A rubber waterproof material for pipeline docking and its preparation method

Abstract

The present invention relates to a rubber waterproof material for pipeline docking and a preparation method thereof, belonging to the technical field of building waterproof materials, and having the characteristics of good stability, strong wear resistance and good waterproof performance. The rubber waterproof material prepared by the present invention mainly consists of three layers, namely an inner sealing ring layer, a high molecular water-absorbing resin layer and an outer protective layer. The inner sealing ring layer mainly ensures that the sealing ring has a dense and uniform appearance and cross-section, without cracks, pores or indentations, and plays a sealing and waterproof function; a high molecular water-absorbing resin layer is added outside the inner sealing ring. The high molecular water-absorbing resin adopts polymers with excellent water absorption performance and their modified polymers, which can expand after encountering water, fill potential pores and further enhance the sealing effect; the outer protective layer uses a weather-resistant material combining organic and inorganic materials, and covers the entire sealing kit by spraying to protect the inner sealing ring and the water-absorbing resin, and increase the stability and waterproofness of the product.

Description

Technical Field

[0001] The present invention relates to the technical field of building waterproof materials and is used for underground engineering construction. Specifically, it relates to a rubber waterproof material for pipeline docking - a water - swelling screw - hole sealing ring. Background Art

[0002] With the progress of technology and the enhancement of people's environmental protection awareness, people are paying more and more attention to the safety and quality of buildings. Waterproof materials are essential materials in the waterproof project that protects the safety and service life of buildings, and building waterproof materials have become the focus of research.

[0003] In the field of waterproof materials, the most widely used are roofs, vertical walls, kitchens and bathrooms. The requirements for waterproof products in such buildings are relatively low, and general products can meet them. However, for waterproof materials in underground engineering, the waterproof performance of existing waterproof materials still needs to be further improved. Existing waterproof materials are prone to problems such as poor mechanical properties, easy aging under the influence of the external environment, and poor anti - corrosion and aging resistance, which limit their further popularization and application.

[0004] In view of this, there is an urgent need for a rubber waterproof material with properties such as aging resistance, corrosion resistance and wear resistance for underground engineering pipeline docking construction. Summary of the Invention

[0005] Regarding the technical problems existing in the prior art, the present invention provides a rubber waterproof material for underground engineering pipeline docking construction. Such materials are mainly composed of an inner sealing ring layer, a high - molecular water - absorbent resin layer and an outer protective layer. They have better aging resistance, temperature resistance, corrosion resistance, good wear resistance, can absorb water and expand to improve sealing performance, have excellent waterproof effect and can be recycled.

[0006] The present invention can be realized through the following technical solutions:

[0007] A rubber waterproof material for pipeline docking, the rubber waterproof material is mainly composed of an inner sealing ring layer, a high - molecular water - absorbent resin layer and an outer protective layer, wherein,

[0008] The inner sealing ring layer is composed of the following raw materials in parts by weight: 30 - 50 parts by weight of water - soluble modified polyurethane prepolymer, 20 - 30 parts by weight of silicone rubber, 10 - 15 parts by weight of polyimide, 1 - 3 parts by weight of surfactant and 1 - 3 parts by weight of defoamer.

[0009] In particular, the defoamer includes at least one of mineral oil, inorganic hydrophobic particles, vegetable oil, fatty acid, and glycerol. The surfactant includes at least one of sodium dodecyl sulfonate, cetyl trimethyl ammonium bromide, polyethylene glycol, glycerol fatty acid ester, fatty acid ester, and fatty alcohol polyoxyethylene ether. Further, a fatty acid is selected as the defoamer and a fatty acid ester is selected as the surfactant. Fatty acid is a natural substance that does not harm the human body and the environment, and has strong adaptability and fast defoaming speed. The combination of fatty acid and surfactant can rapidly reduce the surface tension of the liquid when added to the preparation of waterborne polyurethane. Under the synergistic effect of the two, the prepared materials are more evenly mixed, thereby improving the strength and stability of the material properties.

[0010] The preparation method of the water-soluble modified polyurethane prepolymer includes the following steps:

[0011] Step 1: Weigh 5-10 parts by weight of polyether diol and 10-15 parts by weight of 2,4-toluene diisocyanate and add them to a flask equipped with a stirring device and a thermometer. React at 50-70 °C for 2-3 h, add 10-20 parts by weight of an acetone solution of trimethylolpropane and 1-3 parts by weight of a chain extender, and stir and react for 30-50 min to obtain a water-soluble polyurethane prepolymer.

[0012] Step 2: Weigh 5-10 parts by weight of glass fiber, soak it in an ethanol solution containing 5% hydrochloric acid, stir evenly, and ultrasonicate for 20-30 min to obtain a modified glass fiber solution.

[0013] Step 3: Add the modified glass fiber solution to the water-soluble polyurethane prepolymer, add 1-3 parts by weight of an ethanol solution of surfactant, heat at 80-90 °C, ultrasonically stir for 30-40 min, and filter to obtain a water-soluble modified polyurethane prepolymer.

[0014] In particular, the chain extender includes at least one of ethylene glycol, diamine, and triethylamine. Further, ethylene glycol is selected as the chain extender. Ethylene glycol can react with 2,4-toluene diisocyanate to form a polyurethane with terminal hydroxyl groups. As a molecular chain, ethylene glycol increases the reaction molecular chain and thus increases the molecular weight, thereby enhancing the thermal stability and wear resistance of the material.

