Supramolecular aggregate modified polyurethane damping material and preparation method thereof
Through the preparation method of supramolecular aggregate modified polyurethane materials, the problem of poor damping performance of traditional polyurethane materials above room temperature is solved, and simple and efficient damping performance improvement and mechanical performance enhancement are achieved.
Patent Information
- Application Number
- CN202510569840.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-05
- Publication Date
- 2025-08-01
AI Technical Summary
The glass transition temperature of traditional polyurethane materials is lower than room temperature, resulting in poor damping performance at room temperature and above, and the synthesis process of existing modification methods is complicated and mechanical properties are degraded.
The supramolecular aggregate modification method is used to form a hydrogen bond stacking structure by combining components such as aliphatic isocyanate, aromatic isocyanate, polyol and ureadopyrimidone monomer to form a hydrogen bond stacking structure by self-assembly of supramolecular derivatives.
The preparation process is simple, the raw materials are easy to obtain, the material has reversible dynamic mechanical properties and good damping and vibration damping performance, and is suitable for vibration damping protection of industrial devices.
Smart Images
Figure CN120399428A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of damping and vibration reduction materials, and particularly relates to a supramolecular aggregate modified polyurethane damping material and a preparation method thereof. Background Art
[0002] With the vigorous development of fields such as automotive ships, aerospace, electronic appliances, etc., these device equipment will inevitably bring vibration and noise problems during operation. These problems will not only shorten the service life of mechanical parts, affect the measurement accuracy of precision equipment, but also seriously reduce the quality of human life and affect human physical and mental health. In order to reduce the impact brought by vibration and noise, polymer damping materials have emerged. Among them, polyurethane, which has the characteristics of strong structural designability, good controllability in the preparation process, and excellent mechanical properties, has received more and more attention from researchers. However, the glass transition temperature (Tg) of traditional polyurethane is lower than room temperature, resulting in poor damping performance at room temperature and above, and it is difficult to meet the actual use requirements.
[0003] In order to overcome this shortcoming, in the current related technologies, polyurethane materials are usually modified by means of designing IPN interpenetrating networks, hybridizing with organic small molecules, grafting pendant chains, etc. However, the common problem of the above methods is that the synthesis process is complex, the reaction conditions are difficult to control, and the improvement of the damping performance obtained often leads to a decrease in mechanical properties.
[0004] And supramolecular units, as a non-covalent unit system dominated by hydrogen bonds, can form dimers through self-assembly. Introducing them into the polyurethane structure as fillers can endow the polyurethane material with a unique hydrogen bond stacking structure and greatly enhance the internal energy dissipation effect. For example: Qi Feng (Qi Feng, Qin Yuanbo, Di Chunyang, etc. A high-performance polyurethane damping material containing dynamic disulfide bonds and a preparation method thereof [P]. Chinese Patent, 2024) et al. prepared a polyurethane material with damping performance containing dynamic disulfide bonds in the main chain by means of dynamic disulfide bond covalent modification. This material has good dynamic mechanical performance parameters, but the synthesis process is cumbersome, the reaction conditions are harsh, and the content of each component is not easy to regulate.
[0005] Therefore, there is an urgent need to provide a simple, efficient synthesis method that can effectively improve the damping performance of modified polyurethane materials. Summary of the Invention
[0006] The purpose of the present invention is to solve at least one of the technical problems existing in the prior art, and provide a supramolecular aggregate modified polyurethane damping material and a preparation method thereof.
[0007] To achieve the above object, the technical solution adopted by the present invention is as follows: A supramolecular aggregate modified polyurethane damping material is made from the following parts by weight, including 1.3 - 4.6 parts of aliphatic isocyanate monomer, 72 - 79 parts of aromatic isocyanate monomer, 6.4 - 13 parts of polyol with a molecular weight of 600, 100 - 108 parts of polyol with a molecular weight of 1000, 0.8 - 2.9 parts of ureidopyrimidinone monomer, and 13 - 20 parts of chain extender.
[0008] Further, the aliphatic isocyanate monomer is hexamethylene diisocyanate, benzylidene diisocyanate or tetramethyl benzylidene diisocyanate.
