CN110878132A - Production process of butyl rubber - Google Patents
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- CN110878132A CN110878132A CN201911337130.3A CN201911337130A CN110878132A CN 110878132 A CN110878132 A CN 110878132A CN 201911337130 A CN201911337130 A CN 201911337130A CN 110878132 A CN110878132 A CN 110878132A
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- C08F210/04—Monomers containing three or four carbon atoms
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Abstract
The invention provides a production process of butyl rubber, which comprises the following steps: s1) mixing mono-olefin, diolefin, sulfur-containing organic compound and reaction solvent to obtain reactant solution; the sulfur-containing organic matter is selected from one or more of thiol compounds, thioether compounds and thiophenol compounds; mixing a main catalyst, a cocatalyst and a reaction solvent to obtain a catalytic system; the main catalyst is Lewis acid; s2) aging the catalytic system at low temperature, mixing the aged catalytic system with a reactant solution, and reacting to obtain a product slurry; s3) adding an alcohol compound into the product slurry to terminate the reaction, thereby obtaining the butyl rubber. Compared with the prior art, the invention introduces the sulfur-containing organic compound as a slurry stabilizer in the polymerization process, the existence of the substance can effectively control the polymerization speed, so that the product is uniformly dispersed, thereby effectively improving the mass transfer and the heat transfer of a polymerization system, and the obtained product has stable quality, widened molecular weight distribution and more excellent processing performance.
Description
Technical Field
The invention belongs to the technical field of butyl rubber, and particularly relates to a production process of butyl rubber.
Background
Butyl rubber is one of the synthetic rubbers, which is H2O-AlCl3The system is initiated by cationic polymerization of isobutene and a small amount of isoprene at low temperature (-100 ℃ or so). Butyl rubber has good chemical and thermal stability, most notably air and water tightness, and its polymer also has unique properties, and thus is widely used in many fields of manufacturing inner tubes, anti-vibration rubber, industrial rubber sheets, medical rubber, etc.
In 1943, esox chemical company in the united states first achieved industrial production. Since the realization of industrial production, the raw material route, the production process and the structural form of a polymerization kettle of the butyl rubber are not changed greatly. The butyl rubber polymerization process is typically a cationic polymerization process using methyl chloride as a solvent, a lewis acid as a main catalyst, and a protonic acid as a cocatalyst in a slurry polymerization process. The reaction has the characteristics of high reaction speed, concentrated heat release, easy gelatification and agglomeration of products. An increase in polymerization temperature leads to a drastic decrease in the molecular weight of the polymer; the reactor kiss-coating can cause poor heat transfer effect and influence the heat dissipation efficiency, thereby causing the polymerization temperature rise to be accelerated; the colloidal particles are agglomerated seriously to cause the blockage of an overflow pipe, and the polymerization reaction period is shortened. It can be seen that rapid removal of the heat of polymerization to control the reaction at a constant low temperature is a major problem in production. On the other hand, frequent start and stop of the production device not only increases the production cost, but also greatly fluctuates the product quality. Therefore, the problem of mass and heat transfer of the butyl rubber polymerization system becomes a difficult problem to be solved urgently in the field.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a production process of butyl rubber, which has better mass transfer and heat transfer efficiency.
The invention provides a production process of butyl rubber, which comprises the following steps:
s1) mixing mono-olefin, diolefin, sulfur-containing organic compound and reaction solvent to obtain reactant solution; the sulfur-containing organic compound is selected from one or more of thiol compounds, thioether compounds and thiophenol compounds;
mixing a main catalyst, a cocatalyst and a reaction solvent to obtain a catalytic system; the main catalyst is Lewis acid;
s2) aging the catalytic system at low temperature, mixing the aged catalytic system with a reactant solution, and reacting to obtain a product slurry;
s3) adding an alcohol compound into the product slurry to terminate the reaction, thereby obtaining the butyl rubber.
Preferably, the monoolefin is selected from the group consisting of isomonoolefins having from C4 to C16; the diene is selected from conjugated diene of C4-C14; the sulfur-containing organic compound is selected from one or more of thiol compounds of C2-C20, thioether compounds of C2-C20 and thiophenol compounds of C6-C20.
Preferably, the monoolefin is selected from the group consisting of isomonoolefins having from C4 to C10; the diene is selected from conjugated diene of C4-C8; the sulfur-containing organic compound is selected from one or more of thiol compounds of C2-C10, thioether compounds of C2-C10 and thiophenol compounds of C6-C15.
