CN111138627A - Graphene oxide/carbon nanotube high-strength polyurethane insulation board and preparation method thereof - Google Patents
Graphene oxide/carbon nanotube high-strength polyurethane insulation board and preparation method thereof Download PDFInfo
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- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
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- C08J2203/00—Foams characterized by the expanding agent
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/16—Unsaturated hydrocarbons
- C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
Abstract
The invention relates to a graphene oxide/carbon nanotube high-strength polyurethane insulation board which is composed of the following raw materials, by weight, 120 parts of isophorone diisocyanate 100, 0.5-5 parts of isophorone diisocyanate modified graphene, 60-80 parts of polyether polyol, 10-20 parts of a foaming agent, 0.5-2.5 parts of an amine catalyst, 2-5 parts of an organic silicon foam stabilizer and 5-15 parts of water; the isophorone diisocyanate modified graphene is prepared from isophorone diisocyanate and graphene oxide/carbon nanotube composite materials. The polyurethane insulation board produced by the invention has the advantages of uniform foaming density, high compressive strength, good flame retardance, fine and smooth foam holes, good size stability and the like.
Description
Technical Field
The invention relates to the field of building materials, in particular to a graphene oxide/carbon nanotube high-strength polyurethane insulation board and a preparation method thereof.
Background
The graphene is a honeycomb-shaped planar film formed by carbon atoms in an sp2 hybridization mode, the thickness of the film is less than one nanometer, the graphene is the thinnest and hardest nanometer material known to date in the world, the Young modulus is as high as 1.01TPa, the tensile strength is as high as 130GPa, the film is more than 100 times of that of structural steel, the thermal conductivity is as high as 5300W/m.K, the film is far higher than copper, and the film is also higher than carbon nanotubes and diamond. Since graphene has the lowest density, the highest mechanical properties, the highest thermal conductivity, and the lowest thermal expansion properties, graphene is considered as a very promising reinforcement since birth. The carbon nano tube and the graphene have many similarities in chemical structure, and the heat conduction performance of the carbon nano tube and the graphene is very outstanding in the direction parallel to the graphite crystal lattice of the carbon nano tube and the graphene. In terms of mechanics, the strength of the carbon nanotube in the direction perpendicular to the axial direction is weak, and the strength of graphene in the direction perpendicular to the lattice direction is the highest material found at present. Therefore, the characteristics of the graphene and the carbon nano tube are utilized to synthesize the graphene/carbon nano tube composite material, and more ideal electrochemical, thermal and mechanical properties are obtained through the synergistic effect between the graphene and the carbon nano tube composite material.
The polyurethane insulation board is used as a building insulation material, and breaks through the common defects that the traditional building material has single function, namely waterproof non-insulation and heat-insulation non-waterproof, and once a waterproof layer leaks, the heat insulation layer loses the heat insulation function. Compared with other single-function heat-insulating or waterproof materials, the polyurethane rigid foam has the obvious advantages of heat insulation, water resistance, sound insulation, vibration absorption and the like. In addition, the waterproof and anti-permeability material is low in heat conductivity coefficient, excellent in waterproof and anti-permeability performance, super strong in self-adhesion performance and chemical stability, and is applied and popularized more and more widely as a new energy-saving and consumption-reducing material in the building industry.
However, at present, in order to improve the self-strength, heat preservation and other properties of the polyurethane heat preservation board, inorganic filler is usually introduced, but the compatibility of the inorganic filler and a polymer matrix is poor, so that the stability of a finished product is easily reduced.
Disclosure of Invention
In view of the above problems, the present invention is proposed to provide a graphene oxide/carbon nanotube high strength polyurethane insulation board and a method for preparing the same, which overcome or at least partially solve the above problems.
The first aspect provides a graphene oxide/carbon nanotube high-strength polyurethane insulation board which is composed of, by weight, 120 parts of isophorone diisocyanate, 0.5-5 parts of isophorone diisocyanate modified graphene, 60-80 parts of polyether polyol, 10-20 parts of a foaming agent, 0.5-2.5 parts of an amine catalyst, 2-5 parts of an organic silicon foam stabilizer and 5-15 parts of water; the isophorone diisocyanate modified graphene is prepared from isophorone diisocyanate and graphene oxide/carbon nanotube composite materials.
