A process for the preparation of a branched halogenated butyl rubber

Abstract

The application provides a branched halogenated butyl rubber preparation method, compared with the prior art, the branched butyl rubber synthesized by the application has a bimodal distribution of molecular weight, the molecular weight distribution is widened, and the mechanical properties such as tensile strength are obviously improved, so that the processing performance of the butyl rubber is effectively improved; the branched butyl rubber halogenation method provided by the application improves the neutralization efficiency, reduces the possibility of incomplete neutralization, effectively inhibits the conversion of the secondary allyl bromine substitution product into the primary allyl bromine substitution product, the obtained brominated butyl rubber has excellent indexes, and the structure is more stable; meanwhile, the preparation method provided by the application is simple in operation, easy in condition control and low in cost, and has a wide application prospect.

Description

Technical Field

[0001] This invention belongs to the field of rubber technology, and particularly relates to a method for preparing branched halogenated butyl rubber. Background Technology

[0002] Butyl rubber (IIR) is a copolymer of isobutylene and a small amount of isoprene. Due to its large methyl group in its molecular structure and the tight intermolecular arrangement, it has excellent airtightness, giving it irreplaceable advantages in tire and sealing materials. However, its poor adhesion, slow vulcanization speed, and difficulty in blending with other rubbers also limit its applications.

[0003] Halogenated butyl rubber (HIIR) is divided into two types: chlorinated butyl rubber (CIIR) and brominated butyl rubber (BIIR). They are prepared by adding chlorine or bromine to butyl rubber. HIIR not only retains the excellent properties of butyl rubber but also overcomes its shortcomings, making it suitable for applications such as the airtight layer of automotive radial tires and medical bottle stoppers.

[0004] However, it is precisely because of the close arrangement of IIR / HIIR molecules that they exhibit good damping properties, slow stress relaxation, and poor processability. Compared to linear polymers, polymers with unique three-dimensional shapes and highly branched structures have lower solution and bulk viscosity, faster stress relaxation, and insensitivity to shear. Star-branched butyl rubber / star-branched brominated butyl rubber, with its bimodal distribution, maintains raw rubber strength through branching in the high molecular weight region while simultaneously achieving rapid stress relaxation with the linear polymer in the low molecular weight region. This results in a perfect balance between the physical and mechanical properties and processability of butyl rubber. Star-branched butyl rubber can be used in inner tubes, pharmaceutical stoppers, adhesives, and sealing products, while star-branched halogenated butyl rubber is generally used in the airtight layer of tubeless tires, tire sidewalls, roofing waterproofing membranes, adhesives, and sealing materials.

[0005] Therefore, the present invention aims to provide a method for preparing branched halogenated butyl rubber with a bimodal molecular weight distribution and good mechanical properties such as tensile strength. Summary of the Invention

[0006] In view of this, the technical problem to be solved by the present invention is to provide a method for preparing branched halogenated butyl rubber with a bimodal molecular weight distribution and good mechanical properties such as tensile strength.

[0007] This invention provides a method for preparing branched halogenated butyl rubber, comprising:

[0008] S1) Mix the isomonoolefin, the conjugated diene, and the first diluent to obtain a reactant solution;

[0009] The branching agent is mixed with the second diluent to obtain a branching agent solution;

[0010] S2) The reactant solution, the branching agent solution, and the catalyst solution aged at low temperature are mixed to carry out a polymerization reaction to obtain branched butyl rubber; the catalyst solution includes Lewis acid, co-catalyst, and aliphatic hydrocarbon.

[0011] S3) Branched butyl rubber is mixed with aliphatic hydrocarbons to obtain a rubber solution;

[0012] S4) Mix the adhesive solution and wetting agent evenly, and then mix and react it with the halogenating agent under light-protected conditions to obtain the reacted emulsion;

[0013] S5) The reacted emulsion is mixed with an acid-binding agent to obtain a reaction solution;

[0014] S6) After mixing the reaction solution with the additives, the solvent is removed to obtain branched halogenated butyl rubber.

[0015] Preferably, in step S1), the isomonoolefin has 4 to 16 carbon atoms; the conjugated diene has 4 to 14 carbon atoms; the molar ratio of the isomonoolefin to the conjugated diene is (19 to 50): 1; the branching agent is a hydrochloric acid-acidified styrene-butadiene copolymer; the mass of the branching agent is 0.05 wt% to 5 wt% of the mass of the isomonoolefin; the first diluent and the second diluent are each independently selected from one or more of chloromethane, dichloromethane, n-hexane, cyclohexane, isohexane, and isopentane; and the mass concentration of the isomonoolefin in the reactant solution is 10% to 40%.

[0016] Preferably, a molecular weight regulator is also added in step S2); the molecular weight regulator is selected from olefins with 4 to 14 carbon atoms; the mass of the molecular weight regulator is 0.001 wt% to 10 wt% of the mass of the isomonoolefin.

[0017] Preferably, the Lewis acid is selected from one or more of dichloroethylaluminum, dichlorobutylaluminum, dichlorodiethylaluminum, dichlorodibutylaluminum, titanium tetrachloride, and boron trifluoride; the co-catalyst is selected from water or hydrogen chloride; the aliphatic hydrocarbon is a nonpolar and / or weakly polar aliphatic hydrocarbon; the molar ratio of the Lewis acid to the co-catalyst is (1-10):1; the molar ratio of the Lewis acid to the isomonoolefin is 1:(500-6000); the low-temperature aging temperature is -99℃ to -65℃; and the low-temperature aging time is 1-30 min.

[0018] Preferably, the polymerization reaction temperature is -99℃ to -70℃; the polymerization reaction time is 5 to 20 minutes; after the polymerization reaction is completed, a terminator is added to terminate the reaction, and the reaction product is obtained. After drying, branched butyl rubber is obtained.

[0019] Preferably, the terminating agent is selected from one or more of ethanol, methanol, isopropanol, glycerol and triethylene glycol; the drying is vacuum drying; the drying temperature is 25℃~55℃, and the drying time is 45~50h;

[0020] In step S3), the viscosity of the adhesive solution is 250–650 cp; the content of branched butyl rubber in the adhesive solution is 5–25 wt%.

[0021] Preferably, in step S4), the adhesive is first mixed with water to obtain an emulsion, and then the emulsion is mixed evenly with a wetting agent; the mass ratio of water to adhesive is (0.1-20):100.

