diol is hydroxyl-terminated hydrogenated polybutylene glycol GI-1000 and / or hydroxyl-terminated epoxidized hydrogenated polybutylene glycol Poly bd 600E.

[0021] Preferably, the polyol is composed of polytetramethylene glycol having a hydroxyl value of 110-170 mg KOH / g, polycarbonate diol, and polyolefin diol having a hydroxyl value of 70-130 mg KOH / g.

[0022] The use of polytetrahydrofuran diol in the polyurethane formula of the present invention can ensure that the high-strength and high-toughness plastic steel cable has excellent hydrolysis stability, and further can ensure the outdoor service life of the high-strength and high-toughness plastic steel cable. The use of polycarbonate diol in the polyurethane formula of the present invention can ensure that the high-strength and high-toughness plastic steel cable has excellent hydrolysis stability, mechanical strength, wear resistance, and weather resistance. The combined use of polytetrahydrofuran diol and polycarbonate diol can, on the one hand, ensure the hydrolysis stability, mechanical strength, wear resistance, and weather resistance of the high-strength and high-toughness plastic steel cable, and on the other hand, improve the surface quality of the high-strength and high-toughness plastic steel cable and also reduce the material cost of the polyol. The addition of polyolefin diol in the polyurethane formula, the molecular weight of the polyolefin diol is larger than that of polytetrahydrofuran diol and polycarbonate diol, gives the high-strength and high-toughness plastic steel cable good low-temperature flexibility, tensile mechanical strength, acid and alkali corrosion resistance, and aging resistance. Among them, the hydroxy-terminated epoxidized hydrogenated polybutylene glycol Poly bd 600E has the best reinforcement effect on high-strength and high-toughness plastic steel cables. The epoxy groups it contains will react with the continuous fibers that have been surface-treated with active hydrogen groups, the antibacterial and mildew-proof additives, and the reinforcing fillers that have been surface-treated with active hydrogen groups. The secondary hydroxyl groups formed by the two are located in the side chains of the polymer molecular weight. The secondary hydroxyl groups in the side chains of the polymer molecular weight will react with the NCO in the polyisocyanate to form polyurethane bonds, improving the overall cross-linking density, which is beneficial to improving the overall mechanical strength, wear resistance, hydrolysis resistance, chemical corrosion resistance, weather resistance and UV aging resistance, thereby ensuring the overall service life.

[0023] Preferably, the chain extender includes a diol and a triol, the diol being at least one of 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, and spirodiol in combination with at least one of 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, a diol containing a double Se bond, and a diamine containing a double Se bond; the triol being at least one of glycerol GL, trimethylolpropane TMP, and trishydroxyethyl isocyanurate THEIC.

[0024] The polyurethane formula of the present invention mainly adopts alicyclic diols with diactive hydrogen groups, and auxiliary uses aliphatic diols with diactive hydrogen groups. On the one hand, it can ensure the anti-ultraviolet aging performance and weather resistance of the high-strength and high-toughness plastic-steel cable while improving its mechanical strength; on the other hand, it ensures its rebound performance, which is beneficial to improve the service life and safety risk control coefficient of the high-strength and high-toughness plastic-steel cable.

[0025] Preferably, the ratio of the molar amount of NCO in the triisocyanate to the molar amount of active hydrogen in the polyether triol and the molar amount of active hydrogen in the triol to the molar amount of NCO in the polyisocyanate to the molar amount of active hydrogen in the polyol and the molar amount of active hydrogen in the chain extender is 1:(42-48).

[0026] By adopting the above technical solution, the network structure formed by the polyurethane resin is controlled to be a lightly cross-linked three-dimensional network structure, which can ensure the resilience of the high-strength and high-toughness plastic-steel cable while improving its mechanical strength, wear resistance, hydrolysis resistance, corrosion resistance, weather resistance and UV aging resistance.

[0027] When the sum of the NCO molar amount in the triisocyanate, the active hydrogen molar amount in the polyether triol, and the active hydrogen molar amount in the triol is too large, the crosslinking density of the network structure formed by the polyurethane resin increases, the hardness increases, but its resilience deteriorates, which will affect the service life and safety risk control coefficient of the polyurethane-based composite cable. When the sum of the NCO molar amount in the triisocyanate, the active hydrogen molar amount in the polyether triol, and the active hydrogen molar amount in the triol is too low, the physical and chemical properties of the high-strength and high-toughness plastic steel cable are not significantly improved.

[0028] Preferably, the antibacterial and antifungal agent is at least one of nano zinc oxide, nano titanium dioxide, and nano titanium oxynitride.

[0029] The antibacterial and mildew-proof additive in the polyurethane formula of the present invention can impart good antibacterial and mildew-proof properties to the high-strength and high-toughness plastic-steel cable and can also assist in improving the anti-ultraviolet aging performance.

[0030] The reinforcing filler is composed of at least one of flaky nano-molybdenum disulfide and flaky nano-boron nitride, and at least one of nano-silicon dioxide and nano-silicon nitride.

[0031] The flaky nano-molybdenum disulfide and flaky nano-boron nitride in the polyurethane formula of the present invention can improve the density of the high-strength and high-toughness plastic steel cable, thereby improving the mechanical properties, wear resistance, hydrolysis temperature resistance, ultraviolet aging resistance and weather resistance of the high-strength and high-toughness plastic steel cable. On the other hand, they play a lubricating role and flame retardant and fire-burning resistance, without the need to add additional lubricants, improving the surface extrusion quality of the high-strength and high-toughness plastic steel cable, and facilitating the optimization of the processing performance of the high-strength and high-toughness plastic steel cable. The nano-silicon dioxide and nano-silicon nitride in the polyurethane formula of the present invention can fill the polyurethane network gaps, further improving the density of the high-strength and high-toughness plastic steel cable. At the same time, they have good infrared and ultraviolet light reflection properties, effectively improving the ultraviolet aging resistance and weather resistance of the high-strength and high-toughness plastic steel cable, reducing the amount of anti-ultraviolet aging additives used, avoiding the problem of reduced ultraviolet aging resistance and weather resistance caused by the precipitation of anti-ultraviolet aging additives in long-term outdoor environments, and effectively improving the service life and safety factor of the high-strength and high-toughness plastic steel cable.

[0032] Preferably, the catalyst is any one of dibutyltin dilaurate, stannous octoate, and bismuth isooctanoate.

[0033] Preferably, the surface modifier is at least one of γ-aminopropyltriethoxysilane KH550 and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane KH792.

[0034] By adopting the above technical solution, the antibacterial and anti-mildew additives and reinforcing fillers can be evenly dispersed in the polyurethane resin, thereby ensuring the antibacterial and anti-mildew properties, tensile mechanical properties, UV aging resistance and chemical corrosion resistance of the high-strength and high-toughness plastic-steel cable.

[0035] Preferably, the defoaming agent is at least one of BASF Efka PB 2021 and BASF Efka SI 2722.

[0036] The present invention provides a production process for a high-strength and high-toughness plastic-steel cable for replacing steel strands, which is achieved through the following technical solutions:

[0037] A production process for a high-strength and high-toughness plastic-steel cable for replacing steel strands comprises the following steps:

[0038] Step 1: Evenly mix 21-28 parts of vacuum-dehydrated polyol, 0.005-0.01 parts of catalyst, and 26-37 parts of polyisocyanate, raise the temperature to 85-95° C. and react for 40-80 minutes, then cool to below 40° C. to obtain an isocyanate-terminated polyurethane prepolymer, which is component A.

[0039] Meanwhile, the remaining 21-28 parts of polyol, the remaining 0.01-0.035 parts of catalyst, 5.5-12 parts of chain extender, 0.02-0.04 parts of catalyst, 0.6-0.8 parts of antibacterial and antifungal additive, 2-5 parts of reinforcing filler, 0.4-0.8 parts of antioxidant, 0-0.8 parts of anti-ultraviolet aging additive, 0.1-0.4 parts of surface modifier, and 0.15-0.30 parts of defoamer are mixed uniformly under the protection of inert gas, and vacuum degassing is performed for 5-20 minutes to obtain component B;

[0040] Step 2: Place the isocyanate-terminated polyurethane prepolymer component A in the step one into the A barrel of the glue injection machine, and place the component B in the step one into the B barrel of the glue injection machine. The component A in the A barrel and the component B in the B barrel are mixed and injected into the glue injection box by the glue injection machine. The glue injection box stores the polyurethane resin formed by evenly mixing the components A and B. The polyurethane resin is used to impregnate the continuous fibers, and the impregnated continuous fibers are pultruded. The temperature of zone one is 80-100°C, and the residence time in zone one is 10-20s; the temperature of zone two is 160-200°C, and the residence time in zone two is 30-60s; the temperature of zone three is 80-120°C, and the residence time in zone three is 60-180s; the pultrusion speed is 50-200cm / min, and the fibers are naturally cooled to room temperature to obtain a high-strength and high-toughness plastic-steel wire.

[0041] The pultrusion production process of the present invention is relatively mature, and the pultrusion operation difficulty requirement is relatively simple, which facilitates large-scale production and manufacturing, reduces overall production costs, and facilitates product market promotion and popularization.

[0042] The polyurethane resin formula of the present invention uses an alicyclic diisocyanate that does not contain a benzene ring. Its reactivity is lower than that of an aromatic diisocyanate. Component A needs to be made into a prepolymer for use, thereby shortening the residence time in zone two (thermal polymerization reaction time). By controlling the curing temperature of zone two, the complete curing time of the polyurethane resin is adjusted, thereby better adapting to the pultrusion production line equipment. In addition, by controlling the pultrusion speed, the residence time of zones one, two, and three is controlled. Zone one plays the role of preheating and preliminary polyurethane reaction, and zone two is the main polyurethane reaction zone. After the polyurethane in zone two is completely cured, it is input into zone three for heat treatment to release the thermal stress of the polyurethane high-strength and high-toughness plastic-steel cable, thereby improving the extrusion quality, dimensional stability, and physical and chemical properties of the high-strength and high-toughness plastic-steel cable.

