WO2021135378A1 - Graphene-based polyurethane porous nanometer material and preparation method therefor - Google Patents

Graphene-based polyurethane porous nanometer material and preparation method therefor Download PDF

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Publication number
WO2021135378A1
WO2021135378A1 PCT/CN2020/114657 CN2020114657W WO2021135378A1 WO 2021135378 A1 WO2021135378 A1 WO 2021135378A1 CN 2020114657 W CN2020114657 W CN 2020114657W WO 2021135378 A1 WO2021135378 A1 WO 2021135378A1
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Prior art keywords
graphene
based polyurethane
polyurethane porous
component
resin
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PCT/CN2020/114657
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French (fr)
Chinese (zh)
Inventor
蒋路谣
华永军
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苏州桐力光电股份有限公司
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Publication of WO2021135378A1 publication Critical patent/WO2021135378A1/en

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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • 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
    • C08J2493/00—Characterised by the use of natural resins; Derivatives thereof
    • C08J2493/04—Rosin
    • 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
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

  • the invention belongs to the technical field of polyurethane materials, and relates to a graphene-based polyurethane porous nano material and a preparation method thereof.
  • Polyurethane is formed by the addition polymerization of organic diisocyanate or polyisocyanate and dihydroxy or polyhydroxy compound.
  • the full name is polyurethane, which contains repeating carbamate groups on the main chain and ether groups and ester groups on the side chains. , Urea group or biuret group and other macromolecular compounds introduced groups.
  • Graphene is a two-dimensional planar nanomaterial with advanced performance. Industrial production can be achieved through chemical vapor deposition and chemical reduction. Two-dimensional graphene is the basic unit of carbonaceous materials, which can be rolled into zero-dimensional rich Leene and one-dimensional carbon nanotubes can also be stacked to form three-dimensional graphite.
  • Graphene contains the following characteristics: First, the thinnest material found so far, the thickness of a single-layer graphene is only 0.335nm, which is equivalent to the diameter of carbon atoms; Second, the specific surface area is huge, and the specific surface area of graphene reaches more than 2600m 2 /g.
  • An energy storage material with excellent performance third, strong electrical conductivity, the electrons in graphene have almost no mass, and the speed of electron movement greatly exceeds the speed of electrons in metal conductors and other semiconductors, and can be used as an ideal conductive material; fourth, strong thermal conductivity , The thermal conductivity of graphene is more than 5000W/mk, which exceeds that of metal materials such as gold, silver, copper and aluminum, and can be used as an ideal thermal conductive material.
  • Polyurethane and graphene a widely used polymer material and a revolutionary inorganic material, are inestimable in the materials industry.
  • Graphene-based polymer composites are an important direction for graphene to move towards practical applications.
  • Graphene microchips have certain oxygen-containing functional groups, which are easy to be functionalized, which not only increase their binding force to the polymer matrix, but also improve their solubility. Sex, giving graphene new properties.
  • the combination of graphene and polyurethane research and emerging products, processes and applications around graphene/polyurethane have become popular. After continuous exploration and assiduous research by scientific researchers, graphene/polyurethane composites are emerging in endlessly, graphene/polyurethane composites The application of materials is also becoming more and more extensive.
  • the graphene structure is easy to break, self-generating and easy to agglomerate, and graphene has poor compatibility with polyurethane.
  • China has made certain achievements in the mechanism and preparation technology of graphene, but the application research and industrial layout are still in the research and development stage.
  • the theoretical basis of the combination of graphene and polymer materials and various performance indicators are gradually increasing with the expansion of application fields. Improve and perfect.
  • Preliminary application research has shown the excellent performance and unique advantages of graphene-based composites. Therefore, it is necessary to continue to carry out in-depth application research, combining low-cost and high-quality production technology, to broaden and enrich the space for the downstream application industry chain.
  • the purpose of the present invention is to provide a graphene-based polyurethane porous nano material and a preparation method.
  • a graphene-based polyurethane porous nano-material the graphene-based polyurethane porous nano-material is composed of component A and component B in a ratio of 1-2:1 The mass ratio is mixed to form:
  • the component A includes the following raw material components in mass percentages:
  • the component B includes the following raw material components in mass percentages:
  • the polyether polyol is at least one of polyoxypropylene glycol, polyoxypropylene triol, and polytetramethylene ether glycol.
  • the polyester polyol is at least one of adipic acid polyester polyol, hydroxy-terminated phthalic anhydride polyester polyol and polycaprolactone polyol.
  • the chain extender is at least one of EG, 1,2-PG, 1,4-BD, DEG, HD, HER, HQEE, glycerin, TMP, diethanolamine, triethanolamine, and MOCA .
  • the graphene is at least one of single-layer graphene, double-layer graphene, and few-layer graphene; the loose packing density of graphene is within 0.01-0.05 g/cm 3 , which is compact The density is 0.05 ⁇ 0.1g/cm 3 .
  • the anti-structuring agent is hydroxy silicone oil, diphenyl silicone glycol, alkoxy low molecular polysiloxane, hexamethyldisilazane, cyclic trisilazane and boron-containing At least one of siloxane compounds.
  • the weak reinforcing agent is at least one of calcium carbonate, talc, vapor-phase white carbon black, fullerene, carbon nanotube, and precipitation white carbon black.
  • the blowing agent is sodium bicarbonate, zinc oxide, ammonium bicarbonate, alum, azodicarbonamide, urea, N,N-dinitrosopentamethylenetetramine, benzoic acid , At least one of diphenylsulfonyl hydrazide ether, ethylenediamine, diazoaminobenzene, diphenylguanidine, p-toluenesulfonyl hydrazide and azobisisobutyronitrile.
  • the diluent is at least one of water, toluene, xylene and petroleum ether.
  • the tackifying resin and the tackifier are styrene-methyl methacrylate resin, rosin resin, methyl MQ silicone resin, terpene resin, terpene phenol resin, and silyl-terminated polyether resin.
  • Silyl-terminated polyurethane resin polyvinyl acetate, 3-aminopropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane At least one of silane and ⁇ -isocyanatopropyltriethoxysilane.
  • the isocyanate is at least one of phenylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and lysine diisocyanate.
  • phenylene diisocyanate isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and lysine diisocyanate.
  • the foam stabilizer is low-viscosity dimethyl silicone oil, allyl-terminated polyether, methyl cellulose ether, hydroxyethyl cellulose, hydroxymethyl methyl cellulose, hydroxylactone At least one of base cellulose and lauroyl diethyl amine.
  • the functional additives are thermoplastic resins such as polyvinyl chloride, polyvinyl acetate, polyamide, polymethyl methacrylate, polystyrene, and polyisobutylene; Tin, bismorpholinyl diethyl ether and N,N-dimethylcyclohexylamine, triphenylphosphonate, decabromodiphenyl ether, octabromodiphenyl ether, tetrabromobisphenol A, 2,4 , At least one flame retardant such as 6-tribromophenol, bis(2,3-dialkylpropyl) ether, antimony trioxide and antimony pentoxide.
  • thermoplastic resins such as polyvinyl chloride, polyvinyl acetate, polyamide, polymethyl methacrylate, polystyrene, and polyisobutylene
  • Tin bismorpholinyl diethyl ether and N,N-dimethylcyclohexylamine, triphenylphosphon
  • the technical solution provided by the present invention is: a method for preparing graphene-based polyurethane porous nanomaterials:
  • the preparation method of the component A includes the following steps:
  • Step 1 Add the polyether polyol and polyester polyol to the A reactor and stir until the dispersion is uniform;
  • Step 2 Add chain extender, anti-structuring agent and diluent to the A reactor, stir under negative pressure until the dispersion is uniform;
  • Step 3 Add graphene, weak reinforcing agent and foaming agent to the A reactor, and then stir under negative pressure until the dispersion is uniform to obtain component A;
  • the preparation method of the B component includes the following steps:
  • Step 1 Add the tackifying resin and tackifier, isocyanate, anti-structuring agent, foam leveling agent and functional additives to the B reactor, and stir until the dispersion is uniform under negative pressure;
  • Step 2 Add graphene, weak reinforcing agent and foam stabilizer to the B reaction kettle, and stir under negative pressure until the dispersion is uniform to obtain component B.
  • the negative pressure condition is that the vacuum degree is -0.08 ⁇ -0.1MPa.
  • the graphene-based polyurethane porous nanomaterial prepared by the present invention has the advantages of porosity, low relative density and high specific strength
  • the graphene-based polyurethane porous nano material prepared by the present invention has a flame retardant level of UL94-VO, resistance to chemical solvents, resistance to ultraviolet light rotation and resistance to tearing and tearing, and a large operating temperature range (-60°C to 135°C), It will not break after millions of times of bending between -10°C ⁇ 150°C, and it will rebound quickly after compression. It can maintain the original high elasticity even in harsh environments. It is widely used in sealing, shock absorption, microwave Lightweight application scenarios such as absorption, electromagnetic shielding and heat dissipation protection.
  • Example 1 A graphene-based polyurethane porous nano material and its preparation method
  • a graphene-based polyurethane porous nano material synthesized from component A and component B with a weight ratio of 1.5:1.
  • the A component includes the following components: polyether polyol, polyester polyol, chain extender, graphene, anti-structuring agent, weak reinforcing agent, foaming agent and diluent, wherein the weight of each component The percentages are as follows: polyether polyol 36%, polyester polyol 30%, chain extender 5%, graphene 20%, anti-structuring agent 1%, weak reinforcing agent 1%, foaming agent 5% and diluent 2%.
  • the component B includes the following components: tackifying resin and tackifier, isocyanate, graphene, anti-structuring agent, weak reinforcing agent, foam stabilizer and functional additives, wherein the weight percentage of each component is as follows: Tackifying resin and tackifier 20%, isocyanate 38%, graphene 30%, anti-structuring agent 1%, weak reinforcing agent 1%, foam stabilizer 5% and functional additives 5%.