[0015] Silicone rubber and polyimide are added to the inner sealing ring layer. Both have high heat resistance and chemical corrosion resistance, which can prevent the corrosion of chemical substances during the material preparation process and cause deformation and damage to the material. Moreover, both have good resilience and have a good waterproof effect during the water absorption and swelling process of the material. The modified water-soluble polyurethane prepolymer is modified with glass fiber on the surface of the polyurethane. The combination of their excellent properties can significantly improve the strength, wear resistance and heat resistance of the material. Under the synergistic effect of the surfactant and the defoaming agent, the water-soluble modified polyurethane prepolymer is uniformly mixed with silicone rubber and polyimide, and the components interact synergistically with each other, making the prepared material more stable and wear-resistant. The waterproof performance of the material obtained after high-temperature curing is further improved.

[0016] The high molecular weight water-absorbing resin layer is composed of the following raw materials in parts by weight: 30-40 parts by weight of modified polyacrylamide, 30-40 parts by weight of acrylate grafted polyvinyl alcohol copolymer, 20-30 parts by weight of sodium polyacrylate, 10-15 parts by weight of polyethylene, 5-10 parts by weight of sepiolite, 5-10 parts by weight of wood cellulose, 0.5-3 parts by weight of plasticizer, 0.5-3 parts by weight of emulsifier, 1-3 parts by weight of dispersant, 0.5-2 parts by weight of leveling agent and 30-40 parts by weight of water.

[0017] Particularly, the plasticizer includes at least one of dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, oxalate and azelate. Further, the plasticizer is preferably dimethyl phthalate. As an excellent and environmentally friendly plasticizer, dimethyl phthalate forms a strong intermolecular force with resins and rubbers, improving the compatibility between resins. Moreover, dimethyl phthalate has good viscosity and film-forming properties, which can make the materials adhere better to each other, and then form a dense film on the surface of the material, overall improving the stability and waterproof performance of the material.

[0018] Particularly, the emulsifier includes at least one of gum arabic, sodium alkylbenzene sulfonate, polyvinylpyrrolidone, sodium alkyl alcohol polyoxyethylene sulfate and ammonium alkyl alcohol polyoxyethylene sulfate. Further, the emulsifier is preferably polyvinylpyrrolidone. Polyvinylpyrrolidone has good compatibility, emulsification stability and suspension stability. Adding polyvinylpyrrolidone as the emulsifier for the reaction between resins can not only promote the dissolution and stability between resin molecules, but also increase the viscosity of the material, forming a uniform protective film on the surface of the material prepared from the resin, preventing the penetration of moisture and air, and protecting the stability of the internal material properties. Compared with other emulsifiers, polyvinylpyrrolidone also has low toxicity and no irritation, and has a good protective effect on the human body and the environment during use.

[0019] In particular, the dispersant includes at least one of sodium tripolyphosphate, triethylhexyl phosphate, sodium dodecyl sulfate, methyl pentanol, cellulose derivatives, polyacrylamide, and fatty acid polyethylene glycol ester. Further, the dispersant is preferably sodium dodecyl sulfate. Sodium dodecyl sulfate has good surface activity and can effectively reduce the surface tension of the dispersion system in the mixed resin containing the high molecular polymer and inorganic filler, promoting the uniform mixing of the organic and inorganic fillers, making the mixing of the resin and the filler more uniform in the material preparation, and thus improving the stability of the material. Moreover, sodium dodecyl sulfate is inexpensive, non-irritating and easy to operate, having good economic benefits.

[0020] In particular, the leveling agent includes at least one of silicone leveling agents, polyether leveling agents, polydimethylsiloxane leveling agents, and acrylate leveling agents. Further, the leveling agent is preferably polyether silicone in the polyether leveling agents. Polyether silicone has excellent characteristics of low surface tension, high compatibility and diffusibility. It can reduce the surface tension of each component in the resin molecule, promote the compatibility between components, and has defoaming and dispersing properties. It can effectively eliminate the bubbles and particles in the material, providing a uniform and flat surface effect. Moreover, polysiloxane can also form a dense film on the material surface to protect the material from external influences, making the material have a more lasting leveling effect and not producing harmful substances during use, meeting the concept of green environmental protection.

[0021] Among them, the preparation method of the modified polyacrylamide includes the following steps:

[0022] Step a: Weigh 1-5 parts by weight of organic bentonite, add an ethanol dispersion solution of coupling agent KH-550, stir evenly, and stir and react at 60-70 °C for 10-15 min to obtain a modified organic bentonite solution;

[0023] Step b: Weigh 10-15 parts by weight of polyacrylamide, add it to an aqueous solution, and stir until a uniform emulsion state is formed to obtain a polyacrylamide emulsion;

[0024] Step c: Add the modified organic bentonite solution to the polyacrylamide emulsion, add and stir at the same time, add 0.5-3 parts by weight of initiator benzoyl peroxide, heat to 80-100 °C under the stirring state with a rotation speed of 300-500 r / min, stir and react for 30-40 min. After the stirring reaction is completed, centrifuge, filter, and dry to obtain the modified polyacrylamide.

[0025] Furthermore, the surface of bentonite modified by coupling agent KH-550 has microporous and mesoporous structures, with higher adsorption performance. Using the modified bentonite to modify polyacrylamide, the two are combined through chemical bond action, with better adhesiveness and adsorption, the adsorption swelling index increases rapidly, and it has cyclic reversibility, improving the waterproof effect of the material and reducing the reaction cost.

