Loofah sponge composite material as well as preparation method and application thereof

Abstract

The invention relates to the field of composite materials, in particular to a loofah sponge composite material as well as a preparation method and application thereof, and solves the problems that after the loofah sponge material is used for a long time, surface fibers fall off due to the defect that the natural structure is loose, and the cleaning capacity and the mechanical performance of loofah sponge are reduced due to the fact that the composite material is attached to the loofah sponge surface. Comprising the following steps: performing modified connection on a loofah sponge filament and an inorganic material, then forming an interlocking material outside the modified loofah sponge, placing p-quaterphenyl-2, 6-diformyl chloride in an organic solvent to form a dispersion liquid, immersing the modified loofah sponge in the dispersion liquid, then placing the modified loofah sponge in an organic solution of p-phenylenediamine, performing a reaction for 10-20 min, fishing out the reaction product, and performing standing to obtain the modified loofah sponge. And repeatedly dipping the loofah sponge complex in an organic solution of p-quaterphenyl-2, 6-diformyl chloride and p-phenylenediamine, so as to obtain the loofah sponge complex. According to the plant fiber cleaning device, non-wear-resistant plant fibers can be effectively locked, and chippings are not generated while the cleaning effect is guaranteed.

Description

Technical Field

[0001] The invention relates to the technical field of composite materials, and in particular to a loofah composite material and a preparation method and application thereof. Background Art

[0002] Luffa is a natural fiber extracted from luffa fruit. It is porous, light and high-strength. As a natural plant fiber, luffa does not hang on to oil or water and has good cleaning power. It itself has strong mechanical properties, but does not have good wear resistance. After long-term heavy pressure wiping, it will produce more debris, resulting in poor cleaning effect. The main reason for this defect is due to the natural fiber structure of luffa, which is loose and lacks effective adhesion on the surface of luffa. It is usually necessary to reduce the generation of debris by compounding with other materials.

[0003] In the prior art, loofahs are often combined with synthetic resins or inorganic nano-coatings. The presence of the resin and the coating will cover the surface of the loofah fiber, thereby improving its wear resistance and toughness. However, this treatment operation will affect the original adsorption capacity and decontamination effect of the loofah. Among them, the synthetic resin is combined with the surface of the loofah by in-situ polymerization through the dispersion of monomers. Although its mechanical properties are improved, it also covers the functional groups on the surface of the loofah, resulting in the disappearance of its advantage of not hanging oil or water. This method only uses the loofah as a skeleton to form a new porous material. Although the coating method of the inorganic nano-coating can expose more functional groups of the loofah, thereby less affecting the cleaning ability of the loofah, the combination of the inorganic nano-coating and the loofah is relatively extreme. After the two are in contact, a higher temperature, such as 200-280°C, is required for carbonization and fixation, which leads to the decomposition of cellulose and hemicellulose, making the fiber body of the loofah harder and more brittle. The mechanical properties are seriously reduced after being squeezed by external force during cleaning, and the toughness of the material body is seriously reduced, which is not enough to bear heavier cleaning work.

[0004] Therefore, the present invention provides a loofah composite material and a preparation method thereof to solve the above problems. Summary of the invention

[0005] In order to solve the problem that the surface fibers fall off due to the loose natural structure defect of the loofah material after long-term use, and the composite material adheres to the surface of the loofah, thereby reducing the cleaning ability and mechanical properties of the loofah, the present invention provides a loofah composite material and a preparation method thereof.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0007] First, the present application provides a loofah composite material and a preparation method thereof, comprising the following preparation steps:

[0008] S1, pre-treating the loofah to form a loofah filament;

[0009] S2, modifying and connecting the loofah filaments with the inorganic material, dissolving the inorganic material in deionized water to form a saturated impregnation solution, then irradiating the loofah filaments with plasma for activation, placing the activated loofah in the saturated impregnation solution for immersion and heating, the immersion time is 20-120min, and the heating temperature is 60-80°C to obtain a modified loofah;

[0010] S3, forming an interlocking material on the outside of the modified loofah, placing 2,6-dicarboxylic acid tetraphenyl chloride in an organic solvent to form a dispersion, and then immersing the modified loofah in the dispersion, and then placing the modified loofah in an organic solution of p-phenylenediamine for reaction for 10-20 minutes after ultrasonic treatment, taking it out and letting it stand, and then repeatedly immersing the loofah complex in the organic solution of 2,6-dicarboxylic acid tetraphenyl chloride and p-phenylenediamine to obtain a loofah complex;

[0011] S4, removing excess impurities, washing the loofah composite with deionized water to obtain a loofah composite layer, drying the loofah composite layer, and bonding the loofah composite layer to the handheld material with an adhesive to obtain a loofah composite material.

