CN109265732A - A kind of preparation method of oil absorption material - Google Patents

A kind of preparation method of oil absorption material Download PDF

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CN109265732A
CN109265732A CN201811014955.7A CN201811014955A CN109265732A CN 109265732 A CN109265732 A CN 109265732A CN 201811014955 A CN201811014955 A CN 201811014955A CN 109265732 A CN109265732 A CN 109265732A
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mixing
take
oil absorption
mass ratio
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蒋春霞
陈建春
卢星
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/009—Use of pretreated compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances

Abstract

The invention discloses a kind of preparation methods of oil absorption material, belong to oil absorption material field.The present invention pre-processes carbon nanotube, enhance its surface active groups, then ultrasonication, microwave action, introduce functionalization long-chain, when preparing polyurethane, the oil absorption on surface of the present invention can be improved, reinforce the capillary effect of polyurethane itself, strengthen it to the absorption of oil and to the repulsive interaction of water, improve oil absorption efficiency, expanded graphite alkene has flourishing network-like pass structure, high-specific surface area, so that its surface hydrophobicity oleophylic, the adsorption ability of enhancing system, and then there is good hydrophobic super-oleophilic, still there is loose porous reticular structure inside polyurethane, with huge specific surface area and adsorption space, to realize the absorption to oily substance and encompass, improve protect oil performance.The present invention solves the problems, such as that the oil absorption efficiency of common oil absorption material at present is low, Oil keeping is poor.

Description

A kind of preparation method of oil absorption material
Technical field
The invention belongs to oil absorption material technical fields, and in particular to a kind of preparation method of oil absorption material.
Background technique
As the important energy and the raw material of industry, oils is the indispensable production of the mankind and daily necessities, especially The petroleum of the title of the blood vessels of industrial development.In recent years, with the utilization of continually developing of petroleum resources, marine oil overflow accident it is frequent Occur, very big pollution is caused to ecological environment, causes the concern that people pollute oil leak event and oily waste water, oily waste water Separation has become the research hotspot of environment chemical engineering field.The method of processing oily waste water mainly has absorption, extraction, solidification, biology The methods of degradation, burning and oil barrier interception.Due to simple process, processing convenience, strong operability, it is low in cost the advantages that, suction Receipts method processing oily waste water is widely paid close attention to.High oil-absorbent material is a kind of new function material different from traditional oil absorption material Material has that oil suction multiplying power is high, oil-water selectivity is good and the excellent properties such as reusable, therefore the exploitation of high oil-absorbent material Cause the extensive concern of researchers at home and abroad.Currently, most oil absorption material Oil keepings are poor, oil absorbency is low, have been unable to meet The demand of people.
Summary of the invention
The technical problems to be solved by the invention: for current common oil absorption material oil absorption efficiency is low, Oil keeping is poor Problem provides a kind of preparation method of oil absorption material.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of preparation method of oil absorption material, the preparation method include the following steps:
(1) 1:20 ~ 30 take pretreatment carbon nanotube, dehydrated alcohol mixing in mass ratio, and ultrasonication obtains dispersion liquid, take point The ethyl orthosilicate of dispersion liquid quality 1 ~ 4% is added in dispersion liquid, the reagent A of dispersion liquid quality 1 ~ 4% is mixed, and obtains pretreatment fluid, It takes pretreatment fluid 1:3 in mass ratio ~ 6 that ethanol solution is added to be uniformly mixed, centrifugation takes centrifugation object dry, must pre-process carbon nanometer Pipe-silica composite；
(2) according to the mass fraction, 20 ~ 30 parts of polyether polyol, 15 ~ 25 parts of isocyanates, 20 ~ 30 parts of water, 3 ~ 6 parts of adjuvants, 1 are taken ~ 4 parts of stabilizers, 0.6 ~ 1 part of stannous octoate, 10 ~ 15 parts of pretreatment carbon nanotube-silica composites take in 40 ~ 50 DEG C Polyether polyol, water, adjuvant, stabilizer, stannous octoate are mixed, and isocyanates and pretreatment carbon nanotube-dioxy is added SiClx compound, heating, constant temperature are stirred to react, and obtain compound object, take compound object that the acetum of compound amount of substance 15 ~ 25% is added, Constant temperature stirring, obtains modified polyurethane reaction solution, takes modified polyurethane reaction solution plastotype, be stored at room temperature foaming, cures, and demoulding obtains Modified polyurethane sponge, it is spare；
(3) it taking expanded graphite alkene 1:6 in mass ratio ~ 10 that nitration mixture mixing is added to impregnate, filtering takes filter residue to wash, and it is dry, obtain drying Object takes dried object 1:20 ~ 30:5 in mass ratio that n,N-Dimethylformamide is added, tetrabutylammonium hydroxide is mixed, room temperature It stands, filtering, the dehydrated alcohol ultrasonic wave dispersion for taking filter cake to be added 7 ~ 12 times of filter residue quality obtains graphite dispersing solution；
(4) 5:1 ~ 3 take graphite dispersing solution, reagent B mixing by volume, and the crosslinking agent mixing of reagent B mass 0.1 ~ 0.3% is added, Compound maceration extract is obtained, spare modified polyurethane sponge is taken to be cut into fritter, 10 ~ 15 times of modified polyurethane sponge quality is added Ethanol solution mixing, supersonic oscillations, filtering take filter residue and drying, obtain dried object, take dried object 1:6 in mass ratio ~ 10 to be added multiple It closes maceration extract to impregnate, filtering takes filtration cakes torrefaction, solidifies, obtains solidfied material, take the reagent C room of 5 ~ 8 times of solidfied material solidfied material quality Temperature is impregnated, and is filtered out solidfied material and is cleaned with mixing washing lotion, is dried in vacuo to get oil absorption material.
