Polyurethane foam material and preparation method thereof

Abstract

The invention relates to the technical field of high polymer materials, and particularly discloses a polyurethane foam material and a preparation method thereof. The polyurethane foam material comprises a material A and a material B. The material A comprises 80-90 parts of composite polyol, 1-2 parts of deionized water, 1-3 parts of a chain extender, 2.5-5 parts of a catalyst and 20-25 parts of powder, and the material B comprises 80-90 parts of an isocyanate prepolymer. In addition, the preparation method disclosed by the invention has the advantage of improving the strength of the polyurethane foam.

Description

Technical Field

[0001] The present application relates to the technical field of polymer materials, and more specifically, to a polyurethane foam material and a preparation method thereof. Background Art

[0002] Polyurethane foam materials are widely used in construction, transportation, home appliances, and other fields due to their excellent thermal insulation, sound insulation, lightweight, and mechanical properties. In recent years, with increasing environmental protection and energy conservation requirements, higher performance requirements have been placed on polyurethane foam materials, such as higher mechanical strength, lower thermal conductivity, and improved flame retardancy. Traditional polyurethane foam materials are mainly improved by adjusting the ratio of polyols and isocyanates and adding fillers or additives, but it is often difficult to achieve a balance between these multiple performance indicators.

[0003] The commonly used improvement methods currently used generally include adding inorganic fillers to improve its mechanical properties and flame retardancy, but this will lead to an increase in material density and a decrease in processing performance. The use of nanomaterials has problems with poor dispersibility and high cost. Although these methods can partially improve performance, they all have obvious limitations. Summary of the Invention

[0004] In order to improve the strength of polyurethane foam, the present application provides a polyurethane foam material and a preparation method thereof.

[0005] In a first aspect, the present application provides a polyurethane foam material, which adopts the following technical solution: A polyurethane foam material comprises material A and material B, wherein material A comprises 80-90 parts of a complex polyol, 1-2 parts of deionized water, 1-3 parts of a chain extender, 2.5-5 parts of a catalyst and 20-25 parts of a powder, and material B comprises 80-90 parts of an isocyanate prepolymer.

[0006] By adopting the above technical solution, the complex polyol is mixed with water, a chain extender, a catalyst and a powder to form an isocyanate prepolymer of material A and material B, which is then mixed. The isocyanate prepolymer contacts water to generate carbon dioxide, forming a uniform pore structure and achieving a soft foaming effect. The addition of powder can provide an anchor point for foaming, promote the homogenization and densification of the pores, and at the same time, the addition of powder can effectively improve the mechanical strength of the polyurethane foam material.

[0007] Preferably, the complex polyol comprises polyether polyol, polycarbonate polyol and polyester polyol in a mass ratio of (1.05-1.12):(2.05-2.26):(2.02-2.18).

[0008] By adopting the above technical solution and controlling the mass ratio of polyether polyol, polycarbonate polyol and polyester polyol, the uniformity of the pores of the polyurethane foam material can be effectively maintained, thereby improving the strength of the polyurethane material.

[0009] Preferably, the mass ratio of material A to material B is 1:(1.29-1.45).

[0010] Preferably, the powder is a modified carbon nanotube / modified diatomaceous earth composite material, and the mass ratio of the modified carbon nanotube to the modified diatomaceous earth is (1.35-2.12):(12.25-14.21).

[0011] By adopting the above technical solution, the powder formed by the composite of modified carbon nanotubes and modified diatomaceous earth has higher strength. The modified carbon nanotubes can enter the diatomaceous earth to form an interlaced structure, increasing the complexity of the microstructure, thereby further effectively improving the mechanical properties of the polyurethane foam material.

[0012] Preferably, the preparation method of the modified carbon nanotubes includes the following steps: adding carbon nanotubes to a mixture of concentrated sulfuric acid and concentrated nitric acid, ultrasonically dispersing for 40 min, stirring at 140°C for 1 h, washing, filtering, and drying to obtain acidified carbon nanotubes; adding glycerol, DCC, and DMAP to DMF, adding the acidified carbon nanotubes and ultrasonically dispersing them uniformly; heating at 120°C for 24 h under inert gas protection; washing with anhydrous ethanol, filtering, and drying to obtain modified carbon nanotubes.