[0022] The sizing agent is selected from one or more of fatty alcohols, fatty alcohol esters, epoxidized esters, epoxidized soybean oil, epoxidized linseed oil, alkali metal carboxylates, alkaline earth metal carboxylates, alkali metal stearates, alkaline earth metal stearates, metal oxides and metal hydroxides; the mass ratio of the sizing agent to the branched butyl rubber is (0.001-10):100.

[0023] Preferably, the halogenating agent in step S4) is selected from one or more of the following: a nonpolar or weakly polar aliphatic hydrocarbon solution of Cl2, a nonpolar or weakly polar aliphatic hydrocarbon solution of Br2, HCl, HBr, NaClO, and NaBrO3; the molar ratio of the halogen element in the halogenating agent to the unsaturated bond in the branched butyl rubber is (0.5-2):1.

[0024] The acid-binding agent is selected from one or more of alkali metal hydroxides, strong base weak acid salts, and bisulfites; the adjuvant is selected from antioxidants and / or stabilizers; the antioxidant is selected from one or more of antioxidant 1135, antioxidant 1076, and antioxidant 1010; the stabilizer is selected from stearates and / or epoxidized soybean oil.

[0025] The present invention also provides a branched halogenated butyl rubber prepared by the above preparation method.

[0026] This invention also provides a method for preparing branched butyl rubber, comprising:

[0027] S1) Mix the isomonoolefin, the conjugated diene, and the first diluent to obtain a reactant solution;

[0028] The branching agent is mixed with the second diluent to obtain a branching agent solution;

[0029] S2) The reactant solution, the branching agent solution, and the catalyst solution aged at low temperature are mixed to carry out a polymerization reaction to obtain branched butyl rubber; the catalyst solution includes Lewis acid, co-catalyst, and aliphatic hydrocarbon.

[0030] This invention provides a method for preparing branched halogenated butyl rubber, comprising: S1) mixing an isomonoolefin, a conjugated diene, and a first diluent to obtain a reactant solution; mixing a branching agent with a second diluent to obtain a branching agent solution; S2) mixing the reactant solution, the branching agent solution, and a catalyst solution aged at low temperature to carry out a polymerization reaction to obtain branched butyl rubber; wherein the catalyst solution includes a Lewis acid, a co-catalyst, and an aliphatic hydrocarbon; S3) mixing the branched butyl rubber with the aliphatic hydrocarbon to obtain a rubber solution; S4) mixing the rubber solution with a wetting agent first, and then reacting it with a halogenating agent under light-protected conditions to obtain a reacted emulsion; S5) reacting the reacted emulsion with an acid-binding agent to obtain a reaction solution; S6) mixing the reaction solution with an additive and removing the solvent to obtain branched halogenated butyl rubber. Compared with existing technologies, the branched butyl rubber synthesized by this invention exhibits a bimodal molecular weight distribution with a broadened molecular weight distribution, resulting in significantly improved mechanical properties such as tensile strength, thereby effectively improving the processing performance of butyl rubber. The halogenation method for branched butyl rubber provided by this invention improves neutralization efficiency, reduces the possibility of incomplete neutralization, and effectively inhibits the transformation of secondary allyl brominated products to primary allyl brominated products. The resulting brominated butyl rubber has excellent properties and a more stable structure. Furthermore, the preparation method provided by this invention is simple to operate, has easily controllable conditions, and is low in cost, thus possessing broad application prospects. Attached Figure Description

[0031] Figure 1 The GPC spectra of the branched butyl rubber obtained in Example 1 and Comparative Example 1 of this invention are shown. Detailed Implementation

[0032] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0033] This invention provides a method for preparing branched halogenated butyl rubber, comprising:

[0034] S1) Mix the isomonoolefin, the conjugated diene, and the first diluent to obtain a reactant solution;

[0035] The branching agent is mixed with the second diluent to obtain a branching agent solution;

[0036] S2) The reactant solution, the branching agent solution, and the catalyst solution aged at low temperature are mixed to carry out a polymerization reaction to obtain branched butyl rubber; the catalyst solution includes Lewis acid, co-catalyst, and aliphatic hydrocarbon.

[0037] S3) Branched butyl rubber is mixed with aliphatic hydrocarbons to obtain a rubber solution;

[0038] S4) Mix the adhesive solution and wetting agent evenly, and then mix and react it with the halogenating agent under light-protected conditions to obtain the reacted emulsion;

[0039] S5) The reacted emulsion is mixed with an acid-binding agent to obtain a reaction solution;

[0040] S6) After mixing the reaction solution with the additives, the solvent is removed to obtain branched halogenated butyl rubber.

[0041] In this invention, there are no special restrictions on the source of any raw materials; they can be commercially available.

[0042] The isomonoolefin, conjugated diene, and a first diluent are mixed to obtain a reactant solution; the isomonoolefin preferably has 4-16 carbon atoms, more preferably 4-12, even more preferably 4-10, even more preferably 4-8, and most preferably 4-6; the conjugated diene preferably has 4-14 carbon atoms, more preferably 4-12, even more preferably 4-10, even more preferably 5-8, and most preferably 5-6; the molar ratio of the isomonoolefin to the conjugated diene is preferably (19-50):1; more preferably (20-45):1, even more preferably (25-45):1, even more preferably (30-45):1, and most preferably (35-45):1; The first diluent is preferably one or more selected from chloromethane, dichloromethane, n-hexane, cyclohexane, isohexane, and isopentane; the mixing temperature is preferably -99℃ to -65℃, more preferably -90℃ to -70℃, and even more preferably -85℃ to -80℃; the mixing speed is preferably 100 to 600 r / min; the mass concentration of the isomonoolefin in the obtained reactant solution is preferably 10% to 40%, more preferably 15% to 40%, even more preferably 15% to 35%, and most preferably 18% to 30%; in the embodiments provided by the present invention, the concentration of the isomonoolefin in the reactant solution is specifically 28.3%, 19%, or 23.4%.

[0043] The branching agent is mixed with a second diluent to obtain a branching agent solution; the branching agent is preferably a hydrochloric acid-acidified styrene-butadiene copolymer; wherein the number average molecular weight of the styrene-butadiene copolymer is preferably 50,000 to 500,000, more preferably 50,000 to 400,000, even more preferably 75,000 to 350,000, and most preferably 80,000 to 300,000; the molar content of styrene in the styrene-butadiene copolymer is preferably 5 mol% to 80 mol%, more preferably 10 mol% to 75 mol%, even more preferably 20 mol% to 70 mol%, even more preferably 30 mol% to 65 mol%, and most preferably... The concentration is selected as 35 mol% to 60 mol%; the hydrochloric acid-acidified styrene-butadiene copolymer is preferably prepared by the following method: acidification is achieved by passing hydrochloric acid gas into the styrene-butadiene copolymer solution; the acidification time is preferably 20 to 50 min, more preferably 20 to 40 min, even more preferably 25 to 35 min, and most preferably 30 min; the second diluent is preferably one or more of chloromethane, dichloromethane, n-hexane, cyclohexane, isohexane, and isopentane; the mass concentration of the branching agent in the branching agent solution is preferably 0.1% to 5%, more preferably 0.5% to 4%, even more preferably 0.5% to 3%, and most preferably 1% to 2%.

