CN109942841B - Butyl rubber solution and preparation method thereof - Google Patents

Butyl rubber solution and preparation method thereof Download PDF

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CN109942841B
CN109942841B CN201910238116.1A CN201910238116A CN109942841B CN 109942841 B CN109942841 B CN 109942841B CN 201910238116 A CN201910238116 A CN 201910238116A CN 109942841 B CN109942841 B CN 109942841B
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butyl rubber
glue solution
solution
treatment
solvent
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CN109942841A (en
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徐宏德
任学斌
王衍金
崔红梅
滕杰
王孝海
栾波
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Shandong Jingbo Zhongju New Materials Co., Ltd.
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Shandong Jingbo Zhongju New Materials Co ltd
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Abstract

The invention provides a butyl rubber solution and a preparation method thereof. The preparation method provided by the invention comprises the following steps: a) contacting the polymer slurry with a solvent and a catalyst deactivator in a flash evaporation kettle to obtain a glue solution A; b) feeding the glue solution A into a stripping tower, and reversely contacting with solvent steam in the stripping tower to obtain a glue solution B; c) sequentially carrying out primary water adding treatment, dehydration treatment, concentration adjustment treatment, secondary water adding treatment and heat exchange treatment on the glue solution B to obtain a butyl rubber solution; the catalyst deactivator is a catalyst deactivator of the catalyst remaining in the polymer slurry. The glue solution prepared by the method has proper and stable concentration, low monomer content, proper water content, proper temperature and the like, and the halogenated butyl rubber prepared by the glue solution can have low gel content, low primary structure content and proper Mooney reduction.

Description

Butyl rubber solution and preparation method thereof
Technical Field
The invention relates to the technical field of rubber, and particularly relates to a butyl rubber solution and a preparation method thereof.
Background
At present, the industrial production of halogenated butyl rubber adopts a solution method, specifically, a butyl rubber solution with a certain concentration is obtained by dissolving a base rubber butyl rubber in a solvent, and then the butyl rubber solution reacts with halogen to obtain the halogenated butyl rubber. Thus, the obtainment of a butyl rubber solution is of crucial importance for the preparation of halogenated butyl rubbers, usually by preparing the base rubber butyl rubber and then treating the product to obtain a butyl rubber solution.
Among them, the slurry method is most commonly used for industrial production of the base gum butyl rubber. Specifically, firstly, a monomer is dissolved in chloromethane to obtain a mixed material, and the mixed material is subjected to multi-stage cooling to-100 ℃ and then enters a polymerization reactor. Meanwhile, the chloromethane solution dissolved with the catalyst is subjected to multi-stage cooling to reach-95 ℃ and then enters a polymerization reactor. The two materials are contacted, and the polymerization reaction is instantly finished to generate the butyl rubber polymer. The temperature of the material in the reactor is maintained between-100 ℃ and-90 ℃ by vaporization and heat removal of liquid ethylene. As the continuous operation time of the reaction kettle increases, the temperature of materials in the polymerization kettle gradually increases due to the deterioration of heat removal efficiency. When the temperature is higher than-90 ℃, the polymerization is stopped. The contents of the reactor contain butyl rubber product, unreacted monomer, catalyst, methyl chloride, etc. Among them, butyl rubber products are insoluble in methyl chloride, so that the whole material is always in a slurry state, which is commonly called polymer slurry in the field.
After obtaining the polymer slurry, the methyl chloride and the unreacted monomers are separated from the butyl rubber product and recovered, mainly in two ways: one method is to contact the polymer slurry in the reactor with high temperature water vapor and then to enter a flash evaporation kettle filled with hot water, where unreacted monomers and methyl chloride are recovered in a gas phase. Meanwhile, the polymer exists in a granular state in hot water, that is, a micelle-water mixture (this method is simply referred to as a steam stripping method in the present invention). After the micelle-water mixture is obtained, the mixture can be treated according to the conventional drying process to obtain a butyl rubber finished product and then dissolved to obtain a butyl rubber solution (called dry-process butyl rubber solution), or the micelle-water mixture can be directly contacted with a solvent to obtain the butyl rubber solution (called wet-process butyl rubber solution). Another method is to directly contact the polymer slurry in the reactor with a high temperature solvent, and dissolve the butyl rubber in the solvent to obtain a butyl rubber solution. At the same time, methyl chloride and unreacted monomers are recovered via the gas phase, a process known as solvent stripping.
However, the above steam stripping method has a great disadvantage in that methyl chloride and unreacted monomers are easily hydrolyzed to produce methanol, dimethyl ether and HCl when high-temperature steam and hot water are used to recover methyl chloride and unreacted monomers. Water and hydrolysis products bring a lot of adverse effects to methyl chloride recovery and unreacted monomer recovery systems, wherein methanol and dimethyl ether are poisons for butyl rubber polymerization reaction, and the content of the methyl alcohol and the dimethyl ether must be strictly controlled, otherwise, the polymerization reaction can be seriously affected. In order to remove water and hydrolysis products such as methanol and dimethyl ether in methyl chloride, the whole methyl chloride drying system is very large and complex, and the unit consumption of the methyl chloride is obviously increased; in addition, HCl or other chlorine compounds generated after the hydrolysis of methyl chloride corrode equipment, so that an unreacted monomer recovery processing system generates an autopolymer, one of which, isobutylene dimer is a strong chain transfer agent, which causes a decrease in the Mooney of the product, and therefore, the content thereof must be strictly controlled. The above problems can be well overcome by solvent stripping.
Some solutions for preparing butyl rubber solution by solvent stripping are disclosed in the prior art, for example, patent application CN103483483A discloses a butyl rubber stripping device and a stripping method, the device includes a flash tank and a stripping column. Methyl chloride and unreacted monomers in the polymer slurry from the polymerization kettle are evaporated out from the top of the flash evaporation kettle by using a hot solvent, and the butyl rubber solution is fed into a stripping tower from the bottom of the flash evaporation kettle; in a stripping tower, residual methyl chloride and monomers in the glue solution are evaporated out from the top of the stripping tower through a hot solvent, and a butyl rubber solution is obtained from the bottom of the stripping tower and can be sent to a halogenation system to prepare halogenated butyl rubber. Patent application CN104761659A discloses an apparatus and method for preparing butyl rubber solution for halogenation, the apparatus comprises a flash still and a guide sieve plate tower, methyl chloride and unreacted monomers in polymer slurry from a polymerization still are evaporated from the top of the flash still by using a hot solvent, and butyl rubber solution is fed into the high-efficiency guide sieve plate tower from the bottom of the flash still; in the high-efficiency guide sieve plate tower, residual chloromethane and monomers in the glue solution are evaporated from the top by a hot solvent, and a butyl rubber solution is obtained at the bottom and can be sent to a halogenation system to prepare halogenated butyl rubber.
However, the above prior art only considers the requirements of halogenation reaction on residual monomers and concentration of the butyl rubber dope, but in practice, these are far from sufficient to obtain high quality halogenated butyl rubber products. The Mooney drop from the base rubber to the halogenated butyl rubber and the microstructure of the halogenated butyl rubber have a significant effect on the properties of the halogenated butyl rubber, generally speaking, the Mooney drop cannot be higher than 20% ("Mooney drop" means the ratio of the Mooney of the butyl rubber base rubber entering the flash tank from the polymerization tank minus the Mooney of the halogenated butyl rubber to the Mooney of the base rubber), and the proportion of the primary III structure content in the brominated butyl rubber in the brominated structure is likewise not higher than 20% (brominated structure means the secondary II structure of bromine atoms and the primary III structure of bromine atoms, see patent applications CN105218719A, CN105622821A for details). The catalyst for the polymerization of the butyl rubber is Friedel-Crafts catalyst substances, and if the Friedel-Crafts catalyst substances exist in the high-temperature sol process, the base rubber is easily degraded, and the Mooney drop is increased directly. In addition, if a Friedel-Crafts catalyst species is present in the system during the halogenation reaction, the III structure content of the brominated product increases (see U.S. Pat. No. 4,632,963).
For solvent stripping processes, residual catalyst in the polymer slurry is present throughout the sol process, and the longer the residence time, the greater the Mooney drop, and also the increased III structure content of the brominated product. In addition, in the flash evaporation and stripping processes, the concentration of unreacted monomers in the flash evaporation kettle and the stripping tower is very high, and the residual active catalyst can react with the unreacted monomers at high temperature to form oligomers and can attack unsaturated double bonds in polymers to form gel; excessive oligomers and gels can adversely affect product properties, such as quality defects in the product, clogging of tubing by adhesion to equipment and tubing surfaces, reduced heat transfer efficiency, and the like. Therefore, it is difficult to prepare a halogenated butyl rubber product having a low primary structure content, a low gel content and a suitable Mooney reduction from the butyl rubber solution prepared by the above-mentioned prior art.
Disclosure of Invention
In view of the above, the present invention is directed to a butyl rubber solution and a method for preparing the same. The butyl rubber solution prepared by the invention can be used for preparing halogenated butyl rubber products with low primary structure content, proper Mooney reduction and low gel content.
The invention provides a preparation method of a butyl rubber solution, which comprises the following steps:
a) contacting the polymer slurry with a solvent and a catalyst deactivator in a flash evaporation kettle to obtain a glue solution A;
b) feeding the glue solution A into a stripping tower, and reversely contacting with solvent steam in the stripping tower to obtain a glue solution B;
c) sequentially carrying out primary water adding treatment, dehydration treatment, concentration adjustment treatment, secondary water adding treatment and heat exchange treatment on the glue solution B to obtain a butyl rubber solution;
the catalyst deactivator is a catalyst deactivator of the catalyst remaining in the polymer slurry.
