CN109942841A

CN109942841A - A kind of butyl rubber solution and preparation method thereof

Info

Publication number: CN109942841A
Application number: CN201910238116.1A
Authority: CN
Inventors: 徐宏德; 任学斌; 王衍金; 崔红梅; 滕杰; 王孝海; 栾波
Original assignee: Shandong Jing Bo Petrochemical Co Ltd Rubber Branch
Current assignee: Shandong Jingbo Zhongju New Materials Co., Ltd.
Priority date: 2019-03-27
Filing date: 2019-03-27
Publication date: 2019-06-28
Anticipated expiration: 2039-03-27
Also published as: CN109942841B

Abstract

The present invention provides a kind of butyl rubber solutions and preparation method thereof.Preparation method provided by the invention includes: a) to contact polymer slurries in flash vaporization kettle with solvent, catalyst deactivator, obtains glue A；B) the glue A is sent into stripper, is inversely contacted in the stripper with solvent vapo(u)r, obtains glue liquid B；C) glue liquid B successively carried out once adding water process, dehydration, adjust concentration processing, secondary plus water process and heat exchange processing, obtain butyl rubber solution；The catalyst deactivator is the catalyst deactivator of residual catalyst in polymer slurries.Glue obtained has suitable and stable concentration, low-monomer-content, suitable water content and temperature etc. according to the method described above, halogenated butyl rubber is prepared using the glue, can make halogenated butyl rubber product that there is low-gel content, low primary bit architecture content and suitable Mooney drop.

Description

A kind of butyl rubber solution and preparation method thereof

Technical field

The present invention relates to field of rubber technology, in particular to a kind of butyl rubber solution and preparation method thereof.

Background technique

Currently, the industrial production of halogenated butyl rubber all uses solwution method, specifically, basic glue butyl rubber is dissolved Certain density butyl rubber solution is obtained in a solvent, then reacts to obtain halogenated butyl rubber with halogen.Therefore, butyl rubber The acquisition of solution is most important to halogenated butyl rubber is prepared, and usually first prepares basic glue butyl rubber, then carry out to product It handles and then obtains butyl rubber solution.

Wherein, what the industrial production of basic glue butyl rubber most generallyd use is slurry process.Specifically, first that monomer is molten Solution obtains mixed material in chloromethanes, which enters polymer reactor after Multi-stage cooling reaches -100 DEG C.Together When, the chloromethanes solution for having dissolved catalyst is entered into polymer reactor after Multi-stage cooling reaches -95 DEG C.Two strands of materials connect Touching, polymerization reaction are instantaneously completed, and butyl rubber polymer is generated.Temperature of charge passes through the vaporization cooling of liquid ethylene in reactor To maintain -100 DEG C~-90 DEG C.With the increase of reaction kettle continuous operating time, because cooling deterioration of efficiency causes in polymeric kettle Temperature of charge gradually rises.When temperature is higher than -90 DEG C, stop polymerization.Material in reactor includes butyl rubber product, not Monomer, catalyst, chloromethanes of reaction etc..Wherein, butyl rubber product does not dissolve in chloromethanes, therefore entire material is constantly in silt The polymer slurries that pulpous state state, as this field often claim.

After obtaining polymer slurries, chloromethanes and unreacted monomer need to be separated with butyl rubber product, and recycled, There are mainly two types of mode: a kind of method is after contact the polymer slurries in reactor with high-temperature water vapor into being equipped with hot water Flash vaporization kettle, unreacted monomer and chloromethanes are recycled in flash vaporization kettle through gas phase.Meanwhile polymer is deposited in the hot water with particulate form In as micelle-aqueous mixtures (present invention in by this method be referred to as steam stripping).After obtaining micelle-aqueous mixtures, It can handle after the mixture obtains butyl rubber finished product and be redissolved according to conventional drying process, butyl rubber solution is made (referred to as Dry process butyl rubber solution), micelle-aqueous mixtures directly can also be contacted to obtain with solvent butyl rubber solution (referred to as Wet process prepares butyl rubber solution).Another method is directly to contact the polymer slurries in reactor with high-temperature solvent, fourth Base rubber solution obtains butyl rubber solution in a solvent.Meanwhile chloromethanes and unreacted monomer are recycled by gas phase, this method Referred to as solvent stripping process.

However, above-mentioned steam stripping have the shortcomings that it is one very big, be exactly using high-temperature water vapor and hot water back and forth When receiving chloromethanes and unreacted monomer, chloromethanes facile hydrolysis generates methanol, dimethyl ether and HCl.Water and hydrolysate are to chloromethanes Recycling and unreacted monomer recovery system bring many adverse effects, wherein methanol, dimethyl ether are butyl rubber polymerization reactions Poisonous substance, content must be strictly controlled, and otherwise can cause to seriously affect to polymerization reaction.In order to remove the Shui Heshui in chloromethanes Methanol product, dimethyl ether are solved, entire chloromethanes drying system is very huge and complicated, and will lead to chloromethanes unit consumption and obviously increase Add；In addition, the HCl or other chlorine compounds that generate after chloromethanes hydrolysis can corrode equipment, it is recycled unreacted monomer System generates autopolymer, and the isobutene dimer of one of autopolymer is very strong chain-transferring agent, will cause the reduction of product Mooney, because This its content also must be strictly controlled.And the above problem can be overcome using solvent stripping process well.

Currently, the scheme that some solvent stripping process prepare butyl rubber solution is disclosed in the prior art, such as patent application It includes flash vaporization kettle and stripper that CN103483483A, which discloses a kind of butyl rubber stripper plant and gas stripping process, device,.From poly- The chloromethanes and unreacted monomer hot solvent closed in the polymer slurries that kettle comes out steams at the top of flash vaporization kettle, and butyl rubber is molten Liquid is sent into stripper from flash vaporization kettle bottom；In stripper, chloromethanes and monomer will be remained from tower top by hot solvent in glue It steams, stripper bottom obtains butyl rubber solution, can be sent into halogenation system and prepare halogenated butyl rubber.Patent application CN104761659A discloses a kind of device and method for preparing halogenation butyl rubber solution, and device includes flash vaporization kettle and guiding Sieve-plate tower, from chloromethanes and unreacted monomer the hot solvent steaming at the top of flash vaporization kettle in the polymer slurries that polymeric kettle comes out Out, butyl rubber solution is sent into high-efficiency guide sieve-plate tower from flash vaporization kettle bottom；It, will by hot solvent in high-efficiency guide sieve-plate tower Residual chloromethanes and monomer in glue are steamed from top, and bottom obtains butyl rubber solution, can be sent into halogenation system and be prepared halogen Change butyl rubber.

However, the above-mentioned prior art only accounts for halogenation to residual monomer in butyl rubber glue and gelatin concentration Demand, but in fact, the halogenated butyl rubber product of high quality is obtained, these are also not nearly enough.From basic glue to halobutyl The microstructure of Mooney drop and halogenated butyl rubber between rubber all has a major impact the performance of halogenated butyl rubber, leads to For often, not above 20%, (" Mooney drop " refers to the butyl rubber basis Jiao Men from polymeric kettle into flash vaporization kettle to Mooney drop Buddhist nun subtracts the ratio of difference obtained by halogenated butyl rubber Mooney and basic glue Mooney), III structure of uncle position in brombutyl Equally not above 20%, (brominated structures refer to bromine atom in secondary II structure of position and bromine atom to ratio of the content in brominated structures III structure in uncle position, detailed content is refering to patent application CN105218719A, CN105622821A).And butyl rubber polymerize It is Friedel-Crafts catalyst substance with catalyst, pyrosol is easy to cause in the process if there is this substance Basic glue degradation, direct result are that Mooney drop increases.In addition, during halogenation, if there are Friedel- in system Crafts catalyst substance, III structural content of brominated product will increase (referring to United States Patent (USP) USP4,632,963).

For solvent stripping process, the residual catalyst in polymer slurries can always exist in sol-process, exist Time is longer, and Mooney drop is bigger, and III structural content for also resulting in brominated product increases.In addition, in flash distillation and stripping process, Unreacted monomer concentration is very high in flash vaporization kettle and stripper, and residual activity catalyst at high temperature both can be anti-with unreacted monomer Oligomer should be formed, the unsaturated double-bond in polymer can also be attacked, forms gel；And excessive oligomer and gel can be right The physical property of product has negative effect, for example, forming mass defect in the product, is attached to equipment and pipe surface obstruction pipeline, drop Low heat transfer efficiency etc..Therefore, butyl rubber solution made from the above-mentioned prior art is difficult to prepare low primary bit architecture content, coagulate Glue content is low and suitable halogenated butyl rubber product drops in Mooney.

