Solid fire-retardant buoyancy material with oil flocculation function and preparation method and application thereof

Abstract

The application provides a solid fire-retardant buoyancy material with oil product flocculation and a preparation method and application thereof. The preparation method comprises the following steps: mixing hydroxymethyl cellulose, a binder, ammonium polyphosphate and water to obtain a suspension, mixing the suspension with hollow glass microbeads to obtain hollow glass microbeads coated with ammonium polyphosphate-hydroxymethyl cellulose, mixing the hollow glass microbeads coated with ammonium polyphosphate-hydroxymethyl cellulose with epoxy resin, a diluent, a curing agent and an accelerator and curing and forming to obtain hollow glass microbeads coated with epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose, and reacting the hollow glass microbeads coated with epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose with acrylamide monomers and an initiator to obtain the solid fire-retardant buoyancy material. The solid fire-retardant buoyancy material is prepared by the preparation method. The application also provides application of the solid fire-retardant buoyancy material in inhibiting oil product volatilization. The solid fire-retardant buoyancy material has the advantages of strong oil product volatilization inhibition capacity, superior fire-retardant performance, high mechanical strength, non-toxicity and environmental protection.

Description

Technical Field

[0001] This invention relates to a solid flame-retardant buoyancy material with oil flocculation effect, its preparation method and application, belonging to the field of buoyancy material technology in the petroleum industry. Background Technology

[0002] Petroleum products, especially light fuel oils, contain a large amount of volatile light hydrocarbon components. During production, storage, transportation and application, there are serious evaporation losses, which are related to environmental protection, energy conservation, safety and health issues, and are one of the urgent problems to be solved in this field.

[0003] Compensatory measures after evaporation are complex and require significant investment, making it impractical to promote them across all oil storage and transportation units. To further improve energy conservation and consumption reduction, consumption reduction measures should be controlled at the source of evaporation as much as possible. Factors that reduce evaporation losses include: (1) isolation of the free surface of gasoline evaporation from the gas phase, and (2) the surface area of ​​free gasoline evaporation. Currently, there are many consumption reduction measures adopted in this field, and commonly used methods include: (1) floating roof tanks, (2) oil-resistant lightweight materials, and (3) surface covering films. Among them, floating roof tank covering technology is currently the most commonly used technology for controlling oil evaporation in petroleum and petrochemical enterprises, and it is divided into external floating roof tanks and internal floating roof tanks. Nowadays, floating roof tank technology is very mature, and the consumption reduction results are quite optimistic, but there are many problems that cannot be ignored in terms of its installation, use, maintenance, and safety.

[0004] To address the limitations inherent in floating roof tanks, many experts and scholars have explored surface-floating material covering technology. This involves laying floating materials on the oil surface to reduce the free evaporation surface area, thereby minimizing evaporation loss. Examples of materials used include foam glass, hollow glass, oil-based sealants, fluorosurfactants, smart microspheres, and phenolic resin hollow spheres. The key to using surface covering technology to suppress the evaporation of light oils is increasing the surface coverage rate. Selecting materials with low specific gravity, high coverage, good fluidity, stable chemical properties, and the ability to float on the oil surface for extended periods is crucial for successful implementation.

[0005] However, existing surface floating materials for oil products cannot effectively suppress oil evaporation and cannot meet the requirements for surface floating materials used in flammable liquid storage tanks. Therefore, developing a flame-retardant buoyancy material that is suitable for suppressing oil evaporation and has flame-retardant properties has become one of the urgent problems to be solved in this field. Summary of the Invention

[0006] To address the aforementioned technical problems, the present invention aims to provide a solid flame-retardant buoyancy material with oil flocculation properties, its preparation method, and its application. The solid flame-retardant buoyancy material provided by the present invention has advantages such as strong ability to inhibit oil volatilization, superior flame-retardant performance, and high mechanical strength.

[0007] To achieve the above objectives, the first aspect of the present invention provides a method for preparing a solid flame-retardant buoyancy material with oil flocculation effect, comprising the following steps:

[0008] (1) Preparation of hollow glass microspheres coated with epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose:

[0009] (1)-1 Mix hydroxymethyl cellulose, binder, ammonium polyphosphate and water, stir for a period of time, and then sieve to obtain a suspension;

[0010] (1)-2 The suspension is mixed with hollow glass microspheres and stirred for a period of time to obtain hollow glass microspheres coated with ammonium polyphosphate-hydroxymethyl cellulose;

[0011] (1)-3 After mixing and stirring the epoxy resin, the hollow glass microspheres coated with ammonium polyphosphate-hydroxymethyl cellulose and the diluent for a period of time, the curing agent and the accelerator are added, and the mixture is stirred for a period of time. Then the mixture is cured and molded to obtain hollow glass microspheres coated with epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose.

[0012] (2) Preparation of solid flame-retardant buoyancy materials with oil flocculation effect:

[0013] (2)-1 The hollow glass microspheres coated with epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose were added to water, and then acrylamide monomer was added under nitrogen protection. After stirring for a period of time, an initiator was added. After reacting for a period of time, hollow glass microspheres coated with epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose with polyacrylamide side chains grafted on the surface were obtained, which is the crude product of solid flame retardant buoyancy material with oil flocculation effect.

