Polyurethane elastomer composite material with high toughness and good elasticity and preparation method thereof
By combining magnesium lithium silicate modified with adipic dihydrazide with polyurethane elastomer, hydrogen bonds and crack deflection effects are formed, which solves the problem of insufficient strength and toughness of polyurethane materials and realizes a polyurethane composite material with high strength and high elasticity.
Patent Information
- Application Number
- CN202511449586.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-11
- Publication Date
- 2025-12-09
AI Technical Summary
The performance of pure lithium magnesium silicate modified polyurethane in the current technology still needs to be further improved, especially in terms of mechanical properties, it is difficult to improve the strength and toughness of the material at the same time.
Magnesium lithium silicate modified with adipic acid dihydrazide is composited with polyurethane elastomer. By forming dense hydrogen bonds and connecting multiple amide urea and urethane moieties, combined with the crack deflection effect of nano-magnesium lithium silicate, the strength and toughness of the composite material are improved.
It significantly improves the tensile strength and fracture energy dissipation of polyurethane elastomers while maintaining good elasticity, thus enhancing the overall performance of the material.
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Figure CN121086512A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to a kind of high tough and good elasticity polyurethane elastomer composite material and its preparation method, belong to polyurethane technical field. BACKGROUND
[0002] Polyurethane is a multifunctional multipurpose synthetic polymer material, with its excellent physical and chemical properties is widely used in many fields of national economy.Polyurethane is usually made of oligomer polyol, polyisocyanate and chain extender / crosslinker, its product covers foam plastic, synthetic rubber, plastic, paint, adhesive and many synthetic material fields, is polyethylene, polypropylene, polystyrene, etc High polymer synthetic material is incomparable.At present, how to improve the mechanical properties of polyurethane elastomer is still one of the research hotspots.
[0003] Modifying polyurethane elastomer is one of the methods to improve its mechanical properties, in order to expand the application range of polyurethane material, improve the mechanical properties of polyurethane, add nanometer magnesium lithium silicate filler in polyurethane material, magnesium lithium silicate as a nanoscale layered silicate material, nano clay particles interact with the functional groups of polyurethane, can improve the mechanical properties of polyurethane composite material.However, the performance of pure magnesium lithium silicate modified polyurethane still needs to be further improved. SUMMARY
[0004] Therefore, the purpose of the present application is to provide a kind of high tough and good elasticity polyurethane elastomer composite material and its preparation method.Adjusted magnesium lithium silicate modified by adipic acid dihydrazide modified polyurethane elastomer, both hydrogen bond interface can be maximized and can be efficiently consumed by reversible hydrogen bond rupture and crack deflection, to improve the strength and toughness of composite material, while the composite material also has good elasticity.
[0005] To achieve the above purpose, the technical scheme of the present application is as follows.
[0006] A kind of high tough and good elasticity polyurethane elastomer composite material is obtained by adipic acid dihydrazide modified magnesium lithium silicate modified polyurethane elastomer; The addition amount of adipic acid dihydrazide modified magnesium lithium silicate is 0.3%~0.7% of the mass of polyurethane elastomer;More preferably, it is 0.5%~0.6%; In adipic acid dihydrazide modified magnesium lithium silicate, magnesium lithium silicate is 1.5%~2.5% of the mass of adipic acid dihydrazide; Polyurethane elastomer is obtained by curing viscous polyurethane prepolymer and hydrazide chain extender;Viscous polyurethane prepolymer is obtained by stirring diisocyanate and polyol at 80~85℃ for 4~5h; The molar ratio of diisocyanate, polyol and hydrazide chain extender is 2~2.1:1:1.
