High oil absorption material of styrene-butadiene-styrene block copolymer, preparation method and application thereof

Abstract

The present invention discloses a high-oil-absorbing material, preparation method, and application of a styrene-butadiene-styrene block copolymer. Specifically, the crosslinked polymer is obtained by a light-promoted thiol-ene click reaction between the olefins of the photocrosslinked styrene-butadiene-styrene block copolymer and the thiol groups of a polythiol crosslinker. This method has the advantages of simple and convenient preparation, readily available raw materials, high oil absorption capacity and selectivity, floating on water before and after adsorption, good reusability, and low cost.

Description

Technical Field

[0001] The present invention relates to the technical field of functional polymers, and in particular to a high oil absorption material of a styrene-butadiene-styrene block copolymer, a preparation method and an application thereof. Background Art

[0002] With the rapid development of industry, the extraction, transportation, and use of petroleum and its derivatives are becoming increasingly frequent. Consequently, oil spills and organic solvent leaks occur annually, causing serious environmental, ecological, and health problems worldwide, particularly harming the marine environment. Furthermore, the rapid development of the nuclear industry has generated large quantities of radioactive organic wastewater. In particular, kerosene-diluted tributyl phosphate (TBP) is widely used as an extractant in solvent extraction techniques for the reprocessing of nuclear fuel and spent fuel (the PUREX process). Therefore, the development of efficient technologies and materials to remove and recover oil and organic solvents from water is crucial. The most commonly used oil spill cleanup techniques include physical methods (booms, skimmers, adsorbents), chemical methods (dispersants, solidifiers, in-situ combustion), and bioremediation. Chemical methods and bioremediation are considered non-recoverable, while physical methods are considered recoverable. Furthermore, chemical methods are environmentally unfriendly due to the use of toxic chemicals and the generation of toxic emissions. Bioremediation, which uses specialized microorganisms (such as bacteria, algae, and fungi) to degrade oil, is time-consuming and carries the risk of invasive species. Therefore, physical-based methods are considered the best. In particular, the use of oil absorbents to recover oil spills in water has become the most attractive method due to its simplicity, environmental friendliness, low cost, and recyclability.

[0003] Currently, various inorganic materials (such as zeolites, silica, and activated carbon), natural materials (such as straw, cotton, and fruit peels), and synthetic materials have been used as oil absorbents for oil spill recovery. Inorganic and natural materials generally exhibit low oil absorption capacity, poor oil selectivity, and difficulty in recovery. Some also tend to sink to the bottom, making collection difficult. In contrast, synthetic adsorbents, typically synthetic polymers, often possess inherent hydrophobicity, high oil absorption capacity, good selectivity, and reusability. Synthetic materials can be divided into two categories based on their adsorption mechanism. One type involves porous materials that absorb oil through surface adsorption and capillary action. These materials typically exhibit excellent oil absorption capacity and can be squeezed out and recovered through compression. However, their poor oil retention capacity can cause secondary contamination during transportation, particularly in the case of radioactive organic liquids. The other type involves copolymers or cross-linked polymers that absorb oil through swelling. These materials have excellent oil retention, can prevent secondary contamination, and hold great promise for application in specific applications.

[0004] Currently, common oil-absorbing polymers are primarily based on poly(meth)acrylate resins and polyolefin resins. Their synthesis methods often involve complex monomer polymerization, resulting in lengthy operational processes, low polymerization yields, and high labor and material costs. Furthermore, they suffer from low oil absorption capacity and the tendency to form a sludge after oil absorption, making it difficult to recycle. For example, patent CN1095727A synthesizes oil-absorbing resins using acrylic acid and its esters as monomers via free radical polymerization, achieving chloroform absorption capacities of 24.84 g / g. Patent CN104628926A synthesizes oil-absorbing resins using chloromethylstyrene and styrene as monomers via free radical suspension polymerization, achieving a maximum adsorption ratio of 35 to nitrobenzene. Patent CN111057182A prepares oil-absorbing resin microspheres using octadecyl methacrylate, methyl methacrylate, and butyl acrylate as monomers in the presence of an initiator, crosslinker, porogen, and dispersant, achieving absorption capacities of 33.48 g / g for dichloromethane and 7.42 g / g for diesel. Summary of the Invention

[0005] The technical purpose of the present invention is to provide a high oil absorption material of styrene-butadiene-styrene block copolymer, a preparation method and application.

