A bis-indane-modified polyurethane elastomer and a method for preparing the same

Abstract

The application relates to a b-indanane modified polyurethane elastomer and a preparation method thereof, and belongs to the technical field of polyurethane. The polyurethane elastomer matrix is crosslinked with 5,5', 6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spiral b-indanane to form a large number of intermolecular forces such as hydrogen bonds, nonpolar intermolecular forces, conjugation and pi-pi complexation, so that the mechanical properties and damping properties of the material are enhanced. The material has excellent damping properties, can be applied to vibration and noise reduction, can be completely dissolved in ethanol at normal temperature, and the material still has excellent properties after ethanol volatilization, so that the material can be recycled and reused.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of double indane modified polyurethane elastomer and its preparation method, belong to polyurethane technical field. BACKGROUND

[0002] Polyurethane is a high molecular compound with many urethane groups repeated on the high molecular backbone. From the molecular structure, polyurethane elastomer is a kind of block polymer, generally composed of soft segment of flexible long chain of oligomer polyol, hard segment of diisocyanate and chain extender, soft segment and hard segment can produce microphase separation, and a large number of hydrogen bonds can be formed in and between polyurethane molecules. These structural characteristics make polyurethane have excellent performance, and it is widely used in industrial manufacturing, transportation construction, oil and gas industry and biomedical fields.

[0003] High mechanical strength, high damping performance, high resilience and self-repairing and other excellent performance are the core advantages of polyurethane material, but these performances are often difficult to balance, which limits the application of polyurethane material. Therefore, it is of great significance to modify polyurethane to have good mechanical strength and toughness, and at the same time, have good damping performance, and can be self-repaired and recycled under mild conditions.

[0004] Chinese patent application 202310125972.2 discloses a kind of polyphenol compound modified polyurethane elastomer and its preparation method, by putting polyurethane elastomer into the organic solution of polyphenol substance (such as ellagic acid, punicalin, gallic acid, tannic acid or tea polyphenol) and soaking stirring for 18~24h, after complete soaking, take out solid phase, dry at 25~70℃, get polyphenol compound modified polyurethane elastomer. But in this method, the stirring time of mixing polyphenol into polyurethane is longer, and the drying temperature is higher, the performance of the enhanced polyurethane is not significant at room temperature, and it is difficult to recycle and reuse. SUMMARY

[0005] Therefore, the purpose of the present application is to provide a kind of double indane modified polyurethane elastomer and its preparation method. The mechanical properties and damping properties of the modified polyurethane elastomer are greatly improved compared with the matrix, it can be quickly self-repaired at room temperature by solvent assistance, and it is easy to recycle and reuse, green and environmental protection.

[0006] To achieve the above purpose, the technical scheme of the present application is as follows.

[0007] A kind of double indane modified polyurethane elastomer, the structural formula is:

[0008]

[0009] Among them, indicates hydrogen bond, represents non-polar intermolecular force, represents π-π complexation, n is an integer greater than or equal to 1000.

[0010] Preferably, n is an integer between 1000 and 2000.

[0011] Preferably, the preparation of the bis-indane modified polyurethane elastomer is composed of A component, B component and C component, the A component and the B component are cured to form a polyurethane elastomer matrix, and the polyurethane elastomer matrix is mixed with the C component to obtain the bis-indane modified polyurethane elastomer.

[0012] The total mass of the raw materials for preparing the A component is 100 parts, and the mass fractions of the raw materials are as follows: toluene diisocyanate (TDI) 14% to 16%; polypropylene glycol (PPG) 84% to 86%.

[0013] The B component is isophorone diamine (IPDA), and the C component is 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spiro bis-indane.

[0014] The molar ratio of the -NCO groups (remaining -NCO after the prepolymerization of toluene diisocyanate and polypropylene glycol) in the A component to the amine groups in the B component isophorone diamine is 1:1 to 1.05, and the mass of the C component is 5% to 10% of the mass of the polyurethane elastomer matrix.

[0015] Preferably, the molecular weight of the polypropylene glycol is 960 to 2080.