Preferably, the catalyst deactivator is one or more selected from alcohol compounds, ether compounds, organic carboxylic acids and derivatives thereof, aldehyde compounds, ketone compounds, organic amines and sulfur-containing compounds.
Preferably, the alcohol compound is selected from one or more of monohydric alcohol of C1-C8 and polyhydric alcohol of C1-C8;
the ether compound is selected from one or more of C2-C8 ether compounds;
the organic carboxylic acid is selected from one or more of C1-C18 organic carboxylic acids;
the aldehyde compound is selected from one or more of C1-C18 aldehyde compounds;
the ketone compound is selected from one or more of C2-C18 ketone compounds;
the organic amine is selected from one or more of primary amine of C1-C18, secondary amine of C1-C18 and tertiary amine of C1-C18;
the sulfur-containing compound is selected from one or more of hydrogen sulfide, thioether and mercaptan;
the content of the catalyst deactivator in the glue solution A is 50-5000 ppm.
Preferably, the catalyst deactivator is selected from one or more of alcohol compounds.
Preferably, the water adding amount of the primary water adding treatment is 0.1-10 wt%;
dehydrating the materials until the water content of the materials is 0.1-1.0 wt%;
and the concentration is adjusted until the material concentration is 5wt% -25 wt%.
Preferably, the water adding amount of the secondary water adding is 0.05wt% -5 wt%;
and performing heat exchange treatment until the material temperature is 30-60 ℃.
Preferably, the primary water addition treatment is carried out under first high-speed mixing conditions; the shear rate of the first high-speed mixing is less than or equal to 300s-1(ii) a The processing time of the first high-speed mixing is 10-60 s;
the secondary water addition treatment is carried out under a second high-speed mixing condition; the shear rate of the second high-speed mixing is less than or equal to 300s-1(ii) a The processing time of the second high-speed mixing is 10-60 s.
Preferably, the solvent in the step a) is one or more selected from linear saturated alkanes of C4-C10 and branched saturated alkanes of C4-C10;
the temperature of the solvent in the step a) is 30-200 ℃;
the water content of the solvent in the step a) is less than or equal to 100 ppm;
the concentration of the glue solution A is 5wt% -15 wt%.
Preferably, the solvent in the step b) is one or more selected from linear saturated alkanes of C4-C10 and branched saturated alkanes of C4-C10;
the water content of the solvent in the step b) is less than or equal to 100 ppm;
the working temperature of the bottom of the stripping tower in the step b) is 50-90 ℃;
the concentration of the glue solution B is 5-15 wt%;
the concentration of the butyl rubber solution is 10wt% -20 wt%.
The invention also provides the butyl rubber solution prepared by the preparation method in the technical scheme.
The invention provides a preparation method of a butyl rubber solution, which comprises the following steps: a) contacting the polymer slurry with a solvent and a catalyst deactivator in a flash evaporation kettle to obtain a glue solution A; b) feeding the glue solution A into a stripping tower, and reversely contacting with solvent steam in the stripping tower to obtain a glue solution B; c) sequentially carrying out primary water adding treatment, dehydration treatment, concentration adjustment treatment, secondary water adding treatment and heat exchange treatment on the glue solution B to obtain a butyl rubber solution; the catalyst deactivator is a catalyst deactivator of the catalyst remaining in the polymer slurry. According to the invention, the polymer slurry is firstly contacted with a solvent and a catalyst deactivator in a flash evaporation kettle, the catalyst deactivator in the polymer sludge is deactivated, and then the polymer slurry is subjected to solvent treatment in a stripping tower and then is subjected to primary water adding treatment, dehydration treatment, concentration adjustment treatment, secondary water adding treatment and heat exchange treatment in sequence, so that the butyl rubber solution is obtained. According to the preparation method disclosed by the invention, the butyl rubber solution can be provided with proper and stable concentration, low monomer content, proper water content, proper temperature and the like, and the halogenated butyl rubber can be prepared by feeding the butyl rubber solution into a halogenation reaction system, so that the halogenated butyl rubber product has low primary structure content, proper Mooney reduction and lower gel amount.
The experimental result shows that the butyl rubber solution provided by the invention can reduce the Mooney of halogenated butyl rubber products to 20%, the primary structure content to less than 20% and the gel amount to less than 0.11 wt%, so that the halogenated butyl rubber products with excellent performance are obtained.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are only embodiments of the invention, and that for a person skilled in the art, other drawings can be obtained from the provided drawings without inventive effort.
FIG. 1 is a schematic view of an apparatus for preparing a butyl rubber solution according to an embodiment of the present invention;
fig. 2 is a schematic view of a buffering device according to an embodiment of the present invention.
Detailed Description
The invention provides a preparation method of a butyl rubber solution, which is characterized by comprising the following steps:
a) contacting the polymer slurry with a solvent and a catalyst deactivator in a flash evaporation kettle to obtain a glue solution A;
b) feeding the glue solution A into a stripping tower, and reversely contacting with solvent steam in the stripping tower to obtain a glue solution B;
c) sequentially carrying out primary water adding treatment, dehydration treatment, concentration adjustment treatment, secondary water adding treatment and heat exchange treatment on the glue solution B to obtain a butyl rubber solution;
the catalyst deactivator is a catalyst deactivator of the catalyst remaining in the polymer slurry.
According to the invention, the polymer slurry is firstly contacted with a solvent and a catalyst deactivator in a flash evaporation kettle, the catalyst deactivator in the polymer sludge is deactivated, and then the polymer slurry is subjected to solvent treatment in a stripping tower and then is subjected to primary water adding treatment, dehydration treatment, concentration adjustment treatment, secondary water adding treatment and heat exchange treatment in sequence, so that the butyl rubber solution is obtained. According to the preparation method disclosed by the invention, the butyl rubber solution can be provided with proper and stable concentration, low monomer content, proper water content, proper temperature and the like, and the halogenated butyl rubber can be prepared by feeding the butyl rubber solution into a halogenation reaction system, so that the halogenated butyl rubber product has low primary structure content, proper Mooney reduction and lower gel amount.
In the present invention, unless otherwise specified, "Mooney drop" refers to the ratio of the Mooney of the base rubber to the Mooney of the butyl rubber base rubber minus the Mooney of the halogenated butyl rubber entering the flash tank from the polymerization tank.
According to the invention, the polymer slurry is firstly contacted with a solvent and a catalyst deactivator in a flash evaporation kettle to obtain a glue solution A.
The present invention is not particularly limited in kind and source of the polymer slurry, and is a polymer slurry produced when a butyl rubber base gum is prepared by a slurry process well known to those skilled in the art. For example, halogenated alkane is used as a medium, and the monomer is subjected to polymerization reaction under the action of a catalyst to obtain polymer slurry.
The medium used in butyl rubber slurry polymerization generally needs to satisfy the following conditions: one is that the polymer is in a slurry state in the medium; secondly, the monomer and the catalyst can be dissolved simultaneously; thirdly, the polymer is liquid at the polymerization temperature; the medium used for the industrial polymerization is therefore generally an alkyl halide, preferably methyl chloride.
The monomers preferably include a first monomer and a second monomer. Wherein, the first monomer is preferably one or more of isomonoolefin of C4-C7, and is more preferably isobutene; the second monomer is preferably one or more of C4-C14 conjugated diene and methyl styrene, and is more preferably isoprene.
The catalyst preferably comprises a main catalyst and a cocatalyst; wherein, the main catalyst is preferably HCl and/or water; the cocatalyst is preferably a Friedel-Crafts catalyst, more preferably BF3、TiCl4、AlCl3、AlEtCl2And AlEt2One or more of Cl.
The polymerization temperature of the polymerization reaction is preferably-100 ℃ to-90 ℃. In the polymerization reaction, the use amount of each material is not particularly limited, and the polymerization reaction is carried out according to the conventional proportion for industrially producing butyl rubber in the field. Taking isobutylene/isoprene copolymerization to produce butyl rubber as an example, in normal industrial production, the concentration of isobutylene in a mixed material entering a reactor is 20wt% -40 wt%, and the ratio of isoprene to isobutylene is 2.0 wt% -4.0 wt%. The polymerization reaction is fast, the reaction is completed within milliseconds or even microseconds, and the polymerization product butyl rubber is insoluble in a medium, so that the whole polymerization system is a slurry heterogeneous system, namely polymer slurry in the system.
In the present invention, before entering the flash tank, the flow rate, temperature and pressure of the polymer slurry are not particularly limited, that is, the feeding parameters of the polymer slurry are not particularly limited, and the feeding may be performed according to the transportation conditions of the conventional production flow in the art. In one embodiment of the invention, the polymer slurry has a flow rate of 10.6kg/h, a temperature of-93 ℃ and a pressure of 2 bar.
