Antiskid composite layer for ramp of roll-on-roll-off ship and preparation method of antiskid composite layer
Through the combination of dopamine-modified polyol and modified epoxy resin polyol and modified anti-slip sand, the bonding performance of the anti-slip composite layer of the Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-
Patent Information
- Application Number
- CN202510606443.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-12
- Publication Date
- 2025-08-19
AI Technical Summary
The adhesive force between the cementitious material and the anti-slip sand in the existing anti-slip coating of the Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro
Component A composed of dopamine-modified polyol, modified epoxy resin polyol and vegetable oil polyol and component B composed of modified anti-slip sand is enhanced by the phthaldihydroxy group and polydopamine coating in the dopamine-modified polyol to enhance adhesion and interface binding force, forming high-strength chemical bonds.
It significantly improves the bonding performance of the anti-slip composite layer of the Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-Ro-R
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Figure BDA0005398340590000101
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of roll-on / roll-off ships, and in particular to an anti-skid composite layer for a roll-on / roll-off ship ramp and a preparation method thereof. Background Art
[0002] Ro-ro ships, a crucial mode of transport in the modern maritime transport system, offer a highly efficient solution for the transport of wheeled cargo, such as vehicles and construction machinery, through their unique horizontal loading and unloading method. These vessels connect directly to the dock via a gangway at the bow or stern, creating a transport channel connecting the ship's hold and the mainland. This allows cargo to be transported directly into the hold using its own power or traction equipment. While this loading and unloading method significantly improves operational efficiency, it also places special demands on the reliability of the ship's channel. In a dynamic and complex operating environment, the surface of a ro-ro ship's channel faces multiple risks. Frequent tidal fluctuations cause the angle of the gangway to constantly adjust, creating a slope with varying degrees of inclination. The inevitable slight swaying of the ship during loading and unloading further creates an unstable state between the vehicle tires and the contact surface. These combined physical conditions necessitate a channel surface with a slip resistance far exceeding the standards of land-based facilities to ensure safe operation.
[0003] When anti-skid performance is insufficient, dangerous friction points may form on the channel surface. The lateral shear force generated by heavy vehicles during braking or steering can exceed the friction threshold of the contact surface, causing the vehicle to slip or even roll over. The contact area between the tracks of construction machinery and the metal deck is reduced, making it easy for the equipment to lose control. Even lightly loaded transport vehicles can cause collisions due to tire slippage on slippery surfaces. More seriously, on the sloped channels between multiple decks, any slight slip can, due to gravity, lead to a chain reaction of collisions, threatening the safety of the entire ship's cargo and the lives of the operators.
[0004] The challenge facing ship designers is how to maintain stable friction properties over the long term through surface treatment technology. This requires balancing the depth of the anti-slip texture with smooth vehicle travel, the wear resistance of the anti-slip coating with maintenance costs, and adapting to performance fluctuations in varying climatic conditions. This meticulous control of physical properties directly determines whether the roll-on / roll-off transport system can strike the optimal balance between efficiency and safety.
[0005] Anti-slip sand, a key component in achieving anti-slip performance, is a composite material composed of a resin binder and anti-slip sand. The strong adhesive properties of the resin combined with the high friction properties of the anti-slip sand create a surface coating with high anti-slip properties. However, in recent years, accidents involving sand falling off and damaging paintwork have become frequent, primarily due to insufficient adhesion between the binder and the anti-slip sand. Summary of the Invention
[0006] In view of the shortcomings of the existing technology, the present invention provides an anti-skid composite layer for a roll-on / roll-off ship ramp and a preparation method thereof.
[0007] The technical solution of the present invention is:
[0008] A method for preparing an anti-skid composite layer for a roll-on / roll-off ship ramp comprises the following steps:
[0009] S1. Preparation of component A polyol: dopamine-modified polyol, modified epoxy resin polyol, and vegetable oil polyol were mixed after vacuum dehydration to obtain a mixture, a flame retardant plasticizer, a defoaming agent, a water removal agent, and an anti-aging agent were added to the mixture and mixed, and finally an anti-settling agent and a thixotropic agent were added and mixed to obtain component A polyol;
[0010] S2. Preparation of modified anti-skid sand component B: The gravel was soaked in a dopamine hydrochloride solution and then removed and dried to obtain a modified anti-skid sand;
[0011] S3. Preparation of an anti-slip composite layer for the roll-on / roll-off ship ramp: Mix the polyol component A and the curing agent prepared in S1, apply the mixture on the surface of the steel plate with an anti-corrosion primer, and then sprinkle the modified anti-slip sand component B prepared in S2. After curing, remove the loose modified anti-slip sand to obtain the anti-slip composite layer for the roll-on / roll-off ship ramp.
