Closed hollow shell-shaped resin with high adsorption capacity and high adsorption speed and preparation method of closed hollow shell-shaped resin

Abstract

The invention provides closed hollow shell-shaped resin with high adsorption capacity and high adsorption speed and a preparation method of the closed hollow shell-shaped resin, and belongs to the technical field of high-molecular polymers. The preparation method comprises the following steps: S1, mixing an organic solvent and an oil-soluble active polymer or mixing the oil-soluble active polymer and an oil-soluble active monomer, and mixing an oil-soluble cross-linking agent and an oil-soluble initiator; step S2, free radical polymerization reaction; s3, maintaining the temperature of the oily polymerization mixed system to be + / -20 DEG C of the temperature of the free radical polymerization reaction in the step S2, dropwise adding the oily polymerization mixed system into a precipitant with the temperature of 0-25 DEG C, and precipitating to separate out a closed hollow shell-shaped resin crude product; and S4, filtering, washing with water, and drying to constant weight to obtain the closed hollow shell-shaped resin. The preparation process is simple, the controllability of the technological process is high, and the prepared closed hollow shell-shaped resin not only has high adsorption capacity, but also has high adsorption speed and excellent oil retention.

Description

Technical Field

[0001] The invention relates to the technical field of high molecular polymers, and in particular to a closed hollow shell-shaped resin with high adsorption capacity and fast adsorption speed and a preparation method thereof. Background Art

[0002] With the rapid development of the economy, the number of fossil fuel or chemical leakage accidents has increased rapidly and the harm has become increasingly serious in the context of increasingly frequent oil extraction, transportation and refining. On the other hand, with the improvement of environmental protection requirements and the enhancement of people's environmental awareness, the treatment of industrial oily wastewater and sudden oil spills has also become a major problem. However, traditional treatment methods have problems such as low efficiency, cumbersome process, non-recyclability, and even secondary pollution or deepening pollution. In response to the above problems, technical personnel in the industry have continuously researched and developed high-performance oil-absorbing new materials such as sponges, aerogels and oil-absorbing resins. Among them, sponges and aerogels have attracted much attention due to their high adsorption capacity and recyclability, but their porous structures are very fragile after adsorption saturation, and the adsorbent is easy to leak and cause secondary pollution. Therefore, in the treatment of sudden oil spills and oily wastewater, in order to prevent secondary leakage and realize the reuse of oil-containing organic solvents, three-dimensional network cross-linked adsorption resins with stable oil retention properties have become more advantageous materials.

[0003] The adsorption process of three-dimensional network cross-linked adsorption resin is a process in which the surrounding oil enters the three-dimensional network and accumulates through the surface adsorption and internal capillary diffusion of the resin. In this process, the resin is swollen by the oil molecules adsorbed by itself, and the swelling equilibrium is reached, that is, the adsorption equilibrium is reached. However, under normal circumstances, when the adsorption capacity is increased by reducing the cross-linking density, the swelling process takes a long time, resulting in a low adsorption rate. Therefore, in actual sudden leakage accidents, it is particularly important to improve the three-dimensional network cross-linked adsorption resin so that it can efficiently adsorb a large amount of organic hazardous waste liquid in a short time. Summary of the invention

[0004] The present invention aims to provide a closed hollow shell-shaped resin having both high adsorption capacity and fast adsorption speed and a preparation method thereof. The preparation process is simple and the process is highly controllable. The prepared closed hollow shell-shaped resin not only has high adsorption capacity, but also has fast adsorption speed and excellent oil retention.

