Method for producing high-weather-resistant wear-resistant rubber material for floating delivery pipe

Abstract

The application discloses a preparation method of high-weather-resistance wear-resistant rubber material for floating conveying pipes, belongs to the technical field of rubber material preparation, and aims at solving the technical problem that the weather resistance and wear resistance of rubber material in the prior art need to be further improved. The preparation method comprises the following steps: mixing, foaming and then using composite polyols and isophorone diisocyanate to obtain modified polyurethane foam; the application prepares a reinforcing agent with surface-modified perfluoro groups to enhance the stability of the modified polyurethane foam, and prepares a modified chain extender with nano titanium dioxide as a matrix, so that the structure of the modified toughening agent is enriched, and finally the modified toughening agent fills the foam structure, and finally a modified rubber material with wear resistance, impact resistance, corrosion resistance and weather resistance is prepared.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of rubber material preparation, in particular to a preparation method of high-weather-resistance and high-wear-resistance rubber material for a floating conveying pipe. BACKGROUND

[0002] The floating conveying pipe is a core component in a water conveying system, is commonly used in dredging, desilting, marine mining and other fields, and is subjected to challenges such as ultraviolet aging, salt spray corrosion and material scouring in a complex and harsh working environment, and therefore, high-weather-resistance and high-wear-resistance performance requirements are put forward for the outer covering rubber material.

[0003] Although traditional styrene-butadiene rubber and natural rubber have good processability, they are prone to aging and cracking under strong ultraviolet light and long-term scouring. In order to improve the service life, the industry gradually uses ethylene-propylene-diene rubber, combines nano-aluminum oxide, carbon black and other fillers to optimize the structure, effectively improves the aging resistance and wear resistance, and at the same time, introduces dynamic vulcanization and nano-composite technology, so that the material achieves a better balance between flexibility and strength, and provides stronger support for the stable operation of the floating conveying pipe in more severe working conditions.

[0004] The prior art CN119081271B discloses a weather-resistant and anti-aging polyethylene pipeline and a preparation method thereof, which uses high-density polyethylene resin, linear low-density polyethylene resin, polyimide resin micro powder, nano silicon dioxide, nano hexagonal boron nitride, polybenzimidazole fiber, carnosic acid, zinc glycyrrhizinate, antioxidant 1010, hindered amine light stabilizer, polydimethylsiloxane titanate cross-linked polymer and 3-methacryloylpropyl triethoxysilane as raw materials; the polyimide resin micro powder, the carnosic acid and the zinc glycyrrhizinate are uniformly mixed, and then modified at 300-350 DEG C for 30-60 min to obtain a modified product, which can better improve the weather resistance and anti-aging property of the pipeline, the components are compatible with each other, the special modification preparation method better plays the synergistic effect of the components, and the weather resistance and anti-aging property of the polyethylene pipeline is greatly improved.

[0005] However, the above-mentioned application improves the weather resistance and other composite properties of the material by utilizing the synergistic effect of the polyimide resin micro powder, the carnosic acid and the zinc glycyrrhizinate, but the improvement more depends on the functional superposition of the additives themselves, and the action mechanism mainly embodies physical shielding, free radical scavenging and ultraviolet absorption paths, although the stability of the material in a complex environment can indeed be improved in the short term, but the long-term effect is more easily affected by problems such as component migration, thermal degradation or uneven distribution;

[0006] In addition, the compatibility problem between the filler and the polyethylene matrix always exists, due to the significant difference in polarity, micro defects are easily formed during processing and service, thereby weakening the consistency and controllability of the overall material performance, thereby leading to the performance of the material to be further improved. SUMMARY

[0007] The purpose of the present application is to provide a preparation method of a high-weather-resistant wear-resistant rubber material for a floating conveying pipe, which solves the technical problem that the weather resistance and wear resistance of the rubber material in the prior art need to be further improved.

[0008] The purpose of the present application can be achieved by the following technical scheme: a preparation method of a high-weather-resistant wear-resistant rubber material for a floating conveying pipe, comprising the following steps:

[0009] S1, after mixing and foaming using a composite polyol and isophorone diisocyanate, a modified polyurethane foam is obtained;

[0010] S2, the modified polyurethane foam is transferred to a mold, a modified toughening agent is added to the mold and the foamed polyurethane is immersed, then the mold is transferred to a vacuum instrument, after vacuum injection, the modified rubber material is obtained after post-processing.

[0011] The reaction principle for preparing the modified rubber material is: after the modified toughening agent completely fills the modified polyurethane foam through vacuum injection, under heating conditions, the epoxy ring is prone to ring-opening due to tension, and the unreacted amino or secondary amino in the foam structure can be used as a nucleophile to attack the epoxy carbon, and a nucleophilic ring-opening reaction occurs to form a stable beta-hydroxylamine structure, thereby enhancing the interfacial strength between the foam and the toughening agent through chemical bonding, and closing the pore structure, thereby preparing the modified rubber material.

[0012] Further, in step S2, the vacuum degree of the vacuum instrument is-0.09MPa; the post-processing includes: transferring the material to an oven with a temperature of 80-100℃, and keeping warm for 1-2h, repeating the operation until the modified toughening agent completely fills the modified polyurethane foam, and obtaining the modified rubber material.

[0013] Further, in step S1, the preparation method of the modified polyurethane foam comprises the following steps:

[0014] A1, polydiethylene glycol, glycerol, L-580, stannous octoate T-9, a reinforcing agent and deionized water are added to a reaction kettle, stirred at a speed of 1600-1800rpm for 10-15min at room temperature, and a composite polyol is obtained;

[0015] A2, the composite polyol is added into a reaction kettle, nitrogen is introduced for protection, the temperature of the reaction kettle is increased to 40-60℃, a calculated amount of isophorone diisocyanate is added into the reaction kettle, and stirring is performed at a speed of 3200-3600 rpm for 10-15 s, then the reaction liquid is transferred into a mold, and after natural aging for 20-24 h, post-treatment is performed to obtain the modified polyurethane foam.

