CN102382223A - Method for preparing brominated butyl rubber - Google Patents
Method for preparing brominated butyl rubber Download PDFInfo
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- CN102382223A CN102382223A CN2011102660483A CN201110266048A CN102382223A CN 102382223 A CN102382223 A CN 102382223A CN 2011102660483 A CN2011102660483 A CN 2011102660483A CN 201110266048 A CN201110266048 A CN 201110266048A CN 102382223 A CN102382223 A CN 102382223A
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Abstract
The invention discloses a method for preparing brominated butyl rubber, and belongs to the technical field of brominated butyl rubber. The method comprises the following steps that raw materials of a brominated butyl rubber solution and a bromine solution are added into a reinforced mixing reactor according to a ratio and undergo a replacement reaction of bromine on an allyl group, wherein stay time of the raw materials in the reinforced mixing reactor is controlled; and the products obtained by the previous step are fed into a stirring tank, are washed, are added with a stabilizing agent, are subjected to solvent flash evaporation, and are dried to form brominated butyl rubber products. The method realizes high-efficiency, large-scale, continuous and stable preparation of a brominated butyl rubber product having bromine content of 1.0 to 2.3 wt% and unsaturation of 0.6 to 1.6%, greatly reduces stay time, greatly reduces a reactor volume, and reduces a total operation cost.
Description
Technical field
The present invention relates to the method that a kind of solution halogen process prepares brominated butyl rubber; Comprise its reaction process and device; Also relate to the expansion application of microcosmic hybrid technology in the halogenation substitution reaction fast such as high-gravity technology, microreactor technology, belong to the brominated butyl rubber technical field.
Background technology
Halogenation is to one of best method of modifying of butyl rubber.Brominated butyl rubber (BIIR) is exactly that butyl rubber (IIR) is by the halogenated product of bromo element; It had both possessed excellent resistance to air loss, thermotolerance, resistance to deterioration, erosion resistance and the electrical insulating property of IIR; Remedied again IIR curability, tackiness, and other rubber compatibility aspect shortcoming, have widely at aspects such as high-quality radial, medical grade rubbers and to use.
The bromination reaction of IIR occurs on the undersaturated isoprene, has replacement and two kinds of forms of addition on the allyl group.The preparation of halogenated butyl rubber has the mixing halogenation of dried glue and two kinds of methods of solution halogenation usually.The mixing halogen process of dried glue is to adopt mill or Banbury mixer that bromizating agent or bromine carrier are added butyl rubber; Bromizate agent and under heating condition, emit bromine and butyl rubber generation bromination reaction generation brominated butyl rubber; This method is not removed because of unreacted bromizating agent and its sub product and is remained in the rubber; Influence the performance of sizing material, unstable product quality, thereby the solution halogen processes of using in the current industrial production more.The solution halogen process adds the halogenating agent halogenation from butyl rubber slurry, and through the neutralization washing, solvent removal obtains halogenated butyl rubber again, obtains product through further handling again.Chinese patent " halogenated butyl rubber of low-halogen-content " is offshore company discloses halogenated butyl rubber in the patent of China's registration basic preparation prescription and a production technique (CN97117370.2)." bromination reaction technique for butyl rubber " also introduced related methods of production and technical process in (CN200810059404.2)." working method of brominated butyl rubber " introduced in (CN200810059405.7) and carried out the medium transmission earlier, then the preparation thinking of bromination reaction.In general; Existing production technique be limited in the short period of time can not the Rapid Realization raw material even microcosmic mix; Realize thorough mixing, improve the Br utilization ratio by prolonging reaction time, do not bring into play this and react characteristics fast, and the prolongation of the residence time can cause addition reaction to take place in a large number; Adopt the whole bag of tricks to suppress the generation of addition reaction, cause many difficulties.