[0005] The technical solution adopted by the present invention is:

[0006] A method for preparing a closed hollow shell resin having both high adsorption capacity and fast adsorption speed comprises the following steps:

[0007] Step S1, adding an organic solvent into a reactor equipped with a condensing device and a stirring device, and adding an oil-soluble active polymer or an oil-soluble active polymer and an oil-soluble active monomer, as well as an oil-soluble crosslinking agent and an oil-soluble initiator therein under stirring, continuously stirring, and obtaining an oily mixed system after thorough dissolution;

[0008] Step S2, heating the oily mixed system to 70-90° C. under continuous stirring, and keeping the temperature for 24-48 hours to perform a free radical polymerization reaction to obtain an oily polymer mixed system;

[0009] Step S3, after the free radical polymerization reaction is completed, the temperature of the oily polymerization mixture is maintained at the temperature of the free radical polymerization reaction in step S2 ± 20°C, and the oily polymerization mixture is dropwise added into a precipitant with a temperature of 0-25°C to precipitate a closed hollow shell resin crude product;

[0010] Step S4, filtering, washing with water and drying to constant weight to obtain a closed hollow shell resin.

[0011] Furthermore, in parts by weight, the amount of each raw material is:

[0012] The organic solvent, 150-600 parts;

[0013] The oil-soluble active monomer, 0-5 parts;

[0014] Oil-soluble active polymer, 5-25 parts;

[0015] The oil-soluble cross-linking agent, 1 to 5 parts;

[0016] The oil-soluble initiator is 0.2 to 2 parts.

[0017] Furthermore, the amount of the oil-soluble active monomer is 0.5 to 4.5 parts by weight.

[0018] Furthermore, the organic solvent is one or more of n-hexane, cyclohexane, heptane, petroleum ether, toluene, xylene, chlorobenzene and ethyl acetate.

[0019] Further, the oil-soluble active monomer is one or more of styrene, α-methylstyrene, 2-chlorostyrene, 4-chlorostyrene, 2-fluorostyrene, 4-fluorostyrene, 2-bromostyrene, 4-bromostyrene, 2-iodostyrene, 4-iodostyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-propylstyrene, 4-tert-butylstyrene, pentylstyrene, acrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, octadecyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate and monoglycerol methacrylate.

[0020] Furthermore, the oil-soluble active polymer is one or more of EPDM rubber, butyl rubber, chloroprene rubber, C5 petroleum resin, and C9 petroleum resin.

[0021] Furthermore, the oil-soluble crosslinking agent is one or more of trimethylolpropane triacrylate, diethyl diallyl malonate, divinylbenzene, diallyl phthalate, diallyl isophthalate and diallyl tetrabromophthalate.

[0022] Furthermore, the oil-soluble initiator is one or more of azobisisobutyronitrile and benzoyl peroxide.

[0023] Furthermore, the precipitant is one or more of methanol, ethanol, ethylene glycol, and acetone.

[0024] Based on the same inventive concept, the present invention also provides a closed hollow shell-shaped resin having both high adsorption capacity and fast adsorption speed, which is prepared by the aforementioned preparation method of the closed hollow shell-shaped resin having both high adsorption capacity and fast adsorption speed.

[0025] The beneficial effects of the present invention are:

[0026] 1. The present invention provides a method for preparing a closed hollow shell-shaped resin having both high adsorption capacity and fast adsorption speed. The preparation process is simple, the process is highly controllable, the yield of the closed hollow shell-shaped resin is high, and the wall thickness, cavity size and particle size of the closed hollow shell-shaped resin can be regulated within a wide range.

[0027] 2. The present invention provides a closed hollow shell-shaped resin, which not only has a high adsorption capacity, but also has a fast adsorption speed and excellent oil retention. It solves the contradictory growth problem of traditional cross-linked adsorption resins in terms of adsorption capacity and adsorption rate, and is more applicable to actual scenarios. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0029] Figure 1 This is a microscopic morphology of the resin sample prepared in Example 7.

[0030] Figure 2 This is a microscopic morphology of the resin sample prepared in Example 7 after being cut open. DETAILED DESCRIPTION

[0031] In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise", "axial", "radial", "circumferential" and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as limiting the present invention.

[0032] The disclosure below provides many different embodiments or examples to realize different structures of the present invention. In order to simplify the disclosure of the present invention, the parts and settings of specific examples are described below. Of course, they are only examples, and the purpose is not to limit the present invention.

[0033] The embodiments of the invention are described in detail below with reference to the accompanying drawings.

