CN110585762B - Polymer oil absorption material and preparation method thereof - Google Patents
Polymer oil absorption material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a polymer oil absorption material, which is characterized by comprising the following steps: step S1, preparing poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate, step S2, modifying poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate, step S3, preparing a copolymer, step S4 and performing pore-forming. The invention also discloses the polymer oil absorption material prepared by the preparation method of the polymer oil absorption material. The polymer oil absorption material disclosed by the invention has the advantages of better mechanical property, larger oil absorption, better oil absorption effect, higher oil absorption speed, more excellent comprehensive performance, higher economic value, social value and ecological value.
Description
Technical Field
The invention relates to the technical field of oil absorption materials, in particular to a high-molecular oil absorption material and a preparation method thereof.
Background
In recent years, with the development of world industry, the exploitation, production, transportation and use of various oils as industrial blood are more and more frequent, and the oils can affect the working places and pollute the surrounding ecological environment due to dripping, leakage, sputtering and other reasons in the transportation, replacement and use processes; a large amount of oily wastewater can be generated in the production processes of oil extraction, oil refining, petrochemical industry, food industry and the like in the petroleum industry and the lubricating oil cooling process in the mechanical industry, so that the water environment is polluted, aquatic organisms are harmed, and even the oily wastewater enters a human body through a food chain, and the health of the human body is harmed; a large amount of oil smoke gas pollutes the atmosphere in the catering industry and daily life; the kitchenware is washed in daily life, a large amount of waste water containing edible oil flows into a sewer without any treatment, and the waste water can corrode and block a sewer pipeline after a long time, so that inconvenience is brought to life of people, and therefore, how to treat oil pollution on water surface or soil is a problem to be solved urgently in the current industry.
At present, the oil absorption material is the most common method for treating oil pollution on water surface or soil, and the performance of the oil absorption material directly influences the oil absorption effect, so that the development and development of the novel oil absorption material have great significance. The traditional oil-absorbing materials such as clay, sponge, polypropylene non-woven fabric, polyester non-woven fabric and the like have low oil-absorbing multiplying power, poor oil-water selectivity and weak oil-retaining capacity, and can not meet the requirements of resource and environment management, the high oil-absorbing resin is a functional polymer material which is newly developed in recent decades in China, has a structure similar to that of water-absorbing resin, is a three-dimensional network structure, has extremely strong oil-absorbing capacity and oil-retaining capacity, and can be prepared into different products such as powder particles, emulsion and the like. The oil and grease organic matter can be concentrated and temporarily fixed, so that the oil and grease organic matter can be widely applied to the aspects of environmental protection, industry, agriculture and the like. The performance of the oil absorption material is continuously improved along with the research.
At present, the common high oil absorption resin is poly (methyl) acrylate based high oil absorption resin, which is mostly a single-component crosslinking organic macromolecular compound, has the defects of elasticity, easy viscosity change at high temperature, low strength, difficult recovery due to easy mud shape after oil absorption and the like, and is limited in application. In addition, the high oil absorption resin in the prior art has the problems of strong oil product selectivity, and further improved adsorption performance and adsorption speed.
Lucivance et al (lucivance, lujian mei, proceedings of the Nanjing chemical industry academy, 1995, 2, 43-47) suspension-polymerize 2-ethylhexyl acrylate and butyl methacrylate as monomers in an inert solvent, and extract the solvent in the particles with methanol after the reaction is completed to prepare the porous particulate adsorbent. The methods need a specific means to remove the added pore-foaming agent in the preparation process, have complex preparation process and higher cost, and are not beneficial to industrial amplification of products and popularization and application of the products.
