CN111909422A - Butyl rubber base rubber preparation equipment set and preparation method - Google Patents
Butyl rubber base rubber preparation equipment set and preparation method Download PDFInfo
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- CN111909422A CN111909422A CN202010823787.7A CN202010823787A CN111909422A CN 111909422 A CN111909422 A CN 111909422A CN 202010823787 A CN202010823787 A CN 202010823787A CN 111909422 A CN111909422 A CN 111909422A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/02—Recovery or working-up of waste materials of solvents, plasticisers or unreacted monomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08J2323/22—Copolymers of isobutene; butyl rubber
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Abstract
The invention relates to a butyl rubber base rubber preparation equipment set and a preparation method thereof, and belongs to the technical field of preparation of butyl rubber solution. The equipment group at least comprises storage equipment, flash evaporation equipment, membrane separation equipment and rubber liquid concentration equipment, and the method comprises the following steps of mixing; secondly, flash separation; thirdly, membrane separation; and fourthly, concentrating the rubber liquid. The equipment set and the preparation method can effectively recover the high-purity diluent, each raw material is recycled, the green and environment-friendly idea is met, and the preparation cost of the butyl rubber base rubber is saved.
Description
Technical Field
The invention relates to the technical field of preparation of butyl rubber liquid in a halogenated butyl rubber preparation process, in particular to a butyl rubber base rubber preparation equipment set and a preparation method thereof.
Background
The halogenated butyl rubber is a product of halogenation reaction of common butyl rubber dissolved in aliphatic hydrocarbon (such as hexane) with chlorine and bromine, has the advantages of co-vulcanization with general elastomers, good bonding property, better heat resistance and the like on the basis of keeping the performance advantages of the original butyl rubber, and is a preferred material for producing products such as tubeless radial tires, waterproof sealing tapes and the like.
The production process of halogenated butyl rubber includes the steps of preparing basic glue solution, storing and transporting liquid chlorine and liquid bromine, neutralizing halogenated glue solution, degassing halogenated glue solution, stripping, recovering solvent, treating halogen acid gas, post-treating halogenated butyl rubber, drying and other steps.
Wherein, the preparation of the basic glue solution is the step applied by the new technical scheme. Generally speaking, the preparation method of the basic glue solution comprises a water condensation dissolution method and a solvent replacement method, and compared with the water condensation dissolution method, the solvent replacement method has the advantages of short process flow, low energy consumption, environmental protection, less equipment corrosion, less equipment occupation, low operation cost and the like, so that the method is widely applied.
Referring to fig. 1 attached to the present specification, a butyl rubber slurry is subjected to gas-liquid separation in a flash tank, superheated solvent steam is introduced into the flash tank to take away a part of vaporized diluent and unreacted butyl rubber monomer, a liquid phase in the flash tank enters a stripping tower to further remove the diluent and the unreacted butyl rubber monomer, the stripping tower is also introduced with superheated solvent steam to assist in taking away the vaporized diluent and the unreacted butyl rubber monomer, and a liquid phase distilled out of the stripping tower is subjected to flash evaporation again to concentrate the butyl rubber solution so as to achieve a standard concentration. The process has high operation cost, large solvent consumption and no recovery, and the gasified diluent and the unreacted butyl rubber monomer cannot be reused, thereby further increasing the operation burden.
The invention also provides an improvement of the prior art on the basis of the technical scheme, for example, a method and a device for preparing a butyl rubber solution for halogenation, disclosed in the Chinese patent application publication No. CN 104761659A, contact butyl rubber slurry with hexane steam in a flash evaporation kettle to obtain a gas-phase product and the hexane solution of butyl rubber, directly introduce the hexane solution of butyl rubber into a guide sieve plate tower to reversely contact with the hexane steam to directly obtain the hexane solution of butyl rubber for halogenation. However, in the technical scheme, the diluent and the unreacted butyl rubber monomer cannot be recycled, and the method has defects in the aspect of resource utilization of raw materials.