[0006] In order to achieve the above technical objectives, the technical solution provided by the present invention is:

[0007] A high oil absorption material of styrene-butadiene-styrene block copolymer comprises the following components in parts by mass: 100 parts of styrene-butadiene-styrene block copolymer, 0.5-15 parts of a polythiol crosslinking agent, and 0.5-5 parts of a photoinitiator.

[0008] Furthermore, the polythiol crosslinking agent includes one or more of mercaptopropylmethylsiloxane homopolymer, mercaptopropylmethylsiloxane-dimethylsiloxane copolymer, and pentaerythritol tetrakis-3-mercaptopropionate.

[0009] Furthermore, the photoinitiator includes one or more of 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester, 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 1-hydroxycyclohexylphenyl ketone, preferably 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester.

[0010] Another aspect of the present invention provides a method for preparing a high oil absorption material of a styrene-butadiene-styrene block copolymer, comprising the following steps:

[0011] Step 1: Dissolve styrene-butadiene-styrene block copolymer in a solvent, add a photoinitiator and a polythiol crosslinker, mix well, transfer to a glass dish and let it stand to obtain a flat surface, and then cure under light conditions to produce a thiol-ene click reaction between olefins and thiols to obtain an organogel;

[0012] Step 2: Soak the organogel obtained in step 1 in ethanol to drain the solvent, then take out the organogel and vacuum dry it to obtain a high oil absorption material of styrene-butadiene-styrene block copolymer.

[0013] Furthermore, in step 1, the solvent includes one or more of mesitylene, toluene, dichloromethane, tetrahydrofuran, and cyclohexane, preferably mesitylene.

[0014] Furthermore, the lighting conditions include ultraviolet curing lamps, xenon lamp light sources, and natural sunlight.

[0015] Another aspect of the present invention provides a use of a high oil absorption material of a styrene-butadiene-styrene block copolymer in oil absorption.

[0016] The present invention has the following beneficial effects:

[0017] 1. The high oil absorption material of the present invention has high oil absorption capacity and selectivity. After absorbing oil, it can maintain its structure without becoming muddy and float on the water surface, making it easy to collect. It also has the advantages of excellent oil retention capacity and good reusability.

[0018] 2. The present invention utilizes a light-promoted thiol-ene click reaction between the olefins of the photocrosslinked styrene-butadiene-styrene block copolymer and the thiol groups of the polythiol crosslinking agent to obtain a crosslinked polymer. The preparation method is simple and convenient, the raw materials are easy to obtain, and the cost is low.

[0019] 3. The high oil absorption material disclosed in the present invention can be applied to emergency treatment of organic solvent and oil leakage, as well as absorption and solidification of radioactive organic waste liquid and other application scenarios. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The chemical structure diagram of typical raw materials;

[0021] Figure 2 The chemical structure and physical picture of SBS-based cross-linked polymer;

[0022] Figure 3 The following are photos of the oil absorbents in (a) Example 1, (b) Example 2, and (c) Example 3 before and after oil absorption. DETAILED DESCRIPTION

[0023] The technical solution of the present invention is described clearly and completely below with reference to the accompanying drawings. It is apparent that the embodiments described are only a portion of the embodiments of the present invention, not all of them. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are intended to fall within the scope of protection of the present invention.