[0012] In order to solve the shortcoming that loofahs are prone to falling off, the present application uses an axially swellable polymer material to compound with the loofah to form an interlaced composite material. Relying on the porous structure of the loofah itself, the monomers of the axially swellable polymer material are dispersed in the form of a solution, and then in-situ polymerization is performed to allow the axially swellable polymer material to be interspersed in the porous structure mesh holes of the loofah. The formed loofah composite material can reduce the shedding of the loofah body material, mainly because the axially swellable polymer material will shrink in the longitudinal direction when it is squeezed in the lateral direction. The axially swellable polymer material has a peculiar extrusion and shrinkage property. Therefore, after long-term use, the wood cellulose of the loofah will also be affected by the axially swellable polymer next to it, thereby forming a relatively tight mechanical lock and reducing the occurrence of falling off. After cleaning, the relaxed loofah composite material is stretched without external force, and the mechanical lock of the wood fiber part of the loofah disappears. Then, it is cleaned with clean water to wash away the debris, thereby improving the cleaning effect.

[0013] Before the in-situ polymerization is performed when using the tensile polymer in the present application, the problem of exposed functional groups on the surface of the loofah needs to be solved, otherwise the cleaning effect will be poor. The means used in the present application is to use a water-soluble inorganic material to modify and connect the loofah. This means is achieved by impregnation and assisted by plasma irradiation, so that the surface of the loofah filaments produces more oxygen-containing functional groups, amino functional groups or nitrogen functional groups, thereby enhancing the chemical activity and hydrophilicity of the loofah surface, which is beneficial to the combination of the loofah and the inorganic salt, and the solution can be more evenly distributed in the gaps of the cellulose, and the subsequent heating treatment increases the absorption of salt by the cellulose part. After drying, the inorganic salt forms a salt film on the fiber surface of the loofah, which can not only remain stable at high temperature, but also will not undergo chemical reactions. It will not combine with the polymer monomer during the polymerization of the tensile polymer, and will be washed with clean water in the subsequent cleaning process to facilitate the removal of salt substances, thereby ensuring that the functional groups on the surface of the loofah filaments are retained and will not be covered, thereby reducing the cleaning ability.

[0014] Preferably, the pretreatment of the loofah in step S1 comprises the following steps:

[0015] The loofah raw material is soaked in water, pressed and rubbed, taken out and left to dry, then the dried loofah is placed in a copper ammonia solution with a mass concentration of 10% to react, then the loofah is rinsed alternately with a sodium hydroxide solution and clean water, and the loofah filaments are obtained after drying.

[0016] Use a cuprammonia solution to remove other debris between plant fibers to reduce the impact, and then use sodium hydroxide to remove the cuprammonia to expose as many pores in the fiber as possible.

[0017] Preferably, the inorganic material in step S2 is one of sodium chloride, sodium sulfate, calcium chloride, calcium sulfate, sodium carbonate or potassium nitrate.

[0018] Preferably, in step S2, the frequency of plasma irradiation activation of the loofah filaments is 5 kHz, the output power is 2 kW, the irradiation time is 2-6 min, the gas medium is one of oxygen, air, nitrogen, hydrogen or ammonia, and the vacuum degree of the irradiation environment is 135.0 Pa.

[0019] Preferably, the organic solvent in step S3 is tetrahydrofuran, the mass concentration of 4-quaterphenyl-2,6-dicarbonyl chloride is 0.02-0.2 g / mL, and the mass concentration of 4-phenylenediamine is 0.06-0.1 g / mL.

[0020] The present application limits the monomer concentration used in the above-mentioned in-situ polymerization to ensure the degree of polymerization. It will not be difficult to generate polymers due to too low a concentration, nor will it produce large polymer particles due to too high a concentration, thereby clogging the pores of the loofah.

[0021] Preferably, the mass ratio of the modified loofah to the loofah complex is 1.0:1.3-1.5.

[0022] The present application limits the amount of the expanded polymer combined during in-situ polymerization in the loofah through the examples, so that it will not be too little to effectively lock the plant fibers, nor will it cause the cleaning effect to deteriorate due to too much polymer.

[0023] Preferably, the handheld material is one of polyester fiber, organic polymer sponge, natural sponge or wood pulp sponge.

[0024] Secondly, the present application discloses a loofah composite material prepared by the above preparation method. The loofah composite material includes a loofah composite layer, an adhesive and a handheld material. The adhesive is one of bisphenol A glue, latex glue or polyurethane glue.

