Self-repairing talcum powder polyurethane composite material and preparation method thereof
By developing self-healing talc polyurethane composite materials and using supramolecular multi-stage hydrogen bond construction technology, the problem of polymer materials being difficult to repair after damage is solved, efficient toughness and ductility repair is achieved, and high mechanical properties and reusable characteristics are high.
Patent Information
- Application Number
- CN202510333731.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-20
- Publication Date
- 2025-06-06
AI Technical Summary
Existing polymer materials are difficult to repair after damage, resulting in material waste and waste of resources.
A self-healing talc polyurethane composite material is developed, and its polyurethane matrix is prepared from isophorone diisocyanate, polyetheramine, dodecanediamine and small molecule monohydrogen alcohol. It is constructed through specific process steps to form supramolecular multi-stage hydrogen bonds to achieve efficient toughness and ductility repair.
This material can achieve more than 90% toughness repair and 98% ductility repair at a temperature above 90°C. It has high mechanical properties and stability, and can be recycled and used to extend its service life.
Smart Images
Figure CN120098223A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of self-repairing materials, and in particular to a self-repairing talc-polyurethane composite material and a preparation method thereof. Background Art
[0002] With the continuous development of modern industry and life needs, polymer materials are increasingly used in aerospace, automobile, electronics, construction and other fields. However, many polymer materials are susceptible to mechanical damage, environmental impact and other factors during use, resulting in performance degradation and shortened service life. Traditional polymer materials are usually difficult to repair once damaged, resulting in material waste and increased resource waste. Therefore, the development of polymer materials with self-healing functions has become one of the hot spots in materials science research.
[0003] Self-healing materials are a type of material that can restore its original properties through its own mechanisms after being damaged. These materials can achieve self-repair through physical or chemical reactions after being damaged, thereby extending the service life of the material and reducing maintenance costs. In recent years, polyurethane has become an important basic polymer in the research of self-healing materials due to its excellent mechanical properties, wear resistance and elasticity. In order to further improve the repair ability of polyurethane materials, researchers have explored composite materials with self-healing properties by adding various functional fillers or modifiers.
[0004] As a common inorganic filler, talcum powder can not only improve the mechanical properties of polyurethane materials, but also enhance its compatibility with the polyurethane matrix through appropriate surface modification. In addition, talcum powder has high thermal stability and good dispersibility, and can provide a reinforcing effect in composite materials. Combining polyurethane and talcum powder to prepare self-healing composite materials can not only improve the toughness and ductility of the material, but also give the material self-healing function, greatly improving its durability and adaptability. Summary of the invention
[0005] In view of the problem that the above-mentioned existing polymer materials are usually difficult to repair once damaged, resulting in material waste and increased waste of resources, the present invention is proposed.
[0006] Therefore, the purpose of the present invention is to provide a self-repairing talc polyurethane composite material, which is to achieve efficient toughness repair and ductility repair at a temperature above 90°C, and at the same time have high mechanical properties and stability. At the same time, through this technology, the composite material not only has a self-repairing function, but can also be repeatedly recycled, and has broad market application prospects.
[0007] In order to solve the above technical problems, the present invention provides the following technical solutions: a self-healing talc polyurethane composite material, comprising a polyurethane matrix of the composite material prepared from isophorone diisocyanate, polyetheramine, dodecanediamine and a small molecule monool, wherein the molar ratio of the sum of the molar amounts of the polyetheramine and dodecanediamine to the molar amount of isophorone diisocyanate and the small molecule monool is 100:98-100:20-2000, the total molar amount of the polyetheramine, dodecanediamine and the small molecule monool is greater than the molar amount of isophorone diisocyanate, and the structural formula of the polyetheramine is as follows:
[0008]
[0009] Among them, n≈33.2.