[0016] The reaction equation for preparing the modified polyurethane foam is as follows:

[0017]

[0018] In the formula:

[0019] The reaction principle for preparing the modified polyurethane foam is as follows: under the action of a catalyst, isophorone diisocyanate reacts with active sites on the polyol compound and the reinforcing agent to generate a polyurethane structure, and the deionized water added into the reaction system reacts with isocyanate groups to release carbon dioxide gas, thereby initiating a foaming process to form the modified polyurethane foam with a porous structure.

[0020] Further, in step A1, the polydiethylene glycol, glycerol, L-580, stannous octoate T-9, the reinforcing agent, and the deionized water are used in a ratio of 40-60 g:5-6 g:1-2 g:1-2 g:4-5 g:2-3 g; in step A2, the isophorone diisocyanate is used in an amount of 0.8-1.0 times the molar amount of the hydroxyl groups in the composite polyol, and the post-treatment includes: after aging is completed, the foam material is washed with deionized water and anhydrous ethanol for 3-5 times, then the foam material is transferred into a vacuum drying oven with a temperature of 70-80℃ for vacuum drying until a constant weight is obtained, thereby obtaining the modified polyurethane foam.

[0021] Further, the preparation method of the reinforcing agent is as follows: graphene oxide, deionized water, and anhydrous ethanol are added into a reaction kettle for stirring, nitrogen is introduced for protection, acetic acid is used to adjust the pH of the reaction system to 4-5, then the temperature of the reaction kettle is increased to 40-50℃, and perfluorooctyltrimethoxysilane is added into the reaction kettle, and the system is stirred for 1-2 h, and post-treatment is performed to obtain the reinforcing agent.

[0022] The reaction principle for preparing the reinforcing agent is as follows: under the promotion of an acidic condition, the methoxysilane in the perfluorooctyltrimethoxysilane is hydrolyzed to generate a silicon hydroxyl group, thereby reacting with active functional groups such as hydroxyl groups, epoxy groups, and carboxyl groups on the graphene oxide, so that the perfluoro group is grafted on the surface of the graphene oxide, thereby obtaining the reinforcing agent.

[0023] Further, the ratio of the amounts of graphene oxide, deionized water, anhydrous ethanol and perfluorooctyltrimethoxysilane is as follows, and the post-treatment includes: after the reaction is completed, the temperature of the reaction kettle is reduced to room temperature, the reaction liquid is filtered to collect the filter cake, the filter cake is washed with deionized water and anhydrous ethanol for 3-5 times, and then the filter cake is transferred to a vacuum drying oven and dried at 60-80℃ under vacuum until the weight is constant, to obtain the reinforcing agent.

[0024] Further, the preparation method of the modified toughening agent comprises the following steps:

[0025] B1, 2, 4, 6-trivinyl-2, 4, 6-trimethylcyclotrisiloxane, trifluoropropylmethylcyclotrisiloxane and N, N-dimethylformamide are added to the reaction kettle, the temperature of the reaction kettle is increased to 100-120℃, then sodium hydroxide is added to the reaction kettle, and the reaction is kept for 4-5h, then the modified chain extender is added to the reaction kettle, and the reaction is kept for 2-3h, and then the telomerized silicone oil is obtained by post-treatment;

[0026] B2, the telomerized silicone oil and N, N-dimethylformamide are added to the reaction kettle, and then nitrogen is introduced for protection, then the temperature of the reaction kettle is reduced to 10-15℃, then the oxidizing agent is added to the reaction kettle, and the reaction is kept for 1-2h, and then the modified toughening agent is obtained by post-treatment.

[0027] The reaction equation for preparing the modified toughening agent is as follows:

[0028]

[0029] In the formula: The modified chain extender is represented by R.

[0030] The reaction principle for preparing the modified toughening agent is as follows: under the catalysis of alkali, 2, 4, 6-trivinyl-2, 4, 6-trimethylcyclotrisiloxane and trifluoropropylmethylcyclotrisiloxane are converted into telomerized silicone oil containing vinyl side chains through ring-opening polymerization, and multiple active sites are generated by hydrolysis of the silicon methoxy structure on the modified chain extender, so as to realize chain extension and hybridization, thereby preparing the telomerized silicone oil; and under low temperature and inert atmosphere, the vinyl groups on the polysiloxane chain are selectively oxidized into epoxy groups by using benzoyl peroxide, thereby preparing the modified toughening agent.

[0031] Further, in step B1, the amount ratio of the 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane, trifluoropropylmethylcyclotrisiloxane, N,N-dimethylformamide, sodium hydroxide and modified chain extender is 4-5 g:6-8 g:50-54 mL:0.3-0.5 g:2-3 g, and the post-treatment includes: after the reaction is completed, the temperature of the reaction kettle is reduced to room temperature, after the reaction system is adjusted to neutral with 1M dilute hydrochloric acid aqueous solution, the organic layer is separated by standing, the organic layer is washed with deionized water for 3-5 times, the organic phase is dried with anhydrous sodium sulfate, and then the filtrate is collected by suction filtration, the filtrate is transferred to a rotary evaporator with a temperature of 80-100°C, and the liquid is distilled under reduced pressure to obtain the telomerized silicone oil.

