CN115558283B - Polyurethane sponge for mop and preparation method thereof - Google Patents

Abstract

The invention relates to the technical field of polyurethane foam materials, in particular to a polyurethane sponge for a mop and a preparation method thereof. A polyurethane sponge for a mop comprising: the polyurethane sponge matrix is internally and uniformly dispersed with nano attapulgite; the nano attapulgite accounts for 3.5 to 7 weight percent of the polyurethane sponge matrix; the tough framework is a net structure woven by polyurethane porous fibers and is embedded in the polyurethane sponge matrix, the polyurethane porous fibers contain a phase-change material, and the tough framework accounts for 5-10 wt% of the polyurethane sponge matrix; the connecting piece is detachably connected with the mop rod, and the connecting piece and the polyurethane sponge matrix are integrally formed during molding. The polyurethane sponge for the mop provided by the invention is green and environment-friendly, cannot be dried and hardened, and has the advantages of good use performance, high water absorption rate, high molding quality and excellent mechanical property.

Description

Polyurethane sponge for mop and preparation method thereof

Technical Field

The invention relates to the technical field of polyurethane foam materials, in particular to a polyurethane sponge for a mop and a preparation method thereof.

Background

The mop is one of the cleaning tools commonly used in our home, and in the water absorption mop, the PVA collodion mop has the water absorption capacity which is ten times that of common sponge, so the PVA collodion mop occupies the main market position. However, PVA collodion mops have the following disadvantages: firstly, in the production process of PVA collodion, the PVA collodion is prepared by polycondensation of a polyvinyl alcohol solution and formaldehyde under the catalysis of hydrochloric acid, starch is added into polymerization raw materials to fill pores, after the reaction is completed, the hydrochloric acid needs to be neutralized by an alkali solution, and then redundant formaldehyde and starch are washed away, so that the post-treatment process is complex, the pollution is large, and the production cost is high; secondly, the PVA collodion becomes hard after being completely dried, needs to be soaked for a long time after being used again, and when the collodion is completely dried, slightly wet and completely soaked, the size of a product is greatly different, so that an injection molding part connected with the product is deformed, and the service performance and the service life of the PVA collodion mop are seriously influenced; and thirdly, an extrusion molding process is adopted during production of PVA collodion, the collodion and the connecting piece are bonded by using an adhesive after the product is extruded and molded, so that the process steps are increased, the requirement on the adhesive is high, and the environment is not environment-friendly.

In order to solve the above problems, the invention patent with application number 202010997729.6 discloses a polyurethane material for a mop, the polyurethane composition comprises the following components by mass: 7.5-15 parts of a polyol component; 15-30 parts of an isocyanate component; 0.2-3 parts of a chain extender; 0.1-3 parts of an organometallic compound catalyst; 0.2-10 parts of amine catalyst; 0.2-5 parts of foam stabilizer; 1-5 parts of foaming agent. The product does not consume starch and water in the production process, solves the problems of high energy consumption and high pollution in the production process, and simultaneously solves the difficult problem of the industry that the product is easy to harden in the mop industry. However, the water absorption rate of the polyurethane foam material in the technical scheme can reach more than 6 times, but the polyurethane foam material has a great difference with the traditional PVA collodion, and the water absorption rate of the existing PVA collodion generally reaches about 10 times; in addition, the scheme performs extrusion molding after foaming through the supercritical foaming machine, and the product after extrusion molding is bonded with the connecting piece of the mop into a whole through the adhesive, so that the subsequent process steps are increased, the adhesive is easy to crack at the bonding part, the use effect is influenced, and the environment is not protected.

The invention patent with application number 201510358662.0 discloses a polyurethane mop sponge and a preparation method thereof, wherein the polyurethane mop sponge consists of a component A and a component B, the component A comprises polyether polyol DEP-3600H, polyether polyol DMN-550E, polyether polyol POP-H45, water, a foam stabilizer, an amine catalyst, a cross-linking agent, a chain extender and color paste; the component B is a modified black material. The technical scheme includes that water is used as a foaming agent, the polyurethane sponge is obtained after the A component and the B component are molded, foamed and formed, the process operation is simple, and the environmental protection performance is high, but a low-boiling-point physical foaming agent is not contained in the full-water foaming polyurethane composite material, the system viscosity is high, the fluidity is poor, heat accumulation is generated in the foaming and forming process, the temperature generally can reach more than 150 ℃, the heart burning and yellowing phenomena are easily generated, meanwhile, due to the fact that the reaction is severe, the fluidity of the material is further poor, the formed polyurethane sponge is not easy to fill a mold, defective products are easily generated, the molding and forming quality is reduced, and the production cost is increased.

In summary, in order to meet the environmental protection requirement, it is urgently needed to prepare a polyurethane sponge for a mop, which can be molded, foamed and formed, has good material flowability, less heat accumulation and high foaming forming quality during foaming, and has good water absorption and mechanical property after forming, and cannot be dried and hardened.

Disclosure of Invention

The present invention is directed to solving at least one of the above problems.

Therefore, the first purpose of the invention is to provide a polyurethane sponge for a mop.

The second purpose of the invention is to provide a preparation method of the polyurethane sponge for the mop.

To achieve the first object, the present invention provides a polyurethane sponge for a mop, comprising: the polyurethane sponge matrix is internally and uniformly dispersed with nano attapulgite; the nano attapulgite accounts for 3.5 to 7 weight percent of the polyurethane sponge matrix;

the tough framework is a net structure woven by polyurethane porous fibers and is embedded in the polyurethane sponge matrix, the polyurethane porous fibers contain a phase-change material, and the tough framework accounts for 5-10 wt% of the polyurethane sponge matrix;

the connecting piece is detachably connected with the mop rod, and the connecting piece and the polyurethane sponge matrix are integrally formed during molding.

Preferably, the phase-change material is loaded on the nano-attapulgite/nano-fiber modified mixture to form phase-change particles, and the phase-change particles are loaded in the polyurethane porous fibers; wherein the diameter of the nanofiber is 500-1000 nm, and the length-diameter ratio is 200-500; the particle size of the nano attapulgite is 400-600 nm.

To achieve the second object, the present invention provides a method for preparing a polyurethane sponge for a mop, comprising the steps of:

step S1, preparing a tough framework: weaving the polyurethane porous fiber loaded with the phase-change material into a net shape to obtain a tough framework;

step S2, preparing a polyurethane sponge matrix A material: polyether polyol, a chain extender, a cross-linking agent, a catalyst, water and a surfactant are mixed and stirred uniformly to obtain a polyurethane sponge matrix A material;

step S3, preparing a polyurethane sponge matrix B material: polyether polyol, a chain extender and diisocyanate are mixed and stirred uniformly, and react for 5 to 6 hours at a temperature of between 65 and 85 ℃ to obtain an isocyanate-based prepolymer matrix; mixing and stirring the nano attapulgite and the isocyanate-based prepolymer matrix uniformly, and standing at room temperature for 48 hours to obtain a polyurethane sponge matrix B material;

step S4, molding, foaming and forming: laying the connecting piece and the flexible framework in a mold, preheating the mold to 50-60 ℃, mixing the polyurethane sponge matrix A material and the polyurethane sponge matrix B material at 25 ℃, pouring the mixture into the mold for foaming and molding, curing at 55-65 ℃ for 15-20 minutes, and then demolding to obtain the polyurethane sponge for the mop.

Preferably, in step S2, the catalyst is triethylene diamine;

in step S2, the cross-linking agent is diethanolamine;

in the step S2, the surfactant is silicone oil;

in the step S2 and the step S3, the polyether polyol is polyether triol with the number average molecular weight of 2000-5000;

in the step S2 and the step S3, the chain extender is 1,4-butanediol;

in the step S3, the diisocyanate is at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate.

Preferably, in step S2, the polyether polyol comprises the following components in parts by mass: 100, respectively; chain extender: 1.5 to 3; a crosslinking agent: 1 to 3; catalyst: 0.1 to 0.5; water: 0.1 to 0.5; surfactant (b): 0.05 to 0.1;

in the step S3, the polyether polyol comprises the following components in parts by mass: 60 to 70 percent; chain extender: 1.5 to 3; diisocyanate: 30 to 40 percent; nano attapulgite: 10 to 20; isocyanate-based prepolymer base: 100, respectively;

in the step S4, the polyurethane sponge matrix A comprises the following components in parts by mass: 100, respectively; polyurethane sponge matrix B:60 to 70.

