Sponge material with high air permeability as well as preparation method and application thereof
By combining high EO content polyether polyol and common polyether polyol and using environmentally friendly non-tin metal catalysts, sponge materials with high breathability and good mechanical properties are prepared, which solves the problems of insufficient breathability and poor durability of traditional sponges.
Patent Information
- Application Number
- CN202510274582.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-10
- Publication Date
- 2025-06-27
AI Technical Summary
Traditional sponges are insufficient in breathability, resulting in an increase in the sense of stuffiness during use, and lack of mechanical properties and durability, which is prone to deformation, tearing and collapse.
A sponge material with high breathability is prepared by combining high EO content polyether polyol and common polyether polyol and using an environmentally friendly non-tin metal catalyst. The material has a breathability of >7.0cfm, a tensile strength of >100Kpa, and a tear strength of >400N/m, taking into account the requirements of softness, elasticity and strength.
It realizes the high breathability of the sponge material, while maintaining good mechanical properties and durability, avoiding the problems of prone to deformation, tearing and collapse of traditional sponges.
Smart Images
Figure CN120209256A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to the field of sponge materials, and in particular to a sponge material with high air permeability and a preparation method and application thereof. Background Art
[0002] In the modern furniture industry, sponge is a key filling material, and its performance has a decisive influence on the quality of furniture and user experience. Users usually hope to obtain better air permeability to reduce the feeling of stuffiness during use. The pore structure of polyurethane sponge is a key factor affecting air permeability. If the pores inside the sponge are too closed, the resistance to air flow will increase. When air molecules pass through these pores, the probability of collision with the pore wall will increase, resulting in poor air circulation and difficulty in passing smoothly, which seriously limits the air permeability of the sponge; uneven air permeability pore distribution will form a "bottleneck" for air circulation inside the sponge, which will reduce the uniform diffusion capacity of air in the sponge as a whole. In order to improve the strength and other mechanical properties of polyurethane sponge, methods such as increasing the cross-linking density and adding reinforcing fibers are usually adopted. However, these measures often make the structure of the sponge denser, reduce the porosity, and reduce the air flow space in it, thereby sacrificing air permeability. Summary of the invention
[0003] In response to the problem of insufficient air permeability of traditional sponges, the present application provides a sponge material with high air permeability and a preparation method and application thereof. The obtained polyurethane sponge has good air permeability and at the same time meets the use requirements of softness, sufficient elasticity and good strength.
[0004] The present invention provides a sponge with high air permeability, and the raw materials thereof, calculated by weight, include:
[0005] 60-80 parts of high EO content polyether polyol,
[0006] 20-40 parts of common polyether polyol,
[0007] 27.5-33.5 parts TDI80,
[0008] 0.3-1.4 parts of silicone oil surfactant,
[0009] 0.32-0.42 parts of amine catalyst,
[0010] 0.46-0.54 parts of non-tin metal catalyst,
[0011] 0.2-1.5 parts of cross-linking agent;
[0012] 1.5-2.5 parts water.
[0013] This application uses high-EO content polyether polyols and ordinary polyether polyols in combination. It is impossible to obtain a stable sponge by simply using high-EO content polyether polyols, and the air permeability of the sponge obtained by simply using ordinary polyether polyols is insufficient. The polyurethane material prepared by ordinary polyether polyols usually has a certain flexibility. The use of high-EO content polyether polyols can further improve the flexibility of the sponge product. This is because the EO segment is soft and easy to rotate, which can enhance the mobility of the molecular chain. The prepared sponge material can be better bent and stretched in different environments and is not easy to crack. Therefore, the combination of the two can obtain a sponge product that is stable and highly permeable; and the raw materials use environmentally friendly non-tin metal catalysts, which are not easily affected by the environment and have stable performance. When used in combination with raw materials such as high-EO content polyether polyols and ordinary polyether polyols, a sponge product with high permeability can be obtained.
[0014] As a further invention point, the present invention can also take into account high air permeability and suitable performance, and while ensuring high air permeability, its strength can also be maintained at a good level, and it can also maintain softness and good elasticity. The sponge with high air permeability of the present invention has an air permeability of >7.0cfm (according to ASTM D3574-17 standard), a tensile strength of >100Kpa, and a tear strength of >400N / m.
