CN111117213B - Super-hydrophobic light polyurethane micro-nanofiber sponge and preparation method and application thereof - Google Patents

Super-hydrophobic light polyurethane micro-nanofiber sponge and preparation method and application thereof Download PDF

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CN111117213B
CN111117213B CN201911403536.7A CN201911403536A CN111117213B CN 111117213 B CN111117213 B CN 111117213B CN 201911403536 A CN201911403536 A CN 201911403536A CN 111117213 B CN111117213 B CN 111117213B
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fluorinated
fiber
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nano
resin
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CN111117213A (en
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李维虎
闫成成
朱保凌
赵曦
戴家兵
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Lanzhou Ketian Waterborne Polymer Material Co ltd
Hefei Ketian Waterborne Technology Co ltd
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Lanzhou Ketian Waterborne Polymer Material Co ltd
Hefei Ketian Waterborne Technology Co ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/12—Special parameters characterising the filtering material
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    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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Abstract

The invention provides a super-hydrophobic light polyurethane micro-nanofiber sponge and a preparation method and application thereof, wherein the micro-nanofiber sponge comprises nano-scale fibers with the diameter of 200-800 nm and micro-scale fibers with the diameter of 5-15 um, and the nano-scale fibersThe grade fiber comprises a fluorinated polyurethane having the structure of formula I:
Figure DDA0002348034400000011
the micro-nanofiber sponge is a three-dimensional light sponge with micron-sized fibers as a framework structure and nano-sized fibers as a main body filling structure, has high-efficiency greasy dirt water body purification treatment capacity, and has certain application value in the fields of water body cleaning and purification, self-protection and the like of oily water purification treatment, oil-water separation, self-cleaning, water resistance, stain resistance and the like due to the excellent performance of the polyurethane light sponge.

Description

Super-hydrophobic light polyurethane micro-nanofiber sponge and preparation method and application thereof
Technical Field
The invention belongs to the field of functional fiber materials and polymer synthesis, and particularly relates to a super-hydrophobic light polyurethane micro-nano fiber sponge, and a preparation method and application thereof.
Background
In recent years, with the popularization of global industrialization progress and rapid economic development, accidents that the waste liquid of oil and heavy metal mainly polluted by marine oil and industrial waste water is dumped to pollute river and marine water environment frequently occur, and environmental crisis in the global range is caused. However, although the traditional water treatment methods mainly adopt a membrane separation adsorption method, a gravity precipitation method, a thermochemical treatment method and the like, the water body can be purified to a certain extent, the methods generally have the problems of high energy consumption, low flux, low efficiency and long period, and part of the methods also have the problem of secondary pollution to the environment, so that the high-efficiency purification requirements of the current polluted water body cannot be met. Therefore, how to develop a water treatment purification material with high efficiency, high flux, high recycling rate, energy conservation and small environmental pollution is a difficult problem to be solved urgently in the field of water environment pollution treatment at present.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a super-hydrophobic light polyurethane micro-nanofiber sponge as well as a preparation method and application thereof.
In order to achieve the above objects and other objects, the present invention includes the following technical solutions: the invention firstly provides a super-hydrophobic light polyurethane micro-nanofiber sponge, which comprises nano-scale fibers with the diameter of 200-800 nm and micro-scale fibers with the diameter of 5-15 um, wherein the nano-scale fibers comprise fluorinated polyurethane with a structure shown in a formula I:
Figure BDA0002348034380000011
wherein:
Figure BDA0002348034380000012
RF represents the host group of a fluorinated alcohol monomer, R1Represents the main group of a polyisocyanate, R2Represents a main group of the cationic hydrophilic chain extender, x is 0 or 1, y is 1 or 2, a: b is 0.8-1.0, and n is 20-80.
In one embodiment, the mass ratio of the nano-scale fibers to the micro-scale fibers is 0.5-2.5.
In one embodiment, the molecular weight of the fluorinated polyurethane with the structure shown in formula I is 13000-30000.
In one embodiment, the micron-sized fiber comprises any one or more of aramid fiber, terylene, polyester, vinylon, spandex, acrylon, chinlon, polyaryl oxadiazole, polypropylene fiber, inorganic mineral fiber, cotton fiber and glass fiber.
In one embodiment, the nano-scale fiber is obtained by spinning a first component spinning solution with a concentration of 33 wt% to 35 wt% and a second component spinning solution with a concentration of 13 wt% to 16 wt%, wherein the first component spinning solution and/or the second component spinning solution comprises the fluorinated polyurethane with the structure of formula I, the water-soluble polymer and the thermosetting resin, and the concentration is the concentration of the fluorinated polyurethane with the structure of formula I and the water-soluble polymer.
In one embodiment, the micro-nanofiber sponge has an internal porosity of 83% -95% and a bulk density of 14-200 mg/cm3The hydrophobic angle is 156-162 degrees, and the oleophylic angle is not more than 2 degrees.
In one embodiment, the water-soluble polymer includes any one or more of cationic polyacrylamide, polyvinyl alcohol, cationic starch, cationic cellulose, cationic guar gum, poly (hydroxymethyl) cellulose, poly (dimethyldiallylammonium chloride), polyamine, inorganic polyaluminum, polyquaternium-28, polyquaternium-39, isobutylene-maleic anhydride ammonium salt copolymer, polyacrylic acid, and polymaleic anhydride.
In one embodiment, the thermosetting resin comprises any one or more of benzoxazine resin, silicone resin, polyamide resin, cationic polyacrylamide resin, polyamide polyamine epichlorohydrin resin, acrylic resin, polyamide polyurea epichlorohydrin resin, polyethyleneimine resin, chitosan, dialdehyde starch, maleic acid homopolymer and terpolymer resin, polyethylene maleic acid resin and zirconium titanate amine resin.
In one embodiment, the electrospinning conditions are: the voltage range is 5-20 KV DC voltage, the injection speed is 0.5-3 mL/h, the inner diameter of the needle is 0.5-1 mm, and the receiving distance is 8-20 cm.
