Preparation of functionalized damping brominated grafting agent and damping brominated branched butyl rubber

Abstract

The application discloses a functionalized damping brominated grafting agent and a preparation method thereof, and discloses a linear block copolymer composed of tri-bromophenyl allyl ether and 4-vinyl benzyl ether. The application further discloses a method for preparing damping brominated branched butyl rubber. The method for preparing the damping brominated branched butyl rubber has the characteristics of green environmental protection, short technological process, easy availability of raw materials in the market, and suitability for industrial production.

Description

Technical Field

[0001] This invention relates to a functionalized damping brominated grafting agent and the preparation of damping brominated branched butyl rubber. Background Technology

[0002] With the rapid development of modern science and technology, mechanical equipment in many fields, such as high-speed rail, aerospace, naval vessels, mechanical engineering, automobiles, and electronics, 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 pose an increasingly prominent threat to people's lives and property. Vibration reduction and noise reduction have become one of the most pressing problems to be solved in today's society. Therefore, developing high-performance, high-efficiency damping materials and improving their application in damping and vibration reduction is crucial for improving the operating environment of machinery and for human health and safety.

[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 good adhesion, fast 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. Currently, in practical applications, damping functionality is often required within the temperature range of -50℃ to +50℃. However, the effective damping functional region (damping factor tanδ > 0.3) of brominated butyl rubber is currently concentrated mainly in the low-temperature range, with damping values ​​being relatively low above 15℃. This fails to adequately meet the requirements for wide-temperature-range damping materials. Therefore, expanding the effective damping functional region of butyl rubber above room temperature is one of the current research hotspots in rubber damping materials.

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

[0005] Literature documents CN112574333A, CN102775659B, CN106749816A, CN113969031A, CN103113682A, and CN103113682A demonstrate 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, leading to a decrease in the mechanical properties of the modified materials, complex processes, difficulties in practical operation, large addition amounts, high costs, difficulty in eliminating organic solvents, and environmental pollution. Summary of the Invention

[0006] One objective of this invention is to provide a method for preparing a wide-temperature-range damping brominated butyl rubber with an effective damping temperature range (tanδ≥0.3) exceeding -64℃ to 70℃. This invention first synthesizes a functionalized polymeric damping brominated grafting agent by cationic polymerization of 4-vinylphenylalkyl ether and tribromophenylallyl ether under a protic acid-based catalytic system. Secondly, the functionalized polymeric damping brominated grafting agent is then cationically polymerized with isobutylene and isoprene to prepare the wide-temperature-range damping brominated butyl rubber. This invention uses a cationic reaction to prepare the wide-temperature-range damping brominated butyl rubber, rather than the free radical substitution reaction used in existing technologies, thus endowing the brominated butyl rubber with a wide effective damping temperature range and high efficiency and stability in damping performance. This method not only solves the problem of decreased damping performance due to a wider effective damping temperature range of brominated butyl rubber, but also avoids the problem of decreased tensile strength and airtightness caused by a wider molecular weight distribution.

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

[0008] As one aspect of the present invention, a functionalized polymeric damping brominated grafting agent is disclosed, which is a linear block copolymer composed of tribromophenylallyl ether and 4-vinylphenylalkyl ether, and its general structural formula is shown in Formula I:

[0009]

[0010] Wherein: I represents a small molecule isoprene segment; R represents a C1-C4 alkyl group; n is the number of repeating units: n≥1. The functionalized polymeric damping brominated grafting agent has a number-average molecular weight (Mn) of 40,000-50,000, a molecular weight distribution (Mw / Mn) of 1.68-2.26, and a bromine content of 5.51%-6.73% by mass.

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

[0012] Based on 100% by mass of tribromophenyl allyl ether, 200%–300% mixed solvent (diluent / solvent V:V ratio of 60–40 / 40–60), 100% tribromophenyl allyl ether, and 30%–40% 4-vinylphenylalkyl ether were added sequentially to the polymerization reactor and stirred until the polymerization system temperature dropped to -50 to -60°C. Then, 5%–10% diluent and 0.01%–0.1% co-initiator were mixed and aged at -60 to -70°C for 30–40 min, and then added together to the polymerization reactor and stirred for 1.0–2.0 h. Finally, 3.0%–5.0% isoprene was added to the polymerization reactor for end-capping, and the reaction was carried out for 20–30 min. Subsequently, 2%–4% terminator was added, and the product was discharged, coagulated, washed, and dried to obtain the functionalized polymeric damping brominated grafting agent. Preferably, nitrogen gas is purged 3 to 5 times before adding reactants to the reactor.

[0013] As another aspect of the present invention, a method for preparing a wide-temperature-range damping brominated branched butyl rubber is provided, comprising:

[0014] Add 100%–200% mixed solvent (diluent / solvent V:V ratio of 70–30 / 30–70) and 5%–9% functionalized polymeric damping brominated grafting agent to the polymerization reactor, based on 100% of the mass of the reactant isobutylene. Stir and dissolve for 50–60 minutes until the grafting agent is completely dissolved. Then, when the temperature is lowered to -80 to -70°C, add 100%–200% diluent, 100% isobutylene, and 4%–6% isoprene in sequence. Stir and mix until the polymerization system temperature drops to -90 to -80°C. Then, mix and age 10%–20% diluent and 0.1%–0.3% co-initiator at -100 to -90°C for 40–50 minutes, and then add them together to the polymerization system. Stir and react for 2.0–3.0 hours. Finally, add 3%–5% terminator, discharge and coagulate, wash, and dry to obtain wide-temperature-range damping brominated branched butyl rubber. Preferably, nitrogen gas is purged 3 to 5 times before adding reactants to the reactor.

