CN111114054B - Micro-nano waterborne polyurethane waterproof moisture-permeable film and preparation method and application thereof - Google Patents
Micro-nano waterborne polyurethane waterproof moisture-permeable film and preparation method and application thereof Download PDFInfo
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- CN111114054B CN111114054B CN201911408845.3A CN201911408845A CN111114054B CN 111114054 B CN111114054 B CN 111114054B CN 201911408845 A CN201911408845 A CN 201911408845A CN 111114054 B CN111114054 B CN 111114054B
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
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Abstract
The invention provides a micro-nano waterborne polyurethane waterproof moisture-permeable film and a preparation method and application thereof, wherein the micro-nano waterborne polyurethane waterproof moisture-permeable film comprises a base cloth layer; the fiber layer is formed on the base cloth layer, the fiber diameter of the fiber layer ranges from 200nm to 800nm, and the fiber layer comprises fluorinated polyurethane with a structure shown in a formula I:
the waterproof moisture-permeable film has certain potential application value in the fields of functional fabrics, medical treatment and the like.
Description
Technical Field
The invention belongs to the field of functional fiber materials and polymer synthesis, and particularly relates to a micro-nano waterborne polyurethane waterproof moisture-permeable film, and a preparation method and application thereof.
Background
In recent years, the film material with waterproof and moisture-permeable performances has unique application value in various fields, and the material can effectively transmit water vapor while preventing liquid water from permeating, so that the material has wide application prospect in the fields of outdoor jacket, medical wound dressing, building materials and the like. The waterproof moisture-permeable membrane materials in the current market mainly comprise Polytetrafluoroethylene (PTFE) hydrophobic microporous membranes, polyurethane hydrophilic non-porous membranes and the like, wherein the PTFE materials have good waterproof moisture-permeable performance, but the whole preparation process is complex, and the technology is monopolized by large foreign companies such as Gore-Tex and the like, and the price is high. The polyurethane hydrophilic film has higher water pressure resistance due to the nonporous structure, but has the problems of poorer air permeability, easy wetting when meeting water and poorer moisture permeability at low temperature. Therefore, how to simply and rapidly prepare the high-performance and environment-friendly waterproof moisture-permeable membrane becomes a difficult problem to be solved urgently at present.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a micro-nano waterborne polyurethane waterproof moisture-permeable film, 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 micro-nano waterborne polyurethane waterproof moisture permeable film, which comprises the following components in percentage by weight: a base cloth layer; the fiber layer is formed on the base cloth layer, the fiber diameter of the fiber layer ranges from 200nm to 800nm, and the fiber layer comprises fluorinated polyurethane with a structure shown in a formula I:
wherein:
RF represents the host group of a fluorinated alcohol monomer, R1Represents the main group of a polyisocyanate, R2A host group representing a cationic hydrophilic chain extender; x is 0 or 1, y is 1 or 2, a is 0.8 to 1.0, and n is 20 to 80.
In one embodiment, the base fabric comprises any one of polytetrafluoroethylene, polyphenylene sulfide, and aramid.
In one embodiment, the molecular weight of the fluorinated polyurethane with the structure of formula I is 15000-30000.
In one embodiment, the thickness of the fiber layer is 0.03-0.09 mm.
In one embodiment, the fiber layer further includes a water-soluble polymer and/or a thermosetting resin.
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 fibers in the fiber layer are obtained by spinning from a first component spinning solution with a concentration of 34 wt% to 50 wt% and a second component spinning solution with a concentration of 13 wt% to 17 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 mass ratio of the fluorinated polyurethane with the structure of formula I, the water-soluble polymer and the thermosetting resin in the polyurethane waterproof moisture-permeable film is (90-95): (1-5): 1-5).
In one embodiment, the thermosetting resin is comprised of a benzoxazine resin and a polyamide polyamine epichlorohydrin 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 spinning is performed using a spinning apparatus model TC4080 from Tessmann technologies, Inc., Dalian.
In one embodiment, the first component dope and the second component dope are cross-placed on a spinning apparatus for simultaneous spinning.
The invention also provides a preparation method of the waterproof moisture-permeable film, which comprises the following steps: providing a base cloth; forming a fiber layer on the base fabric to obtain the waterproof moisture-permeable membrane, wherein the fiber diameter of the fiber layer is 200-800 nm, and the fiber layer comprises fluorinated polyurethane with a structure shown in a formula I:
wherein:
RF represents the host group of a fluorinated alcohol monomer, R1Represents the main group of a polyisocyanate, R2A host group representing a cationic hydrophilic chain extender; x is 0 or 1, y is 1 or 2, a is 0.8 to 1.0, and n is 20 to 80.