[0016] A method for preparing the bis-indane modified polyurethane elastomer according to the present application, the method steps comprising:

[0017] (1) Under a protective gas atmosphere, mix the dehydrated A component toluene diisocyanate and polypropylene glycol, stir and react at 80±2℃ for 2 to 3 hours to obtain a polyurethane prepolymer;

[0018] (2) Dissolve the polyurethane prepolymer in a first organic solvent at 0 to 10℃, and stir for more than 10 minutes to obtain a prepolymer solution;

[0019] (3) Dissolve the B component isophorone diamine in the first organic solvent, add the prepolymer solution under a protective gas atmosphere and at 0 to 10℃, and stir for more than 10 hours, then warm up to 83 to 87℃, stir and react for more than 4 hours, then pour into a mold, solidify at 80 to 85℃ for more than 48 hours, and dry to obtain a polyurethane elastomer matrix;

[0020] (4) dissolving the polyurethane elastomer matrix in a second organic solvent, adding component 5, 5', 6, 6'-tetrahydroxy-3, 3, 3', 3'-tetramethyl-1, 1'-spirobisoindoline, stirring and mixing uniformly, and then volatilizing the solvent to obtain a bisindoline modified polyurethane elastomer.

[0021] Preferably, the protective gas is nitrogen or an inert gas (a gas element corresponding to all 0 groups in the periodic table).

[0022] Preferably, the first organic solvent is N, N-dimethylformamide (DMF).

[0023] Preferably, the second organic solvent is one or more of N, N-dimethylformamide, anhydrous ethanol, and tetrahydrofuran.

[0024] Preferably, in steps (1) and (3), the stirring rate is 180-220 r / min.

[0025] Preferably, in step (3), the drying temperature is 80-90℃, and the drying time is more than 24 h.

[0026] Preferably, in step (4), the stirring rate is 800-1000 r / min.

[0027] Beneficial effects

[0028] The present application provides a bisindoline modified polyurethane elastomer. The polyurethane elastomer matrix is cross-linked with 5, 5', 6, 6'-tetrahydroxy-3, 3, 3', 3'-tetramethyl-1, 1'-spirobisoindoline to form a large number of intermolecular forces such as hydrogen bonds, non-polar intermolecular forces, conjugation, and π-π complexation, thereby enhancing the mechanical properties and damping properties of the material. The material has excellent damping properties and can be applied to vibration and noise reduction. Meanwhile, the material can be completely dissolved in ethanol at room temperature, and the material still maintains excellent properties after the ethanol is volatilized, thereby facilitating recycling and reuse.

[0029] The present application provides a bisindoline modified polyurethane elastomer. The modified material has excellent tensile properties and can be stretched to more than 14 times the original length, and the tensile strength can reach more than 12 MPa. Compared with the matrix before modification, the tensile strength is increased by 59%. The material can realize self-repairing under trace solvent conditions at room temperature, and the tensile strength can be recovered by 75% after 3 h. The material has high damping properties in the range of -20℃ to room temperature, and the damping factor is greater than 0.4.

[0030] The application provides a preparation method of a double-indane modified polyurethane elastomer, a polyurethane base and 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spiral double-indane are dissolved in an organic solvent at room temperature, are fully mixed through stirring, and then a finished product is obtained through volatilization of the solvent at room temperature; the method has simple steps, the experimental formula can be changed according to production needs, and industrial production can be carried out.

[0031] The application provides a preparation method of a double-indane modified polyurethane elastomer, by selecting specific organic solvents (such as N,N-dimethylformamide, anhydrous ethanol and tetrahydrofuran), on the one hand, the viscosity of the reaction system can be reduced; on the other hand, when the prepolymer and small molecule components are dissolved, the reaction can be more complete. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 It is an infrared spectrum of the double-indane modified polyurethane elastomer in Example 1.

[0033] Figure 2 It is an infrared spectrum of the double-indane modified polyurethane elastomer in Example 1.

[0034] Figure 3 It is a mechanical property comparison diagram of the polyurethane elastomer base and the modified polyurethane elastomer in Example 1.

[0035] Figure 4 It is a room temperature self-repairing result diagram of the double-indane modified polyurethane elastomer in Example 1.