[0010] A method for preparing a self-repairing talc-polyurethane composite material comprises the following steps: Step 1: dissolving isophorone diisocyanate in N,N'-dimethylformamide solvent under an inert gas atmosphere to prepare a mixed solution I;
[0011] Step 2: dissolving the polyetheramine in N,N'-dimethylformyl solvent to obtain a mixed solution II, then adding the mixed solution II dropwise into the mixed solution I at 0-4°C, stirring for 1 hour to obtain a solution III;
[0012] Step 3: dissolving dodecanediamine in N,N'-dimethylformamide solvent to obtain a mixed solution IV, then adding the mixed solution IV dropwise to the mixed solution III at 0-4°C, maintaining the temperature and stirring the reaction for 4-5h to obtain a reaction intermediate solution V, wherein the ratio of the sum of the molar amounts of the polyetheramine and dodecanediamine to the molar amount of isophorone diisocyanate is 100:98-100;
[0013] Step 4: heat-treating the reaction intermediate solution V at 80-90° C. for 10-12 h to obtain a reaction initial product solution VI;
[0014] Step 5: adding a small molecule monohydric alcohol to the initial reaction product solution VI, stirring and mixing to obtain a polymer solution VII, wherein the molar ratio of the sum of the molar amounts of the polyetheramine and dodecanediamine to the molar amount of isophorone diisocyanate and the small molecule monohydric alcohol is 100:98-100:20-2000, and the total molar amount of the polyetheramine, dodecanediamine and the small molecule monohydric alcohol is greater than the molar amount of isophorone diisocyanate;
[0015] Step 6: degassing the polymer solution VII, and then drying to remove the solvent, to obtain a polyurethane matrix of the self-repairing talc-polyurethane composite material;
[0016] Step 7: dissolving talc powder in N,N'-dimethylformamide solvent, and ultrasonicating for 6 hours to obtain a uniform solution VIII;
[0017] Step 8: crushing the polyurethane matrix of the self-repairing talc-polyurethane composite material and dissolving it in solution VIII to obtain solution IX;
[0018] Step 9: Heat solution IX to 75°C and stir for 3 hours, the viscosity of the solution system increases, and a concentrated solution I is obtained;
[0019] Step 10: Stir the concentrated solution I in a water bath, cool it to room temperature, and then dry it to obtain a self-healing talc-polyurethane composite material.
[0020] As a preferred embodiment of the self-healing talc-polyurethane composite material of the present invention, the specific substance used for the small molecule monohydric alcohol in step 5 can be methanol, ethanol, butanol, n-butanol or propanol, and the molecular weight thereof is between 32-74.
[0021] As a preferred embodiment of the self-healing talc-polyurethane composite material of the present invention, the molecular weight of the polyetheramine described in step 2 is 2000, and the concentration of the polyetheramine in the mixed solution II is 4.5-5.502 g / mL.
[0022] As a preferred embodiment of the self-healing talc-polyurethane composite material of the present invention, the dripping speed in step 2 and step 3 is 800-1000 μL / min, and the concentration of dodecanediamine in the mixed solution IV in step 3 is 0.01-0.05 g / mL.
[0023] As a preferred embodiment of the self-healing talc polyurethane composite material of the present invention, the stirring time in the step five is 10-20 minutes, and the molar ratio of the sum of the molar amounts of isophorone diisocyanate, polyetheramine and dodecanediamine to the small molecule monohydric alcohol is 100:98-100:20-2000.
[0024] As a preferred embodiment of the self-healing talc polyurethane composite material of the present invention, the drying process in step six is to first dry at 80-90°C for 36-48h, and then dry under vacuum conditions at 85-90°C for 12-24h.
[0025] As a preferred solution of the self-repairing talc-polyurethane composite material of the present invention, wherein: the talc added in step seven is 3wt%-15wt%.
[0026] As a preferred embodiment of the self-healing talc polyurethane composite material of the present invention, the drying process in step 10 is to first dry at 80-90°C for 36-48h, and then dry at 85-90°C under vacuum conditions for 12-24h.
[0027] Compared with the prior art, the present invention has at least the following beneficial effects:
[0028] 1. The self-repairing talc-polyurethane composite material of the present invention has excellent self-repairing ability. It can achieve more than 90% toughness repair and 98% ductility repair under the assistance of temperature above 90°C, and complete 85% toughness repair at 90°C for 48 hours.
[0029] 2. The self-healing talc-polyurethane composite material of the present invention has high toughness, with a toughness of 160MJ m-3, a maximum tensile strength of more than 14.8MPa, and a maximum stretching ratio of 15 times; the mechanical properties are stable when exposed to air, and it has good resistance to water vapor adsorption.
[0030] 3. The self-repairing talc-polyurethane composite material of the present invention can be repeatedly re-melted and hot-pressed. Compared with traditional thermosetting polyurethane materials, it can be repeatedly recycled and effectively prolongs the service life of the material.