High-gravity technology is to utilize the hypergravity environment more much bigger than earth gravity acceleration stresses technological to a kind of process intensification that transmits and mixing process is strengthened.Under the hypergravity environment; Great shear forces is torn into film, the silk of micron to nano grade with liquid and is dripped; Produce huge and phase interface fast updating; Make the mass transfer coefficient and the mixing velocity force of gravity of mass transfer and micro mixing improve 1～3 one magnitude after the match, greatly strengthened mass transfer and micro mixing.Open in patents such as one Chinese patent application numbers 91109255.2,91111028.3,200520100685.3,01268009.5,02114174.6,200510032296.6 about the hypergravity reaction unit; Comprise hypergravity swivel arrangements such as RPB, deflector type, helical channel formula, rotating compact disc formula, CN 200410042631.6 also disclose a kind of fixed-rotor-type hypergravity swivel arrangement.The applicant is obtaining impressive progress aspect the applied research of high-gravity technology; Be extended to chemical reaction process to this technology from separation, desorption process; As successful be applied to precipitin reaction; Reaction process such as preparation nano particle (application number: 95105344.2,95105343.4 etc.) and neutralization reaction, carbonating, phase inversion (application number: 200410037885.9), particularly in one Chinese patent application numbers 200710110412.0, disclose a kind of hypergravity polymerization method of butyl rubber, be applied to the hypergravity reaction technology rapid reaction process of macromole elastomeric material; Utilized the very big reinforcement of supergravity reactor just to the microcosmic mixing rate; Microcosmic mixing time and reaction times are adapted, and the reaction process that makes this severe reaction conditions of cationoid polymerisation, speed be exceedingly fast, be prone to the generation side reaction is effectively regulated and control, and it is low to reach cost; Energy consumption is low, the outstanding effect that production efficiency is high.In addition; New hybrid conversion units such as microreactor, double tube reactor, static mixer, venturi-type reactor drum, shooting flow type reactor also have wide influence at contemporary chemical research and production field, and people have darker cognition to these novel reactors in the strengthening effect aspect mixing and the mass transfer.As: Chinese patent CN 200480041082.9,200810228634.7,201010150003.5 etc. discloses the application and the improvement thereof of micro passage reaction.The technology of mixing of reinforcement microcosmic such as high-gravity technology, microreactor technology and mass transfer is applied to the process that the bromination substitution reaction prepares brominated butyl rubber, does not appear in the newspapers at present.In view of this; The applicant proposes that new hybrid conversion units such as supergravity reactor, microreactor, double tube reactor, static mixer, venturi-type reactor drum, shooting flow type reactor are applied to brominated butyl rubber and prepares process on the basis to bromination substitution reaction and device further investigation thereof.
Summary of the invention
The present invention proposes enhancing mixed reactor drums such as supergravity reactor, microreactor, double tube reactor, static mixer, venturi-type reactor drum, shooting flow type reactor are applied to the preparation process of brominated butyl rubber; In conjunction with butyl rubber bromination reaction process outstanding characteristics such as controlled, the microcosmic good mixing effect of the residence time of material in characteristics and these mix reaction equipment fast, corresponding working method and technology have been proposed.The preparation process can be carried out continuously, and production efficiency significantly improves, and is easy and simple to handle, and running steadily can prepare that bromine content height, degree of unsaturation loss are little, the brominated butyl rubber product of good mechanical property.
The method for preparing brominated butyl rubber provided by the present invention is characterized in that, may further comprise the steps:
A puts into solvent with butyl rubber, and swelling obtains uniform sol A after stirring under the room temperature; The liquid bromine is diluted with homogeneous solvent, form solution B; Heat in the charging feed jar separately;
B delivers into the enhancing mixed reactor drum continuously with Sol A, solution B, mixes and reacts;
The material that c leaves the enhancing mixed reactor outlet gets in the stirring tank fill NaOH solution or other basic solns with termination reaction, or in another stirring tank, continues behind reaction 10s～300s the stirring tank termination reaction that input again fills basic soln;
Behind the d reaction terminating, using deionized water cleaning products to pH value is 7; Add stablizer commonly used, flashed solvent, oven dry product.
In step a, the raw material butyl rubber has the degree of unsaturation of 1.0-2.5% (mol), can be the finished product butyl rubber, also in the butyl rubber industrial production without the slurry soln of removing solvent.Solvent can be selected neat solvents such as hexane, tetracol phenixin for use, perhaps in the main solvent of neat solvents such as above hexane, tetracol phenixin, adds Electron Affinities solvents such as trichloromethane, methylene dichloride and carries out to accelerate substitution reaction, and add-on is 5～40% of a solvent TV.In the material A, IIR mass percent 5～25%, preferred 10～20%.The NaClO solution that also can add 0.5～3 times of the molar weight of used bromine in the A colloidal sol is made oxygenant, so that HBr is converted into bromine again.The concentration of bromine is 7.80～46.80g/l in the solution B.The enhancing mixed reactor drum is selected from supergravity reactor, microreactor, double tube reactor, static mixer, venturi-type reactor drum, shooting flow type reactor etc.