Preferably, in step S1, the preparation of the polyurethane porous fiber comprises the following steps:

step S11, mixing and stirring a coupling agent and absolute ethyl alcohol uniformly, adding acetic acid to adjust the pH value of a solution to 4.5-6.5, adding nano-attapulgite and nano-fibers, reacting for 0.5-6 hours, washing and drying to obtain a nano-attapulgite/nano-fiber modified mixture;

s12, putting the nano-attapulgite/nano-fiber modified mixture into a molten phase-change material, pressurizing to 0.2-0.5 MPa at 50-70 ℃, and stirring for 0.5-1 hour to obtain phase-change particles;

s13, stirring and reacting polytetrahydrofuran ether glycol, polyester diol, 1,4-butanediol, disulfide and isophorone diisocyanate at 60-90 ℃ for 1-1.5 hours, and cooling to 40-50 ℃ to obtain a first-order isocyanate-based prepolymer;

s14, stirring the first-order isocyanate-based prepolymer, ethyl acetate and disulfide at the temperature of 30-50 ℃ for reaction for 1-1.5 hours to obtain a second-order isocyanate-based prepolymer;

step S15, adding disulfide, polycarbodiimide and a pore-opening agent into the second-order isocyanate-based prepolymer obtained in the step S14, and stirring and reacting for 1-1.5 hours at 20-40 ℃ to obtain spinning skin-forming liquid;

s16, mixing and stirring the second-order isocyanate-based prepolymer, the phase-change particles, the ethyl acetate and the pore-opening agent uniformly, and performing ultrasonic dispersion for 5-10 minutes at 20-30 ℃ to obtain a spinning core solution;

s17, spinning by a dry-wet method, injecting a spinning skin-forming solution and a spinning core solution into a coagulating bath at 50-70 ℃ through a spinning nozzle at the same time at room temperature for solidification to obtain polyurethane fiber yarns;

s18, soaking the polyurethane fiber yarns in hot water at the temperature of 60-90 ℃ for 15-25 hours, and then carrying out vacuum freeze drying at the temperature of-20-40 ℃ for 20-25 hours to obtain the polyurethane porous fiber.

Preferably, in step S11, the coupling agent is at least one of γ -aminopropyltriethoxysilane, γ -glycidoxypropyltrimethoxysilane, γ -methacryloxypropyltrimethoxysilane, γ -mercaptopropyltriethoxysilane, or γ -mercaptopropyltrimethoxysilane;

in step S11, the nanofibers are at least one of polyolefin, polyester, polyamide, polyvinyl alcohol, or copolymer nanofibers;

in step S12, the phase-change material is paraffin with a melting point of more than 50 ℃;

in the step S13, the polyester diol is at least one of polycarbonate diol, polyhexamethylene adipate diol and polycaprolactone diol;

in step S13, step S14 and step S15, the disulfide is at least one of bis (2-hydroxyethyl) disulfide, 2,2 '-diaminodiphenyl disulfide, 4,4' -diaminodiphenyl disulfide, 4,4 '-dihydroxydiphenyl disulfide, 3,3' -dihydroxydiphenyl disulfide;

in the step S15 and the step S16, the cell opening agent is at least one of polyvinylpyrrolidone or polyethylene glycol with molecular weight more than 4000;

in step S17, the coagulation bath is deionized water, the vertical distance between a spinning nozzle and the coagulation bath is 5-20 cm, and the winding speed is 20-50 m/min.

Preferably, in step S11, the coupling agent comprises the following components in parts by mass: 1 to 10; anhydrous ethanol: 90 to 99 percent; nano attapulgite: 1 to 10; nano-fiber: 5 to 50 percent;

in the step S12, the nano-attapulgite/nanofiber modified mixture comprises the following components in parts by mass: 1; phase change material: 2 to 5;

in step S13, the following polytetrahydrofuran ether glycol is used in parts by mass: 60 to 70 percent; polyester diol: 5 to 10;1,4 butanediol: 0.1 to 0.3; disulfide ethers: 0.1 to 1; isophorone diisocyanate: 20 to 40 percent;

in step S14, the first-order isocyanate-based prepolymer comprises the following components in parts by mass: 40 to 50; ethyl acetate: 50 to 60 percent; disulfide ethers: 0.5 to 1.5;

in step S15, the disulfide comprises the following components in parts by mass: 0.5 to 1; polycarbodiimide: 1 to 5; a pore forming agent: 5 to 15 percent;

in the step S16, the second-order isocyanate-based prepolymer comprises the following components in parts by mass: 50 to 60 percent; phase change particles: 20 to 30 percent; ethyl acetate: 20 to 30 percent; a pore forming agent: 10 to 20;

in step S17, spinning into a sheath liquid by the following components in parts by mass: 15; spinning core liquid: 20.

preferably, the nano attapulgite in step S11 and step S3 is subjected to activation modification, and the activation modification includes the following steps:

step S111, grinding and sieving the attapulgite to obtain nano attapulgite with the particle size of 400-600;

step S112, the nano attapulgite obtained in the step S111 is placed in an electric arc plasma generator, plasma treatment is carried out for 5-10 minutes under the direct current voltage of 30-50 kV, then the nano attapulgite is added into deionized water, ultrasonic cleaning is carried out, and drying is carried out to obtain activated nano attapulgite;

and S113, adding the activated nano-attapulgite obtained in the step S112 into a dilute hydrochloric acid solution, ultrasonically dispersing for 1 hour at 65-75 ℃, under the conditions of ultrasonic power of 200-500W and ultrasonic frequency of 20-25 kHz, then dropwise adding a sodium hydroxide solution, adjusting the pH value to 4-5, adding a silane coupling agent, continuously ultrasonically dispersing for 1-2 hours, washing, filtering and drying to obtain the activated and modified nano-attapulgite.

Preferably, in step S112, the nano-attapulgite comprises the following components in parts by mass: 1; deionized water: 10 to 20;

in step S113, the nano-attapulgite is activated as follows in parts by mass: 1; dilute hydrochloric acid solution: 2 to 3; the concentration of the dilute hydrochloric acid solution is 0.5 to 1 weight percent; the concentration of the sodium hydroxide solution is 10-15 wt%.

Compared with the prior art, the invention has the following beneficial technical effects:

1. according to the invention, the polyurethane sponge matrix, the tough framework and the connecting piece are integrally formed through molding and foaming, and the obtained polyurethane sponge has good mechanical property, does not need to be bonded by an adhesive, is firm in connection, is green and environment-friendly, cannot be dried and hardened, and has good service performance;

2. through the synergistic effect of the phase-change material, the isocyanate-based prepolymer matrix and the nano attapulgite, the problem of over-concentrated heat release in the full-water foaming process is solved, and the obtained polyurethane sponge has no yellowing and core burning phenomenon, high molding forming quality and good process stability;

3. the polyurethane porous fiber in the tough framework has good structural symmetry, contains hydrogen bonds and disulfide bonds, has excellent mechanical properties, and can automatically heal and recover when a breakpoint is generated; the phase-change material-loaded nano-attapulgite/nano-fiber modified mixture is light in weight, has a loose and porous large-volume containing structure, and can form an interpenetrating network structure in the polyurethane porous fiber spinning forming process and the polyurethane sponge matrix foaming forming process, so that the tough framework is firmly combined with the polyurethane sponge matrix, and the mechanical property of the polyurethane sponge is further enhanced;

4. performing composite activation modification such as arc plasma activation, acid modification, alkali modification, silane coupling agent modification and the like on the nano-attapulgite to obtain the nano-attapulgite with higher aperture ratio and activity; the nano attapulgite is dispersed in the polyurethane sponge matrix, so that on one hand, the mechanical strength of the polyurethane sponge matrix can be enhanced, the compression permanent deformation rate is reduced, on the other hand, the wettability of the polyurethane sponge matrix can be increased, and the water absorption rate of the polyurethane sponge matrix is improved;

5. nanometer attapulgite is added into the isocyanate-based prepolymer matrix, the isocyanate-based prepolymer matrix can permeate into pores of the nanometer attapulgite, and when the polyurethane sponge matrix is formed through foaming, an interpenetrating network structure can be formed between the polyurethane sponge matrix and the nanometer attapulgite, so that the dispersion stability and the combination stability of the nanometer attapulgite in the polyurethane sponge matrix are improved;

in conclusion, the polyurethane sponge for the mop provided by the invention is green and environment-friendly, does not dry and harden, and has the advantages of good service performance, high water absorption rate, high molding quality and excellent mechanical property.