[0044] The reactant solution, branching agent solution, and catalyst solution aged at low temperature are mixed for polymerization. The branching agent is preferably 0.05 wt% to 5 wt% of the isomonoolefin mass, more preferably 0.5 wt% to 3 wt%, even more preferably 1 wt% to 2 wt%, and most preferably 1 wt% to 1.25 wt%. The catalyst solution comprises a Lewis acid, a co-catalyst, and an aliphatic hydrocarbon. The Lewis acid is preferably one or more of dichloroethylaluminum, dichlorobutylaluminum, dichlorodiethylaluminum, dichlorobutylaluminum, titanium tetrachloride, and boron trifluoride. The co-catalyst is preferably water or hydrogen chloride. The aliphatic hydrocarbon is preferably a nonpolar and / or weakly polar aliphatic hydrocarbon, more preferably a C5-C8 saturated aliphatic hydrocarbon, and even more preferably one or more of n-hexane, n-pentane, and isohexane; the molar ratio of the Lewis acid to the cocatalyst is preferably (1-10):1, more preferably (3-9):1, even more preferably (5-9):1, even more preferably (6-8):1, and most preferably 7:1; the molar ratio of the Lewis acid to the isomonoolefin is preferably 1:(500-6000), more preferably 1:(800-5000), even more preferably 1:(1000-4000):1, and even more preferably 1:(1000-6000):1. The preferred ratio is 1:(1200-2000), and the most preferred ratio is 1:(1400-1500); the mass concentration of Lewis acid in the catalyst solution is preferably 0.1%-3%, more preferably 0.1%-2%, more preferably 0.1%-1%, more preferably 0.2%-0.8%, and most preferably 0.4%-0.6%; the preferred temperature for low-temperature aging is -99℃ to -65℃, more preferably -99℃ to -70℃, more preferably -99℃ to -80℃, more preferably -99℃ to -90℃, and most preferably -97.5℃ to -95℃; low-temperature aging The preferred time is 1–30 min, more preferably 5–30 min, even more preferably 10–30 min, and most preferably 20–30 min; in this invention, a molecular weight regulator is preferably also added; the mass of the molecular weight regulator is 0.001 wt%–10 wt% of the mass of the isomonoolefin, more preferably 0.005 wt%–6 wt%, even more preferably 0.005 wt%–4 wt%, even more preferably 0.005 wt%–2 wt%, even more preferably 0.05 wt%–1 wt%, even more preferably 0.05 wt%–0.5 wt%, and most preferably 0.05 wt%–0.5 wt%.1 wt%; the molecular weight regulator is preferably an olefin with 4 to 14 carbon atoms, more preferably an olefin with 4 to 12 carbon atoms, even more preferably 4 to 10, and most preferably 6 to 8; the present invention does not have a special limitation on the number of double bonds in the molecular weight regulator, and the molecular weight regulator in the present invention is preferably a mono-olefin, diene, or polyolefin (containing more than 2 double bonds); the polymerization temperature is preferably -99℃ to -70℃, more preferably -99℃ to -80℃, even more preferably -99℃ to -90℃, and most preferably -97.5℃ to -95℃; the polymerization time is preferably 5 to 20 min, more preferably 10 to 20 min; the polymerization reaction is preferably carried out under stirring conditions; the stirring speed is preferably 100 to 600 r / min. In this invention, this step is preferably performed as follows: first, the reactant solution and the branching agent solution are mixed thoroughly, and then a catalyst solution aged at low temperature is added to carry out the polymerization reaction; more preferably, the reactant solution and the branching agent solution are mixed thoroughly, a molecular weight regulator is added, and then a catalyst solution aged at low temperature is added to carry out the polymerization reaction.

[0045] After the polymerization reaction is completed, a terminator is preferably added to terminate the reaction, yielding the reaction product. After drying, branched butyl rubber is obtained. The terminator is preferably an alcohol solvent, more preferably one or more of ethanol, methanol, isopropanol, glycerol, and triethylene glycol; the ratio of the terminator to the isomonoolefin is preferably 1 mL:(10-30) g, more preferably 1 mL:(10-25) g, and even more preferably 1 mL:(10-20) g; the drying is preferably vacuum drying; the drying temperature is preferably 25℃-55℃, more preferably 30℃-50℃, and even more preferably 35℃-45℃; the drying time is preferably 45-50 h, more preferably 48 h.

[0046] Branched butyl rubber is mixed with aliphatic hydrocarbons to obtain a rubber solution; the aliphatic hydrocarbons are preferably nonpolar and / or weakly polar aliphatic hydrocarbons, more preferably C5-C8 saturated aliphatic hydrocarbons, and even more preferably one or more of n-hexane, n-pentane and isohexane; the content of branched butyl rubber in the rubber solution is preferably 5-25 wt%, more preferably 10-25 wt%, even more preferably 10-20 wt%, and most preferably 15-20 wt%; the viscosity of the rubber solution is preferably 250-650 cp.

[0047] The adhesive solution and the wetting agent are mixed evenly. In this invention, it is preferable to first mix the adhesive solution with water to obtain an emulsion, and then mix the emulsion with the wetting agent evenly. The mass ratio of water to adhesive solution is preferably (0.1-20):100, more preferably (1-15):100, and even more preferably (5-10):100. The mixing time of the adhesive solution and water is preferably 5-40 min, more preferably 10-30 min, and even more preferably 20-30 min. In this invention, it is preferable to first mix the emulsion with the wetting agent. The wetting agent is preferably fatty alcohol, fatty alcohol ester, epoxidized ester, epoxidized soybean oil, epoxidized linseed oil, alkali metal carboxylates, alkaline earth metal carboxylates, or alkali... The sizing agent comprises one or more of the following: metal stearates, alkaline earth metal stearates, metal oxides and metal hydroxides, more preferably methanol, ethanol, tert-butanol, epoxidized esters, glycerides of C8-C24 unsaturated fatty acids, calcium hydroxide, calcium oxide, magnesium hydroxide, oxidase, sodium carbonate, sodium bicarbonate, epoxidized soybean oil, epoxidized linseed oil, calcium stearate and stearic acid; the mass ratio of the sizing agent to the branched butyl rubber is preferably (0.001-10):100, more preferably (0.01-10):100, even more preferably (0.1-5):100, even more preferably (0.5-2):100, and most preferably (0.5-10):100.