[0014] (2)-2 The crude product of the solid flame-retardant buoyancy material with oil flocculation effect is subjected to at least impurity removal and drying to obtain the solid flame-retardant buoyancy material with oil flocculation effect.

[0015] In the above preparation method, preferably, in step (1)-1, the mixing mass ratio of the hydroxymethyl cellulose, the binder and the ammonium polyphosphate is (0.3-0.5):(0.05-0.1):(0.4-0.65), more preferably 0.4:(0.08-0.1):(0.5-0.52).

[0016] In the above preparation method, preferably, in step (1)-1, the adhesive includes polyethylene glycol and / or polyvinyl alcohol, etc.

[0017] In the above preparation method, preferably, in step (1)-1, the degree of polymerization (n) of the ammonium polyphosphate is 20 to 100.

[0018] In the above preparation method, preferably, in step (1)-1, the total mass ratio of the hydroxymethyl cellulose, the binder and the ammonium polyphosphate to the water is (1:5)-(1:10).

[0019] In the above preparation method, preferably, in step (1)-1, the stirring time is 1-3 hours and the temperature is 20-35℃ (more preferably room temperature). The stirring speed is preferably 400-1000 rpm.

[0020] In the above preparation method, preferably, in step (1)-1, the sieving is done through a 50-200 mesh sieve.

[0021] In the above preparation method, preferably, in steps (1)-2, the hollow glass microspheres have a particle size of 30-120 μm and a density of 0.15-0.60 g / cm³. 3 More preferably, the hollow glass microspheres include, but are not limited to, one or a combination of several of 3M's K15, S15, K20, VS550, iM30K, etc.

[0022] In the above preparation method, preferably, in steps (1)-2, the mixing mass ratio of the suspension to the hollow glass microspheres is (1-1.5):1.

[0023] In the above preparation method, preferably, in steps (1)-2, the stirring time is 20-60 minutes and the temperature is 20-35℃ (more preferably room temperature). The stirring speed is preferably 400-1000 rpm.

[0024] In the above preparation method, preferably, in steps (1)-3, the epoxy resin includes one or a combination of several of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenolic epoxy resin. More preferably, the epoxy value of the epoxy resin is 0.41 to 0.56 eq / 100g.

[0025] In the above preparation method, preferably, in steps (1)-3, the diluent includes an epoxy reactive diluent. More preferably, the diluent includes a diepoxy reactive diluent. Particularly preferably, the diluent includes one or a combination of several of ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, diethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1,6-hexanediol diglycidyl ether.

[0026] In the above preparation method, preferably, in steps (1)-3, the curing agent includes one or a combination of several of the following: diglycidyl ether, polyglycidyl ether, propylene oxide butyl ether, and methyltetrahydrophthalic anhydride.

[0027] In the above preparation method, preferably, in steps (1)-3, the accelerator includes one or a combination of several of N,N-dimethylbenzylamine, 2,4,6-tris(dimethylaminomethyl)phenol and triethanolamine.

[0028] In the above preparation method, preferably, in steps (1)-3, the mass ratio of the epoxy resin, the ammonium polyphosphate-hydroxymethyl cellulose-coated hollow glass microspheres, the diluent, the curing agent and the accelerator is (0.1-0.2):(0.65-0.87):(0.01-0.05):(0.01-0.05):(0.01-0.05); more preferably, it is 0.15:0.8:0.02:0.02:0.01.

[0029] In the above preparation method, preferably, in steps (1)-3, the epoxy resin, the ammonium polyphosphate-hydroxymethyl cellulose-coated hollow glass microspheres, and the diluent are mixed and stirred for 20-50 minutes at a stirring temperature of 80-150°C. The stirring speed is preferably 400-1000 rpm.

[0030] In the above preparation method, preferably, in steps (1)-3, the time for adding the curing agent and accelerator and continuing to stir is 20-50 minutes, and the stirring temperature is 80-150℃. The stirring speed is preferably 400-1000 rpm.

[0031] In the above preparation method, preferably, in steps (1)-3, the process of mixing and stirring epoxy resin, ammonium polyphosphate-hydroxymethyl cellulose-coated hollow glass microspheres and diluent, adding curing agent and accelerator and continuing to stir can all be carried out in a vacuum glove box.

[0032] In the above preparation method, preferably, in steps (1)-3, the curing temperature is 80-120℃ and the time is 20-60 minutes.

[0033] In the above preparation method, preferably, in step (2)-1, the mass ratio of the amount of acrylamide monomer to the amount of hydroxymethyl cellulose in step (1)-1 is (2:1)-(6:1).

[0034] In the above preparation method, preferably, in step (2)-1, the stirring time is 20-40 minutes and the temperature is 20-35℃. The stirring speed is preferably 400-1000 rpm.

[0035] In the above preparation method, preferably, in step (2)-1, the initiator includes ammonium persulfate and / or anhydrous sodium sulfite. More preferably, the initiator includes ammonium persulfate and anhydrous sodium sulfite in a mass ratio of (2:1) to (1:2).

[0036] In the above preparation method, preferably, in step (2)-1, the mass ratio of the initiator to the acrylamide monomer is (1:10)-(1:30).

[0037] In the above preparation method, preferably, in step (2)-1, the reaction temperature is 40-60℃ and the reaction time is 8-20 hours.