In the invention, the solvent is preferably one or more of linear saturated alkane of C4-C10 and branched saturated alkane of C4-C10; more preferably one or more of C5-C8 straight-chain saturated alkane and C5-C8 branched-chain saturated alkane; in some embodiments of the invention, the solvent is hexane. In the present invention, the water content of the solvent is strictly controlled. During the flash evaporation and stripping, water in the solvent is more likely to enter methyl chloride due to the difference in polarity. If the water content of the solvent is too high, the water value of the recovered materials after polymerization is easily influenced, the subsequent polymerization reaction is influenced, the performance of halogenated butyl rubber products is further influenced, and a great deal of adverse influence is brought to a chloromethane and monomer recovery system. Therefore, the methyl chloride and monomer recovery system needs to be additionally provided with a drying and impurity removing unit, so that the whole methyl chloride system is very large and complicated, the unit consumption of the methyl chloride is obviously increased, the same problem as that generated by a steam stripping method is caused, and the advantages of a solvent stripping method are lost. In the present invention, the water content of the solvent is preferably 100ppm or less, more preferably 50ppm or less, and still more preferably 10ppm or less.
In the invention, before entering the flash evaporation kettle, the technological parameters of the solvent are not specially limited, namely the feeding parameters of the solvent are not specially limited, and the solvent is carried out according to the conveying conditions of the conventional production flow in the field; the method is only required to ensure that most of chloromethane and unreacted monomers enter a recovery system and butyl rubber solution with proper concentration is obtained at the same time. The temperature of the solvent is preferably 30-200 ℃. In one embodiment of the invention, the solvent is supplied at a flow rate of 25.0kg/h, at a temperature of 138 ℃ and at a pressure of 6 bar.
In the present invention, a catalyst deactivator is also added to the flash tank to deactivate residual catalyst and active sites in the polymer slurry. The type of the catalyst deactivator is not particularly limited in the present invention, and may be a deactivator capable of deactivating a catalyst in a polymer slurry, which is well known to those skilled in the art. Preferably, the catalyst deactivator is one or more selected from the group consisting of alcohol compounds, ether compounds, organic carboxylic acids and derivatives thereof, aldehyde compounds, ketone compounds, organic amines and sulfur-containing compounds, and more preferably, the alcohol compounds.
Wherein the alcohol compound is preferably one or more of monohydric alcohol of C1-C8 and polyhydric alcohol of C1-C8; the polyols include dihydric, trihydric and higher alcohol compounds. More preferably, the alcohol compound is selected from one or more of methanol, ethanol, propanol, butanol, tert-butanol, ethylene glycol, diethylene glycol and triethylene glycol. The ether compound is preferably one or more of C2-C8 ether compounds; more preferably one or more of dimethyl ether, diethyl ether, methyl ethyl ether, n-butyl ether, tetrahydrofuran, 1, 4-dioxane and anisole. The organic carboxylic acid is preferably one or more of C1-C18 organic carboxylic acids; more preferably one or more of formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid and stearic acid. The derivative of the organic carboxylic acid is preferably one or more of acyl, nitrile, anhydride and ester of C2-C20; more preferably one or more of acetamide, methylacetamide, acetonitrile, acetic anhydride, methyl acetate, ethyl acetate and stearate. The aldehyde compound is preferably one or more of C1-C18 aldehyde compounds; more preferably one or more of formaldehyde, acetaldehyde, butyraldehyde and crotonaldehyde. The ketone compound is preferably one or more of C2-C18 ketone compounds; more preferably one or more of acetone, butanone and cyclohexanone. The organic amine is preferably a primary amine (i.e., primary amine, RNH) of C1-C182) Secondary amines of C1 to C18 (i.e., secondary amines, R)2NH) and C1-C18 tertiary amines (i.e., tertiary amines, R)3N) one or more of the compounds; more preferably one or more of methylamine, aniline, ethylenediamine, diisopropylamine and triethanolamine. The sulfur-containing compound is preferably one or more of hydrogen sulfide, thioether and mercaptan; more preferably hydrogen sulfide, methyl mercaptan, ethyl mercaptan, methyl sulfide and ethyl sulfideOne or more of them.
The content of the catalyst deactivator in the glue solution A is preferably 50-5000 ppm, more preferably 100-1000 ppm, if the content is too low, the deactivation effect is poor, and if the content is too high, the subsequent halogenation reaction is influenced.
The polymer slurry, the catalyst deactivator and the solvent are respectively conveyed to the flash evaporation kettle through respective conveying pipelines, and before being conveyed to the flash evaporation kettle, the conveying pipelines of the polymer slurry, the catalyst deactivator and the solvent can be merged in advance, namely a feed pipe is communicated with a feed inlet of the flash evaporation kettle and is respectively communicated with the conveying pipeline of the polymer slurry, the conveying pipeline of the solvent and the conveying pipeline of the catalyst deactivator; the catalyst deactivator and solvent may also be transferred to the flash tank through the same conduit. The polymer slurry, the solvent and the catalyst deactivator are conveyed to the feeding pipe through respective conveying pipelines to be mixed, and then are conveyed into the flash evaporation kettle together.
In the invention, the working temperature and pressure of the flash evaporation kettle are not particularly limited and can be implemented according to the process parameters of the conventional production flow in the field; in some embodiments of the invention, the working temperature of the flash evaporation kettle is 30-70 ℃, and the working pressure is 1-5 bar. After the three materials are fully mixed in the flash evaporation kettle, most of the methyl chloride and unreacted monomers in the polymer slurry are gasified, discharged from the top of the flash evaporation kettle along with part of the gas phase solvent and recovered by a recovery system, and most of the methyl chloride and the unreacted monomers in the polymer slurry are removed. At the same time, the catalyst deactivator reacts with the catalyst and active sites in the polymer slurry, deactivating the catalyst and active sites and reducing the adverse effects of the catalyst. And the butyl rubber in the polymer slurry is quickly dissolved in the solvent to form a butyl rubber solution, and the butyl rubber solution, namely the glue solution A, is obtained at the bottom of the flash evaporation kettle. The concentration of the glue solution A is preferably 5wt% -15 wt%.
According to the invention, after the glue solution A is obtained, the glue solution A is sent into a stripping tower and is in reverse contact with solvent steam in the stripping tower to obtain a glue solution B.
The invention has no special limit on the flow, temperature and pressure of the glue solution A fed into the stripping tower, namely the feeding parameters of the stripping tower are not special limit, and the invention can be implemented according to the conveying conditions of the conventional production flow in the field. In one embodiment of the invention, the flow rate of the glue solution A is 24.0kg/h, the temperature is 50 ℃, and the pressure is 1.52 bar.
The structure of the stripping tower is not particularly limited, and the stripping tower is a conventional stripping tower in the field; in some embodiments of the invention, the number of trays in the stripper is 55, with 30 trays in the upper portion and 25 trays in the lower portion of the stripper inlet.
In the invention, the glue solution A enters a stripping tower and then reversely contacts with the solvent steam. The solvent vapor may be from the solvent vapor fed separately to the stripper or from the bottoms stream. The solvent is preferably one or more of linear saturated alkane of C4-C10 and branched saturated alkane of C4-C10; more preferably one or more of C5-C8 straight-chain saturated alkane and C5-C8 branched-chain saturated alkane; in some embodiments of the invention, the solvent is hexane. In the present invention, the water content of the solvent is preferably 100ppm or less, more preferably 50ppm or less, and still more preferably 10ppm or less. The present invention is not particularly limited in the flow rate, temperature and pressure of the solvent vapor, and may be carried out according to the transport conditions of the conventional production flow in the art. In some embodiments of the invention, the solvent vapor is from a bottoms stream; the stripping is achieved by heating the bottoms cycle to produce solvent vapor. The working temperature and pressure of the stripping tower are not particularly limited, and the stripping tower can be implemented according to the process parameters of the conventional production flow in the field; in some embodiments of the invention, the working temperature at the bottom of the stripping tower is 50-90 ℃ and the working pressure is 0.05-5 bar.
And after the glue solution A and the solvent steam are in reverse contact in the stripping tower, forming tower top materials by residual methyl chloride and unreacted monomers in the glue solution A and part of the gas-phase solvent, discharging the materials from the top of the stripping tower, further removing the residual methyl chloride and the unreacted monomers in the glue solution A, and simultaneously obtaining a glue solution B at the bottom of the stripping tower. The concentration of the glue solution B is 5-15 wt%, wherein the content of unreacted monomer isoprene is less than or equal to 20ppm, preferably less than or equal to 10ppm, and more preferably less than or equal to 5 ppm.
In the invention, preferably, the material at the top of the tower is discharged from the top of the stripping tower and then flows in two ways, and one material is recovered through a recovery system. Specifically, the gas phase material can be converged with the gas phase material discharged from the top of the flash evaporation kettle and enter a recovery system together; in one embodiment of the invention, the flow rate of this stream is 2.8kg/h, the temperature is 41 ℃ and the pressure is 1.21 bar. And carrying out reflux treatment on the second strand of material, specifically, carrying out heat exchange and then refluxing to the stripping tower. In an embodiment of the invention, a heat exchanger and a buffer tank are arranged in the reflux passage, the second material is subjected to heat exchange treatment by the heat exchanger, then is sent to the buffer tank, and then is refluxed to the stripping tower to be subjected to steam stripping treatment, so that residual monomers and methyl chloride in the glue solution are removed as far as possible, the residual monomers and the methyl chloride are fully separated from the glue solution, and the separation efficiency is improved.