[0048] Then, under light-protected conditions, it is mixed and reacted with a halogenating agent; the halogenating agent is preferably one or more of the following: a nonpolar or weakly polar aliphatic hydrocarbon solution of Cl2, a nonpolar or weakly polar aliphatic hydrocarbon solution of Br2, HCl, HBr, NaClO, and NaBrO3; depending on the type of halogenating agent, H2O2 may be added as needed to improve the halogenation efficiency; the molar ratio of halogen element in the halogenating agent to the unsaturated bond in the branched butyl rubber is preferably (0.5-2):1, more preferably (0.8-1.5):1, and even more preferably (0.8-1.2):1. The preferred ratio is (0.8-1):1, and the most preferred ratio is (0.9-1):1; in the embodiments provided by the present invention, the molar ratio of halogen element in the halogenating agent to unsaturated bond in branched butyl rubber is specifically 0.92:1; the temperature of the mixing reaction is preferably 10℃-50℃, more preferably 20℃-50℃, and even more preferably 30℃-40℃; the time of the mixing reaction is preferably 5-30 min, more preferably 10-20 min; the mixing reaction is preferably carried out under stirring conditions; the stirring speed is preferably 100-600 r / min.

[0049] The reacted emulsion is mixed with an acid-binding agent to obtain a reaction solution; the acid-binding agent is preferably one or more of alkali metal hydroxides, strong base weak acid salts and bisulfites, more preferably sodium hydroxide and / or potassium hydroxide; the molar ratio of the acid-binding agent to the halogen element in the halogenating agent is preferably (0.3-2):1, more preferably (0.5-1):1, even more preferably (0.7-0.8):1, and most preferably 0.76:1; the reaction between the acid-binding agent and the reacted emulsion is a neutralization reaction, and the time is preferably 1-10 min, more preferably 4-8 min, and even more preferably 5-6 min.

[0050] The obtained reaction solution is preferably washed and then mixed with the auxiliary agent; the washing is preferably done until neutral; the auxiliary agent is preferably an antioxidant and / or a stabilizer, more preferably an antioxidant and a stabilizer; the mass ratio of the antioxidant to the stabilizer is preferably 1:(50-100), more preferably 1:(60-90), even more preferably 1:(70-80), and most preferably 1:(72-75); the antioxidant is preferably one or more of antioxidant 1135, antioxidant 1076, and antioxidant 1010; the stabilizer is preferably stearate and / or epoxy. Soybean oil, more preferably stearate and epoxidized soybean oil; the mass ratio of stearate to epoxidized soybean oil is preferably 2:(1-2), more preferably 2:(1.4-1.8), and even more preferably 2:1.6; the mass ratio of the additive to branched butyl rubber is preferably (1-10):100, more preferably (2-8):100, even more preferably (2-6):100, and most preferably (3-4):100; in the embodiments provided by the present invention, the mass ratio of the additive to branched butyl rubber is specifically 3.65:100.

[0051] After mixing evenly, the solvent is removed; the preferred method for removing the solvent is flash evaporation; the preferred temperature for removing the solvent is 95℃~100℃, more preferably 98℃.

[0052] After removing the solvent, the obtained rubber compound is preferably extruded, dehydrated and dried to obtain branched halogenated butyl rubber; the extrusion dehydration drying temperature is preferably 98℃~105℃, more preferably 100℃; the extrusion dehydration drying time is preferably 1~5min.

[0053] The branched halogenated butyl rubber synthesized by this invention exhibits a bimodal molecular weight distribution and significantly improves mechanical properties such as tensile strength, thereby effectively improving the processing performance of butyl rubber. At the same time, the preparation method provided by this invention is simple to operate, easy to control, and low in cost, and has broad application prospects.

[0054] The present invention also provides a branched halogenated butyl rubber prepared by the above preparation method; the branched halogenated butyl rubber is a branched halogenated butyl rubber with a bimodal distribution.

[0055] This invention also provides a method for preparing branched butyl rubber, comprising:

[0056] S1) Mix the isomonoolefin, the conjugated diene, and the first diluent to obtain a reactant solution;

[0057] The branching agent is mixed with the second diluent to obtain a branching agent solution;

[0058] S2) The reactant solution, the branching agent solution, and the catalyst solution aged at low temperature are mixed to carry out a polymerization reaction to obtain branched butyl rubber; the catalyst solution includes Lewis acid, co-catalyst, and aliphatic hydrocarbon.

[0059] Steps S1) and S2) are the same as described above, and will not be repeated here.

[0060] To further illustrate the present invention, the following describes in detail, with reference to embodiments, a method for preparing branched halogenated butyl rubber.

[0061] All reagents used in the following examples are commercially available; the number-average molecular weight of SBS used in Examples 1 and 2 is 100,000, and the molar content of styrene is 60 mol%; the number-average molecular weight of SBS used in Examples 3 and 4 is 150,000, and the molar content of styrene is 40 mol%; the number-average molecular weight of SBS used in Examples 5 and 6 is 200,000, and the molar content of styrene is 35 mol%.

[0062] Example 1

[0063] 1.1 At -85℃, 40g of isobutylene and 1.5g of isoprene were weighed and added to 100g of chloromethane to obtain a mixture.

[0064] 1.2 Prepare 50g of 1wt% SBS / chloromethane solution and pass HCl gas through it for 30min to obtain hydrochloric acid-acidified SBS / chloromethane solution.

[0065] 1.3 Add the hydrochloric acid-acidified SBS / chloromethane solution obtained in step 1.2 to the mixture obtained in step 1.1, and then add 0.02 g of 1-hexene to obtain the reaction solution.

[0066] 1.4 Weigh 0.3g of dichloroethylaluminum in n-hexane (mass fraction 20%) and add it to 12g of HCl in chloromethane (mass fraction 0.020wt%). Mix well and age at -97.5℃ for 30min to obtain the catalyst solution.

[0067] 1.5 Add the catalyst solution from step 1.4 to the reaction solution from step 1.3 and react at -97.5℃ for 20 min. The temperature rises slowly during polymerization, and the resulting slurry is uniformly dispersed in granular form.