Summary of the invention

In view of this, the purpose of the present invention is to provide a kind of butyl rubber solutions and preparation method thereof.The present invention is made Butyl rubber solution can prepare low primary bit architecture content, the halogenated butyl rubber that Mooney drop is suitable and gel content is low produces Product.

The present invention provides a kind of preparation methods of butyl rubber solution, comprising the following steps:

A) polymer slurries are contacted in flash vaporization kettle with solvent, catalyst deactivator, obtains glue A；

B) the glue A is sent into stripper, is inversely contacted in the stripper with solvent vapo(u)r, obtains glue liquid B；

C) glue liquid B successively carried out once adding water process, dehydration, adjust concentration processing, secondary plus water process It is handled with heat exchange, obtains butyl rubber solution；

The catalyst deactivator is the catalyst deactivator of residual catalyst in polymer slurries.

Preferably, the catalyst deactivator be selected from alcohol compound, ether compound, organic carboxyl acid and its derivative, One or more of aldehyde compound, ketone compounds, organic amine and sulfur-containing compound.

Preferably, the alcohol compound is selected from one of the monohydric alcohol of C1~C8 and the polyalcohol of C1~C8 or several Kind；

The ether compound is selected from one or more of the ether compound of C2~C8；

The organic carboxyl acid is selected from one or more of the organic carboxyl acid of C1~C18；

The aldehyde compound is selected from one or more of the aldehyde compound of C1~C18；

The ketone compounds are selected from one or more of the ketone compounds of C2~C18；

The organic amine is selected from one of tertiary amine of the primary amine of C1~C18, the secondary amine of C1~C18 and C1~C18 or several Kind；

The sulfur-containing compound is selected from one or more of hydrogen sulfide, thioether and mercaptan；

Content of the catalyst deactivator in glue A is 50~5000ppm.

Preferably, the catalyst deactivator is selected from one or more of alcohol compound.

Preferably, primary plus water process the amount of water is 0.1wt%~10wt%；

It is 0.1wt%~1.0wt% that the dehydration, which is dehydrated to material moisture,；

It is 5wt%~25wt% that the adjusting concentration, which is handled to material concentration,.

Preferably, described secondary plus water amount of water is 0.05wt%~5wt%；

It is described change be heat-treated to temperature of charge be 30~60 DEG C.

Preferably, described once water process to be added to carry out under the first high speed mixing conditions；First mixed at high speed is cut Cutting speed rate≤300s^-1；The processing time of first mixed at high speed is 10~60s；

Described secondary plus water process carries out under the second high speed mixing conditions；The shear rate of second mixed at high speed≤ 300s^-1；The processing time of second mixed at high speed is 10~60s.

Preferably, the solvent in the step a) is selected from the linear saturation alkane of C4~C10 and the branch saturation of C4~C10 One or more of alkane；

The temperature of solvent is 30~200 DEG C in the step a)；

Water content≤100ppm of solvent in the step a)；

The concentration of the glue A is 5wt%~15wt%.

Preferably, the solvent in the step b) is selected from the linear saturation alkane of C4~C10 and the branch saturation of C4~C10 One or more of alkane；

Water content≤100ppm of solvent in the step b)；

The operating temperature of stripping tower bottom is 50~90 DEG C in the step b)；

The concentration of the glue liquid B is 5wt%~15wt%；

The concentration of the butyl rubber solution is 10wt%~20wt%.

The present invention also provides butyl rubber solutions made from a kind of preparation method as described in the above technical scheme.

The present invention provides a kind of preparation methods of butyl rubber solution, comprising the following steps: a) by polymer slurries with Solvent, catalyst deactivator contact in flash vaporization kettle, obtain glue A；B) the glue A is sent into stripper, in the stripping It is inversely contacted in tower with solvent vapo(u)r, obtains glue liquid B；C) glue liquid B is successively carried out once adding water process, dehydration, Concentration processing, secondary plus water process and heat exchange processing are adjusted, butyl rubber solution is obtained；The catalyst deactivator is polymer The catalyst deactivator of residual catalyst in slurry.Polymer slurries are first being flashed with solvent, catalyst deactivator in the present invention Contact in kettle, using catalyst deactivator to the catalyst deactivation in polymer mud, after after the processing of the solvent of stripper, It successively carries out once adding water process, dehydration again, adjust concentration processing, secondary plus water process and heat exchange processing, to obtain Butyl rubber solution.Preparation method according to the invention can make butyl rubber solution have suitable and stable concentration, low list Body content, suitable water content and temperature etc. are sent into halogenation system using the butyl rubber solution and prepare halobutyl rubber Glue can make halogenated butyl rubber product have low primary bit architecture content, suitable Mooney drop and lower gel content.

The experimental results showed that butyl rubber solution provided by the invention can be such that the Mooney of halogenated butyl rubber product reduces In 20%, primary bit architecture content is lower than 20%, and gel content is produced in 0.11wt% hereinafter, obtaining the halogenated butyl rubber haveing excellent performance Product.

Detailed description of the invention

In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technical description to be briefly described.It should be evident that the accompanying drawings in the following description is only this The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis The attached drawing of offer obtains other attached drawings.

Fig. 1 is the schematic diagram of the preparation facilities for the butyl rubber solution that one embodiment of the present of invention provides；

Fig. 2 is the schematic diagram for the buffer unit that one embodiment of the present of invention provides.

Specific embodiment

The present invention provides a kind of preparation methods of butyl rubber solution, which comprises the following steps:

Polymer slurries first contact in flash vaporization kettle with solvent, catalyst deactivator in the present invention, utilize catalyst inactivation Agent to the catalyst deactivation in polymer mud, after after the processing of the solvent of stripper, then successively carry out once plus water process, Dehydration adjusts concentration processing, secondary plus water process and heat exchange processing, to obtain butyl rubber solution.According to the present invention Preparation method, can make butyl rubber solution have suitable and stable concentration, low-monomer-content, suitable water content and temperature Degree etc. is sent into halogenation system using the butyl rubber solution and prepares halogenated butyl rubber, halogenated butyl rubber can be made to produce Product have low primary bit architecture content, suitable Mooney drop and lower gel content.

In the present invention, unless otherwise indicated, " Mooney drop " refers to the butyl rubber basis from polymeric kettle into flash vaporization kettle Glue Mooney subtracts the ratio of difference obtained by halogenated butyl rubber Mooney and basic glue Mooney.

According to the present invention, polymer slurries are contacted in flash vaporization kettle with solvent, catalyst deactivator first, obtain glue A.

The present invention is not particularly limited the type of the polymer slurries and source, is well known to those skilled in the art Slurry process prepares generated polymer slurries when the glue of butyl rubber basis.Such as using halogenated alkane as medium, monomer is being catalyzed Agent effect is lower to carry out polymerization reaction, obtains polymer slurries.

Butyl rubber slurry polymerization used medium need to usually meet following condition: first is that polymer is in become silted up in the medium Slurry；Second is that monomer and catalyst can be dissolved simultaneously；Third is that being at the polymerization temperature liquid；Therefore industrially polymerization used medium is logical It is often halogenated alkane, preferably chloromethanes.

The monomer preferably includes the first monomer and second comonomer.Wherein, first monomer is preferably the different of C4~C7 One or more of structure monoolefine, more preferably isobutene；The second comonomer be preferably C4~C14 conjugated diene and One or more of methyl styrene, more preferably isoprene.

The catalyst preferably includes major catalyst and co-catalyst；Wherein, the major catalyst be preferably HCl and/or Water；The co-catalyst is preferably Friedel-Crafts catalyst, more preferably BF₃、TiCl₄、AlCl₃、AlEtCl₂With AlEt₂One or more of Cl.

The polymerization temperature of the polymerization reaction is preferably -100 DEG C~-90 DEG C.In above-mentioned polymerization reaction, the use of each material Amount is not particularly limited, and is executed according to the conventional proportions of this field industrial production butyl rubber.With isobutene/isoprene For copolymerization production butyl rubber, in normal industrial production, into the mixed material in reactor, the concentration of isobutene In 20wt%~40wt%, the ratio of isoprene and isobutene is between 2.0wt%~4.0wt%.Above-mentioned polymerization reaction speed Degree even just completes reaction in microsecond quickly, in millisecond, and polymerizate butyl rubber is not dissolved in medium, therefore entire condensate System is slurry state heterogeneous system, material, that is, polymer slurries in system.

In the present invention, into before flash vaporization kettle, flow, the temperature and pressure of polymer slurries are not particularly limited, i.e., to poly- The charging parameter for closing object slurry is not particularly limited, and is executed according to the transport condition of this field conventional manufacturing procedures.At this In one embodiment of invention, the flow of the polymer slurries is 10.6kg/h, and temperature is -93 DEG C, pressure 2bar.

