CN113150234B - Wear-resistant graphene polyurethane composite sponge material and preparation method and application thereof - Google Patents

Wear-resistant graphene polyurethane composite sponge material and preparation method and application thereof Download PDF

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CN113150234B
CN113150234B CN202110506616.6A CN202110506616A CN113150234B CN 113150234 B CN113150234 B CN 113150234B CN 202110506616 A CN202110506616 A CN 202110506616A CN 113150234 B CN113150234 B CN 113150234B
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graphene
sponge material
black phosphorus
polyurethane composite
composite sponge
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CN113150234A (en
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王炳坤
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De Rucci Healthy Sleep Co Ltd
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    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47C—CHAIRS; SOFAS; BEDS
    • A47C27/00—Spring, stuffed or fluid mattresses or cushions specially adapted for chairs, beds or sofas
    • A47C27/14—Spring, stuffed or fluid mattresses or cushions specially adapted for chairs, beds or sofas with foamed material inlays
    • 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
    • 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
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • C08G2101/00—Manufacture of cellular products
    • 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
    • C08K2003/026—Phosphorus
    • 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

Abstract

The invention relates to a wear-resistant graphene polyurethane composite sponge material and a preparation method and application thereof, wherein the graphene polyurethane composite sponge material is prepared from the following raw materials: the composite material comprises a black phosphorus graphene composite material, nano titanium dioxide, polyol, isocyanate and a solvent. According to the invention, the black phosphorus modified graphene material is added into the polyurethane system, and the modification of the black phosphorus can promote the graphene and the nano titanium dioxide to have better bonding performance, so that the wear resistance of the graphene polyurethane composite sponge material can be further improved, and the graphene polyurethane composite sponge material can be used in bedding such as mattresses, pillows and the like, and can obtain longer service life.

Description

Wear-resistant graphene polyurethane composite sponge material and preparation method and application thereof
Technical Field
The invention relates to the technical field of wear-resistant materials, in particular to a wear-resistant graphene polyurethane composite sponge material and a preparation method and application thereof.
Background
Bedding such as mattresses, pillows and the like is an article between a human body and a bed, which is used for ensuring that consumers can obtain healthy and comfortable sleep, the mattresses are made of various materials, and mattresses made of different materials can bring different sleep effects to people.
Bedding among the prior art can both guarantee that the user has comparatively soft comfortable sleep to experience mostly, but most mattress air permeability is general, and the whole wear resistance of mattress is not good, has used easy wearing and tearing for a long time.
CN204580630U discloses a mattress of soft polyurethane foam of vegetable oil, including the mattress body, the mattress body is formed by the cladding of soft polyurethane foam of vegetable oil and fabric, and the mattress body divide into upper strata and lower floor, be equipped with first buffer layer and second buffer layer between upper strata and the lower floor, the upper surface on upper strata is equipped with the slot and the bleeder vent of massage, the bleeder vent distributes on the upper strata between the slot, on the first buffer layer that corresponds, the lower surface correspondence of second buffer layer upper and lower floor and the position of slot are equipped with the recess, the lower extreme of recess is equipped with the slotted hole that is used for breathing freely, the slot is horizontal even upper surface of establishing on the upper strata, the slot of upper strata mid portion is perpendicular to upper layer surface and is seted up, the slot of front and back part is respectively to the angle of middle slope and sets up. The mattress provided in the prior art has good air permeability, is soft and comfortable, but has poor wear resistance while being soft, is easy to wear after being used for a long time, and is not beautiful.
CN109369884A discloses a preparation method of a soft polyurethane porous composite material capable of releasing negative ions, which takes the following raw materials in parts by mass as a component A: 100 parts of polyol, 1.0-1.5 parts of foam stabilizer, 1.0-3.0 parts of foaming agent, 0.01-1.5 parts of amine catalyst, 0.05-0.5 part of organic tin catalyst and 0.3-4.0 parts of modified anion powder additive, wherein 20-60 parts by mass of isocyanate is used as a component B, and the components are uniformly mixed and foamed to prepare the soft polyurethane porous composite material. The prepared soft polyurethane porous composite material has high anion release amount and controllable material tensile property and resilience, and can be applied to products such as mattresses, sofas, automobile interiors, pillows and the like. But the wear resistance of such polyurethane materials still needs to be improved.
