Modified polyurethane foam material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of materials, and discloses a modified polyurethane foam material and a preparation method and application thereof, the modified polyurethane foam material contains a polyurethane matrix and edge modified graphene dispersed in the polyurethane matrix; on the basis of the total weight of the modified polyurethane foam material, the content of the edge modified graphene is 0.01-15 wt%. The modified polyurethane foam material not only has better sound absorption performance and material compression performance, but also is low in total volatile matter content, and meets the requirement of environmental protection.

Description

Technical Field

[0001] The invention belongs to the technical field of materials, and in particular relates to a modified polyurethane foam material and a preparation method and application thereof. Background Art

[0002] Sound-absorbing materials generally refer to materials with an average sound absorption coefficient greater than 0.2. With the rapid development of economy and technology, noise hazards have become another killer of human public health after air pollution. When it is impossible to control or reduce the noise decibel, the application of sound-absorbing, noise-reducing and sound-insulating materials in relevant places or equipment is a more effective solution. At present, the commonly used sound-absorbing materials are perforated or closed-cell inorganic metal materials, but the material has a high density and the construction process is relatively complicated. As a commonly used polymer material, polyurethane material has low cost, can be cured at room temperature, and is simple and convenient to operate. Actively developing the application of polyurethane foam in the fields of sound absorption, sound insulation and noise reduction has broad prospects and development space.

[0003] The full name of polyurethane is polyurethane (abbreviated as PU), which is a general term for macromolecular compounds containing repeated carbamate groups (NHCOO) on the main chain. It is formed by the addition polymerization of organic diisocyanates or polyisocyanates with dihydroxy or polyhydroxy compounds. The products include block materials, spray-coated products and molded products. The main characteristics of polyurethane foam plastics are porosity, so they have low specific gravity and high specific strength. They have many advantages such as simple processing and molding, light weight, wear resistance, and good oil resistance. In recent years, their applications have become more and more extensive. With the continuous improvement of people's quality of life and the increasing awareness of environmental protection, the requirements for living environment have gradually increased. Various sound-absorbing materials are widely used in noise control, and people have also put forward higher requirements for their performance, from achieving single sound absorption performance to combining high sound absorption, decorative, economical and environmentally friendly performance. Summary of the invention

[0004] In view of the above situation, the purpose of the present invention is to provide a modified polyurethane foam material and a preparation method and application thereof. The modified polyurethane foam material not only has further improved sound absorption coefficient and total amount of volatile organic matter to meet environmental protection requirements, but also has further improved mechanical properties of the material.

[0005] The first aspect of the present invention provides a modified polyurethane foam material, which comprises a polyurethane matrix and edge-modified graphene dispersed in the polyurethane matrix;

[0006] Based on the total weight of the modified polyurethane foam material, the content of the edge-modified graphene is 0.01-15wt%.

[0007] The second aspect of the present invention provides a method for preparing the modified polyurethane foam material, which comprises: uniformly mixing and foaming polymerized polyol, edge-modified graphene, a catalyst, a foaming agent, an isocyanate and an optional foam stabilizer to obtain the modified polyurethane foam material.

[0008] The third aspect of the present invention provides the use of the modified polyurethane foam material in the field of sound absorption, sound insulation and noise reduction.

[0009] Compared with the prior art, the present invention has the following beneficial effects:

[0010] The invention modifies the polyurethane foam material by dispersing edge-modified graphene in the polyurethane foam material, and the modified polyurethane foam material not only has better sound absorption performance and material compression performance, but also has a low total volatile content, thus meeting environmental protection requirements. The modification method of the invention has simple process, easy-to-control conditions, and strong applicability.

[0011] Other features and advantages of the present invention will be described in detail in the following detailed description. DETAILED DESCRIPTION

[0012] The specific embodiments of the present invention are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0013] According to a first aspect of the present invention, the present invention provides a modified polyurethane foam material, the modified polyurethane foam material comprising a polyurethane matrix and edge-modified graphene dispersed in the polyurethane matrix;

[0014] Based on the total weight of the modified polyurethane foam material, the content of the edge-modified graphene is 0.01-15wt%.