Drawings

FIG. 1 is a schematic view of the structure of the present invention;

FIG. 2 is a schematic structural view of a ductile skeleton;

FIG. 3 is a schematic structural view of a nano-attapulgite/nanofiber modification mixture;

FIG. 4 is a schematic view of the structure of the spinneret.

Description of reference numerals:

1. polyurethane sponge matrix, 2, a flexible framework, 3, a connecting piece, 41, a core liquid inlet, 42, a core liquid cavity, 43, a core liquid outlet, 44, a skin forming liquid inlet, 45, a skin forming liquid cavity, 46 and a spinning liquid outlet.

Detailed Description

The following description of the embodiments of the present invention refers to the accompanying drawings and examples:

in order that the above objects, features and advantages of the present invention can be more clearly understood, the present invention will be described in further detail with reference to specific embodiments. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as specifically described herein and, therefore, the scope of the present invention is not limited by the specific embodiments disclosed below.

As shown in fig. 1, an embodiment of the present invention provides a polyurethane sponge for a mop, including: the polyurethane sponge matrix 1 is characterized in that nano attapulgite is uniformly dispersed in the polyurethane sponge matrix 1; the nano attapulgite accounts for 3.5 to 7 weight percent of the polyurethane sponge matrix 1;

the flexible polyurethane foam material comprises a flexible framework 2, wherein the flexible framework 2 is a net structure woven by polyurethane porous fibers and is embedded in a polyurethane foam matrix 1, the polyurethane porous fibers contain a phase-change material, and the flexible framework 2 accounts for 5-10 wt% of the polyurethane foam matrix 1;

and the connecting piece 3 is detachably connected with a mop rod (not shown in the figure), and the connecting piece 3 and the polyurethane sponge matrix 1 are integrally formed during molding.

Among the above-mentioned technical scheme, nanometer attapulgite disperses in polyurethane sponge base member 1, can strengthen the mechanical strength of polyurethane sponge base member 1 on the one hand, reduces the compression set rate, and on the other hand can increase the wettability of polyurethane sponge base member 1, improves the rate of water absorption of polyurethane sponge base member 1. The flexible skeleton 2 and the polyurethane sponge matrix 1 are integrally formed, so that the tensile strength and the tearing strength of the polyurethane sponge matrix 1 can be improved, the flexible skeleton 2 can be adjusted in overall shape according to different polyurethane sponge shapes, for example, in a flat sponge mop, the flexible skeleton 2 can be woven into a planar mesh structure as shown in fig. 2, and in a cylindrical sponge mop, the flexible skeleton 2 can be woven into a cylindrical mesh structure (not shown in the figure). The connecting piece is integrally formed when the polyurethane sponge matrix is molded, bonding by an adhesive is not needed, the environment is protected, drying and hardening are avoided, and the using performance is good.

Preferably, the phase-change material is loaded on the nano-attapulgite/nano-fiber modified mixture to form phase-change particles, and the phase-change particles are loaded in the polyurethane porous fibers; wherein the diameter of the nanofiber is 500-1000 nm, and the length-diameter ratio is 200-500; the particle size of the nano attapulgite is 400-600 nm.

In the above technical solution, the nano-attapulgite/nanofiber modified mixture is a product obtained by mixing and modifying nano-attapulgite and nanofiber, the nano-attapulgite is bonded on the surface of the nanofiber, and a light, loose and porous containing structure (as shown in fig. 3, a circular shape indicates nano-attapulgite and a rectangular shape indicates nanofiber) can be formed, so that more containing spaces are provided for the phase change material, in addition, the loose and porous containing structure can form an interpenetrating network structure in the polyurethane porous fiber spinning forming process on one hand, so as to improve the structural stability of the polyurethane porous fiber, and on the other hand, in the polyurethane sponge matrix foaming forming process, the foaming material of the polyurethane sponge matrix can enter the pores thereof to perform a polymerization reaction, so as to form an interpenetrating network structure between the polyurethane porous fiber and the polyurethane sponge matrix, thereby improving the firm combination of the tough framework and the polyurethane sponge matrix, and further enhancing the mechanical properties of the polyurethane sponge.

The embodiment of the invention provides a preparation method of a polyurethane sponge for a mop, which comprises the following steps:

step S1, preparing a tough framework: weaving the polyurethane porous fiber loaded with the phase-change material into a net shape to obtain a tough framework;

step S2, preparing a polyurethane sponge matrix A material: polyether polyol, a chain extender, a cross-linking agent, a catalyst, water and a surfactant are mixed and stirred uniformly to obtain a polyurethane sponge matrix A material;

step S3, preparing a polyurethane sponge matrix B material: polyether polyol, a chain extender and diisocyanate are mixed and stirred uniformly, and react for 5 to 6 hours at a temperature of between 65 and 85 ℃ to obtain an isocyanate-based prepolymer matrix; mixing and stirring the nano attapulgite and the isocyanate-based prepolymer matrix uniformly, and standing at room temperature for 48 hours to obtain a polyurethane sponge matrix B material;

step S4, molding, foaming and forming: laying the connecting piece and the tough framework in a mould, preheating the mould to 50-60 ℃, mixing the polyurethane sponge matrix A material and the polyurethane sponge matrix B material at 25 ℃, pouring the mixture into the mould for foaming and molding, curing at 55-65 ℃ for 15-20 minutes, and then demoulding to obtain the polyurethane sponge for the mop.

According to the technical scheme, through the phase change heat absorption of the phase change material in the step S1, the isocyanate-based prepolymer substrate prepared in the step S3 releases heat in advance, and the nano attapulgite is added into the isocyanate-based prepolymer substrate, the problems of over concentrated heat release and poor flowability of the full-water foaming polyurethane in the molding process are solved through the synergistic effect of three means, and the obtained polyurethane sponge for the mop has the advantages of no yellowing and burning core phenomena, high molding quality and good process stability.

In the step S1, the phase change material-loaded polyurethane porous fiber may be a product in the prior art, and since the phase change material can change its phase state with the change of temperature, it can absorb a part of heat released by the polyurethane sponge matrix during the foaming process, and the higher the content of the phase change material is, the higher the absorbed heat is.

In the step S2, polyether polyol is used as a main reaction body, so that the hydrolysis stability of the polyurethane sponge can be improved.

In step S3, a part of polyether polyol, a chain extender, a cross-linking agent, and the like are reacted with diisocyanate in advance to prepare an isocyanate-based prepolymer matrix, a large amount of reaction heat is released in advance, so that the heat release of the polyurethane sponge matrix in the foaming process is greatly reduced, meanwhile, nano-attapulgite is added to the isocyanate-based prepolymer matrix, the isocyanate-based prepolymer matrix can permeate into pores of the nano-attapulgite, when the polyurethane sponge matrix is foamed, the content of the isocyanate-based prepolymer matrix is gradually reduced along with the reaction between the isocyanate-based prepolymer matrix and a material a of the polyurethane sponge matrix, at this time, the isocyanate-based prepolymer matrix in the pores of the nano-attapulgite is slowly released to participate in the reaction, the reaction time is prolonged, the heat concentration during the reaction is reduced, and in addition, the material a material of the polyurethane sponge matrix can also enter the pores of the nano-attapulgite to directly react with the isocyanate-based prepolymer matrix remaining in the pores, so that an interpenetrating network structure is formed between the polyurethane sponge matrix and the nano-attapulgite, and the dispersion stability and the bonding stability of the nano-attapulgite in the polyurethane sponge matrix are improved.

Preferably, in step S2, the catalyst is triethylene diamine;

in step S2, the cross-linking agent is diethanolamine;

in the step S2, the surfactant is silicone oil;

in the step S2 and the step S3, the polyether polyol is polyether triol with the number average molecular weight of 2000-5000;

in the step S2 and the step S3, the chain extender is 1,4-butanediol;

in the step S3, the diisocyanate is at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate.

Preferably, in step S2, the polyether polyol comprises the following components in parts by mass: 100; chain extender: 1.5 to 3; a crosslinking agent: 1 to 3; catalyst: 0.1 to 0.5; water: 0.1 to 0.5; surfactant (b): 0.05 to 0.1;

in the step S3, the polyether polyol comprises the following components in parts by mass: 60 to 70 percent; chain extender: 1.5 to 3; diisocyanate: 30 to 40 percent; nano-attapulgite: 10 to 20; isocyanate-based prepolymer base: 100, respectively;

in the step S4, the polyurethane sponge matrix A comprises the following components in parts by mass: 100, respectively; polyurethane sponge matrix B:60 to 70.

