A modified aluminum and its preparation, a high-mechanical-performance acrylate thermoplastic elastomer and its preparation method and application

Abstract

This invention relates to a modified aluminum and its preparation, a high-mechanical-performance acrylate thermoplastic elastomer and its preparation method, and its applications. This invention belongs to the field of anionic polymerization. The purpose of this invention is to solve the technical problems of existing methods for preparing acrylate thermoplastic elastomers, such as complex systems, cumbersome processes, long reaction times, and low mechanical properties and stereoregularity of the resulting acrylate thermoplastic elastomers. The modified aluminum is prepared from aluminum reagents and organic phenols. The elastomer is prepared by anionic polymerization of comonomers in an aluminum-lithium complex system. The acrylate thermoplastic elastomer exhibits a tensile strength ≥5 MPa, an elongation at break ≥300%, a strength at 300% elongation ≥2 MPa, a number-average molecular weight of 10,000-400,000 g / mol, a molecular weight distribution (PDI) of 1.1-1.5, and a stereoregularity (rr) of 80%-90%. This invention provides a high-mechanical-performance acrylate thermoplastic elastomer applicable to aerospace, defense, and automotive fields.

Description

Technical Field

[0001] This invention belongs to the field of anionic polymerization, specifically relating to a modified aluminum and its preparation, a high-mechanical-performance acrylate thermoplastic elastomer and its preparation method and application. Background Technology

[0002] Thermoplastic elastomers (TPEs) are a class of elastomeric materials that exhibit elastomeric properties at room temperature and can be plasticized and molded at high temperatures. Their properties are typically determined by their glass transition temperature (T). g High hard segment polymers and T g Low soft segment polymer composition, while T of both soft and hard segments g This also limits the operating temperature range of TPE materials to some extent. Currently, the largest TPE production and consumption category is styrene-based thermoplastic elastomers, with styrene-butadiene-styrene triblock thermoplastic elastomer (SBS) being the most representative, holding a significant share in footwear, automotive, modifiers, and adhesives. However, this type of elastomer has certain shortcomings: 1) The butadiene polymer in the middle segment contains unsaturated double bonds, which are easily oxidized or (UV) aged, thus affecting the material's mechanical properties and stability. Although hydrogenation of the middle butadiene block (i.e., hydrogenated styrene-butadiene triblock copolymer, SEBS) compensates for this deficiency, the hydrogenation process significantly increases production costs. 2) The glass transition temperature (T...) of styrene-based elastomers... g Lower (PS segment T) g Its performance is affected above approximately 60-80℃, thus limiting its application in high-temperature fields.

[0003] Acrylic thermoplastic elastomers (AC-TPE) are triblock copolymers of methacrylate-acrylate-methacrylate, obtained through catalytic polymerization of methacrylate (hard segment) and acrylate (soft segment) monomers. They are a strategically emerging thermoplastic elastomer material, and their environmentally friendly, non-toxic, and recyclable characteristics make them a standard environmentally friendly material. Compared to traditional styrene-based thermoplastic elastomers, acrylic thermoplastic elastomers exhibit unique properties: the saturated C-H bonds in their molecular backbone provide excellent mechanical properties, transparency, and resistance to oxygen and aging; the polar ester functional groups on the molecular side chains provide excellent oil resistance and sealing properties. Furthermore, the diverse monomer types of acrylates (different side-chain ester functional groups) give acrylic thermoplastic elastomers a wider glass transition temperature range (T0). gThe operating temperature range is -50℃ to 200℃, and by copolymerizing different monomers, thermoplastic elastomers with different operating temperature ranges can be prepared. Therefore, acrylate thermoplastic elastomers have excellent mechanical properties, good light transmittance, oil resistance, heat resistance, weather resistance, and oxidation resistance, and are in high demand in many fields such as aerospace, defense, and automotive parts.

[0004] Currently, the main methods for preparing thermoplastic elastomers of acrylates include blending, coupling, and block copolymerization. Among these, block copolymerization, using a three-step method with monofunctional initiators or a two-step method with difunctional initiators to directly prepare triblock copolymers, is one of the most direct and effective methods. CN103374108A reports a method for preparing triblock thermoplastic elastomers: using a relatively low amount of metal catalyst, controllable and efficient polymerization of triblock copolymers is achieved. However, the free radical polymerization method (ATRP) used typically requires the addition of multiple components, including initiators, catalysts, reducing agents, ligands, and solvents, making the process relatively complex and the reaction time relatively long. CN109251260A and CN108264593A respectively disclose "Living polymerization system for synthesizing ultra-high molecular weight polymers based on phosphine base catalysis" and "Living polymerization method for vinyl polar monomers catalyzed by hindered Lewis acid-base pair--FLP". They have efficiently prepared different types of triblock acrylate copolymers, but the reaction system requires the synergistic catalytic effect of Lewis acid and Lewis base, and the catalytic system is complex and the process is cumbersome.

[0005] Therefore, it is of great significance to achieve the selective preparation of acrylate thermoplastic elastomers with excellent mechanical properties through a simple, controllable, environmentally friendly, and efficient polymerization method. Summary of the Invention

[0006] The purpose of this invention is to solve the technical problems of existing methods for preparing acrylate thermoplastic elastomers, such as complex systems, cumbersome processes, long reaction times, and low mechanical properties and stereoregularity of the resulting acrylate thermoplastic elastomers. This invention provides a modified aluminum and its preparation, a high-mechanical-performance acrylate thermoplastic elastomer and its preparation method, and its applications. The acrylate thermoplastic elastomer exhibits excellent mechanical properties and light transmittance. The entire polymerization process is mild and controllable, simple to operate, and convenient for post-processing.

[0007] The modified aluminum of the present invention is prepared by aluminum reagent and organic phenol, wherein the molar number of organic phenol is 1.0-3.0 times that of aluminum reagent and is not an integer multiple.