[0043] The polyurethane resin in the present invention adopts an alicyclic diisocyanate that does not contain a benzene ring, and its reaction activity is lower than that of an aromatic diisocyanate. Compared with the aromatic diisocyanate system, the polyurethane in the present invention has a relatively long development time and a relatively long gel time, which is beneficial to the pultrusion production of high-strength and high-toughness plastic-steel pull wire; and component A is an isocyanate-terminated polyurethane prepolymer, and the viscosity of the polyurethane resin stored in the injection box is relatively large, which is convenient for the impregnation treatment of continuous fibers, improves the wettability of the polyurethane resin and the continuous fibers, and is beneficial to improving the physical and chemical properties of the high-strength and high-toughness plastic-steel pull wire.

[0044] In summary, the present invention has the following advantages:

[0045] 1. The high-strength and high-toughness polyurethane plastic-steel cable in the present invention has excellent tensile mechanical properties, UV aging resistance and chemical corrosion resistance. It can replace the steel strands of the cable tower, effectively improve the service life and safety risk control coefficient of the polyurethane-based composite cable, and reduce the maintenance cycle of the cable tower cable.

[0046] 2. The pultrusion production process in the present invention is relatively mature, and the pultrusion operation difficulty requirement is relatively simple, which facilitates large-scale production and manufacturing, reduces overall production costs, and facilitates product market promotion and popularization.

[0047] 3. The pultrusion production process of the present invention is environmentally friendly. The resin does not contain volatile small molecules such as styrene and formaldehyde. The VOC released during production and use is extremely low, which is friendly to operators and the environment.

[0048] 4. The high-strength and high-toughness plastic steel cable made by the high-strength glass fiber roving combined with special polyurethane resin through the extrusion process has a tensile strength that can meet the mechanical strength requirements of the cable for the cable tower, and has good resilience, which can improve the safety and risk control coefficient of the cable tower. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 It is a schematic diagram of the pretreatment process of the high-strength glass fiber roving in the present invention.

[0050] Figure 2 This is a physical picture of the high-strength and high-toughness plastic steel cable in Example 1 of the present invention.

[0051] Figure 3 This is a display diagram of the high-strength and high-toughness plastic steel cable in Example 1 of the present invention being assembled on a cable tower. DETAILED DESCRIPTION

[0052] In order to further understand the creativity and technical advancement of the present invention, the preferred embodiments of the present invention are discussed in detail below in conjunction with examples and comparative examples.

[0053] Example 1: A high-strength, high-toughness plastic-steel cable for replacing steel strands comprises continuous fiber and polyurethane resin. The continuous fiber is HS4 high-strength glass fiber roving from Nanjing Fiberglass Research and Design Institute Co., Ltd., a new ecological fiber with a tensile strength of 4600 MPa and an elongation at break of 5.3%. The HS4 high-strength glass fiber roving accounts for 79% by weight of the total mass of the high-strength, high-toughness plastic-steel cable, and the polyurethane resin accounts for 21% by weight of the total mass of the high-strength, high-toughness plastic-steel cable.

[0054] HS4 high-strength glass fiber roving needs to be pretreated before use. The pretreatment includes washing, soaking in KH550 aqueous solution, and drying. The finished product HS4 high-strength glass fiber roving can be obtained by winding.

[0055] See also Figure 1 The pretreatment process of the finished HS4 high-strength glass fiber roving is as follows:

[0056] S1. Purchase HS4 high-strength glass fiber roving and unwind it into a rinsing tank for surface rinsing to remove oil stains, dust and other impurities on the surface. The rinsing tank contains 3g sodium percarbonate / L and 5g AEO-9 / L. The HS4 high-strength glass fiber roving stays in the rinsing tank for 100s.

[0057] S2. The rinsed HS4 high-strength glass fiber roving was placed in a deionized water rinse tank to remove residual sodium percarbonate and AEO-9 on the surface of the HS4 high-strength glass fiber roving. The HS4 high-strength glass fiber roving remained in the deionized water rinse tank for 60 seconds.

[0058] S3 after rinsing with deionized water HS4 high-strength glass fiber roving input surface modification treatment tank, the surface modification treatment tank contains 5g KH550 / L, HS4 high-strength glass fiber roving residence time in the surface modification treatment tank is 120s, you can get KH550 surface modified HS4 high-strength glass fiber roving;

[0059] The HS4 high-strength glass fiber roving treated with S4.KH550 surface modification is put into the oven for drying for 10 minutes at a drying temperature of 80°C. After drying, it can be rolled up.

[0060] The polyurethane resin is made from the following raw materials in parts by weight: 2676.0g of dicyclohexylmethane diisocyanate Wannate H12MDI, 151.4g HDI trimer TPA100, 983.8g polytetramethylene glycol PTMEG-650, 1480g polycarbonate diol CD205HL, 1434.4g hydroxy-terminated hydrogenated polybutylene glycol GI-1000, 151.4g 1.4-butanediol, 501.9g 1,4-dihydroxymethylcyclohexane CHDM, 1.72g dibutyltin dilaurate T12, 15g nano zinc oxide JH-348, 45g nano titanium dioxide JWN-TO-A10, 60g nano boron nitride flakes CW-BN-001, 160g nano boron nitride flakes CW-BN-002, 40g nano silicon nitride AM-Si 3N4-A-1, 36g antioxidant Irganox 1098, 4g of antioxidant 168, 20g of UV-326, 16g of KH550, 16g of defoamer-BASF Efka PB 2021.

[0061] The polyurethane resin's isocyanate index (R') is calculated as (NCO molar weight in the polyisocyanate * 100) / the sum of the molar weights of active hydrogen in the polyol and the molar weights of active hydrogen in the chain extender. The polyurethane resin's isocyanate index (R') is 101.4, and the mass ratio of the hard segment content (X) to the soft segment content (Y) is 47.2 / 52.8. The hard segment content (X) is the sum of the mass of the polyisocyanate and the chain extender. The soft segment content (Y) is the mass of the polyol.

[0062] Raw material sources: Dicyclohexylmethane diisocyanate (4,4'-dicyclohexylmethane diisocyanate H12MDI), Yantai Wanhua Wannate. HDI trimer TPA100, Asahi Kasei, Guangzhou Kostel New Materials Co., Ltd.; Polytetramethylene glycol PTMEG-650, hydroxyl value 168.8 mgKOH / g, Mitsubishi Chemical Corporation, Japan. Polycarbonate diol CD205HL, hydroxyl value 224.4 mgKOH / g, Daicel Corporation, Japan. Hydroxyl-terminated hydrogenated polybutylene glycol GI-1000, hydroxyl value 70.4 mgKOH / g, Japan Soda Co., Ltd.; 1,4-Butanediol, Shandong Jiatai Petrochemical Co., Ltd.; 1,4-Dihydroxymethylcyclohexane (CHDM), 1,4-cyclohexanedimethanol, Aladdin, 99% purity, mixture of cis and trans isomers. Dibutyltin laurate T12, Shandong Wantai Chemical Co., Ltd., organic tin content 18%. 1 nano zinc oxide. JH-348 nano zinc oxide, particle size ≤ 50 nm, Shijiazhuang Jinghuang Technology Co., Ltd. Nano titanium dioxide JWN-TO-A10, anatase nano titanium dioxide, particle size 10-20 nm, Ningbo Jiwei Nano New Materials Technology Co., Ltd. Nano boron nitride flakes CW-BN-002, average particle size 600 nm, and nano boron nitride flakes CW-BN-001, average particle size 50 nm, Shanghai Chaowei Nano Technology Co., Ltd. Nano silicon nitride AM-Si3N4-A-1, particle size 50 nm, Zhejiang Yamei Nano Technology Co., Ltd. Antioxidant 1098, BASF Irganox 1098. Antioxidant 168, Macklin. UV-326, BASF Tinuvin 326. Surface modifier KH550, Hangzhou Jessica Chemical Co., Ltd. BASF Efka PB 2021, Guangzhou Haoyi New Materials Technology Co., Ltd.

[0063] A production process for a high-strength and high-toughness plastic-steel cable for replacing steel strands comprises the following steps:

[0064] Step 1: First, 983.8g of polytetrahydrofuran diol PTMEG-650, 1480g of polycarbonate diol CD205HL, and 1434.4g of terminal hydroxyl hydrogenated polybutylene glycol GI-1000 are placed in a reactor, heated to 120°C and vacuum dehydrated for 2h to obtain a polyol composition, 50wt% (1949.1g) of the polyol composition after vacuum dehydration, 0.72g of dibutyltin dilaurate T12, and 2676.0g of dicyclohexylmethane diisocyanate Wannate H12MDI are put into another reactor, heated to 60°C and stirred, heated to 90°C at a stirring speed of 200rpm for 60min, then cooled to 35°C, 151.4g of HDI trimer TPA100 is added, and the material is discharged at a stirring speed of 200rpm for 5min to obtain an isocyanate-terminated polyurethane prepolymer, which is component A;

[0065] At the same time, the remaining 50wt% (1949.1g) of the polyol composition, the remaining 1g of dibutyltin dilaurate T12, 147.8g of 1.4-butanediol, 507.6g of 1,4-dihydroxymethylcyclohexane CHDM, 1.72g of dibutyltin dilaurate T12, 15g of nano zinc oxide JH-348, 45g of nano titanium dioxide JWN-TO-A10, 60g of nano boron nitride sheet CW-BN-001, 160g of nano boron nitride sheet CW-BN-002, 40g of nano silicon nitride AM-Si3N4-A-1, 36g of antioxidant Irganox1098, 4g of antioxidant 168, 20g of UV-326, 16g of KH550, and 16g of defoamer-BASF Efka PB were added. 2021 was put into another reactor, filled with nitrogen to exhaust the air, and heated to 45°C under nitrogen protection, and then stirred. Vacuum degassing was performed at a stirring speed of 200 rpm for 15 min to obtain component B;

[0066] Step 2: Place the isocyanate-terminated polyurethane prepolymer component A in the step 1 into the A barrel of the glue injection machine, and place the component B in the step 1 into the B barrel of the glue injection machine. The component A in the A barrel and the component B in the B barrel are mixed by the glue injection machine and injected into the glue injection box. The glue injection box stores the polyurethane resin formed by evenly mixing the components A and B. The polyurethane resin is used to impregnate the HS4 high-strength glass fiber roving, and the impregnated HS4 high-strength glass fiber roving is pultruded. The temperature of zone 1 is set at 90°C, and the residence time in zone 1 is 15s; the temperature of zone 2 is 175°C, and the residence time in zone 2 is 45s; the temperature of zone 3 is 105°C, and the residence time in zone 3 is 120s; the pultrusion speed is 120cm / min, and the high-strength and high-toughness plastic steel wire is obtained by natural cooling to room temperature. The diameter Φ of the obtained high-strength and high-toughness plastic steel wire is 7.9mm and the density is 2.05g / cm 3 .