In one embodiment, the first component dope and the second component dope are cross-placed on a spinning apparatus for simultaneous spinning.
In one embodiment, the spinning is performed using a spinning apparatus model TC4080 from Tessmann technologies, Inc., Dalian.
The invention also provides a preparation method of the micro-nano fiber sponge, which comprises the following steps:
providing a nanofiber comprising a fluorinated polyurethane having the structure of formula I:
Figure BDA0002348034380000021
wherein:
Figure BDA0002348034380000031
RF represents the host group of a fluorinated alcohol monomer, R1Represents the main group of a polyisocyanate, R2A main group representing a cationic hydrophilic chain extender, wherein x is 0 or 1, y is 1 or 2, a is 0.8-1.0, and n is 20-80; mixing the nano-scale fiber, the micron-scale fiber and a fiber suspension stabilizer to obtain a fiber suspension; and forming, removing the solvent and carrying out heat treatment on the fiber suspension to obtain the micro-nano fiber sponge.
In one embodiment, the fluorinated polyurethane having the structure of formula I is prepared by an alcohol-soluble method.
In one embodiment, the preparation of the fluorinated polyurethane of formula I comprises: carrying out vacuum dehydration treatment on polyether polyol at 100-120 ℃, reacting the polyether polyol with polyisocyanate at 80-95 ℃, reducing the temperature to 50-70 ℃ after testing that the residual NCO groups reach the theoretical residual value, then adding a fluorinated micromolecule chain extender, a fluorinated alcohol monomer, a micromolecule chain extender, a cationic hydrophilic chain extender, a cross-linking agent and a catalyst for continuous heat preservation reaction, reducing the temperature to 25-45 ℃ after testing that the residual NCO groups reach the theoretical residual value, adding a neutralizing agent and ethanol, emulsifying under the action of high-speed shearing force, then dropwise adding an emulsifying agent and a defoaming agent, and removing the solvent at 35-55 ℃ after emulsifying to obtain the fluorinated polyurethane resin with the structure of the formula I.
In one embodiment, the fluorinated polyurethane having the structure of formula I has a solid content of 32% to 35%.
In one embodiment, the preparation of the fluorinated polyurethane having the structure of formula I comprises introducing an inert gas to protect the reaction.
In one embodiment, the fluorinated polyurethane with the structure of formula I comprises the following raw materials in parts by weight: 80-100 parts of polyether polyol, 30-100 parts of polyisocyanate, 5-30 parts of a fluorinated alcohol monomer, 5-30 parts of a fluorinated small-molecular chain extender, 8-20 parts of a small-molecular chain extender, 5-25 parts of a cationic hydrophilic chain extender, 0.1-10 parts of a cross-linking agent, 0.1-10 parts of a catalyst, 0.1-8 parts of an emulsifier, 1-10 parts of a defoaming agent, 5-30 parts of a neutralizing agent and 80-500 parts of ethanol.
In one embodiment, the fluorinated polyurethane with the structure of formula I comprises the following raw materials in parts by weight: 85-95 parts of polyether polyol, 35-90 parts of polyisocyanate, 8-25 parts of a fluorinated alcohol monomer, 5-25 parts of a fluorinated small-molecular chain extender, 10-18 parts of a small-molecular chain extender, 5-22 parts of a cationic hydrophilic chain extender, 0.3-5 parts of a cross-linking agent, 0.5-6 parts of a catalyst, 0.2-5 parts of an emulsifier, 1-5 parts of an antifoaming agent, 5-30 parts of a neutralizer and 100-450 parts of ethanol.
In one embodiment, the polyether polyol is any one or more of polyoxyethylene glycol, polytetrahydrofuran glycol, polyether triol, polyether tetraol, tetrahydrofuran-ethylene oxide copolymer glycol and Mannich polyether glycol.
In one embodiment, the polyisocyanate is any one or combination of tetramethylxylylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, 1,6 hexyl diisocyanate, tetramethylcyclohexyl methane diisocyanate, methylcyclohexyl diisocyanate, and norbornane diisocyanate.
In one embodiment, the fluorinated alcohol monomer is any one or more of a fluorinated small molecule monohydric alcohol, a fluorinated small molecule dihydric alcohol and a long-chain fluorine-containing dihydric alcohol.
In one embodiment, the fluorinated small molecule diol is any one or two of an aromatic small molecule fluorine-containing diol and an aliphatic small molecule fluorine-containing diol.
In one embodiment, the long-chain type fluorine-containing diol is any one or combination of more of PEVE type, fluorine-containing polyester diol and fluorine-containing polyether diol.
In one embodiment, the fluorinated small molecule chain extender is any one or combination of fluorinated diols, fluorinated diamines.
In one embodiment, the cationic hydrophilic chain extender is any one or combination of more of diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, tert-butyldiethanolamine, dimethylethanolamine and bis (2-hydroxypropyl) aniline.
In one embodiment, the small molecule chain extender is selected from any one or more of 1,4 butanediol, ethylene glycol, diethylene glycol, and neopentyl glycol.
In one embodiment, the cross-linking agent is any one or more of trimethylolpropane, 1,2, 6-hexanetriol, methyl glucoside and sucrose.
In one embodiment, the catalyst is any one or combination of dibutyltin dilaurate, zinc carboxylate, bismuth carboxylate, and tetrabutyl titanate.
In one embodiment, the neutralizing agent is selected from any one or more of glacial acetic acid, glycolic acid, and acetic anhydride.
In one embodiment, the emulsifier is any one or combination of OP-10 and sodium dodecyl benzene sulfonate.
In one embodiment, the defoamer is a polysiloxane copolymer based defoamer.
In one embodiment, the ethanol is industrial grade ethanol with a concentration of not less than 95%.
In one embodiment, the fluorinated alcohol monomer is one or more of a fluorinated small molecule monohydric alcohol, a fluorinated small molecule dihydric alcohol, and a long chain fluorine-containing dihydric alcohol.
