CN111019032A - Production process of butyl rubber - Google Patents
Production process of butyl rubber Download PDFInfo
- Publication number
- CN111019032A CN111019032A CN201911337232.5A CN201911337232A CN111019032A CN 111019032 A CN111019032 A CN 111019032A CN 201911337232 A CN201911337232 A CN 201911337232A CN 111019032 A CN111019032 A CN 111019032A
- Authority
- CN
- China
- Prior art keywords
- organic compound
- containing organic
- nitrogen
- butyl rubber
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
- C08F210/10—Isobutene
- C08F210/12—Isobutene with conjugated diolefins, e.g. butyl rubber
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a production process of butyl rubber, which comprises the following steps: s1) mixing mono-olefin, diene and nitrogen-containing organic compound with a reaction solvent to obtain a reactant solution; the nitrogen-containing organic compound is selected from alkylamine and/or aromatic amine; 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 nitrogen-containing organic compound as the slurry stabilizer in the polymerization process, the existence of the substance can effectively reduce the cationic active polymerization speed, improve the dispersion state of the product in the polymerization system, and uniformly disperse the product so as to effectively enhance the mass transfer and heat transfer of the polymerization system, and the product has stable quality, widened molecular weight distribution and 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 a synthetic rubber, and is a product of cationic polymerization of isobutylene and isoprene at low temperature under the action of a catalyst. The butyl rubber has excellent air tightness and good performances of heat resistance, aging resistance, acid and alkali resistance, ozone resistance, solvent resistance, electric insulation, shock absorption, low water absorption and the like, so that the butyl rubber is widely applied to the aspects of inner tubes, water tires, vulcanized capsules, airtight layers, tire sides, wires and cables, waterproof building materials, shock absorption materials, medicinal bottle stoppers, foods (chewing gum base materials), rubber dams, gas defense devices, adhesives, inner tube valve cores, anti-corrosion products, wharf ship protecting screws, bridge supporting pads, heat-resistant conveyer belts and the like.
The production of butyl rubber began in the 40's of the 20 th century, and Exxon corporation realized the industrial production of butyl rubber in 1943. Since the realization of industrial production, the raw material route, the production process and the structural form of a polymerization kettle 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 lead to poor heat transfer effect and influence heat removal efficiency, thus leading to accelerated polymerization temperature rise; the colloidal particles are agglomerated seriously to cause the blockage of an overflow pipe, and the polymerization reaction period is shortened. The rapid removal of the heat of polymerization to control the reaction at a constant low temperature is a major problem in production. Frequent start and stop of the production device can lead to increased production cost and to substantial fluctuation in 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.
Due to the problems, the device is difficult to continuously and stably operate, so that the production capacity and the yield of Chinese butyl rubber cannot meet the requirements of actual production, and the product self-sufficiency rate is low.
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, diene and nitrogen-containing organic compound with a reaction solvent to obtain a reactant solution; the nitrogen-containing organic compound is selected from alkylamine and/or aromatic amine;
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 nitrogen-containing organic compound is selected from C2-C10 alkylamine and/or C6-C20 aromatic amine.
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 nitrogen-containing organic compound is selected from C2-C5 alkylamine and/or C6-C15 aromatic amine.
Preferably, the sulfur-containing organic compound is selected from one or more of dimethylamine, trimethylamine, tert-butylamine, aniline, and isopropylamine.
Preferably, the concentration of the nitrogen-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 9.9-50 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, diene and nitrogen-containing organic compound with a reaction solvent to obtain a reactant solution; the nitrogen-containing organic compound is selected from alkylamine and/or aromatic amine; 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 nitrogen-containing organic compound as the slurry stabilizer in the polymerization process, the existence of the substance can effectively reduce the polymerization speed of cationic active polymerization, improve the dispersion state of the product in a polymerization system, and uniformly disperse the product so as to effectively enhance the mass transfer and heat transfer of the polymerization system, so that a production device can run in a long period and at a low load, and the production device can continuously produce the product, and the obtained product has stable quality, widened molecular weight distribution and more excellent processing performance.
Drawings
FIG. 1 shows the NMR spectrum 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, diene and nitrogen-containing organic compound with a reaction solvent to obtain a reactant solution; the nitrogen-containing organic compound is selected from alkylamine and/or aromatic amine; 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.