[0067] The difference between Example 2 and Example 1 is that the polyurethane resin is made from the following raw materials in parts by weight: 2676.0 g of dicyclohexylmethane diisocyanate Wannate H12MDI, 151.4g HDI trimer TPA100, 997.1g polytetramethylene glycol PTMEG-650, 1500g polycarbonate diol CD205HL, 1434.4g terminal hydroxyl hydrogenated polybutylene glycol GI-1000, 144.2g 1.4-butanediol, 461.5g 1,4-dihydroxymethylcyclohexane CHDM, 80.2g double Se bond disecondary amine, 1.72g dibutyltin dilaurate T12, 15g nano zinc oxide JH-348, 45g nano titanium dioxide JWN-TO-A10, 60g nano boron nitride sheet CW-BN-001, 160g nano boron nitride sheet CW-BN-002, 40g nano silicon nitride AM-Si 3N4-A-1, 36 g of antioxidant Irganox 1098, 4 g of antioxidant 168, 20 g of UV-326, 16 g of KH550, and 16 g of BASF Efka PB 2021 defoamer. The polyurethane resin has an isocyanate index R' of 101.4, and a mass ratio of the hard segment content X to the soft segment content Y of 47.2 / 52.8.

[0068] Synthesis of di-secondary amine with double Se bond: 4 L tetrahydrofuran THF solvent was added to reactor A, 355 g n-propylamine was added at 240 rpm, and the mixture was stirred for 10 min to obtain n-propylamine THF solution; at the same time, 8 L tetrahydrofuran THF solvent was added to reactor B, 1080 g γ-selenobutyrolactone was added at 240 rpm, and the mixture was stirred for 10 min to obtain γ-selenobutyrolactone THF solution; the γ-selenobutyrolactone THF solution in reactor B was slowly dripped into reactor A at a rate of 1200 g / h, and the γ-selenobutyrolactone THF solution was obtained. After the dropwise addition of solution F was completed, the temperature of the liquid in reactor A was controlled at 30°C and maintained at 30°C with stirring at 240 rpm for 24 h. Finally, reactor A was filtered and the resulting solid was washed three times with tetrahydrofuran and dried in a vacuum oven at 25°C for 24 h to obtain 1014.6 g of a yellow solid with a yield of 82.6%. The structural formula of the double Se bond disecondary amine is as follows: CH3-CH2-CH2-NH-C0-CH2-CH2-Se-Se--CH2-CH2-C0-NH-CH2-CH2-CH3.

[0069] The difference between Example 3 and Example 1 is that the polyurethane resin is made from the following raw materials in parts by weight: 2267.4g of isophorone diisocyanate IPDI (Desmodur I), 151.4g HDI trimer TPA100, 890.7g polytetramethylene glycol PTMEG-650, 1340g polycarbonate diol CD205HL, 1275g terminal hydroxyl hydrogenated polybutylene glycol GI-1000, 171.3g 1.4-butanediol, 545.1g 1,4-dihydroxymethylcyclohexane CHDM, 1.72g dibutyltin dilaurate T12, 15g nano zinc oxide JH-348, 45g nano titanium dioxide JWN-TO-A10, 60g nano boron nitride sheet CW-BN-001, 160g nano boron nitride sheet CW-BN-002, 40g nano silicon nitride AM-Si 3N4-A-1, 36g antioxidant Irganox 1098, 4g of antioxidant 168, 20g of UV-326, 16g of KH550, and 16g of BASF Efka PB2021 defoamer. The polyurethane resin has an isocyanate index R' of 101.4, and a mass ratio of hard segment content X to soft segment content Y of 47.2 / 52.8.

[0070] The difference between Example 4 and Example 1 is that the polyurethane resin is made from the following raw materials in parts by weight: 2108.4 g of norbornane diisocyanate (NBDI, Mitsui Chemicals, Japan), 151.4 g of HDI trimer TPA100, 857.5 g of polytetramethylene glycol PTMEG-650, 1300 g of polycarbonate diol CD205HL, 1195.3 g of hydroxyl-terminated hydrogenated polybutylene glycol GI- 1000, 175.7g of 1.4-butanediol, 563.9g of 1,4-dihydroxymethylcyclohexane CHDM, 1.72g of dibutyltin dilaurate T12, 15g of nano zinc oxide JH-348, 45g of nano titanium dioxide JWN-TO-A10, 60g of nano boron nitride flakes CW-BN-001, 160g of nano boron nitride flakes CW-BN-002, 40g of nano silicon nitride AM-Si 3N4-A-1, 36g of antioxidant Irganox 1098, 4g of antioxidant 168, 20g of UV-326, 16g of KH550, and 16g of defoamer - BASF Efka PB2021. The isocyanate index R' of the polyurethane resin is 101.4, and the mass ratio of the hard segment content X to the soft segment content Y is 47.2 / 52.8.

[0071] The difference between Example 5 and Example 1 is that the polyurethane resin is made from the following raw materials in parts by weight: 2007.0 g of dicyclohexylmethane diisocyanate Wannate H12MDI, 527.1g of norbornane diisocyanate (NBDI, Mitsui Chemicals, Ltd.), 151.4g of HDI trimer TPA100, 960.5g of polytetramethylene glycol PTMEG-650, 1445g of polycarbonate diol CD205HL, 1354.7g of terminal hydroxyl hydrogenated polybutylene glycol GI-1000, 157.7g of 1.4-butanediol, 514.1g of 1,4-dihydroxymethylcyclohexane CHDM, 1.72g of dibutyltin dilaurate T12, 15g of nano zinc oxide JH-348, 45g of nano titanium dioxide JWN-TO-A10, 60g of nano boron nitride sheet CW-BN-001, 160g of nano boron nitride sheet CW-BN-002, 40g of nano silicon nitride AM-Si 3N4-A-1, 36 g of antioxidant Irganox 1098, 4 g of antioxidant 168, 20 g of UV-326, 16 g of KH550, and 16 g of BASF Efka PB 2021 defoamer. The polyurethane resin has an isocyanate index R' of 101.4, and a mass ratio of the hard segment content X to the soft segment content Y of 47.2 / 52.8.

[0072] The difference between Example 6 and Example 1 is that the polyurethane resin is made from the following raw materials in parts by weight: 2676.0 g of dicyclohexylmethane diisocyanate Wannate H12MDI, 151.4g of HDI trimer TPA100, 1030.3g of polytetramethylene glycol PTMEG-650, 1550g of polycarbonate diol CD205HL, 1434.4g of terminal hydroxyl hydrogenated polybutylene glycol GI-1000, 148.7g of 1.4-butanediol, 475.9g of 1,4-dihydroxymethylcyclohexane CHDM, 1.72g of dibutyltin dilaurate T12, 15g of nano zinc oxide JH-348, 45g of nano titanium dioxide JWN-TO-A10, 60g of nano boron nitride sheet CW-BN-001, 160g of nano boron nitride sheet CW-BN-002, 40g of nano silicon nitride AM-Si 3N4-A-1, 36 g of antioxidant Irganox 1098, 4 g of antioxidant 168, 20 g of UV-326, 16 g of KH550, and 16 g of BASF Efka PB 2021 defoamer. The polyurethane resin has an isocyanate index R' of 101.4, and a mass ratio of the hard segment content X to the soft segment content Y of 46.2 / 53.8.

[0073] The difference between Example 7 and Example 1 is that the polyurethane resin is made from the following raw materials in parts by weight: 2676.0 g of dicyclohexylmethane diisocyanate Wannate H12MDI, 151.4g HDI trimer TPA100, 914.0g polytetramethylene glycol PTMEG-650, 1375g polycarbonate diol CD205HL, 1386.6g hydroxy-terminated hydrogenated polybutylene glycol GI-1000, 164.9g 1.4-butanediol, 530g 1,4-dihydroxymethylcyclohexane CHDM, 1.72g dibutyltin dilaurate T12, 15g nano zinc oxide JH-348, 45g nano titanium dioxide JWN-TO-A10, 60g nano boron nitride flakes CW-BN-001, 160g nano boron nitride flakes CW-BN-002, 40g nano silicon nitride AM-Si 3N4-A-1, 36g antioxidant Irganox 1098, 4g of antioxidant 168, 20g of UV-326, 16g of KH550, and 16g of defoamer - BASF Efka PB 2021. The polyurethane resin has an isocyanate index R' = 101.4, and the mass ratio of the hard segment content X to the soft segment content Y is 48.9 / 51.1.