[0038] In the above preparation method, preferably, in step (2)-1, the grafting rate of the polyacrylamide branches in the epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose-coated hollow glass microspheres with polyacrylamide branches grafted onto the surface is 70-100%, more preferably 85-100%, and even more preferably 89-100%. The calculation method of the polyacrylamide branch grafting rate is common knowledge in the art, and it is the ratio of the amount of polyacrylamide branches grafted to the amount of acrylamide monomer added.

[0039] In the above preparation method, preferably, step (2)-2 specifically includes: washing the crude product of the solid flame-retardant buoyancy material with oil flocculation effect, then drying it, extracting it with acetone in a Soxhlet extractor for 8-12 hours, and then vacuum drying it to obtain the solid flame-retardant buoyancy material with oil flocculation effect. The washing can be done with ethanol to remove unreacted monomers and impurities. The drying temperature is preferably 100-120℃, and the drying time is preferably 3-6 hours. Extraction with acetone in a Soxhlet extractor for 8-12 hours removes homopolymer polyacrylamide. The vacuum degree of the vacuum drying can be -0.05MPa to -0.1MPa, the temperature can be 20-35℃, and the time can be 8-12 hours.

[0040] In the above preparation method, the water used in each step can be conventional deionized water or distilled water.

[0041] The present invention provides a method for preparing a solid flame-retardant buoyancy material with oil flocculation effect. The method employs a surface-initiated gelation process, coating the surface of hollow glass microspheres with a composite flame retardant layer formed by high-phosphorus and nitrogen-containing ammonium polyphosphate and high-char-forming hydroxymethyl cellulose. This layer is then cured with an epoxy resin matrix, enhancing the interfacial bonding between the hollow glass microspheres and the epoxy matrix and reducing internal defects. Finally, an initiated polymerization reaction grafts polyacrylamide branches with oil flocculation properties onto the material surface. This results in a solid flame-retardant buoyancy material that not only possesses superior oil flocculation performance but also excellent flame retardant properties. Furthermore, the material exhibits high mechanical strength, is non-toxic and environmentally friendly, and effectively inhibits oil volatilization.

[0042] The second aspect of the present invention provides a solid flame-retardant buoyancy material with oil flocculation effect, which is prepared by the above-described preparation method.

[0043] According to a specific embodiment of the present invention, preferably, the solid flame-retardant buoyancy material with oil flocculation effect is a solid flame-retardant buoyancy material in which an epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose layer is coated on the surface of hollow glass microspheres and polyacrylamide side chains are grafted onto the surface. A schematic diagram of the structure of the solid flame-retardant buoyancy material with oil flocculation effect provided in a specific embodiment of the present invention is shown below. Figure 1 As shown.

[0044] According to a specific embodiment of the present invention, preferably, the solid flame-retardant buoyancy material with oil flocculation effect is microspheres with a particle size of 30-150 μm.

[0045] According to a specific embodiment of the present invention, preferably, the density of the solid flame-retardant buoyancy material with oil flocculation effect is 0.3-0.5 g / mL.

[0046] The solid flame-retardant buoyancy material with oil flocculation effect provided by this invention is a biomass-chemical composite flame-retardant buoyancy microsphere material. The density of this solid flame-retardant buoyancy material is lower than that of flammable liquids, and it can form a flocculated film on the surface of flammable liquids. Furthermore, this solid flame-retardant buoyancy material has high strength, is safe and environmentally friendly, and can effectively inhibit the volatilization of oil in storage tanks (more than 95%) and has a flame-retardant effect.

[0047] The third aspect of the present invention provides an application of the above-mentioned solid flame-retardant buoyancy material with oil flocculation effect in suppressing oil volatilization.

[0048] This invention prepares a biomass-chemical composite flame-retardant solid buoyancy material with flocculating effect on oil and gas molecules by gelling the surface of hollow glass microspheres to form a polyphosphate-hydroxymethyl cellulose composite flame retardant layer, and by mechanical blending, surface curing, and surface grafting polymerization modification.

[0049] Compared with the prior art, the beneficial effects of the present invention include, but are not limited to:

[0050] A surface-initiated gelation method is used to coat the surface of hollow glass microspheres with a layer of ammonium polyphosphate-hydroxymethyl cellulose composite flame retardant, which is high in phosphorus and nitrogen and has a high char-forming ability. This layer then undergoes a curing reaction with an epoxy resin matrix, enhancing the interfacial bonding between the hollow glass microspheres and the epoxy matrix and reducing internal defects. Furthermore, polyacrylamide branches with flocculating organic matter are grafted onto the material surface using surface graft polymerization. This results in a solid flame-retardant buoyancy material with advantages such as strong oil volatilization inhibition, superior flame retardant performance, high mechanical strength, and non-toxicity and environmental friendliness. This invention's solid flame-retardant buoyancy material combines the synergistic effects of gas-phase and condensed-phase flame-retardant mechanisms. After combustion, ammonium polyphosphate releases phosphorus-containing substances and non-combustible gases such as nitrogen dioxide; hydroxymethyl cellulose acts as a char-forming agent, while ammonium polyphosphate promotes char formation. This invention employs a compound of ammonium polyphosphate, hydroxymethyl cellulose, and epoxy resin to form an intumescent composite flame retardant layer integrating a carbon source, an acid source, and a gas source on the surface of air-filled glass microspheres. This gives the solid flame-retardant buoyancy material of this invention excellent flame-retardant properties. The polyacrylamide side chains on the surface of the solid flame-retardant buoyancy material of this invention can effectively adsorb oil and gas molecules in contact with it, bridging them onto the polymer side chains to form flocs, thereby inhibiting the volatilization of lower-layer oil and gas molecules. This gives the solid flame-retardant buoyancy material of this invention excellent oil volatilization inhibition performance. Attached Figure Description

[0051] Figure 1 This is a schematic diagram of the structure of a solid flame-retardant buoyancy material with oil flocculation effect provided in a specific embodiment of the present invention. Detailed Implementation

[0052] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.