In the invention, preferably, the glue solution at the bottom of the tower is divided into two paths, one glue solution is preferably subjected to reflux treatment, and specifically, one glue solution flows out from the bottom of the stripping tower, is subjected to reboiling treatment by a reboiler, and then flows back to the stripping tower to heat the glue solution at the bottom of the tower to generate solvent steam, so that the gasification and discharge of methyl chloride and unreacted monomers in the glue solution are further facilitated, and the separation efficiency of the methyl chloride and the unreacted monomers and the purity of the glue solution at the bottom of the tower are improved. And the other strand of material is used as the tower bottom glue solution B and is sent to the subsequent working procedure for continuously preparing the butyl glue solution.
According to the invention, after the glue solution B is obtained, the glue solution B is subjected to primary water adding treatment, dehydration treatment, concentration treatment, secondary water adding treatment and heat exchange treatment to obtain the butyl rubber solution.
In the present invention, the purpose of the one-time water addition is to further deactivate the residual catalyst in the dope solution to reduce the Mooney drop. The water addition amount of the primary water addition treatment is preferably 0.1wt% to 10wt%, and more preferably 0.5 wt% to 5 wt%. In the present invention, the amount of water added is the ratio of the mass of water added to the material to the mass of the total material after the water is added. The water is preferably deionized water, referenced to standard ISO/TC 147.
In some embodiments, the parameters of the glue solution B during one-time water adding treatment are as follows: the flow rate of the glue solution B is 21.2kg/h, the temperature is 84 ℃, and the pressure is 1.61 bar. The parameters of the water are as follows: the flow rate of water was 1.1kg/h, the temperature was 25 ℃, the pressure was 5bar and the amount of water added was 4.9 wt%.
In the present invention, the primary water addition treatment is preferably performed under the first high-speed mixing condition; the high-speed mixing can be achieved by means of a high-speed mixer with stirring. Preferably, the shear rate of the first high-speed mixing is less than or equal to 300s-1(ii) a The processing time of the first high-speed mixing is 10-60 s. The shear rate is too low, which is not beneficial to the rapid and uniform mixing of the two materials; the shear rate is too high, the polymer molecular chains are easily broken, resulting in an increase in the Mooney drop. The same results are obtained with mixing times which, if too long, are on the one hand an increase in energy consumption and, on the other hand, an increase in the Mooney drop due to the breaking of the polymer chains; if the mixing time is too short, the two materials are not well mixed. Under the mixing condition, the glue solution is fully mixed with water, and the residual catalyst is stopped, so that the Mooney drop is reduced. And uniformly mixing the glue solution B with water to obtain a glue solution C.
Dewatering after the primary water adding treatment. The purpose of the dehydration treatment is three: one is that acidic substances after residual catalyst in a glue solution/water mixed system is deactivated are reduced by removing a water phase, so that the negative influence of the acidic substances on a subsequent halogenation reaction is reduced; secondly, the concentration of the glue solution is stabilized; thirdly, the water-soluble catalyst deactivator of partial species can be removed, and the influence on the subsequent halogenation reaction is avoided. In the present invention, the dehydration treatment is preferably performed until the water content of the material is 0.1wt% to 1.0wt%, more preferably 0.3 wt% to 1.0 wt%. Most of the acidic water is removed through the dehydration treatment, so that the adverse effect of the acidic water on the subsequent halogenation reaction can be reduced, the concentration distribution of the obtained glue solution can be more uniform, and the performance of the subsequent halogenated rubber product can be promoted.
In the invention, the dehydration treatment is preferably carried out by means of a standing water-dividing tank, and most of water in the material can automatically settle and layer from the glue solution to the bottom of the tank in the standing water-dividing tank; in some embodiments of the invention, the retention time of the material in the standing water separation tank is 6-12 h. The retention time is too short to completely achieve the purpose of dehydrating and homogenizing the glue solution; the residence time is too long, the investment and operation costs are too high, and the dewatering effect is not much better. After the residence time, the water content of the material can reach the target dehydration amount and basically keep stable.
In the invention, in the dehydration treatment, besides the standing water diversion tank, a receiving tank and an output tank are preferably connected in parallel, wherein the receiving tank is used for receiving and uniformly mixing the glue solution C, and the output tank is used for conveying the glue solution after the dehydration treatment to the subsequent process. And (4) dehydrating to obtain a glue solution D.
And (4) performing concentration adjustment treatment after the dehydration treatment. In the invention, the concentration adjusting treatment preferably comprises concentration treatment or concentration reduction treatment; in some embodiments of the present invention, if the concentration of the delivered glue solution is low, the concentration of the glue solution is increased by vacuum heating, and if the concentration of the delivered glue solution is high, the concentration is decreased by adding metered solvent; the concentration adjustment process may be performed in a concentration adjuster. In the present invention, the concentration of the material is preferably adjusted to 5 to 25wt%, more preferably 10 to 20 wt%. In some embodiments of the present invention, when performing the concentration adjustment, the delivery parameters of the glue solution D are preferably as follows: the flow rate of the glue solution D is 21.3kg/h, the temperature is 55 ℃, and the pressure is preferably 1.61 bar.
The concentration control of the butyl rubber glue solution is very difficult, mainly due to the characteristic of butyl rubber polymerization, and the butyl polymerization reaction kettle needs to stop reaction periodically to carry out cleaning operation. In practical production, there are usually 3-5 polymerization reaction kettles, and in general, when one reaction kettle stops reaction, another reaction kettle is fed to start reaction, so as to ensure that the whole production system is as stable as possible; however, in the process of stopping-feeding, the amount of butyl rubber fed into the butyl rubber glue solution preparation system by the stopping reaction kettle is gradually reduced, and the amount of butyl rubber fed into the glue solution preparation system by the reaction kettle starting to react is gradually increased, so that the amount of butyl rubber actually fed into the glue solution preparation system is always in a fluctuation state, and further, the concentration of the obtained butyl rubber glue solution is not stable any more and is always in a fluctuation state. This brings great trouble to the subsequent halogenation reaction and the quality of halogenated butyl rubber products, and it is difficult to obtain high quality halogenated butyl rubber products, and the product quality stability is poor, and it is difficult to realize continuous large-scale production of qualified halogenated butyl rubber products. The concentration adjusting step is arranged, the concentration of the glue solution is adjusted in advance, concentration reduction is carried out if the concentration of the conveyed glue solution is higher, concentration extraction is carried out if the concentration of the conveyed glue solution is lower, and the concentration of the glue solution is always stabilized in a proper concentration range, so that the problems are solved, high-quality products can be obtained, smooth continuous large-scale production can be realized, and the quality stability of products in each batch can be ensured. And obtaining the glue solution E after the concentration adjustment treatment.
The applicant finds that the water value and the temperature of the butyl rubber glue solution can also have great influence on the Mooney reduction and the primary structure content of halogenated butyl rubber products besides the glue solution concentration and the monomer content. After the glue solution B is obtained, the glue solution is subjected to the series of primary water adding treatment, dehydration treatment, concentration adjustment treatment and secondary water adding treatment, so that the water value of the butyl rubber glue solution is adjusted to be in a proper range and is kept stable. Meanwhile, the concentration of the glue solution is kept stable, so that the Mooney reduction and the primary structure content of subsequent halogenated butyl rubber products are reduced, and high-quality halogenated butyl rubber products are obtained.
In the secondary water adding step, the water adding amount needs to be strictly controlled. If the water addition amount is too much, the conversion rate of halogenation reaction is reduced, and the consumption of raw materials is increased; if the water addition amount is too small, the content of primary III structure in halogenated products cannot be effectively reduced. In the present invention, the amount of water added in the secondary water addition treatment is preferably 0.05wt% to 5wt%, and more preferably 0.1wt% to 1 wt%. In the present invention, the amount of water added is the ratio of the mass of water added to the material to the mass of the total material after the water is added. The water is preferably deionized water, referenced to standard ISO/TC 147.
In the present invention, the process of the secondary water addition treatment is not particularly limited. In some embodiments of the invention, the process parameters of the secondary addition of water are as follows: the flow rate of the glue solution E is 14.9kg/h, the temperature is 83 ℃, and the pressure is 1.72 bar. The water delivery parameters were as follows: the flow rate of water was 0.1kg/h, the temperature was 25 ℃ and the pressure was 5.01 bar.
In the present invention, the secondary water addition treatment is preferably performed under the second high-speed mixing condition; the high-speed mixing can be achieved by means of a high-speed mixer with stirring. Preferably, the shear rate of the second high-speed mixing is less than or equal to 300s-1(ii) a The processing time of the second high-speed mixing is 10-60 s. The shear rate and mixing time reasons were the same as for the first high-speed mixer. And (3) adjusting the water content of the glue solution to a proper range and keeping the glue solution stable after the secondary water adding treatment, wherein the obtained glue solution is marked as F.
And performing heat exchange treatment after the secondary water adding treatment. The heat exchange treatment can be carried out by means of a heat exchange device, so that the glue solution F is adjusted to a proper temperature. In the invention, the heat exchange treatment is preferably carried out to ensure that the material temperature reaches 30-60 ℃. After the treatment, the glue solution reaches a proper temperature, which is beneficial to improving the quality of subsequent halogenated butyl rubber products.