[0015] When the sponge in existing products focuses on pursuing high air permeability, its performance is often affected to a certain extent. First, in terms of mechanical properties, in order to increase the porosity to improve air permeability, the internal structure of the sponge may become relatively loose, which directly leads to a decrease in the strength and elasticity of the sponge. In daily use, frequent sitting pressure, squeezing or friction will cause the sponge to deform, tear, collapse and other problems more quickly. For example, sofa cushions filled with highly breathable sponges are prone to obvious dents and cracks after a period of use, and cannot be restored to their original shape, which not only affects the appearance of the sofa, but also reduces its comfort and support performance. Secondly, in terms of durability, the highly breathable sponge has a relatively loose structure, and its wear and aging resistance is relatively weak. During long-term friction with human skin or clothing, the surface of the highly breathable sponge is more easily damaged and cracked.
[0016] Preferably, the raw materials of the sponge with high air permeability, calculated by weight, include:
[0017] 62-78 parts of high EO content polyether polyol, 22-38 parts of ordinary polyether polyol, 28.5-32.5 parts of TDI80, 0.3-1.2 parts of silicone oil surfactant, 0.33-0.41 parts of amine catalyst, 0.47-0.53 parts of non-tin metal catalyst, 0.3-1.2 parts of crosslinking agent and 1.6-2.4 parts of water.
[0018] Further, the functionality of the polyether polyol with high EO content is 3, the molecular weight is 3500 - 6000 mw, the EO content is above 60%, and the primary hydroxyl content is above 80%. The EO content is crucial for the cell opening of the sponge, and the EO content is an important factor affecting the primary hydroxyl content. The primary hydroxyl content is important for the foaming stability of the sponge. Polyethers with low primary hydroxyl content will cause phenomena such as unstable foaming and foam collapse in the formulation of the present invention.
[0019] Further, the functionality of the ordinary polyether polyol is 3, the molecular weight is 3000 mw, and the EO content is 5 - 15%.
[0020] Further, the TDI80 is a mixture of 2,4 - toluene diisocyanate and 2,6 - toluene diisocyanate, and the ratio of the two is 80 / 20. TDI80 is the most commonly used isocyanate in the foaming of polyurethane flexible foam sponges. Its activity is between TDI100 and TDI65. Its curing speed is moderate, suitable for application scenarios with balanced requirements for the reaction rate, such as the preparation of foams and elastomers, and the cost is lower than that of aliphatic isocyanates.
[0021] Further, the silicone surfactant is a medium - low activity silicone surfactant. The reaction activity of the medium - low activity silicone surfactant is lower than that of the high - activity silicone surfactant. When participating in the reaction, it can both protect the growth of fine gas nuclei and maintain the stability of foaming, and can also maintain a relatively high cell - opening rate. Therefore, it is necessary to define the silicone surfactant.
[0022] Further, the amine catalyst is a reactive or non - reactive catalyst.
[0023] Further, the non - tin metal catalyst is one of bismuth - based metal catalysts and zinc - based metal catalysts or a composite catalyst of bismuth and zinc metals. Using such non - tin metal catalysts does not contain heavy metal elements that may be harmful to the environment and human body as may exist in tin - based catalysts. The catalytic activity of non - tin metal catalysts is usually relatively mild, the reaction process is easier to control, which is beneficial to improving the quality and stability of products, reducing the defective rate. Non - tin metal catalysts have good hydrolysis resistance and thermal stability and are not easily deactivated due to hydrolysis or thermal decomposition.
[0024] Further, the cross - linker is at least one of glycerol, trihydroxypropane, pentaerythritol, diethanolamine, and triethanolamine.
[0025] The preparation method of the above - mentioned sponge material with high air permeability includes the following steps:
[0026] Step 1, mix the polyether polyol with high EO content, ordinary polyether polyol, silicone surfactant, amine catalyst, non - tin metal catalyst, cross - linker and water according to the above mass fractions to form a mixture.
[0027] Step 2: Mix the obtained mixture with TDI80, and foam and solidify it at a constant temperature of 20-28° C. to form a highly breathable sponge.
[0028] The present application also protects the application of the above-mentioned sponge material with high air permeability in a mattress.