In the present invention, the solvent is preferably in the linear saturation alkane of C4~C10 and the branch saturated alkane of C4~C10 One or more；One of branch saturated alkane of the linear saturation alkane of more preferably C5~C8 and C5~C8 is several Kind；In some embodiments of the invention, the solvent is hexane.In the present invention, the water content of solvent needs strict control.It is dodging In steaming and stripping process, due to polar difference, the water in solvent is easier to enter in chloromethanes.If solvent water content is excessively high, The water number for then easily influencing recovered material after polymerizeing, impacts subsequent polymerisation reaction, and then influence halogenated butyl rubber product Performance, and many detrimental effects are brought to chloromethanes and Monomer Recovery System.Chloromethanes and Monomer Recovery System need in this way It is additional to increase dry and imurity-removal unit, keep entire methyl chloride system very huge and complicated, and will lead to chloromethanes unit consumption It obviously increases, is led to the problem of with steam stripping same, lose the advantage of solvent stripping process.In the present invention, the solvent Water content preferably≤100ppm, more preferably≤50ppm, further preferably≤10ppm.

In the present invention, into before flash vaporization kettle, the technological parameter of solvent is not particularly limited, i.e. the charging parameter of solvent does not have It is specifically limited, it is executed according to the transport condition of this field conventional manufacturing procedures；As long as guaranteeing most chloromethanes and not Reaction monomers enter recovery system, while obtaining the butyl rubber solution of suitable concentration.The temperature of the solvent is preferably 30~200 DEG C.In one embodiment of the invention, the flow of the solvent is 25.0kg/h, and temperature is 138 DEG C, and pressure is 6bar。

In the present invention, in flash vaporization kettle catalyst deactivator is additionally added so that residual catalyst and work in polymer slurries Property center inactivation.The present invention is not particularly limited the type of the catalyst deactivator, is well known to those skilled in the art It can be by the deactivator of the catalyst inactivation in polymer slurries.Preferably, the catalyst deactivator is selected from alcohols In conjunction object, ether compound, organic carboxyl acid and its derivative, aldehyde compound, ketone compounds, organic amine and sulfur-containing compound One or more, more preferably alcohol compound.

Wherein, the alcohol compound is preferably one of the monohydric alcohol of C1~C8 and the polyalcohol of C1~C8 or several Kind；The polyalcohol includes dihydric alcohol, trihydroxylic alcohol and more polynary alcohol compound.It is furthermore preferred that the alcohol compound choosing From one or more of methanol, ethyl alcohol, propyl alcohol, butanol, the tert-butyl alcohol, ethylene glycol, diethylene glycol (DEG) and triethylene glycol.The ethers chemical combination Object is preferably one or more of ether compound of C2~C8；More preferably dimethyl ether, diethyl ether, ethyl methyl ether, n-butyl ether, One or more of tetrahydrofuran, 1,4- dioxane and methyl phenyl ethers anisole.The organic carboxyl acid is preferably organic carboxylic of C1~C18 One or more of acid；More preferably one or more of formic acid, acetic acid, propionic acid, n-butyric acie, isobutyric acid and stearic acid. The derivative of the organic carboxyl acid is preferably one or more of acyl, nitrile, acid anhydride and ester of C2~C20；More preferably acetamide, One or more of methylacetamide, acetonitrile, acetic anhydride, the third acid anhydride of second, methyl acetate, ethyl acetate and stearate.It is described Aldehyde compound is preferably one or more of aldehyde compound of C1~C18；More preferably formaldehyde, acetaldehyde, butyraldehyde and fourth One or more of olefine aldehydr.The ketone compounds are preferably one or more of ketone compounds of C2~C18；It is more excellent It is selected as one or more of acetone, butanone and cyclohexanone.The organic amine be preferably C1~C18 primary amine (i.e. level-one amine, RNH₂), secondary amine (i.e. secondary amine, the R of C1~C18₂) and the tertiary amine of C1~C18 (i.e. tertiary amine, R NH₃One or more of N)； More preferably one or more of methylamine, aniline, ethylenediamine, diisopropylamine and triethanolamine.The sulfur-containing compound is preferred For one or more of hydrogen sulfide, thioether and mercaptan；More preferably hydrogen sulfide, methyl mercaptan, ethyl mercaptan, methyl sulfide and ethyl sulfide One or more of.

Content of the catalyst deactivator in glue A is preferably 50~5000ppm, more preferably 100~ 1000ppm, if content is too low, inactivating efficacy is poor, if too high levels, will affect subsequent halogenation.

The polymer slurries, catalyst deactivator and solvent pass through respective conveyance conduit respectively and are delivered to flash vaporization kettle In, before being delivered to flash vaporization kettle, the conveyance conduit of three can converge in advance, i.e., a feed pipe is connected at the feed inlet of flash vaporization kettle, The feed pipe is connected with the conveyance conduit of the conveyance conduit of polymer slurries, the conveyance conduit of solvent, catalyst deactivator respectively It is logical；Catalyst deactivator and solvent can also be passed through same pipeline to flash vaporization kettle.Polymer slurries, solvent and catalyst lose Agent living is delivered in above-mentioned feed pipe through respective conveyance conduit to be mixed, then in common feeding flash vaporization kettle.

In the present invention, the operating temperature and pressure of the flash vaporization kettle are not particularly limited, and according to this field, routinely production is flowed The technological parameter of journey executes；In some embodiments of the invention, the operating temperature of flash vaporization kettle is 30~70 DEG C, work pressure Power is 1~5bar.After above-mentioned three strands of materials is sufficiently mixed in flash vaporization kettle, most of chloromethanes in polymer slurries and not anti- It answers monomer to gasify, is discharged at the top of flash vaporization kettle with partial gas phase solvent, then recycled by recovery system, by polymer slurries In most of chloromethanes and unreacted monomer removing.Meanwhile catalyst and work in catalyst deactivator and polymer slurries Property central reaction, inactivate catalyst and activated centre, reduce the adverse effect of catalyst.And the butyl rubber in polymer slurries Glue is quickly dissolved in solvent and forms butyl rubber solution, obtains the butyl rubber solution, i.e. glue A in flash vaporization kettle bottom.Institute The concentration for stating glue A is preferably 5wt%~15wt%.

According to the present invention, after obtaining glue A, the glue A is sent into stripper, is steamed in the stripper with solvent Vapour inversely contacts, and obtains glue liquid B.

The present invention is not particularly limited glue A flow, the temperature and pressure for being sent into stripper, i.e. the charging ginseng of stripper Number is not particularly limited, and is executed according to the transport condition of this field conventional manufacturing procedures.In one embodiment of the present of invention In, the flow of the glue A is 24.0kg/h, and temperature is 50 DEG C, pressure 1.52bar.

The present invention is not particularly limited stripping tower structure, is this field routine stripper；Of the invention some In embodiment, the number of plates in stripper is 55 pieces, wherein 30 blocks of column plates are arranged at stripper entrance top, and 25 blocks of column plates are arranged at lower part.

In the present invention, glue A enters after stripper inversely to be contacted with solvent vapo(u)r.The solvent vapo(u)r can come from individually It is sent into the solvent vapo(u)r of stripper, can be from materials at bottom of tower.The solvent be preferably C4~C10 linear saturation alkane and One or more of branch saturated alkane of C4~C10；The linear saturation alkane of more preferably C5~C8 and the branch of C5~C8 One or more of chain saturated alkane；In some embodiments of the invention, the solvent is hexane.It is described in the present invention The water content of solvent is preferably≤100ppm, more preferably≤50ppm, further preferably≤10ppm.The present invention is to described molten Flow, the temperature and pressure of agent steam are not particularly limited, and are executed according to the transport condition of this field conventional manufacturing procedures. In some embodiments of the invention, the solvent vapo(u)r comes from materials at bottom of tower；By heating tower's bottoming cycle material, solvent is generated Steam reaches stripping purpose.The present invention is not particularly limited the operating temperature and pressure of the stripper, according to this field The technological parameter of conventional manufacturing procedures executes；In some embodiments of the invention, the operating temperature of stripping tower bottom is 50 ~90 DEG C, operating pressure is 0.05~5bar.

After glue A is inversely contacted in stripper with solvent vapo(u)r, make residual chloromethanes and the unreacted monomer in glue A Form tower top material with partial gas phase solvent, be discharged from stripper top, be further stripped of residual chloromethanes in glue A and Unreacted monomer, while tower bottom obtains glue liquid B.The concentration of the glue liquid B is 5wt%~15wt%, wherein unreacted monomer is different Content≤20ppm of pentadiene, preferably≤10ppm, more preferably≤5ppm.