[0031] 4. The preparation method of the self-repairing talc-polyurethane composite material of the present invention is simple to operate, has high yield, stable repeatability, and is easy to promote in the market. BRIEF DESCRIPTION OF THE DRAWINGS
[0032] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative labor. Among them:
[0033] Figure 1 This is a schematic diagram of the preparation reaction of the polyurethane matrix of the self-healing talc-polyurethane composite material prepared in Example 1.
[0034] Figure 2 This is the stress-strain curve of the polyurethane matrix of the self-healing talc-polyurethane composite material prepared in Example 1.
[0035] Figure 3 The stress-strain curves of the self-healing talc-polyurethane composite materials and their polyurethane matrices prepared in Example 1, Example 2, Example 3, Example 4, Example 5, and Example 6.
[0036] Figure 4 The stress-strain curves of the self-healing talc-polyurethane composite material prepared in Example 5 at 90° C. and different repair times. DETAILED DESCRIPTION
[0037] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with the accompanying drawings.
[0038] In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein, and those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.
[0039] Example 1
[0040] Reference Figure 1-4 , which is the first embodiment of the present invention, provides a self-healing talc polyurethane composite material, wherein the self-healing talc polyurethane composite material comprises a polyurethane matrix of the composite material prepared from isophorone diisocyanate, polyetheramine, dodecanediamine and small molecule monool, wherein the molar ratio of the sum of the molar amounts of the polyetheramine and dodecanediamine to the molar amount of isophorone diisocyanate and the small molecule monool is 100:98-100:20-2000, the total molar amount of the polyetheramine, dodecanediamine and the small molecule monool is greater than the molar amount of isophorone diisocyanate, and the structural formula of the polyetheramine is as follows:
[0041]
[0042] Among them, n≈33.2.
[0043] A method for preparing a self-repairing talc-polyurethane composite material comprises the following steps:
[0044] Step 1: Under an inert gas atmosphere, isophorone diisocyanate is dissolved in N,N'-dimethylformamide solvent to prepare a mixed solution I;
[0045] Step 2: dissolving the polyetheramine in N,N'-dimethylformyl solvent to obtain a mixed solution II, then adding the mixed solution II dropwise into the mixed solution I at 0-4°C, stirring for 1 hour to obtain a solution III;
[0046] Step 3: dissolving dodecanediamine in N,N'-dimethylformamide solvent to obtain a mixed solution IV, then adding the mixed solution IV dropwise to the mixed solution III at 0-4°C, maintaining the temperature and stirring the reaction for 4-5h to obtain a reaction intermediate solution V, wherein the ratio of the sum of the molar amounts of the polyetheramine and dodecanediamine to the molar amount of isophorone diisocyanate is 100:98-100;
[0047] Step 4: heat-treating the reaction intermediate solution V at 80-90° C. for 10-12 h to obtain a reaction initial product solution VI;
[0048] Step 5: adding a small molecule monohydric alcohol to the initial reaction product solution VI, stirring and mixing to obtain a polymer solution VII, wherein the molar ratio of the sum of the molar amounts of the polyetheramine and dodecanediamine to the molar amount of isophorone diisocyanate and the small molecule monohydric alcohol is 100:98-100:20-2000, and the total molar amount of the polyetheramine, dodecanediamine and the small molecule monohydric alcohol is greater than the molar amount of isophorone diisocyanate;
[0049] Step 6: degassing the polymer solution VII, and then drying to remove the solvent, to obtain a polyurethane matrix of the self-repairing talc-polyurethane composite material;
[0050] Step 7: dissolving talc powder in N,N'-dimethylformamide solvent, and ultrasonicating for 6 hours to obtain a uniform solution VIII;
[0051] Step 8: crushing the polyurethane matrix of the self-repairing talc-polyurethane composite material and dissolving it in solution VIII to obtain solution IX;
[0052] Step 9: Heat solution IX to 75°C and stir for 3 hours, the viscosity of the solution system increases, and a concentrated solution I is obtained;
[0053] Step 10: Stir the concentrated solution I in a water bath, cool it to room temperature, and then dry it to obtain a self-healing talc-polyurethane composite material.
[0054] The specific substance used in the step 5 small molecule monohydric alcohol can be methanol, ethanol, butanol, n-butanol or propanol, and the molecular weight thereof is between 32-74.
[0055] The molecular weight of the polyetheramine described in step 2 is 2000, and the concentration of the polyetheramine in the mixed solution II is 4.5-5.502 g / mL.
[0056] The dropping speed in step 2 and step 3 is 800-1000 μL / min, and the concentration of dodecanediamine in the mixed solution IV in step 3 is 0.01-0.05 g / mL.
