CN114772580A - Long-acting micro-odor aroma-releasing type flame-retardant carbon nanosphere and wood board containing same - Google Patents
Long-acting micro-odor aroma-releasing type flame-retardant carbon nanosphere and wood board containing same Download PDFInfo
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- CN114772580A CN114772580A CN202210389380.7A CN202210389380A CN114772580A CN 114772580 A CN114772580 A CN 114772580A CN 202210389380 A CN202210389380 A CN 202210389380A CN 114772580 A CN114772580 A CN 114772580A
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/04—Impregnating in open tanks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/12—Impregnating by coating the surface of the wood with an impregnating paste
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F13/00—Coverings or linings, e.g. for walls or ceilings
- E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
- E04F13/072—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of specially adapted, structured or shaped covering or lining elements
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F15/00—Flooring
- E04F15/02—Flooring or floor layers composed of a number of similar elements
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F15/00—Flooring
- E04F15/18—Separately-laid insulating layers; Other additional insulating measures; Floating floors
- E04F15/181—Insulating layers integrally formed with the flooring or the flooring elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K2240/00—Purpose of the treatment
- B27K2240/30—Fireproofing
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F2290/00—Specially adapted covering, lining or flooring elements not otherwise provided for
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F2290/00—Specially adapted covering, lining or flooring elements not otherwise provided for
- E04F2290/04—Specially adapted covering, lining or flooring elements not otherwise provided for for insulation or surface protection, e.g. against noise, impact or fire
- E04F2290/045—Specially adapted covering, lining or flooring elements not otherwise provided for for insulation or surface protection, e.g. against noise, impact or fire against fire
- E04F2290/046—Specially adapted covering, lining or flooring elements not otherwise provided for for insulation or surface protection, e.g. against noise, impact or fire against fire with a facing or top layer for fire insulation
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- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
Abstract
The invention provides a long-acting micro-odor aroma-releasing type flame-retardant carbon nanosphere and a wood board containing the same. The carbon nanospheres are applied to the wood board to obtain the long-acting micro-odor fragrance-releasing type flame-retardant wood board, and the prepared wood board not only can release micro-odor for a long time, but also has enhanced mechanical property and excellent flame retardant property.
Description
Technical Field
The invention relates to the technical field of interior decoration materials and processing, in particular to a long-acting micro-odor aroma-releasing type flame-retardant carbon nanosphere and a wood board containing the same.
Background
The wood material for the current home interior decoration mainly comprises wood floor boards, wood wall boards, wood furniture, wood skirting lines and other wood artificial boards which are formed by secondary molding of wood, fibers, wood shavings, veneers, battens and the like. In the indoor decoration process, no matter which material is selected, product safety is one of important indexes for measuring the quality of products. Which comprises the following steps: the wood board is unpleasant in smell and long in release period, the wood board is flammable and easy to induce flame spread to cause serious property loss and casualties, and the defects of mechanical strength and the like of the wood board are greatly reduced through conventional flame retardant treatment.
For a wood board, taking a plywood as an example, the plywood achieves the uniformity of each direction of the plywood board through symmetrical thickness direction and criss-cross assembly of adjacent veneers, the veneers and the veneers must be bonded together by an adhesive, and the prepared plywood product usually has peculiar smell which mainly comes from free ammonia in the adhesive, resin or gum volatile matters of the wood veneers, residual acetic acid in wood and other substances. When the wood-based panel is used, especially when the wood-based panel is used as a geothermal floor or a wallboard, the peculiar smell in the wood-based panel can be continuously released in the room environment space under the continuous excitation of heat, so that unpleasant feeling is brought to people, and even the health of people is harmed for a long time. Therefore, some odorous wooden board substrates are added with some fragrant substances in the adhesive, and the fragrant substances mainly comprise chemical perfumes, Chinese herbal medicines, chemical microcapsules (urea-formaldehyde resin coating, phenolic resin coating are more), and the like. However, the addition of these additional chemical flavor substances can destroy the curing performance of the adhesive, and greatly reduce the mechanical properties of the wood board, especially the static bending strength and the elastic modulus. Therefore, in order to ensure the bonding strength between glue layers, an excessive amount of adhesive is usually applied to the wood veneer to ensure good bonding strength between the veneer and the wood veneer, which undoubtedly increases the formaldehyde emission and the adhesive cost of the wood veneer. Therefore, on the premise of ensuring the mechanical property of the wood board, how to avoid the peculiar smell of the wood board in the using process is a difficult problem facing the wood board industry.
As a middle-high end product in the current building decoration, the wood board is not limited to uncomfortable use feeling caused by bad smell to the wood board. The existing solutions for the problems in the market have the defects of complex manufacturing process, high cost, poor practicability, pungent chemical fragrance, good fragrance when the solution is used for several months, beautiful smell gradually disappears, short timeliness and the like.