In step b, the material A in the reactor drum, the ratio of B are remained: lkg IIR is with 10～65gBr2, preferred 25～60g.The mode that material A, B inject through two material spargers respectively simultaneously, or adopt two kinds of solution to carry out entering in the supergravity reactor again after macroscopical pre-mixing.Macroscopic view premix mode comprises known static mixer, tube mixer, mixing stirring device etc.Mixing and reaction are if use supergravity reactor, the hypergravity level 5～450g (g is universal gravity constant) that then uses.
In step c, if prolong reaction time after going out reactor drum, the time is 10s～300s.Stopping used basic soln consumption makes termination back pH=8～14 get final product the stirring residence time 30s～20min of termination procedure.
In step b, c, temperature of charge is controlled at 20～60 ℃.
For realizing the object of the invention; Implement the required device of above-mentioned steps and mainly be made up of equipment such as novel reactor (comprising new hybrid conversion units such as supergravity reactor, microreactor, double tube reactor, static mixer, venturi-type reactor drum, shooting flow type reactor), stirring tank, hydronics, delivery instrument, key equipment wherein is a novel reactor.
The supergravity reactor characteristic is: be included in the airtight housing rotatable parts are housed; Have liquid import and export and gas import and export on the housing; Liquid-inlet is provided with the liquid distributor that extends in the rotor center cavity; Two bursts of liquid chargings separately separately also can be provided with the sparger of being with premix.As reference of the present invention; About the detailed introduction of supergravity reactor characteristics can be with reference to following technical information and document, like old " high-gravity technology and application-a new generation reacts and stripping technique " of building work such as peak of inventor herein, Chemical Industry Press; Chinese patent ZL95107423.7; ZL92100093.6, ZL91109225.2, ZL95105343.4 etc.Supergravity reactor of the present invention is selected from hypergravity RPB, deflector type, helical channel, rotating compact disc formula or fixed-rotor-type hypergravity swivel arrangement etc., preferred hypergravity RPB.
Other novel reactor is known microreactor, double tube reactor, static mixer, venturi-type reactor drum, shooting flow type reactor etc. in structure aspects.
Whether substitution reaction device of the present invention, premixed device use and structure designs according to the reactor drum of service condition and selection.Two strands of materials are premix not, injects through two material spargers simultaneously, through collision or directly be distributed in the reactor drum; Also can adopt two kinds of solution to carry out entering in the supergravity reactor after macroscopical pre-mixing, macroscopical premix mode comprises known static mixer, tube mixer, mixing stirring device etc. again.The premixed device discharge port is connected with the liquid distributor feed end of reactor drum, and material is able to get into supergravity reactor.
Substitution reaction device of the present invention, the stirring tank that wherein relates to are known pattern in each.
Bromination reaction speed is very fast, and under the effect of electrophilic reagent, this substitution reaction is faster, if within a short period of time can not be with butyl rubber and Br
2Realize that the molecular level microcosmic mixes, then substitution product HBr and butyl rubber addition reaction take place and can take place in a large number, cause the product degree of unsaturation to descend significantly, have a strong impact on quality product; Oxygenants such as adding NaClO can suppress the generation of addition to a certain extent, but the long degree of unsaturation that still can make of reaction times has no small loss.Therefore, how to make Br
2Even with the butyl rubber short mix, reduce reaction time, be a key point of reaction process; Adding electrophilic reagent also is a key with the speed of accelerating substitution reaction.
If can when be mixed into the controlling factor of process, make and realize in the extremely short time in the reaction unit that initial rubber mixes with the quick microcosmic of Br, realizes the coupling of thorough mixing required time and reaction required time; When substitution reaction speed becomes the controlling factor of process, accelerate speed of reaction through the adding of the electric solvent of parent; So just realized the coupling of reactor drum and reaction characteristics; The situation of reaction time prolongation then can not appear making; Also can avoid a large amount of generations of side reaction (addition); Reduce the loss of rubber degree of unsaturation, can or use other method to contain addition reaction less simultaneously as far as possible, significant to the suitability for industrialized production of BIIR.
