阅读说明：本技术 多层式导流多孔体 (Multilayer flow guiding porous body ) 是由 罗金火 于 2020-07-11 设计创作，主要内容包括：本申请公开了一种多层式导流多孔体,采用棉织物作为生产原料,通过进行一系列的的深加工和改性,从而得到具有分子链较长、结构稳定、羟基丰富的乙基纤维素,同时与甲基丙烯酸甲酯和丙烯酸丁酯接枝共聚制备吸油树脂,对于使得该吸油树脂更适合电子雾化器的储油棉进行使用,特别采用多巴胺在其表面形成一层强黏附的涂层,同时配合介孔材料,更进一步提高吸附性能,从而实现从棉织物到电子雾化器用的储油棉的转变,实现了能源的循环利用,同时增强了对烟油的吸附能力。(The application discloses multilayer formula water conservancy diversion porous body adopts cotton fabric as the raw materials for production, through carrying out a series of deep-processing and modification, thereby obtain the ethyl cellulose that has the molecular chain longer, stable in structure, hydroxyl is abundant, simultaneously with methyl methacrylate and butyl acrylate graft copolymerization preparation oil absorption resin, to making this oil absorption resin more be fit for the oil storage cotton of electronic atomizer to use, adopt dopamine to form the coating that a layer is adhered to by force on its surface very much, cooperate with the mesoporous material simultaneously, improve adsorption efficiency further, thereby realize the change from cotton fabric to the oil storage cotton that the electronic atomizer used, realized the cyclic utilization of the energy, strengthened the adsorption capacity to the tobacco tar simultaneously.)

1. The multilayer flow guide porous body is characterized in that the porous body is prepared from ethyl cellulose, and is finally obtained through modification of dopamine for tobacco tar adsorption, and the multilayer flow guide porous body comprises the following specific steps:

s1, shearing the cotton fabric, bleaching, and further processing by a mixed solution of bromoethane and toluene to obtain ethyl cellulose;

s2: mixing and shaking ethyl cellulose, benzoyl peroxide and N, N-methylene-bis-propionamide uniformly, heating in a constant-temperature water bath, taking out, washing with absolute ethyl alcohol and distilled water respectively, and drying to obtain a primary porous body;

s3: washing the primary porous body; dissolving dopamine hydrochloride in distilled water, adjusting the pH value of the solution, then putting the washed primary porous body into the dopamine hydrochloride solution, taking out the primary porous body after reaction, washing the primary porous body with distilled water, and drying the primary porous body to obtain a secondary porous body;

s4: and (3) putting the second-generation porous body into an isocyanate solution, transferring the second-generation porous body into a toluene suspension containing a mesoporous material after a period of time, and finally, fully washing the second-generation porous body with toluene and ethanol and drying the second-generation porous body to obtain the multilayer diversion porous body.

2. The multi-layered porous deflector of claim 1, wherein in step S1, the waste cotton fabric is ground and sheared at a rotation speed of 5000r/min by using an anchor stirrer, so that the fiber bundles in the cotton fabric are broomed and the porosity is increased; and then adding a hydrogen peroxide solution for bleaching, cooking at constant temperature for a period of time, filtering after the color is completely faded, and cleaning and drying to obtain the refined cotton fabric.

3. The multilayer porous deflector of claim 2, wherein the alkali cellulose is obtained by adding a refined cotton fabric to a 40% sodium hydroxide solution, maintaining the mixture at a temperature of 35 ℃ for a period of time, and squeezing the sodium hydroxide solution.

4. The multilayer flow-guiding porous body as claimed in claim 3, wherein alkali cellulose is added into a mixed solution of bromoethane and toluene in a mass ratio of 9:2, sodium hydroxide solid is added, and the mixture is placed in a high-temperature reaction kettle and reacted for a period of time at 140 ℃; and after the reaction is completed, filtering out the product, washing the product with distilled water, then putting the product into distilled water for stirring, titrating with acid, adjusting the pH to about 7, then washing with distilled water, filtering, and drying for later use, namely the ethyl cellulose.

5. The multilayer porous deflector as claimed in claim 1, wherein in step S2, a certain amount of benzoyl peroxide and N, N-methylene-bis-propionamide are weighed, and the N, N-methylene-bis-propionamide, after dissolved in a small amount of absolute ethanol, is poured into a reaction kettle together with benzoyl peroxide and ethyl cellulose to be shaken, a certain amount of butyl acrylate and methyl methacrylate are added to be stirred sufficiently, nitrogen is introduced into the reaction kettle, an electric stirrer and a condenser tube are installed to perform a reaction at a constant temperature of 70 ℃, after a white product generated by the reaction is taken out, the white product is washed with absolute ethanol and distilled water, and then the white product is dried in an oven to a constant weight.

