Rubber composite material with marine antifouling property as well as preparation method and application thereof

Abstract

The invention discloses a rubber composite material with marine antifouling property as well as a preparation method and application thereof, and relates to the technical field of marine fouling organism decay protection materials. The rubber composite material with the marine antifouling property comprises the following components which are blended and vulcanized: rubber, a filler, an antifouling agent, a plasticizer, an activating agent, a scorch retarder, an anti-aging agent, an accelerant and a vulcanizing agent, the antifouling agent comprises a copolymer modified by zwitter-ions and at least one of sodium benzoate, tannic acid, 6-gingerol, capsaicin, sulfobetaine, carboxylic acid betaine, phosphorylcholine, isothiazolinone and zinc pyrithione optionally selected from the group consisting of sodium benzoate, tannic acid, 6-gingerol, capsaicin, sulfobetaine, carboxylic acid betaine, phosphorylcholine, isothiazolinone and zinc pyrithione. The invention solves the three core problems of poor compatibility of an antifouling agent and a rubber matrix, short antifouling period caused by easy loss of the antifouling agent, and difficulty in balancing the antifouling property and mechanical property in the existing marine antifouling rubber material.

Description

Technical Field

[0001] This invention relates to the field of marine fouling and biodegradation protection materials, and more specifically, to a rubber composite material with marine antifouling properties, its preparation method, and its application. Background Technology

[0002] The ocean, humanity's "blue friend," possesses abundant oil resources. The transportation of these oil resources mainly relies on rubber pipes. However, the ocean is also rich in marine life, which can adhere to the surface of rubber pipes, forming thick biofouling that endangers the safe use of the rubber pipes and affects their service life.

[0003] In the field of marine antifouling rubber pipes and other products, the current technical approaches to achieve antifouling function mainly focus on the following two points: first, coating the surface of rubber materials with an antifouling coating; second, introducing antifouling agents into the rubber matrix.

[0004] 1. Surface coating with antifouling coating: This method involves applying a coating layer containing antifouling agent to the surface of the formed rubber pipe product by spraying, brushing or other methods. The coating is usually based on polymer resin (such as acrylic resin, epoxy resin) and loaded with and controlled release of biocidal antifouling agents such as cuprous oxide and organometallic compounds. Its antifouling mechanism mainly relies on the slow and continuous release of toxic substances in seawater by the coating, forming a "toxic micro-layer" on the material surface to repel or kill marine organisms that attempt to attach. However, surface coating technology has many inherent disadvantages, especially in rubber pipes used in dynamic applications. (1) Mismatch between adhesion and flexibility: Conventional antifouling coatings are mostly rigid or semi-rigid, while rubber pipes often need to be bent and deformed during installation and use. The huge difference in modulus between the two leads to the coating being prone to cracking and peeling under dynamic stress, causing the antifouling function to fail instantly. (2) Poor durability: As an independent physical layer, the coating has limited wear resistance and erosion resistance. In marine environments, especially under conditions of silt erosion, equipment friction, or biological collisions, the coating is easily worn away, exposing the underlying "pure" rubber surface, which quickly becomes an attachment point for fouling organisms. (3) Interface problems and secondary pollution: The bonding between the coating and the rubber substrate is a physical interface bonding. When immersed in seawater for a long time, the interface is easily penetrated by water molecules, resulting in swelling and peeling. In addition, this method is essentially still a biocide, and the toxic substances it releases are harmful to non-target organisms, which may exacerbate the burden on the marine ecological environment and cause irreversible damage to the marine environment.

[0005] 2. Introducing antifouling agents into the rubber matrix. This method involves uniformly dispersing antifouling agents as functional additives in the rubber matrix along with raw rubber, vulcanizing agents, reinforcing agents, etc., during the rubber compounding process. Then, a composite material with antifouling function is formed through vulcanization. Compared with surface coating technology, this method shows significant advantages. (1) Long-lasting and stable: The antifouling agent is "wrapped" inside the three-dimensional cross-linked network of the rubber. Its migration and release process to the surface is slower and more controllable, avoiding the functional "quenching" caused by damage to the coating technology, and providing more durable and stable antifouling protection. (2) Integrated function of the matrix: The antifouling performance is integrated with the matrix properties of the rubber (such as elasticity, sealing, and flexibility). There is no risk of coating peeling in the product. Its mechanical properties and antifouling performance work synergistically, making it particularly suitable for rubber pipes working under complex stress. (3) Technological and cost advantages: This technology can be perfectly combined with conventional rubber product manufacturing processes (such as internal mixing, open milling, extrusion, and molding), without the need for additional and complex post-coating processes, which is conducive to large-scale production and cost control, and has better industrial feasibility.

[0006] In summary, the technical approach of introducing antifouling agents into the rubber matrix is ​​considered a more promising development direction for solving the antifouling problem of marine rubber pipelines due to its core advantages such as long-lasting effect, stability, and high degree of integration with the rubber matrix. Current research focuses on key issues such as how to address the compatibility of antifouling agents with the rubber matrix, preventing the antifouling agent from leaking or failing too quickly, and balancing antifouling performance with the physical and mechanical properties of rubber. Summary of the Invention

[0007] To address the problems existing in the prior art, this invention provides a rubber composite material with marine antifouling properties, its preparation method, and its application. This invention solves three core problems of existing marine antifouling rubber materials: poor compatibility between the antifouling agent and the rubber matrix, easy loss of the antifouling agent leading to a short antifouling period, and difficulty in balancing antifouling performance and mechanical properties.

[0008] One of the objectives of this invention is to provide a rubber composite material with marine antifouling properties.

[0009] The rubber composite material with marine antifouling properties described in this invention comprises the following components obtained through blending and vulcanization:

[0010] Rubber, fillers, antifouling agents, plasticizers, activators, scorch inhibitors, antioxidants, accelerators, and vulcanizing agents; The antifouling agent comprises a zwitterionic modified copolymer and optionally at least one of sodium benzoate, tannic acid, 6-gingerol, capsaicin, sulfobetaine, carboxylate, phosphorylcholine, isothiazolinone, and zinc pyrithione. Based on the weight of the rubber as 100 parts by weight: 100 parts by weight of rubber; 1-40 parts by weight of filler; Antifouling agent 1-30 parts by weight; Plasticizer 1-30 parts by weight; Activator 1-20 parts by weight; Anti-scorching agent: 0.1-10 parts by weight; Anti-aging agent 0.1-10 parts by weight; Accelerator: 0.1-10 parts by weight; Vulcanizing agent: 0.1-10 parts by weight.

[0011] In a preferred embodiment of the present invention: Based on the weight of the rubber in 100 parts by weight: 100 parts by weight of rubber; 10-30 parts by weight of filler; Antifouling agent 2-20 parts by weight; Plasticizer 2-15 parts by weight; Activator 2-10 parts by weight; Anti-scorching agent: 0.5-3 parts by weight; Anti-aging agent 0.5-3 parts by weight; Accelerator 0.5-3 parts by weight; Vulcanizing agent 0.5-3 parts by weight.

[0012] In a preferred embodiment of the present invention: The rubber is at least one of the following: natural rubber, chloroprene rubber, styrene-butadiene rubber, polybutadiene rubber, ethylene propylene rubber, butyl rubber, nitrile rubber, silicone rubber, fluororubber, polyurethane rubber, chloroprene rubber, acrylate rubber, and polysulfide rubber; and / or, The filler is calcium carbonate and / or carbon black; the carbon black is at least one selected from carbon black N110, carbon black N121, carbon black N219, carbon black N231, carbon black N330, carbon black N347, carbon black N375, carbon black N550, carbon black N660, carbon black N774, silica, and fumed silica; and / or, The plasticizer is at least one selected from stearic acid, sodium stearate, potassium stearate, coumarone resin, petrolatum, paraffin wax, petroleum resin, coal tar, pine tar, rosin, tall oil, and ointment; and / or, The activator is at least one selected from zinc oxide, magnesium oxide, lead monoxide, zinc peroxide, and titanium dioxide; and / or, The anti-scorching agent is at least one selected from salicylic acid, phthalic anhydride, nitrosodiphenylamine, nitroso-N-phenyl-2-aniline, and N-cyclohexylthiophthalimide; and / or The antioxidant may be at least one of commonly used antioxidants in the art, such as antioxidant NBC, antioxidant RD, antioxidant PBN, antioxidant D, etc.; and / or, The accelerator may be at least one of commonly used accelerators in the art, such as accelerator NA-22, accelerator DM, accelerator NS, accelerator TMTD, accelerator MBTS, accelerator DPG, etc.; and / or, The vulcanizing agent is at least one of sulfur, lead monoxide (PBO), benzoyl peroxide, dicumyl peroxide, 1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, bis(tert-butylperoxyisopropyl)benzene, tert-butylisopropylphenyl peroxide, octylphenolic vulcanizing resin, and brominated octylphenolic resin.