[0008] Further specified, the molar number of organic phenols is 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 2.3, 2.4, 2.5, 2.6, 2.7 or 2.8 times that of aluminum reagent.

[0009] Further specified, the aluminum reagent is any one of triethylaluminum, trimethylaluminum, triisobutylaluminum, diethylaluminum chloride, diethylaluminum chloride, and methylaluminoxane; the general structural formula of the organic phenol is: R1, R2, and R3 are one of hydrogen, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, methoxy, nitro, and trifluoromethyl, while R4 and R5 are one of isopropyl and tert-butyl.

[0010] To further specify, the structure of organic phenols can be any of the following:

[0011]

[0012] The method for preparing modified aluminum according to the present invention is carried out according to the following steps:

[0013] Under anhydrous and oxygen-free conditions, a solvent, organic phenol, and aluminum reagent are added to a reactor, and the reaction is carried out at 0-50℃ for 2-48 hours to obtain modified aluminum.

[0014] Further specified, the reaction is carried out at 30°C for 8 hours, and the solvent is one or a mixture of two of the following in any proportion: n-hexane, cyclohexane, petroleum ether, chloroform, dichloropropane, and solvent oil.

[0015] The present invention discloses a high-mechanical-performance acrylate thermoplastic elastomer based on the above-mentioned modified aluminum, which is prepared by anionic polymerization of comonomers in an aluminum-lithium complex system. The acrylate thermoplastic elastomer has a tensile strength ≥5MPa, an elongation at break ≥300%, a tensile strength ≥2MPa at 300% elongation, a number-average molecular weight of 10,000-400,000 g / mol, a molecular weight distribution (PDI) of 1.1-1.5, and a stereoregularity (rr) ratio of 80%-90%. The comonomers are composed of methyl methacrylate and n-butyl acrylate, and the aluminum-lithium complex system is a mixture of the above-mentioned modified aluminum and a lithium metal compound.

[0016] Further specified, the molar ratio of methyl methacrylate to n-butyl acrylate is 9 / 1 to 1 / 9, the molar ratio of lithium metal compound to modified aluminum is 1 / 3 to 1 / 20, and the molar ratio of lithium metal compound to comonomer is 1 / 100 to 1 / 4000.

[0017] Further specified, the molar ratio of methyl methacrylate to n-butyl acrylate is 3 / 7, the molar ratio of lithium metal compound to modified aluminum is 1 / 8, and the molar ratio of lithium metal compound to comonomer is 1 / 850.

[0018] Further specifying, lithium metal compounds include, but are not limited to, n-butyllithium, sec-butyllithium, tert-butyllithium, and tert-butoxide lithium.

[0019] The method for preparing a high-mechanical-performance acrylate thermoplastic elastomer according to the present invention is carried out according to the following steps:

[0020] Under anhydrous and oxygen-free conditions, solvent, aluminum-lithium complex system, and part of methyl methacrylate monomer were added to a reactor at 0-30℃ and reacted for 10 min-1 h. Then, n-butyl acrylate was added to the reactor at -60-0℃ and reacted for 10 min-1 h. The remaining methyl methacrylate was then added to the reactor at 0-30℃ and reacted for 10 min-12 h. After quenching with methanol, washing, and vacuum drying, a high-mechanical-performance acrylate thermoplastic elastomer was obtained.

[0021] Further specified, the molar ratio of the first added methyl methacrylate monomer to the second added methyl methacrylate monomer is 1:1.

[0022] Further specifying, the solvent is one or a mixture of two of the following in any proportion: ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethoxymethane, methyl tert-butyl ether, dioxane, toluene, xylene, and tetrahydrofuran.

[0023] The present invention provides a high mechanical property acrylate thermoplastic elastomer applicable to aerospace, defense and military and automotive fields.

[0024] The beneficial effects of this invention compared to the prior art are as follows:

[0025] 1) This invention employs an aluminum-lithium complex system, which features a simple operation process, low cost, and effectively prevents side reactions such as monomer cyclization. By selecting a solvent with suitable polarity and coordination ability, it ensures the formation of effective butyl anions while effectively stabilizing the aluminum-lithium complex system, enabling efficient and controllable polymerization of acrylate thermoplastic elastomers with different molecular weights. Furthermore, the structure of the acrylate thermoplastic elastomer can be controlled by adjusting the proportion of comonomers.

[0026] 2) Compared to traditional preparation methods, triblock acrylate elastomers exhibit milder reaction conditions, higher polymerization efficiency, and a narrower molecular weight distribution, with a number-average molecular weight of 10,000-400,000 g / mol and a molecular weight distribution of 1.1-1.5, resulting in superior mechanical properties. They possess excellent light transmittance, weather resistance, and oxidation resistance, making them highly sought after in aerospace, defense, and automotive parts industries.

[0027] 3) This invention obtains a novel complex system of modified aluminum with different structural compositions by adjusting the non-integer ratio of aluminum reagent and organic phenol compound to change the steric hindrance and electrical properties of modified aluminum reagent. At the same time, by changing the type and amount of lithium metal compound, the system structure of aluminum-lithium complex can be further controlled, so that the stereoregularity rr of the polymer can exceed 80%, which is more beneficial to the improvement of polymer mechanical properties and weather resistance. Attached Figure Description

[0028] Figure 1 The triblock acrylate thermoplastic elastomer of Example 13 1 HNMR spectrum;

[0029] Figure 2 The triblock acrylate thermoplastic elastomer of Example 13 13 C NMR spectrum;

[0030] Figure 3 The GPC spectrum of the triblock acrylate thermoplastic elastomer of Example 13 is shown below.