[0068] 1.6 The reaction was terminated by adding 2 mL of cold ethanol, and the product was dried under vacuum at 35 °C for 48 h to obtain branched butyl rubber with a yield of 85.4%. NMR spectroscopy showed an unsaturation of 1.67 mol%. Gel permeation chromatography (GPC) revealed a weight-average molecular weight of 595,665 g / mol and a number-average molecular weight of 115,981 g / mol. The GPC chromatogram showed a bimodal molecular weight distribution with a molecular weight distribution of 5.14, and the fraction with a molecular weight greater than or equal to 4 MPa was 15.45%. The 100% elongation was 2.6 MPa; the 300% elongation was 9.5 MPa; the tensile strength was 18.7 MPa; the elongation at break was 586%; and the tear strength was 73 kN / m (test standard GB / T 528-2009).

[0069] 1.7 Weigh 30g of the branched butyl rubber obtained in step 1.6, add 170g of n-hexane, swell, stir and dissolve to obtain a 15wt% adhesive solution.

[0070] 1.8 Add 10g of deionized water to the obtained gel solution and stir for 30min to obtain an emulsion.

[0071] 1.9 Add 0.15 g of calcium stearate to the emulsion obtained in step 1.8 to obtain a mixture.

[0072] 1.10 Under light-protected conditions at 40°C, add a hexane solution of Br2 (0.42 mL of Br2 and 15 mL of hexane; the molar ratio of Br2 to the unsaturated double bond in the star-branched butyl rubber is 0.92:1) to the mixture obtained in step 1.9, stir for 10 min, and obtain the brominated rubber solution.

[0073] 1.11 Add 25g of NaOH solution (2wt% by mass, with a molar ratio of NaOH to bromine in the brominating agent of 0.76:1) to the obtained bromine-treated adhesive solution and neutralize for 5min to obtain a neutralized adhesive solution.

[0074] 1.12 Wash the obtained neutralized rubber solution with water until neutral, then add calcium stearate, epoxidized soybean oil and antioxidant 1135 (according to the ratio of star-branched butyl rubber: calcium stearate: epoxidized soybean oil: antioxidant = 100: 2: 1.6: 0.05), and stir evenly.

[0075] 1.13 The solvent of the adhesive solution obtained in step 1.12 was removed at 98°C, and then the solution was dehydrated and dried at 100°C in a two-roll mill to obtain a brominated branched butyl rubber with a bimodal molecular weight distribution, wherein structure I is 33 mol%, structure II is 63 mol%, structure III is 4 mol%, unsaturation is 1.50 mol%, and functional bromine is 1.007 mol%.

[0076] Example 2

[0077] 2.1 At -85℃, 40g of isobutylene and 1.5g of isoprene were weighed and added to 100g of chloromethane to obtain a mixture.

[0078] 2.2 Prepare 50g of 1wt% SBS / chloromethane solution and pass HCl gas through it for 30min to obtain hydrochloric acid-acidified SBS / chloromethane solution.

[0079] 2.3 Add the hydrochloric acid-acidified SBS / chloromethane solution obtained in step 2.2 to the mixture to obtain the reaction solution.

[0080] 2.4 Weigh 0.3g of dichloroethylaluminum in n-hexane (mass fraction 20%) and add it to 12g of HCl in chloromethane (mass fraction 0.020wt%). Mix well and age at -97.5℃ for 30min to obtain the catalyst solution.

[0081] 2.5 Add the catalyst solution from step 2.4 to the reaction solution from step 2.3, and react at -97.5℃ for 20 min. The temperature rises slowly during polymerization, and the resulting slurry is uniformly dispersed in granular form.

[0082] 2.6 The reaction was terminated by adding 2 mL of cold ethanol. The product was then vacuum dried at 35°C for 48 h, yielding a yield of 88.5%. NMR spectroscopy showed an unsaturation of 1.71 mol%. Gel permeation chromatography (GPC) analysis revealed a weight-average molecular weight of 501292 g / mol and a number-average molecular weight of 132353 g / mol. The GPC chromatogram showed a bimodal molecular weight distribution with a molecular weight distribution of 3.79. The bimodal distribution was not significant enough to calculate the 4 MPa value. The rubber had a 100% elongation of 2.5 MPa, a 300% elongation of 9.4 MPa, a tensile strength of 18.5 MPa, an elongation at break of 580%, and a tear strength of 71 kN / m (test standard GB / T528-2009).

[0083] 2.7 Weigh 30g of the branched butyl rubber obtained in step 2.6, add 170g of n-hexane, swell, stir and dissolve to obtain a 15wt% adhesive solution.

[0084] 2.8 Add 10g of deionized water to the obtained gel solution and stir for 30min to obtain an emulsion.

[0085] 2.9 Add 0.15 g of calcium stearate to the emulsion obtained in step 2.8 to obtain a mixture.

[0086] 2.10 Under light-protected conditions at 40°C, add a hexane solution of Br2 (0.43 mL of Br2 and 15 mL of hexane; the molar ratio of Br2 to the unsaturated double bond in the star-branched butyl rubber is 0.92:1) to the mixture obtained in step 2.9, stir for 10 min, and obtain the brominated rubber solution.

[0087] 2.11 Add 25g of NaOH solution (2wt% by mass, with a molar ratio of NaOH to bromine in the brominating agent of 0.74:1) to the obtained bromine-treated adhesive solution and neutralize for 5min to obtain a neutralized adhesive solution.

[0088] 2.12 Wash the obtained neutralized rubber solution with water until neutral, then add calcium stearate, epoxidized soybean oil and antioxidant 1135 (in the ratio of star-branched butyl rubber: calcium stearate: epoxidized soybean oil: antioxidant = 100: 2: 1.6: 0.05), and stir evenly.

[0089] 2.13 The solvent in the adhesive solution obtained in step 2.12 was removed at 98°C, and then the solution was dehydrated and dried at 100°C in a two-roll mill to obtain a brominated branched butyl rubber with a bimodal molecular weight distribution, wherein structure I is 36 mol%, structure II is 61 mol%, structure III is 3 mol%, unsaturation is 1.40 mol%, and functional bromine is 0.990 mol%.

[0090] Example 3

[0091] 3.1 At -90℃, weigh 20g of isobutylene and 0.55g of isoprene and add them to 65g of chloromethane to obtain a mixture.

[0092] 3.2 Prepare 20g of 1wt% SBS / chloromethane solution, and pass HCl gas through it for 30min to obtain hydrochloric acid-acidified SBS / chloromethane solution.

[0093] 3.3 Add the hydrochloric acid-acidified SBS / chloromethane solution obtained in step 3.2 to the mixture obtained in step 3.1, and then add 0.02 g of 1-hexene to obtain the reaction solution.