[0032] Further, in step B2, the amount ratio of the telomerized silicone oil, N,N-dimethylformamide and oxidizing agent is 6-8 g:20-24 mL:1-2 g, wherein the oxidizing agent is benzoic acid peroxide, and the post-treatment includes: after the reaction is completed, the temperature of the reaction kettle is reduced to room temperature, sodium bicarbonate is added to the reaction kettle until no gas bubbles are generated, the reaction liquid is extracted with dichloromethane for 3-5 times to obtain an organic layer, the organic layer is washed with deionized water for 3-5 times, the organic phase is dried with anhydrous sodium sulfate, and then the filtrate is collected by suction filtration, the filtrate is transferred to a rotary evaporator with a temperature of 80-100°C, and the liquid is distilled under reduced pressure to obtain the modified toughening agent.

[0033] Further, the preparation method of the modified chain extender is: nano-titanium dioxide, anhydrous ethanol and triethylamine are added to a reaction kettle and stirred, nitrogen is introduced for protection, the temperature of the reaction kettle is increased to 40-60°C, 3-(2,3-epoxypropoxy) propyltrimethoxysilane is added to the reaction kettle, and the temperature is kept constant and stirred for 40-60 min, and the modified chain extender is obtained after post-treatment.

[0034] The structure of the modified chain extender is shown in the following figure:

[0035] The reaction principle for preparing the modified chain extender is: under the promotion of triethylamine and heating, the epoxy group on the 3-(2,3-epoxypropoxy) propyltrimethoxysilane undergoes ring opening, the active free radicals generated react with the silicon hydroxyl groups on the nano-titanium dioxide, the silicon methoxy structure is crosslinked on the modified nano-titanium dioxide, and finally the modified chain extender is prepared.

[0036] Further, the use amount ratio of nanometer titanium dioxide, anhydrous ethanol, triethylamine and 3-(2,3-epoxypropoxy) propyl trimethoxysilane is 5-6 g:40-50 mL:0.3-0.5 g:1-2 g, and the post-treatment includes: after the reaction is completed, the temperature of the reaction kettle is reduced to room temperature, the reaction liquid is filtered to collect the filter cake, the filter cake is washed with deionized water and anhydrous ethanol for 3-5 times, then the filter cake is transferred to a vacuum drying oven and dried at 60-80 DEG C under vacuum until the weight is constant, to obtain the modified chain extender.

[0037] The present application has the following advantages:

[0038] 1、The graphene oxide is modified by perfluoroalkyl trimethoxysilane, and then is connected with a polyurethane matrix to form stable covalent bonds, the sheet structure of the graphene oxide provides rigid support at the micro level, effectively inhibits the expansion of micro cracks in the wear process, the modified chain extender is uniformly dispersed and the interface adhesion is enhanced by the use of an epoxy silane coupling agent, the nanometer skeleton structure cooperates with the foam network to construct a micro-scale reinforced support network, and the overall anti-deformation ability of the material is improved, meanwhile, the introduction of the polyorganosiloxane and the chain extender forms flexible organosilicon segments, which can reversibly deform and absorb impact energy when bearing impact load, and delay crack propagation, after the foam structure is completely filled, a reinforced network with supporting effect is formed, not only the buffering and damping functions are retained, but also the modified toughening agent cooperates to form a strong and tough composite material, the distribution of the foam enables the energy to be effectively absorbed and dispersed when external force acts, the direct impact of the external force on the material is reduced, the impact resistance is improved, and finally a wear-resistant and impact-resistant composite rubber material is obtained.

[0039] 2、The graphene oxide is used as a two-dimensional layered material, the high specific surface area and excellent chemical stability of the graphene oxide endow it with excellent barrier function, and the perfluoro group modified on the surface of the graphene oxide has extremely low surface energy and excellent hydrophobic and oleophobic properties, which can significantly reduce the affinity of the material surface to polar or corrosive media, thereby effectively blocking the penetration of water molecules, oxygen and corrosive ions, and delaying the diffusion of corrosive media to the inside, secondly, the foam structure is fully filled by the vacuum injection molding process, forming a continuous and dense three-dimensional network, significantly prolonging the corrosion path and improving the overall barrier performance, meanwhile, the crosslinked network structure formed by the modified chain extender and polysiloxane in the system further closes the micro channels, enhancing the overall density and chemical inertness of the material, thereby effectively inhibiting the structural degradation and performance loss of the material in a corrosive environment, and the organic combination of the barrier effect, path delay effect and crosslinking sealing effect significantly improves the corrosion resistance of the material.

[0040] 3、The modified toughening agent prepared in the application fully penetrates and fills into the inside of the polyurethane foam structure in the vacuum injection molding process, the high reactivity epoxy structure thereof reacts with the residual amino group in the foam to form a stable beta-hydroxyl amine chemical bond, thereby constructing a dense and stable interface structure, at the same time, the modified nano titanium dioxide introduced in the toughening agent is uniformly dispersed in the foam pores to form a three-dimensional anti-ultraviolet nano network, which not only can directly absorb and scatter ultraviolet light to slow down the main chain degradation, but also has a certain free radical capture ability to effectively interrupt the aging chain reaction induced by ultraviolet, and the covalent connection between the perfluoroalkyl modified graphene oxide and the polyurethane enhances the interface stability, the low surface energy property of the perfluoroalkyl modified graphene oxide helps to construct a hydrophobic self-cleaning layer, thereby reducing the participation of water and oxygen required for photooxidation, under the structure closure and functional synergy among the multiple components, the material as a whole exhibits excellent ultraviolet stability and long-term weather resistance. DETAILED DESCRIPTION

[0041] The technical solutions of the application will be described below in connection with the embodiments, obviously, the described embodiments are only part of the embodiments of the application, not all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor belong to the protection scope of the application.