[0053] Example 1

[0054] This embodiment provides a solid flame-retardant buoyancy material with oil flocculation effect, which is prepared by the following method:

[0055] (1) Preparation of hollow glass microspheres coated with epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose:

[0056] (1)-1 Hydroxymethyl cellulose, polyvinyl alcohol, ammonium polyphosphate and deionized water are mixed and stirred at room temperature for 1 hour (600 rpm), and then sieved (100 mesh sieve) to obtain a suspension; wherein, the degree of polymerization (n) of the ammonium polyphosphate is 20-100; the mixing mass ratio of the hydromethyl cellulose, the polyvinyl alcohol and the ammonium polyphosphate is 0.4:0.08:0.52; the mixing mass ratio of the total mass of the hydromethyl cellulose, the polyvinyl alcohol and the ammonium polyphosphate to the mixing mass of the deionized water is 1:8;

[0057] (1)-2 The suspension and hollow glass microspheres are mixed at a mass ratio of 1:1 and stirred at room temperature for 30 minutes (600 rpm) to obtain hollow glass microspheres coated with ammonium polyphosphate-hydroxymethyl cellulose; wherein the particle size of the hollow glass microspheres is about 30-120 μm and the density is about 0.15 g / cm³. 3 The product model is S15 (3M).

[0058] (1)-3 Bisphenol A type epoxy resin with an epoxy value of 0.45 eq / 100g, the hollow glass microspheres coated with ammonium polyphosphate-hydroxymethyl cellulose, and the diluent ethylene glycol diglycidyl ether are mixed and stirred in a vacuum glove box at 100°C for 25 minutes (600 rpm). Then, the curing agent diglycidyl ether and the accelerator N,N-dimethylbenzylamine are added, and the mixture is stirred at 100°C for 20 minutes (600 rpm). The mixture is then cured (at 100°C for 60 minutes) and cooled to room temperature to obtain epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose coated hollow glass microspheres. The mass ratio of the epoxy resin, the hollow glass microspheres coated with ammonium polyphosphate-hydroxymethyl cellulose, the diluent, the curing agent, and the accelerator is 0.15:0.8:0.02:0.02:0.01.

[0059] (2) Preparation of solid flame-retardant buoyancy materials with oil flocculation effect:

[0060] (2)-1 The epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose coated hollow glass microspheres were added to deionized water, and then acrylamide monomer was added under nitrogen protection. The mixture was stirred at 25°C for 30 minutes (600 rpm) to make them uniform. Ammonium persulfate and anhydrous sodium sulfite in a mass ratio of 1:1 were added as initiators. After reacting at 50°C for 8 hours, the mixture was cooled to room temperature to obtain epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose coated hollow glass microspheres with polyacrylamide side chains grafted on the surface. This is the crude product of solid flame-retardant buoyancy material with oil flocculation effect. The mass ratio of acrylamide monomer to hydroxymethyl cellulose in step (1)-1 is 4:1. The mass ratio of initiator to acrylamide monomer is 1:20.

[0061] The grafting rate of polyacrylamide branches in the epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose-coated hollow glass microspheres with surface grafted polyacrylamide branches is 94%.

[0062] (2)-2 The crude product of the solid flame-retardant buoyancy material with oil flocculation effect is washed with ethanol to remove unreacted monomers and impurities. Then it is dried at 120°C for 5 hours, and then extracted with acetone in a Soxhlet extractor for 10 hours to remove homopolymer polyacrylamide. After that, it is dried under vacuum at a vacuum degree of -0.1MPa, a temperature of 25°C and a time of 10 hours to obtain the solid flame-retardant buoyancy material with oil flocculation effect.

[0063] The solid flame-retardant buoyancy material with oil flocculation effect provided in this embodiment is a microsphere with a particle size of about 30-140 μm and a density of 0.4127 g / mL.

[0064] Example 2

[0065] This embodiment provides a solid flame-retardant buoyancy material with oil flocculation effect, which is prepared by the following method:

[0066] (1) Preparation of hollow glass microspheres coated with epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose:

[0067] (1)-1 Hydroxymethyl cellulose, polyvinyl alcohol, ammonium polyphosphate and deionized water are mixed and stirred at room temperature for 1 hour (600 rpm), and then sieved (100 mesh sieve) to obtain a suspension; wherein, the degree of polymerization (n) of the ammonium polyphosphate is 20-100; the mixing mass ratio of the hydromethyl cellulose, the polyvinyl alcohol and the ammonium polyphosphate is 0.4:0.1:0.5; the mixing mass ratio of the total mass of the hydromethyl cellulose, the polyvinyl alcohol and the ammonium polyphosphate to the mixing mass of the deionized water is 1:8;

[0068] (1)-2 The suspension and hollow glass microspheres are mixed at a mass ratio of 1:1 and stirred at room temperature for 30 minutes (600 rpm) to obtain hollow glass microspheres coated with ammonium polyphosphate-hydroxymethyl cellulose; wherein the particle size of the hollow glass microspheres is about 30-120 μm and the density is about 0.15 g / cm³. 3 The product model is K15 (3M).