In one embodiment, the fluorinated small molecule diol is one or two of an aromatic small molecule fluorine-containing diol and an aliphatic small molecule fluorine-containing diol.
In one embodiment, the long-chain type fluorine-containing diol is PEVE type, fluorine-containing polyester diol, fluorine-containing polyether diol and the like in one or more combinations.
In one embodiment, the fiber suspension stabilizer comprises any one or more of polyacrylamide with the molecular weight of 200-400 ten thousand, polyvinyl alcohol with the molecular weight of 8-20 ten thousand and poly hydroxymethyl cellulose with the molecular weight of 8-20 ten thousand.
In one embodiment, the mass of the fiber suspension stabilizer is 0.1-0.5% of the total mass of the nano-sized fibers and the micro-sized fibers.
In one embodiment, the forming is freeze forming, and the freeze forming temperature is-20 to-200 ℃.
In one embodiment, the desolventizing is performed in a vacuum freeze drying device, and the desolventizing time is 5-24 hours.
In one embodiment, the heat treatment comprises: and (3) gradually heating from room temperature to 150-200 ℃ and keeping for 1-3 hours, wherein the heating rate is 2-5 ℃/min.
The invention also provides application of the polyurethane micro-nanofiber sponge in the fields of water body cleaning and purification and self-protection.
As mentioned above, the invention prepares a micro-nano polyurethane super-hydrophobic oleophylic light sponge, and the micro-nano fiber composite three-dimensional light polyurethane sponge is prepared by designing and automatically synthesizing high molecular weight alcohol-soluble fluorinated polyurethane emulsion, on the basis, through electrostatic spinning technology and combination of freeze drying technology, thermosetting resin and gradient heat treatment technology, the surface energy of a fiber layer is further reduced by introducing fluorocarbon bonds and thermosetting resin, meanwhile, the thermosetting resin forms a cross-linked network under gradient heating in fiber internal components, so that the material is endowed with high elasticity and high porosity and high oil flux performance, the internal porosity is up to 83% -95% by using a bubble point method, and the volume density is 14-200 mg/cm3The volume density and porosity are adjustable, the hydrophobic angle reaches 156-162 degrees, the oleophilic angle is close to 0 degree, and the separation flux of lubricating oil and engine oil can reach 2500 +/-115L/m2·h-1，2300±113L/m2·h-1The excellent performance of the polyurethane light sponge can ensure that the polyurethane light sponge can be used for air filtration and dirtThe method has potential application value in the fields of water purification treatment, self-cleaning, water resistance, pollution resistance, aviation fuel purification and the like.
Drawings
FIG. 1 shows scanning electron micrographs of nanofiber sponges of the present invention at different magnifications.
FIG. 2 shows a flow chart of the preparation method of the present invention.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 1-2. As shown in fig. 1, the invention provides a super-hydrophobic light polyurethane micro-nanofiber sponge, which can comprise nano-scale fibers with the diameter of 200-800 nm and micro-scale fibers with the diameter of 5-15 um, wherein the nano-fibers can be prepared by crushing a nano-fiber film prepared from a spinning solution through electrostatic spinning, the spinning can be spun on a substrate base fabric, the base fabric can be any one of polytetrafluoroethylene, polyphenylene sulfide and aramid, the prepared nano-fiber film can be taken off from the base fabric for standby after the spinning is finished, the nano-fiber film can be dried after the spinning is finished, and the drying temperature can be 80-90 ℃.
The mass ratio of the nano-scale fibers to the micro-scale fibers can be 0.5-2.5, the spinning solution can comprise a first component spinning solution and a second component spinning solution, the mass concentration of the first spinning solution can be 33% -35%, the mass concentration of the second component spinning solution is 13% -16%, and the first component spinning solution and the second component spinning solution can be obtained by adding thermosetting resin after the fluorinated polyurethane emulsion with the structure of the formula I and the water-soluble polymer are matched.
Figure BDA0002348034380000061
Wherein:
Figure BDA0002348034380000062
RF represents the host group of a fluorinated alcohol monomer, R1Represents the main group of a polyisocyanate, R2Represents a main group of the cationic hydrophilic chain extender, x is 0 or 1, y is 1 or 2, a: b is 0.8-1.0, and n is 20-80.
The mass ratio of the fluorinated polyurethane with the formula I structure in the micro-nano fiber sponge, the water-soluble polymer and the thermosetting resin can be (90-95): (1-5): 1-5), and the concentration is the concentration of the fluorinated polyurethane emulsion with the formula I structure and the water-soluble polymer. The matching can comprise the steps of uniformly mixing fluorinated polyurethane emulsion with a structure shown in the formula I and water-soluble polymers at different concentrations according to a certain proportion, carrying out ultrasonic dispersion to obtain a spinning stock solution, and adding the thermosetting resin to prepare a first component spinning solution and a second component spinning solution with different concentrations.
The fluorinated polyurethane emulsion with the structure shown in the formula I can be synthesized by an alcohol-soluble method, and the synthesis method can comprise the following steps: carrying out vacuum dehydration treatment on polyether polyol at 100-120 ℃, reacting the polyether polyol with polyisocyanate at 80-95 ℃, reducing the temperature to 50-70 ℃ after testing that the residual NCO groups reach the theoretical residual value, then adding a fluorinated micromolecule chain extender, a fluorinated alcohol monomer, a micromolecule chain extender, a cationic hydrophilic chain extender, a cross-linking agent and a catalyst, continuing to carry out heat preservation reaction for 1-5 hours, reducing the temperature to 25-45 ℃ after testing that the residual NCO groups reach the theoretical residual value, adding a neutralizing agent and ethanol, emulsifying under the action of high-speed shearing force, then dropwise adding an emulsifying agent and a defoaming agent, and removing the solvent at 35-55 ℃ for 1-2 hours after emulsification to obtain the fluorinated polyurethane resin with the structure shown in the formula I.
