Ultralight material, preparation method thereof and application of ultralight material in shoe material

Abstract

The invention discloses an ultralight material, a preparation method thereof and application of the ultralight material in a shoe material, and belongs to the technical field of materials.The shoe material prepared through the method comprises polyether glycol, isophorone diisocyanate, a functional chain extender, dibutyltin dilaurate, modified hollow glass beads and trifluoromethanesulfonic acid; the functional chain extender is obtained by reacting 3-hexene-1, 6-diol with phenylphosphonic dichloride and then reacting with heptamethylcyclotetrasiloxane; the modified hollow glass beads are obtained by polymerizing isoprene and 1-(4-vinyl-phenyl)-ethanone on the surfaces of pretreated hollow glass beads and then reacting with diethyl oxalate and 2-amino-5-(2-chlorphenyl)-1, 3, 4-thiadiazole; the ultralight material prepared by the invention has excellent anti-aging, flame-retardant and antibacterial properties, and has a wide application prospect in the field of shoe materials.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of materials, and particularly relates to an ultralight material and a preparation method thereof and application of the ultralight material in shoe materials. BACKGROUND

[0002] The shoe sole material is usually made of rubber, EVA (ethylene-vinyl acetate copolymer), polyurethane (PU), thermoplastic polyurethane (TPU) and thermoplastic rubber (TPR) and the like. The polyurethane is widely used in the fields of sports shoes, casual shoes and protective shoes due to its unique performance. The polyurethane shoe sole has the characteristics of low density, soft texture, good elasticity, strong wear resistance and excellent chemical resistance, and can provide good shock absorption, anti-skid and cushioning effect. At the same time, the light weight characteristic significantly reduces the weight of the shoe body and improves the wearing comfort.

[0003] However, the polyurethane material in the prior art still has many deficiencies, for example, it is prone to yellowing and mechanical performance decline, and is prone to aging due to oxidation, ultraviolet radiation or hot and humid environment after long-term use, thereby shortening the service life. In addition, the polyurethane material is prone to generate heat under high temperature or friction conditions and has a risk of combustion, and the lack of flame retardant performance may affect the safety protection function. At the same time, the shoe sole is in long-term contact with the foot and is prone to bacterial growth, which causes odor and foot health problems, and the existing material has insufficient antibacterial performance and cannot meet the health demand. Therefore, developing an ultralight material with anti-aging, flame-retardant and antibacterial performance has become a key direction of shoe sole material research. SUMMARY

[0004] This section aims to summarize some aspects of the embodiments of the present application and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the abstract and title of the specification to avoid obscuring the purpose of this section, abstract and title, and such simplifications or omissions cannot be used to limit the scope of the present application.

[0005] In view of the above and / or problems existing in the prior art, the present application is proposed.

[0006] Therefore, the purpose of the present application is to overcome the deficiencies in the prior art and provide a preparation method of an ultralight material.

[0007] To solve the above technical problems, the present application provides the following technical solutions:

[0008] A preparation method of an ultralight material, comprising the following preparation steps,

[0009] 1) reacting 3-hexene-1,6-diol and phenylphosphonic dichloride to obtain a functional chain extender precursor; and reacting the functional chain extender precursor and heptamethylcyclotetrasiloxane to obtain a functional chain extender;

[0010] 2) reacting the pretreated hollow glass microspheres, isoprene, and 1-(4-vinyl-phenyl)- ethanone to obtain pre-modified hollow glass microspheres;

[0011] 3) reacting the pre-modified hollow glass microspheres, diethyl oxalate, and 2-amino-5-(2- chlorophenyl)-1,3,4-thiadiazole to obtain modified hollow glass microspheres;

[0012] 4) weighing the following components: polyether diol, isophorone diisocyanate, functional chain extender, dibutyltin dilaurate, modified hollow glass microspheres, trifluoromethanesulfonic acid, and acetone; mixing and curing the above components to obtain the ultra-light material.

[0013] As an optimization, the preparation method of the functional chain extender in step 1) is as follows: mixing 3-hexene-1,6-diol, phenyl phosphinic dichloride, and N,N-dimethylaniline, heating to 120-130℃ for 8-10h, after the reaction is completed, using acetone to dissolve the product, using 10wt% sodium bicarbonate solution to adjust the pH to 7, precipitating the crude product at 0-4℃, redissolving, cooling, and crystallizing the crude product in 60-80℃ methanol to obtain the functional chain extender precursor; mixing the functional chain extender precursor, heptamethylcyclo-tetrasiloxane, Karstedt catalyst, and toluene, heating to 100-110℃ for 4-6h to obtain the functional chain extender.

[0014] As an optimization, the molar ratio of 3-hexene-1,6-diol, phenyl phosphinic dichloride, and N,N-dimethylaniline is (2.1-2.2):1:(3.1-3.2); the molar ratio of the functional chain extender precursor and heptamethylcyclo-tetrasiloxane is (1.1-1.2):1; the mass ratio of the functional chain extender precursor, Karstedt catalyst, and toluene is 1:(0.001-0.002):(10-12).