In one embodiment, the fiber layer is formed on the base fabric through a drying step, wherein the drying step comprises a step of raising the temperature from room temperature to 80-180 ℃ in a gradient manner and then preserving the temperature for 2-5 hours, and the temperature raising rate is 2-5 ℃/min.
In one embodiment, the fluorinated polyurethane with 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 with the structure of the formula I.
In one embodiment, the fluorinated polyurethane having the structure of formula I has a solid content of 35% to 55%.
In one embodiment, the preparation of the fluorinated polyurethane having the structure of formula I comprises reacting under an inert gas atmosphere.
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 two 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 technical grade ethanol with a concentration of not less than 95%.
The invention also provides application of the waterproof moisture-permeable film in the aspects of garment materials, medical dressings, building materials and agricultural planting.
As mentioned above, the invention provides a micro-nano waterborne polyurethane waterproof moisture-permeable membrane and a preparation method thereof aiming at the problems of the current waterproof moisture-permeable membrane, the micro-nano waterborne polyurethane waterproof moisture-permeable membrane is prepared by designing and automatically synthesizing alcohol-soluble cation fluorinated polyurethane emulsion with high molecular weight, on the basis, the electrostatic spinning technology is combined with thermosetting resin and gradient heating and drying technology, the surface energy of a fiber layer is further reduced by introducing fluorocarbon bonds and thermosetting resin, meanwhile, the thermosetting resin further forms a cross-linked network in fiber components under gradient heating and drying, the mechanical property of a composite layer is enhanced, meanwhile, the effective adhesion between the fiber layers and the inside of the fiber layer is realized, an effective water vapor transport channel is formed, and finally, the water pressure resistance and the air permeability are obviously improved. The waterproof moisture-permeable film prepared by the method has the water pressure resistance of 100-200 kPa and the moisture permeability of 8-15 kg.m-2·d-1In the range, the tensile strength is 15-25 MPa, the elongation rate is 500-800%, and the composite material has a certain potential application value in the fields of functional fabrics, medical treatment and the like.
Drawings
FIG. 1 shows scanning electron micrographs of a fiber layer of the present invention (a) before drying and (b) after drying.
FIG. 2 is a schematic 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 micro-nano waterborne polyurethane waterproof moisture-permeable membrane, which comprises a fiber layer, wherein the fiber layer can be prepared by electrostatic spinning of spinning solution formed by mixing different high-molecular polymers, the thickness of the fiber layer can be 0.03-0.09 mm, and the diameter of fibers in the fiber layer can be 200-800 nm. The waterproof moisture-permeable membrane can also comprise a base cloth layer arranged on one side of the fiber layer and used for a substrate during electrostatic spinning, and the base cloth layer can comprise any one of Polytetrafluoroethylene (PTFE), polyphenylene sulfide (PPS) and aramid fiber, such as aramid fiber.
The high molecular polymer can comprise fluorinated polyurethane resin with the structure shown in the formula I, water-soluble high molecules and thermosetting resin. The structural formula of the fluorinated polyurethane with the structure of the formula I is as follows:
wherein:
RF represents the host group of a fluorinated alcohol monomer, R1Represents the main group of a polyisocyanate, R2A host group representing a cationic hydrophilic chain extender; x is 0 or 1, y is 1 or 2, a is 0.8 to 1.0, and n is 20 to 80.
The spinning solution can comprise a high-concentration first component spinning solution and a low-concentration second component spinning solution, the first component spinning solution and the second component spinning solution can be prepared by mixing fluorinated polyurethane with a structure shown in formula I and water-soluble polymers into spinning stock solutions with different concentrations and then mixing thermosetting resin, the mass concentration of the fluorinated polyurethane resin with the structure shown in formula I and the water-soluble polymers in the first component spinning solution can be 34-50%, and the mass concentration of the fluorinated polyurethane resin with the structure shown in formula I and the water-soluble polymers in the second component spinning solution can be 13-17%. The mass ratio of the fluorinated polyurethane with the formula I structure in the waterproof moisture-permeable film, the water-soluble polymer and the thermosetting resin can be (90-95): 1-5.
According to the invention, two kinds of 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 waterproof moisture-permeable membrane has excellent waterproof moisture-permeable performance.