Preferably, in step S1, the preparation of the polyurethane porous fiber comprises the following steps:

step S11, mixing and stirring a coupling agent and absolute ethyl alcohol uniformly, adding acetic acid to adjust the pH value of a solution to 4.5-6.5, adding nano-attapulgite and nano-fibers, reacting for 0.5-6 hours, washing and drying to obtain a nano-attapulgite/nano-fiber modified mixture;

s12, putting the nano-attapulgite/nano-fiber modified mixture into a molten phase-change material, pressurizing to 0.2-0.5 MPa at 50-70 ℃, and stirring for 0.5-1 hour to obtain phase-change particles;

s13, stirring and reacting polytetrahydrofuran ether glycol, polyester diol, 1,4-butanediol, disulfide and isophorone diisocyanate at 60-90 ℃ for 1-1.5 hours, and cooling to 40-50 ℃ to obtain a first-order isocyanate-based prepolymer;

s14, stirring the first-order isocyanate-based prepolymer, ethyl acetate and disulfide at the temperature of 30-50 ℃ for reaction for 1-1.5 hours to obtain a second-order isocyanate-based prepolymer;

step S15, adding disulfide, polycarbodiimide and a pore-opening agent into the second-order isocyanate-based prepolymer obtained in the step S14, and stirring and reacting for 1-1.5 hours at 20-40 ℃ to obtain spinning skin-forming liquid;

s16, mixing and stirring the second-order isocyanate-based prepolymer, the phase-change particles, the ethyl acetate and the pore-opening agent uniformly, and performing ultrasonic dispersion for 5-10 minutes at 20-30 ℃ to obtain a spinning core solution;

s17, spinning by a dry-wet method, injecting a spinning skin-forming solution and a spinning core solution into a coagulating bath at 50-70 ℃ through a spinning nozzle at the same time at room temperature for solidification to obtain polyurethane fiber yarns;

s18, soaking the polyurethane fiber yarns in hot water at the temperature of 60-90 ℃ for 15-25 hours, and then carrying out vacuum freeze drying at the temperature of-20-40 ℃ for 20-25 hours to obtain the polyurethane porous fiber.

Above-mentioned technical scheme, in step S11, coupling agent is with the even bonding of nanometer attapulgite on the nanofiber surface, improves nanofiber' S activity and surface roughness, can increase the interval between the adjacent nanofiber simultaneously, provides more accommodation space for phase change material, and phase change material can get into the porosity of nanometer attapulgite self and by in the loose pore that nanofiber and nanometer attapulgite formed jointly.

In the step S13, the first-order isocyanate-based prepolymer adopts polytetrahydrofuran ether glycol, polyester diol, 1,4-butanediol, disulfide and isophorone diisocyanate to react, the polytetrahydrofuran ether glycol and the polyester diol are used for providing a soft section for the first-order isocyanate-based prepolymer, the isophorone diisocyanate is used for providing a hard section for the first-order isocyanate-based prepolymer, 1,4-butanediol and disulfide are used as chain extenders, and finally the self-healing polyurethane fiber with good structural symmetry and hydrogen bonds and disulfide bonds can be obtained.

Through the second-order segmental polymerization in the steps S13 and S14, the stability of the self-healing structure of the second-order isocyanate-based prepolymer can be further improved;

spinning skin forming liquid and spinning core liquid are respectively prepared through the step S15 and the step S16, and spinning is carried out through the dry-wet spinning method in the step S17, so that the polyurethane fiber yarn with a skin-core structure is obtained, and the mechanical property of the polyurethane fiber yarn can be further improved;

the spinneret in the step S17 includes, but is not limited to, the structure shown in fig. 4, the spinning core liquid is injected into the cylindrical core liquid cavity 42 from the core liquid inlet 41, and then is linearly sprayed into the annular Pi Yeqiang 45 from the core liquid outlet 43, at the same time, the spinning sheath liquid is injected into the annular Pi Yeqiang from the sheath liquid inlet 44, and is coated on the periphery of the spinning core liquid, and the spinning core liquid and the spinning sheath liquid are simultaneously sprayed out from the spinning liquid outlet 46, so as to form the polyurethane fiber yarn with the sheath-core structure;

by immersing the polyurethane fiber yarn in hot water in step S18, water-soluble substances in the polyurethane fiber yarn can be sufficiently removed, and the aperture ratio can be increased.

Preferably, in step S11, the coupling agent is at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, or gamma-mercaptopropyltrimethoxysilane;

in step S11, the nanofibers are at least one of polyolefin, polyester, polyamide, polyvinyl alcohol, or copolymer nanofibers;

in the step S12, the phase-change material is paraffin with a melting point of more than 50 ℃;

in the step S13, the polyester diol is at least one of polycarbonate diol, polyhexamethylene adipate diol and polycaprolactone diol;

in step S13, step S14 and step S15, the disulfide is at least one of bis (2-hydroxyethyl) disulfide, 2,2 '-diaminodiphenyl disulfide, 4,4' -diaminodiphenyl disulfide, 4,4 '-dihydroxydiphenyl disulfide, 3,3' -dihydroxydiphenyl disulfide;

in the step S15 and the step S16, the cell opening agent is at least one of polyvinylpyrrolidone or polyethylene glycol with molecular weight more than 4000;

in step S17, the coagulation bath is deionized water, the vertical distance between a spinning nozzle and the coagulation bath is 5-20 cm, and the winding speed is 20-50 m/min.

Preferably, in step S11, the coupling agent comprises the following components in parts by mass: 1 to 10; anhydrous ethanol: 90 to 99 percent; nano attapulgite: 1 to 10; nano-fiber: 5 to 50 percent;

in the step S12, the nano-attapulgite/nanofiber modified mixture comprises the following components in parts by mass: 1; phase change material: 2 to 5;

in step S13, the following polytetrahydrofuran ether glycol is used in parts by mass: 60 to 70 percent; polyester diol: 5 to 10;1,4 butanediol: 0.1 to 0.3; disulfide ethers: 0.1 to 1; isophorone diisocyanate: 20 to 40 percent;

in step S14, the first-order isocyanate-based prepolymer comprises the following components in parts by mass: 40 to 50; ethyl acetate: 50 to 60; disulfide ethers: 0.5 to 1.5;

in step S15, the disulfide comprises the following components in parts by mass: 0.5 to 1; polycarbodiimide: 1 to 5; a pore forming agent: 5 to 15 percent;

in step S16, the second-order isocyanate-based prepolymer comprises the following components in parts by mass: 50 to 60; phase change particles: 20 to 30 percent; ethyl acetate: 20 to 30 percent; a pore forming agent: 10 to 20;

in the step S17, the spinning skin-forming liquid comprises the following components in parts by mass: 15; spinning core liquid: 20.

preferably, the nano attapulgite in step S11 and step S3 is subjected to activation modification, and the activation modification includes the following steps:

step S111, grinding and sieving the attapulgite to obtain nano attapulgite with the particle size of 400-600;

step S112, the nano attapulgite obtained in the step S111 is placed in an electric arc plasma generator, plasma treatment is carried out for 5-10 minutes under the direct current voltage of 30-50 kV, then the nano attapulgite is added into deionized water, ultrasonic cleaning is carried out, and drying is carried out to obtain activated nano attapulgite;

and S113, adding the activated nano-attapulgite obtained in the step S112 into a dilute hydrochloric acid solution, ultrasonically dispersing for 1 hour at 65-75 ℃, under the conditions of ultrasonic power of 200-500W and ultrasonic frequency of 20-25 kHz, then dropwise adding a sodium hydroxide solution, adjusting the pH value to 4-5, adding a silane coupling agent, continuously ultrasonically dispersing for 1-2 hours, washing, filtering and drying to obtain the activated and modified nano-attapulgite.

In the technical scheme, the nano-attapulgite is activated and modified, so that the nano-attapulgite with higher aperture ratio and activity can be obtained.