[0015] The 4-vinylphenylalkyl ether described in this invention is one of 4-vinylanisole, 4-vinylphenethyl ether, 4-vinylphenylpropyl ether, 4-vinylphenylbutyl ether, and 4-vinylphenylisobutyl ether, preferably 4-vinylanisole.

[0016] The diluent described in this invention is a haloalkane, wherein the halogen atom in the haloalkane can be chlorine, bromine, or fluorine; and the number of carbon atoms in the haloalkane is C1-C4. This haloalkane is selected from one of chloromethane, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, fluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane, preferably chloromethane.

[0017] The co-initiator of this invention is composed of alkyl aluminum halides and protic acids in different proportions. The alkyl aluminum halide is selected from at least one of diethylaluminum chloride, diisobutylaluminum chloride, dichloromethylaluminum, sesquiethylaluminum chloride, sesquiisobutylaluminum chloride, dichloro-n-propylaluminum, dichloroisopropylaluminum, dimethylaluminum chloride, and ethylaluminum chloride, preferably sesquiethylaluminum chloride. The protic acid is selected from one of HCl, HF, HBr, H2SO4, H2CO3, H3PO4, and HNO3, preferably HCl. The total amount of co-initiator added is 0.1% to 0.3%, and the molar ratio of protic acid to alkyl aluminum halide is 1:10 to 1:100.

[0018] The terminating agent described in this invention may be selected from one or more of methanol, ethanol, and butanol.

[0019] The polymerization reactions described in this invention are all carried out in an oxygen-free and anhydrous environment, preferably in an inert gas environment. Both the polymerization and dissolution processes are completed in a hydrocarbon solvent. The solvent described in this invention 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.

[0020] The composite functionalized polymeric damping brominated grafting agent prepared in this invention is produced by cationic polymerization, which utilizes two functional reactive monomers to form an interpenetrating polymer network (IPN). The phenyl, bromine, and ether groups produce a significant "synergistic effect" in broadening the effective damping temperature range of brominated branched butyl rubber, greatly expanding the effective damping temperature range of brominated branched butyl rubber. It can prepare wide-temperature-range damping brominated branched butyl rubber with an effective damping temperature range (tanδ≥0.3) exceeding -64℃~70℃.

[0021] The composite functionalized polymeric damping brominated grafting agent prepared in this invention is produced by cationic polymerization, resulting in a narrow molecular weight distribution. This leads to the superposition of "group effect" and "structural effect," which not only avoids the decrease in damping performance of brominated branched butyl rubber due to the widening of the effective damping temperature range, but also avoids the problem of decreased mechanical properties and air tightness of butyl rubber due to the widening of the molecular weight distribution caused by branching. Furthermore, it improves the tensile strength and air tightness of butyl rubber.

[0022] The wide-temperature-range damping brominated branched butyl rubber prepared by this invention is generated by addition polymerization of a composite functionalized polymeric damping brominated grafting agent, rather than by ionic substitution. It produces no volatile organic compounds (VOCs) or byproduct HBr, thus blocking the conditions for bromine structural isomerization. This improves the effective damping temperature range and the stability of the damping performance of the brominated branched butyl rubber, and broadens the application range of the wide-temperature-range damping brominated branched butyl rubber.

[0023] The present invention provides a method for preparing wide-temperature-range damping brominated branched butyl rubber that is green and environmentally friendly, with a short process flow, readily available raw materials, and suitable for industrial production. Detailed Implementation

[0024] 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.

[0025] (1) Source of raw materials:

[0026]

[0027] All other reagents are commercially available industrial products.

[0028] (2) Analysis and testing methods:

[0029] 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 .

[0030] 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:

[0031]

[0032] 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.

[0033] Molecular weight determination: Molecular weight was determined using a Waters 2414 gel permeation chromatography (GPC) system (Waters, Inc., 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.

[0034] Air tightness determination: An automated air tightness tester was used to determine the air permeability number according to ISO 2782:1995.

[0035] The test gas was N2, the test temperature was 23℃, and the test sample was a circular sea sheet with a diameter of 8cm and a thickness of 1mm.

[0036] 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.

[0037] Tensile strength: The method specified in standard GB / T528-2009 shall be applied.

[0038] Example 1

[0039] (1) Preparation of functionalized polymeric damping brominated grafting agent: First, in a 10L stainless steel reactor with a jacket, argon gas was purged three times. Then, 800g of chloromethane, 1200g of cyclohexane, 1000g of tribromophenyl allyl ether, and 300g of 4-vinyl anisole were added to the polymerization reactor and stirred until the temperature of the polymerization system dropped to -50℃. Then, 50g of chloromethane, 0.132g of sesquiethyl aluminum chloride, and 0.014g of HCl were mixed and aged at -60℃ for 30min. Then, they were added to the polymerization system and stirred for 1.0hr. Then, 30g of isoprene was added to the polymerization reactor for end-capping and reacted for 20min. Finally, 20g of methanol was added, the material was discharged, coagulated, washed, and dried to obtain the functionalized polymeric damping brominated grafting agent (Mn is 41000, Mw / Mn is 1.68, and bromine content is 5.51%). The functionalized polymeric damping brominated grafting agent obtained in this embodiment, in the general formula described in Formula I, I is a small molecule isoprene segment; R is methyl (CH3); n is the number of repeating units: n≥1.