[0074] The difference between Example 8 and Example 1 is that the polyurethane resin is made of the following raw materials in parts by weight: 2676.0 g of dicyclohexylmethane diisocyanate Wannate H12MDI, 151.4 g of HDI trimer TPA100, 1003.7 g of polytetramethylene glycol PTMEG-650, 1610.6 g of polycarbonate diol UM-CARB90 (1 / 1) (hydroxyl value 125.4 mgKOH / g, Ube Industries, Ltd., Japan), 1434.4 g of terminal hydroxyl hydrogenated polybutylene glycol GI-1000, 189.3 g of The polyurethane resin contains 1.4-butanediol, 604.2g of 1,4-dihydroxymethylcyclohexane (CHDM), 1.72g of dibutyltin dilaurate (T12), 15g of nano-zinc oxide (JH-348), 45g of nano-titanium dioxide (JWN-TO-A10), 60g of nano-boron nitride flakes (CW-BN-001), 160g of nano-boron nitride flakes (CW-BN-002), 40g of nano-silicon nitride (AM-Si 3N4-A-1), 36g of antioxidant Irganox 1098, 4g of antioxidant 168, 20g of UV-326, 16g of KH550, and 16g of BASF's defoamer (EFKA PB 2021). The polyurethane resin has an isocyanate index of R' = 101.4, and the mass ratio of the hard segment content (X) to the soft segment content (Y) is 47.2 / 52.8.

[0075] The difference between Example 9 and Example 1 is that the polyurethane resin is made from the following raw materials in parts by weight: 2676.0 g of dicyclohexylmethane diisocyanate Wannate H12MDI, 151.4 g of HDI trimer TPA100, 983.8 g of polytetramethylene glycol PTMEG-650, 1480 g of polycarbonate diol CD205HL, 876.6 g of hydroxyl-terminated hydrogenated polybutylene glycol GI-1000, and 540 g of hydroxyl-terminated epoxidized hydrogenated polybutylene glycol Poly bd 600E (hydroxyl value 1.86 mmol / g, epoxy value 410-470, Cray Val, France). ley Company), 154.1g of 1.4-butanediol, 490.3g of 1,4-dihydroxymethylcyclohexane CHDM, 1.72g of dibutyltin dilaurate T12, 15g of nano zinc oxide JH-348, 45g of nano titanium dioxide JWN-TO-A10, 60g of nano boron nitride flakes CW-BN-001, 160g of nano boron nitride flakes CW-BN-002, 40g of nano silicon nitride AM-Si 3N4-A-1, 36g of antioxidant Irganox 1098, 4g of antioxidant 168, 20g of UV-326, 16g of KH550, and 16g of defoamer - BASF EfkaPB 2021. The isocyanate index R' of the polyurethane resin is 101.4, and the mass ratio of the hard segment content X to the soft segment content Y is 47.2 / 52.8.

[0076] The difference between Example 10 and Example 1 is that the polyurethane resin is made of the following raw materials in parts by weight: 2676.0 g of dicyclohexylmethane diisocyanate Wannate H12MDI, 151.4 g of HDI trimer TPA100, 1479.0 g of polytetramethylene glycol PTMEG-650, 2225 g of polycarbonate diol CD205HL, 110.0 g of 1.4-butanediol, 375.7 g of 1,4-dihydroxymethylcyclohexane CHDM, 1.72 g of dibutyltin dilaurate T12, 15 g of nano zinc oxide JH-348, 45 g of nano titanium dioxide JWN-TO-A10, 60 g of nano boron nitride sheet CW-BN-001, 160 g of nano boron nitride sheet CW-BN-002, 40 g of nano silicon nitride AM-Si 3N4-A-1, 36 g of antioxidant Irganox 1098, 4 g of antioxidant 168, 20 g of UV-326, 16 g of KH550, and 16 g of BASF Efka PB 2021 defoamer. The polyurethane resin has an isocyanate index R' of 101.4, and a mass ratio of the hard segment content X to the soft segment content Y of 47.2 / 52.8.

[0077] The difference between Example 11 and Example 1 is that the polyurethane resin is made of the following raw materials in parts by weight: 2676.0 g of dicyclohexylmethane diisocyanate Wannate H12MDI, 151.4 g of HDI trimer TPA100, 3828.7 g of polytetramethylene glycol PTMEG-650, 142.4 g of 1.4-butanediol, 455.7 g of 1,4-dihydroxymethylcyclohexane CHDM, 1.72 g of dibutyltin dilaurate T12, 15 g of nano zinc oxide JH-348, 45 g of nano titanium dioxide JWN-TO-A10, 60 g of nano boron nitride sheet CW-BN-001, 160 g of nano boron nitride sheet CW-BN-002, 40 g of nano silicon nitride AM-Si 3N4-A-1, and 36 g of antioxidant Irganox. 1098, 4g of antioxidant 168, 20g of UV-326, 16g of KH550, and 16g of defoamer - BASF Efka PB 2021. The polyurethane resin has an isocyanate index R' = 101.4, and the mass ratio of the hard segment content X to the soft segment content Y is 47.2 / 52.8.

[0078] The difference between Example 12 and Example 1 is that the polyurethane resin is made of the following raw materials in parts by weight: 2676.0 g of dicyclohexylmethane diisocyanate Wannate H12MDI, 151.4 g of HDI trimer TPA100, 3620 g of polycarbonate diol CD205HL, 97.3 g of 1.4-butanediol, 314.4 g of 1,4-dihydroxymethylcyclohexane CHDM, 1.72 g of dibutyltin dilaurate T12, 15 g of nano zinc oxide JH-348, 45 g of nano titanium dioxide JWN-TO-A10, 60 g of nano boron nitride sheet CW-BN-001, 160 g of nano boron nitride sheet CW-BN-002, 40 g of nano silicon nitride AM-Si 3N4-A-1, and 36 g of antioxidant Irganox. 1098, 4g of antioxidant 168, 20g of UV-326, 16g of KH550, and 16g of BASF Efka PB2021 defoamer. The polyurethane resin has an isocyanate index R' of 101.4, and a mass ratio of hard segment content X to soft segment content Y of 47.2 / 52.8.

[0079] The difference between Example 13 and Example 1 is that the polyurethane resin is made from the following raw materials in parts by weight: 2676.0 g of dicyclohexylmethane diisocyanate Wannate H12MDI, 151.4g HDI trimer TPA100, 1063.5g polytetramethylene glycol PTMEG-650, 1600g polycarbonate diol CD205HL, 1514.1g terminal hydroxyl hydrogenated polybutylene glycol GI-1000, 144.2g 1.4-butanediol, 187.4g 1,4-dihydroxymethylcyclohexane CHDM, 578.3g spirodiol (McLean, CAS No. 1455-42-1), 1.72g dibutyltin dilaurate T12, 15g nano zinc oxide JH-348, 45g nano titanium dioxide JWN-TO-A10, 60g nano boron nitride sheet CW-BN-001, 160g nano boron nitride sheet CW-BN-002, 40g nano silicon nitride AM-Si 3N4-A-1, 36 g of antioxidant Irganox 1098, 4 g of antioxidant 168, 20 g of UV-326, 16 g of KH550, and 16 g of BASF Efka PB 2021 defoamer. The polyurethane resin has an isocyanate index R' of 101.4, and a mass ratio of the hard segment content X to the soft segment content Y of 47.2 / 52.8.

[0080] The difference between Example 14 and Example 1 is that the polyurethane resin is made of the following raw materials in parts by weight: 2715.3g of dicyclohexylmethane diisocyanate Wannate H12MDI, 100.9g of HDI trimer TPA100, 987.1g of polytetramethylene glycol PTMEG-650, 1485g of polycarbonate diol CD205HL, 1415.3g of terminal hydroxyl hydrogenated polybutylene glycol GI-1000, 150.1g of 1.4-butanediol, 481.9g of 1,4-dihydroxymethylcyclohexane CHDM, 26.1g of Trishydroxyethyl isocyanurate THEIC (Aladdin, CAS No. 839-90-7), 1.72g dibutyltin dilaurate T12, 15g nano-zinc oxide JH-348, 45g nano-titanium dioxide JWN-TO-A10, 60g nano-boron nitride flakes CW-BN-001, 160g nano-boron nitride flakes CW-BN-002, 40g nano-silicon nitride AM-Si 3N4-A-1, 36g antioxidant Irganox 1098, 4g antioxidant 168, 20g UV-326, 16g KH550, and 16g defoamer BASF Efka PB 2021. The polyurethane resin has an isocyanate index R' of 101.4, and the mass ratio of hard segment content X to soft segment content Y is 47.2 / 52.8.

[0081] The difference between Example 15 and Example 1 is that the polyurethane resin is made of the following raw materials in parts by weight: 2715.3 g of dicyclohexylmethane diisocyanate Wannate H12MDI, 100.9 g of HDI trimer TPA100, 963.8 g of polytetramethylene glycol PTMEG-650, 1450 g of polycarbonate diol CD205HL, 1426.4 g of hydroxyl-terminated hydrogenated polybutylene glycol GI-1000, 31.5 g of polytrimethylolpropane-propylene oxide polyether triol TO330 (hydroxyl value 535 mgKOH / g, Arkema, France), 1 53.2g of 1.4-butanediol, 491.0g of 1,4-dihydroxymethylcyclohexane CHDM, 1.72g of dibutyltin dilaurate T12, 15g of nano zinc oxide JH-348, 45g of nano titanium dioxide JWN-TO-A10, 60g of nano boron nitride flakes CW-BN-001, 160g of nano boron nitride flakes CW-BN-002, 40g of nano silicon nitride AM-Si 3N4-A-1, 36g of antioxidant Irganox 1098, 4g of antioxidant 168, 20g of UV-326, 16g of KH550, 16g of defoamer - BASF Efka PB 2021. The isocyanate index R' of the polyurethane resin is 101.4, and the mass ratio of the hard segment content X to the soft segment content Y is 47.2 / 52.8.

[0082] The difference between Example 16 and Example 1 is that 16 g of KH550 is replaced by 16 g of KH792 N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane (Hangzhou Jessica Chemical Co., Ltd.).

[0083] Example 17 differs from Example 1 in that the finished HS24 high-strength glass fiber roving is replaced with HS2 high-strength glass fiber roving from Nanjing Fiberglass Research and Design Institute Co., Ltd. The new ecological fiber has a tensile strength of 4200 MPa and an elongation at break of 5.3%. The HS2 high-strength glass fiber roving undergoes a pretreatment process identical to that of the finished HS4 high-strength glass fiber roving.