In the present invention, preferably, divide two-way to move towards after stripper top discharge the tower top material, one material It is recycled by recovery system.Enter recovery system jointly specifically, can converge with the gaseous phase materials being discharged at the top of flash vaporization kettle； In one embodiment of the invention, the flow of this strand of material is 2.8kg/h, and temperature is 41 DEG C, pressure 1.21bar.Second Stock material carries out reflow treatment, specifically, being back to stripper after first being exchanged heat again.In one embodiment of the invention, Heat exchanger and surge tank are set in current return circuit, and above-mentioned second strand of material first after heat exchanger carries out heat exchange processing, is sent to slow Tank is rushed, then is back to stripper and carries out stripping processing, to remove the residual monomer and chloromethanes in glue as far as possible, is made residual It stays monomer and chloromethanes to be sufficiently separated with glue, improves separative efficiency.

In the present invention, preferably, the tower bottom glue preferably divides two-way to move towards, one glue is preferably carried out at reflux Reason, specifically, one glue from stripper tower bottom distribute after after reboiler is boiled processing again, then be back to stripper, Solvent vapo(u)r is generated for heating tower's primer liquid, further helps the chloromethanes in glue, unreacted monomer gasification to be discharged, improves The purity of chloromethanes, the separative efficiency of unreacted monomer and tower bottom glue.Another strand of material is sent into subsequent work as tower bottom glue liquid B Sequence continues the preparation of butyl glue.

According to the present invention, after obtaining glue liquid B, to the glue liquid B carry out once plus water process, dehydration, at concentration Reason, secondary plus water process and heat exchange processing, obtain butyl rubber solution.

In the present invention, primary plus water purpose is in order to further inactivate the residual catalyst in glue, to reduce door Buddhist nun's drop.Primary plus water process the amount of water is preferably 0.1wt%~10wt%, more preferably 0.5wt%~5wt%.This In invention, the amount of water is directed to the mass ratio of the quality of added water and total material after addition water in material.The water Preferably deionized water, reference standard ISO/TC 147.

In the present invention, in some embodiments, when once adding water process, the parameter of glue liquid B is as follows: the flow of glue liquid B is 21.2kg/h, temperature are 84 DEG C, pressure 1.61bar.The parameter of water is as follows: the flow of water is 1.1kg/h, and temperature is 25 DEG C, Pressure is 5bar, amount of water 4.9wt%.

It is described once water process to be added preferably to carry out under the first high speed mixing conditions in the present invention；The mixed at high speed can It is realized by means of the super mixer with stirring.Preferably, shear rate≤300s of first mixed at high speed^-1；It is described The processing time of first mixed at high speed is 10~60s.Shear rate is too low, is unfavorable for two strands of materials and is quickly uniformly mixed；Shearing Rate is too high, and polymer molecular chain is easily broken off, and Mooney drop is caused to increase.Incorporation time has same as a result, if incorporation time It is too long, it is on the one hand that energy consumption increases, another aspect breaking polymer chains cause Mooney drop to increase；If incorporation time is too short, It is unfavorable for two strands of materials to be uniformly mixed.Under above-mentioned mixing condition, glue is sufficiently mixed with water, terminates residual catalyst, favorably It is dropped in reducing Mooney.After glue liquid B and water mix, glue C is obtained.

It once plus after water process is carried out dehydrating through above-mentioned.There are three the purposes of dehydration: one is to pass through removing Water phase reduces the acidic materials in glue/water mixed system after residual catalyst inactivation, reduces it and bears to way of escape halogenation Face is rung；Second is that stablizing gelatin concentration；Third is that the water-soluble catalyst deactivator of Partial Species can be removed, avoid to subsequent halogen Change the influence of reaction.In the present invention, it is 0.1wt%~1.0wt% that the dehydration, which is preferably dehydrated to material moisture, more excellent It is selected as 0.3wt%~1.0wt%.Most of acid water is removed by the dehydration, it is anti-to subsequent halogenation that it can be reduced The adverse effect answered, additionally it is possible to more uniformly spread gained gelatin concentration, be conducive to mentioning for subsequent halogenated rubber properties of product It rises.

In the present invention, the dehydration is carried out preferably by means of water distributing can is stood, in the standing water distributing can, in material Most of water can voluntarily from glue sedimentation layering to tank bottom；In some embodiments of the invention, material divides water in standing Residence time in tank is 6~12h.Residence time is too short, and dehydration cannot be fully achieved and homogenize the purpose of glue；Residence time Too long, investment and operating cost are too high, and dehydrating effect will not be well very much.After above-mentioned stay time, material moisture Above-mentioned desired dehydration amount and kept stable can be reached.

In the present invention, in the dehydration, in addition to using water distributing can is stood, it is preferably also parallel with receiving tank and output Tank, for receiving glue C and mixing, output tank is used to the glue after dehydration being delivered to subsequent handling receiving tank.Through upper After stating dehydration, glue D is obtained.

Concentration processing is adjusted after above-mentioned dehydration.In the present invention, the adjusting concentration processing is preferably included Dense processing drops in concentrate processing；In some embodiments of the invention, if the gelatin concentration of conveying is relatively low, pass through vacuum liter Temperature processing is to improve gelatin concentration, if the gelatin concentration that conveying comes is higher, reduces concentration by the way that the solvent of metering is added；Institute Stating adjusting concentration processing can carry out in consistencyregulator.In the present invention, preferably make material concentration by adjusting concentration processing 5wt%~25wt%, more preferably 10wt%~20wt%.In some embodiments of the invention, concentration processing is adjusted When, the transportation parameters of the glue D are preferably as follows: the flow of glue D is 21.3kg/h, and temperature is 55 DEG C, and pressure is preferably 1.61bar。

The concentration of butyl rubber glue controls very difficult, the characteristic that key factor polymerize in butyl rubber, butyl polymerization Reaction kettle needs regular stopped reaction to carry out cleaning operation.When actual production, usually there are 3~5 polymerization reaction kettles, general feelings Under condition, as soon as have a reaction kettle stopped reaction, there is another reactor feed to start to react, to guarantee that entire production system is most Amount is stablized；But during stopping-feeding intake, stopped reaction kettle is sent into the butyl rubber amount of butyl rubber glue preparation system gradually It reduces, the butyl rubber amount for starting the reaction kettle feeding glue preparation system of reaction gradually increases, and causes to be actually fed into glue system The butyl rubber amount of standby system is constantly in fluctuation status, and then causes the concentration of gained butyl rubber glue also no longer stable, It is constantly in fluctuation status.This can bring very big puzzlement to subsequent halogenation and halogenated butyl rubber product quality, it is difficult to obtain The halogenated butyl rubber product of high quality is obtained, and stable product quality is poor, it is difficult to realize the halogen of continuous large-scale production qualification Change butyl rubber product.And adjusting concentration processing step is arranged in the present invention, and glue is carried out to concentration adjusting processing in advance, if conveying The gelatin concentration come is higher, then carries out dropping dense processing, if the gelatin concentration that conveying comes is relatively low, carries out concentrate processing, makes colloid Concentration is stable always in suitable concentration range, to overcome the above problem, help to obtain high quality of products, and can be real Now continuous large-scale production goes on smoothly, guarantees each batch stable product quality.After the processing of above-mentioned adjusting concentration, obtain Glue E.

It studies for a long period of time discovery through applicant, outside removing glue liquid concentration and content of monomer, the water number and temperature of butyl rubber glue The Mooney of halogenated butyl rubber product can equally be dropped and primary bit architecture content affects greatly.The present invention is obtaining glue liquid B Afterwards, above-mentioned a series of primary plus water process carried out to glue, dehydration, adjust concentration processing and secondary plus water process, made The water number of butyl rubber glue is adjusted in suitable range and keeps stable.Meanwhile gelatin concentration being made to keep stablizing, be conducive to drop The Mooney drop of low subsequent halogenated butyl rubber product and primary bit architecture content, obtain high quality halogenated butyl rubber product.

In secondary plus water step, strict control amount of water is needed.If amount of water is excessive, halogenation conversion ratio is reduced, Consumption of raw materials increases；If amount of water is very few, the uncle position III structural content in halogenation product cannot be effectively reduced.In the present invention, Described secondary plus water process amount of water is preferably 0.05wt%~5wt%, more preferably 0.1wt%~1wt%.The present invention In, the amount of water is directed to the mass ratio of the quality of added water and total material after addition water in material.The water is preferred For deionized water, reference standard ISO/TC147.