[0013] In a preferred embodiment of the present invention: The structural formula of the zwitterionic modified copolymer is:

[0014] Wherein, a is 1-50, preferably 5-30; b is 40-500, preferably 50-400; n is 0-10, preferably 0-5; x is 0-10, preferably 0-5; y is 0-10, preferably 0-5; A1 is , , , , One of them; A2 is , , One of them, where m is any integer from 1 to 6; preferably, The number-average molecular weight of the zwitterionic modified copolymer is 10,000-80,000, preferably 20,000-60,000.

[0015] In a preferred embodiment of the present invention, the zwitterionic modified copolymer is prepared by the following method: A zwitterionic modified copolymer solution is prepared by solution polymerization of zwitterionic salt, acrylate, chain transfer agent, catalyst, and reaction solvent. This solution is then poured into a preparation solvent and stirred to react. Post-treatment is then performed to obtain the zwitterionic modified copolymer. Preferably, The molar ratio of the zwitterionic salt to the acrylate is 1:(1-20), preferably 1:(2-15); and / or, The molar ratio of the dilute ester to the chain transfer agent and catalyst is (15-6000):(0.005-10):1, preferably (40-500):(0.01-2):1; and / or, The molar ratio of the dilute ester to the reaction solvent is 1:(1.5-400), preferably 1:(2-200); and / or, The molar ratio of the dilute ester to the preparation solvent is 1:(1.5-7000), preferably 1:(50-2000); and / or, The structural formula of the zwitterionic salt is: Where n is 0-10, preferably 0-5; A1 is , , , , One of them; A2 is , , One of them, where m is any integer from 1 to 6; more preferably, the zwitterionic salt is at least one of sulfonate betaine salt, carboxylate betaine salt, and phosphorylcholine salt; and / or, The structural formula of the acrylate is: Wherein, x is 0-10, preferably 0-5, and y is 0-10, preferably 0-5; more preferably, the acrylate is at least one selected from 2-ethylhexyl methacrylate, butyl methacrylate, ethyl methacrylate, and octyl methacrylate; and / or, The chain transfer agent is at least one selected from benzene, toluene, ethylbenzene, cumene, tert-butylbenzene, heptane, cyclohexane, n-butanol, acetone, acetic acid, chlorobutane, bromobutane, iodobutane, chloroform, carbon tetrachloride, carbon tetrabromide, tert-butyl disulfide, tert-butyl mercaptan, n-butane mercaptan, and n-dodecyl mercaptan; and / or, The catalyst is at least one selected from the following: azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, diethylhexyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, dicumene peroxide, di-tert-butyl peroxide, benzoyl peroxide, dodecyl peroxide, tert-butyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxide, dicyclohexyl peroxide, potassium persulfate, and ammonium persulfate; and / or, The reaction solvent is at least one selected from dimethyl sulfoxide, dimethylformamide, methanol, ethanol, acetone, dichloromethane, tetrahydrofuran, and toluene; and / or, The preparation solvent is at least one selected from n-hexane, deionized water, dimethylformamide, dichloromethane, tetrahydrofuran, trifluoroethanol, methyl ethyl ketone, dimethylacetamide, and 1,4-dioxane; and / or, The solution polymerization reaction is carried out at a temperature of 0-120°C, preferably 25-100°C, and / or for a reaction time of 0.5-24 h, preferably 1-12 h; and / or The reaction temperature of the stirring reaction is 0-80℃, preferably 25-60℃, and / or the reaction time is 1-24h, preferably 1-12h.

[0016] A second objective of this invention is to provide a method for preparing a rubber composite material with marine antifouling properties as described in one objective of this invention.

[0017] The method for preparing a rubber composite material with marine antifouling properties according to the present invention includes: Rubber, filler, antifouling agent, plasticizer, activator, anti-scorching agent, anti-aging agent and accelerator are mixed in the stated weight parts, then mixed in an intensive mixer, discharged and cooled to obtain a first-stage compound; then the stated weight parts of vulcanizing agent are added and mixed to obtain a second-stage compound, which is then vulcanized to obtain the rubber composite material.

[0018] In a preferred embodiment of the present invention, the method further includes pre-modifying the antifouling agent; preferably, The modification treatment includes at least one of grinding treatment and silane coupling agent modification treatment, which solves the problem that the antifouling agent and the rubber surface are difficult to form good interfacial compatibility.

[0019] In a preferred embodiment of the present invention: The grinding frequency of the grinding process is 10-100 Hz, preferably 40-60 Hz, and / or the grinding time is 1-40 min, preferably 1-10 min, and / or the particle size after grinding is 0.1-100 micrometers, preferably 0.1-10 micrometers; and / or, The silane coupling agent modification treatment includes: diluting the silane coupling agent, adding an antifouling agent, and mixing at high speed; followed by post-treatment to obtain a silane coupling agent modified antifouling agent; preferably, The silane coupling agent is at least one selected from γ-aminopropyltriethoxysilane (KH-550), γ-aminopropyltrimethoxysilane (KH-540), N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (KH-792), anilinemethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane (KH-560), γ-glycidoxypropyltriethoxysilane (KH-561), γ-mercaptopropyltrimethoxysilane (KH-590), γ-mercaptopropyltriethoxysilane (KH-580), γ-isocyanate propyltrimethoxysilane, and γ-isocyanate propyltriethoxysilane; and / or, The diluting solvent is ethanol and / or methanol; and / or, The molar ratio of the antifouling agent to the silane coupling agent and the diluting solvent is 1:(0.001-0.1):(1-50), preferably 1:(0.002-0.02):(1-20); and / or, The high-speed stirring speed is 500-2000 r / min, and / or, the time is 1-12 h; and / or, The post-treatment is a drying process, preferably a process at a temperature of 25-200℃ for 1-3 days.

[0020] The following solutions can be adopted: (1) The silane coupling agent is slowly added dropwise to the diluent to prepare a diluted silane coupling agent solution; (2) The diluted silane coupling agent is added dropwise to the antifouling agent and mixed at high speed. After mixing evenly, it is dried: the agent is treated at a temperature of 25-200℃ for 1-3 days to obtain the dried silane coupling agent modified antifouling agent.

[0021] In a preferred embodiment of the present invention: The mixing temperature is 100-150℃, and / or the mixing time is 5-30 min; and / or, The glue discharge temperature is 140-160℃; and / or, The cooling time is 30-90 minutes; and / or, The mixing temperature is 40-60℃, and / or the mixing time is 5-40 min; and / or, The vulcanization temperature is 140-170℃, and / or the vulcanization time is 20-60 min, and / or the vulcanization pressure is 10-20 MPa.

[0022] The following solutions can be adopted: (1) Mix rubber, filler, antifouling agent, plasticizer, activator, antiscorching agent, anti-aging agent and accelerator, and then perform intensive mixing. After intensive mixing, discharge the rubber and cool it to obtain a first-stage compound. The intensive mixing temperature is 100-150℃ and the intensive mixing time is 5-30min. The discharge temperature is 140-160℃ and the cooling time is 30-90min. (2) After obtaining a first-stage compound, the first-stage compound and the vulcanizing agent are mixed and compounded to obtain a second-stage compound; the compounding temperature is 40-60℃ and the compounding time is 5-40min. The equipment used for mixing is an open mill with a roll gap of 0.5-1mm. The mixing operation method is at least one of the following: thin pass method, triangular bag operation method, oblique knife method, and coiling operation method. The thin-pass method is preferably repeated 1-5 times, the triangular wrapping method is preferably repeated 1-5 times, the oblique knife method is preferably repeated 1-5 times, and the rolling operation method is preferably repeated 1-5 times. After mixing, adjust the roller gap of the open mill to 1-4mm, and then cut the rubber sheet into sheets. Cool the resulting rubber sheet. The cooling method is to place the item at room temperature for 12-48 hours. (3) After obtaining the two-stage compound, the two-stage compound is vulcanized to obtain the rubber composite material; the vulcanization temperature is 140-170℃, the vulcanization time is preferably 20-60min, and the vulcanization pressure is 10-20MPa.

[0023] A third objective of this invention is to provide an application of a rubber composite material with marine antifouling properties as described in one objective of this invention, or a rubber composite material with marine antifouling properties prepared by the method described in another objective of this invention, in the field of green marine antifouling.

[0024] Compared with the prior art, the present invention has at least the following technical effects: (1) The compatibility and mechanical properties of the rubber composite material with marine antifouling properties of the present invention are precisely balanced, and the product is highly practical.