Pretreatment carbon nanotube in the step (1): carbon nanotube plasma treatment is taken, processed material is obtained, takes processed material 4:1:0.3 ~ 0.6:10 in mass ratio ~ 15 is added maleic anhydride, benzoyl peroxide, dimethylbenzene and mixes, super processing sound, at microwave Reason, filters while hot, washs, dry to get pretreatment carbon nanotube.
Reagent A in the step (1): take ammonium hydroxide, sodium carbonate mixing to get reagent A by quality 10:1 ~ 3.
Stabilizer in the step (2): 3:1 ~ 2 take silicone oil, mannitol to mix up to stabilizer in mass ratio.
Adjuvant in the step (2): 5:1 ~ 2:1 in mass ratio takes triethylene diamine, dibutyl phthalate, benzene first Sour sodium mixing is to get adjuvant.
Nitration mixture in the step (3): 7:2 ~ 4 take the concentrated sulfuric acid, concentrated nitric acid mixing to get nitration mixture by volume.
Reagent B in the step (4): 1:0.1:10 ~ 15 take zinc acetate, NaOH solution, dehydrated alcohol mixed in mass ratio It closes, obtains mixture, take mixture 5:1:1 in mass ratio ~ 2 that oleyl amine, ammonia spirit mixing is added to get reagent B.
Crosslinking agent in the step (4): any one in silane resin acceptor kh-550, KH-560, KH-570.
Reagent C in the step (4): 1:20 ~ 30 take lauric acid, dehydrated alcohol mixing to get reagent C in mass ratio.
Mixing washing lotion in the step (4): 5:1 ~ 3 take ethanol solution, acetone mixing to wash to get mixing in mass ratio Liquid.
The present invention is compared with other methods, and advantageous effects are:
The present invention pre-processes carbon nanotube, first carries out plasma electric treatment, enhances its surface active groups, then surpass Sonicated, microwave action, induction maleic anhydride graft on activated carbon nano-tube surface, introduce functionalization long-chain, cooperation When preparing polyurethane, the oil absorption on surface of the present invention can be improved, reinforce the capillary effect of polyurethane itself, that is, strengthen it to oil Absorption and the repulsive interaction to water, improve oil absorption efficiency, and expanded graphite alkene has flourishing network-like pass structure, high-ratio surface Product, so that its surface hydrophobicity oleophylic, surface contact angle is greater than 90 ° and cooperates using zinc acetate as zinc source, alkalization, alcoholysis and ammonium hydroxide, Oleyl amine acts on zinc oxide colloidal sol obtained, can be formed on its surface coarse combined oxidation spelter coating, and the surface for enhancing system is inhaled Attached ability, so that its surface contact angle is greater than 120 ° of hydrophobicitys and is improved, modified polyurethane sponge obtained is silane coupled Under the action of agent, it is surface modified modification with the lauric alcoholic solution in fatty acid, so that its surface contact angle is greater than 150 °, the hydrophobicity on its surface is changed into super-hydrophobicity, and then there is good hydrophobic super-oleophilic, inside polyurethane still With loose porous reticular structure, there is huge specific surface area and adsorption space, to realize the absorption to oily substance With encompass, improve protect oil performance.
Specific embodiment
Pretreatment carbon nanotube: carbon nanotube is taken, in plasma reaction cavity, is evacuated to 1.0 × 10-4Pa leads to argon gas Protection, with 60W 10 ~ 15min of electric treatment, obtains processed material, takes processed material 4:1:0.3 ~ 0.6:10 in mass ratio ~ 15 that maleic acid is added Acid anhydride, benzoyl peroxide, dimethylbenzene mixing, after 10 ~ 15min of 300W super processing sound, with 300W microwave power processing 20 ~ 35min is filtered while hot, after wash 3 ~ 5 times with the ethanol solution that volume fraction is 70%, 5 are dried in vacuo in 80 ~ 90 DEG C of baking ovens ~ 8h is to get pretreatment carbon nanotube.