In addition, the inflammability of the wood board, which is a traditional wood material, is still a prominent disadvantage, which brings about more troubles for application places. At present, some wood boards with flame retardant property are produced and sold in the market, but most of the wood boards adopt a mode that one or more layers of melamine impregnated paper are coated on the surface, and then a wear-resistant layer containing aluminum oxide is coated outside; the liquid flame retardant is also adopted to carry out dipping flame-retardant treatment on the floor base material; these treatments, while having some degree of flame retardant function, have drawbacks. For example, the melamine impregnated paper veneering is mainly in a surface flame-retardant manner, a large amount of melamine chemical raw materials are needed for preparing the melamine impregnated paper, the melamine market selling price is increased dramatically under the influence of international trade at present, the melamine market selling price is increased from 0.7 ten thousand yuan/t at the end of 2020 to 1.5-2.0 ten thousand yuan/t, and the melamine impregnated paper veneering is difficult to return to the selling price of 2020 within a short time. In addition, the melamine impregnated paper mainly adopts raw paper to impregnate melamine formaldehyde resin adhesives, so that the melamine impregnated paper contains a large amount of free formaldehyde, which is harmful to physical and mental health of people, and in order to eliminate the influence of formaldehyde in the impregnated paper, a large amount of chemical additives for adsorbing formaldehyde or degrading formaldehyde are often required to be added, so that the problems of poor surface quality of products, high cost and the like are caused; the liquid flame retardant is used for carrying out impregnation treatment on a base material, and mainly comprises the steps of enabling chemical reagents containing phosphorus and nitrogen such as melamine phosphate, ammonium polyphosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and the like to enter a wood cell cavity, enabling the chemical reagents containing phosphorus and nitrogen to remain in a wood veneer after drying, and enabling the wood veneer to be assembled into wood board products such as plywood and the like through layer-by-layer compounding. The treatment mode adopts the base material for flame retardance, has the advantages of good flame retardant effect, low fire hazard spreading index and the like, and has the defects that the wood veneer is often embrittled by using the nitrogen-phosphorus flame retardant, and the mechanical strength of the wood veneer and the wood board is reduced, so that the bending mechanical strength of the flame-retardant wood board obtained by the flame-retardant technology is generally reduced by 30-50% compared with the same type of non-flame-retardant wood board, and the method is unfavorable for the policy of saving materials and reducing consumption in the field of wood industry, the use of end products of the wood board and the like.
Therefore, the existing wood board can not meet the existing diversified market demand of people for the long-acting micro-odor releasing function, and the wood board has high flame retardant treatment cost, low mechanical strength, and can not meet the application demands of low production cost, multiple effects and simple use.
Disclosure of Invention
In view of the problems in the prior art, it is an object of the present invention to provide a long-lasting micro-odor releasing type flame-retardant carbon nanoball capable of releasing fragrance for a long time and having excellent flame-retardant property.
The second objective of the present invention is to provide a method for preparing long-acting micro-odor aroma-releasing flame-retardant carbon nanospheres corresponding to the first objective.
The invention also aims to provide a long-acting micro-odor fragrance-releasing type flame-retardant wood board containing the long-acting micro-odor fragrance-releasing type flame-retardant carbon nanospheres, which corresponds to the aim.
The fourth purpose of the invention is to provide a preparation method of the long-acting micro-odor fragrance-releasing flame-retardant wood board corresponding to the purpose.
In order to achieve one of the purposes, the technical scheme adopted by the invention is as follows:
a long-acting micro-odor aroma-releasing type flame-retardant carbon nanosphere comprises the following elements: 40.2 to 46.8 percent of C, 5.9 to 10.6 percent of N, 43.2 to 54.1 percent of O, 3.4 to 5.2 percent of B and 0.6 to 1.1 percent of P.
According to the invention, the nanosphere provided by the invention has a specific composition, so that the nanosphere can release fragrance for a long time and has excellent flame retardant property.
In the context of the present invention, the term "long-lasting" means capable of retaining an odor for at least 7 days.
In the context of the present invention, the term "micro-odor" refers to a class 1 or class 2 odor as specified in LY/T3236-2020.
In some preferred embodiments of the present invention, the carbon nanoball has an average particle size of 2nm to 15nm, preferably 4nm to 8 nm.
In some preferred embodiments of the present invention, the carbon nanoball is capable of maintaining the grade 1 odor or the grade 2 odor specified in LY/T3236-2020 for at least 7 days, preferably at least 30 days, more preferably at least 60 days, further preferably at least 180 days, and still further preferably at least 300 days.
In some preferred embodiments of the present invention, the carbon nanoball has a homogeneous structure.
In some preferred embodiments of the present invention, the surface of the carbon nanoball has one or more groups selected from the group consisting of amino group, carboxyl group, hydroxyl group and borohydroxyl group, and preferably, the content of the group is 20 to 35% of the mass of the carbon nanoball.
Without wishing to be bound by theory, the inventors have analyzed that the carbon nanoball provided by the present invention overcomes the strong odor of the prior art to have a slight odor, and the slight odor can be released for a long time because of the large number of "hydrogen bonds" inside the material. In addition, the carbon nanoball provided by the present invention has flame retardant property because it contains a large amount of nitrogen and boron elements and a small amount of phosphorus element.
In order to achieve the second purpose, the invention adopts the following technical scheme:
a preparation method of long-acting micro-odor aroma-releasing flame-retardant carbon nanospheres comprises the following steps:
s1, mixing a pepper shell with a solvent to obtain a first reaction liquid, and carrying out a solvothermal reaction on the reaction liquid to obtain a first reaction product;
s2, carrying out solid-liquid separation treatment on the first reaction product to obtain filtrate and solid residue;
s3, mixing the filtrate, the protein compound and the boron-containing compound to obtain a second reaction solution, and carrying out solvothermal reaction on the second reaction solution to obtain a suspension of carbon-containing nanospheres; and
and optionally, S4, removing the solvent in the suspension of the carbon-containing nanospheres to obtain the carbon nanospheres.
According to the invention, the pepper shells are selected from at least one of green pepper shells and safflower pepper shells. The producing area and the specific variety of the pericarpium zanthoxyli are not limited.
In some preferred embodiments of the present invention, in step S1, the solvent is selected from water and C1～C4At least one of the alcohols, preferably comprising water and at least one C1～C4An alcohol, more preferably water and ethanol, and still more preferably the mass ratio of the water to the ethanol is (10:1) to (5: 1); and/or the mass ratio of the pepper shells to the solvent is (1:100) - (10: 100).