[0040] (2) Preparation of wide-temperature-range damping brominated branched butyl rubber: First, in a jacketed 4L stainless steel reactor, nitrogen was purged three times. Then, 350g of dichloromethane, 150g of cyclohexane, and 25g of functionalized polymeric damping brominated grafting agent were added to the polymerization reactor and stirred for 50 minutes until completely dissolved. Next, the temperature was lowered to -70℃, and then 500g of monochloromethane, 500g of isobutylene, and 20g of isoprene were added sequentially. The mixture was stirred until the polymerization system temperature dropped to -80℃. Then, 50g of monochloromethane, 0.512g of sesquiethylaluminum chloride, and 0.011g of HCl were mixed and aged at -90℃ for 40 minutes, and then added to the polymerization system. The mixture was stirred and reacted for 2.0 hours. Finally, 15g of methanol was added, and the mixture was discharged, coagulated, washed, and dried to obtain the wide-temperature-range damping brominated branched butyl rubber product. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0041] Example 2

[0042] (1) Preparation of functionalized polymeric damping brominated grafting agent: First, in a 10L stainless steel reactor with a jacket, argon gas was purged three times. Then, 1000g of chloromethane, 1000g of cyclohexane, 1000g of tribromophenyl allyl ether, and 310g of 4-vinyl anisole were added to the polymerization reactor and stirred until the temperature of the polymerization system dropped to -52℃. Then, 60g of chloromethane, 0.315g of sesquiethyl aluminum chloride, and 0.019g of HCl were mixed and aged at -62℃ for 32min. Then, they were added to the polymerization system and stirred for 1.1hr. Then, 35g of isoprene was added to the polymerization reactor for end-capping and reacted for 22min. Finally, 25g of methanol was added, the material was discharged, coagulated, washed, and dried to obtain the functionalized polymeric damping brominated grafting agent (Mn is 43100, Mw / Mn is 1.79, and bromine content is 5.83%). The functionalized polymeric damping brominated grafting agent obtained in this embodiment, in the general formula described in Formula I, I is a small molecule isoprene segment; R is methyl (CH3); n is the number of repeating units: n≥1.

[0043] (2) Preparation of wide-temperature-range damping brominated branched butyl rubber: First, in a jacketed 4L stainless steel reactor, nitrogen was purged three times. Then, 300g of dichloromethane, 200g of cyclohexane, and 30g of functionalized polymeric damping brominated grafting agent were added to the polymerization reactor and stirred for 52 minutes until completely dissolved. Next, the temperature was lowered to -72℃, and then 600g of monochloromethane, 500g of isobutylene, and 21g of isoprene were added sequentially. The mixture was stirred until the polymerization system temperature dropped to -82℃. Then, 60g of monochloromethane, 0.835g of sesquiethylaluminum chloride, and 0.026g of HCl were mixed and aged at -92℃ for 41 minutes, and then added to the polymerization system. The mixture was stirred and reacted for 2.2 hours. Finally, 17g of methanol was added, and the mixture was discharged, coagulated, washed, and dried to obtain the wide-temperature-range damping brominated branched butyl rubber product. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0044] Example 3

[0045] (1) Preparation of functionalized polymeric damping brominated grafting agent: First, in a 10L stainless steel reactor with a jacket, argon gas was purged four times. Then, 800g of chloromethane, 1200g of cyclohexane, 1000g of tribromophenyl allyl ether, and 330g of 4-vinyl anisole were added to the polymerization reactor and stirred until the temperature of the polymerization system dropped to -54℃. Then, 70g of chloromethane, 0.467g of sesquiethyl aluminum chloride, and 0.021g of HCl were mixed and aged at -64℃ for 34min. After that, they were added to the polymerization system and stirred for 1.3hr. Then, 40g of isoprene was added to the polymerization reactor for end-capping and reacted for 24min. Finally, 30g of methanol was added, the material was discharged, coagulated, washed, and dried to obtain the functionalized polymeric damping brominated grafting agent (Mn is 45300, Mw / Mn is 1.91, and bromine content is 6.13%). The functionalized polymeric damping brominated grafting agent obtained in this embodiment, in the general formula described in Formula I, I is a small molecule isoprene segment; R is methyl (CH3); n is the number of repeating units: n≥1.

[0046] (2) Preparation of wide-temperature-range damping brominated branched butyl rubber: First, in a jacketed 4L stainless steel reactor, nitrogen was purged four times. Then, 200g of dichloromethane, 300g of cyclohexane, and 35g of functionalized polymeric damping brominated grafting agent were added to the polymerization reactor and stirred for 54 minutes until completely dissolved. Next, the temperature was lowered to -74℃, and then 700g of monochloromethane, 500g of isobutylene, and 23g of isoprene were added sequentially. The mixture was stirred until the polymerization system temperature dropped to -84℃. Then, 70g of monochloromethane, 1.132g of sesquiethylaluminum chloride, and 0.035g of HCl were mixed and aged at -94℃ for 43 minutes, and then added to the polymerization system. The mixture was stirred and reacted for 2.4 hours. Finally, 19g of methanol was added, and the mixture was discharged, coagulated, washed, and dried to obtain the wide-temperature-range damping brominated branched butyl rubber product. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0047] Example 4

[0048] (1) Preparation of functionalized polymeric damping brominated grafting agent: First, in a 10L stainless steel reactor with a jacket, argon gas was purged four times. Then, 1200g of chloromethane, 1800g of cyclohexane, 1000g of tribromophenyl allyl ether, and 350g of 4-vinyl anisole were added to the polymerization reactor and stirred until the temperature of the polymerization system dropped to -55℃. Then, 80g of chloromethane, 0.536g of sesquiethyl aluminum chloride, and 0.035g of HCl were mixed and aged at -66℃ for 36min. After that, they were added to the polymerization system and stirred for 1.5hr. Then, 43g of isoprene was added to the polymerization reactor for end-capping and reacted for 26min. Finally, 34g of methanol was added, the material was discharged, coagulated, washed, and dried to obtain the functionalized polymeric damping brominated grafting agent (Mn is 46700, Mw / Mn is 2.05, and bromine content is 6.37%). The functionalized polymeric damping brominated grafting agent obtained in this embodiment, in the general formula described in Formula I, I is a small molecule isoprene segment; R is methyl (CH3); n is the number of repeating units: n≥1.