In step S112, the nano-attapulgite is activated by an arc plasma method to destroy van der waals force among nano-attapulgite molecules and bonding force of other ionic bonds, so that the structure of the nano-attapulgite becomes loose, and the subsequent acid-base modification effect is improved;

in step S113, the nano attapulgite after plasma activation has a loose structure, which is beneficial to ion exchange between cations, and at the moment, dilute hydrochloric acid solution is adopted for acidification modification, so that gel substances in pores of the nano attapulgite can be dissolved and removed, and the pore channels are dredged; after acidification modification, a sodium hydroxide solution is added, and the sodium hydroxide solution reacts with dilute hydrochloric acid to produce sodium chloride and water, so that the pH value in the modification process can be effectively controlled, the modification environment is kept to be weakly acidic, the generated sodium salt can be used for carrying out secondary modification on the nano attapulgite, and the weakly acidic environment is also beneficial to the subsequent modification of the silane coupling agent.

Preferably, in step S112, the nano-attapulgite comprises the following components in parts by mass: 1; deionized water: 10 to 20;

in step S113, the nano-attapulgite is activated as follows in parts by mass: 1; diluted hydrochloric acid solution: 2 to 3; the concentration of the dilute hydrochloric acid solution is 0.5 to 1 weight percent; the concentration of the sodium hydroxide solution is 10-15 wt%.

Examples 1 to 1

This example prepares a polyurethane porous fiber a loaded with phase-change particles, including the following steps:

step S11, mixing and stirring 1 part by mass of gamma-aminopropyltriethoxysilane and 99 parts by mass of absolute ethanol uniformly, adding acetic acid to adjust the pH of the solution to 4.5-6.5, adding 1 part by mass of nano-attapulgite and 5 parts by mass of polyester nanofiber, reacting for 0.5-6 hours, washing and drying to obtain a nano-attapulgite/nanofiber modified mixture;

s12, putting 1 part by mass of the nano-attapulgite/nano-fiber modified mixture into 2 parts by mass of molten paraffin, pressurizing to 0.2-0.5 MPa at 50-70 ℃, and stirring for 0.5-1 hour to obtain phase change particles;

step S13, stirring and reacting 60 parts by mass of polytetrahydrofuran ether glycol, 10 parts by mass of polycarbonate glycol, 0.1 part by mass of 1,4-butanediol, 0.1 part by mass of bis (2-hydroxyethyl) disulfide and 20 parts by mass of isophorone diisocyanate at the temperature of 60-90 ℃ for 1-1.5 hours, and cooling to the temperature of 40-50 ℃ to obtain a first-order isocyanate-based prepolymer;

step S14, stirring 40 parts by mass of first-order isocyanate-based prepolymer, 50 parts by mass of ethyl acetate and 0.5 part by mass of 4,4' -diaminodiphenyl disulfide for reaction for 1-1.5 hours at 30-50 ℃ to obtain second-order isocyanate-based prepolymer;

step S15, mixing and stirring 50 parts by mass of a second-order isocyanate-based prepolymer, 20 parts by mass of phase change particles, 20 parts by mass of ethyl acetate and 10 parts by mass of polyethylene glycol uniformly, and performing ultrasonic dispersion for 5-10 minutes at 20-30 ℃ to obtain a spinning solution;

s16, spinning by a dry-wet method, injecting the spinning solution into a coagulating bath at 50-70 ℃ through a spinning nozzle at room temperature for solidification to obtain polyurethane fiber yarns;

s17, soaking the polyurethane fiber yarns in hot water at the temperature of 60-90 ℃ for 15-25 hours, and then carrying out vacuum freeze drying at the temperature of-20-40 ℃ for 20-25 hours to obtain the polyurethane porous fiber A.

Examples 1 to 2

This example prepares a polyurethane porous fiber B loaded with phase change particles and having a sheath-core structure, including the following steps:

s11, mixing and stirring 1 part by mass of gamma-aminopropyltriethoxysilane and 99 parts by mass of absolute ethanol uniformly, adding acetic acid to adjust the pH of the solution to 4.5-6.5, adding 1 part by mass of nano-attapulgite and 5 parts by mass of polyester nanofibers, reacting for 0.5-6 hours, washing and drying to obtain a nano-attapulgite/nanofiber modified mixture;

s12, putting 1 part by mass of the nano-attapulgite/nano-fiber modified mixture into 2 parts by mass of molten paraffin, pressurizing to 0.2-0.5 MPa at 50-70 ℃, and stirring for 0.5-1 hour to obtain phase change particles;

step S13, stirring 60 parts by mass of polytetrahydrofuran ether glycol, 10 parts by mass of polycarbonate glycol, 0.1 part by mass of 1,4-butanediol, 0.1 part by mass of bis (2-hydroxyethyl) disulfide and 20 parts by mass of isophorone diisocyanate for reacting for 1-1.5 hours at the temperature of 60-90 ℃, and cooling to 40-50 ℃ to obtain a first-order isocyanate-based prepolymer;

step S14, stirring 40 parts by mass of first-order isocyanate-based prepolymer, 50 parts by mass of ethyl acetate and 0.5 part by mass of 4,4' -diaminodiphenyl disulfide for reaction for 1-1.5 hours at 30-50 ℃ to obtain second-order isocyanate-based prepolymer;

step S15, adding 1 part by mass of 3,3' -dihydroxy diphenyl disulfide, 1 part by mass of polycarbodiimide and 5 parts by mass of polyethylene glycol into the second-order isocyanate-based prepolymer obtained in the step S22, and stirring and reacting at 20-40 ℃ for 1-1.5 hours to obtain spinning skin-forming liquid;

step S16, mixing and stirring 50 parts by mass of second-order isocyanate-based prepolymer, 20 parts by mass of phase-change particles, 20 parts by mass of ethyl acetate and 10 parts by mass of polyethylene glycol uniformly, and performing ultrasonic dispersion for 5-10 minutes at 20-30 ℃ to obtain spinning core liquid;

s17, spinning by a dry-wet method, injecting 15 parts by mass of spinning skin-forming liquid and 20 parts by mass of spinning core liquid into a coagulating bath at 50-70 ℃ through a spinning nozzle at the same time at room temperature for solidification to obtain polyurethane fiber yarns;

s18, soaking the polyurethane fiber yarns in hot water at the temperature of 60-90 ℃ for 15-25 hours, and then carrying out vacuum freeze drying at the temperature of-20-40 ℃ for 20-25 hours to obtain the polyurethane porous fiber B.

Examples 1 to 3

The preparation steps of the polyurethane porous fiber C loaded with phase change particles and having a skin-core structure are the same as those of the embodiment 1-2, except that the nano-attapulgite is subjected to activation modification in the embodiment, and the activation modification of the nano-attapulgite comprises the following steps:

step S111, grinding and sieving the attapulgite to obtain nano attapulgite with the particle size of 400-600;

step S112, putting 1 part by mass of nano-attapulgite into an arc plasma generator, carrying out plasma treatment for 5-10 minutes under the direct-current voltage of 30-50 kV, adding the nano-attapulgite into 10-20 parts by mass of deionized water, carrying out ultrasonic cleaning, and drying to obtain activated nano-attapulgite;

step S113, adding 1 part by mass of activated nano attapulgite into 2-3 parts by mass of a dilute hydrochloric acid solution with the concentration of 0.5-1 wt%, performing ultrasonic dispersion for 1 hour at 65-75 ℃, the ultrasonic power of 200-500W and the ultrasonic frequency of 20-25 kHz, then dropwise adding a sodium hydroxide solution with the concentration of 10-15 wt%, adjusting the pH value to 4-5, adding a silane coupling agent, continuing to perform ultrasonic dispersion for 1-2 hours, and washing, filtering and drying to obtain the activated and modified nano attapulgite.