[0057] The stirring time in step 5 is 10-20 minutes, and the molar ratio of the sum of the molar amounts of isophorone diisocyanate, polyetheramine and dodecanediamine to the small molecule monohydric alcohol is 100:98-100:20-2000.
[0058] The drying process in step six is to first dry at 80-90° C. for 36-48 hours, and then dry under vacuum conditions at 85-90° C. for 12-24 hours.
[0059] The talc powder added in step seven is added in an amount of 3wt%-15wt%.
[0060] The drying process in step 10 is to first dry at 80-90° C. for 36-48 hours, and then dry under vacuum conditions at 85-90° C. for 12-24 hours.
[0061] The method for repairing the self-repairing talc-polyurethane composite material of the present invention specifically comprises placing the self-repairing talc-polyurethane composite material at a temperature above 90°C.
[0062] Furthermore, the self-repairing talc-polyurethane composite material is used in energy-absorbing and shock-absorbing materials or impact-resistant materials.
[0063] The polyurethane matrix of the self-repairing talc-polyurethane composite material of the present invention is constructed by supramolecular multi-level hydrogen bonds, and its soft / hard image unit stacking provides the material with high mechanical strength and good ductility. Under a certain force, its soft and hard phases dissociate and reorganize in turn, dissipate energy, and show high toughness characteristics; at a temperature of 90°C and above, the hard phase hydrogen bond stacking dissociates and reorganizes to achieve repair.
[0064] The preparation method of the polyurethane matrix of the self-repairing talc-polyurethane composite material comprises the following specific steps:
[0065] a. Under an inert gas atmosphere, 0.963 g of isophorone diisocyanate was dissolved in 10 mL of N, N'-dimethylformamide solvent to obtain a mixed solution Ⅰ;
[0066] b. 5.198 g of polyetheramine was dissolved in 10 mL of N, N'-dimethylformamide solvent to obtain a mixed solution II, and then the mixed solution II was added dropwise to the mixed solution I obtained in step a at 0-4 ° C. The dropping speed was 1000 μL / min, and the reaction was stirred for 1 h to obtain a reaction intermediate product solution III;
[0067] c. 0.347 g of dodecanediamine was dissolved in 10 mL of N, N'-dimethylformamide solvent to obtain a mixed solution Ⅳ, and then the mixed solution Ⅳ was added dropwise to the mixed solution Ⅲ obtained in step b at 0-4 ° C, the dropping speed was 1000 μ L / min, the temperature was maintained and the reaction was stirred for 4 h to obtain a reaction intermediate product solution Ⅴ;
[0068] d. The initial reaction product solution V obtained in step c is heated at 85 ° C for 10-12h to obtain an initial reaction product solution VI;
[0069] e. 0.200 g (6.25 mm ° l) of methanol was added to the initial reaction product solution VI obtained in step d and stirred for 10 min to obtain a polymer solution VII;
[0070] f. The polymer solution Ⅶ prepared in step e was dried at 90° C. for 48 h, and then dried at 90° C. under vacuum conditions for 24 h to obtain the polyurethane matrix of the self-healing talc-polyurethane composite material.
[0071] Example 2
[0072] Reference Figure 1-4 , which is the second embodiment of the present invention, and this embodiment is different from the first embodiment in that: a method for preparing a self-repairing talc-polyurethane composite material, the specific steps are as follows:
[0073] a. Under an inert gas atmosphere, 0.963 g of isophorone diisocyanate was dissolved in 10 mL of N, N'-dimethylformamide solvent to obtain a mixed solution Ⅰ;
[0074] b. 5.198 g of polyetheramine was dissolved in 10 mL of N, N'-dimethylformamide solvent to obtain a mixed solution II, and then the mixed solution II was added dropwise to the mixed solution I obtained in step a at 0-4 ° C. The dropping speed was 1000 μL / min, and the reaction was stirred for 1 h to obtain a reaction intermediate product solution III;
[0075] c. 0.347 g of dodecanediamine was dissolved in 10 mL of N, N'-dimethylformamide solvent to obtain a mixed solution Ⅳ, and then the mixed solution Ⅳ was added dropwise to the mixed solution Ⅲ obtained in step b at 0-4 ° C, the dropping speed was 1000 μ L / min, the temperature was maintained and the reaction was stirred for 4 h to obtain a reaction intermediate product solution Ⅴ;
[0076] d. The initial reaction product solution V obtained in step c is heated at 85 ° C for 10-12h to obtain an initial reaction product solution VI;
[0077] e. 0.200 g (6.25 mm ° l) of methanol was added to the initial reaction product solution VI obtained in step d and stirred for 10 min to obtain a polymer solution VII;
[0078] f. The polymer solution Ⅶ prepared in step e was dried at 90° C. for 48 h, and then dried at 90° C. under vacuum conditions for 24 h to obtain the polyurethane matrix of the self-healing talc-polyurethane composite material.