[0031] Figure 4 This is a transparent sheet photograph of the triblock acrylate thermoplastic elastomer of Example 13 after hot pressing. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0033] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, the materials, reagents, methods, and instruments used are all conventional materials, reagents, methods, and instruments in the art, and can be obtained commercially by those skilled in the art.

[0034] The terms “comprising,” “including,” “having,” “containing,” or any other variations thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such a composition, step, method, article, or apparatus.

[0035] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1 to 5” is disclosed, the described range should be interpreted as including ranges “1 to 4”, “1 to 3”, “1 to 2”, “1 to 2 and 4 to 5”, “1 to 3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range. In this specification and claims, range definitions may be combined and / or interchanged, unless otherwise stated, these ranges include all sub-ranges contained therein.

[0036] The indefinite articles “a” and “an” preceding an element or component of this invention do not impose any limitation on the quantity (i.e., number of times) of the element or component. Therefore, “an” or “a” should be interpreted as including one or at least one, and the singular form of an element or component also includes the plural form, unless the quantity clearly refers only to the singular form.

[0037] Preparation of modified aluminum

[0038] Example 1: i-BuAl(OR) 2.3 Preparation:

[0039] Under anhydrous and oxygen-free conditions, 5 mL of n-hexane, organic phenol 2 (2.3 mmol, 2.3 equiv., 506 mg), and i-Bu3Al (1 mmol, 1 equiv., 1 mL) were added to a reactor, and the reaction was carried out at 30 °C for 8 h. The solid product was filtered, washed with n-hexane, and vacuum dried to constant weight to obtain modified aluminum. The structure of organic phenol 2 is as follows:

[0040] Example 2: AlEt(OR) 2.3 Preparation:

[0041] Under anhydrous and oxygen-free conditions, 5 mL of n-hexane, organic phenol 2 (2.3 mmol, 2.3 equiv., 506 mg), and AlEt3 (1 mmol, 1 equiv., 1 mL) were added to a reactor, and the reaction was carried out at 30 °C for 8 h. The solid product was filtered, washed with n-hexane, and vacuum dried to constant weight to obtain modified aluminum. The structure of organic phenol 2 is as follows:

[0042] Example 3: i-BuAl(OR) 1.7 Preparation:

[0043] Under anhydrous and oxygen-free conditions, 5 mL of n-hexane, organic phenol 1 (1.7 mmol, 1.7 equiv., 665 mg), and i-Bu3Al (1 mmol, 1 equiv., 1 mL) were added to a reactor, and the reaction was carried out at 30 °C for 8 h. The solid product was filtered, washed with n-hexane, and vacuum dried to constant weight to obtain modified aluminum. The structure of organic phenol 1 is as follows:

[0044] Example 4: i-BuAl(OR) 1.7 Preparation:

[0045] Under anhydrous and oxygen-free conditions, 5 mL of n-hexane, organic phenol 16 (1.7 mmol, 1.7 equiv., 426 mg), and i-Bu3Al (1 mmol, 1 equiv., 1 mL) were added to a reactor, and the reaction was carried out at 30 °C for 8 h. The solid product was filtered, washed with n-hexane, and vacuum dried to constant weight to obtain modified aluminum. The structure of organic phenol 16 is as follows:

[0046] Example 5: i-BuAl(OR) 1.7 Preparation:

[0047] Under anhydrous and oxygen-free conditions, 5 mL of n-hexane, organic phenol 3 (1.7 mmol, 1.7 equiv., 398 mg), and i-Bu3Al (1 mmol, 1 equiv., 1 mL) were added to a reactor, and the reaction was carried out at 30 °C for 8 h. The solid product was filtered, washed with n-hexane, and vacuum dried to constant weight to obtain modified aluminum. The structure of organic phenol 3 is as follows:

[0048] Example 6: i-BuAl(OR) 1.7 Preparation:

[0049] Under anhydrous and oxygen-free conditions, 5 mL of n-hexane, organic phenol 6 (1.7 mmol, 1.7 equiv., 374 mg), and i-Bu3Al (1 mmol, 1 equiv., 1 mL) were added to a reactor, and the reaction was carried out at 30 °C for 8 h. The solid product was filtered, washed with n-hexane, and vacuum dried to constant weight to obtain modified aluminum. The structure of organic phenol 6 is as follows:

[0050] Example 7: i-BuAl(OR) 2.3 Preparation:

[0051] Under anhydrous and oxygen-free conditions, 5 mL of n-hexane, organic phenol 10 (2.3 mmol, 2.3 equiv., 571 mg), and i-Bu3Al (1 mmol, 1 equiv., 1 mL) were added to a reactor, and the reaction was carried out at 30 °C for 8 h. The solid product was filtered, washed with n-hexane, and vacuum dried to constant weight to obtain modified aluminum. The structure of organic phenol 10 is as follows:

[0052] Example 8: i-BuAl(OR) 1.7 Preparation:

[0053] Under anhydrous and oxygen-free conditions, 5 mL of n-hexane, organic phenol 12 (1.7 mmol, 1.7 equiv., 445 mg), and i-Bu3Al (1 mmol, 1 equiv., 1 mL) were added to a reactor, and the reaction was carried out at 30 °C for 8 h. The solid product was filtered, washed with n-hexane, and vacuum dried to constant weight to obtain modified aluminum. The structure of organic phenol 12 is as follows:

[0054] Example 9: i-BuAl(OR) 1.7 Preparation:

[0055] Under anhydrous and oxygen-free conditions, 5 mL of n-hexane, organic phenol 9 (1.7 mmol, 1.7 equiv., 422 mg), and i-Bu3Al (1 mmol, 1 equiv., 1 mL) were added to a reactor, and the reaction was carried out at 30 °C for 8 h. The solid product was filtered, washed with n-hexane, and vacuum dried to constant weight to obtain modified aluminum. The structure of organic phenol 9 is as follows:

