Preparation of high molecular damping brominating agent and high damping brominated butyl rubber

Abstract

The application discloses a high-molecular damping brominating agent and a preparation method thereof, and discloses a high-damping brominated butyl rubber and a preparation method thereof. The high-molecular damping brominating agent is a linear block copolymer composed of alpha-alkyl styrene, isoprene and 1,2-dibromoethylene. The preparation method of the high-damping brominated butyl rubber is green and environment-friendly, has a short technological process, low production cost and the like, and is suitable for industrialized production.

Description

Technical Field

[0001] This invention relates to a polymeric damping brominizing agent and the preparation of high-damping brominated butyl rubber. Background Technology

[0002] With the rapid development of modern science and technology, mechanical equipment is trending towards high frequency and high speed. While bringing convenience to daily production and life, this has also generated a series of problems, such as high-frequency vibration and noise. These problems not only accelerate the fatigue damage of mechanical structural materials and shorten their service life, but also affect people's daily lives to a certain extent. Therefore, developing high-performance, high-efficiency damping materials and improving their damping and vibration reduction applications is crucial for improving the operating environment of machinery. Due to the unique viscoelasticity of polymers, rubber damping materials have significant damping effects in vibration reduction, noise reduction, and improving the human-machine working environment. They have been widely used in many fields such as high-speed rail, aerospace, naval vessels, mechanical engineering, automobiles, and electronics. In particular, the data storage systems in various IT equipment such as servers, computers, workstations, and switches are subject to vibration and noise from the fan rotation, which seriously affects the service life of hard drives. The demand for high-efficiency damping and vibration reduction products is very urgent. Furthermore, as electronic equipment faces increasingly complex operating environments with lower and higher temperatures, extremely high requirements are placed on rubber damping materials.

[0003] Brominated butyl rubber (BIIR) is produced by introducing bromine atoms into the molecular chain of butyl rubber (IIR) through an electrophilic substitution reaction under the influence of molecular bromine. Compared to IIR, BIIR, in addition to possessing the same excellent airtightness, also exhibits better adhesion, faster vulcanization speed, good thermal stability, and corrosion resistance, enabling its use in extreme environments such as strong corrosion or high temperatures. Furthermore, the introduction of bromine atoms increases the polarity of the molecular chain, leading to increased relaxation resistance and greater internal friction, resulting in excellent damping performance. Therefore, it is one of the most widely used basic damping rubbers. However, brominated butyl rubber currently suffers from drawbacks such as insufficient damping value, unstable damping performance, a limited effective damping temperature range, and unsatisfactory mechanical properties. These limitations prevent it from meeting the damping performance requirements of large equipment and precision instruments, thus becoming a bottleneck for the expanded application of brominated butyl rubber materials.

[0004] In the prior art, the preparation methods of polymer damping materials mainly include blending, copolymerization, interpenetrating polymer networks, and adding organic small molecule functional damping agents.

[0005] Literature documents such as CN102229724A, CN102775659B, CN105906956B, CN113969031A, CN103113682A, CN201110165757.2 have shown that blending, copolymerization, and interpenetrating polymer networks can broaden the effective damping temperature range of rubber and improve its damping performance to some extent. However, these methods still have certain limitations, such as leading to a decrease in the mechanical properties of the modified materials, complex processes, difficult practical operation, large addition amounts, high costs, difficulty in removing organic solvents, and environmental pollution. Summary of the Invention

[0006] One of the objectives of this invention is to provide a maximum damping factor tanδ max A method for preparing high-damping brominated butyl rubber with a strength of ≥2.1. This invention utilizes anionic polymerization. First, using alkyllithium as an initiator, a polymeric damping brominizing agent is synthesized from α-alkylstyrene, isoprene, and an anionicly reactive brominating agent. Second, the polymeric damping brominizing agent and brominated butyl rubber are compounded and then subjected to open milling to prepare the high-damping brominated butyl rubber. This method significantly improves the compatibility between the polymeric damping brominizing agent and brominated butyl rubber, solves the dispersion problem of the polymeric damping brominizing agent in the brominated butyl rubber matrix, and not only greatly enhances the damping performance of brominated butyl rubber but also improves its mechanical properties and permeability, endowing it with high efficiency and stability in damping performance.

[0007] In this invention, "%" refers to mass percentage.

[0008] As one aspect of the present invention, a polymeric damping bromide is disclosed, which is a linear block copolymer composed of α-alkylstyrene, isoprene, and 1,2-dibromoethylene, having the general structural formula shown in Formula I:

[0009]

[0010] Wherein: R is a C1-C4 alkyl group; n is the number of repeating units: n≥1. The polymeric damping bromide has a number-average molecular weight (Mn) of 80,000-90,000, a molecular weight distribution (Mw / Mn) of 1.36-1.95, and a bromine content of 4-5% by mass.

[0011] As another aspect of the present invention, a method for preparing the above-mentioned polymeric damping bromide is provided, comprising:

[0012] Based on 100% by mass of α-alkylstyrene, 300%–400% solvent, 100% α-alkylstyrene, and 0.7%–0.9% structure modifier are added sequentially to a polymerization reactor. The temperature is raised to 50–60°C, and then an initiator is added, reacting for 130–150 min. Next, 10%–20% isoprene and 0.1%–0.3% structure modifier are added sequentially to the polymerization reactor, and the temperature is raised to 60–70°C, reacting for 50–60 min. Finally, 30%–40% 1,2-dibromoethylene and 0.3%–0.5% structure modifier are added sequentially to the polymerization reactor, and the temperature is raised to 80–90°C, reacting for 100–120 min until no free monomers remain. The resulting solution is then wet-coagulated and dried to obtain a high-molecular-weight damping brominating agent. Preferably, the reactor is purged with argon gas 2–4 times before adding the reactants.