[0036] Figure 5 It is a DMA result diagram of the polyurethane elastomer base and the modified polyurethane in Example 1. DETAILED DESCRIPTION

[0037] The application will be further described in detail in combination with specific embodiments.

[0038] Example 1

[0039] A preparation method of a double-indane modified polyurethane elastomer, the method steps include:

[0040] In the first step, dry N2 needs to be continuously introduced throughout the reaction process, 3.49g of TDI is added into a 100ml three-necked flask, 20.1g of PPG2000 is added into a constant pressure dropping funnel and is added dropwise, the oil bath temperature is kept at 60-70 DEG C, and the dropwise addition is completed within 15min. After the dropwise addition of PPG2000 is completed, the temperature of the oil bath is increased to 80±2 DEG C, and the reaction is kept for 2h, so that a polyurethane prepolymer is obtained.

[0041] Second step, 0.4147g of the polyurethane prepolymer from the first step was mixed with 25ml of isopropyl alcohol in a 50°C water bath for 10min, then 4 drops of bromo-cresol blue indicator and 50ml of di-n-butylamine in toluene was added, followed by 0.1mol / L dilute hydrochloric acid titration until the solution did not change color within 30s, the titration was stopped, and the isocyanate content a = 3.6% of the polyurethane prepolymer was calculated.

[0042] Third step, 5.75g of the polyurethane prepolymer was dissolved in 10ml of dimethylformamide (DMF) and added to a 100ml three-necked flask, stirred at 0°C under N2atmosphere for 10min at a stirring speed of 180-220r / min, 0.404g of IPDA dissolved in 10ml of DMF was slowly added using a constant pressure dropping funnel, and the dropping time was more than 10min. The mixture was stirred at 0°C under N2atmosphere for 10h at a stirring speed of 180-220r / min, and then the temperature was raised to 85±2°C for 4h of reaction. After cooling to room temperature, 3ml of ethanol was added to remove residual isocyanate, and the reaction mixture was poured into a polytetrafluoroethylene (PTFE) mold, dried in an oven at 90°C for 48h, and then dried in a vacuum oven at 80°C for 12h to remove solvent and bubbles, to obtain a polyurethane elastomer.

[0043] Fourth step, 5.22g of the polyurethane elastomer was dissolved in 30ml of anhydrous ethanol, and 0.261g of 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisoindane was added for stirring and blending with the polyurethane elastomer at a stirring speed of 800r / min for 2h, and then poured into a polytetrafluoroethylene mold and dried in a fume hood for 24h to obtain a spirobisoindane-modified polyurethane elastomer.

[0044] The obtained elastomer was subjected to infrared spectrum analysis as shown in Figure 1 3332(ν-NH-), 2867 / 2972(ν-CH3), 1544(ν-C7H6-), 1373(δ-CH3), 1223(ν(-C-C-)s), 1092(ν-C-O-C-), 929 / 820(δ-C7H6-). Figure 2 The infrared peak was performed in the wavelength range of 1600-1800, 1730(νC=O, free amide carbonyl), 1700(νC=O, associated amide carbonyl), 1650(νC=O, urea carbonyl), 1600(νbenzene ring skeleton).

[0045] The obtained modified elastomer was subjected to tensile testing and compared with the polyurethane matrix, and the results are shown in Figure 3As shown, the bishindoril-modified polyurethane elastomer greatly improves the mechanical properties compared with the matrix, the tensile rate of the material is increased from the original 9 times to more than 14 times, and the tensile strength is increased by 59%.

[0046] The obtained bishindoril-modified polyurethane elastomer is cut and spliced, and then repaired at room temperature for 3h with 40μl of anhydrous ethanol to assist, and then stretched for testing, and the results are as shown in Figure 4 As shown, the tensile strength is basically restored to 75% of the original.

[0047] The polyurethane matrix and the bishindoril-modified polyurethane elastomer are subjected to DMA testing, and the results are as shown in Figure 5 As shown, the bishindoril-modified polyurethane elastomer greatly improves the damping performance compared with the matrix, and the damping factor is greater than 0.4 in the range of minus 20 degrees Celsius to room temperature, and has good damping performance.