[0015] As an optimization, the preparation method of the pre-modified hollow glass microspheres in step 2) is as follows: uniformly dispersing the hollow glass microspheres in an ethanol / water solution, adding 3-mercaptopropyltrimethoxysilane, using sulfuric acid to adjust the pH of the solution to 3-4, heating to 70-80℃ for 5-6h to obtain the pretreated hollow glass microspheres; the mass ratio of the hollow glass microspheres, 3-mercaptopropyltrimethoxysilane, and the ethanol / water solution is 1:(0.5-1.0):(20-30);

[0016] The pretreated hollow glass microspheres are uniformly dispersed in toluene with 25-35 times of the mass of the hollow glass microspheres to obtain a dispersion liquid; isoprene is dissolved in toluene with 5-6 times of the mass of the isoprene, under the protection of nitrogen, the dispersion liquid, half of the azobisisobutyronitrile are added, after mixing at 60-70 DEG C for 4-5h, the remaining azobisisobutyronitrile and 1-(4-vinyl-phenyl)-ethanone are added, and the reaction is continued for 4-5h, then 0.2% of the photoinitiator benzoin dimethyl ether by mass of the pretreated hollow glass microspheres is added, and after stirring in the dark for 1h, the solvent is volatilized by pouring into a culture dish, and after irradiation for 30-40min by a 365nm ultraviolet lamp (intensity 80mW / cm 2 , distance 15cm), the pre-modified hollow glass microspheres are prepared; the mass ratio of the pretreated hollow glass microspheres, isoprene, 1-(4-vinyl-phenyl)-ethanone and azobisisobutyronitrile is 1:(0.6-0.8):(0.2-0.4):(0.003-0.005).

[0017] As an optimization, the preparation method of the modified hollow glass microspheres in step 3) is as follows: the pre-modified hollow glass microspheres, diethyl oxalate, 2-amino-5-(2-chlorophenyl)-1,3,4-thiadiazole, an alkaline catalyst and N-methyl pyrrolidone are uniformly mixed, and the modified hollow glass microspheres are obtained by reaction under microwave irradiation.

[0018] As an optimization, the mass ratio of the pre-modified hollow glass microspheres, diethyl oxalate, 2-amino-5-(2-chlorophenyl)-1,3,4-thiadiazole, an alkaline catalyst and N-methyl pyrrolidone is 1:(0.2-0.3):(0.2-0.3):(0.3-0.5):(20-30).

[0019] As an optimization, the amounts of the components in step 4) are as follows: 100 parts of polyether diol, 17-23 parts of isophorone diisocyanate, 15-20 parts of functional chain extender, 0.1-0.3 parts of dibutyltin dilaurate, 20-30 parts of modified hollow glass microspheres, 0.5-1.0 parts of trifluoromethanesulfonic acid and 100-150 parts of acetone.

[0020] As an optimization, the preparation method of the ultralight material in step 4) is as follows: isophorone diisocyanate, polyether diol and dibutyltin dilaurate are uniformly mixed, stirred at 70-80 DEG C under a nitrogen atmosphere for 3-4h, the solvent acetone is added, after uniform stirring, the functional chain extender is added and reacted for 1-2h, and then trifluoromethanesulfonic acid and modified hollow glass microspheres are added and uniformly mixed under 2000rpm; the ultralight material is obtained by pouring into a mold and solidifying.

[0021] The application further provides an ultralight material prepared by the preparation method.

[0022] The application further provides an application of the ultralight material in shoe materials.

[0023] The present application has the following advantages:

[0024] In the preparation of the ultra-light material, first, 3-hexene-1,6-diol and phenyl phosphinic dichloride are reacted to generate a functional chain extender precursor with alcohol hydroxyl groups at both ends by controlling the molar ratio, and the silicon-hydrogen addition reaction occurs between heptamethylcyclosiloxane and the alkenyl group on 3-hexene-1,6-diol under the action of a catalyst, thereby introducing cyclosiloxane on the functional chain extender; the functional chain extender forms an urethane bond by the reaction of the active hydroxyl group in the molecule with the isocyanate group (-NCO) of the polyurethane prepolymer, realizing molecular chain extension and crosslinking network strengthening, at the same time, the phosphorus element in the functional chain extender catalyzes dehydration to form a dense barrier layer when burning, giving the material good flame retardant performance; and the cyclosiloxane chain is ring-opened in the presence of an acid catalyst during the synthesis of polyurethane, crosslinking to form a flexible siloxane segment in the polyurethane molecular chain, and the presence of the siloxane segment can give the material good hydrophobic properties, and the crosslinking network significantly improves the toughness of the material;

[0025] Secondly, hollow glass microspheres are a new type of inorganic functional material, and the main component is borosilicate. Hollow glass microspheres have a regular spherical shape, good fluidity, and a particle size in the micron level; the physical and chemical properties are very stable, and the stable hollow structure makes hollow glass microspheres become an ideal lightweight filler, and the surface of the glass microspheres contains mercapto groups after treatment with mercapto silane coupling agent; in the initial stage of the reaction, mercapto groups preferentially undergo mercapto-alkene click reaction with the double bonds of isoprene to anchor the monomer on the surface of the microspheres, and then the remaining isoprene monomer and 1-(4-vinyl-phenyl)-ethanone are polymerized by free radicals to form a crosslinked / linear elastomer network containing ketone groups on the surface of the microspheres; the addition of a photoinitiator is to polymerize the residual monomers on the surface of the microspheres again to ensure the fullness of the reaction and ensure that the elastomer can completely wrap the microspheres; the elastomer-wrapped microspheres build a flexible transition interface between the microspheres and the polyurethane matrix, and the elastomer layer effectively buffers external force impact and uniformly disperses stress, so that the microspheres are transformed from brittle points prone to stress concentration to energy dissipation units, enhancing the impact resistance of the material;