[0042] The L-580 used in the application is purchased from Shanghai Kaijin Chemical Co., Ltd., and the brand is American Mayite Silicone L-580; the stannous octoate is purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd., and the article number is T-9PA42718; the polyethylene glycol is purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd., and the article number is DC00328; the graphene oxide is purchased from Shanghai Aladdin Biochem Technology Co., Ltd., and the article number is G405797; and the nano silicon dioxide is purchased from Shanghai Aladdin Biochem Technology Co., Ltd., and the article number is S104597.

[0043] Example 1

[0044] The embodiment provides a preparation method of a modified polyurethane foam for preparing a high-weather-resistant wear-resistant rubber material for a floating conveying pipe, and comprises the following steps:

[0045] Step 1, preparation of a reinforcing agent

[0046] Take: 40.0 g of graphene oxide, 100.0 mL of deionized water and 100.0 mL of anhydrous ethanol into the reaction kettle, stir, protect with nitrogen, adjust the pH of the reaction system to 5 with acetic acid, then increase the temperature of the reaction kettle to 40℃ and add 10.0 g of perfluorooctyltrimethoxysilane to the reaction kettle, stir for 1 h, after the reaction is completed, when the temperature of the reaction kettle decreases to room temperature, filter the reaction solution to collect the filter cake, wash the filter cake with deionized water and anhydrous ethanol for 3 times, then transfer the filter cake to a vacuum drying oven, vacuum dry at 60℃ until the weight is constant, and obtain the reinforcing agent.

[0047] Step 2, preparation of composite polyol

[0048] Take: 400.0 g of polyethylene glycol, 50.0 g of glycerol, 10.0 g of L-580, 10.0 g of stannous octoate T-9, 40.0 g of reinforcing agent and 20.0 g of deionized water into the reaction kettle, stir at room temperature at a speed of 1600 rpm for 10 min, and obtain the composite polyol.

[0049] Step 3, preparation of modified polyurethane foam

[0050] Take: 400.0 g of composite polyol into the reaction kettle, protect with nitrogen, increase the temperature of the reaction kettle to 40℃, and add isophorone diisocyanate which is 0.8 times the molar amount of hydroxyl in the composite polyol to the reaction kettle, stir at a speed of 3200 rpm for 10 s, then transfer the reaction solution to the mold, naturally cure for 20 h, after curing is completed, wash the foam material with deionized water and anhydrous ethanol for 3 times, then transfer the foam material to a vacuum drying oven with a temperature of 70℃ and vacuum dry until the weight is constant, and obtain the modified polyurethane foam.

[0051] Example 2

[0052] The present embodiment provides a preparation method of modified polyurethane foam for preparing high-weather-resistant wear-resistant rubber material for floating conveying pipe, which comprises the following steps:

[0053] Step 1, preparation of reinforcing agent

[0054] Take: 50.0 g of graphene oxide, 120.0 mL of deionized water and 120.0 mL of anhydrous ethanol into the reaction kettle, stir, protect with nitrogen, adjust the pH of the reaction system to 4 with acetic acid, then increase the temperature of the reaction kettle to 50℃ and add 20.0 g of perfluorooctyltrimethoxysilane to the reaction kettle, stir for 2 h, after the reaction is completed, when the temperature of the reaction kettle decreases to room temperature, filter the reaction solution to collect the filter cake, wash the filter cake with deionized water and anhydrous ethanol for 5 times, then transfer the filter cake to a vacuum drying oven, vacuum dry at 80℃ until the weight is constant, and obtain the reinforcing agent.

[0055] Step 2, preparation of composite polyol

[0056] Weighing: 600.0 g of polydiethylene glycol, 60.0 g of glycerol, 20.0 g of L-580, 20.0 g of stannous octoate T-9, 50.0 g of reinforcing agent and 30.0 g of deionized water into the reaction kettle, stir at room temperature at 1800 rpm for 15 min, to obtain a composite polyol.

[0057] Step ③, preparation of modified polyurethane foam

[0058] Weighing: 400.0 g of composite polyol into the reaction kettle, after nitrogen protection, the temperature of the reaction kettle is increased to 60℃, and 1.0 times the molar amount of isophorone diisocyanate of the hydroxyl group in the composite polyol is added into the reaction kettle, and stirred at 3600 rpm for 15 s, then the reaction solution is transferred to the mold, and naturally aged for 24 h, after aging, the foam material is washed with deionized water and anhydrous ethanol for 5 times, then the foam material is transferred to a vacuum drying oven with a temperature of 80℃ and vacuum dried to constant weight, to obtain a modified polyurethane foam.

[0059] Example 3

[0060] The present embodiment provides a preparation method of a modified polyurethane foam for preparing a high-weather-resistant wear-resistant rubber material for floating conveying pipe, comprising the following steps:

[0061] Step ①, preparation of reinforcing agent

[0062] Weighing: 45.0 g of graphene oxide, 120.0 mL of deionized water and 120.0 mL of anhydrous ethanol into the reaction kettle and stir, after nitrogen protection, adjust the pH of the reaction system to 4 using acetic acid, then increase the temperature of the reaction kettle to 45℃ and add 16.0 g of perfluorooctyltrimethoxysilane into the reaction kettle, and keep stirring for 2 h, after the reaction is completed, when the temperature of the reaction kettle decreases to room temperature, filter the reaction solution to collect the filter cake, wash the filter cake with deionized water and anhydrous ethanol for 4 times, then transfer the filter cake to a vacuum drying oven and vacuum dry at 70℃ to constant weight, to obtain a reinforcing agent.