[0015] Preferably, based on the total weight of the modified polyurethane foam material, the content of the edge-modified graphene is 0.01-5wt%.

[0016] The edge-modified graphene of the present invention has a sheet size of micrometer level, has an adjustable aspect ratio and carbon and oxygen element contents, is obviously different from existing nano-scale graphene, and can overcome the problem that nano-scale graphene is easy to aggregate.

[0017] The specific structural features of the edge-modified graphene may include: the average sheet diameter of the edge-modified graphene is 2-30 μm; the average aspect ratio is 600-10000:1; the electrical conductivity is 200-800 S / m; the oxygen content of the edge-modified graphene is 3-30 at% in terms of oxygen element, and the hydrogen content is 1-10 at% in terms of hydrogen element.

[0018] Preferably, the average sheet diameter of the edge-modified graphene is 5-15 μm; the average aspect ratio is 1200-4500:1, preferably 1500-3800:1; the conductivity is 300-600 S / m; the oxygen content in the edge-modified graphene is 5-18 at%, and the hydrogen content in the edge-modified graphene is 3-8 at%. By selecting edge-modified graphene with preferred structural characteristics, a modified polyurethane foam material with better sound absorption performance and material compression performance can be obtained.

[0019] In the present invention, the edge-modified graphene is prepared by grinding graphite with a grinding disc under supercritical carbon dioxide.

[0020] Under supercritical carbon dioxide conditions, graphite is exfoliated into graphene after shearing by a grinding disc; at the same time, the shearing action of the grinding disc also breaks the graphite or graphene, and the newly generated highly active edges react with carbon dioxide, resulting in the modification of carboxyl groups on the edges of graphene.

[0021] The edge-modified graphene of the present invention can be prepared by a method comprising the following steps:

[0022] Step S1, adding graphite powder into a high-pressure grinding wheel kettle;

[0023] Step S2, introducing carbon dioxide into a high-pressure grinding wheel kettle and making it in a supercritical state to form a material containing graphite powder and supercritical carbon dioxide;

[0024] Step S3, grinding the material containing graphite powder and supercritical carbon dioxide.

[0025] According to the present invention, the graphite powder is selected from flake graphite powder and expanded graphite powder, and preferably, the particle size of the graphite powder is 10-80 mesh, preferably 20-60 mesh. Before grinding, the graphite powder is preferably purified in advance, for example, by ultrasonic cleaning and / or chemical treatment to remove impurities, such as heterophase substances and impurity elements.

[0026] In step S2 of the present invention, the carbon dioxide enters a supercritical state by making the temperature in the kettle exceed 32.26° C. and the pressure exceed 72.9 atm.

[0027] According to the present invention, in step S3, the grinding time is 6-48 hours; after the grinding is completed, the pressure in the high-pressure grinding wheel kettle is rapidly reduced; preferably, the pressure in the high-pressure grinding wheel kettle is reduced to below 1 atm within 5-20 seconds.

[0028] According to the present invention, in the high-pressure grinding wheel kettle, the temperature is 35-200°C, preferably 35-100°C, and more preferably 35-70°C; in the high-pressure grinding wheel kettle, the pressure is 75-165atm, preferably 75-165atm, and more preferably 75-125atm; in the high-pressure grinding wheel kettle, the stirring speed is 500-10000r / min, preferably 500-5000r / min.

[0029] In the present invention, by controlling specific grinding conditions, edge-modified graphene having the above-mentioned structural characteristics can be obtained.

[0030] According to the second aspect of the present invention, the present invention provides a method for preparing the above-mentioned modified polyurethane foam material, the preparation method comprising: uniformly mixing and foaming a polymerized polyol, edge-modified graphene, a catalyst, a foaming agent, an isocyanate and an optional foam stabilizer to obtain a modified polyurethane foam material.