[0025] Preferably, the amount of the adhesive is 100-200 g / m 2 .

[0026] The loofah composite material prepared in the present application can be used in sanitary cleaning materials and environmental care materials. It can not only maintain its natural environmentally friendly cleaning properties, but also has multifunctionality. It is a complex material with great potential.

[0027] The beneficial effects of the present invention are:

[0028] In the process of in-situ polymerization of the tensile polymer, the present invention does not directly mix the two polymerization monomers together to react with the loofah. Instead, the loofah is first placed in an organic solvent of 4-quaterphenyl-2,6-dicarboxylic acid chloride, so that the surface of the loofah has a certain content of 4-quaterphenyl-2,6-dicarboxylic acid chloride, and then the loofah containing 4-quaterphenyl-2,6-dicarboxylic acid chloride is placed in an organic solution of p-phenylenediamine, thereby reducing the number of reactions per unit volume, so that the reaction only occurs on the surface of the loofah fiber, reducing the generation of polymer in the cavity. The porous structure of the loofah is perfectly preserved, and the tensile polymer formed in this way will form a structure of varying thickness due to the tension on the microporous structure, which is convenient for the treatment of the salt film on the surface of the loofah during subsequent water washing, thereby forming a cavity to expose the loofah body, and the exposed space will not affect the cleaning ability of the loofah, and when squeezed, the tensile polymer material can generate sufficient mechanical locking force, which can not only reduce the possibility of loofah falling off, but also significantly enhance the bonding force between fibers, thereby reducing fiber shedding and retaining a strong loofah cleaning ability. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1It is a bar chart comparing the oil residue data of the embodiment of the present invention and the comparative example. DETAILED DESCRIPTION

[0030] The following will refer to the attached Figure 1 The embodiments of the present invention are described in detail. It should be understood by those skilled in the art that these embodiments are only used to explain the technical principles of the present invention and are not intended to limit the protection scope of the present invention.

[0031] Preparation Example 1

[0032] Preparation of loofah composite layer

[0033] S1, soaking the loofah raw material in water, pressing and kneading, taking it out and letting it stand to dry, then placing the dried loofah in a 10% copper ammonia solution to react, then using a 10% sodium hydroxide solution and clean water to alternately rinse the loofah, and obtaining a loofah filament after drying;

[0034] S2, prepare a 50L treatment tank, place sufficient sodium chloride and deionized water in the treatment tank to form a sodium chloride saturated impregnation solution, then place the loofah filaments prepared in S1 in a CD 300PLC vacuum low-temperature plasma surface treatment instrument for plasma irradiation activation, the frequency is 5kHz, the output power is 2kW, the irradiation time is 3min, the gas medium is one of oxygen, the vacuum degree of the irradiation environment is 135.0Pa, the activated loofah is placed in the saturated impregnation solution in the treatment tank for immersion heating, the immersion time is 60min, the heating temperature is 70°C, and the loofah material is pulled out to obtain a modified loofah;

[0035] S3, placing 4-tetraphenyl-2,6-dicarboxylic acid chloride in tetrahydrofuran to form a dispersion with a mass concentration of 0.1 g / mL, and then immersing the modified loofah prepared in S2 in the dispersion, performing ultrasonic treatment, the ultrasonic power is 200 W, the ultrasonic time is 3 min, and then placing the modified loofah in a tetrahydrofuran solution of p-phenylenediamine, the mass concentration of the solution is 0.08 g / mL, reacting for 15 min, taking it out and letting it stand, and then repeatedly immersing the loofah complex in the organic solution of 4-tetraphenyl-2,6-dicarboxylic acid chloride and p-phenylenediamine to form an interlocking material on the outside of the modified loofah, until the mass of the modified loofah increases to 1.4 times the mass of the modified loofah prepared in step S2, to obtain a loofah complex;

[0036] S4, removing excess impurities, washing the loofah composite with deionized water, and then rinsing with an ethanol solution, and drying to obtain a loofah composite layer.