Therefore, the method for preparing the polymer oil absorption material has great significance in seeking more effective method, and the prepared polymer oil absorption material has great oil absorption, better oil absorption effect, higher oil absorption speed and more excellent comprehensive performance.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the high-molecular oil absorption material and the preparation method thereof, and the preparation method has the advantages of simple process, convenient operation, wide raw material source, low price, low requirements on equipment and reaction conditions, high preparation efficiency and high qualification rate of finished products, and meets the requirements of continuous large-scale production; the prepared polymer oil absorption material has the advantages of better mechanical property, larger oil absorption, better oil absorption effect, higher oil absorption speed, more excellent comprehensive performance, higher economic value, social value and ecological value.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: a preparation method of a high polymer oil absorption material comprises the following steps:
step S1, preparation of Poly 1-p-toluenesulfonyl-2, 5-pyrrolidinedimethanol 2, 3-difluorofumarate: adding 1-p-toluenesulfonyl-2, 5-pyrrolidine dimethanol, 2, 3-difluoro fumaric acid, a catalyst and a polymerization inhibitor into a high-boiling point solvent, stirring for 20-30 minutes to obtain a reaction solution, transferring the reaction solution into a high-pressure reaction kettle, replacing air in the kettle with nitrogen or inert gas, carrying out esterification reaction for 3-5 hours at the temperature of 230-280 ℃ and the absolute pressure of 30-90 KPa, finishing esterification, and releasing the pressure to the normal pressure; then under the vacuum condition, controlling the temperature between 240 ℃ and 270 ℃, stirring and reacting for 12-18h, cooling to room temperature after the reaction is finished, discharging and precipitating in a sodium hydroxide aqueous solution with the mass fraction of 0.5-2%, washing the precipitated product for 3-7 times by using ethanol, and then carrying out rotary evaporation to remove the ethanol, thus obtaining the poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluorofumarate;
step S2, modification of poly (1-p-toluenesulfonyl) -2, 5-pyrrolidinedimethanol 2, 3-difluorofumarate: adding poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate into carbon tetrachloride, adding epoxy chloropropane into the carbon tetrachloride, stirring the mixture at the temperature of between 30 and 40 ℃ for reaction for 5 to 6 hours, and then performing rotary evaporation to remove the carbon tetrachloride to obtain epoxy group modified poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate;
step S3, preparation of copolymer: adding the epoxy modified poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate prepared in the step S2, allyl-beta-cyclodextrin, octavinyl-POSS, vinyl silicone oil, 2,4, 5-trifluoropropenoic acid, calcium carbonate, a coupling agent, carbon sponge, an initiator and N-methyl pyrrolidone into a reactor, stirring and polymerizing for 8-10 hours at 75-85 ℃ under the protection of nitrogen, removing the N-methyl pyrrolidone by rotary evaporation, placing the mixture in a vacuum drying oven and drying the mixture at 80-90 ℃ to constant weight to obtain a copolymer;
step S4, pore-forming: and (3) soaking the copolymer prepared in the step S3 in a hydrochloric acid solution with the mass fraction of 10-15% for 10-15 hours, then soaking in water for 5-10 hours, taking out, and drying in a forced air drying oven at 80-90 ℃ to constant weight to obtain the polymer oil absorption material.
Further, the mass ratio of the 1-p-toluenesulfonyl-2, 5-pyrrolidine dimethanol, the 2, 3-difluorofumaric acid, the catalyst, the polymerization inhibitor and the high-boiling point solvent in the step S1 is 1.88:1 (0.4-0.6) to 0.1 (9-15).
Further, the catalyst is at least one of tetrabutyl titanate, titanium dioxide and titanium chloride; the polymerization inhibitor is at least one of tetrachlorobenzoquinone and l, 4-naphthoquinone; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is one of helium, neon and argon.
Further, in step S2, the mass ratio of the poly (1-p-toluenesulfonyl) -2, 5-pyrrolidinedimethanol 2, 3-difluorofumarate to the carbon tetrachloride to the epichlorohydrin is 1 (3-5) to (0.1-0.3).
Furthermore, in the step S3, the mass ratio of the epoxy modified poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate, allyl-beta-cyclodextrin, octavinyl-POSS, vinyl silicone oil, 2,4, 5-trifluoro-phenylpropenoic acid, calcium carbonate, coupling agent, carbon sponge, initiator and N-methyl pyrrolidone is 1 (0.1-0.2):0.1:0.1:0.5:0.15 (0.03-0.06):0.05 (0.01-0.03): 6-10).