[0034] Example 1

[0035] A method for preparing a closed hollow shell resin having both high adsorption capacity and fast adsorption speed comprises the following steps:

[0036] Step S1, adding 150 kg of toluene into a reactor equipped with a condensing device and a stirring device, and adding 5 kg of ethylene propylene rubber, 1 kg of trimethylolpropane triacrylate and 0.2 kg of benzoyl peroxide thereto under stirring, and continuously stirring to obtain an oily mixed system after thorough dissolution;

[0037] Step S2, heating the oily mixed system to 70° C. under continuous stirring, and keeping the temperature for 48 hours to perform a free radical polymerization reaction to obtain an oily polymer mixed system;

[0038] Step S3, after the free radical polymerization reaction is completed, the temperature of the oily polymerization mixture is maintained at 70° C., and the oily polymerization mixture is dropwise added into methanol at a temperature of 15° C. using a syringe to precipitate a closed hollow shell-shaped resin crude product;

[0039] Step S4, filtering, washing with water and drying to constant weight to obtain a closed hollow shell resin.

[0040] Example 2

[0041] A method for preparing a closed hollow shell resin having both high adsorption capacity and fast adsorption speed comprises the following steps:

[0042] Step S1, adding 600 kg of toluene into a reactor equipped with a condensing device and a stirring device, and adding 25 kg of ethylene propylene rubber, 5 kg of trimethylolpropane triacrylate and 2 kg of benzoyl peroxide thereto under stirring, and continuously stirring to obtain an oily mixed system after thorough dissolution;

[0043] Step S2, heating the oily mixed system to 70° C. under continuous stirring, and keeping the temperature for 48 hours to perform a free radical polymerization reaction to obtain an oily polymer mixed system;

[0044] Step S3, after the free radical polymerization reaction is completed, the temperature of the oily polymerization mixture is maintained at 70° C., and the oily polymerization mixture is dropwise added into methanol at a temperature of 15° C. using a syringe to precipitate a closed hollow shell-shaped resin crude product;

[0045] Step S4, filtering, washing with water and drying to constant weight to obtain a closed hollow shell resin.

[0046] Example 3

[0047] A method for preparing a closed hollow shell resin having both high adsorption capacity and fast adsorption speed comprises the following steps:

[0048] Step S1, adding 350 kg of toluene into a reactor equipped with a condensing device and a stirring device, and adding 17 kg of ethylene propylene rubber, 2 kg of trimethylolpropane triacrylate and 0.5 kg of benzoyl peroxide thereto under stirring, and continuously stirring to obtain an oily mixed system after thorough dissolution;

[0049] Step S2, heating the oily mixed system to 70° C. under continuous stirring, and keeping the temperature for 48 hours to perform a free radical polymerization reaction to obtain an oily polymer mixed system;

[0050] Step S3, after the free radical polymerization reaction is completed, the temperature of the oily polymerization mixture is maintained at 70° C., and the oily polymerization mixture is dropwise added into methanol at a temperature of 15° C. using a syringe to precipitate a closed hollow shell-shaped resin crude product;

[0051] Step S4, filtering, washing with water and drying to constant weight to obtain a closed hollow shell resin.

[0052] Example 4

[0053] A method for preparing a closed hollow shell resin having both high adsorption capacity and fast adsorption speed comprises the following steps:

[0054] Step S1, adding 350 kg of toluene into a reactor equipped with a condensing device and a stirring device, and adding 23 kg of ethylene propylene rubber and 2 kg of 4-tert-butyl styrene, as well as 2 kg of trimethylolpropane triacrylate and 0.5 kg of benzoyl peroxide thereto under stirring, continuously stirring, and obtaining an oily mixed system after thorough dissolution;

[0055] Step S2, heating the oily mixed system to 70° C. under continuous stirring, and keeping the temperature for 48 hours to perform a free radical polymerization reaction to obtain an oily polymer mixed system;

[0056] Step S3, after the free radical polymerization reaction is completed, the temperature of the oily polymerization mixture is maintained at 70° C., and the oily polymerization mixture is dropwise added into methanol at a temperature of 15° C. using a syringe to precipitate a closed hollow shell-shaped resin crude product;

[0057] Step S4, filtering, washing with water and drying to constant weight to obtain a closed hollow shell resin.