[0025] (2) The rubber composite material with marine antifouling properties of the present invention has high and long-lasting antifouling performance and a wide range of antifouling properties.

[0026] (3) The rubber composite material with marine antifouling properties of the present invention is green and environmentally friendly without secondary pollution. It has passed the test of "Ozone-depleting substances and greenhouse substances" and meets international standards.

[0027] (4) The process of the rubber composite material with marine antifouling properties of the present invention is simple and easy to industrialize. Attached Figure Description

[0028] Figure 1 Comparison of marine biofouling resistance test results obtained from marine biofouling resistance tests of the rubber composite materials prepared in Examples 1, 2 and Comparative Example 1 of this invention; Figure 2 The image shows a comparison of the results obtained from the quantitative analysis of the removed adhesive substances during the antifouling performance test of the rubber composite materials prepared in Examples 1, 2 and Comparative Example 1 of this invention. Detailed Implementation

[0029] The present invention will now be described in detail with reference to the accompanying drawings and embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0030] The raw materials used in the embodiments and comparative examples of this invention are all commercially available products.

[0031] Example 1 A rubber composite material resistant to marine organism attachment, the preparation method of which includes the following steps: Step 1: First, dissolve [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonylpropyl)ammonium hydroxide (SBMA) and ethyl methacrylate in anhydrous methanol at a molar ratio of 1:3, where 0.03 mol of SBMA and the molar ratio of ethyl methacrylate to anhydrous methanol are 1:40. Add azobisisobutyronitrile and n-dodecyl mercaptan to the flask, and simultaneously raise the temperature to 60°C under nitrogen protection, continuously stirring the reaction for 12 hours. The molar ratio of ethyl methacrylate, n-butanethiol, and azobisisobutyronitrile is 67.5:0.1:1.

[0032] Step 2: After the reaction is complete, the viscous polymer solution is poured into deionized water at a molar ratio of ethyl methacrylate to deionized water of 1:1400 and stirred at 25°C for 4 hours. An amphoteric copolymer solid precipitates out. This precipitated solid is then placed in a 60°C forced-air drying oven for 2 days to obtain a dried amphoteric copolymer antifouling agent. The structural formula is as follows:

[0033] Among them, a is 10-20, b is 50-100, and the number average molecular weight is 15000-25000.

[0034] Step 3: Place the zwitterionic modified copolymer antifouling agent prepared above into a grinder, grind at a frequency of 60 Hz for 2 min, and obtain a zwitterionic modified copolymer antifouling agent with a particle size of approximately 10 micrometers.

[0035] Step 4: Preparation of rubber composite material: Add 100 parts by weight of chloroprene rubber, 5 parts by weight of paraffin wax, 5 parts by weight of magnesium oxide, 1 part by weight of antioxidant RD, 1 part by weight of accelerator NA-22, 1 part by weight of anti-scorching agent salicylic acid, 5 parts by weight of the zwitterionic modified copolymer antifouling agent prepared above, 20 parts by weight of carbon black N330, and 5 parts by weight of silica. After mixing all materials evenly, perform intensive mixing at a temperature of 120°C for 20 minutes. Discharge the rubber at a discharge temperature of 150°C and cool for 90 minutes to obtain a first-stage compound.

[0036] Step 5: Add one part by weight of tert-butylisopropylphenyl peroxide to a two-roll mill with a roller temperature of 50°C. Adjust the roller gap to 0.6 mm and start triangular wrapping, slanted cutting, and rolling mixing. Mixing time is 10 minutes. After mixing, adjust the roller gap to 3.5 mm to cut the rubber sheet to obtain the second-stage compound.

[0037] Step 6: After placing the two-stage compound at room temperature for 24 hours and testing the vulcanization curve on a high-speed vulcanizing apparatus, vulcanize the two-stage compound under vulcanization conditions of 150℃×40min×12MPa to obtain the rubber composite material.

[0038] Example 2 A rubber composite material resistant to marine organism attachment, the preparation method of which includes the following steps: Step 1: First, dissolve [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonylpropyl)ammonium hydroxide (SBMA) and ethyl methacrylate in anhydrous methanol at a molar ratio of 1:3, where 0.03 mol of SBMA and the molar ratio of ethyl methacrylate to anhydrous methanol are 1:40. Add azobisisobutyronitrile and n-dodecyl mercaptan to the flask, and simultaneously raise the temperature to 60°C under nitrogen protection, continuously stirring the reaction for 12 hours. The molar ratio of ethyl methacrylate, n-butanethiol, and azobisisobutyronitrile is 67.5:0.1:1.

[0039] Step 2: After the reaction is complete, the viscous polymer solution is poured into deionized water at a molar ratio of ethyl methacrylate to deionized water of 1:1400 and stirred at 25°C for 4 hours. An amphoteric copolymer solid precipitates out. This precipitated solid is then placed in a 60°C forced-air drying oven for 2 days to obtain a dried amphoteric copolymer antifouling agent. The structural formula is as follows:

[0040] Among them, a is 10-20, b is 50-100, and the number average molecular weight is 15000-25000.

[0041] Step 3: Place the zwitterionic modified copolymer antifouling agent prepared above into a grinder, grind at a frequency of 60 Hz for 2 min, and obtain a zwitterionic modified copolymer antifouling agent with a particle size of approximately 10 micrometers.

[0042] Step 4: Preparation of rubber composite material: Add 100 parts by weight of chloroprene rubber, 5 parts by weight of paraffin wax, 5 parts by weight of magnesium oxide, 1 part by weight of antioxidant RD, 1 part by weight of accelerator NA-22, 1 part by weight of anti-scorching agent salicylic acid, 10 parts by weight of the zwitterionic modified copolymer antifouling agent prepared above, 20 parts by weight of carbon black N330, and 5 parts by weight of silica. After mixing all materials evenly, perform intensive mixing at a temperature of 120°C for 20 minutes. Discharge the rubber at a discharge temperature of 150°C and cool for 90 minutes to obtain a first-stage compound.

[0043] Step 5: Add one part by weight of tert-butylisopropylphenyl peroxide to a two-roll mill with a roller temperature of 50°C. Adjust the roller gap to 0.6 mm and start triangular wrapping, slanted cutting, and rolling mixing. Mixing time is 10 minutes. After mixing, adjust the roller gap to 3.5 mm to cut the rubber sheet to obtain the second-stage compound.

[0044] Step 6: After placing the two-stage compound at room temperature for 24 hours and testing the vulcanization curve on a high-speed vulcanizing apparatus, vulcanize the two-stage compound under vulcanization conditions of 150℃×40min×12MPa to obtain the rubber composite material.

[0045] Example 3 A rubber composite material resistant to marine organism attachment, the preparation method of which includes the following steps: Step 1: First, dissolve [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonylpropyl)ammonium hydroxide (SBMA) and octyl methacrylate in anhydrous methanol at a molar ratio of 1:3, where 0.03 mol of SBMA and the molar ratio of octyl methacrylate to anhydrous methanol are 1:40. Add azobisisobutyronitrile and n-dodecyl mercaptan to the flask, and simultaneously raise the temperature to 60°C under nitrogen protection, continuously stirring the reaction for 12 hours. The molar ratio of octyl methacrylate, n-butanethiol, and azobisisobutyronitrile is 67.5:0.1:1.

[0046] Step 2: After the reaction is complete, the viscous polymer solution is poured into deionized water at a molar ratio of octyl methacrylate to deionized water of 1:1400 and stirred at 25°C for 4 hours. An amphoteric copolymer solid precipitates out. This precipitated amphoteric copolymer solid is then placed in a 60°C forced-air drying oven for 2 days to obtain a dried amphoteric copolymer antifouling agent. The structural formula is as follows:

[0047] Among them, a is 10-20, b is 50-100, and the number average molecular weight is 15000-25000.

[0048] Step 3: Place the zwitterionic modified copolymer antifouling agent prepared above into a grinder, grind at a frequency of 60 Hz for 2 min, and obtain zwitterionic modified copolymer antifouling agent powder with a particle size of approximately 10 micrometers.

[0049] Step 4: Slowly add 0.01 mol of silane coupling agent KH-550 to 1 mol of ethanol solution, mix well, and prepare a diluted silane coupling agent solution.

[0050] Step 5: Add the diluted silane coupling agent solution prepared above to the zwitterionic modified copolymer antifouling agent powder, and react at a high speed of 1000 r / min for 6 h. The molar ratio of antifouling agent to silane coupling agent to ethanol solution is 1:0.05:5. After stirring evenly, dry in a 100℃ oven for 1 day to obtain the silane coupling agent modified zwitterionic modified copolymer antifouling agent.