In a second aspect, an embodiment of the present invention provides a method for preparing a graphene oxide/carbon nanotube high-strength polyurethane insulation board according to the first aspect, including the following steps; (1) preparing an oxidized graphene/carbon nanotube composite material additive: uniformly dispersing graphene oxide powder in a water phase by utilizing ultrasonic waves to prepare a dispersion liquid with the graphene oxide content of 0.05-2 g/L; adding the dispersion liquid into an iron nano catalyst, carrying out ultrasonic treatment for 15min, carrying out hydrothermal reaction under a stirring condition, then naturally cooling to room temperature, carrying out centrifugal separation on a product, washing and drying to obtain a reaction product; and growing nano carbon on the surface of the reaction product by a chemical vapor deposition carbon source method to obtain the graphene oxide/carbon nano tube composite material additive. (2) Preparing isophorone diisocyanate modified graphene/carbon nano tube: adding the graphene oxide/carbon nanotube composite material additive prepared in the step (1) into an organic solvent, and performing ultrasonic dispersion; adding isophorone diisocyanate, and reacting at 80-100 ℃ for 4-8 h; after the reaction is finished, fully washing the mixture by using a washing solvent, and drying the mixture in vacuum to obtain isophorone diisocyanate modified graphene/carbon nano tube; (3) preparing a high-strength heat-insulation board: ultrasonically dispersing the isophorone diisocyanate modified graphene/carbon nano tube obtained in the step (2) in isophorone diisocyanate, then rapidly stirring with polyether triol, amine catalyst, organic silicon foam stabilizer, water and foaming agent, and pouring into a mold to obtain polyurethane foam block foam.
Preferably, in the step (1), the graphene oxide powder has a sheet diameter of 1-20um, a thickness of 1-2nm, and a carbon content of 99.5%.
Preferably, the iron-based nano-catalyst comprises at least one of a mixture of ferric oxide and ferrous oxide, ferric chloride, ferrous lactate, and ferric citrate.
Preferably, in the step (1), the hydrothermal reaction temperature is 50-220 ℃ and the reaction time is 10-12 h.
Preferably, the organic solvent is xylene, DMF, NMP or DMAc.
Preferably, the weight ratio of the isophorone diisocyanate to the graphene/carbon nanotube composite material is 20 (1-2.5).
Preferably, in the step (3), the amine catalyst includes at least one of triethylene diamine and N, N-dimethylcyclohexylamine.
Preferably, the silicone foam stabilizer comprises a silicone surfactant of the silicon-oxygen or silicon-carbon type.
Preferably, the blowing agent comprises at least one of FEA-110, HFC-134a, and Greenmate TM.
The invention has the beneficial effects that:
1. according to the high-strength polyurethane insulation board of the graphene/carbon nano tube and the preparation method, the graphene oxide and the carbon nano tube are compounded in situ by adopting a chemical vapor deposition method, so that the obtained material has more excellent performance. The catalyst is loaded on the graphene oxide surface layer, so that the catalyst and the graphene oxide enter a vapor deposition reaction area in an integrated manner, and the problem that the catalyst enters a reaction cavity is solved.
2. According to the high-strength polyurethane insulation board of the graphene/carbon nano tube and the preparation method, the three-dimensional structural particularity of the graphene oxide/carbon nano tube is utilized, and the produced polyurethane insulation board has the advantages of uniform foaming density, high compressive strength, good flame retardance, fine and smooth pores, good size stability and the like.
3. According to the high-strength polyurethane insulation board of the graphene/carbon nano tube and the preparation method, the interaction between the graphene and a polyurethane molecular chain is improved, the graphene stably exists in polyurethane foam, isophorone diisocyanate is modified on the graphene oxide, and an isocyanate group is introduced to the surface of the graphene/carbon nano tube. The isocyanate group can react with polyether polyol to achieve the purpose of modifying the polyurethane foam by graphene polymerization. The graphene/carbon nano tube modified polyurethane foam prepared by the invention has good mechanical properties.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples.
Example 1
The high-strength polyurethane insulation board of the graphene/carbon nano tube is composed of the following raw materials in parts by weight: 100kg of isophorone diisocyanate, 1.05kg of isophorone diisocyanate modified graphene/carbon nano tube, 70kg of polyether polyol, 20kg of foaming agent, 1.2kg of amine catalyst, 9kg of water and 3.2kg of organic silicon foam stabilizer; wherein the isophorone diisocyanate modified graphene is prepared from 1kg of isophorone diisocyanate and 0.05kg of graphene oxide/carbon nano tube composite material.
