A hydrogenated multi-block sbc thermoplastic elastomer and its preparation method and application
Hydrogenated multi-block SBC thermoplastic elastomers were prepared by anionic polymerization and hydrogenation treatment, which solved the problems of narrow temperature range and poor processability of damping materials, and achieved high damping performance over a wide temperature range and applications in multiple fields.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHINA PETROLEUM & CHEMICAL CORP
- Filing Date
- 2024-12-02
- Publication Date
- 2026-06-02
Smart Images
Figure CN122127556A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a hydrogenated multi-block SBC thermoplastic elastomer, its preparation method, and its applications, specifically relating to the field of damping materials technology. Background Technology
[0002] Viscoelastic damping materials can be widely used in aviation, aerospace, construction, navigation, electromechanical equipment and other fields for vibration reduction and energy consumption reduction. With economic development, damping materials have been rapidly developed in military and civilian fields in my country, and the amount used is also increasing.
[0003] Damping materials are typically composed of synthetic rubber-based polymers or polymer gels. Currently, polymer damping materials are widely used in vibration reduction and noise reduction and are a research hotspot in damping materials.
[0004] To evaluate the performance of polymer damping materials, it is necessary to consider factors such as the level of the damping peak and the effective damping temperature range. These properties are closely related to the glass transition temperature of the material. When the temperature of the polymer material is above the glass transition temperature or the frequency is very high, the molecular chains are frozen, resulting in minimal energy consumption. When the temperature is above the glass transition temperature or the frequency is very low, the molecular motion works in concert, also resulting in minimal energy consumption. Only when the temperature is near the glass transition temperature and at an appropriate frequency does the molecular chain motion lag behind the stress change, resulting in high internal friction, maximum energy consumption, and excellent damping performance.
[0005] However, synthetic rubber-based polymers have only one glass transition temperature, which is generally at room temperature, and their damping peak temperature range is relatively narrow, with the effective damping peak mostly in the 10~20℃ range. Excellent damping materials require a damping temperature range between 50~80℃.
[0006] To increase the damping peak value and temperature range, a common method is to use two materials with different glass transition temperatures to perform physical blending modification, thereby broadening the half-maximum width of the damping peak. However, the performance of physical blending modification is unstable, prone to stratification, requires the addition of various additives, has poor processability, high cost, and the additive composition is complex, which is not conducive to environmental protection. Summary of the Invention
[0007] To address the problems existing in the prior art, one of the objectives of this invention is to provide a hydrogenated multi-block SBC thermoplastic elastomer with good damping performance, a wide glass transition temperature range (-50℃~50℃), and a damping temperature range of 45~85℃. It also has good mechanical properties, flexibility, heat resistance, oil resistance, and aging resistance.
[0008] The second objective of this invention is to provide a method for preparing hydrogenated multi-block SBC thermoplastic elastomers, which has a simple preparation process, does not require vulcanization, and has high production efficiency.
[0009] The third objective of this invention is to provide hydrogenated multi-block SBC thermoplastic elastomers as damping materials. The elastomers provided by this invention exhibit good damping performance and a wide damping temperature range, while also possessing excellent mechanical properties, flexibility, and resistance to heat, oil, and aging. They can be applied in fields such as rail transportation, automobiles, aerospace, construction, and vibration and noise reduction in low-temperature environments.
[0010] To achieve the above objectives, the present invention provides a hydrogenated multi-block SBC thermoplastic elastomer having the structure shown in formula (I): PS1-EP / ES-PS2-EB / EE-PS3 (I). Among them: PS1, PS2, and PS3 are polystyrene blocks; EP / ES are hydrogenated polyisoprene blocks; EB / EE are hydrogenated polybutadiene blocks; The content of 3,4-polyisoprene units in the polyisoprene block is 10~70 wt%; The content of 1,2-polybutadiene units in the polybutadiene block is 10~70wt%.
[0011] The key technology of this invention lies in its use of an anionic polymerization system to synthesize a polystyrene-polyisoprene-polystyrene-polybutadiene-polystyrene multiblock elastomer. After hydrogenation of this multiblock elastomer, the hydrogenated product PS1-EP / ES-PS2-EB / EE-PS3 is obtained, representing a hydrogenated block structure. This elastomer contains at least five blocks, with different phases linked together in a head-to-tail manner, forming a phase-separated structure between the polystyrene and rubber segments. This increases the cohesive energy of the elastomer itself, endowing the material with excellent mechanical properties.
[0012] Furthermore, research has found that the content of 3,4-polyisoprene and 1,2-polybutadiene structures directly affects the glass transition temperature and damping temperature range of the elastomer. This invention employs structure modifiers and activators to jointly control the content of 3,4-polyisoprene in the polyisoprene block and the content of 1,2-polybutadiene in the polybutadiene block, thereby achieving controllable glass transition temperature and flexible adjustment of the elastomer in different application environments.