[0037] Preparation Example 2

[0038] Preparation of loofah composite layer

[0039] S1, soaking the loofah raw material in water, pressing and kneading, taking it out and letting it stand to dry, then placing the dried loofah in a 10% copper ammonia solution to react, then using a 10% sodium hydroxide solution and clean water to alternately rinse the loofah, and obtaining a loofah filament after drying;

[0040] S2, prepare a 50L treatment tank, place sufficient sodium sulfate and deionized water in the treatment tank to form a saturated impregnation solution, then place the loofah filaments prepared in S1 in a CD 300PLC vacuum low-temperature plasma surface treatment instrument for plasma irradiation activation, the frequency is 5kHz, the output power is 2kW, the irradiation time is 2min, the gas medium is nitrogen, the vacuum degree of the irradiation environment is 135.0Pa, the activated loofah is placed in the saturated impregnation solution in the treatment tank for immersion heating, the immersion time is 30min, the heating temperature is 60°C, and the loofah material is fished out to obtain a modified loofah;

[0041] S3, placing 4-tetraphenyl-2,6-dicarboxylic acid chloride in tetrahydrofuran to form a dispersion with a mass concentration of 0.02 g / mL, then immersing the modified loofah prepared in S2 in the dispersion, performing ultrasonic treatment, the ultrasonic power is 250 W, the ultrasonic time is 3 min, and then placing the modified loofah in a tetrahydrofuran solution of p-phenylenediamine, the mass concentration of the solution is 0.06 g / mL, reacting for 10 min, taking it out and letting it stand, and then repeatedly immersing the loofah complex in the organic solution of p-tetraphenyl-2,6-dicarboxylic acid chloride and p-phenylenediamine to form an interlocking material on the outside of the modified loofah, until the mass of the modified loofah increases to 1.3 times the mass of the modified loofah prepared in step S2, to obtain a loofah complex;

[0042] S4, removing excess impurities, washing the loofah composite with deionized water, and then rinsing with an ethanol solution, and drying to obtain a loofah composite layer.

[0043] Preparation Example 3

[0044] Preparation of loofah composite layer

[0045] S1, soaking the loofah raw material in water, pressing and kneading, taking it out and letting it stand to dry, then placing the dried loofah in a 10% copper ammonia solution to react, then using a 10% sodium hydroxide solution and clean water to alternately rinse the loofah, and obtaining a loofah filament after drying;

[0046] S2, prepare a 50L treatment tank, place sufficient calcium chloride and deionized water in the treatment tank to form a saturated impregnation solution, then place the loofah filaments prepared in S1 in a CD 300PLC vacuum low-temperature plasma surface treatment instrument for plasma irradiation activation, the frequency is 5kHz, the output power is 2kW, the irradiation time is 6min, the gas medium is one of ammonia, the vacuum degree of the irradiation environment is 135.0Pa, the activated loofah is placed in the saturated impregnation solution in the treatment tank for immersion heating, the immersion time is 120min, the heating temperature is 80°C, and the loofah material is fished out to obtain a modified loofah;

[0047] S3, placing 4-tetraphenyl-2,6-dicarboxylic acid chloride in tetrahydrofuran to form a dispersion with a mass concentration of 0.2 g / mL, then immersing the modified loofah prepared in S2 in the dispersion, performing ultrasonic treatment, the ultrasonic power is 300 W, the ultrasonic time is 3 min, and then placing the modified loofah in a tetrahydrofuran solution of p-phenylenediamine, the mass concentration of the solution is 0.1 g / mL, reacting for 20 min, taking it out and letting it stand, and then repeatedly immersing the loofah complex in the organic solution of 4-tetraphenyl-2,6-dicarboxylic acid chloride and p-phenylenediamine to form an interlocking material on the outside of the modified loofah, until the mass of the modified loofah increases to 1.5 times the mass of the modified loofah prepared in step S2, to obtain a loofah complex;

[0048] S4, removing excess impurities, washing the loofah composite with deionized water, and then rinsing with an ethanol solution, and drying to obtain a loofah composite layer.

[0049] Preparation Example 4 - Auxetic polymer material is not combined with loofah material by in-situ polymerization

[0050] Preparation of loofah composite layer

[0051] S1, soaking the loofah raw material in water, pressing and kneading, taking it out and letting it stand to dry, then placing the dried loofah in a 10% copper ammonia solution to react, then using a 10% sodium hydroxide solution and clean water to alternately rinse the loofah, and obtaining a loofah filament after drying;

[0052] S2, prepare a 50L treatment tank, place sufficient sodium chloride and deionized water in the treatment tank to form a sodium chloride saturated impregnation solution, then place the loofah filaments prepared in S1 in a CD 300PLC vacuum low-temperature plasma surface treatment instrument for plasma irradiation activation, the frequency is 5kHz, the output power is 2kW, the irradiation time is 3min, the gas medium is one of oxygen, the vacuum degree of the irradiation environment is 135.0Pa, the activated loofah is placed in the saturated impregnation solution in the treatment tank for immersion heating, the immersion time is 60min, the heating temperature is 70°C, and the loofah material is pulled out to obtain a modified loofah;