[0029] The beneficial effects of the present application are as follows: the present application is a sponge material with high air permeability, and a preparation method and application thereof. The present application uses a high-EO content polyether polyol, a common polyether polyol and an environmentally friendly non-tin metal catalyst to obtain a sponge product with high air permeability; in addition, the obtained sponge material with high air permeability can also take into account good performance. BRIEF DESCRIPTION OF THE DRAWINGS
[0030] Figure 1 This is the microstructure diagram of Example 1. DETAILED DESCRIPTION
[0031] The following is an explanation and description of the technical solutions of the embodiments of the present invention in conjunction with the accompanying drawings of the present invention, but the following embodiments are only preferred embodiments of the present invention, not all. Based on the embodiments in the implementation mode, other embodiments obtained by those skilled in the art without creative work are all within the protection scope of the present invention.
[0032] The raw materials used are shown in Table 1.
[0033] Table 1
[0034]
[0035]
[0036] Example 1
[0037] A sponge material with high air permeability, calculated by weight, comprises the following components:
[0038] 70 parts of high EO content polyether polyol, 30 parts of ordinary polyether polyol, 30.9 parts of TDI80, 0.9 parts of silicone oil surfactant, 0.38 parts of amine catalyst, 0.50 parts of non-tin metal catalyst, 0.5 parts of crosslinking agent and 2.0 parts of water.
[0039] Among them, the polyether polyol with high EO content has a functionality of 3, a molecular weight of 3500 - 6000 mw, an EO content of more than 60%, and a primary hydroxyl group content of more than 80%; the ordinary polyether polyol has a functionality of 3, a molecular weight of 3000 mw, and an EO content of 5 - 15%; the TDI80 is a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, and the ratio of the two is 80 / 20; the silicone surfactant is a medium and low activity silicone surfactant DC5950; the amine catalyst is a non-reactive catalyst; the non-tin metal catalyst is a bismuth metal catalyst; the cross-linking agent is triethanolamine.
[0040] The above-mentioned sponge material with high air permeability is prepared by the following steps:
[0041] Step 1, mix the polyether polyol with high EO content, ordinary polyether polyol, silicone surfactant, amine catalyst, non-tin metal catalyst, cross-linking agent and water according to mass parts to form a mixture.
[0042] Step 2, mix the obtained mixture with TDI80, and foam and cure it at a constant temperature of 20 - 28 °C to form a high air permeability sponge.
[0043] The microstructural diagram of this embodiment is as Figure 1 shown. It can be seen from the figure that the prepared sponge material with high air permeability has more voids, which can ensure its high air permeability.
[0044] Example 2
[0045] The raw materials used in this embodiment include, calculated by mass parts: 60 parts of polyether polyol with high EO content, 40 parts of ordinary polyether polyol, 27.5 parts of TDI80, 0.3 part of silicone surfactant, 0.32 part of amine catalyst, 0.46 part of non-tin metal catalyst, 0.2 part of cross-linking agent and 1.5 parts of water.
[0046] Among them, the silicone surfactant is a medium and low silicone surfactant DC5950; the amine catalyst is a reactive catalyst; the non-tin metal catalyst is a zinc metal catalyst; the cross-linking agent is trihydroxypropane.
[0047] The preparation method of this embodiment is the same as that of Example 1.
[0048] Example 3
[0049] The raw materials used in this embodiment include, calculated by mass parts: 80 parts of polyether polyol with high EO content, 20 parts of ordinary polyether polyol, 33.5 parts of TDI80, 1.4 parts of silicone surfactant, 0.42 part of amine catalyst, 0.54 part of non-tin metal catalyst, 1.5 parts of cross-linking agent and 2.5 parts of water.
[0050] Among them, the silicone surfactant is a medium- and low-activity silicone surfactant DC5950; the amine catalyst is a non-reactive catalyst; the non-tin metal catalyst is a bismuth-zinc composite metal catalyst; and the crosslinking agent is glycerol.
[0051] The preparation method of this example is the same as that of Example 1.
[0052] Example 4
[0053] The raw materials used in this example include, by mass: 70 parts of polyether polyol with high EO content, 30 parts of ordinary polyether polyol, 31.5 parts of TDI80, 0.9 part of silicone surfactant, 0.38 part of amine catalyst, 0.53 part of non-tin metal catalyst, 0.4 part of crosslinking agent, and 2.0 parts of water.
[0054] Among them, the silicone surfactant is a medium- and low-activity silicone surfactant DC5950; the amine catalyst is a non-reactive catalyst; the non-tin metal catalyst is a bismuth-based metal catalyst; and the crosslinking agent is diethanolamine.
[0055] The preparation method of this example is the same as that of Example 1.