In some preferred embodiments of the present invention, the reaction temperature of the solvothermal reaction is 60 ℃ to 95 ℃; the reaction time of the solvothermal reaction is 45-90 min.
In some preferred embodiments of the present invention, in step S3, the proteinaceous compound is selected from at least one of soy protein, pea protein, protein isolate, collagen, and protein powder.
In some preferred embodiments of the present invention, the boron-containing compound is selected from at least one of boric acid, polyboronic acid, phenylboronic acid, metaboric acid, carboxyphenylboronic acid, and methylboronic acid.
In some preferred embodiments of the present invention, the reaction temperature of the solvothermal reaction is from 150 ℃ to 240 ℃; the reaction time of the solvothermal reaction is 2.0-5.0 h.
The conventional pepper fragrance extraction mainly adopts hot water extraction, and the temperature of the hot water is generally not higher than 90 ℃; or extracting with ethanol at normal temperature. The obtained fructus Zanthoxyli has strong fragrance, pungent and spicy taste, simple components, single function and easy volatilization, and has no long-lasting effect when used as material. The inventor of the application finds in research that the preparation method provided by the invention can prepare the long-acting micro-odor aroma-releasing type flame-retardant carbon nanosphere with long-acting performance.
In order to achieve the third purpose, the technical scheme adopted by the invention is as follows:
a long-acting micro-odor releasing flame retardant wood-based panel, comprising a wood-based panel substrate and a carbon nanoball on the wood-based panel substrate, wherein the carbon nanoball is selected from at least one of the carbon nanoball of the above embodiments or the carbon nanoball prepared by the preparation method of any one of the above embodiments.
In some preferred embodiments of the present invention, the carbon nanoball may be 5 to 12% by mass based on the total weight of the wood-based panel substrate.
In order to achieve the fourth purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a long-acting micro-odor fragrance-releasing flame-retardant wood board comprises the following steps: a carbon nanoball of any one of the above embodiments or a carbon nanoball manufactured by the manufacturing method of any one of the above embodiments is formed on a wood-based board substrate.
In some preferred embodiments of the present invention, the forming is performed by at least one selected from a spraying process, a dipping process, and a mixing process.
In some preferred embodiments of the present invention, the spraying process comprises the following steps:
the method comprises the following steps: spraying a spraying liquid comprising the carbon nanospheres and a solvent on the wood board substrate to obtain a processed wood board substrate; and
step two: removing the solvent from the treated wood-based panel substrate.
In some preferred embodiments of the present invention, the impregnation process comprises the following steps:
step 1: dipping the wood board substrate by using a dipping solution comprising the carbon nanospheres and a solvent to obtain a dipped wood board substrate; and
step 2: removing the solvent from the impregnated wood-based panel substrate.
In some preferred embodiments of the present invention, the mixing process comprises the following steps:
step a: coating the sizing material comprising the carbon nanospheres and the adhesive on the surface of the wood board substrate to obtain the glued wood board substrate;
step b: assembling and pressing a plurality of glued wood board substrates to obtain the long-acting micro-odor fragrance-releasing flame-retardant wood board.
In some preferred embodiments of the present invention, in step one, the solvent is ethanol; and/or the mass ratio of the carbon nanospheres to the solvent is 1: 5-1: 10.
In some preferred embodiments of the present invention, in step 1, the solvent is water; and/or the mass ratio of the carbon nanoball to the solvent is (1:10) to (1: 20); and/or the conditions of the impregnation treatment include: the pressure is 0.06 MPa-0.1 MPa, the time is calculated according to the following formula (1),
treatment time D/10mm X30 min formula (1)
In the formula (1), D represents the thickness of the wood board substrate and has a unit of mm.
In some preferred embodiments of the present invention, in the step a, the adhesive is at least one selected from urea formaldehyde resin adhesive and wet polyvinyl alcohol-doped zanthoxylum bungeanum crushed powder, wherein the wet polyvinyl alcohol-doped zanthoxylum bungeanum crushed powder is prepared by the solid residue described in the step S2.
In some preferred embodiments of the present invention, the method for preparing the wet polyvinyl alcohol-doped zanthoxylum bungeanum mill comprises the following steps:
step A: crushing the solid residue to 80-120 meshes to obtain crushed pepper powder;
and B: and mixing the ground pepper with polyvinyl alcohol to obtain the ground pepper doped with the wet polyvinyl alcohol.
In some preferred embodiments of the present invention, the polyvinyl alcohol is used in an amount of 0.1 wt% to 5 wt%, preferably 0.5 wt% to 2 wt%, based on the absolute dry mass of the ground zanthoxylum bungeanum, more preferably, the polyvinyl alcohol has an average molecular weight of 500 to 10000, preferably 1000 to 3000.
In some preferred embodiments of the invention, in the step a, the adhesive comprises a urea-formaldehyde resin adhesive and wet polyvinyl alcohol-doped pepper powder, and the mass ratio of the urea-formaldehyde resin adhesive to the wet polyvinyl alcohol-doped pepper powder is (8-20): 1.
In some preferred embodiments of the present invention, in the step a, the mass percentage of the carbon nanoball relative to the adhesive is 5% to 12%.
In the context of the present invention, the content of the surface groups of the carbon nanoball is measured on the basis of the mass of the carbon nanoball.
In the context of the present invention, elemental content refers to the relative elemental content, which is measured on the basis of the total mass of C, N, O, B and P.
The invention has the advantages that at least the following aspects are realized:
firstly, the carbon nanosphere provided by the invention can release fragrance for a long time and has excellent flame retardant property, and the fragrance released by the carbon nanosphere is comfortable and pleasant.
Secondly, the wood-based panel containing the carbon nanoball provided by the invention has the advantages of high mechanical strength and low production cost besides the characteristics of the carbon nanoball.