[0013] Furthermore, selective hydrogenation of the polymer solution improves the aging resistance of the elastomer. In addition to the sterically hindered benzene ring in the main chain, the elastomer also has -CH2-CH3 and -CH(CH3)2- structures on the side chains, which increases the barrier and further enhances the internal friction of the macromolecular chain movement. This improves the efficiency of converting external force into heat energy dissipation and exhibits good damping performance. As a result, the elastomer has a wider glass transition temperature range (-50℃ to 50℃) and the damping temperature range can reach 45~85℃.
[0014] In a preferred embodiment, the content of 3,4-polyisoprene in the polyisoprene block is 10~70wt%; and the content of 1,2-polybutadiene in the polybutadiene block is 25~70wt%. The inventors have discovered that under these preferred conditions, the elastomer has at least two glass transition temperatures, ensuring one glass transition temperature below 0°C and one glass transition temperature above 0°C.
[0015] In a preferred embodiment, the mass ratio of PS1, PS2 and PS3 in PS1-EP / ES-PS2-EB / EE-PS3 is 1:0.8~1.2:0.8~1.2.
[0016] In the preferred embodiment, the total mass of PS1, PS2 and PS3 accounts for 20~30wt%, EP / ES accounts for 35~40wt%, and EB / EE accounts for 35~40wt%.
[0017] In a more preferred embodiment, the total mass percentage of PS1, PS2, and PS3 is 25-30 wt%, the percentage of EP / ES is 35-38 wt%, and the percentage of EB / EE is 35-38 wt%. Studies have found that the proportion of each material has a certain impact on material properties. When the content of styrene monomer is low, the material's physical strength is insufficient; when it is high, the material's processing performance is poor, and the damping effect is affected. When the content of isoprene monomer is low, the material's damping performance does not meet expectations; when it is high, the material's physical properties are affected. When the content of butadiene monomer is low or high, it affects the damping performance at temperatures below 0°C, thus limiting the material's damping temperature range.
[0018] In a preferred embodiment, the number-average molecular weight of the thermoplastic elastomer is 80,000 to 100,000.
[0019] The present invention also provides a method for preparing hydrogenated multiblock SBC thermoplastic elastomer, the method comprising: (1) In an anionic polymerization solution system containing solvent and activator, styrene I is subjected to a single-stage polymerization with an initiator to obtain intermediate I; (2) Intermediate I is subjected to two-stage polymerization with isoprene or butadiene to obtain intermediate II; (3) Intermediate II and styrene II are subjected to three-stage polymerization to obtain intermediate III; (4) The intermediate III is polymerized with butadiene or isoprene in four stages to obtain intermediate IV; and the substances added in steps (2) and (4) are different. (5) After the intermediate IV and styrene III undergo a five-stage reaction, the polymerization reaction is terminated to obtain a polymer solution; (6) The polymer solution is subjected to hydrogenation reaction to obtain the hydrogenated multi-block SBC thermoplastic elastomer.
[0020] It should be noted that the statement in step (4) that "the substances added in step (2) and step (4) are different" means that when isoprene is added in step (2), the substance added in step (4) is butadiene; when butadiene is added in step (2), the substance added in step (4) is isoprene.
[0021] In a preferred embodiment, the conditions for the polymerization step are: a temperature of 40~70℃ and a time of 40~60min.
[0022] In the preferred embodiment, the conditions for the two-stage polymerization are: a temperature of 40~75℃ and a time of 50~70min.
[0023] In the preferred embodiment, the conditions for the three-stage polymerization are: temperature of 40~70℃ and time of 40~60min.
[0024] In the preferred embodiment, the conditions for the four-stage polymerization are: temperature of 40~75℃ and time of 50~70min.
[0025] In the preferred embodiment, the conditions for the five-stage polymerization are: temperature of 40~70℃ and time of 40~60min.
[0026] In a preferred embodiment, the hydrogenation reaction is carried out at a temperature of 70°C to 110°C for a time of 100 to 140 minutes. Studies have shown that under these preferred conditions, unsaturated bonds in 98 wt% of isoprene and butadiene can be hydrogenated.
[0027] In a preferred embodiment, in step (1), the method further includes: first preheating the solvent, activator and optionally structure modifier to 40~60°C, and then adding styrene I and the initiator to carry out a reaction to obtain intermediate I.
[0028] In a preferred embodiment, based on the total amount of styrene I, isoprene, styrene II, butadiene, and styrene III, the total amount of ethylene I, styrene II, and styrene III is 20-30 wt%, the amount of isoprene is 35-40 wt%, and the amount of butadiene monomer is 35-40 wt%.
[0029] In a more preferred embodiment, the mass ratio of styrene I, styrene II, and styrene III is 1:0.8~1.2:0.8~1.2.