Further, the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH 570; the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
The invention also aims to provide the polymer oil absorption material prepared by the preparation method of the polymer oil absorption material.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
(1) the preparation method of the high-molecular oil absorption material provided by the invention has the advantages of simple process, convenience in operation, wide raw material source, low price, low requirements on equipment and reaction conditions, high preparation efficiency and high qualification rate of finished products, and meets the requirements of continuous large-scale production.
(2) The polymer oil absorption material provided by the invention overcomes the defects that the polymer oil absorption material in the prior art is more or less easy to become sticky at high temperature, low in strength, difficult to recover due to easy sludge after oil absorption, strong in oil product selectivity, and the adsorption performance and adsorption speed of oil products such as diesel oil and the like are required to be further improved; the oil absorption agent has the advantages of better mechanical property, larger oil absorption, better oil absorption effect, higher oil absorption speed, more excellent comprehensive performance, wide application range and higher economic value, social value and ecological value.
(3) According to the polymer oil absorption material provided by the invention, the fluorocarbon structure is introduced on the side chain of the copolymer, so that the comprehensive performance of the material is effectively improved; firstly, preparing epoxy modified poly 1-p-toluenesulfonyl-2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate, copolymerizing the epoxy modified poly 1-p-toluenesulfonyl-2, 5-pyrrolidine dimethanol with allyl-beta-cyclodextrin, octavinyl-POSS, vinyl silicone oil, 2,4, 5-trifluoro phenylpropenoic acid, calcium carbonate, carbon sponge and other materials, finally, preparing holes by acid soaking to form a three-dimensional cross-linked network structure with a certain gap in the material, simultaneously, the resin molecules have lipophilic ester groups and siloxane groups, so that oil molecules can enter the resin network to swell the resin, the oil molecules are enclosed in the polymer network structure to play a role in oil absorption and retention, and the material has the advantages of no water absorption, high oil absorption rate, high oil absorption speed, no leakage under pressure after oil absorption and no secondary pollution, the oil absorption material can replace the traditional oil absorption material, has lower density than water, can still float on the water surface after oil absorption, and is convenient to recover and salvage.
(4) The invention provides a high-molecular oil absorption material, which is characterized in that epoxy modified poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate contains quaternary ammonium salt cations and epoxy groups, the quaternary ammonium salt cations can be crosslinked with carboxyl on monomer 2,4, 5-trifluoro-phenylpropenoic acid, the epoxy groups are easy to crosslink with hydroxyl on allyl-beta-cyclodextrin, the side chain of the copolymer has a polymer structure, and each crosslinking site has synergistic effect, so that the chemical structure is stable, the resin performance is also stable, the oil retention is good, the side chain of the polymer structure enables the distance between molecular chains to be larger, the resin has higher network volume, and the oil absorption rate of the high-molecular oil absorption material is enhanced; the introduction of cyclodextrin and POSS structures can increase the void ratio in a polymer network and improve the oil absorption capacity; the silicone oil structure contains oleophilic groups, so that the oil absorption effect can be further improved, and all the components are connected together by forming covalent bonds, so that the material has better performance stability; the addition of the carbon sponge not only plays a role in enhancing, but also can improve the oil absorption capacity under the synergistic effect of other components.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
The allyl-beta-cyclodextrin involved in the following examples of the invention was obtained from Zhiyuan Biotech, Inc., Shandong, Bingzhou; the vinyl silicone oil has the viscosity of 200mPa.s at 25 ℃ and the vinyl content of 2 percent, and is purchased from Hengyu Hengji organic silicon Co., Ltd; other raw materials were all purchased commercially.