6. The multilayer flow-guiding porous body according to claim 5, wherein in step S2, butyl acrylate and methyl methacrylate are mixed and added in a mass ratio of 1: 1; the addition amount of the benzoyl peroxide and the N, N-methylene-bis-propionamide is 0.2 to 0.4 and 0.03 to 0.05 percent of the total mass.

7. A multilayer flow-through porous body according to claim 1, wherein in step S3, the primary porous body is washed several times with toluene and acetone in sequence, and then ultrasonically washed with distilled water for a certain period of time.

8. The multilayer porous flowguide body of claim 1, wherein in step S3, dopamine hydrochloride is dissolved in distilled water, and prepared into a solution with a certain concentration, and tris (hydroxymethyl) aminomethane is used to adjust the pH of the solution to 8.5, thereby obtaining a dopamine solution.

9. The multilayer porous flow guide body according to claim 1, wherein the second-generation porous body with the polydopamine adsorbed thereon is obtained after step S3, and is placed in 10mg/ml isocyanate solution to react for 30min at normal temperature.

10. The multilayer flow-guiding porous body according to claim 9, wherein the oil-storing cotton reacted with isocyanate is transferred to a toluene suspension of 10mg/mL mesoporous material, reacted at normal temperature for 30min, and finally washed with toluene and ethanol sufficiently to obtain dopamine and mesoporous material modified oil-storing cotton, i.e. multilayer flow-guiding porous body.

Technical Field

The invention relates to a new material, in particular to a multilayer flow guide porous body applied in an atomizer and used for adsorbing, storing and releasing tobacco tar.

Background

The electronic atomizer is a product which atomizes electronic cigarette liquid by the atomizer and transmits nicotine and other substances to a respiratory system. The oil storage cotton of the electronic cigarette is a part for storing tobacco tar in the electronic cigarette, and has important influence on the amount, stability and taste of the tobacco tar in the electronic cigarette. The oil storage cotton materials adopted by the electronic cigarette products in the current market mainly comprise Polyester (PET) (and a copolymer with polylactic acid) and cotton. The oil storage cotton in the electronic atomizer needs to have good adsorption and desorption performance to tobacco tar, and the modification of the oil storage cotton by chemical modification or modification is a main way for improving the performance of the oil storage cotton of the existing atomizer under the condition of not changing used base materials.

The oil storage cotton is generally made of cotton fabric, the effective component of the oil storage cotton is cotton fiber which is one of the most common natural fibers, and the content of cellulose in the cotton fiber reaches about 94 percent, so that the internal chemical structure of organic polymers can be changed through appropriate deep processing and conversion of the cotton fiber, and finally the cellulose derivative can be made, thereby reducing the production cost.

Disclosure of Invention

In order to solve the problems, the invention provides a method for extracting cellulose from waste cotton fabrics, performing appropriate deep processing and conversion to obtain ethyl cellulose, and simultaneously performing chemical modification or modification on the ethyl cellulose, so that the good adsorption and desorption performance of tobacco tar is realized by utilizing the characteristics of the ethyl cellulose, and the method is more suitable for being used as oil storage cotton in an electronic atomizer.

In order to achieve the purpose, the invention provides a multilayer flow guide porous body, which is prepared from ethyl cellulose and is finally obtained through modification of dopamine and used for tobacco tar adsorption, and the multilayer flow guide porous body comprises the following specific steps:

s1, shearing the cotton fabric, bleaching, and further processing by a mixed solution of bromoethane and toluene to obtain ethyl cellulose;

s2: mixing and shaking ethyl cellulose, benzoyl peroxide and N, N-methylene-bis-propionamide uniformly, heating in a constant-temperature water bath, taking out, washing with absolute ethyl alcohol and distilled water respectively, and drying to obtain a primary porous body;

s3: washing the primary porous body; dissolving dopamine hydrochloride in distilled water, adjusting the pH value of the solution, then putting the washed primary porous body into the dopamine hydrochloride solution, taking out the primary porous body after reaction, washing the primary porous body with distilled water, and drying the primary porous body to obtain a secondary porous body;

s4: and (3) putting the second-generation porous body into an isocyanate solution, transferring the second-generation porous body into a toluene suspension after a period of time, and finally, fully washing and drying the second-generation porous body by using toluene and ethanol to obtain the multilayer diversion porous body.