Disclosure of Invention
In order to solve the problems, the invention provides a butyl rubber base rubber preparation equipment set and a preparation method thereof, which mainly aim at recovering a solvent, a butyl rubber unreacted monomer and a diluent, can effectively recover the high-purity diluent, does not consider to separate the butyl rubber unreacted monomer from the solvent, but recycles a mixed solution of the butyl rubber unreacted monomer and the solvent in a butyl rubber preparation process, so that all raw materials are recycled, the environment-friendly concept is met, and the preparation cost of the butyl rubber base rubber is saved.
The technical scheme for solving the problems is as follows:
the butyl rubber base rubber preparation equipment set emphasizing resource utilization at least comprises the following equipment:
a storage device for storing a mixed solution of the butyl rubber slurry, the solvent and the diluent;
the flash evaporation equipment is used for receiving the mixed liquid output from the solution storage equipment and outputting a gas phase substance and primary butyl rubber liquid;
the membrane separation equipment is used for receiving the gas phase substance and separating the gas phase substance to obtain diluent recovery liquid and first solvent recovery liquid, and the first solvent recovery liquid can be recycled to the preparation process of the butyl rubber;
and the rubber liquid concentration equipment is used for receiving the primary butyl rubber liquid and obtaining a concentrated butyl rubber liquid and a second solvent recovery liquid, and the second solvent recovery liquid can also be recycled to the preparation process of the butyl rubber.
The membrane separation device adopted by the application throttles polar substances to enable nonpolar substances to pass through by utilizing the polarity difference among the substances, or intercepts the nonpolar substances to enable the polar substances to pass through, thereby realizing the separation of the polar diluent (methane chloride) and the polar solvent (hexane) and the unreacted monomers (isobutene and isoprene) of the butyl rubber.
The inventor believes that the solvent is not required to be separated from the unreacted butyl rubber monomer for recycling, but the mixture of the solvent and the unreacted butyl rubber monomer can be recycled in the preparation process of the butyl rubber, so that the raw material cost can be saved.
This application does not adopt in the superheated hexane lets in flash distillation equipment, but realizes the gasification separation of butyl rubber unreacted monomer and diluent through temperature and pressure in the control flash distillation equipment, can make more butyl rubber unreacted monomer desorption like this to promote the quality of butyl rubber basic glue.
Preferably, in the above technical solution, the butyl rubber slurry, the solvent and the diluent are mixed by a mixing device and then are fed into the storage device.
Preferably, in the above technical solution, the gas phase is fed into the membrane separation device after passing through a cooling device.
When the air temperature is low, the cooling can be realized through the conveying pipeline, and when the air temperature is high, cooling equipment needs to be arranged.
Preferably, in the above aspect, the first solvent-recovered solution and the second solvent-recovered solution are merged and then introduced into the butyl rubber production process.
Preferably, in the above technical solution, the storage device is a storage tank with a stirring device, the flash evaporation device is a flash evaporation tank, the membrane separation device adopts a cross-flow filtration mode and uses a hydrophilic oleophobic filtration membrane as a separation membrane, or adopts a terminal filtration mode and uses an oleophilic hydrophobic filtration membrane as a separation membrane, and the rubber liquid concentration device is a concentration tower or a concentration kettle.
When the content of the solvent in the gas phase is high (for example, more than 50%), a cross-flow type filtration mode can be selected and a hydrophilic oleophobic filtration membrane is used as a separation membrane, so that the permeation of the diluent is facilitated, and the reflux phase is a mixture of the solvent and unreacted butyl rubber monomer; when the diluent content in the gas phase is high (for example, more than 50%), it is considered to select a terminal filtration mode and use an oleophilic hydrophobic filtration membrane as a separation membrane, which is more favorable for the outflow of the solvent and the unreacted butyl rubber monomer, and the trapped phase is the diluent.
Preferably, in the above technical solution, the cooling device is a shell and tube water-cooled cooler.
Preferably, the mixing device is any one of a dynamic mixer, a static mixer, a micromixer and a supergravity mixer.