In one embodiment, the fluorinated polyurethane emulsion having the structure of formula I may be prepared from the following raw materials in percentage by weight: 80-100 parts of polyether polyol, 30-100 parts of polyisocyanate, 5-30 parts of a fluorinated alcohol monomer, 5-30 parts of a fluorinated small-molecular chain extender, 8-20 parts of a small-molecular chain extender, 5-25 parts of a cationic hydrophilic chain extender, 1-25 parts of a thermosetting water-based resin, 0.1-10 parts of a cross-linking agent, 0.1-10 parts of a catalyst, 0.1-8 parts of an emulsifier, 1-10 parts of a defoaming agent, 5-30 parts of a neutralizer and 80-500 parts of ethanol.
In one embodiment, the fluorinated polyurethane emulsion having the structure of formula I may be prepared from the following raw materials in percentage by weight: 85-95 parts of polyether polyol, 35-90 parts of polyisocyanate, 8-25 parts of a fluorinated alcohol monomer, 5-25 parts of a fluorinated small-molecular chain extender, 10-18 parts of a small-molecular chain extender, 5-22 parts of a cationic hydrophilic chain extender, 3-20 parts of a thermosetting water-based resin, 0.3-5 parts of a cross-linking agent, 0.5-6 parts of a catalyst, 0.2-5 parts of an emulsifier, 1-5 parts of a defoaming agent, 5-30 parts of a neutralizer and 100-450 parts of ethanol.
The micron-sized fiber can comprise one or more of aramid fiber, terylene, polyester, vinylon, spandex, acrylon, chinlon, polyaryl oxadiazole, polypropylene fiber, inorganic mineral fiber, cotton fiber and glass fiber. The micro-scale fibers may be micro-scale staple fibers. As can be seen from FIG. 1, under the scanning electron microscope images with different magnifications, the nano-scale fibers and the micro-scale fibers in the nano-fiber sponge prepared by the invention are interwoven, the overall fiber diameter is uniform, and the pores are rich. The sponge has an internal porosity of 83-95% and a bulk density of 14-200 mg/cm3The hydrophobic angle can be 156-162 degrees, and the oleophilic angle can be not more than 2 degrees.
According to the invention, two spinning solutions with different concentrations are adopted, so that the spinning solution with high concentration can obtain fibers with thicker diameter, and the spinning solution with low concentration can obtain fibers with thinner diameter, so that the prepared fiber layer has gradient change on different fiber diameter distributions, and the prepared nanofiber membrane has excellent performance. The fluorinated polyurethane with the structure shown in the formula I can be synthesized by an environment-friendly alcohol-soluble method, the use of high-boiling-point and environmentally-friendly organic solvents such as DMF (dimethyl formamide) and the like can be avoided by using the alcohol-soluble method, certain advantages in the aspects of energy conservation and emission reduction are achieved, the molecular weight of the prepared fluorinated polyurethane resin with the structure shown in the formula I can be 13000-30000, and the solid content of the fluorinated polyurethane emulsion with the structure shown in the formula I can be 30-35%.
In one embodiment, the water-soluble polymer may be cationic polyacrylamide. The thermosetting resin may include any one of or a combination of two of benzoxazine resin, polyamide polyamine epichlorohydrin resin. The thermosetting resin may include benzoxazine resin and polyamide polyamine epichlorohydrin resin, in which case, benzoxazine may enhance the crosslinking effect of polyamide polyamine epichlorohydrin, and the benzoxazine resin used in the present invention is solid, so in an embodiment, when the benzoxazine resin and the polyamide polyamine epichlorohydrin resin are used as the thermosetting resin, the benzoxazine resin may be added during the synthesis of the fluorinated polyurethane emulsion to facilitate the dissolution of the benzoxazine resin, and the polyamide polyamine epichlorohydrin resin may be mixed into the spinning dope of different concentrations after the pH thereof is adjusted to be consistent with the pH of the fluorinated polyurethane emulsion.
In one embodiment, when the fluorinated polyurethane emulsion having the structure of formula I comprises the following raw materials in parts by weight: 80-100 parts of polyether polyol, 30-100 parts of polyisocyanate, 5-30 parts of a fluorinated alcohol monomer, 5-30 parts of a fluorinated small-molecular chain extender, 8-20 parts of a small-molecular chain extender, 5-25 parts of a cationic hydrophilic chain extender, 0.1-10 parts of a cross-linking agent, 0.1-10 parts of a catalyst, 0.1-8 parts of an emulsifier, 1-10 parts of an antifoaming agent, 5-30 parts of a neutralizer and 80-500 parts of ethanol, wherein the addition amount of the thermosetting water-based resin can be 1-25 parts.
In one embodiment, when the fluorinated polyurethane emulsion having the structure of formula I comprises the following raw materials in parts by weight: 85-95 parts of polyether polyol, 35-90 parts of polyisocyanate, 8-25 parts of fluorinated alcohol monomer, 5-25 parts of fluorinated small chain extender, 10-18 parts of small molecular chain extender, 5-22 parts of cationic hydrophilic chain extender, 0.3-5 parts of cross-linking agent, 0.5-6 parts of catalyst, 0.2-5 parts of emulsifier, 1-5 parts of defoaming agent, 5-30 parts of neutralizer and 100-450 parts of ethanol, 3-20 parts of thermosetting water-based resin can be added.
In one embodiment, the electrospinning conditions may be: the voltage range is 5-20 KV DC voltage, the injection speed is 0.5-3 mL/h, the inner diameter of the needle is 0.5-1 mm, and the receiving distance is 8-20 cm. The temperature of the electrostatic spinning can be 20-30 ℃, and the humidity can be 70-80%. The electrostatic spinning equipment can be a spinning device of the Dalian Tessman scientific and technological company with the model number TC 4080.
The invention also provides a preparation method of the micro-nano fiber sponge, which comprises the following steps of S1-S3: s1: providing a nano-scale fiber, wherein the nano-scale fiber comprises fluorinated polyurethane with a structure shown in a formula I; s2: mixing the nano-scale fibers, the micro-scale fibers and a fiber suspension stabilizer to obtain a fiber suspension; s3: and (3) forming, desolventizing and thermally treating the fiber suspension to obtain the super-hydrophobic light polyurethane micro-nano fiber sponge.