[0049] (2) Preparation of wide-temperature-range damping brominated branched butyl rubber: First, in a 4L stainless steel reactor with a jacket, nitrogen gas was purged four times. Then, 700g of dichloromethane, 300g of cyclohexane, and 40g of functionalized polymeric damping brominated grafting agent were added to the polymerization reactor and stirred for 56 minutes until completely dissolved. Then, the temperature was lowered to -76℃, and 800g of monochloromethane, 500g of isobutylene, and 26g of isoprene were added sequentially. The mixture was stirred until the polymerization system temperature dropped to -86℃. Then, 80g of monochloromethane, 1.252g of sesquiethylaluminum chloride, and 0.041g of HCl were mixed and aged at -96℃ for 46 minutes, and then added to the polymerization system. The mixture was stirred and reacted for 2.6 hours. Finally, 21g of methanol was added, and the mixture was discharged, coagulated, washed, and dried to obtain the wide-temperature-range damping brominated branched butyl rubber product. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0050] Example 5

[0051] (1) Preparation of functionalized polymeric damping brominated grafting agent: First, in a 10L stainless steel reactor with a jacket, argon gas was purged 5 times. Then, 1400g of chloromethane, 1600g of cyclohexane, 1000g of tribromophenyl allyl ether, and 370g of 4-vinylphenylethyl ether were added to the polymerization reactor and stirred until the temperature of the polymerization system dropped to -57℃. Then, 90g of chloromethane, 0.671g of sesquiethyl aluminum chloride, and 0.042g of HCl were mixed and aged at -68℃ for 38min. After that, they were added to the polymerization system and stirred for 1.8hr. Then, 47g of isoprene was added to the polymerization reactor for end-capping and reacted for 28min. Finally, 37g of methanol was added, the material was discharged, coagulated, washed, and dried to obtain the functionalized polymeric damping brominated grafting agent (Mn is 48200, Mw / Mn is 2.15, and bromine content is 6.56%). The functionalized polymeric damping brominated grafting agent obtained in this embodiment, in the general formula I, I is a small molecule isoprene segment; R is ethyl (C2H5); n is the number of repeating units: n≥1.

[0052] (2) Preparation of wide-temperature-range damping brominated branched butyl rubber: First, in a jacketed 4L stainless steel reactor, nitrogen was purged five times. Then, 600g of dichloromethane, 400g of cyclohexane, and 43g of functionalized polymeric damping brominated grafting agent were added to the polymerization reactor and stirred for 58 minutes until completely dissolved. Next, the temperature was lowered to -78℃, and then 900g of monochloromethane, 500g of isobutylene, and 28g of isoprene were added sequentially. The mixture was stirred until the polymerization system temperature dropped to -88℃. Then, 90g of monochloromethane, 1.367g of sesquiethylaluminum chloride, and 0.065g of HCl were mixed and aged at -98℃ for 48 minutes, and then added to the polymerization system. The mixture was stirred and reacted for 2.8 hours. Finally, 23g of methanol was added, and the mixture was discharged, coagulated, washed, and dried to obtain the wide-temperature-range damping brominated branched butyl rubber product. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0053] Example 6

[0054] (1) Preparation of functionalized polymeric damping brominated grafting agent: First, in a 10L stainless steel reactor with a jacket, argon gas was purged 5 times. Then, 1200g of chloromethane, 1800g of cyclohexane, 1000g of tribromophenyl allyl ether, and 400g of 4-vinylphenyl butyl ether were added to the polymerization reactor and stirred until the temperature of the polymerization system dropped to -60℃. Then, 100g of chloromethane, 0.965g of sesquiethyl aluminum chloride, and 0.051g of HCl were mixed and aged at -70℃ for 40min. Then, they were added to the polymerization system and stirred for 2.0hr. Then, 50g of isoprene was added to the polymerization reactor for end-capping and reacted for 30min. Finally, 40g of methanol was added, the material was discharged, coagulated, washed, and dried to obtain the functionalized polymeric damping brominated grafting agent (Mn is 49700, Mw / Mn is 2.26, and bromine content is 6.73%). The functionalized polymeric damping brominated grafting agent obtained in this embodiment, in the general formula described in Formula I, I is a small molecule isoprene segment; R is butyl (C4H9); n is the number of repeating units: n≥1.

[0055] (2) Preparation of wide-temperature-range damping brominated branched butyl rubber: First, in a jacketed 4L stainless steel reactor, nitrogen was purged five times. Then, 300g of dichloromethane, 700g of cyclohexane, and 45g of functionalized polymeric damping brominated grafting agent were added to the polymerization reactor and stirred for 60 minutes until completely dissolved. Next, the temperature was lowered to -80℃, and then 1000g of monochloromethane, 500g of isobutylene, and 30g of isoprene were added sequentially. The mixture was stirred until the polymerization system temperature dropped to -90℃. Then, 100g of monochloromethane, 1.498g of sesquiethylaluminum chloride, and 0.089g of HCl were mixed and aged at -100℃ for 50 minutes, and then added to the polymerization system. The mixture was stirred and reacted for 3.0 hours. Finally, 25g of methanol was added, and the mixture was discharged, coagulated, washed, and dried to obtain the wide-temperature-range damping brominated branched butyl rubber product. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0056] Comparative Example 1