[0012] Furthermore, the preparation method of the dopamine-modified polyol in step S1 is: take 100-120 parts of maleic anhydride-modified polypropylene glycol, 60-100 parts of N,N'-dicyclohexylcarbodiimide and 40-60 parts of N-hydroxysuccinimide and dissolve them in anhydrous ethanol, adjust the pH to 4-5, and stir to react for 5-8 hours; continue to add 40-70 parts of dopamine hydrochloride, adjust the pH to 8-9, and stir to react under nitrogen protection for 12-24 hours to obtain the dopamine-modified polyol.
[0013] Furthermore, the preparation method of the modified epoxy resin polyol in step S1 is: add 30-80 parts of oleic acid to 50-80 parts of bisphenol F epoxy resin to obtain intermediate A, add 0.2-0.5 parts of N,N-dimethylformamide to the intermediate A under N2 atmosphere protection at a temperature of 100-110°C and react for 4-6 hours to obtain the modified epoxy resin polyol.
[0014] Furthermore, in step S1, the dopamine-modified polyol is 20-40 parts, the modified epoxy resin polyol is 10-30 parts, the vegetable oil polyol is 30-70 parts, the flame retardant plasticizer is 3-8 parts, the defoaming agent is 0.1-0.5 parts, the water removing agent is 1-5 parts, the anti-aging agent is 0.1-0.3 parts, the anti-settling agent is 0.5-1 parts, and the thixotropic agent is 0.5-1 parts.
[0015] Furthermore, the vegetable oil polyol in step S1 is a mixture of one or more of castor oil, castor oil derivative polyol, soybean oil polyol, and palm oil polyol; the flame retardant plasticizer is a mixture of one or more of tris(chloroethyl) phosphate, triphenyl phosphate, dimethyl methylphosphonate, and triethyl phosphate; the defoamer is a mixture of one or more of BYK-070, BYK-077, BYK-085, and BYK-065; the dewatering agent is a mixture of one or more of 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, and 13X molecular sieve; the anti- The aging agent is prepared by mixing a hindered phenol antioxidant and an ultraviolet absorber in a mass ratio of 1:1, wherein the hindered phenol antioxidant is a mixture of one or more of hindered phenol antioxidant 2246, hindered phenol antioxidant 425, and hindered phenol antioxidant 1010; the ultraviolet absorber is a mixture of one or more of ultraviolet absorber UV-622, ultraviolet absorber UV-531, and ultraviolet absorber UV-326; the anti-settling agent is a mixture of one or more of BYK-405, BYK-410, and BYK-430; and the thixotropic agent is fumed silica.
[0016] Furthermore, the preparation method of the modified anti-skid sand in step S2 is specifically: placing gravel in a dopamine hydrochloride solution with a concentration of 1-2 mg / ml, soaking it for 12-24 hours, and drying it to obtain modified anti-skid sand; the gravel is a mixture of one or more of basalt, corundum, and brown corundum.
[0017] Furthermore, the particle size of the gravel is 1-5 mm.
[0018] Furthermore, the curing agent in step S3 is diphenylmethane diisocyanate.
[0019] Furthermore, in step S3, the weight ratio of the polyol component A to the curing agent is 100:(30-50), and the amount of the mixture of the polyol component A and the curing agent is 1.5-2.5 kg / m 2 The amount of the modified anti-skid sand of component B is 5-13 kg / m 2 .
[0020] The anti-skid composite layer for the roll-on / roll-off ship ramp is prepared according to the preparation method.