[0024] In the description of the present invention, it should be noted that the directions or positional relationships indicated by terms such as "center," "up," "down," "left," "right," "vertical," "horizontal," "inside," and "outside" are based on the directions or positional relationships described in the accompanying drawings and are intended solely to facilitate and simplify the description of the present invention. They are not intended to indicate or imply that the devices or components referred to must have a specific orientation, be constructed, or operate in a specific orientation. Therefore, they should not be construed as limitations on the present invention. Furthermore, terms such as "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0025] In addition, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0026] like Figure 1-2 As shown, a high oil absorption material of styrene-butadiene-styrene block copolymer includes the following components in parts by mass: 100 parts of styrene-butadiene-styrene block copolymer, 0.5-15 parts of polythiol crosslinking agent, and 0.5-5 parts of photoinitiator.

[0027] Specifically, the styrene-butadiene-styrene block copolymer (SBS) is commercially available, with a styrene content of 30-40 wt.%, an average molecular weight of 10,000-200,000, and a linear or star-shaped configuration. SBS analogs are also included, such as styrene-isoprene-styrene block copolymer (SIS).

[0028] Specifically, the polythiol crosslinking agent is commercially available and includes one or more of mercaptopropylmethylsiloxane homopolymer; mercaptopropylmethylsiloxane-dimethylsiloxane copolymer, wherein the mercaptopropylmethylsiloxane content is 2%-20%; and pentaerythritol tetrakis-3-mercaptopropionate.

[0029] Specifically, the photoinitiator includes one or more of 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester (TPO-L), 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide (TPO), 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), and 1-hydroxycyclohexylphenyl ketone (184), preferably 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester (TPO-L). TPO-L is liquid, has good material compatibility, and has a relatively long absorption wavelength (299,366 nm), and has a high photoinitiation efficiency.

[0030] Another aspect of the present invention provides a method for preparing a high oil absorption material of a styrene-butadiene-styrene block copolymer, comprising the following steps:

[0031] Step 1: Dissolve styrene-butadiene-styrene block copolymer in a solvent, add a photoinitiator and a polythiol crosslinker, mix well, transfer to a glass dish and let it stand to obtain a flat surface, then cure under light conditions to cause a thiol-ene click reaction between olefins and thiols to obtain an organogel.

[0032] Specifically, in step 1, the solvent includes one or more of mesitylene, toluene, dichloromethane, tetrahydrofuran, and cyclohexane, preferably mesitylene. Mesitylene has a high boiling point and is not easily volatile, which reduces the harm to the health of operators and the environment during the material preparation process and avoids material inhomogeneity caused by solvent volatilization; the lighting conditions include ultraviolet curing lamps, xenon lamp light sources, and natural sunlight.

[0033] Step 2: Soak the organic gel obtained in step 1 in ethanol to drain the solvent, then take out the gel and vacuum dry it to obtain a high oil absorption material of styrene-butadiene-styrene block copolymer.

[0034] Another aspect of the present invention provides a use of a high oil absorption material of a styrene-butadiene-styrene block copolymer in oil absorption.

[0035] Example 1

[0036] Step 1: Dissolve 1 g of styrene-butadiene-styrene block copolymer (styrene 30 wt.%, average Mw ~ 140000) in 5 mL of mesitylene solution, add TPO-L (7.5 mg, 0.75 wt.%) and mercaptopropylmethylsiloxane homopolymer (SMS-992, 5 mg), mix well with a planetary mixer (2000 rpm, 3 minutes), transfer to a glass dish and let it stand to obtain a flat surface, and then cure under ultraviolet light for 60 seconds to produce a mercapto-ene click reaction between olefins and mercapto groups to obtain an organogel.

[0037] Step 2: Soak the organogel obtained in step 1 in 5 mL of ethanol for 20 min to remove most of the mesitylene, and then vacuum dry it at 50°C for 6 h to obtain the SBS-SMS oil absorbent as a transparent circular film.