[0031] In the present invention, the raw materials and dosage of the polyurethane matrix are conventional technologies in the art. In the preparation of the modified polyurethane foam material, the dosage of each raw material may include: based on 100 parts by weight of the polymerized polyol, the dosage of the edge-modified graphene is 0.01 to 15 parts by weight, preferably 0.01 to 5 parts by weight, and more preferably 0.01 to 1 part by weight; the dosage of the catalyst is 0.01 to 15 parts by weight, preferably 0.01 to 5 parts by weight, and more preferably 0.01 to 2 parts by weight; the dosage of the foaming agent is 0.01 to 100 parts by weight, preferably 0.01 to 50 parts by weight, and more preferably 0.01 to 20 parts by weight; the dosage of the foam stabilizer is 0 to 15 parts by weight, preferably 0.01 to 5 parts by weight, and more preferably 0.01 to 1 part by weight; the molar ratio of the isocyanate to the hydroxyl group in the polymerized polyol is 1:0.8 to 1.2.

[0032] According to the present invention, the polymer polyol can be selected from at least one of polyether polyol, polyester polyol and polymer polyol. The polymer polyol can be compounded by at least one of polyol, diol and small molecule alcohol. Preferably, the molecular weight of the polymer polyol is 100 to 100000.

[0033] In the present invention, the catalyst may be an organic tertiary amine catalyst and / or an organic metal salt catalyst. The organic tertiary amine catalyst may be triethylenediamine and / or triethanolamine, and the organic metal salt catalyst may be stannous octoate.

[0034] There is no special requirement for the selection of the blowing agent in the present invention. Physical blowing agents and / or chemical blowing agents may be used. Preferably, the blowing agent is selected from at least one of water, aliphatic hydrocarbons, chlorinated hydrocarbons, fluorochlorocarbons and carbon dioxide.

[0035] According to the present invention, the foam stabilizer can be an organosilicon surfactant and / or a nonionic surfactant. The main structure of the organosilicon surfactant is a polysiloxane-oxyalkylene block copolymer. The nonionic surfactant is preferably Tween-80 and / or Tween-60.

[0036] In the present invention, the isocyanate is at least one of monoisocyanate (R-N=C=O), diisocyanate (O=C=N-R-N=C=O) and polyisocyanate, or is prepared by compounding or modifying at least one of monoisocyanate, diisocyanate and polyisocyanate.

[0037] The preparation methods involved in the present invention are all carried out at a suitable temperature for the polymerized polyol to dissolve and disperse various additives and react with raw materials such as isocyanate. The specific temperature conditions can be adjusted by those skilled in the art according to the molecular structure of the polymerized polyol and the type of isocyanate.

[0038] According to a third aspect of the present invention, the present invention provides an application of the above-mentioned modified polyurethane foam material in the field of sound absorption, sound insulation and noise reduction.

[0039] The substances and parameters not limited in the present invention can be selected according to the prior art and belong to the conventional technical means in the field. Unless otherwise specified, the operations and processing methods involved in the present invention belong to the conventional methods in the field, the instruments used are conventional instruments in the field, and the raw materials used are commercially available.

[0040] The present invention will be further described below with reference to the following examples, but is not limited to these examples.

[0041] In the following examples and comparative examples, the raw materials and sources used, as well as the determination methods of the relevant data are as follows:

[0042] Polymer polyol: polyether polyol, Sinopec Tianjin Branch, brand / model: TSU-464.

[0043] Catalyst: Stannous octoate, Xindian Chemical Materials Co., Ltd.

[0044] Foam stabilizer: Suzhou Side New Material Technology Co., Ltd., SD-501.

[0045] 141B foaming agent: Shanghai Caoshi Chemical Co., Ltd.

[0046] Isocyanate: polymethylene polyphenyl isocyanate, Yantai Wanhua Polyurethane Co., Ltd., PM-200.