[0013] As another aspect of the present invention, a method for preparing high-damping brominated butyl rubber is disclosed: Based on 100% of the mass of brominated butyl rubber, the internal mixer is first heated to 70–120°C, and then 100% brominated butyl rubber, 10%–15% high-molecular-weight damping brominizing agent, and 0.1%–0.5% stabilizer are sequentially added to the internal mixer and mixed for 50–60 minutes to obtain a masterbatch. After the masterbatch is removed and cooled to room temperature, it is placed on a two-roll mill and 8%–20% vulcanizing agent and 5%–15% vulcanizing agent are added, and mixed for 30–40 minutes to prepare a compound. After the compound is allowed to stand at room temperature for 12–16 hours, it is placed on a flat vulcanizing machine for vulcanization at a temperature of 120–180°C and a pressure of 8–16 MPa for 30–40 minutes to obtain high-damping brominated butyl rubber.

[0014] The α-alkylstyrene described in this invention is one of α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-n-butylstyrene, and α-isobutylstyrene, preferably α-methylstyrene.

[0015] The brominated butyl rubber (BIIR) described in this invention is a polymer obtained by bromine atom substitution of a copolymer of isobutylene and isoprene. The Mooney viscosity ML(1+4) at 100°C is 30-60, and the bromine content is 1wt%-5wt%.

[0016] The initiator described in this invention is a hydrocarbon-based monolithium compound, namely RLi, wherein R is a saturated aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic group, or a complex group containing 1 to 20 carbon atoms. This hydrocarbon-based monolithium compound is selected from one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthenelithium, cyclohexyllithium, and dodecyllithium, preferably n-butyllithium. The amount of organolithium added is determined by the molecular weight of the designed polymer.

[0017] The structure modifier described in this invention is a polar organic compound that produces a solvation effect in the polymerization system, enabling it to adjust the reactivity ratio of styrene and isoprene, thus allowing them to copolymerize randomly. This type of polar organic compound is selected from one of diethylene glycol dimethyl ether (DGE), tetrahydrofuran (THF), diethyl ether, ethyl methyl ether, anisole, diphenyl ether, diethylene glycol dimethyl ether (DME), and triethylamine, preferably tetrahydrofuran (THF).

[0018] The polymerization reactions described in this invention are all carried out in an oxygen-free and anhydrous environment, preferably in an inert gas environment. The polymerization process is completed in a hydrocarbon solvent, which is a hydrocarbon solvent including straight-chain alkanes, aromatics and cycloalkanes. This hydrocarbon solvent is selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene, with cyclohexane being preferred.

[0019] In the preparation process of the high-damping brominated butyl rubber described in this invention, stabilizers, vulcanizing auxiliaries, and vulcanizing agents are required. These auxiliaries are not particularly limited to meet the requirements for stable processing of the rubber material; all can be conventional auxiliaries commonly used in the art. For example, the stabilizer is a stearate, such as zinc stearate, magnesium stearate, or calcium stearate, preferably zinc stearate. The vulcanizing agent is a phenolic resin, such as phenol-formaldehyde resin, alkylphenol-formaldehyde resin, tert-butylphenol-formaldehyde resin, or tert-octylphenol-formaldehyde resin, preferably phenol-formaldehyde resin. The vulcanizing auxiliaries are selected from zinc diacrylate (ZDA), zinc methacrylate, zinc dimethacrylate (ZDMA), trimethylolpropane triacrylate (TMPTA), and zinc oxide (ZnO), preferably ZnO.

[0020] The polymeric damping brominizer prepared in this invention combines p-methyl, bromine, and phenyl atoms on a single macromolecular chain through anionic polymerization. The regular arrangement of the molecular chain results in a significant "synergistic effect" in improving the damping properties of brominated butyl rubber due to the large steric hindrance of the p-phenyl, the inductive force of the bromine atom, and the regular arrangement of the side methyl groups on the main chain.

[0021] Both the polymeric damping brominizer and brominated butyl rubber contain isoprene chain structural units and bromine atoms in their main chains, which can significantly improve the compatibility between the polymeric damping brominizer and brominated butyl rubber. This effectively solves the problem of uneven precipitation and dispersion of the polymeric damping brominizer in the brominated butyl rubber matrix, thus significantly enhancing the "synergistic effect" of the polymeric damping brominizer in improving the damping performance of brominated butyl rubber. This greatly improves the damping performance of brominated butyl rubber and allows for the preparation of materials with the maximum damping factor tanδ. max High-damping brominated butyl rubber with a resistance of ≥2.1.

[0022] The polymeric damping brominizing agent prepared in this invention utilizes the combined effects of "group factors", "structural factors" and "narrow molecular weight distribution" to improve the damping properties of brominated butyl rubber. This not only avoids the problem of decreased mechanical properties and air tightness of brominated butyl rubber, but also improves the tensile strength and air tightness of butyl rubber.

[0023] This invention eliminates the emission of the byproduct HBr during the preparation of polymeric damping brominators, blocks the rearrangement of bromine structures in the polymeric damping brominators, eliminates the need for the HBr alkaline washing and recovery process, and improves the quality stability of the polymeric damping brominators.

[0024] The method for preparing high-damping brominated butyl rubber of this invention is green and environmentally friendly, with a short process flow, low production cost, and is suitable for industrial production. Detailed Implementation

[0025] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0026] (1) Source of raw materials:

[0027] Brominated Butyl Rubber (BIIR2302) - Zhejiang Xinhui New Material Co., Ltd.