[0038] Oil absorption performance was studied: First, a certain amount of SBS-SMS oil absorbent sheet (~50 mg) was cut with scissors and soaked in 10 mL of various organic solvents or oils for a specified period of time (6 hours for dichloromethane, cyclohexane, toluene, mesitylene, and tetrahydrofuran, respectively; 24 hours for 1,4-dioxane, tributyl phosphate, kerosene, and diesel, respectively). The swollen oil absorbent was then removed with tweezers and weighed to calculate the oil absorption. The oil absorption values ​​were 74.6 g / g for dichloromethane, 63.0 g / g for toluene, 58.5 g / g for mesitylene, 59.2 g / g for tetrahydrofuran, 46.0 g / g for cyclohexane, 24.8 g / g for 1,4-dioxane, 20.1 g / g for kerosene, 12.8 g / g for diesel, and 7.3 g / g for tributyl phosphate.

[0039] Example 2

[0040] Step 1: Dissolve 1 g of styrene-butadiene-styrene block copolymer (styrene 30 wt.%, average Mw ~ 140000) in 5 mL of mesitylene solution, add TPO-L (7.5 mg, 0.75 wt.%) and mercaptopropylmethylsiloxane homopolymer (SMS-992, 10 mg), mix well with a planetary mixer (2000 rpm, 3 minutes), transfer to a glass dish and let stand to obtain a flat surface, and then cure under ultraviolet light for 60 seconds to cause a mercapto-ene click reaction between olefins and mercapto groups to obtain an organogel.

[0041] Step 2: Soak the organogel obtained in step 1 in 5 mL of ethanol for 20 min to remove most of the mesitylene, and then vacuum dry it at 50°C for 6 h to obtain the SBS-SMS oil absorbent as a transparent circular film.

[0042] Oil absorption performance was studied: First, a certain amount of SBS-SMS flakes (~50 mg) were cut with scissors and soaked in 10 mL of various organic solvents or oils for a specified time (6 hours for dichloromethane, cyclohexane, toluene, mesitylene, and tetrahydrofuran, respectively; 24 hours for 1,4-dioxane, tributyl phosphate, kerosene, and diesel, respectively). The swollen oil absorbent was removed with tweezers and weighed to calculate the oil absorption. The oil absorption values ​​were 43.9 g / g for dichloromethane, 29.1 g / g for toluene, 29.2 g / g for mesitylene, 30.5 g / g for tetrahydrofuran, 21.3 g / g for cyclohexane, 11.8 g / g for 1,4-dioxane, 11.4 g / g for kerosene, 8.9 g / g for diesel, and 6.4 g / g for tributyl phosphate.

[0043] Example 3

[0044] Step 1: Dissolve 1 g of styrene-butadiene-styrene block copolymer (styrene 30 wt.%, average Mw ~ 140000) in 5 mL of mesitylene solution, add TPO-L (7.5 mg, 0.75 wt.%) and mercaptopropylmethylsiloxane homopolymer (SMS-992, 20 mg), mix well with a planetary mixer (2000 rpm, 3 minutes), transfer to a glass dish and let stand to obtain a flat surface, and then cure under ultraviolet light for 60 seconds to cause a mercapto-ene click reaction between olefins and mercapto groups to obtain an organogel.

[0045] Step 2: Soak the organogel obtained in step 1 in 5 mL of ethanol for 20 min to remove most of the mesitylene, and then vacuum dry it at 50°C for 6 h to obtain the SBS-SMS oil absorbent as a transparent circular film.

[0046] Oil absorption performance was studied: First, a certain amount of SBS-SMS flakes (~50 mg) were cut with scissors and soaked in 10 mL of various organic solvents or oils for a specified period of time (6 hours for dichloromethane, cyclohexane, toluene, mesitylene, and tetrahydrofuran, respectively; 24 hours for 1,4-dioxane, tributyl phosphate, kerosene, and diesel, respectively). The swollen oil absorbent was then removed with tweezers and weighed to calculate the oil absorption. The oil absorption values ​​were 24.8 g / g for dichloromethane, 18.9 g / g for toluene, 17.7 g / g for mesitylene, 18.9 g / g for tetrahydrofuran, 12.3 g / g for cyclohexane, 8.7 g / g for 1,4-dioxane, 7.2 g / g for kerosene, 5.7 g / g for diesel, and 4.5 g / g for tributyl phosphate.