[0007] Preferably, the adipic acid dihydrazide modified magnesium lithium silicate is prepared by the following method, the method steps comprising: dispersing magnesium lithium silicate and adipic acid dihydrazide in water, centrifuging at 8000-9000 r / min for 5-10 min, discarding the supernatant after centrifugation, repeating the centrifugation for 5-6 times, collecting the solid and drying at 75-80℃ to obtain the adipic acid dihydrazide modified magnesium lithium silicate. More preferably, the ratio of the amount of magnesium lithium silicate to adipic acid dihydrazide is 10-12:1.
[0008] Preferably, the diisocyanate is 4,4'-diisocyanate dicyclohexyl methane (HMDI).
[0009] Preferably, the polyhydric alcohol is polytetramethylene glycol (PTMG2000) with a molecular weight of 2000.
[0010] Preferably, the hydrazide chain extender is adipic acid dihydrazide.
[0011] A preparation method of the high-toughness and good-elasticity polyurethane elastomer composite material according to the present application, the method steps comprising: (1) dissolving the hydrazide chain extender in N,N-dimethylacetamide to obtain a chain extender solution; (2) under a protective gas atmosphere, stirring and reacting diisocyanate and polyhydric alcohol at 80-85℃ for 4-5h to obtain a viscous polyurethane prepolymer, and then mixing the viscous polyurethane prepolymer with the chain extender solution when the temperature of the viscous polyurethane prepolymer drops to 35-40℃, and reacting at 200-300 r / min for 10-12h, and then pouring into a mold, and curing at 70-80℃ for 24h or more to obtain a polyurethane elastomer; (3) adding adipic acid dihydrazide modified magnesium lithium silicate into N,N-dimethylacetamide and dispersing uniformly to obtain a dispersion; (4) soaking and stirring the polyurethane elastomer in N,N-dimethylacetamide for 18-24h, then adding the dispersion and mixing and stirring for 12-24h, and then drying to obtain a high-toughness and good-elasticity polyurethane elastomer composite material.
[0012] Preferably, in step (3), the ratio of the amount of adipic acid dihydrazide modified magnesium lithium silicate to N,N-dimethylacetamide is 1-2g:100-150mL.
[0013] Preferably, in step (4), the ratio of the amount of polyurethane elastomer to N,N-dimethylacetamide is 4-5g:80-100mL.
[0014] Preferably, in step (4), the temperature during soaking is 40-60℃, and the stirring rate is 200-500 r / min.
[0015] Advantages The application provides a polyurethane elastomer composite material with high strength and good elasticity, which is modified by using adipic acid dihydrazide (ADH) modified magnesium lithium silicate, and the ADH modified magnesium lithium silicate and the polyurethane elastomer form compact hydrogen bonds, and multiple amido urea and urethane groups are connected to a highly flexible aliphatic six-atom spacer, so that the strength of the composite material is improved. Meanwhile, due to the presence of the nanoscale magnesium lithium silicate, when a crack expands in the matrix, it cannot directly pass through the magnesium lithium silicate nanosheet, but only bypasses it or expands along the interface, so that the crack propagation path becomes tortuous, which means that more energy is consumed to generate a new crack surface, and the macroscopic performance is that the fracture energy is significantly improved; in addition, the modified polyurethane elastomer has good elasticity.
[0016] The application provides a preparation method of a polyurethane elastomer composite material with high strength and good elasticity, in order to efficiently introduce ADH modified magnesium lithium silicate, so that the ADH modified magnesium lithium silicate and polyurethane segments form interaction, the two are mixed with N,N-dimethylacetamide, and then the ADH modified magnesium lithium silicate is well dispersed in the polyurethane matrix by using a soaking method. BRIEF DESCRIPTION OF DRAWINGS
[0017] Figure 1 The figure is a thermogravimetric curve of the ADH modified magnesium lithium silicate in Example 1.
[0018] Figure 2 The figure is an infrared spectrum of the polyurethane elastomer composite material in Example 1.
[0019] Figure 3 The figure is an infrared spectrum of the polyurethane elastomer composite material in Example 1.