[0021] Compared with the prior art, the present invention has at least the following advantages:
[0022] The present invention relates to an anti-skid composite layer for a roll-on / roll-off ship ramp and a preparation method thereof. In the preparation method, components A and B are respectively polyol and modified anti-skid sand, wherein component A contains dopamine-modified polyol, modified epoxy resin polyol and vegetable oil polyol; wherein the dopamine-modified polyol contains o-phthalic dihydroxyl groups, which can improve adhesion through hydrogen bonding, metal coordination, π-π or π-cation interaction; the benzene ring in dopamine generates intermolecular forces with the surface of the substrate or the polar groups in the curing agent to improve adhesion; the modified epoxy resin polyol The high polarity of the epoxy resin makes it highly attractive to metal substrates (such as steel plates), enhancing adhesion through van der Waals forces. The vegetable oil polyol contains multiple hydroxyl groups, which can react with the curing agent to form high-strength chemical bonds. The B component is modified anti-skid sand, which is gravel with a polydopamine coating attached to the surface. The phenolic hydroxyl groups and amino groups in the polydopamine coating can react with the isocyanate in the curing agent to form chemical bonds, thereby improving the interfacial bonding strength between the anti-skid sand and the binder. Experiments have shown that the anti-skid composite layer for roll-on / roll-off ship ramps prepared by the method of the present invention has a synergistic effect. DETAILED DESCRIPTION
[0023] The present invention is described in further detail below. It is necessary to point out that the following specific implementation methods are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention based on the above application content.
[0024] This document provides general and / or specific descriptions of the materials and experimental methods used in the experiments. Unless otherwise specified, all experimental or testing methods are conventional methods. All reagents and instruments used, unless the manufacturer is specified, are commercially available, conventional products and were prepared or used using conventional methods.
[0025] Sources
[0026] Preparation process of maleic anhydride modified polypropylene glycol: 10 parts of polypropylene glycol and 20 parts of maleic anhydride are added to a reactor at 110°C under nitrogen protection, and dibenzoyl peroxide as an initiator is slowly added. The reaction is carried out for 6 hours, and the unreacted maleic anhydride is removed to obtain maleic anhydride modified polypropylene glycol.
[0027] Maleic anhydride was purchased from Jinan Chuangshi Chemical Co., Ltd.;
[0028] Polypropylene glycol: purchased from Wanhua Chemical;
[0029] Castor oil, castor oil derivative polyols, soybean oil polyols, and palm oil polyols were purchased from BASF.
[0030] 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, 13X molecular sieve: purchased from Yingkou Zhongbao Molecular Sieve Co., Ltd.
[0031] Example 1 Preparation method of anti-skid composite layer for ro-ro ship ramp
[0032] S1. Preparation of component A polyol:
[0033] S11 Preparation of dopamine-modified polyol: Weigh 100 parts of maleic anhydride-modified polypropylene glycol, 60 parts of N,N'-dicyclohexylcarbodiimide and 40 parts of N-hydroxysuccinimide and dissolve them in anhydrous ethanol, then adjust the pH to 4 and stir the reaction for 5h; add 40 parts of dopamine hydrochloride thereto, adjust the pH to 8, and stir the reaction under nitrogen for 12h to obtain a dopamine-modified polyol;
[0034] S12 Preparation of modified epoxy resin polyol: To 50 parts of bisphenol F epoxy resin was added 30 parts of excess oleic acid and mixed, under N2 atmosphere, the temperature was controlled at 100 ° C, and the reaction was catalyzed by 0.2 parts of N, N-dimethylformamide for 4h to obtain a modified epoxy resin polyol;
[0035] S13. Preparation of component A polyol: 20 parts of dopamine-modified polyol, 10 parts of modified epoxy resin polyol, 30 parts of castor oil were mixed and vacuum dehydrated to remove moisture from the material, followed by adding 3 parts of flame retardant plasticizer tris (chloroethyl) phosphate, 0.1 parts of defoamer BYK-070, 1 part of dehydrating agent 3A molecular sieve, 0.1 parts of antioxidant and mixed evenly, the antioxidant being 0.05 parts of hindered phenol antioxidant 2246 and 0.05 parts of UV-622 ultraviolet absorber mixed, stirred evenly, and then added 0.5 parts of anti-settling agent BYK-405 and 0.5 parts of thixotropic agent fumed silica, dispersed at a shear rate of 1000 r / min for 3h to obtain component A polyol;
[0036] S2 preparation component B modified anti-skid sand: at room temperature, the basalt was completely immersed in a dopamine hydrochloride solution at a concentration of 1 mg / ml for 12 hours, removed and dried naturally until a polydopamine coating was formed on the surface to obtain component B modified anti-skid sand;
[0037] S3. Preparation of anti-skid composite layer for ro-ro ramp: Take 30 parts of diphenylmethane diisocyanate as curing agent, take 100 parts of component A polyol prepared in S1 and 30 parts of curing agent and mix them, according to 1.5kg / m 2 Pour it on the surface of the steel plate coated with anti-corrosion primer and apply it evenly with a scraper at a rate of 5kg / m 2 An excess amount of modified anti-skid sand of component B was spread, and after curing for 12 hours, the loose anti-skid sand was cleaned to obtain an anti-skid composite layer for the roll-on / roll-off ship ramp.