The preparation method of the high-strength polyurethane insulation board of the graphene/carbon nano tube comprises the following steps:
(1) uniformly dispersing graphene oxide with the sheet diameter of 1-20um, the thickness of 1-2nm and the carbon content of 99.5% in a water phase under the ultrasonic action to prepare a dispersion liquid with the graphene oxide content of 0.1 g/L; adding the dispersion liquid into an iron nano catalyst, carrying out ultrasonic treatment for 15min, carrying out hydrothermal reaction under a stirring condition, then naturally cooling to room temperature, carrying out centrifugal separation on a product, washing and drying to obtain a reaction product; and growing nano carbon on the surface of the reaction product by a chemical vapor deposition carbon source method to obtain the graphene oxide/carbon nano tube composite material additive.
(2) Adding 1kg of the prepared (1) into 25kg of dimethylbenzene for ultrasonic dispersion; then adding 20kg of isophorone diisocyanate, and reacting at the temperature of 80-100 ℃ for 6 h; after the reaction is finished, toluene is used for fully washing, filtering and vacuum drying to obtain isophorone diisocyanate modified graphene/carbon nano tubes;
(3) weighing 1.05kg of isophorone diisocyanate modified graphene/carbon nano tube obtained in the step (2), and ultrasonically dispersing in 100kg of isophorone diisocyanate; then rapidly stirring with 70kg of polyether triol, 1.2kg of triethylene diamine, 1.2kg of organic silicon foam stabilizer Tegostab B84043.2 kg of water and 11020 kg of foaming agent FEA; pouring into a mould to obtain the polyurethane foam block foam.
Example 2
The high-strength polyurethane insulation board of the graphene/carbon nano tube is composed of the following raw materials in parts by weight: 110kg of isophorone diisocyanate, 1.2kg of isophorone diisocyanate modified graphene/carbon nano tube, 80kg of polyether polyol, 15kg of foaming agent, 1.5kg of amine catalyst, 10kg of water and 2.5kg of organosilicon foam stabilizer; wherein the isophorone diisocyanate modified graphene is prepared from 1kg of isophorone diisocyanate and 0.05kg of graphene oxide/carbon nano tube composite material.
The preparation method of the high-strength polyurethane insulation board of the graphene/carbon nano tube comprises the following steps:
(1) uniformly dispersing graphene oxide with the sheet diameter of 1-20um, the thickness of 1-2nm and the carbon content of 99.5% in a water phase under the ultrasonic action to prepare a dispersion liquid with the graphene oxide content of 0.1 g/L; adding the dispersion liquid into an iron nano catalyst, carrying out ultrasonic treatment for 15min, carrying out hydrothermal reaction under a stirring condition, then naturally cooling to room temperature, carrying out centrifugal separation on a product, washing and drying to obtain a reaction product; and growing nano carbon on the surface of the reaction product by a chemical vapor deposition carbon source method to obtain the graphene oxide/carbon nano tube composite material additive.
(2) Adding 1kg of the prepared (1) into 25kg of dimethylbenzene for ultrasonic dispersion; then adding 20kg of isophorone diisocyanate, and reacting at the temperature of 80-100 ℃ for 6 h; after the reaction is finished, toluene is used for fully washing, filtering and vacuum drying to obtain isophorone diisocyanate modified graphene/carbon nano tubes;
(3) weighing 1.2kg of isophorone diisocyanate modified graphene/carbon nano tube obtained in the step (2), and ultrasonically dispersing the weighed isophorone diisocyanate modified graphene/carbon nano tube in 110kg of isophorone diisocyanate; then rapidly stirring with 80kg of polyether triol, 1.5kg of triethylene diamine, 10kg of water and 15kg of foaming agent HFC-134a as an organic silicon foam stabilizer Tegostab B84812.5 kg; pouring into a mould to obtain the polyurethane foam block foam.
Example 3
The high-strength polyurethane insulation board of the graphene/carbon nano tube is composed of the following raw materials in parts by weight: 120kg of isophorone diisocyanate, 2.5kg of isophorone diisocyanate modified graphene/carbon nano tube, 70kg of polyether polyol, 20kg of foaming agent, 2kg of amine catalyst, 3.5kg of organic silicon foam stabilizer and 10kg of water; wherein the isophorone diisocyanate modified graphene is prepared from 1kg of isophorone diisocyanate and 0.05kg of graphene oxide/carbon nano tube composite material.