[0009] Further, the aromatic isocyanate monomer is 4,4 - diphenylmethane diisocyanate.
[0010] Further, the polyol is polypropylene glycol.
[0011] Further, the ureidopyrimidinone monomer is 2 - amino - 4 - hydroxy - 6 - methylpyrimidine.
[0012] Further, the chain extender is 1,4 - butanediol.
[0013] A preparation method of a supramolecular aggregate modified polyurethane damping material, for preparing the above - mentioned supramolecular aggregate modified polyurethane damping material, the method is as follows:
[0014] S1. After drying a certain mass of ureidopyrimidinone monomer overnight at 80 °C, it is mixed with the aliphatic isocyanate monomer solution in a three - necked flask in proportion, sealed and magnetically stirred. Using argon as a protective gas, the reaction is carried out at 90 °C in an oil bath for 23 - 26 h. After the reaction, it is washed and dried to obtain a preliminary pyrimidinone synthon.
[0015] S2. Add the dehydrated polyol monomer with a molecular weight of 600 into the three - necked flask, add the pyrimidinone synthon obtained in step S1, and add an appropriate amount of dehydrated DMF solution as a solvent. Then, using argon as a protective gas, magnetically stir at 70 °C in a sealed condition for 16 h. After the reaction, the product is centrifuged at high speed to obtain a precipitate - supramolecular derivative. Then, the precipitate is vacuum - dried for more than 24 h and stored in a sealed manner after drying.
[0016] S3. Place the supramolecular derivative obtained in step S2 in a non - polar chloroform solution with a certain concentration to carry out self - assembly growth. The supramolecular derivative uses its own quadruple hydrogen - bond characteristics for self - assembly to obtain a polyurethane - based material with an aggregated structure. Then, pour the static liquid into a glass dish and place it in a vacuum oven at 60 °C for drying treatment. After the solvent evaporates, a paste - like supramolecular derivative is obtained.
[0017] S4. After dehydrating the polyol with a molecular weight of 1000, add it to a three-necked flask together with the aromatic isocyanate monomer in proportion. First, carry out a vacuum mechanical stirring reaction at 50 °C for 1 h, then raise the temperature to 80 °C and react for 3 h, and then stop heating to obtain a polyurethane prepolymer;
[0018] S5. Add the paste-like supramolecular derivative obtained in step S3 to the polyurethane prepolymer in step S4 together with the chain extender in a physically blended manner, and carry out high-speed stirring of the sample at a rotation speed of 700-750 rpm / min for 3-5 min. After the stirring is completed, place the sample in a vacuum drying oven at a temperature of 25 °C and vacuum for 10-15 min. Finally, take out the sample and pour it on a prepared polytetrafluoroethylene mold, and let it level naturally to obtain a supramolecular aggregate-modified polyurethane material with damping performance.
[0019] Further, the self-assembly environment of the supramolecular derivative in step S3 is sealed and constant temperature, the temperature is 25-30 °C, and the reaction time is 7-10 days.
[0020] Further, the addition amount of the paste-like supramolecular derivative in step S5 is 1-5%.
[0021] Compared with the prior art, the technical solution of the present application has the following beneficial effects:
[0022] 1. The preparation process of the present application is simple, easy to operate, and the raw material procurement is convenient and fast.
[0023] 2. The polyurethane material prepared by the present application has reversible dynamic mechanical properties and can provide better damping and vibration reduction performance.
[0024] 3. The polyurethane material prepared by the present application has good plasticity and strong process designability, and can be widely used for the vibration reduction protection of industrial devices. Description of the Drawings
[0025] Figure 1 It is a physical picture of the sample after cutting treatment (the fracture length is about 3 cm and the sample thickness is 4 mm) in the preferred embodiment 2 of the present invention;
[0026] Figure 2 It is a physical picture of the sample after standing at 100 °C for 48 h in the preferred embodiment of the present invention. Detailed Embodiments
[0027] Next, the technical solutions in the present invention will be clearly and completely described in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments.