[0038] Example 2: Preparation method of anti-skid composite layer for ro-ro ship ramp
[0039] S1. Preparation of component A polyol:
[0040] S11 Preparation of dopamine-modified polyol: Weigh 110 parts of maleic anhydride-modified polypropylene glycol, 80 parts of N,N'-dicyclohexylcarbodiimide and 50 parts of N-hydroxysuccinimide and dissolve them in anhydrous ethanol, then adjust the pH to 5 and stir the reaction for 6h; 50 parts of dopamine hydrochloride were added thereto, the pH was adjusted to 8.5, and the reaction was stirred under nitrogen for 20h to obtain a dopamine-modified polyol;
[0041] S12 Preparation of modified epoxy resin polyol: To 65 parts of bisphenol F epoxy resin were added 60 parts of excess oleic acid and mixed, under N2 atmosphere, the temperature was controlled at 100 ° C, and the reaction was catalyzed by 0.4 parts of N, N-dimethylformamide for 5h to obtain a modified epoxy resin polyol;
[0042] S13. Preparation of component A polyol: 30 parts of dopamine-modified polyol, 20 parts of modified epoxy resin polyol, 50 parts of castor oil derivative polyol were mixed and vacuum dehydrated to remove moisture from the material. Then, 5 parts of flame retardant plasticizer triphenyl phosphate, 0.3 parts of defoamer BYK-077, 3 parts of water removing agent 4A molecular sieve, 0.2 parts of antioxidant were added and mixed evenly. The antioxidant was a mixture of 0.1 parts of hindered phenol antioxidant 425 and 0.1 parts of ultraviolet absorber UV-531. The mixture was stirred evenly. Then, 0.7 parts of anti-settling agent BYK-410 and 0.7 parts of thixotropic agent fumed silica were added and dispersed at a shear rate of 2000 r / min for 3h to obtain component A polyol;
[0043] S2 preparation component B modified anti-skid sand: at room temperature, the diamond is completely immersed in a dopamine hydrochloride solution at a concentration of 2mg / ml for 18h, removed and dried naturally until a polydopamine coating is formed on the surface to obtain component B modified anti-skid sand;
[0044] S3. Preparation of anti-skid composite layer for ro-ro ramp: Take 40 parts of diphenylmethane diisocyanate as curing agent, take 100 parts of component A polyol prepared in S1 and 40 parts of curing agent and mix them, according to 2kg / m 2 Pour it on the surface of the steel plate coated with anti-corrosion primer and apply it evenly with a scraper at a rate of 8kg / m 2 An excess amount of modified anti-skid sand of component B was spread, and after curing for 18 hours, the loose anti-skid sand was cleaned to obtain an anti-skid composite layer for the roll-on / roll-off ship ramp.