The preparation method of the high-strength polyurethane insulation board of the graphene/carbon nano tube comprises the following steps:
(1) uniformly dispersing graphene oxide with the sheet diameter of 1-20um, the thickness of 1-2nm and the carbon content of 99.5% in a water phase under the ultrasonic action to prepare a dispersion liquid with the graphene oxide content of 0.1 g/L; adding the dispersion liquid into an iron nano catalyst, carrying out ultrasonic treatment for 15min, carrying out hydrothermal reaction under a stirring condition, then naturally cooling to room temperature, carrying out centrifugal separation on a product, washing and drying to obtain a reaction product; and growing nano carbon on the surface of the reaction product by a chemical vapor deposition carbon source method to obtain the graphene oxide/carbon nano tube composite material additive.
(2) Adding 1kg of the prepared (1) into 25kg of dimethylbenzene for ultrasonic dispersion; then adding 20kg of isophorone diisocyanate, and reacting at the temperature of 80-100 ℃ for 6 h; after the reaction is finished, toluene is used for fully washing, filtering and vacuum drying to obtain isophorone diisocyanate modified graphene/carbon nano tubes;
(3) weighing 1.2kg of isophorone diisocyanate modified graphene/carbon nano tube obtained in the step (2), and ultrasonically dispersing in 120kg of isophorone diisocyanate; then rapidly stirring with 70kg of polyether triol, 1.5kg of triethylene diamine, Tegostab B84813.5 kg of organosilicon foam stabilizer, 10kg of water and 20kg of foaming agent HFC-134 a; pouring into a mould to obtain the polyurethane foam block foam.
Comparative example
The graphene polyurethane insulation board is composed of the following raw materials in parts by weight: 100kg of isophorone diisocyanate, 1.05kg of isophorone diisocyanate modified graphene, 70kg of polyether polyol, 20kg of foaming agent, 1.2kg of amine catalyst and 3.2kg of organic silicon foam stabilizer; wherein the isophorone diisocyanate modified graphene is prepared from 1kg of isophorone diisocyanate and 0.05kg of graphene oxide composite material.
The preparation method of the graphene polyurethane insulation board comprises the following steps:
(1) adding 1kg of graphene oxide powder into 25kg of dimethylbenzene, and performing ultrasonic dispersion; then adding 20kg of isophorone diisocyanate, and reacting at the temperature of 80-100 ℃ for 6 h; after the reaction is finished, toluene is used for fully washing, filtering and vacuum drying to obtain isophorone diisocyanate modified graphene;
(2) weighing 1.05kg of isophorone diisocyanate modified graphene obtained in the first step, and ultrasonically dispersing in 100kg of isophorone diisocyanate; then rapidly stirring with 70kg of polyether triol, 1.2kg of triethylene diamine, 1.2kg of organic silicon foam stabilizer Tegostab B84043.2 kg of water and 11020 kg of foaming agent FEA; pouring into a mould to obtain the polyurethane foam block foam.
The graphene/carbon nanotube modified polyurethane foams obtained in the examples are subjected to related performance tests, and the test results are shown in Table 1
Table 1 results of performance testing
By comparing table 1, we can know that the polyurethane foam block foam prepared in the embodiment by introducing isocyanate groups into the three-dimensional structure of graphene oxide/carbon nanotubes has an average value of 0.35MPa of compressive strength and an average value of 0.60MPa of bending strength, and the strength is improved by more than 20%; the average value of the foam density of the example is 21.7kg/m3, and is obviously reduced compared with the comparative example, further showing that the material of the example is a hollow structure, and plays a role in reducing the construction cost. In addition, the heat conductivity coefficient of the embodiment is smaller than that of the comparative example, which shows that the heat preservation effect of the embodiment can basically meet the use requirement, and the heat preservation effect plays a vital role in energy conservation and consumption reduction in the building industry.
Example 4
The graphene oxide/carbon nanotube high-strength polyurethane insulation board is composed of the following raw materials in parts by weight:
100 parts of isophorone diisocyanate, 0.5 part of isophorone diisocyanate modified graphene, 60 parts of polyether polyol, 10 parts of foaming agent, 0.5 part of amine catalyst, 2 parts of organosilicon foam stabilizer and 5 parts of water;
the isophorone diisocyanate modified graphene is prepared from isophorone diisocyanate and a graphene oxide/carbon nanotube composite material.