[0084] Example 18 differs from Example 1 in that the finished HS24 high-strength glass fiber roving is replaced with HS6 high-strength glass fiber roving from Nanjing Fiberglass Research and Design Institute Co., Ltd. The new ecological fiber has a tensile strength of 4800 MPa and an elongation at break of 5.7%. The HS26 high-strength glass fiber roving undergoes a pretreatment process identical to that of the HS4 high-strength glass fiber roving.

[0085] The difference between Example 19 and Example 1 is that the polyurethane resin is made of the following raw materials in parts by weight: 2794.0 g of dicyclohexylmethane diisocyanate Wannate H12MDI, 983.8 g of polytetramethylene glycol PTMEG-650, 1475 g of polycarbonate diol CD205HL, 1402.5 g of terminal hydroxyl hydrogenated polybutylene glycol GI-1000, 147.8 g of 1.4-butanediol, 512.0 g of 1,4-dihydroxymethylcyclohexane CHDM, 1.72 g of dibutyltin dilaurate T12, 15 g of nano zinc oxide JH-348, 45 g of nano titanium dioxide JWN-TO-A10, 60 g of nano boron nitride sheet CW-BN-001, 160 g of nano boron nitride sheet CW-BN-002, 40 g of nano silicon nitride AM-Si 3N4-A-1, 36 g of antioxidant Irganox 1098, 4 g of antioxidant 168, 20 g of UV-326, 16 g of KH550, and 16 g of BASF Efka PB 2021 defoamer. The polyurethane resin has an isocyanate index R' of 101.4, and a mass ratio of the hard segment content X to the soft segment content Y of 47.2 / 52.8.

[0086] The difference between Example 20 and Example 1 is that the polyurethane resin is made from the following raw materials in parts by weight: 2715.4g of dicyclohexylmethane diisocyanate Wannate H12MDI, 151.4g HDI trimer TPA100, 1010.4g polytetramethylene glycol PTMEG-650, 1500g polycarbonate diol CD205HL, 1418.4g terminal hydroxyl hydrogenated polybutylene glycol GI-1000, 152.3g 1.4-butanediol, 490.3g 1,4-dihydroxymethylcyclohexane CHDM, 1.72g dibutyltin dilaurate T12, 15g nano zinc oxide JH-348, 45g nano titanium dioxide JWN-TO-A10, 60g nano boron nitride flakes CW-BN-001, 160g nano boron nitride flakes CW-BN-002, 40g nano silicon nitride AM-Si 3N4-A-1, 36g antioxidant Irganox 1098, 4g of antioxidant 168, 20g of UV-326, 16g of KH550, and 16g of BASF Efka PB2021 defoamer. The polyurethane resin has an isocyanate index R' of 102.86, and a mass ratio of hard segment content X to soft segment content Y of 47.2 / 52.8.

[0087] The difference between Example 21 and Example 1 is that 60 g of nano-boron nitride flakes CW-BN-001 in the polyurethane resin are replaced with nano-molybdenum disulfide flakes CW-MoS2-001 from Shanghai Chaowei Nanotechnology Co., Ltd., with an average particle size of 50 nm.

[0088] The difference between Comparative Example 1 and Example 1 is that the polyurethane resin is made from the following raw materials in parts by weight: 2552.7g of liquid MDI-50 (Yantai Wanhua Wannate), 151.4g of HDI trimer TPA100, 955.2g of polytetramethylene glycol PTMEG-650, 1437g of polycarbonate diol CD205HL, 1386.6g of terminal hydroxyl hydrogenated polybutylene glycol GI-10 00, 158.6g of 1.4-butanediol, 513.3g of 1,4-dihydroxymethylcyclohexane CHDM, 1.72g of dibutyltin dilaurate T12, 15g of nano zinc oxide JH-348, 45g of nano titanium dioxide JWN-TO-A10, 60g of nano boron nitride flakes CW-BN-001, 160g of nano boron nitride flakes CW-BN-002, 40g of nano silicon nitride AM-Si 3N4-A-1, 36g of antioxidant Irganox 1098, 4g of antioxidant 168, 20g of UV-326, 16g of KH550, 16g of defoamer-BASF Efka PB 2021.

[0089] The difference in the production process of high-strength and high-toughness plastic steel wire is that: Step 1, first place 955.2g of polytetramethylene glycol PTMEG-650, 1437g of polycarbonate diol CD205HL, and 1386.6g of terminal hydroxyl hydrogenated polybutylene glycol GI-1000 in a reactor, heat to 120°C and vacuum dehydrate for 2h to obtain a polyol composition, take 50wt% (1889.4g) of the polyol composition after vacuum dehydration, 0 0.72 g of dibutyltin dilaurate T12 and 2552.7 g of liquid MDI-50 were placed in another reactor. The temperature was raised to 60°C and stirring was started. The temperature was raised to 75°C with stirring at 200 rpm and the reaction was carried out for 60 min. The temperature was then lowered to 35°C, and 151.4 g of HDI trimer TPA100 was added. The mixture was stirred at 200 rpm for 5 min. The isocyanate-terminated polyurethane prepolymer was obtained, which is component A.

[0090] At the same time, the remaining 50wt% (1889.4g) of the polyol composition, the remaining 1g of dibutyltin dilaurate T12, 147.8g of 1.4-butanediol, 507.6g of 1,4-dihydroxymethylcyclohexane CHDM, 1.72g of dibutyltin dilaurate T12, 15g of nano zinc oxide JH-348, 45g of nano titanium dioxide JWN-TO-A10, 60g of nano boron nitride sheet CW-BN-001, 160g of nano boron nitride sheet CW-BN-002, 40g of nano silicon nitride AM-Si 3N4-A-1, 36g of antioxidant Irganox 1098, 4g of antioxidant 168, 20g of UV-326, 16g of KH550, and 16g of defoamer-BASF Efka PB were added. 2021 was put into another reactor, filled with nitrogen to exhaust the air, and heated to 45°C under nitrogen protection, and then stirred. Vacuum degassing was performed at a stirring speed of 200 rpm for 15 min to obtain component B;

[0091] Step 2: Place the isocyanate-terminated polyurethane prepolymer component A in the step one into the A barrel of the glue injection machine, and place the component B in the step one into the B barrel of the glue injection machine. The component A in the A barrel and the component B in the B barrel are mixed and injected into the glue injection box by the glue injection machine. The glue injection box stores the polyurethane resin formed by evenly mixing the components A and B. The polyurethane resin is used to impregnate the continuous fibers, and several impregnated continuous fibers are pultruded. The temperature of zone one is set at 90°C, and the residence time in zone one is 15s; the temperature of zone two is 160°C, and the residence time in zone two is 45s; the temperature of zone three is 105°C, and the residence time in zone three is 120s; the pultrusion speed is 120cm / min, and the fibers are naturally cooled to room temperature to obtain a high-strength and high-toughness plastic steel wire.

[0092] The difference between Comparative Example 2 and Example 1 is that the polyurethane resin is made from the following raw materials in parts by weight: 2676.0 g of dicyclohexylmethane diisocyanate Wannate H12MDI, 151.4g HDI trimer TPA100, 1163.2g polytetramethylene glycol PTMEG-650, 1750g polycarbonate diol CD205HL, 1514.1g hydroxy-terminated hydrogenated polybutylene glycol GI-1000, 129.8g 1.4-butanediol, 412.4g 1,4-dihydroxymethylcyclohexane CHDM, 1.72g dibutyltin dilaurate T12, 15g nano zinc oxide JH-348, 45g nano titanium dioxide JWN-TO-A10, 60g nano boron nitride flakes CW-BN-001, 160g nano boron nitride flakes CW-BN-002, 40g nano silicon nitride AM-Si 3N4-A-1, 36g antioxidant Irganox 1098, 4g of antioxidant 168, 20g of UV-326, 16g of KH550, and 16g of BASF's defoamer Efka PB2021. The polyurethane resin has an isocyanate index R' of 101.4, and a mass ratio of the hard segment content X to the soft segment content Y of 43.2 / 56.8.

[0093] The difference between Comparative Example 3 and Example 1 is that the polyurethane resin is made of the following raw materials in parts by weight: 2676.0 g of dicyclohexylmethane diisocyanate Wannate H12MDI, 151.4 g of HDI trimer TPA100, 4076.8 g of polyester diol N-112 (hydroxyl value 110.5 mgKOH / g, Yantai Huada Chemical Industry Co., Ltd.), 194.7 g of 1.4-butanediol, 623.7 g of 1,4-dihydroxymethylcyclohexane CHDM, 1.72 g of dibutyltin dilaurate T12, 15 g of nano zinc oxide JH-348, 45 g of nano titanium dioxide JWN-TO-A10, 60 g of nano boron nitride sheet CW-BN-001, 160 g of nano boron nitride sheet CW-BN-002, 40 g of nano silicon nitride AM-Si 3N4-A-1, 36 g of antioxidant Irganox 1098, 4 g of antioxidant 168, 20 g of UV-326, 16 g of KH550, and 16 g of BASF Efka PB 2021 defoamer. The polyurethane resin has an isocyanate index R' of 101.4, and a mass ratio of the hard segment content X to the soft segment content Y of 47.2 / 52.8.

[0094] The difference between Comparative Example 4 and Example 1 is that the polyurethane resin is made of the following raw materials in parts by weight: 2676.0g of dicyclohexylmethane diisocyanate Wannate H12MDI, 151.4g of HDI trimer TPA100, 943.9g of polytetramethylene glycol PTMEG-650, 1422.5g of polycarbonate diol CD205HL, 1338.8g of terminal hydroxyl hydrogenated polybutylene glycol GI-1000, 486.2g of 1.4-butanediol, 1.72g of dibutyltin dilaurate T12, 15g of nano zinc oxide JH-348, 45g of nano titanium dioxide JWN-TO-A10, 60g of nano boron nitride sheet CW-BN-001, 160g of nano boron nitride sheet CW-BN-002, 40g of nano silicon nitride AM-Si 3N4-A-1, 36g of antioxidant Irganox 1098, 4g of antioxidant 168, 20g of UV-326, 16g of KH550, and 16g of BASF Efka PB 2021 defoamer. The polyurethane resin has an isocyanate index R' of 101.4, and the mass ratio of the hard segment content X to the soft segment content Y is 47.2 / 52.8.

