Sponge capable of maintaining hardness and preparation method thereof
By using polyether modified silicone surfactant and branched polytetrahydrofuran glycol in sponges, combined with specific preparation steps, the problem of sponges hardening at low temperatures is solved, achieving higher low temperature resistance and mechanical properties .
Patent Information
- Application Number
- CN202411528743.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-30
- Publication Date
- 2025-02-25
AI Technical Summary
Sponges are prone to hardening under low temperature conditions, resulting in degradation in performance.
The low temperature resistance of the sponge is improved by adding polyether-modified silicone surfactant and branched polytetrahydrofuran glycol to the sponge, and adopting specific component mixing and vulcanization steps during the preparation process.
It significantly improves the low-temperature resistance of the sponge, reduces the possibility of hardening at low temperatures, and improves the mechanical properties of the sponge.
Smart Images
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Abstract
Description
Technical Field
[0001] The present application relates to the technical field of sponge preparation, and in particular to a sponge capable of maintaining hardness and a preparation method thereof. Background Art
[0002] Sponges are usually made of polyurethane materials. Polyurethane is a polymer containing carbamate groups in the main chain of the macromolecule. Polyurethane is divided into two categories: polyester polyurethane and polyether polyurethane.
[0003] The isocyanate monomer molecules contained in polyurethane have two functional groups that react with each other. The activity of this functional group will decrease as the temperature decreases, causing the reaction rate to slow down, making it difficult for a complete reaction to occur and resulting in hardening. Summary of the invention
[0004] In order to improve the low temperature resistance of the sponge, the present application provides a sponge capable of maintaining hardness and a preparation method thereof.
[0005] In the first aspect, the present application provides a sponge capable of maintaining hardness, which adopts the following technical solution: A sponge capable of maintaining hardness comprises the following raw materials in parts by mass: 42-46 parts of polyether polyol, 23-27 parts of diphenylmethane diisocyanate, 3-5 parts of 1,4-butanediol, 18-22 parts of polyoxypropylene triol, and 1-3 parts of a modifier; the modifier comprises a polyether-modified organic silicon surfactant.
[0006] By adopting the above technical solution, the modifier prepared by the polyether-modified silicone surfactant is added to the sponge, which can improve the low-temperature resistance of the sponge, thereby reducing the possibility of the sponge hardening at low temperatures.
[0007] The polyether-modified silicone surfactant has a polyether segment at one end and a polysiloxane segment at the other end. Due to its flexible molecular structure and its incompatibility with both phases, the polysiloxane segment can isolate the two phases and reduce the movement friction of the polyurethane segment, thereby improving the phenomenon that the relaxation speed of the hard segment phase ordering is slowed down due to the involvement of the soft segment when the polyurethane forms a two-phase separation structure, making it easier for the hard segment to aggregate to form a hard segment phase, thereby increasing the degree of microphase separation of the two phases and reducing the glass transition temperature, thereby improving the low-temperature resistance of the sponge.
[0008] In addition, the polyether segment has good compatibility with the polyether polyols in the system and can play a stable lubricating role, thereby improving the mechanical properties of the sponge.
[0009] Preferably, the modifier also includes branched polytetrahydrofuran diol.
[0010] By adopting the above technical scheme, the branched polytetrahydrofuran diol is obtained by grafting alkyl side chains on the main chain of the polytetrahydrofuran diol, which destroys the regularity of the soft segment structure and reduces the crystallization of the soft segment, thereby improving the low temperature resistance of the sponge.
[0011] In addition, the addition of polyether-modified silicone surfactant increases the degree of microphase separation between the soft and hard segments, reduces the hard segments dissolved in the soft segments, and increases the activity of the soft segment chains, which accelerates the rate at which the branched polytetramethylene glycol destroys the regularity of the soft segment structure. Therefore, the low-temperature resistance of the sponge can be further improved through the composite modification of polyether-modified silicone surfactant and branched polytetramethylene glycol.
[0012] Preferably, the mass ratio of the polyether-modified silicone surfactant to the branched polytetrahydrofuran diol is 1:(1.08-1.22).
[0013] By adopting the above technical scheme, the mass ratio of the polyether-modified silicone surfactant and the branched polytetramethylene glycol is controlled within the above range, which has a positive effect on the low-temperature resistance of the sponge.
[0014] Preferably, the sponge further comprises 0.8-1.4 parts of castor oil.