The preparation method of the butyl rubber base rubber emphasizing resource utilization comprises the following steps:
mixing: mixing butyl rubber slurry, a solvent and a diluent to form a mixed solution;
② flash separation: carrying out flash evaporation treatment on the mixed solution to obtain a gasified gas phase substance and unvaporized primary butyl rubber solution;
③ separating by a membrane: performing membrane separation treatment on the liquid formed by cooling the gas phase substance to obtain diluent recovery liquid and first solvent recovery liquid, wherein the diluent recovery liquid is recycled, and the first solvent recovery liquid is used as a solvent to participate in the preparation of the butyl rubber again;
concentrating the rubber liquid: and concentrating the primary butyl rubber liquid to obtain a concentrated butyl rubber liquid and a second solvent recovery liquid, wherein the concentrated butyl rubber liquid is used for preparing halogenated butyl rubber, and the second solvent recovery liquid is used as a solvent to participate in the preparation of butyl rubber again.
Preferably, in the flash separation step, the operation temperature is 30-100 ℃, and the operation pressure is 200-800 KPag.
Preferably, in the membrane separation step, a cross-flow filtration system is used and a hydrophilic oleophobic filtration membrane is used as a separation membrane, or a dead-end filtration system is used and an oleophilic hydrophobic filtration membrane is used as a separation membrane.
Preferably, in the step of concentrating the rubber solution, the operation temperature is 60-90 ℃ and the operation pressure is 10-200 KPag.
The diluent recovery liquid, the first solvent recovery liquid and the second solvent recovery liquid are mainly recycled in the process for preparing the butyl rubber by the slurry method, and the process of the slurry method is simply introduced as follows:
and a polymerization section, namely preparing isobutene, isoprene and a diluent into a raw material solution according to a certain proportion, respectively cooling the prepared raw material solution and the catalyst solution to about-95 ℃, and feeding the cooled raw material solution and the catalyst solution into a polymerization kettle for reaction, wherein the temperature of the polymerization reaction is about-97 to-90 ℃, and the pressure of the polymerization reaction is about 80 to 250 kPag.
The catalyst solution needs to be separately prepared, because the purity of the methane chloride (namely, a diluent) for dissolving the catalyst is high, the purity of the methane chloride is generally required to be not less than 99.9%, and the purity of isobutene is not more than 50ppm, otherwise the catalyst solution is easy to perform a complex reaction with isobutene.
The slurry process is followed by a solvent displacement process for the subsequent preparation of the base gum solution for halogenation, the relevant prior art being briefly described as follows:
and (3) introducing the butyl rubber slurry, the solvent, the terminating agent and the diluent into a mixer, then further mixing with the butyl rubber solution, and after the reaction is terminated, introducing the obtained butyl rubber solution into a low-temperature dissolving tank to further mix with the solvent and completely dissolve.
And pressurizing the butyl rubber solution by a pump, feeding the butyl rubber solution into a flash evaporation kettle, and removing part of the diluent and unreacted monomers by flash evaporation to obtain the butyl rubber solution with part of the diluent and unreacted monomers removed preliminarily.
Introducing the butyl rubber solution of which part of the diluent and unreacted monomers are primarily removed into a methane-removing tower, introducing solvent steam into a tower kettle of the methane-removing tower, leading the butyl rubber solution and the solvent steam to be in countercurrent contact mass transfer in the tower, completely removing the diluent and the unreacted monomers in the butyl rubber solution, then introducing the butyl rubber solution into a glue solution concentration tower for concentration, removing the solvent in the butyl rubber solution in the tower through gasification, and improving the glue solution concentration to obtain the butyl rubber solution for halogenation.
And introducing the removed diluent and unreacted monomers into a solvent recovery tower, and distilling and separating the solvent, the diluent and the unreacted monomers to obtain tower top gas with the solvent content of less than 0.1 wt%. The bottom of the column is substantially free of diluent and unreacted monomer.