Examples 1 to 4

This example prepares a phase change particle-loaded polyurethane porous fiber D having a sheath-core structure, including the following steps:

step S11, mixing and stirring 10 parts by mass of gamma-glycidyl ether propyl trimethoxy silane and 90 parts by mass of absolute ethyl alcohol uniformly, adding acetic acid to adjust the pH value of the solution to 4.5-6.5, adding 10 parts by mass of activated and modified nano-attapulgite and 50 parts by mass of polyamide nano-fibers, reacting for 0.5-6 hours, washing and drying to obtain a nano-attapulgite/nano-fiber modified mixture; the steps of the activation modification of the nano-attapulgite are the same as those of the examples 1 to 3;

s12, putting 1 part by mass of the nano-attapulgite/nano-fiber modified mixture into 5 parts by mass of molten paraffin, pressurizing to 0.2-0.5 MPa at 50-70 ℃, and stirring for 0.5-1 hour to obtain phase change particles;

step S13, stirring 70 parts by mass of polytetrahydrofuran ether glycol, 5 parts by mass of polyhexamethylene adipate glycol, 0.3 part by mass of 1,4-butanediol, 1 part by mass of bis (2-hydroxyethyl) disulfide and 40 parts by mass of isophorone diisocyanate for reacting for 1-1.5 hours at the temperature of 60-90 ℃, and cooling to 40-50 ℃ to obtain a first-order isocyanate-based prepolymer;

s14, stirring and reacting 50 parts by mass of first-order isocyanate-based prepolymer, 60 parts by mass of ethyl acetate and 1.5 parts by mass of 2,2' -diaminodiphenyl disulfide for 1-1.5 hours at 30-50 ℃ to obtain second-order isocyanate-based prepolymer;

step S15, adding 1 part by mass of 4,4' -dihydroxy diphenyl disulfide, 5 parts by mass of polycarbodiimide and 15 parts by mass of polyvinylpyrrolidone into the second-order isocyanate-based prepolymer obtained in the step S22, and stirring and reacting at 20-40 ℃ for 1-1.5 hours to obtain spinning skin forming liquid;

step S16, mixing and stirring 60 parts by mass of a second-order isocyanate-based prepolymer, 30 parts by mass of phase-change particles, 30 parts by mass of ethyl acetate and 20 parts by mass of polyvinylpyrrolidone uniformly, and performing ultrasonic dispersion for 5-10 minutes at 20-30 ℃ to obtain a spinning core solution;

s17, spinning by a dry-wet method, injecting 15 parts by mass of spinning skin-forming liquid and 20 parts by mass of spinning core liquid into a coagulating bath at 50-70 ℃ through a spinning nozzle at the same time at room temperature for solidification to obtain polyurethane fiber yarns;

s18, soaking the polyurethane fiber filaments in hot water at the temperature of 60-90 ℃ for 15-25 hours, and then carrying out vacuum freeze drying at the temperature of-20-40 ℃ for 20-25 hours to obtain the polyurethane porous fiber D.

Example 2-1

This example prepares a polyurethane sponge for a mop, including the following steps:

step S1, preparing a tough framework: weaving the polyurethane porous fiber A obtained in the example 1-1 into a net shape to obtain a tough skeleton;

step S2, preparing a polyurethane sponge matrix A material: mixing and stirring 100 parts by mass of polyether triol, 1.5 parts by mass of 1,4-butanediol, 1 part by mass of diethanolamine, 0.1 part by mass of triethylene diamine, 0.5 part by mass of water and 0.05 part by mass of silicone oil uniformly to obtain a polyurethane sponge matrix A material;

step S3, preparing a polyurethane sponge matrix B material: mixing and stirring 60 parts by mass of polyether triol, 1.5 parts by mass of 1,4-butanediol and 30 parts by mass of diphenylmethane diisocyanate uniformly, and reacting at 65-85 ℃ for 5-6 hours to obtain an isocyanate-based prepolymer matrix; mixing and stirring 10 parts by mass of nano attapulgite and 100 parts by mass of isocyanate-based prepolymer matrix uniformly, and standing at room temperature for 48 hours to obtain a polyurethane sponge matrix B material;

step S4, molding, foaming and forming: laying a connecting piece and a flexible framework in a mould, preheating the mould to 50-60 ℃, and mixing a polyurethane sponge matrix A material and a polyurethane sponge matrix B material at 25 ℃ according to a ratio of 100:60, pouring the mixture into a mold for foaming molding, curing the mixture at the temperature of between 55 and 65 ℃ for 15 to 20 minutes, and then demolding the mixture to obtain the polyurethane sponge for the mop.

Examples 2 to 2

This example prepares a polyurethane sponge for a mop, including the following steps:

step S1, preparing a tough framework: the polyurethane porous fiber B obtained in example 1-2 was woven into a mesh shape to obtain a flexible skeleton;

steps S2 to S4 are the same as those in example 2-1.

Examples 2 to 3

This example prepares a polyurethane sponge for mop, includes the following steps:

step S1, preparing a tough framework: weaving the polyurethane porous fiber C obtained in examples 1-3 into a net shape to obtain a tough skeleton;

steps S2 to S4 are the same as those in example 2-1.

Examples 2 to 4

This example prepares a polyurethane sponge for mop, includes the following steps:

step S1, preparing a tough framework: weaving the polyurethane porous fiber C obtained in examples 1-3 into a net shape to obtain a tough skeleton;

step S2, preparing a polyurethane sponge matrix A material: mixing and stirring 100 parts by mass of polyether triol, 1.5 parts by mass of 1,4-butanediol, 1 part by mass of diethanolamine, 0.1 part by mass of triethylene diamine, 0.5 part by mass of water and 0.05 part by mass of silicone oil uniformly to obtain a polyurethane sponge matrix A material;

step S3, preparing a polyurethane sponge matrix B material: mixing and stirring 60 parts by mass of polyether triol, 1.5 parts by mass of 1,4-butanediol and 30 parts by mass of diphenylmethane diisocyanate uniformly, and reacting at 65-85 ℃ for 5-6 hours to obtain an isocyanate-based prepolymer matrix; mixing and stirring 10 parts by mass of activated and modified nano attapulgite and 100 parts by mass of isocyanate-based prepolymer matrix uniformly, and standing at room temperature for 48 hours to obtain a polyurethane sponge matrix B material; the steps of the activation modification of the nano-attapulgite are the same as those of the examples 1 to 3;

step S4, molding, foaming and forming: laying a connecting piece and a flexible framework in a mould, preheating the mould to 50-60 ℃, and mixing a polyurethane sponge matrix A material and a polyurethane sponge matrix B material at 25 ℃ according to a ratio of 100:60, pouring the mixture into a mold for foaming molding, curing the mixture at the temperature of between 55 and 65 ℃ for 15 to 20 minutes, and then demolding the mixture to obtain the polyurethane sponge for the mop.

Examples 2 to 5

This example prepares a polyurethane sponge for mop, includes the following steps:

step S1, preparing a tough framework: weaving the polyurethane porous fiber C obtained in examples 1-3 into a net shape to obtain a tough skeleton;

step S2, preparing a polyurethane sponge matrix A material: mixing and uniformly stirring 100 parts by mass of polyether triol, 3 parts by mass of 1,4-butanediol, 3 parts by mass of diethanolamine, 0.5 part by mass of triethylene diamine, 0.1 part by mass of water and 0.1 part by mass of surfactant to obtain a polyurethane sponge matrix A material;

step S3, preparing a polyurethane sponge matrix B material: mixing and stirring 70 parts by mass of polyether triol, 3 parts by mass of 1,4-butanediol and 40 parts by mass of isophorone diisocyanate uniformly, and reacting for 5-6 hours at 65-85 ℃ to obtain an isocyanate-based prepolymer matrix; mixing and stirring 20 parts by mass of activated and modified nano attapulgite and 100 parts by mass of isocyanate-based prepolymer matrix uniformly, and standing at room temperature for 48 hours to obtain a polyurethane sponge matrix B material; the steps of the activation and modification of the nano-attapulgite are the same as those of the embodiment 1-3;

step S4, molding, foaming and forming: laying a connecting piece and a flexible framework in a mould, preheating the mould to 50-60 ℃, and mixing a polyurethane sponge matrix A material and a polyurethane sponge matrix B material at 25 ℃ according to a ratio of 100:70, pouring the mixture into a mold for foaming molding, curing the mixture at the temperature of between 55 and 65 ℃ for 15 to 20 minutes, and then demolding the mixture to obtain the polyurethane sponge for the mop.