Preferably, in step S1, the waste cotton fabric is ground and sheared at a rotation speed of 5000r/min by using an anchor stirrer, so that fiber bundles in the cotton fabric are broomed and the porosity is increased; and then adding a hydrogen peroxide solution for bleaching, cooking at constant temperature for a period of time, filtering after the color is completely faded, and cleaning and drying to obtain the refined cotton fabric.

Preferably, the refined cotton fabric is added to a 40% sodium hydroxide solution, held at a temperature of 35 ℃ for a period of time, and the sodium hydroxide solution is squeezed to obtain the alkali cellulose.

Preferably, adding alkali cellulose into a mixed solution of bromoethane and toluene in a mass ratio of 9:2, adding sodium hydroxide solid, placing the mixture into a high-temperature reaction kettle, and reacting for a period of time at 140 ℃; and after the reaction is completed, filtering out the product, washing the product with distilled water, then putting the product into distilled water for stirring, titrating with acid, adjusting the pH to about 7, then washing with distilled water, filtering, and drying for later use, namely the ethyl cellulose.

Preferably, in step S2, a certain amount of benzoyl peroxide and N, N-methylene-bis-propionamide are weighed, the N, N-methylene-bis-propionamide is dissolved by a small amount of absolute ethyl alcohol, then poured into a reaction kettle to shake with benzoyl peroxide and ethyl cellulose, a certain amount of butyl acrylate and methyl methacrylate are added to be fully stirred, nitrogen is introduced into the reaction kettle, an electric stirrer and a condenser tube are installed, the reaction is carried out at a constant temperature of 70 ℃, after a white product generated by the reaction is taken out, the white product is washed by absolute ethyl alcohol and distilled water respectively, and then the white product is placed into an oven to be dried to constant weight.

Preferably, in step S2, butyl acrylate and methyl methacrylate are mixed and added in a mass ratio of 1: 1; the addition amount of the benzoyl peroxide and the N, N-methylene-bis-propionamide is 0.2 to 0.4 and 0.03 to 0.05 percent of the total mass.

Preferably, in step S3, the primary porous body is washed with toluene and acetone in this order a plurality of times, and then ultrasonically washed with distilled water for a certain period of time.

Preferably, in step S3, dopamine hydrochloride is dissolved in distilled water, and prepared into a solution with a certain concentration, and tris (hydroxymethyl) aminomethane is used to adjust the pH of the solution to 8.5, thereby obtaining a dopamine solution.

Preferably, the second-generation porous material having polydopamine adsorbed thereon is obtained after step S3, and is placed in a 10mg/ml isocyanate solution to be reacted at room temperature for 30 min.

Preferably, the oil storage cotton reacted with isocyanate is transferred into a toluene suspension of 10mg/mL mesoporous material, reacted at normal temperature for 30min, and finally fully washed with toluene and ethanol to obtain the dopamine and mesoporous material modified oil storage cotton, namely the multilayer flow guide porous body.

The invention has the beneficial effects that: according to the application, cotton fabrics are used as production raw materials for further deep processing and modification, so that ethyl cellulose with a longer molecular chain, a stable structure and rich hydroxyl groups is obtained, and meanwhile, the ethyl cellulose is graft copolymerized with methyl methacrylate and butyl acrylate to prepare the oil absorption resin.

Drawings

FIG. 1 is a flow chart of the steps of the present invention;

FIG. 2 is a diagram of the modification mechanism of cotton fabric;

FIG. 3 is a schematic diagram of dopamine crosslinking at position.

Detailed Description

In order to more clearly describe the present invention, the present invention will be further described with reference to the accompanying drawings.

The invention provides a multilayer flow guide porous body, which is prepared from ethyl cellulose, and is finally obtained through modification of dopamine for tobacco tar adsorption, and comprises the following specific steps: s1, shearing the cotton fabric, bleaching, and further processing by a mixed solution of bromoethane and toluene to obtain ethyl cellulose; s2: mixing and shaking ethyl cellulose, benzoyl peroxide and N, N-methylene-bis-propionamide uniformly, heating in a constant-temperature water bath, taking out, washing with absolute ethyl alcohol and distilled water respectively, and drying to obtain a primary porous body; s3: washing the primary porous body; dissolving dopamine hydrochloride in distilled water, adjusting the pH value of the solution, then putting the washed primary porous body into the dopamine hydrochloride solution, taking out the primary porous body after reaction, washing the primary porous body with distilled water, and drying the primary porous body to obtain a secondary porous body; s4: and (3) putting the second-generation porous body into an isocyanate solution, transferring the second-generation porous body into a toluene suspension containing a mesoporous material after a period of time, and finally, fully washing the second-generation porous body with toluene and ethanol and drying the second-generation porous body to obtain the multilayer diversion porous body.