[0028] Embodiment 1
[0029] A preparation method of a supramolecular aggregate modified polyurethane damping material, and the preparation steps are as follows:
[0030] S1. Take 1.8 parts of 2-amino-4-hydroxy-6-methylpyrimidine, dry it overnight at 80 °C in a vacuum oven, and then mix it with 18 parts of hexamethylene diisocyanate solution in a three-necked flask, seal it and stir magnetically. Using argon as a protective gas, react at 90 °C in an oil bath for 24 h. After the reaction is completed, wash it three times with 1000 mL of n-hexane and then dry it at room temperature in a vacuum oven for 24 h to obtain a preliminary pyrimidinone synthon, and the yield is about 50%;
[0031] S2. Add 4.5 parts of dehydrated polyol monomer with a molecular weight of 600 to a three-necked flask, add the pyrimidinone synthon synthesized in step S1, add 100 mL of dehydrated DMF solution as a solvent, and then use argon as a protective gas. Under sealed conditions, stir magnetically at 70 °C in an oil bath for 16 h. After the reaction is completed, centrifuge the product three times with 3000 mL of deionized water. The final lower-layer precipitate is the supramolecular derivative, which is dried in a vacuum at room temperature for 24 h and then stored sealed;
[0032] S3. Place the derivative obtained in step S2 in an aqueous solution of chloroform at 0.1 g / L for 7 days to allow self-assembly growth. Ensure that the self-assembly environment of the derivative is sealed and at a constant temperature, and the optimum temperature is controlled at 25 °C. After 7 days, pour the static solution into a glass dish and place it in a vacuum oven for drying at 60 °C for 2 h. The paste product obtained after the solvent evaporates is the required supramolecular aggregate, which is reserved;
[0033] S4. Add 100 parts of dehydrated polyol with a molecular weight of 1000 and 75 parts of aromatic isocyanate monomer to a three-necked flask and stir evenly. First, carry out mechanical stirring reaction under vacuum at 50 °C in an oil bath for 1 h, then raise the temperature to 80 °C and react for 3 h, and then stop heating to obtain a polyurethane prepolymer;
[0034] S5. Add the paste-like supramolecular derivative cultured in step S3 to the polyurethane matrix by physical blending together with 17 parts of chain extender, and then use mechanical stirring to carry out high-speed stirring on the sample system at a speed of 700 rpm / min for 3 min. After the stirring is completed, place the polyurethane sample in a vacuum drying oven for vacuum operation. The vacuum operation time is 10 min, and the temperature is controlled at 25 °C. Then take out the sample, pour it on a prepared polytetrafluoroethylene mold, level it naturally, cure it in an oven at 80 °C for 24 h, and then cure it at room temperature for 7 days. The addition amount of the supramolecular derivative is about 1% to prepare a supramolecular aggregate modified polyurethane material with damping performance.
[0035] Example 2
[0036] A preparation method of a supramolecular aggregate modified polyurethane damping material, the preparation steps are as follows:
[0037] S1. Take 2.0 parts of 2-amino-4-hydroxy-6-methylpyrimidine, dry it overnight at 80 °C in a vacuum oven, then mix it with 20 parts of hexamethylene diisocyanate solution in a three-necked flask, seal it and stir magnetically. Using argon as a protective gas, react at 90 °C in an oil bath for 24 h. After the reaction is completed, wash it three times with 1100 mL of n-hexane and then dry it at room temperature in a vacuum oven for 24 h to obtain a preliminary pyrimidinone synthon, and the yield is about 50%;
[0038] S2. Add 5.5 parts of dehydrated polyol monomer with a molecular weight of 600 to a three-necked flask, add the pyrimidinone synthon synthesized in step S1, add 100 mL of dehydrated DMF solution as a solvent, and then use argon as a protective gas. Under sealed conditions, stir magnetically at 70 °C in an oil bath for 16 h. After the reaction is completed, centrifuge the product three times with 3000 mL of deionized water. The final lower layer precipitate is the supramolecular derivative, which is dried in a vacuum at room temperature for 24 h and then stored sealed;