[0015] By adopting the above technical solution, castor oil is a natural polyhydroxy fatty acid glyceride, so adding castor oil to the sponge can increase the cross-linking degree of the sponge, which not only improves the mechanical properties of the sponge, but also increases the dispersed particle size of the system, promotes the degree of microphase separation, and further improves the low-temperature resistance of the sponge.
[0016] Therefore, adding castor oil to the sponge, the synergistic effect between castor oil and polyether-modified silicone surfactant has a positive effect on promoting the degree of microphase separation, thereby promoting the improvement of the low-temperature resistance of the sponge.
[0017] Preferably, the modified preparation method of castor oil comprises the following steps: S100, mixing bentonite and deionized water, heating and stirring, adding nickel nitrate hexahydrate aqueous solution and copper nitrate trihydrate aqueous solution and mixing evenly, adding sodium carbonate aqueous solution until the pH value is 9, aging, filtering, washing, drying, calcining the precipitate, placing it in nitrogen and hydrogen mixed gas for reduction reaction, and then cooling to obtain a catalyst; S200, taking the catalyst in S100 and castor oil to react, after the reaction is completed, cooling to room temperature, dissolving in tetrahydrofuran, filtering and separating, to obtain modified castor oil.
[0018] By adopting the above technical solution, the catalyst reduces the unsaturated double bonds in the castor oil molecules into single bonds, thereby increasing the stability of the molecular chain, making it more tear-resistant, and further improving the mechanical properties of the sponge.
[0019] Preferably, the mass concentration of the nickel nitrate hexahydrate aqueous solution is (0.25-0.33) mol / L.
[0020] Preferably, the mass concentration of the copper nitrate trihydrate aqueous solution is (0.12-0.18) mol / L.
[0021] In a second aspect, the present application provides a method for preparing a sponge capable of maintaining hardness as in the first aspect, which adopts the following technical solution: A method for preparing a sponge capable of maintaining hardness comprises the following steps: S1. Component A: Mix diphenylmethane diisocyanate, polyether polyol and modifier, and heat to react to obtain component A; S2, component B: 1,4-butanediol and polyoxypropylene triol are mixed uniformly at room temperature, and then sealed and stored to obtain component B; S3, mixing: mix component A and component B, stir quickly and place under vacuum, pour after removing bubbles, wait for leveling, pressurize and vulcanize before demoulding, heat and vulcanize, and finally place at room temperature for cooling to obtain a sponge.
[0022] In summary, the present application includes at least one of the following beneficial technical effects: 1. On the one hand, the polyether-modified silicone surfactant can improve the microphase separation degree of the two phases and reduce the glass transition temperature, thereby improving the low-temperature resistance of the sponge and reducing the possibility of hardening of the sponge at low temperatures; on the other hand, the polyether chain segment has good compatibility with the polyether polyol of the system and can play a stable lubricating role, thereby improving the mechanical properties of the sponge.
[0023] 2. Adding castor oil to the sponge can increase the cross-linking degree of the sponge, which not only improves the mechanical properties of the sponge, but also increases the dispersed particle size of the system, promotes the degree of microphase separation, and further improves the low-temperature resistance of the sponge; and the synergistic effect between castor oil and polyether-modified silicone surfactant has a positive effect on promoting the degree of microphase separation, thereby promoting the improvement of the low-temperature resistance of the sponge. DETAILED DESCRIPTION
[0024] The present application is further described in detail below in conjunction with the examples and comparative examples. The raw materials involved in the present application can be obtained commercially, wherein the polyether-modified silicone surfactant is provided by Qingdao Deming Chemical Co., Ltd., and the branched polytetrahydrofuran diol is provided by Hodogaya Chemical Industry Co., Ltd. of Japan.
[0025] Example 1 The sponge includes the following raw materials in mass: 44 g of polyether polyol, 25 g of diphenylmethane diisocyanate, 4 g of 1,4-butanediol, 20 g of polyoxypropylene triol, and 2 g of a modifier, wherein the modifier includes a polyether-modified silicone surfactant.
[0026] The preparation method of the sponge comprises the following steps: S1. Component A: Mix diphenylmethane diisocyanate, polyether polyol and modifier, heat to 80°C, and react for 1 hour to obtain component A; S2. Component B: Mix 1,4-butanediol and polyoxypropylene triol evenly at 25°C, seal and store, to obtain component B: S3, mixing: after mixing component A and component B for 1 minute, place them under vacuum for 5 minutes to remove bubbles, pour them into a flat mold preheated to 100°C, wait for leveling, pressurize and vulcanize for 20 minutes, demould, then post-vulcanize in an oven at 100°C for 10 hours, and place them in an environment of 25°C for 7 days to obtain a sponge.