[0056] Example 5
[0057] The raw materials used in this example include, by mass: 70 parts of polyether polyol with high EO content, 30 parts of ordinary polyether polyol, 29.6 parts of TDI80, 0.9 part of silicone surfactant, 0.35 part of amine catalyst, 0.46 part of non-tin metal catalyst, 0.9 part of crosslinking agent, and 2.0 parts of water.
[0058] Among them, the silicone surfactant is a medium- and low-activity silicone surfactant DC5950; the amine catalyst is a non-reactive catalyst; the non-tin metal catalyst is a bismuth-based metal catalyst; and the crosslinking agent is pentaerythritol.
[0059] The preparation method of this example is the same as that of Example 1.
[0060] Comparative Example 1
[0061] A sponge, which is different from that of Example 1 in that the polyether polyol with high EO content is replaced by a low primary hydroxyl polyether polyol.
[0062] Calculated by mass, it includes the following components:
[0063] 70 parts of low primary hydroxyl polyether polyol, 30 parts of ordinary polyether polyol, 30.9 parts of TDI80, 0.9 part of silicone surfactant, 0.38 part of amine catalyst, 0.50 part of non-tin metal catalyst, 0.5 part of crosslinking agent, and 2.0 parts of water.
[0064] Among them, the primary hydroxyl polyether polyol has a primary hydroxyl content of 70% or less; the silicone surfactant is a medium-low activity silicone surfactant DC5950; the amine catalyst is a non-reactive catalyst; the non-tin metal catalyst is a bismuth metal catalyst; the crosslinking agent is triethanolamine.
[0065] The preparation method of this example is the same as that of Example 1.
[0066] Comparative Example 2
[0067] A sponge, different from Example 1 in that a tin metal catalyst is added.
[0068] Calculated by mass parts, it includes the following components:
[0069] 70 parts of polyether polyol with high EO content, 30 parts of ordinary polyether polyol, 30.9 parts of TDI80, 0.9 part of silicone surfactant, 0.38 part of amine catalyst, 0.50 part of non-tin metal catalyst, 0.03 part of tin metal catalyst, 0.5 part of crosslinking agent and 2.0 parts of water.
[0070] Among them, the silicone surfactant is a medium-low activity silicone surfactant DC5950; the amine catalyst is a non-reactive catalyst; the non-tin metal catalyst is a bismuth metal catalyst; the tin metal catalyst is stannous octoate catalyst; the crosslinking agent is triethanolamine.
[0071] The preparation method of this example is the same as that of Example 1.
[0072] Comparative Example 3
[0073] A sponge, different from Example 1 in that the silicone surfactant is replaced with a high activity silicone surfactant.
[0074] Calculated by mass parts, it includes the following components:
[0075] 70 parts of polyether polyol with high EO content, 30 parts of ordinary polyether polyol, 30.9 parts of TDI80, 0.9 part of silicone surfactant, 0.38 part of amine catalyst, 0.50 part of bismuth metal catalyst, 0.5 part of crosslinking agent and 2.0 parts of water.
[0076] Among them, the silicone surfactant is a high activity silicone surfactant L580; the amine catalyst is a non-reactive catalyst; the non-tin metal catalyst is a bismuth metal catalyst; the crosslinking agent is triethanolamine.
[0077] The preparation method of this example is the same as that of Example 1.
[0078] Comparative Example 4
[0079] A sponge, which is different from that of Example 1 in that all of the polyether polyols are high-EO-content polyether polyols.
[0080] Calculated by mass parts, it includes the following components:
[0081] 100 parts of high-EO-content polyether polyols, 29.9 parts of TDI80, 0.9 part of silicone oil surfactant, 0.38 part of amine catalyst, 0.50 part of bismuth-based metal catalyst, 0.5 part of crosslinking agent and 2.0 parts of water.
[0082] Among them, the silicone oil surfactant is a medium-low activity silicone oil surfactant DC5950; the amine catalyst is a non-reactive catalyst; the non-tin-based metal catalyst is a bismuth-based metal catalyst; the crosslinking agent is triethanolamine.
[0083] The preparation method of this example is the same as that of Example 1.
[0084] In order to more clearly illustrate the present invention, the foaming situation and performance of the sponges prepared in the examples and Comparative Examples 1-4 were detected and compared. The tensile strength and elongation at break were measured according to the method of GB / T 6344, the tear strength was measured according to the method of GB / T10808, the resilience was measured according to the method of GB / T 6670, the 40% indentation hardness was measured according to the method of GB / T 10807, and the air permeability was measured according to the method of ASTM D3574. The foaming situation and test results are shown in Table 2.
