CN112852008A - Manufacturing process of graphene composite sponge - Google Patents

Manufacturing process of graphene composite sponge Download PDF

Info

Publication number
CN112852008A
CN112852008A CN202011565445.6A CN202011565445A CN112852008A CN 112852008 A CN112852008 A CN 112852008A CN 202011565445 A CN202011565445 A CN 202011565445A CN 112852008 A CN112852008 A CN 112852008A
Authority
CN
China
Prior art keywords
graphene
slurry
latex
dispersing
sponge
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202011565445.6A
Other languages
Chinese (zh)
Other versions
CN112852008B (en
Inventor
王炳坤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
De Rucci Healthy Sleep Co Ltd
Original Assignee
De Rucci Healthy Sleep Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by De Rucci Healthy Sleep Co Ltd filed Critical De Rucci Healthy Sleep Co Ltd
Priority to CN202011565445.6A priority Critical patent/CN112852008B/en
Publication of CN112852008A publication Critical patent/CN112852008A/en
Application granted granted Critical
Publication of CN112852008B publication Critical patent/CN112852008B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2400/00—Characterised by the use of unspecified polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0856—Iron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0862—Nickel
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The embodiment of the invention discloses a manufacturing process of graphene composite sponge, which is used for solving the technical problem that the sponge structure of the existing mattress cannot detect the sleeping posture of a user. The embodiment of the invention comprises the following steps: s1, providing a graphene polyurethane sponge matrix, wherein the graphene polyurethane sponge matrix sequentially comprises a first part, a second part and a third part which are connected with each other from top to bottom; s2, providing insulating electromagnetic paste, and impregnating the second part and the third part with the insulating electromagnetic paste; s3, providing graphene latex conductive slurry, and dipping the third part by using the graphene latex conductive slurry; and S4, obtaining the graphene composite sponge.

