CN105777966A - Technology for directly producing brominated butyl rubber through solution method - Google Patents
Technology for directly producing brominated butyl rubber through solution method Download PDFInfo
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Abstract
The invention belongs to the technical field of catalysts, and relates to a technology for directly producing brominated butyl rubber through a solution method.The technology sequentially comprises the three steps of butyl rubber synthesis (I) through the solution method, chloromethane removal (II) and butyl rubber bromination (III), wherein brominated butyl rubber is produced through a butyl rubber bromination reaction of the solution method, the molecular weight of the brominated butyl rubber is 50,000 g/mol-500,000 g/mol, the molecular weight distribution is 1.1-4.0, and the brominated butyl rubber combined bromine content is 1.0-2.8%.In an alkane and chloromethane mixed solvent, on the low-temperature condition, a butyl rubber solution is produced through isobutene and isoprene positive ion copolymerization of the solution method, the butyl rubber solution is subjected to chloromethane removal and the brominated butyl rubber is obtained through a bromination stage.The technology has the advantage that the solvent switching or rubber dissolution procedure needed by brominated butyl rubber preparation through the slurry process technology is avoided.
Description
Technical field
The invention belongs to catalyst technical field, the technique that the technique relating to preparing brominated rubber, particularly solwution method are directly produced brombutyl.
Background technology
Brombutyl (bromobutylrubber) be the butyl rubber of saturation scarcely in aliphatic hydrocarbon (such as hexane) with the product of bromine reaction.This reaction is to complete when strict control, and therefore in butyl rubber molecules, original double bond is maintained, and bromine is to combine in pi-allyl mode.
At present, Exxon and Lanxess Corporation prepare brombutyl production technology by slurry process technology and all include the synthesis of butyl rubber, the elimination of chloromethanes and unreacted monomer, the parts such as rubber dissolves in good solvent, the recovery of bromination and the neutralization after bromination and washing and rubber.
The synthesis of butyl rubber
Butyl rubber carries out cationic polymerization production by isobutene., isoprene under the catalyst such as Friedel-Craft exist.Typical reaction is to make catalyst with aluminum chloride, makes solvent with chloromethanes, and isobutene. (95-98%), isoprene (2-5%) are configured to the solution of the chloromethanes of 25%, and polyreaction occurs rapidly.Reaction heat is taken away by the liquid ethylene evaporation in the cooling tubulation passing into polymeric kettle.After polymerization, the slurry containing butyl rubber microgranule is derived from polymeric kettle top.Low temperature rapid polymerization and reactant viscosity height are the two major features that butyl rubber produces, polyreaction generally carries out at about-100 DEG C, to control extremely fast exothermic reaction (raw material contacts, and polyreaction just occurs immediately) with catalyst one, prepare high molecular weight products.For prepared high molecular weight products, raw material isobutene. must have significantly high purity, and n-butene content requirement is less than 0.5%, and isoprene purity should be greater than 94%, and the water content of chloromethanes and monomer must be very low.
Chloromethanes and the elimination of unreacted monomer, sedimentation and dissolving
The cooling butyl rubber slurry in enpara (preferred chloromethanes) from polymer reactor is transported to equipped with in the stirred tank of high-temperature water vapor.Alkyl chloride diluent and unreacted monomer is flashed off from top.Butyl rubber slurry and water deliver to settling tank carries out settlement separate.Butyl rubber after sedimentation is dissolved in hexane solution.
The bromination stage
Brombutyl, bromine is first diluted in alkane solvent, injects in the reactor equipped with butyl rubber glue by multiple spot, high-speed stirred, and reaction temperature is typically in 20～150 DEG C, and owing to being react between liquid phase, Stress control is not key factor.
Neutralize the washing stage
Glue after bromination sodium carbonate neutralizes, and then washes with water.Owing to washing process forms suspension, glue is dispersed into drop, increases the contact area of glue and aqueous solution, be beneficial to the HCl that neutralizes from glue diffusion inside to cleaning mixture with the interface of glue, thus reaching the purpose fully neutralized.The pH value of neutralization procedure is between 3～4, and the time that neutralizes was less than 10 minutes.Stabilizer is added, such as calcium stearate, epoxy soybean oil, antioxidant etc. after washing.Enter recovery process.Recovery process and conventional butyl rubbers are without much differences.Difference is only the use of solvent higher than the boiling point of chloromethanes as hexane, so the condition of recovered temperature and stripping monomer requires relatively stricter, the quantity of steam of consumption is bigger.
