Supramolecular aggregate modified vinyl resin material and preparation method thereof
By modifying vinyl resin materials through supramolecular aggregates, self-assembly of aliphatic isocyanate monomers and other compositions to form a non-covalent hydrogen bond structure, solving the toughness and energy consumption problems of traditional vinyl resin materials, and achieving high-performance damping and vibration-resistance and impact resistance.
Patent Information
- Application Number
- CN202510569842.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-05
- Publication Date
- 2025-07-22
AI Technical Summary
Traditional vinyl resin materials have poor toughness, and their energy consumption performance at room temperature and above are poor, making it difficult to meet the usage requirements in different environments, and the synthesis process is cumbersome and difficult to industrialize.
The self-assembly of supramolecular derivatives is used to form a non-covalent hydrogen bond structure by combining aliphatic isocyanate monomers, urea pyrimidinone monomers, curing agents and accelerators and vinyl resins, and self-assembly of supramolecular derivatives is used to form a non-covalent hydrogen bond structure to enhance the toughness and energy consumption performance of the material.
The prepared vinyl resin material has reversible dynamic mechanical properties, provides good damping and vibration damping performance, excellent impact toughness, and is suitable for applications in many fields.
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Figure CN120349624A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of functional materials, and in particular to a supramolecular aggregate modified vinyl resin material and a preparation method thereof. Background Art
[0002] As a polymer material with fiber-reinforced structure, vinyl resin has been widely developed and applied in the fields of automobiles, ships, aerospace, electronics and electrical appliances in recent years. Its unique multi-level structure not only brings excellent mechanical strength, but also has the characteristics of highly free design of internal space, good controllability of synthesis process, and strong and excellent comprehensive mechanical properties, which has led more and more researchers to conduct in-depth research and exploration on this material system. However, the internal structure of traditional vinyl resin materials is relatively simple. Due to the lack of flexible molecular chain groups and reversible intermolecular interaction force units, the toughness of the material is generally poor. In addition, due to the weak movement friction of the molecular chain, its energy consumption performance at room temperature and above is poor, which makes it difficult to meet the use requirements in different environments.
[0003] In order to overcome this shortcoming, in the current related technologies, vinyl resin materials are usually modified by designing IPN interpenetrating networks, introducing various polar groups, and accessing hanging chain modifications. For example, Bai Guodong (Bai Guodong, Wei Hanhui, Zhao Weiguo, Sun Jiakuan. A method for preparing a modified vinyl ester resin [P]. Chinese Patent, 2023) et al. used linear polydimethylsiloxane with an epoxy functional group as the modified reactive site, and synthesized a modified silicone oil with an isocyanate group as the terminal group to react with the vinyl ester resin. The prepared material has good mechanical properties, but the performance parameters related to the toughness of the material are still relatively low, and the low energy consumption phenomenon has not been solved. In addition, the synthesis process of the material is cumbersome, the reaction conditions are harsh, the content of each component is not easy to control, and it is difficult to carry out large-scale industrial production. Therefore, it is urgent to provide a simple and efficient method for synthesizing modified vinyl resin materials. Summary of the invention
[0004] The purpose of the present invention is to solve at least one of the technical problems existing in the prior art and to provide a supramolecular aggregate modified vinyl resin material and a preparation method thereof.
[0005] To achieve the above-mentioned purpose, the technical scheme adopted by the present invention is as follows: a supramolecular aggregate modified vinyl resin material, composed of the following raw materials in parts by weight: 1.3 to 4.6 parts of aliphatic isocyanate monomer, 5 to 15 parts of small molecule polyol, 0.8 to 2.9 parts of ureidopyrimidone monomer, 1 to 3 parts of curing agent, 50 to 100 parts of vinyl resin, and 0.5 to 2.3 parts of accelerator.
[0006] Further, the aliphatic isocyanate monomer is hexamethylene diisocyanate, xylylene diisocyanate or tetramethyl xylylene diisocyanate.
[0007] Further, the small molecule polyol is 4-methylbenzyl alcohol and n-butanol.