Nitration mixture: 7:2 ~ 4 take the nitric acid mixing of the sulfuric acid of concentration 1.84g/mL, mass fraction 65% to get mixed by volume Acid.
Adjuvant: 5:1 ~ 2:1 in mass ratio takes triethylene diamine, dibutyl phthalate, sodium benzoate mixing to get auxiliary Agent.
Reagent A: the ammonium hydroxide of concentration 1mol/L, sodium carbonate is taken to mix to get reagent A by quality 10:1 ~ 3.
Reagent B: 1:0.1:10 ~ 15 take zinc acetate, the NaOH solution of mass fraction 10%, dehydrated alcohol mixing in mass ratio, Mixture is obtained, takes mixture 5:1:1 in mass ratio ~ 2 that the ammonia spirit mixing of oleyl amine, concentration 1mol/L is added, with 300 ~ 500r/ 3 ~ 5h of min magnetic agitation is to get reagent B.
Reagent C: 1:20 ~ 30 take lauric acid, dehydrated alcohol mixing to get reagent C in mass ratio.
Stabilizer: 3:1 ~ 2 take silicone oil, mannitol to mix up to stabilizer in mass ratio.
Mixing washing lotion: 5:1 ~ 3 take the ethyl alcohol of volume fraction 70%, acetone mixing to get mixing washing lotion in mass ratio.
Crosslinking agent: any one in silane resin acceptor kh-550, KH-560, KH-570.
A kind of preparation method of oil absorption material, includes the following steps:
(1) 1:20 ~ 30 take pretreatment carbon nanotube, dehydrated alcohol to mix in container in mass ratio, with 55 ~ 65kHz frequency ultrasound Wave handles 30 ~ 50min, obtains dispersion liquid, takes dispersion liquid that the ethyl orthosilicate of dispersion liquid quality 1 ~ 4%, dispersion liquid quality 1 ~ 4% is added Reagent A mixing, with 400 ~ 600r/min, 4 ~ 6h of magnetic agitation, obtain pretreatment fluid, take pretreatment fluid 1:3 in mass ratio ~ 6 be added The ethanol solution of volume fraction 60% is uniformly mixed, and is centrifuged 10 ~ 15min with 2000 ~ 3000r/min, takes centrifugation object in 65 ~ 80 DEG C 12 ~ 15h of oven drying obtains pretreatment carbon nanotube-silica composite；
(2) according to the mass fraction, 20 ~ 30 parts of polyether polyol, 15 ~ 25 parts of isocyanates, 20 ~ 30 parts of water, 3 ~ 6 parts of adjuvants, 1 are taken ~ 4 parts of stabilizers, 0.6 ~ 1 part of stannous octoate, 10 ~ 15 parts of pretreatment carbon nanotube-silica composites take in 40 ~ 50 DEG C Polyether polyol, water, adjuvant, stabilizer, stannous octoate are mixed in reaction kettle, after stirring 30 ~ 50min with 400 ~ 600r/min, Isocyanates and pretreatment carbon nanotube-silica composite is added, 65 ~ 85 DEG C are warming up to, with 500 ~ 800r/min constant temperature It is stirred to react 3 ~ 5h, obtains compound object, takes compound object that the acetum that the mass fraction of compound amount of substance 15 ~ 25% is 20% is added, Constant temperature stirring, obtains modified polyurethane reaction solution, takes modified polyurethane reaction solution in mold, be stored at room temperature 4 ~ 8min of foaming, in 55 ~ 60 DEG C, 24 ~ 30h is cured, demoulding obtains modified polyurethane sponge, spare；
(3) it takes the expanded graphite alkene 1:6 in mass ratio ~ 10 that expansion rate is 320 ~ 350mL/g that nitration mixture is added to mix, immersion 20 ~ For 24 hours, it filters, after taking filter residue to be rinsed with deionized water and be neutrality to washing lotion, in 65 ~ 80 DEG C of oven dryings to constant weight, obtains dried object, Take dried object 1:20 ~ 30:5 in mass ratio that n,N-Dimethylformamide, tetrabutylammonium hydroxide mixing is added, with 500 ~ 800r/ After 20 ~ 40min of min magnetic agitation, it is stored at room temperature 40 ~ 44h, is filtered, takes filter cake that 7 ~ 12 times of filter residue quality of dehydrated alcohol is added Disperse 3 ~ 5h with 400W ultrasonic wave, obtains graphite dispersing solution；
(4) 5:1 ~ 3 take graphite dispersing solution, reagent B mixing by volume, and the crosslinking agent mixing of reagent B mass 0.1 ~ 0.3% is added, Compound maceration extract is obtained, after taking spare modified polyurethane sponge to be cut into the irregular fritter of 1 ~ 3g, modified polyurethane sponge is added The ethanol solution for the volume fraction 70% that 10 ~ 15 times of quality mixes, and vibrates 1 ~ 3h with 45 ~ 55kHz frequency ultrasonic wave, filtering takes filter Slag obtains dried object in 70 ~ 90 DEG C of oven dryings to constant weight, take dried object 1:6 in mass ratio ~ 10 be added compound maceration extract impregnate 3 ~ 5h, filtering, takes filter cake after 70 ~ 90 DEG C of oven dryings, in 160 ~ 175 DEG C of 4 ~ 8min of solidification, obtains solidfied material, takes solidfied material with admittedly The reagent C that 5 ~ 8 times of compound quality impregnates 20 at room temperature ~ for 24 hours after, filter out solidfied material and cleaned 3 ~ 5 times with mixing washing lotion, in 100 ~ 110 DEG C are dried under vacuum to constant weight to get oil absorption material.