[0051] Step Six: Preparation of Rubber Composite Material: Add 100 parts by weight of natural rubber, 2 parts by weight of rosin, 2 parts by weight of zinc peroxide, 0.6 parts by weight of antioxidant PBN, 0.6 parts by weight of accelerator TMTD, 0.6 parts by weight of scorch inhibitor N-cyclohexylthiophthalimide, 5 parts by weight of antifouling agent modified by the above-prepared silane coupling agent zwitterionic copolymer, 20 parts by weight of carbon black N330, and 15 parts by weight of silica. After mixing all materials evenly, perform intensive mixing at 120℃ for 10 minutes, discharge the rubber at 150℃, and cool for 90 minutes to obtain a first-stage compound.

[0052] Step 7: Add a first-stage compound and 0.6 parts by weight of octylphenol aldehyde vulcanizate to a two-roll mill with a roller temperature of 50°C. Adjust the roller gap to 0.6 mm and start triangular wrapping, slanted cutting, and rolling mixing. Mix for 5 minutes. After mixing, adjust the roller gap to 3.5 mm and cut the rubber sheet to obtain the second-stage compound.

[0053] Step 8: After placing the two-stage compound at room temperature for 24 hours and testing the vulcanization curve on a high-speed vulcanizing apparatus, vulcanize the two-stage compound under vulcanization conditions of 150℃×20min×12MPa to obtain the rubber composite material.

[0054] Example 4 A rubber composite material resistant to marine organism attachment, the preparation method of which includes the following steps: Step 1: First, dissolve [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonylpropyl)ammonium hydroxide (SBMA) and octyl methacrylate in anhydrous methanol at a molar ratio of 1:3, where 0.03 mol of SBMA and the molar ratio of octyl methacrylate to anhydrous methanol are 1:40. Add azobisisobutyronitrile and n-dodecyl mercaptan to the flask, and simultaneously raise the temperature to 60°C under nitrogen protection, continuously stirring the reaction for 12 hours. The molar ratio of octyl methacrylate, n-butanethiol, and azobisisobutyronitrile is 67.5:0.1:1.

[0055] Step 2: After the reaction is complete, the viscous polymer solution is poured into deionized water at a molar ratio of octyl methacrylate to deionized water of 1:1400 and stirred at 25°C for 4 hours. An amphoteric copolymer solid precipitates out. This precipitated amphoteric copolymer solid is then placed in a 60°C forced-air drying oven for 2 days to obtain a dried amphoteric copolymer antifouling agent. The structural formula is as follows:

[0056] Among them, a is 10-20, b is 50-100, and the number average molecular weight is 15000-25000.

[0057] Step 3: Place the zwitterionic modified copolymer antifouling agent prepared above into a grinder, grind at a frequency of 60 Hz for 2 min, and obtain zwitterionic modified copolymer antifouling agent powder with a particle size of approximately 10 micrometers.

[0058] Step 4: Slowly add 0.01 mol of silane coupling agent KH-550 to 1 mol of ethanol solution, mix well, and prepare a diluted silane coupling agent solution.

[0059] Step 5: Add the diluted silane coupling agent solution prepared above to the zwitterionic modified copolymer antifouling agent powder, and react at a high speed of 1000 r / min for 6 h. The molar ratio of antifouling agent to silane coupling agent to ethanol solution is 1:0.05:5. After stirring evenly, dry in a 100℃ oven for 1 day to obtain the silane coupling agent modified zwitterionic modified copolymer antifouling agent.

[0060] Step Six: Prepare the rubber composite material by weight: Add 100 parts by weight of natural rubber, 2 parts by weight of rosin, 2 parts by weight of zinc peroxide, 0.6 parts by weight of antioxidant PBN, 0.6 parts by weight of accelerator TMTD, 0.6 parts by weight of scorch inhibitor N-cyclohexylthiophthalimide, 10 parts by weight of the antifouling agent modified by the above-prepared silane coupling agent zwitterionic copolymer, 20 parts by weight of carbon black N330, and 15 parts by weight of silica. After mixing all materials evenly, perform intensive mixing at a temperature of 120°C for 10 minutes, discharge the rubber at a discharge temperature of 150°C, and cool for 90 minutes to obtain a first-stage compound.

[0061] Step 7: Add a first-stage compound and 0.6 parts by weight of octylphenol aldehyde vulcanizate to a two-roll mill with a roller temperature of 50°C. Adjust the roller gap to 0.6 mm and start triangular wrapping, slanted cutting, and rolling mixing. Mix for 5 minutes. After mixing, adjust the roller gap to 3.5 mm and cut the rubber sheet to obtain the second-stage compound.

[0062] Step 8: After placing the two-stage compound at room temperature for 24 hours and testing the vulcanization curve on a high-speed vulcanizing apparatus, vulcanize the two-stage compound under vulcanization conditions of 150℃×20min×12MPa to obtain the rubber composite material.

[0063] Example 5 A rubber composite material resistant to marine organism attachment, the preparation method of which includes the following steps: Step 1: First, dissolve [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonylpropyl)ammonium hydroxide (SBMA) and ethyl methacrylate in anhydrous methanol at a molar ratio of 1:3, where 0.03 mol of SBMA and the molar ratio of ethyl methacrylate to anhydrous methanol are 1:40. Add azobisisobutyronitrile and n-dodecyl mercaptan to the flask, and simultaneously raise the temperature to 60°C under nitrogen protection, continuously stirring the reaction for 12 hours. The molar ratio of ethyl methacrylate, n-butanethiol, and azobisisobutyronitrile is 67.5:0.1:1.

[0064] Step 2: After the reaction is complete, the viscous polymer solution is poured into deionized water at a molar ratio of ethyl methacrylate to deionized water of 1:1400 and stirred at 25°C for 4 hours. An amphoteric copolymer solid precipitates out. This precipitated solid is then placed in a 60°C forced-air drying oven for 2 days to obtain a dried amphoteric copolymer antifouling agent. The structural formula is as follows:

[0065] Among them, a is 10-20, b is 50-100, and the number average molecular weight is 15000-25000.

[0066] Step 3: Place the zwitterionic modified copolymer antifouling agent prepared above into a grinder, grind at a frequency of 60 Hz for 2 min, and obtain a zwitterionic modified copolymer antifouling agent with a particle size of approximately 10 micrometers.

[0067] Step 4: Slowly add 0.01 mol of silane coupling agent KH-540 to 1 mol of ethanol solution, mix well, and prepare a diluted silane coupling agent solution.

[0068] Step 5: Add the diluted silane coupling agent solution prepared above to the zwitterionic modified copolymer antifouling agent and capsaicin antifouling agent, with a weight ratio of 1:1. React at a high speed of 1000 r / min for 6 h, wherein the molar ratio of antifouling agent to silane coupling agent to ethanol solution is 1:0.05:5. After stirring evenly, dry in a 100℃ oven for 1 day to obtain the silane coupling agent modified antifouling agent.

[0069] Step Six: Preparation of Rubber Composite Material: Add 100 parts by weight of styrene-butadiene rubber, 10 parts by weight of paraffin wax, 10 parts by weight of magnesium oxide, 2.5 parts by weight of antioxidant RD, 2.5 parts by weight of accelerator NA-22, 2.5 parts by weight of anti-scorching agent salicylic acid, 5 parts by weight of the silane coupling agent modified antifouling agent prepared above, 20 parts by weight of carbon black N550, and 10 parts by weight of silica. After mixing all materials evenly, perform intensive mixing at a temperature of 120℃ for 30 minutes. Discharge the rubber at a discharge temperature of 150℃ and cool for 90 minutes to obtain a first-stage compound.

[0070] Step 7: Add 2.5 parts by weight of tert-butylisopropylphenyl peroxide to a two-roll mill with a roller temperature of 50°C. Adjust the roller gap to 0.6 mm and start triangular wrapping, slanted cutting, and rolling mixing. Mixing time is 15 minutes. After mixing, adjust the roller gap to 3.5 mm to cut the rubber sheet to obtain the second-stage compound.

[0071] Step 8: After placing the two-stage compound at room temperature for 24 hours and testing the vulcanization curve on a high-speed vulcanizing apparatus, vulcanize the two-stage compound under vulcanization conditions of 150℃×60min×12MPa to obtain the rubber composite material.

[0072] Example 6 A rubber composite material resistant to marine organism attachment, the preparation method of which includes the following steps: Step 1: First, dissolve [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonylpropyl)ammonium hydroxide (SBMA) and ethyl methacrylate in anhydrous methanol at a molar ratio of 1:3, where 0.03 mol of SBMA and the molar ratio of ethyl methacrylate to anhydrous methanol are 1:40. Add azobisisobutyronitrile and n-dodecyl mercaptan to the flask, and simultaneously raise the temperature to 60°C under nitrogen protection, continuously stirring the reaction for 12 hours. The molar ratio of ethyl methacrylate, n-butanethiol, and azobisisobutyronitrile is 67.5:0.1:1.