[0056] Example 10: i-BuAl(OR) 1.7 Preparation:

[0057] Under anhydrous and oxygen-free conditions, 5 mL of n-hexane, organic phenol 13 (1.7 mmol, 1.7 equiv., 303 mg), and i-Bu3Al (1 mmol, 1 equiv., 1 mL) were added to a reactor, and the reaction was carried out at 30 °C for 8 h. The solid product was filtered, washed with n-hexane, and vacuum dried to constant weight to obtain modified aluminum. The structure of organic phenol 13 is as follows:

[0058] Example 11: i-BuAl(OR) 1.7 Preparation:

[0059] Under anhydrous and oxygen-free conditions, 5 mL of n-hexane, organic phenol 2 (1.7 mmol, 1.7 equiv., 374 mg), and i-Bu3Al (1 mmol, 1 equiv., 1 mL) were added to a reactor, and the reaction was carried out at 30 °C for 8 h. The solid product was filtered, washed with n-hexane, and vacuum dried to constant weight to obtain modified aluminum. The structure of organic phenol 2 is as follows:

[0060] Example 12: i-BuAl(OR) 1.5 Preparation:

[0061] Under anhydrous and oxygen-free conditions, 5 mL of n-hexane, organic phenol 2 (1.5 mmol, 1.5 equiv., 330 mg), and i-Bu3Al (1 mmol, 1 equiv., 1 mL) were added to a reactor, and the reaction was carried out at 30 °C for 8 h. The solid product was filtered, washed with n-hexane, and vacuum dried to constant weight to obtain modified aluminum. The structure of organic phenol 2 is as follows:

[0062] Preparation of high mechanical property acrylate thermoplastic elastomers

[0063] Example 13

[0064] In a 500 mL reaction flask under an argon atmosphere, at 25 °C, 62 mL of ethylene glycol dimethyl ether solution and i-BuAl(OR) from Example 1 were added sequentially. 2.3 (5 mL, 1.6 mmol, 8 equivalents), sec-butyllithium (0.15 mL, 0.2 mmol, 1 equivalent), and methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) were added. After one hour, the reaction system temperature was adjusted to -30°C, and n-butyl acrylate (17.2 mL, 120 mmol, 600 equivalents) was added. After another hour of reaction, methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) was added at 25°C, and the reaction was continued for 4 hours. After the reaction was completed, the mixture was quenched with cold methanol and washed three times. It was then vacuum dried to constant weight to obtain acrylate thermoplastic elastomer.

[0065] The calculated yield was >99%. NMR characterization showed that the block ratio of methyl methacrylate to n-butyl acrylate was 3:7; the stereospecific proportion was 83%. GPC characterization showed the number-average molecular weight M0. n The molecular weight is 57885 g / mol, the molecular weight distribution (PDI) is 1.4, and molecular weight information is shown in Table 1. The tensile strength of the acrylate thermoplastic elastomer is 6.14 MPa, the elongation at break is 351.0%, and the tensile strength at 300% of its elongation is 4.81 MPa.

[0066] Table 1

[0067]

[0068] Example 14

[0069] Under an argon atmosphere, ethylene glycol dimethyl ether (62 mL) solution and AlEt(OR) from Example 2 were added sequentially to a 500 mL reaction flask at 25 °C. 2.3 (0.792 g, 1.6 mmol, 8 equivalents), sec-butyllithium (0.15 mL, 0.2 mmol, 1 equivalent), and methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) were added. After one hour, the reaction system temperature was adjusted to -30 °C, and n-butyl acrylate (17.2 mL, 120 mmol, 600 equivalents) was added. After another hour of reaction, methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) was added at 25 °C, and the reaction was continued for 4 hours. After the reaction was completed, the mixture was quenched with cold methanol and washed three times. The mixture was then dried under vacuum to constant weight to obtain the acrylate thermoplastic elastomer.

[0070] The calculated yield was >99%. NMR characterization showed that the block ratio of methyl methacrylate to n-butyl acrylate was 3:7; the stereospecific proportion was 82%. GPC characterization showed the number-average molecular weight M0. n The molecular weight is 115783 g / mol, and the molecular weight distribution (PDI) is 1.3. The tensile strength of the acrylate thermoplastic elastomer is 6.38 MPa, the elongation at break is 300.5%, and the tensile strength at 300% of its elongation is 5.78 MPa.

[0071] Example 15

[0072] Under an argon atmosphere, ethylene glycol dimethyl ether (62 mL) solution and i-BuAl(OR) from Example 3 were added sequentially to a 500 mL reaction flask at 25 °C. 1.7 (11.4 mL, 1.6 mmol, 8 equivalents), sec-butyllithium (0.15 mL, 0.2 mmol, 1 equivalent), and methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) were added. After one hour, the reaction system temperature was adjusted to -30°C, and n-butyl acrylate (17.2 mL, 120 mmol, 600 equivalents) was added. After another hour of reaction, methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) was added at 25°C, and the reaction was continued for 4 hours. After the reaction was completed, the mixture was quenched with cold methanol and washed three times. The mixture was then dried under vacuum to constant weight to obtain the acrylate thermoplastic elastomer.

[0073] The calculated yield was >99%. NMR characterization showed that the block ratio of methyl methacrylate to n-butyl acrylate was 3:7; the stereospecific proportion was 82%. GPC characterization showed the number-average molecular weight M0. n It has a concentration of 61251 g / mol and a molecular weight distribution (PDI) of 1.5.