More specifically, firstly, an anchor stirrer is utilized to polish and shear the waste cotton fabric at the rotating speed of 5000r/min, so that fiber bundles in the cotton fabric are broomed, and the porosity is increased; and then adding a hydrogen peroxide solution for bleaching, cooking at constant temperature for a period of time, filtering after the color is completely faded, and cleaning and drying to obtain the refined cotton fabric. In this embodiment, the waste cotton fabric is ground and cut by using the stirrer, so that the fiber morphology can be effectively changed, the particle size of the natural fiber is reduced, the specific surface area of the natural fiber is increased, and then bleaching and constant-temperature cooking are performed, so that moisture and air in the fiber escape to form a gap, and in addition, hydroxyl groups in cellulose and hemicellulose are subjected to dehydration condensation to form a three-dimensional network structure, so that a multilayer structure is formed, and the oil absorption performance is improved.

Adding refined cotton fabric into a 40% sodium hydroxide solution, keeping the solution at the temperature of 35 ℃ for a period of time, extruding the sodium hydroxide solution to obtain alkali cellulose, adding the alkali cellulose into a mixed solution of bromoethane and toluene in a mass ratio of 9:2, adding sodium hydroxide solid, placing the mixture into a high-temperature reaction kettle, and reacting at the temperature of 140 ℃ for a period of time; and after the reaction is completed, filtering out the product, washing the product with distilled water, then putting the product into distilled water for stirring, titrating with acid, adjusting the pH to about 7, then washing with distilled water, filtering, and drying for later use, namely the ethyl cellulose. The steps are illustrated by specific examples: weighing 100g of refined cotton fabric, shearing (the length is not more than 3 mm), adding into 3L of 40% sodium hydroxide solution, keeping at 35 ℃ for 3 hours, taking out, squeezing out the sodium hydroxide solution adsorbed in the refined cotton fabric, and obtaining the residue which is alkali cellulose; adding 100g of alkali cellulose into a mixed solution of bromoethane and toluene in a mass ratio of 9:2, adding 200 g of sodium hydroxide solid, placing the mixture into a high-temperature reaction kettle, reacting for 12 hours at 140 ℃, filtering a product after complete reaction, washing the product with distilled water for several times, then placing the product into a container, dropwise adding distilled water, stirring for half an hour, dropwise adding phenolphthalein as an indicator, titrating with acid until the product is colorless, washing with distilled water for several times, filtering, and drying at 70 ℃.

Weighing a certain mass of Benzoyl Peroxide (BPO) and N, N-methylene-bis-propionamide (MBA), dissolving the N, N-methylene-bis-propionamide with a small amount of absolute ethyl alcohol, pouring the dissolved N, N-methylene-bis-propionamide, benzoyl peroxide and Ethyl Cellulose (EC) into a reaction kettle, shaking the mixture evenly, adding a certain mass of Butyl Acrylate (BA) and Methyl Methacrylate (MMA), fully stirring the mixture, introducing nitrogen into the reaction kettle, installing an electric stirrer and a condenser pipe, reacting the mixture at a constant temperature of 70 ℃, taking out a white product generated by the reaction, washing the white product with absolute ethyl alcohol and distilled water respectively, and then putting the white product into an oven to dry the white product to constant weight. More specifically, for example, 5g of ethyl cellulose is weighed and placed in a 250ml three-neck flask (a reaction kettle is used in actual production), 0.075g of benzoyl peroxide and 0.01g of N, N-methylene-bis-propionamide are respectively weighed, the N, N-methylene-bis-propionamide and the benzoyl peroxide are dissolved by a small amount of absolute ethyl alcohol and then poured into the three-neck flask and shaken uniformly, then 10g of Butyl Acrylate (BA) and 10g of Methyl Methacrylate (MMA) are added, the three-neck flask is connected with nitrogen and provided with an electric stirrer and a condenser tube, then the three-neck flask is placed in a constant temperature water bath kettle at 70 ℃ for reaction for 2 hours to generate a large amount of white products, the products are taken out and washed by the absolute ethyl alcohol and distilled water respectively, and then the products are placed in an oven to be dried under the condition of 60 ℃ until the constant weight is achieved, and the.