The preparation process comprises the following steps:
(1) preparing an oxidized graphene/carbon nanotube composite material additive:
uniformly dispersing graphene oxide powder in a water phase by utilizing ultrasonic waves to prepare a dispersion liquid with the graphene oxide content of 0.05 g/L;
adding the dispersion liquid into an iron nano catalyst, carrying out ultrasonic treatment for 15min, carrying out hydrothermal reaction under a stirring condition, then naturally cooling to room temperature, carrying out centrifugal separation on a product, washing and drying to obtain a reaction product;
and growing nano carbon on the surface of the reaction product by a chemical vapor deposition carbon source method to obtain the graphene oxide/carbon nano tube composite material additive.
(2) Preparing isophorone diisocyanate modified graphene/carbon nano tube:
adding the graphene oxide/carbon nanotube composite material additive prepared in the step (1) into an organic solvent, and performing ultrasonic dispersion; adding isophorone diisocyanate, and reacting at 80 ℃ for 4 h; after the reaction is finished, fully washing the mixture by using a washing solvent, and drying the mixture in vacuum to obtain isophorone diisocyanate modified graphene/carbon nano tube;
(3) preparing a high-strength heat-insulation board:
ultrasonically dispersing the isophorone diisocyanate modified graphene/carbon nano tube obtained in the step (2) in isophorone diisocyanate, then rapidly stirring with polyether triol, amine catalyst, organic silicon foam stabilizer, water and foaming agent, and pouring into a mold to obtain polyurethane foam block foam.
In this embodiment, in the step (1), the graphene oxide powder has a sheet diameter of 1um, a thickness of 1nm, and a carbon content of 99.5%.
In this embodiment, the iron-based nano catalyst includes at least one of a mixture of ferric oxide and ferrous oxide, ferric chloride, ferrous lactate, and ferric citrate.
In this example, in the step (1), the hydrothermal reaction temperature was 50 ℃ and the reaction time was 10 hours.
In this example, the organic solvent is xylene, DMF, NMP, or DMAc.
In this embodiment, the weight ratio of the isophorone diisocyanate to the graphene/carbon nanotube composite material is 20:1.
In this embodiment, in the step (3), the amine catalyst includes at least one of triethylene diamine and N, N-dimethylcyclohexylamine.
In this example, the silicone foam stabilizer is primarily a silicone surfactant of the silicon-oxygen or silicon-carbon type, and may be selected from the foam stabilizers Tegostab B8404, Tegostab B8453, Tegostab B8462, Tegostab B8471, Tegostab B8481 from Goldschmidt, Germany; foam stabilizers DC193, DC5357 from Air Products, usa; foam stabilizers lbykTP3799, Silbyk TP 3805 and Silbyk TP 9100 from BYK, Germany, and foam stabilizers AK-8801, AK-8805, AK-8806, AK-8807 and AK-6602 from Demei, Ltd, Nanjing, were used. The silicone foam stabilizer may be a mixture of one or more of the above.
In this embodiment, the blowing agent comprises at least one of FEA-110, HFC-134a, and Greenmate TM.
Example 5
The graphene oxide/carbon nanotube high-strength polyurethane insulation board is composed of the following raw materials in parts by weight:
110 parts of isophorone diisocyanate, 2.5 parts of isophorone diisocyanate modified graphene, 70 parts of polyether polyol, 15 parts of foaming agent, 1.5 parts of amine catalyst, 3.5 parts of organosilicon foam stabilizer and 10 parts of water;
the isophorone diisocyanate modified graphene is prepared from isophorone diisocyanate and a graphene oxide/carbon nanotube composite material.
The preparation process comprises the following steps:
(1) preparing an oxidized graphene/carbon nanotube composite material additive:
uniformly dispersing graphene oxide powder in a water phase by utilizing ultrasonic waves to prepare a dispersion liquid with the graphene oxide content of 1 g/L;
adding the dispersion liquid into an iron nano catalyst, carrying out ultrasonic treatment for 15min, carrying out hydrothermal reaction under a stirring condition, then naturally cooling to room temperature, carrying out centrifugal separation on a product, washing and drying to obtain a reaction product;
and growing nano carbon on the surface of the reaction product by a chemical vapor deposition carbon source method to obtain the graphene oxide/carbon nano tube composite material additive.