Description

Manufacturing process of graphene composite sponge
Technical Field
The invention relates to the technical field of sponge manufacturing, in particular to a manufacturing process of a graphene composite sponge.
Background
Bedding is the place on which most people spend the longest time, and in the traditional health preserving concept, a user not only allows the brain to rest but also repairs the internal organs of the body during sleeping, so the quality of sleeping not only affects the mental state of the next day, but also seriously affects the long-term physical health.
The user reduces various physiological activities in the sleeping process, only basic metabolism is reserved, the basic metabolism is constant metabolism, the activity degree of the basic metabolism is related to the health condition of internal organs, and by detecting and analyzing the physiological parameters of the body of the user and the sleeping dynamic posture change of the user for a long time, the quality of sleeping can be known, and health, such as the condition of basic diseases, can be inferred. And the sponge structure in the existing mattress lacks corresponding detection function, so that the user can not further know the sleeping process of the user.
Therefore, it is an important subject of research by those skilled in the art to find a manufacturing process of graphene composite sponge to produce sponge capable of solving the above technical problems.
Disclosure of Invention
The embodiment of the invention discloses a manufacturing process of graphene composite sponge, which is used for solving the technical problem that the sponge structure of the existing mattress cannot detect the sleeping posture of a user.
The embodiment of the invention provides a manufacturing process of a graphene composite sponge, which comprises the following steps:
s1, providing a graphene polyurethane sponge matrix, wherein the graphene polyurethane sponge matrix sequentially comprises a first part, a second part and a third part which are connected with each other from top to bottom;
s2, providing insulating electromagnetic paste, and impregnating the second part and the third part with the insulating electromagnetic paste;
s3, providing graphene latex conductive slurry, and dipping the third part by using the graphene latex conductive slurry;
and S4, obtaining the graphene composite sponge.
Optionally, the thickness of the third portion is greater than the thickness of the second portion.
Optionally, the manufacturing method of the graphene polyurethane sponge matrix includes the following steps:
a1, heating nano graphene, carbon nanotubes and polyol with a hydroxyl value of 50-600mgKOH/g to 30-150 ℃ in a reaction kettle according to a weight ratio of 5-20%, and uniformly stirring to obtain graphene polyol slurry;
a2, circularly dispersing the graphene polyol slurry by using a three-roll machine with the diameter larger than 150mm to obtain the graphene polyol slurry with the average graphene particle size smaller than 20 microns;
a3, adding a foaming agent, a surfactant, a cell opening agent and a catalyst into the graphene polyol slurry, and uniformly mixing to obtain a component A; the weight ratio of the foaming agent, the surfactant, the pore-forming agent, the catalyst and the graphene polyol slurry is 0.3-2.5: 0.1-1.5: 0.3-2.5: 0.1-1.2: 100;
isocyanate is selected as a component B, and the number of reaction functional groups in the component A and the component B is equimolar;
a4, respectively maintaining the component A and the component B at 25-60 ℃, respectively pumping the components A and B into a dynamic mixer according to a proportion, uniformly mixing, and then sending into a continuous foaming production line to obtain graphene polyurethane sponge;
a5, cutting the graphene polyurethane sponge block into preset thickness by adopting a high-speed saw blade cutting machine to obtain the graphene polyurethane sponge matrix.
Optionally, the method for manufacturing the insulating electromagnetic paste in step S2 includes the following steps:
b1, mixing the nano ceramic powder and the nano magnetic powder into the water-based resin according to a proportion, adding a dispersing agent, and dispersing by adopting a high-speed fluted disc dispersing machine to obtain first primary dispersion slurry;
and B2, continuously grinding the first primary dispersion slurry for a preset time by using a high-speed nano sand mill to obtain the insulating electromagnetic slurry.
Optionally, the step S2 is followed by a step S21, and the step S21 includes:
and (3) sending the graphene polyurethane sponge matrix impregnated with the insulating electromagnetic paste into a forced air oven, and quickly drying, wherein the temperature of the forced air oven is 40-125 ℃.
Optionally, the method for manufacturing the graphene latex conductive paste in step S3 includes the following steps:
c1, dispersing sulfur, zinc oxide, N-cyclohexyl-2-benzothiazole sulfonamide and 2, 6-di-tert-butyl-4-methylphenol of the latex vulcanization additive and deionized water with the total amount being 3-5 times of the total amount of the sulfur, the zinc oxide, the N-cyclohexyl-2-benzothiazole sulfonamide and the 2, 6-di-tert-butyl-4-methylphenol by using a high-speed fluted disc dispersing machine to obtain second primary dispersion slurry;
c2, continuously grinding the second primary dispersed slurry for a preset time by using a high-speed nano sand mill to obtain uniformly dispersed intermediate slurry with the particle size of less than 100 nanometers;
and C3, confirming the particle size of the intermediate slurry in the step C2 by using a laser particle sizer, adding graphene according to a preset proportion, dispersing the intermediate slurry to be below 10 micrometers at a high speed by using a high-speed fluted disc dispersing machine, adding a latex solution according to a preset proportion, and uniformly dispersing the intermediate slurry with the latex solution to obtain the graphene latex conductive slurry.
Optionally, the step S3 is followed by a step S31, and the step S31 includes:
and (3) sending the graphene polyurethane sponge matrix impregnated with the graphene latex conductive slurry into a forced air drying oven, and rapidly drying, wherein the temperature of the forced air drying oven is 40-125 ℃.
Optionally, the step S2 specifically includes:
providing insulating electromagnetic slurry, uniformly coating the insulating electromagnetic slurry on a continuous and circulating rotating conveying belt by 0.5-5 mm through the thickness of a scraper, placing the second part and the third part of the graphene polyurethane sponge matrix on the slurry, and extruding the insulating electromagnetic slurry into the second part and the third part through a double-roller extruder.
Optionally, the step S3 specifically includes:
providing graphene latex conductive slurry, uniformly coating the graphene latex conductive slurry on a continuous and circular rotating conveying belt by 0.5-5 mm through the thickness of a scraper, placing the third part on the slurry, and extruding the graphene latex conductive slurry into the third part through a double-roller extruder.
Optionally, the high-speed fluted disc disperser is a fluted disc disperser with a fluted disc edge linear velocity exceeding 20 m/s;
the high-speed nanometer sand mill adopts zirconium bead grinding media with the particle size of less than 1mm, and the rotating speed per minute exceeds 500 revolutions.
According to the technical scheme, the embodiment of the invention has the following advantages:
the embodiment of the invention provides a manufacturing process of a graphene composite sponge, which comprises the following steps: s1, providing a graphene polyurethane sponge matrix, wherein the graphene polyurethane sponge matrix sequentially comprises a first part, a second part and a third part which are connected with each other from top to bottom; s2, providing insulating electromagnetic paste, and impregnating the second part and the third part with the insulating electromagnetic paste; s3, providing graphene latex conductive slurry, and dipping the third part by using the graphene latex conductive slurry; and S4, obtaining the graphene composite sponge. In this embodiment, the second portion is impregnated with the insulating electromagnetic paste, the third portion is impregnated with the graphene latex conductive paste, the first portion and the third portion can be connected to an external ac circuit, a dc short circuit does not occur between the first portion and the third portion of the graphene polyurethane sponge base, and a high-capacity capacitive reactance and inductive reactance are formed between the first portion and the third portion, the capacitive reactance and the inductive reactance change rapidly with a change in the ambient environment (a change in humidity and a change in temperature) and a deformation of the graphene composite sponge base (a change in pressure), the change is detected by the external ac circuit and converted into an ac signal of a change in the ambient environment and a deformation of the graphene composite sponge by the ac circuit, and a user can know a change in the ambient environment and a change in the sleep posture of the user through the ac signal, thereby knowing the level of the sleep quality of the user, the health condition of the user can be known.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
Fig. 1 is a flow chart of a manufacturing process of a graphene composite sponge;
fig. 2 is another flow chart of a process for manufacturing a graphene composite sponge;
FIG. 3 is a schematic structural diagram of a graphene composite sponge;
fig. 4 is a graph showing the change of strain and impedance of the graphene composite sponge;
FIG. 5 is a graph showing the relationship between the water content and the impedance of the graphene composite sponge at a working frequency of 1000 Hz;
FIG. 6 is a schematic structural diagram of a continuous production device for extruding and impregnating a graphene polyurethane sponge matrix;