In step S1, the fluorinated polyurethane has the following structure:
Figure BDA0002348034380000081
wherein:
Figure BDA0002348034380000082
RF represents the host group of a fluorinated alcohol monomer, R1Represents the main group of a polyisocyanate, R2Represents a main group of the cationic hydrophilic chain extender, x is 0 or 1, y is 1 or 2, a: b is 0.8-1.0, and n is 20-80.
In step S2, the mixing may include dispersing the nano-scale fibers and the micro-scale fibers into an alcohol-water solution together, and adding a fiber suspension stabilizer for mixing, where the mixing time may be 0.3 to 1 hour, the mixing may include high-speed shearing, fragmenting, and mixing, the fiber suspension stabilizer may be a high molecular weight hydrophilic resin with a certain thickening effect to increase steric hindrance during fiber suspension and prevent micro-scale fibers from settling, and more specifically may be polyacrylamide with a molecular weight of 200 to 400 ten thousand or polyvinyl alcohol or polymethylol with a molecular weight of 8 to 20 ten thousand, and the addition amount of the fiber suspension stabilizer may be 0.1% to 0.5% of the total mass of the fibers.
In step S3, the fiber suspension may be rapidly frozen and formed at a low temperature, and then placed in a vacuum freeze-drying device for desolvation for 5-24 hours. The freeze forming may be performed at a temperature of-20 ℃ to-190 ℃, for example, in a freezer or liquid nitrogen, the vacuum freeze drying may be performed in an FD-1-135Plus type instrument of the beijing bokaokang laboratory instruments ltd, the vacuum freeze drying may be performed at a temperature of-20 ℃ to-50 ℃, and the freeze drying conditions may be: vacuum degree < 3Pa, cold trap temperature: -135 ℃.
The heat treatment may include an infrared heat treatment, and the heat treatment may be a heating from room temperature to 150 to 200 ℃ for 1 to 3 hours, the heating rate can be 2-5 ℃/min, the surface energy of the fluorinated polyurethane fiber can be further reduced by adopting a gradient heating heat treatment process, meanwhile, the modification of the thermosetting resin on the surface of the micron-sized fiber in the fiber mixing process enhances the water resistance of the micron-sized fiber after heat treatment, realizes the super-hydrophobic oleophylic property, meanwhile, the thermosetting resin is further cured in the heat treatment process, so that effective bonding points are formed among the micro-nano fibers, the fiber frame is reinforced, and furthermore, elasticity is given to the material, and meanwhile, the accumulation and bonding among the micro-nanofibers further form a transmission channel inside the light polyurethane sponge, so that conditions are provided for realizing high porosity and high oil flux. And (3) obtaining the micro-nano fiber sponge after the heat treatment, wherein the micro-nano fiber sponge can be a three-dimensional stacked three-dimensional material as shown in figure 1.
The invention also provides application of the micro-nano fiber sponge in the fields of water body cleaning and purification and self-protection. The invention combines the preparation method of high molecular weight fluorinated alcohol soluble polyurethane emulsion with electrostatic spinning technology and low temperature freeze drying technology, and adopts the introduction of thermosetting resin and gradient heat treatment method to prepare the three-dimensional light sponge with super-hydrophobic oleophylic micron-sized fiber as a frame structure and nano-sized fiber as a main body filling structure, and the three-dimensional light sponge has high-efficiency oil stain water body purification treatment capacity.
Note that "%" and "part(s)" shown herein mean "% by mass" and "part(s) by mass", respectively, unless otherwise specified.
Hereinafter, the present invention will be more specifically explained by referring to examples, which should not be construed as limiting. Appropriate modifications may be made within the scope consistent with the gist of the present invention, and all of them fall within the technical scope of the present invention.
In one embodiment, a preparation method of a super-hydrophobic light polyurethane micro-nanofiber sponge comprises the following steps:
carrying out vacuum dehydration on polyoxyethylene glycol at the temperature of 90-110 ℃ for later use; weighing 90g of polyoxyethylene glycol and 35g of isophorone diisocyanate, fully reacting for 2.5h at 90 ℃, then measuring the NCO group to reach the theoretical residual value, quickly cooling to 50 ℃ by adopting a refrigerant, then adding 8g of fluorinated micromolecule monohydric alcohol, 5g of fluorinated diol, 6g of micromolecule ethylene glycol chain extender, 5g of cationic hydrophilic chain extender diethanol amine, 3g of thermosetting benzoxazine resin, 0.5g of 1,2, 6-hexanetriol and 0.5g of bismuth carboxylate catalyst, introducing nitrogen for protection, then carrying out heat preservation reaction for 3h, testing that the residual NCO value is not changed, slowly cooling to 30 ℃ by adopting circulating water, then adding 5.2g of glacial acetic acid neutralizer and 300g of diluted viscosity reducing solvent ethanol, then adding 0.2g of OP-10 for emulsification under the action of high-speed shearing, adding 1g of defoaming agent during emulsification, stirring for 5-10 min to complete emulsification, and (3) obtaining the fluorinated polyurethane emulsion with the structure shown in the formula I, wherein the solid content of the fluorinated polyurethane emulsion with the structure shown in the formula I is 35.4%, and the molecular weight is 13000-15000.