[0027] Example 2 The sponge includes the following raw materials by mass: 42 g of polyether polyol, 23 g of diphenylmethane diisocyanate, 3 g of 1,4-butanediol, 18 g of polyoxypropylene triol, and 1 g of a modifier; The modifier includes a polyether-modified silicone surfactant and branched polytetramethylene glycol, and the mass ratio of the polyether-modified silicone surfactant and the branched polytetramethylene glycol is 1:1.08.
[0028] The preparation method of the sponge comprises the following steps: S1. Component A: Mix diphenylmethane diisocyanate, polyether polyol and modifier, heat to 80°C, and react for 1 hour to obtain component A; S2. Component B: Mix 1,4-butanediol and polyoxypropylene triol evenly at 25°C, seal and store, to obtain component B: S3, mixing: after mixing component A and component B for 1 minute, place them under vacuum for 5 minutes to remove bubbles, pour them into a flat mold preheated to 100°C, wait for leveling, pressurize and vulcanize for 20 minutes, demould, then post-vulcanize in an oven at 100°C for 10 hours, and place them in an environment of 25°C for 7 days to obtain a sponge.
[0029] Example 3 The sponge includes the following raw materials by mass: 46 g of polyether polyol, 27 g of diphenylmethane diisocyanate, 5 g of 1,4-butanediol, 22 g of polyoxypropylene triol, and 3 g of a modifier; The modifier includes a polyether-modified silicone surfactant and branched polytetramethylene glycol, and the mass ratio of the polyether-modified silicone surfactant and the branched polytetramethylene glycol is 1:1.22.
[0030] The preparation method of the sponge comprises the following steps: S1. Component A: Mix diphenylmethane diisocyanate, polyether polyol and modifier, heat to 80°C, and react for 1 hour to obtain component A; S2. Component B: Mix 1,4-butanediol and polyoxypropylene triol evenly at 25°C, seal and store, to obtain component B: S3, mixing: after mixing component A and component B for 1 minute, place them under vacuum for 5 minutes to remove bubbles, pour them into a flat mold preheated to 100°C, wait for leveling, pressurize and vulcanize for 20 minutes, demould, then post-vulcanize in an oven at 100°C for 10 hours, and place them in an environment of 25°C for 7 days to obtain a sponge.
[0031] Example 4 The sponge includes the following raw materials by mass: 44 g of polyether polyol, 25 g of diphenylmethane diisocyanate, 4 g of 1,4-butanediol, 20 g of polyoxypropylene triol, and 2 g of a modifier; The modifier includes a polyether-modified silicone surfactant and branched polytetramethylene glycol, and the mass ratio of the polyether-modified silicone surfactant and the branched polytetramethylene glycol is 1:1.15.
[0032] The preparation method of the sponge comprises the following steps: S1. Component A: Mix diphenylmethane diisocyanate, polyether polyol and modifier, heat to 80°C, and react for 1 hour to obtain component A; S2. Component B: Mix 1,4-butanediol and polyoxypropylene triol evenly at 25°C, seal and store, to obtain component B: S3, mixing: after mixing component A and component B for 1 minute, place them under vacuum for 5 minutes to remove bubbles, pour them into a flat mold preheated to 100°C, wait for leveling, pressurize and vulcanize for 20 minutes, demould, then post-vulcanize in an oven at 100°C for 10 hours, and place them in an environment of 25°C for 7 days to obtain a sponge.
[0033] Example 5 The difference between Example 5 and Example 4 is that the mass ratio of the polyether-modified silicone surfactant to the branched polytetrahydrofuran diol is 1:1.02.
[0034] Example 6 The difference between Example 6 and Example 4 is that the mass ratio of the polyether-modified silicone surfactant to the branched polytetrahydrofuran diol is 1:1.28.
[0035] Example 7 The difference between Example 7 and Example 4 is that the sponge further contains 0.8 g of castor oil.
[0036] The preparation method of the sponge comprises the following steps: S1. Component A: Mix diphenylmethane diisocyanate, polyether polyol and modifier, heat to 80°C, and react for 1 hour to obtain component A; S2. Component B: Mix 1,4-butanediol and polyoxypropylene triol evenly at 25°C, seal and store, to obtain component B: S3, mixing: After mixing component A, component B and castor oil for 1 minute, place under vacuum for 5 minutes to remove bubbles, pour into a flat mold preheated to 100°C, wait for leveling, pressurize and vulcanize for 20 minutes, demould, then post-vulcanize in an oven at 100°C for 10 hours, and place in an environment of 25°C for 7 days to obtain a sponge.