[0079] g. Dissolve 0.18 g of talc in N,N'-dimethylformamide solvent and perform ultrasonication for 6 h to obtain a uniform solution VIII;
[0080] h. crushing 6 g of the polyurethane matrix of the self-repairing talc-polyurethane composite material and dissolving it in solution VIII to obtain solution IX;
[0081] i. Heat solution IX to 75°C and stir for 3 hours to increase the viscosity of the solution system to obtain concentrated solution I;
[0082] j. The concentrated solution I was stirred and cooled to room temperature in a water bath, dried at 90°C for 48 hours, and then dried at 90°C under vacuum conditions for 24 hours to obtain a self-healing talc-polyurethane composite material.
[0083] The remaining structures are the same as those of Example 1.
[0084] Example 3
[0085] Reference Figure 1-4 , which is the third embodiment of the present invention, and this embodiment is different from the second embodiment in that: a method for preparing a self-repairing talc-polyurethane composite material, the specific steps are as follows:
[0086] a. Under an inert gas atmosphere, 0.963 g of isophorone diisocyanate was dissolved in 10 mL of N, N'-dimethylformamide solvent to obtain a mixed solution Ⅰ;
[0087] b. 5.198 g of polyetheramine was dissolved in 10 mL of N, N'-dimethylformamide solvent to obtain a mixed solution II, and then the mixed solution II was added dropwise to the mixed solution I obtained in step a at 0-4 ° C. The dropping speed was 1000 μL / min, and the reaction was stirred for 1 h to obtain a reaction intermediate product solution III;
[0088] c. 0.347 g of dodecanediamine was dissolved in 10 mL of N, N'-dimethylformamide solvent to obtain a mixed solution Ⅳ, and then the mixed solution Ⅳ was added dropwise to the mixed solution Ⅲ obtained in step b at 0-4 ° C, the dropping speed was 1000 μ L / min, the temperature was maintained and the reaction was stirred for 4 h to obtain a reaction intermediate product solution Ⅴ;
[0089] d. The initial reaction product solution V obtained in step c is heated at 85 ° C for 10-12h to obtain an initial reaction product solution VI;
[0090] e. 0.200 g (6.25 mm ° l) of methanol was added to the initial reaction product solution VI obtained in step d and stirred for 10 min to obtain a polymer solution VII;
[0091] f. The polymer solution Ⅶ prepared in step e was dried at 90° C. for 48 h, and then dried at 90° C. under vacuum conditions for 24 h to obtain the polyurethane matrix of the self-healing talc-polyurethane composite material.
[0092] g. Dissolve 0.36 g of talc in N,N'-dimethylformamide solvent and perform ultrasonication for 6 h to obtain a uniform solution VIII;
[0093] h. crushing 6 g of the polyurethane matrix of the self-repairing talc-polyurethane composite material and dissolving it in solution VIII to obtain solution IX;
[0094] i. Heat solution IX to 75°C and stir for 3 hours to increase the viscosity of the solution system to obtain concentrated solution I;
[0095] j. The concentrated solution I was stirred and cooled to room temperature in a water bath, dried at 90°C for 48 hours, and then dried at 90°C under vacuum conditions for 24 hours to obtain a self-healing talc-polyurethane composite material.
[0096] The remaining structure is the same as that of Example 2.