[0053] S3, placing 4-quaterphenyl-2,6-dicarboxylic acid chloride in tetrahydrofuran to form a dispersion with a mass concentration of 0.1 g / mL, then placing p-phenylenediamine in the tetrahydrofuran solution to form a titration solution with a mass concentration of 0.08 g / mL, using a funnel to drop the titration solution into the dispersion, reacting at room temperature for 90 minutes to form an axially swellable polymer material, then filtering and washing, and immersing the modified loofah prepared in S2 in the tetrahydrofuran solution, the mass ratio of the axially swellable polymer material to the modified loofah being 0.4:1, performing ultrasonic treatment, the ultrasonic power being 200 W, the ultrasonic time being 3 minutes, and finally heating to 65° C. to react for 15 minutes to obtain a loofah complex;

[0054] S4, removing excess impurities, washing the loofah composite with deionized water, and then rinsing with an ethanol solution, and drying to obtain a loofah composite layer.

[0055] Preparation Example 5 - No Inorganic Materials Were Used to Modify the Loofah

[0056] Preparation of loofah composite layer

[0057] S1, soaking the loofah raw material in water, pressing and kneading, taking it out and letting it stand to dry, then placing the dried loofah in a 10% copper ammonia solution to react, then using a 10% sodium hydroxide solution and clean water to alternately rinse the loofah, and obtaining a loofah filament after drying;

[0058] S2, placing 4-tetraphenyl-2,6-dicarboxylic acid chloride in tetrahydrofuran to form a dispersion with a mass concentration of 0.1 g / mL, and then immersing the loofah filaments prepared in S1 in the dispersion, performing ultrasonic treatment, the ultrasonic power is 200 W, the ultrasonic time is 3 min, and then placing the loofah filaments in a tetrahydrofuran solution of p-phenylenediamine, the mass concentration of the solution is 0.08 g / mL, reacting for 15 min, taking it out and letting it stand, and then repeatedly immersing the loofah filaments in the organic solution of 4-tetraphenyl-2,6-dicarboxylic acid chloride and p-phenylenediamine to form an interlocking material on the outside of the loofah filaments, until the mass of the loofah filaments increases to 1.4 times the mass of the modified loofah prepared in step S1, to obtain a loofah composite;

[0059] S3, removing excess impurities, washing the loofah composite with deionized water, and then rinsing with an ethanol solution, and drying to obtain a loofah composite layer.

[0060] Preparation Example 6 - The concentration of tetrahydrofuran dispersion of p-quaterphenyl-2,6-dicarbonyl chloride and p-phenylenediamine in step S3 is too high

[0061] Preparation of loofah composite layer

[0062] S1, soaking the loofah raw material in water, pressing and kneading, taking it out and letting it stand to dry, then placing the dried loofah in a 10% copper ammonia solution to react, then using a 10% sodium hydroxide solution and clean water to alternately rinse the loofah, and obtaining a loofah filament after drying;

[0063] S2, prepare a 50L treatment tank, place sufficient sodium chloride and deionized water in the treatment tank to form a sodium chloride saturated impregnation solution, then place the loofah filaments prepared in S1 in a CD 300PLC vacuum low-temperature plasma surface treatment instrument for plasma irradiation activation, the frequency is 5kHz, the output power is 2kW, the irradiation time is 3min, the gas medium is one of oxygen, the vacuum degree of the irradiation environment is 135.0Pa, the activated loofah is placed in the saturated impregnation solution in the treatment tank for immersion heating, the immersion time is 60min, the heating temperature is 70°C, and the loofah material is pulled out to obtain a modified loofah;

[0064] S3, placing 4-tetraphenyl-2,6-dicarboxylic acid chloride in tetrahydrofuran to form a dispersion with a mass concentration of 0.3 g / mL, and then immersing the modified loofah prepared in S2 in the dispersion, performing ultrasonic treatment, the ultrasonic power is 200 W, the ultrasonic time is 3 minutes, and then placing the modified loofah in a tetrahydrofuran solution of p-phenylenediamine, the mass concentration of the solution is 0.2 g / mL, reacting for 15 minutes, taking it out and letting it stand, and then repeatedly immersing the loofah complex in the organic solution of 4-tetraphenyl-2,6-dicarboxylic acid chloride and p-phenylenediamine to form an interlocking material on the outside of the modified loofah, until the mass of the modified loofah increases to 1.4 times the mass of the modified loofah prepared in step S2, to obtain a loofah complex;

[0065] S4, removing excess impurities, washing the loofah composite with deionized water, and then rinsing with an ethanol solution, and drying to obtain a loofah composite layer.

