Polyacrylate resin for absorbing pump oil and preparation method thereof

Abstract

The invention discloses polyacrylate resin for absorbing pump oil and a preparation method of the polyacrylate resin, relates to the technical field of oil-absorbing resin materials, and solves the problem that the existing polyacrylate is difficult to adsorb high-viscosity pump oil. The pump oil is vacuum pump oil with the kinematic viscosity of ISO VG 100; the polyacrylic resin is obtained by carrying out suspension polymerization reaction on two acrylate monomers in a specific ratio under the action of a suspending agent and a free radical initiator: octadecyl methacrylate and docosyl methacrylate or methyl methacrylate in a mass ratio of 4: 1; or octadecyl methacrylate and butyl acrylate in a mass ratio of 3: 2; the oil absorption rate of the polyacrylic resin is greater than or equal to 13g / g. The method can be applied to the recovery efficiency of waste pump oil and the treatment work of nuclear waste.

Description

Technical Field

[0001] The invention relates to the technical field of oil-absorbing resin materials, in particular to a polyacrylate resin for absorbing pump oil and a preparation method thereof. Background Art

[0002] Oil-absorbing materials are functional materials that selectively capture oils through physical adsorption or chemical bonding. They have irreplaceable applications in marine oil spill management, industrial oily wastewater purification, and mechanical lubrication system maintenance. Based on their source and chemical structure, oil-absorbing materials can be categorized into three main groups: inorganic (e.g., bentonite, zeolite), organic (e.g., wood fiber, cotton, and linen), and synthetic (e.g., polyurethane foam, polyacrylate resin). Synthetic organic oil-absorbing materials have become a research hotspot due to their designability and controllable pore structure.

[0003] In recent years, with the development of preparation technologies such as suspension polymerization and emulsion polymerization, polyacrylate oil-absorbing resins have made significant breakthroughs in adsorption capacity and cyclic stability. However, existing technologies still have many limitations. Existing research focuses on low-viscosity oils (such as toluene, chloroform, and kerosene), optimizing swelling properties by adjusting the degree of cross-linking or short-chain monomers (such as butyl acrylate), but it is almost impossible to adsorb high-viscosity pump oils; in addition, pump oils are the main component of nuclear waste and are often exposed to high-dose radiation in high-risk scenarios such as nuclear waste treatment. Resins on the market are prone to chain breakage and cross-linking failure after irradiation, resulting in a catastrophic decrease in oil absorption performance, making it difficult to meet the needs of nuclear waste treatment.

[0004] It is worth noting that pump oil is a typical high viscosity industrial oil (dynamic viscosity is usually > 40mm 2 / s, some can even reach up to 100mm 2 / s or more). Due to its long molecular chain, low polarity, and high diffusion resistance, traditional oil-absorbing resins struggle to effectively absorb waste pump oil. As industrial equipment scales up, the global annual production of waste pump oil exceeds 2 million tons, creating urgent environmental risks and resource waste that require urgent solutions. Experiments have shown that resins prepared using conventional polyacrylate monomers absorb virtually no pump oil at all. This technical bottleneck severely restricts waste pump oil recovery and increases the difficulty of nuclear waste disposal.

[0005] Therefore, developing a functionalized polyacrylate oil-absorbing resin designed for the molecular characteristics of pump oil and breaking through the limitations of existing technologies through coordinated regulation of monomer selection, copolymerization ratio, etc. has become an urgent research direction in this field. Summary of the Invention

[0006] In order to solve the problem that existing polyacrylates are difficult to adsorb high-viscosity pump oil, the present invention provides a polyacrylate resin for absorbing pump oil and a preparation method thereof.

[0007] The technical solutions of the present invention are as follows:

[0008] A polyacrylate resin for absorbing high-viscosity pump oil, wherein the pump oil is a vacuum pump oil with a kinematic viscosity of ISO VG 100;

[0009] The polyacrylic acid resin is obtained by suspension polymerization of two acrylic acid ester monomers in a specific ratio under the action of a suspending agent and a free radical initiator;

[0010] The two acrylate monomers in the specific ratio are:

[0011] Stearyl methacrylate and behenyl methacrylate or methyl methacrylate in a mass ratio of 4:1; or stearyl methacrylate and butyl acrylate in a mass ratio of 3:2;

[0012] The oil absorption rate of the polyacrylic acid resin is ≥13g / g.

[0013] Preferably, the suspending agent is water-soluble nano calcium carbonate.

