A high-damping, fatigue-resistant, and aging-resistant polyurethane elastomer and its preparation method

Abstract

This invention belongs to the technical field of polyurethane materials and proposes a high-damping, fatigue-resistant, and aging-resistant polyurethane elastomer and its preparation method. The raw materials, by weight, include 20-30 parts of polydiethylene glycol adipate (PDA), 30-50 parts of polytetramethylene ether glycol (PTMEG), 5-15 parts of a chain extender, 0.1-0.3 parts of A33, 0.1-0.2 parts of an organotin catalyst, 2-5 parts of a hindered phenolic antioxidant, 1-3 parts of a hindered amine light stabilizer, 3-8 parts of nanoparticles, and 30-50 parts of an isocyanate prepolymer. The isocyanate prepolymer is prepared from 1,4-phenylenediisocyanate (PPDI) and branched polytetramethylene glycol (PTXG) in a mass ratio of 1:1.8-2.2. This polyurethane elastomer exhibits excellent damping and fatigue-resistant properties, meeting the requirements for use in complex working conditions.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane materials and relates to a high-damping fatigue-resistant and aging-resistant polyurethane elastomer and a preparation method thereof. Background Art

[0002] Polyurethane elastomers possess excellent physical and mechanical properties, such as high strength, high elasticity, and wear resistance, and are widely used in numerous fields, including automotive manufacturing, building shock absorption, and sporting goods. However, in practical applications, polyurethane elastomers are often subject to the influence of dynamic loads and environmental factors, resulting in insufficient damping performance and prone to fatigue aging, limiting their application in areas requiring high damping and durability. Therefore, the development of polyurethane elastomers with high damping and fatigue aging resistance is of great practical significance. Summary of the Invention

[0003] The present invention provides a high-damping, fatigue-resistant and aging-resistant polyurethane elastomer and a preparation method thereof, which solves the problem in the prior art that the damping performance and fatigue-resistant aging performance of polyurethane materials need to be improved. The polyurethane elastomer meets the use requirements under complex working conditions.

[0004] The technical solution of the present invention is achieved as follows:

[0005] A high-damping, fatigue-resistant, and aging-resistant polyurethane elastomer comprises, by weight, 20-30 parts of polydiethylene glycol adipate diol, 30-50 parts of polytetramethylene ether diol, 5-15 parts of a chain extender, 0.1-0.3 parts of A33, 0.1-0.2 parts of an organotin catalyst, 2-5 parts of a hindered phenol antioxidant, 1-3 parts of a hindered amine light stabilizer, 3-8 parts of nanoparticles, and 30-50 parts of an isocyanate prepolymer.

[0006] The isocyanate prepolymer is prepared from 1,4-phenylenediisocyanate and branched polytetrahydrofuran diol PTXG in a mass ratio of 1:1.8-2.2.

[0007] Preferably, the preparation method of the isocyanate prepolymer comprises the following steps:

[0008] The branched polytetrahydrofuran diol PTXG is heated to 100-110° C. and vacuumed for 1.5-3 hours. The temperature is then lowered to 70-80° C. In the presence of an inert gas, 1,4-phenylenediisocyanate is added to the branched polytetrahydrofuran diol PTXG at a stirring speed of 1500-2500 rpm. The stirring is stopped after 1-2 hours to obtain an isocyanate prepolymer.

[0009] The reaction formula of the preparation process is as follows:

[0010]

[0011] Preferably, the branched polytetrahydrofuran diol PTXG is dried in a vacuum drying oven at 80-100° C. for 2-4 hours; this step removes moisture to prevent the moisture from reacting with 1,4-phenylenediisocyanate and affecting the reaction.

[0012] Preferably, during the synthesis of the isocyanate prepolymer, the reaction temperature is controlled at 70-80° C. to ensure uniform reaction and obtain a prepolymer with a narrow molecular weight distribution, which is beneficial to the stability of subsequent reactions and the performance of the final product.

[0013] Preferably, the trade mark containing branched polytetrahydrofuran diol PTXG is PTXG-1000, PTXG-1500 or PTXG-1800.

[0014] Preferably, the brand of the branched polytetrahydrofuran diol PTXG is PTXG-1500; and the mass ratio of 1,4-phenylene diisocyanate to the branched polytetrahydrofuran diol PTXG is 1:2.

[0015] Preferably, the chain extender is selected from one or more of 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylene glycol dipropionate.

[0016] Preferably, the organotin catalyst is one or more selected from dibutyltin dilaurate, stannous octoate, dibutyltin didodecylsulfide, dibutyltin diacetate, dioctyltin dilaurate and dibutyltin diacetate.

[0017] Preferably, the particle size of the nanoparticles is 0.5-1 μm, and the nanoparticles are nano-silicon dioxide and / or nano-calcium carbonate.

[0018] Preferably, the hindered phenol antioxidant is selected from one or more of antioxidant 1010, antioxidant 245, and antioxidant 1135. This component can effectively capture free radicals, inhibit oxidation reactions, and improve the material's resistance to thermal oxidative aging.

[0019] Preferably, the hindered amine light stabilizer is selected from one or more of Tinuvin 770, Tinuvin 711 and Tinuvin 144. This component can absorb ultraviolet light and convert it into harmless heat energy, preventing the material from degradation due to light aging.

[0020] Preferably, the molecular weight of the poly(diethylene glycol adipate) diol is 1000-2000; the molecular weight of the poly(tetramethylene ether) diol is 1000-3000.

[0021] Preferably, the molecular weight of polydiethylene glycol adipate diol is 2000; the molecular weight of polytetramethylene ether diol is 2000.

[0022] The method for preparing the high-damping fatigue-resistant and aging-resistant polyurethane elastomer comprises the following steps:

[0023] A. Ultrasonic dispersion of nanoparticles using a dispersant;

[0024] B. Adding the nanoparticles, hindered phenol antioxidant, hindered amine light stabilizer, chain extender, A33, organotin catalyst and polydiethylene glycol adipate diol after ultrasonic dispersion treatment to polytetramethylene ether diol, and then stirring at a speed of 1500-2000 rpm for 10-15 minutes; then adding the isocyanate prepolymer, rapidly stirring at 1500-2000 rpm for 10-20 seconds, pouring into a mold preheated to 100-120° C., and continuing to react in the mold for 10-15 minutes to obtain a molded polyurethane elastomer; this step allows the material to fully chain extend and crosslink to obtain a high-damping fatigue-resistant and aging-resistant polyurethane elastomer. During the chain extension and crosslinking reaction stages, the reaction temperature and time are reasonably controlled to ensure that the components are evenly dispersed and fully reacted to form a stable crosslinked network structure. At the same time, the nanoparticles are evenly embedded in the polymer matrix to play its role in enhancing damping and fatigue resistance;

[0025] C. Remove the formed polyurethane elastomer from the mold and allow it to cool naturally at room temperature for 24-48 hours to post-cure. This step, as a post-processing step, further improves the material's performance stability. The finished product can then be processed, such as cutting and polishing, as needed, to obtain the final product.

[0026] Preferably, the step A further includes raw material pretreatment, which includes the following steps:

[0027] The poly(diethylene glycol adipate) glycol, polytetramethylene ether glycol and chain extender are dried separately in a vacuum drying oven at 80-100° C. for 2-4 hours. This step removes moisture to prevent the moisture from reacting with isocyanate and affecting the polymerization reaction.

[0028] Preferably, in step A, the dispersant is acetone, the ultrasonic dispersion treatment is carried out for 30-60 minutes, the amount of the dispersant is 1-2 times the mass of the nanoparticles, the ultrasonic power is 200-500W, and the frequency is 20-50kHz;

[0029] Preferably, the temperature is lowered to 30-60° C. before adding the isocyanate prepolymer in step B.

[0030] The working principle and beneficial effects of the present invention are:

[0031] 1. In the polyurethane elastomer raw material system provided by the present invention, the various components work together to improve the comprehensive performance of the polyurethane elastomer. On the basis of maintaining the original excellent physical and mechanical properties of the polyurethane material, such as high strength, high elasticity, and wear resistance, it also has high damping and fatigue aging resistance, which can meet the demand for high-performance materials in various engineering fields, such as automotive parts, building shock-absorbing materials, and aerospace structural parts.

[0032] The isocyanate prepolymer serves as the basic skeleton of the polyurethane elastomer, providing the primary crosslinking points and network structure. The compact molecular structure of 1,4-phenylenediisocyanate (PPDI) gives the resulting polyurethane elastomer excellent dynamic mechanical properties. The addition of branched polytetramethylene glycol (PTXG) further enhances the polyurethane's flexibility and elasticity, helping to improve its fatigue resistance. The two react to form the crosslinked structure of the isocyanate prepolymer. This crosslinked structure helps disperse stress, reducing the initiation and propagation of cracks, thereby improving the polyurethane's damping and fatigue resistance. By controlling the prepolymer's composition and degree of crosslinking, it exhibits excellent damping properties.

[0033] The isocyanate groups (-NCO) in the isocyanate prepolymer react with the subsequently added polyethylene glycol adipate diol and polytetramethylene ether diol to form a highly cross-linked network. The synergistic effect of the cross-linked structure of the isocyanate prepolymer and the soft segments polyethylene glycol adipate diol and polytetramethylene ether diol gives the material excellent fatigue resistance during repeated loading and unloading.

[0034] 2. In the present invention, by adding nanoparticles, the friction loss inside the material is increased, and the damping performance of the polyurethane elastomer is effectively improved, so that it can better absorb energy under vibration and impact conditions, reduce vibration transmission and noise generation; at the same time, its small size effect and surface effect help to enhance the overall performance of the material and disperse stress, thereby improving fatigue resistance.

[0035] 3. The synergistic effect of the hindered phenol antioxidant and the hindered amine light stabilizer in the present invention effectively inhibits the aging and degradation of the material in thermal oxygen and light environments. The reinforcement and stress dispersion effects of the nanoparticles improve the fatigue resistance of the material, so that the polyurethane elastomer can still maintain good performance under long-term dynamic loads and complex environments, extending the service life of the material and broadening its application range. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0037] Figure 1 This is the infrared spectrum of the isocyanate prepolymer prepared in Example 1 of the present invention;

[0038] In the figure: PPDI represents p-phenylene diisocyanate, and PPDI+PTXG represents an isocyanate prepolymer synthesized from p-phenylene diisocyanate and branched polytetramethylene glycol. DETAILED DESCRIPTION

[0039] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0040] The materials used in the present invention can all be purchased from commercial sources. The molecular weight refers to the index-average molecular weight. Some of the materials can be purchased from the following sources:

[0041] Polyethylene glycol adipate (PDA) with a molecular weight of 1000-2000 was purchased from Zhejiang Huafeng New Materials Co., Ltd.

[0042] Polytetramethylene ether glycol (PTMEG) with a molecular weight of 1000-3000 was purchased from BASF (China) Co., Ltd.

[0043] 1,4-Butanediol (BDO) was purchased from Meike Chemical Co., Ltd.;

[0044] A33 (triethylenediamine solution) was purchased from Momentive Chemical Co., Ltd.

[0045] Dibutyltin dilaurate (DBTDL, T12) was purchased from Momentive Chemical Co., Ltd.

[0046] 1,4-phenylenediisocyanate (PPDI) was purchased from Zhejiang Lishui Youbang Chemical Co., Ltd.

[0047] The brands of branched polytetramethylene glycol PTXG are PTXG-1000, PTXG-1500, and PTXG-1800, which were purchased from Asahi Kasei Corporation of Japan;

[0048] The particle size of nano-silicon dioxide and nano-calcium carbonate is 0.5-1 μm.

[0049] Example 1

[0050] (1) A high-damping, fatigue-resistant, and aging-resistant polyurethane elastomer, comprising, by weight, 25 parts of polydiethylene glycol adipate diol, 40 parts of polytetramethylene ether diol, 10 parts of a chain extender, 0.2 parts of A33, 0.15 parts of an organic tin catalyst, 3 parts of a hindered phenol antioxidant, 2 parts of a hindered amine light stabilizer, 5 parts of nanoparticles, and 40 parts of an isocyanate prepolymer;

[0051] The molecular weight of polydiethylene glycol adipate diol is 2000; the molecular weight of polytetramethylene ether diol is 2000;

[0052] The chain extender is 1,4-butanediol and diethylene glycol dipropionate in a mass ratio of 3:1;

[0053] The organotin catalyst is dibutyltin dilaurate;

[0054] The nanoparticles are nanosilica;

[0055] The hindered phenol antioxidant is antioxidant 1010;

[0056] The hindered amine light stabilizer is Tinuvin770;

[0057] The isocyanate prepolymer is prepared from 1,4-phenylenediisocyanate and branched polytetrahydrofuran diol PTXG in a mass ratio of 1:2; the brand of branched polytetrahydrofuran diol PTXG is PTXG-1500;

[0058] The preparation method of the isocyanate prepolymer comprises the following steps:

[0059] The dried branched polytetrahydrofuran diol PTXG was heated to 105° C. and vacuumed for 2 hours, then cooled to 75° C. In the presence of an inert gas, 1,4-phenylene diisocyanate was added to the branched polytetrahydrofuran diol PTXG. During the process, the temperature was controlled at 75° C., the stirring speed was 2000 rpm, and the stirring was stopped after 1.5 hours to obtain an isocyanate prepolymer.

[0060] (2) The method for preparing the above-mentioned high-damping fatigue-resistant polyurethane elastomer comprises the following steps:

[0061] A. Ultrasonic dispersion of the nanoparticles with acetone (dispersant) for 40 minutes, with the amount of dispersant being 1.5 times the mass of the nanoparticles, the ultrasonic power being 400 W, and the frequency being 30 kHz;

[0062] Before step A, the raw material pretreatment is also included, which includes the following steps:

[0063] Poly(diethylene glycol adipate) glycol, polytetramethylene ether glycol and chain extender were dried separately in a vacuum drying oven at 90 °C for 3 h;

[0064] B. Cooling the isocyanate prepolymer to 55° C., sequentially adding ultrasonically dispersed nanoparticles, hindered phenol antioxidant, hindered amine light stabilizer, chain extender, A33, organotin catalyst, and polydiethylene glycol adipate diol to polytetramethylene ether diol, and stirring at 1800 rpm for 12 minutes; then adding the isocyanate prepolymer, rapidly stirring at 1800 rpm for 15 seconds, and pouring the mixture into a mold preheated to 110° C., and continuing the reaction in the mold for 12 minutes to obtain a molded polyurethane elastomer;

[0065] C. Remove the molded polyurethane elastomer from the mold and place it at room temperature for 32 hours to allow it to cool naturally and post-curing.

[0066] Example 2

[0067] (1) A high-damping, fatigue-resistant, and aging-resistant polyurethane elastomer, comprising, by weight, 20 parts of polydiethylene glycol adipate diol, 50 parts of polytetramethylene ether diol, 5 parts of a chain extender, 0.3 parts of A33, 0.1 parts of an organic tin catalyst, 5 parts of a hindered phenol antioxidant, 1 part of a hindered amine light stabilizer, 8 parts of nanoparticles, and 30 parts of an isocyanate prepolymer;

[0068] The molecular weight of polydiethylene glycol adipate diol is 2000; the molecular weight of polytetramethylene ether diol is 1000;

[0069] The chain extender is 1,6-hexanediol;

[0070] The organotin catalyst is dioctyltin dilaurate and dibutyltin didodecylsulfide in a mass ratio of 1:1;

[0071] The nanoparticles are nano-calcium carbonate;

[0072] The hindered phenol antioxidant is antioxidant 245;

[0073] The hindered amine light stabilizer is Tinuvin711;

[0074] The isocyanate prepolymer is prepared from 1,4-phenylenediisocyanate and branched polytetrahydrofuran diol PTXG in a mass ratio of 1:2.2; the brand of branched polytetrahydrofuran diol PTXG is PTXG-1000;

[0075] The preparation method of the isocyanate prepolymer comprises the following steps:

[0076] The branched polytetrahydrofuran diol PTXG was heated to 100° C. and vacuumed for 3 hours, then cooled to 70° C. In the presence of an inert gas, 1,4-phenylene diisocyanate was added to the branched polytetrahydrofuran diol PTXG. During the process, the temperature was controlled at 70° C. and the stirring speed was 2500 rpm. The stirring was stopped after 1 hour to obtain an isocyanate prepolymer.

[0077] (2) The method for preparing the above-mentioned high-damping fatigue-resistant polyurethane elastomer comprises the following steps:

[0078] A. Ultrasonic dispersion of nanoparticles with acetone (dispersant) for 60 minutes, with the amount of dispersant being 1 times the mass of the nanoparticles, the ultrasonic power being 500 W, and the frequency being 20 kHz;

[0079] Before step A, the raw material pretreatment is also included, which includes the following steps:

[0080] Poly(diethylene glycol adipate) glycol, polytetramethylene ether glycol and chain extender were dried in a vacuum drying oven at 100 °C for 2 h.

[0081] B. Cooling the isocyanate prepolymer to 60° C., sequentially adding the ultrasonically dispersed nanoparticles, hindered phenol antioxidant, hindered amine light stabilizer, chain extender, A33, organotin catalyst, and polydiethylene glycol adipate diol to polytetramethylene ether diol, and stirring at 1500 rpm for 15 minutes; then adding the isocyanate prepolymer, rapidly stirring at 1500 rpm for 20 seconds, and pouring the mixture into a mold preheated to 120° C., and continuing the reaction in the mold for 10 minutes to obtain a molded polyurethane elastomer;

[0082] C. Remove the molded polyurethane elastomer from the mold and place it at room temperature for 48 hours to allow it to cool naturally and post-curing.

[0083] Example 3

[0084] (1) A high-damping, fatigue-resistant, and aging-resistant polyurethane elastomer, comprising, by weight, 30 parts of polydiethylene glycol adipate diol, 30 parts of polytetramethylene ether diol, 15 parts of a chain extender, 0.1 parts of A33, 0.2 parts of an organic tin catalyst, 2 parts of a hindered phenol antioxidant, 3 parts of a hindered amine light stabilizer, 3 parts of nanoparticles, and 50 parts of an isocyanate prepolymer;

[0085] The molecular weight of polydiethylene glycol adipate diol is 1000; the molecular weight of polytetramethylene ether diol is 3000;

[0086] The chain extender is neopentyl glycol;

[0087] The organotin catalyst is dibutyltin diacetate and stannous octoate in a mass ratio of 1:2;

[0088] The nanoparticles are nanosilica;

[0089] The hindered phenol antioxidant is antioxidant 1135;

[0090] The hindered amine light stabilizer is Tinuvin 144;

[0091] The isocyanate prepolymer is prepared from 1,4-phenylenediisocyanate and branched polytetrahydrofuran diol PTXG in a mass ratio of 1:1.8; the brand of branched polytetrahydrofuran diol PTXG is PTXG-1800;

[0092] The preparation method of the isocyanate prepolymer comprises the following steps:

[0093] The branched polytetrahydrofuran diol PTXG was heated to 110° C. and vacuumed for 1.5 hours, then cooled to 80° C. In the presence of an inert gas, 1,4-phenylene diisocyanate was added to the branched polytetrahydrofuran diol PTXG. During the process, the temperature was controlled at 80° C. and the stirring speed was 1500 rpm. The stirring was stopped after 2 hours to obtain an isocyanate prepolymer.

[0094] (2) The method for preparing the above-mentioned high-damping fatigue-resistant polyurethane elastomer comprises the following steps:

[0095] A. Ultrasonic dispersion of the nanoparticles with acetone (a dispersant) for 30 minutes, with the amount of dispersant being twice the mass of the nanoparticles, the ultrasonic power being 200 W, and the frequency being 50 kHz;

[0096] Before step A, the raw material pretreatment is also included, which includes the following steps:

[0097] Poly(diethylene glycol adipate) glycol, poly(tetramethylene ether) glycol and chain extender were dried separately in a vacuum drying oven at 80°C for 4 h;

[0098] B. Cooling the isocyanate prepolymer to 50° C., sequentially adding ultrasonically dispersed nanoparticles, hindered phenol antioxidant, hindered amine light stabilizer, chain extender, A33, organotin catalyst, and polydiethylene glycol adipate diol to polytetramethylene ether diol, and stirring at 2000 rpm for 10 minutes; then adding the isocyanate prepolymer, rapidly stirring at 2000 rpm for 10 seconds, and pouring the mixture into a mold preheated to 100° C., and continuing the reaction in the mold for 15 minutes to obtain a molded polyurethane elastomer;

[0099] C. Remove the molded polyurethane elastomer from the mold and place it at room temperature for 24 hours to allow it to cool naturally and post-curing.

[0100] Example 4

[0101] (1) A high-damping, fatigue-resistant, and aging-resistant polyurethane elastomer, comprising, by weight, 25 parts of polydiethylene glycol adipate diol, 40 parts of polytetramethylene ether diol, 10 parts of a chain extender, 0.2 parts of A33, 0.15 parts of an organic tin catalyst, 3 parts of a hindered phenol antioxidant, 2 parts of a hindered amine light stabilizer, 5 parts of nanoparticles, and 40 parts of an isocyanate prepolymer;

[0102] The molecular weight of polydiethylene glycol adipate diol is 2000; the molecular weight of polytetramethylene ether diol is 2000;

[0103] The chain extender is diethylene glycol dipropionate;

[0104] The organotin catalyst is dibutyltin dilaurate;

[0105] The nanoparticles are nanosilica;

[0106] The hindered phenol antioxidant is antioxidant 1010;

[0107] The hindered amine light stabilizer is Tinuvin770;

[0108] The isocyanate prepolymer is prepared from 1,4-phenylenediisocyanate and branched polytetrahydrofuran diol PTXG in a mass ratio of 1:2; the brand of branched polytetrahydrofuran diol PTXG is PTXG-1500;

[0109] The preparation method of the isocyanate prepolymer comprises the following steps:

[0110] The dried branched polytetrahydrofuran diol PTXG was heated to 105° C. and vacuumed for 2 hours, then cooled to 75° C. In the presence of an inert gas, 1,4-phenylene diisocyanate was added to the branched polytetrahydrofuran diol PTXG. During the process, the temperature was controlled at 75° C., the stirring speed was 2000 rpm, and the stirring was stopped after 1.5 hours to obtain an isocyanate prepolymer.

[0111] (2) The method for preparing the above-mentioned high-damping fatigue-resistant polyurethane elastomer comprises the following steps:

[0112] A. Ultrasonic dispersion of the nanoparticles with acetone (dispersant) for 40 minutes, with the amount of dispersant being 1.5 times the mass of the nanoparticles, the ultrasonic power being 400 W, and the frequency being 30 kHz;

[0113] Before step A, the raw material pretreatment is also included, which includes the following steps:

[0114] Poly(diethylene glycol adipate) glycol, polytetramethylene ether glycol and chain extender were dried separately in a vacuum drying oven at 90 °C for 3 h;

[0115] B. Cooling the isocyanate prepolymer to 55° C., sequentially adding ultrasonically dispersed nanoparticles, hindered phenol antioxidant, hindered amine light stabilizer, chain extender, A33, organotin catalyst, and polydiethylene glycol adipate diol to polytetramethylene ether diol, and stirring at 1800 rpm for 12 minutes; then adding the isocyanate prepolymer, rapidly stirring at 1800 rpm for 15 seconds, and pouring the mixture into a mold preheated to 110° C., and continuing the reaction in the mold for 12 minutes to obtain a molded polyurethane elastomer;

[0116] C. Remove the molded polyurethane elastomer from the mold and place it at room temperature for 32 hours to allow it to cool naturally and post-curing.

[0117] Example 5

[0118] (1) A high-damping, fatigue-resistant, and aging-resistant polyurethane elastomer, comprising, by weight, 25 parts of polydiethylene glycol adipate diol, 40 parts of polytetramethylene ether diol, 10 parts of a chain extender, 0.2 parts of A33, 0.15 parts of an organic tin catalyst, 3 parts of a hindered phenol antioxidant, 2 parts of a hindered amine light stabilizer, 5 parts of nanoparticles, and 40 parts of an isocyanate prepolymer;

[0119] The molecular weight of polydiethylene glycol adipate diol is 2000; the molecular weight of polytetramethylene ether diol is 2000;

[0120] The chain extender is 1,4-butanediol;

[0121] The organotin catalyst is dibutyltin dilaurate;

[0122] The nanoparticles are nanosilica;

[0123] The hindered phenol antioxidant is antioxidant 1010;

[0124] The hindered amine light stabilizer is Tinuvin770;

[0125] The isocyanate prepolymer is prepared from 1,4-phenylenediisocyanate and branched polytetrahydrofuran diol PTXG in a mass ratio of 1:2; the brand of branched polytetrahydrofuran diol PTXG is PTXG-1500;

[0126] The preparation method of the isocyanate prepolymer comprises the following steps:

[0127] The dried branched polytetrahydrofuran diol PTXG was heated to 105° C. and vacuumed for 2 hours, then cooled to 75° C. In the presence of an inert gas, 1,4-phenylene diisocyanate was added to the branched polytetrahydrofuran diol PTXG. During the process, the temperature was controlled at 75° C., the stirring speed was 2000 rpm, and the stirring was stopped after 1.5 hours to obtain an isocyanate prepolymer.

[0128] (2) The method for preparing the above-mentioned high-damping fatigue-resistant polyurethane elastomer comprises the following steps:

[0129] A. Ultrasonic dispersion of the nanoparticles with acetone (dispersant) for 40 minutes, with the amount of dispersant being 1.5 times the mass of the nanoparticles, the ultrasonic power being 400 W, and the frequency being 30 kHz;

[0130] Before step A, the raw material pretreatment is also included, which includes the following steps:

[0131] Poly(diethylene glycol adipate) glycol, polytetramethylene ether glycol and chain extender were dried separately in a vacuum drying oven at 90 °C for 3 h;

[0132] B. Cooling the isocyanate prepolymer to 55° C., sequentially adding ultrasonically dispersed nanoparticles, hindered phenol antioxidant, hindered amine light stabilizer, chain extender, A33, organotin catalyst, and polydiethylene glycol adipate diol to polytetramethylene ether diol, and stirring at 1800 rpm for 12 minutes; then adding the isocyanate prepolymer, rapidly stirring at 1800 rpm for 15 seconds, and pouring the mixture into a mold preheated to 110° C., and continuing the reaction in the mold for 12 minutes to obtain a molded polyurethane elastomer;

[0133] C. Remove the molded polyurethane elastomer from the mold and place it at room temperature for 32 hours to allow it to cool naturally and post-curing.

[0134] Comparative Example 1

[0135] (1) A high-damping, fatigue-resistant, and aging-resistant polyurethane elastomer, comprising, by weight, 25 parts of polydiethylene glycol adipate diol, 40 parts of polytetramethylene ether diol, 10 parts of a chain extender, 0.2 parts of A33, 0.15 parts of an organic tin catalyst, 3 parts of a hindered phenol antioxidant, 2 parts of a hindered amine light stabilizer, 5 parts of nanoparticles, and 40 parts of an isocyanate prepolymer;

[0136] The molecular weight of polydiethylene glycol adipate diol is 2000; the molecular weight of polytetramethylene ether diol is 2000;

[0137] The chain extender is 1,4-butanediol and diethylene glycol dipropionate in a mass ratio of 3:1;

[0138] The organotin catalyst is dibutyltin dilaurate;

[0139] The nanoparticles are nanosilica;

[0140] The hindered phenol antioxidant is antioxidant 1010;

[0141] The hindered amine light stabilizer is Tinuvin770;

[0142] The isocyanate prepolymer is prepared from 1,4-phenylenediisocyanate and PTMEG-2000 in a mass ratio of 1:2;

[0143] The preparation method of the isocyanate prepolymer comprises the following steps:

[0144] The dried PTMEG-2000 was heated to 105°C and vacuumed for 2 hours, then cooled to 75°C. In the presence of an inert gas, 1,4-phenylenediisocyanate was added to the PTMEG-2000. During the process, the temperature was controlled at 75°C and the stirring speed was 2000 rpm. The stirring was stopped after 1.5 hours to obtain an isocyanate prepolymer.

[0145] (2) The method for preparing the above-mentioned high-damping fatigue-resistant polyurethane elastomer comprises the following steps:

[0146] A. Ultrasonic dispersion of the nanoparticles with acetone (dispersant) for 40 minutes, with the amount of dispersant being 1.5 times the mass of the nanoparticles, the ultrasonic power being 400 W, and the frequency being 30 kHz;

[0147] Before step A, the raw material pretreatment is also included, which includes the following steps:

[0148] Poly(diethylene glycol adipate) glycol, polytetramethylene ether glycol and chain extender were dried separately in a vacuum drying oven at 90 °C for 3 h;

[0149] B. Cooling the isocyanate prepolymer to 55° C., sequentially adding ultrasonically dispersed nanoparticles, hindered phenol antioxidant, hindered amine light stabilizer, chain extender, A33, organotin catalyst, and polydiethylene glycol adipate diol to polytetramethylene ether diol, and stirring at 1800 rpm for 12 minutes; then adding the isocyanate prepolymer, rapidly stirring at 1800 rpm for 15 seconds, and pouring the mixture into a mold preheated to 110° C., and continuing the reaction in the mold for 12 minutes to obtain a molded polyurethane elastomer;

[0150] C. Remove the molded polyurethane elastomer from the mold and place it at room temperature for 32 hours to allow it to cool naturally and post-curing.

[0151] Comparative Example 2

[0152] (1) A high-damping, fatigue-resistant, and aging-resistant polyurethane elastomer, comprising, by weight, 25 parts of polydiethylene glycol adipate diol, 40 parts of polytetramethylene ether diol, 10 parts of a chain extender, 0.2 parts of A33, 0.15 parts of an organic tin catalyst, 3 parts of a hindered phenol antioxidant, 2 parts of a hindered amine light stabilizer, 5 parts of nanoparticles, and 40 parts of an isocyanate prepolymer;

[0153] The molecular weight of polydiethylene glycol adipate diol is 2000; the molecular weight of polytetramethylene ether diol is 2000;

[0154] The chain extender is 1,4-butanediol and diethylene glycol dipropionate in a mass ratio of 3:1;

[0155] The organotin catalyst is dibutyltin dilaurate;

[0156] The nanoparticles are nanosilica;

[0157] The hindered phenol antioxidant is antioxidant 1010;

[0158] The hindered amine light stabilizer is Tinuvin770;

[0159] The isocyanate prepolymer is prepared from MDI-50 and branched polytetrahydrofuran diol PTXG in a mass ratio of 1:2; the brand of branched polytetrahydrofuran diol PTXG is PTXG-1500;

[0160] The preparation method of the isocyanate prepolymer comprises the following steps:

[0161] The dried branched polytetrahydrofuran diol PTXG was heated to 105° C. and vacuumed for 2 h, then cooled to 75° C. In the presence of an inert gas, MDI-50 was added to the branched polytetrahydrofuran diol PTXG. During the process, the temperature was controlled at 75° C. and the stirring speed was 2000 rpm. The stirring was stopped after 1.5 h to obtain an isocyanate prepolymer.

[0162] (2) The method for preparing the above-mentioned high-damping fatigue-resistant polyurethane elastomer comprises the following steps:

[0163] A. Ultrasonic dispersion of the nanoparticles with acetone (dispersant) for 40 minutes, with the amount of dispersant being 1.5 times the mass of the nanoparticles, the ultrasonic power being 400 W, and the frequency being 30 kHz;

[0164] Before step A, the raw material pretreatment is also included, which includes the following steps:

[0165] Poly(diethylene glycol adipate) glycol, polytetramethylene ether glycol and chain extender were dried separately in a vacuum drying oven at 90 °C for 3 h;

[0166] B. Cooling the isocyanate prepolymer to 55° C., sequentially adding ultrasonically dispersed nanoparticles, hindered phenol antioxidant, hindered amine light stabilizer, chain extender, A33, organotin catalyst, and polydiethylene glycol adipate diol to polytetramethylene ether diol, and stirring at 1800 rpm for 12 minutes; then adding the isocyanate prepolymer, rapidly stirring at 1800 rpm for 15 seconds, and pouring the mixture into a mold preheated to 110° C., and continuing the reaction in the mold for 12 minutes to obtain a molded polyurethane elastomer;

[0167] C. Remove the molded polyurethane elastomer from the mold and place it at room temperature for 32 hours to allow it to cool naturally and post-curing.

[0168] Comparative Example 3

[0169] (1) A high-damping, fatigue-resistant, and aging-resistant polyurethane elastomer, comprising, by weight, 25 parts of polydiethylene glycol adipate diol, 40 parts of polytetramethylene ether diol, 10 parts of a chain extender, 0.2 parts of A33, 0.15 parts of an organic tin catalyst, 3 parts of a hindered phenol antioxidant, 2 parts of a hindered amine light stabilizer, 5 parts of nanoparticles, and 40 parts of 1,4-phenylenediisocyanate;

[0170] The molecular weight of polydiethylene glycol adipate diol is 2000; the molecular weight of polytetramethylene ether diol is 2000;

[0171] The chain extender is 1,4-butanediol and diethylene glycol dipropionate in a mass ratio of 3:1;

[0172] The organotin catalyst is dibutyltin dilaurate;

[0173] The nanoparticles are nanosilica;

[0174] The hindered phenol antioxidant is antioxidant 1010;

[0175] The hindered amine light stabilizer is Tinuvin770;

[0176] (2) The method for preparing the above-mentioned high-damping fatigue-resistant polyurethane elastomer comprises the following steps:

[0177] A. Ultrasonic dispersion of the nanoparticles with acetone (dispersant) for 40 minutes, with the amount of dispersant being 1.5 times the mass of the nanoparticles, the ultrasonic power being 400 W, and the frequency being 30 kHz;

[0178] Before step A, the raw material pretreatment is also included, which includes the following steps:

[0179] Poly(diethylene glycol adipate) glycol, polytetramethylene ether glycol and chain extender were dried separately in a vacuum drying oven at 90 °C for 3 h;

[0180] B. Adding the nanoparticles after ultrasonic dispersion treatment, hindered phenol antioxidant, hindered amine light stabilizer, chain extender, A33, organotin catalyst, and polydiethylene glycol adipate diol to polytetramethylene ether diol in sequence, and then stirring at 1800 rpm for 12 minutes; then adding 1,4-phenylene diisocyanate, after rapid stirring at 1800 rpm for 15 seconds, pouring into a mold preheated to 110° C., and continuing to react in the mold for 12 minutes to obtain a molded polyurethane elastomer;

[0181] C. Remove the molded polyurethane elastomer from the mold and place it at room temperature for 32 hours to allow it to cool naturally and post-curing.

[0182] The polyurethane elastomers obtained in the above examples and comparative examples were subjected to performance tests, as shown in Table 1 below. The test results show that, compared with ordinary polyurethane elastomers, the high-damping, fatigue-resistant, and aging-resistant polyurethane elastomer of the present invention has significantly improved damping performance, and the loss factor can be increased by 30%-50%. It is significantly better than ordinary polyurethane elastomer in fatigue resistance and mechanical property retention rate, and has good anti-aging performance.

[0183] The test method is as follows:

[0184] Tensile strength and elongation at break refer to GB / T528-2009;

[0185] Damping factor is determined according to ASTM D5418-23, with a sample size of 40 mm x 7 mm x 2 mm, a tensile test mode, a heating rate of 1°C / min, a test temperature range of -80°C to 100°C, and a vibration frequency of 1 Hz. tanδmax is the maximum damping factor.

[0186] Fatigue aging test: using MTS fatigue testing machine, sample size 400mm*400mm*12mm, test conditions: room temperature, force 20-80kN, 1 million cycles, frequency 4Hz.

[0187] Table 1

[0188]

[0189] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A high-damping, fatigue-resistant, and aging-resistant polyurethane elastomer, comprising, by weight, 20 parts of polydiethylene glycol adipate diol, 50 parts of polytetramethylene ether diol, 5 parts of a chain extender, 0.3 parts of A33, 0.1 parts of an organotin catalyst, 5 parts of a hindered phenol antioxidant, 1 part of a hindered amine light stabilizer, 8 parts of nanoparticles, and 30 parts of an isocyanate prepolymer; The molecular weight of polydiethylene glycol adipate diol is 2000; the molecular weight of polytetramethylene ether diol is 1000; The chain extender is 1,6-hexanediol; The organotin catalyst is dioctyltin dilaurate and dibutyltin didodecylsulfide in a mass ratio of 1:1; The nanoparticles are nano-calcium carbonate; The hindered phenol antioxidant is antioxidant 245; The hindered amine light stabilizer is Tinuvin711; The isocyanate prepolymer is prepared from 1,4-phenylenediisocyanate and branched polytetrahydrofuran diol PTXG in a mass ratio of 1:2.2; the brand of branched polytetrahydrofuran diol PTXG is PTXG-1000; The preparation method of the isocyanate prepolymer comprises the following steps: Heating the branched polytetrahydrofuran diol PTXG to 100° C. and evacuating the mixture for 3 hours, cooling the mixture to 70° C., and adding 1,4-phenylene diisocyanate to the branched polytetrahydrofuran diol PTXG in the presence of an inert gas, wherein the temperature is controlled at 70° C. and the stirring speed is 2500 rpm. The stirring is stopped after 1 hour to obtain an isocyanate prepolymer; The preparation method of the high-damping fatigue-resistant and aging-resistant polyurethane elastomer comprises the following steps: A. Ultrasonic dispersion of the nanoparticles with acetone (dispersant) for 60 minutes, with the amount of dispersant being 1 times the mass of the nanoparticles, the ultrasonic power being 500 W, and the frequency being 20 kHz; Before step A, the raw material pretreatment is also included, which includes the following steps: Poly(diethylene glycol adipate) glycol, polytetramethylene ether glycol and chain extender were dried in a vacuum drying oven at 100 °C for 2 h. B. Cooling the isocyanate prepolymer to 60° C., sequentially adding the ultrasonically dispersed nanoparticles, hindered phenol antioxidant, hindered amine light stabilizer, chain extender, A33, organotin catalyst, and polydiethylene glycol adipate diol to polytetramethylene ether diol, and stirring at 1500 rpm for 15 minutes; then adding the isocyanate prepolymer, rapidly stirring at 1500 rpm for 20 seconds, and pouring the mixture into a mold preheated to 120° C., and continuing the reaction in the mold for 10 minutes to obtain a molded polyurethane elastomer; C. Remove the molded polyurethane elastomer from the mold and place it at room temperature for 48 hours to allow it to cool naturally and post-curing.

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