[0008] Further, the ureidopyrimidinone monomer is 2-amino-4-hydroxy-6-methylpyrimidine.
[0009] Further, the curing agent is curing agent M50.
[0010] Further, the accelerator is accelerator 1350.
[0011] A preparation method of a supramolecular aggregate modified vinyl resin material, for preparing the above-mentioned supramolecular aggregate modified vinyl resin material, the method is as follows:
[0012] 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, and reacted at 90 °C in an oil bath for 23-26 h with argon as the protective gas. After the reaction is completed, it is washed and dried to obtain a preliminary pyrimidinone synthon;
[0013] S2. Add the dehydrated small molecule polyol monomer into the three-necked flask, add the pyrimidinone synthon obtained in step S1 in proportion, add an appropriate amount of dehydrated DMF solution as a solvent, and then use argon as the protective gas. Under sealed conditions, magnetically stir at 70 °C for 16 h with an oil bath. After the reaction is completed, the product is centrifuged at high speed to obtain a precipitate - a supramolecular derivative; then the precipitate is vacuum dried for more than 24 h and stored in a sealed manner after drying;
[0014] 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 vinyl resin-based material with an aggregated structure. Then pour the standing liquid into a glass dish and place it in a vacuum oven at 60 °C for drying treatment. After the solvent volatilizes, a paste-like supramolecular derivative is obtained;
[0015] S4. Add the paste-like supramolecular derivative cultured in step S3 to the vinyl resin matrix by physical blending together with the accelerator, and then stir the sample at a speed of 700-750 rpm / min for 3-5 min. Add the curing agent to the stirred vinyl resin sample for secondary stirring, and then place it in a vacuum drying oven to evacuate for 2-5 min at a temperature of 25 °C. Finally, take out the sample, pour it on a prepared polytetrafluoroethylene mold, and let it level naturally to obtain a supramolecular aggregate modified vinyl resin material with damping performance.
[0016] Further, the self-assembly environment of the supramolecular derivative in step S3 is sealed and at a constant temperature, the temperature is 25-30 °C, and the reaction time is 7-10 days.
[0017] Further, the addition amount of the paste-like supramolecular derivative in step S4 is 1-5%.
[0018] Compared with the prior art, the technical solution of the present application has the following beneficial effects:
[0019] 1. The preparation process of the present application is simple, easy to operate, and the raw materials are convenient and fast to purchase.
[0020] 2. The vinyl resin material prepared by the present application has reversible dynamic mechanical properties and can provide good damping and vibration reduction performance.
[0021] 3. The vinyl resin material prepared by the present application has good mechanical properties, and the impact toughness of the material is very excellent, and it can be widely used as a high-performance functional material in various fields. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 It is a physical diagram after the sample of Example 2 is cut and processed (the fracture length is about 1 cm, and the sample thickness is 4 mm);
[0023] Figure 2 It is a physical diagram of the sample of Example 2 after standing at 100 °C for 48 h. DETAILED DESCRIPTION OF THE INVENTION
[0024] The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying 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 of the embodiments.
[0025] As a non-covalent unit system dominated by hydrogen bonds, the supramolecular unit can form dimers through self-assembly. Introducing it into the structure of vinyl resin as a filler can endow the polymer material with a unique hydrogen bond stacking structure. The introduction of this group can endow the material with a large number of non-covalent interactions, while strengthening the toughness of the material, greatly enhancing the internal energy dissipation effect; based on this idea, it is of great research significance to design and prepare a simple and efficient supramolecular aggregate-modified vinyl resin material that can effectively improve toughness and energy consumption.