[0097] Example 4
[0098] Reference Figure 1-4 , which is the fourth embodiment of the present invention, and this embodiment is different from the third embodiment in that: a method for preparing a self-repairing talc-polyurethane composite material, the specific steps are as follows:
[0099] a. Under an inert gas atmosphere, 0.963 g of isophorone diisocyanate was dissolved in 10 mL of N, N'-dimethylformamide solvent to obtain a mixed solution Ⅰ;
[0100] b. 5.198 g of polyetheramine was dissolved in 10 mL of N, N'-dimethylformamide solvent to obtain a mixed solution II, and then the mixed solution II was added dropwise to the mixed solution I obtained in step a at 0-4 ° C. The dropping speed was 1000 μL / min, and the reaction was stirred for 1 h to obtain a reaction intermediate product solution III;
[0101] c. 0.347 g of dodecanediamine was dissolved in 10 mL of N, N'-dimethylformamide solvent to obtain a mixed solution Ⅳ, and then the mixed solution Ⅳ was added dropwise to the mixed solution Ⅲ obtained in step b at 0-4 ° C, the dropping speed was 1000 μ L / min, the temperature was maintained and the reaction was stirred for 4 h to obtain a reaction intermediate product solution Ⅴ;
[0102] d. The initial reaction product solution V obtained in step c is heated at 85 ° C for 10-12h to obtain an initial reaction product solution VI;
[0103] e. 0.200 g (6.25 mm ° l) of methanol was added to the initial reaction product solution VI obtained in step d and stirred for 10 min to obtain a polymer solution VII;
[0104] f. The polymer solution Ⅶ prepared in step e was dried at 90° C. for 48 h, and then dried at 90° C. under vacuum conditions for 24 h to obtain the polyurethane matrix of the self-healing talc-polyurethane composite material.
[0105] g. Dissolve 0.54 g of talc in N,N'-dimethylformamide solvent and perform ultrasonication for 6 h to obtain a uniform solution VIII;
[0106] h. crushing 6 g of the polyurethane matrix of the self-repairing talc-polyurethane composite material and dissolving it in solution VIII to obtain solution IX;
[0107] i. Heat solution IX to 75°C and stir for 3 hours to increase the viscosity of the solution system to obtain concentrated solution I;
[0108] j. The concentrated solution I was stirred and cooled to room temperature in a water bath, dried at 90°C for 48 hours, and then dried at 90°C under vacuum conditions for 24 hours to obtain a self-healing talc-polyurethane composite material.
[0109] The remaining structure is the same as that of Example 3.
[0110] Example 5
[0111] Reference Figure 1-4 , which is the fifth embodiment of the present invention, and this embodiment is different from the fourth embodiment in that: a method for preparing a self-repairing talc-polyurethane composite material, the specific steps are as follows:
[0112] a. Under an inert gas atmosphere, 0.963 g of isophorone diisocyanate was dissolved in 10 mL of N, N'-dimethylformamide solvent to obtain a mixed solution Ⅰ;
[0113] b. 5.198 g of polyetheramine was dissolved in 10 mL of N, N'-dimethylformamide solvent to obtain a mixed solution II, and then the mixed solution II was added dropwise to the mixed solution I obtained in step a at 0-4 ° C. The dropping speed was 1000 μL / min, and the reaction was stirred for 1 h to obtain a reaction intermediate product solution III;
[0114] c. 0.347 g of dodecanediamine was dissolved in 10 mL of N, N'-dimethylformamide solvent to obtain a mixed solution Ⅳ, and then the mixed solution Ⅳ was added dropwise to the mixed solution Ⅲ obtained in step b at 0-4 ° C, the dropping speed was 1000 μ L / min, the temperature was maintained and the reaction was stirred for 4 h to obtain a reaction intermediate product solution Ⅴ;
[0115] d. The initial reaction product solution V obtained in step c is heated at 85 ° C for 10-12h to obtain an initial reaction product solution VI;
[0116] e. 0.200 g (6.25 mm ° l) of methanol was added to the initial reaction product solution VI obtained in step d and stirred for 10 min to obtain a polymer solution VII;
[0117] f. The polymer solution Ⅶ prepared in step e was dried at 90° C. for 48 h, and then dried at 90° C. under vacuum conditions for 24 h to obtain the polyurethane matrix of the self-healing talc-polyurethane composite material.
[0118] g. Dissolve 0.72 g of talc in N,N'-dimethylformamide solvent and perform ultrasonication for 6 h to obtain a uniform solution VIII;
[0119] h. crushing 6 g of the polyurethane matrix of the self-repairing talc-polyurethane composite material and dissolving it in solution VIII to obtain solution IX;
[0120] i. Heat solution IX to 75°C and stir for 3 hours to increase the viscosity of the solution system to obtain concentrated solution I;
[0121] j. The concentrated solution I was stirred and cooled to room temperature in a water bath, dried at 90°C for 48 hours, and then dried at 90°C under vacuum conditions for 24 hours to obtain a self-healing talc-polyurethane composite material.
[0122] The remaining structures are the same as those of Example 4.