[0047] The preparation method of edge-modified graphene A comprises: ultrasonically cleaning 100g of 32-mesh flake graphite powder (washing with water once and washing with ethanol twice) to remove impurity substances and impurity elements, then placing the flake graphite in a high-pressure grinding wheel kettle, sealing the high-pressure grinding wheel kettle, and then heating the high-pressure grinding wheel kettle to 70°C, pumping CO2 to increase the pressure in the high-pressure grinding wheel kettle to 125atm, rotating at a speed of 1000r / min, grinding and peeling the graphite by the shear force generated by the grinding wheel, stirring for 24h, reducing the pressure to 1atm within 10s, sampling from the high-pressure grinding wheel kettle to obtain the edge-modified graphene A; characterization shows that the average sheet diameter is 6.2μm, the average thickness is 2.9nm, the average aspect ratio is 2138:1, the oxygen content is 13.40at% in terms of oxygen element, the hydrogen content is 7.3at% in terms of hydrogen element, and the electrical conductivity is 339S / m.

[0048] The preparation method of edge-modified graphene B comprises: ultrasonically cleaning 40g of 32-mesh expanded graphite powder (washing with water once and washing with ethanol twice) to remove heterogeneous substances and impurity elements, then placing the expanded graphite powder in a high-pressure grinding wheel kettle, sealing the high-pressure grinding wheel kettle, and then heating the high-pressure grinding wheel kettle to 40°C, pumping CO2 to increase the pressure in the high-pressure grinding wheel kettle to 85atm, rotating at a speed of 500r / min, grinding and peeling graphite by the shear force generated by the grinding wheel, stirring for 48h, reducing the pressure to 1atm within 10s, sampling from the high-pressure grinding wheel kettle to obtain the edge-modified graphene B; characterization shows that the average sheet diameter is 9.6μm, the average thickness is 3.2nm, the average aspect ratio is 3000:1, the oxygen content is 7.83at% in terms of oxygen element, the hydrogen content is 3.23at% in terms of hydrogen element, and the electrical conductivity is 425S / m.

[0049] The preparation method of edge-modified graphene C comprises: ultrasonically cleaning 100g of 32-mesh flake graphite powder (washing with water once and washing with ethanol twice) to remove heterogeneous substances and impurity elements, then placing the flake graphite in a high-pressure grinding wheel kettle, sealing the high-pressure grinding wheel kettle, and then heating the high-pressure grinding wheel kettle to 40°C, pumping CO2 to increase the pressure in the high-pressure grinding wheel kettle to 85atm, rotating at a speed of 500r / min, grinding and peeling the graphite by the shear force generated by the grinding wheel, stirring for 24h, reducing the pressure to 1atm within 10s, sampling from the high-pressure grinding wheel kettle to obtain the edge-modified graphene C; characterization shows that the average sheet diameter is 12.6μm, the average thickness is 3.4nm, the average aspect ratio is 3706:1, the oxygen content is 5.60at% in terms of oxygen element, the hydrogen content is 3.22at% in terms of hydrogen element, and the electrical conductivity is 506S / m.

[0050] Chemically exfoliated graphene: purchased from Nanjing Jicang Nanotechnology Co., Ltd., and characterized to have an average sheet diameter of 6.1 μm and an average thickness of 1.2 nm.

[0051] 1. Compression strength determination: Determined in accordance with national standard GB / T 8813-2008.

[0052] 2. Determination of average sound absorption coefficient: Determined in accordance with national standard GB / T18696.2-2002.

[0053] 3. Determination of total volatile organic compound: TVOC is determined according to the standard VDA277 of the German Association of the Automotive Industry.

[0054] Example 1

[0055] 100 parts by weight of polyether polyol TSU-464, 0.4 parts by weight of edge-modified graphene A, 2 parts by weight of catalyst stannous octoate, 3.2 parts by weight of water (foaming agent), isocyanate PM-200 and 1 part by weight of foam stabilizer SD-501 were mixed and quickly and fully stirred and foamed, wherein the molar ratio of isocyanate to hydroxyl group in polyether polyol was 1:1, to obtain a modified polyurethane foam material, the properties of which are shown in Table 1.