Example 1
A preparation method of a high polymer oil absorption material comprises the following steps:
step S1, preparation of Poly 1-p-toluenesulfonyl-2, 5-pyrrolidinedimethanol 2, 3-difluorofumarate: adding 18.8g of 1-p-toluenesulfonyl-2, 5-pyrrolidine dimethanol, 10g of 2, 3-difluorofumaric acid, 4g of tetrabutyl titanate and 1g of tetrachlorobenzoquinone into 90g of dimethyl sulfoxide, stirring for 20 minutes to obtain a reaction solution, transferring the reaction solution into a high-pressure reaction kettle, replacing the air in the kettle with nitrogen, carrying out esterification reaction for 3 hours under the conditions of the temperature of 230 ℃ and the absolute pressure of 30KPa, finishing esterification, and releasing the pressure to the normal pressure; then under the vacuum condition, controlling the temperature to be 240 ℃, stirring and reacting for 12h, cooling to room temperature after the reaction is finished, discharging, precipitating in a sodium hydroxide aqueous solution with the mass fraction of 0.5%, washing the precipitated product with ethanol for 3 times, and then performing rotary evaporation to remove the ethanol to obtain poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate;
step S2, modification of poly (1-p-toluenesulfonyl) -2, 5-pyrrolidinedimethanol 2, 3-difluorofumarate: adding 10g of poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate into 30g of carbon tetrachloride, adding 1g of epoxy chloropropane, stirring and reacting at 30 ℃ for 5 hours, and then performing rotary evaporation to remove the carbon tetrachloride to obtain epoxy group modified poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate;
step S3, preparation of copolymer: adding 10g of epoxy modified poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate prepared in step S2, 1g of allyl-beta-cyclodextrin, 1g of octavinyl-POSS, 1g of vinyl silicone oil, 5g of 2,4, 5-trifluoro-phenylpropenoic acid, 1.5g of calcium carbonate, 0.3g of silane coupling agent KH550, 0.5g of carbon sponge, 0.1g of azodiisobutyronitrile and 60g of N-methyl pyrrolidone into a reactor, stirring and polymerizing at 75 ℃ under the protection of nitrogen for 8 hours, removing the N-methyl pyrrolidone by rotary evaporation, and drying at 80 ℃ in a vacuum drying oven to constant weight to obtain a copolymer;
step S4, pore-forming: and (3) soaking the copolymer prepared in the step S3 in a hydrochloric acid solution with the mass fraction of 10% for 10 hours, then soaking in water for 5 hours, then taking out, and drying in a forced air drying oven at 80 ℃ to constant weight to obtain the polymer oil absorption material.
A macromolecular oil absorption material prepared by the preparation method of the macromolecular oil absorption material.
Example 2
A preparation method of a high polymer oil absorption material comprises the following steps:
step S1, preparation of Poly 1-p-toluenesulfonyl-2, 5-pyrrolidinedimethanol 2, 3-difluorofumarate: adding 18.8g of 1-p-toluenesulfonyl-2, 5-pyrrolidine dimethanol, 10g of 2, 3-difluoro fumaric acid, 4.5g of titanium dioxide and 1g of 1, 4-naphthoquinone into 110g of N, N-dimethylformamide, stirring for 23 minutes to obtain a reaction solution, transferring the reaction solution into a high-pressure reaction kettle, replacing the air in the kettle with helium, carrying out esterification reaction for 3.5 hours under the conditions of the temperature of 250 ℃ and the absolute pressure of 50KPa, finishing esterification, and relieving pressure to normal pressure; then under the vacuum condition, controlling the temperature to be 250 ℃, stirring and reacting for 14h, cooling to room temperature after the reaction is finished, discharging, precipitating in a sodium hydroxide aqueous solution with the mass fraction of 0.8%, washing the precipitated product with ethanol for 4 times, and then performing rotary evaporation to remove the ethanol to obtain poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate;
step S2, modification of poly (1-p-toluenesulfonyl) -2, 5-pyrrolidinedimethanol 2, 3-difluorofumarate: adding 10g of poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate into 35g of carbon tetrachloride, adding 1.5g of epoxy chloropropane, stirring and reacting at 32 ℃ for 5.3 hours, and then performing rotary evaporation to remove the carbon tetrachloride to obtain epoxy group modified poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate;
step S3, preparation of copolymer: adding 10g of epoxy modified poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate prepared in the step S2, 1.3g of allyl-beta-cyclodextrin, 1g of octavinyl-POSS, 1g of vinyl silicone oil, 5g of 2,4, 5-trifluoro-phenylpropenoic acid, 1.5g of calcium carbonate, 0.45g of silane coupling agent KH5600, 0.5g of carbon sponge, 0.2g of azodiisoheptonitrile and 70g of N-methyl pyrrolidone into a reactor, stirring and polymerizing for 8.5 hours at 77 ℃ under the protection of nitrogen, removing the N-methyl pyrrolidone by rotary evaporation, and drying at 83 ℃ in a vacuum drying oven to constant weight to obtain a copolymer;
step S4, pore-forming: and (3) soaking the copolymer prepared in the step S3 in a hydrochloric acid solution with the mass fraction of 11% for 11 hours, then soaking in water for 6 hours, taking out, and drying in a forced air drying oven at 82 ℃ to constant weight to obtain the polymer oil absorption material.