The invention provides a preparation method of a butyl rubber solution, which comprises the steps of firstly contacting polymer slurry with a solvent and a catalyst deactivator in a flash evaporation kettle, deactivating a catalyst and an active center in the polymer slurry by using the catalyst deactivator, then sequentially carrying out primary water adding treatment, dehydration treatment, concentration adjustment treatment, secondary water adding treatment and heat exchange treatment after the polymer slurry is subjected to solvent treatment in a stripping tower, and thus obtaining the butyl rubber solution. According to the preparation method disclosed by the invention, the butyl rubber solution can be provided with proper and stable concentration, low monomer content, proper water content, proper temperature and the like, and the halogenated butyl rubber can be prepared by feeding the butyl rubber solution into a halogenation reaction system, so that the halogenated butyl rubber product has low primary structure content, proper Mooney reduction and lower gel amount. Specifically, the preparation method can control the concentration of the butyl rubber solution to be 10-20 wt%, the monomer content to be less than or equal to 5ppm, the water content to be 0.1-1 wt%, and the temperature to be 30-60 ℃, and the concentration and the water value can be kept stable, so that the primary structure content of the halogenated butyl rubber is lower than 20%, the Mooney property is reduced by 20%, the gel content is reduced, and excellent product quality is shown.
The invention also provides a butyl rubber solution prepared by the preparation method in the technical scheme. The obtained butyl rubber solution has proper and stable concentration, low monomer content, proper water content, temperature and the like, so that the subsequent halogenated butyl rubber product has low primary structure content, proper Mooney reduction and lower gel content, and the high-quality halogenated butyl rubber product is obtained.
The invention also provides halogenated butyl rubber which is prepared from the butyl rubber solution; the butyl rubber solution is the butyl rubber solution in the technical scheme. The resulting halogenated butyl rubber product has a low primary structure content, a suitable Mooney reduction and a low gel content.
The preparation method of the halogenated butyl rubber product prepared by the butyl rubber solution is not particularly limited, and the method is a conventional process flow for preparing the halogenated butyl rubber by using the butyl rubber solution in the field; such as halogenating reaction, neutralization, addition of an auxiliary agent, coagulation and drying of the butyl rubber solution to obtain a halogenated butyl rubber product. The present invention is not particularly limited with respect to the above-mentioned conditions and parameters in the halogenation, neutralization, addition of an auxiliary, coagulation and drying steps, and the kind and proportion of the materials used, and may be carried out according to the conventional procedures in the art for preparing halogenated butyl rubber from a butyl rubber solution. The temperature of the halogenation reaction is preferably 10-80 ℃, and more preferably 30-60 ℃; the time of the halogenation reaction is preferably 3-10 min.
The invention also provides a device for preparing the butyl rubber solution, which comprises the following components:
a flash evaporation kettle 1;
the feeding port of the stripping tower 2 is communicated with the discharging port of the flash evaporation kettle 1;
a first high-speed mixer 3 with a feeding hole communicated with a discharging hole of the stripping tower 2;
the feeding hole of the buffering device 4 is communicated with the discharging hole of the first high-speed mixer 3;
the feed inlet is communicated with the discharge outlet of the buffer device 4;
a second high-speed mixer 6 with a feed inlet communicated with the discharge port of the concentration regulator 5;
and the feeding hole of the heat exchange device 7 is communicated with the discharging hole of the second high-speed mixer 6.
Referring to fig. 1, fig. 1 is a schematic view of a butyl rubber solution preparation apparatus according to an embodiment of the present invention. Wherein, 1 is the flash distillation cauldron, 2 is the stripper, 3 is first high-speed mixer, 4 is buffer, 5 is concentration regulator, 6 is the second high-speed mixer, 7 is heat transfer device.
The flash evaporation kettle 1 is used for receiving polymer slurry generated by a polymerization reaction kettle in the production industry of butyl rubber, a catalyst deactivator and an externally sent solvent, and the three are contacted in the flash evaporation kettle 1. Most of the methyl chloride and unreacted monomers in the polymer slurry are vaporized and discharged from the top of the flash tank along with part of the gas phase solvent, and then recovered by a recovery system. The catalyst deactivator deactivates the catalyst in the polymer slurry, and simultaneously, the butyl rubber in the polymer slurry is quickly dissolved in the solvent to form a butyl rubber solution, and the butyl rubber solution, namely the glue solution A, is obtained at the bottom of the flash evaporation kettle. The conveying parameters of the polymer slurry, the types and the conveying parameters of the solvent, the working parameters of the flash evaporation kettle and the like are consistent with those in the technical scheme, and are not described again.
Referring to fig. 1, in some embodiments of the present invention, the preparation apparatus further comprises a polymerization reactor 10, wherein a discharge port of the polymerization reactor 10 is communicated with a feed port of the flash tank 1 for feeding the polymer slurry into the flash tank 1. The structure of the polymerization reactor 10 is not particularly limited, and may be a conventional polymerization reactor in the butyl rubber production industry in the field.
In some embodiments of the present invention, the preparation apparatus further comprises a recovery system (not shown in the figure), wherein a gas inlet of the recovery system is communicated with a gas outlet of the flash evaporation kettle 1 and is used for recovering gas-phase materials (comprising methyl chloride, unreacted monomers and part of solvent) discharged from the top of the flash evaporation kettle 1. The present invention is not particularly limited in the structure of the recovery system, and may be a conventional recovery system in the art of preparing a butyl rubber solution.
The feed inlet of the stripping tower 2 is communicated with the discharge outlet of the flash evaporation kettle 1, and particularly communicated with the glue solution discharge outlet at the kettle bottom of the flash evaporation kettle 1. The structure of the stripping tower 2 is not particularly limited, and the stripping tower is a conventional stripping tower in the field; in some embodiments of the invention, the number of trays in the stripper is 55, with 30 trays in the upper portion of the stripper feed and 25 trays in the lower portion. And the glue solution A generated at the bottom of the flash evaporation kettle enters the stripping tower from a feed inlet of the stripping tower 2, meanwhile, solvent steam is generated at the bottom of the stripping tower, and the glue solution A is in reverse contact with the solvent steam, so that residual methyl chloride and unreacted monomers in the glue solution A and part of gas-phase solvent form tower top materials, the materials are discharged from the top of the stripping tower and enter a recovery system, and meanwhile, the glue solution B is obtained at the bottom of the stripping tower. The conveying parameters, the types and the conveying parameters of the glue solution A, the working parameters of the stripping tower and the like are consistent with those in the technical scheme, and are not described again.
Referring to fig. 1, in some embodiments of the invention, the preparation apparatus further comprises: and the kettle material conveying pump 12 is connected between the flash kettle 1 and the stripping tower 2 and is used for pumping the glue solution A obtained at the kettle bottom of the flash kettle 1 into the stripping tower 2.
Referring to fig. 1, in some embodiments of the invention, the preparation apparatus further comprises: the gas inlet is communicated with the gas outlet of the stripping tower 2, and the discharge port is communicated with the first return port of the stripping tower 2; the reflux device 8 comprises a heat exchanger 8-1 and a buffer tank 8-2 which are communicated with each other, wherein an air inlet of the heat exchanger 8-1 is communicated with an air outlet of the stripping tower 2, and a discharge hole of the buffer tank 8-2 is communicated with a first return hole of the stripping tower 2.
The top material of stripping tower 2 divides two tunnel trends promptly, and a material is retrieved through recovery system, and is concrete, can join with flash distillation 1 top exhaust material and get into recovery system jointly. And the other stream of material is treated by the reflux device 8 and then refluxed into the stripping tower 2 again. The reflux device 8 is internally provided with a heat exchanger 8-1 and a buffer tank 8-2, materials are subjected to heat exchange treatment through the heat exchanger 8-1, then sent to the buffer tank 8-2, and then refluxed to a stripping tower for steam stripping treatment, so that residual monomers and methyl chloride in the glue solution are removed as far as possible, the residual monomers and the methyl chloride are fully separated from the glue solution, and the separation efficiency is improved. Wherein, the temperature of the heat exchange treatment is the same as that in the technical scheme, and is not described herein again.
Referring to fig. 1, in one embodiment of the present invention, the reflux unit 8 further comprises a material transfer pump 13, and the material transfer pump 13 is disposed between the buffer tank 8-2 and the stripping tower 2, and is used for pumping the material received by the buffer tank 8-2 back to the stripping tower 2.
Referring to fig. 1, in some embodiments of the invention, the preparation apparatus further comprises: the feeding hole is communicated with the discharging hole of the stripping tower 2, and the discharging hole is communicated with the second return hole of the stripping tower 2. The bottom glue solution of the stripping tower 2 is divided into two paths, one glue solution flows from the bottom of the stripping tower and is heated by a first reboiler 9, and then flows back to the stripping tower to be used for heating the bottom glue solution to generate solvent steam, so that the gasification and discharge of the residual methyl chloride and unreacted monomers in the glue solution are further facilitated, and the separation efficiency of the methyl chloride and the unreacted monomers and the purity of the bottom glue solution are improved; wherein the processing temperature of the first reboiler 9 is the same as that in the above technical solution, and is not described herein again. And the other strand of material is used as the tower bottom glue solution B and is sent to the subsequent working procedure for continuously preparing the butyl glue solution.
Referring to fig. 1, in some embodiments of the present invention, the preparation apparatus includes a glue solution transfer pump 14 connected to the stripping column for transferring the glue solution at the bottom of the stripping column 2 to the first reboiler 9 and the first high-speed mixer 3, respectively.
The feed inlet of the first high-speed mixer 3 is communicated with the discharge outlet of the stripping tower 2, and specifically communicated with the liquid outlet at the bottom of the stripping tower 2. The first high-speed mixer 3 receives the glue solution B from the bottom of the stripping tower 2, receives externally fed water at the same time, and carries out primary water adding treatment on the glue solution B. Wherein, the conveying parameters of the glue solution B, the conveying parameters of the water, the adding amount and the like are consistent with those in the technical scheme, and are not described again here.