[0063] Step ②, preparation of composite polyol

[0064] Weighing: 500.0 g of polydiethylene glycol, 54.0 g of glycerol, 16.0 g of L-580, 16.0 g of stannous octoate T-9, 45.0 g of reinforcing agent and 25.0 g of deionized water into the reaction kettle, stir at room temperature at 1700 rpm for 12 min, to obtain a composite polyol.

[0065] Step ③, preparation of modified polyurethane foam

[0066] Weighing: 400.0 g of the composite polyol is added to the reaction kettle, and after nitrogen protection, the temperature of the reaction kettle is raised to 50°C, and 0.9 times the molar amount of isophorone diisocyanate based on the hydroxyl group in the composite polyol is added to the reaction kettle, and after stirring at 3600 rpm for 12 s, the reaction liquid is transferred to the mold, and after natural curing for 21 h, after curing is completed, the foam material is washed with deionized water and anhydrous ethanol 4 times, and then the foam material is transferred to a vacuum drying oven with a temperature of 75°C and vacuum dried to constant weight, to obtain a modified polyurethane foam.

[0067] Example 4

[0068] The present embodiment provides a method for preparing a modified toughening agent for preparing a high-weather-resistant wear-resistant rubber material for a floating conveying pipe, comprising the following steps:

[0069] Step I, preparation of modified chain extender

[0070] Weighing: 50.0 g of nano-titanium dioxide, 400.0 mL of anhydrous ethanol, and 3.0 g of triethylamine are added to the reaction kettle and stirred, and after nitrogen protection, the temperature of the reaction kettle is raised to 40°C, and 10.0 g of 3-(2,3-epoxypropoxy) propyl trimethoxysilane is added to the reaction kettle, and stirred for 40 min, and after the reaction is completed, the temperature of the reaction kettle is reduced to room temperature, and the reaction liquid is collected by filtration, and the filter cake is washed with deionized water and anhydrous ethanol 3 times, and then the filter cake is transferred to a vacuum drying oven and dried to constant weight at 60°C under vacuum, to obtain a modified chain extender.

[0071] Step II, preparation of a modified toughening agent

[0072] Weighing: 40.0 g of 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane, 60.0 g of trifluoropropylmethylcyclotrisiloxane, and 500.0 mL of N,N-dimethylformamide are added to the reaction kettle, and after the temperature of the reaction kettle is raised to 100°C, 3.0 g of sodium hydroxide is added to the reaction kettle, and after 4 h of heat preservation, 20.0 g of the modified chain extender is added to the reaction kettle, and after 2 h of heat preservation, the reaction is completed, and after the temperature of the reaction kettle is reduced to room temperature, the reaction system is adjusted to neutral with 1M dilute hydrochloric acid aqueous solution, and then the organic layer is separated by standing, and the organic layer is washed with deionized water 3 times, and then the organic phase is dried with anhydrous sodium sulfate, and the filtrate is collected by filtration, and then the filtrate is transferred to a rotary evaporator with a temperature of 80°C, and distilled under reduced pressure to obtain a modified toughening agent.

[0073] Step III, preparation of a modified toughening agent

[0074] Take: 60.0 g of polydisperse silicone oil and 200.0 mL of N,N-dimethylformamide into the reaction kettle, after purging with nitrogen, the temperature of the reaction kettle is reduced to 15 ℃, then 10.0 g of benzoyl peroxide is added into the reaction kettle, and the reaction is kept for 1 h. After the reaction is completed, the temperature of the reaction kettle is reduced to room temperature, then sodium bicarbonate is added into the reaction kettle until no bubbles are generated. The reaction solution is extracted with dichloromethane for 3 times to obtain an organic layer. The organic layer is washed with deionized water for 3 times, then dried with anhydrous sodium sulfate, and the filtrate is collected by suction filtration. The filtrate is transferred to a rotary evaporator with a temperature of 80 ℃, and distilled under reduced pressure to obtain the modified toughening agent.

[0075] Example 5

[0076] The present embodiment provides a preparation method of a modified toughening agent for preparing a high-weather-resistant wear-resistant rubber material for a floating conveying pipe, comprising the following steps:

[0077] Step I, preparation of modified chain extender

[0078] Take 60.0 g of nano-titanium dioxide, 500.0 mL of anhydrous ethanol, and 5.0 g of triethylamine into the reaction kettle and stir. After purging with nitrogen, the temperature of the reaction kettle is increased to 60 ℃, and 20.0 g of 3-(2,3-epoxypropoxy) propyl trimethoxysilane is added into the reaction kettle. Stir for 60 min, and the reaction is completed. After the temperature of the reaction kettle is reduced to room temperature, the reaction solution is collected by suction filtration, and the filter cake is washed with deionized water and anhydrous ethanol for 5 times. Then, the filter cake is transferred to a vacuum drying oven and dried at 70 ℃ under vacuum until the weight is constant to obtain the modified chain extender.

[0079] Step II, preparation of polydisperse silicone oil

[0080] Take 50.0 g of 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane, 80.0 g of trifluoropropylmethylcyclotrisiloxane, and 540.0 mL of N,N-dimethylformamide into the reaction kettle. After the temperature of the reaction kettle is increased to 120 ℃, 5.0 g of sodium hydroxide is added into the reaction kettle. After keeping for 5 h, 30.0 g of modified chain extender is added into the reaction kettle, and the reaction is kept for 2-3 h. After the reaction is completed, the temperature of the reaction kettle is reduced to room temperature, and the reaction system is adjusted to neutral with 1M dilute hydrochloric acid aqueous solution. Then, the organic layer is separated by standing, washed with deionized water for 5 times, dried with anhydrous sodium sulfate, and collected by suction filtration. The filtrate is transferred to a rotary evaporator with a temperature of 100 ℃, and distilled under reduced pressure to obtain the polydisperse silicone oil.