Then 3.5g of cationic polyacrylamide solution with the concentration of 50 percent and 100g of fluorinated polyurethane emulsion with the structure of the formula I obtained in the previous step are mixed and defoamed by ultrasonic dispersion and high-speed stirring, then the mixture is prepared into a first component spinning solution with the concentration of 35 percent with 12g of polyamide polyamine epichlorohydrin aqueous solution with the solid content of 8 percent, simultaneously 1.5g of polymethylol cellulose is mixed with the fluorinated polyurethane emulsion with the structure of the formula I diluted by 2.3 times, and the mixture is prepared into a second component spinning solution with the concentration of 16 percent with 12g of polyamide polyamine epichlorohydrin aqueous solution with the solid content of 8 percent after ultrasonic dispersion and high-speed stirring, and before the polyamide polyamine epichlorohydrin aqueous solution is mixed, the pH value is adjusted to be consistent with the pH value of the fluorinated polyurethane emulsion with the structure of the formula I by using 0.1N alkali liquor and 0.1N. And then pouring the first component spinning solution and the second component spinning solution into 10 100mL injection containers, fixing the containers on a spinning device in a crossed mode for cross synchronous spinning, wherein a receiving guide roller firstly adopts a copper net as a bottom base material (easy to receive fibers), then a layer of PTFE base cloth is fixed on the copper net, the voltage is selected to be 18.5KV, the receiving distance is 18cm, the injection speed is 0.45mL/h, and the stacking thickness of the nanofiber membrane is controlled to be 0.05-0.08mm by adjusting the spinning time.
And after spinning is finished, simultaneously removing the fiber film and the base fabric from the copper mesh, then drying the fiber film and the base fabric at 90 ℃ for 0.5h, then removing the fiber film from the base fabric, weighing 2g of the nano fiber film, putting the nano fiber film into a high-speed shearing machine, adding 250g of a mixed solution of ethanol and water, then starting fragmentation treatment for 0.5h, then adding 0.1% of polyacrylamide particles with fiber mass parts and 0.8g of aramid fiber short fibers with the diameter of 5 mu m, then uniformly stirring the mixture on a high-speed stirrer and ultrasonically dispersing the mixture for 1h to obtain a fiber suspension.
Pouring the fiber suspension into a prepared volume of 200cm3The cylindrical grinding tool is then frozen for 24 hours at the low temperature of minus 20 ℃, then taken out and demoulded, and then put into a vacuum freeze drying device for freeze drying for 18 hours, so as to preliminarily obtain a micro-nano fiber accumulation body after a solvent is taken out, then the preliminarily obtained fiber accumulation body is put into an infrared heat treatment box to be heated to 200 ℃, the temperature rise rate of the first stage heat treatment is from the room temperature of 25 ℃ to 100 ℃, the temperature rise rate is 5 ℃/min, the temperature rise rate of the second stage heat treatment is from 100 ℃ to 200 ℃, the temperature rise rate is 2 ℃/min, the temperature is kept for 0.5 hour after the temperature is raised to 200 ℃, then the heat treated sample is taken out to obtain a sample 1, and the volume density of the sample 1 is calculated to be 14mg/cm by adopting an ultramicro balance for weighing3The porosity of a sample 1 tested by a bubble point method is up to 95 percent, the hydrophobic angle is 158 degrees, the lipophilic angle is 2 degrees, and the separation flux of the sample 1 to lubricating oil, engine oil and gasoline respectively reaches 2435L/m2·h-1，2207L/m2·h-1，2695L/m2·h-1And the oil flux of more than 95% can be still maintained after 50 times of recycling. The scanning electron micrograph of sample 1 is shown in FIG. 1.
In one embodiment, a preparation method of a super-hydrophobic light polyurethane micro-nanofiber sponge comprises the following steps:
dehydrating polytetrahydrofuran diol at 90-110 ℃ in vacuum for later use; weighing 95g of polytetrahydrofuran diol and 40g of tetramethylxylylene diisocyanate, fully reacting for 2 hours at 92 ℃, measuring the NCO group to reach the theoretical residual value, quickly cooling to 65 ℃ by adopting a refrigerant, then adding 6g of PEVE type fluorine-containing diol, 7g of fluorinated diamine, 5g of micromolecule 1, 4-butanediol chain extender, 8g of cationic hydrophilic chain extender triethanolamine, 4.5g of thermosetting benzoxazine resin, 0.9g of trimethylolpropane and 0.6g of bismuth carboxylate catalyst, introducing nitrogen for protection, then carrying out heat preservation reaction for 2.5 hours, testing that the residual NCO value is not changed, slowly cooling to 35 ℃ by adopting circulating water, then adding 6.5g of glacial acetic acid neutralizer and 350g of diluted viscosity-reducing solvent ethanol, then adding 0.2g of OP-10 for emulsification under the action of high-speed shearing, adding 1g of defoaming agent during emulsification, stirring for 5-10 minutes to complete emulsification, obtaining the fluorinated polyurethane emulsion with the structure shown in the formula I. The fluorinated polyurethane emulsion with the structure shown in the formula I has the solid content of 33.14% and the molecular weight of 20000-25000.
Then 5.5g of cationic polyacrylamide solution with the concentration of 50 percent and 100g of fluorinated polyurethane emulsion with the structure of the formula I obtained in the previous step are mixed and defoamed by ultrasonic dispersion and high-speed stirring, then the mixture is prepared into a first component spinning solution with the concentration of 34 percent with 12g of polyamide polyamine epichlorohydrin aqueous solution with the solid content of 15 percent, simultaneously 1.5g of polyvinyl alcohol 1788 is mixed with the fluorinated polyurethane emulsion with the structure of the formula I diluted by 2.5 times, and the mixture is prepared into a second component spinning solution with the concentration of 13 percent with 12g of polyamide polyamine epichlorohydrin aqueous solution with the solid content of 15 percent after ultrasonic dispersion and high-speed stirring, before the polyamide polyamine epichlorohydrin aqueous solution is mixed, the pH value of the polyamide polyamine epichlorohydrin aqueous solution is adjusted to be consistent with the pH value of the fluorinated polyurethane emulsion with the structure of the formula I by using 0.1N alkali liquor and 0.1N acid solution. And then, pouring the first component spinning solution and the second component spinning solution into 10 100mL injection containers, fixing the containers on a spinning device in a crossed mode for cross synchronous spinning, wherein a copper net is adopted as a bottom base material (easy to receive fibers) by a receiving guide roller, then a layer of PTFE or aramid fiber base cloth is fixed on the copper net, the voltage is selected to be 20KV, the receiving distance is 20cm, the injection speed is 0.35mL/h, and the stacking thickness of the nanofiber membrane is controlled to be 0.05-0.08mm by adjusting the spinning time.
