阅读说明：本技术 一种丁基橡胶的生产工艺 (Production process of butyl rubber ) 是由 李立霞 栾波 刘振学 王孝海 张�杰 卜立敏 李芬芬 谢晴 荆帅林 张晓岭 韩飞 于 2019-12-23 设计创作，主要内容包括：本发明提供了一种丁基橡胶的生产工艺,包括：S1)将单烯烃、二烯烃、含硫有机化合物与反应溶剂混合,得到反应物溶液；所述含硫有机物选自硫醇类化合物、硫醚类化合物与硫酚类化合物中的一种或多种；将主催化剂、助催化剂与反应溶剂混合,得到催化体系；所述主催化剂为路易斯酸；S2)将所述催化体系在低温下陈化后与反应物溶液混合,反应,得到产物浆料；S3)在产物浆料中加入醇类化合物终止反应,得到丁基橡胶。与现有技术相比,本发明在聚合过程中引入含硫有机化合物作为淤浆稳定剂,该物质的存在可以有效控制聚合速度,使产物均匀分散从而有效改善聚合体系的传质和传热,并且得到的产物质量稳定,分子量分布加宽,加工性能更为优良。(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.)

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.

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.