[0026] The 1-(4-vinyl-phenyl)-ethanone, diethyl oxalate, 2-amino-5-(2-chlorophenyl)-1,3,4-thiadiazole are reacted by a one-pot method; the amino of 2-aminothiadiazole attacks the carbonyl carbon of diethyl oxalate to form an intermediate, in the presence of a strong base, the alpha-hydrogen of 1-(4-vinyl-phenyl)-ethanone is deprotonated to form a carbanion, which attacks the carbonyl carbon of the intermediate to undergo Claisen condensation, and is dehydrated under microwave conditions to form a conjugated enone (chalcone) structure, generating an imidazothiadiazole ring; the conjugated enone system in the molecular structure of the chalcone efficiently absorbs ultraviolet light through π→π* transition and intramolecular charge transfer, converts light energy into heat energy, and releases heat, thereby imparting good ultraviolet aging resistance to the material.

[0027] The aminothiadiazole is condensed with the carbonyl group to form an imidazothiadiazole ring containing an ortho-chloro substituent, and the ortho-chloro substituent reduces the electron density of the molecule through an inductive effect, enhances the ability to penetrate bacterial cell membranes, and the imidazothiadiazole ring contains multiple electronegative nitrogen atoms, which can further reduce the electron density and improve the antibacterial activity. As an active unit, the ring can impart good antibacterial properties to the material.

[0028] The experimental principle of the one-pot method is as follows:

[0029] DETAILED DESCRIPTION

[0030] In order to make the above-mentioned purposes, features and advantages of the present application more apparent and easy to understand, the specific embodiments of the present application will be described in detail below with reference to the embodiments of the present application.

[0031] In the following description, a large number of specific details are set forth in order to provide a thorough understanding of the present application, but the present application can also be implemented in other ways different from the description, and those skilled in the art can make similar extensions without departing from the connotation of the present application, therefore the present application is not limited by the specific embodiments disclosed below.

[0032] Secondly, the "one embodiment" or "embodiment" referred to herein means that a specific feature, structure or characteristic can be included in at least one implementation of the present application. "In one embodiment" appearing in different places in this specification does not mean the same embodiment, nor does it mean an embodiment that is separate or selectively excluded from other embodiments.

[0033] The hollow glass microbeads used in the present application are HN60, purchased from Shanxi Hainuo Technology Co., Ltd.; the polyether diol has a molecular weight of 1000; the base catalyst DBU is 1,8-diazabicyclo[5.4.0]undec-7-ene.

[0034] Example 1 provides a preparation method of a super-light material, specifically:

[0035] 1) 3-hexene-1,6-diol, benzenephosphonic dichloride, N,N-dimethylaniline were mixed and heated to 130℃ for 10h. After the reaction, the product was dissolved in acetone and the pH was adjusted to 7 using 10wt% sodium bicarbonate solution. The crude product was precipitated by cold water at 4℃, and then redissolved in methanol at 80℃, cooled and crystallized to obtain the functional chain extender precursor. The molar ratio of 3-hexene-1,6-diol, benzenephosphonic dichloride, N,N-dimethylaniline was 2.1:1:3.1;

[0036] The functional chain extender precursor, heptamethylcyclotetrasiloxane, Karstedt catalyst platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, toluene were mixed and heated to 110℃ for 6h. The crude product was obtained by rotary evaporation under reduced pressure, and then purified by silica gel column (eluent: petroleum ether / ethyl acetate = 1:1 (v / v)) and dried to obtain the functional chain extender. The molar ratio of the functional chain extender precursor, heptamethylcyclotetrasiloxane was 1.1:1. The mass ratio of the functional chain extender precursor, Karstedt catalyst, toluene was 1:0.001:10;

[0037] 2) Hollow glass microspheres were uniformly dispersed in an ethanol / water solution (ethanol / water = 4:1 (v / v)), and 3-mercaptopropyltrimethoxysilane was added. The pH of the solution was adjusted to 4 using 20% molar fraction of dilute sulfuric acid, and then heated to 80℃ for 6h. The pretreated hollow glass microspheres were obtained by filtration, washing and drying. The mass ratio of hollow glass microspheres, 3-mercaptopropyltrimethoxysilane, ethanol / water solution was 1:0.5:20;