[0066] Preparation Example 7 - The concentration of tetrahydrofuran dispersion of p-quaterphenyl-2,6-dicarbonyl chloride and p-phenylenediamine in step S3 is too low

[0067] The specific change steps are as follows:

[0068] S3, placing 2,6-dicarboxylic acid p-tetraphenylene chloride in tetrahydrofuran to form a dispersion with a mass concentration of 0.01 g / mL, and then immersing the modified loofah prepared in S2 in the dispersion, performing ultrasonic treatment, the ultrasonic power is 200 W, the ultrasonic time is 3 min, and then placing the modified loofah in a tetrahydrofuran solution of p-phenylenediamine, the mass concentration of the solution is 0.03 g / mL, reacting for 15 min, taking it out and letting it stand, and then repeatedly immersing the loofah complex in the organic solution of 2,6-dicarboxylic acid p-tetraphenylene chloride and p-phenylenediamine to form an interlocking material on the outside of the modified loofah, until the mass of the modified loofah increases to 1.4 times the mass of the modified loofah prepared in step S2, to obtain a loofah complex;

[0069] The remaining steps are the same as those in Preparation Example 1.

[0070] Preparation Example 8 - The mass of the composite modified loofah with pulverized polymer material in step S3 is too much

[0071] The specific change steps are as follows:

[0072] S3, placing 4-tetraphenyl-2,6-dicarboxylic acid chloride in tetrahydrofuran to form a dispersion with a mass concentration of 0.1 g / mL, then immersing the modified loofah prepared in S2 in the dispersion, performing ultrasonic treatment, the ultrasonic power is 200 W, the ultrasonic time is 3 min, and then placing the modified loofah in a tetrahydrofuran solution of p-phenylenediamine, the mass concentration of the solution is 0.08 g / mL, reacting for 15 min, taking it out and letting it stand, and then repeatedly immersing the loofah complex in the organic solution of p-tetraphenyl-2,6-dicarboxylic acid chloride and p-phenylenediamine to form an interlocking material on the outside of the modified loofah, until the mass of the modified loofah increases to twice the mass of the modified loofah prepared in step S2, to obtain a loofah complex;

[0073] The remaining steps are the same as those in Preparation Example 1.

[0074] Preparation Example 9 - The mass of the composite modified loofah made of axially swellable polymer material in step S3 is too small

[0075] The specific change steps are as follows:

[0076] S3, placing 2,6-dicarboxylic acid p-tetraphenylene chloride in tetrahydrofuran to form a dispersion with a mass concentration of 0.1 g / mL, then immersing the modified loofah prepared in S2 in the dispersion, performing ultrasonic treatment, the ultrasonic power is 200 W, the ultrasonic time is 3 min, and then placing the modified loofah in a tetrahydrofuran solution of p-phenylenediamine, the mass concentration of the solution is 0.08 g / mL, reacting for 15 min, taking it out and letting it stand, and then repeatedly immersing the loofah complex in the organic solution of 2,6-dicarboxylic acid p-tetraphenylene chloride and p-phenylenediamine to form an interlocking material on the outside of the modified loofah, until the mass of the modified loofah increases to 1.2 times the mass of the modified loofah prepared in step S2, to obtain a loofah complex;

[0077] The remaining steps are the same as those in Preparation Example 1.

[0078] Example 1

[0079] The loofah composite layer prepared in Preparation Example 1 was cut to form a square block of loofah, and then bisphenol A glue was sprayed on one side of the square block of loofah by spraying, and then polyester fiber was adhered to the surface to obtain a loofah composite material.

[0080] Example 2

[0081] The loofah composite layer prepared in Preparation Example 2 is cut to form a square block of loofah, and then latex glue is sprayed on one side of the square block of loofah by spraying, and then an organic polymer sponge made of polyurethane is adhered to the surface to obtain a loofah composite material.

[0082] The organic polymer in this embodiment can also be prepared from polyether.

[0083] Example 3

[0084] The loofah composite layer prepared in Preparation Example 3 was cut to form a square block of loofah, and then polyurethane glue was sprayed on one side of the square block of loofah by spraying, and then the wood pulp sponge was adhered to the surface to obtain a loofah composite material.

[0085] The handheld material in the above embodiment uses polyester fiber, organic polymer sponge and wood pulp sponge to adhere to form a loofah composite material. In addition to the three materials given above, the handheld material can also be replaced by bamboo fiber materials, natural sponges, cotton fibers, linen fibers, scouring pads and other materials to form different loofah composite materials.