Additionally, dry process brombutyl, in rubber, namely add organic bromating agent on a mill until, such as N-bromo-succinimide or N-bromo acetamide, then elastomeric compound is placed in calorstat and is heated under the decomposition temperature of bromating agent.This method belongs to free radical addition course.But this method easily makes butyl rubber processing mixing middle degraded, thus bringing the difficulty in the course of processing, nor can prepare uniform and stable halogenated butyl rubber.
The production method of butyl rubber mainly has slurry process and solwution method, slurry process technology is prepared butyl rubber and halogenated butyl rubber and is monopolized by EXXON company of the U.S. and Lanxess Corporation of Germany. and solwution method technology prepares the exploitation of butyl rubber Russia Tao Liyadi synthetic rubber company, and current solwution method technology of passing through directly is prepared brombutyl and be have not been reported.
Chinese patent application CN102702409A, disclose a kind of solwution method and prepare the technique that butyl rubber is directly produced halogenated butyl rubber, this technique includes four steps in order, respectively: solwution method butyl rubber synthesis (I), chloromethanes elimination (II), precipitate and separate (III) and halogenating butyl rubber (IV)；The molecular weight 50,000g/mol of halogenated butyl rubber, molecular weight distribution is 1.1～4.0, and halogenated butyl rubber combined chloride content is 1.1%～1.9%, is 1.0%～2.8% in conjunction with bromine content.
Butyl rubber synthesis (I): under cryogenic conditions ,-100 DEG C～-50 DEG C, the mixed solvent of alkane and the composition of chloromethanes is the solvent that cationic polymerization reacts, and wherein alkane and chloromethanes mass ratio are 50:50～80:20；In the solvent of cationic polymerization, adding isobutene. and isoprene monomer, wherein isobutene. is 98:2～85:15 with the quality rate of charge of isoprene；Isobutene. and isoprene monomer concentration in polymerization system are 15wt%～45wt%；Adding the initiator system being made up of main initiator, the 3rd component and coinitiator in polymerization system and cause cationic polymerization, wherein main initiator in the concentration of polymerization system is: 0.01mol/L～10-5Moml/L, the 3rd concentration of component is: 0mol/L～1moml/L, and coinitiator concentration is: 1mol/L～10-4Moml/L, initiator, the 3rd component and coinitiator molar ratio be: 1.0:0～10:1.0～60；Synthesizing after (I) technique through butyl rubber, form polymerization glue, the molecular weight 50,000g/mol～500 of butyl rubber, 000g/mol, molecular weight distribution is 1.1～4.0, and the isoprene mass content in butyl rubber is at 1mol%.～10mol%.
Butyl rubber synthesis technique (I) resulting polymers glue afterwards, entering chloromethanes elimination (II) technique, adopting temperature is that 25 DEG C～100 DEG C water mix with glue, and chloromethanes evaporates, water and glue volume ratio 1:1～20:1, incorporation time is 10min～180min.
After chloromethanes evaporation, through precipitate and separate technique (III), the water in glue and glue static layering, remove water layer with pump and be directly entered Halogenation process, halogenating butyl rubber technique (IV) is: add alkane in glue, gelatin concentration adjusts 10wt%～35wt%, and under 10 DEG C～80 DEG C conditions of temperature, after dilution, after bromine or dilution, chlorine adds in glue, after stirring reaction 10s～60min, neutralize, washing, dry and prepare halogenated butyl rubber.
The weak point of this patent application is: processing step is four, and wherein the 3rd step is settlement separate, owing to this step to use a large amount of water vapour, and to use a settling tank；Being pass in high-temperature water vapor by the butyl rubber slurry of cooling at second step, therefore technological process is complicated, and cost of investment is higher.
Summary of the invention
The object of the invention technical scheme is to overcome the technological process existed in prior art complicated, the weak point that cost of investment is higher, and provides the technique that a kind of solwution method technology is directly produced brombutyl by butyl glue.