[0069] (1)-3 Phenolic epoxy resin with an epoxy value of 0.50 eq / 100g, hollow glass microspheres coated with ammonium polyphosphate-hydroxymethyl cellulose, and diluent neopentyl glycol diglycidyl ether are mixed and stirred for 30 minutes (800 rpm) in a vacuum glove box at 100°C. Then, curing agent polyglycidyl ether and accelerator 2,4,6-tris(dimethylaminomethyl)phenol are added, and stirring is continued at 100°C for 20 minutes (800 rpm). The mixture is then cured (at 100°C for 60 minutes) and cooled to room temperature to obtain hollow glass microspheres coated with epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose. The mass ratio of the epoxy resin, the hollow glass microspheres coated with ammonium polyphosphate-hydroxymethyl cellulose, the diluent, the curing agent, and the accelerator is 0.15:0.8:0.02:0.02:0.01.

[0070] (2) Preparation of solid flame-retardant buoyancy materials with oil flocculation effect:

[0071] (2)-1 The epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose coated hollow glass microspheres were added to deionized water, and then acrylamide monomer was added under nitrogen protection. The mixture was stirred at 30°C for 30 minutes (600 rpm) to make them uniform. Ammonium persulfate and anhydrous sodium sulfite in a mass ratio of 1:1 were added as initiators. After reacting at 50°C for 8 hours, the mixture was cooled to room temperature to obtain epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose coated hollow glass microspheres with polyacrylamide side chains grafted on the surface. This is the crude product of solid flame-retardant buoyancy material with oil flocculation effect. The mass ratio of acrylamide monomer to hydroxymethyl cellulose in step (1)-1 is 4:1. The mass ratio of initiator to acrylamide monomer is 1:10.

[0072] The grafting rate of polyacrylamide branches in the epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose-coated hollow glass microspheres with surface grafted polyacrylamide branches is 89%.

[0073] (2)-2 The crude product of the solid flame-retardant buoyancy material with oil flocculation effect is washed with ethanol to remove unreacted monomers and impurities. Then it is dried at 120°C for 5 hours, and then extracted with acetone in a Soxhlet extractor for 10 hours to remove homopolymer polyacrylamide. After that, it is dried under vacuum at a vacuum degree of -0.1MPa, a temperature of 25°C and a time of 10 hours to obtain the solid flame-retardant buoyancy material with oil flocculation effect.

[0074] The solid flame-retardant buoyancy material with oil flocculation effect provided in this embodiment is a microsphere with a particle size of 30-150μm and a density of 0.4219g / mL.

[0075] Comparative Example 1

[0076] This comparative example provides a solid flame-retardant buoyancy material with oil flocculation effect, which is prepared by the following method:

[0077] (1) Preparation of epoxy resin-hydroxymethyl cellulose coated hollow glass microspheres:

[0078] (1)-1 Hydroxymethyl cellulose, hollow glass microspheres, and deionized water were mixed in a mass ratio of 1:1:8 and stirred at room temperature for 30 minutes (600 rpm) to obtain hydroxymethyl cellulose-coated hollow glass microspheres; wherein the particle size of the hollow glass microspheres was approximately 30-120 μm and the density was approximately 0.15 g / cm³. 3 The product model is S15 (3M).

[0079] (1)-2 Bisphenol A type epoxy resin with an epoxy value of 0.45 eq / 100g, the hollow glass microspheres coated with hydroxymethyl cellulose, and the diluent ethylene glycol diglycidyl ether are mixed and stirred for 25 minutes (600 rpm) in a vacuum glove box at 100°C. Then, the curing agent diglycidyl ether and the accelerator N,N-dimethylbenzylamine are added, and the mixture is stirred at 100°C for another 20 minutes (600 rpm). The mixture is then cured (at 100°C for 60 minutes) and cooled to room temperature to obtain epoxy resin-hydroxymethyl cellulose coated hollow glass microspheres. The mass ratio of the epoxy resin, the hollow glass microspheres coated with hydroxymethyl cellulose, the diluent, the curing agent, and the accelerator is 0.15:0.8:0.02:0.02:0.01.

[0080] (2) Preparation of solid flame-retardant buoyancy materials with oil flocculation effect:

[0081] (2)-1 The epoxy resin-hydroxymethyl cellulose coated hollow glass microspheres were added to deionized water, and then acrylamide monomer was added under nitrogen protection. The mixture was stirred at 25°C for 30 minutes (600 rpm) to make them uniform. Ammonium persulfate and anhydrous sodium sulfite in a mass ratio of 1:1 were added as initiators. After reacting at 50°C for 8 hours, the mixture was cooled to room temperature to obtain epoxy resin-hydroxymethyl cellulose coated hollow glass microspheres with polyacrylamide side chains grafted on the surface. This is the crude product of solid flame-retardant buoyancy material with oil flocculation effect. The mass ratio of acrylamide monomer to hydroxymethyl cellulose in step (1)-1 is 4:1. The mass ratio of initiator to acrylamide monomer is 1:20.