[0045] Example 3 Preparation method of anti-skid composite layer for ro-ro ship ramp
[0046] S1. Preparation of component A polyol:
[0047] S11 Preparation of dopamine-modified polyol: Weigh 120 parts of maleic anhydride-modified polypropylene glycol, 100 parts of N,N'-dicyclohexylcarbodiimide and 60 parts of N-hydroxysuccinimide and dissolve them in anhydrous ethanol, then adjust the pH to 5 and stir the reaction for 8h; add 70 parts of dopamine hydrochloride thereto, adjust the pH to 9, and stir the reaction under nitrogen for 24h to obtain a dopamine-modified polyol;
[0048] S12 Preparation of modified epoxy resin polyol: To 80 parts of bisphenol F epoxy resin were added 80 parts of excess oleic acid and mixed, under N2 atmosphere, the temperature was controlled at 110 ° C, and the reaction was catalyzed by 0.5 parts of N, N-dimethylformamide for 6h to obtain a modified epoxy resin polyol;
[0049] S13. Preparation of component A polyol: 40 parts of dopamine-modified polyol, 30 parts of modified epoxy resin polyol, 70 parts of soybean oil polyol were mixed and vacuum dehydrated to remove moisture from the material, followed by adding 8 parts of flame retardant plasticizer dimethyl methylphosphonate, 0.5 parts of defoamer BYK-085, 5 parts of water removing agent 5A molecular sieve, 0.3 parts of antioxidant and mixed evenly, the antioxidant being 0.15 parts of hindered phenol antioxidant 1010 and 0.15 parts of UV-326 ultraviolet absorber mixed, stirred evenly, and then added 1 part of anti-settling agent BYK-430 and 1 part of thixotropic agent fumed silica, dispersed at a shear rate of 3000 r / min for 3h to obtain component A polyol;
[0050] S2 preparation component B modified anti-skid sand: at room temperature, the brown corundum was completely immersed in a dopamine hydrochloride solution at a concentration of 2mg / ml for 24h, removed and dried naturally until a polydopamine coating was formed on the surface to obtain component B modified anti-skid sand;
[0051] S3. Preparation of anti-skid composite layer for ro-ro ramp: Take 50 parts of diphenylmethane diisocyanate as curing agent, take 100 parts of component A polyol prepared in S1 and 50 parts of curing agent and mix them, according to 2.5kg / m 2 Pour it on the surface of the steel plate coated with anti-corrosion primer and apply it evenly with a scraper at a rate of 13kg / m 2 An excess amount of modified anti-skid sand of component B was spread, and after curing for 15 hours, the loose anti-skid sand was cleaned to obtain an anti-skid composite layer for the roll-on / roll-off ship ramp.
[0052] Comparative Example 1 Preparation method of anti-skid composite layer for ro-ro ship ramp
[0053] The preparation method of the anti-skid composite layer for the ro-ro ship ramp provided in this comparative example is basically the same as that in Example 2, except that the anti-skid sand is not modified.
[0054] S1. Preparation of component A polyol:
[0055] S11 Preparation of dopamine-modified polyol: Weigh 110 parts of maleic anhydride-modified polypropylene glycol, 80 parts of N,N'-dicyclohexylcarbodiimide and 50 parts of N-hydroxysuccinimide and dissolve them in anhydrous ethanol, then adjust the pH to 5 and stir the reaction for 6h; 50 parts of dopamine hydrochloride were added thereto, the pH was adjusted to 8.5, and the reaction was stirred under nitrogen for 20h to obtain a dopamine-modified polyol;
[0056] S12 Preparation of modified epoxy resin polyol: To 65 parts of bisphenol F epoxy resin were added 60 parts of excess oleic acid and mixed, under N2 atmosphere, the temperature was controlled at 100 ° C, and the reaction was catalyzed by 0.4 parts of N, N-dimethylformamide for 5h to obtain a modified epoxy resin polyol;
[0057] S13. Preparation of component A polyol: 30 parts of dopamine-modified polyol, 20 parts of modified epoxy resin polyol, 50 parts of castor oil derivative polyol were mixed and vacuum dehydrated to remove moisture from the material. Then, 5 parts of flame retardant plasticizer triphenyl phosphate, 0.3 parts of defoamer BYK-077, 3 parts of water removing agent 4A molecular sieve, 0.2 parts of antioxidant were added and mixed evenly. The antioxidant was a mixture of 0.1 parts of hindered phenol antioxidant 425 and 0.1 parts of ultraviolet absorber UV-531. The mixture was stirred evenly. Then, 0.7 parts of anti-settling agent BYK-410 and 0.7 parts of thixotropic agent fumed silica were added and dispersed at a shear rate of 2000 r / min for 3h to obtain component A polyol;
[0058] S2. Preparation of anti-skid composite layer for ro-ro ramp: Take 40 parts of diphenylmethane diisocyanate as curing agent, mix 100 parts of component A polyol prepared in S1 and 40 parts of curing agent, according to 2kg / m 2 Pour it on the surface of the steel plate coated with anti-corrosion primer and apply it evenly with a scraper at a rate of 8kg / m 2 Spread excess corundum, clean the loose corundum after curing for 18 hours, and obtain the anti-skid composite layer for the roll-on / roll-off ship ramp.