[0038] The pretreated hollow glass microspheres were uniformly dispersed in toluene with a mass of 25 times that of the pretreated hollow glass microspheres to obtain a dispersion liquid. Isoprene was dissolved in toluene with a mass of 5 times that of the isoprene. Under nitrogen protection, the dispersion liquid, half of the azobisisobutyronitrile, the remaining azobisisobutyronitrile and 1-(4-vinyl-phenyl)-ethanone were added and mixed at 70℃ for 5h. Then, 0.2% of the photoinitiator benzoin dimethyl ether based on the mass of the pretreated hollow glass microspheres was added. After stirring in the dark for 1h, the solvent was volatilized by pouring into a petri dish. After completion, it was irradiated with a 365nm ultraviolet lamp (intensity 80mW / cm 2 , distance 15cm) for 40min. After washing and drying, the pre-modified hollow glass microspheres were obtained. The mass ratio of the pretreated hollow glass microspheres, isoprene, 1-(4-vinyl-phenyl)-ethanone, azobisisobutyronitrile was 1:0.6:0.2:0.003;

[0039] 3) ultrasonic mixing of the pre-modified hollow glass microspheres, diethyl oxalate, 2-amino-5-(2-chlorophenyl)-1,3,4-thiadiazole, base catalyst DBU, N-methyl pyrrolidone, reaction under microwave irradiation (one stage 80℃, 100W, 10min; two stages 130℃, 250W, 15min), cooling to 50℃, filtering, washing and drying in sequence with N,N-dimethylformamide, tetrahydrofuran, diethyl ether to obtain modified hollow glass microspheres; the mass ratio of the pre-modified hollow glass microspheres, diethyl oxalate, 2-amino-5-(2-chlorophenyl)-1,3,4-thiadiazole, base catalyst DBU, N-methyl pyrrolidone is 1:0.2:0.2:0.3:20;

[0040] 4) weighing the following components: by mass fraction, polyether diol 100 parts, isophorone diisocyanate 17 parts, functional chain extender 15 parts, dibutyltin dilaurate 0.1 parts, modified hollow glass microspheres 20 parts, trifluoromethanesulfonic acid 0.5 parts, acetone 100 parts;

[0041] Mixing isophorone diisocyanate, polyether diol, dibutyltin dilaurate, stirring at 80℃ for 4h under nitrogen atmosphere, adding solvent acetone, stirring uniformly, then adding functional chain extender and reacting for 2h, adding trifluoromethanesulfonic acid and modified hollow glass microspheres under 2000rpm; pouring into a preheated mold at 60℃ for stepwise temperature rise and curing to obtain the material, heating at 60℃ for 1h, heating at 80℃ for 3h, heating at 100℃ for 1h, demolding and heat treating at 100℃ for 2h to obtain the ultra-light material.

[0042] Example 2 provides a preparation method of an ultra-light material, in particular:

[0043] 1) mixing 3-hexene-1,6-diol, phenyl phosphinic dichloride and N,N-dimethylaniline, heating to 125℃ and reacting for 9h, after the reaction, using acetone to dissolve the product, using 10wt% sodium bicarbonate solution to adjust the pH to 7, precipitating the crude product with 3℃ cold water, redissolving, cooling and crystallizing the functional chain extender precursor by filtering and drying; the molar ratio of 3-hexene-1,6-diol, phenyl phosphinic dichloride and N,N-dimethylaniline is 2.15:1:3.15;

[0044] The functional chain extender precursor, heptamethylcyclotetrasiloxane, and toluene were mixed, heated to 105°C for 5h, and then rotary evaporated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column (eluent: petroleum ether / ethyl acetate = 1:1 (v / v)) and dried to obtain the functional chain extender. The molar ratio of the functional chain extender precursor to heptamethylcyclotetrasiloxane was 1.15:1. The mass ratio of the functional chain extender precursor, the Caster catalyst, and toluene was 1:0.001:11.

[0045] 2) The hollow glass microbeads were uniformly dispersed in an ethanol / water solution (ethanol / water = 4:1 (v / v)), 3-mercaptopropyltrimethoxysilane was added, and the pH of the solution was adjusted to 3.5 using 20% molar fraction of dilute sulfuric acid. After being heated to 75°C for 5.5h, the pretreated hollow glass microbeads were obtained by filtration, washing, and drying. The mass ratio of the hollow glass microbeads, 3-mercaptopropyltrimethoxysilane, and the ethanol / water solution was 1:0.7:25.

[0046] The pretreated hollow glass microbeads were uniformly dispersed in toluene with a mass of 30 times that of the pretreated hollow glass microbeads to obtain a dispersion liquid. Isoprene was dissolved in toluene with a mass of 5.5 times that of the isoprene. Under the protection of nitrogen, the dispersion liquid and half of the azobisisobutyronitrile were added, and after being mixed at 65°C for 4.5h, the remaining azobisisobutyronitrile and 1-(4-vinyl-phenyl)-ethanone were added, and the reaction was continued for 4.5h. Then, 0.2% of the photoinitiator benzoin dimethyl ether based on the mass of the pretreated hollow glass microbeads was added, and after being stirred in the dark for 1h, the solvent was volatilized by pouring into a petri dish. After irradiation with a 365nm ultraviolet lamp (intensity 80mW / cm 2 , distance 15cm) for 35min, the pre-modified hollow glass microbeads were obtained by washing and drying. The mass ratio of the pretreated hollow glass microbeads, isoprene, 1-(4-vinyl-phenyl)-ethanone, and azobisisobutyronitrile was 1:0.7:0.3:0.004.