[0028] Isoprene Polymer Grade Zhejiang Xinhui New Materials Co., Ltd.

[0029] α-Methylstyrene, Polymer Grade, Jining Yuze Industrial Technology Co., Ltd.

[0030] α-Ethylstyrene, Polymer Grade, Jining Yuze Industrial Technology Co., Ltd.

[0031] α-n-Butylstyrene, Polymer Grade, Jining Yuze Industrial Technology Co., Ltd.

[0032] 1,2-Dibromoethylene, Polymer Grade, Shanghai Yishi Chemical Co., Ltd.

[0033] Sesquiethylaluminum chloride, 98% purity. Bailingwei Technology Co., Ltd.

[0034] Phenol-Formaldehyde Resin Shenzhen Yoshida Chemical Co., Ltd.

[0035] All other reagents are commercially available industrial products.

[0036] (2) Analysis and testing methods:

[0037] Molecular weight and its distribution were determined using a Waters 2414 gel permeation chromatography (GPC) system (USA). A polystyrene standard was used as the calibration curve. The mobile phase was tetrahydrofuran, the column temperature was 40℃, the sample concentration was 1 mg / mL, the injection volume was 50 μL, the elution time was 40 min, and the flow rate was 1 mL / min. -1 .

[0038] Dynamic mechanical analysis (DMA): Measurements were performed in tensile mode on a Netzsch 242C dynamic mechanical analyzer (Germany). Sample dimensions were 10 mm long, 6 mm wide, and 2 mm thick. The temperature range was -90℃ to 90℃, with a heating rate of 3℃ / min. Data were analyzed at a frequency of 10 Hz.

[0039] Bromine content determination: Weigh 10 mg of sample and use a Q600 TG / DTG thermogravimetric analyzer at a heating rate of 10℃ / min in a nitrogen atmosphere with a flow rate of 50 mL / min to perform thermal degradation of the sample. The first stage of thermal degradation involves the debromination of bromine-containing units in the sample to form HBr. The bromine content (X) in the sample is then inferred from the percentage of HBr removed, using the following formula:

[0040]

[0041] In the formula: Y—percentage content of the sample at 220℃; 79.904—relative atomic mass of bromine; 1.008—relative atomic mass of hydrogen.

[0042] Air tightness determination: An automated air tightness tester was used to determine the air permeability number according to ISO 2782:1995. The test gas was N2, the test temperature was 23℃, and the test sample was an 8cm diameter circular sea sheet with a thickness of 1mm.

[0043] Tensile strength: The method specified in standard GB / T528-2009 shall be applied.

[0044] Example 1

[0045] (1) Preparation of polymeric damping bromide: First, in a 15L stainless steel reactor with a jacket, argon gas was purged twice. Then, 3000g of cyclohexane, 1000g of α-methylstyrene, and 7.0g of THF were added to the polymerization reactor in sequence. After heating to 50℃, 40.7mmol of n-butyllithium was added to start the reaction for 130min. Then, 100g of isoprene and 1.0g of THF were added to the polymerization reactor in sequence. After heating to 60℃, the reaction was carried out for 50min. Finally, 300g of 1,2-dibromoethylene and 3.0g of THF were added to the polymerization reactor in sequence. After heating to 80℃, the reaction was carried out for 100min. The colloid was then wet-coagulated and dried to obtain the polymeric damping bromide (Mn is 80100, Mw / Mn is 1.36, and bromine content is 4.02%). The polymeric damping bromide obtained in this embodiment, in the general formula described in Formula I, R is methyl (CH3); n is the number of repeating units: n≥1.

[0046] (2) Preparation of high-damping brominated butyl rubber: First, heat the internal mixer to 70℃, then add 1000g BIIR2302, 100g high-molecular-weight damping brominating agent, and 1.0g zinc stearate sequentially to the internal mixer, and mix for 50min to obtain the masterbatch; after cooling the masterbatch to room temperature, place it on a two-roll mill and add 80g ZnO and 50g phenol-formaldehyde resin, mix for 30min to prepare the compound; after letting the above compound stand at room temperature for 12 hours, place it on a flat vulcanizing machine for vulcanization, heat to 120℃, pressure 8MPa, and vulcanize for 30min to prepare the high-damping brominated butyl rubber. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0047] Example 2

[0048] (1) Preparation of polymeric damping bromide: First, in a 15L stainless steel reactor with a jacket, argon gas was purged twice. Then, 3200g of cyclohexane, 1000g of α-methylstyrene, and 7.2g of THF were added to the polymerization reactor in sequence. After heating to 52℃, 42.5mmol of n-butyllithium was added to start the reaction for 133min. Then, 120g of isoprene and 1.3g of THF were added to the polymerization reactor in sequence. After heating to 61℃, the reaction was carried out for 51min. Finally, 310g of 1,2-dibromoethylene and 3.3g of THF were added to the polymerization reactor in sequence. After heating to 81℃, the reaction was carried out for 110min. The colloid was wet coagulated and dried to obtain the polymeric damping bromide (Mn is 81500, Mw / Mn is 1.41, and bromine content is 4.33%). The polymeric damping bromide obtained in this embodiment, in the general formula described in Formula I, R is methyl (CH3); n is the number of repeating units: n≥1.