[0026] Among them, the preparation method of the methyl acrylate grafted polyvinyl alcohol copolymer includes the following steps:

[0027] (1) By weight, weigh 5-10 parts by weight of methyl acrylate and dissolve it in 20-30 parts by weight of ethanol solution, heat to 70-80 °C, stir and react for 10-15 min to prepare an ethanol solution of methyl acrylate for use;

[0028] (2) By weight, weigh 5-10 parts by weight of polyvinyl alcohol and dissolve it in 10-15 parts by weight of aqueous solution, heat to 90-110 °C, stir and react for 20-30 min to prepare a polyvinyl alcohol solution for use;

[0029] (3) Add the polyvinyl alcohol solution to the ethanol solution of methyl acrylate, stir while adding, add 1-3 parts by weight of initiator azobisisobutyronitrile, raise the temperature to 80-90 °C, keep stirring and reacting for 2-3 h. After the reaction is completed, filter, wash and dry the reaction to obtain methyl acrylate grafted polyvinyl alcohol.

[0030] Furthermore, the alcoholic hydroxyl groups existing in the polyvinyl alcohol molecular chain make it have good water solubility, which is beneficial to form a polymer solution by dispersing in water. The introduction of methyl acrylate increases the polarity of polyvinyl alcohol, making it easier to interact with water molecules, further improving its water solubility, film-forming performance and stability. Since both have good water solubility, a resin with high water absorption performance is prepared by graft polymerization, with good water retention performance, and the polymerization method is simple and controllable.

[0031] Furthermore, the superabsorbent polymer layer is combined with modified polyacrylamide with good water absorption performance, methyl acrylate grafted polyvinyl alcohol copolymer, sodium polyacrylate and polyethylene, and inorganic materials sepiolite and wood cellulose with a relatively large water absorption expansion coefficient are added as functional fillers. Under the synergistic action of other functional additives, the water absorption performance of the material is greatly improved, and the water absorption has cyclic reversibility, improving the use efficiency.

[0032] The outer protective layer mainly consists of the following raw materials by weight: 30-50 parts by weight of polytetrafluoroethylene, 20-30 parts by weight of polypropylene, 20-30 parts by weight of chloroprene rubber, 1-5 parts by weight of curing agent, 1-3 parts by weight of antioxidant and 1-5 parts by weight of wear-resistant filler.

[0033] In particular, the antioxidant includes at least one of aluminum hydroxide, silicon carbide, 2,6-di-tert-butyl-p-cresol, tert-butyl-p-hydroxyanisole, vitamin E, N-phenyl-α-naphthylamine, and pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. Preferably, the safe and non-toxic pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] is used as the antioxidant. This compound has good chemical stability and antioxidant properties, and has good compatibility and mixing properties with rubber, resin, etc., and can maintain the stability of the material properties at high temperatures.

[0034] In particular, the wear-resistant filler includes at least one of molybdenum disulfide, graphite, glass fiber, carbon fiber composite, polyimide, and polytetrafluoroethylene. Preferably, it is graphite. Graphite belongs to common non-metallic mineral fillers and has excellent wear resistance and heat resistance. After graphite is combined with resin, it can enhance the strength and rigidity between resins, improve the overall strength and wear resistance of the material, and extend the service life of the material.

[0035] Furthermore, the outer protective layer of the waterproof material uses chemically stable and wear-resistant polytetrafluoroethylene, polypropylene, and chloroprene rubber as the main materials, adds wear-resistant fillers and antioxidants as functional fillers to further improve the stability, strength, and wear resistance of the material, and selects amino resin with high reaction activity and fast curing speed as the curing agent, which increases the reaction speed between resins, completes the curing process in a short time, improves the reaction efficiency, and the amino resin can undergo cross-linking reactions with polymers to form a three-dimensional cross-linked structure, thereby improving the comprehensive performance of the material.

[0036] A preparation method of a rubber waterproof material for pipeline docking, the preparation method of the rubber waterproof material includes the following steps:

[0037] S1. By weight, the components of the inner sealing ring layer and the superabsorbent polymer layer are mixed and stirred evenly, and the mixed material is added to a mixer for mixing. It is mixed at 200-250 °C for 30-50 min, and then extruded through a twin-screw extruder, pressed into shape, and cooled to obtain a multifunctional waterproof layer;

[0038] S2. The components of the outer protective layer are mixed and stirred evenly, added to a mixer, mixed at 200-220 °C for 20-30 min, and after mixing, it is placed in a spraying device, and the spraying device is used to spray on the pre-treated multifunctional waterproof layer. The spraying thickness is 0.5-1 mm, and after spraying, it is heated and cured to obtain a rubber waterproof material.

[0039] Compared with the prior art, the present invention has the following beneficial effects:

[0040] The rubber waterproof material prepared by the present invention mainly consists of a three-layer structure, namely an inner sealing ring layer, a polymer water-absorbing resin layer and an outer protective layer. The inner sealing ring layer mainly ensures that the sealing ring has a dense and uniform appearance and cross-section, without cracks, pores or dents, and plays a sealing and waterproofing function; a polymer water-absorbing resin layer is added to the outside of the inner sealing ring to increase the waterproof performance. The polymer water-absorbing resin adopts a polymer with excellent water absorption performance and its modified polymer, which can swell after contacting water, fill potential pores and further enhance the sealing effect; the outer protective layer uses a weather-resistant material combined with organic and inorganic materials, and covers the entire sealing kit by spraying, protects the inner sealing ring and the water-absorbing resin, and increases the stability and durability of the product.