[0058] Example 5

[0059] A method for preparing a closed hollow shell resin having both high adsorption capacity and fast adsorption speed comprises the following steps:

[0060] Step S1, adding 350 kg of toluene into a reactor equipped with a condensing device and a stirring device, and adding 16.5 kg of ethylene propylene rubber and 0.5 kg of 4-tert-butyl styrene, as well as 2 kg of trimethylolpropane triacrylate and 0.5 kg of benzoyl peroxide thereto under stirring, and continuously stirring to obtain an oily mixed system after thorough dissolution;

[0061] Step S2, heating the oily mixed system to 70° C. under continuous stirring, and keeping the temperature for 48 hours to perform a free radical polymerization reaction to obtain an oily polymer mixed system;

[0062] Step S3, after the free radical polymerization reaction is completed, the temperature of the oily polymerization mixture is maintained at 70° C., and the oily polymerization mixture is dropwise added into methanol at a temperature of 15° C. using a syringe to precipitate a closed hollow shell-shaped resin crude product;

[0063] Step S4, filtering, washing with water and drying to constant weight to obtain a closed hollow shell resin.

[0064] Example 6

[0065] A method for preparing a closed hollow shell resin having both high adsorption capacity and fast adsorption speed comprises the following steps:

[0066] Step S1, adding 350 kg of toluene into a reactor equipped with a condensing device and a stirring device, and adding 23 kg of ethylene propylene rubber and 2 kg of 4-tert-butyl styrene, as well as 2 kg of trimethylolpropane triacrylate and 0.5 kg of benzoyl peroxide thereto under stirring, continuously stirring, and obtaining an oily mixed system after thorough dissolution;

[0067] Step S2, heating the oily mixed system to 70° C. under continuous stirring, and keeping the temperature for 48 hours to perform a free radical polymerization reaction to obtain an oily polymer mixed system;

[0068] Step S3, after the free radical polymerization reaction is completed, the temperature of the oily polymerization mixture is maintained at 70° C., and the oily polymerization mixture is added dropwise into a mixture of methanol and acetone (the volume ratio of the two is 1:1) at a temperature of 15° C. using a syringe to precipitate a closed hollow shell resin crude product;

[0069] Step S4, filtering, washing with water and drying to constant weight to obtain a closed hollow shell resin.

[0070] Example 7

[0071] A method for preparing a closed hollow shell resin having both high adsorption capacity and fast adsorption speed comprises the following steps:

[0072] Step S1, adding 130 kg of toluene and 220 kg of n-hexane into a reactor equipped with a condensing device and a stirring device, and adding 23 kg of ethylene propylene rubber and 2 kg of 4-tert-butyl styrene, as well as 2 kg of trimethylolpropane triacrylate and 0.5 kg of benzoyl peroxide thereto under stirring, continuously stirring, and obtaining an oily mixed system after thorough dissolution;

[0073] Step S2, heating the oily mixed system to 70° C. under continuous stirring conditions, and keeping the temperature for 48 hours to perform a free radical polymerization reaction to obtain an oily polymer mixed system;

[0074] Step S3, after the free radical polymerization reaction is completed, the temperature of the oily polymerization mixture is maintained at 70° C., and the oily polymerization mixture is dropwise added into methanol at a temperature of 15° C. using a syringe to precipitate a closed hollow shell-shaped resin crude product;

[0075] Step S4, filtering, washing with water and drying to constant weight to obtain a closed hollow shell resin.

[0076] The microscopic morphology of the resin sample prepared in this example is as follows: Figure 1 and Figure 2 As shown in . It can be clearly seen from the figure that the resin particles are in the shape of closed hollow shells.