illustration of the drawings: a first portion 1 of a graphene polyurethane sponge matrix; a second portion 2 of the graphene polyurethane sponge matrix; a third portion 3 of the graphene polyurethane sponge matrix; a conductive electrode 4 connected to the first part by an external AC circuit; a conductive electrode 5 connected to the third part via an external AC circuit; a feed roller 6; insulating electromagnetic paste or graphene latex conductive paste 7; a conveyor belt 8; a twin roll extruder 9; a forced air oven 10; a receiving roller 11; a graphene polyurethane sponge matrix 12.
Detailed Description
The embodiment of the invention discloses a manufacturing process of graphene composite sponge, which is used for solving the technical problem that the sponge structure of the existing mattress cannot detect the sleeping posture of a user.
In order that those skilled in the art will better understand the disclosure, the invention will be described in further detail with reference to the accompanying drawings and specific embodiments. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1 to 6, the specific technical solution of the present invention is: a manufacturing process of a graphene composite sponge comprises the following steps:
s1, providing a graphene polyurethane sponge matrix, wherein the graphene polyurethane sponge matrix sequentially comprises a first part, a second part and a third part which are connected with each other from top to bottom;
s2, providing insulating electromagnetic paste, and impregnating the second part and the third part with the insulating electromagnetic paste;
s3, providing graphene latex conductive slurry, and dipping the third part by using the graphene latex conductive slurry;
and S4, obtaining the graphene composite sponge.
In this embodiment, the second portion is impregnated with the insulating electromagnetic paste, the third portion is impregnated with the graphene latex conductive paste, the first portion and the third portion can be connected to an external ac circuit, a dc short circuit does not occur between the first portion and the third portion of the graphene polyurethane sponge base, and a high-capacity capacitive reactance and inductive reactance are formed between the first portion and the third portion, the capacitive reactance and the inductive reactance change rapidly with a change in the ambient environment (a change in humidity and a change in temperature) and a deformation of the graphene composite sponge base (a change in pressure), the change is detected by the external ac circuit and converted into an ac signal of a change in the ambient environment and a deformation of the graphene composite sponge by the ac circuit, and a user can know a change in the ambient environment and a change in the sleep posture of the user through the ac signal, thereby knowing the level of the sleep quality of the user, the health condition of the user can be known.
Further, the thickness of the third portion is greater than the thickness of the second portion.
The first portion, the second portion, and the third portion are all integrally formed.
Further, the manufacturing method of the graphene polyurethane sponge matrix comprises the following steps:
a1, heating nano graphene, carbon nanotubes and polyol with a hydroxyl value of 50-600mgKOH/g to 30-150 ℃ in a reaction kettle according to a weight ratio of 5-20%, and uniformly stirring to obtain graphene polyol slurry;
the polyol is polyether polyol; preferably, the weight percentage of the nano carbon material is 7-15%; the weight ratio of graphene to carbon nanotubes is 10: 0 to 3; the carbon content of the nano graphene is more than 97%, and the specific surface area of the nano graphene is 40-200 m2Per g, the average length-diameter ratio of the carbon nano tube is more than 1000.
In the step A1, various highly conductive graphene, such as reduced graphene oxide, material-exfoliated graphene, with a specific surface area of 40-200 m, may be used2G, if 200m is selected2The addition amount of the graphene in the sponge matrix is reduced, and the improvement range of the thermal conductivity is reduced. The index of the purity of the graphene is carbon content, and the carbon content is higher than 97%, so that the requirement of the invention can be met. Under the condition of achieving the same electric conductivity and thermal conductivity, the use amount of graphene can be reduced by using the carbon nano tubes, the hardness and modulus of the sponge matrix are reduced, the difficulty of process operation is possibly increased due to the entanglement effect of the carbon nano tubes, and therefore the weight ratio of the graphene to the carbon nano tubes is not less than 10: 3, the adding effect of the carbon nano tube is related to the length-diameter ratio of the carbon nano tube, the higher the length-diameter ratio is, the better the effect is, and the requirement is not lower than 1000. The hydroxyl number of the polyol directly influences the hardness of the sponge obtained. The graphene composite sponge produced by the invention is mainly used as a raw material of a mattress, so that the hardness of the sponge matrix is required to be in accordance with the comfort level of a human body. Through a series of tests, the hardness of the graphene polyurethane sponge matrix prepared by the polyol with the hydroxyl value of less than 300 is better for the comfort of human bodies.
A2, circularly dispersing the graphene polyol slurry by using a three-roll machine with the diameter larger than 150mm to obtain the graphene polyol slurry with the average graphene particle size smaller than 20 microns;
it should be noted that, unlike the graphene production process, the three-roll dispersion method does not require a shearing force to peel off the graphene, and although the shearing effect of the three-roll dispersion method is not the strongest, the snap of the carbon nanotubes can be reduced.
A3, adding a foaming agent, a surfactant, a cell opening agent and a catalyst into the graphene polyol slurry, and uniformly mixing to obtain a component A; the weight ratio of the foaming agent, the surfactant, the pore-forming agent, the catalyst and the graphene polyol slurry is 0.3-2.5: 0.1-1.5: 0.3-2.5: 0.1-1.2: 100;
isocyanate is selected as a component B, and the number of reaction functional groups in the component A and the component B is equimolar;
the foaming agent is water, freon, low-boiling organic solvent or carbon dioxide, the surfactant is silicone oil, the cell opening agent is methyl siloxane, and the catalyst is T9 (polyurethane organic tin catalyst) or A33 (polyurethane catalyst); the isocyanate is TDI (toluene diisocyanate) and MDI (diphenylmethane diisocyanate);
a4, respectively maintaining the component A and the component B at 25-60 ℃, respectively pumping the components A and B into a dynamic mixer according to a proportion, uniformly mixing, and then sending into a continuous foaming production line to obtain graphene polyurethane sponge;
it should be noted that, a continuous foaming production line is adopted, namely, foaming is carried out on a continuous circulating conveying belt in a closed constant temperature environment, polyurethane foaming slurry mixed by a high-speed dynamic mixer is pumped into one end of the conveying belt, and the completely foamed sponge is cut into required lengths by an opening at the other end according to requirements. The temperature of the closed environment is 20-60 ℃.
A5, cutting the graphene polyurethane sponge block into preset thickness by adopting a high-speed saw blade cutting machine to obtain the graphene polyurethane sponge matrix.
It should be noted that, the high-speed horizontal band saw is adopted, and the thickness of the sliced sponge substrate is controlled by adjusting the height of the band saw. Preferably, the thickness of the graphene polyurethane sponge matrix is 10-30 mm.
Further, the method for manufacturing the insulating electromagnetic paste in step S2 includes the following steps:
b1, mixing the nano ceramic powder and the nano magnetic powder into the water-based resin according to a proportion, adding a dispersing agent, and dispersing by adopting a high-speed fluted disc dispersing machine to obtain first primary dispersion slurry;
b2, continuously grinding the first primary dispersion slurry for a preset time by using a high-speed nano sand mill to obtain insulating electromagnetic slurry;
the predetermined time is determined according to an actual polishing condition, and the viscosity of the insulating electromagnetic paste is higher than 2.5Pa · s. The nano ceramic powder is a ceramic material with the dielectric constant larger than 50, the nano magnetic powder is nano alloy powder and ferrite powder with the magnetic conductivity larger than 20, and the water-based resin is self-crosslinking water-based resin.
The nano ceramic powder is one or more of barium titanate, calcium titanate, copper calcium titanate, barium strontium titanate, rutile titanium dioxide and the like; the nano magnetic powder is one or more of carbonyl iron, iron-nickel alloy, iron-cobalt-nickel alloy, iron-cobalt-vanadium alloy, iron-silicon-aluminum alloy, nickel-zinc ferrite, manganese-zinc ferrite, barium ferrite and the like;
the diameters of the two kinds of nano powder are both less than 100 nanometers, and the content of the two kinds of nano powder in the solid resin is 5-80%, preferably 20-60%. The weight ratio of the nano ceramic powder to the nano magnetic powder is 1: 0.1-10, preferably 1: 0.3 to 2. The self-crosslinking water-based resin is one of self-crosslinking polyacrylate and self-crosslinking water-based polyurethane. The dispersant is water-based titanate dispersant, and the weight percentage of the dispersant in the slurry is 0.5-3.0%.
Further, the step S2 is followed by a step S21, and the step S21 includes:
and (3) sending the graphene polyurethane sponge matrix impregnated with the insulating electromagnetic paste into a forced air oven, and quickly drying, wherein the temperature of the forced air oven is 40-125 ℃.