[0014] Preferably, the free radical initiator is selected from one or a combination of at least two of azobisisobutyronitrile, dibenzoyl peroxide, isopropylbenzene hydroperoxide, tert-butyl hydroperoxide, diisopropylbenzene peroxide, di-tert-butyl peroxide, dibenzoyl peroxide, dodecyl peroxide, tert-butyl perbenzoate, tert-butyl pervalerate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, potassium persulfate, and ammonium persulfate.

[0015] Preferably, the total mass of the acrylic acid ester monomers accounts for 0.1% to 60% of the total mass of the suspension polymerization reaction system.

[0016] Preferably, the amount of the suspending agent is 0.1% to 30% of the total mass of the acrylate monomer.

[0017] Preferably, the amount of the free radical initiator is 0.05% to 10% of the total amount of the acrylate monomer.

[0018] Preferably, the reaction temperature of the suspension polymerization reaction is 80-100° C., and the reaction time is 2-4 hours.

[0019] Compared with the prior art, the present invention has the following specific beneficial effects:

[0020] Those skilled in the art generally believe that the dense network of short-chain monomers is the core design for efficient oil absorption, and generally believe that organic resins cannot withstand high-dose radiation, resulting in the long-term reliance on inorganic solidification schemes (such as cement solidification) in the field of nuclear waste treatment. The present invention achieves a dual breakthrough in high-viscosity pump oil adsorption and anti-radiation stability, solving the technical pain points of low recovery efficiency of waste pump oil and difficulty in nuclear waste treatment. The present invention utilizes the different lengths and chemical structures of the side chains of polymerized monomers to construct a high-performance oil-absorbing material that is conducive to the absorption of high-viscosity pump oil. The non-polarity of its side chain is similar to that of pump oil, which solves the problem of low absorption rate of existing oil-absorbing resins for oils with higher viscosity such as pump oil, and fills the gap in oil-absorbing resins for pump oil.

[0021] The raw materials of the present invention are readily available, the method is simple and easy to implement, and the high-performance oil-absorbing resin prepared has a high absorption rate for pump oil, reaching up to 17.4g / g in testing. Even after prolonged high-dose radiation exposure, the adsorption capacity can still meet the requirements of nuclear waste treatment. The preparation process does not use any organic solvents, making it safe and environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 Schematic diagram of the oil absorption test process;

[0023] Figure 2 This is a diagram of the oil-absorbing resin particles before and after oil absorption in Example 1;

[0024] Figure 3 The state diagram of the resin particles before and after absorbing toluene, kerosene and chloroform in Comparative Example 1;

[0025] Figure 4 Schematic diagram of the resin particles before and after absorbing pump oil in Comparative Example 1;

[0026] Figure 5 The state diagram of the resin particles before and after absorbing toluene, kerosene and chloroform in Comparative Example 3;

[0027] Figure 6 This is a schematic diagram of the resin particles before and after absorbing pump oil in Comparative Example 3. DETAILED DESCRIPTION

[0028] To make the technical solution of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings of the present invention. It should be noted that the following embodiments are only used to better understand the technical solution of the present invention and should not be understood as limiting the present invention. The substances mentioned in the following examples can all be obtained commercially.

[0029] Example 1.

[0030] Under nitrogen protection, 15 grams of octadecyl methacrylate, 10 grams of butyl acrylate, and 2.25 grams of nano-calcium carbonate were added to 180 milliliters of water and stirred until completely dispersed. The temperature was raised, and when the temperature reached 50°C, 0.05 grams of initiator BPO was added. The reaction was maintained at 95°C for 3 hours. The polymerized monomer accounted for 12% of the total mass of the reaction system. After the reaction was completed, oil-absorbing resin particles with a small amount of nano-calcium carbonate coated on the surface were obtained by filtration.

[0031] Oil absorption rate test: Place the obtained resin particles in a stainless steel filter bag, weigh it, and put the stainless steel filter bag into pump oil (Gonghua vacuum pump oil, viscosity is 100mm 2 / s) for 48 h, then take it out and wipe off the pump oil on the surface, and weigh it again. Figure 1 The oil absorption process is shown in Figure 2. The oil absorption rate of the obtained oil absorption resin is 17.4 g / g after testing.

[0032] The resulting oil-absorbing resin particles were irradiated at a high dose (200 kGy) for 200 hours. The oil absorption rate of the irradiated resin was then tested according to the aforementioned testing procedure, resulting in a value of over 2 g / g. Although the oil absorption decreased due to cross-linking during irradiation, the resin still met the practical requirements for nuclear waste disposal.

[0033] Example 2.