[0047] 3) The pre-modified hollow glass microbeads, diethyl oxalate, 2-amino-5-(2-chlorophenyl)-1,3,4-thiadiazole, the base catalyst DBU, and N-methylpyrrolidone were uniformly mixed by ultrasonic. The reaction was carried out under microwave irradiation (one stage 80°C, 100W, 10min; two stages 130°C, 250W, 15min). After being cooled to 50°C, the modified hollow glass microbeads were obtained by filtration, washing with N,N-dimethylformamide, tetrahydrofuran, and diethyl ether, and drying. The mass ratio of the pre-modified hollow glass microbeads, diethyl oxalate, 2-amino-5-(2-chlorophenyl)-1,3,4-thiadiazole, the base catalyst DBU, and N-methylpyrrolidone was 1:0.25:0.25:0.4:25.

[0048] 4) Take the following components: by mass fraction, polyether diol 100 parts, isophorone diisocyanate 20 parts, functional chain extender 17 parts, dibutyltin dilaurate 0.2 parts, modified hollow glass microsphere 25 parts, trifluoromethanesulfonic acid 0.7 parts, acetone 120 parts;

[0049] Mix isophorone diisocyanate, polyether diol, and dibutyltin dilaurate, stir at 75℃ for 3.5h under nitrogen atmosphere, add solvent acetone, stir uniformly, then add functional chain extender and react for 1.5h, add trifluoromethanesulfonic acid and modified hollow glass microsphere under 2000rpm; pour into a preheated mold at 60℃, step up the temperature for curing, get the material, heat at 60℃ for 1h, heat at 80℃ for 3h, heat at 100℃ for 1h, after demolding, heat treat at 100℃ for 2h, get the ultra-light material.

[0050] Example 3, the embodiment provides a preparation method of an ultra-light material, in particular:

[0051] 1) Mix 3-hexene-1,6-diol, phenyl phosphinic dichloride, and N,N-dimethylaniline, heat to 120℃ for 8h, after the reaction, dissolve the product with acetone, adjust the pH to 7 with 10wt% sodium bicarbonate solution, precipitate the crude product at 0℃ cold water, then redissolve, cool, crystallize, filter and dry to get the functional chain extender precursor; the molar ratio of 3-hexene-1,6-diol, phenyl phosphinic dichloride, and N,N-dimethylaniline is 2.2:1:3.2;

[0052] Mix the functional chain extender precursor, heptamethylcyclotetrasiloxane, and platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, and toluene, heat to 100℃ for 4h, then rotary evaporation under reduced pressure to get the crude product, purify and dry by silica gel column (eluent: petroleum ether / ethyl acetate = 1:1(v / v)) to get the functional chain extender; the molar ratio of the functional chain extender precursor and heptamethylcyclotetrasiloxane is 1.2:1; the mass ratio of the functional chain extender precursor, platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, and toluene is 1:0.002:12;

[0053] 2) Disperse the hollow glass microspheres uniformly in an ethanol / water solution (ethanol / water = 4:1(v / v)), add 3-mercaptopropyltrimethoxysilane, adjust the pH of the solution to 3 with 20% molar fraction of dilute sulfuric acid, heat to 70℃ for 5h, then filter, wash and dry to get the pretreated hollow glass microspheres; the mass ratio of the hollow glass microspheres, 3-mercaptopropyltrimethoxysilane, and ethanol / water solution is 1:1.0:30;

[0054] The pretreated hollow glass microspheres were uniformly dispersed in toluene with 35 times of the mass of the hollow glass microspheres to obtain a dispersion liquid; isoprene was dissolved in toluene with 6 times of the mass of the isoprene, and then the dispersion liquid, half of the azobisisobutyronitrile were added under nitrogen protection; after mixing at 60°C for 4h, the remaining azobisisobutyronitrile and 1-(4-vinyl-phenyl)-ethanone were added, and the reaction was continued for 4h; 0.2% of the photoinitiator benzoin dimethyl ether by mass of the pretreated hollow glass microspheres was added, and the mixture was stirred in the dark for 1h; then the solvent was volatilized by pouring the mixture into a culture dish; after completion, the modified hollow glass microspheres were obtained by irradiation with a 365nm ultraviolet lamp (intensity 80mW / cm 2 , distance 15cm) for 30min, and then washed and dried.

[0055] The mass ratio of the pretreated hollow glass microspheres, isoprene, 1-(4-vinyl-phenyl)-ethanone and azobisisobutyronitrile was 1:0.8:0.4:0.005.

[0056] 3) The pretreated hollow glass microspheres, diethyl oxalate, 2-amino-5-(2-chlorophenyl)-1,3,4-thiadiazole, base catalyst DBU and N-methyl pyrrolidone were uniformly mixed by ultrasonic, and then reacted under microwave irradiation (one stage 80°C, 100W, 10min; two stages 130°C, 250W, 15min); after cooling to 50°C, the modified hollow glass microspheres were obtained by filtration, washing with N,N-dimethylformamide, tetrahydrofuran and diethyl ether in sequence and drying; the mass ratio of the pretreated hollow glass microspheres, diethyl oxalate, 2-amino-5-(2-chlorophenyl)-1,3,4-thiadiazole, base catalyst DBU and N-methyl pyrrolidone was 1:0.3:0.3:0.5:30.