[0074] Example 16

[0075] Under an argon atmosphere, ethylene glycol dimethyl ether (62 mL) solution and i-BuAl(OR) from Example 4 were added sequentially to a 500 mL reaction flask at 25 °C. 1.7 (4.6 mL, 1.6 mmol, 8 equivalents), sec-butyllithium (0.15 mL, 0.2 mmol, 1 equivalent), and methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) were added. After one hour, the reaction system temperature was adjusted to -30 °C, and n-butyl acrylate (17.2 mL, 120 mmol, 600 equivalents) was added. The reaction continued. After one hour, methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) was added at 25 °C, and the reaction continued for 4 hours. After the reaction was completed, the mixture was quenched with cold methanol and washed three times. The mixture was then dried under vacuum to constant weight to obtain the acrylate thermoplastic elastomer.

[0076] The calculated yield was 78%. NMR characterization showed that the block ratio of methyl methacrylate to n-butyl acrylate was 3:7; the stereospecific proportion was 83%. GPC characterization showed the number-average molecular weight M0. n It has a molecular weight of 67352 g / mol and a molecular weight distribution (PDI) of 1.3.

[0077] Example 17

[0078] Under an argon atmosphere, ethylene glycol dimethyl ether (62 mL) solution and i-BuAl(OR) from Example 5 were added sequentially to a 500 mL reaction flask at 25 °C. 1.7 (4.6 mL, 1.6 mmol, 8 equivalents), sec-butyllithium (0.15 mL, 0.2 mmol, 1 equivalent), and methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) were added. After one hour, the reaction system temperature was adjusted to -30 °C and n-butyl acrylate (17.2 mL, 120 mmol, 600 equivalents) was added. After another hour of reaction, methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) was added at 25 °C and the reaction was continued for 4 hours. After the reaction was completed, the mixture was quenched with cold methanol and washed three times. The mixture was then dried under vacuum to constant weight to obtain the acrylate thermoplastic elastomer.

[0079] The calculated yield was >99%. NMR characterization showed that the block ratio of methyl methacrylate to n-butyl acrylate was 3:7; the stereospecific proportion was 86%. GPC characterization showed the number-average molecular weight M0. n The molecular weight is 53495 g / mol, and the molecular weight distribution (PDI) is 1.7. The tensile strength of the acrylate thermoplastic elastomer is 6.86 MPa, the elongation at break is 389.5%, and the tensile strength at 300% of its elongation is 3.4 MPa.

[0080] Example 18

[0081] Under an argon atmosphere, ethylene glycol dimethyl ether (62 mL) solution and i-BuAl(OR) from Example 6 were added sequentially to a 500 mL reaction flask at 25 °C. 1.7 (5 mL, 1.6 mmol, 8 equivalents), sec-butyllithium (0.15 mL, 0.2 mmol, 1 equivalent), and methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) were added. After one hour, the reaction system temperature was adjusted to -30°C, and n-butyl acrylate (17.2 mL, 120 mmol, 600 equivalents) was added. After another hour of reaction, methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) was added at 25°C, and the reaction was continued for 4 hours. After the reaction was completed, the mixture was quenched with cold methanol and washed three times. The mixture was then dried under vacuum to constant weight to obtain the acrylate thermoplastic elastomer.

[0082] The calculated yield was >99%. NMR characterization showed that the block ratio of methyl methacrylate to n-butyl acrylate was 3:7; the stereospecific proportion was 85%. GPC characterization showed the number-average molecular weight M0. n It has a molecular weight of 59725 g / mol and a molecular weight distribution (PDI) of 1.2.

[0083] Example 19

[0084] Under an argon atmosphere, ethylene glycol dimethyl ether (62 mL) solution and i-BuAl(OR) from Example 7 were added sequentially to a 500 mL reaction flask at 25 °C. 2.3(5 mL, 1.6 mmol, 8 equivalents), sec-butyllithium (0.15 mL, 0.2 mmol, 1 equivalent), and methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) were added. After one hour, the reaction system temperature was adjusted to -30°C, and n-butyl acrylate (17.2 mL, 120 mmol, 600 equivalents) was added. After another hour of reaction, methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) was added at 25°C, and the reaction was continued for 4 hours. After the reaction was completed, the mixture was quenched with cold methanol and washed three times. The mixture was then dried under vacuum to constant weight to obtain the acrylate thermoplastic elastomer.

[0085] The calculated yield was >99%. NMR characterization showed that the block ratio of methyl methacrylate to n-butyl acrylate was 3:7; the stereospecific proportion was 83%. GPC characterization showed the number-average molecular weight M0. n It has a molecular weight of 73655 g / mol and a molecular weight distribution (PDI) of 1.2.

[0086] Example 20

[0087] Under an argon atmosphere, ethylene glycol dimethyl ether (62 mL) solution and i-BuAl(OR) from Example 8 were added sequentially to a 500 mL reaction flask at 25 °C. 1.7 (5 mL, 1.6 mmol, 8 equivalents), sec-butyllithium (0.15 mL, 0.2 mmol, 1 equivalent), and methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) were added. After one hour, the reaction system temperature was adjusted to -30°C, and n-butyl acrylate (17.2 mL, 120 mmol, 600 equivalents) was added. After another hour of reaction, methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) was added at 25°C, and the reaction was continued for 4 hours. After the reaction was completed, the mixture was quenched with cold methanol and washed three times. The mixture was then dried under vacuum to constant weight to obtain the acrylate thermoplastic elastomer.

[0088] The calculated yield was 83%. NMR characterization showed that the block ratio of methyl methacrylate to n-butyl acrylate was 3:7; the stereospecific proportion was 86%. GPC characterization showed the number-average molecular weight (M). n It has a molecular weight of 64890 g / mol and a molecular weight distribution (PDI) of 1.1.