[0030] In a preferred embodiment, the polymerization reaction is terminated using an alcohol solvent.
[0031] In a preferred embodiment, the alcohol solvent is ethanol.
[0032] In a preferred embodiment, the total concentration of styrene I, isoprene, styrene II, butadiene, and styrene III in the solvent is 70-110 g / L.
[0033] In a preferred embodiment, the solvent is a nonpolar solvent. In a more preferred embodiment, the solvent is cyclohexane.
[0034] In a preferred embodiment, the initiator is a lithium-based initiator, more preferably an alkyl lithium, and even more preferably n-butyl lithium.
[0035] In a preferred embodiment, the activator is tetrahydrofuran.
[0036] In a preferred embodiment, the total concentration of the activator in the solvent is 10-20 mg / L. Studies have shown that under this preferred condition, the content of 3,4-polyisoprene units and 1,2-polybutadiene units can be simultaneously adjusted to 10-70 wt%.
[0037] In a preferred embodiment, the structure modifier is selected from at least one of bis(tetrahydrofurfuryl)propane, diethyl ether, and bis(tetrahydrofurfuryl)hexyl ether.
[0038] In a more preferred embodiment, the structure modifier is bis(tetrahydrofurfuryl)propane.
[0039] In a preferred embodiment, in steps (1) to (4), a structure modifier is selectively added, and the concentration of the structure modifier does not exceed 180 mg / L. In a more preferred embodiment, the concentration of the structure modifier is 10~180 mg / L. The inventors have found that under these preferred conditions, a hydrogenated multi-block SBC thermoplastic elastomer with one glass transition temperature below 0°C and one glass transition temperature above 0°C can be obtained.
[0040] It should be noted that the operation of "selectively adding a structure modifier in steps (1) to (4)" means that a structure modifier can be added in any one, two or more steps of steps (1), (2), (3) and (4), or it can be omitted. For example, a structure modifier can be added in step (1), in step (2), or in both steps (1) and (2).
[0041] This invention allows for the regulation of the content of 3,4-polyisoprene and 1,2-polybutadiene by adjusting the amount or method of adding the structure regulator. Specifically, the 3,4-polyisoprene content is adjusted by adding the structure regulator before the isoprene completes the polymerization reaction; the more structure regulator added, the higher the 3,4-polyisoprene content. Similarly, the 1,2-polybutadiene content is adjusted by adding the structure regulator before the butadiene completes the polymerization reaction; the more structure regulator added, the higher the 1,2-polybutadiene content.
[0042] Meanwhile, the amount of activator can also affect the content of 3,4-polyisoprene and 1,2-polybutadiene. The more activator added, the higher the content of 3,4-polyisoprene and 1,2-polybutadiene.
[0043] In a preferred embodiment, the catalyst for the hydrogenation reaction is a Ni / Al catalyst, and the molar ratio of Al to Ni is 1:3.0~3.8.
[0044] It should be noted that the present invention does not have any special requirements for the preparation of the catalyst, and any catalyst known in the art can be used.
[0045] In a preferred embodiment, the amount of catalyst used is 3 to 50 mmol relative to 1 kg of the polymer solution.
[0046] In a preferred embodiment, step (6) further includes: post-processing the product obtained after hydrogenation reaction to obtain the hydrogenated multiblock SBC thermoplastic elastomer.
[0047] The present invention does not have any special requirements for the post-processing method. For example, the product obtained after hydrogenation is added to an antioxidant at a weight of 0.4 to 0.8 wt% based on the product, stirred for 5 to 20 minutes, and the product is then added to a mixture of steam and water. The solvent is evaporated, while the elastomer is separated in a solid state and suspended in water. The solid is separated, and the water is squeezed out using an extrusion dehydrator and the volatiles are removed using a drying oven to obtain hydrogenated multi-block SBC thermoplastic elastomer.
[0048] In a preferred embodiment, the antioxidant is antioxidant 1076.
[0049] This invention also provides an application of hydrogenated multi-block SBC thermoplastic elastomer as a damping material.
[0050] Compared with the prior art, the advantages of this invention are as follows: (1) In view of the limitations of existing rubber damping materials technology, the damping loss factor is generally not high enough, the damping temperature range is narrow, and it is difficult to make wide temperature range and high damping materials, the hydrogenated multi-block SBC thermoplastic elastomer prepared in this invention contains at least 5 block elastomers, so that the elastomers of different phases are connected together in a head-to-tail manner to form a polystyrene segment and rubber segment phase separation structure, which can increase the cohesive energy of the material itself, endow the material with good mechanical properties, and has better characteristics than traditional rubber. It exhibits rubber elasticity at room temperature and can be processed like plastic at high temperature.
[0051] (2) The preparation method provided by the present invention has a simple preparation process, does not require sulfidation, and has high production efficiency.