[0020] Figure 4 The figure is a DMA result graph of the polyurethane elastomer composite material in Example 2. DETAILED DESCRIPTION
[0021] The application will be further described in detail below in combination with specific embodiments.
[0022] Example 1 (1) 5.262 g of 4,4'-diisocyanate dicyclohexyl methane and 20.103 g of polybutylene glycol (PTMG2000) are added to a 250 ml three-necked flask, and the temperature is raised to 80 DEG C, 0.5 μl of dibutyl tin dilaurate is added, and the raw materials are stirred at a speed of 200 r / min to mix uniformly, and a polyurethane prepolymer is obtained after 4 h of reaction.
[0023] (3) Synthesis of adipic acid dihydrazide modified lithium magnesium silicate: 1 g of lithium magnesium silicate and 0.1 g of adipic acid dihydrazide were dispersed in water, and centrifuged in a centrifuge at a speed of 8000 r / min for 5 min. After centrifugation, the supernatant was discarded, and the above steps were repeated 5 times. Drying was performed at 75-80°C to obtain adipic acid dihydrazide modified lithium magnesium silicate.
[0024] 5 g of polyurethane elastomer was placed in N,N-dimethylacetamide and stirred for 18-24 h. When the polyurethane was completely dissolved in the N,N-dimethylacetamide solution, 0.015 g of adipic acid dihydrazide modified lithium magnesium silicate was dispersed in N,N-dimethylacetamide to obtain a dispersion of lithium magnesium silicate in N,N-dimethylacetamide. The two solutions were mixed, and after stirring for 12 h, they were poured into a tetrafluoroethylene mold and cured in an oven at 70-80°C to obtain a hydrazide modified lithium magnesium silicate modified polyurethane elastomer.
[0025] The obtained hydrazide modified lithium magnesium silicate was subjected to TGA test, and the results are shown in Figure 1 , indicating that 20% of adipic acid dihydrazide was adsorbed in the lithium magnesium silicate.
[0026] The hydrazide modified lithium magnesium silicate modified polyurethane elastomer was subjected to infrared test, and the results are shown in Figures 2-3 , indicating that the polyurethane elastomer composite material appeared a peak value of -N-H- stretching vibration at 3327 cm -1 , and a peak value of -C-O- stretching vibration at 1693 cm -1 and 1713 cm -1 , indicating the formation of ordered and disordered hydrogen bonds.
[0027] The obtained hydrazide modified lithium magnesium silicate modified polyurethane elastomer was subjected to tensile test, and the test results showed that the maximum tensile strength of the modified composite material was increased from 60.4 MPa to 65 MPa, and the plasticity and toughness were also improved to a certain extent.
[0028] Example 2 (1) 5.265 g of 4,4'-diisocyanate dicyclohexyl methane and 20.018 g of polybutylene glycol were added to a 250 ml three-necked flask, and heated to 80°C. 0.5 μl of dibutyltin dilaurate was added, and the raw materials were stirred at a speed of 200 r / min to mix uniformly. After 4 h of reaction, a polyurethane prepolymer was obtained.
[0029] (3) Synthesis of adipic acid dihydrazide modified magnesium lithium silicate: 1 g of magnesium lithium silicate and 0.1 g of adipic acid dihydrazide were dispersed in water, centrifuged in a centrifuge at a speed of 8000 r / min for 5 min, after centrifugation, the supernatant was poured out, and the above steps were repeated 6 times, and dried at 75-80°C to obtain adipic acid dihydrazide modified magnesium lithium silicate.
[0030] 5 g of polyurethane elastomer was taken and soaked in N,N-dimethylacetamide for 18-24 h, and when the polyurethane was completely dissolved in the N,N-dimethylacetamide solution, 0.025 g of adipic acid dihydrazide modified magnesium lithium silicate was dispersed in N,N-dimethylacetamide to obtain a dispersion of magnesium lithium silicate in N,N-dimethylacetamide, the above two solutions were mixed, stirred for 24 h, then poured into a tetrafluoroethylene mold, and cured in an oven at 70-80°C to obtain a hydrazide modified magnesium lithium silicate modified polyurethane elastomer.