[0077] Example 8

[0078] A method for preparing a closed hollow shell resin having both high adsorption capacity and fast adsorption speed comprises the following steps:

[0079] Step S1, adding 130 kg of toluene and 220 kg of n-hexane into a reactor equipped with a condensing device and a stirring device, and adding 23 kg of C5 petroleum resin and 2 kg of styrene, as well as 2 kg of divinylbenzene and 0.5 kg of benzoyl peroxide thereto under stirring, continuously stirring, and obtaining an oily mixed system after thorough dissolution;

[0080] Step S2, heating the oily mixed system to 70° C. under continuous stirring, and keeping the temperature for 48 hours to perform a free radical polymerization reaction to obtain an oily polymer mixed system;

[0081] Step S3, after the free radical polymerization reaction is completed, the temperature of the oily polymerization mixture is maintained at 70° C., and the oily polymerization mixture is dropwise added into methanol at a temperature of 15° C. using a syringe to precipitate a closed hollow shell-shaped resin crude product;

[0082] Step S4, filtering, washing with water and drying to constant weight to obtain a closed hollow shell resin.

[0083] Example 9

[0084] A method for preparing a closed hollow shell resin having both high adsorption capacity and fast adsorption speed comprises the following steps:

[0085] Step S1, adding 130 kg of toluene and 220 kg of n-hexane into a reactor equipped with a condensing device and a stirring device, and adding 23 kg of ethylene propylene rubber and 2 kg of 4-tert-butyl styrene, as well as 2 kg of trimethylolpropane triacrylate and 0.5 kg of benzoyl peroxide thereto under stirring, continuously stirring, and obtaining an oily mixed system after thorough dissolution;

[0086] Step S2, heating the oily mixed system to 90° C. under continuous stirring conditions, and keeping the temperature for 24 hours to perform a free radical polymerization reaction to obtain an oily polymer mixed system;

[0087] Step S3, after the free radical polymerization reaction is completed, the temperature of the oily polymerization mixture is maintained at 70° C., and the oily polymerization mixture is dropwise added into methanol at a temperature of 15° C. using a syringe to precipitate a closed hollow shell-shaped resin crude product;

[0088] Step S4, filtering, washing with water and drying to constant weight to obtain a closed hollow shell resin.

[0089] Example 10

[0090] A method for preparing a closed hollow shell resin having both high adsorption capacity and fast adsorption speed comprises the following steps:

[0091] Step S1, adding 130 kg of toluene and 220 kg of n-hexane into a reactor equipped with a condensing device and a stirring device, and adding 23 kg of ethylene propylene rubber and 2 kg of 4-tert-butyl styrene, as well as 2 kg of trimethylolpropane triacrylate and 0.5 kg of benzoyl peroxide thereto under stirring, continuously stirring, and obtaining an oily mixed system after thorough dissolution;

[0092] Step S2, heating the oily mixed system to 80° C. under continuous stirring, and keeping the temperature for 36 hours to perform a free radical polymerization reaction to obtain an oily polymer mixed system;

[0093] Step S3, after the free radical polymerization reaction is completed, the temperature of the oily polymerization mixture is maintained at 70° C., and the oily polymerization mixture is dropwise added into methanol at a temperature of 15° C. using a syringe to precipitate a closed hollow shell-shaped resin crude product;

[0094] Step S4, filtering, washing with water and drying to constant weight to obtain a closed hollow shell resin.

[0095] Embodiment 11

[0096] A method for preparing a closed hollow shell resin having both high adsorption capacity and fast adsorption speed comprises the following steps:

[0097] Step S1, adding 130 kg of toluene and 220 kg of n-hexane into a reactor equipped with a condensing device and a stirring device, and adding 23 kg of ethylene propylene rubber and 2 kg of methyl methacrylate, as well as 2 kg of trimethylolpropane triacrylate and 0.5 kg of benzoyl peroxide thereto under stirring, continuously stirring, and obtaining an oily mixed system after thorough dissolution;

[0098] Step S2, heating the oily mixed system to 70° C. under continuous stirring, and keeping the temperature for 48 hours to perform a free radical polymerization reaction to obtain an oily polymer mixed system;

[0099] Step S3, after the free radical polymerization reaction is completed, the temperature of the oily polymerization mixture is maintained at 70° C., and the oily polymerization mixture is dropwise added into methanol at a temperature of 15° C. using a syringe to precipitate a closed hollow shell-shaped resin crude product;

[0100] Step S4, filtering, washing with water and drying to constant weight to obtain a closed hollow shell resin.