[0048] Example 2

[0049] A preparation method of a bishindoril-modified polyurethane elastomer, the method steps comprising:

[0050] In the first step, dry N2 is continuously introduced throughout the reaction process, 3.52g of TDI is added to a 100ml three-necked flask, 19.9g of PPG2000 is added to a constant pressure dropping funnel and added dropwise, and the oil bath temperature is maintained at 60-70℃, and the dropping is completed within 15min. After the PPG2000 is added dropwise, the temperature of the oil bath is increased to 80±2℃, and the reaction is maintained for 2h to obtain a polyurethane prepolymer.

[0051] In the second step, 0.3995g of the polyurethane prepolymer obtained in the first step and 25mL of isopropanol are mixed in a 50℃ water bath environment for 10min, then 4 drops of bromocresol blue indicator and 50mL of di-n-butylamine toluene solution are added, and then 0.1mol / L dilute hydrochloric acid is used for titration until the solution does not change color within 30s, and the titration is stopped. After the titration is completed, the isocyanate content a of the polyurethane prepolymer is calculated to be 3.63%.

[0052] Third step, 5.74g of polyurethane prepolymer was dissolved in 10ml DMF, added to a 100ml three-necked flask, stirred at 0℃ under N2atmosphere for 10min, the stirring speed was 180-220r / min, 0.409g IPDA dissolved in 10ml DMF was slowly added by constant pressure dropping funnel, the dropping time was more than 10min. The mixture was stirred at 0℃ under N2atmosphere for 10h, the stirring speed was 180-220r / min, then the temperature was increased to 85±2℃ and reacted for 4h. After cooling to room temperature, 3ml of ethanol was added to remove residual isocyanate, the reaction mixture was poured into a PTFE mold, dried in an oven at 90℃ for 48h, then dried in a vacuum oven at 80℃ for 12h to remove solvent and bubbles, and a polyurethane elastomer was obtained.

[0053] Fourth step, 6.23g of polyurethane elastomer was dissolved in 30ml of anhydrous ethanol, 0.313g of 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisoindane was added, and the polyurethane elastomer was stirred and blended at a stirring speed of 800r / min for 2h, and then poured into a polytetrafluoroethylene mold and dried in a fume hood for 24h to obtain a spirobisoindane-modified polyurethane elastomer.

[0054] The tensile strength of the polyurethane matrix was 8.2MPa, and the tensile rate was 1100%. The tensile strength of the spirobisoindane-modified polyurethane elastomer was 11.9MPa, and the tensile rate was 1380%, and the damping factor was greater than 0.4 in the range of 20 degrees Celsius below zero to room temperature.

[0055] Example 3

[0056] A method for preparing a spirobisoindane-modified polyurethane elastomer, the method steps comprising:

[0057] First step, dry N2was continuously introduced throughout the reaction process, 3.52g of TDI was added to a 100ml three-necked flask, 20.4g of PPG2000 was added to a constant pressure dropping funnel and added dropwise, the oil bath temperature was maintained at 60-70℃, and the dropping was completed within 15min. After the PPG2000 was added dropwise, the temperature of the oil bath was increased to 80±2℃, and the reaction was maintained for 2h to obtain a polyurethane prepolymer.

[0058] Second step, 0.3975g of the polyurethane prepolymer obtained in the first step was mixed with 25ml of isopropyl alcohol under a 50℃ water bath environment for 10min, then 4 drops of bromocresol blue indicator and 50ml of di-n-butylamine toluene solution were added, and titration was performed using 0.1mol / L dilute hydrochloric acid until the solution did not change color within 30s, the titration was stopped, and the isocyanate content a of the polyurethane prepolymer was calculated to be 3.6%.

[0059] Third step, 5.77g of polyurethane prepolymer was dissolved in 10ml DMF, added to a 100ml three-necked flask, stirred at 0℃ under N2atmosphere for 10min, the stirring speed was 180-220r / min, 0.410g IPDA dissolved in 10ml DMF was slowly added by constant pressure dropping funnel, the dropping time was more than 10min. The mixture was stirred at 0℃ under N2atmosphere for 10h, the stirring speed was 180-220r / min, then the temperature was raised to 85±2℃ and reacted for 4h. After cooling to room temperature, 3ml of ethanol was added to remove the residual isocyanate, the reaction mixture was poured into a polytetrafluoroethylene (PTFE) mold, dried in an oven at 90℃ for 48h, then dried in a vacuum oven at 80℃ for 12h to remove the solvent and bubbles, and a polyurethane elastomer was obtained.