[0031] The obtained hydrazide modified magnesium lithium silicate modified polyurethane elastomer was subjected to infrared testing, and the test results showed that the polyurethane elastomer composite material had a peak value of -N-H- stretching vibration at 3330 cm -1 -1 -1 and a peak value of -C-O- stretching vibration at 1697 cm -1 -1 and 1721 cm -1 , indicating the formation of ordered and disordered hydrogen bonds.
[0032] The obtained hydrazide modified magnesium lithium silicate modified polyurethane elastomer was subjected to tensile testing, and the test results showed that the maximum tensile strength of the modified composite material was increased from 61 MPa to 72.1 MPa, and the elongation at break was increased from 1390% to 1535%, indicating that the tensile strength of the modified composite material was greatly improved and the elongation at break was improved. The toughness was increased from 316.67 MJ / m 3 to 378.30 MJ / m 3 , and the toughness was significantly improved.
[0033] The obtained hydrazide modified magnesium lithium silicate modified polyurethane elastomer was subjected to DMA testing, and the results are shown in Figure 4 The test results showed that the damping at room temperature was very low, and the elasticity was good, which was a very good elastic vibration isolation material.
[0034] Example 3 (1) 5.268 g of 4,4'-diisocyanate dicyclohexyl methane and 20.014 g of polybutylene glycol were added to a 250 ml three-necked flask, and heated to 80°C, 0.5 ul of dibutyltin dilaurate was added, and the raw materials were stirred at a speed of 200 r / min to mix uniformly, and a polyurethane prepolymer was obtained after reaction for 4 h.
[0035] (3) Synthesis of adipic acid dihydrazide modified magnesium lithium silicate: 1g of magnesium lithium silicate and 0.1g of adipic acid dihydrazide were dispersed in water, centrifuged in a centrifuge at a speed of 8000r / min for 5min, after centrifugation, the supernatant was poured out, and the above steps were repeated 5-6 times, and dried at 75-80℃ to obtain adipic acid dihydrazide modified magnesium lithium silicate.
[0036] 5g of polyurethane elastomer was placed in N,N-dimethylacetamide and stirred for 18-24h, until the polyurethane was completely dissolved in the N,N-dimethylacetamide solution, 0.035g of adipic acid dihydrazide modified magnesium lithium silicate was dispersed in N,N-dimethylacetamide to obtain a dispersion of magnesium lithium silicate in N,N-dimethylacetamide, the above two solutions were mixed, stirred for 24h, then poured into a tetrafluoroethylene mold, and cured in an oven at 70-80℃ to obtain a hydrazide modified magnesium lithium silicate modified polyurethane elastomer.
[0037] The obtained hydrazide modified magnesium lithium silicate modified polyurethane elastomer was tested by infrared, and the test results showed that the polyurethane elastomer composite material had a peak value of -N-H- stretching vibration at 3332cm -1 -1 appeared, and a peak value of -C-O- stretching vibration appeared at 1695cm -1 -1 and 1728m -1 -1, indicating the formation of ordered and disordered hydrogen bonds.
[0038] The obtained hydrazide modified magnesium lithium silicate modified polyurethane elastomer was tested by tensile test, and the test results showed that the maximum tensile strength of the modified composite material was increased from 61.3MPa to 67MPa, and the plasticity and toughness were also improved to a certain extent.
[0039] In summary, the present application includes but is not limited to the above embodiments, any equivalent replacement or partial improvement made within the spirit and principles of the present application shall be considered within the scope of protection of the present application.