[0095] The difference between Comparative Example 5 and Example 1 is that KH550 is not added to the polyurethane resin formula. The polyurethane resin is made from the following raw materials in parts by weight: 2676.0 g of dicyclohexylmethane diisocyanate Wannate H12MDI, 151.4g HDI trimer TPA100, 983.8g polytetramethylene glycol PTMEG-650, 1480g polycarbonate diol CD205HL, 1434.4g terminal hydroxyl hydrogenated polybutylene glycol GI-1000, 147.8g 1.4-butanediol, 507.6g 1,4-dihydroxymethylcyclohexane CHDM, 1.72g dibutyltin dilaurate T12, 15g nano zinc oxide JH-348, 45g nano titanium dioxide JWN-TO-A10, 60g nano boron nitride flakes CW-BN-001, 160g nano boron nitride flakes CW-BN-002, 40g nano silicon nitride AM-Si3N4-A-1, 36g antioxidant Irganox 1098, 4g of antioxidant 168, 20g of UV-326, 16g of defoamer-BASF Efka PB 2021.

[0096] The difference between Comparative Example 6 and Example 1 is that the finished HS24 high-strength glass fiber roving in Example 1 is replaced with HS4 high-strength glass fiber roving that has only been surface washed and dried, and has not been soaked in the KH550 aqueous solution. Specifically, the pretreatment process of the HS4 high-strength glass fiber roving used in Comparative Example 6 is as follows:

[0097] S1. Purchase HS4 high-strength glass fiber roving and unwind it into a rinsing tank for surface rinsing to remove oil stains, dust and other impurities on the surface. The rinsing tank contains 3g sodium percarbonate / L and 5g AEO-9 / L. The HS4 high-strength glass fiber roving stays in the rinsing tank for 100s.

[0098] S2. The rinsed HS4 high-strength glass fiber roving was placed in a deionized water rinse tank to remove residual sodium percarbonate and AEO-9 on the surface of the HS4 high-strength glass fiber roving. The HS4 high-strength glass fiber roving remained in the deionized water rinse tank for 60 seconds.

[0099] After rinsing with deionized water, the HS4 high-strength glass fiber roving is placed in an oven for drying at 80°C for 10 minutes. After drying, it can be rolled up.

[0100] Comparative Example 7 differs from Example 1 in that the finished HS24 high-strength glass fiber roving is replaced with Jushi's E6DR24-2400-386T alkali-free glass fiber roving. This roving undergoes a pretreatment process identical to that used for the finished HS4 high-strength glass fiber roving.

[0101] The difference between Comparative Example 8 and Example 1 is that the polyurethane resin is made from the following raw materials in parts by weight: 2676.0 g of dicyclohexylmethane diisocyanate Wannate H12MDI, 151.4g HDI trimer TPA100, 983.8g polytetramethylene glycol PTMEG-650, 1480g polycarbonate diol CD205HL, 1434.4g terminal hydroxyl hydrogenated polybutylene glycol GI-1000, 147.8g 1.4-butanediol, 507.6g 1,4-dihydroxymethylcyclohexane CHDM, 1.72g dibutyltin dilaurate T12, 15g nano zinc oxide JH-348, 45g nano titanium dioxide JWN-TO-A10, 220g nano calcium carbonate (ML-CaCo3-N100 of Zhejiang Manli Nano Technology Co., Ltd., particle size 100nm), 40g nano silicon nitride AM-Si 3N4-A-1, 36g antioxidant Irganox 1098, 4g of antioxidant 168, 20g of UV-326, 16g of KH550, and 16g of BASF Efka PB2021.

[0102] The difference between Comparative Example 9 and Example 1 is that the polyurethane resin is made from the following raw materials in parts by weight: 2676.0 g of dicyclohexylmethane diisocyanate Wannate H12MDI, 151.4g of HDI trimer TPA100, 983.8g of polytetramethylene glycol PTMEG-650, 1480g of polycarbonate diol CD205HL, 1434.4g of terminal hydroxyl hydrogenated polybutylene glycol GI-1000, 147.8g of 1.4-butanediol, 507.6g of 1,4-dihydroxymethylcyclohexane CHDM, 1.72g of dibutyltin dilaurate T12, 15g of nano zinc oxide JH-348, 45g of nano titanium dioxide JWN-TO-A10, 260g of nano calcium carbonate (ML-CaCo3-N100 of Zhejiang Manli Nano Technology Co., Ltd., particle size 100nm), 36g of antioxidant Irganox 1098, 4g of antioxidant 168, 20g of UV-326, 16g of KH550, and 16g of BASF Efka PB 2021.

[0103] The difference between Comparative Example 10 and Example 1 is that no antibacterial and antifungal additives and reinforcing fillers are added to the polyurethane resin formula. The polyurethane resin is made from the following raw materials in parts by weight: 2676.0 g of dicyclohexylmethane diisocyanate Wannate H12MDI, 151.4 g of HDI trimer TPA100, 983.8 g of polytetramethylene glycol PTMEG-650, 1480 g of polycarbonate diol CD205HL, 1434.4 g of terminal hydroxyl hydrogenated polybutylene glycol GI-1000, 147.8 g of 1.4-butanediol, 507.6 g of 1,4-dihydroxymethylcyclohexane CHDM, 1.72 g of dibutyltin dilaurate T12, 36 g of antioxidant Irganox 1098, 4 g of antioxidant 168, 20 g of UV-326, 16 g of KH550, and 16 g of BASF Efka PB 2021.

[0104] Performance test 1: Longitudinal tensile strength is measured in accordance with GB / T 1447-2005 “Test method for tensile properties of fiber reinforced plastics”.

[0105] Performance test 2: Longitudinal flexural strength is measured in accordance with GB / T 1449-2005 “Fiber reinforced plastics flexural properties test method”.

[0106] Performance test 3: Longitudinal compressive strength is measured in accordance with GB / T 1448-2005 “Test method for compression properties of fiber reinforced plastics”.

[0107] Performance test 4: UV resistance test: According to the method specified in 6.8 of GB / T 22040-2008, after 2000h of artificial accelerated aging test using fluorescent UV lamp, if the appearance of the product is free from defects specified in 5.1, it shall be marked as OK. If the appearance of the product has defects specified in 5.1, it shall be marked as NG.

[0108] Performance test 5: UV aging resistance: According to the method specified in 6.8 of GB / T 22040-2008, the longitudinal tensile strength, longitudinal bending strength and longitudinal compressive strength of the high-strength and high-toughness plastic-steel wire are measured after 2000 hours of artificial accelerated aging test using fluorescent ultraviolet lamp.

[0109] Performance test 6: Xenon arc lamp artificial accelerated aging performance According to the method specified in 6.9 of GB / T 22040-2008, the cumulative energy of the artificial accelerated aging test reaches 3.5x10 6 kJ / m, the appearance of the product shall be free from defects specified in 5.1 and marked as OK. If the appearance of the product has defects specified in 5.1, it shall be marked as NG.

[0110] Table 1: Test parameters of high-strength and high-toughness plastic-steel wire in Examples 1-5 and Comparative Example 1

[0111]

[0112] Combining Example 1 and Comparative Example 1 and Table 1, it can be seen that although the polyurethane-based glass fiber composite wire prepared in Comparative Example 1 has better mechanical properties, its tensile strength retention rate, bending retention rate, and compression retention rate after UV exposure aging are all less than 80%, while the tensile strength retention rate, bending retention rate, and compression retention rate of the polyurethane-based glass fiber composite wire in Example 1 are all maintained above 90%, that is, the UV aging resistance of the polyurethane-based glass fiber composite wire in Comparative Example 1 is significantly lower than the UV aging resistance of the polyurethane-based glass fiber composite wire in Example 1. In addition, the UV exposure resistance and xenon arc lamp artificial accelerated aging resistance of the polyurethane-based glass fiber composite wire in Comparative Example 1 are both below standard. Therefore, the selection of alicyclic diisocyanate as the polyisocyanate can give the polyurethane-based glass fiber composite wire good UV aging resistance, UV exposure resistance, and xenon arc lamp artificial accelerated aging resistance.

[0113] Combining Example 1 and Examples 3-5 with Table 1, it can be seen that from the perspective of tensile strength retention, bending retention, and compression retention of the polyurethane-based glass fiber composite pull wire, the tensile strength retention, bending retention, and compression retention of the polyurethane-based glass fiber composite pull wire in Examples 1 and Examples 3-5 are all maintained at more than 90%, and all have good UV aging resistance. From the perspective of mechanical properties, NBDI polyurethane-based glass fiber composite pull wire (Example 4) > NBDI / H12MDI polyurethane-based glass fiber composite pull wire (Example 5) > H12MDI polyurethane-based glass fiber composite pull wire (Example 1) > IPDI polyurethane-based glass fiber composite pull wire (Example 3). Norbornane diisocyanate NBDI is used as a polyisocyanate to produce polyurethane-based glass fiber composite pull wire with the best mechanical properties. However, norbornane diisocyanate NBDI relies on imports, the price remains high, and small batch customization is used, which is not suitable for industrial-scale production. Therefore, the mechanical properties of the polyurethane-based glass fiber composite pulling wire produced by selecting hydrogenated MDI as the polyisocyanate meet the mechanical property requirements of the pulling wire for the pulling tower, and its original source is wide and the price is relatively low, which is suitable for industrial-scale production.