[0049] (2) Preparation of high-damping brominated butyl rubber: First, the internal mixer was heated to 80℃, and 1000g of BIIR2302, 110g of high-molecular-weight damping brominating agent, and 2.0g of zinc stearate were added sequentially to the internal mixer. The mixture was mixed for 51min to obtain the masterbatch. After the masterbatch was removed and cooled to room temperature, it was placed on a two-roll mill and 100g of ZnO and 70g of phenol-formaldehyde resin were added. The mixture was mixed for 32min to prepare the compound. After the above compound was allowed to stand at room temperature for 13 hours, it was placed on a flat vulcanizing machine for vulcanization. The temperature was raised to 130℃, the pressure was 9MPa, and the vulcanization was carried out for 31min to prepare the high-damping brominated butyl rubber. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0050] Example 3

[0051] (1) Preparation of polymeric damping bromide: First, in a 15L stainless steel reactor with a jacket, argon gas was purged three times. Then, 3300g of cyclohexane, 1000g of α-methylstyrene, and 7.6g of THF were added to the polymerization reactor in sequence. After heating to 54℃, 44.5mmol of n-butyllithium was added to start the reaction for 135min. Then, 140g of isoprene and 1.8g of THF were added to the polymerization reactor in sequence. After heating to 63℃, the reaction was carried out for 53min. Finally, 330g of 1,2-dibromoethylene and 3.7g of THF were added to the polymerization reactor in sequence. After heating to 83℃, the reaction was carried out for 140min. The colloid was then wet-coagulated and dried to obtain a polymeric damping bromide (Mn is 83700, Mw / Mn is 1.49, and bromine content is 4.47%). The polymeric damping bromide obtained in this embodiment, in the general formula described in Formula I, R is methyl (CH3); n is the number of repeating units: n≥1.

[0052] (2) Preparation of high-damping brominated butyl rubber: First, heat the internal mixer to 90℃, then add 1000g BIIR2302, 120g high-molecular-weight damping brominating agent, and 3.0g zinc stearate sequentially to the internal mixer, and mix for 53min to obtain the masterbatch; after cooling the masterbatch to room temperature, place it on a two-roll mill and add 120g ZnO and 90g phenol-formaldehyde resin, and mix for 34min to prepare the compound; after letting the above compound stand at room temperature for 14 hours, place it on a flat vulcanizing machine for vulcanization, heat to 140℃, pressure 10MPa, and vulcanize for 33min to prepare the high-damping brominated butyl rubber. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0053] Example 4

[0054] (1) Preparation of polymeric damping bromide: First, in a 15L stainless steel reactor with a jacket, argon gas was purged three times. Then, 3500g of cyclohexane, 1000g of α-methylstyrene, and 8.0g of THF were added to the polymerization reactor in sequence. After heating to 55℃, 45.9mmol of n-butyllithium was added to start the reaction for 140min. Then, 160g of isoprene and 2.1g of THF were added to the polymerization reactor in sequence. After heating to 65℃, the reaction was carried out for 55min. Finally, 350g of 1,2-dibromoethylene and 4.0g of THF were added to the polymerization reactor in sequence. After heating to 85℃, the reaction was carried out for 150min. The colloid was then wet-coagulated and dried to obtain a polymeric damping bromide (Mn is 84900, Mw / Mn is 1.56, and bromine content is 4.52%). The polymeric damping bromide obtained in this embodiment, in the general formula described in Formula I, R is methyl (CH3); n is the number of repeating units: n≥1.

[0055] (2) Preparation of high-damping brominated butyl rubber: First, heat the internal mixer to 100℃, then add 1000g BIIR2302, 130g high-molecular-weight damping brominating agent, and 3.5g zinc stearate sequentially to the internal mixer, and mix for 55min to obtain the masterbatch; after cooling the masterbatch to room temperature, place it on a two-roll mill and add 140g ZnO and 100g phenol-formaldehyde resin, mix for 35min to prepare the compound; after letting the above compound stand at room temperature for 15 hours, place it on a flat vulcanizing machine for vulcanization, heat to 150℃, pressure 11MPa, and vulcanize for 35min to prepare the high-damping brominated butyl rubber. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0056] Example 5

[0057] (1) Preparation of polymeric damping bromide: First, in a 15L stainless steel reactor with a jacket, argon gas was purged three times. Then, 3600g of cyclohexane, 1000g of α-methylstyrene, and 8.3g of THF were added to the polymerization reactor in sequence. After heating to 56℃, 48.5mmol of n-butyllithium was added to start the reaction for 143min. Then, 170g of isoprene and 2.5g of THF were added to the polymerization reactor in sequence. After heating to 66℃, the reaction was carried out for 56min. Finally, 360g of 1,2-dibromoethylene and 4.4g of THF were added to the polymerization reactor in sequence. After heating to 86℃, the reaction was carried out for 160min. The colloid was then wet-coagulated and dried to obtain a polymeric damping bromide (Mn is 86100, Mw / Mn is 1.63, and bromine content is 4.68%). The polymeric damping bromide obtained in this embodiment, in the general formula described in Formula I, R is methyl (CH3); n is the number of repeating units: n≥1.

[0058] (2) Preparation of high-damping brominated butyl rubber: First, the internal mixer was heated to 110℃, and 1000g of BIIR2302, 135g of high-molecular-weight damping brominating agent, and 4.0g of zinc stearate were added sequentially to the internal mixer. The mixture was mixed for 56 minutes to obtain the masterbatch. After the masterbatch was removed and cooled to room temperature, it was placed on a two-roll mill and 160g of ZnO and 120g of phenol-formaldehyde resin were added. The mixture was mixed for 36 minutes to prepare the compound. After the above compound was allowed to stand at room temperature for 15 hours, it was placed on a flat vulcanizing machine for vulcanization. The temperature was raised to 160℃ and the pressure was 13MPa. The vulcanization was carried out for 36 minutes to prepare the high-damping brominated butyl rubber. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0059] Example 6