[0041] The present invention adopts a multi-layer structure design, which makes the product perform better in terms of water expansion and sealing, ensuring good waterproof and water-stopping effects of the joint; the polymer water-absorbent resin layer can fill small pores and reduce the possibility of leakage, thereby improving the reliability of the system. Under the protection of the multi-layer material, it not only relies on the inner sealing ring, but also has the synergistic effect of the water-absorbent resin layer and the outer protective layer, thereby enhancing the durability and waterproof performance of the product. DETAILED DESCRIPTION

[0042] The present invention proposes a rubber waterproof material for underground engineering pipeline docking construction. This material has good comprehensive performance and can absorb water and swell to improve sealing. It has excellent waterproof effect and can be recycled. In order to further explain the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation methods, features and effects of the present invention are described in detail below in combination with the embodiments. The materials and reagents used in the present invention can be purchased on the market or synthesized.

[0043] Example 1

[0044] A rubber waterproof material for pipe jointing, the rubber waterproof material comprises: an inner sealing ring layer, a polymer water-absorbing resin layer and an outer protective layer, wherein:

[0045] The inner sealing ring layer is composed of the following raw materials in parts by weight: 30 parts by weight of water-soluble modified polyurethane prepolymer, 20 parts by weight of silicone rubber, 10 parts by weight of polyimide, 1 part by weight of fatty acid ester and 1 part by weight of fatty acid;

[0046] Wherein, the preparation method of the water-soluble modified polyurethane prepolymer in the inner sealing ring layer comprises the following steps:

[0047] Step 1: Weigh 5 parts by weight of polyether diol and 15 parts by weight of 2,4-toluene diisocyanate and add them to a flask equipped with a stirring device and a thermometer. React at 70 °C for 2 h, then add 15 parts by weight of an acetone solution of trimethylolpropane and 1 part by weight of chain extender ethylene glycol, and stir and react for 35 min to obtain a water-soluble polyurethane prepolymer;

[0048] Step 2: Weigh 5 parts by weight of glass fiber, soak it in an ethanol solution containing 5% hydrochloric acid, stir evenly, and ultrasonicate for 20 min to obtain a modified glass fiber solution;

[0049] Step 3: Add the modified glass fiber solution to the water-soluble polyurethane prepolymer, add 1 part by weight of an ethanol solution of sodium dodecyl sulfate, heat at 90 °C, ultrasonically stir for 40 min, and filter to obtain a water-soluble modified polyurethane prepolymer.

[0050] The superabsorbent polymer layer is composed of the following raw materials in parts by weight: 30 parts by weight of modified polyacrylamide, 30 parts by weight of acrylate grafted polyvinyl alcohol copolymer, 20 parts by weight of sodium polyacrylate, 10 parts by weight of polyethylene, 5 parts by weight of sepiolite, 5 parts by weight of wood cellulose, 0.5 part by weight of dimethyl phthalate, 1 part by weight of polyvinylpyrrolidone, 1 part by weight of sodium dodecyl sulfate, 0.5 part by weight of polyether silicone and 35 parts by weight of water;

[0051] The preparation method of the modified polyacrylamide in the superabsorbent polymer layer includes the following steps:

[0052] Step a: Weigh 5 parts by weight of organic bentonite, add an ethanol dispersion solution of coupling agent KH-550, stir evenly, and stir and react at 70 °C for 15 min to obtain a modified organic bentonite solution;

[0053] Step b: Weigh 10 parts by weight of polyacrylamide, add it to an aqueous solution, and stir until a uniform emulsion state is formed to obtain a polyacrylamide emulsion;

[0054] Step c: Add the modified organic bentonite solution to the polyacrylamide emulsion, add and stir while adding 0.5 part by weight of initiator benzoyl peroxide, heat to 100 °C under stirring at a speed of 300 r / min, stir and react for 35 min. After the stirring reaction is completed, centrifuge, filter, and dry to obtain modified polyacrylamide.

[0055] The preparation method of the acrylate grafted polyvinyl alcohol copolymer in the superabsorbent polymer layer includes the following steps:

[0056] (1) Weigh 5 parts by weight of methyl acrylate and dissolve it in 25 parts by weight of ethanol solution. Heat it to 70 °C and stir for 15 min to prepare an ethanol solution of methyl acrylate for later use.

[0057] (2) Weigh 5 parts by weight of polyvinyl alcohol and dissolve it in 15 parts by weight of aqueous solution. Heat it to 105 °C and stir for 25 min to prepare a polyvinyl alcohol solution for later use.

[0058] (3) Add the polyvinyl alcohol solution to the ethanol solution of methyl acrylate while stirring. Add 1 part by weight of initiator azobisisobutyronitrile, raise the temperature to 80 °C, and keep stirring for 2 h. After the reaction is completed, filter, wash, and dry the reaction product to obtain methyl acrylate grafted polyvinyl alcohol.

[0059] The outer protective layer mainly consists of the following raw materials in parts by weight: 30 parts by weight of polytetrafluoroethylene, 20 parts by weight of polypropylene, 20 parts by weight of chloroprene rubber, 1 part by weight of curing agent amino resin, 1 part by weight of pentaerythritol tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], and 2 parts by weight of graphite.