Advantage of the present invention: the present invention proposes and new hybrid conversion units such as supergravity reactor are applied to brominated butyl rubber prepare process, in conjunction with butyl rubber bromination reaction process characteristics and the residence time of material in these reactor drums is short and outstanding characteristics such as microcosmic good mixing effect.After adopting present method; But high-level efficiency, in enormous quantities, continuously, stable bromine content 1.0～2.3 (wt%), degree of unsaturation 0.6～1.6%, the brominated butyl rubber product that mechanical property is high prepared; Reaction time shortens more than 20～30 times, has significantly reduced preparation cost.
Description of drawings
Fig. 1 is the brominated butyl rubber preparation flow figure that goes out the direct termination reaction of reactor drum of the present invention;
Fig. 2 is the brominated butyl rubber preparation flow figure that goes out the reactor drum direct reaction of the present invention;
1 butyl rubber solution A storage tank wherein, 2 pumps, 3 under meters, 4 bromine solutions B storage tanks, 5 pumps, 6 enhancing mixed reactor drums, 7 contain the stirring tank of basic soln, 8 circulation fluid storage tanks, 9 circulation fluid circulation power equipment, 10 stirring tanks, 11 power-equipments.
Embodiment
Further specify the method for preparing brominated butyl rubber under the reinforcement microcosmic mixing condition provided by the invention below, but therefore the present invention does not receive any restriction.
The preferred embodiment of the present invention realizes in technical process as illustrated in fig. 1 and 2 and reaction unit, below mainly is that enforcement of the present invention is introduced in representative with the supergravity reactor, but the present invention is not limited only to this reactor drum.The invention is not restricted to listed embodiment, also should be included in other any known changes in the butyl rubber bromination device and processing range in the novel reactor that the present invention protects.
As shown in Figure 1, the device of present method comprises butyl rubber solution A storage tank 1, bromine solutions B storage tank 4, liquid premix sparger and enhancing mixed reactor drum 6 and stirring tank 7.Wherein: the raw material A in the storage tank 1 is through pump 2 outputs, and a part refluxes in jar 1, and a part of material A is input liquid premix sparger or sparger after under meter 3 meterings; Material B in the storage tank 4 is by pump 5 outputs and metering input liquid premix sparger or sparger; A further mixes in reactor drum with the even spray of B premix or collision back and reacts.The discharge port of reactor drum connects stirring tank 7, is used for termination reaction, and stirring tank is known structure.Reaction terminating after the deionized water repetitive scrubbing, add stablizer, solvent is deviate from, is dried, and obtains the brominated butyl rubber product.Accompanying drawing 2 is applied to out the situation that the reactor drum continued prolongs the reaction times, and Fig. 1 difference is that enhancing mixed reactor drum 6 and 7 of stirring tanks have increased the stirring tank 10 that prolongs reaction time, reach power-equipment 11.
In the above-mentioned reaction process flow process, the reaction and before process guarantee temperature with circulation fluid, comprise circulation fluid storage tank 8 shown in Fig. 1 or Fig. 2, circulation fluid circulation power equipment 9, each still jar and reactor jacket, pipeline heat insulation etc. in interior temperature safeguards system.
In the above-mentioned reaction process flow process, 6 representatives of enhancing mixed reactor drum comprise new hybrid conversion units such as supergravity reactor, microreactor, double tube reactor, static mixer, venturi-type reactor drum, shooting flow type reactor.If use supergravity reactor, then preferably adopt the hypergravity rotating packed-bed reactor, be filled with the wire mesh packing of sintering or compression moulding on its rotor.
Adopt device shown in Figure 1, reactor drum is the hypergravity RPB.