[0039] S3. Place the derivative obtained in step S2 in an aqueous solution of chloroform at 0.1 g / L for 8 days to allow self-assembly growth. Ensure that the self-assembly environment of the derivative is sealed and at a constant temperature, and the optimum temperature is controlled at 27 °C. After 8 days, pour the standing solution into a glass dish and place it in a vacuum oven for drying at 60 °C for 2 h. The paste product obtained after the solvent evaporates is the required supramolecular aggregate, which is reserved;
[0040] S4. Add 105 parts of dehydrated polyol with a molecular weight of 1000 and 78 parts of aromatic isocyanate monomer to a three-necked flask and stir evenly. First, carry out a vacuum mechanical stirring reaction at 50 °C in an oil bath for 1 h, then raise the temperature to 80 °C and react for 3 h, and then stop heating to obtain a polyurethane prepolymer;
[0041] S5. Add the paste-like supramolecular derivative cultured in step S3 and 19 parts of chain extender to the polyurethane matrix in a physically blended manner, and then use mechanical stirring to carry out high-speed stirring on the sample system at a speed of 720 rpm / min for 4 min. After the stirring is completed, place the polyurethane sample in a vacuum drying oven for vacuum operation. The vacuum operation time is 10 min, and the temperature is controlled at 25 °C. Then take out the sample, pour it on a prepared polytetrafluoroethylene mold, level it naturally, cure it in an oven at 80 °C for 24 h, and then cure it at room temperature for 7 days. The addition amount of the supramolecular derivative is about 3% to prepare a supramolecular aggregate modified polyurethane material with damping performance.
[0042] Example 3
[0043] A preparation method of a supramolecular aggregate modified polyurethane damping material, the preparation steps are as follows:
[0044] S1. Take 5.2 parts of 2-amino-4-hydroxy-6-methylpyrimidine, dry it overnight at 80 °C in a vacuum oven, and then mix it with 52 parts of hexamethylene diisocyanate solution in a three-necked flask, seal it and stir magnetically. Using argon as a protective gas, react at 90 °C in an oil bath for 24 h. After the reaction is completed, wash it three times with 2500 mL of n-hexane and then dry it at room temperature in a vacuum oven for 24 h to obtain a preliminary pyrimidinone synthon, and the yield is about 50%;
[0045] S2. Add 12.8 parts of dehydrated polyol monomer with a molecular weight of 600 to a three-necked flask, add the pyrimidinone synthon synthesized in step S1, add 220 mL of dehydrated DMF solution as a solvent, and then use argon as a protective gas. Under sealed conditions, stir magnetically at 70 °C in an oil bath for 16 h. After the reaction is completed, centrifuge the product three times with 6000 mL of deionized water. The final lower layer precipitate is the supramolecular derivative, which is vacuum dried at room temperature for 24 h and then stored sealed;
[0046] S3. Place the derivative obtained in step S2 in an aqueous chloroform solution of 0.1 g / L for 10 days to allow self-assembly growth. Ensure that the self-assembly environment of the derivative is sealed and at a constant temperature, and the optimum temperature is controlled at 30 °C. After 10 days, pour the standing liquid into a glass dish and place it in a vacuum oven for drying at 60 °C for 2 h. The paste product obtained after the solvent evaporates is the required supramolecular aggregate, which is reserved;
[0047] S4. Add 105 parts of dehydrated polyol with a molecular weight of 1000 and 77 parts of aromatic isocyanate monomer to a three-necked flask and stir evenly. First, carry out vacuum mechanical stirring reaction at 50 °C in an oil bath for 1 h, then raise the temperature to 80 °C and react for 3 h, and then stop heating to obtain a polyurethane prepolymer;
[0048] S5. Add the paste-like supramolecular derivative cultured in step S3 together with 18 parts of chain extender to the polyurethane matrix in a physical blending manner, and then use mechanical stirring to carry out high-speed stirring on the sample system at a speed of 750 rpm / min for 5 min. After the stirring is completed, place the polyurethane sample in a vacuum drying oven for vacuuming. The vacuuming time is 10 min, and the temperature is controlled at 25 °C. Then take out the sample, pour it on a prepared polytetrafluoroethylene mold, let it level naturally, cure it in an 80 °C oven for 24 h, and then cure it at room temperature for 7 days. The addition amount of the supramolecular derivative is about 5% to prepare a supramolecular aggregate modified polyurethane material with damping performance.