Technical scheme:
A kind of solwution method is directly produced the technique of brombutyl, and this technique is made up of three steps in order, is solwution method butyl rubber synthesis (I) respectively, chloromethanes elimination (II) and butyl rubber bromination (III)；The molecular weight 50,000g/mol～500 of brombutyl, 000g/mol, molecular weight distribution is 1.1～4.0, and brombutyl is 1.0%～2.8% in conjunction with bromine content.
Described butyl rubber synthesis technique (I): under cryogenic conditions, the mixed solvent that alkane and chloromethanes form is the solvent that cationic polymerization reacts, and wherein alkane and chloromethanes mass ratio are 50:50～80:20；In the solvent of cationic polymerization, adding isobutene. and isoprene monomer, wherein isobutene. is 98:2～85:15 with the quality rate of charge of isoprene；Isobutene. and isoprene monomer concentration in polymerization system are 15wt%～45wt%；In polymerization system, add the initiator system being made up of main initiator, the 3rd component and coinitiator cause cationic polymerization, synthesize after (I) technique through butyl rubber, form polymer glue, butyl rubber synthesis technique (I) resulting polymers glue afterwards, enters chloromethanes elimination (II) stage；Chloromethanes elimination (II) technique, it is in 25 DEG C～70 DEG C hexane solutions that glue passes into temperature, and chloromethanes evaporates, hexane and glue volume ratio 1:1～20:1, and incorporation time is 10min～180min；After chloromethanes evaporation, hexane and glue are sufficiently mixed, it is directly entered the bromination stage, the technique of butyl rubber bromination technique (III) is: gelatin concentration adjusts 10wt%～35wt%, and under 10 DEG C～80 DEG C conditions of temperature, after dilution, bromine adds in glue, after stirring reaction 10s～60min, neutralize, washing, dry and prepare brombutyl.
Described main initiator includes: the one in chloro-2,4, the 4-trimethylpentanes of water, hydrogen chloride, 1-, cumyl chlorine, dicumyl chlorine.
Described coinitiator includes: the one in aluminum chloride, a chloroethyl aluminum, ethyl aluminum dichloride, sesquialter ethylmercury chloride aluminum.
The 3rd described component includes: hexahydropyridine.
Described main initiator in the concentration of polymerization system is: 0.01mol/L～10-5Mol/L, coinitiator concentration is 1mol/L～10-4Mol/L, the 3rd concentration of component is: 0mol/L～1mol/L,
Described initiator, the 3rd component and coinitiator molar ratio are 1.0:0～10:1.0～60.
The molecular weight 50,000g/mol～500 of described butyl rubber, 000g/mol, molecular weight distribution is 1.1～4.0, and the isoprene mass content in butyl rubber is at 1～10mol%.
The described temperature under cryogenic conditions is-100 DEG C～-50 DEG C.
Beneficial effects of the present invention:
The present invention relates to solwution method and prepare the technique that butyl glue is directly produced brombutyl.Present invention, avoiding slurry process technology and prepare the dissolution process of the solvent switching needed for brombutyl or sizing material, this technique replaces high-temperature water vapor to strip with the hexane of 20 DEG C～70 DEG C, save substantial amounts of high-temperature steam, decreased this step process settlement separate, shorten technological process.Adding hexahydropyridine makes butyl rubber polymeric reaction temperature improve 10 DEG C, has saved the substantial amounts of energy.
It is settlement separate that the technique of the present invention decreases the 3rd step than the technique of prior art, has saved a large amount of water vapour, reduces by a settling tank, shortens technological process, reduce cost of investment.
3rd component adopts the purpose of hexahydropyridine to be up butyl rubber polymeric reaction temperature and stable primosome, butyl rubber polymeric reaction temperature is between spending-80～-100, polymeric reaction temperature can be made after adding hexahydropyridine to improve 10 DEG C, temperature raises 10 DEG C in the industrial production, it is possible to save the substantial amounts of energy.
Not only produce extra crosslinking sites after butyl rubber bromination, add the reactivity of double bond, improve the curingprocess rate of butyl rubber, further improve the intervulcanizability with unsaturated rubber and improve metal and the cohesiveness of rubber, curing efficiency etc..
Accompanying drawing explanation
The present invention has 1 width accompanying drawing.
Fig. 1. the process schematic representation of brombutyl is prepared for butyl glue of the present invention.