Pretreatment carbon nanotube: carbon nanotube is taken, in plasma reaction cavity, is evacuated to 1.0 × 10-4Pa leads to argon gas Protection, with 60W electric treatment 10min, obtains processed material, takes processed material 4:1:0.3:10 in mass ratio that maleic anhydride, peroxidating is added Benzoyl, dimethylbenzene mixing are handled 20min with 300W microwave power, are filtered while hot, use body after 300W super processing sound 10min After the ethanol solution that fraction is 70% washs 3 times, in 80 DEG C of baking oven vacuum drying 5h to get pretreatment carbon nanotube.
Nitration mixture: 7:2 takes the nitric acid of the sulfuric acid of concentration 1.84g/mL, mass fraction 65% to mix to get nitration mixture by volume.
Adjuvant: 5:1:1 in mass ratio takes triethylene diamine, dibutyl phthalate, sodium benzoate mixing to get auxiliary Agent.
Reagent A: the ammonium hydroxide of concentration 1mol/L, sodium carbonate is taken to mix to get reagent A by quality 10:1.
Reagent B: 1:0.1:10 in mass ratio takes zinc acetate, the NaOH solution of mass fraction 10%, dehydrated alcohol mixing, obtains Mixture takes mixture 5:1:1 in mass ratio that the ammonia spirit mixing of oleyl amine, concentration 1mol/L is added, with 300r/min magnetic force 3h is stirred to get reagent B.
Reagent C: 1:20 in mass ratio takes lauric acid, dehydrated alcohol mixing to get reagent C.
Stabilizer: 3:1 in mass ratio takes silicone oil, mannitol to mix up to stabilizer.
Mixing washing lotion: 5:1 in mass ratio takes the ethyl alcohol of volume fraction 70%, acetone mixing to get mixing washing lotion.
Crosslinking agent: silane resin acceptor kh-550.
A kind of preparation method of oil absorption material, includes the following steps:
(1) 1:20 in mass ratio takes pretreatment carbon nanotube, dehydrated alcohol to mix in container, is handled with 55kHz frequency ultrasonic wave 30min obtains dispersion liquid, takes dispersion liquid that the reagent A mixing of the ethyl orthosilicate of dispersion liquid quality 1%, dispersion liquid quality 1% is added, With 400r/min magnetic agitation 4h, pretreatment fluid is obtained, the ethyl alcohol for taking pretreatment fluid 1:3 in mass ratio that volume fraction 60% is added is molten Liquid is uniformly mixed, and is centrifuged 10min with 2000r/min, is taken centrifugation object in 65 DEG C of oven drying 12h, is obtained pretreatment carbon nanotube-two Silica composite；
(2) according to the mass fraction, take 20 parts of polyether polyol, 15 parts of isocyanates, 20 parts of water, 3 parts of adjuvants, 1 part of stabilizer, 0.6 part of stannous octoate, 10 parts of pretreatment carbon nanotube-silica composites, in 40 DEG C, take polyether polyol, water, adjuvant, Stabilizer, stannous octoate are mixed in reaction kettle, and after stirring 30min with 400r/min, isocyanates and pretreatment carbon nanometer is added Pipe-silica composite is warming up to 65 DEG C, is stirred to react 3h with 500r/min constant temperature, obtains compound object, takes compound object to be added multiple The acetum that the mass fraction of mixed amount of substance 15% is 20%, constant temperature stirring, obtains modified polyurethane reaction solution, takes modified polyurethane Reaction solution is stored at room temperature foaming 4min in mold, and in 55 DEG C, for 24 hours, demoulding obtains modified polyurethane sponge, spare for curing；
(3) it takes the expanded graphite alkene 1:6 in mass ratio that expansion rate is 320mL/g that nitration mixture mixing is added, impregnates 20h, filtering takes filter Slag is rinsed with deionized water be neutrality to washing lotion after, in 65 DEG C of oven dryings to constant weight, obtain dried object, take dried object in mass ratio N,N-Dimethylformamide, tetrabutylammonium hydroxide mixing, after 500r/min magnetic agitation 20min, room temperature is added in 1:20:5 40h, filtering are stood, the dehydrated alcohol for taking filter cake to be added 7 times of filter residue quality disperses 3h with 400W ultrasonic wave, obtains graphite dispersing solution；