[0047] Example 4

[0048] Step 1: Dissolve 1 g of styrene-butadiene-styrene block copolymer (styrene 30 wt.%, average Mw ~ 140000) in 5 mL of mesitylene solution, add TPO-L (7.5 mg, 0.75 wt.%) and mercaptopropylmethylsiloxane-dimethylsiloxane copolymer (SMS-042, mercapto content 4-6%, 150 mg), mix well with a planetary mixer (2000 rpm, 3 minutes), transfer to a glass dish and let stand to obtain a flat surface, and then cure under ultraviolet light for 60 seconds to cause a mercapto-ene click reaction between olefins and mercapto groups to obtain an organogel.

[0049] Step 2: Soak the organogel obtained in step 1 in 5 mL of ethanol for 20 min to remove most of the mesitylene, and then vacuum dry it at 50°C for 6 h to obtain the SBS-SMS oil absorbent as a transparent circular film.

[0050] Study on the absorption performance of dichloromethane: First, a certain amount of SBS-SMS flakes (~50 mg) were cut with scissors, soaked in 10 mL of dichloromethane for 6 hours, and then taken out and weighed. The absorption capacity was calculated to be 54.8 g / g.

[0051] Example 5

[0052] Step 1: Dissolve 1 g of styrene-butadiene-styrene block copolymer (styrene 30 wt.%, average Mw ~ 140000) in 5 mL of mesitylene solution, add TPO-L (7.5 mg, 0.75 wt.%) and mercaptopropylmethylsiloxane-dimethylsiloxane copolymer (SMS-142, mercapto content 13-17%, 50 mg), mix well with a planetary mixer (2000 rpm, 3 minutes), transfer to a glass dish and let stand to obtain a flat surface, and then cure under ultraviolet light for 60 seconds to cause a mercapto-ene click reaction between olefins and mercapto groups to obtain an organogel.

[0053] Step 2: Soak the organogel obtained in step 1 in 5 mL of ethanol for 20 min to remove most of the mesitylene, and then vacuum dry it at 50°C for 6 h to obtain the SBS-SMS oil absorbent as a transparent circular film.

[0054] Study on the absorption performance of dichloromethane: First, a certain amount of SBS-SMS flakes (~50 mg) were cut with scissors, soaked in 10 mL of dichloromethane for 6 h, taken out and weighed, and the absorption capacity was calculated to be 30.0 g / g.

[0055] Example 6

[0056] Step 1: Dissolve 1 g of styrene-butadiene-styrene block copolymer (styrene 30 wt.%, average Mw ~ 140000) in 5 mL of mesitylene solution, add TPO-L (7.5 mg, 0.75 wt.%) and pentaerythritol tetrakis-3-mercaptopropionate (PTMP, 10 mg), mix well using a planetary mixer (2000 rpm, 3 minutes), transfer to a glass dish and let stand to obtain a flat surface, then cure under ultraviolet light for 60 seconds to cause a thiol-ene click reaction between olefins and thiols to obtain an organogel.

[0057] Step 2: Soak the organogel obtained in step 1 in 5 mL of ethanol for 20 min to remove most of the mesitylene, and then vacuum dry it at 50°C for 6 h to obtain the SBS-PTMP oil absorbent as a transparent circular film.

[0058] Study on the absorption performance of dichloromethane: First, a certain amount of SBS-PTMP flakes (~50 mg) were cut with scissors, soaked in 10 mL of dichloromethane for 6 hours, and then taken out and weighed. The absorption capacity was calculated to be 32.6 g / g.

[0059] Example 7

[0060] Step 1: Dissolve 1 g of styrene-butadiene-styrene block copolymer (styrene 30 wt.%, average Mw ~ 140000) in 5 mL of mesitylene solution, add TPO-L (7.5 mg, 0.75 wt.%) and mercaptopropylmethylsiloxane homopolymer (SMS-992, 10 mg), mix well with a planetary mixer (2000 rpm, 3 minutes), transfer to a glass dish and let stand to obtain a flat surface, then cure under ultraviolet light for 10 seconds to cause a mercapto-ene click reaction between olefins and mercapto groups to obtain an organogel.