[0081] Step III, preparation of modified toughening agent

[0082] Take: 80.0 g of polydisperse silicone oil and 240.0 mL of N,N-dimethylformamide into the reaction kettle, after purging with nitrogen, the temperature of the reaction kettle is reduced to 10℃, then 20.0 g of benzoyl peroxide is added into the reaction kettle, and the reaction is carried out for 2 h. After the reaction is completed, the temperature of the reaction kettle is reduced to room temperature, and sodium bicarbonate is added into the reaction kettle until no bubbles are generated. The reaction solution is extracted with dichloromethane for 5 times to obtain an organic layer. The organic layer is washed with deionized water for 5 times, and then dried with anhydrous sodium sulfate. The filtrate is collected by suction filtration, and then transferred to a rotary evaporator with a temperature of 100℃. The liquid is distilled under reduced pressure to obtain the modified toughening agent.

[0083] Example 6

[0084] The present embodiment provides a preparation method of a modified toughening agent for preparing a high-weather-resistant wear-resistant rubber material for a floating conveying pipe, comprising the following steps:

[0085] Step I, preparation of modified chain extender

[0086] Take 54.0 g of nano-titanium dioxide, 450.0 mL of anhydrous ethanol, and 4.0 g of triethylamine into the reaction kettle and stir. After purging with nitrogen, the temperature of the reaction kettle is increased to 50℃, and 16.0 g of 3-(2,3-epoxypropoxy) propyl trimethoxysilane is added into the reaction kettle. Stir for 50 min, and then the reaction is completed. After the temperature of the reaction kettle is reduced to room temperature, the reaction solution is collected by suction filtration, and then the filter cake is washed with deionized water and anhydrous ethanol for 4 times. The filter cake is transferred to a vacuum drying oven and dried at 70℃ until the weight is constant to obtain the modified chain extender.

[0087] Step II, preparation of polydisperse silicone oil

[0088] Take 45.0 g of 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane, 70.0 g of trifluoropropylmethylcyclotrisiloxane, and 540.0 mL of N,N-dimethylformamide into the reaction kettle. After the temperature of the reaction kettle is increased to 120℃, 4.0 g of sodium hydroxide is added into the reaction kettle. After reaction for 5 h, 25.0 g of modified chain extender is added into the reaction kettle, and then the reaction is carried out for 3 h. After the reaction is completed, the temperature of the reaction kettle is reduced to room temperature, and then the reaction system is adjusted to neutral with 1M dilute hydrochloric acid aqueous solution. The organic layer is separated by standing, and then washed with deionized water for 4 times. The organic phase is dried with anhydrous sodium sulfate, and then the filtrate is collected by suction filtration. The filtrate is transferred to a rotary evaporator with a temperature of 90℃, and then the liquid is distilled under reduced pressure to obtain the polydisperse silicone oil.

[0089] Step III, preparation of modified toughening agent

[0090] Take: 70.0 g of the polyols and 210.0 mL of N,N-dimethylformamide into the reaction kettle, after the protection of nitrogen, the temperature of the reaction kettle is reduced to 12 ℃, then 16.0 g of benzoyl peroxide is added into the reaction kettle, and the reaction is carried out for 2 h. After the reaction is completed, the temperature of the reaction kettle is reduced to room temperature, then sodium bicarbonate is added into the reaction kettle until no bubbles are generated. After the reaction solution is extracted with dichloromethane for 4 times, the organic layer is washed with deionized water for 4 times, then the organic phase is dried with anhydrous sodium sulfate, and the filtrate is collected by filtration. The filtrate is transferred to a rotary evaporator with a temperature of 90 ℃, and the liquid is collected by vacuum distillation. The modified toughening agent is obtained.

[0091] Example 7

[0092] The preparation method of the modified toughening agent for preparing the high-weather-resistant wear-resistant rubber material for the floating conveying pipe provided in the embodiment includes the following steps:

[0093] The modified polyurethane foam prepared in Example 1 is transferred into a mold, and the modified toughening agent prepared in Example 4 is added into the mold and immersed in the foamed polyurethane. Then, the mold is transferred into a vacuum instrument, the vacuum degree of the vacuum instrument is set to -0.09 MPa, and the material is transferred into an oven with a temperature of 80 ℃ after vacuum injection molding. The material is kept for 1 h, and the operation is repeated until the modified toughening agent is completely filled with the modified polyurethane foam. The modified rubber material is obtained.

[0094] Example 8

[0095] The preparation method of the modified toughening agent for preparing the high-weather-resistant wear-resistant rubber material for the floating conveying pipe provided in the embodiment includes the following steps:

[0096] The modified polyurethane foam prepared in Example 2 is transferred into a mold, and the modified toughening agent prepared in Example 5 is added into the mold and immersed in the foamed polyurethane. Then, the mold is transferred into a vacuum instrument, the vacuum degree of the vacuum instrument is set to -0.09 MPa, and the material is transferred into an oven with a temperature of 100 ℃ after vacuum injection molding. The material is kept for 2 h, and the operation is repeated until the modified toughening agent is completely filled with the modified polyurethane foam. The modified rubber material is obtained.

[0097] Example 9

[0098] The preparation method of the modified toughening agent for preparing the high-weather-resistant wear-resistant rubber material for the floating conveying pipe provided in the embodiment includes the following steps:

[0099] The modified polyurethane foam prepared in Example 3 was transferred to a mold, and the modified toughening agent prepared in Example 6 was added to the mold and immersed in the foamed polyurethane, then the mold was transferred to a vacuum instrument, the vacuum degree of the vacuum instrument was set to-0.09 MPa, after vacuum injection, the material was transferred to an oven with a temperature of 90℃, and was kept for 2h, and the operation was repeated until the modified toughening agent was completely filled with the modified polyurethane foam, to obtain a modified rubber material.