[0013] By adopting the above technical solution, the surface active groups of the carbon nanotubes increase after acid treatment, which is beneficial to the grafting of propylene glycol. The obtained modified carbon nanotubes have good dispersibility and the hydroxyl groups increase, which is beneficial to the composite and fixation of the modified carbon nanotubes and modified diatomaceous earth.

[0014] Preferably, the preparation method of the modified carbon nanotube / modified diatomite composite material comprises the following steps: mixing an aluminate coupling agent with ethanol and water, dispersing diatomite in the mixed solution, stirring evenly, adding modified carbon nanotubes, and ultrasonically dispersing them evenly, stirring at 50-60°C for 3-4 hours, centrifuging, separating, filtering, and freeze-drying to obtain the modified carbon nanotube / modified diatomite composite material.

[0015] By adopting the above technical solution, after the diatomaceous earth is modified by the aluminate coupling agent, propylene glycol is added to graft carbon nanotubes. The aluminate coupling agent can cross-link and bond the modified carbon nanotubes with the modified diatomaceous earth, thereby improving the bonding degree between the two, so that the reinforcing agent can improve the rigidity of the polyurethane foam material without reducing its toughness.

[0016] Preferably, the added amount of the aluminate coupling agent is 2.35-3.28 wt% of the mass of the diatomaceous earth.

[0017] By adopting the above technical solution, the addition amount of the aluminate coupling agent is controlled, thereby effectively controlling the bonding strength between the diatomaceous earth and the modified carbon nanotubes, thereby improving the strength of the powder and the polyurethane foam material.

[0018] In the second aspect, the present application provides a method for preparing a polyurethane foam material, adopting the following technical solution: a method for preparing a polyurethane foam material, comprising the following steps: mixing a complex polyol, a catalyst, a chain extender, a powder and water, ultrasonically dispersing them evenly, adding an isocyanate prepolymer while stirring, stirring evenly, and curing at 80°C to obtain a polyurethane foam material.

[0019] By adopting the above technical solution, the prepared polyurethane foam material has good mechanical properties, and the foam cells formed by foaming are dense and uniform, which is conducive to maintaining the strength of the polyurethane foam material.

[0020] In summary, this application has the following beneficial effects: 1. Since this application uses a composite polyol to mix with water, a chain extender, a catalyst and a powder to form an isocyanate prepolymer of material A and material B for mixing, the isocyanate prepolymer contacts with water to generate carbon dioxide, forming a uniform pore structure to achieve a soft foaming effect. The addition of powder can provide an anchor point for foaming, promote the homogenization and densification of the pores, and at the same time, the addition of powder can effectively improve the mechanical strength of the polyurethane foam material.

[0021] 2. In this application, controlling the mass ratio of polyether polyol, polycarbonate polyol and polyester polyol can effectively maintain the uniformity of the pores of the polyurethane foam material, thereby improving the strength of the polyurethane material.

[0022] 3. The powder formed by the composite of modified carbon nanotubes and modified diatomaceous earth in this application has high strength. The modified carbon nanotubes can enter the diatomaceous earth to form an interpenetrating structure, increasing the complexity of the microstructure, thereby further effectively improving the mechanical properties of the polyurethane foam material. DETAILED DESCRIPTION

[0023] The present application is further described in detail below with reference to the embodiments.