In figure: reactor 1 be solwution method butyl rubber synthesis, reactor 2 be chloromethanes and unreacted monomer elimination and bromination.
Detailed description of the invention
Below in conjunction with accompanying drawing, embodiments of the invention are further described:
As it is shown in figure 1, solwution method prepares butyl glue is directly produced the technique of brombutyl, include three steps in order, be butyl rubber synthesis (I) respectively, chloromethanes elimination (II) and butyl rubber bromination (III)；The molecular weight 50,000g/mol～500 of brombutyl, 000g/mol, molecular weight distribution, 1.1～4.0, is 1.0%～2.8% in conjunction with bromine content.
The synthesis of butyl rubber is to carry out in reactor 1, butyl rubber synthesis technique (I): under-100 DEG C～-50 DEG C cryogenic conditions, the solvent that the mixed solvent 3 of alkane and the composition of chloromethanes reacts for cationic polymerization, this solvent adds in reactor 1, and wherein alkane and chloromethanes mass ratio are 50:50～80:20；In the solvent of cationic polymerization, adding isobutene. and isoprene monomer, wherein isobutene. is 98:2～85:15 with the quality rate of charge of isoprene；Isobutene. and isoprene monomer concentration in polymerization system are 15wt%～45wt%；Adding the initiator system being made up of main initiator, the 3rd component and coinitiator in polymerization system and cause cationic polymerization, wherein main initiator is in concentration 0.01mol/L～10 of polymerization system-5Mol/L, coinitiator concentration is 1mol/L～10-4Mol/L, the 3rd concentration of component 0mol/L～1mol/L, initiator, the 3rd component and coinitiator molar ratio are 1.0:0～10:1.0～60；Synthesizing after (I) technique through butyl rubber, form polymer glue, the molecular weight 50,000～500 of butyl rubber, 000g/mol, molecular weight distribution is 1.1～4.0, and the isoprene mass content in butyl rubber is at 1%～10mol%.
Described main initiator includes: the one in chloro-2,4, the 4-trimethylpentanes of water, hydrogen chloride, 1-, cumyl chlorine, dicumyl chlorine；Coinitiator includes: the one in aluminum chloride, a chloroethyl aluminum, ethyl aluminum dichloride, sesquialter ethylmercury chloride aluminum；3rd component includes: hexahydropyridine.
Described butyl rubber synthesis technique (I) resulting polymers glue afterwards, enters chloromethanes elimination (II) step.Polymer glue adds in reactor 2, and chloromethanes elimination (II) technique adopts temperature to be that 20 DEG C～70 DEG C hexanes mixs with glue, chloromethanes evaporation, hexane and glue volume ratio 1:1～20:1, and incorporation time is 10min～180min.
Described chloromethanes elimination (II) technique, glue is passed in the hexane solvent of 20 DEG C～70 DEG C, gelatin concentration adjusts 10wt%～35wt%, after dilution, bromine adds in glue, after stirring reaction 10s～60min, neutralize, washing, dry brombutyl 5, chloromethanes and the unreacted isobutylene monomer 4 prepared is discharged from reactor 2 top.
The technique of described butyl rubber bromination technique (III), after dilution, bromine is to adopt alkane dilution bromine, and alkane and bromine volume ratio are 1:1～50:1.
5 embodiments being set forth below, the present invention is further illustrated with, the present invention is not limited solely to these embodiments.
Embodiment 1
Under-100 DEG C of conditions, in reactor 1, add hexane and chloromethanes composition mixed solvent 3, mixed solvent 3 consist of hexane 160mL, chloromethanes 72mL, chloromethanes and hexane mass ratio 38:62；In solvent, 140mL isobutene. and isoprene is added again after mix homogeneously, isobutene. and isoprene mass ratio are 97:3, monomer concentration is 36wt%, initiator system has water, sesquialter ethylmercury chloride aluminum forms, water is 0.0012mol/L, water and sesquialter ethylmercury chloride aluminum (0.0036mol/L) mol ratio are 1:3, in polymeric kettle, add initiator system cause polymerization, polyase 13 0 minute, obtains butyl rubber glue, and the number-average molecular weight of butyl rubber is 500 after measured, 000g/mol, molecular weight distribution is 1.9.Polymer glue enters back into reactor 2, is fully contacted with 50 DEG C of hexanes, is sufficiently stirred for chloromethanes, unreacted isobutylene monomer 4 from the eliminating of reactor 2 top, and adjustment gelatin concentration is 15wt%.Adding the bromine of dilution, alkane and bromine volume ratio are 20:1, and bromination reaction, after 2 minutes, prepares brombutyl 5.