[0060] (1) Preparation of polymeric damping bromide: First, in a 15L stainless steel reactor with a jacket, argon gas was purged three times. Then, 3800g of cyclohexane, 1000g of α-ethylstyrene, and 8.7g of THF were added to the polymerization reactor in sequence. After heating to 58℃, 50.6mmol of n-butyllithium was added to start the reaction for 146min. Then, 180g of isoprene and 2.7g of THF were added to the polymerization reactor in sequence. After heating to 68℃, the reaction was carried out for 58min. Finally, 380g of 1,2-dibromoethylene and 4.6g of THF were added to the polymerization reactor in sequence. After heating to 88℃, the reaction was carried out for 170min. The colloid was then wet-coagulated and dried to obtain the polymeric damping bromide (Mn is 88200, Mw / Mn is 1.78, and bromine content is 4.85%). The polymeric damping bromide obtained in this embodiment, in the general formula described in Formula I, R is ethyl (C2H5); n is the number of repeating units: n≥1.

[0061] (2) Preparation of high-damping brominated butyl rubber: First, the internal mixer was heated to 115℃, and 1000g of BIIR2302, 140g of high-molecular-weight damping brominating agent, and 4.5g of zinc stearate were added sequentially to the internal mixer. The mixture was mixed for 58 minutes to obtain the masterbatch. After the masterbatch was removed and cooled to room temperature, it was placed on a two-roll mill and 180g of ZnO and 140g of phenol-formaldehyde resin were added. The mixture was mixed for 38 minutes to prepare the compound. After the above compound was allowed to stand at room temperature for 16 hours, it was placed on a flat vulcanizing machine for vulcanization. The temperature was raised to 170℃ and the pressure was 15MPa. The vulcanization was carried out for 38 minutes to prepare the high-damping brominated butyl rubber. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0062] Example 7

[0063] (1) Preparation of polymeric damping bromide: First, in a 15L stainless steel reactor with a jacket, argon gas was purged three times. Then, 4000g of cyclohexane, 1000g of α-n-butylstyrene, and 9.0g of THF were added to the polymerization reactor in sequence. After heating to 60℃, 52.3mmol of n-butyllithium was added to start the reaction for 150min. Then, 200g of isoprene and 3.0g of THF were added to the polymerization reactor in sequence. After heating to 70℃, the reaction was carried out for 60min. Finally, 400g of 1,2-dibromoethylene and 5.0g of THF were added to the polymerization reactor in sequence. After heating to 90℃, the reaction was carried out for 200min. The colloid was wet coagulated and dried to obtain the polymeric damping bromide (Mn is 89700, Mw / Mn is 1.95, and bromine content is 4.98%). The polymeric damping bromide obtained in this embodiment, in the general formula described in Formula I, R is butyl (C4H9); n is the number of repeating units: n≥1.

[0064] (2) Preparation of high-damping brominated butyl rubber: First, the internal mixer was heated to 120℃, and 1000g of BIIR2302, 150g of high-molecular-weight damping brominating agent, and 5.0g of zinc stearate were added sequentially to the internal mixer. The mixture was mixed for 60min to obtain the masterbatch. After the masterbatch was removed and cooled to room temperature, it was placed on a two-roll mill and 200g of ZnO and 150g of phenol-formaldehyde resin were added. The mixture was mixed for 40min to prepare the compound. After the above compound was allowed to stand at room temperature for 16 hours, it was placed on a flat vulcanizing machine for vulcanization. The temperature was raised to 180℃ and the pressure was 16MPa. The vulcanization was carried out for 40min to prepare the high-damping brominated butyl rubber. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0065] Comparative Example 1

[0066] (1) Preparation of polymeric damping bromide: Other conditions were the same as in Example 1, except that α-methylstyrene was not added during the preparation of the polymeric damping agent. Instead, styrene was added in an amount of 1000g. Specifically, in a 15L stainless steel reactor with a jacket, argon gas was purged twice. Then, 3000g of cyclohexane, 1000g of styrene, and 7.0g of THF were added to the polymerization reactor in sequence. After heating to 50°C, 40.7mmol of n-butyllithium was added to start the reaction for 130min. Then, 100g of isoprene and 1.0g of THF were added to the polymerization reactor in sequence. After heating to 60°C, the reaction was carried out for 50min. Finally, 300g of 1,2-dibromoethylene and 3.0g of... THF was heated to 80℃ and reacted for 100 min. The resulting solution was then wet-coagulated and dried to obtain a polymeric damping brominated agent-1 (Mn = 79000, Mw / Mn = 1.33, bromine content = 4.01%). In the polymeric damping brominated agent obtained in this comparative example, in the general formula described in Formula I, R represents a hydrogen atom (H); n is the number of repeating units: n ≥ 1.

[0067] (2) Preparation of high-damping brominated butyl rubber: Other conditions are the same as in Example 1, except that: no polymeric damping brominator is added during the preparation of high-damping brominated butyl rubber, but polymeric damping brominator-1 is added, with an addition amount of 100g. That is: first, when the internal mixer is heated to 70°C, 1000g of BIIR2302, 100g of polymeric damping brominator-1 and 1.0g of zinc stearate are added to the internal mixer in sequence, and the mixture is mixed for 50min to obtain the masterbatch; after the masterbatch is taken out and cooled to room temperature, it is placed on a two-roll open mill and 80g of ZnO and 50g of phenol-formaldehyde resin are added, and the mixture is mixed for 30min to prepare the compound; after the above compound is left to stand at room temperature for 12 hours, it is placed on a flat vulcanizing machine for vulcanization, heated to 120°C, pressure of 8MPa, and vulcanized for 30min to prepare high-damping brominated butyl rubber. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0068] Comparative Example 2