Further, the method for preparing the graphene latex conductive paste in step S3 includes the following steps:
c1, dispersing sulfur, zinc oxide, N-cyclohexyl-2-benzothiazole sulfonamide and 2, 6-di-tert-butyl-4-methylphenol of the latex vulcanization additive and deionized water with the total amount being 3-5 times of the total amount of the sulfur, the zinc oxide, the N-cyclohexyl-2-benzothiazole sulfonamide and the 2, 6-di-tert-butyl-4-methylphenol by using a high-speed fluted disc dispersing machine to obtain second primary dispersion slurry;
c2, continuously grinding the second primary dispersed slurry for a preset time by using a high-speed nano sand mill to obtain uniformly dispersed intermediate slurry with the particle size of less than 100 nanometers;
the preset time is determined according to the actual polishing condition;
and C3, confirming the particle size of the intermediate slurry in the step C2 by using a laser particle sizer, adding graphene according to a preset proportion, dispersing the intermediate slurry to be below 10 micrometers at a high speed by using a high-speed fluted disc dispersing machine, adding a latex solution according to a preset proportion, and uniformly dispersing the intermediate slurry with the latex solution to obtain the graphene latex conductive slurry.
The graphene latex conductive paste has a viscosity higher than 1.5Pa · s. The weight ratio of the solid content of the latex in the latex aqueous solution to the sulfur, the N-cyclohexyl-2-benzothiazole sulfonamide, the zinc oxide and the 2, 6-di-tert-butyl-4-methylphenol is 100: 0.5-3: 0.2-2: 0.5-6: 0.2-3. The weight percentage of the graphene in the solid content of the latex is 3-15%.
Further, the step S3 is followed by a step S31, and the step S31 includes:
and (3) sending the graphene polyurethane sponge matrix impregnated with the graphene latex conductive slurry into a forced air drying oven, and rapidly drying, wherein the temperature of the forced air drying oven is 40-125 ℃.
Further, the step S2 specifically includes:
providing insulating electromagnetic slurry, uniformly coating the insulating electromagnetic slurry on a continuous and circulating rotating conveying belt by 0.5-5 mm through the thickness of a scraper, placing the second part and the third part of the graphene polyurethane sponge matrix on the slurry, and extruding the insulating electromagnetic slurry into the second part and the third part through a double-roller extruder.
It should be noted that, in the step S2, the viscosity of the slurry is required, and is too low, before the drying is completed, the slurry in the sponge matrix may flow downward under the action of gravity, so that the thickness distribution of the slurry is uneven, the viscosity is too high, the slurry cannot uniformly enter the sponge matrix during the extrusion process, and even the sponge matrix cannot rebound to the original thickness. The viscosity is suitably 1 to 5 pas, and the viscosity can be adjusted by adding water. Preferably, the viscosity of the insulating electromagnetic paste is adjusted to be between 2.5 and 5 Pa-s.
Further, the step S3 specifically includes:
providing graphene latex conductive slurry, uniformly coating the graphene latex conductive slurry on a continuous and circular rotating conveying belt by 0.5-5 mm through the thickness of a scraper, placing the third part on the slurry, and extruding the graphene latex conductive slurry into the third part through a double-roller extruder.
It should be noted that, in the step S3, the viscosity of the slurry is required, and is too low, before the drying is completed, the slurry in the sponge matrix may flow downward under the action of gravity, so that the thickness distribution of the slurry is uneven, the viscosity is too high, the slurry cannot uniformly enter the sponge matrix during the extrusion process, and even the sponge matrix cannot rebound to the original thickness. The viscosity is suitably 1 to 5 pas, and the viscosity can be adjusted by adding water. Preferably, the viscosity of the graphene latex conductive paste is adjusted to be 1.5-3 Pa-s.
Further, in the manufacturing process of the insulating electromagnetic slurry and the graphene latex conductive slurry, the high-speed fluted disc dispersion machine is a fluted disc dispersion machine with the linear velocity of the fluted disc edge exceeding 20 m/s;
the high-speed nanometer sand mill adopts zirconium bead grinding media with the particle size of less than 1mm, and the rotating speed per minute exceeds 500 revolutions.
Furthermore, the frequency of the alternating current signal adopted by the graphene composite sponge prepared by the preparation process is 110-100000 Hz, and preferably 1000-10000 Hz. The test voltage is less than 3V, preferably less than 1V.
Further, the impedance of the graphene composite sponge prepared by the manufacturing process of the invention is reduced in direct proportion to the thickness reduction.
Further, as shown in fig. 5, when the graphene composite sponge prepared by the manufacturing process of the present invention absorbs 1% of its own weight of moisture, the impedance is reduced by more than 5%.
Example 1
Production of the graphene polyurethane sponge matrix:
a. heating nano graphene, a carbon nano tube and polyether polyol with a hydroxyl value of 300mgKOH/g in a reaction kettle according to a weight ratio of 7% to 60 ℃, stirring and dispersing uniformly, wherein the weight ratio of the graphene to the carbon nano tube is 10: 1. the carbon content of the multilayer graphene is more than 97.5 percent, and the specific surface area is 120m2Per g, the average length-diameter ratio of the carbon nano tube is more than 1000.
b. And circularly dispersing the graphene polyol slurry by using a three-roller machine with the diameter of more than 150mm to obtain the graphene polyol slurry with the average graphene particle size of less than 20 microns.
c. Adding a foaming agent, a surfactant, a pore-opening agent and a catalyst into the graphene polyol slurry, and uniformly mixing to obtain a component A; the foaming agent is water, the surfactant is silicone oil, the pore-forming agent is methyl siloxane, the catalyst is T9, and the weight ratio of the foaming agent, the surfactant, the pore-forming agent, the catalyst and the graphene polyol slurry is 0.5:0.65:0.7:0.5: 100. Alternatively, isocyanate TDI is used as component B. The number of reactive functional groups in component a and component B is equimolar.
d. Maintaining component a and component B at 25 ℃, respectively, components a and B are maintained at a ratio of 80: and respectively pumping the mixture into a dynamic mixer in a ratio of 20, uniformly mixing, and then sending into a continuous foaming production line to obtain a large graphene polyurethane sponge block.
e. And cutting the sponge block into pieces with the thickness of 20mm by adopting a high-speed saw blade cutting machine to obtain the graphene polyurethane sponge matrix. The density and the conductivity after compaction of the graphene polyurethane sponge matrix were measured.
Production of insulating electromagnetic paste:
f. the rutile titanium dioxide nano powder and the iron-nickel (20: 80) alloy nano magnetic powder are mixed into the water-based resin according to a proportion, the dispersing agent is added, a high-speed fluted disc dispersing machine is adopted to disperse to obtain primary dispersed slurry, and then a high-speed nano sand mill is used to continuously grind to obtain slurry with uniformly dispersed nano powder. The viscosity of the slurry was 5 pas. The diameter of the nano powder is less than 100 nanometers, the content of the nano powder in the slurry is 50 percent, the weight ratio of the nano ceramic powder to the nano magnetic powder is 1:0.5, the self-crosslinking aqueous resin is self-crosslinking aqueous polyurethane, the dispersant is aqueous titanate dispersant, and the weight percentage of the dispersant in the slurry is 1.0 percent.
The slurry was coated on a polytetrafluoroethylene plate, dried at room temperature, and cured at 70 ℃ to determine the dielectric constant.
Production of graphene latex conductive slurry:
g. dispersing sulfur, zinc oxide, N-cyclohexyl-2-benzothiazole sulfonamide, 2, 6-di-tert-butyl-4-methylphenol and the like of a latex vulcanization additive and deionized water with the total amount being 4 times of the deionized water by using a high-speed fluted disc dispersing machine to obtain primary dispersed slurry, continuously grinding by using a high-speed nano sand mill to obtain uniformly dispersed slurry with the particle size being less than 100 nanometers, confirming the particle size by using a laser particle sizer, adding graphene in proportion, dispersing at high speed by using the high-speed fluted disc dispersing machine to be less than 10 micrometers, adding a latex solution in proportion, dispersing at medium speed and mixing uniformly to obtain the graphene latex conductive slurry. The viscosity of the slurry is higher than 1.5 pas. The weight ratio of the solid content of the latex in the latex aqueous solution to the sulfur, the N-cyclohexyl-2-benzothiazole sulfonamide, the zinc oxide and the 2, 6-di-tert-butyl-4-methylphenol is 100: 1:0.5:3:0.5. The percentage of graphene in the solid latex content was 7%.
Coating the slurry on a polytetrafluoroethylene plate, drying at room temperature, and curing at 70 ℃ to measure the electrical conductivity and the magnetic conductivity.
Impregnating insulating electromagnetic paste:
h. the method comprises the steps of adopting continuous transfer type extrusion coating, adjusting the viscosity to be about 3Pa s, uniformly coating 2.5mm of insulating electromagnetic slurry on a continuous circulating rotating conveying belt through a scraper, placing a graphene polyurethane sponge matrix on the slurry, extruding the slurry into a second part and a third part of the graphene polyurethane sponge matrix through a double-roll extruder together, wherein the pressure of the extruder is 5kPa, and the distance between two rolls is 3.5 mm. After extrusion and impregnation, the sponge is sent into a blast oven for rapid drying, and the temperature of the oven is 85 ℃.