[0073] Step 2: After the reaction is complete, the viscous polymer solution is poured into deionized water at a molar ratio of ethyl methacrylate to deionized water of 1:1400 and stirred at 25°C for 4 hours. An amphoteric copolymer solid precipitates out. This precipitated solid is then placed in a 60°C forced-air drying oven for 2 days to obtain a dried amphoteric copolymer antifouling agent. The structural formula is as follows:

[0074] Among them, a is 10-20, b is 50-100, and the number average molecular weight is 15000-25000.

[0075] Step 3: Place the zwitterionic modified copolymer antifouling agent prepared above into a grinder, grind at a frequency of 60 Hz for 2 min, and obtain a zwitterionic modified copolymer antifouling agent with a particle size of approximately 10 micrometers.

[0076] Step 4: Slowly add 0.01 mol of silane coupling agent KH-540 to 1 mol of ethanol solution, mix well, and prepare a diluted silane coupling agent solution.

[0077] Step 5: Add the diluted silane coupling agent solution prepared above to the zwitterionic modified copolymer antifouling agent and capsaicin antifouling agent, with a weight ratio of 1:1. React at a high speed of 1000 r / min for 6 h, wherein the molar ratio of antifouling agent to silane coupling agent to ethanol solution is 1:0.05:5. After stirring evenly, dry in a 100℃ oven for 1 day to obtain the silane coupling agent modified antifouling agent.

[0078] Step Six: Preparation of Rubber Composite Material: Add 100 parts by weight of styrene-butadiene rubber, 10 parts by weight of paraffin wax, 10 parts by weight of magnesium oxide, 2.5 parts by weight of antioxidant RD, 2.5 parts by weight of accelerator NA-22, 2.5 parts by weight of anti-scorching agent salicylic acid, 10 parts by weight of the silane coupling agent modified antifouling agent prepared above, 20 parts by weight of carbon black N550, and 10 parts by weight of silica. After mixing all materials evenly, perform intensive mixing at a temperature of 120℃ for 30 minutes. Discharge the rubber at a discharge temperature of 150℃ and cool for 90 minutes to obtain a first-stage compound.

[0079] Step 7: Add 2.5 parts by weight of tert-butylisopropylphenyl peroxide to a two-roll mill with a roller temperature of 50°C. Adjust the roller gap to 0.6 mm and start triangular wrapping, slanted cutting, and rolling mixing. Mixing time is 15 minutes. After mixing, adjust the roller gap to 3.5 mm to cut the rubber sheet to obtain the second-stage compound.

[0080] Step 8: After placing the two-stage compound at room temperature for 24 hours and testing the vulcanization curve on a high-speed vulcanizing apparatus, vulcanize the two-stage compound under vulcanization conditions of 150℃×60min×12MPa to obtain the rubber composite material.

[0081] Example 7 A rubber composite material resistant to marine organism attachment, the preparation method of which includes the following steps: Step 1: First, dissolve [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonylpropyl)ammonium hydroxide (SBMA) and octyl methacrylate in anhydrous methanol at a molar ratio of 1:3, where 0.03 mol of SBMA and the molar ratio of octyl methacrylate to anhydrous methanol are 1:40. Add azobisisobutyronitrile and n-dodecyl mercaptan to the flask, and simultaneously raise the temperature to 60°C under nitrogen protection, continuously stirring the reaction for 12 hours. The molar ratio of octyl methacrylate, n-butanethiol, and azobisisobutyronitrile is 67.5:0.1:1.

[0082] Step 2: After the reaction is complete, the viscous polymer solution is poured into deionized water at a molar ratio of octyl methacrylate to deionized water of 1:1400 and stirred at 25°C for 4 hours. An amphoteric copolymer solid precipitates out. This precipitated amphoteric copolymer solid is then placed in a 60°C forced-air drying oven for 2 days to obtain a dried amphoteric copolymer antifouling agent. The structural formula is as follows:

[0083] Among them, a is 10-20, b is 50-100, and the number average molecular weight is 15000-25000.

[0084] Step 3: Place the zwitterionic modified copolymer antifouling agent prepared above into a grinder, grind at a frequency of 60 Hz for 2 min, and obtain zwitterionic modified copolymer antifouling agent powder with a particle size of approximately 10 micrometers.

[0085] Step 4: Slowly add 0.02 mol of silane coupling agent KH-792 to 1 mol of ethanol solution, mix well, and prepare a diluted silane coupling agent solution.

[0086] Step 5: Add the diluted silane coupling agent solution prepared above to the zwitterionic modified copolymer antifouling agent and sodium benzoate antifouling agent, with a weight ratio of 1:1. React at a high speed of 1000 r / min for 6 h, wherein the molar ratio of antifouling agent to silane coupling agent to ethanol solution is 1:0.1:5. After stirring evenly, dry in a 150℃ oven for 1 day to obtain the silane coupling agent modified sodium benzoate antifouling agent.

[0087] Step Six: Preparation of Rubber Composite Material: Add 100 parts by weight of styrene-butadiene rubber, 10 parts by weight of rosin, 10 parts by weight of zinc peroxide, 2.5 parts by weight of antioxidant PBN, 2.5 parts by weight of accelerator TMTD, 2.5 parts by weight of scorch inhibitor N-cyclohexylthiophthalimide, 5 parts by weight of the silane coupling agent modified antifouling agent prepared above, 20 parts by weight of carbon black N550, and 10 parts by weight of silica. After mixing all materials evenly, perform intensive mixing at a temperature of 120℃ for 30 minutes. Discharge the rubber at a discharge temperature of 150℃ and cool for 90 minutes to obtain a first-stage compound.

[0088] Step 7: Add a first-stage compound and 2.5 parts by weight of octylphenol aldehyde vulcanizing resin to an open mill with a roller temperature of 50°C. Adjust the roller gap to 0.6 mm and start triangular wrapping, slanted cutting, and rolling mixing. The mixing time is 15 minutes. After mixing, adjust the roller gap to 3.5 mm and cut the rubber sheet to obtain the second-stage compound.

[0089] Step 8: After placing the two-stage compound at room temperature for 24 hours and testing the vulcanization curve on a high-speed vulcanizing apparatus, vulcanize the two-stage compound under vulcanization conditions of 150℃×60min×12MPa to obtain the rubber composite material.

[0090] Example 8 A rubber composite material resistant to marine organism attachment, the preparation method of which includes the following steps: Step 1: First, dissolve [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonylpropyl)ammonium hydroxide (SBMA) and octyl methacrylate in anhydrous methanol at a molar ratio of 1:3, where 0.03 mol of SBMA and the molar ratio of octyl methacrylate to anhydrous methanol are 1:40. Add azobisisobutyronitrile and n-dodecyl mercaptan to the flask, and simultaneously raise the temperature to 60°C under nitrogen protection, continuously stirring the reaction for 12 hours. The molar ratio of octyl methacrylate, n-butanethiol, and azobisisobutyronitrile is 67.5:0.1:1.

[0091] Step 2: After the reaction is complete, the viscous polymer solution is poured into deionized water at a molar ratio of octyl methacrylate to deionized water of 1:1400 and stirred at 25°C for 4 hours. An amphoteric copolymer solid precipitates out. This precipitated amphoteric copolymer solid is then placed in a 60°C forced-air drying oven for 2 days to obtain a dried amphoteric copolymer antifouling agent. The structural formula is as follows:

[0092] Among them, a is 10-20, b is 50-100, and the number average molecular weight is 15000-25000.

[0093] Step 3: Place the zwitterionic modified copolymer antifouling agent prepared above into a grinder, grind at a frequency of 60 Hz for 2 min, and obtain zwitterionic modified copolymer antifouling agent powder with a particle size of approximately 10 micrometers.

[0094] Step 4: Slowly add 0.02 mol of silane coupling agent KH-792 to 1 mol of ethanol solution, mix well, and prepare a diluted silane coupling agent solution.

[0095] Step 5: Add the diluted silane coupling agent solution prepared above to the zwitterionic modified copolymer antifouling agent and sodium benzoate antifouling agent, with a weight ratio of 1:1. React at a high speed of 1000 r / min for 6 h, wherein the molar ratio of antifouling agent to silane coupling agent to ethanol solution is 1:0.1:5. After stirring evenly, dry in a 150℃ oven for 1 day to obtain the silane coupling agent modified sodium benzoate antifouling agent.