[0057] 4) The following components were weighed: 100 parts of polyether diol, 23 parts of isophorone diisocyanate, 20 parts of functional chain extender, 0.3 parts of dibutyltin dilaurate, 30 parts of modified hollow glass microspheres, 1.0 parts of triflic acid, and 150 parts of acetone;

[0058] The isophorone diisocyanate, polyether diol and dibutyltin dilaurate were uniformly mixed, and then stirred at 70°C for 3h under nitrogen atmosphere; the solvent acetone was added, and then the functional chain extender was added after uniform stirring for 1h; the triflic acid and modified hollow glass microspheres were uniformly mixed under 2000rpm; the material was obtained by pouring the mixture into a preheated mold at 60°C and stepwise temperature rising and solidification; the material was heated at 60°C for 1h, at 80°C for 3h and at 100°C for 1h; after demolding, the ultralight material was obtained by heat treatment at 100°C for 2h.

[0059] Comparative Example 1, the difference between this comparative example and Example 2 is that it does not contain a functional chain extender, specifically, it does not contain step (1), and step (4) is modified as follows: isophorone diisocyanate, polyether diol, dibutyltin dilaurate are mixed, stirred at 75°C for 3.5h under nitrogen atmosphere, solvent acetone is added, after stirring uniformly, functional chain extender is added and stirred at 2000rpm; pour into a preheated mold at 60°C, stepwise temperature rise curing, get the material, heated at 60°C for 1h, heated at 80°C for 3h, heated at 100°C for 1h, after demolding, heat treatment at 100°C for 2h, get the ultra-light material. The rest of the steps are the same as Example 2.

[0060] Comparative Example 2, the difference between this comparative example and Example 2 is that it uses a functional chain extender precursor as a functional chain extender, specifically, step (1) is modified as follows: 3-hexene-1,6-diol, phenyl phosphinic dichloride, N,N-dimethylaniline are mixed, heated to 125°C and reacted for 9h, after the reaction is completed, the product is dissolved using acetone, and 10wt% sodium bicarbonate solution is used to adjust the pH to 7, the crude product is precipitated out by 3°C cold water, and then re-dissolved in 70°C methanol, cooled, crystallized, filtered and dried to obtain the functional chain extender; the molar ratio of 3-hexene-1,6-diol, phenyl phosphinic dichloride, N,N-dimethylaniline is 2.15:1:3.15.

[0061] Step (4) is modified as follows: isophorone diisocyanate, polyether diol, dibutyltin dilaurate are mixed, stirred at 75°C for 3.5h under nitrogen atmosphere, solvent acetone is added, after stirring uniformly, functional chain extender is added and stirred for 1.5h, modified hollow glass microspheres are added at 2000rpm; pour into a preheated mold at 60°C, stepwise temperature rise curing, get the material, heated at 60°C for 1h, heated at 80°C for 3h, heated at 100°C for 1h, after demolding, heat treatment at 100°C for 2h, get the ultra-light material.

[0062] Comparative Example 3, the difference between this comparative example and Example 2 is that the pre-modified hollow glass microspheres are not modified: specifically, it does not contain step (3), and step (4) is modified as follows: isophorone diisocyanate, polyether diol, dibutyltin dilaurate are mixed, stirred at 75°C for 3.5h under nitrogen atmosphere, solvent acetone is added, after stirring uniformly, functional chain extender is added and stirred for 1.5h, triflic acid and pre-modified hollow glass microspheres are added at 2000rpm; pour into a preheated mold at 60°C, stepwise temperature rise curing, get the material, heated at 60°C for 1h, heated at 80°C for 3h, heated at 100°C for 1h, after demolding, heat treatment at 100°C for 2h, get the ultra-light material.

[0063] Test Example 1, test of flame retardant performance, according to GB / T 2406.1-2008, test the limiting oxygen index, the sample size is 120mmx6mmx4mm. The results are shown in Table 1.

[0064] Table 1

[0065] LOI (%) LOI (%) Example 1 31.5 Comparative Example 1 24.0 Example 2 31.8 Comparative Example 2 27.8 Example 3 32.2 Comparative Example 3 28.5

[0066] As can be seen from Table 1, the material prepared by the present application has good flame retardant performance, which is due to the fact that in the preparation of the ultra-light material, 3-hexene-1, 6-diol is reacted with phenylphosphonic dichloride to generate a functional chain extender precursor with alcohol hydroxyl groups at both ends by controlling the molar ratio, and the silicon-hydrogen addition reaction of heptamethylcyclotetrasiloxane under the action of a catalyst and the alkenyl group on 3-hexene-1, 6-diol to obtain a functional chain extender, the phosphorus element in the functional chain extender catalyzes dehydration to form a dense barrier layer when burning, which gives the material good flame retardant performance. This feature is crucial for shoe materials, especially for work safety shoes, fire boots, children's shoes and sports shoes or outdoor shoes that pay attention to fire safety. It can significantly improve the flame retardant grade of the shoe product, delay the flame spread speed, provide valuable escape time for the wearer when accidental fire contact, and meet strict shoe safety standards.