In one embodiment of the invention, the first high-speed mixer 3 is a high-speed mixer with a stirrer. The working parameters of the first high-speed mixer are the same as those in the above technical solution, and are not described herein again. After the primary water adding treatment by the first high-speed mixer 3, the glue solution B is uniformly mixed with water to obtain a glue solution C.
And the feeding hole of the buffer device 4 is communicated with the discharging hole of the first high-speed mixer 3 and is used for receiving the glue solution C from the first high-speed mixer 3 and dehydrating the glue solution C. Referring to fig. 2, fig. 2 is a schematic view of a buffering device according to an embodiment of the present invention; in one embodiment of the present invention, the buffer device 4 comprises 3 parallel buffer tanks with stirring, and the feed inlets of all the buffer tanks are communicated with the discharge outlet of the first high-speed mixer 3. The three tank bodies are in periodic circulation, and one tank body is used for receiving the glue solution C from the first high-speed mixer 3 and carrying out homogenization treatment on the glue solution C (marked as a receiving tank); one is used for standing separation and dehydration (marked as a standing water diversion tank, which is abbreviated as a water diversion tank in the figure); one for outputting the cement to a concentration regulator (denoted as output tank). Three buffer tank rotation operations: the receiving tank is in a working state when receiving the glue solution, and is switched to a standing separation dehydration function after reaching a specified liquid level, and the stirring is in a non-working state at the moment. Then the function of the output tank is switched to the function of receiving the glue solution from the first high-speed mixer, the function of starting stirring of the standing separation tank is switched to the function of outputting the glue solution to the concentration regulator. In the standing water separation tank, most of water can settle and layer to the bottom of the tank from the glue solution C, so that the dehydration effect is achieved. The staying time of the glue solution C in the standing water separation tank is consistent with that in the technical scheme, and is not described again here.
And the feed inlet of the concentration regulator 5 is communicated with the discharge outlet of the buffer device 4 and is used for regulating the concentration of the glue solution D sent by the buffer device 4. The operation of concentration adjustment, the target concentration to be achieved, and the transmission parameters when the buffer device 4 transmits the glue solution to the concentration adjuster 5 are the same as those in the above technical solution, and are not described herein again.
Referring to fig. 1, in an embodiment of the present invention, a liquid material delivery pump 15 is further disposed between the buffer device 4 and the concentration regulator 5, and is used for pumping the liquid material D generated by the buffer device 4 into the concentration regulator 5.
Referring to fig. 1, in one embodiment of the present invention, a second reboiler 11 is further disposed between the buffer device 4 and the concentration regulator 5. And heating the glue solution D when the concentration of the glue solution D generated by the buffer device 4 is lower than a set value, so that part of the solvent is gasified and removed, and the glue solution E is obtained by increasing the concentration of the glue solution to the set value.
The feed inlet of the second high-speed mixer 6 is communicated with the discharge outlet of the concentration regulator 5, receives the glue solution E from the concentration regulator 5, receives externally fed water, and performs secondary water adding treatment on the glue solution. Wherein, the conveying parameters of the glue solution E, the conveying parameters of the water, the adding amount and the like are consistent with those in the technical scheme, and are not described again here.
In one embodiment of the invention, the second high-speed mixer 6 is a high-speed mixer with a stirrer. The working parameters of the second high-speed mixer are the same as those in the above technical solution, and are not described herein again. After the secondary water adding treatment of the second high-speed mixer 6, the glue solution E is uniformly mixed with water to obtain a glue solution F.
And a feed inlet of the heat exchange device 7 is communicated with a discharge outlet of the second high-speed mixer 6 and is used for carrying out heat exchange treatment on the glue solution F obtained by the second high-speed mixer 6. The temperature of the heat exchange treatment is the same as that in the technical scheme, and is not described again. The structure of the heat exchange device 7 is not particularly limited in the invention, and the heat exchange device is only a conventional heat exchanger in the field. The discharge hole of the heat exchange device 7 is communicated with the feed inlet of the halogenation reaction system and is used for feeding the butyl rubber solution prepared by the preparation device into the halogenation reaction system for halogenation reaction, so that a halogenated butyl rubber product can be prepared.
The preparation device provided by the invention comprises a flash evaporation kettle 1, a stripping tower 2, a first high-speed mixer 3, a buffer device 4, a concentration regulator 5, a second high-speed mixer 6 and a heat exchange device 7 which are communicated in sequence. By using the preparation device of the invention, the polymer slurry and the solvent can be contacted in the flash evaporation kettle, and the glue solution A is obtained at the bottom of the kettle. And then the glue solution A and the solvent steam are in reverse contact in a stripping tower, and a glue solution B is obtained at the bottom of the stripping tower. And then sequentially carrying out primary water adding treatment, dehydration treatment, concentration adjustment treatment, secondary water adding treatment and heat exchange treatment on the glue solution B to obtain a butyl rubber solution. The glue solution obtained by the device has proper and stable concentration, low monomer content, proper water content, temperature and the like, so that the subsequent halogenated butyl rubber product has low primary structure content, proper Mooney reduction and lower gel content, and the high-quality halogenated butyl rubber product is obtained.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Example 1
1.1 the apparatus of FIG. 1 was used to prepare a butyl rubber solution as follows:
using chloromethane as medium, AlEtCl2And HCl as catalyst (AlEtCl)2HCl in a mass ratio of 18:1), and isobutene and isoprene as monomers (the mass ratio of isobutene to isoprene is 100: 3). AlEtCl2Dissolved in methyl chloride to obtain a catalyst solution with the concentration of 0.3 wt% and the flow rate of 0.6 kg/h. The concentration of the mixture obtained by mixing the monomer and methyl chloride was 30 wt%, and the flow rate was 10 kg/h. The polymerization reaction was carried out in a polymerization reactor 10 (polymerization temperature-95 ℃ C.), and the monomer conversion was 90%.
The above polymer slurry was fed into flash tank 1 (flow 10.6kg/h, temperature-93 ℃ C., pressure 2bar), while hexane hot solvent and triethylene glycol deactivator were fed into flash tank 1. Hot hexane flow 25.0kg/h, temperature 138 ℃, pressure 6 bar; the triethylene glycol flow rate was 23.6g/h, the temperature was 25 ℃ and the pressure was 6 bar. After the three materials are mixed in the flash evaporation kettle 1, most of methyl chloride, unreacted monomers and part of hexane are discharged from the top of the flash evaporation kettle 1 and enter a recovery system (when discharged, the flow rate of the part of materials is 11.7kg/h, the temperature is 50 ℃, and the pressure is 1.51 bar). The bottom of the kettle gave a hexane solution of butyl rubber, i.e., gum solution A, at a concentration of 11.3 wt% and triethylene glycol at a concentration of 980 ppm.
The glue solution A is pumped into a stripping tower 2 by a delivery pump 11 (the flow is 24.0kg/h, the temperature is 50 ℃, and the pressure is 1.52bar), and reversely contacts with hexane steam generated at the bottom of the tower, and two materials reversely contact, so that part of methyl chloride and unreacted monomers in the glue solution A and part of gas-phase solvent form tower top materials which are discharged from the top of the stripping tower. Meanwhile, the residual glue solution A is dissolved in the solvent to form a bottom glue solution. Wherein, the material at the top of the tower is divided into two parts, one part of the material (the flow is 2.8kg/h, the temperature is 41 ℃, the pressure is 1.21bar) enters a recovery system along with the decompressed gas phase discharged from the flash evaporation kettle 1, and the other part of the material flows back to the stripping tower 2 through a heat exchanger 8-1, a buffer tank 8-2 and a delivery pump 12 in sequence. The glue solution at the bottom of the tower is also divided into two strands, one strand of glue solution is sent to a reboiler 8-2 through a delivery pump 13 for reboiling treatment and then flows back to the stripping tower 2 to heat the glue solution at the bottom of the tower; the other strand of the gum solution B (flow rate 21.2kg/h, temperature 84 ℃, pressure 1.61bar, concentration 12.8 wt%, isoprene monomer content 1.6ppm) was fed into the first high-speed mixer 3 via the feed pump 13.
At the same time, water was fed into the first high-speed mixer 3 (flow 1.1kg/h, temperature 25 ℃ C., pressure 5 bar). The glue solution B and water are uniformly mixed in a first high-speed mixer 3, and the shear rate is 250s in the mixing process-1The residence time was 20s and the amount of water added was 5.0 wt%. After mixing, the obtained glue solution C (temperature 55 ℃) is sent to a buffer device 4 and stays in a standing water-dividing tank for 8 hours. During the standing period, 7.9kg of water was discharged from the bottom of the tank, and the water content of the dehydrated material was 0.5 wt%, which was recorded as gum solution D.
The dope D was concentrated in a concentration regulator 5, and a part of hexane was distilled off (flow: 6.4kg/h, temperature: 83 ℃ C., pressure: 1.71bar) to obtain a dope E (concentration: 18.2 wt%, water content: 0.37 wt%) at the bottom of the pot.
Feeding the glue solution E into a second high-speed mixer 6 (flow 14.9kg/h, temperature 83 ℃ C., pressure 1.72bar), and simultaneously feeding water into the second high-speed mixer 6 (flow 0.1kg/h, temperature 25 ℃ C., pressure 5.01bar), wherein the shear rate is 250s during the mixing process-1The residence time was 20 s. After mixing, a gum solution F (water content 1.0 wt%) was obtained. And performing heat exchange treatment on the glue solution F through a heat exchanger 7 to obtain a butyl rubber solution (the temperature is 43 ℃, and the water content is 1.0 wt%).