Preferably, the sulfur-containing organic compound is selected from one or more of thiophenol, thioglycolic acid, mercaptoethanol, 1-dimethylthiol, ethanethiol and dimethylsulfide.
Preferably, the concentration of the sulfur-containing organic compound in the reactant solution is 1-1000 mg/kg.
Preferably, the molar ratio of monoolefin to diolefin is 1: (0.01 to 0.1); the concentration of the mono-olefin in the reactant solution is 10-50 wt%.
Preferably, the main catalyst is selected from one or more of aluminum trichloride, ethyl aluminum dichloride, diethyl aluminum monochloride, butyl aluminum dichloride, dibutyl aluminum monochloride, boron trifluoride, titanium tetrachloride and ethyl sesquialuminum chloride; the cocatalyst is H2O or HCl.
Preferably, the molar ratio of the main catalyst to the monoolefine is (0.0001-0.005): 1; the molar ratio of the main catalyst to the cocatalyst is (1-20): 1; the concentration of the cocatalyst in the catalytic system is 0.01-0.05 wt%.
Preferably, the temperature for aging in the step S2) is-80 ℃ to-95 ℃; the aging time is 1-45 min; the reaction temperature is-80 ℃ to-98 ℃; the reaction time is 1-20 min.
Preferably, the alcohol is selected from methanol and/or ethanol; after the reaction was terminated, the solvent was removed to obtain a butyl rubber.
The invention provides a production process of butyl rubber, which comprises the following steps: s1) mixing mono-olefin, diolefin, sulfur-containing organic compound and reaction solvent to obtain reactant solution; the sulfur-containing organic matter is selected from one or more of thiol compounds, thioether compounds and thiophenol compounds; mixing a main catalyst, a cocatalyst and a reaction solvent to obtain a catalytic system; the main catalyst is Lewis acid; s2) aging the catalytic system at low temperature, mixing the aged catalytic system with a reactant solution, and reacting to obtain a product slurry; s3) adding an alcohol compound into the product slurry to terminate the reaction, thereby obtaining the butyl rubber. Compared with the prior art, the invention introduces the sulfur-containing organic compound as a slurry stabilizer in the polymerization process, and the existence of the substance can effectively control the polymerization speed, so that the product is uniformly dispersed, thereby effectively improving the mass transfer and the heat transfer of a polymerization system, enabling a production device to operate at low load for a long period, and the obtained product has stable quality, widened molecular weight distribution and more excellent processing performance.
Drawings
FIG. 1 is a NMR chart of butyl rubber obtained in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a production process of butyl rubber, which comprises the following steps: s1) mixing mono-olefin, diolefin, sulfur-containing organic compound and reaction solvent to obtain reactant solution; the sulfur-containing organic compound is selected from one or more of thiol compounds, thioether compounds and thiophenol compounds; mixing a main catalyst, a cocatalyst and a reaction solvent to obtain a catalytic system; the main catalyst is Lewis acid; s2) aging the catalytic system at low temperature, mixing the aged catalytic system with a reactant solution, and reacting to obtain a product slurry; s3) adding an alcohol compound into the product slurry to terminate the reaction, thereby obtaining the butyl rubber.
The present invention is not particularly limited in terms of the source of all raw materials, and may be commercially available.
In the present invention, the monoolefin is preferably an isomonoolefin having from C4 to C16, more preferably an isomonoolefin having from C4 to C10, still more preferably an isomonoolefin having from C4 to C6, and most preferably isobutylene; the diene is preferably C4-C14 conjugated diene, more preferably C4-C8 conjugated diene, still more preferably C4-C6 conjugated diene, and most preferably isoprene; the sulfur-containing organic compound is one or more of thiol compounds, thioether compounds and thiophenol compounds, preferably one or more of thiol compounds of C2-C20, thioether compounds of C2-C20 and thiophenol compounds of C6-C20, more preferably one or more of thiol compounds of C2-C15, thioether compounds of C2-C15 and thiophenol compounds of C6-C15, still more preferably one or more of thiol compounds of C2-C10, thioether compounds of C2-C10 and thiophenol compounds of C6-C15, still more preferably thiol compounds of C2-C6, one or more of C2-C6 thioether compounds and C6-C10 thioether compounds, most preferably one or more of thiophenol, thioglycolic acid, mercaptoethanol, 1-dimethyl mercaptan, ethanethiol and dimethyl sulfide; the reaction solvent is preferably a halogenated alkane, more preferably methyl chloride, and most preferably methyl chloride.