[0094] 3.4 Weigh 0.12 g of dichloroethylaluminum in n-hexane (mass fraction 20%) and add it to 4 g of HCl in chloromethane (mass fraction 0.020 wt%). Mix well and age at -97.5℃ for 30 min to obtain the catalyst solution.

[0095] 3.5 Add the catalyst solution from step 3.4 to the reaction solution from step 3.3, and react at -97.5℃ for 10 min. The temperature rises slowly during polymerization, and the resulting slurry is uniformly dispersed in granular form.

[0096] 3.6 The reaction was terminated by adding 2 mL of cold ethanol. The product was then vacuum dried at 40 °C for 48 h to obtain branched butyl rubber with a yield of 86.9%. NMR spectroscopy showed an unsaturation of 1.68 mol%. Gel permeation chromatography (GPC) analysis revealed a weight-average molecular weight of 469,781 g / mol, a number-average molecular weight of 106,703 g / mol, a molecular weight distribution of 4.4 (the bimodal distribution was not obvious, making it impossible to calculate the 4 MPa value), and a 100% elongation at break of 2.4 MPa. The rubber's 300% elongation at break was 8.9 MPa, tensile strength was 18.3 MPa, elongation at break was 577%, and tear strength was 68 kN / m (test standard GB / T 528-2009).

[0097] 3.7 Weigh 15g of the branched butyl rubber obtained in step 3.6, add 80g of n-hexane, swell, stir and dissolve to obtain a rubber solution with a mass fraction of 15.8wt%.

[0098] 3.8 Add 4.5g of deionized water to the obtained gel solution and stir for 30min to obtain an emulsion.

[0099] 3.9 Add 0.10g of antioxidant 1135 to the emulsion obtained in step 8) to obtain a mixture.

[0100] 3.10 Under light-protected conditions at 40°C, add a hexane solution of Br2 (0.23 mL of Br2 and 10 mL of hexane; the molar ratio of Br2 to the unsaturated double bond in the star-branched butyl rubber is 1:1) to the mixture obtained in step 3.9, stir for 10 min, and obtain the brominated rubber solution.

[0101] 3.11 Add 15g of NaOH solution (2wt% by mass, with a molar ratio of NaOH to bromine in the brominating agent of 0.84:1) to the obtained bromine-treated adhesive solution and neutralize for 5min to obtain a neutralized adhesive solution.

[0102] 3.12 Wash the obtained neutralized rubber solution with water until neutral, then add calcium stearate, epoxidized soybean oil and antioxidant 1135 (according to the ratio of star-branched butyl rubber: calcium stearate: epoxidized soybean oil: antioxidant = 100: 2: 1.6: 0.05), and stir evenly.

[0103] 3.13 The solvent of the adhesive solution obtained in step 3.12 was removed at 98°C, and then the solution was dehydrated and dried at 100°C in a two-roll mill to obtain a brominated branched butyl rubber with a bimodal molecular weight distribution, wherein structure I is 37 mol%, structure II is 54 mol%, structure III is 9 mol%, unsaturation is 1.44 mol%, and functional bromine is 0.899 mol%.

[0104] Example 4

[0105] 4.1 At -90℃, weigh 40g of isobutylene and 1.5g of isoprene and add them to 170g of chloromethane to obtain a mixture.

[0106] 4.2 Prepare 50g of 1wt% SBS / chloromethane solution and pass HCl gas through it for 30min to obtain hydrochloric acid-acidified SBS / chloromethane solution.

[0107] 4.3 Add the hydrochloric acid-acidified SBS / chloromethane solution obtained in step 4.2 to the mixture obtained in step 4.1, and then add 0.02 g of 1,4-hexadiene to obtain the reaction solution.

[0108] 4.4 Weigh 0.3g of dichloroethylaluminum in n-hexane (mass fraction 20%) and add it to 12g of HCl in chloromethane (mass fraction 0.020wt%). Mix well and age at -97.5℃ for 30min to obtain the catalyst solution.

[0109] 4.5 Add the catalyst solution from step 4.4 to the reaction solution from step 4.3, and react at -97.5℃ for 10 min. The temperature rises slowly during polymerization, and the resulting slurry is uniformly dispersed in granular form.

[0110] 4.6 The reaction was terminated by adding 2 mL of cold ethanol. The product was then vacuum dried at 40 °C for 48 h to obtain branched butyl rubber with a yield of 88.9%. NMR spectroscopy showed an unsaturation of 1.72 mol%. Gel permeation chromatography (GPC) analysis revealed a weight-average molecular weight of 718,299 g / mol, a number-average molecular weight of 154,726 g / mol, a molecular weight distribution of 4.64 (the bimodal distribution was not obvious, making it impossible to calculate the 4 MPa value), a 100% elongation of 2.6 MPa, a 300% elongation of 9.2 MPa, a tensile strength of 18.1 MPa, an elongation at break of 552%, and a tear strength of 70 kN / m (test standard GB / T 528-2009).

[0111] 4.7 Weigh 30g of the branched butyl rubber obtained in step 4.6, add 170g of n-hexane, swell, stir and dissolve to obtain a 15wt% adhesive solution.

[0112] 4.8 Add 10g of deionized water to the obtained gel solution and stir for 30min to obtain an emulsion.

[0113] 4.9 Add 0.15g of epoxidized soybean oil to the emulsion obtained in step 4.8.

[0114] 4.10 Under light-protected conditions at 40°C, a hexane solution of Br2 (0.445 mL of Br2 and 15 mL of hexane; the molar ratio of Br2 to the unsaturated double bond in the star-branched butyl rubber is 0.95:1) was added to the obtained mixture, and the mixture was stirred for 10 min to obtain the brominated rubber solution.

[0115] 4.11 Add 30g of NaOH solution (2wt% by mass, with a molar ratio of NaOH to bromine in the brominating agent of 0.85:1) to the obtained bromine-treated adhesive solution and neutralize for 5min to obtain a neutralized adhesive solution.

[0116] 4.12 Wash the obtained neutralized rubber solution with water until neutral, then add calcium stearate, epoxidized soybean oil and antioxidant 1135 (in the ratio of star-branched butyl rubber: calcium stearate: epoxidized soybean oil: antioxidant = 100: 2: 1.6: 0.05), and stir evenly.

[0117] 4.13 The solvent of the adhesive solution obtained in step 4.12 was removed at 98°C, and then the solution was dehydrated and dried at 100°C in a two-roll mill to obtain a brominated branched butyl rubber with a bimodal molecular weight distribution, wherein structure I is 35 mol%, structure II is 58 mol%, structure III is 7 mol%, unsaturation is 1.55 mol%, and functional bromine is 0.893 mol%.