[0061] Step 2: Soak the organogel obtained in step 1 in 5 mL of ethanol for 20 min to remove most of the mesitylene, and then vacuum dry it at 50°C for 6 h to obtain the SBS-SMS oil absorbent as a transparent circular film.

[0062] Study on the absorption performance of dichloromethane: First, a certain amount of SBS-SMS flakes (~50 mg) were cut with scissors, soaked in 10 mL of dichloromethane for 6 hours, and then taken out and weighed. The absorption capacity was calculated to be 50.7 g / g.

[0063] Example 8

[0064] Step 1: Dissolve 1 g of styrene-butadiene-styrene block copolymer (styrene 30 wt.%, average Mw ~ 140000) in 5 mL of mesitylene solution, add TPO-L (7.5 mg, 0.75 wt.%) and mercaptopropylmethylsiloxane homopolymer (SMS-992, 10 mg), mix well with a planetary mixer (2000 rpm, 3 minutes), transfer to a glass dish and let stand to obtain a flat surface, and then cure under ultraviolet light for 120 seconds to cause a mercapto-ene click reaction between olefins and mercapto groups to obtain an organogel.

[0065] Step 2: Soak the organogel obtained in step 1 in 5 mL of ethanol for 20 min to remove most of the mesitylene, and then vacuum dry it at 50°C for 6 h to obtain the SBS-SMS oil absorbent as a transparent circular film.

[0066] Study on the absorption performance of dichloromethane: First, a certain amount of SBS-SMS flakes (~50 mg) were cut with scissors, soaked in 10 mL of dichloromethane for 6 hours, and then taken out and weighed. The absorption capacity was calculated to be 31.3 g / g.

[0067] Example 9

[0068] Step 1: Dissolve 1 g of styrene-butadiene-styrene block copolymer (30 wt.%, styrene, average Mw ~140000) in 5 mL of mesitylene solution, add TPO-L (7.5 mg, 0.75 wt.%) and mercaptopropylmethylsiloxane homopolymer (SMS-992, 10 mg), mix well with a planetary mixer (2000 rpm, 3 minutes), transfer to a glass dish and let stand to obtain a flat surface, then irradiate and cure under natural sunlight for 5 minutes to cause a mercapto-ene click reaction between olefins and mercapto groups to obtain an organogel.

[0069] Step 2: Soak the organogel obtained in step 1 in 5 mL of ethanol for 20 min to remove most of the mesitylene, and then vacuum dry it at 50°C for 6 h to obtain the SBS-SMS oil absorbent as a transparent circular film.

[0070] Study on the absorption performance of dichloromethane: First, a certain amount of SBS-SMS flakes (~50 mg) were cut with scissors, soaked in 10 mL of dichloromethane for 6 hours, and then taken out and weighed. The absorption capacity was calculated to be 34.9 g / g.

[0071] Example 10

[0072] Step 1: Dissolve 1 g of industrial-grade linear SBS (styrene content: 30 wt.%) in 5 mL of mesitylene solution, add TPO-L (7.5 mg, 0.75 wt.%) and mercaptopropylmethylsiloxane homopolymer (SMS-992, 10 mg), mix thoroughly using a planetary mixer (2000 rpm, 3 minutes), transfer to a glass dish, and let stand to obtain a flat surface. Curing under UV light for 60 seconds causes a mercapto-ene click reaction between olefins and mercapto groups to produce an organogel.

[0073] Step 2: Soak the organogel obtained in step 1 in 5 mL of ethanol for 20 min to remove most of the mesitylene, and then vacuum dry it at 50°C for 6 h to obtain the SBS-SMS oil absorbent as a transparent circular film.