[0085] Table 2
[0086]
[0087] In the above table, the higher the air permeability value, the more breathable the prepared sponge; the greater the tensile strength value, the less likely the prepared sponge is to be broken; the greater the elongation at break value, the better the stretching performance of the prepared sponge; the greater the tear strength value, the less likely the prepared sponge is to be torn; the greater the resilience value, the better the elasticity of the prepared sponge.
[0088] As can be seen from the above table, Example 1 has the best air permeability, and its tensile strength, tear strength, and rebound rate are also the best among all examples and comparative examples; the air permeability, tensile strength, tear strength, and rebound rate of Example 2, Example 3, Example 4, and Example 5 are all inferior to those of Example 1, but their overall performance is relatively stable, and their air permeability is better than that of all comparative examples; Comparative Example 1 severely sinks and collapses, probably because the low activity of low primary hydroxyl polyether polyol leads to too slow gel reaction rate; compared with Examples 1-5, the insufficient air permeability and tear strength of Comparative Example 2 may be due to the addition of tin-based metal catalyst resulting in a decrease in the open cell rate, and the change in the gel reaction rate affects the internal microstructure. The insufficient air permeability of Comparative Example 3 may be that the high activity silicone oil surfactant leads to a decrease in the bubble breaking ratio, resulting in an increase in closed cells and a decrease in air permeability; the cell structure of Comparative Example 4 is thick and the closed cells are serious, probably because all high EO content polyether polyols are used, with too high activity and it is difficult for the cells to open.
[0089] As described above, the above are only specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that the present invention includes but is not limited to the content described in the drawings and the above specific embodiments. Any modification that does not deviate from the functional and structural principles of the present invention will be included in the scope of the claims.
Claims
1. A sponge material with high air permeability, characterized in that: The raw materials are calculated by weight, including: 60-80 parts of high EO content polyether polyol; 20-40 parts of common polyether polyol; 27.5-33.5 parts TDI80; 0.3-1.4 parts of silicone oil surfactant; 0.32-0.42 parts of amine catalyst; 0.46-0.54 parts of non-tin metal catalyst; 0.2-1.5 parts of cross-linking agent; 1.5-2.5 parts water.
2. The sponge material with high air permeability according to claim 1, characterized in that: The raw materials are calculated by weight, including: 62-78 parts of high EO content polyether polyol, 22-38 parts of ordinary polyether polyol, 28.5-32.5 parts of TDI80, 0.3-1.2 parts of silicone oil surfactant, 0.33-0.41 parts of amine catalyst, 0.47-0.53 parts of non-tin metal catalyst, 0.3-1.2 parts of crosslinking agent and 1.6-2.4 parts of water.
3. The sponge material with high air permeability according to claim 1 or 2, characterized in that: The high EO content polyether polyol has a functionality of 3, a molecular weight of 3500-6000mw, an EO content of more than 60%, and a primary hydroxyl content of more than 80%.
4. The sponge material with high air permeability according to claim 1 or 2, characterized in that: The common polyether polyol has a functionality of 3, a molecular weight of 3000mw, and an EO content of 5-15%.
5. The sponge material with high air permeability according to claim 1 or 2, characterized in that: The silicone oil surfactant is a medium-low activity silicone oil surfactant.
6. The sponge material with high air permeability according to claim 1 or 2, characterized in that: The non-tin metal catalyst is a bismuth metal catalyst, a zinc metal catalyst, or a composite catalyst of bismuth and zinc.
7. The sponge material with high air permeability according to claim 1 or 2, characterized in that: The cross-linking agent is at least one of glycerol, trihydroxypropane, pentaerythritol, diethanolamine and triethanolamine.
8. A method for preparing a sponge, characterized in that: The sponge is a sponge material with high air permeability as claimed in any one of claims 1 to 7, comprising the following steps: Step 1, mixing a high EO content polyether polyol, a common polyether polyol, a silicone oil surfactant, an amine catalyst, a non-tin metal catalyst, a crosslinking agent and water according to the mass fractions of the sponge material raw material with high air permeability to form a mixture; Step 2: Mix the obtained mixture with TDI80, and foam and solidify it at a constant temperature of 20-28° C. to form a highly breathable sponge.
9. Use of the sponge material with high air permeability according to any one of claims 1 to 7 in a mattress.