[0059] Comparative Example 2: Preparation method of anti-skid composite layer for ro-ro ship ramp
[0060] The preparation method of the anti-skid composite layer for the ro-ro ship ramp provided in this comparative example is basically the same as that of Example 2, except that no dopamine-modified polyol is added.
[0061] S1. Preparation of component A polyol:
[0062] S11 Preparation of modified epoxy resin polyol: To 65 parts of bisphenol F epoxy resin were added 60 parts of excess oleic acid and mixed, under N2 atmosphere, the temperature was controlled at 100 ° C, and the reaction was catalyzed by 0.4 parts of N, N-dimethylformamide for 5h to obtain a modified epoxy resin polyol;
[0063] S12. Preparation of component A polyol: 20 parts of modified epoxy resin polyol and 50 parts of castor oil derivative polyol were mixed and vacuum dehydrated to remove moisture from the material. Then, 5 parts of flame retardant plasticizer triphenyl phosphate, 0.3 parts of defoamer BYK-077, 3 parts of water removing agent 4A molecular sieve, and 0.2 parts of anti-aging agent were added and mixed evenly. The anti-aging agent was a mixture of 0.1 parts of hindered phenol antioxidant 425 and 0.1 parts of ultraviolet absorber UV-531. The mixture was stirred evenly. Then, 0.7 parts of anti-settling agent BYK-410 and 0.7 parts of thixotropic agent fumed silica were added and dispersed evenly at a shear rate of 2000 r / min to obtain component A polyol.
[0064] S2 preparation component B modified anti-skid sand: at room temperature, the diamond is completely immersed in a dopamine hydrochloride solution at a concentration of 2mg / ml for 18h, removed and dried naturally until a polydopamine coating is formed on the surface to obtain component B modified anti-skid sand;
[0065] S3. Preparation of anti-skid composite layer for ro-ro ramp: Take 40 parts of diphenylmethane diisocyanate as curing agent, mix 100 parts of component A polyol prepared in S1 and 40 parts of curing agent, according to 2kg / m 2 Pour it on the surface of the steel plate coated with anti-corrosion primer and apply it evenly with a scraper at a rate of 8kg / m 2 An excess amount of modified anti-skid sand of component B was spread, and after curing for 18 hours, the loose anti-skid sand was cleaned to obtain an anti-skid composite layer for the roll-on / roll-off ship ramp.
[0066] Comparative Example 3 Preparation method of anti-skid composite layer for ro-ro ship ramp
[0067] The preparation method of the anti-skid composite layer for the roll-on / roll-off ship ramp provided in this comparative example is basically the same as that in Example 2, except that dopamine-modified polyol is not added and the anti-skid sand is not modified.
[0068] S1. Preparation of component A polyol:
[0069] S11 Preparation of modified epoxy resin polyol: To 65 parts of bisphenol F epoxy resin were added 60 parts of excess oleic acid and mixed, under N2 atmosphere, the temperature was controlled at 100 ° C, and the reaction was catalyzed by 0.4 parts of N, N-dimethylformamide for 5h to obtain a modified epoxy resin polyol;
[0070] S12. Preparation of component A polyol: 20 parts of modified epoxy resin polyol and 50 parts of castor oil derivative polyol were mixed and vacuum dehydrated to remove moisture from the material. Then, 5 parts of flame retardant plasticizer triphenyl phosphate, 0.3 parts of defoamer BYK-077, 3 parts of water removing agent 4A molecular sieve, and 0.2 parts of anti-aging agent were added and mixed evenly. The anti-aging agent was a mixture of 0.1 parts of hindered phenol antioxidant 425 and 0.1 parts of ultraviolet absorber UV-531. The mixture was stirred evenly. Then, 0.7 parts of anti-settling agent BYK-410 and 0.7 parts of thixotropic agent fumed silica were added and dispersed evenly at a shear rate of 2000 r / min to obtain component A polyol.