[0074] Study on the absorption performance of dichloromethane: First, a certain amount of SBS-SMS flakes (~50 mg) were cut with scissors, soaked in 10 mL of dichloromethane for 6 hours, and then taken out and weighed. The absorption capacity was calculated to be 39.7 g / g.

[0075] Example 11

[0076] Step 1: Dissolve 1 g of industrial-grade star-shaped SBS (styrene content: 40 wt.%) in 5 mL of mesitylene solution, add TPO-L (7.5 mg, 0.75 wt.%) and mercaptopropylmethylsiloxane homopolymer (SMS-992, 10 mg), mix thoroughly using a planetary mixer (2000 rpm, 3 minutes), transfer to a glass dish, and let stand to obtain a flat surface. Then, cure under ultraviolet light for 60 seconds to cause a mercapto-ene click reaction between olefins and mercapto groups to obtain an organogel.

[0077] Step 2: Soak the organogel obtained in step 1 in 5 mL of ethanol for 20 min to remove most of the mesitylene, and then vacuum dry it at 50°C for 6 h to obtain the SBS-SMS oil absorbent as a transparent circular film.

[0078] Study on the absorption performance of dichloromethane: First, a certain amount of SBS-SMS flakes (~50 mg) were cut with scissors, soaked in 10 mL of dichloromethane for 6 hours, and then taken out and weighed. The absorption capacity was calculated to be 33.8 g / g.

[0079] Example 12

[0080] Step 1: Dissolve 1 g of industrial-grade SIS (styrene content: 15 wt.%) in 5 mL of mesitylene solution, add TPO-L (7.5 mg, 0.75 wt.%) and mercaptopropylmethylsiloxane homopolymer (SMS-992, 10 mg), mix well using a planetary mixer (2000 rpm, 3 minutes), transfer to a glass dish, and let stand to obtain a flat surface. Then, cure under ultraviolet light for 60 seconds to cause a mercapto-ene click reaction between olefins and mercapto groups to obtain an organogel.

[0081] Step 2: Soak the organogel obtained in step 1 in 5 mL of ethanol for 20 min to remove most of the mesitylene, and then vacuum dry it at 50°C for 6 h to obtain the SIS-SMS oil absorbent as a transparent circular film.

[0082] Study on the absorption performance of dichloromethane: First, a certain amount of SIS-SMS sheets (~50 mg) were cut with scissors, soaked in 10 mL of dichloromethane for 6 hours, and then taken out and weighed. The absorption capacity was calculated to be 39.0 g / g.

[0083] As can be seen from Example 1, the photocrosslinked SBS-based oil-absorbing material of the present invention can absorb oil of 74.6 g / g of dichloromethane, 63.0 g / g of toluene, 58.5 g / g of mesitylene, 59.2 g / g of tetrahydrofuran, 46.0 g / g of cyclohexane, 24.8 g / g of 1,4-dioxane, 20.1 g / g of kerosene, 12.8 g / g of diesel, and 7.3 g / g of tributyl phosphate, which is higher than that of the disclosed patents, such as patent CN1095727A, which uses acrylic acid and its esters as monomers through free radical initiation polymerization. The oil-absorbing resin prepared in patent CN104628926A uses chloromethylstyrene and styrene as monomers through free radical suspension polymerization, achieving an adsorption rate of up to 35 times that of nitrobenzene. Furthermore, oil-absorbing resin microspheres prepared in patent CN111057182A using octadecyl methacrylate, methyl methacrylate, and butyl acrylate as monomers in the presence of an initiator, crosslinker, porogen, and dispersant have adsorption rates of 33.48 and 7.42 g / g for dichloromethane and diesel, respectively. Furthermore, a comparison of the oil absorption performance of oil-absorbing polymers reported in international journals in Table 1 shows that the oil-absorbing material disclosed in this invention also exhibits relatively superior oil absorption performance and is relatively simple to prepare.