[0101] Comparative Example 1

[0102] A method for preparing a closed hollow shell resin having both high adsorption capacity and fast adsorption speed comprises the following steps:

[0103] Step S1, adding 130 kg of toluene and 220 kg of n-hexane into a reactor equipped with a condensing device and a stirring device, and adding 23 kg of ethylene propylene rubber and 2 kg of 4-tert-butyl styrene, as well as 2 kg of trimethylolpropane triacrylate and 0.5 kg of benzoyl peroxide thereto under stirring, continuously stirring, and obtaining an oily mixed system after thorough dissolution;

[0104] Step S2, heating the oily mixed system to 70° C. under continuous stirring, and keeping the temperature for 48 hours to perform a free radical polymerization reaction to obtain an oily polymer mixed system;

[0105] Step S3, after the free radical polymerization reaction is completed, the temperature of the oily polymerization mixture is maintained at 40° C., and the oily polymerization mixture is dropwise added into methanol at a temperature of 15° C. using a syringe to precipitate a closed hollow shell resin crude product;

[0106] Step S4, filtering, washing with water and drying to constant weight to obtain a closed hollow shell resin.

[0107] Comparative Example 2

[0108] A method for preparing a closed hollow shell resin having both high adsorption capacity and fast adsorption speed comprises the following steps:

[0109] Step S1, adding 130 kg of toluene and 220 kg of n-hexane into a reactor equipped with a condensing device and a stirring device, and adding 23 kg of ethylene propylene rubber and 2 kg of 4-tert-butyl styrene, as well as 2 kg of trimethylolpropane triacrylate and 0.5 kg of benzoyl peroxide thereto under stirring, continuously stirring, and obtaining an oily mixed system after thorough dissolution;

[0110] Step S2, heating the oily mixed system to 70° C. under continuous stirring, and keeping the temperature for 48 hours to perform a free radical polymerization reaction to obtain an oily polymer mixed system;

[0111] Step S3, after the free radical polymerization reaction is completed, the temperature of the oily polymerization mixture is maintained at 70° C., and the oily polymerization mixture is dropwise added into methanol at a temperature of 35° C. using a syringe to precipitate a closed hollow shell-shaped resin crude product;

[0112] Step S4, filtering, washing with water and drying to constant weight to obtain a closed hollow shell resin.

[0113] Comparative Example 3

[0114] A method for preparing a closed hollow shell resin having both high adsorption capacity and fast adsorption speed comprises the following steps:

[0115] Step S1, adding 130 kg of toluene and 220 kg of n-hexane into a reactor equipped with a condensing device and a stirring device, and adding 1 kg of ethylene propylene rubber and 10 kg of 4-tert-butyl styrene, as well as 7 kg of trimethylolpropane triacrylate and 0.5 kg of benzoyl peroxide thereto under stirring, continuously stirring, and obtaining an oily mixed system after thorough dissolution;

[0116] Step S2, heating the oily mixed system to 70° C. under continuous stirring, and keeping the temperature for 48 hours to perform a free radical polymerization reaction to obtain an oily polymer mixed system;

[0117] Step S3, after the free radical polymerization reaction is completed, the temperature of the oily polymerization mixture is maintained at 70° C., and the oily polymerization mixture is dropwise added into methanol at a temperature of 15° C. using a syringe to precipitate a closed hollow shell-shaped resin crude product;

[0118] Step S4, filtering, washing with water and drying to constant weight to obtain a closed hollow shell resin.