Mixing mono-olefin, diene, sulfur-containing organic compound and reaction solvent to obtain reactant solution; in the present invention, preferably, after the monoolefin, the diolefin and the reaction solvent are mixed, the sulfur-containing organic compound is added to obtain the reaction solution; the mixing temperature is preferably-60 ℃ to-90 ℃, and more preferably-70 ℃ to-85 ℃; the molar ratio of monoolefin to diolefin is preferably 1: (0.01 to 0.1), more preferably 1: (0.01 to 0.08), and preferably 1: (0.01 to 0.05); in some embodiments provided herein, the molar ratio of monoolefin to diolefin is preferably 1: 0.04; in some embodiments provided herein, the molar ratio of monoolefin to diolefin is preferably 1: 0.05; in some embodiments provided herein, the molar ratio of monoolefin to diolefin is preferably 1: 0.08; the concentration of the mono-olefin in the reactant solution is preferably 10-50 wt%, more preferably 10-40 wt%, still more preferably 10-30 wt%, and most preferably 10-26 wt%; in some embodiments provided herein, the concentration of mono-olefin in the reactant solution is preferably 14.9 wt%; in some embodiments provided herein, the concentration of mono-olefin in the reactant solution is preferably 14.8 wt%; in some embodiments provided herein, the concentration of mono-olefin in the reactant solution is preferably 26.3 wt%; in other embodiments provided herein, the concentration of mono-olefin in the reactant solution is preferably 9.9 wt%; the concentration of the sulfur-containing organic compound in the reactant solution is preferably 1-1000 mg/kg, more preferably 10-200 mg/kg, still more preferably 20-198 mg/kg, still more preferably 33-198 mg/kg; in some embodiments provided herein, the concentration of the sulfur-containing organic compound in the reactant solution is preferably 33 mg/kg; in some embodiments provided herein, the concentration of the sulfur-containing organic compound in the reactant solution is preferably 74 mg/kg; in some embodiments provided herein, the concentration of the sulfur-containing organic compound in the reactant solution is preferably 198 mg/kg; in some embodiments provided herein, the concentration of sulfur-containing organic compounds in the reactant solution is preferably 165 mg/kg.
Mixing a main catalyst, a cocatalyst and a reaction solvent to obtain a catalytic system; the main catalyst is Lewis acid, preferably one or more of aluminum trichloride, ethyl aluminum dichloride, diethyl aluminum monochloride, butyl aluminum dichloride, dibutyl aluminum monochloride, boron trifluoride, titanium tetrachloride and ethyl sesquialuminum chloride; the cocatalyst is preferably H2O or HCl; the molar ratio of the main catalyst to the cocatalyst is preferably (1-20): 1, more preferably (1 to 15): 1, and preferably (1-10): 1, most preferably (4-8): 1; in some embodiments provided herein, the molar ratio of the primary catalyst to the secondary catalyst is preferably 4.6: 1; in some embodiments provided herein, the molar ratio of the primary catalyst to the secondary catalyst is preferably 7.2: 1; in some embodiments provided herein, the molar ratio of the primary catalyst to the secondary catalyst is preferably 5.4: 1; in some embodiments provided herein, the molar ratio of the primary catalyst to the secondary catalyst is preferably 4.3: 1; the concentration of the cocatalyst in the catalytic system is preferably 0.01-0.05 wt%, and more preferably 0.02-0.05 wt%; the temperature of the mixing is preferably-60 ℃ to-90 ℃, more preferably-70 ℃ to-85 ℃.
Aging the catalytic system at low temperature; the temperature of the aging is preferably-80 ℃ to-95 ℃, more preferably-85 ℃ to-95 ℃, still more preferably-88 ℃ to-95 ℃, and most preferably-88 ℃ to-90 ℃; the aging time is preferably 1-45 min, more preferably 5-30 min, and still more preferably 10-30 min.
Mixing the aged catalytic system with a reactant solution; preferably, the aged system and the reactant solution are mixed at a reaction temperature and then reacted to obtain a product slurry; the mixing ratio is preferably (0.0001-0.005) according to the molar ratio of the main catalyst to the monoolefine: 1, more preferably (0.0001 to 0.002): 1, more preferably (0.0005 to 0.001): 1; the temperature of the reaction is preferably-80 ℃ to-98 ℃, more preferably-88 ℃ to-98 ℃, and further preferably-90 ℃ to-97.5 ℃; the reaction time is preferably 1-20 min, more preferably 5-20 min, and still more preferably 10-20 min.