(4) 5:1 takes graphite dispersing solution, reagent B mixing by volume, and the crosslinking agent mixing of reagent B mass 0.1% is added, obtains compound After taking spare modified polyurethane sponge to be cut into the irregular fritter of 1g, 10 times of modified polyurethane sponge quality is added in maceration extract Volume fraction 70% ethanol solution mixing, with 45kHz frequency ultrasonic wave vibrate 1h, filtering, take filter residue in 70 DEG C of oven dryings To constant weight, dried object is obtained, takes dried object 1:6 in mass ratio that compound maceration extract is added and impregnates 3h, filtering takes filter cake in 70 DEG C of baking ovens After drying, in 160 DEG C of solidification 4min, solidfied material is obtained, solidfied material is taken to impregnate 20h at room temperature with 5 times of solidfied material quality of reagent C Afterwards, it filters out solidfied material to be cleaned 3 times with mixing washing lotion, is dried under vacuum to constant weight in 100 DEG C to get oil absorption material.
Pretreatment carbon nanotube: carbon nanotube is taken, in plasma reaction cavity, is evacuated to 1.0 × 10-4Pa leads to argon gas Protection, with 60W electric treatment 15min, obtains processed material, takes processed material 4:1:0.6:15 in mass ratio that maleic anhydride, peroxidating is added Benzoyl, dimethylbenzene mixing are handled 35min with 300W microwave power, are filtered while hot, use body after 300W super processing sound 15min After the ethanol solution that fraction is 70% washs 5 times, in 90 DEG C of baking oven vacuum drying 8h to get pretreatment carbon nanotube.
Nitration mixture: 7:4 takes the nitric acid of the sulfuric acid of concentration 1.84g/mL, mass fraction 65% to mix to get nitration mixture by volume.
Adjuvant: 5:2:1 in mass ratio takes triethylene diamine, dibutyl phthalate, sodium benzoate mixing to get auxiliary Agent.
Reagent A: the ammonium hydroxide of concentration 1mol/L, sodium carbonate is taken to mix to get reagent A by quality 10:3.
Reagent B: 1:0.1:15 in mass ratio takes zinc acetate, the NaOH solution of mass fraction 10%, dehydrated alcohol mixing, obtains Mixture takes mixture 5:1:2 in mass ratio that the ammonia spirit mixing of oleyl amine, concentration 1mol/L is added, with 500r/min magnetic force 5h is stirred to get reagent B.
Reagent C: 1:30 in mass ratio takes lauric acid, dehydrated alcohol mixing to get reagent C.
Stabilizer: 3:2 in mass ratio takes silicone oil, mannitol to mix up to stabilizer.
Mixing washing lotion: 5:3 in mass ratio takes the ethyl alcohol of volume fraction 70%, acetone mixing to get mixing washing lotion.
Crosslinking agent: silane coupling agent KH-560.
A kind of preparation method of oil absorption material, includes the following steps:
(1) 1:30 in mass ratio takes pretreatment carbon nanotube, dehydrated alcohol to mix in container, is handled with 65kHz frequency ultrasonic wave 50min obtains dispersion liquid, takes dispersion liquid that the reagent A mixing of the ethyl orthosilicate of dispersion liquid quality 4%, dispersion liquid quality 4% is added, With 600r/min magnetic agitation 6h, pretreatment fluid is obtained, the ethyl alcohol for taking pretreatment fluid 1:6 in mass ratio that volume fraction 60% is added is molten Liquid is uniformly mixed, and is centrifuged 15min with 3000r/min, is taken centrifugation object in 80 DEG C of oven drying 15h, is obtained pretreatment carbon nanotube-two Silica composite；