In the present invention, described secondary plus water process technique is not particularly limited.In some embodiments of the invention, Secondary plus water technological parameter is as follows: the flow of glue E is 14.9kg/h, and temperature is 83 DEG C, pressure 1.72bar.Water it is defeated Send parameter as follows: the flow of water is 0.1kg/h, and temperature is 25 DEG C, pressure 5.01bar.

In the present invention, described secondary plus water process is preferably carried out under the second high speed mixing conditions；The mixed at high speed can It is realized by means of the super mixer with stirring.Preferably, shear rate≤300s of second mixed at high speed^-1；It is described The processing time of second mixed at high speed is 10~60s.Shear rate and incorporation time reason are the same as the first super mixer.By upper Secondary plus water process is stated, so that glue water content is adjusted to OK range and keeps stable, gained glue is denoted as F.

After above-mentioned secondary plus water process, heat exchange processing is carried out.The heat exchange processing can be carried out by means of heat-exchanger rig, be made Glue F is adjusted to suitable temperature.In the present invention, the heat exchange processing preferably makes temperature of charge reach 30~60 DEG C.By above-mentioned Processing, makes glue reach suitable temperature, is conducive to the quality for promoting subsequent halogenated butyl rubber product.

The present invention provides a kind of preparation methods of butyl rubber solution, first lose polymer slurries and solvent, catalyst Agent living contacts in flash vaporization kettle, using catalyst deactivator in polymer slurries catalyst and activated centre inactivate, later After the solvent of stripper is handled, then successively carry out that water process, dehydration, adjusting concentration is once added to handle, at secondary plus water Reason and heat exchange processing, to obtain butyl rubber solution.Preparation method according to the invention can be such that butyl rubber solution has It is anti-to be sent into halogenation using the butyl rubber solution for suitable and stable concentration, low-monomer-content, suitable water content and temperature etc. It answers system to prepare halogenated butyl rubber, can make halogenated butyl rubber product that there is low primary bit architecture content, suitable Mooney to drop And lower gel content.Specifically, preparation method through the invention, the concentration that can control butyl rubber solution exists 10wt%~20wt%, content of monomer≤5ppm, water content 0.1wt%~1wt%, 30~60 DEG C of temperature, and concentration and water number It is able to maintain stabilization, further makes the primary bit architecture content of halogenated butyl rubber lower than 20%, Mooney is reduced to 20%, and gel contains Amount reduces, and shows excellent product quality.

The present invention also provides butyl rubber solutions made from preparation method described in a kind of above-mentioned technical proposal.Gained fourth Base rubber solutions have suitable and stable concentration, low-monomer-content, suitable water content and temperature etc., can make subsequent halogenation Butyl rubber product has low primary bit architecture content, suitable Mooney drop and lower gel content, obtains high quality halogenation fourth Base rubber product.

The present invention also provides a kind of halogenated butyl rubbers, are made by butyl rubber solution；The butyl rubber solution is Butyl rubber solution as described in the above technical scheme.Gained halogenated butyl rubber product have low primary bit architecture content, properly Mooney drop and lower gel content.

The preparation method that the present invention prepares halogenated butyl rubber product to butyl rubber solution is not particularly limited, and is ability Domain prepares the conventional flowsheet of halogenated butyl rubber using butyl rubber solution；Butyl rubber solution is such as subjected to halogenation Reaction, neutralization, adding assistant, cohesion and drying, obtain halogenated butyl rubber product.The present invention is to above-mentioned halogenation, neutralization plus helps The material variety and ratio of conditional parameter and use in agent, cohesion and drying steps are not particularly limited, according to this field benefit It is carried out with the routine operation that butyl rubber solution prepares halogenated butyl rubber.The temperature of the halogenation is preferably 10~ 80 DEG C, more preferably 30~60 DEG C；The time of the halogenation is preferably 3~10min.

The present invention also provides a kind of preparation facilities of butyl rubber solution described in above-mentioned technical proposal, comprising:

Flash vaporization kettle 1；

The stripper 2 that feed inlet is connected with the discharge port of the flash vaporization kettle 1；

The first super mixer 3 that feed inlet is connected with the discharge port of the stripper 2；

The buffer unit 4 that feed inlet is connected with the discharge port of first super mixer 3；

The consistencyregulator 5 that feed inlet is connected with the discharge port of the buffer unit 4；

The second super mixer 6 that feed inlet is connected with the discharge port of the consistencyregulator 5；

The heat-exchanger rig 7 that feed inlet is connected with the discharge port of second super mixer 6.

Referring to Fig. 1, Fig. 1 is the schematic diagram of the preparation facilities for the butyl rubber solution that one embodiment of the present of invention provides. Wherein, 1 is flash vaporization kettle, and 2 be stripper, and 3 be the first super mixer, and 4 be buffer unit, and 5 be consistencyregulator, and 6 be second Super mixer, 7 be heat-exchanger rig.

Flash vaporization kettle 1 is used to receive polymer slurries, the catalyst that polymerization reaction kettle generates in butyl rubber production industry and loses Agent living and the solvent sent outside, three contact in flash vaporization kettle 1.Most of chloromethanes and unreacted monomer in polymer slurries Gasification is discharged at the top of flash vaporization kettle with partial gas phase solvent, then is recycled by recovery system.Catalyst deactivator makes to polymerize Catalyst inactivation in object slurry, meanwhile, the butyl rubber in polymer slurries, which is quickly dissolved in solvent, forms butyl rubber Solution obtains the butyl rubber solution, i.e. glue A in flash vaporization kettle bottom.Transportation parameters, the kind of solvent of the polymer slurries Class and transportation parameters, flash vaporization kettle running parameter etc. with it is consistent described in above-mentioned technical proposal, details are not described herein.

Referring to Fig. 1, in some embodiments of the invention, the preparation facilities further includes polymerization reaction kettle 10, described poly- The discharge port for closing reaction kettle 10 is connected with the feed inlet of the flash vaporization kettle 1, for conveying polymer slurries into flash vaporization kettle 1. The structure of the polymerization reaction kettle 10 is not particularly limited, for the typical polymerization reaction kettle in the production industry of this field butyl rubber ?.

In some embodiments of the invention, the preparation facilities further includes recovery system (not shown), and described time The air inlet of receipts system is connected with the gas outlet of the flash vaporization kettle 1, for recycling the gaseous phase materials being discharged at the top of flash vaporization kettle 1 (including chloromethanes, unreacted monomer and partial solvent).The present invention is not particularly limited the structure of the recovery system, for this Field prepares the conventional recovery system in butyl rubber solution.

The feed inlet of stripper 2 is connected with the discharge port of flash vaporization kettle 1, specifically, the glue with 1 bottom of flash vaporization kettle discharges Mouth is connected.The present invention is not particularly limited the structure of stripper 2, is this field routine stripper；Of the invention In some embodiments, the number of plates in stripper is 55 pieces, wherein 30 blocks of column plates are arranged at stripper feed inlet top, and lower part has 25 Block column plate.The glue A that flash vaporization kettle bottom generates enters stripper from the feed inlet of stripper 2, meanwhile, stripper bottom generates molten Agent steam, glue A are inversely contacted with solvent vapo(u)r, keep residual chloromethanes in glue A and unreacted monomer and partial gas phase molten Dosage form is discharged into recovery system at tower top material, from stripper top, meanwhile, tower bottom obtains glue liquid B.The glue A's is defeated Send parameter, the type of solvent and transportation parameters, stripper running parameter etc. with it is consistent described in above-mentioned technical proposal, herein It repeats no more.

Referring to Fig. 1, in some embodiments of the invention, the preparation facilities further include: be connected to flash vaporization kettle 1 and stripping Kettle material conveying pump 12 between tower 2, the glue A for obtaining 1 bottom of flash vaporization kettle are pumped in stripper 2.

Referring to Fig. 1, in some embodiments of the invention, the preparation facilities further include: air inlet and the stripper 2 Gas outlet be connected, and the reflux unit 8 that discharge port is connected with the first feedback outlet of the stripper 2；The reflux dress Setting 8 includes interconnected heat exchanger 8-1 and surge tank 8-2, wherein the air inlet of the heat exchanger 8-1 and going out for stripper 2 Port is connected, and the discharge port of the surge tank 8-2 is connected with the first feedback outlet of stripper 2.

That is the top material of stripper 2 divides two-way to move towards, one material is recycled by recovery system, specifically, can Converge with the material being discharged at the top of flash vaporization kettle 1 and enters recovery system jointly.Another strand of material is handled by the reflux unit 8 Afterwards, it is flowed back into stripper 2 again.Heat exchanger 8-1 and surge tank 8-2 is set in reflux unit 8, and material is first through heat exchanger 8- It after 1 carries out heat exchange processing, send to surge tank 8-2, then is back to stripper and carries out stripping processing, to remove glue as far as possible In residual monomer and chloromethanes, be sufficiently separated residual monomer and chloromethanes with glue, improve separative efficiency.Wherein, it changes Consistent described in the temperature and above-mentioned technical proposal of heat treatment, details are not described herein.