CN100497430A discloses a preparation method of full MDI polyurethane slow-recovery foam, which comprises the following components: MDI system isocyanates, functionality 2.1 to 2.5; b. a polyether polyol component; c. a foaming agent; d. catalyst, surfactant. In the preparation method, the combined polyether comprises a bulk polyether product and related auxiliary agents, does not contain a physical foaming agent and can be stably stored; the isocyanate component comprises MDI and a prepolymer thereof, TDI is not contained, 50% of the prepared slow rebound foam has the permanence of less than 10%, and the prepared foam is suitable for household articles such as pillow cores, waist pads, mattresses and the like. Also, the polyurethane materials provided in this prior art have a problem of poor abrasion resistance.
Therefore, there is a need in the art to develop a polyurethane material with excellent wear resistance, which can be applied to bedding such as a mattress and a pillow to achieve a longer service life.
Disclosure of Invention
In view of the defects of the prior art, an object of the present invention is to provide a wear-resistant graphene polyurethane composite sponge material. The graphene polyurethane composite sponge material has excellent wear resistance, and can be used in bedding such as mattresses, pillows and the like to obtain longer service life.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a wear-resistant graphene polyurethane composite sponge material, which is prepared from the following raw materials in parts by weight: the composite material comprises a black phosphorus graphene composite material, nano titanium dioxide, polyol, isocyanate and a solvent.
According to the invention, the black phosphorus modified graphene material is added into the polyurethane system, and the modification of the black phosphorus can promote the graphene and the nano titanium dioxide to have better bonding performance, so that the wear resistance of the graphene polyurethane composite sponge material can be further improved, and the graphene polyurethane composite sponge material can be used in bedding such as mattresses, pillows and the like, and can obtain longer service life.
Preferably, the mass ratio of black phosphorus to graphene in the black phosphorus graphene composite material is 1 (35-50), such as 1:36, 1:37, 1:38, 1:39, 1:40, 1:41, 1:42, 1:43, 1:44, 1:45, 1:46, 1:47, 1:48, 1:49, 1:50, and the like.
According to the invention, the mass ratio of black phosphorus to graphene in the black phosphorus graphene composite material is preferably 1 (35-50), and in the range of the mass ratio, the graphene and the nano titanium dioxide are better in binding property, so that the wear resistance of the graphene polyurethane composite sponge material can be further improved. Increasing the proportion of black phosphorus or increasing the proportion of graphene both results in poor wear resistance.
Preferably, the preparation method of the black phosphorus graphene composite material comprises the following steps: mixing black phosphorus nanosheets and graphene, and performing ball milling to obtain the black phosphorus graphene composite material.
Preferably, the mass ratio of the black phosphorus nanosheet to the graphene is 1 (35-50), such as 1:36, 1:37, 1:38, 1:39, 1:40, 1:41, 1:42, 1:43, 1:44, 1:45, 1:46, 1:47, 1:48, 1:49, 1:50, and the like.
Preferably, the ball milling is carried out under an inert gas shield, preferably under an argon shield.
Preferably, the preparation method of the black phosphorus graphene composite material further comprises the following steps: after ball milling, washing, suction filtration and drying were carried out.
Preferably, the washing comprises washing with ethanol and water, respectively.
Preferably, the nano-titania has a particle size of 50-80nm, such as 51nm, 52nm, 53nm, 54nm, 55nm, 56nm, 57nm, 58nm, 59nm, 60nm, 61nm, 62nm, 63nm, 64nm, 65nm, 66nm, 67nm, 68nm, 69nm, 70nm, 71nm, 72nm, 73nm, 74nm, 75nm, 76nm, 77nm, 78nm, 79nm, and the like.