[0060] Fourth step, 5.75g of polyurethane elastomer was dissolved in 30ml of anhydrous ethanol, 0.288g of 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisoindoline was added and stirred with the polyurethane elastomer at a stirring speed of 800r / min for 2h, and then poured into a polytetrafluoroethylene mold and dried in a fume hood for 24h to obtain a bisindoline-modified polyurethane elastomer.

[0061] The tensile strength of the polyurethane matrix was 7.9MPa, and the tensile rate was 930%. The tensile strength of the bisindoline-modified polyurethane elastomer was 12.3MPa, and the tensile rate was 1410%, and the damping factor was greater than 0.4 in the range of 20 degrees Celsius below zero to room temperature.

[0062] Example 4

[0063] A method for preparing a bisindoline-modified polyurethane elastomer, the method steps comprising:

[0064] First step, dry N2was continuously introduced throughout the reaction process, 3.48g of TDI was added to a 100ml three-necked flask, 19.9g of PPG2000 was added by constant pressure dropping funnel and added dropwise, the oil bath temperature was maintained at 60-70℃, and the dropping was completed within 15min. After the PPG2000 was added dropwise, the temperature of the oil bath was raised to 80±2℃ and reacted for 2h to obtain a polyurethane prepolymer.

[0065] Second step, 0.4049g of the polyurethane prepolymer obtained in the first step was mixed with 25ml of isopropyl alcohol at 50℃ in a water bath environment for 10min, then 4 drops of bromocresol blue indicator and 50ml of di-n-butylamine in toluene solution were added, and titration was carried out using 0.1mol / L dilute hydrochloric acid until the solution did not change color within 30s, the titration was stopped, and the isocyanate content a of the polyurethane prepolymer was calculated to be 3.6%.

[0066] Third step, 5.75g of polyurethane prepolymer was dissolved in 10ml DMF, added to a 100ml three-necked flask, stirred at 0°C under N2atmosphere for 10min, the stirring speed was 180-220r / min, 0.409g IPDA dissolved in 10ml DMF was slowly added by constant pressure dropping funnel, the dropping time was more than 10min. The mixture was stirred at 0°C under N2atmosphere for 10h, the stirring speed was 180-220r / min, then the temperature was raised to 85±2°C for 4h. After cooling to room temperature, 3ml of ethanol was added to remove residual isocyanate, the reaction mixture was poured into a polytetrafluoroethylene (PTFE) mold, dried in an oven at 90°C for 48h, then dried in a vacuum oven at 80°C for 12h to remove solvent and bubbles, to obtain a polyurethane elastomer.

[0067] Fourth step, 5.38g of polyurethane elastomer was dissolved in 30ml of anhydrous ethanol, 0.377g of 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisoindoline was added, and the polyurethane elastomer was stirred and blended at a stirring speed of 800r / min for 2h, and poured into a polytetrafluoroethylene mold and dried in a fume hood for 24h to obtain a bisindoline modified polyurethane elastomer.

[0068] The tensile strength of the polyurethane matrix was 8.3MPa, and the tensile rate was 900%. The tensile strength of the bisindoline modified polyurethane elastomer was 12.5MPa, and the tensile rate was 1440%, and the damping factor was greater than 0.4 in the range of minus 20 degrees Celsius to room temperature.

[0069] Example 5

[0070] A method for preparing a bisindoline modified polyurethane elastomer, the method steps comprising:

[0071] First step, dry N2was continuously introduced throughout the reaction process, 3.49g of TDI was added to a 100ml three-necked flask, 20.2g of PPG2000 was added to a constant pressure dropping funnel and added dropwise, the oil bath temperature was maintained at 60-70°C, and the dropping was completed within 15min. After the PPG2000 was added dropwise, the temperature of the oil bath was raised to 80±2°C, and the reaction was maintained for 2h to obtain a polyurethane prepolymer.