[0114] Combining Example 1 and Example 2 and Table 1, it can be seen that in actual polyurethane-based glass fiber composite pull wire application scenarios, hard objects may pierce the outer surface of the polyurethane-based glass fiber composite pull wire to form stress accumulation points, resulting in a decrease in the local tensile performance of the polyurethane-based glass fiber composite pull wire. In order to cope with the above situation, the inventors have developed a polyurethane-based glass fiber composite pull wire with room temperature self-healing effect, and its main self-healing effect relies on dynamic double Se bonds. The polyurethane-based glass fiber composite pull wire in Example 2 was tested in the company's laboratory. A "knife-edge" scratch with a length of 20 mm, a width of 0.5 mm, and a depth of 1 mm was made on the surface of the polyurethane-based glass fiber composite pull wire. After being placed in a room temperature environment for 3 days, the "knife-edge" scratch was basically healed, confirming that the polyurethane-based glass fiber composite pull wire in Example 2 has a self-healing effect. However, the raw material for synthesizing the bis-Se-bonded di-secondary amine, γ-selenobutyrolactone, requires laboratory synthesis and is also synthesized in a small reactor, resulting in a relatively high production cost for the raw material. The self-healing polyurethane-based glass fiber composite cable in Example 2 is currently in the laboratory stage and is suitable for customized products for special scenarios. Furthermore, the mechanical properties and mechanical strength retention of the polyurethane-based glass fiber composite cable in Example 2 are lower than those of the polyurethane-based glass fiber composite cable in Example 1, indicating that replacing part of the small molecule diol chain extender with the bis-Se-bonded di-secondary amine affects the mechanical properties and UV aging resistance of the polyurethane-based glass fiber composite cable.

[0115] Table 2: Test parameters of high-strength and high-toughness plastic-steel cables in Examples 1, 6-7, and Comparative Example 2

[0116]

[0117] From Example 1, Examples 6-7 and Comparative Example 2 and Table 2, it can be seen that when the polyurethane hard segment content is controlled at 46-49%, the mechanical properties, UV aging resistance, UV exposure resistance, and resistance to artificial accelerated aging by xenon arc lamps of the prepared polyurethane-based glass fiber composite pull wire are relatively good. When the polyurethane hard segment content is lower than 46%, the mechanical properties of the polyurethane-based glass fiber composite pull wire in Comparative Example 2 decline significantly, and the UV exposure resistance also fails to meet the standards. Therefore, the hard segment content needs to be strictly controlled in the polyurethane formula design. On the one hand, the invention can improve the mechanical properties, UV aging resistance, UV exposure resistance, and resistance to artificial accelerated aging by xenon arc lamps. On the other hand, it can improve the overall hardness (the Barcol hardness of the polyurethane-based glass fiber composite pull wire in Example 1 is 58, while the Barcol hardness of the polyurethane-based glass fiber composite pull wire in Comparative Example 2 is 53) and wear resistance. In addition, the hard segment content will also affect the interfacial bonding performance between the polyurethane resin and the glass fiber yarn, and improve its wetting effect with the glass fiber yarn.

[0118] Table 3: Test parameters of high-strength and high-toughness plastic-steel cables in Examples 1, 8-16 and Comparative Examples 3-5

[0119]

[0120]

[0121] Combining Example 1 and Comparative Example 3 and Table 3, it can be seen that the hydrolysis resistance of the polyurethane-based glass fiber composite pull wire prepared by polyester diol N-112 in Comparative Example 3 is poor, and the resistance to artificial accelerated aging by xenon arc lamp is not up to standard. Combining Example 1 and Example 10 and Table 3, it can be seen that the mechanical properties of the polyurethane-based glass fiber composite pull wire produced by Example 10 without adding terminal hydroxyl hydrogenated polytetramethylene glycol are improved, which is mainly affected by the increase in the content of polycarbonate diol (the content of polycarbonate diol in Example 1 is 19.2%, and the content of polycarbonate diol in Example 10 is 30.2), and the mechanical strength retention rate of Example 10 shows a downward trend. Therefore, the appropriate addition of terminal hydroxyl hydrogenated polytetramethylene glycol GI-1000 can improve the anti-ultraviolet aging performance and weather resistance of the polyurethane-based glass fiber composite pull wire, and can also improve the overall low temperature resistance and solvent corrosion resistance. In conjunction with Example 1 and Example 11-12 and in conjunction with Table 3, it can be seen that the mechanical property of the polyurethane-based glass fiber composite cable produced by only polytetrahydrofuran diol PTMEG in Example 11 shows a relatively obvious decline, but still can meet the use demand of replacing traditional steel strands. In Example 12, the mechanical property of the polyurethane-based glass fiber composite cable produced by only using polycarbonate diol CD205HL improves to some extent, but the cost of polycarbonate diol CD205HL is more expensive than polytetrahydrofuran diol PTMEG, and the production cost is high, which is unfavorable for industrialized production. In addition, in the production process, the local surface smoothness of the polyurethane-based glass fiber composite cable in Example 12 also has an impact. Therefore, the selection of the polyol of the polyurethane resin for the polyurethane-based glass fiber composite cable is to select polytetrahydrofuran diol, polycarbonate diol, and polyolefin diol with excellent hydrolysis performance.

[0122] From Example 1 and Examples 8-9 and Table 3, it can be seen that the mechanical properties of the polyurethane-based glass fiber composite wire prepared by replacing the polycarbonate diol UM-CARB90 (1 / 1) with the polycarbonate diol CD205HL in Example 8 are relatively better. This is mainly because the polycarbonate diol UM-CARB90 (1 / 1) molecular chain contains 1,4-dihydroxymethylcyclohexane CHDM as an initiator, and the CHDM / HDO molar ratio is 1:1, that is, the six-membered ring structure contained therein can improve the mechanical properties, wear resistance, and heat resistance of the polyurethane-based glass fiber composite wire. In Example 9, the polyurethane-based glass fiber composite cable prepared by replacing part of the terminal hydroxyl hydrogenated polybutylene glycol GI-1000 with terminal hydroxyl epoxidized hydrogenated polybutylene glycol Poly bd 600E has improved mechanical properties, UV resistance, wear resistance, and heat resistance. During the thermal curing stage, the epoxy groups in the terminal hydroxyl epoxidized hydrogenated polybutylene glycol Poly bd 600E react with the surface-treated antibacterial and mildew-proof additives and reinforcing fillers with active hydrogen groups. The secondary hydroxyl groups formed by the two are located in the side chains of the polymer molecular weight. The secondary hydroxyl groups in the side chains of the polymer molecular weight react with the residual NCO in the polyisocyanate to form polyurethane bonds, thereby improving the overall cross-linking density, which is beneficial to improving the overall mechanical strength, wear resistance, hydrolysis resistance, chemical corrosion resistance, weather resistance, and UV aging resistance, thereby ensuring the overall service life. Although the hydroxy-terminated epoxidized hydrogenated polybutylene glycol has a good effect on improving the comprehensive performance of polyurethane-based glass fiber composite pulling wire, the commercialization of hydroxy-terminated epoxidized hydrogenated polybutylene glycol currently relies on Cray Valley Company, resulting in a relatively high cost of using hydroxy-terminated epoxidized hydrogenated polybutylene glycol. It is only suitable for customized production needs and is not suitable for industrial mass production due to its cost issues.

[0123] Combining Example 1 and Comparative Example 4 with Table 3, it can be seen that although the weather resistance of the polyurethane-based glass fiber composite cable prepared in Comparative Example 4 using only 1,4-butanediol meets the requirements, its mechanical properties show a significant decline. In order to make up for the defects in its mechanical properties, it is necessary to use HS6 high-strength glass fiber yarn roving with better tensile strength. This will result in a relatively high production cost for this polyurethane-based glass fiber composite cable, which is not conducive to market promotion and sales. In addition, the polyurethane-based glass fiber composite cable in Comparative Example 4 has a Barcol hardness of 55, which is also lower than the Barcol hardness of 58 of the polyurethane-based glass fiber composite cable in Example 1, and its wear resistance is reduced. Therefore, the best production method is to use 1,4-dihydroxymethylcyclohexane and or spirodiol with 1,4-butanediol as a chain extender to produce polyurethane-based glass fiber composite cables. In combination with Example 13, the comprehensive performance of the polyurethane-based glass fiber composite pulling wire prepared by replacing 1,4-dihydroxymethylcyclohexane with spirodiol is better, but the raw material cost of spirodiol is relatively more expensive than that of 1,4-dihydroxymethylcyclohexane. In the actual production process, the chain extender in the polyurethane resin is mainly 1,4-dihydroxymethylcyclohexane, and spirodiol and 1,4-butanediol are supplementary. The polyurethane-based glass fiber composite pulling wire produced in this way has relatively good comprehensive performance and relatively low production cost.

[0124] From Example 1 and Comparative Example 5 and Table 3, it can be seen that the polyurethane-based glass fiber composite wire prepared in Comparative Example 5 has xenon arc lamp artificial accelerated aging resistance and UV exposure resistance that meet the standards. This is mainly because the reinforcing fillers and antibacterial and mildew-proof additives in the polyurethane resin have not been surface-modified with KH550, and their dispersion performance in the polyurethane resin is relatively poor. They are easily locally agglomerated to form stress defect points, which also affects their density. As a result, the mechanical properties of the prepared polyurethane-based glass fiber composite wire are significantly reduced, and the tensile strength retention rate, bending retention rate, and compression retention rate also decline significantly. Therefore, the surface modifier is a necessary added component in the polyurethane formula. In combination with Example 16, the mechanical properties and UV aging resistance of the polyurethane-based glass fiber composite pull wire prepared using KH792 are relatively better. KH792 contains a primary amine group and a secondary amine group. The filler treated with KH792 has better bonding performance with the polyurethane matrix, which can improve the overall density, and then utilize the improvement of the mechanical properties and UV aging resistance of the polyurethane-based glass fiber composite pull wire. The Barcol hardness of the polyurethane-based glass fiber composite pull wire in Example 16 is 60, which is better than the Barcol hardness of the polyurethane-based glass fiber composite pull wire in Example 1. The use of KH792 can also improve the overall wear resistance.