  • the polyether polyol includes:
  • the polyester polyol includes:
  • Adipic acid polyester polyol (wherein, hydroxyl value/[mgKOH/g] is within 30-300, molecular weight is within 200-4000, viscosity is within 50-1500mpa ⁇ s at 60°C, acid value/[ mgKOH/g] ⁇ 0.05);
  • Polycaprolactone polyol (wherein, the hydroxyl value/[mgKOH/g] is within 50-150, the molecular weight is within 500-3000, the viscosity is within 50-2000mpa ⁇ s at 60°C, and the acid value/[mgKOH/ g] ⁇ 0.1); one or more of them.
  • the chain extender is one or more of EG, 1,2-PG, 1,4-BD, DEG, HD, HER, HQEE, glycerin, TMP, diethanolamine, triethanolamine, and MOCA.
  • the graphene is one or more of single-layer graphene, double-layer graphene, and few-layer graphene.
  • the bulk density of the graphene is controlled within 0.01 ⁇ 0.05g/cm 3 and the tap density is 0.05 Within ⁇ 0.1g/cm 3.
  • the anti-structuring agent is hydroxy silicone oil, diphenyl silicone glycol, alkoxy low molecular polysiloxane, hexamethyldisilazane, cyclic trisilazane and borosiloxane compounds At least one of.
  • the weak reinforcing agent is one or more of calcium carbonate, talc powder, gas phase method white carbon black, fullerene, carbon nanotube and precipitation method white carbon black.
  • the blowing agent is sodium bicarbonate, zinc oxide, ammonium bicarbonate, alum, azodicarbonamide, urea, N,N-dinitrosopentamethylenetetramine, benzoic acid, dibenzenesulfonyl One or more of hydrazine ether, ethylenediamine, diazoaminobenzene, diphenylguanidine, p-toluenesulfonyl hydrazide and azobisisobutyronitrile.
  • the diluent is one or more of water, toluene, xylene and petroleum ether.
  • Said tackifier resin and tackifier are styrene-methyl methacrylate resin, rosin resin, methyl MQ silicone resin, terpene resin, terpene phenol resin, silyl-terminated polyether resin, and silyl-terminated polyether resin.
  • cyanate propyl triethoxy silane is styrene-methyl methacrylate resin, rosin resin, methyl MQ silicone resin, terpene resin, terpene phenol resin, silyl-terminated polyether resin, and silyl-terminated polyether resin.
  • the isocyanate includes one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and lysine diisocyanate ; Among them, -NCO content/% is within 20-50%, and the molecular weight is within 50-500.
  • the foam stabilizer is low-viscosity dimethyl silicone oil, allyl-terminated polyether, methyl cellulose ether, hydroxyethyl cellulose, hydroxymethyl methyl cellulose, hydroxy lactyl methyl cellulose and laurel
  • acyl diethyl amines One or more of the acyl diethyl amines.
  • the functional additives include: polyvinyl chloride, polyvinyl acetate, polyamide, polymethyl methacrylate, polystyrene and polyisobutylene and other thermoplastic resins; dibutyltin dilaurate, stannous octoate, dimethoate Catalysts such as lindiethyl ether and N,N-dimethylcyclohexylamine; triphenylphosphonate, decabromodiphenyl ether, octabromodiphenyl ether, tetrabromobisphenol A, 2,4,6 -Tribromophenol, bis(2,3-dialkylpropyl) ether, antimony trioxide, antimony pentoxide and other flame retardants.
  • the preparation method of graphene-based polyurethane porous nano material includes the following steps:
  • the method for preparing component A includes the following steps:
  • the method for preparing component B includes the following steps:
  • High-speed stirring is 40-60r/min
  • low-speed stirring is 10-20r/min
  • high temperature is 110-130°C
  • medium temperature is 70-90°C
  • normal temperature is room temperature.
  • the negative pressure condition is that the degree of vacuum is -0.08 ⁇ -0.1Mpa.
  • the high-speed stirring is 50r/min
  • the low-speed stirring is 15r/min
  • the high temperature is 120°C
  • the medium temperature is 70-90°C
  • the normal temperature is room temperature.
  • the negative pressure condition is that the degree of vacuum is -0.089Mpa.
  • Embodiment 2 A graphene-based polyurethane porous nano material and its preparation method
  • a graphene-based polyurethane porous nano-material is composed of a mixture of component A and component B in a mass ratio of 1:1:
  • the component A includes the following raw material components in mass percentages:
  • the component B includes the following raw material components in mass percentages:
  • the polyether polyol is polyoxypropylene glycol.
  • polyester polyol is an adipic acid series polyester polyol.
  • the chain extender is EG.
  • the graphene is a single-layer graphene.
  • the anti-structuring agent is hydroxy silicone oil.
  • the weak reinforcing agent is calcium carbonate.
  • the blowing agent is zinc oxide.
  • the diluent is toluene.
  • tackifying resin and the tackifier are rosin resins.
  • the preferred technical solution is that the isocyanate is hexamethylene diisocyanate.
  • the foam stabilizer is allyl-terminated polyether or methyl cellulose ether.
  • the functional additive is polyvinyl chloride.
  • the technical solution provided by the present invention is: a method for preparing graphene-based polyurethane porous nanomaterials:
  • the preparation method of the component A includes the following steps:
  • Step 1 Add the polyether polyol and polyester polyol to the A reactor and stir until the dispersion is uniform;
  • Step 2 Add chain extender, anti-structuring agent and diluent to the A reactor, stir under negative pressure until the dispersion is uniform;
  • Step 3 Add graphene, weak reinforcing agent and foaming agent to the A reactor, and then stir under negative pressure until the dispersion is uniform to obtain component A;
  • the preparation method of the B component includes the following steps:
  • Step 1 Add the tackifying resin and tackifier, isocyanate, anti-structuring agent, foam leveling agent and functional additives to the B reactor, and stir until the dispersion is uniform under negative pressure;
  • Step 2 Add graphene, weak reinforcing agent and foam stabilizer to the B reaction kettle, and stir under negative pressure until the dispersion is uniform to obtain component B.
  • the negative pressure condition is that the vacuum degree is -0.08MPa.
  • Example 3 A graphene-based polyurethane porous nano material and its preparation method
  • a graphene-based polyurethane porous nano-material is composed of a mixture of component A and component B in a mass ratio of 2:1:
  • the component A includes the following raw material components in mass percentages:
  • the component B includes the following raw material components in mass percentages:
  • the polyether polyol is a mixture of polyoxypropylene glycol and polyoxypropylene triol in a mass ratio of 1:1.
  • the polyester polyol is a mixture of adipic acid polyester polyol and hydroxy-terminated phthalic anhydride polyester polyol in a mass ratio of 1:1.
  • the chain extender is a mixture of glycerol, diethanolamine, and triethanolamine in a mass ratio of 1:1:1.
  • the graphene is a mixture of single-layer graphene, double-layer graphene, and few-layer graphene in a mass ratio of 1:1; the graphene bulk density is within 0.01 g/cm 3 , The tap density is 0.05g/cm 3 .
  • the anti-structuring agent is a mixture of hydroxy silicone oil and diphenyl silicone glycol in a mass ratio of 1:1.
  • the weak reinforcing agent is a mixture of talc powder and fumed white carbon black in a mass ratio of 1:1.
  • the foaming agent is a mixture of azodicarbonamide and urea in a mass ratio of 1:1.
  • the diluent is a mixture of xylene and petroleum ether in a mass ratio of 1:1.
  • the tackifier resin and the tackifier are a mixture of methyl MQ silicone resin and terpene resin in a mass ratio of 1:1.
  • the isocyanate is a mixture of phenylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate in a mass ratio of 1:1:1.
  • the foam stabilizer is a mixture of hydroxyethyl cellulose and hydroxymethyl methyl cellulose in a mass ratio of 1:1.
  • the functional additive is a mixture of stannous octoate and bismorpholinyl diethyl ether in a mass ratio of 1:1.
  • the preparation method of the component A includes the following steps:
  • Step 1 Add polyether polyol and polyester polyol to the A reactor, stir until they are evenly dispersed;
  • Step 2 Add chain extender, anti-structuring agent and diluent to the A reactor, stir under negative pressure until the dispersion is uniform;
  • Step 3 Add graphene, weak reinforcing agent and foaming agent to the A reactor, and then stir under negative pressure until the dispersion is uniform to obtain component A;
  • the preparation method of the B component includes the following steps:
  • Step 1 Add the tackifying resin and tackifier, isocyanate, anti-structuring agent, foam leveling agent and functional additives to the B reactor, and stir until the dispersion is uniform under negative pressure;
  • Step 2 Add graphene, weak reinforcing agent and foam stabilizer to the B reaction kettle, and stir under negative pressure until the dispersion is uniform to obtain component B.
  • the negative pressure condition is that the vacuum degree is -0.1MPa.
  • Embodiment 4 A graphene-based polyurethane porous nano material and preparation method
  • the polyether polyol is polytetramethylene ether glycol.
  • the polyester polyol is polycaprolactone polyol.
  • the preferred technical solution is that the chain extender is MOCA.
  • the graphene is a double-layer graphene; the graphene loose packing density is within 0.01 g/cm 3 , and the tap density is 0.05 g/cm 3 .
  • the anti-structuring agent is hexamethyldisilazane.
  • the weak reinforcing agent is fullerene.
  • the blowing agent is a mixture of zinc oxide and azobisisobutyronitrile in a mass ratio of 1:1.
  • the diluent is water.
  • the tackifier resin and the tackifier are a mixture of polyvinyl acetate and ⁇ -mercaptopropyltrimethoxysilane in a mass ratio of 1:1.
  • the isocyanate is lysine diisocyanate.
  • the foam stabilizer is hydroxymethyl methyl cellulose.