Examples 2 to 6

This example prepares a polyurethane sponge for a mop, including the following steps:

step S1, preparing a tough framework: weaving the polyurethane porous fiber D obtained in examples 1 to 4 into a net shape to obtain a tough skeleton;

step S2, preparing a polyurethane sponge matrix A material: mixing and stirring 100 parts by mass of polyether triol, 2 parts by mass of 1,4-butanediol, 2 parts by mass of diethanolamine, 0.3 part by mass of triethylene diamine, 0.3 part by mass of water and 0.08 part by mass of silicone oil uniformly to obtain a polyurethane sponge matrix A material;

step S3, preparing a polyurethane sponge matrix B material: mixing 65 parts by mass of polyether triol, 2 parts by mass of 1,4-butanediol and 35 parts by mass of dicyclohexylmethane diisocyanate, uniformly stirring, and reacting at 65-85 ℃ for 5-6 hours to obtain an isocyanate-based prepolymer matrix; mixing and stirring uniformly 15 parts by mass of activated and modified nano attapulgite and 100 parts by mass of isocyanate-based prepolymer matrix, and standing at room temperature for 48 hours to obtain a polyurethane sponge matrix B material; the steps of the activation modification of the nano-attapulgite are the same as those of the examples 1 to 3;

step S4, molding, foaming and forming: laying a connecting piece and a flexible framework in a mould, preheating the mould to 50-60 ℃, and mixing a polyurethane sponge matrix A material and a polyurethane sponge matrix B material at 25 ℃ according to a ratio of 100:65, pouring the mixture into a mold for foaming molding, curing the mixture at the temperature of between 55 and 65 ℃ for 15 to 20 minutes, and then demolding the mixture to obtain the polyurethane sponge for the mop.

Comparative example 1

The comparative example prepares a polyurethane sponge for a mop without a tough framework and nano-attapulgite, and comprises the following steps:

step S1, preparing a polyurethane sponge matrix A material: mixing and stirring 100 parts by mass of polyether triol, 1.5 parts by mass of 1,4-butanediol, 1 part by mass of diethanolamine, 0.1 part by mass of triethylene diamine, 0.5 part by mass of water and 0.05 part by mass of silicone oil uniformly to obtain a polyurethane sponge matrix A material;

step S2, preparing a polyurethane sponge matrix B material: mixing and stirring 60 parts by mass of polyether triol, 1.5 parts by mass of 1,4-butanediol and 30 parts by mass of diphenylmethane diisocyanate uniformly, and reacting at 65-85 ℃ for 5-6 hours to obtain a polyurethane sponge matrix B material;

step S3, molding, foaming and forming: laying the connecting piece in a mold at 40-50 ℃, and mixing a polyurethane sponge matrix A material and a polyurethane sponge matrix B material at 25 ℃ according to the ratio of 100:60, pouring the mixture into a mold for foaming molding, curing the mixture at the temperature of between 55 and 65 ℃ for 15 to 20 minutes, and then demolding the mixture to obtain the polyurethane sponge for the mop.

Comparative example 2

The comparative example prepared a polyurethane sponge for a mop that did not contain nano-attapulgite in the polyurethane sponge matrix, comprising the steps of:

step S1, preparing a tough framework: weaving the polyurethane porous fiber A obtained in the example 1-1 into a net shape to obtain a tough skeleton;

step S2, preparing a polyurethane sponge matrix A material: mixing and stirring 100 parts by mass of polyether triol, 1.5 parts by mass of 1,4-butanediol, 1 part by mass of diethanolamine, 0.1 part by mass of triethylene diamine, 0.5 part by mass of water and 0.05 part by mass of silicone oil uniformly to obtain a polyurethane sponge matrix A material;

step S3, preparing a polyurethane sponge matrix B material: mixing and stirring 60 parts by mass of polyether triol, 1.5 parts by mass of 1,4-butanediol and 30 parts by mass of diphenylmethane diisocyanate uniformly, and reacting at 65-85 ℃ for 5-6 hours to obtain a polyurethane sponge matrix B material;

step S4, molding, foaming and forming: laying the connecting piece and the tough framework in a mould, preheating the mould to 50-60 ℃, and mixing the polyurethane sponge matrix A material and the polyurethane sponge matrix B material at 25 ℃ according to the ratio of 100:60, pouring the mixture into a mold for foaming molding, curing the mixture at the temperature of between 55 and 65 ℃ for 15 to 20 minutes, and then demolding the mixture to obtain the polyurethane sponge for the mop.

Comparative example 3

The comparative example prepared a polyurethane sponge for a mop without a malleable skeleton comprising the steps of:

step S1, preparing a polyurethane sponge matrix A material: mixing and stirring 100 parts by mass of polyether triol, 1.5 parts by mass of 1,4-butanediol, 1 part by mass of diethanolamine, 0.1 part by mass of triethylene diamine, 0.5 part by mass of water and 0.05 part by mass of silicone oil uniformly to obtain a polyurethane sponge matrix A material;

step S2, preparing a polyurethane sponge matrix B material: mixing and stirring 60 parts by mass of polyether triol, 1.5 parts by mass of 1,4-butanediol and 30 parts by mass of diphenylmethane diisocyanate uniformly, and reacting at 65-85 ℃ for 5-6 hours to obtain an isocyanate-based prepolymer matrix; mixing and stirring 10 parts by mass of nano attapulgite and 100 parts by mass of isocyanate-based prepolymer matrix uniformly, and standing at room temperature for 48 hours to obtain a polyurethane sponge matrix B material;

step S3, molding, foaming and forming: laying a connecting piece in a mold at 40-50 ℃, and mixing a polyurethane sponge matrix A material and a polyurethane sponge matrix B material at 25 ℃ according to a ratio of 100:60, pouring the mixture into a mold for foaming molding, curing the mixture at the temperature of between 55 and 65 ℃ for 15 to 20 minutes, and then demolding the mixture to obtain the polyurethane sponge for the mop.

Performance detection

The polyurethane sponges for mops obtained in examples 2-1 to 2-6 and comparative examples 1 to 3 and commercially available PVA collodion for mops were cut out to prepare samples and tested for properties according to the following test standards, wherein the tough skeleton accounts for 10wt% of the polyurethane sponge in the test samples of examples 2-1 to 2-6 and comparative example 2, and the test results are shown in Table 1,

1. carrying out water absorption rate test by adopting GB/T8810-2005 standard;

2. performing density test by using a GB6343-86 standard;

3. testing the tensile strength by adopting a GB6344-86 standard;

4. adopting GB10808-89 standard to carry out tearing strength test;

5. the compression set rate is tested by adopting the GB6669-86 standard;

TABLE 1 polyurethane sponge Performance testing

As can be seen from Table 1, examples 2-1 to 2-6 and comparative example 3, in which the polyurethane sponge matrix contained nano-attapulgite, had a water absorption rate not lower than that of commercially available PVA collodion and significantly higher than that of comparative examples 1 and 2, in which the polyurethane sponge matrix contained no nano-attapulgite; wherein, the nano-attapulgite in the examples 2-4 to 2-6 is activated and modified, and the water absorption rate is higher than that of the commercially available PVA collodion cotton, and the examples 2-1 to 2-3 and the comparative example 3 which are not activated and modified.

Examples 2-1 to 2-6 and comparative example 3, in which the polyurethane sponge matrix contained nano-attapulgite, had a compression set significantly lower than those of commercially available PVA collodions and comparative examples 1 and 2, in which the polyurethane sponge matrix contained no nano-attapulgite.

The tensile strength and tear strength of examples 2-1 to 2-6 and comparative example 2, which contain a tough skeleton in the polyurethane sponge matrix, are significantly higher than those of commercially available PVA collodion and comparative examples 1 and 3, which do not contain a tough skeleton; among them, the polyurethane porous fibers of examples 2-2 to 2-6 have a sheath-core structure, and the tensile strength and tear strength thereof are higher than those of example 2-1 and comparative example 2 which are not sheath-core structures.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.