The spinning can comprise fixing the spinning solution in an electrostatic spinning device, grounding a guide rail part at a fiber collecting end, fixing a base fabric on a copper net, and receiving fiber tows, namely, fixing the two spinning solutions with different concentrations on the electrostatic spinning device in a crossed and synchronous manner. The fiber diameter distribution range is adjustable to a certain degree by adjusting the concentration of the spinning solution, the voltage intensity and the spinning distance in the spinning process, the injection speed and other parameters, so that the smooth transition from a micron-level fiber layer to a nanometer-level fiber layer is realized, and the interlayer bonding strength is further increased.
The fluorinated polyurethane resin 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) can be avoided by using the alcohol-soluble method, certain advantages are achieved in the aspects of energy conservation and emission reduction, and the molecular weight of the prepared fluorinated polyurethane resin with the structure shown in the formula I can be 15000-30000. The synthesis method may include: 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 ℃ after emulsification for 1-2 hours to obtain the fluorinated polyurethane emulsion with the structure shown in the formula I.
In one embodiment, the fluorinated polyurethane 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, 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 resin with 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-molecule chain extender, 10-18 parts of a small-molecule 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 a defoaming agent, 5-30 parts of a neutralizing agent and 100-450 parts of ethanol.
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. In one embodiment, the thermosetting resin may be composed of benzoxazine resin and polyamide polyamine epichlorohydrin resin, in which case, benzoxazine may enhance the crosslinking of polyamide polyamine epichlorohydrin, and considering that the present invention employs non-water-soluble benzoxazine resin, when thermosetting resin is used in combination of both, the benzoxazine resin may be added at the time of synthesizing the fluorinated polyurethane of the structure of formula I by an alcohol-soluble method, and the polyamide polyamine epichlorohydrin resin may be mixed with the fluorinated polyurethane of the structure of formula I and a water-soluble polymer at the time of preparing the spinning solution. The polyamide polyamine epichlorohydrin resin can be mixed into spinning stock solutions with different concentrations after the pH value of the polyamide polyamine epichlorohydrin resin is adjusted to be consistent with that of the fluorinated polyurethane with the structure of the formula I, the mixing can include that fluorinated polyurethane emulsion with the structure of the formula I and water-soluble polymers with different concentrations are uniformly mixed according to a certain proportion, the spinning stock solutions are obtained after ultrasonic dispersion, and the thermosetting resin is added into the spinning stock solutions to prepare a first component spinning solution and a second component spinning solution with different concentrations.
In one embodiment, when the fluorinated polyurethane of 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 of 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.
The conditions of the electrostatic spinning can be as follows: 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 TC4080 spinning device of Dalian Tessman technologies Co.
As shown in fig. 2, the invention also provides a preparation method of the micro-nano waterborne polyurethane waterproof moisture-permeable film, which comprises the following steps of S1-S2: s1: providing a base cloth; s2: and forming a fiber layer on the base cloth to obtain the waterproof moisture-permeable membrane, wherein the fiber diameter of the fiber layer is 200 nm-800 nm.
In step S1, the base fabric may be made of any one of Polytetrafluoroethylene (PTFE), polyphenylene sulfide (PPS), and aramid, such as aramid.
In step S2, the fiber layer may be spun onto the base fabric by electrospinning, and the fiber layer may include a fluorinated polyurethane having a structure of formula I:
wherein:
RF represents the host group of a fluorinated alcohol monomer, R1Represents the main group of a polyisocyanate, R2A host group representing a cationic hydrophilic chain extender; x is 0 or 1, y is 1 or 2, a is 0.8 to 1.0, and n is 20 to 80.
In step S2, the fiber layer may be formed on the base fabric through a drying step, where the drying step may be performed by heating the base fabric to 80-180 ℃ at room temperature for 2-5 hours, the heating rate may be 2-5 ℃/min, and the drying step is performed by gradient heating, so as to remove the residual solvent and simultaneously achieve adhesion between fibers of the curing agent of the thermosetting resin in the fibers and reduction of the surface energy of the fiber surface. The gradient heating and drying can ensure that the fiber layers are uniformly heated and air layers are not easy to generate, and the like, and can be quickly dried and initiate ring-opening polymerization and thermosetting crosslinking reaction for promoting benzoxazine resin or polyamide polyamine epichlorohydrin resin, so that the surface energy of the fiber layers is reduced, a water vapor transport channel is formed, and a better waterproof, moisture permeable and breathable effect is achieved.