[0060] A preparation method of a rubber waterproof material for pipeline docking, the preparation method of the rubber waterproof material includes the following steps:

[0061] S1. By weight, mix the components of the inner sealing ring layer and the superabsorbent polymer layer proportionally and stir evenly. Add the mixed material to a mixer for mixing. Mix at 250 °C for 30 min, then extrude through a twin-screw extruder, press into shape, and cool to obtain a multi-functional waterproof layer.

[0062] S2. Mix the components of the outer protective layer evenly, add them to a mixer, mix at 200 °C for 30 min. After mixing, place it in a spraying device and use the spraying device to spray on the pre-treated multi-functional waterproof layer. The spraying thickness is 0.5 mm. After spraying, heat and cure to obtain the rubber waterproof material.

[0063] Example 2

[0064] A rubber waterproof material for pipeline docking, the rubber waterproof material includes: an inner sealing ring layer, a superabsorbent polymer layer, and an outer protective layer, where,

[0065] The inner sealing ring layer consists of the following raw materials in parts by weight: 40 parts by weight of water-soluble modified polyurethane prepolymer, 25 parts by weight of silicone rubber, 13 parts by weight of polyimide, 1 part by weight of fatty acid ester, and 1 part by weight of fatty acid.

[0066] Among them, the preparation method of the water-soluble modified polyurethane prepolymer in the inner sealing ring layer includes the following steps:

[0067] Step 1: Weigh 5 parts by weight of polyether diol and 15 parts by weight of 2,4-toluene diisocyanate and add them to a flask equipped with a stirring device and a thermometer. React at 70 °C for 2 h, add 15 parts by weight of an acetone solution of trimethylolpropane and 1 part by weight of chain extender ethylene glycol, and stir and react for 35 min to obtain a water-soluble polyurethane prepolymer.

[0068] Step 2: Weigh 5 parts by weight of glass fiber, soak it in an ethanol solution containing 5% hydrochloric acid, stir evenly, and ultrasonicate for 20 min to obtain a modified glass fiber solution.

[0069] Step 3: Add the modified glass fiber solution to the water-soluble polyurethane prepolymer, add 1 part by weight of an ethanol solution of sodium dodecyl sulfate, heat at 90 °C, ultrasonically stir for 40 min, and filter to obtain a water-soluble modified polyurethane prepolymer.

[0070] The high molecular water-absorbing resin layer is composed of the following raw materials in parts by weight: 35 parts by weight of modified polyacrylamide, 35 parts by weight of acrylate grafted polyvinyl alcohol copolymer, 25 parts by weight of sodium polyacrylate, 12 parts by weight of polyethylene, 5 parts by weight of sepiolite, 5 parts by weight of wood cellulose, 0.5 part by weight of dimethyl phthalate, 0.5 part by weight of polyvinylpyrrolidone, 1 part by weight of sodium dodecyl sulfate, 0.5 part by weight of polyether siloxane, and 35 parts by weight of water;

[0071] The preparation method of the modified polyacrylamide in the high molecular water-absorbing resin layer includes the following steps:

[0072] Step a: Weigh 5 parts by weight of organic bentonite, add an ethanol dispersion solution of coupling agent KH-550, stir evenly, and stir and react at 70 °C for 15 min to obtain a modified organic bentonite solution.

[0073] Step b: Weigh 10 parts by weight of polyacrylamide, add it to an aqueous solution, and stir until a uniform emulsion state is formed to obtain a polyacrylamide emulsion.

[0074] Step c: Add the modified organic bentonite solution to the polyacrylamide emulsion, add and stir while adding 0.5 part by weight of initiator benzoyl peroxide, heat to 100 °C under stirring at a speed of 300 r / min, stir and react for 35 min. After the stirring reaction is completed, centrifuge, filter, and dry to obtain modified polyacrylamide.

[0075] The preparation method of the acrylate grafted polyvinyl alcohol copolymer in the high molecular water-absorbing resin layer includes the following steps:

[0076] (1) Weigh 5 parts by weight of methyl acrylate and dissolve it in 25 parts by weight of ethanol solution. Heat it to 70 °C and stir for 15 min to prepare an ethanol solution of methyl acrylate for later use.

[0077] (2) Weigh 5 parts by weight of polyvinyl alcohol and dissolve it in 15 parts by weight of aqueous solution. Heat it to 105 °C and stir for 25 min to prepare a polyvinyl alcohol solution for later use.

[0078] (3) Add the polyvinyl alcohol solution to the ethanol solution of methyl acrylate while stirring. Add 1 part by weight of initiator azobisisobutyronitrile, raise the temperature to 80 °C, and keep stirring for 2 h. After the reaction ends, filter, wash, and dry the reaction to obtain methyl acrylate grafted polyvinyl alcohol.

[0079] The outer protective layer is mainly composed of the following raw materials in parts by weight: 40 parts by weight of polytetrafluoroethylene, 25 parts by weight of polypropylene, 25 parts by weight of chloroprene rubber, 1 part by weight of curing agent amino resin, 1 part by weight of pentaerythritol tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], and 2 parts by weight of graphite.

[0080] A preparation method of a rubber waterproof material for pipeline docking, the preparation method of the rubber waterproof material includes the following steps:

[0081] S1. By weight, mix the components of the inner sealing ring layer and the superabsorbent polymer layer proportionally and stir evenly. Add the mixed material to a mixer for mixing. Mix at 250 °C for 30 min, then extrude through a twin-screw extruder, press into shape, and cool to obtain a multi-functional waterproof layer.