[0123] Example 6
[0124] Reference Figure 1-4 , which is the sixth embodiment of the present invention, and this embodiment is different from the fifth embodiment in that: a method for preparing a self-repairing talc-polyurethane composite material, the specific steps are as follows:
[0125] a. Under an inert gas atmosphere, 0.963 g of isophorone diisocyanate was dissolved in 10 mL of N, N'-dimethylformamide solvent to obtain a mixed solution Ⅰ;
[0126] b. 5.198 g of polyetheramine was dissolved in 10 mL of N, N'-dimethylformamide solvent to obtain a mixed solution II, and then the mixed solution II was added dropwise to the mixed solution I obtained in step a at 0-4 ° C. The dropping speed was 1000 μL / min, and the reaction was stirred for 1 h to obtain a reaction intermediate product solution III;
[0127] c. 0.347 g of dodecanediamine was dissolved in 10 mL of N, N'-dimethylformamide solvent to obtain a mixed solution Ⅳ, and then the mixed solution Ⅳ was added dropwise to the mixed solution Ⅲ obtained in step b at 0-4 ° C, the dropping speed was 1000 μ L / min, the temperature was maintained and the reaction was stirred for 4 h to obtain a reaction intermediate product solution Ⅴ;
[0128] d. The initial reaction product solution V obtained in step c is heated at 85 ° C for 10-12h to obtain an initial reaction product solution VI;
[0129] e. 0.200 g (6.25 mm ° l) of methanol was added to the initial reaction product solution VI obtained in step d and stirred for 10 min to obtain a polymer solution VII;
[0130] f. The polymer solution Ⅶ prepared in step e was dried at 90° C. for 48 h, and then dried at 90° C. under vacuum conditions for 24 h to obtain the polyurethane matrix of the self-healing talc-polyurethane composite material.
[0131] g. Dissolve 0.9 g of talc in N,N'-dimethylformamide solvent and perform ultrasonication for 6 h to obtain a uniform solution VIII;
[0132] h. crushing 6 g of the polyurethane matrix of the self-repairing talc-polyurethane composite material and dissolving it in solution VIII to obtain solution IX;
[0133] i. Heat solution IX to 75°C and stir for 3 hours to increase the viscosity of the solution system to obtain concentrated solution I;
[0134] j. The concentrated solution I was stirred and cooled to room temperature in a water bath, dried at 90°C for 48 hours, and then dried at 90°C under vacuum conditions for 24 hours to obtain a self-healing talc-polyurethane composite material.
[0135] The remaining structures are the same as those of Example 5.
[0136] in conclusion
[0137] refer to Figure 1 This is a reaction schematic diagram of the self-healing talc-polyurethane composite material prepared in Example 1. It can be seen from the figure that the preparation method of the present invention is simple.
[0138] refer to Figure 2 The stress-strain curve of the polyurethane matrix of the self-repairing talc-polyurethane composite material prepared in Example 1, the toughness value of the polyurethane matrix material of the present invention is as high as 106MJ m-3, the maximum tensile strength is above 9MPa, and the maximum stretching ratio is about 25.5 times;
[0139] refer to Figure 3 The stress-strain curves of the self-healing talc-polyurethane composite materials and the matrix prepared in Example 1, Example 2, Example 3, Example 4, Example 5, and Example 6 show that as the mass fraction of talc added gradually increases from 0wt% to 12wt%, the maximum tensile strength and toughness values of the composite materials of the present invention show a trend of gradual increase; when the mass fraction of talc is further increased to 15wt%, the tensile strength and toughness of the composite materials both decrease. The results show that under the conditions of the present invention, the optimal mass fraction of talc added is 12wt%, and a self-healing talc-polyurethane composite material with the best comprehensive mechanical properties can be obtained;
[0140] refer to Figure 4The stress-strain curves of the self-repairing talc-polyurethane composite material prepared in Example 5 at different repair times at 90°C. The experimental results show that after 48 hours of repair at 90°C, the toughness recovery rate of the material of the present invention reaches 85%; after 72 hours of repair, the toughness recovery rate reaches 91%, and the ductility recovery rate reaches 98%. This result shows that the self-repairing talc-polyurethane composite material has excellent self-repairing properties, can quickly complete damage repair at higher temperatures, and exhibits good mechanical property recovery capabilities.
[0141] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.