[0056] Example 2

[0057] 100 parts by weight of polyether polyol TSU-464, 0.8 parts by weight of edge-modified graphene A, 2 parts by weight of catalyst stannous octoate, 3.2 parts by weight of water (foaming agent), isocyanate PM-200 and 1 part by weight of foam stabilizer SD-501 were mixed and quickly and fully stirred and foamed, wherein the molar ratio of isocyanate to hydroxyl group in polyether polyol was 1:1, to obtain a modified polyurethane foam material, the properties of which are shown in Table 1.

[0058] Example 3

[0059] 100 parts by weight of polyether polyol TSU-464, 0.6 parts by weight of edge-modified graphene A, 2 parts by weight of catalyst stannous octoate, 10 parts by weight of 141B (foaming agent), isocyanate PM-200 and 1 part by weight of foam stabilizer SD-501 were mixed and quickly and fully stirred and foamed, wherein the molar ratio of isocyanate to hydroxyl group in polyether polyol was 1:1, to obtain a modified polyurethane foam material, the properties of which are shown in Table 1.

[0060] Example 4

[0061] 100 parts by weight of polyether polyol TSU-464, 0.1 parts by weight of edge-modified graphene A, 2 parts by weight of catalyst stannous octoate, 3.2 parts by weight of water (foaming agent), isocyanate PM-200 and 1 part by weight of foam stabilizer SD-501 were mixed and quickly and fully stirred and foamed, wherein the molar ratio of isocyanate to hydroxyl group in polyether polyol was 1:1, to obtain a modified polyurethane foam material, the properties of which are shown in Table 1.

[0062] Example 5

[0063] 100 parts by weight of polyether polyol TSU-464, 5 parts by weight of edge-modified graphene A, 2 parts by weight of catalyst stannous octoate, 3.2 parts by weight of water (foaming agent), isocyanate PM-200 and 1 part by weight of foam stabilizer SD-501 were mixed and quickly and fully stirred and foamed, wherein the molar ratio of isocyanate to hydroxyl group in polyether polyol was 1:1, to obtain a modified polyurethane foam material, the properties of which are shown in Table 1.

[0064] Example 6

[0065] Same as Example 2, except that edge-modified graphene B is used instead of edge-modified graphene A to prepare a modified polyurethane foam material, the properties of which are shown in Table 1.

[0066] Example 7

[0067] Same as Example 2, except that edge-modified graphene C is used instead of edge-modified graphene A to prepare a modified polyurethane foam material, the properties of which are shown in Table 1.

[0068] Comparative Example 1

[0069] 100 parts by weight of polyether polyol TSU-464, 2 parts by weight of catalyst stannous octoate, 3.2 parts by weight of water (foaming agent), isocyanate PM-200 and 1 part by weight of foam stabilizer SD-501 were mixed and quickly and fully stirred and foamed, wherein the molar ratio of isocyanate to hydroxyl group in polyether polyol was 1:1, to obtain a modified polyurethane foam material, the properties of which are shown in Table 1.

[0070] Comparative Example 2

[0071] 100 parts by weight of polyether polyol TSU-464, 2 parts by weight of catalyst stannous octoate, 10 parts by weight of 141B (foaming agent), isocyanate PM-200 and 1 part by weight of foam stabilizer SD-501 were mixed and quickly and fully stirred and foamed, wherein the molar ratio of isocyanate to hydroxyl group in polyether polyol was 1:1, to obtain a modified polyurethane foam material, the properties of which are shown in Table 1.

[0072] Comparative Example 3

[0073] Same as Example 2, except that chemically exfoliated graphene is used instead of edge-modified graphene A to prepare a modified polyurethane foam material, the properties of which are shown in Table 1.

[0074] Table 1

[0075]

[0076] As can be seen from Table 1, the polyurethane foam material using edge-modified graphene in the present invention has better sound absorption performance and material compression performance, and has a low total volatile content, meeting environmental protection requirements. In addition, the edge-modified graphene with a specific structure has a better modification effect on the polyurethane foam material.