[0052] (3) The present invention uses structure regulators and activators to control the content of 3,4-polyisoprene in polyisoprene blocks and the content of 1,2-polybutadiene in polybutadiene blocks, thereby achieving controllable glass transition temperature of the elastomer.
[0053] (4) When the content of 3,4-polyisoprene in the polyisoprene block of the hydrogenated multi-block SBC thermoplastic elastomer provided by the present invention is 10~70wt%, and the content of 1,2-polybutadiene in the polybutadiene block is 25~70wt%, the elastomer has at least two glass transition temperatures, ensuring that it has one glass transition temperature below 0°C and one glass transition temperature above 0°C.
[0054] (5) In this invention, the polymerized adhesive is selectively hydrogenated through a hydrogenation process. On the one hand, this improves the aging resistance of the elastomer. On the other hand, in addition to the sterically hindered benzene ring in the main chain, the elastomer also has -CH2-CH3 and -CH(CH3)2- structures on the side chains, which increases the barrier and further increases the internal friction of the macromolecular chain segment movement. This improves the efficiency of converting external force into heat energy dissipation and exhibits good damping performance. As a result, the elastomer has a wider glass transition temperature range (-50℃~50℃) and the damping temperature range can reach 45~85℃. Attached Figure Description
[0055] Figure 1 This is the 1H NMR spectrum of 3,4-polyisoprene and 1,2-polybutadiene before hydrogenation of the polymer solution in Example 4 of this invention. Figure 2 This is the DSC diagram of the hydrogenated multiblock SBC thermoplastic elastomer prepared in Example 4 of this invention; Figure 3 This is the DMA diagram of the hydrogenated multiblock SBC thermoplastic elastomer prepared in Example 4 of this invention. Detailed Implementation
[0056] The endpoints and any values of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and individual point values, and individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.
[0057] The present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited to the following specific embodiments. Obviously, the embodiments described below are only a part of the embodiments, and all other embodiments obtained by those skilled in the art without creative effort are still within the scope of protection of the present invention.
[0058] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be purchased from the market or prepared by existing methods.
[0059] In the following examples, since the reaction is exothermic, the temperature cannot be precisely controlled, so the temperature is a range.
[0060] Example 1
[0061] (1) Add 3000ml cyclohexane, 50mg tetrahydrofuran and 20mg bistetrahydrofuran propane to a 5L polymerization reactor purified by nitrogen. After heating to 50℃, add 2.4 mmol of n-butyllithium and then add 30g of styrene to carry out a first reaction (temperature 50~65℃, time 45min) to obtain intermediate I. (2) Intermediate I was reacted with 105g of isoprene in a two-stage reaction (temperature 50℃~70℃, time 60min) to obtain intermediate II; (3) Intermediate II was reacted with 30g of styrene in a three-stage reaction (temperature 50℃~65℃, time 45min) to obtain intermediate III; (4) Intermediate III was reacted with 105g butadiene in a four-stage reaction (temperature 50℃~65℃, time 60min) to obtain intermediate IV; (5) Intermediate IV was reacted with 30g of styrene in a five-stage reaction (temperature 50℃~65℃, time 45min), and 10ml of ethanol was added to terminate the reaction to obtain polymer solution. (6) The obtained polymer solution (0.3Kg) was pressed into a 5L hydrogenation reactor, and 9mmol of Ni / Al catalyst (Al / Ni=1:3.5) was added to carry out hydrogenation reaction (temperature 80℃~100℃, time 120min). The product obtained after hydrogenation was added to antioxidant 1076 at 0.6wt% of the product weight, stirred for 5min, and the product was added to a mixture of steam and water. The solvent was evaporated, and the elastomer was separated in a solid state and suspended in water. The solid was separated, and the water was squeezed out by an extrusion dehydrator and the volatile matter was removed by a drying oven to obtain hydrogenated multi-block SBC thermoplastic elastomer.
[0062] Example 2
[0063] (1) Add 3000ml cyclohexane, 50mg tetrahydrofuran and 460mg bistetrahydrofurfurylene to a 5L polymerization reactor purified by nitrogen. After heating to 50℃, add 2.4 mmol of n-butyllithium and then add 30g of styrene to carry out a first reaction (temperature 50℃~65℃, time 45min) to obtain intermediate I. (2) Intermediate I was reacted with 105g of isoprene in a two-stage reaction (temperature 45~60℃, time 60min) to obtain intermediate II; (3) Intermediate II was reacted with 30g of styrene in a three-stage reaction (temperature 45~60℃, time 45min) to obtain intermediate III; (4) Intermediate III was reacted with 105g butadiene in a four-stage reaction (temperature 45~60℃, time 60min) to obtain intermediate IV; (5) Intermediate IV was reacted with 30g of styrene in a five-stage reaction (temperature 50℃~65℃, time 45min), and 10ml of ethanol was added to terminate the reaction to obtain polymer solution. (6) The obtained polymer solution (0.3Kg) was pressed into a 5L hydrogenation reactor, and 9mmol of Ni / Al catalyst (Al / Ni=1:3.5) was added to carry out hydrogenation reaction (temperature 80℃~100℃, time 120min). The product obtained after hydrogenation was added to antioxidant 1076 at 0.6wt% of the product weight, stirred for 5min, and the product was added to a mixture of steam and water. The solvent was evaporated, and the elastomer was separated in a solid state and suspended in water. The solid was separated, and the water was squeezed out by an extrusion dehydrator and the volatile matter was removed by a drying oven to obtain hydrogenated multi-block SBC thermoplastic elastomer.