[0119] The resin samples prepared in Examples 1 to 11 and Comparative Examples 1 to 3 were subjected to the following tests:

[0120] (1) Particle size distribution: The particle size of the resin sample was statistically analyzed using scanning electron microscopy (SEM, Zeiss Ultra 55).

[0121] (2) Single particle micromorphology and single particle wall thickness: After cutting, the microstructure of the resin sample was observed using a scanning electron microscope (SEM, Zeiss Ultra55).

[0122] (3) Oil absorption: In a sealed container, place 0.1 g of resin sample (M1) in a 4×4×2 cm 3 The stainless steel mesh cage (M0) is immersed in oil (chloroform CHCl3 is used as a representative in this embodiment) and left to stand for a period of time at room temperature to achieve saturated absorption. During this process, the stainless steel mesh cage is taken out of the oil at different times and wiped with filter paper to remove excess oil in the stainless steel mesh cage to weigh the mass (M2).

[0123] The oil absorption of the resin sample is calculated by the following formula:

[0124] (Formula 1);

[0125] Among them, Q (mL g -1 ) is the oil absorption, defined as the volume of oil absorbed per gram of dry resin sample.

[0126] (4) Oil absorption rate: The time it takes for the resin sample to reach saturated oil absorption is used to characterize the oil absorption rate of the resin sample.

[0127] By testing the oil absorption Q (mL.g -1 ), and draw a curve of the change of oil absorption Q value over time to obtain the saturated oil absorption time of the resin sample.

[0128] (5) Oil retention rate: Centrifuge the saturated resin sample (mass m1) at 1000 rpm for 5 minutes, immediately separate the spilled oil through a 1000-mesh sieve, and wipe it with filter paper to remove the spilled oil. Weigh the mass of the centrifuged resin sample (m2). The ratio of the two, i.e. (m2 / m1), corresponds to the oil retention of the resin sample at the centrifugal speed.

[0129] The test results of the resin samples prepared in Examples 1 to 11 and Comparative Examples 1 to 3 are shown in Table 1 below.

[0130] Table 1 Test results of the resin samples prepared in Examples 1 to 11 and Comparative Examples 1 to 3

[0131] Project Number Example 1 Example 2 Example 3 Example 4 Example 5 Particle size distribution / mm 1.8~2.8 2.0~2.8 2.0~2.8 1~1.8 1~1.6 Single microscopic morphology Hollow shell Hollow shell Hollow shell Hollow shell Hollow shell Single particle wall thickness / μm 120 125 116 75 75 Oil absorption / mL / g 28.7 26.9 36.9 42.5 38.5 Oil absorption rate / min 75 75 70 65 70 Oil retention rate / % 86 89 86 93 95

[0132] Table 1-1 Test results of the resin samples prepared in Examples 1 to 11 and Comparative Examples 1 to 3

[0133] Project Number Example 6 Example 7 Example 8 Example 9 Example 10 Particle size distribution / mm 1.2~2.0 1.2~1.8 1~2 1.3~2.0 1.2~1.8 Single microscopic morphology Hollow shell Hollow shell Hollow shell Hollow shell Hollow shell Single particle wall thickness / μm 90 75 130 80 75 Oil absorption / mL / g 40.7 55.6 28.2 49.8 52.1 Oil absorption rate / min 80 60 80 60 60 Oil retention rate / % 90 99 90 99 99

[0134] Table 1-2 Test results of the resin samples prepared in Examples 1 to 11 and Comparative Examples 1 to 3

[0135] Project Number Embodiment 11 Comparative Example 1 Comparative Example 2 Comparative Example 3 Particle size distribution / mm 1.2~1.8 1.5~2.5 1.5~2.5 0.5~1 Single microscopic morphology Hollow shell Hollow shell shape (sphericity deteriorates) Hollow shell (agglomerate) Solid particles Single particle wall thickness / μm 78 93 103 / Oil absorption / mL / g 48.8 50.3 47.9 7.8 Oil absorption rate / min 65 60 65 30 Oil retention rate / % 98 99 99 81

[0136] It can be seen from the test data in Table 1 that the closed hollow shell resin prepared by the method in this embodiment not only has a high adsorption capacity, but also has a fast adsorption speed and excellent oil retention.