[0067] Test Example 2, test of antibacterial performance, according to GB / T 20944—2008, the antibacterial performance of the material was tested by the oscillation method, and the bacteria used for testing was gram-negative bacteria Escherichia coli (ATCC 8099). The results are shown in Table 2.

[0068] Table 2

[0069] Antibacterial rate (%) Antibacterial rate (%) Example 1 96.5 Comparative Example 1 87.3 Example 2 97.1 Comparative Example 2 91.7 Example 3 97.7 Comparative Example 3 35.6

[0070] As can be seen from Table 2, the material prepared by the application has good antibacterial performance, which is due to the fact that in the preparation of the ultra-light material, 1-(4-vinyl-phenyl)-ethanone, diethyl oxalate and 2-amino-5-(2-chlorophenyl)-1,3,4-thiadiazole are reacted by one-pot method; the amino group of 2-aminothiadiazole attacks the carbonyl carbon of diethyl oxalate to form an intermediate; in the presence of a strong base, the alpha-hydrogen of 1-(4-vinyl-phenyl)-ethanone is deprotonated to form a carbon anion, which attacks the carbonyl carbon of the intermediate to undergo Claisen condensation, and then dehydrates under microwave conditions to form a conjugated enone (chalcone) structure and an imidazothiadiazole ring; the ring contains an ortho-chloro substituent, which reduces the electron density of the molecule by induction effect and enhances the ability to penetrate the bacterial cell membrane; the imidazothiadiazole ring contains multiple electronegative nitrogen atoms, which can further reduce the electron density and improve the antibacterial activity; the ring as an active unit can endow the material with good antibacterial performance; when the material is applied to insole, insole, upper material, the special performance can effectively inhibit the breeding of common bacteria (such as staphylococcus and bacillus which cause odor) and fungi (such as mold which causes athlete's foot) in the shoe environment. This not only significantly reduces the odor in the shoe, keeps the shoe environment fresh and clean, but also reduces the risk of foot health caused by bacterial infection (such as athlete's foot and dermatitis), greatly improves the wearing comfort and health properties of the shoe.

[0071] Test Example 3, the mechanical properties were tested according to the standard GB / T 1040.2-2006 to test the tensile strength of the material; the material prepared in the examples and comparative examples was cut into dumbbell-shaped strips, and the dumbbell-shaped strips were I-shaped samples; a universal testing machine was used to perform tensile test at a speed of 50 mm / min. The results are shown in Table 3.

[0072] The anti-aging performance was tested by cutting the material prepared in the examples and comparative examples into dumbbell-shaped strips, and the dumbbell-shaped strips were I-shaped samples, which were placed in an ultraviolet light accelerated aging box and irradiated by a 200W mercury light source for 360h; the aged samples were tested according to the mechanical property test method, and the tensile strength retention rate before and after aging was calculated; the results are shown in Table 3.

[0073] Table 3

[0074]

[0075]

[0076] As can be seen from table 3, the material prepared by the application has good mechanical properties and anti-aging performance, which is due to the fact that, in the preparation of the ultra-light material, first, 3-hexene-1,6-diol and phenyl phosphinic dichloride are reacted to generate a functional chain extender precursor with alcohol hydroxyl groups at both ends by controlling the molar ratio, and then, under the action of a catalyst, a silicon-hydrogen addition reaction occurs between heptamethylcyclosiloxane and the alkenyl group on 3-hexene-1,6-diol, so as to introduce cyclosiloxane on the functional chain extender; the functional chain extender reacts with the isocyanate group (-NCO) of the polyurethane prepolymer through the active hydroxyl group in the molecule to form an urethane bond, so as to realize molecular chain extension and crosslinking network strengthening, and the cyclosiloxane chain is opened in the presence of an acid catalyst in the synthesis process of the polyurethane, and is crosslinked to form a flexible siloxane segment in the polyurethane molecular chain; the presence of the siloxane segment can endow the material with good hydrophobic properties, and the crosslinking network can significantly improve the toughness of the material; as a sole material (midsole, outsole) or an upper material (such as sports shoes, casual shoes) that needs to bear repeated bending, this characteristic endows the shoes with excellent tear resistance, impact resistance and bending resistance, effectively resists wear and deformation in daily wear and sports, and greatly prolongs the service life of the shoes.

[0077] 1-(4-vinyl-phenyl)-ethanone, diethyl oxalate and 2-amino-5-(2-chlorophenyl)-1,3,4-thiadiazole are reacted by a one-pot method; the amino group of 2-aminothiadiazole attacks the carbonyl carbon of diethyl oxalate to form an intermediate; in the presence of a strong base, the alpha-hydrogen of 1-(4-vinyl-phenyl)-ethanone is deprotonated to form a carbon anion, which attacks the carbonyl carbon of the intermediate to undergo Claisen condensation, and then, under microwave conditions, dehydration forms a conjugated enone (chalcone) structure and an imidazothiadiazole ring; the conjugated enone system in the molecular structure of the chalcone efficiently absorbs ultraviolet light through π→π* transition and intramolecular charge transfer, converts light energy into heat energy and releases it, and endows the material with good anti-ultraviolet aging performance; this characteristic enables the shoe material (especially the upper and the upper part exposed to sunlight) to have excellent anti-ultraviolet aging ability. It can effectively prevent the material from fading, yellowing, surface powdering, embrittlement and strength reduction due to long-term sun exposure. It can maintain the bright and long-lasting appearance of the shoes, and at the same time, maintain the long-term stability of the mechanical properties and protective properties (such as water resistance and toughness) of the shoes, and ensure that the shoes maintain good functionality and aesthetics throughout their life cycle;