[0072] Second step, mix 0.4041 g of polyurethane prepolymer and 25 mL of isopropyl alcohol obtained in the first step in a water bath environment at 50°C, the mixing time is 10 min, then add 4 drops of bromo-cresol blue indicator and 50 mL of di-n-butylamine in toluene solution, then use 0.1 mol / L dilute hydrochloric acid for titration until the solution does not change color within 30 s, end the titration, calculate the isocyanate content a = 3.6% in the polyurethane prepolymer after the titration is completed.

[0073] Third step, dissolve 5.74 g of polyurethane prepolymer in 10 mL of DMF, add it into a 100 mL three-necked flask, stir at 0°C under N2 atmosphere for 10 min, the stirring speed is 180-220 r / min, slowly add 0.401 g of IPDA dissolved in 10 mL of DMF using a constant pressure dropping funnel, the dropping time is more than 10 min. Stir the mixture at 0°C under N2 atmosphere for 10 h, the stirring speed is 180-220 r / min, then increase the temperature to 85±2°C and react for 4 h. After cooling to room temperature, add 3 mL of ethanol to remove residual isocyanate, pour the reaction mixture into a PTFE mold, dry in an oven at 90°C for 48 h, then dry in a vacuum oven at 80°C for 12 h to remove solvent and bubbles, obtain a polyurethane elastomer.

[0074] Fourth step, dissolve 6.03 g of polyurethane elastomer in 30 mL of anhydrous ethanol, add 0.485 g of 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisoindane, stir and blend with the polyurethane elastomer, the stirring speed is 800 r / min, mix for 2 h, pour into a polytetrafluoroethylene mold, dry in a fume hood for 24 h, obtain a spirobisoindane modified polyurethane elastomer.

[0075] The tensile strength of the polyurethane matrix is 7.6 MPa, and the tensile rate is 890%. The tensile strength of the spirobisoindane modified polyurethane elastomer is 12.1 MPa, and the tensile rate is 1420%, and the damping factor is greater than 0.4 in the range of minus 20 degrees Celsius to room temperature.

[0076] Comparative Example 1

[0077] A method for preparing a spirobisoindane modified polyurethane elastomer, the method steps comprising:

[0078] First step, continuously introduce dry N2 during the whole reaction process, add 3.49 g of TDI in a 100 mL three-necked flask, add 20.2 g of PPG2000 drop by drop using a constant pressure dropping funnel, the oil bath temperature is maintained at 60-70°C, and the dropping is completed within 15 min. After the dropping of PPG2000 is completed, increase the temperature of the oil bath to 80±2°C, and maintain the reaction for 2 h to obtain a polyurethane prepolymer.

[0079] Second step, 0.4041g of the polyurethane prepolymer obtained in the first step and 25mL of isopropanol were mixed in a water bath at 50℃ for 10min, then 4 drops of bromocresol blue indicator and 50mL of di-n-butylamine in toluene were added, and 0.1mol / L dilute hydrochloric acid was used for titration until the solution did not change color within 30s, the titration was stopped, and the isocyanate content a of the polyurethane prepolymer was calculated to be 3.6%.

[0080] Third step, 7.36g of the polyurethane prepolymer and 0.83g of TDI were dissolved in 20ml of DMF, added to a 100ml three-necked flask, stirred at 0℃ under N2atmosphere for 20min at a stirring speed of 180-220r / min, 1.36g of IPDA dissolved in 10mL of DMF was slowly added by using a constant pressure dropping funnel, and the dropping time was more than 10min. The mixture was stirred at 0℃ under N2atmosphere for 10h at a stirring speed of 180-220r / min, and then the temperature was increased to 85±2℃ for reaction for 12h. After cooling to room temperature, 3mL of ethanol was added to remove residual isocyanate, the reaction mixture was poured into a PTFE mold, dried in an oven at 90℃ for 48h, and then dried in a vacuum oven at 80℃ for 24h to remove solvent and bubbles, to obtain a polyurethane elastomer.