Furthermore, the particle size of the nano titanium dioxide is preferably 50-80nm, and the titanium dioxide in the particle size range can be better adsorbed on the outer layer surface and between layers of the graphene laminated structure, so that the wear resistance can be further improved. The wear resistance is deteriorated by the large or small particle size of the nano titanium dioxide.
Preferably, the polyol has a hydroxyl value of 50 to 600mgKOH/g, such as 100mgKOH/g, 200mgKOH/g, 300mgKOH/g, 400mgKOH/g, 500mgKOH/g, and the like.
Preferably, the polyol comprises a polyester polyol and/or a polyether polyol.
Preferably, the number average molecular weight of the polyol is 250-10000, such as 300, 500, 1000, 1500, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000 and the like.
Preferably, the polyester polyol comprises any one or at least two of poly neopentyl glycol adipate diol, poly 1,4 butylene glycol adipate diol, poly 1,6 hexanediol adipate diol, poly ethylene glycol adipate diol, poly methyl propylene glycol adipate diol, poly diethylene glycol adipate diol or poly butylene glycol methyl propylene glycol adipate diol.
Preferably, the polyether polyol comprises any one or a combination of at least two of polyoxypropylene glycol, polyoxyethylene glycol or polytetramethylene ether glycol.
Preferably, the isocyanate comprises any one or a combination of at least two of 2, 4-toluene diisocyanate, toluene 2, 6-diisocyanate or diphenylmethane diisocyanate.
Preferably, the solvent comprises any one or a combination of at least two of ethanol, toluene, xylene, acetone, cyclohexanone, or butanone.
Preferably, the raw materials for preparing the graphene polyurethane composite sponge material comprise the following components in percentage by mass:
Figure BDA0003058678030000051
in the formula, the addition amount of the black phosphorus graphene composite material is 2% -10%, such as 3%, 4%, 5%, 6%, 7%, 8%, 9% and the like; the addition amount of the nano titanium dioxide is 3-8%, such as 4%, 5%, 6%, 7%, 8% and the like; the amount of the polyhydric alcohol added is 20% to 30%, for example, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, etc.; the amount of the isocyanate added is 25% to 40%, for example, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, etc.
Preferably, the preparation raw material of the graphene polyurethane composite sponge material further comprises any one or at least two of a foaming agent, a surfactant, a cell opening agent, a catalyst or carbon nanotubes.
Preferably, the blowing agent comprises any one or a combination of at least two of F11, HCFC-141b, HFC-245fa, HFC-365mfc, HFC-227 ea.
Preferably, the surfactant comprises a silicone surfactant, preferably BYK 346.
Preferably, the cell opener comprises dibutyl maleate and/or polyoxypropylene-oxyethylene copolyethers.
Preferably, the catalyst comprises any one or a combination of at least two of 1, 4-diazo (2,2, 2-cyclooctane), triethyldiamine (DABCO), N ', N ″ -pentamethyl-diethyltriamine (PMDETA), N-Dimethylcyclohexylamine (DMCHA), N-dimethylbenzylamine, N ' -Tetramethylethylenediamine (TMEDA), N-Dimethylethanolamine (DMEA), 2,4, 6-tris (dimethylaminomethyl) phenol, N-ethylmorpholine (NEM), bis-N, N ' -dimethylaminoethylether or dibutyl tin dilaurate (DBTDL).
The second purpose of the present invention is to provide a preparation method of the wear-resistant graphene polyurethane composite sponge material, which comprises the following steps:
(1) mixing and dispersing the black phosphorus graphene composite material, nano titanium dioxide, polyol, isocyanate and a solvent to obtain graphene polyol slurry;
(2) and respectively preserving the heat of the graphene polyol slurry and isocyanate, mixing and sending the mixture into a foaming production line to prepare the wear-resistant graphene polyurethane composite sponge material.