Claims

1. A method for preparing a closed hollow shell resin having both high adsorption capacity and fast adsorption speed, characterized in that: The following steps are involved: Step S1, adding an organic solvent into a reactor equipped with a condensing device and a stirring device, and adding an oil-soluble active polymer or an oil-soluble active polymer and an oil-soluble active monomer, as well as an oil-soluble crosslinking agent and an oil-soluble initiator therein under stirring, continuously stirring, and obtaining an oily mixed system after thorough dissolution; Step S2, heating the oily mixed system to 70-90° C. under continuous stirring, and keeping the temperature for 24-48 hours to perform a free radical polymerization reaction to obtain an oily polymer mixed system; Step S3, after the free radical polymerization reaction is completed, the temperature of the oily polymerization mixture is maintained at the temperature of the free radical polymerization reaction in step S2 ± 20°C, and the oily polymerization mixture is dropwise added into a precipitant with a temperature of 0-25°C to precipitate a closed hollow shell resin crude product; Step S4, filtering, washing with water and drying to constant weight to obtain a closed hollow shell resin.

2. The method for preparing a closed hollow shell resin having high adsorption capacity and fast adsorption speed according to claim 1, characterized in that: In parts by weight, the amount of each raw material is: The organic solvent, 150-600 parts; The oil-soluble active monomer, 0-5 parts; Oil-soluble active polymer, 5-25 parts; The oil-soluble cross-linking agent, 1 to 5 parts; The oil-soluble initiator is 0.2 to 2 parts.

3. The method for preparing a closed hollow shell resin having high adsorption capacity and fast adsorption speed according to claim 1, characterized in that: The amount of the oil-soluble active monomer used is 0.5 to 4.5 parts by weight.

4. The method for preparing a closed hollow shell resin having high adsorption capacity and fast adsorption speed according to claim 1, characterized in that: The organic solvent is one or more of n-hexane, cyclohexane, heptane, petroleum ether, toluene, xylene, chlorobenzene and ethyl acetate.

5. The method for preparing a closed hollow shell resin having high adsorption capacity and fast adsorption speed according to claim 1, characterized in that: The oil-soluble active monomer is one or more of styrene, α-methylstyrene, 2-chlorostyrene, 4-chlorostyrene, 2-fluorostyrene, 4-fluorostyrene, 2-bromostyrene, 4-bromostyrene, 2-iodostyrene, 4-iodostyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-propylstyrene, 4-tert-butylstyrene, pentylstyrene, acrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, octadecyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate and monoglycerol methacrylate.

6. The method for preparing a closed hollow shell resin having high adsorption capacity and fast adsorption speed according to claim 1, characterized in that: The oil-soluble active polymer is one or more of EPDM rubber, butyl rubber, chloroprene rubber, C5 petroleum resin and C9 petroleum resin.

7. The method for preparing a closed hollow shell resin having high adsorption capacity and fast adsorption speed according to claim 1, characterized in that: The oil-soluble crosslinking agent is one or more of trimethylolpropane triacrylate, diethyl diallyl malonate, divinylbenzene, diallyl phthalate, diallyl isophthalate and diallyl tetrabromophthalate.

8. The method for preparing a closed hollow shell resin having high adsorption capacity and fast adsorption speed according to claim 1, characterized in that: The oil-soluble initiator is one or more of azobisisobutyronitrile and benzoyl peroxide.

9. The method for preparing a closed hollow shell resin having high adsorption capacity and fast adsorption speed according to any one of claims 1 to 8, characterized in that: The precipitant is one or more of methanol, ethanol, ethylene glycol and acetone.

10. A closed hollow shell resin having both high adsorption capacity and fast adsorption speed, characterized in that: The method for preparing a closed hollow shell resin having high adsorption capacity and fast adsorption speed as described in any one of claims 1 to 9 is adopted.

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