The waterproof moisture permeable membrane can promote effective adhesion among fibers to form a stable microporous structure through gradient heating and drying treatment, and meanwhile, the waterproof moisture permeable fiber layer is changed from hydrophilicity to hydrophobicity, so that a pore channel for water vapor transportation is formed, and effective combination of the fiber layer and a base cloth layer can be realized through drying. As can be seen from FIG. 1, the fibers are more tightly cross-linked after gradient drying.
The invention also provides application of the waterproof moisture-permeable film. According to the invention, the high molecular weight alcohol-soluble fluorinated polyurethane is designed and automatically synthesized, and the micro-nanofiber composite waterborne polyurethane waterproof moisture-permeable membrane is prepared by an electrostatic spinning technology, so that a membrane material with high water pressure resistance and high moisture permeability is obtained, and the membrane material has good application value in the fields of functional fabrics and medical treatment, such as garment fabrics, medical dressings, building materials, agricultural planting and the like.
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, the preparation of the micro-nano waterborne polyurethane waterproof moisture-permeable film 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, 3g 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, obtaining the fluorinated polyurethane emulsion with the structure shown in the formula I, wherein the solid content of the fluorinated polyurethane emulsion is 34.5%, and the molecular weight of the fluorinated polyurethane emulsion is 15000-18000.
2g 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 ultrasonically dispersed, mixed and defoamed by high-speed stirring, then the mixture is mixed with 10g of polyamide polyamine epichlorohydrin aqueous solution with the solid content of 15 percent to prepare a first component spinning solution with the concentration of 34 percent, simultaneously 0.5g of polyvinyl alcohol (1788) is mixed with the fluorinated polyurethane emulsion with the structure of the formula I which is diluted by 2.5 times, and the mixture is ultrasonically dispersed, defoamed by high-speed stirring to be prepared with 10g of polyamide polyamine epichlorohydrin aqueous solution with the solid content of 15 percent to prepare a second component spinning solution with the concentration of 13 percent, and before the mixture of the polyamide polyamine epichlorohydrin aqueous solution, 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.
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 for synchronous spinning, selecting 10KV voltage by a receiving guide roller by using a copper net as a bottom base material, fixing a layer of PTFE base cloth on the copper net, receiving the distance of 15cm, controlling the injection speed of 0.8mL/h, and controlling the stacking thickness of the micro-nano fiber layer to be 0.05-0.08mm by adjusting the spinning time. And after spinning, simultaneously removing the fiber layer and the base fabric from the copper mesh, and drying to obtain a sample 1. The drying conditions are as follows: and (3) heating from room temperature to 180 ℃ by adopting a gradient heating mode, drying, controlling the heating rate at 5 ℃/min in the first stage, the heating time at 15min, controlling the heating rate at 1.78 ℃/min in the second stage, and keeping the temperature for 2.5h after the temperature is increased to 180 ℃.
Cutting the sample 1 into a circle with the diameter larger than 80mm, and testing by adopting a hydrostatic pressure measuring instrument and a fabric moisture permeability and air permeability measuring instrument to obtain the sample 1The water pressure resistance of the water-based paint reaches 150kPa, and the moisture permeability is 10 kg.m-2·d-1And the tensile strength of the fiber layer after the base cloth is removed is 20MPa and the elongation is 750 percent by adopting a tensile machine test. The microstructure of sample 1 before and after drying is shown in fig. 1.
In one embodiment, the preparation of the micro-nano waterborne polyurethane waterproof moisture-permeable film comprises the following steps:
carrying out vacuum dehydration on polyoxyethylene glycol at the temperature of 90-110 ℃ for later use; weighing 95g of polytetrahydrofuran diol and 55g of isophorone diisocyanate, fully reacting for 2 hours at 95 ℃, then measuring the NCO group to reach the theoretical residual value, quickly cooling to 65 ℃ by adopting a refrigerant, then adding 10g of long-chain PEVE fluorinated diol, 5g of fluorinated diol, 4.5g of micromolecule ethylene glycol chain extender, 8g of cationic hydrophilic chain extender N-ethyldiethanolamine, 5g of thermosetting benzoxazine resin, 0.5g of trimethylolpropane and 0.4g of dibutyltin dilaurate catalyst, introducing nitrogen for protection, then carrying out heat preservation reaction for 4.5 hours, testing that the residual NCO value is not changed, slowly cooling to 35 ℃ by adopting circulating water, then adding 7.5g of acetic anhydride neutralizer and 200g of diluted viscosity-reducing solvent ethanol, then adding 0.5g of OP-10 for emulsification under the action of high-speed shearing, adding 1g of defoamer during emulsification, stirring for 5-10 minutes to complete emulsification, and obtaining the fluorinated polyurethane emulsion with the structure shown in the formula I, wherein the solid content of the fluorinated polyurethane emulsion is 48.8% and the molecular weight of the fluorinated polyurethane emulsion is 20000-25000.