[0026] Example 1
[0027] A preparation method of a supramolecular aggregate-modified vinyl resin material, the preparation steps are as follows:
[0028] S1. Take 1.8 parts of 2-amino-4-hydroxy-6-methylpyrimidine, dry it overnight at 80 °C in a vacuum oven, then mix it with 18 parts of hexamethylene diisocyanate solution in a three-necked flask, seal it and stir magnetically. React at 90 °C in an oil bath for 24 h with argon as the protective gas. 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, with a yield of approximately 50%;
[0029] S2. Add 5 parts of dehydrated small molecule polyol monomer into a three-necked flask, add the pyrimidinone synthon synthesized in step S1, add 100 mL of dehydrated DMF solution as the solvent, and then use argon as the protective gas. Stir magnetically at 70 °C in an oil bath under sealed conditions 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 vacuum dried at room temperature for 24 h and then stored in a sealed manner;
[0030] S3. Place the derivative obtained in step S2 in an aqueous chloroform solution of 0.15 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 optimal temperature is controlled at 25 °C. After 7 days, pour the static 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 for use;
[0031] S4. Add the paste-like supramolecular derivative cultured in step S3 and the accelerator to 70 parts of vinyl resin matrix in a physically blended manner, with an addition amount of about 1.5%. Then, use mechanical stirring to stir the sample system at a speed of 700 rpm / min for 3 min. Add 2 parts of M50 curing agent to the stirred vinyl resin sample and perform secondary mechanical stirring under the same operating conditions as the first time. Then, place the sample in a vacuum drying oven for vacuum pumping to remove possible bubbles in the material system. The vacuum pumping operation time is 2 min and the temperature is 25 °C. Then, take out the sample, pour it onto a prepared polytetrafluoroethylene mold, let it level naturally, cure it at 80 °C in a high-temperature oven for 24 h, and then let it stand at room temperature for 7 days to prepare a multifunctional supramolecular aggregate modified vinyl resin material.
[0032] Example 2
[0033] A preparation method of a supramolecular aggregate modified vinyl resin material, the preparation steps are as follows:
[0034] 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. React at 90 °C in an oil bath for 24 h with argon as the protective gas. After the reaction, 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, with a yield of approximately 50%;
[0035] S2. Add 5.5 parts of dehydrated small molecule polyol monomer into a three-necked flask, add the pyrimidinone synthon synthesized in step S1, add 100 mL of dehydrated DMF solution as the solvent, and then use argon as the protective gas. Stir magnetically at 70 °C in an oil bath under sealed conditions for 16 h. After the reaction, 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;
[0036] S3. Place the derivative obtained in step S2 in an aqueous chloroform solution of 0.15 g / L for 8 days to allow self-assembly growth. Ensure that the self-assembly environment of the derivative is sealed and constant temperature, and the optimal temperature is controlled at 27 °C. After 8 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 volatilizes is the required supramolecular aggregate, which is reserved for use;
[0037] S4. Add the paste-like supramolecular derivative cultured in step S3 to 75 parts of vinyl resin matrix by physical blending together with a promoter, with an addition amount of about 2%. Then, use mechanical stirring to stir the sample system at a speed of 720 rpm / min for 4 min. Add 2.3 parts of M50 curing agent to the stirred vinyl resin sample and perform secondary mechanical stirring under the same operating conditions as the first time. Then, place the sample in a vacuum drying oven for vacuuming to remove possible bubbles in the material system. The vacuuming operation time is 3 min and the temperature is 25 °C. Then, take out the sample, pour it on a prepared polytetrafluoroethylene mold, let it level naturally, cure it at 80 °C in a high-temperature oven for 24 h, and then let it stand at room temperature for 7 days to prepare a multifunctional supramolecular aggregated modified vinyl resin material.