[0024] Powder Preparation Examples 1-6 Preparation Example 1 The powder is a modified carbon nanotube / modified diatomite composite material. 4 g of carbon nanotubes were added to a mixture of 100 mL of concentrated sulfuric acid and concentrated nitric acid in a mass ratio of 1:3, ultrasonically dispersed for 40 min, stirred at 140 ° C for 1 h, washed, filtered, and dried to obtain acidified carbon nanotubes. 2.5 g of propylene glycol, 2 g of DCC, and 0.2 g of DMAP were added to 100 mL of DMF, and 0.8 g of acidified carbon nanotubes were added and ultrasonically dispersed uniformly. Under inert gas protection, the mixture was heated at 120 ° C for 24 h, washed with anhydrous ethanol, filtered, and dried to obtain modified carbon nanotubes. After mixing the aluminate coupling agent with 120 mL of ethanol and 40 mL of water, 25 g of diatomaceous earth was dispersed in the mixed solution and stirred evenly. Then, the modified carbon nanotubes were added and ultrasonically dispersed evenly. The mixture was stirred at 50° C. for 4 h, centrifuged, separated, filtered, and freeze-dried to obtain a modified carbon nanotube / modified diatomaceous earth composite material. The mass ratio of the modified carbon nanotubes to the modified diatomaceous earth was 1.35:12.25, and the amount of the aluminate coupling agent added was 2.35 wt% of the mass of the diatomaceous earth.

[0025] Preparation Example 2 The powder is a modified carbon nanotube / modified diatomite composite material. 4 g of carbon nanotubes were added to a mixture of 100 mL of concentrated sulfuric acid and concentrated nitric acid in a mass ratio of 1:3, ultrasonically dispersed for 40 min, stirred at 140 ° C for 1 h, washed, filtered, and dried to obtain acidified carbon nanotubes. 2.5 g of propylene glycol, 2 g of DCC, and 0.2 g of DMAP were added to 100 mL of DMF, and 0.8 g of acidified carbon nanotubes were added and ultrasonically dispersed uniformly. Under inert gas protection, the mixture was heated at 120 ° C for 24 h, washed with anhydrous ethanol, filtered, and dried to obtain modified carbon nanotubes. After mixing the aluminate coupling agent with 120 mL of ethanol and 40 mL of water, 25 g of diatomaceous earth was dispersed in the mixed solution and stirred evenly. Then, the modified carbon nanotubes were added and ultrasonically dispersed evenly. The mixture was stirred at 60° C. for 3 h, centrifuged, separated, filtered, and freeze-dried to obtain a modified carbon nanotube / modified diatomaceous earth composite material. The mass ratio of the modified carbon nanotubes to the modified diatomaceous earth was 1.35:14.21, and the amount of the aluminate coupling agent added was 3.28 wt% of the mass of the diatomaceous earth.

[0026] Preparation Example 3 The difference between Preparation Example 3 and Preparation Example 1 is that in Preparation Example 3, the mass ratio of modified carbon nanotubes to modified diatomaceous earth is 1.35:5.98.

[0027] Preparation Example 4 The difference between Preparation Example 4 and Preparation Example 1 is that in Preparation Example 4, the mass ratio of modified carbon nanotubes to modified diatomaceous earth is 1.35:20.21.

[0028] Preparation Example 5 The difference between Preparation Example 5 and Preparation Example 1 is that in Preparation Example 5, the amount of the aluminate coupling agent added is 1.25 wt % of the mass of the diatomaceous earth.

[0029] Preparation Example 6 The difference between Preparation Example 6 and Preparation Example 1 is that in Preparation Example 6, the amount of the aluminate coupling agent added is 5.65 wt % of the mass of the diatomaceous earth. Example

[0030] Example 1 A polyurethane foam material is characterized by comprising material A and material B, wherein the mass ratio of material A to material B is 1:1.29, material A comprises 80 kg of a composite polyol, 1 kg of deionized water, 1 kg of a chain extender, 2.5 kg of a catalyst, and 20 kg of a powder, the composite polyol comprises a polyether polyol, a polycarbonate polyol, and a polyester polyol in a mass ratio of 1.05:2.05:2.02, material B comprises 80 kg of an isocyanate prepolymer, and the powder is the powder prepared in Preparation Example 1.

[0031] The preparation method of the above-mentioned polyurethane foam material includes the following steps: mixing a complex polyol, a catalyst, a chain extender, a powder and water, uniformly dispersing them by ultrasonication, adding an isocyanate prepolymer while stirring, stirring evenly, and curing at 80°C to obtain a polyurethane foam material.