In summary, the embodiment of the present application has the following beneficial effects:
1) the equipment set can prepare the butyl rubber base glue solution with the concentration and the quality meeting the requirements under the corresponding preparation method, and the hexane solvent, the isobutylene reaction monomer and the methyl chloride diluent are separated by utilizing the polarity difference, so that the hexane solution of the reaction monomer and the diluent with higher purity are obtained, and the hexane solution and the diluent can be directly reused in the preparation process of the butyl rubber, so that the resource utilization of the raw materials is realized.
2) According to the method, superheated hexane steam is not used as a heating medium, but the temperature and pressure in the flash evaporation equipment are controlled, so that the removal of the butyl rubber reaction monomer is effectively improved, and the quality of the butyl rubber basic glue solution is guaranteed.
3) The application takes the membrane separation equipment as the purification equipment of the diluent, and has the advantages of small occupied space and low energy consumption.
Drawings
FIG. 1 is a schematic process flow diagram of a solvent displacement process of the prior art;
FIG. 2 is a schematic diagram of a butyl rubber base stock preparation plant set according to an embodiment of the present application;
in the figure, 1-storage equipment, 2-flash evaporation equipment, 3-membrane separation equipment, 4-rubber liquid concentration equipment, 5-mixing equipment and 6-cooling equipment.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. The embodiments of the present invention, and all other embodiments obtained by those skilled in the art without any inventive step, are within the scope of the present invention.
The present invention will be described in detail below by way of examples with reference to the accompanying drawings.
Example 1: referring to fig. 2, a butyl rubber base rubber preparation equipment set and a preparation method thereof, wherein a solvent involved in the method is hexane, and a diluent is methane chloride.
The equipment group comprises a mixing device 5, a storage device 1 consisting of a storage tank, a flash evaporation device 2 consisting of a flash evaporation tank, a membrane separation device 3 for separating gas phase substances output by the flash evaporation tank and a rubber liquid concentration device 4 for concentrating primary dilute butyl rubber liquid output by the flash evaporation tank in sequence according to the operation sequence of materials, wherein the rubber liquid concentration device 4 can specifically select a concentration tower kettle.
The mixing device 5 only needs to play a role of homogenization, specifically any one of a dynamic mixer, a static mixer, a micro mixer and a supergravity mixer can be selected, the gas phase substance is composed of hexane, methane chloride and unreacted monomers of butyl rubber, the primary butyl rubber solution is mainly hexane dilute solution of the butyl rubber, and in addition, a little residual methane chloride and unreacted monomers of the butyl rubber are also contained.
The gas phase material is cooled into liquid phase material by a tubular water cooling device 6 before entering the membrane separation device 3.
If a hydrophilic oleophobic filtering membrane is adopted, a membrane component of cross-flow type filtering is selected, and the filtering membrane can specifically adopt a symmetric membrane of a hydrophilic modified polyvinylidene fluoride polymer membrane or an asymmetric membrane of which a hydrophilic layer is loaded on a carrier; if an oleophylic and hydrophobic filtering membrane is adopted, a terminal filtering membrane component is selected, and the filtering membrane can be specifically a membrane element made of hydrophobic materials such as polytetrafluoroethylene, polyvinylidene fluoride and polypropylene.
The phase with higher polarity obtained after separation by the membrane separation equipment 3 is diluent recovery liquid, and the phase with higher non-polarity is hexane solvent containing unreacted monomers of the butyl rubber, and both can be directly reused in the preparation process of the butyl rubber.
And the second solvent recovery liquid obtained by concentrating the kettle of the concentration tower is the butyl rubber base glue liquid with the concentration reaching the standard, and the distilled second solvent recovery liquid is a hexane solvent containing unreacted monomers of the butyl rubber and can be directly reused in the preparation process of the butyl rubber.