[0057] (1) Preparation of functionalized polymeric damping brominated grafting agent: Other conditions are the same as in Example 1, except that: tribromophenyl allyl ether is not added during the preparation of the functionalized polymeric damping brominated grafting agent, but cis-2-methyl-1,4-dibromo-2-butene is added, with an addition amount of 1000g, that is: first, in a 10L stainless steel reactor with a jacket, argon gas is purged three times, and 800g of chloromethane, 1200g of cyclohexane, 1000g of cis-2-methyl-1,4-dibromo-2-butene, and 300g of 4-vinylphenylalkyl ether are added to the polymerization reactor. The mixture is stirred until the temperature of the polymerization system drops to -50℃, and then 50g of chloromethane, 0.132g of sesquiethylaluminum chloride, and HCl are added. 0.014g of the mixture was aged at -60℃ for 30 min and then added to the polymerization system and stirred for 1.0 hr. Then, 30g of isoprene was added to the polymerization reactor for end-capping, and the reaction was allowed to proceed for 20 min. Finally, 20g of methanol was added, and the mixture was discharged, coagulated, washed, and dried to obtain functionalized polymeric damping brominated grafting agent-1 (Mn = 39000, Mw / Mn = 1.78, bromine content = 5.76%). In the functionalized polymeric damping brominated grafting agent obtained in this comparative example, in Formula I, I represents a small molecule isoprene segment; R represents methyl (CH3); and n is the number of repeating units: n ≥ 1.

[0058] (2) Preparation of wide-temperature-range damping brominated branched butyl rubber: Other conditions are the same as in Example 1, except that: no functionalized polymer damping brominated grafting agent is added during the preparation of wide-temperature-range damping brominated branched butyl rubber, but functionalized polymer damping brominated grafting agent-1 is added, with an addition amount of 25g, that is: first, in a 4L stainless steel reactor with a jacket, nitrogen gas is purged three times, and 350g of dichloromethane, 150g of cyclohexane, and 25g of functionalized polymer damping brominated grafting agent-1 are added to the polymerization reactor, and stirred and dissolved for 50min until completely dissolved; then, when the temperature is lowered to -70℃, 500g of monochloromethane, 500g of isobutylene, and 20g of isoprene are added in sequence, and stirred and mixed until the temperature of the polymerization system drops to -80℃, and then 50g of monochloromethane, 0.512g of sesquiethylaluminum chloride, and HCl are added. 0.011g of the mixture was aged at -90℃ for 40 minutes and then added to the polymerization system. After stirring for 2.0 hours, 15g of methanol was added, and the mixture was discharged, coagulated, washed, and dried to obtain a wide-temperature-range damping brominated branched butyl rubber product. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0059] Comparative Example 2

[0060] (1) Preparation of functionalized polymeric damping brominated grafting agent: Other conditions are the same as in Example 2, except that 4-vinyl anisole is not added during the preparation of the functionalized polymeric damping brominated grafting agent, but vinyl methyl ether is added, with an addition amount of 310g. That is: first, in a 10L stainless steel reactor with a jacket, argon gas is purged three times, and then 1000g of chloromethane, 1000g of cyclohexane, 1000g of tribromophenyl allyl ether, and 310g of vinyl ether are added to the polymerization reactor. The mixture is stirred until the temperature of the polymerization system drops. At -52℃, 60g of chloromethane, 0.315g of sesquiethylaluminum chloride, and 0.019g of HCl were mixed and aged at -62℃ for 32 min. Then, these were added to the polymerization system and stirred for 1.1 hr. Next, 35g of isoprene was added to the polymerization reactor for end-capping, and the reaction was allowed to proceed for 22 min. Finally, 25g of methanol was added, and the mixture was discharged, coagulated, washed, and dried to obtain functionalized polymeric damping brominated grafting agent-2 (Mn = 39500, Mw / Mn = 1.81, bromine content = 5.91%). In the functionalized polymeric damping brominated grafting agent obtained in this comparative example, in Formula I, I represents a small molecule isoprene segment; R represents methyl (CH3); and n is the number of repeating units: n ≥ 1.

[0061] (2) Preparation of wide-temperature-range damping brominated branched butyl rubber: Other conditions are the same as in Example 2, except that: no functionalized polymer damping brominated grafting agent is added during the preparation of wide-temperature-range damping brominated branched butyl rubber, but functionalized polymer damping brominated grafting agent-2 is added, with an addition amount of 30g. That is: first, in a 4L stainless steel reactor with a jacket, nitrogen gas is purged three times, and 300g of dichloromethane, 200g of cyclohexane, and 30g of functionalized polymer damping brominated grafting agent-2 are added to the polymerization reactor, and stirred and dissolved for 52min until completely dissolved; then, when the temperature is lowered to -72℃, 600g of monochloromethane, 500g of isobutylene, and 21g of isoprene are added in sequence, and stirred and mixed until the temperature of the polymerization system drops to -82℃, and then 60g of monochloromethane, 0.835g of sesquiethylaluminum chloride, and HCl are added. 0.026g of the mixture was aged at -92℃ for 41 min, then added to the polymerization system and stirred for 2.2 hr. Finally, 17g of methanol was added, and the mixture was discharged, coagulated, washed, and dried to obtain a wide-temperature-range damping brominated branched butyl rubber product. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0062] Comparative Example 3

[0063] (1) Preparation of functionalized polymeric damping brominated grafting agent: Other conditions are the same as in Example 3, except that 4-vinylanisole is not added during the preparation of the functionalized polymeric damping brominated grafting agent. That is: First, in a 10L stainless steel reactor with a jacket, argon gas is purged four times. Then, 800g of chloromethane, 1200g of cyclohexane, and 1000g of tribromophenyl allyl ether are added to the polymerization reactor. The mixture is stirred until the temperature of the polymerization system drops to -54℃. Then, 70g of chloromethane, 0.467g of sesquiethylaluminum chloride, and HCl are added. 0.021g of the mixture was aged at -64℃ for 34 min and then added to the polymerization system and stirred for 1.3 hr. Then, 40g of isoprene was added to the polymerization reactor for end-capping, and the reaction was allowed to proceed for 24 min. Finally, 30g of methanol was added, and the mixture was discharged, coagulated, washed, and dried to obtain functionalized polymeric damping brominated grafting agent-3 (Mn = 35100, Mw / Mn = 1.85, bromine content = 6.53%). In the functionalized polymeric damping brominated grafting agent obtained in this comparative example, in Formula I, I represents a small molecule isoprene segment; n is the number of repeating units: n ≥ 1.