A macromolecular oil absorption material prepared by the preparation method of the macromolecular oil absorption material.
Example 3
A preparation method of a high polymer oil absorption material comprises the following steps:
step S1, preparation of Poly 1-p-toluenesulfonyl-2, 5-pyrrolidinedimethanol 2, 3-difluorofumarate: adding 18.8g of 1-p-toluenesulfonyl-2, 5-pyrrolidine dimethanol, 10g of 2, 3-difluorofumaric acid, 5g of titanium chloride and 1g of tetrachlorobenzoquinone into 125g of N, N-dimethylacetamide, stirring for 25 minutes to obtain a reaction solution, transferring the reaction solution into a high-pressure reaction kettle, replacing air in the kettle with neon, carrying out esterification reaction for 4 hours under the conditions of the temperature of 260 ℃ and the absolute pressure of 70KPa, finishing esterification, and releasing pressure to normal pressure; then under the vacuum condition, controlling the temperature to be 255 ℃, stirring and reacting for 15h, cooling to room temperature after the reaction is finished, discharging, precipitating in a sodium hydroxide aqueous solution with the mass fraction of 1.3%, washing the precipitated product with ethanol for 5 times, and then performing rotary evaporation to remove the ethanol to obtain poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate;
step S2, modification of poly (1-p-toluenesulfonyl) -2, 5-pyrrolidinedimethanol 2, 3-difluorofumarate: adding 10g of poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate into 40g of carbon tetrachloride, adding 2g of epoxy chloropropane, stirring and reacting at 35 ℃ for 5.5 hours, and then performing rotary evaporation to remove the carbon tetrachloride to obtain epoxy group modified poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate;
step S3, preparation of copolymer: adding 10g of epoxy modified poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate prepared in step S2, 1.5g of allyl-beta-cyclodextrin, 1g of octavinyl-POSS, 1g of vinyl silicone oil, 5g of 2,4, 5-trifluoro-phenylpropenoic acid, 1.5g of calcium carbonate, KH5700.45g of silane coupling agent, 0.5g of carbon sponge, 0.2g of azobisisobutyronitrile and 80g of N-methyl pyrrolidone into a reactor, stirring and polymerizing at 80 ℃ under the protection of nitrogen for 9 hours, removing the N-methyl pyrrolidone by rotary evaporation, and drying at 85 ℃ in a vacuum drying oven to constant weight to obtain a copolymer;
step S4, pore-forming: and (3) soaking the copolymer prepared in the step S3 in a hydrochloric acid solution with the mass fraction of 13% for 13 hours, then soaking in water for 7 hours, taking out, and drying in a forced air drying oven at 85 ℃ to constant weight to obtain the polymer oil absorption material.
A macromolecular oil absorption material prepared by the preparation method of the macromolecular oil absorption material.