Drawings
Fig. 1 is an elemental energy spectrum of the long-acting micro-odor aroma-releasing flame-retardant carbon nanoball of preparation example 1.
Fig. 2 is a distribution energy spectrogram of the long-acting micro-odor aroma-releasing type flame-retardant carbon nanospheres in the wood board. Wherein, (a) is the surface appearance of the functional wood board; (b) is a functional wood board surface carbon energy spectrum; (c) the surface oxygen energy spectrum of the functional wood board is obtained; (d) the method is a functional wood board surface nitrogen energy spectrum; (e) is a functional wood board surface boron energy spectrum; (f) is a functional wood board surface phosphorus energy spectrum.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are commercially available, and are not indicated by manufacturers.
In the following embodiments:
(1) and the odor is evaluated according to LY/T3236 and 2020 odor grading and evaluation method of artificial boards and products thereof.
(2) Flame retardancy oxygen index was determined according to GB/T2406.2-2009 method, oxygen index indicating whether the material is easily combustible, > 30.0% indicating a nonflammable material (B1 rating).
(3) The mechanical properties are evaluated according to GBT 17657 and 2013 physicochemical property test method for artificial boards and veneered artificial boards.
(4) Evaluation of long-acting odor performance was evaluated based on the fluorescence intensity of water extract of wood-based panels. The method specifically comprises the steps of weighing 10g of wood board (based on air-dried mass under the condition of 12% of water content), crushing, placing in 1000mL of distilled water, soaking for 24 hours under the normal temperature condition, stirring, centrifuging at 8000 rpm, taking supernatant, and testing the fluorescence intensity of liquid under the 365nm excitation condition by using a fluorescence spectrophotometer. The wood board has low fluorescence intensity because the precipitates of water soaking mainly comprise a small amount of extracts, pigments and the like under the normal temperature condition. The long-acting micro-odor aroma-releasing type flame-retardant carbon nanospheres developed by the patent have good water solubility and excellent fluorescence intensity, so that when the wood material is soaked by water, the carbon nanospheres on the surface and in the deep layer of the wood material can enter the aqueous solution, the fluorescence intensity of the aqueous solution is increased, the retention amount of the fluorescent carbon nanomaterials is estimated by testing the fluorescence intensity of the liquid, and the feasibility of long-acting micro-odor aroma release is further verified.
In the following embodiment, polyvinyl alcohol was used in a type of MW 1788.
Preparation example 1 preparation of long-acting micro-odor aroma-releasing type flame-retardant carbon nanoball
1) Firstly taking 3.2g of shells of the red pepper, preparing a water/alcohol mixed solvent, wherein the mass ratio of water to ethanol is 5:1, mixing the pepper mixture (absolute dry mass) and the mixed solvent according to the mass ratio of 2:100, and carrying out solvothermal reaction for 60min at the temperature of 80 ℃. The filtrate was then collected by filtration using a 200 mesh sieve and the solid residue was collected.
2) The solid residue is physically crushed to be within the particle size range of 80 meshes, 1% of polyvinyl alcohol is added according to the absolute dry mass of the solid residue, and the solid residue and the polyvinyl alcohol are fully mixed to be used as an adhesive admixture for standby.
3) The pepper shell filtrate, the soybean protein isolate and the phenylboronic acid functional auxiliary agent are mixed according to the mass ratio of 100: 0.05: 0.5, mixing, and fully and magnetically stirring at 45 ℃ to form a suspension.
5) And (3) putting 180.0g of the suspension in a 250mL sealed reactor, carrying out solvothermal reaction for 4.0 hours at the temperature of 200 ℃, naturally cooling to room temperature, taking out the solution, filtering by a 200-mesh filter screen, and collecting filtrate.
6) And freeze-drying the filtrate to obtain the long-acting micro-odor aroma-releasing type flame-retardant carbon nanospheres.
The elemental analysis shows that the elemental composition comprises: the elemental energy spectrum of the long-acting micro-odor aroma-releasing flame-retardant carbon nanosphere obtained by 43.2% of C, 8.4% of N, 43.5% of O, 4.1% of B and 0.8% of P is shown in figure 1. The surface of the sample was found to contain 5.2% of amino groups, 10.6% of carboxyl groups, 12.4% of hydroxyl groups and 3.8% of borohydroxyl groups by X-ray photoelectron spectroscopy.
The average particle diameter of the carbon nanoball is 6.35nm as determined by transmission electron microscope analysis.
Preparation example 2 preparation of long-acting micro-odor aroma-releasing flame-retardant carbon nanospheres
The only difference from preparation example 1 was that the temperature of the solvothermal reaction in step 1) was 60 ℃ and the time was 45 min.
The elemental analysis shows that the elemental composition comprises: 40.2% of C, 6.1% of N, 48.2% of O, 4.8% of B and 0.7% of P.
The surface of the sample was found to contain 3.6% of amino groups, 14.5% of carboxyl groups, 11.4% of hydroxyl groups and 4.6% of borohydroxyl groups by X-ray photoelectron spectroscopy.
The average particle diameter of the carbon nanoball is 7.24nm as determined by transmission electron microscope analysis.
Preparation example 3 preparation of long-acting micro-odor aroma-releasing flame-retardant carbon nanospheres
The only difference from preparation example 1 is that the temperature of the solvothermal reaction in step 1) was 95 ℃ and the time was 90 min.
The elemental analysis shows that the elemental composition comprises: 41.8% of C, 8.8% of N, 43.4% of O, 5.1% of B and 0.9% of P.
As can be seen from X-ray photoelectron spectroscopy analysis, the surface thereof contained 6.3% of amino groups, 12.8% of carboxyl groups, 10.6% of hydroxyl groups and 4.8% of borohydroxyl groups.