  • the functional additive is a mixture of stannous octoate and decabromodiphenyl ether in a mass ratio of 1:1.
  • Embodiment 5 A graphene-based polyurethane porous nano material and its preparation method
  • the polyether polyol is a mixture composed of polyoxypropylene glycol and polytetramethylene ether glycol in a mass ratio of 1:1.
  • polyester polyol is an adipic acid series polyester polyol.
  • the chain extender is a mixture of 1,2-PG and 1,4-BD in a mass ratio of 1:1.
  • the graphene is a few-layer graphene; the graphene has a loose packing density of within 0.05 g/cm 3 and a tap density of 0.1 g/cm 3 .
  • the anti-structuring agent is cyclic trisilazane.
  • the weak reinforcing agent is precipitation method white carbon black.
  • the blowing agent is a mixture of benzoic acid and diphenylsulfonyl hydrazide ether in a mass ratio of 1:1.
  • the diluent is petroleum ether.
  • the tackifier resin and the tackifier are silyl-terminated polyurethane resins.
  • the isocyanate is a mixture of diphenylmethane diisocyanate and dicyclohexylmethane diisocyanate in a mass ratio of 1:1.
  • the foam stabilizer is lauroyl diethyl amine.
  • the functional additive is a mixture of bismorpholinyl diethyl ether, tetrabromobisphenol A, and 2,4,6-tribromophenol in a mass ratio of 1:1.

Abstract

A graphene-based polyurethane porous nanometer material and a preparation method therefor. The graphene-based polyurethane porous nanometer material is formed by mixing component A and component B according to a mass ratio of (1-2): 1. The component A comprises the following components: polyether polyol, polyester polyol, a chain extender, graphene, an anti-structuring agent, a weak reinforcing agent, a foaming agent, and a diluent; the component B comprises the following components: a tackifying resin, a tackifier, isocyanate, graphene, an anti-structuring agent, a weak reinforcing agent, a foam stabilizer, and a functional additive. The graphene-based polyurethane porous nanometer material has the advantages of porosity and small relative density.

Description

一种石墨烯基聚氨酯多孔纳米材料及其制备方法Graphene-based polyurethane porous nano material and preparation method thereof 技术领域Technical field
本发明属于聚氨酯材料技术领域，涉及一种石墨烯基聚氨酯多孔纳米材料及其制备方法。The invention belongs to the technical field of polyurethane materials, and relates to a graphene-based polyurethane porous nano material and a preparation method thereof.
背景技术Background technique
聚氨酯由有机二异氰酸酯或多异氰酸酯与二羟基或多羟基化合物加聚而成，全称为聚氨基甲酸酯，是主链上含有重复氨基甲酸酯基团和侧链上含有醚基、酯基、脲基或者缩二脲基等引进基团的大分子化合物的统称。石墨烯是一种性能先进的二维平面纳米材料，通过化学气相沉积法和化学还原法可以实现工业化生产，二维石墨烯是碳质材料的基本组成单元，可以将它卷曲成零维的富勒烯和一维的碳纳米管，也可以将它重叠堆积成三维的石墨。石墨烯包含以下特性：一，目前发现最薄的材料，单层石墨烯厚度只有0.335nm，相当于碳原子的直径；二，比表面积庞大，石墨烯的比表面积达到2600m 2/g以上，是一种性能优异的储能材料；三，导电性强，石墨烯中电子几乎没有质量，电子运动速度大大超过金属导体和其他半导体中电子运动速度，可作为理想的导电材料；四，导热性强，石墨烯的热导率达到5000W/mk以上，超过金、银、铜和铝等金属材料，可作为理想的导热材料。聚氨酯和石墨烯，一个应用广泛的高分子材料，一个革命性的无机材料，均在材料行业中不可估量。 Polyurethane is formed by the addition polymerization of organic diisocyanate or polyisocyanate and dihydroxy or polyhydroxy compound. The full name is polyurethane, which contains repeating carbamate groups on the main chain and ether groups and ester groups on the side chains. , Urea group or biuret group and other macromolecular compounds introduced groups. Graphene is a two-dimensional planar nanomaterial with advanced performance. Industrial production can be achieved through chemical vapor deposition and chemical reduction. Two-dimensional graphene is the basic unit of carbonaceous materials, which can be rolled into zero-dimensional rich Leene and one-dimensional carbon nanotubes can also be stacked to form three-dimensional graphite. Graphene contains the following characteristics: First, the thinnest material found so far, the thickness of a single-layer graphene is only 0.335nm, which is equivalent to the diameter of carbon atoms; Second, the specific surface area is huge, and the specific surface area of graphene reaches more than 2600m 2 /g. An energy storage material with excellent performance; third, strong electrical conductivity, the electrons in graphene have almost no mass, and the speed of electron movement greatly exceeds the speed of electrons in metal conductors and other semiconductors, and can be used as an ideal conductive material; fourth, strong thermal conductivity , The thermal conductivity of graphene is more than 5000W/mk, which exceeds that of metal materials such as gold, silver, copper and aluminum, and can be used as an ideal thermal conductive material. Polyurethane and graphene, a widely used polymer material and a revolutionary inorganic material, are inestimable in the materials industry.
基于石墨烯的聚合物复合材料是石墨烯迈向实际应用的一个重要方向，石墨烯微片具有一定含氧官能团，易于进行功能化，不仅增加其与高分子基体结合力，而且可以提高其溶解性，赋予石墨烯新的性质。近年来，结合石墨烯和聚氨酯的研究以及围绕石墨烯/聚氨酯的新兴产品、工艺和应用炙手可热，经过科研工作者的不断探索和刻苦专研，石墨烯/聚氨酯复合材料层出不穷，石墨烯/聚氨酯复合材料的应用也越来越广泛。但是，石墨烯/聚氨酯在人们日常生活中应用的深度和广度还未达到该领域科研工作者的预期，主要原因有以下两点：1，石墨烯/聚氨酯复合材料作为前沿材料，研发主体以高校和研究机构为主，偏重于基础科学而非实用技术，高端生产工艺不成熟，尚无法实现低成本，而下游应用主体缺乏积极性，难 以形成规模化产业；2，石墨烯/聚氨酯复合材料本身还存在一定的技术难题需要较长时间去攻克，例如石墨烯结构容易破坏、自生容易团聚和石墨烯跟聚氨酯相容性差等缺陷。中国在石墨烯机理和制备技术等方面取得了一定成绩，但应用研究和产业布局尚处于研发阶段，石墨烯与高分子材料结合的理论基础以及各项性能指标随着应用领域的拓展也逐步的提高和完善。初步应用研究显示了石墨烯基复合材料优异的性能和独特的优势，因此应继续深入开展应用研究，结合低成本和高质量生产技术，拓宽和丰富下游应用产业链的空间。Graphene-based polymer composites are an important direction for graphene to move towards practical applications. Graphene microchips have certain oxygen-containing functional groups, which are easy to be functionalized, which not only increase their binding force to the polymer matrix, but also improve their solubility. Sex, giving graphene new properties. In recent years, the combination of graphene and polyurethane research and emerging products, processes and applications around graphene/polyurethane have become popular. After continuous exploration and assiduous research by scientific researchers, graphene/polyurethane composites are emerging in endlessly, graphene/polyurethane composites The application of materials is also becoming more and more extensive. However, the depth and breadth of graphene/polyurethane applications in people’s daily lives has not yet reached the expectations of scientific researchers in this field. The main reasons are as follows: 1. Graphene/polyurethane composite materials are the cutting-edge materials, and the research and development subjects are universities and colleges And research institutions, focusing on basic science rather than practical technology, high-end production technology is immature, and low cost cannot be achieved yet, and the main body of downstream applications lacks enthusiasm and it is difficult to form a large-scale industry; 2. The graphene/polyurethane composite material itself is still There are certain technical problems that take a long time to overcome. For example, the graphene structure is easy to break, self-generating and easy to agglomerate, and graphene has poor compatibility with polyurethane. China has made certain achievements in the mechanism and preparation technology of graphene, but the application research and industrial layout are still in the research and development stage. The theoretical basis of the combination of graphene and polymer materials and various performance indicators are gradually increasing with the expansion of application fields. Improve and perfect. Preliminary application research has shown the excellent performance and unique advantages of graphene-based composites. Therefore, it is necessary to continue to carry out in-depth application research, combining low-cost and high-quality production technology, to broaden and enrich the space for the downstream application industry chain.
发明内容Summary of the invention
本发明的目的在于提供一种石墨烯基聚氨酯多孔纳米材料及制备方法。The purpose of the present invention is to provide a graphene-based polyurethane porous nano material and a preparation method.
为实现上述目的及其他相关目的，本发明提供的技术方案是：一种石墨烯基聚氨酯多孔纳米材料，所述石墨烯基聚氨酯多孔纳米材料由A组份和B组份按照1-2:1的质量比例混合后构成：In order to achieve the above objectives and other related objectives, the technical solution provided by the present invention is: a graphene-based polyurethane porous nano-material, the graphene-based polyurethane porous nano-material is composed of component A and component B in a ratio of 1-2:1 The mass ratio is mixed to form:
所述A组份包括以下质量百分比的原料组分：The component A includes the following raw material components in mass percentages:
Figure PCTCN2020114657-appb-000001
Figure PCTCN2020114657-appb-000001
所述B组份包括以下质量百分比的原料组分：The component B includes the following raw material components in mass percentages:
Figure PCTCN2020114657-appb-000002
Figure PCTCN2020114657-appb-000002
Figure PCTCN2020114657-appb-000003
Figure PCTCN2020114657-appb-000003
优选的技术方案为：所述聚醚多元醇为聚氧化丙烯二醇、聚氧化丙烯三醇、聚四亚甲基醚二醇中的至少一种。The preferred technical solution is that the polyether polyol is at least one of polyoxypropylene glycol, polyoxypropylene triol, and polytetramethylene ether glycol.