[0038] Example 3
[0039] A preparation method of a supramolecular aggregated modified vinyl resin material, and its preparation steps are as follows:
[0040] S1. Take 5.2 parts of 2-amino-4-hydroxy-6-methylpyrimidine, dry it overnight at 80 °C in a vacuum oven, then mix it with 52 parts of hexamethylene diisocyanate solution in a three-necked flask, seal it and stir magnetically. React at 90 °C in an oil bath with argon as the protective gas for 24 h. After the reaction, 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 the preliminary pyrimidinone synthon, with a yield of approximately 50%;
[0041] S2. Add 12.8 parts of dehydrated small molecule polyol monomer into a three-necked flask, add the pyrimidinone synthon synthesized in step S1, add 220 mL of dehydrated DMF solution as the solvent, and then use argon as the protective gas. Stir magnetically at 70 °C in an oil bath under sealed conditions for 16 h. After the reaction, centrifuge the product three times with 6000 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;
[0042] S3. Place the derivative obtained in step S2 in an aqueous chloroform solution of 0.15 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 optimal temperature is controlled at 30 °C. After 10 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 for use;
[0043] S4. Add the paste-like supramolecular derivative cultured in step S3 and the promoter together into 98 parts of vinyl resin matrix in a physically blended manner, with an addition amount of about 3%. Then, use mechanical stirring to stir the sample system at a speed of 720 rpm / min for 4 min. Add 2.5 parts of M50 curing agent to the stirred vinyl resin sample for secondary mechanical stirring, with the operating conditions being the same as the first time. Then, place the sample in a vacuum drying oven for vacuum pumping to remove the possible bubbles in the material system. The vacuum pumping operation time is 4 min, and the temperature is 25 °C. Then, take out the sample, pour it on a polytetrafluoroethylene mold, let it level naturally, cure it at 80 °C in a high-temperature oven for 24 h, and then let it stand at room temperature for 7 days to prepare the multifunctional supramolecular aggregate modified vinyl resin material.
[0044] Comparative Example 1
[0045] A preparation method of a vinyl resin material, and its preparation steps are as follows:
[0046] S1. Add 1.5 parts of accelerator to 95 parts of vinyl resin matrix. Subsequently, use mechanical stirring to carry out high-speed stirring on the sample system at a speed of 700 rpm / min for 2 min. Add 2.2 parts of M50 curing agent to the stirred vinyl resin sample and conduct secondary mechanical stirring with the same operating conditions as the first time. Then place the sample in a vacuum drying oven for vacuum pumping to remove possible bubbles in the material system. The vacuum pumping operation time is 4 min and the temperature is 25 °C. Then take out the sample, pour it on a polytetrafluoroethylene mold, let it level naturally, cure it in a high-temperature oven at 80 °C for 24 h, and then let it stand at room temperature for 7 days to prepare an unmodified vinyl resin material. In this way, a comparative material is obtained, with all other conditions being the same as those in Examples 1, 2, and 3, only excluding the influence of supramolecular aggregate modification.
[0047] Performance Test
[0048] Use an FBS-5 / 5SJ pendulum impact testing machine to conduct performance tests on the impact toughness of the vinyl resin samples in Examples 1, 2, 3, and Comparative Example 1. It can be seen from the tests that the relevant parameters of the impact toughness of the materials refer to Table 1. It can be clearly seen from Table 1 that the impact toughness of the vinyl resin material modified by supramolecular aggregates has been significantly enhanced, which proves that the toughness of the vinyl resin material modified by this method has been significantly improved.
[0049] Table 1 Impact Toughness Test Data
[0050] Test Items Impact Toughness (KJ / m2) Example 1 5.1 Example 2 5.8 Example 3 6.1 Comparative Example 1 2.4
[0051] Use an INSTRON-3365 universal testing machine to conduct conventional mechanical property tests on the vinyl resin samples in Examples 1, 2, 3, and Comparative Example 1. It can be seen from the tests that the maximum stress-strain parameters corresponding to the stress yield point in the compression mode refer to Table 2. It can be clearly seen from Table 2 that the mechanical strength of the vinyl material modified by supramolecular aggregates has not decreased significantly with the introduction of the modification groups. On the contrary, the corresponding strain has been strengthened, which proves that the mechanical strength of the vinyl resin material modified by this method is also guaranteed.
[0052] Table 2 Stress-Strain Test Data in Compression Mode
[0053]
[0054]
[0055] The dynamic mechanical properties of the vinyl resin samples of Examples 1, 2, 3 and Comparative Example 1 were tested using a DMA+1000 dynamic thermomechanical analyzer. Through testing, it can be seen that the relevant parameters of the dynamic mechanical properties in the free stretching mode refer to Table 3. It can be clearly seen from Table 3 that the temperature range corresponding to the effective loss factor of the supramolecular aggregate-modified vinyl resin material becomes wider, and the peak value of the loss factor has been significantly increased, which proves that the damping performance of the vinyl resin material modified by this method has been significantly improved.