[0069] (1) Preparation of polymeric damping brominating agent: Other conditions are the same as in Example 2, except that 1,2-dibromoethylene is not added during the preparation of the polymeric damping brominating agent, but ethylene bromide is added instead, with an addition amount of 310g. That is: First, in a 15L stainless steel reactor with a jacket, argon gas is purged twice, and 3200g cyclohexane, 1000g α-methylstyrene, and 7.2g THF are added to the polymerization reactor in sequence. After heating to 52°C, 42.5mmol n-butyllithium is added to start the reaction for 133min; then 120g isoprene and 1.3g THF are added to the polymerization reactor in sequence, and the temperature is raised to 61°C for 51min; finally, 310g ethylene bromide and 3.3g THF are added to the polymerization reactor in sequence. THF was heated to 81℃ and reacted for 110 min. The resulting solution was then wet-coagulated and dried to obtain a polymeric damping brominated agent-2 (Mn = 62000, Mw / Mn = 1.39, bromine content = 0.33%). In the polymeric damping brominated agent obtained in this comparative example, in the general formula described in Formula I, R is methyl (CH3); n is the number of repeating units: n ≥ 1.

[0070] (2) Preparation of high-damping brominated butyl rubber: Other conditions are the same as in Example 2, except that: no polymeric damping brominator is added during the preparation of high-damping brominated butyl rubber, but polymeric damping brominator-2 is added, and the amount added is 110g. That is: first, when the internal mixer is heated to 80°C, 1000g of BIIR2302, 110g of polymeric damping brominator-2 and 2.0g of zinc stearate are added to the internal mixer in sequence, and the mixture is mixed for 51min to obtain the masterbatch; after the masterbatch is taken out and cooled at room temperature, it is placed on a two-roll open mill and 100g of ZnO and 70g of phenol-formaldehyde resin are added, and the mixture is mixed for 32min to prepare the compound; after the above compound is left to stand at room temperature for 13 hours, it is placed on a flat vulcanizing machine for vulcanization, heated to 130°C, pressure of 9MPa, and vulcanized for 31min to prepare high-damping brominated butyl rubber. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0071] Comparative Example 3

[0072] (1) Preparation of polymeric damping bromide: Other conditions were the same as in Example 3, except that the amount of 1,2-dibromoethylene added during the preparation of the polymeric damping agent was 260g. Specifically: First, in a 15L stainless steel reactor with a jacket, argon gas was purged three times. Then, 3300g of cyclohexane, 1000g of α-methylstyrene, and 7.6g of THF were added to the polymerization reactor in sequence. After heating to 54°C, 44.5mmol of n-butyllithium was added to start the reaction for 135min. Then, 140g of isoprene and 1.8g of THF were added to the polymerization reactor in sequence. After heating to 63°C, the reaction was carried out for 53min. Finally, 260g of 1,2-dibromoethylene and 3.7g of THF were added to the polymerization reactor in sequence. THF was heated to 83℃ and reacted for 140 min. The resulting solution was then wet-coagulated and dried to obtain a polymeric damping brominated agent-3 (Mn = 78100, Mw / Mn = 1.52, bromine content = 4.13%). In the polymeric damping brominated agent obtained in this comparative example, in the general formula described in Formula I, R is methyl (CH3); n is the number of repeating units: n ≥ 1.

[0073] (2) Preparation of high-damping brominated butyl rubber: Other conditions are the same as in Example 3, except that: no polymeric damping brominator is added during the preparation of high-damping brominated butyl rubber, but polymeric damping brominator-3 is added, with an addition amount of 120g. That is: first, when the internal mixer is heated to 90°C, 1000g of BIIR2302, 120g of polymeric damping brominator-3 and 3.0g of zinc stearate are added to the internal mixer in sequence, and the mixture is mixed for 53min to obtain the masterbatch; after the masterbatch is taken out and cooled to room temperature, it is placed on a two-roll open mill and 120g of ZnO and 90g of phenol-formaldehyde resin are added, and the mixture is mixed for 34min to prepare the compound; after the above compound is left to stand at room temperature for 14 hours, it is placed on a flat vulcanizing machine for vulcanization, heated to 140°C, pressure of 10MPa, and vulcanized for 33min to prepare high-damping brominated butyl rubber. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0074] Comparative Example 4

[0075] (1) Preparation of polymeric damping bromide: Other conditions were the same as in Example 4, except that the amount of α-methylstyrene added during the preparation of the polymeric damping agent was 800g. Specifically: First, in a 15L stainless steel reactor with a jacket, argon gas was purged three times. Then, 3500g of cyclohexane, 800g of α-methylstyrene, and 8.0g of THF were added to the polymerization reactor in sequence. After heating to 55°C, 45.9 mmol of n-butyllithium was added to start the reaction for 140 min. Then, 160g of isoprene and 2.1g of THF were added to the polymerization reactor in sequence. After heating to 65°C, the reaction was carried out for 55 min. Finally, 350g of 1,2-dibromoethylene and 4.0g of... THF was heated to 85℃ and reacted for 150 min. The resulting solution was then wet-coagulated and dried to obtain a polymeric damping brominated agent-4 (Mn = 69200, Mw / Mn = 1.53, bromine content = 4.61%). In the polymeric damping brominated agent obtained in this comparative example, in the general formula described in Formula I, R is methyl (CH3); n is the number of repeating units: n ≥ 1.