优选的技术方案为：所述聚酯多元醇为己二酸系聚酯多元醇、端羟基苯酐聚酯多元醇和聚己内酯多元醇中的至少一种。The preferred technical solution is that the polyester polyol is at least one of adipic acid polyester polyol, hydroxy-terminated phthalic anhydride polyester polyol and polycaprolactone polyol.
优选的技术方案为：所述扩链剂为EG、1,2-PG、1,4-BD、DEG、HD、HER、HQEE、甘油、TMP、二乙醇胺、三乙醇胺、MOCA中的至少一种。The preferred technical solution is: the chain extender is at least one of EG, 1,2-PG, 1,4-BD, DEG, HD, HER, HQEE, glycerin, TMP, diethanolamine, triethanolamine, and MOCA .
优选的技术方案为：所述石墨烯为单层石墨烯、双层石墨烯和少层石墨烯中的至少一种；所述石墨烯松装密度为0.01-0.05g/cm 3以内，振实密度为0.05～0.1g/cm 3。 The preferred technical solution is: the graphene is at least one of single-layer graphene, double-layer graphene, and few-layer graphene; the loose packing density of graphene is within 0.01-0.05 g/cm 3 , which is compact The density is 0.05～0.1g/cm 3 .
优选的技术方案为：所述抗结构化剂为羟基硅油、二苯基硅二醇、烷氧基低分子聚硅氧烷、六甲基二硅氨烷、环状三硅氨烷和含硼硅氧烷类化合物中的至少一种。The preferred technical solution is: the anti-structuring agent is hydroxy silicone oil, diphenyl silicone glycol, alkoxy low molecular polysiloxane, hexamethyldisilazane, cyclic trisilazane and boron-containing At least one of siloxane compounds.
优选的技术方案为：所述弱补强剂为碳酸钙、滑石粉、气相法白炭黑、富勒烯、碳纳米管和沉淀法白炭黑中的至少一种。The preferred technical solution is: the weak reinforcing agent is at least one of calcium carbonate, talc, vapor-phase white carbon black, fullerene, carbon nanotube, and precipitation white carbon black.
优选的技术方案为：所述发泡剂为碳酸氢钠、氧化锌、碳酸氢铵、明矾、偶氮二甲酰胺、尿素、N,N-二亚硝基五次甲基四胺、苯甲酸、二苯磺酰肼醚、乙二胺、二偶氮氨基苯、二苯胍、对甲苯磺酰肼和偶氮二异丁腈中的至少一种。The preferred technical solution is: the blowing agent is sodium bicarbonate, zinc oxide, ammonium bicarbonate, alum, azodicarbonamide, urea, N,N-dinitrosopentamethylenetetramine, benzoic acid , At least one of diphenylsulfonyl hydrazide ether, ethylenediamine, diazoaminobenzene, diphenylguanidine, p-toluenesulfonyl hydrazide and azobisisobutyronitrile.
优选的技术方案为：所述稀释剂为水、甲苯、二甲苯和石油醚中的至少一种。The preferred technical solution is: the diluent is at least one of water, toluene, xylene and petroleum ether.
优选的技术方案为：所述增粘树脂及增粘剂为苯乙烯-甲基丙烯酸甲酯树脂、松香树脂、甲基MQ硅树脂、萜烯树脂、萜烯酚醛树脂、端硅烷基聚醚树脂、端硅烷基聚氨基甲酸酯树脂、聚乙酸乙烯酯、3-氨丙基三乙氧基硅烷、γ-巯丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷和γ-异氰酸丙基三乙氧基硅烷中的至少一种。The preferred technical solution is: the tackifying resin and the tackifier are styrene-methyl methacrylate resin, rosin resin, methyl MQ silicone resin, terpene resin, terpene phenol resin, and silyl-terminated polyether resin. , Silyl-terminated polyurethane resin, polyvinyl acetate, 3-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane At least one of silane and γ-isocyanatopropyltriethoxysilane.
优选的技术方案为：所述异氰酸酯为苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、赖氨酸二异氰酸酯中的至少一种。The preferred technical solution is that the isocyanate is at least one of phenylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and lysine diisocyanate. One kind.
优选的技术方案为：所述匀泡剂为低粘度二甲基硅油、端烯丙基 聚醚、甲基纤维素醚、羟乙基纤维素、羟甲基甲基纤维素、羟内基甲基纤维素和月桂酰二乙醉胺中的至少一种。The preferred technical solution is: the foam stabilizer is low-viscosity dimethyl silicone oil, allyl-terminated polyether, methyl cellulose ether, hydroxyethyl cellulose, hydroxymethyl methyl cellulose, hydroxylactone At least one of base cellulose and lauroyl diethyl amine.
优选的技术方案为：所述功能型添加剂为聚氯乙烯、聚乙酸乙烯酯、聚酰胺、聚甲基丙烯酸甲酯、聚苯乙烯和聚异丁烯等热塑性树脂；二丁基锡二月桂酸酯、辛酸亚锡、双吗啉基二乙基醚和N,N-二甲基环已胺、三苯基膦酸酯、十溴二苯醚、八溴二苯醚、四溴双酚A、2，4，6-三溴苯酚、双(2，3-二烷丙基)醚和三氧化二锑和五氧化二锑等阻燃剂至少一种。The preferred technical solution is: the functional additives are thermoplastic resins such as polyvinyl chloride, polyvinyl acetate, polyamide, polymethyl methacrylate, polystyrene, and polyisobutylene; Tin, bismorpholinyl diethyl ether and N,N-dimethylcyclohexylamine, triphenylphosphonate, decabromodiphenyl ether, octabromodiphenyl ether, tetrabromobisphenol A, 2,4 , At least one flame retardant such as 6-tribromophenol, bis(2,3-dialkylpropyl) ether, antimony trioxide and antimony pentoxide.
为实现上述目的及其他相关目的，本发明提供的技术方案是：一种制备石墨烯基聚氨酯多孔纳米材料的方法：In order to achieve the above objectives and other related objectives, the technical solution provided by the present invention is: a method for preparing graphene-based polyurethane porous nanomaterials:
所述A组份的制备方法包括以下步骤：The preparation method of the component A includes the following steps:
步骤1：将聚醚多元醇、聚酯多元醇加到A反应釜里，搅拌至分散均匀；Step 1: Add the polyether polyol and polyester polyol to the A reactor and stir until the dispersion is uniform;
步骤2：向A反应釜加入扩链剂、抗结构化剂和稀释剂，在负压条件下搅拌至分散均匀；Step 2: Add chain extender, anti-structuring agent and diluent to the A reactor, stir under negative pressure until the dispersion is uniform;
步骤3：向A反应釜加入加入石墨烯、弱补强剂和发泡剂，然后在负压条件下，搅拌至分散均匀，得到A组份；Step 3: Add graphene, weak reinforcing agent and foaming agent to the A reactor, and then stir under negative pressure until the dispersion is uniform to obtain component A;
所述B组份的制备方法包括以下步骤：The preparation method of the B component includes the following steps:
步骤1：将增粘树脂及增粘剂、异氰酸酯、抗结构化剂、匀泡剂和功能型添加剂，加到B反应釜里，在负压条件下，搅拌至分散均匀；Step 1: Add the tackifying resin and tackifier, isocyanate, anti-structuring agent, foam leveling agent and functional additives to the B reactor, and stir until the dispersion is uniform under negative pressure;
步骤2：向B反应釜加入石墨烯、弱补强剂和匀泡剂，在负压条件下搅拌至分散均匀，得到B组份。Step 2: Add graphene, weak reinforcing agent and foam stabilizer to the B reaction kettle, and stir under negative pressure until the dispersion is uniform to obtain component B.
优选的技术方案为：负压条件为真空度为-0.08～-0.1MPa。The preferred technical solution is: the negative pressure condition is that the vacuum degree is -0.08～-0.1MPa.
由于上述技术方案运用，本发明与现有技术相比具有的优点是：Due to the application of the above technical solutions, the advantages of the present invention compared with the prior art are:
1、本发明制得的石墨烯基聚氨酯多孔纳米材料具有多孔性、相对密度小、比强度高的优点1. The graphene-based polyurethane porous nanomaterial prepared by the present invention has the advantages of porosity, low relative density and high specific strength
2、本发明制得的石墨烯基聚氨酯多孔纳米材料，阻燃级别达到UL94-VO，耐化学溶剂、耐紫外旋光和耐撕裂扯断，作业温幅大(-60℃至135℃)，在－10℃～150℃之间经过千百万次的曲挠不会断裂，压缩后迅速回弹，即使在恶劣环境下作业也能保持原有的高弹性，广泛 应用于密封减震、微波吸收、电磁屏蔽和散热保护等轻量化应用场景。2. The graphene-based polyurethane porous nano material prepared by the present invention has a flame retardant level of UL94-VO, resistance to chemical solvents, resistance to ultraviolet light rotation and resistance to tearing and tearing, and a large operating temperature range (-60°C to 135°C), It will not break after millions of times of bending between -10℃～150℃, and it will rebound quickly after compression. It can maintain the original high elasticity even in harsh environments. It is widely used in sealing, shock absorption, microwave Lightweight application scenarios such as absorption, electromagnetic shielding and heat dissipation protection.
具体实施方式Detailed ways
以下由特定的具体实施例说明本发明的实施方式，熟悉此技术的人士可由本说明书所揭露的内容轻易地了解本发明的其他优点及功效。The following specific examples illustrate the implementation of the present invention. Those familiar with the technology can easily understand the other advantages and effects of the present invention from the content disclosed in this specification.
实施例1：一种石墨烯基聚氨酯多孔纳米材料及制备方法Example 1: A graphene-based polyurethane porous nano material and its preparation method
一种石墨烯基聚氨酯多孔纳米材料，由重量比1.5:1的组份A和组份B合成。A graphene-based polyurethane porous nano material, synthesized from component A and component B with a weight ratio of 1.5:1.