[0082] S2. Mix the components of the outer protective layer evenly, add them to a mixer, mix at 200 °C for 30 min, place the mixture in a spraying device, and use the spraying device to spray on the pre-treated multi-functional waterproof layer. The spraying thickness is 0.5 mm. After spraying, heat and cure to obtain the rubber waterproof material.

[0083] Example 3

[0084] A rubber waterproof material for pipeline docking, the rubber waterproof material includes: an inner sealing ring layer, a superabsorbent polymer layer, and an outer protective layer, where

[0085] The inner sealing ring layer is composed of the following raw materials in parts by weight: 50 parts by weight of water-soluble modified polyurethane prepolymer, 30 parts by weight of silicone rubber, 15 parts by weight of polyimide, 1 part by weight of fatty acid ester, and 1 part by weight of fatty acid.

[0086] Among them, the preparation method of the water-soluble modified polyurethane prepolymer in the inner sealing ring layer includes the following steps:

[0087] Step 1: Weigh 5 parts by weight of polyether diol and 15 parts by weight of 2,4-toluene diisocyanate and add them to a flask equipped with a stirring device and a thermometer. React at 70 °C for 2 h, then add 15 parts by weight of an acetone solution of trimethylolpropane and 1 part by weight of chain extender ethylene glycol, and stir and react for 35 min to obtain a water-soluble polyurethane prepolymer;

[0088] Step 2: Weigh 5 parts by weight of glass fiber, soak it in an ethanol solution containing 5% hydrochloric acid, stir evenly, and ultrasonicate for 20 min to obtain a modified glass fiber solution;

[0089] Step 3: Add the modified glass fiber solution to the water-soluble polyurethane prepolymer, add 1 - 3 parts by weight of an ethanol solution of sodium dodecyl sulfate, heat at 90 °C, ultrasonically stir for 40 min, and filter to obtain a water-soluble modified polyurethane prepolymer.

[0090] The high molecular water-absorbing resin layer is composed of the following raw materials in parts by weight: 40 parts by weight of modified polyacrylamide, 40 parts by weight of acrylate grafted polyvinyl alcohol copolymer, 30 parts by weight of sodium polyacrylate, 15 parts by weight of polyethylene, 5 parts by weight of sepiolite, 5 parts by weight of wood cellulose, 0.5 part by weight of dimethyl phthalate, 0.5 part by weight of polyvinylpyrrolidone, 1 part by weight of sodium dodecyl sulfate, 0.5 part by weight of polyether siloxane, and 40 parts by weight of water;

[0091] The preparation method of the modified polyacrylamide in the high molecular water-absorbing resin layer includes the following steps:

[0092] Step a: Weigh 5 parts by weight of organic bentonite, add an ethanol dispersion solution of coupling agent KH-550, stir evenly, and stir and react at 70 °C for 15 min to obtain a modified organic bentonite solution;

[0093] Step b: Weigh 10 parts by weight of polyacrylamide, add it to an aqueous solution, and stir until a uniform emulsion state is formed to obtain a polyacrylamide emulsion;

[0094] Step c: Add the modified organic bentonite solution to the polyacrylamide emulsion, add and stir while adding 0.5 part by weight of initiator benzoyl peroxide, heat to 100 °C under stirring at a speed of 300 r / min, stir and react for 35 min. After the stirring reaction ends, centrifuge, filter, and dry to obtain modified polyacrylamide.

[0095] The preparation method of the acrylate grafted polyvinyl alcohol copolymer in the high molecular water-absorbing resin layer includes the following steps:

[0096] (1) Weigh 5 parts by weight of methyl acrylate and dissolve it in 25 parts by weight of ethanol solution. Heat it to 70 °C and stir for 15 min to prepare an ethanol solution of methyl acrylate for later use.

[0097] (2) Weigh 5 parts by weight of polyvinyl alcohol and dissolve it in 15 parts by weight of aqueous solution. Heat it to 105 °C and stir for 25 min to prepare a polyvinyl alcohol solution for later use.

[0098] (3) Add the polyvinyl alcohol solution to the ethanol solution of methyl acrylate while stirring. Add 1 part by weight of initiator azobisisobutyronitrile, raise the temperature to 80 °C, and keep stirring for 2 h. After the reaction is completed, filter, wash, and dry the reaction to obtain methyl acrylate grafted polyvinyl alcohol.

[0099] The outer protective layer mainly consists of the following raw materials in parts by weight: 50 parts by weight of polytetrafluoroethylene, 30 parts by weight of polypropylene, 30 parts by weight of chloroprene rubber, 1 part by weight of curing agent amino resin, 1 part by weight of pentaerythritol tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], and 2 parts by weight of graphite.

[0100] A preparation method of a rubber waterproof material for pipeline docking, the preparation method of the rubber waterproof material includes the following steps:

[0101] S1. By weight, mix the components of the inner sealing ring layer and the superabsorbent polymer layer in proportion and stir evenly. Add the mixed material to a mixer for mixing. Mix at 250 °C for 30 min, then extrude through a twin-screw extruder, press into shape, and cool to obtain a multifunctional waterproof layer.

[0102] S2. Mix the components of the outer protective layer evenly, add them to a mixer, mix at 200 °C for 30 min, place the mixture in a spraying device after mixing, and use the spraying device to spray on the pre-treated multifunctional waterproof layer. The spraying thickness is 0.5 mm, and heat curing is carried out after spraying to obtain the rubber waterproof material.