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 nitrogen-containing organic compound is alkylamine and/or aromatic amine, preferably C2-C10 alkylamine and/or C6-C20 aromatic amine, more preferably C2-C8 alkylamine and/or C6-C15 aromatic amine, still more preferably C2-C5 alkylamine and/or C6-C15 aromatic amine, and most preferably one or more of dimethylamine, trimethylamine, tert-butylamine, aniline and isopropylamine; the reaction solvent is preferably a halogenated alkane, more preferably methyl chloride, and still more preferably methyl chloride.
Mixing mono-olefin, diene, nitrogen-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 nitrogen-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 9.9-50 wt%, more preferably 9.9-40 wt%, still more preferably 9.9-30 wt%, and most preferably 9.9-26.3 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 nitrogen-containing organic compound in the reactant solution is preferably 1-1000 mg/kg, more preferably 10-200 mg/kg, still more preferably 10-150 mg/kg, still more preferably 10-131.6 mg/kg, still more preferably 13-131.6 mg/kg; in some embodiments provided herein, the concentration of the nitrogen-containing organic compound in the reactant solution is preferably 13 mg/kg; in some embodiments provided herein, the concentration of the nitrogen-containing organic compound in the reactant solution is preferably 18.5 mg/kg; in some embodiments provided herein, the concentration of the nitrogen-containing organic compound in the reactant solution is preferably 131.6 mg/kg; in some embodiments provided herein, the concentration of the nitrogen-containing organic compound in the reactant solution is preferably 66 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 (4-8.4): 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 8.4: 1; in some embodiments provided herein, the molar ratio of the primary catalyst to the secondary catalyst is preferably 5.4: 1; (ii) a 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 further preferably 10-30 min; in some embodiments provided herein, the aging time is preferably 30 min; in some embodiments provided herein, the aging time is preferably 20 min; in other embodiments provided herein, the aging time is preferably 10 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, most preferably (0.0005 to 0.00088): 1; in some embodiments provided herein, the molar ratio of procatalyst to monoolefin is preferably 0.00079: 1; in some embodiments provided herein, the molar ratio of procatalyst to monoolefin is preferably 0.00066: 1; in some embodiments provided herein, the molar ratio of procatalyst to monoolefin is preferably 0.00077: 1; in other embodiments provided herein, the molar ratio of procatalyst to monoolefin is preferably 0.00088: 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 nitrogen-containing organic compound is introduced as a slurry stabilizer in the polymerization process, the existence of the substance can effectively reduce the polymerization speed of cationic active polymerization, improve the dispersion state of products in a polymerization system, and uniformly disperse the products so as to effectively enhance the mass transfer and heat transfer of the polymerization system, so that a production device can run in a long period and at a low load, the continuous production can be realized, and the obtained products have 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 0.002g of tert-butylamine and adding into the monomer solution to obtain a reactant solution, and 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 0.0025g of trimethylamine and adding it to the monomer solution to obtain a 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 517500 and a molecular weight distribution of 3.8, and had a tensile strength of 16.8MPa at 300% elongation of 7.0 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 aniline into monomer solution to get reactant solution, cooling the solution to-90 ℃.
3.3 at-85 deg.C, weighing 0.35g 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 51500 and a molecular weight distribution of 3.5, and had a tensile strength of 17.0MPa at 300% elongation of 6.8 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 0.01g dimethylamine and adding to the monomer solution to get 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 514000 and a molecular weight distribution of 3.2, and had a tensile strength of 16.6MPa at 300% elongation of 6.5 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 nitrogen-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, diene and nitrogen-containing organic compound with a reaction solvent to obtain a reactant solution; the nitrogen-containing organic compound is selected from alkylamine and/or aromatic amine;
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 nitrogen-containing organic compound is selected from C2-C10 alkylamine and/or C6-C20 aromatic amine.
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 nitrogen-containing organic compound is selected from C2-C5 alkylamine and/or C6-C15 aromatic amine.
4. The process according to claim 1, wherein the sulfur-containing organic compound is selected from one or more of dimethylamine, trimethylamine, tert-butylamine, aniline, and isopropylamine.
5. The production process according to claim 1, wherein the concentration of the nitrogen-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 9.9-50 wt%.