所述的A组份包括以下各组分：聚醚多元醇、聚酯多元醇、扩链剂、石墨烯、抗结构化剂、弱补强剂、发泡剂和稀释剂，其中各成分重量百分数如下：聚醚多元醇36％、聚酯多元醇30％、扩链剂5％、石墨烯20％、抗结构化剂1％、弱补强剂1％、发泡剂5％和稀释剂2％。The A component includes the following components: polyether polyol, polyester polyol, chain extender, graphene, anti-structuring agent, weak reinforcing agent, foaming agent and diluent, wherein the weight of each component The percentages are as follows: polyether polyol 36%, polyester polyol 30%, chain extender 5%, graphene 20%, anti-structuring agent 1%, weak reinforcing agent 1%, foaming agent 5% and diluent 2%.
所述的B组份包括以下各组分：增粘树脂及增粘剂、异氰酸酯、石墨烯、抗结构化剂、弱补强剂、匀泡剂和功能型添加剂，其中各成分重量百分数如下：增粘树脂及增粘剂20％、异氰酸酯38％、石墨烯30％、抗结构化剂1％、弱补强剂1％、匀泡剂5％和功能型添加剂5％。The component B includes the following components: tackifying resin and tackifier, isocyanate, graphene, anti-structuring agent, weak reinforcing agent, foam stabilizer and functional additives, wherein the weight percentage of each component is as follows: Tackifying resin and tackifier 20%, isocyanate 38%, graphene 30%, anti-structuring agent 1%, weak reinforcing agent 1%, foam stabilizer 5% and functional additives 5%.
所述的聚醚多元醇包括：The polyether polyol includes:
a)聚氧化丙烯二醇(其中，羟值/[mgKOH/g]在20-50以内，分子量在2000～6000以内，25℃时粘度在500～5000mpa·s以内，酸值/[mgKOH/g]≤0.05)；a) Polyoxypropylene glycol (where the hydroxyl value/[mgKOH/g] is within 20-50, the molecular weight is within 2000-6000, the viscosity is within 500-5000mpa·s at 25°C, and the acid value/[mgKOH/g ]≤0.05);
b)聚氧化丙烯三醇(其中，羟值/[mgKOH/g]在20-100以内，分子量在1000～4000以内，25℃时粘度在100～2000mpa·s以内，酸值/[mgKOH/g]≤0.05)；b) Polyoxypropylene triol (where the hydroxyl value/[mgKOH/g] is within 20-100, the molecular weight is within 1000-4000, the viscosity is within 100-2000mpa·s at 25°C, and the acid value/[mgKOH/g ]≤0.05);
c)聚四亚甲基醚二醇(其中，羟值/[mgKOH/g]在30-200以内，分子量在500～4000以内，25℃时粘度在100～2000mpa·s以内，酸值/[mgKOH/g]≤0.05)；中的一种或几种。c) Polytetramethylene ether glycol (wherein, the hydroxyl value/[mgKOH/g] is within 30-200, the molecular weight is within 500-4000, the viscosity is within 100-2000mpa·s at 25°C, the acid value/[ mgKOH/g]≤0.05); one or more of them.
所述的聚酯多元醇包括：The polyester polyol includes:
a)己二酸系聚酯多元醇(其中，羟值/[mgKOH/g]在30-300以内，分子量在200～4000以内，60℃时粘度在50～1500mpa·s以内，酸值/[mgKOH/g]≤0.05)；a) Adipic acid polyester polyol (wherein, hydroxyl value/[mgKOH/g] is within 30-300, molecular weight is within 200-4000, viscosity is within 50-1500mpa·s at 60℃, acid value/[ mgKOH/g]≤0.05);
b)端羟基苯酐聚酯多元醇(其中，羟值/[mgKOH/g]在100-300以内，分子量在1000～2000以内，60℃时粘度在100～2000mpa·s以内，酸值/[mgKOH/g]≤0.1)；b) Hydroxy-terminated phthalic anhydride polyester polyol (where the hydroxyl value/[mgKOH/g] is within 100-300, the molecular weight is within 1000-2000, the viscosity is within 100-2000mpa·s at 60℃, and the acid value/[mgKOH /g]≤0.1);
c)聚己内酯多元醇(其中，羟值/[mgKOH/g]在50-150以内，分子量在500～3000以内，60℃时粘度在50～2000mpa·s以内，酸值/[mgKOH/g]≤0.1)；中的一种或几种。c) Polycaprolactone polyol (wherein, the hydroxyl value/[mgKOH/g] is within 50-150, the molecular weight is within 500-3000, the viscosity is within 50-2000mpa·s at 60℃, and the acid value/[mgKOH/ g]≤0.1); one or more of them.
所述的扩链剂为EG、1,2-PG、1,4-BD、DEG、HD、HER、HQEE、甘油、TMP、二乙醇胺、三乙醇胺、MOCA中的一种或几种。The chain extender is one or more of EG, 1,2-PG, 1,4-BD, DEG, HD, HER, HQEE, glycerin, TMP, diethanolamine, triethanolamine, and MOCA.
所述的石墨烯为单层石墨烯、双层石墨烯和少层石墨烯中的一种或几种，上述石墨烯松装密度控制在0.01～0.05g/cm 3以内，振实密度为0.05～0.1g/cm 3以内。 The graphene is one or more of single-layer graphene, double-layer graphene, and few-layer graphene. The bulk density of the graphene is controlled within 0.01～0.05g/cm 3 and the tap density is 0.05 Within ～0.1g/cm 3.
所述抗结构化剂为羟基硅油、二苯基硅二醇、烷氧基低分子聚硅氧烷、六甲基二硅氨烷、环状三硅氨烷和含硼硅氧烷类化合物中的至少一种。The anti-structuring agent is hydroxy silicone oil, diphenyl silicone glycol, alkoxy low molecular polysiloxane, hexamethyldisilazane, cyclic trisilazane and borosiloxane compounds At least one of.
所述的弱补强剂为碳酸钙、滑石粉、气相法白炭黑、富勒烯、碳纳米管和沉淀法白炭黑中一种或几种。The weak reinforcing agent is one or more of calcium carbonate, talc powder, gas phase method white carbon black, fullerene, carbon nanotube and precipitation method white carbon black.
所述的发泡剂为碳酸氢钠、氧化锌、碳酸氢铵、明矾、偶氮二甲酰胺、尿素、N,N-二亚硝基五次甲基四胺、苯甲酸、二苯磺酰肼醚、乙二胺、二偶氮氨基苯、二苯胍、对甲苯磺酰肼和偶氮二异丁腈中的一种或几种。The blowing agent is sodium bicarbonate, zinc oxide, ammonium bicarbonate, alum, azodicarbonamide, urea, N,N-dinitrosopentamethylenetetramine, benzoic acid, dibenzenesulfonyl One or more of hydrazine ether, ethylenediamine, diazoaminobenzene, diphenylguanidine, p-toluenesulfonyl hydrazide and azobisisobutyronitrile.
所述的稀释剂为水、甲苯、二甲苯和石油醚中的一种或几种。The diluent is one or more of water, toluene, xylene and petroleum ether.
所述的增粘树脂及增粘剂为苯乙烯-甲基丙烯酸甲酯树脂、松香树脂、甲基MQ硅树脂、萜烯树脂、萜烯酚醛树脂、端硅烷基聚醚树脂、端硅烷基聚氨基甲酸酯树脂、聚乙酸乙烯酯、3-氨丙基三乙氧基硅烷、γ-巯丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷和γ-异氰酸丙基三乙氧基硅烷中的一种或几种。Said tackifier resin and tackifier are styrene-methyl methacrylate resin, rosin resin, methyl MQ silicone resin, terpene resin, terpene phenol resin, silyl-terminated polyether resin, and silyl-terminated polyether resin. Urethane resin, polyvinyl acetate, 3-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and γ-iso One or more of cyanate propyl triethoxy silane.
所述的异氰酸酯包括：甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、赖氨酸二异氰酸酯中的一种或几种；其中-NCO含量/％在20-50％以内，分子量在50-500以内。The isocyanate includes one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and lysine diisocyanate ; Among them, -NCO content/% is within 20-50%, and the molecular weight is within 50-500.
所述的匀泡剂为低粘度二甲基硅油、端烯丙基聚醚、甲基纤维素 醚、羟乙基纤维素、羟甲基甲基纤维素、羟内基甲基纤维素和月桂酰二乙醉胺中的一种或几种。The foam stabilizer is low-viscosity dimethyl silicone oil, allyl-terminated polyether, methyl cellulose ether, hydroxyethyl cellulose, hydroxymethyl methyl cellulose, hydroxy lactyl methyl cellulose and laurel One or more of the acyl diethyl amines.
所述的功能型添加剂包括：聚氯乙烯、聚乙酸乙烯酯、聚酰胺、聚甲基丙烯酸甲酯、聚苯乙烯和聚异丁烯等热塑性树脂；二丁基锡二月桂酸酯、辛酸亚锡、双吗啉基二乙基醚和N,N-二甲基环已胺等催化剂；三苯基膦酸酯、十溴二苯醚、八溴二苯醚、四溴双酚A、2，4，6-三溴苯酚、双(2，3-二烷丙基)醚和三氧化二锑和五氧化二锑等阻燃剂中的一种或几种。The functional additives include: polyvinyl chloride, polyvinyl acetate, polyamide, polymethyl methacrylate, polystyrene and polyisobutylene and other thermoplastic resins; dibutyltin dilaurate, stannous octoate, dimethoate Catalysts such as lindiethyl ether and N,N-dimethylcyclohexylamine; triphenylphosphonate, decabromodiphenyl ether, octabromodiphenyl ether, tetrabromobisphenol A, 2,4,6 -Tribromophenol, bis(2,3-dialkylpropyl) ether, antimony trioxide, antimony pentoxide and other flame retardants.