Preferably, in the step (1), the dispersing method comprises heating dispersion and/or circulating dispersion, and preferably the heating dispersion is carried out before the circulating dispersion is carried out.
Preferably, the cyclic dispersion is carried out using a three-roll mill having a diameter greater than 150 mm.
Preferably, the cyclic dispersion is carried out until the graphene has an average particle size of less than 20 μm, such as 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, and the like.
Preferably, the preparation method further comprises: adding any one or at least two of foaming agent, surfactant, cell opening agent, catalyst or carbon nano tube into the graphene polyol slurry.
Preferably, in the step (2), the graphene polyol slurry has a heat-preserving temperature of 25 to 60 ℃, for example, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃, 40 ℃, 41 ℃, 42 ℃, 43 ℃, 44 ℃, 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃ and the like.
Preferably, in step (2), the isocyanate has a heat-retaining temperature of 25 to 60 ℃, for example, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃, 40 ℃, 41 ℃, 42 ℃, 43 ℃, 44 ℃, 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃ and the like.
Preferably, in step (2), the mixing is performed using a dynamic mixer.
Preferably, in the step (2), the foaming line is a continuous foaming line.
Preferably, the preparation method specifically comprises the following steps:
(1) mixing the black phosphorus graphene composite material, nano titanium dioxide, polyol, isocyanate and a solvent, heating and dispersing in a reaction kettle, and then circularly dispersing graphene polyol slurry by adopting a three-roll machine with the diameter of more than 150mm to obtain graphene polyol slurry with the average graphene particle size of less than 20 microns;
(2) and respectively preserving the heat of the graphene polyol slurry and isocyanate at the temperature of 25-60 ℃, pumping into a dynamic mixer, uniformly mixing, and sending into a continuous foaming production line to prepare the wear-resistant graphene polyurethane composite sponge material.
The invention also aims to provide an application of the wear-resistant graphene polyurethane composite sponge material in preparation of bedding.
The fourth purpose of the present invention is to provide a sponge structure, which comprises the wear-resistant graphene polyurethane composite sponge material according to one of the purposes.
In a preferred technical scheme of the present invention, the sponge structure is as shown in fig. 1, the sponge structure includes a graphene polyurethane sponge body, and the material of the graphene polyurethane sponge body is the wear-resistant graphene polyurethane composite sponge material;
the graphene polyurethane sponge body sequentially comprises a first part 1, a second part 2 and a third part 3 from top to bottom;
the second part is coated with an insulating electromagnetic layer, and the third part is coated with a graphene latex conducting layer;
the top surface of the first portion is provided with a first conductive electrode 4 and the bottom surface of the third portion is provided with a second conductive electrode 5.
The fifth purpose of the invention is to provide a sponge mattress, which comprises the wear-resistant graphene polyurethane composite sponge material.
In a preferred embodiment of the present invention, the sponge mattress is shown in fig. 2, and includes a mattress body;
the mattress body comprises a support layer 22 and a comfort layer 11;
the comfort layer is arranged on the top surface of the supporting layer;
the comfort layer comprises a graphene polyurethane sponge body, and the graphene polyurethane sponge body sequentially comprises a first part 102, a second part 103 and a third part 104 from top to bottom;
the graphene polyurethane sponge body is made of the wear-resistant graphene polyurethane composite sponge material;
the first part is coated with a graphene latex conducting layer, and the second part is coated with an insulating electromagnetic layer;
the top surface of the first portion is provided with a first conductive electrode 101 and the bottom surface of the third portion is provided with a second conductive electrode 105.
The supporting layer comprises a spring layer 201 and a high-elasticity sponge layer 202 which are arranged in a stacked mode.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the black phosphorus modified graphene material is added into the polyurethane system, and the modification of the black phosphorus can promote the graphene and the nano titanium dioxide to have better bonding performance, so that the wear resistance of the graphene polyurethane composite sponge material can be further improved, and the graphene polyurethane composite sponge material can obtain longer service life when being used in bedding such as mattresses, pillows and the like.