[0096] Step Six: Preparation of Rubber Composite Material: Add 100 parts by weight of styrene-butadiene rubber, 10 parts by weight of rosin, 10 parts by weight of zinc peroxide, 2.5 parts by weight of antioxidant PBN, 2.5 parts by weight of accelerator TMTD, 2.5 parts by weight of scorch inhibitor N-cyclohexylthiophthalimide, 10 parts by weight of the silane coupling agent modified antifouling agent prepared above, 20 parts by weight of carbon black N550, and 10 parts by weight of silica. After mixing all materials evenly, perform intensive mixing at a temperature of 120℃ for 30 minutes. Discharge the rubber at a discharge temperature of 150℃ and cool for 90 minutes to obtain a first-stage compound.

[0097] Step 7: Add a first-stage compound and 2.5 parts by weight of octylphenol aldehyde vulcanizing resin to an open mill with a roller temperature of 50°C. Adjust the roller gap to 0.6 mm and start triangular wrapping, slanted cutting, and rolling mixing. The mixing time is 15 minutes. After mixing, adjust the roller gap to 3.5 mm and cut the rubber sheet to obtain the second-stage compound.

[0098] Step 8: After placing the two-stage compound at room temperature for 24 hours and testing the vulcanization curve on a high-speed vulcanizing apparatus, vulcanize the two-stage compound under vulcanization conditions of 150℃×60min×12MPa to obtain the rubber composite material.

[0099] Example 9 A rubber composite material resistant to marine organism attachment, the preparation method of which includes the following steps: Step 1: First, dissolve [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonylpropyl)ammonium hydroxide (SBMA) and ethyl methacrylate in anhydrous methanol at a molar ratio of 1:3, where 0.03 mol of SBMA and the molar ratio of ethyl methacrylate to anhydrous methanol are 1:40. Add azobisisobutyronitrile and n-dodecyl mercaptan to the flask, and simultaneously raise the temperature to 60°C under nitrogen protection, continuously stirring the reaction for 12 hours. The molar ratio of ethyl methacrylate, n-butanethiol, and azobisisobutyronitrile is 67.5:0.1:1.

[0100] Step 2: After the reaction is complete, the viscous polymer solution is poured into deionized water at a molar ratio of ethyl methacrylate to deionized water of 1:1400 and stirred at 25°C for 4 hours. An amphoteric copolymer solid precipitates out. This precipitated solid is then placed in a 60°C forced-air drying oven for 2 days to obtain a dried amphoteric copolymer antifouling agent. The structural formula is as follows:

[0101] Among them, a is 10-20, b is 50-100, and the number average molecular weight is 15000-25000.

[0102] Step 3: Preparation of rubber composite material: Add 100 parts by weight of chloroprene rubber, 5 parts by weight of paraffin wax, 5 parts by weight of magnesium oxide, 1 part by weight of antioxidant RD, 1 part by weight of accelerator NA-22, 1 part by weight of anti-scorching agent salicylic acid, 5 parts by weight of the zwitterionic modified copolymer antifouling agent prepared above, 20 parts by weight of carbon black N330, and 5 parts by weight of silica. After mixing all materials evenly, perform intensive mixing at a temperature of 120℃ for 20 minutes. Discharge the rubber at a discharge temperature of 150℃ and cool for 90 minutes to obtain a first-stage compound.

[0103] Step 5: Add one part by weight of tert-butylisopropylphenyl peroxide to a two-roll mill with a roller temperature of 50°C. Adjust the roller gap to 0.6 mm and start triangular wrapping, slanted cutting, and rolling mixing. Mixing time is 10 minutes. After mixing, adjust the roller gap to 3.5 mm to cut the rubber sheet to obtain the second-stage compound.

[0104] Step 6: After placing the two-stage compound at room temperature for 24 hours and testing the vulcanization curve on a high-speed vulcanizing apparatus, vulcanize the two-stage compound under vulcanization conditions of 150℃×40min×12MPa to obtain the rubber composite material.

[0105] Example 10 A rubber composite material resistant to marine organism attachment, the preparation method of which includes the following steps: Step 1: First, dissolve [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonylpropyl)ammonium hydroxide (SBMA) and ethyl methacrylate in anhydrous methanol at a molar ratio of 1:3, where 0.03 mol of SBMA and the molar ratio of ethyl methacrylate to anhydrous methanol are 1:40. Add azobisisobutyronitrile and n-dodecyl mercaptan to the flask, and simultaneously raise the temperature to 60°C under nitrogen protection, continuously stirring the reaction for 12 hours. The molar ratio of ethyl methacrylate, n-butanethiol, and azobisisobutyronitrile is 67.5:0.1:1.

[0106] Step 2: After the reaction is complete, the viscous polymer solution is poured into deionized water at a molar ratio of ethyl methacrylate to deionized water of 1:1400 and stirred at 25°C for 4 hours. An amphoteric copolymer solid precipitates out. This precipitated solid is then placed in a 60°C forced-air drying oven for 2 days to obtain a dried amphoteric copolymer antifouling agent. The structural formula is as follows:

[0107] Among them, a is 10-20, b is 50-100, and the number average molecular weight is 15000-25000.

[0108] Step 3: Place the zwitterionic modified copolymer antifouling agent prepared above into a grinder, grind at a frequency of 60 Hz for 2 min, and obtain a zwitterionic modified copolymer antifouling agent with a particle size of approximately 10 micrometers.

[0109] Step 4: Take the zwitterionic modified copolymer antifouling agent and capsaicin antifouling agent prepared above and prepare a composite antifouling agent in a 1:1 weight ratio.

[0110] Step 5: Preparation of rubber composite material: Add 100 parts by weight of styrene-butadiene rubber, 10 parts by weight of paraffin wax, 10 parts by weight of magnesium oxide, 2.5 parts by weight of antioxidant RD, 2.5 parts by weight of accelerator NA-22, 2.5 parts by weight of anti-scorching agent salicylic acid, 5 parts by weight of the composite antifouling agent prepared above, 20 parts by weight of carbon black N550, and 10 parts by weight of silica. After mixing all materials evenly, perform intensive mixing at a temperature of 120℃ for 30 minutes. Discharge the rubber at a discharge temperature of 150℃ and cool for 90 minutes to obtain a first-stage compound rubber.

[0111] Step 6: Add 2.5 parts by weight of tert-butylisopropylphenyl peroxide to a two-roll mill with a roller temperature of 50°C. Adjust the roller gap to 0.6 mm and start triangular wrapping, slanted cutting, and rolling mixing. Mix for 15 minutes. After mixing, adjust the roller gap to 3.5 mm and cut the rubber sheet to obtain the second-stage compound.

[0112] Step 7: After placing the two-stage compound at room temperature for 24 hours and testing the vulcanization curve on a high-speed vulcanizing apparatus, vulcanize the two-stage compound under vulcanization conditions of 150℃×60min×12MPa to obtain the rubber composite material.

[0113] Comparative Example 1 A rubber composite material, the preparation method of which includes the following steps: Step 1: Preparation of rubber composite material: Add 100 parts by weight of chloroprene rubber, 5 parts by weight of paraffin wax, 5 parts by weight of magnesium oxide, 1 part by weight of antioxidant RD, 1 part by weight of accelerator NA-22, 1 part by weight of anti-scorching agent salicylic acid, 20 parts by weight of carbon black N330, and 5 parts by weight of silica. After mixing all materials evenly, carry out intensive mixing at a temperature of 120℃ for 20 minutes. Discharge the rubber at a discharge temperature of 150℃ and cool for 90 minutes to obtain a first-stage compound rubber.

[0114] Step 2: Add one part by weight of tert-butylisopropylphenyl peroxide to a two-roll mill with a roller temperature of 50°C. Adjust the roller gap to 0.6 mm and start triangular wrapping, slanted cutting, and rolling mixing. Mix for 10 minutes. After mixing, adjust the roller gap to 3.5 mm and cut the rubber sheet to obtain the second-stage compound.

[0115] Step 3: After placing the two-stage compound at room temperature for 24 hours and testing the vulcanization curve on a high-speed vulcanizing apparatus, vulcanize the two-stage compound under vulcanization conditions of 150℃×40min×12MPa to obtain the rubber composite material.

[0116] Comparative Example 2 A rubber composite material, the preparation method of which includes the following steps: Step 1: Prepare rubber composite material by weight parts: Add 100 parts by weight of natural rubber, 2 parts by weight of rosin, 2 parts by weight of zinc peroxide, 0.6 parts by weight of antioxidant PBN, 0.6 parts by weight of accelerator TMTD, 0.6 parts by weight of scorch inhibitor N-cyclohexylthiophthalimide, 20 parts by weight of carbon black N330, and 15 parts by weight of silica. Mix all materials evenly and then perform intensive mixing at 120℃ for 10 minutes. Discharge the rubber at 150℃ and cool for 90 minutes to obtain a first-stage compound.