[0064] (2) Preparation of wide-temperature-range damping brominated branched butyl rubber: Other conditions are the same as in Example 3, except that no functionalized polymeric damping brominated grafting agent is added during the preparation of wide-temperature-range damping brominated branched butyl rubber. Instead, functionalized polymeric damping brominated grafting agent-3 is added, with an addition amount of 35g. That is: First, in a 4L stainless steel reactor with a jacket, nitrogen gas is purged four times. Then, 200g of dichloromethane, 300g of cyclohexane, and 35g of functionalized polymeric damping brominated grafting agent-3 are added to the polymerization reactor and stirred for 54min until completely dissolved. Then, when the temperature is lowered to -74℃, 700g of monochloromethane, 500g of isobutylene, and 23g of isoprene are added sequentially and stirred until the polymerization system temperature drops to -84℃. Then, 70g of monochloromethane, 1.132g of sesquiethylaluminum chloride, and HCl are added. 0.035g of the mixture was aged at -94℃ for 43 minutes and then added to the polymerization system. After stirring and reacting for 2.4 hours, 19g of methanol was added. The mixture was then discharged, coagulated, washed, and dried to obtain a wide-temperature-range damping brominated branched butyl rubber product. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0065] Comparative Example 4

[0066] (1) Preparation of functionalized polymeric damping brominated grafting agent: Other conditions are the same as in Example 4, except that tribromophenyl allyl ether is not added during the preparation of the functionalized polymeric damping brominated grafting agent. That is: first, in a 10L stainless steel reactor with a jacket, argon gas is purged four times, and 1200g of chloromethane, 1800g of cyclohexane, and 350g of 4-vinyl anisole are added to the polymerization reactor. The mixture is stirred until the temperature of the polymerization system drops to -55℃. Then, 80g of chloromethane, 0.536g of sesquiethyl aluminum chloride, and HCl are added. 0.035g of the mixture was aged at -66℃ for 36 min and then added to the polymerization system and stirred for 1.5 hr. Then, 43g of isoprene was added to the polymerization reactor for end-capping, and the reaction was continued for 26 min. Finally, 34g of methanol was added, the mixture was discharged, coagulated, washed, and dried to obtain the functionalized polymeric damping brominated grafting agent-4 (Mn = 21000, Mw / Mn = 1.93). In the functionalized polymeric damping brominated grafting agent obtained in this comparative example, in the general formula described in Formula I, I represents a small molecule isoprene segment; R represents methyl (CH3); and n is the number of repeating units: n ≥ 1.

[0067] (2) Preparation of wide-temperature-range damping brominated branched butyl rubber: Other conditions are the same as in Example 4, except that no functionalized polymeric damping brominated grafting agent is added during the preparation of wide-temperature-range damping brominated branched butyl rubber. Instead, functionalized polymeric damping brominated grafting agent-4 is added, with an addition amount of 40g. That is: First, in a 4L stainless steel reactor with a jacket, nitrogen gas is purged four times. Then, 700g of dichloromethane, 300g of cyclohexane, and 40g of functionalized polymeric damping brominated grafting agent-4 are added to the polymerization reactor and stirred to dissolve for 56min until completely dissolved. Then, when the temperature is lowered to -76℃, 800g of monochloromethane, 500g of isobutylene, and 26g of isoprene are added sequentially and stirred until the polymerization system temperature drops to -86℃. Then, 80g of monochloromethane, 1.252g of sesquiethylaluminum chloride, and HCl are added. 0.041g of the mixture was aged at -96℃ for 46 minutes and then added to the polymerization system. After stirring and reacting for 2.6 hours, 21g of methanol was added. The mixture was then discharged, coagulated, washed, and dried to obtain a wide-temperature-range damping brominated branched butyl rubber product. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0068] Comparative Example 5

[0069] (1) Preparation of functionalized polymer damping brominated grafting agent: Other conditions are the same as in Example 5, except that the amount of tribromophenyl allyl ether added in the preparation of the functionalized polymer damping brominated grafting agent is 800g, that is: first, in a 10L stainless steel reactor with a jacket, argon gas is purged 5 times, and 1400g of chloromethane, 1600g of cyclohexane, 800g of tribromophenyl allyl ether, and 370g of 4-vinylphenylethyl ether are added to the polymerization reactor. The mixture is stirred until the temperature of the polymerization system drops to -57℃, and then 90g of chloromethane, 0.671g of sesquiethylaluminum chloride, and HCl are added. 0.042g of the mixture was aged at -68℃ for 38 min and then added to the polymerization system and stirred for 1.8 hr. Then, 47g of isoprene was added to the polymerization reactor for end-capping, and the reaction was allowed to proceed for 28 min. Finally, 37g of methanol was added, and the mixture was discharged, coagulated, washed, and dried to obtain the functionalized polymeric damping brominated grafting agent-5 (Mn = 37000, Mw / Mn = 2.03, bromine content = 4.95%). In the functionalized polymeric damping brominated grafting agent obtained in this comparative example, in Formula I, I represents a small molecule isoprene segment; R represents ethyl (C2H5); and n is the number of repeating units: n ≥ 1.