[0103] Comparative Example 1

[0104] Compared with Example 1, the difference in Comparative Example 1 is that the water-soluble modified polyurethane prepolymer in the inner sealing ring layer of Comparative Example 1 is replaced with a water-soluble polyurethane prepolymer.

[0105] Comparative Example 2

[0106] Compared with Example 1, the difference in Comparative Example 2 is that the water-soluble modified polyurethane prepolymer in the inner sealing ring layer of Comparative Example 2 is replaced with modified glass fiber.

[0107] Comparative Example 3

[0108] Compared with Example 1, the difference in Comparative Example 3 is that the water-soluble modified polyurethane prepolymer in the inner sealing ring layer in Comparative Example 3 is replaced with glass fiber.

[0109] Comparative Example 4

[0110] Compared with Example 1, the difference in Comparative Example 4 is that the modified polyacrylamide in the superabsorbent polymer layer in Comparative Example 4 is replaced with polyacrylamide.

[0111] Comparative Example 5

[0112] Compared with Example 1, the difference in Comparative Example 5 is that the modified polyacrylamide in the superabsorbent polymer layer in Comparative Example 5 is replaced with modified organic bentonite.

[0113] Comparative Example 6

[0114] Compared with Example 1, the difference in Comparative Example 6 is that the modified polyacrylamide in the superabsorbent polymer layer in Comparative Example 6 is replaced with organic bentonite.

[0115] Comparative Example 7

[0116] Compared with Example 1, the difference in Comparative Example 7 is that the methyl acrylate grafted polyvinyl alcohol copolymer in the superabsorbent polymer layer in Comparative Example 7 is replaced with methyl acrylate.

[0117] Comparative Example 8

[0118] Compared with Example 1, the difference in Comparative Example 8 is that the methyl acrylate grafted polyvinyl alcohol copolymer in the superabsorbent polymer layer in Comparative Example 8 is replaced with polyvinyl alcohol.

[0119] Comparative Example 9

[0120] Compared with Example 1, the difference in Comparative Example 9 is that in the preparation of the rubber waterproof material in Comparative Example 9, the layered preparation is not carried out, and the components of the inner sealing ring layer, the superabsorbent polymer layer and the outer protective layer are directly put into a mixer for mixing and extrusion to prepare the rubber waterproof material.

[0121] Relevant performance tests were carried out on the rubber waterproof materials prepared in all examples and comparative examples, and the test results are recorded in Table 1 below. The tensile property test was carried out according to the ISO 37-2017 standard of "Vulcanized or thermoplastic rubber - Determination of tensile stress-strain properties", the compressibility test was carried out according to the ASTM D1895-96(2010) standard, the aging resistance test was carried out according to the GB / T 3512-2014 standard, and the volume expansion rate test was carried out according to the GB / T 18173.3-2014 "Polymer waterproof materials - Part 3: Water-swelling rubber" standard.

[0122] Table 1 Performance test results of the rubber waterproof materials prepared in all the examples and comparative examples

[0123]

[0124] Through the data analysis of the above table, Examples 1-3 are respectively the increases in the component contents of the rubber material preparation. It can be known by comparison that too much or too little component content will affect the comprehensive performance of the rubber material. In Comparative Examples 1-8, when the preparation components of the inner sealing ring layer and the superabsorbent polymer layer are changed, the performance of the waterproof material is significantly reduced. In Comparative Example 9, when the preparation process of the material is changed, its comprehensive performance is reduced, but the impact is not significant. Thus, it shows that in the preparation process of the waterproof material, the choice of materials determines the performance of the materials.

[0125] The above-described examples are only used to illustrate the technical solutions of the present invention and are not intended to limit them; although the present invention has been described in detail with reference to the foregoing examples, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing examples or perform equivalent replacements on some of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention and should all be included within the protection scope of the present invention.