(2) The wear-resistant graphene polyurethane composite sponge material provided by the invention has the tensile strength of more than 30MPa, the elongation at break of more than 890 percent and the abrasion of 13mm3The following.
Drawings
FIG. 1 is a schematic diagram of a sponge structure provided in one embodiment of the present invention;
wherein 1-the first portion, 2-the second portion, 3-the third portion, 4-the first conductive electrode, 5-the second conductive electrode.
FIG. 2 is a schematic diagram of a sponge mattress according to one embodiment of the present invention;
wherein 11-comfort layer, 101-first conductive electrode, 102-first portion, 103-second portion, 104-third portion, 105-second conductive electrode, 22-support layer, 201-spring layer, 202-high elastic sponge.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the following examples are set forth herein. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a wear-resistant graphene polyurethane composite sponge material, which comprises the following components in percentage by mass:
Figure BDA0003058678030000091
in the formula, the mass ratio of black phosphorus to graphene in the black phosphorus graphene composite material is 1:40, and the preparation method comprises the following steps: mixing the black phosphorus nanosheet and graphene according to a mass ratio of 1:40, carrying out ball milling under the protection of argon, respectively washing with ethanol and water, carrying out suction filtration, and drying to obtain the black phosphorus graphene composite material.
The preparation method of the wear-resistant graphene polyurethane composite sponge material comprises the following steps:
(1) mixing a black phosphorus graphene composite material, nano titanium dioxide, polyol, isocyanate and a solvent, heating and dispersing in a reaction kettle, and then circularly dispersing graphene polyol slurry by adopting a three-roll machine with the diameter of more than 150mm to obtain graphene polyol slurry with the average graphene particle size of 18 microns;
(2) and (3) respectively preserving the heat of the graphene polyol slurry and isocyanate at the temperature of 40 ℃, pumping into a dynamic mixer, uniformly mixing, and sending into a continuous foaming production line to prepare the wear-resistant graphene polyurethane composite sponge material.
Example 2
The only difference from example 1 is that the mass ratio of black phosphorus to graphene in the black phosphorus graphene composite material is 1:35, and in the preparation of the black phosphorus graphene composite material, black phosphorus nanosheets and graphene are mixed according to the mass ratio of 1: 35.
Example 3
The only difference from example 1 is that the mass ratio of black phosphorus to graphene in the black phosphorus graphene composite material is 1:50, and in the preparation of the black phosphorus graphene composite material, black phosphorus nanosheets and graphene are mixed according to the mass ratio of 1: 50.
Example 4
The only difference from example 1 is that the mass ratio of black phosphorus to graphene in the black phosphorus graphene composite material is 1:30, and in the preparation of the black phosphorus graphene composite material, black phosphorus nanosheets and graphene are mixed according to the mass ratio of 1: 30.
Example 5
The only difference from example 1 is that the mass ratio of black phosphorus to graphene in the black phosphorus graphene composite material is 1:55, and in the preparation of the black phosphorus graphene composite material, black phosphorus nanosheets and graphene are mixed according to the mass ratio of 1: 55.
Example 6
The only difference from example 1 is that the particle size of the nano titanium dioxide is 50 nm.
Example 7
The only difference from example 1 is that the particle size of the nano titanium dioxide is 80 nm.
Example 8
The only difference from example 1 is that the particle size of the nano-titania is 40 nm.
Example 9
The only difference from example 1 is that the particle size of the nano titanium dioxide is 90 nm.
Example 10
The embodiment provides a wear-resistant graphene polyurethane composite sponge material, which comprises the following components in percentage by mass:
Figure BDA0003058678030000111
in the formula, the mass ratio of black phosphorus to graphene in the black phosphorus graphene composite material is 1:40, and the preparation method comprises the following steps: mixing the black phosphorus nanosheet and graphene according to a mass ratio of 1:40, carrying out ball milling under the protection of argon, respectively washing with ethanol and water, carrying out suction filtration, and drying to obtain the black phosphorus graphene composite material.