[0086] Comparative Example 1

[0087] The difference between this comparative example and Example 1 is that the loofah composite layer used is prepared in Preparation Example 4.

[0088] Comparative Example 2

[0089] The difference between this comparative example and Example 1 is that the loofah composite layer used is prepared in Preparation Example 5.

[0090] Comparative Example 3

[0091] The difference between this comparative example and Example 1 is that the loofah composite layer used is prepared in Preparation Example 6.

[0092] Comparative Example 4

[0093] The difference between this comparative example and Example 1 is that the loofah composite layer used is prepared in Preparation Example 7.

[0094] Comparative Example 5

[0095] The difference between this comparative example and Example 1 is that the loofah composite layer used is prepared in Preparation Example 8.

[0096] Comparative Example 6

[0097] The difference between this comparative example and Example 1 is that the loofah composite layer used is prepared in Preparation Example 9.

[0098] Experiments and data

[0099] The loofah composite materials prepared in the above embodiments and comparative examples were subjected to performance tests to detect the cleaning effect of the loofah composite materials and their wear resistance under a heavy pressure wear test. The specific experimental methods are as follows:

[0100] Cleaning effect experiment: soak the oil stains on the surface of tiles, cement and wood for 24 hours, use the loofah composite material to perform 30 horizontal frictions, and then press the oil-absorbing paper on the oil-soaked surface to obtain the size of the residual oil stain area (oil stain area of ​​the oil-absorbing paper / total area of ​​the oil-absorbing paper*100%), so as to determine the cleaning effect of the loofah surface functional groups.

[0101] Heavy pressure wear test: The loofah composite material was subjected to a long-term friction test. 430 stainless steel was used as the test substrate. The loofah composite material was attached to the 430 stainless steel surface at pressures of 80N, 120N and 200N, and then reciprocated friction was performed. During this period, water was continuously poured on the contact surface to keep it moist. The friction time was obtained when plant fiber residue appeared on the steel surface, thereby determining the heavy pressure wear resistance.

[0102] The experimental data of the cleaning effect are shown in Table 1 below:

[0103] Table 1

[0104]

[0105]

[0106] By drawing a bar graph of the residual oil ratio in Table 1, Figure 1 The experimental data of heavy pressure wear resistance are shown in Table 2:

[0107] Table 2

[0108] 80N duration 120N down time 200N duration Example 1 ＞72h ＞72h 61h Example 2 ＞72h ＞72h 55h Example 3 ＞72h ＞72h 63h Comparative Example 1 21h 12h 4h Comparative Example 2 ＞72h ＞72h ＞72h Comparative Example 3 ＞72h ＞72h 66h Comparative Example 4 24h 13 2h Comparative Example 5 ＞72h ＞72h ＞72h Comparative Example 6 33h 20h 7h

[0109] analyze

[0110] The experimental data obtained above show that the loofah composite materials prepared in Example 1, Example 2 and Example 3 have significant cleaning effects on oil stains on tile, cement and wood surfaces, and can maintain no debris for more than 72 hours under the heavy pressure test of 80N and 120N, and can maintain no debris for more than 55 hours under the extreme heavy pressure of 200N.

[0111] According to the experimental data in Table 1 and Table 2, the cleaning effect of Comparative Example 1 is good, but its wear resistance time is extremely short. The difference between Comparative Example 1 and the embodiment is that the composite between the axially expanding polymer material and the loofah material does not adopt the in-situ polymerization method. Therefore, it can be known that the in-situ polymerization method can effectively make the axially expanding polymer and the loofah fiber form an interlaced structure, and then form a mechanical lock under heavy pressure to prevent debris from falling.

[0112] According to the experimental data in Table 1 and Table 2, the cleaning effect of Comparative Example 2 is poor, the wear resistance time is very long, and the wear resistance is very good. The difference between Comparative Example 2 and the embodiment of the present application is that the loofah is not modified and linked with inorganic materials. Therefore, it can be known that the use of inorganic materials to connect the surface of the loofah fiber can effectively separate the tensile polymer material from the surface of the loofah fiber, prevent the functional groups on the surface of the loofah from being covered, thereby improving the cleaning effect.

[0113] According to the experimental data in Table 1 and Table 2, the experimental data of Comparative Examples 3 and 4 show that the cleaning effect of Comparative Example 3 is poor and the wear-resistant time is long, while the cleaning effect of Comparative Example 4 is extremely good and the wear-resistant time is short. Therefore, it can be known that the size of the in-situ polymerization concentration can effectively distribute the expansion polymer material in the gaps of the loofah, and it will not be difficult to form a compact locking distance due to too low concentration, nor will it be difficult for inorganic materials to seep out during subsequent cleaning due to too high concentration, and the functional groups of the loofah will be difficult to expose, thereby ultimately forming better cleaning and locking effects.