The hexane solution A 8000ml of butyl rubber is joined in the storage tank 1, and the volume(tric)fraction that the A solution dichloromethane accounts for solvent is 30%, virgin rubber degree of unsaturation 1.82%, and the glue mass concentration is 10%, adds the aqueous sodium hypochlorite solution 400ml of 29.15g/l; The hexane solution B 900ml of liquid bromine is joined in the storage tank 4 bromine elemental concentration 31.2g/l; Material in storage tank 1 and storage tank 4 is heated to 45 ℃ respectively; Respectively two strands of materials are sent into the liquid premix sparger of supergravity reactor with volume ratio at 10: 1 through pump and volumetric flow meter 3, peristaltic pump 5, mixture is sprayed in the rotor packing layer, further mix and react by liquid distributor; Material gets into stirring tank 7 through the RPB liquid exit.Regulate the spinner velocity of hypergravity rotating packed-bed reactor, making its hypergravity level is 8.94g, and the temperature maintenance of reaction system is at 45 ℃.The supergravity reactor outlet material is directly stopped by 1.5 (wt%) NaOH solution in stirring tank 7; PH=8～14 got final product after consumption made and stops; Subsequently product with deionized water is washed the neutrality to pH, add epoxy soybean oil, calcium stearate used as stabilizers, flash distillation removes and desolvates.The bromine content that obtains the brominated butyl rubber product is 1.81 (wt%), degree of unsaturation 1.40%.
Technical process and step are with embodiment 1, and material proportion is also identical, and different is that used aqueous sodium hypochlorite solution concentration is 88.00g/l; The horizontal 20.12g of hypergravity; 30 ℃ of temperature, the bromine content of gained brominated butyl rubber product are 1.91 (wt%), degree of unsaturation 1.46%.
Technical process and step are with embodiment 1, and material proportion is also identical, and that different is the horizontal 55.89g of hypergravity, and the bromine content of gained brominated butyl rubber product is 1.93 (wt%), degree of unsaturation 1.40%.
Adopt the technical process shown in the accompanying drawing 2, the virgin rubber mass concentration is 15%, and solvent is a tetracol phenixin; To account for the volume(tric)fraction of solvent be 40% to methylene dichloride among the A, bromine solutions B concentration 46.8g/l, and the volume of material ratio is 8: 1; Aqueous sodium hypochlorite solution is 29.15g/l, 60 ℃ of temperature of reaction, the horizontal 450g of hypergravity; Other are with embodiment 1; Get into stirring tank 7 the supergravity reactor outlet material reacts 60s again in stirring tank 10 after and stop, the bromine content of gained brominated butyl rubber product is 2.26 (wt%), degree of unsaturation 1.06%.
Technical process and step are made solvent for pure hexane with embodiment 1 among the A, do not add the chlorine bleach liquor; Bromine solutions B concentration 46.78g/l; The horizontal 67.63g of hypergravity, 20 ℃ of temperature, all the other conditions are all with embodiment 1; The bromine content of gained brominated butyl rubber product is 1.25 (wt%), degree of unsaturation 1.07%.
Technical process and step be with embodiment 1, the horizontal 181.09g of hypergravity, and 45 ℃ of temperature, all the other conditions are all with embodiment 5, and the bromine content of gained brominated butyl rubber product is 1.57 (wt%), degree of unsaturation 0.98%.
Technical process and step are with embodiment 4, and the virgin rubber mass concentration is 25%, do not contain methylene dichloride among the A; Aqueous sodium hypochlorite solution concentration 22.00g/l, bromine solutions B concentration 46.78g/l, the volume of material ratio is 5: 1; 45 ℃ of temperature of reaction, the horizontal 67.63g of hypergravity, the supergravity reactor outlet material stops after reacting 10s again; The bromine content of gained brominated butyl rubber product is 1.54 (wt%), degree of unsaturation 1.12%.
Technical process and step are made solvent for pure hexane with embodiment 4 among the A, rubber quality concentration 10%; Do not add the chlorine bleach liquor, bromine solutions B concentration 46.78g/l, the horizontal 67.63g of hypergravity; 45 ℃ of temperature; The supergravity reactor outlet material stops after reacting 60s again, and the bromine content of gained brominated butyl rubber product is 1.83 (wt%), degree of unsaturation 1.02%.
Technical process and step are with embodiment 8; Conditions such as material proportion, temperature, hypergravity level are also like embodiment 8; The supergravity reactor outlet material stops after reacting 300s again, and the bromine content of gained brominated butyl rubber product is 1.89 (wt%), degree of unsaturation 0.63%.