Referring to Fig. 1, in one embodiment of the invention, the reflux unit 8 further includes material-handling pump 13, the object Material conveying pump 13 is set between surge tank 8-2 and stripper 2, for the received material pumping of surge tank 8-2 to be back to vapour In stripper 2.

Referring to Fig. 1, in some embodiments of the invention, the preparation facilities further include: feed inlet and the stripper 2 Discharge port be connected, and the first reboiler 9 that discharge port is connected with the second feedback outlet of the stripper 2.Stripper 2 Tower bottom glue divides two-way to move towards, one glue is diverted from tower bottom and heats through the first reboiler 9, then is back to stripper, For heating tower's primer liquid to generate solvent vapo(u)r, remaining chloromethanes in glue, unreacted monomer gasification row are further helped Out, chloromethanes, the separative efficiency of unreacted monomer and the purity of tower bottom glue are improved；Wherein, the processing of first reboiler 9 Consistent described in temperature and above-mentioned technical proposal, details are not described herein.Another strand of material is sent into subsequent handling as tower bottom glue liquid B Continue the preparation of butyl glue.

Referring to Fig. 1, in some embodiments of the invention, the preparation facilities includes the glue conveying connecting with stripper Pump 14, for the glue of 2 bottom of stripper to be delivered to respectively in the first reboiler 9 and the first super mixer 3.

The feed inlet of first super mixer 3 is connected with the discharge port of the stripper 2, specifically, with 2 tower of stripper The liquid outlet at bottom is connected.First super mixer 3 receives the glue liquid B from 2 tower bottom of stripper, while receiving external feeding Water carries out glue liquid B once to add water process.Wherein, the transportation parameters of glue liquid B and the transportation parameters of water, additional amount etc. with it is upper It states described in technical solution unanimously, details are not described herein.

In one embodiment of the invention, first super mixer 3 is the super mixer of belt stirrer.It is described Consistent described in the running parameter and above-mentioned technical proposal of first super mixer, details are not described herein.Through the first mixed at high speed After the primary plus water process of device 3, glue liquid B is uniformly mixed with water, obtains glue C.

The feed inlet of buffer unit 4 is connected with the discharge port of first super mixer 3, comes from first for receiving The glue C of super mixer 3, and it is carried out dehydrating.Referring to fig. 2, Fig. 2 is provided slow for one embodiment of the present of invention The schematic diagram of flushing device；In one embodiment of the invention, the buffer unit 4 includes 3 in parallel and slow with stirring Tank is rushed, the feed inlet of all surge tanks is connected with the discharge port of first super mixer 3.The functional cycle of three tank bodies Circulation, one is used to receive the glue C from the first super mixer 3, and carries out Homogenization Treatments (being denoted as receiving tank) to it； One for settle and separate dehydration (being denoted as standing water distributing can, " water distributing can " is abbreviated as in figure)；One for exporting glue to dense Degree adjuster (is denoted as output tank).Three surge tank alternate operations: receiving tank stirs in running order when receiving glue, reaches It is switched to settle and separate dehydrating function after to regulation liquid level, stirring is in off working state at this time.Output tank function is transferred to immediately It receives and comes from the first super mixer glue function, settle and separate tank, which is opened, stirs and be transferred to output glue to consistencyregulator Function.In standing water distributing can, most of water is understood oneself settles layering to tank bottom from glue C, reaches dehydrating effect.Glue C Consistent described in residence time and above-mentioned technical proposal in water distributing can standing, details are not described herein.

The feed inlet of consistencyregulator 5 is connected with the discharge port of the buffer unit 4, for sending to buffer unit 4 Glue D carry out concentration adjusting.Operation, aimed concn to be achieved and the buffer unit 4 that the concentration is adjusted are to concentration tune Save transportation parameters etc. when device 5 conveys glue with it is consistent described in above-mentioned technical proposal, details are not described herein.

Referring to Fig. 1, in one embodiment of the invention, it is additionally provided between the buffer unit 4 and consistencyregulator 5 Liquid material delivery pump 15, the glue D for generating buffer unit 4 are pumped in consistencyregulator 5.

Referring to Fig. 1, in one embodiment of the invention, it is additionally provided between the buffer unit 4 and consistencyregulator 5 Second reboiler 11.This gang of glue D is heated when the glue D concentration that buffer unit 4 generates is lower than setting value, makes partial solvent gas Change removing, obtains glue E to improve gelatin concentration to setting value.

The feed inlet of second super mixer 6 is connected with the discharge port of the consistencyregulator 5, receives and comes from concentration tune The glue E of device 5 is saved, meanwhile, the external water being sent into is received, secondary plus water process is carried out to glue.Wherein, the conveying ginseng of glue E Several and water transportation parameters, additional amount etc. with unanimously, details are not described herein described in above-mentioned technical proposal.

In one embodiment of the invention, second super mixer 6 is the super mixer of belt stirrer.It is described Consistent described in the running parameter and above-mentioned technical proposal of second super mixer, details are not described herein.Through the second mixed at high speed After the secondary plus water process of device 6, glue E is uniformly mixed with water, obtains glue F.

The feed inlet of heat-exchanger rig 7 is connected with the discharge port of second super mixer 6, for mixed to the second high speed The glue F that clutch 6 obtains carries out heat exchange processing.It is consistent described in the temperature and above-mentioned technical proposal of the heat exchange processing, herein It repeats no more.The present invention is not particularly limited the structure of the heat-exchanger rig 7, is this field usual heat exchanger.It is described The discharge port of heat-exchanger rig 7 is connected with the feed inlet of halogenation system, is used for butyl made from preparation facilities of the present invention Rubber solutions are sent into halogenation system and carry out halogenation, and then halogenated butyl rubber product can be made.

Preparation facilities provided by the invention includes the flash vaporization kettle 1 being sequentially communicated, stripper 2, the first super mixer 3, delays Flushing device 4, consistencyregulator 5, the second super mixer 6, heat-exchanger rig 7.It, can be first by polymerization using preparation facilities of the invention Object slurry contacts in flash vaporization kettle with solvent, and bottom obtains glue A.Glue A and solvent vapo(u)r are inversely connect in stripper again Touching, tower bottom obtain glue liquid B.Then glue liquid B is successively carried out once adding water process, dehydration, adjust concentration processing, it is secondary plus Water process and heat exchange processing, to obtain butyl rubber solution.Using glue obtained by the device have suitable and stable concentration, Low-monomer-content, suitable water content and temperature etc., can make subsequent halogenated butyl rubber product have low primary bit architecture content, Suitable Mooney drop and lower gel content, obtain high quality halogenated butyl rubber product.

For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention Limitation.

Embodiment 1

1.1 carry out the preparation of butyl rubber solution using the preparation facilities of Fig. 1, specific as follows:

Using chloromethanes as medium, AlEtCl₂And HCl is catalyst (AlEtCl₂: the mass ratio of HCl is 18:1), isobutene And isoprene is monomer (isobutene: the mass ratio of isoprene is 100:3).AlEtCl₂It is dissolved in chloromethanes and is urged Agent solution, concentration 0.3wt%, flow 0.6kg/h.Monomer mixes gained mixed material concentration with chloromethanes 30wt%, flow 10kg/h.Polymerization reaction carries out (polymerization temperature is -95 DEG C), monomer conversion in polymerization reaction kettle 10 It is 90%.

Above-mentioned polymer slurries are sent into flash vaporization kettle 1 (flow 10.6kg/h, -93 DEG C of temperature, pressure 2bar), meanwhile, it will Hexane hot solvent and triethylene glycol deactivator are sent into flash vaporization kettle 1.Hot hexane flow 25.0kg/h, 138 DEG C of temperature, pressure 6bar；Three Glycol flow is 23.6g/h, and temperature is 25 DEG C, pressure 6bar.After three strands of materials mixes in flash vaporization kettle 1, most of chloromethanes, Unreacted monomer and part hexane are discharged into recovery system at the top of flash vaporization kettle 1, and (when discharge, the flow of the partial material is 11.7kg/h, temperature are 50 DEG C, pressure 1.51bar).Bottom obtains the hexane solution of butyl rubber, i.e. glue A, concentration is 11.3wt%, triethylene glycol concentration are 980ppm.