[0070] (2) Preparation of wide-temperature-range damping brominated branched butyl rubber: Other conditions are the same as in Example 5, except that: no functionalized polymer damping brominated grafting agent is added during the preparation of wide-temperature-range damping brominated branched butyl rubber, but functionalized polymer damping brominated grafting agent-5 is added, with an addition amount of 43g. That is: first, in a 4L stainless steel reactor with a jacket, nitrogen gas is purged 5 times, and 600g of dichloromethane, 400g of cyclohexane, and 43g of functionalized polymer damping brominated grafting agent-5 are added to the polymerization reactor, and stirred and dissolved for 58min until completely dissolved; then, when the temperature is lowered to -78℃, 900g of monochloromethane, 500g of isobutylene, and 28g of isoprene are added in sequence, and stirred and mixed until the temperature of the polymerization system drops to -88℃, and then 90g of monochloromethane, 1.367g of sesquiethylaluminum chloride, and HCl are added. 0.065g of the mixture was aged at -98℃ for 48 minutes, then added to the polymerization system and stirred for 2.8 hours. Finally, 23g of methanol was added, and the mixture was discharged, coagulated, washed, and dried to obtain a wide-temperature-range damping brominated branched butyl rubber product. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0071] Comparative Example 6

[0072] (1) Preparation of functionalized polymeric damping brominated grafting agent: Other conditions are the same as in Example 6, except that: in the preparation of the functionalized polymeric damping brominated grafting agent, cationic polymerization is not used, but free radical polymerization is used. Instead of adding sesquiethylaluminum chloride and HCl as initiators, benzoyl peroxide (BPO) is added, with an addition amount of 1.016 g. That is: first, in a 10L stainless steel reactor with a jacket, argon gas is purged 5 times, and then 1200 g of chloromethane, 1800 g of cyclohexane, 1000 g of tribromophenyl allyl ether, and 400 g of 4-vinylphenylbutyl ether are added to the polymerization reactor. The mixture is stirred until the temperature of the polymerization system drops to -60°C, and then BPO is added. 1.016g was added to the polymerization system and stirred for 2.0 hours. Then, 50g of isoprene was added to the polymerization reactor for end-capping, and the reaction was carried out for 30 minutes. Finally, 40g of methanol was added, and the product was discharged, coagulated, washed, and dried to obtain functionalized polymeric damping brominated grafting agent-6 (Mn is 38000, Mw / Mn is 4.65, and bromine content is 6.02%). In the functionalized polymeric damping brominated grafting agent obtained in this comparative example, in the general formula described in Formula I, I is a small molecule isoprene segment; R is butyl (C4H9); and n is the number of repeating units: n≥1.

[0073] (2) Preparation of wide-temperature-range damping brominated branched butyl rubber: Other conditions are the same as in Example 6, except that no functionalized polymeric damping brominated grafting agent is added during the preparation of wide-temperature-range damping brominated branched butyl rubber. Instead, functionalized polymeric damping brominated grafting agent-6 is added, with an addition amount of 45g. That is: First, in a 4L stainless steel reactor with a jacket, nitrogen gas is purged 5 times. Then, 300g of dichloromethane, 700g of cyclohexane, and 45g of functionalized polymeric damping brominated grafting agent-6 are added to the polymerization reactor and stirred for 60min until completely dissolved. Then, when the temperature is lowered to -80℃, 1000g of monochloromethane, 500g of isobutylene, and 30g of isoprene are added sequentially and stirred until the polymerization system temperature drops to -90℃. Then, 100g of monochloromethane, 1.498g of sesquiethylaluminum chloride, and HCl are added. 0.089g of the mixture was aged at -100℃ for 50 min, then added to the polymerization system and stirred for 3.0 hr. Finally, 25g of methanol was added, and the mixture was discharged, coagulated, washed, and dried to obtain a wide-temperature-range damping brominated branched butyl rubber product. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0074] Comparative Example 7

[0075] (1) Preparation of functionalized polymer damping brominated grafting agent: Same as in Example 6.

[0076] (2) Preparation of wide-temperature-range damping brominated branched butyl rubber: Other conditions are the same as in Example 6, except that the amount of functionalized polymer damping brominated grafting agent added during the preparation of wide-temperature-range damping brominated branched butyl rubber is 19g. That is: first, in a 4L stainless steel reactor with a jacket, nitrogen gas is purged 5 times, and 300g of dichloromethane, 700g of cyclohexane, and 19g of functionalized polymer damping brominated grafting agent are added to the polymerization reactor. The mixture is stirred and dissolved for 60min until completely dissolved. Then, when the temperature is lowered to -80℃, 1000g of monochloromethane, 500g of isobutylene, and 30g of isoprene are added sequentially. The mixture is stirred and mixed until the temperature of the polymerization system drops to -90℃. Then, 100g of monochloromethane, 1.498g of sesquiethylaluminum chloride, and HCl are added. 0.089g of the mixture was aged at -100℃ for 50 min, then added to the polymerization system and stirred for 3.0 hr. Finally, 25g of methanol was added, and the mixture was discharged, coagulated, washed, and dried to obtain a wide-temperature-range damping brominated branched butyl rubber product. Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0077] Table 1 Properties of Wide Temperature Range Damping Brominated Branched Butyl Rubber

[0078]