[0089] Example 21

[0090] Under an argon atmosphere, ethylene glycol dimethyl ether (62 mL) solution and i-BuAl(OR) from Example 9 were added sequentially to a 500 mL reaction flask at 25 °C. 1.7(5 mL, 1.6 mmol, 8 equivalents), sec-butyllithium (0.15 mL, 0.2 mmol, 1 equivalent), and methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) were added. After one hour, the reaction system temperature was adjusted to -30°C, and n-butyl acrylate (17.2 mL, 120 mmol, 600 equivalents) was added. After another hour of reaction, methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) was added at 25°C, and the reaction was continued for 4 hours. After the reaction was completed, the mixture was quenched with cold methanol and washed three times. The mixture was then dried under vacuum to constant weight to obtain the acrylate thermoplastic elastomer.

[0091] The calculated yield was 94%. NMR characterization showed that the block ratio of methyl methacrylate to n-butyl acrylate was 3:7; the stereospecific proportion was 85%. GPC characterization showed the number-average molecular weight M... n The molecular weight is 79580 g / mol, and the molecular weight distribution (PDI) is 1.1. The tensile strength of the acrylate thermoplastic elastomer is 6.36 MPa, the elongation at break is 378.0%, and the tensile strength at 300% of its elongation is 3.47 MPa.

[0092] Example 22

[0093] Under an argon atmosphere, ethylene glycol dimethyl ether (62 mL) solution and i-BuAl(OR) from Example 10 were added sequentially to a 500 mL reaction flask at 25 °C. 1.7 (5 mL, 1.6 mmol, 8 equivalents), sec-butyllithium (0.15 mL, 0.2 mmol, 1 equivalent), and methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) were added. After one hour, the reaction system temperature was adjusted to -30°C, and n-butyl acrylate (17.2 mL, 120 mmol, 600 equivalents) was added. After another hour of reaction, methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) was added at 25°C, and the reaction was continued for 4 hours. After the reaction was completed, the mixture was quenched with cold methanol and washed three times. The mixture was then dried under vacuum to constant weight to obtain the acrylate thermoplastic elastomer.

[0094] The calculated yield was 87%. NMR characterization showed that the block ratio of methyl methacrylate to n-butyl acrylate was 3:7; the stereospecific proportion was 83%. GPC characterization showed the number-average molecular weight M... n It has a molecular weight of 73481 g / mol and a molecular weight distribution (PDI) of 1.2.

[0095] Example 23

[0096] Under an argon atmosphere, ethylene glycol dimethyl ether (62 mL) solution and i-BuAl(OR) from Example 11 were added sequentially to a 500 mL reaction flask at 25 °C. 1.7 (4.6 mL, 1.6 mmol, 8 equivalents), sec-butyllithium (0.15 mL, 0.2 mmol, 1 equivalent), and methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) were added. After one hour, the reaction system temperature was adjusted to -30 °C, and n-butyl acrylate (17.2 mL, 120 mmol, 600 equivalents) was added. After another hour of reaction, methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) was added at 25 °C, and the reaction was continued for 4 hours. After the reaction was completed, the mixture was quenched with cold methanol and washed three times. The mixture was then dried under vacuum to constant weight to obtain the acrylate thermoplastic elastomer.

[0097] The calculated yield was >99%. NMR characterization showed that the block ratio of methyl methacrylate to n-butyl acrylate was 3:7; the stereospecific proportion was 82%. GPC characterization showed the number-average molecular weight M0. n It has a molecular weight of 71658 g / mol and a molecular weight distribution (PDI) of 1.3.

[0098] Example 24

[0099] Under an argon atmosphere, ethylene glycol dimethyl ether (62 mL) solution and i-BuAl(OR) from Example 12 were added sequentially to a 500 mL reaction flask at 25 °C. 1.5 (4.6 mL, 1.6 mmol, 8 equivalents), sec-butyllithium (0.15 mL, 0.2 mmol, 1 equivalent), and methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) were added. After one hour, the reaction system temperature was adjusted to -30 °C, and n-butyl acrylate (17.2 mL, 120 mmol, 600 equivalents) was added. After another hour of reaction, methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) was added at 25 °C, and the reaction was continued for 4 hours. After the reaction was completed, the mixture was quenched with cold methanol and washed three times. The mixture was then dried under vacuum to constant weight to obtain the acrylate thermoplastic elastomer.

[0100] The calculated yield was >99%. NMR characterization showed that the block ratio of methyl methacrylate to n-butyl acrylate was 3:7; the stereospecific proportion was 84%. GPC characterization showed the number-average molecular weight M0. n It has a molecular weight of 77349 g / mol and a molecular weight distribution (PDI) of 1.3.

[0101] Example 25

[0102] Under an argon atmosphere, ethylene glycol dimethyl ether (62 mL) solution and i-BuAl(OR) from Example 11 were added sequentially to a 500 mL reaction flask at 25 °C. 1.7 (3.13 mL, 1.0 mmol, 5 equiv.), sec-butyllithium (0.15 mL, 0.2 mmol, 1 equiv.) and methyl methacrylate (2.7 mL, 25 mmol, 125 equiv.) were added. After one hour, the reaction system temperature was adjusted to -30 °C, and n-butyl acrylate (17.2 mL, 120 mmol, 600 equiv.) was added. After another hour of reaction, methyl methacrylate (2.7 mL, 25 mmol, 125 equiv.) was added at 25 °C, and the reaction was continued for 4 hours. After the reaction was completed, the mixture was quenched with cold methanol and washed three times. The mixture was then dried under vacuum to constant weight to obtain the acrylate thermoplastic elastomer.

[0103] The calculated yield was >99%. NMR characterization showed that the block ratio of methyl methacrylate to n-butyl acrylate was 3:7; the stereospecific proportion was 83%. GPC characterization showed the number-average molecular weight M0. n The molecular weight is 69260 g / mol, and the molecular weight distribution (PDI) is 1.3. The tensile strength of the acrylate thermoplastic elastomer is 5.89 MPa, the elongation at break is 364.0%, and the tensile strength at 300% of its elongation is 4.27 MPa.