[0117] Step 2: Add a first-stage compound and 0.6 parts by weight of octylphenol aldehyde vulcanizing resin to an open mill with a roller temperature of 50°C. Adjust the roller gap to 0.6 mm and start triangular wrapping, slanted cutting, and rolling mixing. Mix for 5 minutes. After mixing, adjust the roller gap to 3.5 mm and cut the rubber sheet to obtain the second-stage compound.

[0118] Step 3: After placing the two-stage compound at room temperature for 24 hours and testing the vulcanization curve on a high-speed vulcanizing apparatus, vulcanize the two-stage compound under vulcanization conditions of 150℃×20min×12MPa to obtain the rubber composite material.

[0119] Comparative Example 3 A rubber composite material, the preparation method of which includes the following steps: Step 1: Prepare rubber composite material by weight parts: Add 100 parts by weight of styrene-butadiene rubber, 10 parts by weight of paraffin wax, 10 parts by weight of magnesium oxide, 2.5 parts by weight of antioxidant RD, 2.5 parts by weight of accelerator NA-22, 2.5 parts by weight of anti-scorching agent salicylic acid, 20 parts by weight of carbon black N550, and 10 parts by weight of silica. After mixing all materials evenly, perform intensive mixing at a temperature of 120℃ for 30 minutes. Discharge the rubber at a discharge temperature of 150℃ and cool for 90 minutes to obtain a first-stage compound.

[0120] Step 2: Add 2.5 parts by weight of tert-butylisopropylphenyl peroxide to a two-roll mill with a roller temperature of 50°C. Adjust the roller gap to 0.6 mm and start triangular wrapping, slanted cutting, and rolling mixing. Mix for 15 minutes. After mixing, adjust the roller gap to 3.5 mm to cut the rubber sheet to obtain the second-stage compound.

[0121] Step 3: After placing the two-stage compound at room temperature for 24 hours and testing the vulcanization curve on a high-speed vulcanizing apparatus, vulcanize the two-stage compound under vulcanization conditions of 150℃×60min×12MPa to obtain the rubber composite material.

[0122] Comparative Example 4 A rubber composite material, the preparation method of which includes the following steps: Step 1: Prepare rubber composite material by weight parts: Add 100 parts by weight of styrene-butadiene rubber, 10 parts by weight of rosin, 10 parts by weight of zinc peroxide, 2.5 parts by weight of antioxidant PBN, 2.5 parts by weight of accelerator TMTD, 2.5 parts by weight of scorch inhibitor N-cyclohexylthiophthalimide, 20 parts by weight of carbon black N550, and 10 parts by weight of silica. After mixing all materials evenly, perform intensive mixing at a temperature of 120℃ for 30 minutes. Discharge the rubber at a discharge temperature of 150℃ and cool for 90 minutes to obtain a first-stage compound.

[0123] Step 2: Add a first-stage compound and 2.5 parts by weight of octylphenol aldehyde vulcanizing resin to an open mill with a roller temperature of 50℃. Adjust the roller gap to 0.6mm and start triangular wrapping, slanted cutting, and rolling mixing. The mixing time is 15min. After mixing, adjust the roller gap to 3.5mm and cut the rubber sheet to obtain the second-stage compound.

[0124] Step 3: After placing the two-stage compound at room temperature for 24 hours and testing the vulcanization curve on a high-speed vulcanizing apparatus, vulcanize the two-stage compound under vulcanization conditions of 150℃×60min×12MPa to obtain the rubber composite material.

[0125] The rubber composite materials obtained in the above embodiments and comparative examples were subjected to the following tests: 1. Detection of Ozone-Depleting Substances and Greenhouse Effect Substances The rubber composite material prepared in Example 1 was tested for ozone-depleting substances and greenhouse gases according to US EPA 5021A:2014, and analyzed by HS-GC-MS.

[0126] Table 1

[0127] Notes: (1) 1 μg / g = 1 ppm = 0.0001%, (2) ND = Not detected As can be seen from the test results in Table 1, the rubber composite material prepared in Example 1 of this invention did not leak ozone-depleting substances or greenhouse gas substances during the testing process. This indicates that adding zwitterionic modified polymer antifouling agents to rubber composite materials does not pose a risk of leakage and will not damage the marine ecological environment. It is a green and environmentally friendly antifouling agent.

[0128] 2. Physical and mechanical property testing The physical and mechanical properties of the rubber composite materials prepared in the examples and comparative examples were tested, and the test results are shown in Tables 2-7.

[0129] 1. Tensile property test Tensile strength, elongation at break, and tensile strength (300%) were tested in accordance with the national standard GB / T 528-2009 "Determination of tensile properties of vulcanized rubber".

[0130] 2. Tear strength test According to the national standard GB / T 529-2008 "Determination of tear strength of vulcanized rubber or thermoplastic rubber (trouser-shaped, right-angled and crescent-shaped specimens)", a right-angle tear test was selected. Five tests were performed and the average value was taken.

[0131] 3. According to the national standard GB / T 531.1-2008 "Determination of Hardness of Vulcanized Rubber and Thermoplastic Rubber", a Shore A hardness tester was used to test five different points and the average value was taken.

[0132] Table 2

[0133] In Table 2, Example 1 involves adding 5 parts by weight of mill-modified zwitterionic modified copolymer antifouling agent, while Example 9 involves adding 5 parts by weight of unmodified zwitterionic modified copolymer antifouling agent. The comparison shows that mill modification treatment can effectively improve the dispersibility of antifouling agent in rubber matrix and reduce its damage to the physical and mechanical properties of rubber, fully verifying the effectiveness of the modification process.

[0134] Table 3

[0135] In Table 3, Example 5 involves adding 5 parts by weight of a zwitterionic modified copolymer and capsaicin antifouling agent modified with silane coupling agent, while Example 10 involves adding 5 parts by weight of a zwitterionic modified copolymer and capsaicin antifouling agent not modified with silane coupling agent. The comparison shows that silane coupling agent modification can effectively improve the dispersibility of antifouling agent in rubber matrix and reduce its damage to the physical and mechanical properties of rubber, fully verifying the effectiveness of the modification process.

[0136] 3. Antifouling performance test To observe the actual antifouling effect of the rubber composite material in the ocean, the rubber composite materials prepared in Comparative Example 1, Example 1, and Example 2 were released into the Yellow Sea near the Institute of Oceanology, Chinese Academy of Sciences in Qingdao for 8 months. The test results are as follows: Figure 1 As shown.

[0137] Depend on Figure 1 The test results show that Comparative Example 1 has a large number of plankton and other marine organisms attached to its surface, Example 1 has a significantly reduced amount of plankton attached to its surface, and Example 2 has almost no marine organisms attached to its surface.

[0138] Marine pollutants adhering to the surface of the rubber composite material were removed, and the adhering substances on the surface of the rubber composite material were quantitatively analyzed. The results are as follows: Figure 2 As shown, the average pollutant content in Comparative Example 1 was 453g, the average pollutant content in Example 1 was 335g, and the average pollutant content in Example 2 was 122g. Compared with Comparative Example 1, in an 8-month field marine antifouling test, the surface of the rubber composite sample in Example 2 showed a reduction of more than 72% (mass fraction) of marine organism adhesion. This indicates that introducing zwitterionic modified copolymer antifouling agents into rubber can significantly reduce marine organism adhesion on the surface of rubber hoses within nearly a year.

[0139] The above characterization results show that the antifouling agent of this invention exhibits excellent dispersibility in the rubber matrix, shows no leakage risk according to the "Ozone-depleting and Greenhouse-enhancing Substances" test, and has minimal impact on the physical and mechanical properties of the rubber. Furthermore, the antifouling effect of the composite material can be precisely adjusted by controlling the amount of antifouling agent added. The rubber composite material prepared by this invention exhibits excellent anti-adhesion capabilities against marine fouling organisms such as bacteria, diatoms, and barnacles, and its antifouling performance is long-lasting and stable, maintaining a high level of antifouling effectiveness even after 8 months of field application in the Yellow Sea. The preparation and modification process of the antifouling agent prepared by this invention is simple, requires no complex and precise equipment, and is easy to industrialize.

[0140] The above embodiments are preferred embodiments of the present invention, but are not intended to limit the embodiments of the present invention. Any modifications, equivalent substitutions, and combinations made without departing from the spirit and principle of the present invention should be included within the protection scope of the claims of the present invention.