1.2 preparation of halogenated butyl rubber
The obtained butyl rubber liquid cement was fed into a halogenation reactor (flow 15.0kg/h, concentration 18.2 wt%, water content 1.0wt%, temperature 43 ℃), and at the same time, bromine was fed into the halogenation reactor (flow 111g/h), and the two were left to react in the reactor for 5 min. Then sent to a neutralization reactor, neutralized by NaOH solution, and sodium bisulfite solution reduces residual bromine. The neutralization reactor is kept for 5min for reaction, and the pH value of the water phase after neutralization is 8.0. And after the neutralization is finished, adding an auxiliary agent (comprising calcium stearate, epoxidized soybean oil serving as a stabilizer and an antioxidant 1076), uniformly mixing the auxiliary agent and the glue solution, then feeding the mixture into a condensation unit, and finally removing moisture through a drying system to obtain the brominated butyl rubber. Wherein, on the basis of dry glue, the addition amount of calcium stearate is 2.2 wt%, the addition amount of stabilizer is 1.4 wt%, and the addition amount of antioxidant is 0.06 wt%.
1.3 Performance testing
Performing primary structure characterization, Mooney drop test and gel content test on the brominated butyl rubber product. The structural representation of the brominated product adopts an AVANCE 400MHz NMR Boppler of Bruker company of Switzerland, the magnetic field intensity is 9.40 Tesla, the diameter of a sample tube is 5mm, a sample is dissolved by deuterated chloroform at normal temperature to prepare a solution with the content of about 2 wt%, and TMS is used as an internal standard to test at room temperature. The Mooney of the polymer was determined in accordance with the standard ASTM D1646, using the instrument type alpha MV 2000. The gel content of the brominated product was obtained using centrifugation: firstly, a sample (after the sample is taken from neutralization and before the addition of the auxiliary agent) is dissolved in toluene for 30min at 25 ℃ and the concentration is 12.5g/l, then a super centrifuge (20000rpm) is used for centrifugal treatment at 25 ℃ for 1h, and the gel content of the sample can be calculated after insoluble substances are taken out and dried.
The results of the tests show that the Mooney of the butyl rubber base rubber taken in flash tank 1 was 36.3 and the Mooney of the final bromobutyl rubber was 33.3, calculated to be 8.2% Mooney drop. The content of primary III structure in the brominated butyl rubber product in the brominated structure is 10.4%. The gel content of the product was 0.05 wt%.
Example 2
A butyl rubber solution was prepared according to the preparation procedure of example 1 except that the catalyst deactivator added in the flash tank 1 was butanol, and the butanol content in the gum solution a was 500 ppm; the amount of water added to the first high-speed mixer 3 was 4.0 wt%, water was added to the second mixer 6 until the water content of the glue solution was 0.6 wt%, the temperature of the glue solution was 45 ℃ after heat exchange treatment by the heat exchanger 7, and the concentration of the butyl rubber solution finally obtained was 18.0 wt%, the monomer content was 1.7ppm, the water content was 0.6 wt%, and the temperature was 45 ℃.
Brominated butyl rubber was prepared using the butyl rubber solution obtained according to the procedure of example 1.
The Mooney drop and the primary structure content of the obtained bromobutyl rubber were tested according to the test method of example 1 and showed a Mooney drop of 9.5%, a primary structure content of 10.8% and a gel content of 0.08% by weight.
Example 3
A butyl rubber solution was prepared according to the preparation procedure of example 1, except that the catalyst deactivator added in the flash tank 1 was ethanol, and the ethanol content in the gum solution a was 110 ppm; the amount of water added to the first high-speed mixer 3 was 3.0 wt%, water was added to the second mixer 6 until the water content of the glue solution was 0.8 wt%, the temperature of the glue solution was 40 ℃ after heat exchange treatment by the heat exchanger 7, and the final butyl rubber solution had a concentration of 18.3 wt%, a monomer content of 1.8ppm, a water content of 0.8 wt%, and a temperature of 40 ℃.
Brominated butyl rubber was prepared using the butyl rubber solution obtained according to the procedure of example 1.
The Mooney drop and the primary structure content of the obtained bromobutyl rubber were tested in accordance with the test methods of example 1 and showed a Mooney drop of 10.0%, a primary structure content of 11.2% and a gel content of 0.10% by weight.
Example 4
A butyl rubber solution was prepared by following the procedure of example 1, except that the catalyst deactivator introduced into the flash tank 1 was n-butyl ether, and the n-butyl ether content in the dope A was 210 ppm; the amount of water added to the first high-speed mixer 3 was 3.5 wt%, water was added to the second mixer 6 until the water content of the glue solution was 0.8 wt%, the temperature of the glue solution was 40 ℃ after heat exchange treatment by the heat exchanger 7, and the final butyl rubber solution had a concentration of 18.3 wt%, a monomer content of 1.9ppm, a water content of 0.8 wt%, and a temperature of 40 ℃.
Brominated butyl rubber was prepared using the butyl rubber solution obtained according to the procedure of example 1.
The Mooney drop and the primary structure content of the obtained bromobutyl rubber were tested according to the test methods of example 1 and showed a Mooney drop of 9.9%, a primary structure content of 11.5% and a gel content of 0.11% by weight.
Example 5
A butyl rubber solution was prepared in accordance with the procedure of example 1, except that isobutyric acid was added as the catalyst deactivator in the flash tank 1, and the content of isobutyric acid in the dope A was 410 ppm; the amount of water added to the first high-speed mixer 3 was 2.0 wt%, water was added to the second mixer 6 until the water content of the glue solution was 3.5 wt%, the temperature of the glue solution was 40 ℃ after heat exchange treatment by the heat exchanger 7, and the final butyl rubber solution had a concentration of 15.4 wt%, a monomer content of 1.6ppm, a water content of 3.5 wt%, and a temperature of 40 ℃.
Brominated butyl rubber was prepared using the butyl rubber solution obtained according to the procedure of example 1.
The Mooney drop and the primary structure content of the obtained bromobutyl rubber were tested in accordance with the test methods of example 1 and showed a Mooney drop of 9.7%, a primary structure content of 10.0% and a gel content of 0.10% by weight.
Example 6
A butyl rubber solution was prepared according to the procedure of example 1, except that the catalyst deactivator added in the flash tank 1 was ethyl acetate, and the ethyl acetate content in the gum solution a was 610 ppm; the amount of water added to the first high-speed mixer 3 was 2.5 wt%, water was added to the second mixer 6 until the water content of the glue solution was 0.7 wt%, the temperature of the glue solution was 40 ℃ after heat exchange treatment by the heat exchanger 7, and the final butyl rubber solution had a concentration of 13.1 wt%, a monomer content of 2.0ppm, a water content of 0.7 wt%, and a temperature of 40 ℃.
Brominated butyl rubber was prepared using the butyl rubber solution obtained according to the procedure of example 1.
The Mooney drop and the primary structure content of the obtained bromobutyl rubber were tested according to the test method of example 1 and showed a Mooney drop of 9.6%, a primary structure content of 11.7% and a gel content of 0.09% by weight.
Example 7
A butyl rubber solution was prepared according to the procedure of example 1, except that acetamide was added as the catalyst deactivator in the flash tank 1, and the acetamide content in the gum solution A was 710 ppm; the amount of water added to the first high-speed mixer 3 was 6.0 wt%, water was added to the second mixer 6 until the water content of the glue solution was 1.8 wt%, the temperature of the glue solution was 40 ℃ after heat exchange treatment by the heat exchanger 7, and the final butyl rubber solution had a concentration of 12.3 wt%, a monomer content of 1.8ppm, a water content of 1.8 wt%, and a temperature of 40 ℃.
Brominated butyl rubber was prepared using the butyl rubber solution obtained according to the procedure of example 1.
The Mooney drop and the primary structure content of the obtained bromobutyl rubber were tested according to the test method of example 1 and showed a Mooney drop of 9.5%, a primary structure content of 10.2% and a gel content of 0.09% by weight.
Example 8
A butyl rubber solution was prepared according to the procedure of example 1, except that the catalyst deactivator added in the flash tank 1 was butyraldehyde, and the butyraldehyde content in the gum solution a was 830 ppm; the amount of water added to the first high-speed mixer 3 was 7.0 wt%, water was added to the second mixer 6 until the water content of the glue solution was 2.5 wt%, the temperature of the glue solution was 35 ℃ after heat exchange treatment by the heat exchanger 7, and the concentration of the butyl rubber solution finally obtained was 16.3 wt%, the monomer content was 1.8ppm, the water content was 2.5 wt%, and the temperature was 35 ℃.
Brominated butyl rubber was prepared using the butyl rubber solution obtained according to the procedure of example 1.
The Mooney drop and the primary structure content of the obtained bromobutyl rubber were tested according to the test method of example 1 and showed a Mooney drop of 9.3%, a primary structure content of 10.5% and a gel content of 0.08% by weight.