[0032] Example 2 A polyurethane foam material is characterized by comprising material A and material B, wherein the mass ratio of material A to material B is 1:1.45, material A comprises 90 kg of a composite polyol, 2 kg of deionized water, 3 kg of a chain extender, 5 kg of a catalyst, and 25 kg of a powder, the composite polyol comprises polyether polyol, polycarbonate polyol, and polyester polyol in a mass ratio of 1.12:2.26:2.18, material B comprises 90 kg of an isocyanate prepolymer, and the powder is the powder prepared in Preparation Example 1.

[0033] The preparation method of the above-mentioned polyurethane foam material includes the following steps: mixing a complex polyol, a catalyst, a chain extender, a powder and water, uniformly dispersing them by ultrasonication, adding an isocyanate prepolymer while stirring, stirring evenly, and curing at 80°C to obtain a polyurethane foam material.

[0034] Example 3 The difference between Example 3 and Example 1 is that in Example 3, the mass ratio of material A to material B is 1:0.8.

[0035] Example 4 The difference between Example 4 and Example 1 is that in Example 4, the mass ratio of material A to material B is 1:1.8.

[0036] Example 5 The difference between Example 5 and Example 1 is that in Example 5, the complex polyol includes polyether polyol, polycarbonate polyol, and polyester polyol in a mass ratio of 1.05:1.15:3.15.

[0037] Example 6 The difference between Example 6 and Example 1 is that in Example 6, the complex polyol includes polyether polyol, polycarbonate polyol, and polyester polyol in a mass ratio of 1.05:3.25:1.25.

[0038] Example 7 The difference between Example 7 and Example 1 is that in Example 7, the powder material is the powder material prepared in Preparation Example 3.

[0039] Example 8 The difference between Example 8 and Example 1 is that in Example 8, the powder material is the powder material prepared in Preparation Example 4.

[0040] Example 9 The difference between Example 9 and Example 1 is that in Example 9, the powder material is the powder material prepared in Preparation Example 5.

[0041] Example 10 The difference between Example 10 and Example 1 is that in Example 10, the powder material is the powder material prepared in Preparation Example 6.

[0042] Comparative Example Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that in Comparative Example 1, no powder is added.

[0043] Performance testing Polyurethane foam materials were prepared according to Examples 1-10 and Comparative Example 1, and the compressive strength and compression modulus of the polyurethane foam materials were tested, and the results are recorded in Table 1.

[0044] Table 1 Performance test of polyurethane foam material According to Table 1, Examples 1-2, and Comparative Example 1, it can be seen that the polyurethane foam material prepared in Examples 1-2 has high compressive strength and compression modulus. The isocyanate prepolymer generates carbon dioxide upon contact with water, forming a uniform pore structure and achieving a soft foaming effect. The addition of powder can provide an anchor point for foaming, promote the homogenization and densification of the pores, and at the same time, the addition of powder can effectively improve the mechanical strength of the polyurethane foam material. The powder used in Examples 1-2 can improve the mechanical strength of the polyurethane foam material, and the composite polyol can maintain the uniformity of the pores and also improve the strength of the polyurethane foam material. The modified carbon nanotubes and modified diatomaceous earth form an interlaced structure through an aluminate coupling agent, and are cross-linked and fixed by the aluminate coupling agent, thereby increasing the complexity of the microstructure and further improving the mechanical properties of the polyurethane foam material.

[0045] Compared with Example 1-2, the compressive strength and compression modulus of Example 3-4 are reduced. In Example 3-4, the mass ratio of material A to material B is changed, thereby changing the mass ratio of the complex polyol to the isocyanate prepolymer, which directly affects the foaming effect of the polyurethane foam material and the strength of the substrate, thereby reducing the mechanical properties of the polyurethane foam material.

[0046] Compared with Example 1-2, the compressive strength and compression modulus of Example 5-6 are reduced. In Example 5-6, the mass ratio of polyether polyol, polycarbon polyol and polyester polyol in the composite polyol is changed, which shows that the mass ratio of polyether polyol, polycarbon polyol and polyester polyol will affect the strength of the polyurethane foam material. It affects the mechanical strength of the polyurethane material by affecting the uniformity of the bubbles of the polyurethane foam material. When the uniformity decreases, its mechanical strength decreases.