[0049] Comparative Example 1
[0050] A preparation method of a polyurethane damping material, the preparation steps are as follows:
[0051] S1. After dehydrating 100 parts of polyol with a molecular weight of 1000, add it to a three-necked flask together with 75 parts of aromatic isocyanate monomer and stir evenly. First, carry out mechanical stirring reaction under vacuum at 50 °C in an oil bath for 1 h, then raise the temperature to 80 °C and react for 3 h, and then stop heating to obtain a polyurethane prepolymer;
[0052] S2. Directly add 17 parts of chain extender to the prepolymer, stir evenly, defoam more than 2 times, 15 minutes each time, then place it in an oven at 80 °C for curing for 24 h, and then cure at room temperature for 7 days, so as to obtain a polyurethane material of a comparative example with the same other conditions as in Examples 1, 2, and 3, only excluding the influence of supramolecular aggregate modification.
[0053] Performance Test
[0054] Use a DMA + 1000 dynamic thermomechanical analyzer to conduct dynamic mechanical property tests on the polyurethane samples of Examples 1, 2, 3 and Comparative Example 1. It can be seen from the tests that the relevant parameters of the dynamic mechanical properties in the free stretching mode refer to Table 1. It can be clearly seen from Table 1 that the temperature range corresponding to the effective loss factor of the polyurethane material modified by supramolecular aggregates becomes wider, and the peak value of the loss factor has been significantly increased, which proves that the damping performance of the polyurethane material modified by this method has been significantly improved.
[0055] Table 1 Test data of effective damping temperature range
[0056] Test items Effective damping temperature range (tanδ≥0.3) Peak loss factor (tanδmax) Example 1 4.1℃～55.0℃ 1.12 Example 2 3.2℃～58.0℃ 1.23 Example 3 5.9℃～53.0℃ 1.16 Comparative example 1 14.2℃～47.0℃ 0.64
[0057] Use an INSTRON-3365 universal tensile testing machine to conduct conventional mechanical property tests on the polyurethane samples of Examples 1, 2, 3 and Comparative Example 1. It can be seen from the tests that the relevant parameters of the tensile strength and elongation at break in the free stretching mode refer to Table 2. It can be clearly seen from Table 2 that the tensile strength of the polyurethane material modified by supramolecular aggregates has been significantly increased, and the elongation at break has also been significantly improved, which proves that the toughness of the polyurethane material modified by this method has also been significantly improved.
[0058] Table 2 Test data of tensile performance and effective damping temperature range
[0059] Test items Tensile strength (MPa) Elongation at break (%) Example 1 9.1 610 Example 2 10.1 690 Example 3 9.4 635 Comparative example 1 6.5 450
[0060] By cutting the sample of Example 2, then splicing the fracture surfaces together, and standing still in an environment of 100 °C for 48 h, it can be seen from Figure 1, 2 It was observed that the fracture of the sample of Example 1 was self-healed, and the scratch became visibly shallower to the naked eye, proving that the supramolecular aggregate-modified polyurethane material has certain self-healing properties.
[0061] On the premise of no conflict, those skilled in the art can freely combine and superimpose the above additional technical features.
[0062] It can be understood that the present invention is described through some embodiments. As is known to those skilled in the art, without departing from the spirit and scope of the present invention, various changes or equivalent substitutions can be made to these features and embodiments. Additionally, under the teaching of the present invention, these features and embodiments can be modified to adapt to specific situations and materials without departing from the spirit and scope of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed herein, and all embodiments falling within the scope of the claims of this application belong to the scope protected by the present invention.