The preparation method comprises the following steps:
mixing: mixing the butyl rubber slurry, the solvent and the diluent to form a mixed solution, storing the mixed solution in a storage tank, and stirring and homogenizing the mixed solution in the storage tank;
② flash separation: carrying out flash evaporation treatment on the mixed solution, wherein the operating conditions of the flash evaporation tank are set according to the state parameters and the actual working conditions of the mixed solution, the operating temperature is usually 30-100 ℃, and the operating pressure is usually 200-800 KPag, so as to obtain a gasified gas phase substance and unvaporized primary butyl rubber liquid;
the gas phase substance in the solvent is mainly a mixed solution of a diluent and a solvent, and certainly contains a small amount of unreacted butyl rubber monomer, the primary butyl rubber solution is a hexane solution of butyl rubber, the concentration of the hexane solution is about 5-15%, the hexane solution does not meet the processing conditions of subsequent processes, and the hexane solution needs to be further concentrated;
③ separating by a membrane: carrying out membrane separation treatment on liquid formed after the gas phase object is cooled by a water-cooled tube array cooler to obtain diluent recovery liquid and first solvent recovery liquid, recovering and recycling the diluent recovery liquid, and taking the first solvent recovery liquid as a solvent to participate in the preparation of the butyl rubber again;
the membrane separation device 3 can be flexibly arranged according to the composition of the gas phase, and the specific selection is as follows: when the content of the solvent in the gas phase is high (for example, more than 50%), a cross-flow type filtration mode can be considered and a hydrophilic oleophobic filtration membrane is used as a separation membrane, so that the permeation of the diluent is facilitated, the reflux phase is a mixture of the solvent and unreacted butyl rubber monomer, and the hydrophilic oleophobic filtration membrane can be a symmetric membrane of a hydrophilic modified polyvinylidene fluoride polymer membrane or an asymmetric membrane of which a hydrophilic layer is loaded on a carrier; when the diluent content in the gas phase is high (for example, more than 50%), a terminal type filtration mode can be considered and an oleophylic and hydrophobic filtration membrane is used as a separation membrane, so that the solvent and the unreacted butyl rubber monomer can flow out more favorably, the trapped phase is the diluent, and the oleophylic and hydrophobic filtration membrane can be a membrane element made of hydrophobic materials such as polytetrafluoroethylene, polyvinylidene fluoride and polypropylene.
Concentrating the rubber liquid: concentrating the primary butyl rubber liquid at an operating temperature of 60-90 ℃ and an operating pressure of 10-200 KPag to obtain a concentrated butyl rubber liquid and a second solvent recovery liquid, wherein the concentrated butyl rubber liquid is used for preparing halogenated butyl rubber, the second solvent recovery liquid is used as a solvent to participate in the preparation of the butyl rubber again, hexane is used as a main component in the second solvent recovery liquid, a small amount of diluent methane chloride and a small amount of unreacted butyl rubber monomer are contained, the concentration of the concentrated butyl rubber liquid is about 15% -20%, and the processing conditions of subsequent steps are met.
The solvent recovery liquid obtained by the membrane separation equipment 3 and the solvent recovery liquid obtained by the rubber liquid concentration equipment 4 are mixed liquid of a solvent and an unreacted butyl rubber monomer, and can be directly recycled in the preparation process of the butyl rubber.
The purity of the diluent recovery liquid obtained after separation by the membrane separation equipment 3 can reach more than 95.5 percent, meets the purity requirement of the diluent, and can be directly reused in the preparation process of the butyl rubber.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. Butyl rubber base rubber preparation equipment group, its characterized in that contains the following equipment at least:
a storage device (1) for storing a mixed solution of butyl rubber slurry, solvent and diluent;
the flash evaporation equipment (2) is used for receiving the mixed liquid output from the solution storage equipment (1) and outputting a gas phase substance and primary butyl rubber liquid;
the membrane separation equipment (3) is used for receiving the gas phase substance and separating the gas phase substance to obtain a diluent recovery liquid and a first solvent recovery liquid;
and the rubber liquid concentration device (4) is used for receiving the primary butyl rubber liquid and obtaining concentrated butyl rubber liquid and second solvent recovery liquid.