Glue A is pumped in stripper 2 through delivery pump 11 to (flow 24.0kg/h, temperature are 50 DEG C, pressure 1.52bar), the hexane steam generated with tower bottom inversely contacts, and two strands of materials inversely contact, and make the part chloromethanes in glue A Tower top material is formed with unreacted monomer and partial gas phase solvent, is discharged from stripper top.Meanwhile remaining glue A be dissolved in it is molten Dosage form is at tower bottom glue.Wherein, tower top material is divided into two strands, and one material (flow 2.8kg/h, 41 DEG C of temperature, pressure 1.21bar) gas phase enters recovery system together after the decompression being discharged with flash vaporization kettle 1, another strand of material successively through heat exchanger 8-1, Surge tank 8-2 and delivery pump 12 flow back into stripper 2.Tower bottom glue is also classified into two strands, one glue through delivery pump 13 send to Processing is boiled in reboiler 8-2 again, then is back in stripper 2, with heating tower's primer liquid；Another strand of glue liquid B (flow 21.2kg/h, 84 DEG C of temperature, pressure 1.61bar, concentration 12.8wt%, isoprene monomer content 1.6ppm) through delivery pump 13 It send into the first super mixer 3.

Meanwhile water is sent into the first super mixer 3 to (flow 1.1kg/h, temperature are 25 DEG C, pressure 5bar).Glue liquid B It is uniformly mixed in the first super mixer 3 with water, in mixed process, shear rate 250s^-1, residence time 20s adds water Amount is 5.0wt%.After mixing, gained glue C (temperature is 55 DEG C) is sent to buffer unit 4, and is stopped standing in water distributing can Stay 8h.It during standing, shares 7.9kg water and is discharged from tank bottom, material moisture is 0.5wt% after dehydration, is denoted as glue D.

Glue D is sent to progress concentrate processing in consistencyregulator 5, a part of hexane is steamed into (flow 6.4kg/h, temperature 83 DEG C of degree, pressure 1.71bar), tank bottom obtains glue E (concentration 18.2wt%, water content 0.37wt%).

Glue E is sent into the second super mixer 6 (flow 14.9kg/h, 83 DEG C of temperature, pressure 1.72bar), meanwhile, It feeds the water into the second super mixer 6 (flow 0.1kg/h, 25 DEG C of temperature, pressure 5.01bar), in mixed process, shearing speed Rate is 250s^-1, residence time 20s.After mixing, glue F (water content 1.0wt%) is obtained.Glue F is carried out through heat exchanger 7 Heat exchange processing, obtains butyl rubber solution (43 DEG C of temperature, water content 1.0wt%).

The preparation of 1.2 halogenated butyl rubbers

Gained butyl rubber glue is sent into (flow 15.0kg/h, concentration 18.2wt%, water content in halogenation reactor 1.0wt%, 43 DEG C of temperature), meanwhile, bromine is sent into halogenation reactor (flow 111g/h), the two stops in the reactor React 5min.It is subsequently sent to neutralization reactor, is neutralized by NaOH solution, solution of sodium bisulfite reduction residual bromine.In 5min is reacted with stopping in reactor, water phase pH is 8.0 after neutralization.After the completion of neutralization, it is (including calcium stearate, steady that auxiliary agent is added Determine agent epoxidized soybean oil, antioxidant 1076), enter cohesion unit after auxiliary agent and glue mixing, finally removes water through drying system After point, brombutyl is obtained.Wherein, based on dry glue, the additional amount of calcium stearate is 2.2wt%, and stabilizer adds Entering amount is 1.4wt%, and the additional amount of antioxidant is 0.06wt%.

1.3 performance detection

Primary bit architecture characterization, the test of Mooney drop and gel content test are carried out to brombutyl product.Wherein, bromination The structural characterization of product uses Switzerland Bruker company AVANCE 400MHz NMR pop instrument, 9.40 tesla of magnetic field strength, sample Quality control diameter 5mm, sample is configured to the solution of content about 2wt% with deuterated chloroform dissolution at normal temperature, using TMS as internal standard, It tests at room temperature.The Mooney of polymer is measured according to standard ASTM D1646, instrument model Alpha MV2000.Bromination The gel content of product is obtained using centrifugal process: by sample, (after sample is derived from neutralization, it is added in auxiliary agent at 25 DEG C first Before) 30min, concentration 12.5g/l are dissolved in toluene, then use ultracentrifuge (20000rpm) at 25 DEG C at centrifugation 1h is managed, the gel content of sample can be calculated in insoluble matter through being dried after taking out.

Test result shows that the Mooney of taken butyl rubber basis glue is 36.3 in flash vaporization kettle 1, final brombutyl Mooney be 33.3, be computed, Mooney is reduced to 8.2%.III structure of uncle position is in brominated structures in brombutyl product Content is 10.4%.Product gel content is 0.05wt%.

Embodiment 2

Butyl rubber solution is prepared according to the preparation process of embodiment 1, unlike, the catalysis being added in flash vaporization kettle 1 Agent deactivator is butanol, and butanol content is 500ppm in glue A；The amount of water that the first super mixer 3 is added is 4.0wt%, It is 0.6wt% that glue water content is added water into the second mixer 6, makes 45 DEG C of glue temperature after 7 heat exchange of heat exchanger processing, The concentration of final gained butyl rubber solution is 18.0wt%, content of monomer 1.7ppm, water content 0.6wt%, and temperature is 45℃。

Brombutyl is prepared using gained butyl rubber solution according to the preparation process of embodiment 1.

According to the Mooney drop and primary bit architecture content of the test method test gained brombutyl of embodiment 1, as a result It has been shown that, Mooney are reduced to 9.5%, primary bit architecture content 10.8%, gel content 0.08wt%.

Embodiment 3

Butyl rubber solution is prepared according to the preparation process of embodiment 1, unlike, the catalysis being added in flash vaporization kettle 1 Agent deactivator is ethyl alcohol, and ethanol content is 110ppm in glue A；The amount of water that the first super mixer 3 is added is 3.0wt%, It is 0.8wt% that glue water content is added water into the second mixer 6, makes 40 DEG C of glue temperature after 7 heat exchange of heat exchanger processing, The concentration of final gained butyl rubber solution is 18.3wt%, content of monomer 1.8ppm, water content 0.8wt%, and temperature is 40℃。

According to the Mooney drop and primary bit architecture content of the test method test gained brombutyl of embodiment 1, as a result It has been shown that, Mooney are reduced to 10.0%, primary bit architecture content 11.2%, gel content 0.10wt%.

Embodiment 4

Butyl rubber solution is prepared according to the preparation process of embodiment 1, unlike, the catalysis being added in flash vaporization kettle 1 Agent deactivator is n-butyl ether, and n-butyl ether content is 210ppm in glue A；The amount of water that the first super mixer 3 is added is 3.5wt%, it is 0.8wt% that glue water content is added water into the second mixer 6, makes glue temperature after 7 heat exchange of heat exchanger processing Degree is 40 DEG C, and the concentration of final gained butyl rubber solution is 18.3wt%, content of monomer 1.9ppm, and water content is 0.8wt%, temperature are 40 DEG C.

According to the Mooney drop and primary bit architecture content of the test method test gained brombutyl of embodiment 1, as a result It has been shown that, Mooney are reduced to 9.9%, primary bit architecture content 11.5%, gel content 0.11wt%.

Embodiment 5

Butyl rubber solution is prepared according to the preparation process of embodiment 1, unlike, the catalysis being added in flash vaporization kettle 1 Agent deactivator is isobutyric acid, and isobutyl acid content is 410ppm in glue A；The amount of water that the first super mixer 3 is added is 2.0wt%, it is 3.5wt% that glue water content is added water into the second mixer 6, makes glue temperature after 7 heat exchange of heat exchanger processing Degree is 40 DEG C, and the concentration of final gained butyl rubber solution is 15.4wt%, content of monomer 1.6ppm, and water content is 3.5wt%, temperature are 40 DEG C.

According to the Mooney drop and primary bit architecture content of the test method test gained brombutyl of embodiment 1, as a result It has been shown that, Mooney are reduced to 9.7%, primary bit architecture content 10.0%, gel content 0.10wt%.

Embodiment 6

Butyl rubber solution is prepared according to the preparation process of embodiment 1, unlike, the catalysis being added in flash vaporization kettle 1 Agent deactivator is ethyl acetate, and ethyl acetate content is 610ppm in glue A；The amount of water that the first super mixer 3 is added is 2.5wt%, it is 0.7wt% that glue water content is added water into the second mixer 6, makes glue temperature after 7 heat exchange of heat exchanger processing Degree is 40 DEG C, and the concentration of final gained butyl rubber solution is 13.1wt%, content of monomer 2.0ppm, and water content is 0.7wt%, temperature are 40 DEG C.