[0104] Example 26

[0105] Under an argon atmosphere, ethylene glycol dimethyl ether (62 mL) solution and i-BuAl(OR) from Example 11 were added sequentially to a 500 mL reaction flask at 25 °C. 1.7 (4.38 mL, 1.4 mmol, 7 equiv.), sec-butyllithium (0.15 mL, 0.2 mmol, 1 equiv.) and methyl methacrylate (2.7 mL, 25 mmol, 125 equiv.) were added. After one hour, the temperature of the reaction system was adjusted to -30 °C, and n-butyl acrylate (17.2 mL, 120 mmol, 600 equiv.) was added. After another hour of reaction, methyl methacrylate (2.7 mL, 25 mmol, 125 equiv.) was added at 25 °C, and the reaction was continued for 4 hours. After the reaction was completed, the mixture was quenched with cold methanol and washed three times. The mixture was then dried under vacuum to constant weight to obtain the acrylate thermoplastic elastomer.

[0106] The calculated yield was >99%. NMR characterization showed that the block ratio of methyl methacrylate to n-butyl acrylate was 3:7; the stereospecific proportion was 82%. GPC characterization showed the number-average molecular weight M0. n It has a molecular weight of 46477 g / mol and a molecular weight distribution (PDI) of 1.2.

[0107] Example 27

[0108] Under an argon atmosphere, ethylene glycol dimethyl ether (62 mL) solution and i-BuAl(OR) from Example 11 were added sequentially to a 500 mL reaction flask at 25 °C. 1.7 (5.63 mL, 1.8 mmol, 9 equiv.), sec-butyllithium (0.15 mL, 0.2 mmol, 1 equiv.), and methyl methacrylate (2.7 mL, 25 mmol, 125 equiv.) were added. After one hour, the reaction system temperature was adjusted to -30 °C, and n-butyl acrylate (17.2 mL, 120 mmol, 600 equiv.) was added. After another hour of reaction, methyl methacrylate (2.7 mL, 25 mmol, 125 equiv.) was added at 25 °C, and the reaction was continued for 4 hours. After the reaction was completed, the mixture was quenched with cold methanol and washed three times. The mixture was then dried under vacuum to constant weight to obtain the acrylate thermoplastic elastomer.

[0109] The calculated yield was >99%. NMR characterization showed that the block ratio of methyl methacrylate to n-butyl acrylate was 3:7; the stereospecific proportion was 84%. GPC characterization showed the number-average molecular weight M0. n It has a molecular weight of 57832 g / mol and a molecular weight distribution (PDI) of 1.2.

[0110] Example 28

[0111] Under an argon atmosphere, ethylene glycol dimethyl ether (62 mL) solution and i-BuAl(OR) from Example 11 were added sequentially to a 500 mL reaction flask at 25 °C. 1.7 (6.25 mL, 2.0 mmol, 10 equiv.), sec-butyllithium (0.15 mL, 0.2 mmol, 1 equiv.), and methyl methacrylate (2.7 mL, 25 mmol, 125 equiv.) were added. After one hour, the reaction system temperature was adjusted to -30 °C, and n-butyl acrylate (17.2 mL, 120 mmol, 600 equiv.) was added. After another hour of reaction, methyl methacrylate (2.7 mL, 25 mmol, 125 equiv.) was added at 25 °C, and the reaction was continued for 4 hours. After the reaction was completed, the mixture was quenched with cold methanol and washed three times. The mixture was then dried under vacuum to constant weight to obtain the acrylate thermoplastic elastomer.

[0112] The calculated yield was >99%. NMR characterization showed that the block ratio of methyl methacrylate to n-butyl acrylate was 3:7; the stereospecific proportion was 84%. GPC characterization showed the number-average molecular weight M0. n It has a molecular weight of 52625 g / mol and a molecular weight distribution (PDI) of 1.2.

[0113] Example 29

[0114] Under an argon atmosphere, ethylene glycol diethyl ether (62 mL) solution and i-BuAl(OR) from Example 11 were added sequentially to a 500 mL reaction flask at 25 °C. 1.7 (5 mL, 1.6 mmol, 8 equivalents), sec-butyllithium (0.15 mL, 0.2 mmol, 1 equivalent), and methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) were added. After one hour, the reaction system temperature was adjusted to -30°C, and n-butyl acrylate (17.2 mL, 120 mmol, 600 equivalents) was added. After another hour of reaction, methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) was added at 25°C, and the reaction was continued for 4 hours. After the reaction was completed, the mixture was quenched with cold methanol and washed three times. The mixture was then dried under vacuum to constant weight to obtain the acrylate thermoplastic elastomer.

[0115] The calculated yield was >99%. NMR characterization showed that the block ratio of methyl methacrylate to n-butyl acrylate was 3:7; the stereospecific proportion was 83%. GPC characterization showed the number-average molecular weight M0. n It has a molecular weight of 83900 g / mol and a molecular weight distribution (PDI) of 1.2.

[0116] Example 30

[0117] Under an argon atmosphere, toluene (60 mL) solution, ethylene glycol dimethyl ether (2.5 mL) solution, and i-BuAl(OR) from Example 11 were added sequentially to a 500 mL reaction flask at 25 °C. 1.7 (5 mL, 1.6 mmol, 8 equivalents), sec-butyllithium (0.15 mL, 0.2 mmol, 1 equivalent), and methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) were added. After one hour, the reaction system temperature was adjusted to -30°C, and n-butyl acrylate (17.2 mL, 120 mmol, 600 equivalents) was added. After another hour of reaction, methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) was added at 25°C, and the reaction was continued for 4 hours. After the reaction was completed, the mixture was quenched with cold methanol and washed three times. The mixture was then dried under vacuum to constant weight to obtain the acrylate thermoplastic elastomer.