石墨烯基聚氨酯多孔纳米材料制备方法，包括以下步骤：The preparation method of graphene-based polyurethane porous nano material includes the following steps:
所述的A组份制备方法包括以下步骤：The method for preparing component A includes the following steps:
A)将聚醚多元醇、聚酯多元醇加到反应釜里，在高温和负压的条件下，高速搅拌1.5小时，至分散均匀；A) Add polyether polyol and polyester polyol to the reaction kettle, and stir at high speed for 1.5 hours under the conditions of high temperature and negative pressure until the dispersion is uniform;
B)在常温和低速搅拌的条件下，加入扩链剂、抗结构化剂和稀释剂，在负压条件下高速搅拌1.5小时，至分散均匀；B) Under normal temperature and low-speed stirring conditions, add chain extenders, anti-structuring agents and diluents, and stir at high speed for 1.5 hours under negative pressure until the dispersion is uniform;
C)在低速搅拌的条件下，加入石墨烯、弱补强剂和发泡剂，然后在负压条件下，高速搅拌至分散均匀；C) Under the condition of low-speed stirring, add graphene, weak reinforcing agent and foaming agent, and then under negative pressure, high-speed stirring until the dispersion is uniform;
所述的B组份制备方法包括以下步骤：The method for preparing component B includes the following steps:
A)将增粘树脂及增粘剂、异氰酸酯、抗结构化剂、匀泡剂和功能型添加剂，加到反应釜里，在中温和负压的条件下，高速搅拌1.5小时，至分散均匀；A) Add the tackifying resin and tackifier, isocyanate, anti-structuring agent, foam leveling agent and functional additives to the reaction kettle, and stir at high speed for 1.5 hours under the conditions of medium temperature and negative pressure until the dispersion is uniform;
B)在常温和低速搅拌的条件下，加入石墨烯、弱补强剂和匀泡剂,在负压条件下高速搅拌1.5小时，至分散均匀；B) Under normal temperature and low-speed stirring conditions, add graphene, weak reinforcing agent and foam stabilizer, and stir at high speed for 1.5 hours under negative pressure until the dispersion is uniform;
使用时，按比例将A组份和B组份混合均匀即可。When using, just mix the A component and B component evenly in proportion.
高速搅拌为40～60r/min，低速搅拌为10～20r/min，高温为110～130℃，中温为70～90℃，常温是室温。负压条件为真空度为-0.08～-0.1Mpa。本实施例：高速搅拌为50r/min，低速搅拌为15r/min，高温为120℃，中温为70～90℃，常温是室温。负压条件为真空度为-0.089Mpa。High-speed stirring is 40-60r/min, low-speed stirring is 10-20r/min, high temperature is 110-130°C, medium temperature is 70-90°C, and normal temperature is room temperature. The negative pressure condition is that the degree of vacuum is -0.08～-0.1Mpa. In this embodiment, the high-speed stirring is 50r/min, the low-speed stirring is 15r/min, the high temperature is 120°C, the medium temperature is 70-90°C, and the normal temperature is room temperature. The negative pressure condition is that the degree of vacuum is -0.089Mpa.
实施例2：一种石墨烯基聚氨酯多孔纳米材料及制备方法Embodiment 2: A graphene-based polyurethane porous nano material and its preparation method
一种石墨烯基聚氨酯多孔纳米材料，所述石墨烯基聚氨酯多孔纳米材料由A组份和B组份按照1:1的质量比例混合后构成：A graphene-based polyurethane porous nano-material, the graphene-based polyurethane porous nano-material is composed of a mixture of component A and component B in a mass ratio of 1:1:
所述A组份包括以下质量百分比的原料组分：The component A includes the following raw material components in mass percentages:
Figure PCTCN2020114657-appb-000004
Figure PCTCN2020114657-appb-000004
所述B组份包括以下质量百分比的原料组分：The component B includes the following raw material components in mass percentages:
Figure PCTCN2020114657-appb-000005
Figure PCTCN2020114657-appb-000005
优选的技术方案为：所述聚醚多元醇为聚氧化丙烯二醇。The preferred technical solution is: the polyether polyol is polyoxypropylene glycol.
优选的技术方案为：所述聚酯多元醇为己二酸系聚酯多元醇。The preferred technical solution is that the polyester polyol is an adipic acid series polyester polyol.
优选的技术方案为：所述扩链剂为EG。The preferred technical solution is: the chain extender is EG.
优选的技术方案为：所述石墨烯为单层石墨烯。A preferred technical solution is: the graphene is a single-layer graphene.
优选的技术方案为：所述抗结构化剂为羟基硅油。The preferred technical solution is: the anti-structuring agent is hydroxy silicone oil.
优选的技术方案为：所述弱补强剂为碳酸钙。The preferred technical solution is that the weak reinforcing agent is calcium carbonate.
优选的技术方案为：所述发泡剂为氧化锌。The preferred technical solution is: the blowing agent is zinc oxide.
优选的技术方案为：所述稀释剂为甲苯。The preferred technical solution is: the diluent is toluene.
优选的技术方案为：所述增粘树脂及增粘剂为松香树脂。The preferred technical solution is that the tackifying resin and the tackifier are rosin resins.
优选的技术方案为：所述异氰酸酯为六亚甲基二异氰酸酯。The preferred technical solution is that the isocyanate is hexamethylene diisocyanate.
优选的技术方案为：所述匀泡剂为端烯丙基聚醚、甲基纤维素醚。The preferred technical solution is: the foam stabilizer is allyl-terminated polyether or methyl cellulose ether.
优选的技术方案为：所述功能型添加剂为聚氯乙烯。The preferred technical solution is: the functional additive is polyvinyl chloride.
为实现上述目的及其他相关目的，本发明提供的技术方案是：一种制备石墨烯基聚氨酯多孔纳米材料的方法：In order to achieve the above objectives and other related objectives, the technical solution provided by the present invention is: a method for preparing graphene-based polyurethane porous nanomaterials:
所述A组份的制备方法包括以下步骤：The preparation method of the component A includes the following steps:
步骤1：将聚醚多元醇、聚酯多元醇加到A反应釜里，搅拌至分散均匀；Step 1: Add the polyether polyol and polyester polyol to the A reactor and stir until the dispersion is uniform;
步骤2：向A反应釜加入扩链剂、抗结构化剂和稀释剂，在负压条件下搅拌至分散均匀；Step 2: Add chain extender, anti-structuring agent and diluent to the A reactor, stir under negative pressure until the dispersion is uniform;
步骤3：向A反应釜加入加入石墨烯、弱补强剂和发泡剂，然后在负压条件下，搅拌至分散均匀，得到A组份；Step 3: Add graphene, weak reinforcing agent and foaming agent to the A reactor, and then stir under negative pressure until the dispersion is uniform to obtain component A;
所述B组份的制备方法包括以下步骤：The preparation method of the B component includes the following steps:
步骤1：将增粘树脂及增粘剂、异氰酸酯、抗结构化剂、匀泡剂和功能型添加剂，加到B反应釜里，在负压条件下，搅拌至分散均匀；Step 1: Add the tackifying resin and tackifier, isocyanate, anti-structuring agent, foam leveling agent and functional additives to the B reactor, and stir until the dispersion is uniform under negative pressure;
步骤2：向B反应釜加入石墨烯、弱补强剂和匀泡剂，在负压条件下搅拌至分散均匀，得到B组份。Step 2: Add graphene, weak reinforcing agent and foam stabilizer to the B reaction kettle, and stir under negative pressure until the dispersion is uniform to obtain component B.
优选的技术方案为：负压条件为真空度为-0.08MPa。The preferred technical solution is: the negative pressure condition is that the vacuum degree is -0.08MPa.
实施例3：一种石墨烯基聚氨酯多孔纳米材料及制备方法Example 3: A graphene-based polyurethane porous nano material and its preparation method
一种石墨烯基聚氨酯多孔纳米材料，所述石墨烯基聚氨酯多孔纳米材料由A组份和B组份按照2:1的质量比例混合后构成：A graphene-based polyurethane porous nano-material, the graphene-based polyurethane porous nano-material is composed of a mixture of component A and component B in a mass ratio of 2:1:
所述A组份包括以下质量百分比的原料组分：The component A includes the following raw material components in mass percentages:
Figure PCTCN2020114657-appb-000006
Figure PCTCN2020114657-appb-000006
所述B组份包括以下质量百分比的原料组分：The component B includes the following raw material components in mass percentages:
Figure PCTCN2020114657-appb-000007
Figure PCTCN2020114657-appb-000007
Figure PCTCN2020114657-appb-000008
Figure PCTCN2020114657-appb-000008
优选的技术方案为：所述聚醚多元醇为聚氧化丙烯二醇、聚氧化丙烯三醇按照1：1的质量比例构成的混合物。The preferred technical solution is: the polyether polyol is a mixture of polyoxypropylene glycol and polyoxypropylene triol in a mass ratio of 1:1.
优选的技术方案为：所述聚酯多元醇为己二酸系聚酯多元醇、端羟基苯酐聚酯多元醇按照1：1的质量比例构成的混合物。The preferred technical solution is that the polyester polyol is a mixture of adipic acid polyester polyol and hydroxy-terminated phthalic anhydride polyester polyol in a mass ratio of 1:1.
优选的技术方案为：所述扩链剂为甘油、二乙醇胺、三乙醇胺按照1：1：1的质量比例构成的混合物。The preferred technical solution is that the chain extender is a mixture of glycerol, diethanolamine, and triethanolamine in a mass ratio of 1:1:1.
优选的技术方案为：所述石墨烯为单层石墨烯、双层石墨烯和少层石墨烯按照1：1的质量比例构成的混合物；所述石墨烯松装密度为0.01g/cm 3以内，振实密度为0.05g/cm 3。 The preferred technical solution is: the graphene is a mixture of single-layer graphene, double-layer graphene, and few-layer graphene in a mass ratio of 1:1; the graphene bulk density is within 0.01 g/cm 3 , The tap density is 0.05g/cm 3 .