[0064] Example 3
[0065] (1) Add 3000ml cyclohexane and 50mg tetrahydrofuran to a 5L polymerization reactor purified by nitrogen. After heating to 50℃, add 2.4 mmol of n-butyllithium and 30g of styrene to carry out a first reaction (temperature 50℃~65℃, time 45min) to obtain intermediate I. (2) Intermediate I was reacted with 105g of isoprene in a two-stage reaction (temperature 50℃~60℃, time 60min) to obtain intermediate II; (3) Intermediate II was reacted with 30g of styrene in a three-stage reaction (temperature 50℃~60℃, time 45min) to obtain intermediate III; (4) Intermediate III was reacted with 105g butadiene and 460mg bis(tetrahydrofurfuryl) in a four-stage reaction (temperature 45℃~60℃, time 60min) to obtain intermediate IV; (5) Intermediate IV was reacted with 30g of styrene in a five-stage reaction (temperature 45℃~65℃, time 45min), and 10ml of ethanol was added to terminate the reaction to obtain polymer solution. (6) The obtained polymer solution (0.3Kg) was pressed into a 5L hydrogenation reactor, and 9mmol of Ni / Al catalyst (Al / Ni=1:3.5) was added to carry out hydrogenation reaction (temperature 80℃~100℃, time 120min). The product obtained after hydrogenation was added to antioxidant 1076 at 0.6wt% of the product weight, stirred for 5min, and the product was added to a mixture of steam and water. The solvent was evaporated, and the elastomer was separated in a solid state and suspended in water. The solid was separated, and the water was squeezed out by an extrusion dehydrator and the volatile matter was removed by a drying oven to obtain hydrogenated multi-block SBC thermoplastic elastomer.
[0066] Example 4
[0067] (1) Add 3000ml cyclohexane, 50mg tetrahydrofuran and 200mg bistetrahydrofurfurylene to a 5L polymerization reactor purified by nitrogen. After heating to 50℃, add 2.4 mmol of n-butyllithium and then add 30g of styrene to carry out a first reaction (temperature 45℃~65℃, time 45min) to obtain intermediate I. (2) Intermediate I was reacted with 105g of isoprene in a two-stage reaction (temperature 45℃~60℃, time 60min) to obtain intermediate II; (3) Intermediate II was reacted with 30g of styrene in a three-stage reaction (temperature 50℃~60℃, time 45min) to obtain intermediate III; (4) Intermediate III was reacted with 260 mg of bis(tetrahydrofurfuryl) and 105 g of butadiene in a four-stage reaction (temperature 45~60℃, time 60 min) to obtain intermediate IV; (5) Intermediate IV was reacted with 30g of styrene in a five-stage reaction (temperature 45℃~65℃, time 45min), and 10ml of ethanol was added to terminate the reaction to obtain polymer solution. (6) The obtained polymer solution (0.3Kg) was pressed into a 5L hydrogenation reactor, and 9mmol of Ni / Al catalyst (Al / Ni=1:3.5) was added to carry out hydrogenation reaction (temperature 80℃~100℃, time 120min). The product obtained after hydrogenation was added to antioxidant 1076 at 0.6wt% of the product weight, stirred for 5min, and the product was added to a mixture of steam and water. The solvent was evaporated, and the elastomer was separated in a solid state and suspended in water. The solid was separated, and the water was squeezed out by an extrusion dehydrator and the volatile matter was removed by a drying oven to obtain hydrogenated multi-block SBC thermoplastic elastomer.
[0068] This invention provides, by way of example, 1H NMR spectra of 3,4-polyisoprene and 1,2-polybutadiene before hydrogenation of the polymer solution in this embodiment; see details below. Figure 1 ,from Figure 1 It can be seen that the content of 1,2-polybutadiene is 67.1% and the content of 3,4-polyisoprene is 35.11%.