The molecular weight of brombutyl 5 is 420,000g/mol after measured, and molecular weight distribution is 2.0, and bromine content is 2.0wt%.
Embodiment 2
Under-80 DEG C of conditions, in reactor 1, add hexane and chloromethanes composition mixed solvent 3, mixed solvent 3 consist of hexane 120mL, chloromethanes 90mL, chloromethanes and hexane mass ratio 50:50；Adding 155mL isobutene. and isoprene after mix homogeneously again in solvent, isobutene. and isoprene mass ratio are 98:2, and concentration is 40wt%.Initiator system has cumyl chlorine, ethyl aluminum dichloride, and cumyl chlorine is 0.01mol/L, and ethyl aluminum dichloride is 0.24mol/L, water: the mol ratio of ethyl aluminum dichloride is 1:24.Adding initiator system in polymerization reaction kettle 1 and cause polymerization, be polymerized 40 minutes, obtain butyl rubber glue, the molecular weight of butyl rubber is 29,000g/mol after measured, and molecular weight distribution is 1.9.Polymer glue enters back into reactor 2, is fully contacted with 50 DEG C of hexanes.Be sufficiently stirred for chloromethanes, unreacted isobutylene monomer 4 is got rid of from still top, and adjustment gelatin concentration is 15wt%, adds and washes the bromine released, and alkane and bromine volume ratio are 10:1, and bromination reaction, after 2 minutes, prepares brombutyl 5.
The molecular weight of brombutyl 5 is 25,000g/mol after measured, and molecular weight distribution is 2.1, and bromine content is 1.6wt%.
Embodiment 3
Under-70 DEG C of conditions, in reactor 1, add hexane and chloromethanes composition mixed solvent 3, mixed solvent 3 consist of hexane 160mL, chloromethanes 72mL, chloromethanes and hexane mass ratio 38:62；In solvent, 140mL isobutene. and isoprene is added again after mix homogeneously, isobutene. and isoprene mass ratio are 97:3, monomer concentration is 36wt%, and initiator system has 1-chloro-2,4,4-trimethylpentane, ethyl aluminum dichloride forms, 1-chloro-2,4,4-trimethylpentane is 0.002mol/L, and ethyl aluminum dichloride is 0.008mol/L.
The present embodiment initiator system is dicumyl chlorine: the mol ratio of ethyl aluminum dichloride is 1:4, adds initiator system and causes polymerization, be polymerized 40 minutes in polymeric kettle, obtain butyl rubber glue, the molecular weight of butyl rubber is 260,000g/mol after measured, and molecular weight distribution is 1.8.Polymer glue enters back into reactor 2, is fully contacted with 50 DEG C of hexanes.Be sufficiently stirred for chloromethanes, unreacted isobutylene monomer 4 is got rid of from reactor 2 top, and adjustment gelatin concentration is 10wt%, at 30 DEG C, adds and washes the bromine released, and alkane and bromine volume ratio are 10:1, and bromination reaction, after 30 seconds, prepares brombutyl 5.
The molecular weight of brombutyl 5 is 255,000g/mol after measured, and molecular weight distribution is 2.0, and bromine content is 1.7wt%.,
Embodiment 4
Under-60 DEG C of conditions, in reactor, add hexane and chloromethanes composition mixed solvent 3, mixed solvent 3 consist of hexane 160mL, chloromethanes 72mL, chloromethanes and hexane mass ratio 38:62；Adding 140mL isobutene. and isoprene after mix homogeneously again in solvent, isobutene. and isoprene mass ratio are 97:3. monomer concentration is 36wt%.Initiator system has hydrogen chloride, and ethyl aluminum dichloride forms, and hydrogen chloride is 0.002mol/L, and ethyl aluminum dichloride is 0.008mol/L.