[0037] Example 8 The difference between Example 8 and Example 7 is that the sponge also contains 1.4g castor oil Example 9 The difference between Example 9 and Example 7 is that the sponge further contains 1.1 g of castor oil.
[0038] Example 10 The difference between Example 10 and Example 7 is that the modified preparation method of castor oil comprises the following steps: S100, 7.5g of bentonite and 50g of deionized water were mixed and stirred at 70°C for 20min, 40g of nickel nitrate hexahydrate aqueous solution (the mass concentration of nickel nitrate hexahydrate aqueous solution was 0.25mol / L) and 30g of copper nitrate trihydrate aqueous solution (the mass concentration of copper nitrate trihydrate aqueous solution was 0.12mol / L) were added and mixed evenly, and then sodium carbonate aqueous solution (the mass concentration of sodium carbonate aqueous solution was 0.5mol / L) was added until the pH value was 9, and then the precipitate was aged at 75°C for 2h, filtered, and repeatedly washed with distilled water until the precipitate was neutral, and then dried at 120°C for 12h to remove residual moisture, and then placed in a muffle furnace and calcined at 400°C for 4h, and reduced in a nitrogen-hydrogen mixed gas at 300°C for 4h, and then cooled in a nitrogen atmosphere to obtain a catalyst; S200, taking 4 g of the catalyst in step S100 and loading it into a high-pressure reactor with 100 g of castor oil, exhausting the air, heating the reactor to a preset temperature, introducing a certain pressure of hydrogen to start the reaction, and after the reaction is completed, cooling the reactor to 25° C., dissolving the resulting mixture in tetrahydrofuran, and filtering and separating to obtain modified castor oil.
[0039] Embodiment 11 The difference between Example 11 and Example 10 is that the mass concentration of the nickel nitrate hexahydrate aqueous solution is 0.33 mol / L, and the mass concentration of the copper nitrate trihydrate aqueous solution is 0.18 mol / L.
[0040] Example 12 The difference between Example 12 and Example 10 is that the mass concentration of the nickel nitrate hexahydrate aqueous solution is 0.29 mol / L, and the mass concentration of the copper nitrate trihydrate aqueous solution is 0.15 mol / L.
[0041] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that no modifier is added to the sponge.
[0042] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that the modifier only contains branched polytetrahydrofuran diol.
[0043] Performance testing: 1. Low temperature resistance The sponges prepared in Examples 1-12 and Comparative Examples 1-2 were cut into 10 cm x 10 cm x 2 cm, and tested using a Shore durometer at a low temperature of -10°C. The test results are recorded in Table 1. The lower the hardness, the better the low temperature resistance of the sponge.
[0044] 2. Mechanical properties After the sponges prepared in Examples 1-12 and Comparative Examples 1-2 were cut into 10 cm x 10 cm x 2 cm, the tensile strength of the sponges was tested according to ISO 1798-2008 Test method for determination of tensile strength and elongation at break of flexible foam polymeric materials, and the test results were recorded in Table 1. The higher the tensile strength, the better the mechanical properties of the sponge.
[0045] Table 1 Data Analysis: Specifically combining the test results of Examples 2-4 and Example 1, the low temperature hardness of Examples 2-4 at -10°C is 64-67, and the low temperature hardness of Example 1 at -10°C is 83. The analysis is as follows. The difference between Examples 2-4 and Example 1 is that: in addition to the polyether-modified silicone surfactant, the modifier also contains branched polytetrahydrofuran diol, which destroys the regularity of the soft segment structure and reduces the crystallization of the soft segment. The composite modification of the polyether-modified silicone surfactant and the branched polytetrahydrofuran diol can further improve the low temperature resistance of the sponge.
[0046] Specifically combining the test results of Example 9 and Example 4, Example 9 has a low-temperature hardness of 59 at -10°C and a tensile strength of 14.7 MPa; Example 4 has a low-temperature hardness of 64 at -10°C and a tensile strength of 11.58 MPa. The analysis is as follows. The difference between Example 9 and Example 4 is that castor oil is also added to the sponge. On the one hand, castor oil itself can promote the degree of microphase separation, and the synergistic effect between castor oil and polyether-modified silicone surfactant has a positive effect on promoting the degree of microphase separation, thereby promoting the improvement of the low-temperature resistance of the sponge. On the other hand, castor oil can increase the cross-linking degree of the sponge, thereby promoting the improvement of the mechanical properties of the sponge.