Claims
1. A self-repairing talc-polyurethane composite material, characterized in that: The polyurethane matrix of the composite material is prepared from isophorone diisocyanate, polyetheramine, dodecanediamine and small molecule monool, wherein the molar ratio of the sum of the molar amounts of the polyetheramine and dodecanediamine to the molar amount of isophorone diisocyanate and the small molecule monool is 100:98-100:20-2000, the total molar amount of the polyetheramine, dodecanediamine and the small molecule monool is greater than the molar amount of isophorone diisocyanate, and the structural formula of the polyetheramine is as follows: Among them, n≈33.
2.
2. A method for preparing a self-repairing talc-polyurethane composite material, which is applied to the self-repairing talc-polyurethane composite material described in claim 1, characterized in that: The following steps are involved: Step 1: Under an inert gas atmosphere, isophorone diisocyanate is dissolved in N,N'-dimethylformamide solvent to prepare a mixed solution I; Step 2: dissolving the polyetheramine in N,N'-dimethylformyl solvent to obtain a mixed solution II, then adding the mixed solution II dropwise into the mixed solution I at 0-4°C, stirring for 1 hour to obtain a solution III; Step 3: dissolving dodecanediamine in N,N'-dimethylformamide solvent to obtain a mixed solution IV, then adding the mixed solution IV dropwise to the mixed solution III at 0-4°C, maintaining the temperature and stirring the reaction for 4-5h to obtain a reaction intermediate solution V, wherein the ratio of the sum of the molar amounts of the polyetheramine and dodecanediamine to the molar amount of isophorone diisocyanate is 100:98-100; Step 4: heat-treating the reaction intermediate solution V at 80-90° C. for 10-12 h to obtain a reaction initial product solution VI; Step 5: adding a small molecule monohydric alcohol to the initial reaction product solution VI, stirring and mixing to obtain a polymer solution VII, wherein the molar ratio of the sum of the molar amounts of the polyetheramine and dodecanediamine to the molar amount of isophorone diisocyanate and the small molecule monohydric alcohol is 100:98-100:20-2000, and the total molar amount of the polyetheramine, dodecanediamine and the small molecule monohydric alcohol is greater than the molar amount of isophorone diisocyanate; Step 6: degassing the polymer solution VII, and then drying to remove the solvent, to obtain a polyurethane matrix of the self-repairing talc-polyurethane composite material; Step 7: dissolving talc powder in N,N'-dimethylformamide solvent, and ultrasonicating for 6 hours to obtain a uniform solution VIII; Step 8: crushing the polyurethane matrix of the self-repairing talc-polyurethane composite material and dissolving it in solution VIII to obtain solution IX; Step 9: Heat solution IX to 75°C and stir for 3 hours, the viscosity of the solution system increases, and a concentrated solution I is obtained; Step 10: Stir the concentrated solution I in a water bath, cool it to room temperature, and then dry it to obtain a self-healing talc-polyurethane composite material.
3. The self-repairing talc-polyurethane composite material according to claim 2, characterized in that: The specific substance used in the small molecule monohydric alcohol in step 5 can be methanol, ethanol, butanol, n-butanol or propanol, and the molecular weight thereof is between 32-74.
4. The self-repairing talc-polyurethane composite material according to claim 3, characterized in that: The molecular weight of the polyetheramine described in step 2 is 2000, and the concentration of the polyetheramine in the mixed solution II is 4.5-5.502 g / mL.
5. The self-repairing talc-polyurethane composite material according to claim 4, characterized in that: The dropping speed in step 2 and step 3 is 800-1000 μL / min, and the concentration of dodecanediamine in the mixed solution IV in step 3 is 0.01-0.05 g / mL.
6. The self-repairing talc-polyurethane composite material according to claim 5, characterized in that: The stirring time in step 5 is 10-20 minutes, and the molar ratio of the sum of the molar amounts of isophorone diisocyanate, polyetheramine and dodecanediamine to the small molecule monohydric alcohol is 100:98-100:20-2000.
7. The self-repairing talc-polyurethane composite material according to claim 6, characterized in that: The drying process in step six is to first dry at 80-90° C. for 36-48 hours, and then dry under vacuum conditions at 85-90° C. for 12-24 hours.
8. The self-repairing talc-polyurethane composite material according to claim 7, characterized in that: The talc powder added in step seven is added in an amount of 3wt%-15wt%.
9. The self-repairing talc-polyurethane composite material according to claim 8, characterized in that: The drying process in step 10 is to first dry at 80-90° C. for 36-48 hours, and then dry under vacuum conditions at 85-90° C. for 12-24 hours.