The density of the impregnated sponge was measured and the weight gain was calculated.
Dipping the graphene latex conductive slurry:
i. the method comprises the steps of adopting continuous transfer type extrusion coating, adjusting the viscosity to be about 2Pa s, uniformly coating the graphene latex conductive slurry on a continuous circulating rotating conveying belt by 2mm through the thickness of a scraper, placing a graphene polyurethane sponge matrix on the slurry, extruding the slurry into the third part of the graphene polyurethane sponge matrix through a double-roll extruder together, wherein the pressure of the extruder is 10kPa, and the distance between the double rolls is 3.5 mm. And (3) after extrusion and impregnation, sending the sponge into a blast oven, and quickly drying, wherein the temperature of the oven is 40-125 ℃.
And measuring the density of the soaked sponge, calculating the weight gain rate, measuring the indentation pressure, the tensile strength, the electric conductivity and the thermal conductivity, and observing the heights of the insulating electromagnetic coating and the graphene latex conductive coating.
The measured stress, strain and 1000Hz impedance curves are shown in figure 4. The strain of the graphene composite sponge increases along with the increase of the pressure, and the impedance decreases along with the increase of the strain; the change of the impedance at different water contents is shown in fig. 5, and the impedance of the graphene composite sponge is rapidly reduced along with the increase of the water content; other data are collated in Table 2.
Example 2
Production of the graphene polyurethane sponge matrix:
a. heating nano graphene, a carbon nano tube and polyether polyol with a hydroxyl value of 300mgKOH/g in a reaction kettle according to a weight ratio of 8% to 60 ℃, stirring and dispersing uniformly, wherein the weight ratio of the graphene to the carbon nano tube is 10: 1.5. the carbon content of the multilayer graphene is more than 97.5 percent, and the specific surface area is 120m2Per g, the average length-diameter ratio of the carbon nano tube is more than 1000.
b. And circularly dispersing the graphene polyol slurry by using a three-roller machine with the diameter of more than 150mm to obtain the graphene polyol slurry with the average graphene particle size of less than 20 microns.
c. Adding a foaming agent, a surfactant, a pore-opening agent and a catalyst into the graphene polyol slurry, and uniformly mixing to obtain a component A; the foaming agent is water, the surfactant is silicone oil, the pore-forming agent is methyl siloxane, the catalyst is T9, and the weight ratio of the foaming agent, the surfactant, the pore-forming agent, the catalyst and the graphene polyol slurry is 0.5:0.65:0.7:0.5: 100. Alternatively, isocyanate TDI is used as component B. The number of reactive functional groups in component a and component B is equimolar.
d. Maintaining component a and component B at 25 ℃, respectively, components a and B are maintained at a ratio of 80: and respectively pumping the mixture into a dynamic mixer in a ratio of 20, uniformly mixing, and then sending into a continuous foaming production line to prepare the large graphene polyurethane sponge.
e. And cutting the sponge block into pieces with the thickness of 20mm by adopting a high-speed saw blade cutting machine to obtain the graphene polyurethane sponge matrix. The density and the conductivity after compaction of the graphene polyurethane sponge matrix were measured.
Production of insulating electromagnetic paste:
f. electromagnetic paste was prepared using the same components and process conditions as in example 1. The slurry was coated on a polytetrafluoroethylene plate, dried at room temperature, and cured at 70 ℃ to measure the dielectric constant and magnetic permeability.
Production of graphene latex conductive slurry:
g. graphene latex conductive paste was prepared using the same components and process conditions as in example 1. The slurry was coated on a polytetrafluoroethylene plate, dried at room temperature, and cured at 70 ℃ to measure the electrical conductivity.
Impregnating insulating electromagnetic paste:
h. the insulating electromagnetic paste was extrusion-coated using the same process conditions as in example 1, and the density of the impregnated sponge was measured and the weight gain was calculated.
Dipping the graphene latex conductive slurry:
i. the graphene latex conductive paste was extrusion coated using the same process conditions as in example 1, but the thickness of the paste was 2.2mm, the pressure of the extruder was 12kPa, and the distance between the rolls was 3.7 mm. And measuring the density and the weight gain rate of the soaked sponge, measuring the indentation pressure, the tensile strength, the electric conductivity and the thermal conductivity, and observing the insulating electromagnetic coating and the graphene and graphene latex conductive coating.
Example 3
Production of the graphene polyurethane sponge matrix:
a. heating nano graphene, a carbon nano tube and polyether polyol with a hydroxyl value of 280mgKOH/g according to the weight ratio of 10% in a reaction kettle to 60 ℃, stirring and dispersing uniformly, wherein the weight ratio of the graphene to the carbon nano tube is 10: 1. the carbon content of the multilayer graphene is more than 97.5 percent, and the specific surface area is 150m2Per g, the average length-diameter ratio of the carbon nano tube is more than 1000.
b. And circularly dispersing the graphene polyol slurry by using a three-roller machine with the diameter of more than 150mm to obtain the graphene polyol slurry with the average graphene particle size of less than 20 microns.
c. Adding a foaming agent, a surfactant, a pore-opening agent and a catalyst into the graphene polyol slurry, and uniformly mixing to obtain a component A; the foaming agent is water, the surfactant is silicone oil, the pore-forming agent is methyl siloxane, the catalyst is A33, and the weight ratio of the foaming agent, the surfactant, the pore-forming agent, the catalyst and the graphene polyol slurry is 0.47:0.6:0.7:0.5: 100. Alternatively, isocyanate TDI is used as component B. The number of reactive functional groups in component a and component B is equimolar.
d. Maintaining component a and component B at 25 ℃, respectively, components a and B are maintained at a ratio of 80: and respectively pumping the mixture into a dynamic mixer in a ratio of 20, uniformly mixing, and then sending into a continuous foaming production line to prepare the large graphene polyurethane sponge.
e. And cutting the sponge block into pieces with the thickness of 20mm by adopting a high-speed saw blade cutting machine to obtain the graphene polyurethane sponge matrix. The density and the conductivity after compaction of the graphene polyurethane sponge matrix were measured.
Production of insulating electromagnetic paste:
f. mixing barium strontium titanate nano powder and manganese zinc ferrite nano powder into aqueous resin according to a proportion, adding a dispersing agent, dispersing by adopting a high-speed fluted disc dispersing machine to obtain primary dispersed slurry, and continuously grinding by using a high-speed nano sand mill to obtain slurry with uniformly dispersed nano powder. The viscosity of the slurry was 5 pas. The diameter of the nano powder is less than 100 nanometers, the content of the nano powder in the slurry is 55 percent, the weight ratio of the nano ceramic powder to the nano magnetic powder is 1:0.7, the self-crosslinking aqueous resin is self-crosslinking aqueous polyacrylate, the dispersing agent is aqueous titanate dispersing agent, and the weight percentage of the dispersing agent in the slurry is 1.0 percent.
The slurry was coated on a polytetrafluoroethylene plate, dried at room temperature, and cured at 70 ℃ to determine the dielectric constant.
Production of graphene latex conductive slurry:
g. dispersing sulfur, zinc oxide, N-cyclohexyl-2-benzothiazole sulfonamide, 2, 6-di-tert-butyl-4-methylphenol and the like of a latex vulcanization additive and deionized water with the total amount being 4 times of the deionized water by using a high-speed fluted disc dispersing machine to obtain primary dispersed slurry, continuously grinding by using a high-speed nano sand mill to obtain uniformly dispersed slurry with the particle size being less than 100 nanometers, confirming the particle size by using a laser particle sizer, adding graphene in proportion, dispersing at high speed by using the high-speed fluted disc dispersing machine to be less than 10 micrometers, adding a latex solution in proportion, dispersing at medium speed and mixing uniformly to obtain the graphene latex conductive slurry. The viscosity of the slurry is higher than 1.5 pas. The weight ratio of the solid content of the latex in the latex aqueous solution to the sulfur, the N-cyclohexyl-2-benzothiazole sulfonamide, the zinc oxide and the 2, 6-di-tert-butyl-4-methylphenol is 100: 1:0.5:3:0.5. The percentage of graphene in the solid latex content was 9%.
Coating the slurry on a polytetrafluoroethylene plate, drying at room temperature, and curing at 70 ℃ to measure the electrical conductivity and the magnetic conductivity.
Impregnation of insulating electromagnetic paste
h. The method comprises the steps of adopting continuous transfer type extrusion coating, adjusting the viscosity to be about 3Pa s, uniformly coating 3mm of insulating electromagnetic slurry on a transmission belt which continuously and circularly rotates through a scraper, placing a graphene polyurethane sponge matrix on the slurry, extruding the slurry into a second part and a third part of the sponge matrix through a double-roller extruder together, wherein the pressure of the extruder is 7kPa, and the distance between two rollers is 4 mm. After extrusion and impregnation, the sponge is sent into a blast oven for rapid drying, and the temperature of the oven is 85 ℃. The density of the impregnated sponge was measured and the weight gain was calculated.