[0082] The grafting rate of polyacrylamide branches in the epoxy resin-hydroxymethyl cellulose-coated hollow glass microspheres with surface grafted polyacrylamide branches is 92%.

[0083] (2)-2 The crude product of the solid flame-retardant buoyancy material with oil flocculation effect is washed with ethanol to remove unreacted monomers and impurities. Then it is dried at 120°C for 5 hours, and then extracted with acetone in a Soxhlet extractor for 10 hours to remove homopolymer polyacrylamide. After that, it is dried under vacuum at a vacuum degree of -0.1MPa, a temperature of 25°C and a time of 10 hours to obtain the solid flame-retardant buoyancy material with oil flocculation effect.

[0084] The solid flame-retardant buoyancy material with oil flocculation effect provided in this comparative example is a microsphere with a particle size of about 30-140 μm and a density of 0.3805 g / mL.

[0085] Comparative Example 2

[0086] This comparative example provides a solid flame-retardant buoyancy material with oil flocculation effect, which is prepared by the following method:

[0087] (1) Preparation of hollow glass microspheres coated with ammonium polyphosphate-hydroxymethyl cellulose:

[0088] (1)-1 Hydroxymethyl cellulose, polyvinyl alcohol, ammonium polyphosphate and deionized water are mixed and stirred at room temperature for 1 hour (600 rpm), and then sieved (100 mesh sieve) to obtain a suspension; wherein, the degree of polymerization (n) of the ammonium polyphosphate is 20-100; the mixing mass ratio of the hydromethyl cellulose, the polyvinyl alcohol and the ammonium polyphosphate is 0.4:0.1:0.5; the mixing mass ratio of the total mass of the hydromethyl cellulose, the polyvinyl alcohol and the ammonium polyphosphate to the mixing mass of the deionized water is 1:8;

[0089] (1)-2 The suspension and hollow glass microspheres were mixed at a mass ratio of 1:1 and stirred at room temperature for 30 minutes (600 rpm) to obtain hollow glass microspheres coated with ammonium polyphosphate-hydroxymethyl cellulose; wherein the particle size of the hollow glass microspheres was approximately 30-120 μm and the density was approximately 0.15 g / cm³. 3 The product model is S15 (3M).

[0090] (2) Preparation of solid flame-retardant buoyancy materials with oil flocculation effect:

[0091] (2)-1 The hollow glass microspheres coated with ammonium polyphosphate-hydroxymethyl cellulose were added to deionized water, and then acrylamide monomer was added under nitrogen protection. The mixture was stirred at 25°C for 30 minutes (600 rpm) to make them uniform. Ammonium persulfate and anhydrous sodium sulfite in a mass ratio of 1:1 were added as initiators. After reacting at 50°C for 8 hours, the mixture was cooled to room temperature to obtain hollow glass microspheres coated with ammonium polyphosphate-hydroxymethyl cellulose with polyacrylamide side chains grafted on the surface. This is the crude product of solid flame-retardant buoyancy material with oil flocculation effect. The mass ratio of acrylamide monomer to hydroxymethyl cellulose in step (1)-1 is 4:1. The mass ratio of initiator to acrylamide monomer is 1:20.

[0092] The grafting rate of polyacrylamide branches in the hollow glass microspheres coated with ammonium polyphosphate-hydroxymethyl cellulose with polyacrylamide branches grafted onto the surface is 92%.

[0093] (2)-2 The crude product of the solid flame-retardant buoyancy material with oil flocculation effect is washed with ethanol to remove unreacted monomers and impurities. Then it is dried at 120°C for 5 hours, and then extracted with acetone in a Soxhlet extractor for 10 hours to remove homopolymer polyacrylamide. After that, it is dried under vacuum at a vacuum degree of -0.1MPa, a temperature of 25°C and a time of 10 hours to obtain the solid flame-retardant buoyancy material with oil flocculation effect.

[0094] The solid flame-retardant buoyancy material with oil flocculation effect provided in this comparative example is a microsphere with a particle size of about 30-140 μm and a density of 0.3913 g / mL.

[0095] Comparative Example 3

[0096] This comparative example provides a solid flame-retardant buoyancy material, which is a hollow glass microsphere coated with epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose, and is prepared by the following method:

[0097] (1) Hydroxymethyl cellulose, polyvinyl alcohol, ammonium polyphosphate and deionized water are mixed and stirred at room temperature for 1 hour (600 rpm), and then sieved (100 mesh sieve) to obtain a suspension; wherein, the degree of polymerization (n) of the ammonium polyphosphate is 20 to 100; the mixing mass ratio of the hydroxymethyl cellulose, the polyvinyl alcohol and the ammonium polyphosphate is 0.4:0.1:0.5; the mixing mass ratio of the total mass of the hydroxymethyl cellulose, the polyvinyl alcohol and the ammonium polyphosphate to the mixing mass of the deionized water is 1:8;

[0098] (2) The suspension and hollow glass microspheres were mixed at a mass ratio of 1:1 and stirred at room temperature for 30 minutes (600 rpm) to obtain hollow glass microspheres coated with ammonium polyphosphate-hydroxymethyl cellulose; wherein the particle size of the hollow glass microspheres was approximately 30-120 μm and the density was approximately 0.15 g / cm³. 3 The product model is S15 (3M).