In the last step, butyl acrylate and methyl methacrylate are mixed and added according to the optimal mass ratio of 1: 1; the addition amount of the benzoyl peroxide and the N, N-methylene-bis-propionamide is optimally 0.3 percent and 0.04 percent of the total mass; thus, as the monomer mass ratio of Butyl Acrylate (BA) and Methyl Methacrylate (MMA) can affect the hydrophobicity of the generated product and the effective volume of the net structure, thereby affecting the oil absorption and oil absorption performance, for butyl acrylate, a very long alkyl chain and space volume exist, but excessive butyl acrylate can reduce the effective volume of the net structure, thereby reducing the oil absorption rate, therefore, the addition of a proper amount of methyl methacrylate can increase the effective volume of the net structure to a certain extent, and through a plurality of tests, the optimal ratio of the butyl acrylate to the methyl methacrylate is finally selected to be 1: 1; for the crosslinking agent N, N-methylene-bis-propionamide (MBA) and the initiator Benzoyl Peroxide (BPO), the crosslinking agent influences the crosslinking degree of resin, so that the length between crosslinking points is determined, when the MBA is insufficient, the network structure is very loose due to long chain segments between the crosslinking points, the tobacco tar is easy to flow out of the material, and when the MBA is excessive, the chain segments between the crosslinking points are short, the flowability is insufficient, and the tobacco tar is difficult to enter the network structure; the same reasoning applies to the initiator, and it has been determined through several tests that the amounts of benzoyl peroxide and N, N-methylene-bis-propionamide added are optimally 0.3% and 0.04% of the total mass.

Referring to fig. 2, after the cotton fabric is subjected to alkalization and etherification, ethyl cellulose with a large number of hydroxyl groups on the surface is obtained, and more specifically: the initiator decomposes under the heating condition to generate BPO free radicals, and the BPO free radicals are combined with hydroxyl groups on the ethyl cellulose to abandon hydrogen atoms with more hydroxyl groups and generate EC free radicals; at the same time, BPO free radicals are combined with monomers (MMA and BA) to generate united monomer free radicals, and through polymerization reaction, long chains are formed between adjacent united monomer free radicals, and the long chains are connected with EC free radicals; meanwhile, the long chain is combined with the tail end of the MBA vinyl group, so that each branched chain is connected to form a three-dimensional space network structure.

In order to further enhance the oil absorption effect of the primary porous body, particularly dopamine is adopted for modification, the primary porous body is sequentially washed for 3 times by toluene and acetone respectively, and then is ultrasonically washed for a period of time by distilled water; dissolving dopamine hydrochloride in distilled water to prepare a solution with a certain concentration; regulating the pH value of the solution to 8.5 by adopting tris (hydroxymethyl) aminomethane to obtain a dopamine solution; placing the initial porous body subjected to ultrasonic cleaning into a dopamine solution for reaction, more specifically, sequentially washing the initial porous body for 3 times by respectively adopting toluene and acetone, and then ultrasonically washing the initial porous body for 3 hours by using distilled water; dissolving dopamine hydrochloride in distilled water, preparing a solution with the concentration of 2mg/ml, and adjusting the pH of the solution to 8.5 by adopting tris (hydroxymethyl) aminomethane to obtain a dopamine solution; taking the initial porous body after ultrasonic cleaning according to the proportion of 1: 10 mass ratio is put into a dopamine solution to react for 24 hours at room temperature, and then the mixture is taken out to be washed by distilled water and dried to obtain a second-generation porous body with the surface adsorbed with the polydopamine, because the cross-linking of the dopamine occurs in the state of aqueous solution, and a strong adhesion coating-the polydopamine is formed on the solid surface.

And (2) putting the second-generation porous body into 10mg/mL isocyanate solution, reacting for 30min at normal temperature, transferring the oil storage cotton reacted with the isocyanate into a toluene suspension of a 10mg/mL mesoporous material, reacting for 30min at normal temperature, and finally fully washing with toluene and ethanol to obtain the dopamine and mesoporous material modified oil storage cotton, namely the multilayer diversion porous body. More specifically, the mesoporous material is a silicon-based mesoporous molecular sieve, various modification modifications can be easily carried out by utilizing silicon hydroxyl groups rich on the surface of the mesoporous material, and meanwhile, the single specific surface area of the mesoporous material is larger, so that the adsorption performance can be further improved.

The invention has the advantages that:

1) waste cotton fabrics are used as raw materials to produce the tobacco tar adsorbing material of the electronic atomizer, so that the energy is recycled;

2) compared with the traditional tobacco tar adsorbing material, the tobacco tar adsorbing capacity is further enhanced through modification of dopamine.

The above disclosure is only for the specific embodiment of the present invention, but the present invention is not limited thereto, and any variations that can be considered by those skilled in the art are intended to fall within the scope of the present invention.