[0118] Comparative Example 1

[0119] The process flow and steps are the same as in Example 1, and the proportions of other materials are also the same, except that no branching agent is added.

[0120] The butyl rubber and halogenated butyl rubber products obtained in Comparative Example 1 were analyzed and characterized. NMR analysis showed that the butyl rubber had an unsaturation of 1.65 mol%. Gel permeation chromatography (GPC) analysis revealed that the butyl rubber had a weight-average molecular weight of 826,318 g / mol and a number-average molecular weight of 228,697 g / mol. The GPC spectrum showed a unimodal molecular weight distribution with a molecular weight distribution of 3.6. The rubber had a tensile strength of 17.2 MPa at 100% elongation (2.4 MPa), a tensile strength of 8.0 MPa at 300% elongation (8.0 MPa), an elongation at break of 547%, and a tear strength of 65 kN / m (test standard GB / T 528-2009). The halogenated butyl rubber showed a unimodal molecular weight distribution: structure I 35 mol%, structure II 57 mol%, structure III 8 mol%, unsaturation of 1.30 mol%, and functional bromine of 0.880 mol%.

[0121] Comparative Example 2

[0122] 2.1 At -90℃, 20g of isobutylene and 0.55g of isoprene were weighed and added to 65g of chloromethane to obtain a mixture.

[0123] 2.2 Prepare 20g of 1wt% SBS / chloromethane solution, and pass HCl gas through it for 30min to obtain hydrochloric acid-acidified SBS / chloromethane solution.

[0124] 2.3 Add the hydrochloric acid-acidified SBS / chloromethane solution obtained in step 2.2 to the mixture obtained in step 2.1 to obtain the reaction solution.

[0125] 2.4 Weigh 0.12 g of dichloroethylaluminum in n-hexane (mass fraction 20%) and add it to 4 g of HCl in chloromethane (mass fraction 0.020 wt%). Mix well and age at -97.5℃ for 30 min to obtain the catalyst solution.

[0126] 2.5 Add the catalyst solution from step 2.4 to the reaction solution from step 2.3, and react at -97.5℃ for 10 min. The temperature rises slowly during polymerization, and the resulting slurry is uniformly dispersed in granular form.

[0127] 2.6 The reaction was terminated by adding 2 mL of cold ethanol. The product was then vacuum dried at 40 °C for 48 h to obtain branched butyl rubber with a yield of 80.5%. NMR analysis showed an unsaturation of 1.75 mol%. Gel permeation chromatography (GPC) analysis revealed a weight-average molecular weight of 467,191 g / mol, a number-average molecular weight of 116,018 g / mol, a molecular weight distribution of 4.02 (the bimodal distribution was not obvious, making it impossible to calculate the 4 MPa value), a 100% elongation of 2.4 MPa, a 300% elongation of 8.8 MPa, a tensile strength of 17.2 MPa, an elongation at break of 579%, and a tear strength of 71 kN / m.

[0128] 2.7 Weigh 15g of the branched butyl rubber obtained in step 2.6, add 80g of n-hexane, swell, stir and dissolve to obtain a rubber solution with a mass fraction of 15.8wt%.

[0129] 2.8 Add 4.5g of deionized water to the obtained gel solution and stir for 30min to obtain an emulsion.

[0130] 2.9 Under light-protected conditions at 40°C, a hexane solution of Br2 (0.23 mL of Br2 and 10 mL of hexane; the molar ratio of Br2 to the unsaturated double bond in the star-branched butyl rubber is 0.96:1) was added to the obtained emulsion, and the mixture was stirred for 10 min to obtain the brominated emulsion.

[0131] 2.10 Add 15g of NaOH solution (2wt% by mass, with a molar ratio of NaOH to bromine in the brominating agent of 0.84:1) to the obtained bromine-treated adhesive solution and neutralize for 5min to obtain a neutralized adhesive solution.

[0132] 2.11 Wash the obtained neutralized rubber solution with water until neutral, then add calcium stearate, epoxidized soybean oil and antioxidant 1135 (in the ratio of star-branched butyl rubber: calcium stearate: epoxidized soybean oil: antioxidant = 100: 2: 1.6: 0.05), and stir evenly.

[0133] 2.12 The solvent in the adhesive solution obtained in step 2.11 was removed at 98°C, and then the solution was dehydrated and dried at 100°C in a two-roll mill to obtain a brominated branched butyl rubber with a bimodal molecular weight distribution, wherein structure I is 38 mol%, structure II is 49 mol%, structure III is 13 mol%, unsaturation is 1.40 mol%, and functional bromine is 0.880 mol%.

[0134] Comparative Example 3

[0135] 3.1 At -90℃, 40g of isobutylene and 1.5g of isoprene were weighed and added to 170g of chloromethane to obtain a mixture.

[0136] 3.2 Prepare 50g of 1wt% SBS / chloromethane solution and pass HCl gas through it for 30min to obtain hydrochloric acid-acidified SBS / chloromethane solution.

[0137] 3.3 Add the hydrochloric acid-acidified SBS / chloromethane solution obtained in step 3.2 to the mixture obtained in step 3.1 to obtain the reaction solution.

[0138] 3.4 Weigh 0.3g of dichloroethylaluminum in n-hexane (mass fraction 20%) and add it to 12g of HCl in chloromethane (mass fraction 0.020wt%). Mix well and age at -97.5℃ for 30min to obtain the catalyst solution.

[0139] 3.5 Add the catalyst solution from step 3.4 to the reaction solution from step 3.3, and react at -97.5℃ for 10 min. The temperature rises slowly during polymerization, and the resulting slurry is uniformly dispersed in granular form.

[0140] 3.6 The reaction was terminated by adding 2 mL of cold ethanol, and the product was dried under vacuum at 40 °C for 48 h to obtain branched butyl rubber with a yield of 82.8%. NMR spectroscopy showed an unsaturation of 1.69 mol%. Gel permeation chromatography (GPC) analysis revealed a weight-average molecular weight of 738,497 g / mol, a number-average molecular weight of 190,716 g / mol, a molecular weight distribution of 3.87, and an indistinct bimodal distribution, making it impossible to calculate the 4 MPa value. The 100% elongation was 2.4 MPa; the 300% elongation was 8.5 MPa; the tensile strength was 17.5 MPa; the elongation at break was 552%; and the tear strength was 68 kN / m (test standard GB / T 528-2009).