The average particle diameter of the carbon nanoball is 4.78nm as determined by transmission electron microscope analysis.
Preparation example 4 preparation of long-acting micro-odor aroma-releasing flame-retardant carbon nanospheres
The only difference from preparation example 1 was that the temperature of the solvothermal reaction in step 5) was 150 ℃ and the time was 2.0 hours.
The elemental composition of the material is shown by elemental analysis to comprise: 46.2% of C, 10.1% of N, 39.5% of O, 3.6% of B and 0.6% of P.
The surface of the sample was found to contain 7.4% of amino groups, 8.2% of carboxyl groups, 10.1% of hydroxyl groups and 3.2% of borohydroxyl groups by X-ray photoelectron spectroscopy.
The average particle diameter of the carbon nanoball is 7.69nm as determined by transmission electron microscope analysis.
Preparation example 5 preparation of long-acting micro-odor aroma-releasing flame-retardant carbon nanospheres
The only difference from preparation example 1 was that the temperature of the solvothermal reaction in step 5) was 240 ℃ and the time was 5.0 hours.
The elemental composition of the material is shown by elemental analysis to comprise: 40.6% of C, 6.7% of N, 47.3% of O, 4.8% of B and 0.9% of P.
As a result of X-ray photoelectron spectroscopy, the surface contained 4.9% of amino groups, 14.0% of carboxyl groups, 11.4% of hydroxyl groups and 4.5% of borohydroxyl groups.
The average particle diameter of the carbon nanoball is 4.21nm as determined by transmission electron microscope analysis.
Comparative preparation example 1 preparation of long-acting micro-odor aroma-releasing flame-retardant carbon nanoball
The only difference from preparation example 1 was that the temperature of the solvothermal reaction in step 1) was 50 ℃ and the time was 60 min.
The elemental composition of the material is shown by elemental analysis to comprise: 42.7% of C, 4.3% of N, 51.2% of O, 1.6% of B and 0.2% of P.
As a result of X-ray photoelectron spectroscopy, the surface contained 1.6% of amino groups, 9.4% of carboxyl groups, 13.7% of hydroxyl groups and 1.2% of borohydroxyl groups.
The average particle diameter of the carbon nanoball is 9.73nm as determined by transmission electron microscope analysis.
Comparative preparation example 2 preparation of long-acting micro-odor aroma-releasing flame-retardant carbon nanospheres
The only difference from preparation example 1 is that the temperature of the solvothermal reaction in step 1) was 100 ℃ and the time was 60 min.
The elemental analysis shows that the elemental composition comprises: 40.6% of C, 4.7% of N, 52.9% of O, 1.5% of B and 0.3% of P.
As a result of X-ray photoelectron spectroscopy, the surface contained 1.7% of amino groups, 11.2% of carboxyl groups, 10.6% of hydroxyl groups and 1.1% of borohydroxyl groups.
The average particle diameter of the carbon nanoball is 2.31nm as determined by transmission electron microscope analysis.
Comparative preparation example 3 preparation of long-acting micro-odor aroma-releasing flame-retardant carbon nanoball
The only difference from preparation example 1 was that the temperature of the solvothermal reaction in step 5) was 120 ℃ and the time was 4.0 hours.
The elemental analysis shows that the elemental composition comprises: 47.5% of C, 2.1% of N, 49.6% of O, 0.7% of B and 0.1% of P.
The surface of the sample was found to contain 1.2% of amino groups, 7.8% of carboxyl groups, 8.1% of hydroxyl groups and 0.4% of borohydroxyl groups by X-ray photoelectron spectroscopy.
The average particle diameter of the carbon nanoball is 16.54nm as determined by transmission electron microscope analysis.
Comparative preparation example 4 preparation of long-acting micro-odor aroma-releasing flame-retardant carbon nanospheres
The only difference from preparation example 1 was that the temperature of the solvothermal reaction in step 5) was 260 ℃ and the time was 4.0 hours.
The elemental analysis shows that the elemental composition comprises: 39.5% C, 3.2% N, 56.4% O, 0.8% B, 0.1% P.
The surface of the sample was found to contain 1.5% of amino groups, 13.8% of carboxyl groups, 11.6% of hydroxyl groups and 0.5% of borohydroxyl groups by X-ray photoelectron spectroscopy.
The average particle diameter of the carbon nanoball is 1.78nm as determined by transmission electron microscope analysis.
Example 1 preparation of Long-acting micro-odor aroma-releasing flame-retardant charcoal wood board
Using poplar veneer (2mm thick) as a unit, urea-formaldehyde resin adhesive as a binder, wherein the single surface of the adhesive coating amount is 100g/m2And hot pressing after assembly to prepare the wood plywood. The hot pressing temperature is 180 ℃, the hot pressing time is 1mm/min, and the multilayer wood plywood product with the thickness of 9.2mm is obtained.
The carbon nanoball prepared by preparation example 1 is mixed with ethanol in a mass ratio of 1:5Mixing to obtain a solution, and spraying the solution on the surface of the wood board with the spraying amount of 15-25 g/m2And stopping spraying until liquid beads are formed on the surface, performing oven heat treatment at 40 ℃ to volatilize the solvent, repeatedly spraying for 2-4 times according to the requirement of odor intensity, and drying to obtain the long-acting micro-odor fragrance-releasing type flame-retardant wood board.
Through the weight difference analysis before and after, the mass percentage content of the carbon nanosphere is 4.6 percent based on the total weight of the wood plate. The distribution energy spectrogram of the obtained long-acting micro-odor aroma-releasing type flame-retardant carbon nanospheres in the wood board is shown in fig. 2. As shown in fig. 2, the long-acting micro-odor aroma-releasing flame-retardant carbon nanospheres are distributed relatively uniformly in the wood-based panel, and have a positive effect on long-acting micro-odor aroma release and flame retardance of the wood-based panel.