[0069] The present invention also provides, by way of example, the DSC pattern of the hydrogenated multiblock SBC thermoplastic elastomer prepared in this embodiment; see details below. Figure 2 ,from Figure 2 It can be seen that the glass transition temperature below 0℃ is -46℃, and the glass transition temperature above 0℃ is 44℃.
[0070] The present invention also provides, by way of example, the DMA diagram of the hydrogenated multiblock SBC thermoplastic elastomer prepared in this embodiment; see details. Figure 3 ,from Figure 3 It can be seen that the damping temperature range tanδ≥0.3 reaches 84.57℃.
[0071] Example 5
[0072] (1) Add 3000ml cyclohexane and 50mg tetrahydrofuran to a 5L polymerization reactor purified by nitrogen. After heating to 50℃, add 2.4 mmol of n-butyllithium and 30g of styrene to carry out a first reaction (temperature 45℃~65℃, time 45min) to obtain intermediate I. (2) Intermediate I was reacted with 260 mg of bis(tetrahydrofurfuryl) and 105 g of butadiene in a two-stage reaction (temperature 45℃~60℃, time 60 min) to obtain intermediate II; (3) Intermediate II was reacted with 30g of styrene in a three-stage reaction (temperature 45℃~65℃, time 45min) to obtain intermediate III; (4) Intermediate III was reacted with 105g of isoprene in a four-stage reaction (temperature 45℃~60℃, time 60min) to obtain intermediate IV; (5) Intermediate IV was reacted with 30g of styrene in a five-stage reaction (temperature 45℃~65℃, time 45min), and 10ml of ethanol was added to terminate the reaction to obtain polymer solution. (6) The obtained polymer solution (0.3Kg) was pressed into a 5L hydrogenation reactor, and 9mmol of Ni / Al catalyst (Al / Ni=1:3.5) was added to carry out hydrogenation reaction (temperature 80℃~100℃, time 120min). The product obtained after hydrogenation was added to antioxidant 1076 at 0.6wt% of the product weight, stirred for 5min, and the product was added to a mixture of steam and water. The solvent was evaporated, and the elastomer was separated in a solid state and suspended in water. The solid was separated, and the water was squeezed out by an extrusion dehydrator and the volatile matter was removed by a drying oven to obtain hydrogenated multi-block SBC thermoplastic elastomer.
[0073] Example 6
[0074] (1) Add 3000ml cyclohexane and 50mg tetrahydrofuran to a 5L polymerization reactor purified by nitrogen. After heating to 50℃, add 2.4 mmol of n-butyllithium and 25g of styrene to carry out a first-stage reaction (temperature 50~60℃, time 45min) to obtain intermediate I. (2) Intermediate I was reacted with 105g of isoprene in a two-stage reaction (temperature 50~65℃, time 60min) to obtain intermediate II; (3) Intermediate II was reacted with 22.5% styrene in a three-stage reaction (temperature 50~65℃, time 45min) to obtain intermediate III; (4) Intermediate III was reacted with 120g butadiene in a four-stage reaction (temperature 60~65℃, time 60min) to obtain intermediate IV; (5) Intermediate IV was reacted with 27.5g of styrene in a five-stage reaction (temperature 60~65℃, time 45min), and 10ml of ethanol was added to terminate the reaction to obtain polymer solution. Step (6) is the same as in Example 1, to obtain hydrogenated multiblock SBC thermoplastic elastomer.
[0075] Comparative Example 1 (1) Add 3000ml cyclohexane, 50mg tetrahydrofuran and 460g bis(tetrahydrofuran)propane to a 5L polymerization reactor purified by nitrogen. After heating to 50℃, add 2.4 mmol n-butyllithium and 45g styrene to carry out a first-stage reaction (temperature 50~65℃, time 45min) to obtain intermediate I. (2) Intermediate I was reacted with 210g of isoprene in a two-stage reaction (temperature 50℃~70℃, time 60min) to obtain intermediate II; (3) Intermediate II was reacted with 45g of styrene in a three-stage reaction (temperature 50℃~65℃, time 45min), and 10ml of ethanol was added to terminate the reaction to obtain polymer solution. (4) The obtained polymer solution (0.3Kg) was pressed into a 5L hydrogenation reactor and 9mmol of Ni / Al catalyst (Al / Ni=1:3.5) was added to carry out hydrogenation reaction (temperature 80℃~100℃, time 120min). The product obtained after hydrogenation was added to antioxidant 1076 at 0.6wt% of the product weight and stirred for 5min. The product was then added to a mixture of steam and water. The solvent was evaporated and the elastomer was separated in a solid state and suspended in water. The solid was separated and dehydrated by a dehydrator and the volatiles were removed by a drying oven to obtain hydrogenated triblock elastomer.