[0114] According to the experimental data of Table 1 and Table 2, the experimental data of Comparative Examples 5 and 6 show that the cleaning effect of Comparative Example 5 is also very poor, but the wear resistance time is very high, while the cleaning effect of Comparative Example 6 is very good and the wear resistance time is very short. Therefore, it can be known that too much polymerization of the axially expanding polymer substance will make it difficult to form gaps, less exposure of the loofah, and reduced cleaning effect. Too little polymerization of the axially expanding polymer substance will reduce the ability of mechanical locking, making it easier to fall off.

[0115] So far, the technical solutions of the present invention have been described in conjunction with the preferred embodiments shown in the accompanying drawings. However, it is easy for those skilled in the art to understand that the protection scope of the present invention is obviously not limited to these specific embodiments. Without departing from the principle of the present invention, those skilled in the art can make equivalent changes or substitutions to the relevant technical features, and the technical solutions after these changes or substitutions will fall within the protection scope of the present invention.

Claims

1. A loofah composite material and a preparation method thereof, characterized in that, The method comprises the following preparation steps: S1, pre-treating the loofah to form a loofah filament; S2, modifying and connecting the loofah filaments with the inorganic material, dissolving the inorganic material in deionized water to form a saturated impregnation solution, then irradiating the loofah filaments with plasma for activation, placing the activated loofah in the saturated impregnation solution for immersion and heating, the immersion time is 20-120min, and the heating temperature is 60-80°C to obtain a modified loofah; S3, forming an interlocking material on the outside of the modified loofah, placing 2,6-dicarboxylic acid tetraphenyl chloride in an organic solvent to form a dispersion, and then immersing the modified loofah in the dispersion, and then placing the modified loofah in an organic solution of p-phenylenediamine for reaction for 10-20 minutes after ultrasonic treatment, taking it out and letting it stand, and then repeatedly immersing the loofah complex in the organic solution of 2,6-dicarboxylic acid tetraphenyl chloride and p-phenylenediamine to obtain a loofah complex; S4, removing excess impurities, washing the loofah composite with deionized water to obtain a loofah composite layer, drying the loofah composite layer, and bonding the loofah composite layer to the handheld material with an adhesive to obtain a loofah composite material.

2. The method for preparing a loofah composite material according to claim 1, wherein The pre-treatment of the loofah in step S1 comprises the following steps: The loofah raw material is soaked in water, pressed and rubbed, taken out and left to dry, then the dried loofah is placed in a copper ammonia solution with a mass concentration of 10% to react, then the loofah is rinsed alternately with a sodium hydroxide solution and clean water, and the loofah filaments are obtained after drying.

3. The method for preparing a loofah composite material according to claim 1, wherein The inorganic material in step S2 is one of sodium chloride, sodium sulfate, calcium chloride, calcium sulfate, sodium carbonate or potassium nitrate.

4. The method for preparing a loofah composite material according to claim 1, wherein In the step S2, the frequency of plasma irradiation activation of the loofah filaments is 5kHz, the output power is 2kW, the irradiation time is 2-6min, the gas medium is one of oxygen, air, nitrogen, hydrogen or ammonia, and the vacuum degree of the irradiation environment is 135.0Pa.

5. The method for preparing a loofah composite material according to claim 1, wherein The organic solvent in step S3 is tetrahydrofuran, the mass concentration of p-quaterphenyl-2,6-dicarbonyl chloride is 0.02-0.2 g / mL, and the mass concentration of p-phenylenediamine is 0.06-0.1 g / mL.

6. The method for preparing a loofah composite material according to claim 1, wherein The mass ratio of the modified loofah to the loofah complex is 1.0:1.3-1.

5.

7. The method for preparing a loofah composite material according to claim 1, wherein The handheld material is one of polyester fiber, organic polymer sponge, natural sponge or wood pulp sponge.

8. A loofah composite material prepared by the preparation method of a loofah composite material as described in any one of claims 1-7, characterized in that, The loofah composite material comprises a loofah composite layer, an adhesive and a handheld material, wherein the adhesive is one of bisphenol A glue, latex glue or polyurethane glue.

9. A loofah composite material according to claim 8, characterized in that, The amount of the adhesive is 100-200 g / m 2 .

10. Use of the loofah composite material according to any one of claims 8 to 9 in sanitary cleaning materials and environmental care materials.

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