[0077] The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A modified polyurethane foam material, characterized in that: The modified polyurethane foam material contains a polyurethane matrix and edge-modified graphene dispersed in the polyurethane matrix; Based on the total weight of the modified polyurethane foam material, the content of the edge-modified graphene is 0.01-15wt%, preferably 0.01-5wt%.

2. The modified polyurethane foam material according to claim 1, wherein The edge-modified graphene has an average sheet diameter of 2-30 μm, an average aspect ratio of 600-10000:1, and an electrical conductivity of 200-800 S / m. In the edge-modified graphene, the oxygen content calculated as oxygen element is 3-30 at%, and the hydrogen content calculated as hydrogen element is 1-10 at%.

3. The modified polyurethane foam material according to claim 2, wherein The edge-modified graphene has an average sheet diameter of 5-15 μm; an average aspect ratio of 1200-4500:1, preferably 1500-3800:1; and an electrical conductivity of 300-600 S / m; and in the edge-modified graphene, the oxygen content in terms of oxygen element is 5-18 at%, and the hydrogen content in terms of hydrogen element is 3-8 at%.

4. The modified polyurethane foam material according to claim 1, wherein The edge-modified graphene is prepared by grinding graphite with a grinding disc under supercritical carbon dioxide.

5. The method for preparing the modified polyurethane foam material according to any one of claims 1 to 4, characterized in that: The preparation method comprises: uniformly mixing and foaming polymerized polyol, edge-modified graphene, a catalyst, a foaming agent, an isocyanate and an optional foam stabilizer to obtain a modified polyurethane foam material.

6. The method for preparing the modified polyurethane foam material according to claim 5, wherein: Based on 100 parts by weight of the polymerized polyol, the amount of the edge-modified graphene is 0.01 to 15 parts by weight, preferably 0.01 to 5 parts by weight, and more preferably 0.01 to 1 part by weight; the amount of the catalyst is 0.01 to 15 parts by weight, preferably 0.01 to 5 parts by weight, and more preferably 0.01 to 2 parts by weight; the amount of the foaming agent is 0.01 to 100 parts by weight, preferably 0.01 to 50 parts by weight, and more preferably 0.01 to 20 parts by weight; the amount of the foam stabilizer is 0 to 15 parts by weight, preferably 0.01 to 5 parts by weight, and more preferably 0.01 to 1 part by weight; the molar ratio of the isocyanate to the hydroxyl group in the polymerized polyol is 1:0.8 to 1.

2.

7. The method for preparing the modified polyurethane foam material according to claim 5, wherein: The polymer polyol is selected from at least one of polyether polyol, polyester polyol and polymer polyol; the polymer polyol is compounded by at least one of polyol, diol and small molecule alcohol; preferably, the molecular weight of the polymer polyol is 100 to 100,000.

8. The method for preparing the modified polyurethane foam material according to claim 5, wherein: The catalyst is an organic tertiary amine catalyst and / or an organic metal salt catalyst; the organic tertiary amine catalyst is triethylenediamine and / or triethanolamine, and the organic metal salt catalyst is stannous octoate; The foaming agent is selected from at least one of water, aliphatic hydrocarbons, chlorinated hydrocarbons, fluorochlorocarbons and carbon dioxide; The foam stabilizer is an organic silicon surfactant and / or a nonionic surfactant; the main structure of the organic silicon surfactant is a polysiloxane-oxidized olefin block copolymer; and the nonionic surfactant is Tween-80 and / or Tween-60.

9. The method for preparing the modified polyurethane foam material according to claim 5, wherein: The isocyanate is at least one of monoisocyanate, diisocyanate and polyisocyanate, or is prepared by compounding or modifying at least one of monoisocyanate, diisocyanate and polyisocyanate.

10. Use of the modified polyurethane foam material according to any one of claims 1 to 4 in the field of sound absorption, sound insulation and noise reduction.

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