Dipping the graphene latex conductive slurry:
i. the method comprises the steps of adopting continuous transfer type extrusion coating, adjusting the viscosity to be about 2Pa s, uniformly coating the graphene latex conductive slurry on a continuous circulating rotating conveying belt by 2mm in thickness through a scraper, placing a graphene polyurethane sponge matrix on the slurry, extruding the slurry into a third part of the sponge matrix through a double-roller extruder together, wherein the pressure of the extruder is 12kPa, and the distance between two rollers is 3.5 mm. And (3) after extrusion and impregnation, sending the sponge into a blast oven, and quickly drying, wherein the temperature of the oven is 40-125 ℃. And measuring the density of the soaked sponge, calculating the weight gain rate, measuring the indentation pressure, the tensile strength, the electric conductivity and the thermal conductivity, and observing the heights of the insulating electromagnetic coating and the graphene latex conductive coating.
Example 4
Production of the graphene polyurethane sponge matrix:
a. heating nano graphene, a carbon nano tube and polyether polyol with a hydroxyl value of 280mgKOH/g in a reaction kettle according to a weight ratio of 11.5% to 60 ℃, stirring and dispersing uniformly, wherein the weight ratio of the graphene to the carbon nano tube is 10: 1.5. the carbon content of the multilayer graphene is more than 97.5 percent, and the specific surface area is 120m2Per g, the average length-diameter ratio of the carbon nano tube is more than 1000.
b. And circularly dispersing the graphene polyol slurry by using a three-roller machine with the diameter of more than 150mm to obtain the graphene polyol slurry with the average graphene particle size of less than 20 microns.
c. Adding a foaming agent, a surfactant, a pore-opening agent and a catalyst into the graphene polyol slurry, and uniformly mixing to obtain a component A; the foaming agent is water, the surfactant is silicone oil, the pore-forming agent is methyl siloxane, the catalyst is T9, and the weight ratio of the foaming agent, the surfactant, the pore-forming agent, the catalyst and the graphene polyol slurry is 0.45:0.65:0.7:0.5: 100. Alternatively, isocyanate TDI is used as component B. The number of reactive functional groups in component a and component B is equimolar.
d. Maintaining component a and component B at 25 ℃, respectively, components a and B are maintained at a ratio of 80: and respectively pumping the mixture into a dynamic mixer in a ratio of 20, uniformly mixing, and then sending into a continuous foaming production line to prepare the large graphene polyurethane sponge.
e. And cutting the sponge block into pieces with the thickness of 20mm by adopting a high-speed saw blade cutting machine to obtain the graphene polyurethane sponge matrix. The density and the conductivity after compaction of the graphene polyurethane sponge matrix were measured.
Production of insulating electromagnetic paste:
f. mixing barium strontium titanate nano powder and manganese zinc ferrite nano powder into aqueous resin according to a proportion, adding a dispersing agent, dispersing by adopting a high-speed fluted disc dispersing machine to obtain primary dispersed slurry, and continuously grinding by using a high-speed nano sand mill to obtain slurry with uniformly dispersed nano powder. The viscosity of the slurry was 5 pas. The diameter of the nano powder is less than 100 nanometers, the content of the nano powder in the slurry is 60 percent, the weight ratio of the nano ceramic powder to the nano magnetic powder is 1:0.8, the self-crosslinking aqueous resin is self-crosslinking aqueous polyurethane, the dispersant is aqueous titanate dispersant, and the weight percentage of the dispersant in the slurry is 1.0 percent.
The slurry was coated on a polytetrafluoroethylene plate, dried at room temperature, and cured at 70 ℃ to determine the dielectric constant.
Production of graphene latex conductive slurry:
g. dispersing sulfur, zinc oxide, N-cyclohexyl-2-benzothiazole sulfonamide, 2, 6-di-tert-butyl-4-methylphenol and the like of a latex vulcanization additive and deionized water with the total amount being 4 times of the deionized water by using a high-speed fluted disc dispersing machine to obtain primary dispersed slurry, continuously grinding by using a high-speed nano sand mill to obtain uniformly dispersed slurry with the particle size being less than 100 nanometers, confirming the particle size by using a laser particle sizer, adding graphene in proportion, dispersing at high speed by using the high-speed fluted disc dispersing machine to be less than 10 micrometers, adding a latex solution in proportion, dispersing at medium speed and mixing uniformly to obtain the graphene latex conductive slurry. The viscosity of the slurry is higher than 1.5 pas. The weight ratio of the solid content of the latex in the latex aqueous solution to the sulfur, the N-cyclohexyl-2-benzothiazole sulfonamide, the zinc oxide and the 2, 6-di-tert-butyl-4-methylphenol is 100: 1:0.5:3:0.5. The percentage of graphene in the solid latex content was 9%.
Coating the slurry on a polytetrafluoroethylene plate, drying at room temperature, and curing at 70 ℃ to measure the electrical conductivity and the magnetic conductivity.
Impregnating insulating electromagnetic conductive slurry:
h. the method comprises the steps of adopting continuous transfer type extrusion coating, adjusting the viscosity to be about 3Pa s, uniformly coating 3mm of insulating electromagnetic slurry on a transmission belt which continuously and circularly rotates through a scraper, placing a graphene polyurethane sponge matrix on the slurry, extruding the slurry into a second part and a third part of the sponge matrix through a double-roller extruder together, wherein the pressure of the extruder is 5kPa, and the distance between two rollers is 4 mm. After extrusion and impregnation, the sponge is sent into a blast oven for rapid drying, and the temperature of the oven is 85 ℃.
The density of the impregnated sponge was measured and the weight gain was calculated.
Dipping the graphene latex conductive slurry:
i. the method comprises the steps of adopting continuous transfer type extrusion coating, adjusting the viscosity to be about 2Pa s, uniformly coating the graphene latex conductive slurry on a continuous circulating rotating conveying belt by 2.2mm in thickness through a scraper, placing a graphene polyurethane sponge matrix on the slurry, extruding the slurry into a third part of the sponge matrix through a double-roller extruder together, wherein the pressure of the extruder is 10kPa, and the distance between two rollers is 3.5 mm. And (3) after extrusion and impregnation, sending the sponge into a blast oven, and quickly drying, wherein the temperature of the oven is 40-125 ℃.
And measuring the density and the weight gain rate of the soaked sponge, measuring the indentation pressure, the tensile strength, the electric conductivity and the thermal conductivity, and observing the insulating electromagnetic coating and the graphene latex conductive coating.
Table 1: test content, sample size used and detection standard
Serial number Content of test Sample size (mm) National standard
1 Density of 100x100 QB/T 4839-2015
2 Degree of indentation 100x100 GB/T 10807-2006
3 Tensile strength 150x50 GB/T 6344-2008
4 Conductivity (1kHz) 200x200 GB/T 1410-2006
5 Dielectric constant (1kHz) 50x50x2 GB/T 1409-2006
6 Magnetic permeability 10x10x0.5 VSM vibration sample magnetometer
7 Thermal conductivity 300x300 GB/T 10294-2008
Table 2: test data for the four embodiments described above
Figure BDA0002860705610000171
Application example
The graphene composite sponge prepared by the manufacturing process can be applied to a common mattress, wherein the first part and the third part of the graphene polyurethane matrix are electrically connected with an external alternating current circuit; further, the working frequency of the graphene composite sponge is 110-100000 Hz, and the alternating current impedance can be tested by an LCR digital bridge.
The user sleeps on the mattress, and when the user changes the sleep gesture (for example, turning over) on the mattress, certain pressure is generated on the graphene composite sponge to cause the graphene composite sponge to deform, at the moment, capacitive reactance and inductive reactance formed between the first portion and the third portion rapidly change, an external alternating current circuit detects the change and converts the change into an alternating current signal, and the user can know the change of pressure distribution in the sleep process through the alternating current signal, so that the change of the sleep gesture is known.
Specifically, the external ac circuit includes a computer, and the computer can analyze and process the ac signal through its own installed related software to obtain a related display chart, for example, at which time point the user performs a turning-over action in the chart, so that the user can more intuitively know the change of the surrounding environment and the change of the sleeping posture during the sleeping process through the above specific design. The above mentioned ac circuit, related software and so on are only used for detecting and analyzing the change of the capacitive reactance and the inductive reactance, the ac circuit and related software are essentially the prior art, and the specific structure of the ac circuit is not the technical content protected by the present invention.
The above-mentioned details of the manufacturing process of the graphene composite sponge provided by the present invention are introduced, and a person skilled in the art may change the specific implementation manner and the application range according to the idea of the embodiment of the present invention, so to sum up, the content of the present description should not be understood as a limitation to the present invention.