Example 4
A preparation method of a high polymer oil absorption material comprises the following steps:
step S1, preparation of Poly 1-p-toluenesulfonyl-2, 5-pyrrolidinedimethanol 2, 3-difluorofumarate: adding 18.8g of 1-p-toluenesulfonyl-2, 5-pyrrolidine dimethanol, 10g of 2, 3-difluoro fumaric acid, 5.5g of tetrabutyl titanate and 1g of l, 4-naphthoquinone into 140g of N-methyl pyrrolidone, stirring for 28 minutes to obtain a reaction solution, transferring the reaction solution into a high-pressure reaction kettle, replacing the air in the kettle with argon, carrying out esterification reaction for 4.5 hours under the conditions of the temperature of 270 ℃ and the absolute pressure of 80KPa, finishing esterification, and relieving pressure to normal pressure; then under the vacuum condition, controlling the temperature to be 260 ℃, stirring and reacting for 17h, cooling to room temperature after the reaction is finished, discharging, precipitating in a sodium hydroxide aqueous solution with the mass fraction of 1.7%, washing the precipitated product with ethanol for 6 times, and then performing rotary evaporation to remove the ethanol to obtain poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate;
step S2, modification of poly (1-p-toluenesulfonyl) -2, 5-pyrrolidinedimethanol 2, 3-difluorofumarate: adding 10g of poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate into 48g of carbon tetrachloride, adding 2.8g of epoxy chloropropane, stirring and reacting at 38 ℃ for 5.8 hours, and then performing rotary evaporation to remove the carbon tetrachloride to obtain epoxy group modified poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate;
step S3, preparation of copolymer: adding 10g of epoxy modified poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate prepared in step S2, 1.9g of allyl-beta-cyclodextrin, 1g of octavinyl-POSS, 1g of vinyl silicone oil, 5g of 2,4, 5-trifluoro-phenylpropenoic acid, 1.5g of calcium carbonate, 0.55g of silane coupling agent KH550, 0.5g of carbon sponge, 0.25g of azobisisoheptonitrile and 95g of N-methyl pyrrolidone into a reactor, stirring and polymerizing at 84 ℃ under the protection of nitrogen for 9.5 hours, removing the N-methyl pyrrolidone by rotary evaporation, and drying at 88 ℃ in a vacuum drying oven to constant weight to obtain a copolymer;
step S4, pore-forming: and (3) soaking the copolymer prepared in the step S3 in a hydrochloric acid solution with the mass fraction of 14% for 14 hours, then soaking in water for 9 hours, then taking out, and drying in a forced air drying oven at 88 ℃ to constant weight to obtain the polymer oil absorption material.
A macromolecular oil absorption material prepared by the preparation method of the macromolecular oil absorption material.
Example 5
A preparation method of a high polymer oil absorption material comprises the following steps:
step S1, preparation of Poly 1-p-toluenesulfonyl-2, 5-pyrrolidinedimethanol 2, 3-difluorofumarate: adding 18.8g of 1-p-toluenesulfonyl-2, 5-pyrrolidine dimethanol, 10g of 2, 3-difluoro fumaric acid, 6g of catalyst and 1g of polymerization inhibitor into 150g of high-boiling-point solvent, stirring for 30 minutes to obtain a reaction solution, transferring the reaction solution into a high-pressure reaction kettle, replacing the air in the kettle with nitrogen, carrying out esterification reaction for 5 hours under the conditions of the temperature of 280 ℃ and the absolute pressure of 90KPa, finishing esterification, and releasing pressure to normal pressure; then under the vacuum condition, controlling the temperature to be 270 ℃, stirring and reacting for 18h, cooling to room temperature after the reaction is finished, discharging, precipitating in a sodium hydroxide aqueous solution with the mass fraction of 2%, washing the precipitated product with ethanol for 7 times, and then performing rotary evaporation to remove the ethanol to obtain poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate; the catalyst is formed by mixing tetrabutyl titanate, titanium dioxide and titanium chloride according to the mass ratio of 1:1: 2; the polymerization inhibitor is formed by mixing tetrachlorobenzoquinone and l, 4-naphthoquinone according to a mass ratio of 3: 5; the high-boiling-point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone according to a mass ratio of 1:2:2: 4;
step S2, modification of poly (1-p-toluenesulfonyl) -2, 5-pyrrolidinedimethanol 2, 3-difluorofumarate: adding 10g of poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate into 50g of carbon tetrachloride, adding 3g of epoxy chloropropane, stirring and reacting at 40 ℃ for 6 hours, and then performing rotary evaporation to remove the carbon tetrachloride to obtain epoxy group modified poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate;
step S3, preparation of copolymer: adding 10g of epoxy modified poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate prepared in the step S2, 2g of allyl-beta-cyclodextrin, 1g of octavinyl-POSS, 1g of vinyl silicone oil, 5g of 2,4, 5-trifluoro-phenylpropenoic acid, 1.5g of calcium carbonate, 0.6g of coupling agent, 0.5g of carbon sponge, 0.3g of initiator and 100g of N-methyl pyrrolidone into a reactor, stirring and polymerizing for 10 hours at 85 ℃ under the protection of nitrogen, removing the N-methyl pyrrolidone by rotary evaporation, and drying at 90 ℃ in a vacuum drying oven to constant weight to obtain a copolymer; the coupling agent is formed by mixing a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH570 according to the mass ratio of 1:3: 5; the initiator is formed by mixing azodiisobutyronitrile and azodiisoheptonitrile according to the mass ratio of 3: 5;
step S4, pore-forming: and (3) soaking the copolymer prepared in the step S3 in a hydrochloric acid solution with the mass fraction of 15% for 15 hours, then soaking in water for 10 hours, taking out, and drying in a forced air drying oven at 90 ℃ to constant weight to obtain the polymer oil absorption material.