[0076] Comparative Example 2 (1) Add 3000ml cyclohexane, 50mg tetrahydrofuran and 460mg bistetrahydrofurfurylene to a 5L polymerization reactor purified by nitrogen. After heating to 50℃, add 2.4 mmol of n-butyllithium and then add 45g of styrene to carry out a first reaction (temperature 50℃~65℃, time 45min) to obtain intermediate I. (2) Intermediate I was reacted with 210g butadiene in a two-stage reaction (temperature 50℃~70℃, time 60min) to obtain intermediate II; (3) Intermediate II was reacted with 45g of styrene in a three-stage reaction (temperature 50℃~65℃, time 45min), and 10ml of ethanol was added to terminate the reaction to obtain polymer solution. (4) The obtained polymer solution (0.3Kg) was pressed into a 5L hydrogenation reactor and 9mmol of Ni / Al catalyst (Al / Ni=1:3.5) was added to carry out hydrogenation reaction (temperature 80℃~100℃, time 120min). The product obtained after hydrogenation was added to antioxidant 1076 at 0.6wt% of the product weight and stirred for 5min. The product was then added to a mixture of steam and water. The solvent was evaporated and the elastomer was separated in a solid state and suspended in water. The solid was separated and dehydrated by a dehydrator and the volatiles were removed by a drying oven to obtain hydrogenated triblock elastomer.
[0077] Comparative Example 3 (1) Add 3000ml cyclohexane, 50mg tetrahydrofuran and 260mg bistetrahydrofurfurylene to a 5L polymerization reactor purified by nitrogen. After heating to 50℃, add 2.2 mmol of n-butyllithium and then add 30g of styrene to carry out a first reaction (temperature 50~65℃, time 45min) to obtain intermediate I. (2) Intermediate I was reacted with 105g of isoprene in a two-stage reaction (temperature 50℃~70℃, time 60min) to obtain intermediate II; (3) Intermediate II was reacted with 30g of styrene in a three-stage reaction (temperature 50℃~65℃, time 45min) to obtain intermediate III; (4) Intermediate III was reacted with 105g butadiene in a four-stage reaction (temperature 50℃~65℃, time 60min), and 10ml ethanol was added to terminate the reaction to obtain polymer solution. (5) The polymer solution obtained at termination (0.27Kg) was pressed into a 5L hydrogenation reactor, and 8.1mmol Ni / Al catalyst (Al / Ni=1:3.5) was added to carry out hydrogenation reaction (temperature 80℃~100℃, time 120min). The product obtained after hydrogenation was added to antioxidant 1076 at 0.6wt% of the product weight, stirred for 5min, and the product was added to a mixture of steam and water. The solvent was evaporated, and the elastomer was separated in a solid state and suspended in water. The solid was separated, water was squeezed out by a dehydrator, and volatiles were removed by a drying oven to obtain hydrogenated tetrablock elastomer.
[0078] Comparative Example 4 (1) Add 3000ml cyclohexane and 20mg tetrahydrofuran to a 5L polymerization reactor purified by nitrogen. After heating to 50℃, add 2.4 mmol of n-butyllithium and 30g of styrene to carry out a first reaction (temperature 50~65℃, time 45min) to obtain intermediate I. Steps (2) to (6) are the same as in Example 1, and hydrogenated multiblock SBC thermoplastic elastomer is obtained.
[0079] Comparative Example 5 Steps (1), (2), (3), (4) and (5) are the same as in Example 1, and a polymer adhesive is obtained.
[0080] Step (6) was not performed.
[0081] Test case The microstructure and composition of the elastomers prepared in the above examples were characterized. The microstructure was characterized by proton nuclear magnetic resonance (NMR) spectroscopy, and the molecular weight was measured by gel permeation chromatography (GPC). The test results are shown in Table 1.
[0082] The elastomers prepared in the above examples were subjected to tensile, hardness, thermal, and damping property tests. Tensile properties were measured using a universal testing machine according to GB / T528-2009, with a tensile rate of 500 mm / min. Hardness was measured using a Shore A hardness tester according to GB / T531.1-2008. Thermal properties were measured using a differential scanning calorimeter (DSC) under the following conditions: temperature range -150℃ to 150℃, temperature change rate 10℃ / min. Damping properties were measured using a dynamic thermomechanical analyzer (DMA) under the following conditions: temperature range -60℃ to 100℃, heating rate 3℃ / min, frequency 11 Hz, and strain 0.3%. The test results are shown in Table 2.
[0083]
[0084]
[0085] A comparison of the data in Tables 1 and 2 shows that when the structures in Comparative Examples 1 and 2 are both triblock copolymers, the strength and damping performance of the elastomer decrease significantly. In Comparative Example 2, the damping temperature range (tanδ ≥ 0.3) is essentially nonexistent. In Comparative Example 3, with its PS1-EP / ES-PS2-EB / EE structure, the lack of the PS3 block results in some damping performance, but very low strength and a narrow damping temperature range. In Comparative Example 4, the content of 3,4-polyisoprene units in the polyisoprene block and the content of 1,2-polybutadiene units in the polybutadiene block are too low. Although the hydrogenated multiblock structure imparts some damping performance, the effective damping temperature range is very narrow. In Comparative Example 5, the polyisoprene and polybutadiene segments were not hydrogenated, resulting in a multiblock SBC thermoplastic elastomer with poor performance, no damping performance, and no damping temperature range (tanδ ≥ 0.3).