Example 2
Using a poplar veneer (2mm thick) as a unit, using a urea-formaldehyde resin adhesive as a binder, and crushing the carbon nanospheres, the urea-formaldehyde resin adhesive and the wet polyvinyl alcohol (type: MW1788) doped pepper prepared in the preparation example 1 according to a mass ratio of 5: 100: 5 mixing, coating amount of single side 100g/m2And hot pressing after assembly to prepare the wood plywood. The hot pressing temperature is 180 ℃, the hot pressing time is 1mm/min, and the multilayer wood plywood product with the thickness of 9.2mm is obtained.
And then, further spraying the wood board, so as to improve the fragrance releasing particle ratio and the surface flame retardant property of the surface material of the wood board. Mixing a 'multi-active-site carbon sphere' nano material with ethanol according to a mass ratio of 1:5 to prepare a solution, and spraying the solution on the surface of a wood board, wherein the spraying amount is 15-25 g/m2And stopping spraying until liquid beads are formed on the surface, performing oven heat treatment at 40 ℃ to volatilize the solvent, repeatedly spraying for 2-4 times according to the requirement of odor intensity, and drying to obtain the long-acting micro-odor fragrance-releasing type flame-retardant wood board.
Through the weight difference analysis before and after, the mass percentage content of the carbon nanospheres is 9.5 percent based on the total weight of the wood plate.
Example 3
The only difference from example 1 is that the carbon nanoball prepared in preparation example 2 is used.
Example 4
The only difference from example 1 is that the carbon nanoball prepared in preparation example 3 is used.
Example 5
The only difference from example 1 is that the carbon nanoball prepared in preparation example 4 is used.
Example 6
The only difference from example 1 is that the carbon nanoball prepared in preparation example 5 is used.
Comparative example 1
Using poplar veneer (2mm thick) as unit, adopting urea-formaldehyde resin adhesive as binder, and its adhesive coating quantity is 100g/m2And assembling and hot pressing to prepare the wood plywood. The hot pressing temperature is 180 ℃, the hot pressing time is 1mm/min, and the multilayer wood plywood product with the thickness of 9.2mm is obtained.
Comparative example 2
The only difference from example 1 is that the carbon nanoball prepared in comparative preparation example 1 is used.
Using poplar veneer (2mm thick) as unit, adopting urea-formaldehyde resin adhesive as binder, and its adhesive coating quantity is 100g/m2And assembling and hot pressing to prepare the wood plywood. The hot pressing temperature is 180 ℃, the hot pressing time is 1mm/min, and a multilayer wood plywood product with the thickness of 9.2mm is obtained.
Mixing the carbon nanospheres prepared in the comparative preparation example 1 with ethanol according to the mass ratio of 1:5 to prepare a solution, and spraying the solution on the surface of a wood plate, wherein the spraying amount is 15-25 g/m2And stopping spraying until liquid beads are formed on the surface, volatilizing the solvent by oven heat treatment at 40 ℃, repeatedly spraying for 2-4 times, and drying to obtain the wood board. Through the weight difference analysis before and after, the mass percentage content of the carbon nanosphere is 3.2 percent based on the total weight of the wood plate.
The difference from example 1 is that the wood board sprayed with carbon nanoball obtained in comparative example 2 reaches class 1 odor (slightly odor) specified in LY/T3236-. It was confirmed that the first solvothermal reaction, the solvothermal reaction at a lower temperature (50 ℃), resulted in the subsequent preparation of carbon nanoball having no long-lasting fragrance releasing function and the lasting of fragrance was too short (< 7 days).
Comparative example 3
The only difference from example 1 is that the carbon nanoball prepared in comparative preparation example 2 is used.
Using poplar veneer (2mm thick) as a unit, urea-formaldehyde resin adhesive as a binder, wherein the single surface of the adhesive coating amount is 100g/m2And hot pressing after assembly to prepare the wood plywood. The hot pressing temperature is 180 ℃, the hot pressing time is 1mm/min, and the multilayer wood plywood product with the thickness of 9.2mm is obtained.
Mixing the carbon nanospheres prepared in the comparative preparation example 2 with ethanol according to the mass ratio of 1:5 to prepare a solution, and spraying the solution on the surface of a wood board, wherein the spraying amount is 15-25 g/m2And stopping spraying until liquid beads are formed on the surface, performing oven heat treatment at 40 ℃ to volatilize the solvent, repeatedly spraying for 2-4 times, and drying to obtain the wood board. As can be seen from the weight difference analysis before and after the process, the carbon nanoball has a mass percentage of 5.3% based on the total weight of the wooden board.
The significant difference from example 1 is that the carbon nanoball-sprayed wood board obtained in comparative example 3 achieved class 3 odor (with an odor clearly perceived as unpleasant) specified in LY/T3236-2020, was strong and pungent and long-lasting. It was confirmed that the first solvothermal reaction, in which the solvothermal reaction is carried out at a higher temperature (100 ℃), causes the carbon nanoball to be subsequently prepared to have no flavor-releasing function but to have a flavor that is perceived as unpleasant.
Comparative example 4
The only difference from example 1 is that the carbon nanoball prepared in comparative preparation example 3 is used.
Using poplar veneer (2mm thick) as unit, adopting urea-formaldehyde resin adhesive as binder, and its adhesive coating quantity is 100g/m2And assembling and hot pressing to prepare the wood plywood. The hot pressing temperature is 180 ℃, the hot pressing time is 1mm/min, and the multilayer wood plywood product with the thickness of 9.2mm is obtained.