Claims

1. A method for preparing functionalized damping brominated grafting agents, characterized in that, include: Based on 100% by mass of tribromophenyl allyl ether, 200% to 300% of a mixed solvent (a diluent / solvent mixture of 60 to 40 / 40 to 60), 100% tribromophenyl allyl ether, and 30% to 40% 4-vinylphenylalkyl ether are added sequentially to the polymerization reactor. The mixture is stirred until the polymerization system temperature drops to -50 to -60°C. Then, 5% to 10% of the diluent and 0.01% to 0.1% of the co-initiator are mixed and aged at -60 to -70°C for 30 to 40 minutes. The mixture is then added to the polymerization reactor and stirred for 1.0 to 2.0 hours. Finally, 3.0% to 5.0% of isoprene is added to the polymerization reactor for end-capping, and the reaction is carried out for 20 to 30 minutes. After that, 2% to 4% of the terminator is added, and the mixture is discharged, coagulated, washed, and dried to obtain the functionalized damping brominated grafting agent. The co-initiator is composed of a combination of alkyl aluminum halide and a protic acid; The functionalized damping brominated grafting agent has a number average molecular weight of 40,000 to 50,000, a molecular weight distribution of 1.68 to 2.26, and a bromine content of 5.51% to 6.73% by mass.

2. The method according to claim 1, characterized in that, The 4-vinylphenylalkyl ether is one of 4-vinylanisole, 4-vinylphenylethyl ether, 4-vinylphenylpropyl ether, 4-vinylphenylbutyl ether, and 4-vinylphenylisobutyl ether.

3. The method according to claim 2, characterized in that, The 4-vinylphenylalkyl ether is 4-vinylanisole.

4. The method according to claim 1, characterized in that, The diluent is a haloalkane, wherein the halogen atom in the haloalkane is chlorine, bromine or fluorine; and the number of carbon atoms in the haloalkane is C1-C4.

5. The method according to claim 4, characterized in that, The haloalkane is selected from one of the following: chloromethane, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, fluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane.

6. The method according to claim 5, characterized in that, The haloalkane is chloromethane.

7. The method according to claim 1, characterized in that, The alkyl aluminum halide is selected from at least one of diethylaluminum chloride, diisobutylaluminum chloride, dichloromethylaluminum, sesquiethylaluminum chloride, sesquiisobutylaluminum chloride, dichloro-n-propylaluminum, dichloroisopropylaluminum, dimethylaluminum chloride, and ethylaluminum chloride; the protic acid is selected from one of HCl, HF, HBr, H2SO4, H2CO3, H3PO4, and HNO3.

8. The method according to claim 7, characterized in that, The alkyl aluminum halide is sesquiethyl aluminum chloride, and the protic acid is HCl.

9. The method according to claim 1, characterized in that, In the co-initiator, the molar ratio of protic acid to alkyl aluminum halide is 1:10 to 1:

100.

10. The method according to claim 1, characterized in that, The terminator is selected from one or more of methanol, ethanol, and butanol.

11. The method according to claim 1, characterized in that, The solvent is selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.

12. The method of claim 11, characterized in that, The solvent is cyclohexane.

13. The functionalized damping brominated grafting agent prepared by any one of claims 1-12.

14. A method for preparing damped brominated branched butyl rubber, characterized in that, include: Add 100% to 200% of a mixed solvent (of 70% to 30% by mass of isobutylene, the mixed solvent being a diluent / solvent mixture) and 5% to 9% of the functionalized damping brominated grafting agent as described in claim 13 to the polymerization reactor. Stir and dissolve for 50 to 60 minutes until the grafting agent is completely dissolved. Then, when the temperature is lowered to -80 to -70°C, add 100% to 200% of the diluent, 100% of isobutylene, and 4% to 6% of isoprene in sequence. Stir and mix until the polymerization system temperature drops to -90 to -80°C. Then, mix and age 10% to 20% of the diluent and 0.1% to 0.3% of the co-initiator at -100 to -90°C for 40 to 50 minutes, and then add them together to the polymerization system. Stir and react for 2.0 to 3.0 hours. Finally, add 3% to 9% of the diluent. After adding 5% terminator, the material is discharged, coagulated, washed, and dried to obtain damped brominated branched butyl rubber.

15. The method of claim 14, characterized in that, The diluent is a haloalkane, wherein the halogen atom in the haloalkane is chlorine, bromine or fluorine; and the number of carbon atoms in the haloalkane is C1-C4.

16. The method of claim 15, characterized in that, The haloalkane is selected from one of the following: chloromethane, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, fluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane.

17. The method of claim 16, characterized in that, The haloalkane is chloromethane.

18. The method of claim 14, characterized in that, The co-initiator is a combination of alkyl aluminum halide and protic acid.

19. The method of claim 18, characterized in that, The alkyl aluminum halide is selected from at least one of diethylaluminum chloride, diisobutylaluminum chloride, dichloromethylaluminum, sesquiethylaluminum chloride, sesquiisobutylaluminum chloride, dichloro-n-propylaluminum, dichloroisopropylaluminum, dimethylaluminum chloride, and ethylaluminum chloride; the protic acid is selected from one of HCl, HF, HBr, H2SO4, H2CO3, H3PO4, and HNO3.

20. The method of claim 19, characterized in that, The alkyl aluminum halide is sesquiethyl aluminum chloride, and the protic acid is HCl.

21. The method of claim 14, characterized in that, The total amount of the co-initiator added is 0.1% to 0.3%, and the molar ratio of protic acid to alkyl aluminum halide is 1:10 to 1:

100.

22. The method of claim 14, characterized in that, The terminator is selected from one or more of methanol, ethanol, and butanol.

23. The method of claim 14, characterized in that, The solvent is selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.

24. The method of claim 23, characterized in that, The solvent is cyclohexane.

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