[0125] Table 4: Test parameters of high-strength and high-toughness plastic-steel cables in Examples 1, 17-21, and Comparative Examples 6-10

[0126]

[0127] It can be seen from Example 1 and Comparative Example 6 in combination with Table 4 that the mechanical properties and anti-ultraviolet aging properties of the polyurethane-based glass fiber composite pull wire in Comparative Example 6 have declined significantly, and the compatibility and impregnation effect of the glass fiber yarn interface with the polyurethane resin have a more obvious influence on the physical and chemical properties of the finished polyurethane-based glass fiber composite pull wire. Therefore, the high-strength glass fiber yarn roving needs to be pretreated at one end before use, and the surface of the high-strength glass fiber yarn roving is modified with γ-aminopropyltriethoxysilane KH550 to ensure the physical and chemical properties of the prepared polyurethane-based glass fiber composite pull wire.

[0128] In combination with Example 1, Examples 17-18 and Comparative Example 7 and Table 4, it can be seen that the mechanical properties of the polyurethane-based glass fiber composite pull wire prepared by HS6 high-strength glass fiber yarn roving (Example 18) are greater than the mechanical properties of the polyurethane-based glass fiber composite pull wire prepared by HS4 high-strength glass fiber yarn roving (Example 1) and the mechanical properties of the polyurethane-based glass fiber composite pull wire prepared by HS2 high-strength glass fiber yarn roving (Example 17) and the mechanical properties of the polyurethane-based glass fiber composite pull wire prepared by JS-E6DR24-2400-386T roving (Comparative Example 7). Therefore, in order to make the mechanical properties of the prepared polyurethane-based glass fiber composite pull wire meet the mechanical property requirements of the pull wire for the pull tower, it is necessary to select HS2 high-strength glass fiber yarn roving, HS4 high-strength glass fiber yarn roving, and HS6 high-strength glass fiber yarn roving with high tensile strength.

[0129] From Example 1, Examples 14-15, Examples 19-20 and Table 3-4, it can be seen that the ratio of the sum of the NCO molar amount in triisocyanate, the active hydrogen molar amount in polyether triol and the active hydrogen molar amount in triol to the sum of the NCO molar amount in polyisocyanate, the active hydrogen molar amount in polyol and the active hydrogen molar amount in chain extender is 1:(42-48), and the comprehensive performance of the prepared polyurethane-based glass fiber composite pulling wire is good.

[0130] It can be seen from Example 1, Example 21 and Comparative Examples 8-10 and Table 4 that the comprehensive performance of the polyurethane-based glass fiber composite pull wire prepared based on nano-zinc oxide and nano-titanium dioxide as antibacterial and anti-mildew additives and flaky nano-boron nitride and nano-silicon nitride as reinforcing fillers is relatively excellent.

[0131] To sum up, the high-strength and high-toughness polyurethane plastic-steel cable in the present invention has excellent tensile mechanical properties, UV aging resistance and chemical corrosion resistance. It can replace the steel strands of the cable tower, effectively improve the service life and safety risk control coefficient of the polyurethane-based composite cable, and reduce the maintenance cycle of the cable tower cable.

[0132] It should be noted that this specific embodiment is merely an explanation of the technical solution of the present invention and is not a limitation of the present invention. After reading this specification, those skilled in the art may make non-creative modifications to this embodiment as needed, but as long as they are within the scope of the claims of the present invention, they are protected by patent law.

Claims

1. A high-strength and high-toughness plastic steel cable for replacing steel strands, characterized by: The invention comprises continuous fibers and polyurethane resin, wherein the mass percentage of the continuous fibers is 76-80w% of the total mass of the high-strength and high-toughness plastic-steel cable, and the polyurethane resin is 20-24w% of the total mass of the high-strength and high-toughness plastic-steel cable; the polyurethane resin is made of the following raw materials in parts by weight: 26-37 parts of polyisocyanate, 42-56 parts of polyol, 5.5-12 parts of chain extender, 0.02-0.04 parts of catalyst, 0.6-0.8 parts of antibacterial and anti- The invention relates to a novel polyisocyanate comprising a mildew preventive agent, 2-5 parts of a reinforcing filler, 0.4-0.8 parts of an antioxidant, 0-0.8 parts of an anti-ultraviolet aging agent, 0.1-0.4 parts of a surface modifier, and 0.15-0.30 parts of a defoaming agent; the polyisocyanate comprises an alicyclic diisocyanate, and the alicyclic diisocyanate is at least one of dicyclohexylmethane diisocyanate H12MDI, isophorone diisocyanate IPDI, and norbornane diisocyanate NBDI.

2. The high-strength and high-toughness plastic-steel cable for replacing steel strands according to claim 1, characterized in that: The continuous fiber is any one of HS2 high-strength glass fiber roving, HS4 high-strength glass fiber roving, and HS6 high-strength glass fiber roving with a tensile strength of ≥4000 MPa.

3. The high-strength and high-toughness plastic-steel cable for replacing steel strands according to claim 1, characterized in that: The R value of the polyurethane resin is 1.00-1.03, and the NCO molar amount in the polyisocyanate is 1.00-1.03 times the sum of the active hydrogen molar amount in the polyol and the active hydrogen molar amount in the chain extender.

4. The high-strength and high-toughness plastic-steel cable for replacing steel strands according to claim 3, characterized in that: The polyisocyanate further comprises triisocyanate, wherein the NCO molar amount in the triisocyanate accounts for 0-0.5% of the total NCO molar amount in the polyisocyanate; the triisocyanate is at least one of HDI trimer, IPDI trimer and L-lysine triisocyanate.

5. The high-strength and high-toughness plastic-steel cable for replacing steel strands according to claim 4, characterized in that: The polyol comprises at least one of polytetramethylene glycol with a hydroxyl value of 110-170 mg KOH / g and polycarbonate diol, or at least one of polytetramethylene glycol with a hydroxyl value of 110-170 mg KOH / g and polycarbonate diol, combined with at least one of polyolefin diol with a hydroxyl value of 70-130 mg KOH / g and polyether triol with a hydroxyl value of 200-550 mg KOH / g; the polyolefin diol is hydroxyl-terminated hydrogenated polybutylene glycol GI-1000 and / or hydroxyl-terminated epoxidized hydrogenated polybutylene glycol Poly bd 600E.

6. The high-strength and high-toughness plastic-steel cable for replacing steel strands according to claim 5, characterized in that: The chain extender includes a diol and a triol, wherein the diol is at least one of 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, and spirodiol, and is combined with at least one of 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, a diol containing a double Se bond, and a diamine containing a double Se bond; and the triol is at least one of glycerol GL, trimethylolpropane TMP, and trishydroxyethyl isocyanurate THEIC.

7. The high-strength and high-toughness plastic-steel cable for replacing steel strands according to claim 6, characterized in that: The ratio of the sum of the NCO molar amount in the triisocyanate, the active hydrogen molar amount in the polyether triol and the active hydrogen molar amount in the triol to the sum of the NCO molar amount in the polyisocyanate, the active hydrogen molar amount in the polyol and the active hydrogen molar amount in the chain extender is 1:(42-48).

8. The high-strength and high-toughness plastic-steel cable for replacing steel strands according to claim 5, characterized in that: The antibacterial and antifungal agent is at least one of nano zinc oxide, nano titanium dioxide, and nano titanium oxynitride; the reinforcing filler is at least one of flaky nano molybdenum disulfide and flaky nano boron nitride combined with at least one of nano silicon dioxide and nano silicon nitride.

9. The high-strength and high-toughness plastic-steel cable for replacing steel strands according to claim 5, characterized in that: The catalyst is any one of dibutyltin dilaurate, stannous octoate, and bismuth isooctanoate; the surface modifier is at least one of γ-aminopropyltriethoxysilane KH550 and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane KH792; and the defoamer is at least one of BASF Efka PB 2021 and BASF Efka SI 2722.

10. A production process for high-strength and high-toughness plastic-steel wire for replacing steel strands according to any one of claims 1 to 9, characterized in that: The following steps are involved: Step 1: Evenly mix 21-28 parts of vacuum-dehydrated polyol, 0.005-0.01 parts of catalyst, and 26-37 parts of polyisocyanate, raise the temperature to 85-95° C. and react for 40-80 minutes, then cool to below 40° C. to obtain an isocyanate-terminated polyurethane prepolymer, which is component A. Meanwhile, the remaining 21-28 parts of polyol, the remaining 0.01-0.035 parts of catalyst, 5.5-12 parts of chain extender, 0.02-0.04 parts of catalyst, 0.6-0.8 parts of antibacterial and antifungal additive, 2-5 parts of reinforcing filler, 0.4-0.8 parts of antioxidant, 0-0.8 parts of anti-ultraviolet aging additive, 0.1-0.4 parts of surface modifier, and 0.15-0.30 parts of defoamer are mixed uniformly under the protection of inert gas, and vacuum degassing is performed for 5-20 minutes to obtain component B; Step 2: Place the isocyanate-terminated polyurethane prepolymer component A in the step one into the A barrel of the glue injection machine, and place the component B in the step one into the B barrel of the glue injection machine. The component A in the A barrel and the component B in the B barrel are mixed and injected into the glue injection box by the glue injection machine. The glue injection box stores the polyurethane resin formed by evenly mixing the components A and B. The polyurethane resin is used to impregnate the continuous fibers, and the impregnated continuous fibers are pultruded. The temperature of zone one is 80-100°C, and the residence time in zone one is 10-20s; the temperature of zone two is 160-200°C, and the residence time in zone two is 30-60s; the temperature of zone three is 80-120°C, and the residence time in zone three is 60-180s; the pultrusion speed is 50-200cm / min, and the fibers are naturally cooled to room temperature to obtain a high-strength and high-toughness plastic-steel wire.

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