(2) according to the mass fraction, 30 parts of polyether polyol, 25 parts of isocyanates, 30 parts of water, 6 parts of adjuvants, 4 parts of stabilizers, 1 are taken Part stannous octoate, 15 parts of pretreatment carbon nanotube-silica composites take polyether polyol, water, adjuvant, stabilization in 50 DEG C Agent, stannous octoate are mixed in reaction kettle, and after stirring 50min with 600r/min, isocyanates and pretreatment carbon nanotube-two is added Silica composite is warming up to 85 DEG C, is stirred to react 5h with 800r/min constant temperature, obtains compound object, takes compound object that compound object is added The acetum that the mass fraction of quality 25% is 20%, constant temperature stirring, obtains modified polyurethane reaction solution, modified polyurethane is taken to react Liquid is stored at room temperature foaming 8min in mold, in 60 DEG C, cures 30h, demoulding obtains modified polyurethane sponge, spare；
(3) it takes the expanded graphite alkene 1:10 in mass ratio that expansion rate is 350mL/g that nitration mixture mixing is added, impregnates for 24 hours, filtering takes Filter residue is rinsed with deionized water be neutrality to washing lotion after, in 80 DEG C of oven dryings to constant weight, obtain dried object, take dried object by quality N,N-Dimethylformamide, tetrabutylammonium hydroxide mixing, after 800r/min magnetic agitation 40min, room is added than 1:30:5 Temperature stands 44h, filtering, and the dehydrated alcohol for taking filter cake to be added 12 times of filter residue quality disperses 5h with 400W ultrasonic wave, obtains graphite dispersion Liquid；
(4) 5:3 takes graphite dispersing solution, reagent B mixing by volume, and the crosslinking agent mixing of reagent B mass 0.3% is added, obtains compound After taking spare modified polyurethane sponge to be cut into the irregular fritter of 3g, 15 times of modified polyurethane sponge quality is added in maceration extract Volume fraction 70% ethanol solution mixing, with 55kHz frequency ultrasonic wave vibrate 3h, filtering, take filter residue in 90 DEG C of oven dryings To constant weight, dried object is obtained, takes dried object 1:10 in mass ratio that compound maceration extract is added and impregnates 5h, filtering takes filter cake to dry in 90 DEG C After case is dry, in 175 DEG C of solidification 8min, solidfied material is obtained, solidfied material is taken to be impregnated at room temperature with 8 times of solidfied material quality of reagent C After for 24 hours, filters out solidfied material and cleaned 5 times with mixing washing lotion, be dried under vacuum to constant weight in 110 DEG C to get oil absorption material.
Pretreatment carbon nanotube: carbon nanotube is taken, in plasma reaction cavity, is evacuated to 1.0 × 10-4Pa leads to argon gas Protection, with 60W electric treatment 13min, obtains processed material, takes processed material 4:1:0.5:13 in mass ratio that maleic anhydride, peroxidating is added Benzoyl, dimethylbenzene mixing are handled 25min with 300W microwave power, are filtered while hot, use body after 300W super processing sound 12min After the ethanol solution that fraction is 70% washs 4 times, in 85 DEG C of baking oven vacuum drying 6h to get pretreatment carbon nanotube.
Nitration mixture: 7:3 takes the nitric acid of the sulfuric acid of concentration 1.84g/mL, mass fraction 65% to mix to get nitration mixture by volume.
Adjuvant: 5:1.5:1 in mass ratio takes triethylene diamine, dibutyl phthalate, sodium benzoate mixing to get auxiliary Agent.
Reagent A: the ammonium hydroxide of concentration 1mol/L, sodium carbonate is taken to mix to get reagent A by quality 10:2.
Reagent B: 1:0.1:12 in mass ratio takes zinc acetate, the NaOH solution of mass fraction 10%, dehydrated alcohol mixing, obtains Mixture takes mixture 5:1:1.5 in mass ratio that the ammonia spirit mixing of oleyl amine, concentration 1mol/L is added, with 400r/min magnetic Power stirs 4h to get reagent B.
Reagent C: 1:25 in mass ratio takes lauric acid, dehydrated alcohol mixing to get reagent C.
Stabilizer: 3:1.5 in mass ratio takes silicone oil, mannitol to mix up to stabilizer.
Mixing washing lotion: 5:2 in mass ratio takes the ethyl alcohol of volume fraction 70%, acetone mixing to get mixing washing lotion.
Crosslinking agent: Silane coupling reagent KH-570.