A macromolecular oil absorption material prepared by the preparation method of the macromolecular oil absorption material.
Comparative example 1
A method for preparing a polymeric oil absorbing material, which is substantially the same as in example 1, except that poly-1-p-toluenesulfonyl-2, 5-pyrrolidinedimethanol 2, 3-difluorofumarate is used in place of epoxy-modified poly-1-p-toluenesulfonyl-2, 5-pyrrolidinedimethanol 2, 3-difluorofumarate during the preparation of the copolymer.
Comparative example 2
A method for preparing a polymer oil-absorbing material, which is substantially the same as that in example 1, except that no allyl-beta-cyclodextrin and calcium carbonate are added in the preparation process of the copolymer.
Comparative example 3
A method for preparing a polymeric oil absorbing material, substantially the same as in example 1, except that the octavinyl-POSS and carbon sponge are not added during the preparation of the copolymer.
Comparative example 4
A method for preparing a polymer oil absorption material, which is basically the same as the embodiment 1, except that vinyl silicone oil and 2,4, 5-trifluorophenylacrylic acid are not added in the preparation process of the copolymer.
The polymer oil-absorbing materials prepared by the preparation methods of the polymer oil-absorbing materials described in the above examples 1 to 5 and comparative examples 1 to 5 were subjected to performance tests, the test results are shown in table 1, the test oil type is gasoline, and the test is carried out according to the corresponding national standard.
TABLE 1
| Test items | Saturated oil absorption rate | Saturated oil absorption time | Oil retention rate | Number of cycles |
| Unit of | g/g | Min | ％ | ％ |
| Example 1 | 33.2 | 55 | 97.8 | 15 |
| Example 2 | 33.5 | 53 | 98.2 | 15 |
| Example 3 | 33.8 | 53 | 98.4 | 15 |
| Example 4 | 34.2 | 52 | 98.7 | 15 |
| Example 5 | 34.5 | 50 | 99.0 | 15 |
| Comparative example 1 | 30.2 | 63 | 93.1 | 12 |
| Comparative example 2 | 30.5 | 60 | 93.3 | 12 |
| Comparative example 3 | 30.6 | 62 | 92.8 | 12 |
| Comparative example 4 | 31.1 | 64 | 92.6 | 12 |
As can be seen from table 1, the polymeric oil absorbing material disclosed in the embodiment of the present invention has excellent oil absorbing ability, which is a result of the synergistic effect of epoxy-modified poly-1-p-toluenesulfonyl-2, 5-pyrrolidinedimethanol 2, 3-difluorofumarate, allyl- β -cyclodextrin, octavinyl-POSS, vinyl silicone oil, 2,4, 5-trifluorophenylacrylic acid, calcium carbonate, and carbon sponge.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. A preparation method of a high polymer oil absorption material is characterized by comprising the following steps:
step S1, preparation of Poly 1-p-toluenesulfonyl-2, 5-pyrrolidinedimethanol 2, 3-difluorofumarate: adding 1-p-toluenesulfonyl-2, 5-pyrrolidine dimethanol, 2, 3-difluoro fumaric acid, a catalyst and a polymerization inhibitor into a high-boiling point solvent, stirring for 20-30 minutes to obtain a reaction solution, transferring the reaction solution into a high-pressure reaction kettle, replacing air in the kettle with nitrogen or inert gas, carrying out esterification reaction for 3-5 hours at the temperature of 230-280 ℃ and the absolute pressure of 30-90 KPa, finishing esterification, and releasing the pressure to the normal pressure; then under the vacuum condition, controlling the temperature between 240 ℃ and 270 ℃, stirring and reacting for 12-18h, cooling to room temperature after the reaction is finished, discharging and precipitating in a sodium hydroxide aqueous solution with the mass fraction of 0.5-2%, washing the precipitated product for 3-7 times by using ethanol, and then carrying out rotary evaporation to remove the ethanol, thus obtaining the poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluorofumarate;