[0076] (2) Preparation of high-damping brominated butyl rubber: Other conditions are the same as in Example 4, except that: no polymeric damping brominator is added during the preparation of high-damping brominated butyl rubber, but polymeric damping brominator-4 is added, with an addition amount of 130g. That is: first, when the internal mixer is heated to 100°C, 1000g of BIIR2302, 130g of polymeric damping brominator-4 and 3.5g of zinc stearate are added to the internal mixer in sequence, and the mixture is mixed for 55min to obtain the masterbatch; after the masterbatch is taken out and cooled to room temperature, it is placed on a two-roll mill and 140g of ZnO and 100g of phenol-formaldehyde resin are added, and the mixture is mixed for 35min to prepare the compound; after the above compound is left to stand at room temperature for 15 hours, it is placed on a flat vulcanizing machine for vulcanization, heated to 150°C, pressure of 11MPa, and vulcanized for 35min to prepare high-damping brominated butyl rubber. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0077] Comparative Example 5

[0078] (1) Preparation of polymeric damping bromide: Other conditions are the same as in Example 5, except that isoprene is not added in the preparation of polymeric damping bromide. That is: first, in a 15L stainless steel reactor with a jacket, argon gas is purged three times, and 3600g cyclohexane, 1000g α-methylstyrene, and 8.3g THF are added to the polymerization reactor in sequence. After heating to 56°C, 48.5mmol n-butyllithium is added to start the reaction for 143min; then 360g 1,2-dibromoethylene and 4.4g THF are added to the polymerization reactor in sequence, and the temperature is raised to 86°C. After reacting for 160min, the gel is wet coagulated and dried to obtain polymeric damping bromide-5 (Mn is 71000, Mw / Mn is 1.61, and bromine content is 4.73%). The polymeric damping bromide obtained in this comparative example, in the general formula described in Formula I, R is methyl (CH3); n is the number of repeating units: n≥1.

[0079] (2) Preparation of high-damping brominated butyl rubber: Other conditions are the same as in Example 5, except that: no polymeric damping brominator is added during the preparation of high-damping brominated butyl rubber, but polymeric damping brominator-5 is added, and the amount added is 135g. That is: first, when the internal mixer is heated to 110°C, 1000g of BIIR2302, 135g of polymeric damping brominator-5 and 4.0g of zinc stearate are added to the internal mixer in sequence, and the mixture is mixed for 56min to obtain the masterbatch; after the masterbatch is taken out and cooled at room temperature, it is placed on a two-roll open mill and 160g of ZnO and 120g of phenol-formaldehyde resin are added, and the mixture is mixed for 36min to prepare the compound; after the above compound is left to stand at room temperature for 15 hours, it is placed on a flat vulcanizing machine for vulcanization, heated to 160°C, pressure of 13MPa, and vulcanized for 36min to prepare high-damping brominated butyl rubber. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0080] Comparative Example 6

[0081] (1) Preparation of polymeric damping bromide: Other conditions were the same as in Example 6, except that the amount of isoprene added during the preparation of the polymeric damping agent was 70g. That is: first, in a 15L stainless steel reactor with a jacket, argon gas was purged three times, and 3800g of cyclohexane, 1000g of α-ethylstyrene, and 8.7g of THF were added to the polymerization reactor in sequence. After heating to 58°C, 50.6mmol of n-butyllithium was added to start the reaction for 146min; then, 70g of isoprene and 2.7g of THF were added to the polymerization reactor in sequence, and the temperature was raised to 68°C for 58min; finally, 380g of isoprene was added to the polymerization reactor in sequence. 1,2-Dibromoethylene, 4.6 g THF, heated to 88 °C, reacted for 170 min, and the resulting solution was wet-coagulated and dried to obtain a polymeric damping brominated agent-6 (Mn = 79100, Mw / Mn = 1.75, bromine content = 4.89%). In the polymeric damping brominated agent obtained in this comparative example, in the general formula described in Formula I, R is ethyl (C2H5); n is the number of repeating units: n ≥ 1.

[0082] (2) Preparation of high-damping brominated butyl rubber: Other conditions are the same as in Example 6, except that: no polymeric damping brominator is added during the preparation of high-damping brominated butyl rubber, but polymeric damping brominator-6 is added, with an addition amount of 140g. That is: first, when the internal mixer is heated to 115°C, 1000g of BIIR2302, 140g of polymeric damping brominator-6 and 4.5g of zinc stearate are added to the internal mixer in sequence, and the mixture is mixed for 58min to obtain the masterbatch; after the masterbatch is taken out and cooled to room temperature, it is placed on a two-roll open mill and 180g of ZnO and 140g of phenol-formaldehyde resin are added, and the mixture is mixed for 38min to prepare the compound; after the above compound is left to stand at room temperature for 16 hours, it is placed on a flat vulcanizing machine for vulcanization, heated to 170°C, pressure of 15MPa, and vulcanized for 38min to prepare high-damping brominated butyl rubber. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0083] Comparative Example 7

[0084] (1) Preparation of polymeric damping bromide: Same as in Example 7.

[0085] (2) Preparation of high-damping brominated butyl rubber: Other conditions were the same as in Example 7, except that the amount of polymeric damping agent added during the preparation of high-damping brominated butyl rubber was 70g. Specifically, when the internal mixer was heated to 120°C, 1000g of BIIR2302, 70g of polymeric damping brominizing agent, and 5.0g of zinc stearate were added sequentially to the internal mixer and mixed for 60min to obtain the masterbatch. After the masterbatch was removed and cooled to room temperature, it was placed on a two-roll mill and 200g of ZnO and 150g of phenol-formaldehyde resin were added and mixed for 40min to prepare the compound. After the above compound was allowed to stand at room temperature for 16 hours, it was placed on a flat vulcanizing machine for vulcanization. The temperature was raised to 180°C and the pressure was 16MPa. The vulcanization was carried out for 40min to prepare high-damping brominated butyl rubber. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0086] Comparative Example 8