[0078] The ultra-light material prepared by the application has multiple core functions such as flame retardation, antibiosis and strong anti-ultraviolet aging, which are perfectly combined through ingenious molecular design; these characteristics perfectly meet the core needs of modern shoe materials for safety, hygiene, durability, appearance durability and lightness and comfort. The material provides an ideal material solution for the development of a new generation of high-performance, multi-functional, high-value safety shoes, sports shoes, outdoor shoes, casual shoes and daily shoes that pay attention to health and hygiene, and has a broad market application prospect.

[0079] It should be noted that the above examples are only used to illustrate the technical solutions of the present application but not to limit the present application. Although the present application is described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or equivalently replaced, without departing from the spirit and scope of the technical solutions of the present application, which should be covered in the scope of the claims of the present application.

Claims

1. A method for preparing an ultralight material, characterized in that: The method comprises the following preparation steps: 1) reacting 3-hexene-1,6-diol and phenylphosphonyl dichloride to obtain a functional chain extender precursor; reacting the functional chain extender precursor and heptamethylcyclotetrasiloxane to obtain a functional chain extender; 2) reacting the pretreated hollow glass microspheres, isoprene, and 1-(4-vinyl-phenyl)-ethanone to obtain pre-modified hollow glass microspheres; 3) reacting the pre-modified hollow glass microspheres, diethyl oxalate, and 2-amino-5-(2-chlorophenyl)-1,3,4-thiadiazole to obtain modified hollow glass microspheres; 4) Weighing the following components: polyether diol, isophorone diisocyanate, functional chain extender, dibutyltin dilaurate, modified hollow glass microspheres, trifluoromethanesulfonic acid, and acetone; mixing and curing the above components to obtain an ultralight material.

2. The method for preparing an ultralight material according to claim 1, wherein: Step 1) The functional chain extender is prepared by mixing 3-hexene-1,6-diol, phenylphosphonic dichloride, and N,N-dimethylaniline, heating the mixture to 120-130° C. and reacting for 8-10 hours to obtain a functional chain extender precursor; mixing the functional chain extender precursor, heptamethylcyclotetrasiloxane, Custer catalyst, and toluene, heating the mixture to 100-110° C. and reacting for 4-6 hours to obtain a functional chain extender.

3. The method for preparing an ultralight material according to claim 2, wherein: The molar ratio of the 3-hexene-1,6-diol, phenylphosphonic dichloride, and N,N-dimethylaniline is (2.1-2.2):1:(3.1-3.2); the molar ratio of the functional chain extender precursor and heptamethylcyclotetrasiloxane is (1.1-1.2):1; and the mass ratio of the functional chain extender precursor, Custer catalyst, and toluene is 1:(0.001-0.002):(10-12).

4. The method for preparing an ultralight material according to claim 1, wherein: Step 2) The preparation method of the pre-modified hollow glass microspheres is as follows: treating the hollow glass microspheres with 3-mercaptopropyltrimethoxysilane to obtain pre-treated hollow glass microspheres; reacting isoprene with 1-(4-vinyl-phenyl)-ethanone and the pre-treated hollow glass microspheres under nitrogen protection at 60-70° C. in the presence of azobisisobutyronitrile, adding a photoinitiator, and irradiating under ultraviolet light to obtain pre-modified hollow glass microspheres.

5. The method for preparing an ultralight material according to claim 4, wherein: The mass ratio of the pretreated hollow glass microspheres, isoprene, 1-(4-vinyl-phenyl)-ethanone, and azobisisobutyronitrile is 1:(0.6-0.8):(0.2-0.4):(0.003-0.005).

6. The method for preparing an ultralight material according to claim 1, wherein: Step 3) The modified hollow glass microspheres are prepared by mixing pre-modified hollow glass microspheres, diethyl oxalate, 2-amino-5-(2-chlorophenyl)-1,3,4-thiadiazole, a base catalyst, and N-methylpyrrolidone, and reacting the mixture under microwave irradiation to obtain modified hollow glass microspheres.

7. The method for preparing an ultralight material according to claim 6, wherein: The mass ratio of the pre-modified hollow glass microspheres, diethyl oxalate, 2-amino-5-(2-chlorophenyl)-1,3,4-thiadiazole, base catalyst and N-methylpyrrolidone is 1:(0.2-0.3):(0.2-0.3):(0.3-0.5):(20-30).

8. The method for preparing an ultralight material according to claim 1, wherein: Step 4) The amounts of the components are as follows: by mass, 100 parts of polyether diol, 17-23 parts of isophorone diisocyanate, 15-20 parts of a functional chain extender, 0.1-0.3 parts of dibutyltin dilaurate, 20-30 parts of modified hollow glass microspheres, 0.5-1.0 parts of trifluoromethanesulfonic acid, and 100-150 parts of acetone.

9. An ultralight material prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the ultralight material according to claim 9 in shoe materials.

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