Claims
1. A supramolecular aggregate modified polyurethane damping material, characterized in that, It is made from the following parts by weight, including 1.3 - 4.6 parts of aliphatic isocyanate monomer, 72 - 79 parts of aromatic isocyanate monomer, 6.4 - 13 parts of 600 - molecular - weight polyol, 100 - 108 parts of 1000 - molecular - weight polyol, 0.8 - 2.9 parts of ureidopyrimidinone monomer, and 13 - 20 parts of chain extender.
2. The supramolecular aggregate modified polyurethane damping material according to claim 1, wherein: The aliphatic isocyanate monomer is hexamethylene diisocyanate, xylylene diisocyanate or tetramethylxylylene diisocyanate.
3. The supramolecular aggregate-modified polyurethane damping material according to claim 1, wherein: The aromatic isocyanate monomer is 4,4 - diphenylmethane diisocyanate.
4. The supramolecular aggregate modified polyurethane damping material according to claim 1, wherein: The polyol is polypropylene glycol.
5. The supramolecular aggregate modified polyurethane damping material according to claim 1, characterized in that: The ureidopyrimidinone monomer is 2 - amino - 4 - hydroxy - 6 - methylpyrimidine.
6. The supramolecular aggregate modified polyurethane damping material according to claim 1, wherein: The chain extender is 1,4 - butanediol.
7. A preparation method of a supramolecular aggregate modified polyurethane damping material, characterized in that: To prepare the supramolecular aggregate - modified polyurethane damping material according to any one of claims 1 - 6, the method is as follows: S1. After drying a certain mass of ureidopyrimidinone monomer overnight at 80 °C, it is mixed with an aliphatic isocyanate monomer solution in a three - necked flask in proportion, sealed and magnetically stirred. Using argon as a protective gas, the reaction is carried out in an oil bath at 90 °C for 23 - 26 h. After the reaction, it is washed and dried to obtain a preliminary pyrimidinone synthon. S2. The dehydrated 600 - molecular - weight polyol monomer is added into the three - necked flask, the pyrimidinone synthon obtained in step S1 is added, and an appropriate amount of dehydrated DMF solution is added as a solvent. Then, using argon as a protective gas, under sealed conditions, it is magnetically stirred at 70 °C in an oil bath for 16 h. After the reaction, the product is centrifuged at high speed to obtain a precipitate - supramolecular derivative. Then the precipitate is vacuum - dried for more than 24 h and stored in a sealed manner after drying. S3. The supramolecular derivative obtained in step S2 is placed in a non - polar chloroform solution with a certain concentration to carry out self - assembly growth. The supramolecular derivative self - assembles using its own quadruple hydrogen - bond characteristics to obtain a polyurethane - based material with an aggregated structure. Then the static liquid is poured into a glass dish and placed in a vacuum oven for drying at 60 °C. After the solvent evaporates, a paste - like supramolecular derivative is obtained. S4. After dehydrating the 1000 - molecular - weight polyol, it is added into the three - necked flask with the aromatic isocyanate monomer in proportion. First, it is vacuum - mechanically stirred at 50 °C for 1 h, then heated to 80 °C and reacted for 3 h, and then the heating is stopped to obtain a polyurethane prepolymer. S5. The paste - like supramolecular derivative obtained in step S3 is added to the polyurethane prepolymer in step S4 by physical blending together with the chain extender, and the sample is vigorously stirred at a speed of 700 - 750 rpm / min for 3 - 5 min. After stirring, the sample is placed in a vacuum drying oven at 25 °C and evacuated for 10 - 15 min. Finally, the sample is taken out and poured onto a prepared polytetrafluoroethylene mold, and it naturally levels to obtain a supramolecular aggregate - modified polyurethane material with damping performance.
8. The preparation method of the supramolecular aggregate modified polyurethane damping material according to claim 7, characterized in that: The self - assembly environment of the supramolecular derivative in step S3 is sealed and at a constant temperature, and this temperature is 25 - 30 °C, and the reaction time is 7 - 10 days.
9. The preparation method of the supramolecular aggregate modified polyurethane damping material according to claim 7, characterized in that: The addition amount of the paste - like supramolecular derivative in step S5 is 1 - 5%.