Claims (10)

1. The preparation process of the graphene composite sponge is characterized by comprising the following steps:
s1, providing a graphene polyurethane sponge matrix, wherein the graphene polyurethane sponge matrix sequentially comprises a first part, a second part and a third part which are connected with each other from top to bottom;
s2, providing insulating electromagnetic paste, and impregnating the second part and the third part with the insulating electromagnetic paste;
s3, providing graphene latex conductive slurry, and dipping the third part by using the graphene latex conductive slurry;
and S4, obtaining the graphene composite sponge.
2. The process for manufacturing the graphene composite sponge according to claim 1, wherein the thickness of the third portion is greater than the thickness of the second portion.
3. The manufacturing process of the graphene composite sponge according to claim 1, wherein the manufacturing method of the graphene polyurethane sponge matrix comprises the following steps:
a1, heating nano graphene, carbon nanotubes and polyol with a hydroxyl value of 50-600mgKOH/g to 30-150 ℃ in a reaction kettle according to a weight ratio of 5-20%, and uniformly stirring to obtain graphene polyol slurry;
a2, circularly dispersing the graphene polyol slurry by using a three-roll machine with the diameter larger than 150mm to obtain the graphene polyol slurry with the average graphene particle size smaller than 20 microns;
a3, adding a foaming agent, a surfactant, a cell opening agent and a catalyst into the graphene polyol slurry, and uniformly mixing to obtain a component A; the weight ratio of the foaming agent, the surfactant, the pore-forming agent, the catalyst and the graphene polyol slurry is 0.3-2.5: 0.1-1.5: 0.3-2.5: 0.1-1.2: 100;
isocyanate is selected as a component B, and the number of reaction functional groups in the component A and the component B is equimolar;
a4, respectively maintaining the component A and the component B at 25-60 ℃, respectively pumping the components A and B into a dynamic mixer according to a proportion, uniformly mixing, and then sending into a continuous foaming production line to obtain graphene polyurethane sponge;
a5, cutting the graphene polyurethane sponge block into preset thickness by adopting a high-speed saw blade cutting machine to obtain the graphene polyurethane sponge matrix.
4. The manufacturing process of the graphene composite sponge according to claim 1, wherein the manufacturing method of the insulating electromagnetic paste in the step S2 includes the following steps:
b1, mixing the nano ceramic powder and the nano magnetic powder into the water-based resin according to a proportion, adding a dispersing agent, and dispersing by adopting a high-speed fluted disc dispersing machine to obtain first primary dispersion slurry;
and B2, continuously grinding the first primary dispersion slurry for a preset time by using a high-speed nano sand mill to obtain the insulating electromagnetic slurry.
5. The manufacturing process of the graphene composite sponge according to claim 4, wherein the step S2 is followed by a step S21, and the step S21 includes:
and (3) sending the graphene polyurethane sponge matrix impregnated with the insulating electromagnetic paste into a forced air oven, and quickly drying, wherein the temperature of the forced air oven is 40-125 ℃.
6. The manufacturing process of the graphene composite sponge according to claim 1, wherein the manufacturing method of the graphene latex conductive paste in the step S3 includes the following steps:
c1, dispersing sulfur, zinc oxide, N-cyclohexyl-2-benzothiazole sulfonamide and 2, 6-di-tert-butyl-4-methylphenol of the latex vulcanization additive and deionized water with the total amount being 3-5 times of the total amount of the sulfur, the zinc oxide, the N-cyclohexyl-2-benzothiazole sulfonamide and the 2, 6-di-tert-butyl-4-methylphenol by using a high-speed fluted disc dispersing machine to obtain second primary dispersion slurry;
c2, continuously grinding the second primary dispersed slurry for a preset time by using a high-speed nano sand mill to obtain uniformly dispersed intermediate slurry with the particle size of less than 100 nanometers;
and C3, confirming the particle size of the intermediate slurry in the step C2 by using a laser particle sizer, adding graphene according to a preset proportion, dispersing the intermediate slurry to be below 10 micrometers at a high speed by using a high-speed fluted disc dispersing machine, adding a latex solution according to a preset proportion, and uniformly dispersing the intermediate slurry with the latex solution to obtain the graphene latex conductive slurry.
7. The manufacturing process of the graphene composite sponge according to claim 1, wherein the step S3 is followed by a step S31, and the step S31 includes:
and (3) sending the graphene polyurethane sponge matrix impregnated with the graphene latex conductive slurry into a forced air drying oven, and rapidly drying, wherein the temperature of the forced air drying oven is 40-125 ℃.
8. The manufacturing process of the graphene composite sponge according to claim 1, wherein the step S2 specifically includes:
providing insulating electromagnetic slurry, uniformly coating the insulating electromagnetic slurry on a continuous and circulating rotating conveying belt by 0.5-5 mm through the thickness of a scraper, placing the second part and the third part of the graphene polyurethane sponge matrix on the slurry, and extruding the insulating electromagnetic slurry into the second part and the third part through a double-roller extruder.
9. The manufacturing process of the graphene composite sponge according to claim 1, wherein the step S3 specifically includes:
providing graphene latex conductive slurry, uniformly coating the graphene latex conductive slurry on a continuous and circular rotating conveying belt by 0.5-5 mm through the thickness of a scraper, placing the third part on the slurry, and extruding the graphene latex conductive slurry into the third part through a double-roller extruder.
10. The manufacturing process of the graphene composite sponge according to claim 4 or 6, wherein the high-speed fluted disc dispersion machine is a fluted disc dispersion machine with a fluted disc edge linear velocity exceeding 20 m/s;
the high-speed nanometer sand mill adopts zirconium bead grinding media with the particle size of less than 1mm, and the rotating speed per minute exceeds 500 revolutions.
CN202011565445.6A 2020-12-25 2020-12-25 Manufacturing process of graphene composite sponge Active CN112852008B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011565445.6A CN112852008B (en) 2020-12-25 2020-12-25 Manufacturing process of graphene composite sponge