Adding an alcohol compound into the product slurry to terminate the reaction; the alcohol compound is preferably methanol and/or ethanol; the mass ratio of the alcohol compound to the monoolefin is preferably 1: (5-25), more preferably 1: (7.5 to 20).
After the reaction is terminated, the solvent is removed; obtaining styrene butadiene rubber; the method of removing the solvent is preferably vacuum drying.
In the invention, a sulfur-containing organic compound is introduced as a slurry stabilizer in the polymerization process, and the existence of the substance can effectively control the polymerization speed, so that the product is uniformly dispersed, thereby effectively improving the mass transfer and heat transfer of a polymerization system, enabling a production device to operate in a long period and a low load, and obtaining the product with stable quality, widened molecular weight distribution and more excellent processing performance.
In order to further illustrate the present invention, the following will describe the production process of butyl rubber provided by the present invention in detail with reference to the examples. The reagents used in the following examples are all commercially available.
Example 1
1.1 at-70 deg.C, 22.5g of isobutylene was weighed into 127.5g of methyl chloride, and then 1g of isoprene was added and mixed well to obtain a monomer solution.
1.2 weighing 0.005g 1, 1-dimethyl mercaptan and adding into the monomer solution to obtain reactant solution, cooling the solution to-95 ℃.
1.3 at-70 deg.C, weighing 0.2g of 20% ethyl aluminum dichloride solution, adding into 10g of 0.025 wt% HCl methane chloride solution, mixing well to obtain a catalytic system, aging at-88 deg.C for 30min, and cooling to-95 deg.C.
1.4 adding the catalytic system into the reactant solution to react for 20min at the temperature of minus 95 ℃ to obtain the granular uniformly dispersed slurry.
1.5 Add 2g ethanol to stop the reaction, put the slurry in a vacuum oven to remove the solvent to get butyl rubber.
The butyl rubber obtained in example 1 was subjected to nuclear magnetic resonance analysis, Mooney viscosity analysis (preheating at 125 ℃ for 1min and then testing for 8min using MV2000 Mooney viscometer), GPC testing (using waters ALC/GPC 244 liquid chromatograph, column: μ -Styragel)
Three columns are used in series. A pre-column filter is arranged in front of the column. Mobile phase: tetrahydrofuran (used after filtration and degassing); flow rate: 1 mL/min. A detector: differential refraction, sensitivity 8 x grade. Column pressure: 750 lb/in 2. Sample introduction amount: 0.3% sample solution in 100 μ L); the obtained nuclear magnetic resonance hydrogen spectrum is shown in figure 1; the unsaturation degree of the obtained butyl rubber is 1.79 mol%, the Mooney viscosity ML (1+8) is 51 at 125 ℃, the weight-average molecular weight is 518000, the molecular weight distribution is 4.2, the 300% definite elongation of the obtained rubber is 7.5MPa, and the tensile strength is 17.5 MPa.
Example 2
2.1 at-70 deg.C, 20g of isobutylene was weighed into 113.5g of methyl chloride, and then 1.3g of isoprene was added and mixed well to obtain a monomer solution.
2.2 weighing 0.01g dimethyl sulfide and adding into the monomer solution to obtain reactant solution, and cooling the solution to-97 ℃.
2.3 at-70 deg.C, weighing 0.15g of 20% ethyl aluminum dichloride solution, adding into 6g of 0.02 wt% HCl methane chloride solution, mixing well to obtain a catalytic system, aging at-90 deg.C for 20min, and cooling to-97 deg.C.
2.4 adding the catalytic system into the reactant solution to react for 10min at the temperature of minus 97 ℃ to obtain the granular uniformly dispersed slurry.
2.5 Add 2g of ethanol to stop the reaction and place the slurry in a vacuum oven to remove the solvent to obtain butyl rubber.
The butyl rubber obtained in example 2 was subjected to nuclear magnetic resonance analysis, Mooney viscosity analysis and GPC measurement, and the obtained butyl rubber had an unsaturation degree of 1.8. + -. 0.1 mol%, a Mooney viscosity ML (1+8) at 125 ℃ of 49, a weight-average molecular weight of 510000 and a molecular weight distribution of 4.0, and had a tensile strength of 17.0MPa at 300% elongation of 7.2 MPa.