Claims (9)

1. A preparation method of polyurethane sponge for a mop is characterized by comprising the following steps:

step S1, preparing a tough framework: weaving the polyurethane porous fiber loaded with the phase-change material into a net shape to obtain a tough framework; the preparation method of the polyurethane porous fiber comprises the following steps:

step S11, mixing and stirring a coupling agent and absolute ethyl alcohol uniformly, adding acetic acid to adjust the pH value of a solution to 4.5-6.5, adding nano-attapulgite and nano-fibers, reacting for 0.5-6 hours, washing and drying to obtain a nano-attapulgite/nano-fiber modified mixture;

s12, putting the nano-attapulgite/nano-fiber modified mixture into a molten phase-change material, pressurizing to 0.2-0.5 MPa at 50-70 ℃, and stirring for 0.5-1 hour to obtain phase-change particles;

s13, stirring and reacting polytetrahydrofuran ether glycol, polyester diol, 1,4-butanediol, disulfide and isophorone diisocyanate at 60-90 ℃ for 1-1.5 hours, and cooling to 40-50 ℃ to obtain a first-order isocyanate-based prepolymer;

s14, stirring the first-order isocyanate-based prepolymer, ethyl acetate and disulfide at the temperature of 30-50 ℃ for reaction for 1-1.5 hours to obtain a second-order isocyanate-based prepolymer;

step S15, adding disulfide, polycarbodiimide and a pore-forming agent into the second-order isocyanate-based prepolymer obtained in the step S14, and stirring and reacting at 20-40 ℃ for 1-1.5 hours to obtain spinning skin-forming liquid;

s16, mixing and stirring the second-order isocyanate-based prepolymer, the phase-change particles, the ethyl acetate and the pore-opening agent uniformly, and performing ultrasonic dispersion for 5-10 minutes at 20-30 ℃ to obtain a spinning core solution;

s17, spinning by a dry-wet method, injecting a spinning skin-forming solution and a spinning core solution into a coagulating bath at 50-70 ℃ through a spinning nozzle at the same time at room temperature for solidification to obtain polyurethane fiber yarns;

s18, soaking the polyurethane fiber yarns in hot water at the temperature of 60-90 ℃ for 15-25 hours, and then carrying out vacuum freeze drying at the temperature of-20-40 ℃ for 20-25 hours to obtain polyurethane porous fibers;

step S2, preparing a polyurethane sponge matrix A material: mixing polyether polyol, a chain extender, a cross-linking agent, a catalyst, water and a surfactant uniformly to obtain a polyurethane sponge matrix A material;

step S3, preparing a polyurethane sponge matrix B material: polyether polyol, a chain extender and diisocyanate are mixed and stirred uniformly, and react for 5 to 6 hours at a temperature of between 65 and 85 ℃ to obtain an isocyanate-based prepolymer matrix; mixing and stirring the nano attapulgite and the isocyanate-based prepolymer matrix uniformly, and standing at room temperature for 48 hours to obtain a polyurethane sponge matrix B material;

step S4, molding, foaming and forming: laying the connecting piece and the tough framework in a mould, preheating the mould to 50-60 ℃, mixing the polyurethane sponge matrix A material and the polyurethane sponge matrix B material at 25 ℃, pouring the mixture into the mould for foaming and molding, curing at 55-65 ℃ for 15-20 minutes, and then demoulding to obtain the polyurethane sponge for the mop;

in step S11, the nanofibers are at least one of polyolefin, polyester, polyamide, and polyvinyl alcohol nanofibers;

in step S12, the phase-change material is paraffin with a melting point of more than 50 ℃;

in step S15 and step S16, the cell opener is at least one of polyvinylpyrrolidone or polyethylene glycol with a molecular weight greater than 4000.

2. The method for preparing a polyurethane sponge for a mop according to claim 1, wherein in step S2, the catalyst is triethylene diamine;

in step S2, the crosslinking agent is diethanolamine;

in the step S2, the surfactant is silicone oil;

in the step S2 and the step S3, the polyether polyol is polyether triol with the number average molecular weight of 2000-5000;

in the step S2 and the step S3, the chain extender is 1,4-butanediol;

in the step S3, the diisocyanate is at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate.

3. The method for preparing a polyurethane sponge for a mop according to claim 1,

in the step S2, the polyether polyol comprises the following components in parts by mass: 100; chain extender: 1.5 to 3; a crosslinking agent: 1 to 3; catalyst: 0.1 to 0.5; water: 0.1 to 0.5; surfactant (B): 0.05 to 0.1;

in the step S3, the polyether polyol comprises the following components in parts by mass: 60 to 70 percent; chain extender: 1.5 to 3; diisocyanate: 30 to 40 percent; nano-attapulgite: 10 to 20; isocyanate-based prepolymer base: 100, respectively;

in the step S4, the polyurethane sponge matrix A comprises the following components in parts by mass: 100, respectively; polyurethane sponge matrix B:60 to 70.

4. The method of claim 3, wherein in step S11, the coupling agent is at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, and gamma-mercaptopropyltrimethoxysilane;

in the step S13, the polyester diol is at least one of polycarbonate diol, polyhexamethylene adipate diol and polycaprolactone diol;

in step S13, step S14 and step S15, the disulfide is at least one of bis (2-hydroxyethyl) disulfide, 2,2 '-diaminodiphenyl disulfide, 4,4' -diaminodiphenyl disulfide, 4,4 '-dihydroxydiphenyl disulfide, 3,3' -dihydroxydiphenyl disulfide;

in step S17, the coagulation bath is deionized water, the vertical distance between a spinning nozzle and the coagulation bath is 5-20 cm, and the winding speed is 20-50 m/min.

5. The preparation method of the polyurethane sponge for the mop as claimed in claim 3, wherein in step S11, the coupling agent comprises the following components in parts by mass: 1 to 10; anhydrous ethanol: 90 to 99 percent; nano-attapulgite: 1 to 10; nano-fiber: 5 to 50 percent;

in step S12, the nano-attapulgite/nanofiber modified mixture comprises the following components in parts by mass: 1; phase change material: 2 to 5;

in step S13, polytetrahydrofuran ether glycol comprises the following components in parts by mass: 60 to 70 percent; polyester diol: 5 to 10;1,4 butanediol: 0.1 to 0.3; disulfide ethers: 0.1 to 1; isophorone diisocyanate: 20 to 40 percent;

in step S14, the first-order isocyanate-based prepolymer comprises the following components in parts by mass: 40 to 50; ethyl acetate: 50 to 60; disulfide: 0.5 to 1.5;

in step S15, the following components, in parts by mass, are disulfide: 0.5 to 1; polycarbodiimide: 1 to 5; a pore forming agent: 5 to 15 percent;

in step S16, the second-order isocyanate-based prepolymer comprises the following components in parts by mass: 50 to 60; phase change particles: 20 to 30 percent; ethyl acetate: 20 to 30 percent; a pore forming agent: 10 to 20;

in step S17, spinning into a sheath liquid by the following components in parts by mass: 15; spinning core liquid: 20.

6. the method for preparing polyurethane sponge for mop as claimed in claim 3, wherein the nano-attapulgite in step S11 and step S3 is subjected to activation modification, and the activation modification comprises the following steps:

step S111, grinding and sieving the attapulgite to obtain nano attapulgite with the particle size of 400-600;

step S112, placing the nano-attapulgite obtained in the step S111 into an arc plasma generator, carrying out plasma treatment for 5-10 minutes under the direct-current voltage of 30-50 kV, adding the nano-attapulgite into deionized water, carrying out ultrasonic cleaning, and drying to obtain activated nano-attapulgite;

and S113, adding the activated nano-attapulgite obtained in the step S112 into a dilute hydrochloric acid solution, ultrasonically dispersing for 1 hour at 65-75 ℃, under the conditions of ultrasonic power of 200-500W and ultrasonic frequency of 20-25 kHz, then dropwise adding a sodium hydroxide solution, adjusting the pH value to 4-5, adding a silane coupling agent, continuously ultrasonically dispersing for 1-2 hours, washing, filtering and drying to obtain the activated and modified nano-attapulgite.

7. The method for preparing a polyurethane sponge for a mop according to claim 6,

in step S112, the nano-attapulgite comprises the following components in parts by mass: 1; deionized water: 10 to 20;

in step S113, the nano-attapulgite is activated as follows in parts by mass: 1; dilute hydrochloric acid solution: 2 to 3; the concentration of the dilute hydrochloric acid solution is 0.5 to 1 weight percent; the concentration of the sodium hydroxide solution is 10-15 wt%.

8. A polyurethane sponge for mops, which is prepared by the method for preparing a polyurethane sponge for mops according to claim 1, and which comprises:

the polyurethane sponge matrix is internally and uniformly dispersed with nano attapulgite; the nano attapulgite accounts for 3.5 to 7 weight percent of the polyurethane sponge matrix;

the tough framework is a net structure woven by polyurethane porous fibers and is embedded in the polyurethane sponge matrix, the polyurethane porous fibers contain a phase-change material, and the tough framework accounts for 5-10 wt% of the polyurethane sponge matrix;

the connecting piece is detachably connected with the mop rod, and the connecting piece and the polyurethane sponge matrix are integrally formed during molding.

9. The polyurethane sponge as claimed in claim 8, wherein the phase-change material is supported on the nano-attapulgite/nano-fiber modified mixture to form phase-change particles, and the phase-change particles are supported in the polyurethane porous fibers; wherein the diameter of the nanofiber is 500-1000 nm, and the length-diameter ratio is 200-500; the particle size of the nano attapulgite is 400-600 nm.

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