优选的技术方案为：所述抗结构化剂为羟基硅油、二苯基硅二醇按照1：1的质量比例构成的混合物。The preferred technical solution is: the anti-structuring agent is a mixture of hydroxy silicone oil and diphenyl silicone glycol in a mass ratio of 1:1.
优选的技术方案为：所述弱补强剂为滑石粉、气相法白炭黑按照1：1的质量比例构成的混合物。The preferred technical solution is: the weak reinforcing agent is a mixture of talc powder and fumed white carbon black in a mass ratio of 1:1.
优选的技术方案为：所述发泡剂为偶氮二甲酰胺、尿素按照1：1的质量比例构成的混合物。The preferred technical solution is that the foaming agent is a mixture of azodicarbonamide and urea in a mass ratio of 1:1.
优选的技术方案为：所述稀释剂为二甲苯和石油醚按照1：1的质量比例构成的混合物。The preferred technical solution is: the diluent is a mixture of xylene and petroleum ether in a mass ratio of 1:1.
优选的技术方案为：所述增粘树脂及增粘剂为甲基MQ硅树脂、萜烯树脂按照1：1的质量比例构成的混合物。The preferred technical solution is that the tackifier resin and the tackifier are a mixture of methyl MQ silicone resin and terpene resin in a mass ratio of 1:1.
优选的技术方案为：所述异氰酸酯为苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯按照1：1：1的质量比例构成的混合物。The preferred technical solution is that the isocyanate is a mixture of phenylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate in a mass ratio of 1:1:1.
优选的技术方案为：所述匀泡剂为羟乙基纤维素、羟甲基甲基纤维素按照1：1的质量比例构成的混合物。The preferred technical solution is that the foam stabilizer is a mixture of hydroxyethyl cellulose and hydroxymethyl methyl cellulose in a mass ratio of 1:1.
优选的技术方案为：所述功能型添加剂为辛酸亚锡、双吗啉基二乙基醚按照1：1的质量比例构成的混合物。The preferred technical solution is: the functional additive is a mixture of stannous octoate and bismorpholinyl diethyl ether in a mass ratio of 1:1.
制备石墨烯基聚氨酯多孔纳米材料的方法：Method for preparing graphene-based polyurethane porous nano material:
所述A组份的制备方法包括以下步骤：The preparation method of the component A includes the following steps:
步骤1：将聚醚多元醇、聚酯多元醇加到A反应釜里，搅拌至分 散均匀；Step 1: Add polyether polyol and polyester polyol to the A reactor, stir until they are evenly dispersed;
步骤2：向A反应釜加入扩链剂、抗结构化剂和稀释剂，在负压条件下搅拌至分散均匀；Step 2: Add chain extender, anti-structuring agent and diluent to the A reactor, stir under negative pressure until the dispersion is uniform;
步骤3：向A反应釜加入加入石墨烯、弱补强剂和发泡剂，然后在负压条件下，搅拌至分散均匀，得到A组份；Step 3: Add graphene, weak reinforcing agent and foaming agent to the A reactor, and then stir under negative pressure until the dispersion is uniform to obtain component A;
所述B组份的制备方法包括以下步骤：The preparation method of the B component includes the following steps:
步骤1：将增粘树脂及增粘剂、异氰酸酯、抗结构化剂、匀泡剂和功能型添加剂，加到B反应釜里，在负压条件下，搅拌至分散均匀；Step 1: Add the tackifying resin and tackifier, isocyanate, anti-structuring agent, foam leveling agent and functional additives to the B reactor, and stir until the dispersion is uniform under negative pressure;
步骤2：向B反应釜加入石墨烯、弱补强剂和匀泡剂，在负压条件下搅拌至分散均匀，得到B组份。Step 2: Add graphene, weak reinforcing agent and foam stabilizer to the B reaction kettle, and stir under negative pressure until the dispersion is uniform to obtain component B.
优选的技术方案为：负压条件为真空度为-0.1MPa。The preferred technical solution is: the negative pressure condition is that the vacuum degree is -0.1MPa.
实施例4：一种石墨烯基聚氨酯多孔纳米材料及制备方法Embodiment 4: A graphene-based polyurethane porous nano material and preparation method
其它实施方式同实施例3，不同之处在于：Other implementations are the same as in Example 3, but the differences are:
优选的技术方案为：所述聚醚多元醇为聚四亚甲基醚二醇。The preferred technical solution is: the polyether polyol is polytetramethylene ether glycol.
优选的技术方案为：所述聚酯多元醇为聚己内酯多元醇。The preferred technical solution is: the polyester polyol is polycaprolactone polyol.
优选的技术方案为：所述扩链剂为MOCA。The preferred technical solution is that the chain extender is MOCA.
优选的技术方案为：所述石墨烯为双层石墨烯；所述石墨烯松装密度为0.01g/cm 3以内，振实密度为0.05g/cm 3。 A preferred technical solution is: the graphene is a double-layer graphene; the graphene loose packing density is within 0.01 g/cm 3 , and the tap density is 0.05 g/cm 3 .
优选的技术方案为：所述抗结构化剂为六甲基二硅氨烷。The preferred technical solution is: the anti-structuring agent is hexamethyldisilazane.
优选的技术方案为：所述弱补强剂为富勒烯。The preferred technical solution is that the weak reinforcing agent is fullerene.
优选的技术方案为：所述发泡剂为氧化锌和偶氮二异丁腈按照1：1的质量比例构成的混合物。The preferred technical solution is: the blowing agent is a mixture of zinc oxide and azobisisobutyronitrile in a mass ratio of 1:1.
优选的技术方案为：所述稀释剂为水、。The preferred technical solution is: the diluent is water.
优选的技术方案为：所述增粘树脂及增粘剂为聚乙酸乙烯酯和γ-巯丙基三甲氧基硅烷按照1：1的质量比例构成的混合物。The preferred technical solution is that the tackifier resin and the tackifier are a mixture of polyvinyl acetate and γ-mercaptopropyltrimethoxysilane in a mass ratio of 1:1.
优选的技术方案为：所述异氰酸酯为赖氨酸二异氰酸酯。The preferred technical solution is: the isocyanate is lysine diisocyanate.
优选的技术方案为：所述匀泡剂为羟甲基甲基纤维素。The preferred technical solution is: the foam stabilizer is hydroxymethyl methyl cellulose.
优选的技术方案为：所述功能型添加剂为辛酸亚锡和十溴二苯醚按照1：1的质量比例构成的混合物。The preferred technical solution is: the functional additive is a mixture of stannous octoate and decabromodiphenyl ether in a mass ratio of 1:1.
实施例5：一种石墨烯基聚氨酯多孔纳米材料及制备方法Embodiment 5: A graphene-based polyurethane porous nano material and its preparation method
其它实施方式同实施例3，不同之处在于：Other implementations are the same as in Example 3, but the differences are:
优选的技术方案为：所述聚醚多元醇为聚氧化丙烯二醇和聚四亚甲基醚二醇按照1：1的质量比例构成的混合物。The preferred technical solution is: the polyether polyol is a mixture composed of polyoxypropylene glycol and polytetramethylene ether glycol in a mass ratio of 1:1.
优选的技术方案为：所述聚酯多元醇为己二酸系聚酯多元醇。The preferred technical solution is that the polyester polyol is an adipic acid series polyester polyol.
优选的技术方案为：所述扩链剂为1,2-PG、1,4-BD按照1：1的质量比例构成的混合物。The preferred technical solution is that the chain extender is a mixture of 1,2-PG and 1,4-BD in a mass ratio of 1:1.
优选的技术方案为：所述石墨烯为少层石墨烯；所述石墨烯松装密度为0.05g/cm 3以内，振实密度为0.1g/cm 3。 The preferred technical solution is: the graphene is a few-layer graphene; the graphene has a loose packing density of within 0.05 g/cm 3 and a tap density of 0.1 g/cm 3 .
优选的技术方案为：所述抗结构化剂为环状三硅氨烷。The preferred technical solution is: the anti-structuring agent is cyclic trisilazane.
优选的技术方案为：所述弱补强剂为沉淀法白炭黑。The preferred technical solution is that the weak reinforcing agent is precipitation method white carbon black.
优选的技术方案为：所述发泡剂为苯甲酸、二苯磺酰肼醚按照1：1的质量比例构成的混合物。The preferred technical solution is: the blowing agent is a mixture of benzoic acid and diphenylsulfonyl hydrazide ether in a mass ratio of 1:1.
优选的技术方案为：所述稀释剂为石油醚。The preferred technical solution is: the diluent is petroleum ether.
优选的技术方案为：所述增粘树脂及增粘剂为端硅烷基聚氨基甲酸酯树脂。The preferred technical solution is that the tackifier resin and the tackifier are silyl-terminated polyurethane resins.
优选的技术方案为：所述异氰酸酯为二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯按照1：1的质量比例构成的混合物。The preferred technical solution is that the isocyanate is a mixture of diphenylmethane diisocyanate and dicyclohexylmethane diisocyanate in a mass ratio of 1:1.
优选的技术方案为：所述匀泡剂为月桂酰二乙醉胺。The preferred technical solution is: the foam stabilizer is lauroyl diethyl amine.
优选的技术方案为：所述功能型添加剂为双吗啉基二乙基醚和四溴双酚A、2，4，6-三溴苯酚按照1：1的质量比例构成的混合物。The preferred technical solution is: the functional additive is a mixture of bismorpholinyl diethyl ether, tetrabromobisphenol A, and 2,4,6-tribromophenol in a mass ratio of 1:1.