Example 3
3.1 at-85 deg.C, 40g of isobutylene was weighed into 110g of methyl chloride, and then 2g of isoprene was added and mixed well to obtain a monomer solution.
3.2 weighing 0.02g of ethanethiol into the monomer solution to obtain a reactant solution, and cooling the reactant solution to-90 ℃.
3.3 at-85 deg.C, weighing 0.3g of 20% ethyl aluminum dichloride solution, adding into 12g of 0.02 wt% HCl methane chloride solution, mixing well to obtain the catalytic system, aging at-90 deg.C for 30 min.
3.4 adding the catalytic system into the reactant solution to react for 20min at-90 ℃ to obtain the granular uniformly-dispersed slurry.
3.5 Add 2g ethanol to stop the reaction, put the slurry in a vacuum oven to remove the solvent to get butyl rubber.
The butyl rubber obtained in example 3 was subjected to nuclear magnetic resonance analysis, Mooney viscosity analysis and GPC measurement, and the obtained butyl rubber had an unsaturation degree of 1.6. + -. 0.1 mol%, a Mooney viscosity ML (1+8) at 125 ℃ of 52, a weight-average molecular weight of 515000 and a molecular weight distribution of 3.5, and had a tensile strength of 17.2MPa at 300% elongation of 6.9 MPa.
Example 4
4.1 at-80 deg.C, 15g of isobutylene was weighed into 135g of methyl chloride, and then 1.5g of isoprene was added and mixed well to obtain a monomer solution.
4.2 weighing 0.03g thiophenol and adding to the monomer solution to get the reactant solution, cooling the solution to-97.5 ℃.
4.3 at-80 deg.C, weighing 0.15g of 20% ethyl aluminum dichloride solution, adding into 8g of 0.02 wt% HCl methane chloride solution, mixing well to obtain a catalytic system, aging at-90 deg.C for 10min, and cooling to-97.5 deg.C.
4.4 adding the catalytic system into the reactant solution to react for 15min at the temperature of minus 97.5 ℃ to obtain the granular uniformly dispersed slurry.
4.5 Add 2g of ethanol to stop the reaction and place the slurry in a vacuum oven to remove the solvent to obtain butyl rubber.
The butyl rubber obtained in example 4 was subjected to nuclear magnetic resonance analysis, Mooney viscosity analysis and GPC measurement, and the obtained butyl rubber had an unsaturation degree of 1.6. + -. 0.1 mol%, a Mooney viscosity ML (1+8) at 125 ℃ of 43, a weight-average molecular weight of 512000 and a molecular weight distribution of 3.2, and had a tensile strength of 16.8MPa at 300% elongation of 7.0 MPa.
Example 5
5.1 at-75 deg.C, 30g of isobutylene was weighed into 270g of methyl chloride, and then 3g of isoprene was added and mixed well to obtain a monomer solution.
5.2 weighing 0.05g of thioglycolic acid and adding the thioglycolic acid into the monomer solution to obtain a reactant solution, and cooling the reactant solution to-97.5 ℃.
5.3 at-80 deg.C, weighing 0.15g of 40% ethyl aluminum dichloride solution, adding into 8g of 0.05 wt% HCl methane chloride solution, mixing well to obtain a catalytic system, aging at-90 deg.C for 10min, and cooling to-97.5 deg.C.
5.4 adding the catalytic system into the reactant solution to react for 10min at the temperature of minus 97.5 ℃ to obtain the granular uniformly dispersed slurry.
5.5 Add 5g ethanol to stop the reaction, put the slurry in a vacuum oven to remove the solvent to obtain butyl rubber.
The butyl rubber obtained in example 5 was subjected to nuclear magnetic resonance analysis, Mooney viscosity analysis and GPC measurement, and the obtained butyl rubber had an unsaturation degree of 1.5. + -. 0.1 mol%, a Mooney viscosity ML (1+8) at 125 ℃ of 41, a weight-average molecular weight of 502000 and a molecular weight distribution of 3.4, and had a tensile strength of 16.5MPa at 300% elongation of 6.8 MPa.
Comparative example 1
The process flow and the steps are the same as those of the example 1, and the mixture ratio of other materials is also the same, except that no sulfur-containing organic compound is added. The product is agglomerated and stuck on the stirring paddle and the kettle wall.