A kind of preparation method of oil absorption material, includes the following steps:
(1) 1:25 in mass ratio takes pretreatment carbon nanotube, dehydrated alcohol to mix in container, is handled with 60kHz frequency ultrasonic wave 40min obtains dispersion liquid, takes dispersion liquid that the reagent A mixing of the ethyl orthosilicate of dispersion liquid quality 3%, dispersion liquid quality 3% is added, With 500r/min magnetic agitation 5h, pretreatment fluid is obtained, the ethyl alcohol for taking pretreatment fluid 1:4 in mass ratio that volume fraction 60% is added is molten Liquid is uniformly mixed, and is centrifuged 12min with 2500r/min, is taken centrifugation object in 70 DEG C of oven drying 13h, is obtained pretreatment carbon nanotube-two Silica composite；
(2) according to the mass fraction, take 25 parts of polyether polyol, 20 parts of isocyanates, 25 parts of water, 4 parts of adjuvants, 3 parts of stabilizers, 0.9 part of stannous octoate, 12 parts of pretreatment carbon nanotube-silica composites, in 45 DEG C, take polyether polyol, water, adjuvant, Stabilizer, stannous octoate are mixed in reaction kettle, and after stirring 40min with 500r/min, isocyanates and pretreatment carbon nanometer is added Pipe-silica composite is warming up to 70 DEG C, is stirred to react 4h with 600r/min constant temperature, obtains compound object, takes compound object to be added multiple The acetum that the mass fraction of mixed amount of substance 20% is 20%, constant temperature stirring, obtains modified polyurethane reaction solution, takes modified polyurethane Reaction solution is stored at room temperature foaming 6min in mold, in 57 DEG C, cures 27h, demoulding obtains modified polyurethane sponge, spare；
(3) it takes the expanded graphite alkene 1:8 in mass ratio that expansion rate is 340mL/g that nitration mixture mixing is added, impregnates 22h, filtering takes filter Slag is rinsed with deionized water be neutrality to washing lotion after, in 75 DEG C of oven dryings to constant weight, obtain dried object, take dried object in mass ratio N,N-Dimethylformamide, tetrabutylammonium hydroxide mixing, after 600r/min magnetic agitation 30min, room temperature is added in 1:25:5 42h, filtering are stood, the dehydrated alcohol for taking filter cake to be added 9 times of filter residue quality disperses 4h with 400W ultrasonic wave, obtains graphite dispersing solution；
(4) 5:2 takes graphite dispersing solution, reagent B mixing by volume, and the crosslinking agent mixing of reagent B mass 0.2% is added, obtains compound After taking spare modified polyurethane sponge to be cut into the irregular fritter of 2g, 12 times of modified polyurethane sponge quality is added in maceration extract Volume fraction 70% ethanol solution mixing, with 50kHz frequency ultrasonic wave vibrate 2h, filtering, take filter residue in 80 DEG C of oven dryings To constant weight, dried object is obtained, takes dried object 1:8 in mass ratio that compound maceration extract is added and impregnates 4h, filtering takes filter cake in 80 DEG C of baking ovens After drying, in 170 DEG C of solidification 6min, solidfied material is obtained, solidfied material is taken to impregnate 22h at room temperature with 7 times of solidfied material quality of reagent C Afterwards, it filters out solidfied material to be cleaned 4 times with mixing washing lotion, is dried under vacuum to constant weight in 107 DEG C to get oil absorption material.
Comparative example: the oil absorption material of company of Suzhou City production.
The oil absorption material that above-mentioned comparative example is obtained with embodiment is tested by JTT560-2004.Sample is cut into 30 × 30 × 5mm thin slice claims its quality, takes thin slice to be immersed respectively in different excessive oil products at room temperature, takes after 5min Out, it is placed on metal mesh and is weighed rapidly after drip 5min.Oil suction multiple calculates according to the following formula: (quality-sample is inhaled after sample oil suction Quality before oil) quality before/sample oil suction；30 × 30 × 5mm thin slice that sample is cut into, takes thin slice at room temperature It is immersed in excessive gasoline respectively, is taken out after 5min, be placed on metal mesh and weighed rapidly after drip 5min, be 1KPa pressing through pressure 1min claims its weight again, protects oil cut rate and calculates according to the following formula: quality after (quality after quality-pressing after sample oil suction)/sample oil suction, It is averaged three times, obtains that the results are shown in Table 1.
Table 1:
Project Embodiment 1 Embodiment 2 Embodiment 3 Comparative example
Rape oil (again) 50 60 84 35
Kerosene (again) 85 80 105 40
Machine oil (again) 81 83 145 78
Vegetable oil (again) 140 89 172 70
Gasoline (again) 80 58 120 25
Protect oil cut rate (%) for the first time 89.8 88.8 92.8 86.1
Second of guarantor oil cut rate (%) 86.7 89.3 91.7 86.3
Third time protects oil cut rate (%) 87.5 88.9 90 85.6
Averagely protect oil cut rate (%) 88 89 91.5 86
In conclusion as shown in Table 1, the oil absorption material of oil absorption material prepared by the present invention and comparative example is higher than oil absorption efficiency, protects Oiliness is good, is worth advocating using energetically.