The preparation method of the wear-resistant graphene polyurethane composite sponge material comprises the following steps:
(1) mixing a black phosphorus graphene composite material, nano titanium dioxide, polyol, isocyanate and a solvent, heating and dispersing in a reaction kettle, and then circularly dispersing graphene polyol slurry by adopting a three-roll machine with the diameter of more than 150mm to obtain graphene polyol slurry with the average graphene particle size of 18 microns;
(2) and (3) respectively preserving the heat of the graphene polyol slurry and isocyanate at the temperature of 60 ℃, pumping into a dynamic mixer, uniformly mixing, and sending into a continuous foaming production line to prepare the wear-resistant graphene polyurethane composite sponge material.
Example 11
The embodiment provides a wear-resistant graphene polyurethane composite sponge material, which comprises the following components in percentage by mass:
Figure BDA0003058678030000121
in the formula, the mass ratio of black phosphorus to graphene in the black phosphorus graphene composite material is 1:40, and the preparation method comprises the following steps: mixing the black phosphorus nanosheet and graphene according to a mass ratio of 1:40, carrying out ball milling under the protection of argon, respectively washing with ethanol and water, carrying out suction filtration, and drying to obtain the black phosphorus graphene composite material.
The preparation method of the wear-resistant graphene polyurethane composite sponge material comprises the following steps:
(1) mixing a black phosphorus graphene composite material, nano titanium dioxide, polyol, isocyanate and a solvent, heating and dispersing in a reaction kettle, and then circularly dispersing graphene polyol slurry by adopting a three-roll machine with the diameter of more than 150mm to obtain graphene polyol slurry with the average graphene particle size of 18 microns;
(2) and (3) respectively preserving the heat of the graphene polyol slurry and isocyanate at the temperature of 25 ℃, pumping into a dynamic mixer, uniformly mixing, and sending into a continuous foaming production line to prepare the wear-resistant graphene polyurethane composite sponge material.
Example 12
The embodiment provides a wear-resistant graphene polyurethane composite sponge material, which comprises the following components in percentage by mass:
Figure BDA0003058678030000122
Figure BDA0003058678030000131
in the formula, the mass ratio of black phosphorus to graphene in the black phosphorus graphene composite material is 1:40, and the preparation method comprises the following steps: mixing the black phosphorus nanosheet and graphene according to a mass ratio of 1:40, carrying out ball milling under the protection of argon, respectively washing with ethanol and water, carrying out suction filtration, and drying to obtain the black phosphorus graphene composite material.
The preparation method of the wear-resistant graphene polyurethane composite sponge material comprises the following steps:
(1) mixing a black phosphorus graphene composite material, nano titanium dioxide, polyol, isocyanate and a solvent, heating and dispersing in a reaction kettle, and then circularly dispersing graphene polyol slurry by adopting a three-roll machine with the diameter of more than 150mm to obtain graphene polyol slurry with the average graphene particle size of 18 microns;
(2) adding a foaming agent, a surfactant, a cell opening agent and a catalyst in formula amounts into the graphene polyol slurry;
(3) and (3) respectively preserving the heat of the graphene polyol slurry obtained in the step (2) and isocyanate at the temperature of 40 ℃, then pumping the slurry into a dynamic mixer, uniformly mixing, and then sending the mixture into a continuous foaming production line to obtain the wear-resistant graphene polyurethane composite sponge material.
Comparative example 1
The difference from example 1 is only that the black phosphorus graphene composite material is replaced with graphene of equal addition amount.
Comparative example 2
The only difference from example 1 is that nano-titania is replaced with nano-silver (particle size 60nm) in an equal amount.
Performance testing
The following tests were carried out on the graphene polyurethane composite sponge materials provided in the above examples and comparative examples:
(1) testing the tensile strength and the elongation at break according to the GB/T528-2009 standard;
(2) the abrasion performance test is carried out according to the GB/T1689-.