[0099] (3) Bisphenol A type epoxy resin with an epoxy value of 0.45 eq / 100g, the hollow glass microspheres coated with ammonium polyphosphate-hydroxymethyl cellulose, and the diluent ethylene glycol diglycidyl ether are mixed and stirred for 25 minutes (600 rpm) in a vacuum glove box at 100°C. Then, the curing agent diglycidyl ether and the accelerator N,N-dimethylbenzylamine are added, and the mixture is stirred at 100°C for another 20 minutes (600 rpm). The mixture is then cured (at 100°C for 60 minutes) and cooled to room temperature to obtain epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose coated hollow glass microspheres. The mass ratio of the epoxy resin, the hollow glass microspheres coated with ammonium polyphosphate-hydroxymethyl cellulose, the diluent, the curing agent, and the accelerator is 0.15:0.8:0.02:0.02:0.01.

[0100] The solid flame-retardant buoyancy material provided in this comparative example is a microsphere with a particle size of approximately 30-140 μm and a density of 0.3126 g / mL.

[0101] Performance testing

[0102] Flame retardancy was tested according to the limiting oxygen index (GB2406-80 oxygen index test method) and horizontal burning (GB / T2408-2008 determination of the flammability of plastics by horizontal and vertical methods).

[0103] The antistatic properties were tested according to GB / T 15738-2008 Test Method for Resistivity of Conductive and Antistatic Fiber Reinforced Plastics.

[0104] Methods for testing the inhibition of oil volatility:

[0105] Step 1: Prepare four 50mL glass containers and weigh each one.

[0106] Step 2: Add 30mL of diesel fuel to a glass container, weigh it, and calculate the mass of diesel fuel in the container;

[0107] Step 3: Calculate the mass of solid flame-retardant buoyancy material with thicknesses of 0mm, 2mm, 5mm, and 10mm laid in the glass container;

[0108] Step 4: Weigh the required solid flame-retardant buoyancy material and lay it into the four glass containers mentioned above. Place them in a fume hood (strong ventilation) and keep them at a constant temperature (25℃) for 24h, 36h, 72h and 168h respectively. Weigh and calculate the mass of the remaining diesel fuel in the glass containers after evaporation, and calculate the evaporation inhibition rate (mass of remaining diesel fuel / mass of original diesel fuel, %).

[0109] Methods for verifying the flocculation effect of oil products:

[0110] Step 1: Add 200 ml of water to a 500 mL beaker and then spread a layer of diesel fuel on the surface of the water;

[0111] Step 2: Sprinkle 0.5g of solid flame-retardant buoyancy material onto the oil surface and observe whether the oil accumulates on the material surface. If so, it has an oil flocculation effect.

[0112] Test Results

[0113] The test results for flame retardancy and antistatic properties are as follows: the solid flame retardant buoyancy materials provided in Examples 1 and 2 both meet the requirements for flame retardancy and antistatic properties.

[0114] The test results of oxygen index, thermal conductivity, resistivity, compressive strength and oil flocculation effect of the solid flame-retardant buoyancy materials provided in the examples and comparative examples are shown in Table 1.

[0115] Table 1

[0116]

[0117]

[0118] The test results of the solid flame-retardant buoyancy materials provided in Examples 1 and 2 on the inhibition of oil volatility are shown in Table 2.

[0119] Table 2

[0120]

[0121] As can be seen from the above test results, the solid flame-retardant buoyancy material with oil flocculation effect provided by the present invention has the advantages of strong ability to inhibit oil volatilization, excellent flame retardant performance, high mechanical strength, and non-toxicity and environmental protection.

Claims

1. A method for preparing a solid flame-retardant buoyancy material with oil flocculation effect, comprising the following steps: (1) Preparation of hollow glass microspheres coated with epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose: (1) -1 Mix hydroxymethyl cellulose, binder, ammonium polyphosphate and water, stir for a period of time, and then sieve to obtain a suspension; (1)-2 The suspension is mixed with hollow glass microspheres and stirred for a period of time to obtain hollow glass microspheres coated with ammonium polyphosphate-hydroxymethyl cellulose; (1)-3 After mixing and stirring the epoxy resin, the hollow glass microspheres coated with ammonium polyphosphate-hydroxymethyl cellulose and the diluent for a period of time, the curing agent and the accelerator are added, and the mixture is stirred for a period of time. Then the mixture is cured and molded to obtain hollow glass microspheres coated with epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose. (2) Preparation of solid flame-retardant buoyancy materials with oil flocculation effect: (2)-1 The hollow glass microspheres coated with epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose were added to water, and then acrylamide monomer was added under nitrogen protection. After stirring for a period of time, an initiator was added. After reacting for a period of time, hollow glass microspheres coated with epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose with polyacrylamide side chains grafted on the surface were obtained, which is the crude product of solid flame retardant buoyancy material with oil flocculation effect. (2) -2 The crude product of the solid flame-retardant buoyancy material with oil flocculation effect is subjected to at least impurity removal and drying to obtain the solid flame-retardant buoyancy material with oil flocculation effect. In step (1)-1, the mixing mass ratio of the hydroxymethyl cellulose, the binder, and the ammonium polyphosphate is (0.3-0.5):(0.05-0.1):(0.4-0.65); the mixing mass ratio of the total mass of the hydroxymethyl cellulose, the binder, and the ammonium polyphosphate to water is (1:5)-(1:10). In steps (1)-2, the mixing mass ratio of the suspension to the hollow glass microspheres is (1-1.5):1; In steps (1)-3, the mass ratio of the epoxy resin, the ammonium polyphosphate-hydroxymethyl cellulose-coated hollow glass microspheres, the diluent, the curing agent, and the accelerator is (0.1-0.2):(0.65-0.87):(0.01-0.05):(0.01-0.05):(0.01-0.05); In step (2)-1, the mass ratio of the amount of acrylamide monomer to the amount of hydroxymethyl cellulose in step (1)-1 is (2:1)-(6:1).