Claims
1. A high-strength, high-toughness, and highly elastic polyurethane elastomer composite material, characterized in that: The polyurethane elastomer is obtained by post-modifying the polyurethane elastomer with the adipic acid dihydrazide modified magnesium lithium silicate; The amount of the adipic acid dihydrazide modified magnesium lithium silicate is 0.3% to 0.7% of the mass of the polyurethane elastomer; In the adipic acid dihydrazide modified magnesium lithium silicate, the magnesium lithium silicate is 1.5% to 2.5% of the mass of the adipic acid dihydrazide; The polyurethane elastomer is obtained by curing the viscous polyurethane prepolymer with the hydrazide chain extender; the viscous polyurethane prepolymer is obtained by stirring and reacting diisocyanate and polyhydric alcohol at 80 to 85℃ for 4 to 5h; The molar ratio of diisocyanate, polyhydric alcohol and hydrazide chain extender is 2 to 2.1:1:
1.
2. A high-toughness and high-elasticity polyurethane elastomer composite material according to claim 1, characterized in that: The adipic acid dihydrazide modified magnesium lithium silicate is prepared by the following method, the method steps comprising: dispersing the magnesium lithium silicate and adipic acid dihydrazide in water, centrifuging at 8000 to 9000r / min for 5 to 10min, discarding the supernatant after centrifugation, repeating the centrifugation for 5 to 6 times, collecting the solid and drying at 75 to 80℃ to obtain the adipic acid dihydrazide modified magnesium lithium silicate.
3. A high-toughness and high-elasticity polyurethane elastomer composite material according to claim 2, characterized in that: The amount ratio of the magnesium lithium silicate and the adipic acid dihydrazide is 10 to 12:
1.
4. The high-toughness and high-elasticity polyurethane elastomer composite material according to claim 1, characterized in that: The diisocyanate is 4,4'-diisocyanate dicyclohexyl methane.
5. The high-toughness and high-elasticity polyurethane elastomer composite material according to claim 1, characterized in that: The polyhydric alcohol is polybutylene glycol with a molecular weight of 2000.
6. A high-toughness and high-elasticity polyurethane elastomer composite material according to claim 1, characterized in that: The hydrazide chain extender is adipic acid dihydrazide.
7. A method for producing the high-toughness and high-elasticity polyurethane elastomer composite material according to any one of claims 1 to 6, characterized by: The method steps comprise: (1) dissolving the hydrazide chain extender in N,N-dimethylacetamide to obtain a chain extender solution; (2) under a protective gas atmosphere, stirring and reacting diisocyanate and polyhydric alcohol at 80 to 85℃ for 4 to 5h to obtain a viscous polyurethane prepolymer, when the temperature of the viscous polyurethane prepolymer drops to 35 to 40℃, mixing with the chain extender solution, and reacting at 200 to 300r / min for 10 to 12h, after the reaction, pouring into a mold, and curing at 70 to 80℃ for 24h or more to obtain a polyurethane elastomer; (3) adding the adipic acid dihydrazide modified magnesium lithium silicate into N,N-dimethylacetamide and dispersing uniformly to obtain a dispersion; (4) soaking and stirring the polyurethane elastomer in N,N-dimethylacetamide for 18 to 24h, then adding the dispersion and mixing and stirring for 12 to 24h, after the mixing, drying to obtain a polyurethane elastomer composite material with high strength and good elasticity.
8. The method of claim 7, wherein the polyurethane elastomer composite has a high toughness and good elasticity. In step (3), the amount ratio of the adipic acid dihydrazide modified magnesium lithium silicate and N,N-dimethylacetamide is 1 to 2g:100 to 150mL.
9. The method of claim 7, wherein the polyurethane elastomer composite has a high toughness and good elasticity. In step (4), the amount ratio of the polyurethane elastomer and N,N-dimethylacetamide is 4 to 5g:80 to 100mL.
10. The method of claim 7, wherein the polyurethane elastomer composite has high toughness and good elasticity. In step (4), when soaking, the temperature is 40 to 60℃ and the stirring rate is 200 to 500r / min.