[0100] Comparative Example 1

[0101] The difference between this comparative example and Example 9 is that the modified polyurethane foam used in the preparation process cancels step ①, and uses graphene oxide instead of the reinforcing agent in step ②.

[0102] Comparative Example 2

[0103] The difference between this comparative example and Example 9 is that the modified polyurethane foam used in the preparation process cancels the use of reinforcing agent in step ②.

[0104] Comparative Example 3

[0105] The difference between this comparative example and Example 9 is that the modified toughening agent used in the preparation process cancels the use of modified chain extender in step II.

[0106] Performance test:

[0107] The impact resistance of the modified rubber materials prepared in Examples 7-9 and Comparative Examples 1-3 was tested according to the standard GB / T 1843-2008 "Determination of the impact strength of plastics by means of a cantilever beam".

[0108] The volume abrasion of the modified rubber materials prepared in Examples 7-9 and Comparative Examples 1-3 was tested according to the standard GB / T 9867-2008 "Determination of the abrasion resistance of vulcanized or thermoplastic rubber (rotating cylinder abrasion machine method)".

[0109] The corrosion resistance of the modified rubber materials prepared in Examples 7-9 and Comparative Examples 1-3 was tested according to the standard HG / T 4087-2009 "Plastic alloy anticorrosion composite pipe".

[0110] After the modified rubber materials prepared in Examples 7-9 and Comparative Examples 1-3 were treated by ultraviolet radiation according to the standard GB / T 16422.3-2022 "Plastics-Laboratory light source exposure test methods-Part 3: Fluorescent ultraviolet lamps", the performance change rate of the modified rubber materials was determined according to the standards GB / T 1843-2008 and GB / T 9867-2008; the specific data is shown in Table 1.

[0111] Table 1-Performance test data table of each sample

[0112]

[0113] Data analysis:

[0114] After comparing and analyzing the data in Table 1, it can be found that the cantilever beam impact strength of the prepared suspension arm is 70.1 kJ·m -2 , the volume wear amount is 11 mm 3 , the 30% H2SO4 corrosion is 0.9 g·m -2 , the 40% NaOH corrosion is 1.1 g·m -2 , and the cantilever beam impact strength retention rate is 99.4% and the volume wear amount change rate is 100.7% after ultraviolet aging, and all the data are better than those of the comparative example;

[0115] After comparing and analyzing the data in Table 1, it can be found that although the comparative example 1 retains graphene oxide as a reinforcing agent, the interfacial affinity in the polyurethane matrix is significantly reduced due to the lack of perfluoroalkyl modification. The unmodified graphene oxide surface is rich in polar functional groups such as carboxyl and hydroxyl groups, which are easy to agglomerate and difficult to disperse uniformly in the foam pore structure, thereby causing the graphene to fail to effectively transfer the load at the interface, and stress concentration exists between the reinforcing phase and the matrix. Secondly, during the impact process, the impact load is not dispersed and absorbed in time, and the material is more prone to fracture. At the same time, the lack of hydrophobic protection of perfluoro groups also reduces the surface stability of the material, causing the corrosion medium to penetrate into the pore structure more easily, causing chemical degradation, thereby significantly weakening the corrosion resistance. In addition, although graphene oxide has certain ultraviolet shielding ability, without dispersant and modifier, its shielding effect is unstable and easy to fail due to agglomeration, thereby greatly reducing the weather resistance of the material;

[0116] In the comparative example 2, the use of reinforcing agent is completely cancelled, which means that there is a lack of any nano-reinforcing filler in the foam structure, which significantly weakens the overall mechanical support of the material, causing the material surface to be easily worn and peeled off during friction contact. Due to the lack of high modulus filler support, the foam matrix softens and the bearing capacity decreases. Secondly, due to the lack of stress sharing of the reinforcing phase, the material deforms and accumulates when subjected to instantaneous impact load, which is easy to cause crack initiation and propagation. At the same time, since the material does not form a space barrier to block the medium, the corrosion medium can quickly spread in the micropore, causing the chemical degradation of the structure to intensify. Moreover, the material surface lacks hydrophobic functional groups or ultraviolet absorbing components, and UV radiation directly acts on the polymer main chain, accelerating the aging reaction and rapidly deteriorating the weather resistance of the material;

[0117] In Comparative Example 3, the use of the modified chain extender was cancelled, and the original nano-enhancing and chain-extending dual functions in the system were stripped, thereby significantly adversely affecting the structural stability and service performance of the material. First, the lack of chain extension reaction path will directly lead to the shortening of the polymer main chain, the narrowing of the molecular weight distribution, and the overall decline of the mechanical properties of the rubber material, which is manifested as a significant weakening of the compression modulus and resilience, and a significant weakening of the structure's resistance to load. Second, the absence of nano-titanium dioxide as an inorganic reinforcing phase makes the system lack an effective stress transfer and dispersion mechanism. When subjected to periodic friction or instantaneous impact load, stress concentration is likely to occur in the material, inducing the initiation and propagation of cracks. Moreover, due to the lack of uniform distribution of reinforcing phase in the cell structure, the ability of the micro-pore gap to effectively block the corrosion medium is weakened, and the liquid or gas medium can quickly propagate in the cell channel, thereby accelerating the internal chemical degradation process.