以上所述者仅为用以解释本发明之较佳实施例，并非企图具以对本发明做任何形式上之限制，是以，凡有在相同之发明精神下所作有关本发明之任何修饰或变更，皆仍应包括在本发明意图保护之范畴。The above descriptions are only used to explain the preferred embodiments of the present invention, and are not intended to restrict the present invention in any form. Therefore, any modification or alteration related to the present invention is made under the same spirit of the invention. , Should still be included in the scope of the present invention's intended protection.

Claims (15)

  1. 一种石墨烯基聚氨酯多孔纳米材料，其特征在于：所述石墨烯基聚氨酯多孔纳米材料由A组份和B组份按照1-2:1的质量比例混合后构成：A graphene-based polyurethane porous nano-material, characterized in that: the graphene-based polyurethane porous nano-material is composed of a mixture of component A and component B in a mass ratio of 1-2:1:
    所述A组份包括以下质量百分比的原料组分：The component A includes the following raw material components in mass percentages:
    Figure PCTCN2020114657-appb-100001
    Figure PCTCN2020114657-appb-100001
    所述B组份包括以下质量百分比的原料组分：The component B includes the following raw material components in mass percentages:
    Figure PCTCN2020114657-appb-100002
    Figure PCTCN2020114657-appb-100002
  2. 根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述聚醚多元醇为聚氧化丙烯二醇、聚氧化丙烯三醇、聚四亚甲基醚二醇中的至少一种。The graphene-based polyurethane porous nanomaterial according to claim 1, wherein the polyether polyol is at least one of polyoxypropylene glycol, polyoxypropylene triol, and polytetramethylene ether glycol. Kind.
  3. 根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述聚酯多元醇为己二酸系聚酯多元醇、端羟基苯酐聚酯多元醇和聚己内酯多元醇中的至少一种。The graphene-based polyurethane porous nanomaterial according to claim 1, wherein the polyester polyol is selected from the group consisting of adipic acid polyester polyol, hydroxy-terminated phthalic anhydride polyester polyol, and polycaprolactone polyol. At least one.
  4. 根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述扩链剂为EG、1,2-PG、1,4-BD、DEG、HD、HER、HQEE、甘油、TMP、二乙醇胺、三乙醇胺、MOCA中的至少一种。The graphene-based polyurethane porous nanomaterial according to claim 1, wherein the chain extender is EG, 1,2-PG, 1,4-BD, DEG, HD, HER, HQEE, glycerin, TMP , At least one of diethanolamine, triethanolamine, and MOCA.
  5. 根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述石墨烯为单层石墨烯、双层石墨烯和少层石墨烯中的至少一种；所述石墨烯松装密度为0.01-0.05g/cm 3以内，振实密度为0.05～0.1g/cm 3。 The graphene-based polyurethane porous nanomaterial according to claim 1, wherein the graphene is at least one of single-layer graphene, double-layer graphene, and few-layer graphene; and the graphene is loosely packed The density is within 0.01-0.05g/cm 3 , and the tap density is 0.05-0.1g/cm 3 .
  6. 根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所 述抗结构化剂为羟基硅油、二苯基硅二醇、烷氧基低分子聚硅氧烷、六甲基二硅氨烷、环状三硅氨烷和含硼硅氧烷类化合物中的至少一种。The graphene-based polyurethane porous nanomaterial according to claim 1, wherein the anti-structuring agent is hydroxy silicone oil, diphenyl silicone glycol, alkoxy low-molecular polysiloxane, hexamethyl two At least one of silazanes, cyclic trisilazanes, and borosiloxane compounds.
  7. 根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述弱补强剂为碳酸钙、滑石粉、气相法白炭黑、富勒烯、碳纳米管和沉淀法白炭黑中的至少一种。The graphene-based polyurethane porous nanomaterial according to claim 1, wherein the weak reinforcing agent is calcium carbonate, talc, fumed white carbon, fullerene, carbon nanotubes, and precipitation white carbon At least one of black.
  8. 根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述发泡剂为碳酸氢钠、氧化锌、碳酸氢铵、明矾、偶氮二甲酰胺、尿素、N,N-二亚硝基五次甲基四胺、苯甲酸、二苯磺酰肼醚、乙二胺、二偶氮氨基苯、二苯胍、对甲苯磺酰肼和偶氮二异丁腈中的至少一种。The graphene-based polyurethane porous nanomaterial according to claim 1, wherein the foaming agent is sodium bicarbonate, zinc oxide, ammonium bicarbonate, alum, azodicarbonamide, urea, N,N- At least one of dinitrosopentamethylenetetramine, benzoic acid, diphenylsulfonyl hydrazide ether, ethylenediamine, diazoaminobenzene, diphenylguanidine, p-toluenesulfonyl hydrazide and azobisisobutyronitrile One kind.
  9. 根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述稀释剂为水、甲苯、二甲苯和石油醚中的至少一种。The graphene-based polyurethane porous nanomaterial according to claim 1, wherein the diluent is at least one of water, toluene, xylene and petroleum ether.
  10. 根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述增粘树脂及增粘剂为苯乙烯-甲基丙烯酸甲酯树脂、松香树脂、甲基MQ硅树脂、萜烯树脂、萜烯酚醛树脂、端硅烷基聚醚树脂、端硅烷基聚氨基甲酸酯树脂、聚乙酸乙烯酯、3-氨丙基三乙氧基硅烷、γ-巯丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷和γ-异氰酸丙基三乙氧基硅烷中的至少一种。The graphene-based polyurethane porous nanomaterial according to claim 1, wherein the tackifier resin and tackifier are styrene-methyl methacrylate resin, rosin resin, methyl MQ silicone resin, terpene Resin, terpene phenolic resin, silyl-terminated polyether resin, silyl-terminated polyurethane resin, polyvinyl acetate, 3-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, At least one of 3-methacryloxypropyltrimethoxysilane and γ-isocyanatopropyltriethoxysilane.
  11. 根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述异氰酸酯为苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、赖氨酸二异氰酸酯中的至少一种。The graphene-based polyurethane porous nanomaterial according to claim 1, wherein the isocyanate is phenylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, bicyclic At least one of hexylmethane diisocyanate and lysine diisocyanate.
  12. 根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述匀泡剂为低粘度二甲基硅油、端烯丙基聚醚、甲基纤维素醚、羟乙基纤维素、羟甲基甲基纤维素、羟内基甲基纤维素和月桂酰二乙醉胺中的至少一种。The graphene-based polyurethane porous nanomaterial according to claim 1, wherein the foam stabilizer is low-viscosity dimethyl silicone oil, allyl-terminated polyether, methyl cellulose ether, and hydroxyethyl cellulose , At least one of hydroxymethyl methyl cellulose, hydroxy lacto methyl cellulose and lauroyl diethyl amine.
  13. 根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述功能型添加剂为聚氯乙烯、聚乙酸乙烯酯、聚酰胺、聚甲基丙烯酸甲酯、聚苯乙烯和聚异丁烯等热塑性树脂；二丁基锡二月桂酸酯、辛酸亚锡、双吗啉基二乙基醚和N,N-二甲基环已胺、三苯基膦酸酯、十溴二苯醚、八溴二苯醚、四溴双酚A、2，4，6-三溴苯酚、双(2，3-二烷丙基)醚和三氧化二锑和五氧化二锑等阻燃剂至少一种。The graphene-based polyurethane porous nanomaterial according to claim 1, wherein the functional additives are polyvinyl chloride, polyvinyl acetate, polyamide, polymethyl methacrylate, polystyrene, and polyisobutylene Other thermoplastic resins; dibutyltin dilaurate, stannous octoate, bismorpholinyl diethyl ether and N,N-dimethylcyclohexylamine, triphenylphosphonate, decabromodiphenyl ether, octabromo At least one flame retardant such as diphenyl ether, tetrabromobisphenol A, 2,4,6-tribromophenol, bis(2,3-dialkylpropyl)ether, and antimony trioxide and antimony pentoxide.
  14. 一种制备权利要求1-13任一所述的石墨烯基聚氨酯多孔纳米材料的方法：其特征在于：A method for preparing the graphene-based polyurethane porous nanomaterial according to any one of claims 1-13, characterized in that:
    所述A组份的制备方法包括以下步骤：The preparation method of the component A includes the following steps:
    步骤1：将聚醚多元醇、聚酯多元醇加到A反应釜里，搅拌至分散均匀；Step 1: Add the polyether polyol and polyester polyol to the A reactor and stir until the dispersion is uniform;
    步骤2：向A反应釜加入扩链剂、抗结构化剂和稀释剂，在负压条件下搅拌至分散均匀；Step 2: Add chain extender, anti-structuring agent and diluent to the A reactor, stir under negative pressure until the dispersion is uniform;
    步骤3：向A反应釜加入加入石墨烯、弱补强剂和发泡剂，然后在负压条件下，搅拌至分散均匀，得到A组份；Step 3: Add graphene, weak reinforcing agent and foaming agent to the A reactor, and then stir under negative pressure until the dispersion is uniform to obtain component A;
    所述B组份的制备方法包括以下步骤：The preparation method of the B component includes the following steps:
    步骤1：将增粘树脂及增粘剂、异氰酸酯、抗结构化剂、匀泡剂和功能型添加剂，加到B反应釜里，在负压条件下，搅拌至分散均匀；Step 1: Add the tackifying resin and tackifier, isocyanate, anti-structuring agent, foam leveling agent and functional additives to the B reactor, and stir until the dispersion is uniform under negative pressure;
    步骤2：向B反应釜加入石墨烯、弱补强剂和匀泡剂，在负压条件下搅拌至分散均匀，得到B组份。Step 2: Add graphene, weak reinforcing agent and foam stabilizer to the B reaction kettle, and stir under negative pressure until the dispersion is uniform to obtain component B.
  15. 根据权利要求14所述的方法，其特征在于：负压条件为真空度为-0.08～-0.1MPa。The method according to claim 14, wherein the negative pressure condition is that the degree of vacuum is -0.08 to -0.1 MPa.
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