(2) Preparing isophorone diisocyanate modified graphene/carbon nano tube:
adding the graphene oxide/carbon nanotube composite material additive prepared in the step (1) into an organic solvent, and performing ultrasonic dispersion; then adding isophorone diisocyanate, and reacting at the temperature of 90 ℃ for 6 hours; after the reaction is finished, fully washing the mixture by using a washing solvent, and drying the mixture in vacuum to obtain isophorone diisocyanate modified graphene/carbon nano tube;
(3) preparing a high-strength heat-insulation board:
ultrasonically dispersing the isophorone diisocyanate modified graphene/carbon nano tube obtained in the step (2) in isophorone diisocyanate, then rapidly stirring with polyether triol, amine catalyst, organic silicon foam stabilizer, water and foaming agent, and pouring into a mold to obtain polyurethane foam block foam.
In this embodiment, in the step (1), the graphene oxide powder has a sheet diameter of 10um, a thickness of 1.5nm, and a carbon content of 99.5%.
In this embodiment, the iron-based nano catalyst includes at least one of a mixture of ferric oxide and ferrous oxide, ferric chloride, ferrous lactate, and ferric citrate.
In this example, in step (1), the hydrothermal reaction temperature was 130 ℃ and the reaction time was 11 hours.
In this example, the organic solvent is xylene, DMF, NMP, or DMAc.
In this embodiment, the weight ratio of the isophorone diisocyanate to the graphene/carbon nanotube composite material is 20: 1.5.
In this embodiment, in the step (3), the amine catalyst includes at least one of triethylene diamine and N, N-dimethylcyclohexylamine.
In this example, the silicone foam stabilizer is mainly a silicon-oxygen or silicon-carbon type silicone surfactant.
In this embodiment, the blowing agent comprises at least one of FEA-110, HFC-134a, and Greenmate TM.
Example 6
The graphene oxide/carbon nanotube high-strength polyurethane insulation board is composed of the following raw materials in parts by weight:
120 parts of isophorone diisocyanate, 5 parts of isophorone diisocyanate modified graphene, 80 parts of polyether polyol, 20 parts of foaming agent, 2.5 parts of amine catalyst, 5 parts of organosilicon foam stabilizer and 15 parts of water;
the isophorone diisocyanate modified graphene is prepared from isophorone diisocyanate and a graphene oxide/carbon nanotube composite material.
The preparation process comprises the following steps:
(1) preparing an oxidized graphene/carbon nanotube composite material additive:
uniformly dispersing graphene oxide powder in a water phase by utilizing ultrasonic waves to prepare a dispersion liquid with the graphene oxide content of 2 g/L;
adding the dispersion liquid into an iron nano catalyst, carrying out ultrasonic treatment for 15min, carrying out hydrothermal reaction under a stirring condition, then naturally cooling to room temperature, carrying out centrifugal separation on a product, washing and drying to obtain a reaction product;
and growing nano carbon on the surface of the reaction product by a chemical vapor deposition carbon source method to obtain the graphene oxide/carbon nano tube composite material additive.
(2) Preparing isophorone diisocyanate modified graphene/carbon nano tube:
adding the graphene oxide/carbon nanotube composite material additive prepared in the step (1) into an organic solvent, and performing ultrasonic dispersion; then adding isophorone diisocyanate, and reacting at the temperature of 100 ℃ for 8 hours; after the reaction is finished, fully washing the mixture by using a washing solvent, and drying the mixture in vacuum to obtain isophorone diisocyanate modified graphene/carbon nano tube;
(3) preparing a high-strength heat-insulation board:
ultrasonically dispersing the isophorone diisocyanate modified graphene/carbon nano tube obtained in the step (2) in isophorone diisocyanate, then rapidly stirring with polyether triol, amine catalyst, organic silicon foam stabilizer, water and foaming agent, and pouring into a mold to obtain polyurethane foam block foam.
In this embodiment, in the step (1), the graphene oxide powder has a sheet diameter of 20um, a thickness of 2nm, and a carbon content of 99.5%.
In this embodiment, the iron-based nano catalyst includes at least one of a mixture of ferric oxide and ferrous oxide, ferric chloride, ferrous lactate, and ferric citrate.
In this example, in the step (1), the hydrothermal reaction temperature was 220 ℃ and the reaction time was 12 hours.
In this example, the organic solvent is xylene, DMF, NMP, or DMAc.
In this embodiment, the weight ratio of the isophorone diisocyanate to the graphene/carbon nanotube composite material is 20: 2.5.
In this embodiment, in the step (3), the amine catalyst includes at least one of triethylene diamine and N, N-dimethylcyclohexylamine.