After spinning is finished, the fiber membrane and the base fabric are simultaneously taken off from the copper mesh, then the fiber membrane and the base fabric are thermally dried for 0.5h at 90 ℃, then the fiber membrane is taken off from the base fabric, 5g of the nano fiber membrane is weighed and put into a high-speed shearing machine, 250g of mixed solution of ethanol and water is added, and then fragmentation treatment is started for 0.8 h; then, 0.3% by mass of polyacrylamide particles and 5g of 10 μm-diameter polyester staple fibers were added, followed by uniform stirring in a high-speed stirrer and ultrasonic dispersion for 1.5 hours to obtain a fiber suspension.
Pouring the fiber suspension into a prepared volume of 200cm3Then freezing the cylindrical grinding tool for 0.5h at the low temperature of minus 190 ℃, then taking out the cylindrical grinding tool, demoulding, putting the cylindrical grinding tool into a vacuum low-temperature device for freeze-drying treatment for 24h to obtain a micro-nano fiber accumulation body with a solvent taken out preliminarily, then putting the preliminarily obtained fiber accumulation body into an infrared heat treatment box for heating to 200 ℃, carrying out heat treatment at the first stage from the room temperature of 25 ℃ to 100 ℃, with the heating rate of 5 ℃/min, at the second stage from 100 ℃ to 200 ℃, with the heating rate of 2 ℃/min, keeping the temperature for 1h after heating to 200 ℃, then taking out the heat-treated sample to obtain a sample 2, wherein the volume density of the sample 2 is 50mg/cm3The porosity is up to 90 percent, the hydrophobic angle is 160 degrees and the hydrophilic angle is 0 degree according to the bubble point method, and the separation flux of the sample 2 to the lubricating oil, the engine oil and the gasoline respectively reaches 2520L/m2·h-1，2314L/m2·h-1，2768L/m2·h-1And the oil flux can still be maintained to be more than 97 percent after the oil is repeatedly used for 50 times.
In one embodiment, a preparation method of a super-hydrophobic light polyurethane micro-nanofiber sponge comprises the following steps:
dehydrating polytetrahydrofuran diol and Mannich polyether diol at 90-110 ℃ in vacuum for later use; weighing 65g of polytetrahydrofuran diol, 25g of Mannich polyether diol, 35g of tetramethylxylylene diisocyanate and 10g of tetramethylcyclohexylmethane diisocyanate, fully reacting at 92 ℃ for 3h, measuring the NCO group to reach the theoretical residual value, quickly cooling to 70 ℃ by using a refrigerant, adding 7g of PEVE type fluorine-containing dihydric alcohol, 4.5g of fluorinated diamine, 4.8g of micromolecule 1,6 hexanediol chain extender, 6.5g of cationic hydrophilic chain extender tert-butyl diethanol amine, 4.5g of thermosetting benzoxazine resin, 0.5g of trimethylolpropane and 0.6g of bismuth carboxylate catalyst, introducing nitrogen for protection, carrying out heat preservation reaction for 2.5h, slowly cooling to 35 ℃ by using circulating water after the residual NCO value is not changed, adding 5.5g of glacial acetic acid neutralizer and 350g of diluting solvent ethanol, adding 0.5g of sodium dodecyl benzene sulfonate, emulsifying under the action of high-speed shearing, and adding 1g of defoaming agent during emulsification, and stirring for 5-10 min to complete emulsification to obtain the fluorinated polyurethane emulsion with the structure shown in the formula I. The fluorinated polyurethane emulsion with the structure shown in the formula I has the solid content of 32.54% and the molecular weight of 25000-30000.
Then 2.5g of cationic polyacrylamide solution with the concentration of 50 percent and 2g of 50 percent PVA1788 solution are mixed with 100g of fluorinated polyurethane emulsion with the structure of the formula I obtained in the previous step, the mixture is subjected to ultrasonic dispersion and high-speed stirring, defoamed, and prepared with 10g of polyamide polyamine epichlorohydrin aqueous solution with the solid content of 20 percent into a first component spinning solution with the concentration of 33 percent, simultaneously, 2.5g of isobutylene maleic anhydride copolymer ammonium salt is mixed with the fluorinated polyurethane emulsion with the structure of the formula I which is diluted by 2.5 times, and preparing 13% second component spinning solution by 10g of 20% solid content polyamide polyamine epichlorohydrin aqueous solution after ultrasonic dispersion and high-speed stirring defoaming, and adjusting the pH value of the polyamide polyamine epichlorohydrin aqueous solution to be consistent with the pH value of the fluorinated polyurethane emulsion with the structure of the formula I by using 0.1N alkali liquor and 0.1N acid solution before mixing the polyamide polyamine epichlorohydrin aqueous solution. And then, pouring the first component spinning solution and the second component spinning solution into 10 100mL injection containers, fixing the containers on a spinning device in a crossed manner, wherein a receiving guide roller firstly adopts a copper net as a bottom base material (easy to receive fibers), then a layer of PTFE or aramid base cloth is fixed on the copper net, the voltage is selected to be 20KV, the receiving distance is 20cm, the injection speed is 0.45mL/h, and the stacking thickness of the nanofiber membrane is controlled to be 0.05-0.08mm by adjusting the spinning time.
After spinning is finished, simultaneously removing the fiber membrane and the base fabric from the copper mesh, then drying at 90 ℃ for 0.5h, then removing the fiber membrane from the base fabric, then weighing 15g of the nanofiber membrane, putting the nanofiber membrane into a high-speed shearing machine, adding 250g of mixed solution of ethanol and water, and then starting fragmentation treatment for 2 h; then, 0.5% by mass of a fiber of polyacrylamide particles and 25g of a 15 μm-diameter polyester staple fiber were added, followed by uniform stirring in a high-speed stirrer and ultrasonic dispersion for 3 hours to obtain a fiber suspension.