[0056] Table 3 Test data of effective damping temperature range
[0057] Test Items Effective Damping Temperature Range (tanδ≥0.3) Peak Loss Factor (tanδmax) Example 1 60.1℃～111.2℃ 1.12 Example 2 58.2℃～110.1℃ 1.15 Example 3 55.4℃～103.2℃ 1.21 Comparative Example 1 68.2℃～112.2℃ 1.01
[0058] By cutting the sample of Example 2 and then splicing the fracture surfaces together, after standing for 48 h at 100 °C, it can be observed from Figure 1 、 2 that the fracture surface of the sample of Example 1 has self-healed, and the scratches have visibly become shallower to the naked eye, proving that the supramolecular aggregate-modified vinyl resin material has certain self-healing properties.
[0059] On the premise of no conflict, those skilled in the art can freely combine and superimpose the above additional technical features.
[0060] It can be understood that the present invention is described by some embodiments. Those skilled in the art know that without departing from the spirit and scope of the present invention, various changes or equivalent replacements can be made to these features and embodiments. In addition, 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 vinyl resin material, characterized in that, It consists of the following raw materials in parts by weight: 1.3 - 4.6 parts of aliphatic isocyanate monomer, 5 - 15 parts of small molecule polyol, 0.8 - 2.9 parts of ureidopyrimidinone monomer, 1 - 3 parts of curing agent, 50 - 100 parts of vinyl resin, and 0.5 - 2.3 parts of accelerator.
2. The supramolecular aggregate-modified vinyl resin material according to claim 1, wherein: The aliphatic isocyanate monomer is hexamethylene diisocyanate, xylylene diisocyanate or tetramethyl xylylene diisocyanate.
3. The supramolecular aggregate-modified vinyl resin material according to claim 1, wherein: The small molecule polyol is 4-methylbenzyl alcohol and n-butanol.
4. The supramolecular aggregate modified vinyl resin material according to claim 1, characterized in that: The ureidopyrimidinone monomer is 2-amino-4-hydroxy-6-methylpyrimidine.
5. The supramolecular aggregate-modified vinyl resin material according to claim 1, characterized in that: The curing agent is curing agent M50.
6. The supramolecular aggregate-modified vinyl resin material according to claim 1, wherein: The accelerator is accelerator 1350.
7. A preparation method of a supramolecular aggregate-modified vinyl resin material, characterized in that: To prepare the supramolecular aggregate modified vinyl resin material described in 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 the aliphatic isocyanate monomer solution in a three-necked flask in proportion, sealed and magnetically stirred. Using argon as the 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. S2. The dehydrated small molecule polyol monomer is added into the three-necked flask, and the pyrimidinone synthon obtained in step S1 is added in proportion. An appropriate amount of dehydrated DMF solution is added as a solvent, and then, using argon as the protective gas, it is magnetically stirred at 70°C in a sealed condition for 16 h. After the reaction, the product is subjected to high-speed centrifugation 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 vinyl resin-based material with an aggregated structure. Then the standing liquid is poured into a glass dish and placed in a vacuum oven at 60°C for drying treatment. After the solvent evaporates, a paste-like supramolecular derivative is obtained. S4. The paste-like supramolecular derivative cultured in step S3 is added to the vinyl resin matrix by physical blending together with the accelerator. Then the sample is stirred at a high speed at 700 - 750 rpm / min for 3 - 5 min. After the stirring is completed, the vinyl resin sample is added with the curing agent for secondary stirring, and then placed in a vacuum drying oven to evacuate for 2 - 5 min at a temperature of 25°C. Finally, the sample is taken out and poured onto a prepared polytetrafluoroethylene mold to level naturally, and a supramolecular aggregate modified vinyl resin material with damping performance is prepared.
8. The preparation method of the supramolecular aggregate modified vinyl resin material according to claim 7, characterized in that: In step S3, the self-assembly environment of the supramolecular derivative 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 vinyl resin material according to claim 7, characterized in that: In step S4, the addition amount of the paste-like supramolecular derivative is 1 - 5%.
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