In this example, the silicone foam stabilizer is mainly a silicon-oxygen or silicon-carbon type silicone surfactant.
In this embodiment, the blowing agent comprises at least one of FEA-110, HFC-134a, and Greenmate TM.
The above embodiments are provided to further explain the objects, technical solutions and advantages of the present invention in detail, it should be understood that the above embodiments are merely exemplary embodiments of the present invention and are not intended to limit the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The graphene oxide/carbon nanotube high-strength polyurethane insulation board is characterized by comprising the following raw materials in parts by weight:
100-120 parts of isophorone diisocyanate, 0.5-5 parts of isophorone diisocyanate modified graphene, 60-80 parts of polyether polyol, 10-20 parts of foaming agent, 0.5-2.5 parts of amine catalyst, 2-5 parts of organosilicon foam stabilizer and 5-15 parts of water;
the isophorone diisocyanate modified graphene is prepared from isophorone diisocyanate and a graphene oxide/carbon nanotube composite material.
2. The preparation method of the graphene oxide/carbon nanotube high-strength polyurethane insulation board according to claim 1, which comprises the following steps;
(1) preparing an oxidized graphene/carbon nanotube composite material additive:
uniformly dispersing graphene oxide powder in a water phase by utilizing ultrasonic waves to prepare a dispersion liquid with the graphene oxide content of 0.05-2 g/L;
adding the dispersion liquid into an iron nano catalyst, carrying out ultrasonic treatment for 15min, carrying out hydrothermal reaction under a stirring condition, then naturally cooling to room temperature, carrying out centrifugal separation on a product, washing and drying to obtain a reaction product;
growing nano carbon on the surface of the reaction product by a chemical vapor deposition carbon source method to obtain a graphene oxide/carbon nanotube composite material additive;
(2) preparing isophorone diisocyanate modified graphene/carbon nano tube:
adding the graphene oxide/carbon nanotube composite material additive prepared in the step (1) into an organic solvent, and performing ultrasonic dispersion; adding isophorone diisocyanate, and reacting at 80-100 ℃ for 4-8 h; after the reaction is finished, fully washing the mixture by using a washing solvent, and drying the mixture in vacuum to obtain isophorone diisocyanate modified graphene/carbon nano tube;
(3) preparing a high-strength heat-insulation board:
ultrasonically dispersing the isophorone diisocyanate modified graphene/carbon nano tube obtained in the step (2) in isophorone diisocyanate, then rapidly stirring with polyether triol, amine catalyst, organic silicon foam stabilizer, water and foaming agent, and pouring into a mold to obtain polyurethane foam block foam.
3. The preparation method of the graphene oxide/carbon nanotube high-strength polyurethane insulation board according to claim 2, wherein in the step (1), the sheet diameter of the graphene oxide powder is 1-20um, the thickness is 1-2nm, and the carbon content is 99.5%.
4. The preparation method of the graphene oxide/carbon nanotube high-strength polyurethane insulation board according to claim 2, wherein the iron-based nano catalyst comprises at least one of a mixture of ferric oxide and ferrous oxide, ferric chloride, ferrous lactate and ferric citrate.
5. The preparation method of the graphene oxide/carbon nanotube high-strength polyurethane insulation board according to claim 2, wherein in the step (1), the hydrothermal reaction temperature is 50-220 ℃, and the reaction time is 10-12 h.
6. The preparation method of the graphene oxide/carbon nanotube high-strength polyurethane insulation board according to claim 2, wherein the organic solvent is xylene, DMF, NMP or DMAc.
7. The preparation method of the graphene oxide/carbon nanotube high-strength polyurethane insulation board according to claim 2, wherein the weight ratio of isophorone diisocyanate to the graphene/carbon nanotube composite material is 20 (1-2.5).
8. The method for preparing the graphene oxide/carbon nanotube high-strength polyurethane insulation board according to claim 2, wherein in the step (3), the amine catalyst comprises at least one of triethylene diamine and N, N-dimethylcyclohexylamine.
9. The method for preparing the graphene oxide/carbon nanotube high-strength polyurethane insulation board according to claim 2, wherein the silicone foam stabilizer comprises a silicon-oxygen or silicon-carbon type silicone surfactant.
10. The method for preparing the graphene oxide/carbon nanotube high-strength polyurethane insulation board according to claim 2, wherein the foaming agent comprises at least one of FEA-110, HFC-134a and Greenmate TM.
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