Mixing the carbon nanospheres prepared in the comparative preparation example 3 with ethanol according to the mass ratio of 1:5 to prepare a solution, and spraying the solution on the surface of a wood plate, wherein the spraying amount is 15-25 g/m2Stopping spraying when liquid beads are formed on the surface, and at 40 deg.CAnd (4) carrying out heat treatment in an oven to volatilize the solvent, repeatedly spraying for 2-4 times, and drying to obtain the wood board. As can be seen from the weight difference analysis before and after the process, the carbon nanoball has a mass percentage of 1.6% based on the total weight of the wooden board.
The significant difference from example 1 is that the carbon nanoball-sprayed wood-based panel obtained in comparative example 4 achieved a class 3 odor (with an odor that is clearly perceived as unpleasant) as specified in LY/T3236-. It was confirmed that the carbon nanoball does not have the function of releasing fragrance but has an unpleasant odor due to the solvothermal reaction at an excessively low temperature (120 deg.c) in the second solvothermal reaction.
Comparative example 5
The only difference from example 1 is that the carbon nanoball prepared in comparative preparation example 4 is used.
Using poplar veneer (2mm thick) as a unit, urea-formaldehyde resin adhesive as a binder, wherein the single surface of the adhesive coating amount is 100g/m2And assembling and hot pressing to prepare the wood plywood. The hot pressing temperature is 180 ℃, the hot pressing time is 1mm/min, and the multilayer wood plywood product with the thickness of 9.2mm is obtained.
Mixing the carbon nanospheres prepared in the comparative preparation example 4 with ethanol according to the mass ratio of 1:5 to prepare a solution, and spraying the solution on the surface of a wood plate, wherein the spraying amount is 15-25 g/m2And stopping spraying until liquid beads are formed on the surface, performing oven heat treatment at 40 ℃ to volatilize the solvent, repeatedly spraying for 2-4 times, and drying to obtain the wood board. Through the weight difference analysis before and after, the mass percentage content of the carbon nanosphere is 1.6 percent based on the total weight of the wood plate.
The significant difference from example 1 is that the carbon nanoball-sprayed wood board obtained in comparative example 5 achieved class 3 odor (with an odor clearly perceived as unpleasant) specified in LY/T3236-2020, was strong and pungent and long-lasting. It was confirmed that the carbon nanoball does not have the function of releasing fragrance by the solvothermal reaction at an excessively high temperature (260 deg.c) at the second solvothermal reaction.
Test example 1
The properties of the wood-based boards obtained in examples 1 to 6 and comparative examples 1 to 5 were measured, and the results are shown in tables 1 to 3 below.
TABLE 1 flame retardant property and smell experimental results of slightly-smelling fragrance-releasing wood board
Table 2 mechanical property experiment results of wood board releasing fragrance with slight smell
| Types of | Static bending strength | Modulus of elasticity | Bonding strength | Impact strength |
| Comparative example 1 | 28.71MPa | 5260MPa | 0.72MPa | 18.32kJ/m2 |
| Comparative example 2 | 28.78MPa | 5310MPa | 0.73MPa | 18.41kJ/m2 |
| Comparative example 3 | 29.42MPa | 5680MPa | 0.75MPa | 18.52kJ/m2 |
| Comparative example 4 | 29.77MPa | 5240MPa | 0.76MPa | 18.54kJ/m2 |
| Comparative example 5 | 27.94MPa | 5035MPa | 0.69MPa | 17.92kJ/m2 |
| Example 1 | 30.65MPa | 5510MPa | 0.74MPa | 19.64kJ/m2 |
| Example 2 | 31.72MPa | 5840MPa | 0.82MPa | 21.27kJ/m2 |
| Example 3 | 30.76MPa | 5460MPa | 0.75MPa | 19.73kJ/m2 |
| Example 4 | 30.95MPa | 5495MPa | 0.78MPa | 19.85kJ/m2 |
| Example 5 | 30.85MPa | 5380MPa | 0.81MPa | 20.14kJ/m2 |
| Example 6 | 31.24MPa | 5675MPa | 0.80MPa | 20.85kJ/m2 |
TABLE 3 odor long-term performance monitoring of micro-odor fragrance-releasing wood board
TABLE 4 odor long-term performance monitoring of micro-odor fragrance-releasing wood board
TABLE 5 odor long-term Performance monitoring of micro-odor fragrance-releasing Wood boards
TABLE 6 odor long-acting performance monitoring of micro-odor fragrance-releasing wood board
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A long-acting micro-odor aroma-releasing flame-retardant carbon nanosphere comprises the following elements: 40.2 to 46.8 percent of C, 5.9 to 10.6 percent of N, 43.2 to 54.1 percent of O, 3.4 to 5.2 percent of B and 0.6 to 1.1 percent of P;
preferably, the carbon nanoball has an average particle size of 2nm to 15nm, preferably 4nm to 8 nm;
more preferably, the carbon nanoball is capable of retaining the grade 1 odor or the grade 2 odor specified in LY/T3236-.
2. The carbon nanoball of claim 1, having a homogeneous structure; preferably, the surface of the carbon nanosphere has one or more groups of amino group, carboxyl group, hydroxyl group and boron hydroxyl group, and preferably, the content of the group is 20-35% of the mass of the carbon nanosphere.
3. A preparation method of long-acting micro-odor aroma-releasing flame-retardant carbon nanospheres comprises the following steps:
s1, mixing a pepper shell with a solvent to obtain a first reaction liquid, and carrying out a solvothermal reaction on the reaction liquid to obtain a first reaction product;
s2, carrying out solid-liquid separation treatment on the first reaction product to obtain filtrate and solid residue;
s3, mixing the filtrate, the protein compound and the boron-containing compound to obtain a second reaction solution, and carrying out solvothermal reaction on the second reaction solution to obtain a suspension of carbon-containing nanospheres; and
and optionally S4, removing the solvent in the suspension of the carbon-containing nanospheres to obtain the carbon nanospheres.