2. The butyl rubber base rubber manufacturing apparatus group according to claim 1, wherein: the butyl rubber slurry, the solvent and the diluent are mixed by a mixing device (5) and then input into the storage device (1).
3. The butyl rubber base rubber manufacturing apparatus group according to claim 1, wherein: the gas phase material passes through a cooling device (6) and then is input into the membrane separation device (3).
4. The butyl rubber base rubber manufacturing apparatus group according to claim 1, wherein: and merging the first solvent recovery solution and the second solvent recovery solution, and inputting the merged solution into a preparation process of the butyl rubber.
5. The butyl rubber base rubber manufacturing apparatus group according to claim 1, wherein: the storage device (1) is a storage tank with a stirring device, the flash evaporation device (2) is a flash evaporation tank, the membrane separation device (3) adopts a cross-flow type filtration mode and uses a hydrophilic oleophobic filtration membrane as a separation membrane or a terminal type filtration mode and uses an oleophilic hydrophobic filtration membrane as a separation membrane, and the rubber liquid concentration device (4) is a concentration tower or a concentration kettle.
6. The butyl rubber base rubber production equipment set according to claim 3, wherein: the cooling equipment (6) is a tube array type water-cooling cooler.
7. The preparation method of the butyl rubber base rubber is characterized by comprising the following steps:
mixing: mixing butyl rubber slurry, a solvent and a diluent to form a mixed solution;
② flash separation: carrying out flash evaporation treatment on the mixed solution to obtain a gasified gas phase substance and unvaporized primary butyl rubber solution;
③ separating by a membrane: performing membrane separation treatment on the liquid formed by cooling the gas phase substance to obtain diluent recovery liquid and first solvent recovery liquid, wherein the diluent recovery liquid is recycled, and the first solvent recovery liquid is used as a solvent to participate in the preparation of the butyl rubber again;
concentrating the rubber liquid: and concentrating the primary butyl rubber liquid to obtain a concentrated butyl rubber liquid and a second solvent recovery liquid, wherein the concentrated butyl rubber liquid is used for preparing halogenated butyl rubber, and the second solvent recovery liquid is used as a solvent to participate in the preparation of butyl rubber again.
8. The process for preparing a butyl rubber base according to claim 7, wherein: in the flash separation step, the operation temperature is 30-100 ℃, and the operation pressure is 200-800 KPag.
9. The process for preparing a butyl rubber base according to claim 7, wherein: in the membrane separation step, a cross-flow type filtration mode is adopted and a hydrophilic oleophobic filtration membrane is used as a separation membrane, or a terminal type filtration mode is adopted and an oleophilic hydrophobic filtration membrane is used as a separation membrane.
10. The process for preparing a butyl rubber base according to claim 7, wherein: in the step of concentrating the rubber liquid, the operation temperature is 60-90 ℃, and the operation pressure is 10-200 KPag.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044598A (en) * | 2011-10-17 | 2013-04-17 | 中国石油天然气股份有限公司 | Method for flash evaporating and concentrating of liquid ethylene propylene rubber |
| DE102013111066A1 (en) * | 2013-10-07 | 2015-04-09 | List Holding Ag | Process for producing halobutyl rubber |
| CN110563233A (en) * | 2019-08-23 | 2019-12-13 | 山东京博中聚新材料有限公司 | Method for reducing unit consumption of brominated butyl rubber material |
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2020
- 2020-08-17 CN CN202010823787.7A patent/CN111909422A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044598A (en) * | 2011-10-17 | 2013-04-17 | 中国石油天然气股份有限公司 | Method for flash evaporating and concentrating of liquid ethylene propylene rubber |
| DE102013111066A1 (en) * | 2013-10-07 | 2015-04-09 | List Holding Ag | Process for producing halobutyl rubber |
| CN110563233A (en) * | 2019-08-23 | 2019-12-13 | 山东京博中聚新材料有限公司 | Method for reducing unit consumption of brominated butyl rubber material |
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Application publication date: 20201110 |