[0084] Table 1 Comparison of oil absorption properties of oil-absorbing polymers reported in international journals

[0085]

[0086] like Figure 3 As shown in the figure, after immersion in different solvents or oils, the oil-absorbing polymer swells from its original thin, circular flakes (approximately 15 mm in diameter and 0.32 mm thick) into thick, gel-like flakes with significantly increased area and thickness. Furthermore, the flake skeleton does not collapse after oil absorption, but rather maintains its original shape despite swelling. Furthermore, because the prepared polymer membrane contains no inorganic materials and has a low density, it floats on water after oil absorption, facilitating practical applications in oil-water separation.

[0087] The present invention utilizes a light-promoted thiol-olefin click reaction between olefins of a photo-crosslinked styrene-butadiene-styrene block copolymer and thiol groups of a polythiol crosslinking agent to obtain a crosslinked polymer. On the one hand, the disadvantage of a simple styrene-butadiene-styrene block copolymer that it is easily soluble in organic solvents and cannot be used in the field of oil absorption is improved. On the other hand, the formed crosslinked structure can well wrap solvent / oil molecules therein, thereby achieving a higher oil absorption capacity.

[0088] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

[0089] The above specific implementation methods are detailed descriptions of the present invention. It cannot be considered that the specific implementation methods of the present invention are limited to these descriptions. For ordinary technicians in the technical field to which the present invention belongs, they can make several simple deductions and substitutions without departing from the concept of the present invention, which should be regarded as falling within the scope of protection of the present invention.

Claims

1. Application of a high oil absorption material of a styrene-butadiene-styrene block copolymer in oil absorption, characterized in that: The invention comprises the following components in parts by mass: 100 parts of styrene-butadiene-styrene block copolymer, 0.5-15 parts of polythiol crosslinking agent and 0.5-5 parts of photoinitiator.

2. Use of a high oil absorption material of a styrene-butadiene-styrene block copolymer according to claim 1 in oil absorption, characterized in that: The polythiol crosslinking agent includes one or more of mercaptopropylmethylsiloxane homopolymer, mercaptopropylmethylsiloxane-dimethylsiloxane copolymer, and pentaerythritol tetrakis-3-mercaptopropionate.

3. Use of a high oil absorption material of a styrene-butadiene-styrene block copolymer according to claim 1 in oil absorption, characterized in that: The photoinitiator includes one or more of 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester, 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 1-hydroxycyclohexylphenyl ketone.

4. Use of a high oil absorption material of a styrene-butadiene-styrene block copolymer according to claim 3 in oil absorption, characterized in that: The photoinitiator is ethyl 2,4,6-trimethylbenzoylphenylphosphonate.

5. Use of a high oil absorption material of a styrene-butadiene-styrene block copolymer according to claim 1 in oil absorption, characterized in that: The preparation method of the high oil absorption material of styrene-butadiene-styrene block copolymer comprises the following steps: Step 1: Dissolve styrene-butadiene-styrene block copolymer in a solvent, add a photoinitiator and a polythiol crosslinker, mix well, transfer to a glass dish and let it stand to obtain a flat surface, and then cure under light conditions to produce a thiol-ene click reaction between olefins and thiols to obtain an organogel; Step 2: Soak the organogel obtained in step 1 in ethanol to drain the solvent, then take out the organogel and vacuum dry it to obtain a high oil absorption material of styrene-butadiene-styrene block copolymer.

6. Use of a high oil absorption material of a styrene-butadiene-styrene block copolymer according to claim 5 in oil absorption, characterized in that: In the step 1, the solvent includes one or more of mesitylene, toluene, dichloromethane, tetrahydrofuran, and cyclohexane.

7. Use of a high oil absorption material of a styrene-butadiene-styrene block copolymer according to claim 6 in oil absorption, characterized in that: The solvent is mesitylene.

8. Use of a high oil absorption material of a styrene-butadiene-styrene block copolymer according to claim 5 in oil absorption, characterized in that: The lighting conditions include ultraviolet curing lamps, xenon lamp light sources, and natural sunlight.

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