The test results are shown in table 1.
TABLE 1
Figure BDA0003058678030000141
Figure BDA0003058678030000151
As shown in Table 1, the graphene polyurethane composite sponge material provided by the invention has good elasticity and excellent wear resistance, the tensile strength is more than 30MPa, the elongation at break is more than 890%, and the abrasion is 13mm3The following.
The comparative example 1 adopts unmodified graphene, and the comparative example 2 adopts nano silver to replace nano titanium dioxide, so that the effect is not as good as that of the embodiment.
It can be known from comparative examples 1 to 5 that when the mass ratio of the black phosphorus to the graphene is in the range of 1 (35-50), the wear resistance is further improved, and the wear resistance is deteriorated when either ratio is increased (examples 4 and 5); it can be seen from comparison of examples 1 and 6-9 that the use of titanium dioxide with a particle size of 50-80nm is more beneficial to improving the wear resistance of the material, and that both too small and too large particle sizes (examples 8 and 9) lead to poor wear resistance.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. The wear-resistant graphene polyurethane composite sponge material is characterized in that the graphene polyurethane composite sponge material is prepared from the following raw materials: the composite material comprises a black phosphorus graphene composite material, nano titanium dioxide, polyol, isocyanate and a solvent;
the preparation method of the black phosphorus graphene composite material comprises the following steps: mixing black phosphorus nanosheets and graphene, and performing ball milling to obtain the black phosphorus graphene composite material;
the mass ratio of the black phosphorus nanosheet to the graphene is 1 (35-50);
the ball milling is carried out under the protection of inert gas;
the particle size of the nano titanium dioxide is 50-79 nm;
the graphene polyurethane composite sponge material comprises the following raw materials in percentage by mass:
2 to 10 percent of black phosphorus graphene composite material
3 to 8 percent of nano titanium dioxide
20 to 30 percent of polyhydric alcohol
25 to 40 percent of isocyanate
Solvent to 100%;
the polyol comprises a polyester polyol and/or a polyether polyol;
the polyester polyol comprises any one or at least two of poly neopentyl glycol adipate diol, poly 1,4 butylene glycol adipate diol, poly 1,6 hexanediol adipate diol, poly ethylene glycol adipate diol, poly methyl propylene glycol adipate diol, poly diethylene glycol adipate diol or poly butylene glycol methyl propylene glycol adipate diol;
the polyether polyol comprises any one or at least two of polypropylene oxide glycol, polyethylene oxide glycol or polytetramethylene ether glycol;
the isocyanate comprises any one or at least two of 2, 4-toluene diisocyanate, toluene 2, 6-diisocyanate or diphenylmethane diisocyanate.
2. The graphene polyurethane composite sponge material according to claim 1, wherein the ball milling is performed under argon protection.
3. The graphene polyurethane composite sponge material as claimed in claim 1, wherein the preparation method of the black phosphorus graphene composite material further comprises: after ball milling, washing, suction filtration and drying were carried out.
4. The graphene polyurethane composite sponge material according to claim 3, wherein the washing comprises washing with ethanol and water, respectively.
5. The graphene polyurethane composite sponge material according to claim 1, wherein the hydroxyl value of the polyol is 50-600 mgKOH/g.
6. The graphene polyurethane composite sponge material as claimed in claim 1, wherein the number average molecular weight of the polyol is 250-10000.
7. The graphene polyurethane composite sponge material according to claim 1, wherein the solvent comprises any one or a combination of at least two of ethanol, toluene, xylene, acetone, cyclohexanone or butanone.
8. Use of the wear resistant graphene polyurethane composite sponge material according to any one of claims 1 to 7 in the preparation of bedding.
9. A sponge structure, characterized in that it comprises a wear resistant graphene polyurethane composite sponge material according to any one of claims 1 to 7.
10. A sponge mattress, characterized in that it comprises the abrasion-resistant graphene polyurethane composite sponge material according to any one of claims 1 to 7.
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