Claims (10)

1. a kind of preparation method of oil absorption material, which is characterized in that the preparation method includes the following steps:
(1) 1:20 ~ 30 take pretreatment carbon nanotube, dehydrated alcohol mixing in mass ratio, and ultrasonication obtains dispersion liquid, take point The ethyl orthosilicate of dispersion liquid quality 1 ~ 4% is added in dispersion liquid, the reagent A of dispersion liquid quality 1 ~ 4% is mixed, and obtains pretreatment fluid, It takes pretreatment fluid 1:3 in mass ratio ~ 6 that ethanol solution is added to be uniformly mixed, centrifugation takes centrifugation object dry, must pre-process carbon nanometer Pipe-silica composite；
(2) according to the mass fraction, 20 ~ 30 parts of polyether polyol, 15 ~ 25 parts of isocyanates, 20 ~ 30 parts of water, 3 ~ 6 parts of adjuvants, 1 are taken ~ 4 parts of stabilizers, 0.6 ~ 1 part of stannous octoate, 10 ~ 15 parts of pretreatment carbon nanotube-silica composites take in 40 ~ 50 DEG C Polyether polyol, water, adjuvant, stabilizer, stannous octoate are mixed, and isocyanates and pretreatment carbon nanotube-dioxy is added SiClx compound, heating, constant temperature are stirred to react, and obtain compound object, take compound object that the acetum of compound amount of substance 15 ~ 25% is added, Constant temperature stirring, obtains modified polyurethane reaction solution, takes modified polyurethane reaction solution plastotype, be stored at room temperature foaming, cures, and demoulding obtains Modified polyurethane sponge, it is spare；
(3) it taking expanded graphite alkene 1:6 in mass ratio ~ 10 that nitration mixture mixing is added to impregnate, filtering takes filter residue to wash, and it is dry, obtain drying Object takes dried object 1:20 ~ 30:5 in mass ratio that n,N-Dimethylformamide is added, tetrabutylammonium hydroxide is mixed, room temperature It stands, filtering, the dehydrated alcohol ultrasonic wave dispersion for taking filter cake to be added 7 ~ 12 times of filter residue quality obtains graphite dispersing solution；
(4) 5:1 ~ 3 take graphite dispersing solution, reagent B mixing by volume, and the crosslinking agent mixing of reagent B mass 0.1 ~ 0.3% is added, Compound maceration extract is obtained, spare modified polyurethane sponge is taken to be cut into fritter, 10 ~ 15 times of modified polyurethane sponge quality is added Ethanol solution mixing, supersonic oscillations, filtering take filter residue and drying, obtain dried object, take dried object 1:6 in mass ratio ~ 10 to be added multiple It closes maceration extract to impregnate, filtering takes filtration cakes torrefaction, solidifies, obtains solidfied material, take the reagent C room of 5 ~ 8 times of solidfied material solidfied material quality Temperature is impregnated, and is filtered out solidfied material and is cleaned with mixing washing lotion, is dried in vacuo to get oil absorption material.
2. a kind of preparation method of oil absorption material according to claim 1, which is characterized in that the pre- place in the step (1) Reason carbon nanotube: taking carbon nanotube plasma treatment, obtain processed material, and processed material 4:1:0.3 ~ 0.6:10 ~ 15 in mass ratio is taken to add Enter maleic anhydride, benzoyl peroxide, dimethylbenzene mixing, super processing sound, microwave treatment filters while hot, washs, it is dry to get Pre-process carbon nanotube.
3. a kind of preparation method of oil absorption material according to claim 1, which is characterized in that the reagent in the step (1) A: take ammonium hydroxide, sodium carbonate mixing to get reagent A by quality 10:1 ~ 3.
4. a kind of preparation method of oil absorption material according to claim 1, which is characterized in that the stabilization in the step (2) Agent: 3:1 ~ 2 take silicone oil, mannitol to mix up to stabilizer in mass ratio.
5. a kind of preparation method of oil absorption material according to claim 1, which is characterized in that the adjuvant in the step (2): 5:1 ~ 2:1 in mass ratio takes triethylene diamine, dibutyl phthalate, sodium benzoate mixing to get adjuvant.
6. a kind of preparation method of oil absorption material according to claim 1, which is characterized in that the nitration mixture in the step (3): 7:2 ~ 4 take the concentrated sulfuric acid, concentrated nitric acid mixing to get nitration mixture by volume.
7. a kind of preparation method of oil absorption material according to claim 1, which is characterized in that the reagent in the step (4) B: 1:0.1:10 ~ 15 take zinc acetate, NaOH solution, dehydrated alcohol mixing in mass ratio, obtain mixture, take mixture in mass ratio Oleyl amine is added in 5:1:1 ~ 2, ammonia spirit is mixed to get reagent B.
8. a kind of preparation method of oil absorption material according to claim 1, which is characterized in that the crosslinking in the step (4) Agent: any one in silane resin acceptor kh-550, KH-560, KH-570.
9. a kind of preparation method of oil absorption material according to claim 1, which is characterized in that the reagent in the step (4) C: 1:20 ~ 30 take lauric acid, dehydrated alcohol mixing to get reagent C in mass ratio.
10. a kind of preparation method of oil absorption material according to claim 1, which is characterized in that the mixing in the step (4) Washing lotion: 5:1 ~ 3 take ethanol solution, acetone mixing to get mixing washing lotion in mass ratio.
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