Technical process and step are with embodiment 1, and the virgin rubber mass concentration is 5%, contain the methylene dichloride of volume(tric)fraction 5% among the A; Bromine solutions B concentration 7.8g/l, the volume of material ratio is 12: 1, aqueous sodium hypochlorite solution concentration 22.00g/l; The horizontal 67.63g of hypergravity; All the other are all with embodiment 1, and the bromine content of gained brominated butyl rubber product is 1.93 (wt%), degree of unsaturation 1.35%.
Adopt device shown in Figure 1, reactor drum 6 is micro passage reactions.Each condition that adopts consistent with embodiment 1, reactor outlet material is directly stopped by 1.5 (wt%) NaOH solution in stirring tank 7, subsequently product with deionized water is washed to pH neutrally, adds epoxy soybean oil, calcium stearate used as stabilizers, flash distillation removes and desolvates.The bromine content that obtains the brominated butyl rubber product is 1.98 (wt%), degree of unsaturation 1.30%.
Embodiment 12
Adopt device shown in Figure 1, reactor drum 6 is double tube reactors.Each condition that adopts consistent with embodiment 1, reactor outlet material is directly stopped by 1.5 (wt%) NaOH solution in stirring tank 7, subsequently product with deionized water is washed to pH neutrally, adds epoxy soybean oil, calcium stearate used as stabilizers, flash distillation removes and desolvates.The bromine content that obtains the brominated butyl rubber product is 1.86 (wt%), degree of unsaturation 1.35%.
Embodiment 13
Adopt device shown in Figure 2, reactor drum 6 is static mixer formula reactor drums.Reactor outlet material reacts 120s again in stirring tank 10; Then stop by 1.5 (wt%) NaOH solution in the stirring tank 7; Other adopts each condition consistent with embodiment 1; Subsequently product with deionized water is washed the neutrality to pH, add epoxy soybean oil, calcium stearate used as stabilizers, flash distillation removes and desolvates.The bromine content that obtains the brominated butyl rubber product is 2.11 (wt%), degree of unsaturation 1.28%.
Embodiment 14
Adopt device shown in Figure 1, reactor drum 6 is venturi-type reactor drums.Reactor outlet material reacts 120s again in stirring tank 10; Then stop by 1.5 (wt%) NaOH solution in the stirring tank 7; Other adopts each condition consistent with embodiment 1; Subsequently product with deionized water is washed the neutrality to pH, add epoxy soybean oil, calcium stearate used as stabilizers, flash distillation removes and desolvates.The bromine content that obtains the brominated butyl rubber product is 1.75 (wt%), degree of unsaturation 1.25%.
Embodiment 15
Adopt device shown in Figure 1, reactor drum 6 is shooting flow type reactors.Reactor outlet material reacts 60s again in stirring tank 10; Then stop by 1.5 (wt%) NaOH solution in the stirring tank 7; Other adopts each condition consistent with embodiment 1; Subsequently product with deionized water is washed the neutrality to pH, add epoxy soybean oil, calcium stearate used as stabilizers, flash distillation removes and desolvates.The bromine content that obtains the brominated butyl rubber product is 1.73 (wt%), degree of unsaturation 1.34%.
Claims (10)
1. a solution halogen process prepares the method for brominated butyl rubber, it is characterized in that, may further comprise the steps:
A puts into solvent with butyl rubber, and swelling obtains uniform colloidal solution A after stirring under the room temperature; The liquid bromine is diluted with homogeneous solvent, form solution B; Heat in the charging feed jar separately;
B delivers into the enhancing mixed reactor drum continuously with solution A, solution B, mixes and reacts;
The material that c leaves the enhancing mixed reactor outlet gets in the stirring tank fill NaOH basic soln or other basic solns with termination reaction, or in another stirring tank, continues behind reaction 10s～300s the stirring tank termination reaction that input again fills basic soln;
Behind the d reaction terminating, using deionized water cleaning products to pH value is 7; Add stablizer commonly used, flashed solvent, oven dry product.
2. according to the method for claim 1, it is characterized in that the enhancing mixed reactor drum is selected from supergravity reactor, microreactor, double tube reactor, static mixer, venturi-type reactor drum, shooting flow type reactor.
3. according to the method for claim 1, it is characterized in that said raw material butyl rubber is that degree of unsaturation is the finished product butyl rubber of 1.0-2.5% or the butyl rubber slurry in the industrial production.
4. according to the method for claim 1, it is characterized in that described solvent is selected from hexane, tetracol phenixin, perhaps in the main solvent of above hexane or tetracol phenixin, add the Electron Affinities solvent, add-on is 5～40% of a solvent TV.
5. according to the method for claim 1, it is characterized in that 0.5～3 times the NaClO solution that also adds used bromine molar weight in the A solution is made oxygenant.
6. according to the method for claim 1, it is characterized in that in step c, the used basic soln consumption of termination reaction makes and stops back pH=8～14, the stirring residence time 30s～20min of termination procedure.
7. according to the method for claim 1, it is characterized in that the temperature of reaction of step b and c is controlled at 20～60 ℃.
8. according to the method for claim 1, it is characterized in that, in the solution A, butyl rubber mass percent 5～25%, the concentration of bromine is 7.80～46.80g/l in the solution B.
9. according to the method for claim 1, it is characterized in that among the step b, the solution A in the enhancing mixed reactor drum, the ratio of B are kept: the 1kg butyl rubber is with 10～65g Br
2
10. according to the method for claim 2, it is characterized in that when using supergravity reactor, then the hypergravity level is 5～450g.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102775541A (en) * | 2012-08-07 | 2012-11-14 | 浙江信汇合成新材料有限公司 | Synthesis technique of brominated butyl rubber |
| CN103333290A (en) * | 2013-07-23 | 2013-10-02 | 蒲城瑞鹰新材料科技有限公司 | Continuous production technology for microchannel reactor of hydrogenated butadiene-acrylonitrile rubber |
| CN103467637A (en) * | 2013-09-29 | 2013-12-25 | 浙江信汇合成新材料有限公司 | Chlorinated butyl rubber production process |
| CN103467636A (en) * | 2013-09-29 | 2013-12-25 | 浙江信汇合成新材料有限公司 | Production technology of brominated butyl rubber |
| CN103665229A (en) * | 2012-09-10 | 2014-03-26 | 中国石油化工股份有限公司 | Method of preparing butyl rubber liquor and application of method |
| CN104479059A (en) * | 2014-12-30 | 2015-04-01 | 安徽美祥实业有限公司 | Method for preparing brominated butyl rubber |
| CN104941558A (en) * | 2015-06-18 | 2015-09-30 | 天津大学 | Jet flow flash condensation pot for continuous preparation of hydrogenated nitrile rubber |
| CN105218719A (en) * | 2014-06-16 | 2016-01-06 | 中国石油化工股份有限公司 | The method preparing halogenated butyl rubber and the halogenated butyl rubber obtained thus |
| CN105294903A (en) * | 2014-05-27 | 2016-02-03 | 北京化工大学 | Preparation method for brominated butyl rubber |
| CN105820281A (en) * | 2015-01-09 | 2016-08-03 | 中国石油化工股份有限公司 | Method for preparing halogenated polymer |
| CN110642965A (en) * | 2019-10-30 | 2020-01-03 | 山东京博中聚新材料有限公司 | Preparation method of brominated butyl rubber |
| CN112142884A (en) * | 2020-09-01 | 2020-12-29 | 中北大学 | Brominated butyl rubber synthesis device and process |
| CN115232238A (en) * | 2022-09-21 | 2022-10-25 | 山东海化集团有限公司 | Method for preparing brominated butyl rubber by using microchannel reactor |
| CN114752006B (en) * | 2022-05-23 | 2023-09-01 | 山东京博中聚新材料有限公司 | Nano material composite brominated butyl rubber and preparation method thereof |
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| 张扬等: "溴化反应条件对溴化丁基橡胶微观结构的影响", 《石油化工高等学校学报》 * |
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| CN110642965A (en) * | 2019-10-30 | 2020-01-03 | 山东京博中聚新材料有限公司 | Preparation method of brominated butyl rubber |
| CN112142884A (en) * | 2020-09-01 | 2020-12-29 | 中北大学 | Brominated butyl rubber synthesis device and process |
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