[0047] Compared with Example 1-2, the compressive strength and compression modulus of Example 7-8 are reduced. When preparing the powder of Example 7-8, the mass ratio of modified carbon nanotubes and modified diatomaceous earth is changed. The powder formed by the composite of modified carbon nanotubes and modified diatomaceous earth has higher strength. The modified carbon nanotubes can enter the diatomaceous earth to form an interlaced structure, increasing the complexity of the microstructure, thereby further effectively improving the mechanical properties of the polyurethane foam material. When the mass ratio changes, the composite effect of the modified carbon nanotubes and modified diatomaceous earth is poor, which reduces the reinforcing effect of the powder.

[0048] Compared with Examples 1-2, the compressive strength and compression modulus of Examples 9-10 are reduced. When preparing the powder of Examples 9-10, the amount of the aluminate coupling agent added was changed. The amount of the aluminate coupling agent added was controlled to effectively control the bonding strength between the diatomaceous earth and the modified carbon nanotubes. Too much or too little can easily affect the bonding strength between the diatomaceous earth and the modified carbon nanotubes, thereby affecting the strength of the powder and the polyurethane foam material.

[0049] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A polyurethane foam material, characterized in that: The invention comprises material A and material B, wherein the material A comprises 80-90 parts of complex polyol, 1-2 parts of deionized water, 1-3 parts of chain extender, 2.5-5 parts of catalyst and 20-25 parts of powder, and the material B comprises 80-90 parts of isocyanate prepolymer.

2. The polyurethane foam material according to claim 1, characterized in that: The complex polyol comprises polyether polyol, polycarbonate polyol and polyester polyol in a mass ratio of (1.05-1.12):(2.05-2.26):(2.02-2.18).

3. The polyurethane foam material according to claim 1, characterized in that: The mass ratio of the material A to the material B is 1:(1.29-1.45).

4. The polyurethane foam material according to claim 1, characterized in that: The powder is a modified carbon nanotube / modified diatomite composite material, and the mass ratio of the modified carbon nanotube to the modified diatomite is (1.35-2.12):(12.25-14.21).

5. The polyurethane foam material according to claim 4, characterized in that: The preparation method of the modified carbon nanotubes comprises the following steps: adding carbon nanotubes to a mixture of concentrated sulfuric acid and concentrated nitric acid, ultrasonically dispersing the mixture for 40 min, stirring the mixture at 140° C. for 1 h, washing, filtering, and drying the mixture to obtain acidified carbon nanotubes; adding glycerol, DCC, and DMAP to DMF, adding the acidified carbon nanotubes to the mixture, ultrasonically dispersing the mixture evenly, heating the mixture at 120° C. for 24 h under inert gas protection, washing the mixture with anhydrous ethanol, filtering, and drying the mixture to obtain the modified carbon nanotubes.

6. The polyurethane foam material according to claim 4, characterized in that: The preparation method of the modified carbon nanotube / modified diatomite composite material comprises the following steps: mixing an aluminate coupling agent with ethanol and water, dispersing diatomite in the mixed solution, stirring evenly, adding the modified carbon nanotubes, and uniformly dispersing them by ultrasonication, stirring at 50-60° C. for 3-4 hours, centrifuging, separating, filtering, and freeze-drying to obtain the modified carbon nanotube / modified diatomite composite material.

7. The polyurethane foam material according to claim 6, characterized in that: The addition amount of the aluminate coupling agent is 2.35-3.28 wt % of the diatomite mass.

8. The method for preparing a polyurethane foam material according to any one of claims 1 to 7, characterized in that: The following steps are involved: The composite polyol, catalyst, chain extender, powder and water are mixed, ultrasonically dispersed evenly, and then the isocyanate prepolymer is added while stirring. After stirring evenly, the mixture is cured at 80° C. to obtain a polyurethane foam material.

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