[0087] (1) Preparation of polymeric damping bromide: Other conditions are the same as in Example 7, except that the polymeric damping bromide is prepared by free radical polymerization instead of anionic polymerization. That is, instead of adding n-butyllithium, organic peroxide benzoyl peroxide (BPO) is added in an amount of 52.3 mmol. Specifically: First, in a 15L stainless steel reactor with a jacket, argon gas is purged three times. Then, 4000g of cyclohexane, 1000g of α-n-butylstyrene, and 9.0g of THF are added to the reactor in sequence. After heating to 60°C, 52.3 mmol of BPO is added to start the reaction for 150 min. Then, 200g of isoprene and 3.0g of THF are added to the reactor in sequence. After heating to 70°C, the reaction is carried out for 60 min. Finally, 400g of 1,2-dibromoethylene and 5.0g of... THF was heated to 90°C and reacted for 200 min. The resulting solution was then wet-coagulated and dried to obtain a polymeric damping brominated agent-7 (Mn = 78000, Mw / Mn = 6.15, bromine content = 4.31%). In the polymeric damping brominated agent obtained in this embodiment, R is butyl (C4H9) in the general formula described in Formula I; n is the number of repeating units: n ≥ 1.

[0088] (2) Preparation of high-damping brominated butyl rubber: Other conditions are the same as in Example 7, except that: no polymeric damping brominator is added during the preparation of high-damping brominated butyl rubber, but polymeric damping brominator-7 is added, with an addition amount of 150g. That is: first, when the internal mixer is heated to 120°C, 1000g of BIIR2302, 150g of polymeric damping brominator-7 and 5.0g of zinc stearate are added to the internal mixer in sequence, and the mixture is mixed for 60min to obtain the masterbatch; after the masterbatch is taken out and cooled to room temperature, it is placed on a two-roll open mill and 200g of ZnO and 150g of phenol-formaldehyde resin are added, and the mixture is mixed for 40min to prepare the compound; after the above compound is left to stand at room temperature for 16 hours, it is placed on a flat vulcanizing machine for vulcanization, heated to 180°C, pressure of 16MPa, and vulcanized for 40min to prepare high-damping brominated butyl rubber. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0089] Table 1 Properties of high-damping brominated butyl rubber

[0090]

Claims

1. A polymeric damping brominating agent, which is a linear block copolymer composed of α-alkylstyrene, isoprene, and 1,2-dibromoethylene, characterized in that, Its general structural formula is shown in Formula I: ； Where: R is a C1 to C4 alkyl group; n is the number of repeating units: n≥1; The polymeric damping brominator has a number average molecular weight of 80,000 to 90,000, a molecular weight distribution of 1.36 to 1.95, and a bromine content of 4% to 5% by mass. The preparation method of the polymeric damping bromide includes: Based on 100% by mass of α-alkylstyrene, 300%–400% solvent, 100% α-alkylstyrene, and 0.7%–0.9% structure modifier are sequentially added to the polymerization reactor. The temperature is raised to 50–60°C, and then an initiator is added, reacting for 130–150 min. The initiator is R'Li, where R' is a saturated aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic group, or a complex group containing 1–20 carbon atoms. Then, 10%–20% isoprene and 0.1%–0.3% structure modifier are sequentially added to the polymerization reactor, and the temperature is raised to 60–70°C, reacting for 50–60 min. Finally, 30%–40% 1,2-dibromoethylene and 0.3%–0.5% structure modifier are sequentially added to the polymerization reactor, and the temperature is raised to 80–90°C, reacting for 100–150 min. After 120 minutes until no free monomers remain, the adhesive solution is wet-coagulated and dried to obtain a high-molecular-weight damping bromide.

2. The polymeric damping bromide agent according to claim 1, characterized in that, The α-alkylstyrene is one of α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-n-butylstyrene, and α-isobutylstyrene.

3. The polymeric damping bromide agent according to claim 2, characterized in that, The α-alkylstyrene mentioned is α-methylstyrene.

4. The polymeric damping bromide agent according to claim 1, characterized in that, The initiator is selected from one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthalenelithium, cyclohexyllithium, and dodecyllithium.

5. The polymeric damping bromide agent according to claim 4, characterized in that, The initiator is n-butyllithium.

6. The polymeric damping bromide agent according to claim 1, characterized in that, The structure modifier is selected from one of diethylene glycol dimethyl ether, tetrahydrofuran, diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether, and triethylamine.

7. The polymeric damping bromide agent according to claim 6, characterized in that, The structure modifier is tetrahydrofuran.

8. The polymeric damping bromide agent according to claim 1, characterized in that, The solvent is selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.

9. The polymeric damping bromide agent according to claim 8, characterized in that, The solvent is cyclohexane.

10. A method for preparing high-damping brominated butyl rubber, characterized in that, include: Based on 100% of the mass of brominated butyl rubber, when the internal mixer is heated to 70-120°C, 100% brominated butyl rubber, 10%-15% of the high molecular weight damping brominizing agent as described in any one of claims 1-9, and 0.1%-0.5% stabilizer are added sequentially to the internal mixer and mixed for 50-60 minutes to obtain a masterbatch. After the masterbatch is removed and cooled to room temperature, it is placed on a two-roll open mill and 8%-20% vulcanizing aid and 5%-15% vulcanizing agent are added and mixed for 30-40 minutes to prepare a compound. After the above compound is allowed to stand at room temperature for 12-16 hours, it is placed on a flat vulcanizing machine for vulcanization at a temperature of 120-180°C and a pressure of 8-16 MPa for 30-40 minutes to obtain high damping brominated butyl rubber.

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