Pouring the fiber suspension into a prepared volume of 200cm3The cylindrical grinding tool is then frozen for 0.5h at the low temperature of minus 190 ℃, and then taken out and demoulded, and then put into a vacuum low-temperature device for freeze-drying treatment for 18h, and finally the micro-nano fiber accumulation body after the solvent is taken out is obtained preliminarily. Then placing the fiber accumulation body obtained primarily into an infrared heat treatment box to be heated to 200 ℃, carrying out heat treatment from room temperature 25 ℃ to 100 ℃ in the first stage at the heating rate of 5 ℃/min, carrying out heat treatment from 100 ℃ to 200 ℃ in the second stage at the heating rate of 2 ℃/min, keeping the temperature for 2h after heating to 200 ℃, taking out the sample after heat treatment to obtain a sample 3, wherein the volume density of the sample 3 is 200mg/cm3The porosity is up to 83 percent, the hydrophobic angle is 162 degrees and the hydrophilic angle is 0 degrees in a bubble point method test, and the separation flux of the porous material on lubricating oil, engine oil and gasoline respectively reaches 2480L/m through a test2·h-1，2306L/m2·h-1，2715L/m2·h-1And the oil flux of more than 95% can be still maintained after 50 times of recycling.
Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value. The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims (9)

1. The utility model provides a little nanofiber sponge of super hydrophobic light polyurethane which characterized in that includes:
the nano-scale fiber is 200-800 nm in diameter; and
the fiber comprises micron-sized fibers, wherein the diameter of each micron-sized fiber is 5-15 mu m;
wherein the nano-scale fibers comprise fluorinated polyurethane, and the fluorinated polyurethane is obtained by an alcohol-soluble method, and the preparation of the fluorinated polyurethane comprises the following steps: reacting polyether polyol with polyisocyanate, adding a fluorinated micromolecule chain extender, a fluorinated alcohol monomer, a micromolecule chain extender, a cationic hydrophilic chain extender, a cross-linking agent and a catalyst to continue reacting after testing that the residual NCO group reaches a theoretical residual value, adding a neutralizing agent and ethanol after testing that the residual NCO group reaches the theoretical residual value, dropwise adding an emulsifying agent and a defoaming agent, and removing a solvent after emulsifying to obtain the fluorinated polyurethane;
wherein the fluorinated micromolecule chain extender is any one or two combinations of fluorinated diol and fluorinated diamine;
the fluorinated alcohol monomer is fluorinated micromolecular monohydric alcohol;
the micron-sized fiber comprises any one or a combination of more of aramid fiber, terylene, polyester, vinylon, spandex, acrylon, chinlon, polyaryl oxadiazole, polypropylene fiber, inorganic mineral fiber, cotton fiber and glass fiber.
2. The micro-nanofiber sponge according to claim 1, wherein: the mass ratio of the nano-scale fibers to the micro-scale fibers is 0.5-2.5.
3. The micro-nanofiber sponge according to claim 1, wherein: the nano-scale fiber also comprises a water-soluble polymer and a thermosetting resin, wherein the mass ratio of the fluorinated polyurethane to the water-soluble polymer to the thermosetting resin in the nano-scale fiber is (90-95): (1-5): 1-5).
4. The micro-nanofiber sponge according to claim 3, wherein: the water-soluble polymer comprises any one or combination of more of cationic polyacrylamide, polyvinyl alcohol, cationic starch, cationic cellulose, cationic guar gum, poly (hydroxymethyl) cellulose, poly (dimethyl diallyl ammonium chloride), polyamine, inorganic polyaluminium, polyquaternium-28, polyquaternium-39, isobutylene-maleic anhydride ammonium salt copolymer, polyacrylic acid and polymaleic anhydride.
5. The micro-nanofiber sponge according to claim 3, wherein: the thermosetting resin comprises any one or combination of more of benzoxazine resin, silicone resin, polyamide resin, cationic polyacrylamide resin, polyamide polyamine epichlorohydrin resin, acrylic resin, polyamide polyurea epichlorohydrin resin, polyethyleneimine resin, chitosan, dialdehyde starch, maleic acid homopolymer and terpolymer resin, polyethylene maleic acid resin and zirconium titanate amine resin.
6. The micro-nanofiber sponge according to claim 3, wherein: the nano-scale fiber is obtained by spinning a first component spinning solution with the concentration of 33-35 wt% and a second component spinning solution with the concentration of 13-16 wt%, wherein the first component spinning solution and/or the second component spinning solution comprise the fluorinated polyurethane, the water-soluble polymer and the thermosetting resin, and the concentration is the concentration of the fluorinated polyurethane and the water-soluble polymer.
7. A method for preparing the micro-nanofiber sponge as claimed in any one of claims 1 to 6, comprising the following steps:
providing a nanofiber, wherein the nanofiber comprises fluorinated polyurethane:
mixing the nano-scale fiber, the micron-scale fiber and a fiber suspension stabilizer to obtain a fiber suspension;
and forming, removing the solvent and carrying out heat treatment on the fiber suspension to obtain the micro-nano fiber sponge.
8. The method of claim 7, wherein: the fluorinated polyurethane is prepared by adopting an alcohol-soluble method, and the preparation of the fluorinated polyurethane comprises the following steps: reacting polyether polyol with polyisocyanate, adding a fluorinated micromolecule chain extender, a fluorinated alcohol monomer, a micromolecule chain extender, a cationic hydrophilic chain extender, a cross-linking agent and a catalyst to continue reacting after testing that the residual NCO group reaches a theoretical residual value, adding a neutralizing agent and ethanol after testing that the residual NCO group reaches the theoretical residual value, dropwise adding an emulsifying agent and a defoaming agent, and removing a solvent after emulsifying to obtain the fluorinated polyurethane, wherein the fluorinated micromolecule chain extender is any one or the combination of two of fluorinated diol and fluorinated diamine; the fluorinated alcohol monomer is fluorinated small-molecular monohydric alcohol.
9. Use of the micro-nano fiber sponge as claimed in any one of claims 1 to 6 in the fields of water body cleaning and purification and self-protection.
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