Example 9
A butyl rubber solution was prepared according to the procedure of example 1, except that butanone was the catalyst deactivator added in the flash tank 1, and the butanone content in the gum solution A was 450 ppm; the amount of water added to the first high-speed mixer 3 was 9.2 wt%, water was added to the second mixer 6 until the water content of the glue solution was 4.5 wt%, the temperature of the glue solution was 40 ℃ after heat exchange treatment by the heat exchanger 7, and the final butyl rubber solution had a concentration of 18.5 wt%, a monomer content of 2.2ppm, a water content of 4.5 wt%, and a temperature of 40 ℃.
Brominated butyl rubber was prepared using the butyl rubber solution obtained according to the procedure of example 1.
The Mooney drop and the primary structure content of the obtained bromobutyl rubber were tested according to the test methods of example 1 and showed a Mooney drop of 9.7%, a primary structure content of 10.2% and a gel content of 0.11% by weight.
Example 10
A butyl rubber solution was prepared according to the procedure of example 1, except that the catalyst deactivator added to the flash tank 1 was ethylenediamine and the ethylenediamine content in the dope A was 530 ppm; the amount of water added to the first high-speed mixer 3 was 3.5 wt%, water was added to the second mixer 6 until the water content of the glue solution was 0.8 wt%, the temperature of the glue solution was 40 ℃ after heat exchange treatment by the heat exchanger 7, and the final butyl rubber solution had a concentration of 18.2 wt%, a monomer content of 3.6ppm, a water content of 0.8 wt%, and a temperature of 40 ℃.
Brominated butyl rubber was prepared using the butyl rubber solution obtained according to the procedure of example 1.
The Mooney drop and the primary structure content of the obtained bromobutyl rubber were tested according to the test method of example 1 and showed a Mooney drop of 9.5%, a primary structure content of 11.3% and a gel content of 0.09% by weight.
Example 11
A butyl rubber solution was prepared according to the procedure of example 1 except that the catalyst deactivator added to the flash tank 1 was ethyl sulfide, and the ethyl sulfide content in the gum solution a was 850 ppm; the amount of water added to the first high-speed mixer 3 was 7.2 wt%, water was added to the second mixer 6 until the water content of the glue solution was 0.8 wt%, the temperature of the glue solution was 40 ℃ after heat exchange treatment by the heat exchanger 7, and the final butyl rubber solution had a concentration of 18.4 wt%, a monomer content of 4.7ppm, a water content of 0.8 wt%, and a temperature of 40 ℃.
Brominated butyl rubber was prepared using the butyl rubber solution obtained according to the procedure of example 1.
The Mooney drop and the primary structure content of the obtained bromobutyl rubber were tested according to the test methods of example 1 and showed a Mooney drop of 9.0%, a primary structure content of 11.5% and a gel content of 0.07% by weight.
Comparative example 1
A butyl rubber solution was prepared according to the procedure of example 1, except that no catalyst deactivator was added to flash tank 1, and the final butyl rubber solution had a concentration of 18.2 wt%, a monomer content of 1.6ppm, a water content of 1.0wt%, and a temperature of 43 ℃.
Brominated butyl rubber was prepared using the butyl rubber solution obtained according to the procedure of example 1.
The Mooney drop and the primary structure content of the obtained bromobutyl rubber were tested according to the test methods of example 1 and showed a Mooney drop of 10.5%, a primary structure content of 10.3% and a gel content of 0.15% by weight.
Comparative example 2
A butyl rubber solution was prepared according to the preparation process of comparative example 1 except that the amount of water added to the first high-speed mixer 3 was 4.0 wt%, water was added to the second mixer 6 until the water content of the dope became 0.6 wt%, the temperature of the dope was 45 ℃ after heat exchange treatment by the heat exchanger 7, and the concentration of the butyl rubber solution finally obtained was 18.0 wt%, the monomer content was 1.7ppm, the water content was 0.6 wt%, and the temperature was 45 ℃.
Brominated butyl rubber was prepared using the butyl rubber solution obtained according to the procedure of example 1.
The Mooney drop and primary structure content of the obtained bromobutyl rubber were tested in accordance with the test methods of example 1 and showed a Mooney drop of 12.5%, a primary structure content of 11.3% and a gel content of 0.18% by weight.
Comparative example 3
A butyl rubber solution was prepared according to the preparation process of comparative example 1 except that the amount of water added to the first high-speed mixer 3 was 3.0% by weight, water was added to the second mixer 6 until the water content of the dope became 0.8% by weight, the temperature of the dope was controlled to 40 ℃ after heat exchange treatment by the heat exchanger 7, and the final butyl rubber solution had a concentration of 18.3% by weight, a monomer content of 1.8ppm, a water content of 0.8% by weight, and a temperature of 40 ℃.
Brominated butyl rubber was prepared using the butyl rubber solution obtained according to the procedure of example 1.
The Mooney drop and the primary structure content of the obtained bromobutyl rubber were tested in accordance with the test methods of example 1 and showed a Mooney drop of 13.3%, a primary structure content of 11.0% and a gel content of 0.16% by weight.
From the above test results, it can be seen that the butyl rubber solution obtained in the present invention can reduce the mooney of the halogenated butyl rubber product by less than 20%, the primary structure content by less than 20%, the gel content by significantly reducing after introducing the catalyst deactivator, and the obtained halogenated butyl rubber product exhibits high quality.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1. The preparation method of the butyl rubber solution is characterized by comprising the following steps of:
a) contacting the polymer slurry with a solvent and a catalyst deactivator in a flash evaporation kettle to obtain a glue solution A;
b) feeding the glue solution A into a stripping tower, and reversely contacting with solvent steam in the stripping tower to obtain a glue solution B;
c) sequentially carrying out primary water adding treatment, dehydration treatment, concentration adjustment treatment, secondary water adding treatment and heat exchange treatment on the glue solution B to obtain a butyl rubber solution;
the catalyst deactivator is a catalyst deactivator of the catalyst remaining in the polymer slurry;
the water adding amount of the primary water adding treatment is 0.1-10 wt%;
dehydrating the material until the water content of the material is 0.1-1.0 wt%;
the concentration is adjusted until the material concentration is 5-25 wt%;
the water adding amount of the secondary water adding is 0.05-5 wt%;
the water content of the solvent in the step a) is less than or equal to 100 ppm;
the concentration of the glue solution A is 5-15 wt%;
the water content of the solvent in the step b) is less than or equal to 100 ppm;
the concentration of the glue solution B is 5-15 wt%.
2. The preparation method according to claim 1, wherein the catalyst deactivator is one or more selected from the group consisting of alcohol compounds, ether compounds, organic carboxylic acids, aldehyde compounds, ketone compounds, organic amines, and sulfur-containing compounds.
3. The preparation method according to claim 2, wherein the alcohol compound is one or more selected from C1-C8 monohydric alcohol and C1-C8 polyhydric alcohol;
the ether compounds are selected from one or more of C2-C8 ether compounds;
the organic carboxylic acid is selected from one or more of C1-C18 organic carboxylic acids;
the aldehyde compound is selected from one or more of C1-C18 aldehyde compounds;
the ketone compound is selected from one or more of C2-C18 ketone compounds;
the organic amine is selected from one or more of primary amines of C1-C18, secondary amines of C1-C18 and tertiary amines of C1-C18;
the sulfur-containing compound is selected from one or more of hydrogen sulfide, thioether and mercaptan;
the content of the catalyst deactivator in the glue solution A is 50-5000 ppm.
4. The preparation method according to claim 1, wherein the catalyst deactivator is selected from one or more alcohol compounds.
5. The preparation method according to claim 1, wherein the heat exchange treatment is carried out until the material temperature is 30-60 ℃.
6. The method of claim 1, wherein the primary water addition treatment is performed under first high-speed mixing conditions; the shear rate of the first high-speed mixing is less than or equal to 300s-1(ii) a The processing time of the first high-speed mixing is 10-60 s;
the secondary water addition treatment is carried out under a second high-speed mixing condition; the shear rate of the second high-speed mixing is less than or equal to 300s-1(ii) a The processing time of the second high-speed mixing is 10-60 s.
7. The preparation method according to claim 1, wherein the solvent in the step a) is one or more selected from linear saturated alkanes of C4-C10 and branched saturated alkanes of C4-C10;
the temperature of the solvent in the step a) is 30-200 ℃.
8. The preparation method according to claim 1, wherein the solvent in the step b) is one or more selected from linear saturated alkanes of C4-C10 and branched saturated alkanes of C4-C10;
the working temperature of the bottom of the stripping tower in the step b) is 50-90 ℃;
the concentration of the butyl rubber solution is 10-20 wt%.
9. A butyl rubber solution obtained by the production method according to any one of claims 1 to 8.
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CN112745436B (en) * 2019-10-31 2022-07-12 中国石油化工股份有限公司 Solvent recycling method and butyl rubber production method
CN112745435B (en) * 2019-10-31 2022-07-12 中国石油化工股份有限公司 Process for converting polymer slurry into polymer solution and process for producing butyl rubber
CN112745437B (en) * 2019-10-31 2022-07-12 中国石油化工股份有限公司 Production method of butyl rubber glue solution
CN111234077B (en) * 2020-04-03 2021-03-02 浙江信汇新材料股份有限公司 Production method and device of butyl rubber
CN111548436B (en) * 2020-04-26 2021-04-16 浙江信汇新材料股份有限公司 Preparation method of butyl rubber base rubber solution for halogenation reaction
CN114426610A (en) * 2020-10-29 2022-05-03 中国石油化工股份有限公司 Method for adjusting scorching time and normal vulcanization time of butadiene rubber

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