The present embodiment initiator system is hydrogen chloride: the mol ratio of ethyl aluminum dichloride is 1:4, adds initiator system and causes polymerization, be polymerized 40 minutes in reactor 1, obtain butyl rubber glue, the molecular weight of butyl rubber is 150,000g/mol after measured, and molecular weight distribution is 1.8.Polymer glue enters back into reactor 2, is fully contacted with 50 DEG C of hexanes.Be sufficiently stirred for chloromethanes, unreacted isobutene. is got rid of from still top, and adjustment gelatin concentration is 20wt%, at 40 DEG C, adds and washes the bromine released, and alkane and bromine volume ratio are 10:1, and bromination reaction, after 60 seconds, prepares brombutyl 5.
The molecular weight of brombutyl 5 is 152,000g/mol after measured, and molecular weight distribution is 2.1, and bromine content is 1.86wt%.
Embodiment 5
Under-60 DEG C of conditions, in reactor 1, add hexane and chloromethanes composition mixed solvent 3, mixed solvent 3 consist of hexane 160mL, chloromethanes 72mL, chloromethanes and hexane mass ratio 38:62；Adding 140mL isobutene. and isoprene after mix homogeneously again in solvent, isobutene. and isoprene mass ratio are 97:3. monomer concentration is 36wt%.Initiator system is made up of hydrogen chloride, ethyl aluminum dichloride and hexahydropyridine, and hydrogen chloride is 0.002mol/L, and hexahydropyridine is 0.004mol/L, and ethyl aluminum dichloride is 0.008mol/L.
The present embodiment initiator system is hydrogen chloride: hexahydropyridine: the mol ratio of ethyl aluminum dichloride is 1:2:4, adds initiator system and causes polymerization, be polymerized 40 minutes in reactor 1, obtain butyl rubber glue, the molecular weight of butyl rubber is 160,000g/mol after measured, and molecular weight distribution is 1.9.Polymer glue enters back into reactor 2, is fully contacted with 50 DEG C of hexanes.Be sufficiently stirred for chloromethanes, unreacted isobutene. is got rid of from still top, and adjustment gelatin concentration is 10wt%, adds and washes the bromine released, and alkane and bromine volume ratio are 20:1, and bromination reaction, after 60 seconds, prepares brombutyl 5.
The molecular weight of brombutyl 5 is 162,000g/mol after measured, and molecular weight distribution is 2.2, and bromine content is 1.76wt%.
Claims (9)
1. the technique that a solwution method is directly produced brombutyl, it is characterized in that: this technique is made up of three steps in order, it is solwution method butyl rubber synthesis (I) respectively, chloromethanes elimination (II) and butyl rubber bromination (III)；The molecular weight 50,000g/mol～500 of brombutyl, 000g/mol, molecular weight distribution is 1.1～4.0, and brombutyl is 1.0%～2.8% in conjunction with bromine content.
2. the technique that a kind of solwution method according to claim 1 is directly produced brombutyl, it is characterized in that: described butyl rubber synthesis technique (I): under cryogenic conditions, the mixed solvent that alkane and chloromethanes form is the solvent that cationic polymerization reacts, and wherein alkane and chloromethanes mass ratio are 50:50～80:20；In the solvent of cationic polymerization, adding isobutene. and isoprene monomer, wherein isobutene. is 98:2～85:15 with the quality rate of charge of isoprene；Isobutene. and isoprene monomer concentration in polymerization system are 15wt%～45wt%；In polymerization system, add the initiator system being made up of main initiator, the 3rd component and coinitiator cause cationic polymerization, synthesize after (I) technique through butyl rubber, form polymer glue, butyl rubber synthesis technique (I) resulting polymers glue afterwards, enters chloromethanes elimination (II) stage；Chloromethanes elimination (II) technique, it is in 25 DEG C～70 DEG C hexane solutions that glue passes into temperature, and chloromethanes evaporates, hexane and glue volume ratio 1:1～20:1, and incorporation time is 10min～180min；After chloromethanes evaporation, hexane and glue are sufficiently mixed, it is directly entered the bromination stage, the technique of butyl rubber bromination technique (III) is: gelatin concentration adjusts 10wt%～35wt%, and under 10 DEG C～80 DEG C conditions of temperature, after dilution, bromine adds in glue, after stirring reaction 10s～60min, neutralize, washing, dry and prepare brombutyl.
3. the technique that a kind of solwution method according to claim 1 and 2 is directly produced brombutyl, it is characterised in that: described main initiator includes: the one in chloro-2,4, the 4-trimethylpentanes of water, hydrogen chloride, 1-, cumyl chlorine, dicumyl chlorine.
4. the technique that a kind of solwution method according to claim 1 and 2 is directly produced brombutyl, it is characterised in that: described coinitiator includes: the one in aluminum chloride, a chloroethyl aluminum, ethyl aluminum dichloride, sesquialter ethylmercury chloride aluminum.
5. the technique that a kind of solwution method according to claim 1 and 2 is directly produced brombutyl, it is characterised in that: the 3rd described component includes: hexahydropyridine.
6. the technique that a kind of solwution method according to claim 3,4 and 5 is directly produced brombutyl, it is characterised in that: described main initiator in the concentration of polymerization system is: 0.01mol/L～10-5Mol/L, coinitiator concentration is 1mol/L～10-4Mol/L, the 3rd concentration of component is: 0mol/L～1mol/L.
7. the technique that a kind of solwution method according to claim 3 is directly produced brombutyl, it is characterised in that: described initiator, the 3rd component and coinitiator molar ratio are 1.0:0～10:1.0～60.
8. the technique that a kind of solwution method according to claim 2 is directly produced brombutyl, it is characterized in that: the molecular weight 50,000g/mol～500 of described butyl rubber, 000g/mol, molecular weight distribution is 1.1～4.0, and the isoprene mass content in butyl rubber is at 1～10mol%.
9. the technique that a kind of solwution method according to claim 2 is directly produced brombutyl, it is characterised in that: the described temperature under cryogenic conditions is-100 DEG C～-50 DEG C.
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| CN110054716A (en) * | 2018-01-17 | 2019-07-26 | 中国石油化工股份有限公司 | The low temperature butyl rubber method isolated in slurry |
| CN111019250A (en) * | 2019-12-20 | 2020-04-17 | 山东京博中聚新材料有限公司 | Anti-aging method of brominated butyl rubber |
| CN114874373A (en) * | 2021-02-05 | 2022-08-09 | 中国石油化工股份有限公司 | Liquid butyl rubber and preparation method thereof |
| CN114874371A (en) * | 2021-02-05 | 2022-08-09 | 中国石油化工股份有限公司 | Method for preparing liquid butyl rubber and liquid butyl rubber prepared by method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110054716A (en) * | 2018-01-17 | 2019-07-26 | 中国石油化工股份有限公司 | The low temperature butyl rubber method isolated in slurry |
| CN110054716B (en) * | 2018-01-17 | 2021-07-30 | 中国石油化工股份有限公司 | Low temperature butyl rubber slurry separation process |
| CN108559016A (en) * | 2018-05-30 | 2018-09-21 | 邢月军 | A kind of amination graphene oxide bromobutyl acceptable packaging material and preparation method thereof |
| CN111019250A (en) * | 2019-12-20 | 2020-04-17 | 山东京博中聚新材料有限公司 | Anti-aging method of brominated butyl rubber |
| CN114874373A (en) * | 2021-02-05 | 2022-08-09 | 中国石油化工股份有限公司 | Liquid butyl rubber and preparation method thereof |
| CN114874371A (en) * | 2021-02-05 | 2022-08-09 | 中国石油化工股份有限公司 | Method for preparing liquid butyl rubber and liquid butyl rubber prepared by method |
| CN114874372A (en) * | 2021-02-05 | 2022-08-09 | 中国石油化工股份有限公司 | Liquid butyl rubber and method for preparing liquid butyl rubber |
| CN114874373B (en) * | 2021-02-05 | 2023-07-21 | 中国石油化工股份有限公司 | Liquid butyl rubber and preparation method thereof |
| CN114874371B (en) * | 2021-02-05 | 2023-07-21 | 中国石油化工股份有限公司 | Method for preparing liquid butyl rubber and liquid butyl rubber prepared by same |
| CN114874372B (en) * | 2021-02-05 | 2023-07-21 | 中国石油化工股份有限公司 | Liquid butyl rubber and method for preparing liquid butyl rubber |
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