[0141] 3.7 Weigh 30g of the branched butyl rubber obtained in step 3.6, add 170g of n-hexane, swell, stir and dissolve to obtain a 15wt% adhesive solution.

[0142] 3.8 Add 10g of deionized water to the obtained gel solution and stir for 30min to obtain an emulsion.

[0143] 3.9 Under light-protected conditions at 40°C, a hexane solution of Br2 (0.445 mL of Br2 and 15 mL of hexane; the molar ratio of Br2 to the unsaturated double bond in the star-branched butyl rubber is 0.93:1) was added to the obtained mixture, and the mixture was stirred for 10 min to obtain the brominated rubber solution.

[0144] 3.10 Add 30g of NaOH solution (2wt% by mass, with a molar ratio of NaOH to bromine in the brominating agent of 0.85:1) to the obtained bromine-treated adhesive solution and neutralize for 5min to obtain a neutralized adhesive solution.

[0145] 3.11 Wash the obtained neutralized rubber solution with water until neutral, then add calcium stearate, epoxidized soybean oil and antioxidant 1135 (according to the ratio of star-branched butyl rubber: calcium stearate: epoxidized soybean oil: antioxidant = 100: 2: 1.6: 0.05), and stir evenly.

[0146] 3.12 The solvent in the adhesive solution obtained in step 3.11 was removed at 98°C, and then the solution was dehydrated and dried at 100°C in a two-roll mill to obtain brominated branched butyl rubber with a bimodal molecular weight distribution, wherein structure I is 33 mol%, structure II is 52 mol%, structure III is 15 mol%, unsaturation is 1.49 mol%, and functional bromine is 0.893 mol%.

Claims

1. A method for preparing branched halogenated butyl rubber, characterized in that, include: S1) Mix the isomonoolefin, the conjugated diene, and the first diluent to obtain a reactant solution; The branching agent is mixed with the second diluent to obtain a branching agent solution; S2) First, the reactant solution and the branching agent solution are mixed and homogenized, then a molecular weight regulator is added, followed by a catalyst solution aged at low temperature to carry out a polymerization reaction, thereby obtaining branched butyl rubber; the catalyst solution includes Lewis acid, co-catalyst and aliphatic hydrocarbon; S3) Branched butyl rubber is mixed with aliphatic hydrocarbons to obtain a rubber solution; S4) Mix the adhesive solution and wetting agent evenly, and then mix and react it with the halogenating agent under light-protected conditions to obtain the reacted emulsion; S5) The reacted emulsion is mixed with an acid-binding agent to obtain a reaction solution; S6) After mixing the reaction solution with the additives, the solvent is removed to obtain branched halogenated butyl rubber; In step S1), the isomonoolefin has 4 carbon atoms; the conjugated diene has 5 carbon atoms; the molar ratio of the isomonoolefin to the conjugated diene is 35:1; the branching agent is a hydrochloric acid-acidified styrene-butadiene copolymer; the number average molecular weight of the styrene-butadiene copolymer is 80,000 to 300,000; the molar content of styrene in the styrene-butadiene copolymer is 60 mol%; and the mass of the branching agent is 1 wt% to 2 wt% of the mass of the isomonoolefin. The Lewis acid is selected from one or more of dichloroethylaluminum, dichlorobutylaluminum, dichlorodiethylaluminum, dichlorodibutylaluminum, titanium tetrachloride, and boron trifluoride; the co-catalyst is selected from water or hydrogen chloride; the aliphatic hydrocarbon is a nonpolar and / or weakly polar aliphatic hydrocarbon; the molar ratio of the Lewis acid to the co-catalyst is (6-8):1; the molar ratio of the Lewis acid to the isomonoolefin is 1:(1400-1500). In step S1), the first diluent and the second diluent are each independently selected from one or more of chloromethane, dichloromethane, n-hexane, cyclohexane, isohexane, and isopentane; the mass concentration of the isomonoolefin in the reactant solution is 18% to 30%. In step S2), the molecular weight regulator is selected from olefins with 6 carbon atoms; the molecular weight regulator is a monoolefin; the mass of the molecular weight regulator is 0.05 wt% to 0.5 wt% of the mass of the isomonoolefin. The low-temperature aging temperature is -99℃ to -65℃; the low-temperature aging time is 10 to 30 minutes. The polymerization reaction temperature is -99℃ to -90℃; the polymerization reaction time is 10 to 20 minutes; after the polymerization reaction is completed, a terminator is added to terminate the reaction, and the reaction product is obtained. After drying, branched butyl rubber is obtained. The terminating agent is selected from one or more of ethanol, methanol, isopropanol, glycerol and triethylene glycol; the drying is vacuum drying; the drying temperature is 25℃~55℃, and the drying time is 45~50h; In step S3), the viscosity of the adhesive solution is 250–650 cp; the content of branched butyl rubber in the adhesive solution is 15–25 wt%. In step S4), the adhesive is first mixed with water to obtain an emulsion, and then the emulsion is mixed evenly with a wetting agent; the mass ratio of water to adhesive is (5-10):

100. The sizing agent is selected from one or more of fatty alcohols, fatty alcohol esters, epoxidized esters, epoxidized soybean oil, epoxidized linseed oil, alkali metal carboxylates, alkaline earth metal carboxylates, alkali metal stearates, alkaline earth metal stearates, metal oxides and metal hydroxides; the mass ratio of the sizing agent to the branched butyl rubber is (0.5-10):

100. The mixing reaction temperature in step S4) is 30℃~40℃; the mixing reaction time is 10~20min; In step S5), the molar ratio of the acid-binding agent to the halogen element in the halogenating agent is (0.7-0.8):1; The additives are selected from antioxidants and stabilizers; The mass ratio of the antioxidant to the stabilizer is 1:(50-100); The mass ratio of the additive to the branched butyl rubber is (3-4):100; The halogenating agent in step S4) is selected from one or more of the following: a nonpolar or weakly polar aliphatic hydrocarbon solution of Cl2, a nonpolar or weakly polar aliphatic hydrocarbon solution of Br2, HCl, HBr, NaClO, and NaBrO3; the molar ratio of the halogen element in the halogenating agent to the unsaturated bond in the branched butyl rubber is (0.5-2):

1. The acid-binding agent is selected from one or more of alkali metal hydroxides, strong base weak acid salts, and bisulfites; the antioxidant is selected from one or more of antioxidant 1135, antioxidant 1076, and antioxidant 1010; and the stabilizer is selected from stearate and / or epoxidized soybean oil.

2. The branched halogenated butyl rubber prepared by the preparation method of claim 1.

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