According to the Mooney drop and primary bit architecture content of the test method test gained brombutyl of embodiment 1, as a result It has been shown that, Mooney are reduced to 9.6%, primary bit architecture content 11.7%, gel content 0.09wt%.

Embodiment 7

Butyl rubber solution is prepared according to the preparation process of embodiment 1, unlike, the catalysis being added in flash vaporization kettle 1 Agent deactivator is acetamide, and acetyl amine content is 710ppm in glue A；The amount of water that the first super mixer 3 is added is 6.0wt%, it is 1.8wt% that glue water content is added water into the second mixer 6, makes glue temperature after 7 heat exchange of heat exchanger processing Degree is 40 DEG C, and the concentration of final gained butyl rubber solution is 12.3wt%, content of monomer 1.8ppm, and water content is 1.8wt%, temperature are 40 DEG C.

According to the Mooney drop and primary bit architecture content of the test method test gained brombutyl of embodiment 1, as a result It has been shown that, Mooney are reduced to 9.5%, primary bit architecture content 10.2%, gel content 0.09wt%.

Embodiment 8

Butyl rubber solution is prepared according to the preparation process of embodiment 1, unlike, the catalysis being added in flash vaporization kettle 1 Agent deactivator is butyraldehyde, and butyraldehyde content is 830ppm in glue A；The amount of water that the first super mixer 3 is added is 7.0wt%, It is 2.5wt% that glue water content is added water into the second mixer 6, makes 35 DEG C of glue temperature after 7 heat exchange of heat exchanger processing, The concentration of final gained butyl rubber solution is 16.3wt%, content of monomer 1.8ppm, water content 2.5wt%, and temperature is 35℃。

According to the Mooney drop and primary bit architecture content of the test method test gained brombutyl of embodiment 1, as a result It has been shown that, Mooney are reduced to 9.3%, primary bit architecture content 10.5%, gel content 0.08wt%.

Embodiment 9

Butyl rubber solution is prepared according to the preparation process of embodiment 1, unlike, the catalysis being added in flash vaporization kettle 1 Agent deactivator is butanone, and butanone content is 450ppm in glue A；The amount of water that the first super mixer 3 is added is 9.2wt%, It is 4.5wt% that glue water content is added water into the second mixer 6, makes 40 DEG C of glue temperature after 7 heat exchange of heat exchanger processing, The concentration of final gained butyl rubber solution is 18.5wt%, content of monomer 2.2ppm, water content 4.5wt%, and temperature is 40℃。

According to the Mooney drop and primary bit architecture content of the test method test gained brombutyl of embodiment 1, as a result It has been shown that, Mooney are reduced to 9.7%, primary bit architecture content 10.2%, gel content 0.11wt%.

Embodiment 10

Butyl rubber solution is prepared according to the preparation process of embodiment 1, unlike, the catalysis being added in flash vaporization kettle 1 Agent deactivator is ethylenediamine, and ethylenediamine content is 530ppm in glue A；The amount of water that the first super mixer 3 is added is 3.5wt%, it is 0.8wt% that glue water content is added water into the second mixer 6, makes glue temperature after 7 heat exchange of heat exchanger processing Degree is 40 DEG C, and the concentration of final gained butyl rubber solution is 18.2wt%, content of monomer 3.6ppm, and water content is 0.8wt%, temperature are 40 DEG C.

According to the Mooney drop and primary bit architecture content of the test method test gained brombutyl of embodiment 1, as a result It has been shown that, Mooney are reduced to 9.5%, primary bit architecture content 11.3%, gel content 0.09wt%.

Embodiment 11

Butyl rubber solution is prepared according to the preparation process of embodiment 1, unlike, the catalysis being added in flash vaporization kettle 1 Agent deactivator is ethyl sulfide, and ethyl sulfide content is 850ppm in glue A；The amount of water that the first super mixer 3 is added is 7.2wt%, it is 0.8wt% that glue water content is added water into the second mixer 6, makes glue temperature after 7 heat exchange of heat exchanger processing Degree is 40 DEG C, and the concentration of final gained butyl rubber solution is 18.4wt%, content of monomer 4.7ppm, and water content is 0.8wt%, temperature are 40 DEG C.

According to the Mooney drop and primary bit architecture content of the test method test gained brombutyl of embodiment 1, as a result It has been shown that, Mooney are reduced to 9.0%, primary bit architecture content 11.5%, gel content 0.07wt%.

Comparative example 1

Butyl rubber solution is prepared according to the preparation process of embodiment 1, unlike, it is added without in flash vaporization kettle 1 any Catalyst deactivator, the concentration of final gained butyl rubber solution are 18.2wt%, content of monomer 1.6ppm, and water content is 1.0wt%, temperature are 43 DEG C.

According to the Mooney drop and primary bit architecture content of the test method test gained brombutyl of embodiment 1, as a result It has been shown that, Mooney are reduced to 10.5%, primary bit architecture content 10.3%, gel content 0.15wt%.

Comparative example 2

Butyl rubber solution is prepared according to the preparation process of comparative example 1, unlike, the first super mixer 3 is added Amount of water is 4.0wt%, and it is 0.6wt% that glue water content is added water into the second mixer 6, after 7 heat exchange of heat exchanger processing Make 45 DEG C of glue temperature, the concentration of final gained butyl rubber solution is 18.0wt%, content of monomer 1.7ppm, water content For 0.6wt%, temperature is 45 DEG C.

According to the Mooney drop and primary bit architecture content of the test method test gained brombutyl of embodiment 1, as a result It has been shown that, Mooney are reduced to 12.5%, primary bit architecture content 11.3%, gel content 0.18wt%.

Comparative example 3

Butyl rubber solution is prepared according to the preparation process of comparative example 1, unlike, the first super mixer 3 is added Amount of water is 3.0wt%, and it is 0.8wt% that glue water content is added water into the second mixer 6, after 7 heat exchange of heat exchanger processing Make 40 DEG C of glue temperature, the concentration of final gained butyl rubber solution is 18.3wt%, content of monomer 1.8ppm, water content For 0.8wt%, temperature is 40 DEG C.

According to the Mooney drop and primary bit architecture content of the test method test gained brombutyl of embodiment 1, as a result It has been shown that, Mooney are reduced to 13.3%, primary bit architecture content 11.0%, gel content 0.16wt%.

By the above test result it is found that present invention gained butyl rubber solution can make the Mooney of halogenated butyl rubber product It is reduced to 20%, primary bit architecture content is lower than 20%, and gel content is substantially reduced after introducing catalyst deactivator, gained halogen Change butyl rubber product and shows high quality.

The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.To these embodiments A variety of modifications will be readily apparent to those skilled in the art, the general principles defined herein can be with Without departing from the spirit or scope of the present invention, it realizes in other embodiments.Therefore, the present invention will not be limited In the embodiments shown herein, and it is to fit to widest model consistent with the principles and novel features disclosed in this article It encloses.

Claims

1. a kind of preparation method of butyl rubber solution, which comprises the following steps:

C) glue liquid B successively carried out once adding water process, dehydration, adjust concentration processing, secondary plus water process and changes Heat treatment, obtains butyl rubber solution；

2. preparation method according to claim 1, which is characterized in that the catalyst deactivator be selected from alcohol compound, One in ether compound, organic carboxyl acid and its derivative, aldehyde compound, ketone compounds, organic amine and sulfur-containing compound Kind is several.

3. preparation method according to claim 1 or 2, which is characterized in that the alcohol compound is selected from the one of C1~C8 One or more of the polyalcohol of the pure and mild C1~C8 of member；

The organic amine is selected from one or more of the primary amine of C1~C18, the secondary amine of C1~C18 and tertiary amine of C1~C18；

Content of the catalyst deactivator in glue A is 50~5000ppm.

4. preparation method according to claim 1, which is characterized in that the catalyst deactivator is in alcohol compound One or more.

5. preparation method according to claim 1, which is characterized in that described primary plus water process amount of water is 0.1wt%~10wt%；

6. preparation method according to claim 1, which is characterized in that the amount of water of the secondary plus water be 0.05wt%~ 5wt%；It is described change be heat-treated to temperature of charge be 30~60 DEG C.

7. preparation method according to claim 1, which is characterized in that described once to add water process in the first mixed at high speed item It is carried out under part；Shear rate≤300s of first mixed at high speed^-1；The processing time of first mixed at high speed be 10~ 60s；

Described secondary plus water process carries out under the second high speed mixing conditions；Shear rate≤300s of second mixed at high speed^-1；The processing time of second mixed at high speed is 10~60s.

8. preparation method according to claim 1, which is characterized in that the solvent in the step a) is selected from C4~C10's One or more of linear saturation alkane and the branch saturated alkane of C4~C10；