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011565445.6A CN112852008B (en) 2020-12-25 2020-12-25 Manufacturing process of graphene composite sponge

Publications (2)

Publication Number Publication Date
CN112852008A true CN112852008A (en) 2021-05-28
CN112852008B CN112852008B (en) 2021-09-10

Family

ID=75997182

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011565445.6A Active CN112852008B (en) 2020-12-25 2020-12-25 Manufacturing process of graphene composite sponge

Country Status (1)

Country Link
CN (1) CN112852008B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107007071A (en) * 2017-06-17 2017-08-04 合肥市晨雷思建筑材料科技有限公司 A kind of multifunctional mattress and preparation method
CN107525123A (en) * 2016-06-21 2017-12-29 苏州汉纳材料科技有限公司 Highly conductive ultra-thin two-dimension carbon composite face heater and its application
CN109517208A (en) * 2018-10-12 2019-03-26 苏州鼎烯聚材纳米科技有限公司 The continuous producing method of high thermal conductivity graphene polyurethane composite sponge for mattress
CN109648927A (en) * 2018-11-15 2019-04-19 江苏健睡宝健康科技有限公司 A kind of graphene mattress
CN110180513A (en) * 2019-06-27 2019-08-30 中素新科技有限公司 Titanium dioxide-graphene oxide composite sponge and its preparation method and application
KR20200089078A (en) * 2019-01-16 2020-07-24 성균관대학교산학협력단 A graphene sponge-polymer composite and fabricating method of the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107525123A (en) * 2016-06-21 2017-12-29 苏州汉纳材料科技有限公司 Highly conductive ultra-thin two-dimension carbon composite face heater and its application
CN107007071A (en) * 2017-06-17 2017-08-04 合肥市晨雷思建筑材料科技有限公司 A kind of multifunctional mattress and preparation method
CN109517208A (en) * 2018-10-12 2019-03-26 苏州鼎烯聚材纳米科技有限公司 The continuous producing method of high thermal conductivity graphene polyurethane composite sponge for mattress
CN109648927A (en) * 2018-11-15 2019-04-19 江苏健睡宝健康科技有限公司 A kind of graphene mattress
KR20200089078A (en) * 2019-01-16 2020-07-24 성균관대학교산학협력단 A graphene sponge-polymer composite and fabricating method of the same
CN110180513A (en) * 2019-06-27 2019-08-30 中素新科技有限公司 Titanium dioxide-graphene oxide composite sponge and its preparation method and application

Also Published As

Publication number Publication date
CN112852008B (en) 2021-09-10

Similar Documents

Publication Publication Date Title
CN101022053B (en) Composite magnetic sheet and production method thereof
US8263515B2 (en) Nanostructured dielectric materials for high energy density multi layer ceramic capacitors
CN100575398C (en) The purposes that on film thickness direction, has stretch polytetrafluoroethylraw porous-film, its preparation method and this porous-film of elastic recovery
US9652569B2 (en) Nanostructured dielectric materials for high energy density multi layer ceramic capacitors
EP2065433B1 (en) Ptfe porous body, ptfe mixture, method for producing ptfe porous body, and electric wire/cable using ptfe porous body
Nayak et al. Development of polyurethane–titania nanocomposites as dielectric and piezoelectric material
CN107936547A (en) Nylon/graphene/carbon fiber composite powder and preparation method thereof and the application in Selective Laser Sintering
CN112852008B (en) Manufacturing process of graphene composite sponge
CN113025030B (en) Antibacterial graphene polyurethane composite sponge material and preparation method and application thereof
CN110564085A (en) Manufacturing method of PTFE ceramic modified substrate film for high-performance circuit board
Guo et al. Superior energy storage properties in (1− x)(0.65 Bi0. 5Na0. 5TiO3-0.35 Bi0. 2Sr0. 7TiO3)-xCaZrO3 ceramics with excellent temperature stability
CN102653469A (en) Chip multilayer ceramic capacitor dielectric ceramic slurry and preparation method of dielectric
CN207958226U (en) A kind of heat-conducting glue band
WO2003049935A1 (en) Compact inorganic micro-powder sheet, method for producing thereof and product resulted from the sheet
CN113121777A (en) Flame-retardant graphene polyurethane composite sponge material and application thereof
Caba et al. A green and simple process to develop conductive polyurethane foams for biomedical applications
TW200540884A (en) Organic PTC thermistor and production
Li et al. Preparation of poly (acrylic acid) grafted reduced graphene oxide/polyacrylamide composite hydrogels with good electronic and mechanical properties by in-situ polymerization
CN113201170B (en) Graphene polyurethane composite sponge material with good anti-fouling performance and application thereof
CN114752092B (en) Production process of aerogel polyurethane thermal insulation material
CN114211903B (en) High-heat-conductivity silica gel embossing roller and preparation method thereof
CN104918734A (en) Method for preparing capacitor-grade tantalum powder with high nitrogen content, capacitor-grade tantalum powder prepared thereby, and anode and capacitor prepared from tantalum powder
CN101921553A (en) Teflon insulating self-adhesive tape and application method thereof
DE19809679A1 (en) Polycrystalline sintered ceramic grinding medium for producing bonded or backed grinding media
CN112159583A (en) Mesoporous carbon flexible polyurethane elastomer material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant