High-damping anti-fatigue and anti-aging polyurethane elastomer and preparation method thereof

Abstract

The invention belongs to the technical field of polyurethane materials, and provides a high-damping anti-fatigue and anti-aging polyurethane elastomer and a preparation method thereof. The high-temperature-resistant polyurethane elastomer is prepared from the following raw materials in parts by weight: 20 to 30 parts of poly (diethylene glycol adipate) glycol (PDA), 30 to 50 parts of polytetrahydrofuran ether glycol (PTMEG), 5 to 15 parts of chain extender, 0.1 to 0.3 part of A33, 0.1 to 0.2 part of organic tin catalyst, 2 to 5 parts of hindered phenol antioxidant, 1 to 3 parts of hindered amine light stabilizer, 3 to 8 parts of nano particles and 30 to 50 parts of isocyanate prepolymer. The isocyanate prepolymer is prepared from 1, 4-phenyl diisocyanate (PPDI) and branched chain-containing polytetrahydrofuran glycol PTXG according to a mass ratio of 1: (1.8 to 2.2). The polyurethane elastomer is excellent in damping performance and fatigue aging resistance, and meets the use requirements under 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 aging polyurethane elastomer and a preparation method thereof. Background Art

[0002] Polyurethane elastomers have excellent physical and mechanical properties, such as high strength, high elasticity, and wear resistance, and are widely used in many fields, such as automobile manufacturing, building shock absorption, and sporting goods. However, in practical applications, polyurethane elastomers are often affected by dynamic loads and environmental factors, resulting in insufficient damping performance and prone to fatigue aging, which limits their application in some fields with high requirements for damping and durability. Therefore, it is of great practical significance to develop a polyurethane elastomer with high damping and anti-fatigue aging performance. Summary of the invention

[0003] The present invention provides a high-damping fatigue-resistant aging 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 in this way: A high-damping fatigue-resistant polyurethane elastomer, wherein the raw materials include, by weight, 20-30 parts of polydiethylene glycol adipate diol, 30-50 parts of polytetramethylene ether diol, 5-15 parts of chain extender, 0.1-0.3 parts of A33, 0.1-0.2 parts of organic tin catalyst, 2-5 parts of hindered phenol antioxidant, 1-3 parts of hindered amine light stabilizer, 3-8 parts of nanoparticles and 30-50 parts of isocyanate prepolymer; The isocyanate prepolymer is prepared from 1,4-phenylene diisocyanate and branched polytetrahydrofuran diol PTXG in a mass ratio of 1:1.8-2.2.

[0005] Preferably, the method for preparing the isocyanate prepolymer comprises the following steps: The branched polytetrahydrofuran diol PTXG is heated to 100-110° C. and vacuumed for 1.5-3 hours, then cooled to 70-80° C., and 1,4-phenylene diisocyanate is added to the branched polytetrahydrofuran diol PTXG in the presence of an inert gas, with a stirring speed of 1500-2500 rpm. The stirring is stopped after 1-2 hours to obtain an isocyanate prepolymer.

[0006] The reaction formula of the preparation process is as follows: 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-phenylene diisocyanate and affecting the reaction.

[0007] 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 final product performance.

[0008] Preferably, the grade of the branched polytetrahydrofuran diol PTXG is PTXG-1000, PTXG-1500 or PTXG-1800.

[0009] Preferably, the grade of the branched polytetrahydrofuran diol PTXG is PTXG-1500; the mass ratio of 1,4-phenylene diisocyanate to the branched polytetrahydrofuran diol PTXG is 1:2.

[0010] Preferably, the chain extender is selected from one or more of 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylene glycol dipropionate.

[0011] Preferably, the organotin catalyst is selected from one or more of dibutyltin dilaurate, stannous octoate, dibutyltin didodecylsulfide, dibutyltin diacetate, dioctyltin dilaurate and dibutyltin diacetate.

[0012] Preferably, the particle size of the nanoparticles is 0.5-1 μm, and the nanoparticles are nano-silicon dioxide and / or nano-calcium carbonate.

[0013] 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 thermal oxidation aging resistance of the material.

[0014] 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.

[0015] Preferably, the molecular weight of the poly(diethylene glycol adipate) glycol is 1000-2000; the molecular weight of the poly(tetramethylenetetramethylene ether) glycol is 1000-3000.

[0016] Preferably, the molecular weight of poly(diethylene glycol adipate) glycol is 2000; the molecular weight of poly(tetramethylenetetramethylene ether) glycol is 2000.

[0017] The method for preparing the above-mentioned high-damping fatigue-resistant polyurethane elastomer comprises the following steps: A. subjecting the nanoparticles to ultrasonic dispersion treatment using a dispersant; B. Add the nanoparticles, hindered phenol antioxidant, hindered amine light stabilizer, chain extender, A33, organotin catalyst and poly(diethylene glycol adipate) diol after ultrasonic dispersion treatment to polytetrahydrofuran ether diol, and then stir at 1500-2000rpm for 10-15min; then add isocyanate prepolymer, stir rapidly at 1500-2000rpm for 10-20s, pour into a mold preheated to 100-120°C, and continue to react in the mold for 10-15min to obtain a molded polyurethane elastomer; this step allows the material to fully chain extend and crosslink to obtain a high-damping fatigue-resistant polyurethane elastomer. In the chain extension and crosslinking reaction stage, the reaction temperature and time are reasonably controlled to ensure that each component is evenly dispersed and fully reacted to form a stable crosslinked network structure, and the nanoparticles are evenly embedded in the polymer matrix to play its role in enhancing damping and fatigue resistance; C. Take the formed polyurethane elastomer out of the mold and place it at room temperature for 24-48 hours to allow it to cool naturally and post-cured. This step is a post-processing step to further improve the performance stability of the material. Then, the product is cut, polished, and processed as needed to obtain the final product.

[0018] Preferably, the step A further includes raw material pretreatment, which includes the following steps: The poly(diethylene glycol adipate) glycol, poly(tetramethylene ether) glycol and chain extender are dried in a vacuum drying oven at 80-100° C. for 2-4 hours respectively; this step removes moisture to prevent the moisture from reacting with isocyanate and affecting the polymerization reaction.

[0019] Preferably, in step A, the dispersant is acetone, the ultrasonic dispersion treatment is performed 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; Preferably, in step B, the temperature is lowered to 30-60° C. before adding the isocyanate prepolymer.

[0020] The working principle and beneficial effects of the present invention are: 1. In the polyurethane elastomer raw material system provided by the present invention, the various components cooperate with each other to jointly 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, wear resistance, etc., it also has high damping and anti-fatigue and aging properties, and can meet the needs of various engineering fields for high-performance materials, such as automotive parts, building shock-absorbing materials, aerospace structural parts, etc.

[0021] Among them, isocyanate prepolymer serves as the basic skeleton of polyurethane elastomer, providing the main cross-linking points and network structure. 1,4-phenylene diisocyanate (PPDI) has a compact molecular structure, which makes the polyurethane elastomer prepared from it have excellent dynamic mechanical properties. The addition of branched polytetramethylene glycol PTXG further enhances the flexibility and elasticity of polyurethane, which helps to improve its fatigue resistance. The two react to form the cross-linked structure of isocyanate prepolymer. The cross-linked structure of isocyanate prepolymer helps to disperse stress and reduce the generation and expansion of cracks, thereby improving the damping performance and fatigue resistance of polyurethane. By controlling the composition and cross-linking degree of the prepolymer, it exhibits good damping performance.

[0022] The isocyanate group (-NCO) in the isocyanate prepolymer reacts with the subsequently added poly(diethylene glycol adipate) diol and poly(tetramethylene furan ether diol) to form a highly cross-linked network structure. The synergistic effect of the cross-linked structure of the isocyanate prepolymer and the soft segment poly(diethylene glycol adipate) diol and poly(tetramethylene furan ether diol) makes the material exhibit good fatigue resistance during repeated loading and unloading.

[0023] 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.

[0024] 3. The synergistic effect of the hindered phenol antioxidant and the hindered amine light stabilizer in the present invention effectively inhibits the aging degradation of the material under thermal oxygen and light environments. The reinforcement and stress dispersion effect 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, extend the service life of the material, and broaden its application range. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments.

[0026] Figure 1 This is the infrared spectrum of the isocyanate prepolymer prepared in Example 1 of the present invention; 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

[0027] 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 described embodiments 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 creative work are within the scope of protection of the present invention.

[0028] The materials used in the present invention can all be purchased from the market, and the molecular weight refers to the number-average molecular weight. Some of the materials can be purchased from the following sources: Poly(diethylene glycol adipate) (PDA) had a molecular weight of 1000-2000 and was purchased from Zhejiang Huafeng New Materials Co., Ltd.; Polytetramethylene glycol (PTMEG) has a molecular weight of 1000-3000 and was purchased from BASF (China) Co., Ltd.; 1,4-Butanediol (BDO) was purchased from Meike Chemical Co., Ltd.; A33 (triethylenediamine solution), purchased from Momentive Chemical Co., Ltd.; Dibutyltin dilaurate (DBTDL, T12) was purchased from Momentive Chemical Co., Ltd.; 1,4-phenylene diisocyanate (PPDI) was purchased from Zhejiang Lishui Youbang Chemical Co., Ltd.; The grades of branched polytetrahydrofurandiol PTXG are PTXG-1000, PTXG-1500 and PTXG-1800, which were purchased from Asahi Kasei Corporation of Japan; The particle size of nano silicon dioxide and nano calcium carbonate is 0.5-1 μm.

[0029] Example 1 (1) A high damping fatigue and aging resistant polyurethane elastomer, the raw materials comprising, by weight, 25 parts of poly(diethylene glycol adipate), 40 parts of polytetramethylene ether glycol, 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; The molecular weight of poly(diethylene glycol adipate) glycol is 2000; the molecular weight of poly(tetramethylene ether) glycol is 2000; The chain extender is 1,4-butanediol and diethylene glycol dipropionate in a mass ratio of 3:1; The organotin catalyst is dibutyltin dilaurate; The nanoparticles are nanosilicon dioxide; The hindered phenol antioxidant is antioxidant 1010; The hindered amine light stabilizer is Tinuvin 770; The isocyanate prepolymer is prepared from 1,4-phenylene diisocyanate and branched polytetrahydrofuran diol PTXG in a mass ratio of 1:2; the grade of branched polytetrahydrofuran diol PTXG is PTXG-1500; The preparation method of the isocyanate prepolymer comprises the following steps: 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.

[0030] (2) The method for preparing the above-mentioned high damping anti-fatigue and aging polyurethane elastomer comprises the following steps: A. The nanoparticles were ultrasonically dispersed with dispersant acetone for 40 minutes, the amount of dispersant was 1.5 times the mass of the nanoparticles, the ultrasonic power was 400 W, and the frequency was 30 kHz; Before step A, the raw material pretreatment is also included: comprising the following steps: Poly(diethylene glycol adipate) glycol, poly(tetramethylene ether) glycol and chain extender were dried in a vacuum drying oven at 90°C for 3 h; B. Cooling the isocyanate prepolymer to 55° C., adding the nanoparticles, hindered phenol antioxidant, hindered amine light stabilizer, chain extender, A33, organic tin catalyst and poly(diethylene glycol adipate) diol treated with ultrasonic dispersion to polytetramethylene ether diol in sequence, and then stirring at 1800 rpm for 12 min; then adding the isocyanate prepolymer, stirring rapidly at 1800 rpm for 15 s, pouring into a mold preheated to 110° C., and continuing to react in the mold for 12 min to obtain a formed polyurethane elastomer; C. Take the formed polyurethane elastomer out of the mold and place it at room temperature for 32 hours to allow it to cool naturally and post-curing.

[0031] Example 2 (1) A high damping fatigue aging resistant polyurethane elastomer, the raw materials comprising, by weight, 20 parts of polydiethylene glycol adipate diol, 50 parts of polytetramethylene ether diol, 5 parts of chain extender, 0.3 parts of A33, 0.1 parts of organic tin catalyst, 5 parts of hindered phenol antioxidant, 1 part of hindered amine light stabilizer, 8 parts of nanoparticles and 30 parts of isocyanate prepolymer; The molecular weight of poly(diethylene glycol adipate) glycol is 2000; the molecular weight of poly(tetramethylenetetramethylene ether) glycol 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 Tinuvin 711; The isocyanate prepolymer is prepared from 1,4-phenylene diisocyanate and branched polytetrahydrofuran diol PTXG in a mass ratio of 1:2.2; the grade of branched polytetrahydrofuran diol PTXG is PTXG-1000; The preparation method of the isocyanate prepolymer comprises the following steps: The branched polytetrahydrofuran diol PTXG is heated to 100°C and evacuated for 3 hours, then cooled to 70°C. In the presence of an inert gas, 1,4-phenylene diisocyanate is added to the branched polytetrahydrofuran diol PTXG. During the process, the temperature is controlled at 70°C, the stirring speed is 2500 rpm, and the stirring is stopped after 1 hour to obtain an isocyanate prepolymer.

[0032] (2) The method for preparing the above-mentioned high damping anti-fatigue and aging polyurethane elastomer comprises the following steps: A. The nanoparticles were subjected to ultrasonic dispersion treatment with dispersant acetone for 60 minutes, the amount of dispersant used was 1 times the mass of the nanoparticles, the ultrasonic power was 500 W, and the frequency was 20 kHz; Before step A, the raw material pretreatment is also included: comprising the following steps: Poly(diethylene glycol adipate) glycol, poly(tetramethylene 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., adding the nanoparticles, hindered phenol antioxidant, hindered amine light stabilizer, chain extender, A33, organic tin catalyst and poly(diethylene glycol adipate) diol treated with ultrasonic dispersion to polytetramethylene ether diol in sequence, and then stirring at 1500 rpm for 15 min; then adding the isocyanate prepolymer, stirring rapidly at 1500 rpm for 20 s, pouring into a mold preheated to 120° C., and continuing to react in the mold for 10 min to obtain a formed polyurethane elastomer; C. Take the formed polyurethane elastomer out of the mold and place it at room temperature for 48 hours to allow it to cool naturally and post-curing.

[0033] Example 3 (1) A high damping fatigue aging resistant polyurethane elastomer, the raw materials 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; The molecular weight of poly(diethylene glycol adipate) glycol is 1000; the molecular weight of poly(tetramethylenetetramethylene ether) glycol is 3000; The chain extender is neopentyl glycol; The organotin catalyst is dibutyltin diacetate and stannous octoate in a mass ratio of 1:2; The nanoparticles are nanosilicon dioxide; The hindered phenol antioxidant is antioxidant 1135; The hindered amine light stabilizer is Tinuvin 144; The isocyanate prepolymer is prepared from 1,4-phenylene diisocyanate and branched polytetrahydrofuran diol PTXG in a mass ratio of 1:1.8; the grade of branched polytetrahydrofuran diol PTXG is PTXG-1800; The preparation method of the isocyanate prepolymer comprises the following steps: The branched polytetrahydrofuran diol PTXG is heated to 110°C and evacuated for 1.5 hours, then cooled to 80°C. In the presence of an inert gas, 1,4-phenylene diisocyanate is added to the branched polytetrahydrofuran diol PTXG. During the process, the temperature is controlled at 80°C, the stirring speed is 1500 rpm, and the stirring is stopped after 2 hours to obtain an isocyanate prepolymer.

[0034] (2) The method for preparing the above-mentioned high damping anti-fatigue and aging polyurethane elastomer comprises the following steps: A. The nanoparticles were subjected to ultrasonic dispersion treatment with dispersant acetone for 30 minutes, the amount of dispersant used was twice the mass of the nanoparticles, the ultrasonic power was 200 W, and the frequency was 50 kHz; Before step A, the raw material pretreatment is also included: comprising the following steps: Poly(diethylene glycol adipate) glycol, poly(tetramethylene ether) glycol and chain extender were dried in a vacuum drying oven at 80°C for 4 h; B. Cooling the isocyanate prepolymer to 50° C., sequentially adding the nanoparticles, hindered phenol antioxidant, hindered amine light stabilizer, chain extender, A33, organic tin catalyst and poly(diethylene glycol adipate) diol treated with ultrasonic dispersion to polytetramethylene ether diol, and then stirring at 2000 rpm for 10 min; then adding the isocyanate prepolymer, rapidly stirring at 2000 rpm for 10 s, pouring into a mold preheated to 100° C., and continuing to react in the mold for 15 min to obtain a molded polyurethane elastomer; C. Take the formed polyurethane elastomer out of the mold and place it at room temperature for 24 hours to allow it to cool naturally and post-curing.

[0035] Example 4 (1) A high damping fatigue and aging resistant polyurethane elastomer, the raw materials comprising, by weight, 25 parts of poly(diethylene glycol adipate), 40 parts of polytetramethylene ether glycol, 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; The molecular weight of poly(diethylene glycol adipate) glycol is 2000; the molecular weight of poly(tetramethylene ether) glycol is 2000; The chain extender is diethylene glycol dipropionate; The organotin catalyst is dibutyltin dilaurate; The nanoparticles are nanosilicon dioxide; The hindered phenol antioxidant is antioxidant 1010; The hindered amine light stabilizer is Tinuvin 770; The isocyanate prepolymer is prepared from 1,4-phenylene diisocyanate and branched polytetrahydrofuran diol PTXG in a mass ratio of 1:2; the grade of branched polytetrahydrofuran diol PTXG is PTXG-1500; The preparation method of the isocyanate prepolymer comprises the following steps: 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.

[0036] (2) The method for preparing the above-mentioned high damping anti-fatigue and aging polyurethane elastomer comprises the following steps: A. The nanoparticles were ultrasonically dispersed with dispersant acetone for 40 minutes, the amount of dispersant was 1.5 times the mass of the nanoparticles, the ultrasonic power was 400 W, and the frequency was 30 kHz; Before step A, the raw material pretreatment is also included: comprising the following steps: Poly(diethylene glycol adipate) glycol, poly(tetramethylene ether) glycol and chain extender were dried in a vacuum drying oven at 90°C for 3 h; B. Cooling the isocyanate prepolymer to 55° C., adding the nanoparticles, hindered phenol antioxidant, hindered amine light stabilizer, chain extender, A33, organic tin catalyst and poly(diethylene glycol adipate) diol treated with ultrasonic dispersion to polytetramethylene ether diol in sequence, and then stirring at 1800 rpm for 12 min; then adding the isocyanate prepolymer, stirring rapidly at 1800 rpm for 15 s, pouring into a mold preheated to 110° C., and continuing to react in the mold for 12 min to obtain a formed polyurethane elastomer; C. Take the formed polyurethane elastomer out of the mold and place it at room temperature for 32 hours to allow it to cool naturally and post-curing.

[0037] Example 5 (1) A high damping fatigue and aging resistant polyurethane elastomer, the raw materials comprising, by weight, 25 parts of poly(diethylene glycol adipate), 40 parts of polytetramethylene ether glycol, 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; The molecular weight of poly(diethylene glycol adipate) glycol is 2000; the molecular weight of poly(tetramethylene ether) glycol is 2000; The chain extender is 1,4-butanediol; The organotin catalyst is dibutyltin dilaurate; The nanoparticles are nanosilicon dioxide; The hindered phenol antioxidant is antioxidant 1010; The hindered amine light stabilizer is Tinuvin 770; The isocyanate prepolymer is prepared from 1,4-phenylene diisocyanate and branched polytetrahydrofuran diol PTXG in a mass ratio of 1:2; the grade of branched polytetrahydrofuran diol PTXG is PTXG-1500; The preparation method of the isocyanate prepolymer comprises the following steps: 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.

[0038] (2) The method for preparing the above-mentioned high damping anti-fatigue and aging polyurethane elastomer comprises the following steps: A. The nanoparticles were ultrasonically dispersed with dispersant acetone for 40 minutes, the amount of dispersant was 1.5 times the mass of the nanoparticles, the ultrasonic power was 400 W, and the frequency was 30 kHz; Before step A, the raw material pretreatment is also included: comprising the following steps: Poly(diethylene glycol adipate) glycol, poly(tetramethylene ether) glycol and chain extender were dried in a vacuum drying oven at 90°C for 3 h; B. Cooling the isocyanate prepolymer to 55° C., adding the nanoparticles, hindered phenol antioxidant, hindered amine light stabilizer, chain extender, A33, organic tin catalyst and poly(diethylene glycol adipate) diol treated with ultrasonic dispersion to polytetramethylene ether diol in sequence, and then stirring at 1800 rpm for 12 min; then adding the isocyanate prepolymer, stirring rapidly at 1800 rpm for 15 s, pouring into a mold preheated to 110° C., and continuing to react in the mold for 12 min to obtain a formed polyurethane elastomer; C. Take the formed polyurethane elastomer out of the mold and place it at room temperature for 32 hours to allow it to cool naturally and post-curing.

[0039] Comparative Example 1 (1) A high damping fatigue and aging resistant polyurethane elastomer, the raw materials comprising, by weight, 25 parts of poly(diethylene glycol adipate), 40 parts of polytetramethylene ether glycol, 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; The molecular weight of poly(diethylene glycol adipate) glycol is 2000; the molecular weight of poly(tetramethylene ether) glycol is 2000; The chain extender is 1,4-butanediol and diethylene glycol dipropionate in a mass ratio of 3:1; The organotin catalyst is dibutyltin dilaurate; The nanoparticles are nanosilicon dioxide; The hindered phenol antioxidant is antioxidant 1010; The hindered amine light stabilizer is Tinuvin 770; The isocyanate prepolymer is prepared from 1,4-phenylene diisocyanate and PTMEG-2000 in a mass ratio of 1:2; The preparation method of the isocyanate prepolymer comprises the following steps: 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-phenylene diisocyanate 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.

[0040] (2) The method for preparing the above-mentioned high damping anti-fatigue and aging polyurethane elastomer comprises the following steps: A. The nanoparticles were ultrasonically dispersed with dispersant acetone for 40 minutes, the amount of dispersant was 1.5 times the mass of the nanoparticles, the ultrasonic power was 400 W, and the frequency was 30 kHz; Before step A, the raw material pretreatment is also included: comprising the following steps: Poly(diethylene glycol adipate) glycol, poly(tetramethylene ether) glycol and chain extender were dried in a vacuum drying oven at 90°C for 3 h; B. Cooling the isocyanate prepolymer to 55° C., adding the nanoparticles, hindered phenol antioxidant, hindered amine light stabilizer, chain extender, A33, organic tin catalyst and poly(diethylene glycol adipate) diol treated with ultrasonic dispersion to polytetramethylene ether diol in sequence, and then stirring at 1800 rpm for 12 min; then adding the isocyanate prepolymer, stirring rapidly at 1800 rpm for 15 s, pouring into a mold preheated to 110° C., and continuing to react in the mold for 12 min to obtain a formed polyurethane elastomer; C. Take the formed polyurethane elastomer out of the mold and place it at room temperature for 32 hours to allow it to cool naturally and post-curing.

[0041] Comparative Example 2 (1) A high damping fatigue and aging resistant polyurethane elastomer, the raw materials comprising, by weight, 25 parts of poly(diethylene glycol adipate), 40 parts of polytetramethylene ether glycol, 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; The molecular weight of poly(diethylene glycol adipate) glycol is 2000; the molecular weight of poly(tetramethylene ether) glycol is 2000; The chain extender is 1,4-butanediol and diethylene glycol dipropionate in a mass ratio of 3:1; The organotin catalyst is dibutyltin dilaurate; The nanoparticles are nanosilicon dioxide; The hindered phenol antioxidant is antioxidant 1010; The hindered amine light stabilizer is Tinuvin 770; The isocyanate prepolymer is prepared from MDI-50 and branched polytetrahydrofuran diol PTXG in a mass ratio of 1:2; the grade of branched polytetrahydrofuran diol PTXG is PTXG-1500; The preparation method of the isocyanate prepolymer comprises the following steps: The dried branched polytetrahydrofuran diol PTXG was heated to 105° C. and vacuumed for 2 h, then cooled to 75° C., and MDI-50 was added to the branched polytetrahydrofuran diol PTXG in the presence of an inert gas. During the process, the temperature was controlled at 75° C., the stirring speed was 2000 rpm, and the stirring was stopped after 1.5 h to obtain an isocyanate prepolymer.

[0042] (2) The method for preparing the above-mentioned high damping anti-fatigue and aging polyurethane elastomer comprises the following steps: A. The nanoparticles were ultrasonically dispersed with dispersant acetone for 40 minutes, the amount of dispersant was 1.5 times the mass of the nanoparticles, the ultrasonic power was 400 W, and the frequency was 30 kHz; Before step A, the raw material pretreatment is also included: comprising the following steps: Poly(diethylene glycol adipate) glycol, poly(tetramethylene ether) glycol and chain extender were dried in a vacuum drying oven at 90°C for 3 h; B. Cooling the isocyanate prepolymer to 55° C., adding the nanoparticles, hindered phenol antioxidant, hindered amine light stabilizer, chain extender, A33, organic tin catalyst and poly(diethylene glycol adipate) diol treated with ultrasonic dispersion to polytetramethylene ether diol in sequence, and then stirring at 1800 rpm for 12 min; then adding the isocyanate prepolymer, stirring rapidly at 1800 rpm for 15 s, pouring into a mold preheated to 110° C., and continuing to react in the mold for 12 min to obtain a formed polyurethane elastomer; C. Take the formed polyurethane elastomer out of the mold and place it at room temperature for 32 hours to allow it to cool naturally and post-curing.

[0043] Comparative Example 3 (1) A high damping fatigue aging resistant polyurethane elastomer, the raw materials comprising, by weight, 25 parts of poly(diethylene glycol adipate), 40 parts of polytetramethylene ether glycol, 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-phenylene diisocyanate; The molecular weight of poly(diethylene glycol adipate) glycol is 2000; the molecular weight of poly(tetramethylene ether) glycol is 2000; The chain extender is 1,4-butanediol and diethylene glycol dipropionate in a mass ratio of 3:1; The organotin catalyst is dibutyltin dilaurate; The nanoparticles are nanosilicon dioxide; The hindered phenol antioxidant is antioxidant 1010; The hindered amine light stabilizer is Tinuvin 770; (2) The method for preparing the above-mentioned high damping anti-fatigue and aging polyurethane elastomer comprises the following steps: A. The nanoparticles were ultrasonically dispersed with dispersant acetone for 40 minutes, the amount of dispersant was 1.5 times the mass of the nanoparticles, the ultrasonic power was 400 W, and the frequency was 30 kHz; Before step A, the raw material pretreatment is also included: comprising the following steps: Poly(diethylene glycol adipate) glycol, poly(tetramethylene ether) glycol and chain extender were dried in a vacuum drying oven at 90°C for 3 h; B. Add the nanoparticles, hindered phenol antioxidant, hindered amine light stabilizer, chain extender, A33, organic tin catalyst and poly(diethylene glycol adipate) diol treated with ultrasonic dispersion to polytetramethylene ether diol in sequence, and then stir at 1800 rpm for 12 min; then add 1,4-phenylene diisocyanate, stir rapidly at 1800 rpm for 15 s, pour into a mold preheated to 110° C., and continue to react in the mold for 12 min to obtain a molded polyurethane elastomer; C. Take the formed polyurethane elastomer out of the mold and place it at room temperature for 32 hours to allow it to cool naturally and post-curing.

[0044] The polyurethane elastomers obtained in the above embodiments 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 and aging resistant polyurethane elastomer of the present invention has significantly improved damping performance, and the loss factor can be increased by 30%-50%; the fatigue resistance and mechanical property retention rate are significantly better than those of ordinary polyurethane elastomers, and it has good anti-aging performance.

[0045] The test method is as follows: Tensile strength and elongation at break refer to GB / T 528-2009; The damping factor refers to ASTM D5418-23, the sample size is 40mm*7mm*2mm, the mode is tensile, the heating rate is 1℃ / min, the test temperature range is -80℃ to 100℃, and the vibration frequency is 1Hz. tanδ max is the maximum value of the damping factor.

[0046] 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.

[0047] Table 1 The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A high damping anti-fatigue and aging polyurethane elastomer, characterized in that: The raw materials include, by weight, 20-30 parts of poly(diethylene glycol adipate) glycol, 30-50 parts of polytetramethylene ether glycol, 5-15 parts of a chain extender, 0.1-0.3 parts of A33, 0.1-0.2 parts of an organic tin 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; The isocyanate prepolymer is prepared from 1,4-phenylene diisocyanate and branched polytetrahydrofuran diol PTXG in a mass ratio of 1:1.8-2.

2.

2. The high damping anti-fatigue and aging polyurethane elastomer according to claim 1, characterized in that: The preparation method of the isocyanate prepolymer comprises the following steps: The branched polytetrahydrofuran diol PTXG is heated to 100-110° C. and vacuumed for 1.5-3 hours, then cooled to 70-80° C., and 1,4-phenylene diisocyanate is added to the branched polytetrahydrofuran diol PTXG in the presence of an inert gas, with a stirring speed of 1500-2500 rpm. The stirring is stopped after 1-2 hours to obtain an isocyanate prepolymer.

3. The high damping anti-fatigue and aging polyurethane elastomer according to claim 1, characterized in that: The brand of the branched polytetrahydrofuran diol PTXG is PTXG-1000, PTXG-1500 or PTXG-1800.

4. The high damping anti-fatigue and anti-aging polyurethane elastomer according to claim 1, characterized in that: The grade of the branched polytetrahydrofuran diol PTXG is PTXG-1500; the mass ratio of 1,4-phenylene diisocyanate to the branched polytetrahydrofuran diol PTXG is 1:

2.

5. The high damping anti-fatigue and anti-aging polyurethane elastomer according to claim 1, characterized in that: The chain extender is selected from one or more of 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylene glycol dipropionate; The organic tin catalyst is selected from one or more of dibutyltin dilaurate, stannous octoate, dibutyltin didodecylsulfide, dibutyltin diacetate, dioctyltin dilaurate and dibutyltin diacetate.

6. The high damping anti-fatigue and anti-aging polyurethane elastomer according to claim 1, characterized in that: The particle size of the nanoparticles is 0.5-1 μm, and the nanoparticles are nano-silicon dioxide and / or nano-calcium carbonate; The hindered phenol antioxidant is selected from one or more of antioxidant 1010, antioxidant 245 and antioxidant 1135; The hindered amine light stabilizer is selected from one or more of Tinuvin 770, Tinuvin 711 and Tinuvin 144.

7. The high damping anti-fatigue and anti-aging polyurethane elastomer according to claim 1, characterized in that: The molecular weight of the poly(diethylene glycol adipate) glycol is 1000-2000; the molecular weight of the poly(tetramethylene glycol) ether glycol is 1000-3000.

8. The high damping anti-fatigue and anti-aging polyurethane elastomer according to claim 1, characterized in that: The molecular weight of poly(diethylene glycol adipate) diol is 2000; the molecular weight of poly(tetramethylenetetramethylene ether) diol is 2000.

9. The method for preparing a high damping fatigue-resistant and aging-resistant polyurethane elastomer according to any one of claims 1 to 8, characterized in that: The following steps are involved: A. subjecting the nanoparticles to ultrasonic dispersion treatment using a dispersant; B. Add the nanoparticles, hindered phenol antioxidant, hindered amine light stabilizer, chain extender, A33, organic tin catalyst and poly(diethylene glycol adipate) diol after ultrasonic dispersion treatment to polytetramethylene ether diol, and then stir at 1500-2000 rpm for 10-15 min; then add isocyanate prepolymer, stir rapidly at 1500-2000 rpm for 10-20 s, pour into a mold preheated to 100-120° C., and continue to react in the mold for 10-15 min to obtain a molded polyurethane elastomer; C. Take the formed polyurethane elastomer out of the mold and place it at room temperature for 24-48 hours to allow it to cool naturally and post-curing.

10. The method for preparing a high damping fatigue aging resistant polyurethane elastomer according to claim 9, characterized in that: The step A also includes raw material pretreatment, which includes the following steps: Drying poly(diethylene glycol adipate) glycol, poly(tetramethylene ether) glycol and chain extender in a vacuum drying oven at 80-100° C. for 2-4 h; In step A, the dispersant is acetone, the ultrasonic dispersion treatment is performed 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; In step B, the temperature is lowered to 30-60° C. before adding the isocyanate prepolymer.

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