[0118] The calculated yield was >99%. NMR characterization showed that the block ratio of methyl methacrylate to n-butyl acrylate was 3:7; the stereospecific proportion was 86%. GPC characterization showed the number-average molecular weight M0. nThe molecular weight is 66601 g / mol, and the molecular weight distribution (PDI) is 1.4. The tensile strength of the acrylate thermoplastic elastomer is 6.58 MPa, the elongation at break is 342.0%, and the tensile strength at 300% of its elongation is 3.50 MPa.

[0119] Example 31

[0120] Under an argon atmosphere, xylene (60 mL) solution, ethylene glycol dimethyl ether (2.5 mL) solution, and i-BuAl(OR) from Example 11 were added sequentially to a 500 mL reaction flask at 25 °C. 1.7 (5 mL, 1.6 mmol, 8 equivalents), sec-butyllithium (0.15 mL, 0.2 mmol, 1 equivalent), and methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) were added. After one hour, the reaction system temperature was adjusted to -30°C, and n-butyl acrylate (17.2 mL, 120 mmol, 600 equivalents) was added. After another hour of reaction, methyl methacrylate (2.7 mL, 25 mmol, 125 equivalents) was added at 25°C, and the reaction was continued for 4 hours. After the reaction was completed, the mixture was quenched with cold methanol and washed three times. The mixture was then dried under vacuum to constant weight to obtain the acrylate thermoplastic elastomer.

[0121] The calculated yield was >99%. NMR characterization showed that the block ratio of methyl methacrylate to n-butyl acrylate was 3:7; the stereospecific proportion was 85%. GPC characterization showed the number-average molecular weight M0. n It has a concentration of 94317 g / mol and a molecular weight distribution (PDI) of 1.3.

[0122] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the listed embodiments. Any changes, modifications, combinations, substitutions, or simplifications made without departing from the core ideas and principles of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A high-mechanical-performance acrylate thermoplastic elastomer based on modified aluminum, characterized in that, This acrylate thermoplastic elastomer is prepared by anionic polymerization of comonomers in an aluminum-lithium complex system. The acrylate thermoplastic elastomer has a tensile strength ≥ 5 MPa, an elongation at break ≥ 300%, a tensile strength at 300% elongation ≥ 2 MPa, a number-average molecular weight of 10,000-115,783 g / mol, a PDI of 1.1-1.5, and a stereoregularity (rr) ratio of 80%-90%. The comonomers are composed of methyl methacrylate and n-butyl acrylate. The aluminum-lithium complex system is composed of modified aluminum and lithium metal compounds. The modified aluminum is prepared by aluminum reagent and organic phenol. The molar number of organic phenol is 1.0-3.0 times that of aluminum reagent and is not an integer multiple.

2. The high mechanical properties acrylate thermoplastic elastomer according to claim 1, characterized in that, The molar number of the organic phenol is 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 2.3, 2.4, 2.5, 2.6, 2.7, or 2.8 times that of the aluminum reagent, and the aluminum reagent is one of triethylaluminum, trimethylaluminum, triisobutylaluminum, diethylaluminum chloride, diethylaluminum chloride, and methylaluminoxane; the general structural formula of the organic phenol is: R1, R2, and R3 are one of hydrogen, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, methoxy, nitro, and trifluoromethyl, and R4 and R5 are one of isopropyl and tert-butyl.

3. The high mechanical properties acrylate thermoplastic elastomer according to claim 2, characterized in that, Organic phenols have one of the following structures: 。 4. The high mechanical properties acrylate thermoplastic elastomer according to claim 1, characterized in that, The modified aluminum is prepared according to the following steps: Under anhydrous and oxygen-free conditions, a solvent, organic phenol, and aluminum reagent are added to a reactor, and the reaction is carried out at 0-50℃ for 2-48 hours to obtain modified aluminum.

5. The high mechanical properties acrylate thermoplastic elastomer according to claim 4, characterized in that, The modified aluminum is prepared by reacting at 30°C for 8 hours, using one or a mixture of two of the following solvents: n-hexane, cyclohexane, petroleum ether, chloroform, dichloropropane, and solvent oil.

6. The high mechanical properties acrylate thermoplastic elastomer according to claim 1, characterized in that, The molar ratio of methyl methacrylate to n-butyl acrylate is 9 / 1 to 1 / 9, the molar ratio of lithium metal compound to modified aluminum is 1 / 3 to 1 / 20, and the molar ratio of lithium metal compound to comonomer is 1 / 100 to 1 / 4000. The lithium metal compound includes, but is not limited to, n-butyllithium, sec-butyllithium, tert-butyllithium, and tert-butoxide lithium.

7. The method for preparing a high-mechanical-performance acrylate thermoplastic elastomer according to claim 1, characterized in that, This method is performed in the following steps: Under anhydrous and oxygen-free conditions, solvent, aluminum-lithium complex system, and part of methyl methacrylate monomer were added to a reactor at 0-30℃ and reacted for 10 min-1 h. Then, n-butyl acrylate was added to the reactor at -60-0℃ and reacted for 10 min-1 h. The remaining methyl methacrylate was added to the reactor at 0-30℃ and reacted for 10 min-12 h. After quenching with methanol, washing, and vacuum drying, a high-mechanical-performance acrylate thermoplastic elastomer was obtained.

8. The method according to claim 7, characterized in that, The solvent is one or two of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethoxymethane, methyl tert-butyl ether, dioxane, toluene, xylene, and tetrahydrofuran.

9. The high mechanical properties acrylate thermoplastic elastomer of claim 1 is applicable to the aerospace, defense and military and automotive fields.

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