The product is agglomerated and stuck on the stirring paddle and the kettle wall.
The above-mentioned butyl rubber product prepared in comparative example 1 was subjected to nuclear magnetic resonance analysis, Mooney viscosity analysis, GPC measurement, and the resulting butyl rubber had an unsaturation degree of 1.70 mol%, a Mooney viscosity ML (1+8) at 125 ℃ of 38, a weight-average molecular weight of 373000, a molecular weight distribution of 2.7, a elongation at 300% of the resulting rubber of 6.0MPa, and a tensile strength of 16.1 MPa.
Claims (10)
1. A production process of butyl rubber is characterized by comprising the following steps:
s1) mixing mono-olefin, diolefin, sulfur-containing organic compound and reaction solvent to obtain reactant solution; the sulfur-containing organic compound is selected from one or more of thiol compounds, thioether compounds and thiophenol compounds;
mixing a main catalyst, a cocatalyst and a reaction solvent to obtain a catalytic system; the main catalyst is Lewis acid;
s2) aging the catalytic system at low temperature, mixing the aged catalytic system with a reactant solution, and reacting to obtain a product slurry;
s3) adding an alcohol compound into the product slurry to terminate the reaction, thereby obtaining the butyl rubber.
2. The process of claim 1, wherein the mono-olefin is selected from the group consisting of C4-C16 isomonoolefin; the diene is selected from conjugated diene of C4-C14; the sulfur-containing organic compound is selected from one or more of thiol compounds of C2-C20, thioether compounds of C2-C20 and thiophenol compounds of C6-C20.
3. The process of claim 1, wherein the mono-olefin is selected from the group consisting of C4-C10 isomonoolefin; the diene is selected from conjugated diene of C4-C8; the sulfur-containing organic compound is selected from one or more of thiol compounds of C2-C10, thioether compounds of C2-C10 and thiophenol compounds of C6-C15.
4. The process according to claim 1, wherein the sulfur-containing organic compound is one or more selected from thiophenol, thioglycolic acid, mercaptoethanol, 1-dimethylmercaptan, ethanethiol, dimethylsulfide, etc.
5. The production process according to claim 1, wherein the concentration of the sulfur-containing organic compound in the reactant solution is 1 to 1000 mg/kg.
6. The process according to claim 1, wherein the molar ratio of monoolefin to diolefin is 1: (0.01 to 0.1); the concentration of the mono-olefin in the reactant solution is 10-50 wt%.
7. The process of claim 1, wherein the procatalyst is selected from one or more of aluminum trichloride, ethylaluminum dichloride, diethylaluminum monochloride, butylaluminum dichloride, dibutylaluminum monochloride, boron trifluoride, titanium tetrachloride, and ethylaluminum sesquichloride; the cocatalyst is H2O or HCl.
8. The production process according to claim 1, wherein the molar ratio of the main catalyst to the monoolefin is (0.0001 to 0.005): 1; the molar ratio of the main catalyst to the cocatalyst is (1-20): 1; the concentration of the cocatalyst in the catalytic system is 0.01-0.05 wt%.
9. The production process according to claim 1, wherein the temperature for aging in the step S2) is-80 ℃ to-95 ℃; the aging time is 1-45 min; the reaction temperature is-80 ℃ to-98 ℃; the reaction time is 1-20 min.
10. The process according to claim 1, wherein the alcohol is selected from methanol and/or ethanol; after the reaction was terminated, the solvent was removed to obtain a butyl rubber.
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| CN111925661A (en) * | 2020-08-20 | 2020-11-13 | 山东京博中聚新材料有限公司 | Butyl rubber/asphalt waterproof material and preparation method thereof |
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| CN108219050A (en) * | 2017-12-29 | 2018-06-29 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of butyl rubber |
| CN110452323A (en) * | 2019-08-28 | 2019-11-15 | 黄河三角洲京博化工研究院有限公司 | A kind of butyl rubber and preparation method thereof |
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| CN108219050A (en) * | 2017-12-29 | 2018-06-29 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of butyl rubber |
| CN110452323A (en) * | 2019-08-28 | 2019-11-15 | 黄河三角洲京博化工研究院有限公司 | A kind of butyl rubber and preparation method thereof |
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| CN111925661A (en) * | 2020-08-20 | 2020-11-13 | 山东京博中聚新材料有限公司 | Butyl rubber/asphalt waterproof material and preparation method thereof |
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