[0071] S2. Preparation of anti-skid composite layer for ro-ro ramp: Take 40 parts of diphenylmethane diisocyanate as curing agent, mix 100 parts of component A polyol prepared in S1 and 40 parts of curing agent, according to 2kg / m 2 Pour it on the surface of the steel plate coated with anti-corrosion primer and apply it evenly with a scraper at a rate of 8kg / m 2 Spread excess corundum, clean the loose corundum after curing for 18 hours, and obtain the anti-skid composite layer for the roll-on / roll-off ship ramp.
[0072] Test Case
[0073] The present application conducted an anti-skid performance test on the anti-skid composite layer of the roll-on / roll-off ship ramp prepared in Examples 1-3 and Comparative Examples 1-3, and the test results are shown in Table 1.
[0074] Table 1 Performance test of the anti-skid composite layer for the ro-ro ramp prepared in Examples 1-3 and Comparative Examples 1-3
[0075]
[0076] The accelerated loading test method in Table 1 is to form a 300mm long and 300mm wide roll-on / roll-off ramp anti-skid layer sample. With the help of a full-scale accelerated loading test system (the accelerated loading test instrument uses four 250mm*80mm pneumatic tires to simulate real car tires), the load is 0.7MPa, the speed is 62 cycles / min, the temperature is room temperature, and the number of loading times is 150,000. After the accelerated loading is completed, the pendulum value of the anti-skid layer is tested.
[0077] The component A in the anti-skid composite layer of the roll-on / roll-off ramp of the present invention contains dopamine-modified polyol, modified epoxy resin polyol and vegetable oil polyol. The dopamine-modified polyol contains o-phthalic dihydroxyl groups, which form hydrogen bonds with polar groups (such as metal oxides, hydroxyl groups, etc.) on the surface of the substrate to enhance the bonding strength of the interface. The o-phthalic dihydroxyl groups can also coordinate with metal ions in the substrate to form stable chemical bonds. The benzene rings in dopamine generate intermolecular forces with the polar groups on the surface of the substrate or in the curing agent to enhance adhesion. The high polarity of the epoxy resin makes it have a strong attraction to the metal substrate (such as steel plate), and the adhesion is enhanced by van der Waals forces. The vegetable oil polyol contains multiple hydroxyl groups and can react with the curing agent to form high-strength chemical bonds.
[0078] The anti-skid composite layer of the roll-on / roll-off ship ramp of the present invention contains modified anti-skid sand of component B. The modified anti-skid sand is gravel with a polydopamine coating attached to the surface. The phenolic hydroxyl groups and amino groups in the polydopamine coating can react with the curing agent to form chemical bonds, thereby improving the interfacial bonding strength between the anti-skid sand and the binder.
[0079] As can be seen from Table 1, the anti-skid composite layer for the roll-on / roll-off ramp of Examples 1-3 prepared by the method of the present invention significantly improves the bonding performance, wherein the bonding strength with the steel plate at 25°C is 14.9-15.5 MPa, the swing value before accelerated loading is 78, and the swing value after accelerated loading is 70-72, which is better than the anti-skid effect of Comparative Examples 1-3; and based on the data of Example 2 and Comparative Examples 1-3, it can be seen that the increase in the data of Example 2 relative to Comparative Example 3 is greater than the sum of the increases in the data of Example 2 relative to Comparative Examples 1 and 2, that is, the anti-skid composite layer for the roll-on / roll-off ramp prepared by the method of the present invention has a synergistic effect.
[0080] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some or all of the technical features therein. These modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present invention, and they should all be included in the scope of the claims and description of the present invention.
Claims
1. A method for preparing an anti-skid composite layer for a ro-ro ship ramp, characterized in that: The following steps are involved: S1. Preparation of component A polyol: dopamine-modified polyol, modified epoxy resin polyol, and vegetable oil polyol were mixed after vacuum dehydration to obtain a mixture, a flame retardant plasticizer, a defoaming agent, a water removal agent, and an anti-aging agent were added to the mixture and mixed, and finally an anti-settling agent and a thixotropic agent were added and mixed to obtain component A polyol; S2. Preparation of modified anti-skid sand component B: The gravel was soaked in a dopamine hydrochloride solution and then removed and dried to obtain a modified anti-skid sand; S3. Preparation of an anti-slip composite layer for the roll-on / roll-off ship ramp: Mix the polyol component A and the curing agent prepared in S1, apply the mixture on the surface of the steel plate with an anti-corrosion primer, and then sprinkle the modified anti-slip sand component B prepared in S2. After curing, remove the loose modified anti-slip sand to obtain the anti-slip composite layer for the roll-on / roll-off ship ramp.