4. The method according to claim 3, wherein in step S1, the solvent is selected from the group consisting of water and C1～C4At least one of the alcohols, preferably comprising water and at least one C1～C4An alcohol, more preferably water and ethanol, and further preferably the mass ratio of the water to the ethanol is (10:1) to (5: 1); and/or the mass ratio of the pepper shells to the solvent is (1:100) - (10: 100);
preferably, the reaction temperature of the solvothermal reaction is 60-95 ℃; the reaction time of the solvothermal reaction is 45-90 min.
5. The method according to claim 3 or 4, wherein in step S3, the protein compound is at least one selected from the group consisting of soy protein, pea protein, protein isolate, collagen and protein powder; and/or
The boron-containing compound is at least one selected from boric acid, polyboric acid, phenylboronic acid, metaboric acid, carboxyphenylboronic acid and methylboronic acid;
preferably, the reaction temperature of the solvothermal reaction is 150-240 ℃; the reaction time of the solvothermal reaction is 2.0-5.0 h.
6. A long-acting micro-odor releasing flame retardant wooden board, which comprises a wooden board substrate and a carbon nanosphere positioned on the wooden board substrate, wherein the carbon nanosphere is at least one of the carbon nanosphere as claimed in claim 1 or 2 or the carbon nanosphere prepared according to the preparation method of any one of claims 3-5.
7. The wood-based panel according to claim 6, wherein the carbon nanoball is 5-12% by weight based on the total weight of the wood-based panel substrate.
8. A preparation method of a long-acting micro-odor fragrance-releasing flame-retardant wood board comprises the following steps: a carbon nanoball of claim 1 or 2 or manufactured by the manufacturing method of any one of claims 3 to 5 is formed on a substrate of a wooden board.
9. The method of claim 8, wherein the forming is performed by at least one selected from a spraying process, a dipping process, and a mixing process;
when the spraying process is adopted, the method comprises the following steps:
the method comprises the following steps: spraying a spraying liquid comprising the carbon nanospheres and a solvent on the wood board substrate to obtain a processed wood board substrate; and
step two: removing the solvent from the treated wood board substrate;
when the dipping process is adopted, the method comprises the following steps:
step 1: dipping the wood board substrate by using a dipping solution comprising the carbon nanospheres and a solvent to obtain a dipped wood board substrate; and
and 2, step: removing the solvent from the impregnated wood panel substrate;
when the mixing process is adopted, the method comprises the following steps:
a, step a: coating the sizing material comprising the carbon nanospheres and the adhesive on the surface of the wood board substrate to obtain the glued wood board substrate;
step b: assembling and pressing a plurality of wood board substrates after gluing to obtain the long-acting micro-odor fragrance-releasing flame-retardant wood board.
10. The method according to claim 9, wherein in the first step, the solvent is ethanol; and/or the mass ratio of the carbon nanospheres to the solvent is 1: 5-1: 10; and/or
In the step 1, the solvent is water; and/or the mass ratio of the carbon nanoball to the solvent is (1:10) to (1: 20); and/or the conditions of the impregnation treatment include: the pressure is 0.06 MPa-0.1 MPa, the time is calculated according to the following formula (1),
the processing time is D/10mm multiplied by 30min formula (1) in formula (1), wherein D represents the thickness of the wood board matrix and the unit is mm; and/or
In the step a, the adhesive is selected from at least one of urea-formaldehyde resin adhesive and wet polyvinyl alcohol-doped ground pepper, wherein the wet polyvinyl alcohol-doped ground pepper is prepared from the solid residue in the step S2; preferably, the preparation method of the wet polyvinyl alcohol doped pepper powder comprises the following steps:
step A: crushing the solid residue to 80-120 meshes to obtain crushed pepper powder;
and B: mixing the ground pepper with polyvinyl alcohol to obtain the wet-state polyvinyl alcohol-doped ground pepper, preferably, according to the absolute dry mass of the ground pepper, the using amount of the polyvinyl alcohol is 0.1-5 wt%, preferably 0.5-2 wt%, more preferably, the average molecular weight of the polyvinyl alcohol is 500-10000, preferably 1000-3000;
preferably, in the step a, the adhesive comprises a urea-formaldehyde resin adhesive and wet polyvinyl alcohol-doped pepper powder, and the mass ratio of the urea-formaldehyde resin adhesive to the wet polyvinyl alcohol-doped pepper powder is (8-20): 1;
more preferably, in the step a, the mass percentage of the carbon nanoball to the adhesive is 5 to 12%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106629655A (en) * | 2017-01-05 | 2017-05-10 | 中国科学院新疆理化技术研究所 | Application and preparation method of biomass-based nitrogen-doped porous carbon |
| CN108557803A (en) * | 2018-05-08 | 2018-09-21 | 闽南师范大学 | A kind of Nano carbon balls of solid phase microwave method synthesis doping nitrogen sulphur, preparation method and applications |
| CN109467073A (en) * | 2018-09-25 | 2019-03-15 | 江苏天雨环保集团有限公司 | A kind of preparation method and applications of porous carbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106629655A (en) * | 2017-01-05 | 2017-05-10 | 中国科学院新疆理化技术研究所 | Application and preparation method of biomass-based nitrogen-doped porous carbon |
| CN108557803A (en) * | 2018-05-08 | 2018-09-21 | 闽南师范大学 | A kind of Nano carbon balls of solid phase microwave method synthesis doping nitrogen sulphur, preparation method and applications |
| CN109467073A (en) * | 2018-09-25 | 2019-03-15 | 江苏天雨环保集团有限公司 | A kind of preparation method and applications of porous carbon |
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