[0118] Finally, it is shown that the graphene oxide modified by perfluoroalkyl not only enhances the interfacial affinity with the polyurethane matrix, significantly improves its uniform dispersibility in the cell structure, but also imparts excellent hydrophobicity and shielding properties to the material. While improving the mechanical properties, it effectively blocks the diffusion of corrosive media, enhancing the corrosion resistance and environmental stability of the material. On the other hand, the introduction of nano-titanium dioxide not only plays an inorganic reinforcing role, but also forms stable interfacial bonding with the matrix through its surface activity, further promoting stress conduction and structural stability, and improving impact resistance and wear resistance. In addition, the modified chain extender optimizes the cell structure on the basis of controlling the molecular weight distribution of polyurethane, enhances the continuity and density of the matrix, and provides stable support for overall performance. The three form a benign synergy in structure construction, interface regulation, and performance reinforcement, thereby achieving balanced and significant improvement in mechanical properties, corrosion resistance, wear resistance, and weather resistance in multiple dimensions.

[0119] The above content is merely an example and description of the structure of the present application. Those skilled in the art can make various modifications or supplements to the described specific embodiments or use similar methods to replace them, as long as they do not deviate from the structure of the invention or exceed the scope defined by the present claims, and should belong to the protection scope of the present application.

Claims

1. A method for preparing a high weather-resistant and wear-resistant rubber material for floating conveying pipes, characterized in that, Includes the following steps: S1. Modified polyurethane foam is obtained by mixing and foaming a composite polyol and isophorone diisocyanate. S2. The modified polyurethane foam is transferred into a mold, and a modified toughening agent is added to the mold and the foamed polyurethane is immersed in it. The mold is then transferred to a vacuum instrument, vacuum injection is performed, and post-treatment is carried out to obtain the modified rubber material. The method for preparing the modified polyurethane foam includes the following steps: A1. Add polyethylene glycol, glycerol, L-580, stannous octoate T-9, reinforcing agent and deionized water to a reaction vessel, and stir at 1600-1800 rpm for 10-15 min at room temperature to obtain a composite polyol. A2. Add the composite polyol to the reactor, purge with nitrogen, raise the reactor temperature to 40-60℃, add the calculated amount of isophorone diisocyanate to the reactor, stir at 3200-3600 rpm for 10-15 seconds, transfer the reaction solution to the mold, allow it to mature naturally for 20-24 hours, and then perform post-treatment to obtain modified polyurethane foam. The preparation method of the modified toughening agent includes the following steps: B1. 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane, trifluoropropylmethylcyclotrisiloxane and N,N-dimethylformamide are added to a reaction vessel. After the temperature of the reaction vessel is raised to 100-120℃, sodium hydroxide is added to the reaction vessel. After the reaction is kept at this temperature for 4-5 hours, a modified chain extender is added to the reaction vessel. The reaction is kept at this temperature for 2-3 hours. The post-treatment yields telomerized silicone oil. B2. Add telomerized silicone oil and N,N-dimethylformamide to the reactor, purge with nitrogen for protection, and then lower the reactor temperature to 10-15℃. Add oxidant to the reactor and keep it at the temperature for 1-2 hours. The modified toughening agent is then obtained after post-treatment. The preparation method of the reinforcing agent is as follows: graphene oxide, deionized water and anhydrous ethanol are added to the reaction vessel and stirred. After nitrogen protection, the pH of the reaction system is adjusted to 4-5 with acetic acid. Then, the temperature of the reaction vessel is raised to 40-50℃ and perfluorooctyltrimethoxysilane is added to the reaction vessel. The mixture is kept at the temperature and stirred for 1-2 hours. The reinforcing agent is obtained after post-treatment. The modified chain extender is prepared by adding nano-titanium dioxide, anhydrous ethanol and triethylamine into a reaction vessel and stirring. After purging with nitrogen, the temperature of the reaction vessel is raised to 40-60℃, and 3-(2,3-epoxypropoxy)propyltrimethoxysilane is added to the reaction vessel. The mixture is kept at this temperature and stirred for 40-60 minutes. The modified chain extender is then obtained through post-treatment.

2. The method for preparing the high weather-resistant and wear-resistant rubber material for floating conveying pipes according to claim 1, characterized in that, In step A1, the ratio of the amounts of polyethylene glycol, glycerol, L-580, stannous octoate T-9, reinforcing agent, and deionized water is 40-60g:5-6g:1-2g:1-2g:4-5g:2-3g; in step A2, the amount of isophorone diisocyanate is 0.8-1.0 times the molar amount of hydroxyl groups in the composite polyol.

3. The method for preparing the high weather-resistant and wear-resistant rubber material for floating conveying pipes according to claim 1, characterized in that, The ratio of graphene oxide, deionized water, anhydrous ethanol, and perfluorooctyltrimethoxysilane is 4-5g:10-12mL:10-12mL:1-2g.

4. The method for preparing the high weather-resistant and wear-resistant rubber material for floating conveying pipes according to claim 1, characterized in that, In step B1, the ratio of 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane, trifluoropropylmethylcyclotrisiloxane, N,N-dimethylformamide, sodium hydroxide, and modified chain extender is 4-5g:6-8g:50-54mL:0.3-0.5g:2-3g; in step B2, the ratio of telomerized silicone oil, N,N-dimethylformamide, and oxidant is 6-8g:20-24mL:1-2g, wherein the oxidant is benzoic acid peroxide.

5. The method for preparing the high weather-resistant and wear-resistant rubber material for floating conveying pipes according to claim 1, characterized in that, The ratio of nano-titanium dioxide, anhydrous ethanol, triethylamine, and 3-(2,3-epoxypropoxy)propyltrimethoxysilane is 5-6g:40-50mL:0.3-0.5g:1-2g.

Images