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 ultrasonically dispersed, stirred, mixed and defoamed at a high speed, then the mixture is prepared into a first component spinning solution with the concentration of 48 percent with 12g of polyamide polyamine epichlorohydrin aqueous solution with the solid content of 10 percent, simultaneously 1.5g of polymethylol cellulose is mixed with the fluorinated polyurethane emulsion with the structure of the formula I which is diluted by 3 times, and the mixture is ultrasonically dispersed, stirred and defoamed at a high speed, then 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 10 percent, and before the polyamide polyamine epichlorohydrin aqueous solution is mixed, 0.1N alkali liquor and 0.1N acid solution are utilized to adjust 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.
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 for synchronous spinning, selecting 20KV voltage by a receiving guide roller as a bottom base material, fixing a layer of PTFE base cloth on the copper mesh, receiving the distance of 18cm, and controlling the stacking thickness of the micro-nano fiber layer to be 0.05-0.08mm by adjusting the spinning time, wherein the receiving guide roller adopts a copper mesh as the bottom base material. And after spinning, the fiber layer and the base fabric are simultaneously taken off from the copper mesh, and the sample 2 is obtained after drying. The drying conditions are as follows: and (3) heating from room temperature to 180 ℃ by adopting a gradient heating mode, drying, controlling the heating rate at 5 ℃/min in the first stage, the heating time at 15min, controlling the heating rate at 1.78 ℃/min in the second stage, and keeping the temperature for 2.5h after the temperature is increased to 180 ℃.
Cutting the sample 2 into a circle with the diameter larger than 80mm, and testing by adopting a hydrostatic pressure measuring instrument and a fabric moisture permeability and air permeability measuring instrument to obtain the sample 2 with the water pressure resistance as high as 180kPa and the moisture permeability of 15 kg.m-2·d-1And the tensile strength of the fiber layer after the base cloth is removed is 25MPa and the elongation is 780 percent by adopting a tensile machine test.
In one embodiment, the preparation of the micro-nano waterborne polyurethane waterproof moisture-permeable film comprises the following steps:
dehydrating polytetrahydrofuran diol and tetrahydrofuran-ethylene oxide copolyol at 90-110 ℃ in vacuum for later use; weighing 55g of polytetrahydrofuran diol, 45g of tetrahydrofuran-ethylene oxide copolymer diol, 35g of isophorone diisocyanate and 40g of tetramethylxylene diisocyanate, fully reacting at 95 ℃ for 2.5h, then measuring that NCO groups reach the theoretical residual value, quickly cooling to 65 ℃ by using a refrigerant, then adding 6g of long-chain PEVE fluorinated diol, 3g of fluorine-containing polyester diol, 3g of fluorinated diol, 4g of micromolecule 1, 4-butanediol chain extender, 10g of cationic hydrophilic chain extender bis (2-hydroxypropyl) aniline, 8g of thermosetting benzoxazine resin, 0.8g of methyl glucoside and 0.6g of dibutyltin dilaurate catalyst, introducing nitrogen for protection, then carrying out heat preservation reaction for 5h, after testing that the residual NCO value is not changed, slowly cooling to 35 ℃ by using circulating water, then adding 9.5g of glycolic acid neutralizer and 180g of diluted solvent ethanol, and then adding 1g of OP-10 to emulsify under the action of high-speed shearing, adding 1g of defoaming agent during emulsification, stirring for 5-10 min to complete emulsification, and obtaining the fluorinated polyurethane emulsion with the structure shown in the formula I, wherein the solid content of the fluorinated polyurethane emulsion is 55%, and the molecular weight of the fluorinated polyurethane emulsion is 30000-35000.