[0081] Fourth step, 7.7g of the obtained polyurethane elastomer was dissolved in 30ml of anhydrous ethanol, 0.385g of 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisoindane was added, and the polyurethane elastomer was stirred and blended at a stirring speed of 800r / min for 2h, poured into a polytetrafluoroethylene mold, and dried in a fume hood for 24h to obtain a modified polyurethane elastomer.

[0082] The tensile strength of the polyurethane matrix was 40.7MPa, and the tensile rate was 1641%. The tensile strength of the modified polyurethane was 7.1MPa, and the tensile rate was 626%, and the damping factor did not change much. It can be seen that 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisoindane only has a good improvement effect on the polyurethane of a specific system.

[0083] In summary, the invention includes but is not limited to the above embodiments, any equivalent replacement or partial improvement made within the spirit and principles of the invention shall be considered within the protection scope of the invention.

Claims

1. A bis-indenyl modified polyurethane elastomer characterized by: The structural formula is: wherein, represents a hydrogen bond, represents a nonpolar intermolecular force, represents a π-π complex, n is an integer greater than or equal to 1000.

2. A bis-indenyl modified polyurethane elastomer as claimed in claim 1, wherein: n is an integer of 1000-2000.

3. A bis-indenyl modified polyurethane elastomer as claimed in claim 1 or 2, characterized in that: The preparation of the double-indane modified polyurethane elastomer is composed of A component, B component and C component, the A component and the B component are cured to form a polyurethane elastomer matrix, and the polyurethane elastomer matrix is mixed with the C component to obtain the double-indane modified polyurethane elastomer. The total mass of the raw materials for preparing the A component is 100 parts, and the components and their mass fractions are as follows: toluene diisocyanate 14%-16%; polypropylene glycol 84%-86%. The B component is isophorone diamine, and the C component is 5,5', 6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spiral double-indane. The molar ratio of the -NCO groups in the A component to the amine groups in the B component isophorone diamine is 1:1-1.05, and the mass of the C component is 5-10% of the mass of the polyurethane elastomer matrix.

4. A bis-indenyl modified polyurethane elastomer as claimed in claim 3, wherein: The molecular weight of the polypropylene glycol is 960-2080.

5. A process for the preparation of the bis-indane modified polyurethane elastomer as claimed in any one of claims 1 to 4, characterized by: The method steps include: (1) Under a protective gas atmosphere, mix the dehydrated A component toluene diisocyanate and polypropylene glycol, stir and react at 80±2℃ for 2-3h to obtain a polyurethane prepolymer; (2) Dissolve the polyurethane prepolymer in a first organic solvent at 0-10℃, and stir for more than 10min to obtain a prepolymer solution; (3) Dissolve the B component isophorone diamine in a first organic solvent, add the prepolymer solution under a protective gas atmosphere and at 0-10℃, and stir for more than 10h, then warm to 83-87℃, stir and react for more than 4h, then pour into a mold, and solidify at 80-85℃ for more than 48h, and dry to obtain a polyurethane elastomer matrix; (4) Dissolve the polyurethane elastomer matrix in a second organic solvent, add the C component 5,5', 6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spiral double-indane, stir and mix uniformly, and then volatilize the solvent to obtain a double-indane modified polyurethane elastomer.

6. The process for preparing a bis-indane modified polyurethane elastomer as claimed in claim 5, wherein: The protective gas is nitrogen or an inert gas.

7. The method for preparing a bis-indene-modified polyurethane elastomer as described in claim 5, characterized in that: The first organic solvent is N,N-dimethylformamide; The second organic solvent is one or more of N,N-dimethylformamide, anhydrous ethanol and tetrahydrofuran.

8. The method for preparing a bis-indene-modified polyurethane elastomer as described in claim 5, characterized in that: In steps (1) and (3), the stirring rate is 180-220r / min.

9. The process for preparing a bis-indane modified polyurethane elastomer as claimed in claim 5, wherein: In step (3), the drying temperature is 80-90℃, and the drying time is more than 24h.

10. The process for preparing a bis-indane modified polyurethane elastomer as claimed in claim 5, wherein: In step (4), the stirring rate is 800-1000r / min.

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