Claims

1. A rubber waterproof material for pipe docking, characterized in that, The rubber waterproof material includes: an inner sealing ring layer, a high molecular water-absorbing resin layer, and an outer protective layer, where The inner sealing ring layer is composed of the following raw materials by weight: 30-50 parts by weight of water-soluble modified polyurethane prepolymer, 20-30 parts by weight of silicone rubber, 10-15 parts by weight of polyimide, 1-3 parts by weight of surfactant, and 1-3 parts by weight of defoamer; The high molecular water-absorbing resin layer is composed of the following raw materials by weight: 30-40 parts by weight of modified polyacrylamide, 30-40 parts by weight of acrylate grafted polyvinyl alcohol copolymer, 20-30 parts by weight of sodium polyacrylate, 10-15 parts by weight of polyethylene, 5-10 parts by weight of sepiolite, 5-10 parts by weight of wood cellulose, 0.5-3 parts by weight of plasticizer, 0.5-3 parts by weight of emulsifier, 1-3 parts by weight of dispersant, 0.5-2 parts by weight of leveling agent, and 30-40 parts by weight of water; The outer protective layer is mainly composed of the following raw materials by weight: 30-50 parts by weight of polytetrafluoroethylene, 20-30 parts by weight of polypropylene, 20-30 parts by weight of chloroprene rubber, 1-5 parts by weight of curing agent, 1-3 parts by weight of antioxidant, and 1-5 parts by weight of wear-resistant filler; The preparation method of the water-soluble modified polyurethane prepolymer in the inner sealing ring layer includes the following steps: Step 1: Weigh 5-10 parts by weight of polyether diol and 10-15 parts by weight of 2,4-toluene diisocyanate and add them to a flask equipped with a stirring device and a thermometer. React at 50-70 °C for 2-3 h, add 10-20 parts by weight of an acetone solution of trimethylolpropane and 1-3 parts by weight of chain extender, and stir and react for 30-50 min to obtain a water-soluble polyurethane prepolymer; Step 2: Weigh 5-10 parts by weight of glass fiber, soak it in an ethanol solution containing 5% hydrochloric acid, stir evenly, and ultrasonicate for 20-30 min to obtain a modified glass fiber solution; Step 3: Add the modified glass fiber solution to the water-soluble polyurethane prepolymer, add 1-3 parts by weight of an ethanol solution of surfactant, heat at 80-90 °C, ultrasonically stir for 30-40 min, and filter to obtain a water-soluble modified polyurethane prepolymer; Among them, the preparation method of the modified polyacrylamide in the high molecular water-absorbing resin layer includes the following steps: Step a: Weigh 1-5 parts by weight of organic bentonite, add an ethanol dispersion solution of coupling agent KH-550, stir evenly, and stir and react at 60-70 °C for 10-15 min to obtain a modified organic bentonite solution; Step b: Weigh 10-15 parts by weight of polyacrylamide, add it to an aqueous solution, and stir until a uniform emulsion state is formed to obtain a polyacrylamide emulsion; Step c: Add the modified organic bentonite solution to the polyacrylamide emulsion, stir while adding, add 0.5-3 parts by weight of initiator benzoyl peroxide, heat to 80-100 °C under stirring at a speed of 300-500 r / min, stir and react for 30-40 min. After the stirring reaction is completed, centrifuge, filter, and dry to obtain modified polyacrylamide; Among them, the preparation method of the methyl acrylate grafted polyvinyl alcohol copolymer in the superabsorbent polymer layer comprises the following steps: (1) By weight, weigh 5-10 parts by weight of methyl acrylate and dissolve it in 20-30 parts by weight of ethanol solution, heat to 70-80 °C, and stir and react for 10-15 min to prepare an ethanol solution of methyl acrylate for later use; (2) By weight, weigh 5-10 parts by weight of polyvinyl alcohol and dissolve it in 10-15 parts by weight of aqueous solution, heat to 90-110 °C, and stir and react for 20-30 min to prepare a polyvinyl alcohol solution for later use; (3) Add the polyvinyl alcohol solution to the ethanol solution of methyl acrylate, stir while adding, add 1-3 parts by weight of initiator azobisisobutyronitrile, raise the temperature to 80-90 °C, keep stirring and reacting for 2-3 h. After the reaction ends, filter, wash, and dry the reaction to obtain methyl acrylate grafted polyvinyl alcohol.

2. The rubber waterproof material for pipe docking according to claim 1, characterized in that: The surfactant in the inner sealing ring layer includes at least one of sodium dodecyl sulfonate, cetyl trimethyl ammonium bromide, polyethylene glycol, fatty acid glyceride, fatty acid ester, and fatty alcohol polyoxyethylene ether.

3. The rubber waterproof material for pipe docking according to claim 1, characterized in that: The defoaming agent in the inner sealing ring layer includes at least one of mineral oil, inorganic hydrophobic particles, vegetable oil, fatty acid, and glycerol.

4. The rubber waterproof material for pipe docking according to claim 1, characterized in that: The plasticizer in the superabsorbent polymer layer includes at least one of dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, oxalate ester, and azelate ester; the emulsifier includes at least one of arabic gum, alkylbenzene sulfonate, polyvinylpyrrolidone, sodium alkyl alcohol polyoxyethylene sulfate, and ammonium alkyl alcohol polyoxyethylene sulfate.

5. The rubber waterproof material for pipe docking according to claim 1, characterized in that: The dispersant in the superabsorbent polymer layer includes at least one of sodium tripolyphosphate, triethylhexyl phosphate, sodium dodecyl sulfate, methyl amyl alcohol, cellulose derivative, polyacrylamide, and fatty acid polyethylene glycol ester; the leveling agent includes at least one of silicone leveling agent, polyether leveling agent, polydimethylsiloxane leveling agent, and acrylate leveling agent.

6. The rubber waterproof material for pipe docking according to claim 1, characterized in that: The antioxidant in the outer protective layer includes at least one of aluminum hydroxide, silicon carbide, 2,6-di-tert-butyl-p-cresol, tert-butyl-p-hydroxyanisole, vitamin E, N-phenyl-α-naphthylamine, and pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; the wear-resistant filler includes at least one of molybdenum disulfide, graphite, glass fiber, carbon fiber composite, polyimide, and polytetrafluoroethylene.

7. A preparation method of the rubber waterproof material for pipe docking according to any one of claims 1-6, characterized in that: The preparation method of the rubber waterproof material comprises the following steps: S1. By weight, mix and stir the components of the inner sealing ring layer and the superabsorbent polymer layer in proportion, add the mixed material to a mixer for mixing, mix at 200-250 °C for 30-50 min, then extrude through a twin-screw extruder, press into shape, and cool to obtain a multi-functional waterproof layer; S2. Mix and stir all components of the outer protective layer evenly, add them into a kneader, knead at 200 - 220 °C for 20 - 30 min, place the kneaded mixture in a spraying device after kneading, and use the spraying device to spray on the pre-treated multi-functional waterproof layer. The spraying thickness is 0.5 - 1 mm. After spraying, heat and cure to obtain a waterproof material.

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