Claims

1. A rubber composite material with marine antifouling properties, characterized in that... The rubber composite material comprises the following components that have been blended and vulcanized: Rubber, fillers, antifouling agents, plasticizers, activators, scorch inhibitors, antioxidants, accelerators, and vulcanizing agents; The antifouling agent comprises a zwitterionic modified copolymer and optionally at least one of sodium benzoate, tannic acid, 6-gingerol, capsaicin, sulfobetaine, carboxylate, phosphorylcholine, isothiazolinone, and zinc pyrithione. Based on the weight of the rubber as 100 parts by weight: 100 parts by weight of rubber; 1-40 parts by weight of filler; Antifouling agent 1-30 parts by weight; Plasticizer 1-30 parts by weight; Activator 1-20 parts by weight; Anti-scorching agent: 0.1-10 parts by weight; Anti-aging agent 0.1-10 parts by weight; Accelerator: 0.1-10 parts by weight; Vulcanizing agent: 0.1-10 parts by weight.

2. The rubber composite material according to claim 1, characterized in that: Based on the weight of the rubber as 100 parts by weight: 100 parts by weight of rubber; 10-30 parts by weight of filler; Antifouling agent 2-20 parts by weight; Plasticizer 2-15 parts by weight; Activator 2-10 parts by weight; Anti-scorching agent: 0.5-3 parts by weight; Anti-aging agent 0.5-3 parts by weight; Accelerator 0.5-3 parts by weight; Vulcanizing agent 0.5-3 parts by weight.

3. The rubber composite material according to claim 1 or 2, characterized in that: The rubber is at least one of the following: natural rubber, chloroprene rubber, styrene-butadiene rubber, polybutadiene rubber, ethylene propylene rubber, butyl rubber, nitrile rubber, silicone rubber, fluororubber, polyurethane rubber, chloroprene rubber, acrylate rubber, and polysulfide rubber; and / or, The filler is calcium carbonate and / or carbon black; and / or, The plasticizer is at least one selected from stearic acid, sodium stearate, potassium stearate, coumarone resin, petrolatum, paraffin wax, petroleum resin, coal tar, pine tar, rosin, tall oil, and ointment; and / or, The activator is at least one selected from zinc oxide, magnesium oxide, lead monoxide, zinc peroxide, and titanium dioxide; and / or, The anti-scorching agent is at least one selected from salicylic acid, phthalic anhydride, nitrosodiphenylamine, nitroso-N-phenyl-2-aniline, and N-cyclohexylthiophthalimide; and / or The antioxidant may be at least one of commonly used antioxidants in the art, such as antioxidant NBC, antioxidant RD, antioxidant PBN, antioxidant D, etc.; and / or, The accelerator may be at least one of commonly used accelerators in the art, such as accelerator NA-22, accelerator DM, accelerator NS, accelerator TMTD, accelerator MBTS, accelerator DPG, etc.; and / or, The vulcanizing agent is at least one of sulfur, lead monoxide, benzoyl peroxide, dicumyl peroxide, 1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, bis(tert-butylperoxyisopropyl)benzene, tert-butylisopropylphenyl peroxide, octylphenolic vulcanizing resin, and brominated octylphenolic resin.

4. The rubber composite material according to claim 1, characterized in that: The structural formula of the zwitterionic modified copolymer is: Wherein, a is 1-50, preferably 5-30; b is 40-500, preferably 50-400; n is 0-10, preferably 0-5; x is 0-10, preferably 0-5; y is 0-10, preferably 0-5; A1 is , , , , One of them; A2 is , , One of them, where m is any integer from 1 to 6; preferably, The number-average molecular weight of the zwitterionic modified copolymer is 10,000-80,000, preferably 20,000-60,000.

5. The rubber composite material according to claim 4, characterized in that... The zwitterionic modified copolymer was prepared by the following method: A zwitterionic modified copolymer solution is prepared by solution polymerization of zwitterionic salt, acrylate, chain transfer agent, catalyst, and reaction solvent. This solution is then poured into a preparation solvent and stirred to react. Post-treatment is then performed to obtain the zwitterionic modified copolymer. Preferably, The molar ratio of the zwitterionic salt to the acrylate is 1:(1-20), preferably 1:(2-15); and / or, The molar ratio of the dilute ester to the chain transfer agent and catalyst is (15-6000):(0.005-10):1, preferably (40-500):(0.01-2):1; and / or, The molar ratio of the dilute ester to the reaction solvent is 1:(1.5-400), preferably 1:(2-200); and / or, The molar ratio of the dilute ester to the preparation solvent is 1:(1.5-7000), preferably 1:(50-2000); and / or, The structural formula of the zwitterionic salt is: Where n is 0-10, preferably 0-5; A1 is , , , , One of them; A2 is , , One of them, where m is any integer from 1 to 6; more preferably, the zwitterionic salt is at least one of sulfonate betaine salt, carboxylate betaine salt, and phosphorylcholine salt; and / or, The structural formula of the acrylate is: Wherein, x is 0-10, preferably 0-5, and y is 0-10, preferably 0-5; more preferably, the acrylate is at least one selected from 2-ethylhexyl methacrylate, butyl methacrylate, ethyl methacrylate, and octyl methacrylate; and / or, The chain transfer agent is at least one selected from benzene, toluene, ethylbenzene, cumene, tert-butylbenzene, heptane, cyclohexane, n-butanol, acetone, acetic acid, chlorobutane, bromobutane, iodobutane, chloroform, carbon tetrachloride, carbon tetrabromide, tert-butyl disulfide, tert-butyl mercaptan, n-butane mercaptan, and n-dodecyl mercaptan; and / or, The catalyst is at least one selected from the following: azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, diethylhexyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, dicumene peroxide, di-tert-butyl peroxide, benzoyl peroxide, dodecyl peroxide, tert-butyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxide, dicyclohexyl peroxide, potassium persulfate, and ammonium persulfate; and / or, The reaction solvent is at least one selected from dimethyl sulfoxide, dimethylformamide, methanol, ethanol, acetone, dichloromethane, tetrahydrofuran, and toluene; and / or, The preparation solvent is at least one selected from n-hexane, deionized water, dimethylformamide, dichloromethane, tetrahydrofuran, trifluoroethanol, methyl ethyl ketone, dimethylacetamide, and 1,4-dioxane; and / or, The solution polymerization reaction is carried out at a temperature of 0-120°C, preferably 25-100°C, and / or for a reaction time of 0.5-24 h, preferably 1-12 h; and / or The reaction temperature of the stirring reaction is 0-80℃, preferably 25-60℃, and / or the reaction time is 1-24h, preferably 1-12h.

6. A method for preparing a rubber composite material with marine antifouling properties as described in any one of claims 1-5, characterized in that... The method includes: Rubber, filler, antifouling agent, plasticizer, activator, anti-scorching agent, anti-aging agent and accelerator are mixed in the stated weight parts, then mixed in an intensive mixer, discharged and cooled to obtain a first-stage compound; then the stated weight parts of vulcanizing agent are added and mixed to obtain a second-stage compound, which is then vulcanized to obtain the rubber composite material.

7. The method according to claim 6, characterized in that... The method further includes pre-modifying the antifouling agent; preferably, The modification treatment includes at least one of grinding treatment and silane coupling agent modification treatment.

8. The method according to claim 7, characterized in that: The grinding frequency of the grinding process is 10-100Hz, preferably 40-60Hz, and / or the grinding time is 1-40min, preferably 1-10min, and / or the particle size after grinding is 0.1-100 micrometers, preferably 0.1-10 micrometers; And / or, The silane coupling agent modification treatment includes: diluting the silane coupling agent, adding an antifouling agent, and mixing at high speed; followed by post-treatment to obtain a silane coupling agent modified antifouling agent; preferably, The silane coupling agent is at least one selected from γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, anilinemethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-isocyanate propyltrimethoxysilane, and γ-isocyanate propyltriethoxysilane; and / or, The diluting solvent is ethanol and / or methanol; and / or, The molar ratio of the antifouling agent to the silane coupling agent and the diluting solvent is 1:(0.001-0.1):(1-50), preferably 1:(0.002-0.02):(1-20); and / or, The high-speed stirring speed is 500-2000 r / min, and / or, the time is 1-12 h; and / or, The post-treatment is a drying process, preferably a process at a temperature of 25-200℃ for 1-3 days.

9. The method according to claim 6, characterized in that: The mixing temperature is 100-150℃, and / or the mixing time is 5-30 min; and / or, The glue discharge temperature is 140-160℃; and / or, The cooling time is 30-90 minutes; and / or, The mixing temperature is 40-60℃, and / or the mixing time is 5-40 min; and / or, The vulcanization temperature is 140-170℃, and / or the vulcanization time is 20-60 min, and / or the vulcanization pressure is 10-20 MPa.

10. The application of a rubber composite material with marine antifouling properties as described in any one of claims 1-5, or a rubber composite material with marine antifouling properties prepared by the method described in any one of claims 6-9, in the field of green marine antifouling.

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