2. The preparation method according to claim 1, wherein, In step (1)-1, the adhesive comprises polyethylene glycol and / or polyvinyl alcohol.

3. The preparation method according to claim 1, wherein, In step (1)-1, the degree of polymerization of the ammonium polyphosphate is 20~100.

4. The preparation method according to claim 1, wherein, In step (1)-1, the stirring time is 1-3 hours and the temperature is 20-35℃.

5. The preparation method according to claim 1, wherein, In step (1)-1, the sieving is through a 50-200 mesh sieve.

6. The preparation method according to claim 1, wherein, In steps (1)-2, the hollow glass microspheres have a particle size of 30~120 µm and a density of 0.15~0.60 g / cm³. 3 .

7. The preparation method according to claim 1, wherein, In steps (1)-2, the stirring time is 20-60 minutes and the temperature is 20-35℃.

8. The preparation method according to claim 1, wherein, In steps (1)-3, the epoxy resin includes one or a combination of several of bisphenol A type epoxy resin, bisphenol F type epoxy resin and phenolic epoxy resin.

9. The preparation method according to claim 1, wherein, In steps (1)-3, the epoxy value of the epoxy resin is 0.41~0.56 eq / 100g.

10. The preparation method according to claim 1, wherein, In steps (1)-3, the diluent includes an epoxy reactive diluent.

11. The preparation method according to claim 10, wherein, In steps (1)-3, the diluent includes a diepoxy reactive diluent.

12. The preparation method according to claim 11, wherein, In steps (1)-3, the diluent includes one or a combination of several of ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, diethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether and 1,6-hexanediol diglycidyl ether.

13. The preparation method according to claim 1, wherein, In steps (1)-3, the curing agent includes one or a combination of several of diglycidyl ether, polyglycidyl ether, propylene oxide butyl ether, and methyltetrahydrophthalic anhydride.

14. The preparation method according to claim 1, wherein, In steps (1)-3, the promoter includes one or a combination of several of N,N-dimethylbenzylamine, 2,4,6-tris(dimethylaminomethyl)phenol and triethanolamine.

15. The preparation method according to claim 1, wherein, In steps (1)-3, the epoxy resin, the hollow glass microspheres coated with ammonium polyphosphate-hydroxymethyl cellulose and the diluent are mixed and stirred for 20-50 minutes at a temperature of 80-150°C.

16. The preparation method according to claim 1, wherein, In steps (1)-3, the curing agent and accelerator are added and stirring is continued for 20-50 minutes at a temperature of 80-150℃.

17. The preparation method according to claim 1, wherein, In steps (1)-3, the curing temperature is 80-120℃ and the time is 20-60 minutes.

18. The preparation method according to claim 1, wherein, In step (2)-1, the initiator includes ammonium persulfate and / or anhydrous sodium sulfite.

19. The preparation method according to claim 18, wherein, In step (2)-1, the initiator comprises ammonium persulfate and anhydrous sodium sulfite in a mass ratio of (2:1)-(1:2).

20. The preparation method according to claim 1, wherein, In step (2)-1, the mass ratio of the initiator to the acrylamide monomer is (1:10)-(1:30).

21. The preparation method according to claim 1, wherein, In step (2)-1, the stirring time is 20-40 minutes and the temperature is 20-35 ℃.

22. The preparation method according to claim 1, wherein, In step (2)-1, the reaction temperature is 40-60℃ and the reaction time is 8-20 hours.

23. The preparation method according to claim 1, wherein, In step (2)-1, the grafting rate of polyacrylamide branches in the epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose-coated hollow glass microspheres with polyacrylamide branches grafted on the surface is 70-100%.

24. The preparation method according to claim 23, wherein, In step (2)-1, the grafting rate of polyacrylamide branches in the epoxy resin-ammonium polyphosphate-hydroxymethyl cellulose-coated hollow glass microspheres with polyacrylamide branches grafted on the surface is 85-100%.

25. A solid flame-retardant buoyancy material with oil flocculation effect, which is prepared by the preparation method of the solid flame-retardant buoyancy material with oil flocculation effect according to any one of claims 1-24.

26. The solid flame-retardant buoyancy material with oil flocculation effect according to claim 25, wherein, The solid flame-retardant buoyancy material with oil flocculation effect is a microsphere with a particle size of 30-150µm.

27. The solid flame-retardant buoyancy material with oil flocculation effect according to claim 25, wherein, The density of the solid flame-retardant buoyancy material with oil flocculation effect is 0.3-0.5 g / mL.

28. The application of a solid flame-retardant buoyancy material with oil flocculation effect as described in any one of claims 25-27 in suppressing oil volatilization.

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