[0034] Under nitrogen protection, 20 grams of octadecyl methacrylate, 5 grams of behenyl methacrylate, and 2.25 grams of nano-calcium carbonate were added to 180 milliliters of water and stirred until completely dispersed. The temperature was raised. When the temperature reached 50°C, 0.05 grams of initiator BPO was added and the reaction was maintained at 95°C for 3 hours. The polymerized monomer accounted for 12% of the total mass of the reaction system. After the reaction was completed, oil-absorbing resin particles with a small amount of nano-calcium carbonate coated on the surface were obtained by filtration.

[0035] The oil absorption rate of the oil-absorbing resin obtained by testing is 15.1 g / g.

[0036] Example 3.

[0037] Under nitrogen protection, 20 grams of octadecyl methacrylate, 5 grams of methyl methacrylate, and 2.25 grams of nano-calcium carbonate were added to 180 milliliters of water and stirred until completely dispersed. The temperature was raised. When the temperature reached 50°C, 0.05 grams of initiator BPO was added and the reaction was maintained at 95°C for 3 hours. The polymerized monomer accounted for 12% of the total mass of the reaction system. After the reaction was completed, oil-absorbing resin particles with a small amount of nano-calcium carbonate coated on the surface were obtained by filtration.

[0038] The oil absorption rate of the oil-absorbing resin obtained by testing is 13.1 g / g.

[0039] Comparative Example 1.

[0040] Poly methacrylate octadecyl homopolymer (PMA18) can absorb toluene, kerosene, and chloroform with oil absorption rates of 10.3 g / g, 13.1 g / g, and 13.2 g / g. The actual oil absorption diagram is as follows: Figure 3 As shown, a is the original PMA18 material, b is PMA18 after absorbing toluene, c is PMA18 after absorbing kerosene, and d is PMA18 after absorbing chloroform. Figure 4 As shown, a is the original PMA18 material, and b is the PMA18 after absorbing pump oil.

[0041] Comparative Example 2.

[0042] Polymethyl methacrylate homopolymer (PMMA) is soluble in chloroform and has little absorption to toluene, kerosene and pump oil.

[0043] Comparative Example 3.

[0044] Polybutyl acrylate homopolymer (PA4) can absorb toluene, kerosene, and chloroform, with oil absorption rates of 14.6g / g, 3.2g / g, and 18.1g / g, respectively. The actual oil absorption diagram is as follows: Figure 5 As shown, a is the original PA4 material, b is PA4 after absorbing toluene, c is PA4 after absorbing kerosene, and d is PA4 after absorbing chloroform. Figure 6 As shown, a is the original PA4 material, and b is the PA4 after absorbing pump oil.

[0045] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will readily appreciate that other variations or modifications based on the above descriptions are possible. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. A polyacrylate resin for absorbing high-viscosity pump oil, characterized in that: The pump oil is a vacuum pump oil with a kinematic viscosity of ISO VG 100; The polyacrylic acid resin is obtained by suspension polymerization of two acrylic acid ester monomers in a specific ratio under the action of a suspending agent and a free radical initiator; The two acrylate monomers in the specific ratio are: Stearyl methacrylate and behenyl methacrylate or methyl methacrylate in a mass ratio of 4:1; or stearyl methacrylate and butyl acrylate in a mass ratio of 3:2; The oil absorption rate of the polyacrylic acid resin is ≥13g / g.

2. The polyacrylate resin for absorbing high-viscosity pump oil according to claim 1, characterized in that: The suspending agent is water-soluble nano calcium carbonate.

3. The polyacrylate resin for absorbing high-viscosity pump oil according to claim 1, characterized in that: The free radical initiator is selected from one or a combination of at least two of azobisisobutyronitrile, dibenzoyl peroxide, isopropylbenzene hydroperoxide, tert-butyl hydroperoxide, diisopropylbenzene peroxide, di-tert-butyl peroxide, dibenzoyl peroxide, dodecyl peroxide, tert-butyl perbenzoate, tert-butyl pervalerate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, potassium persulfate, and ammonium persulfate.

4. The polyacrylate resin for absorbing high-viscosity pump oil according to claim 1, characterized in that: The total mass of the acrylic acid ester monomer accounts for 0.1% to 60% of the total mass of the suspension polymerization reaction system.

5. The polyacrylate resin for absorbing high-viscosity pump oil according to claim 1, characterized in that: The amount of the suspending agent used is 0.1% to 30% of the total mass of the acrylic ester monomer.

6. The polyacrylate resin for absorbing high-viscosity pump oil according to claim 1, characterized in that: The amount of the free radical initiator is 0.05% to 10% of the total amount of the acrylate monomer.

7. The polyacrylate resin for absorbing high-viscosity pump oil according to claim 1, characterized in that: The reaction temperature of the suspension polymerization reaction is 80-100° C., and the reaction time is 2-4 hours.

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