10g of 8 percent aqueous solution of polymethylol cellulose with concentration and 100g of fluorinated polyurethane emulsion with the structure of the formula I obtained in the previous step are ultrasonically dispersed, stirred, mixed and defoamed at high speed, then the mixture is prepared into 50 percent spinning solution of a first component with concentration with 15g of 13 percent aqueous solution of polyamide polyamine epichlorohydrin, 1.5g of isobutylene-maleic anhydride copolymer ammonium salt is mixed with the fluorinated polyurethane emulsion with the structure of the formula I diluted by 3 times, and the mixture is ultrasonically dispersed, stirred and defoamed at high speed, then the mixture is prepared into 17 percent spinning stock solution of a second component with 15g of 13 percent aqueous solution of polyamide polyamine epichlorohydrin, and before the mixing of the aqueous solution of polyamide polyamine epichlorohydrin, the pH value of the aqueous solution of polyamide polyamine epichlorohydrin 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.
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 for synchronous spinning, selecting 20KV voltage by a receiving guide roller as a bottom base material, fixing a layer of PTFE base cloth on the copper mesh, receiving the distance of 18cm, and controlling the stacking thickness of the micro-nano fiber layer to be 0.05-0.08mm by adjusting the spinning time, wherein the receiving guide roller adopts a copper mesh as the bottom base material. And after spinning, the fiber layer and the base fabric are simultaneously taken off from the copper mesh, and the sample 3 is obtained after drying. The drying conditions are as follows: and (3) heating to 180 ℃ from room temperature by adopting a gradient heating mode, drying, controlling the heating rate at 3 ℃/min in the first stage, the heating time at 25min, controlling the heating rate at 1.78 ℃/min in the second stage, and keeping the temperature for 2.5h after the temperature is increased to 180 ℃.
Cutting a sample 3 into a circle with the diameter larger than 80mm, and testing by adopting a hydrostatic pressure measuring instrument and a fabric moisture permeability and air permeability measuring instrument to obtain the sample 3 with the water pressure resistance up to 200kPa and the moisture permeability of 13 kg.m-2·d-1And the tensile strength of the fiber layer after the base cloth is removed is 25MPa and the elongation is 800 percent by adopting a tensile machine test.
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 (8)
1. A micro-nano waterborne polyurethane waterproof moisture permeable film is characterized in that,
a base cloth layer;
the fiber layer is formed on the base cloth layer, the fiber diameter of the fiber layer ranges from 200nm to 800nm, and the fiber layer comprises fluorinated polyurethane with a structure shown in a formula I:
wherein:
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;
the fibers in the fiber layer are obtained by spinning a first component spinning solution with the concentration of 34-50 wt% and a second component spinning solution with the concentration of 13-17 wt%;
the first component spinning solution and/or the second component spinning solution comprise the fluorinated polyurethane with the structure shown in the formula I, a water-soluble polymer and a thermosetting resin, and the concentration is the concentration of the fluorinated polyurethane with the structure shown in the formula I and the water-soluble polymer.
2. The micro-nano waterborne polyurethane waterproof moisture-permeable film according to claim 1, which is characterized in that: the fiber layer further includes the water-soluble polymer and/or the thermosetting resin.
3. The micro-nano waterborne polyurethane waterproof moisture-permeable film according to claim 2, which is characterized in that: 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.
4. The micro-nano waterborne polyurethane waterproof moisture-permeable film according to claim 2, which is characterized in that: 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.
5. The micro-nano waterborne polyurethane waterproof moisture-permeable film according to claim 2, which is characterized in that: the mass ratio of the fluorinated polyurethane with the structure shown in the formula I, the water-soluble polymer and the thermosetting resin in the polyurethane waterproof moisture-permeable film is (90-95): (1-5): 1-5).
6. A method for preparing the micro-nano waterborne polyurethane waterproof moisture-permeable film according to any one of claims 1 to 5, which comprises the following steps:
providing a base cloth;
forming a fiber layer on the base fabric to obtain the waterproof moisture-permeable membrane, wherein the fiber diameter of the fiber layer is 200-800 nm, and the fiber layer comprises fluorinated polyurethane with a structure shown in a formula I:
wherein:
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.
7. The method of claim 6, wherein: the fiber layer is formed on the base fabric through a drying step, wherein the drying step comprises the step of raising the temperature from room temperature to 80-180 ℃ in a gradient manner and then preserving the temperature for 2-5 hours, and the temperature raising rate is 2-5 ℃/min.
8. Use of the micro-nano waterborne polyurethane waterproof moisture-permeable film according to any one of claims 1 to 5 in the aspects of garment materials, medical dressings, building materials and agricultural planting.
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