step S2, modification of poly (1-p-toluenesulfonyl) -2, 5-pyrrolidinedimethanol 2, 3-difluorofumarate: adding poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate into carbon tetrachloride, adding epoxy chloropropane into the carbon tetrachloride, stirring the mixture at the temperature of between 30 and 40 ℃ for reaction for 5 to 6 hours, and then performing rotary evaporation to remove the carbon tetrachloride to obtain epoxy group modified poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate;
step S3, preparation of copolymer: adding the epoxy modified poly (1-p-toluenesulfonyl) -2, 5-pyrrolidine dimethanol 2, 3-difluoro fumarate prepared in the step S2, allyl-beta-cyclodextrin, octavinyl-POSS, vinyl silicone oil, 2,4, 5-trifluoropropenoic acid, calcium carbonate, a coupling agent, carbon sponge, an initiator and N-methyl pyrrolidone into a reactor, stirring and polymerizing for 8-10 hours at 75-85 ℃ under the protection of nitrogen, removing the N-methyl pyrrolidone by rotary evaporation, placing the mixture in a vacuum drying oven and drying the mixture at 80-90 ℃ to constant weight to obtain a copolymer;
step S4, pore-forming: and (3) soaking the copolymer prepared in the step S3 in a hydrochloric acid solution with the mass fraction of 10-15% for 10-15 hours, then soaking in water for 5-10 hours, taking out, and drying in a forced air drying oven at 80-90 ℃ to constant weight to obtain the polymer oil absorption material.
2. The method for preparing a polymeric oil absorbing material according to claim 1, wherein the mass ratio of the 1-p-toluenesulfonyl-2, 5-pyrrolidinedimethanol to the 2, 3-difluorofumaric acid, the catalyst, the polymerization inhibitor and the high boiling point solvent in step S1 is 1.88:1 (0.4-0.6) to 0.1 (9-15).
3. The method for preparing the polymeric oil absorbing material according to claim 1, wherein the catalyst is at least one of tetrabutyl titanate, titanium dioxide and titanium chloride; the polymerization inhibitor is at least one of tetrachlorobenzoquinone and l, 4-naphthoquinone; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is one of helium, neon and argon.
4. The method for preparing a polymeric oil absorbing material according to claim 1, wherein the mass ratio of the poly (1-p-toluenesulfonyl) -2, 5-pyrrolidinedimethanol 2, 3-difluorofumarate, carbon tetrachloride and epichlorohydrin in step S2 is 1 (3-5) to (0.1-0.3).
5. The method for preparing a polymeric oil absorbing material according to claim 1, wherein in step S3, the mass ratio of the epoxy-modified poly (1-p-toluenesulfonyl) -2, 5-pyrrolidinedimethanol 2, 3-difluorofumarate, allyl- β -cyclodextrin, octavinyl-POSS, vinyl silicone oil, 2,4, 5-trifluorophenylacrylic acid, calcium carbonate, coupling agent, carbon sponge, initiator, and N-methylpyrrolidone is 1 (0.1-0.2):0.1:0.1:0.5:0.15 (0.03-0.06):0.05 (0.01-0.03): 6-10).
6. The method for preparing the polymeric oil absorbing material of claim 1, wherein the coupling agent is at least one of silane coupling agent KH550, silane coupling agent KH560 and silane coupling agent KH 570.
7. The method for preparing a polymeric oil absorbing material according to claim 1, wherein the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
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