[0047] Specifically combining the test results of Examples 10-12 and Example 9, the tensile strength of Examples 10-12 is 18.32-18.57 MPa, and the tensile strength of Example 9 is 14.72 MPa. The analysis is as follows. The difference between Examples 10-12 and Example 9 is that the castor oil is modified to increase the stability of the castor oil molecular chain, thereby improving the low temperature resistance of the sponge.
[0048] Specifically combining the test results of Example 1 and Comparative Example 1, Example 1 has a low-temperature hardness of 83 at -10°C and a tensile strength of 11.53 MPa, while Comparative Example 1 has a low-temperature hardness of 118 at -10°C and a tensile strength of 7.54 MPa. The analysis is as follows: the difference between Example 1 and Comparative Example 1 is that: a polyether-modified silicone surfactant is added to the sponge. On the one hand, the polyether-modified silicone surfactant can reduce the glass transition temperature, thereby improving the low-temperature resistance of the sponge; on the other hand, the polyether-modified silicone surfactant is compatible with the polyether polyol, thereby being able to play a stable lubricating role, thereby improving the mechanical properties of the sponge.
[0049] Specifically combining the test results of Example 1 and Comparative Example 2, the tensile strength of Example 1 is 11.53 MPa, and the tensile strength of Comparative Example 2 is 7.88 MPa. The analysis is as follows. The difference between Example 1 and Comparative Example 2 is that the modifier is a polyether-modified silicone surfactant, and the polyether-modified silicone surfactant can play a stable lubricating role, thereby improving the mechanical properties of the sponge.
[0050] The above are all preferred embodiments of the present application, and the protection scope of the present application is not limited thereto. Therefore, any equivalent changes made according to the structure, shape, and principle of the present application should be included in the protection scope of the present application.
Claims
1. A sponge capable of maintaining hardness, characterized in that: The invention comprises the following raw materials in parts by weight: 42-46 parts of polyether polyol, 23-27 parts of diphenylmethane diisocyanate, 3-5 parts of 1,4-butanediol, 18-22 parts of polyoxypropylene triol and 1-3 parts of a modifier; the modifier comprises a polyether-modified organic silicon surfactant.
2. A sponge capable of maintaining hardness according to claim 1, characterized in that: The modifier also includes branched polytetrahydrofuran diol.
3. A sponge capable of maintaining hardness according to claim 2, characterized in that: The mass ratio of the polyether-modified organic silicon surfactant to the branched polytetrahydrofuran diol is 1:(1.08-1.22).
4. A sponge capable of maintaining hardness according to claim 1, characterized in that: The sponge also includes 0.8-1.4 parts of castor oil.
5. A sponge capable of maintaining hardness according to claim 4, characterized in that: The modified preparation method of castor oil comprises the following steps: S100, mixing bentonite and deionized water, heating and stirring, adding nickel nitrate hexahydrate aqueous solution and copper nitrate trihydrate aqueous solution and mixing evenly, adding sodium carbonate aqueous solution until the pH value is 9, aging, filtering, washing, drying, calcining the precipitate, placing it in nitrogen and hydrogen mixed gas for reduction reaction, and then cooling to obtain a catalyst; S200, taking the catalyst in S100 and castor oil to react, after the reaction is completed, cooling to room temperature, dissolving in tetrahydrofuran, filtering and separating, to obtain modified castor oil.
6. A sponge capable of maintaining hardness according to claim 5, characterized in that: The mass concentration of the nickel nitrate hexahydrate aqueous solution is (0.25-0.33) mol / L.
7. The sponge capable of maintaining hardness according to claim 5, characterized in that: The mass concentration of the copper nitrate trihydrate aqueous solution is (0.12-0.18) mol / L.
8. A method for preparing a sponge capable of maintaining hardness as claimed in claim 1, characterized in that: The steps include: S1. Component A: Mix diphenylmethane diisocyanate, polyether polyol and modifier, and heat to react to obtain component A; S2, component B: 1,4-butanediol and polyoxypropylene triol are mixed uniformly at room temperature, and then sealed and stored to obtain component B; S3, mixing: mix component A and component B, stir quickly and place under vacuum, pour after removing bubbles, wait for leveling, pressurize and vulcanize before demoulding, heat and vulcanize, and finally place at room temperature for cooling to obtain a sponge.