2. The preparation method according to claim 1, characterized in that The preparation method of the dopamine-modified polyol in step S1 is as follows: 100-120 parts of maleic anhydride-modified polypropylene glycol, 60-100 parts of N,N'-dicyclohexylcarbodiimide and 40-60 parts of N-hydroxysuccinimide are dissolved in anhydrous ethanol, the pH is adjusted to 4-5, and the reaction is stirred for 5-8 hours; 40-70 parts of dopamine hydrochloride are continuously added, the pH is adjusted to 8-9, and the reaction is stirred under nitrogen protection for 12-24 hours to obtain the dopamine-modified polyol.
3. The preparation method according to claim 1, characterized in that The preparation method of the modified epoxy resin polyol in step S1 is as follows: 30-80 parts of oleic acid are added to 50-80 parts of bisphenol F epoxy resin to obtain an intermediate A; under N2 atmosphere protection, the temperature is 100-110°C, 0.2-0.5 parts of N,N-dimethylformamide are added to the intermediate A and reacted for 4-6 hours to obtain the modified epoxy resin polyol.
4. The preparation method according to claim 1, characterized in that In step S1, the dopamine-modified polyol is 20-40 parts, the modified epoxy resin polyol is 10-30 parts, the vegetable oil polyol is 30-70 parts, the flame retardant plasticizer is 3-8 parts, the defoaming agent is 0.1-0.5 parts, the water removing agent is 1-5 parts, the anti-aging agent is 0.1-0.3 parts, the anti-settling agent is 0.5-1 parts, and the thixotropic agent is 0.5-1 parts.
5. The preparation method according to claim 1, characterized in that The vegetable oil polyol in step S1 is a mixture of one or more of castor oil, castor oil derivative polyol, soybean oil polyol, and palm oil polyol; the flame retardant plasticizer is a mixture of one or more of tris(chloroethyl) phosphate, triphenyl phosphate, dimethyl methylphosphonate, and triethyl phosphate; the defoamer is a mixture of one or more of BYK-070, BYK-077, BYK-085, and BYK-065; the dewatering agent is a mixture of one or more of 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, and 13X molecular sieve; the anti-aging agent The invention is prepared by mixing a hindered phenol antioxidant and an ultraviolet absorber in a mass ratio of 1:1, wherein the hindered phenol antioxidant is a mixture of one or more of hindered phenol antioxidant 2246, hindered phenol antioxidant 425, and hindered phenol antioxidant 1010; the ultraviolet absorber is a mixture of one or more of ultraviolet absorber UV-622, ultraviolet absorber UV-531, and ultraviolet absorber UV-326; the anti-settling agent is a mixture of one or more of BYK-405, BYK-410, and BYK-430; and the thixotropic agent is fumed silica.
6. The preparation method according to claim 1, characterized in that The preparation method of the modified anti-skid sand in step S2 is specifically as follows: placing gravel in a dopamine hydrochloride solution with a concentration of 1-2 mg / ml, soaking for 12-24 hours, and drying to obtain modified anti-skid sand; the gravel is a mixture of one or more of basalt, corundum, and brown corundum.
7. The preparation method according to claim 6, characterized in that The particle size of the crushed stone is 1-5 mm.
8. The preparation method according to claim 7, characterized in that The curing agent in step S3 is diphenylmethane diisocyanate.
9. The preparation method according to claim 8, characterized in that In step S3, the weight ratio of the polyol component A to the curing agent is 100:(30-50), and the amount of the mixture of the polyol component A and the curing agent is 1.5-2.5 kg / m 2 The amount of the modified anti-skid sand of component B is 5-13 kg / m 2 .
10. The anti-skid composite layer for the ramp of a roll-on / roll-off ship prepared by the preparation method according to any one of claims 1 to 9.