Claims
1. A hydrogenated multi-block SBC thermoplastic elastomer, characterized in that: It has the structure shown in formula (I): PS1-EP / ES-PS2-EB / EE-PS3 (I). Among them: PS1, PS2, and PS3 are polystyrene blocks; EP / ES are hydrogenated polyisoprene blocks; EB / EE are hydrogenated polybutadiene blocks; The content of 3,4-polyisoprene units in the polyisoprene block is 10~70 wt%; The content of 1,2-polybutadiene units in the polybutadiene block is 10~70wt%.
2. The hydrogenated multi-block SBC thermoplastic elastomer according to claim 1, characterized in that: The content of 3,4-polyisoprene in the polyisoprene block is 10~70wt%; the content of 1,2-polybutadiene in the polybutadiene block is 25~70wt%.
3. The hydrogenated multi-block SBC thermoplastic elastomer according to claim 1, characterized in that: In the PS1-EP / ES-PS2-EB / EE-PS3, the mass ratio of PS1, PS2 and PS3 is 1:0.8~1.2:0.8~1.2; And / or, the total mass of PS1, PS2 and PS3 accounts for 20~30wt%, EP / ES accounts for 35~40wt%, and EB / EE accounts for 35~40wt%.
4. A hydrogenated multi-block SBC thermoplastic elastomer according to claim 1 or 2, characterized in that: The number-average molecular weight of the thermoplastic elastomer is 80,000 to 100,000.
5. A method for preparing the hydrogenated multiblock SBC thermoplastic elastomer according to any one of claims 1 to 4, characterized in that: (1) In an anionic polymerization solution system containing solvent and activator, styrene I is subjected to a single-stage polymerization with an initiator to obtain intermediate I; (2) Intermediate I is subjected to two-stage polymerization with isoprene or butadiene to obtain intermediate II; (3) Intermediate II and styrene II are subjected to three-stage polymerization to obtain intermediate III; (4) The intermediate III is polymerized with butadiene or isoprene in four stages to obtain intermediate IV; and the substances added in steps (2) and (4) are different. (5) After the intermediate IV and styrene III undergo a five-stage reaction, the polymerization reaction is terminated to obtain a polymer solution; (6) The polymer solution is subjected to hydrogenation reaction to obtain the hydrogenated multi-block SBC thermoplastic elastomer.
6. The method for preparing hydrogenated multi-block SBC thermoplastic elastomer according to claim 5, characterized in that: The conditions for the polymerization of a single segment include: a temperature of 40~70℃ and a time of 40~60min; And / or, the conditions for the two-stage polymerization are: temperature of 40~75℃ and time of 50~70min; And / or, the conditions for the three-stage polymerization are: temperature 40~70℃, time 40~60min; And / or, the conditions for the four-stage polymerization are: temperature 40~75℃, time 50~70min; And / or, the conditions for the five-stage polymerization are: temperature of 40~70℃ and time of 40~60min; And / or, the conditions for the hydrogenation reaction are: a temperature of 70℃~110℃ and a time of 100~140min.
7. The method for preparing hydrogenated multi-block SBC thermoplastic elastomer according to claim 5 or 6, characterized in that: The polymerization reaction is terminated using an alcohol solvent.
8. The method for preparing hydrogenated multi-block SBC thermoplastic elastomer according to claim 5 or 6, characterized in that: The total concentration of styrene I, isoprene, styrene II, butadiene, and styrene III in the solvent is 70-110 g / L; And / or, the total concentration of the activator in the solvent is 10~20 mg / L.
9. The method for preparing hydrogenated multi-block SBC thermoplastic elastomer according to claim 5 or 6, characterized in that: The structure modifier is selected from at least one of bis(tetrahydrofurfuryl ether), diethyl ether, and bis(tetrahydrofurfuryl ethyl ether). And / or, the catalyst for the hydrogenation reaction is a Ni / Al catalyst, and the molar ratio of Al content to Ni content is 1:3.0~3.
8.
10. The method for preparing hydrogenated multi-block SBC thermoplastic elastomer according to claim 5 or 6, characterized in that: In steps (1) to (4), a structure modifier is selectively added, and the concentration of the structure modifier added does not exceed 180 mg / L.
11. The application of the hydrogenated multi-block SBC thermoplastic elastomer according to any one of claims 1 to 4 as a damping material.