7. The process of claim 1, wherein the procatalyst is selected from the group consisting of aluminum trichloride, ethylaluminum dichloride, diethylaluminum monochloride, and dichlorobutaneOne or more of aluminum chloride, chlorodibutyl aluminum, boron trifluoride, titanium tetrachloride and ethyl aluminum 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911337232.5A CN111019032A (en) | 2019-12-23 | 2019-12-23 | Production process of butyl rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911337232.5A CN111019032A (en) | 2019-12-23 | 2019-12-23 | Production process of butyl rubber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111019032A true CN111019032A (en) | 2020-04-17 |
Family
ID=70211656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911337232.5A Pending CN111019032A (en) | 2019-12-23 | 2019-12-23 | Production process of butyl rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111019032A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393556A (en) * | 2020-05-15 | 2020-07-10 | 山东京博中聚新材料有限公司 | Isomonoolefin-alkylstyrene copolymer and preparation method thereof |
| CN112409522A (en) * | 2020-11-16 | 2021-02-26 | 山东京博中聚新材料有限公司 | Preparation method of butyl rubber |
| WO2023016561A1 (en) * | 2021-08-13 | 2023-02-16 | 南京中科康润新材料科技有限公司 | Catalyst system for cationic polymerization of c4 liquefied petroleum gas and polybutylene production method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110483671A (en) * | 2019-08-27 | 2019-11-22 | 黄河三角洲京博化工研究院有限公司 | A kind of butyl rubber and its production technology |
-
2019
- 2019-12-23 CN CN201911337232.5A patent/CN111019032A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110483671A (en) * | 2019-08-27 | 2019-11-22 | 黄河三角洲京博化工研究院有限公司 | A kind of butyl rubber and its production technology |
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393556A (en) * | 2020-05-15 | 2020-07-10 | 山东京博中聚新材料有限公司 | Isomonoolefin-alkylstyrene copolymer and preparation method thereof |
| CN111393556B (en) * | 2020-05-15 | 2023-04-07 | 山东京博中聚新材料有限公司 | Isomonoolefin-alkylstyrene copolymer and preparation method thereof |
| CN112409522A (en) * | 2020-11-16 | 2021-02-26 | 山东京博中聚新材料有限公司 | Preparation method of butyl rubber |
| WO2023016561A1 (en) * | 2021-08-13 | 2023-02-16 | 南京中科康润新材料科技有限公司 | Catalyst system for cationic polymerization of c4 liquefied petroleum gas and polybutylene production method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111019032A (en) | Production process of butyl rubber | |
| RU2333224C2 (en) | Butyl rubber and method for obtaining same | |
| CA1235543A (en) | Process for producing propylene block copolymer | |
| US3789036A (en) | Process for preparing saturated and unsaturated elastomeric copolymers of ethylene and/or higher alpha-olefins | |
| US3953543A (en) | Polymerization process and polymer produced thereby | |
| CN110452323B (en) | Butyl rubber and preparation method thereof | |
| CN108192005B (en) | Polyolefin and preparation method thereof | |
| CN113087845A (en) | Preparation method of long-chain olefin modified C9 petroleum resin | |
| CN111892778B (en) | Impact-resistant co-polypropylene and polypropylene composition and respective preparation method | |
| CN112409522A (en) | Preparation method of butyl rubber | |
| CN113480690B (en) | Multipolymer and preparation method thereof | |
| CN110878132A (en) | Production process of butyl rubber | |
| CN107686536B (en) | Industrial production method of trans-1, 4-butadiene-isoprene copolymer rubber and device for implementing method | |
| CN113637105A (en) | Preparation method of SAN resin with low crystal point and low yellow index | |
| US3658770A (en) | Unsaturated partially crystalline terpolymers of ethylene propylene and hydrocarbon dienes or polyenes and process for preparing said terpolymers | |
| EP0763551B1 (en) | Process for the production of ethylene-propylene elastomeric copolymers | |
| US11613600B2 (en) | Capped dual-headed organoaluminum compositions | |
| US3846387A (en) | Chain saturated copolymers of ethylene, alpha monoolefins, and trienes containing side-chains with non-terminal conjugated unsaturation | |
| US3674754A (en) | Vulcanizable ethylene/propylene copolymers and process for their preparation | |
| RU2337111C2 (en) | Method for butyl rubber production | |
| CN106916244B (en) | Process for producing ethylene random copolymer | |
| CN112079953B (en) | Medical rubber and preparation method and application thereof | |
| CN116410413A (en) | Preparation method of secondary brominated branched butyl rubber | |
| Markina et al. | Production of butyl rubber by suspension polymerisation using a modified catalytic system | |
| CN106536618A (en) | Highly unsaturated multi-modal polyisoolefin composition and process for preparation thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200417 |