CN111303328A - Deacidifying method for butyl rubber halogenation reaction product - Google Patents
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Abstract
A method for deacidifying a butyl rubber halogenation reaction product comprises the following steps: (1) reacting a solution comprising butyl rubber with a halogenating agent to obtain a halogenated butyl rubber solution; (2) adding alkali liquor into the halogenated butyl rubber solution obtained in the step (1), quickly mixing, and stopping reaction; wherein the halogenation reaction in the step (1) is carried out in the presence of a high-efficiency deacidifying agent. Wherein, the high-efficiency deacidification agent comprises: water, surfactant, stearate. Through the process flow of the invention, the secondary substitution content (the proportion of secondary to the substituted structure) in the halogenation reaction product can be increased from 90wt% to more than 95 wt%.
Description
Technical Field
The invention belongs to the technical field of chemistry and chemical engineering, and particularly relates to a deacidification method for a butyl rubber halogenation reaction product.
Background
With the development of scientific technology, chemical engineering technology is continuously developing in the directions of high efficiency, energy conservation and safety, in order to achieve the aim of sustainable development and comprehensively utilize resource and energy, numerous new requirements are provided in the production process of chemical engineering, Ackson corporation prepares butyl rubber in 1937, people research a halogenation method of butyl rubber in 1953, compared with the traditional butyl rubber, the halogenated butyl rubber has obvious advantages in the aspects of heat resistance, acid and alkali resistance, vulcanization activity, and regeneration performance of blending with other rubbers, and is a main raw material of high-grade automobile inner tubes and medical rubber bottle stoppers.
Butyl rubber is a synthetic rubber prepared by copolymerizing isobutene and a small amount of isoprene, and is abbreviated as IIR. The reaction mechanism of the butyl halogenated rubber is that secondary hydrogen atoms on double bonds of the rubber are replaced by halogen atoms, hydrogen halide is generated in the reaction process, and the hydrogen halide and unreacted halogen simple substance are neutralized by an alkali solution. However, since the primary structure is more stable than the secondary structure during the reaction, a part of the secondary structure is isomerized into the primary structure during the halogenation reaction of the butyl rubber. The temperature and the presence of lewis acids, transition metal ions have an effect on the relative content of primary structures. Therefore, in order to obtain a high-quality product, the reaction process must ensure secondary halogenation while inhibiting the transfer of halogen substitution sites. The application number CN103467635A discloses a method for controlling halogen substitution position in halogenated butyl rubber, which utilizes water in the system to extract halogen hydrogen acid generated in the halogenation reaction process in situ, to reduce the acid concentration in the organic phase, thereby inhibiting the halogen substitution position conversion (secondary position to primary position), and finally uses alkali liquor to neutralize the reaction solution to terminate the reaction process.
However, the above method has the following problems: 1. the halogenation reaction time in the production of halogenated butyl rubber is generally controlled to be about 2-5min, and the reaction product stays for too long time under the acidic condition, so that high-sec-position halogenated butyl rubber cannot be obtained; 2. the alkaline aqueous solution and the high-viscosity halogenated butyl rubber hexane solution are immiscible and are not uniformly mixed, so that incomplete neutralization is caused, and the rearrangement of a molecular structure cannot be inhibited.
Disclosure of Invention
In view of the above-mentioned problems, it is an object of the present invention to provide a method for deacidifying a butyl rubber halogenation reaction product, by which the secondary substitution content (the proportion of secondary to the substitution structure) in the halogenation reaction product can be increased from 90wt% to 95wt% or more.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for deacidifying a butyl rubber halogenation reaction product comprises the following steps: (1) reacting a solution comprising butyl rubber with a halogenating agent to obtain a halogenated butyl rubber solution; (2) adding alkali liquor into the halogenated butyl rubber solution obtained in the step (1), quickly mixing, and stopping reaction; wherein the halogenation reaction in the step (1) is carried out in the presence of a high-efficiency deacidifying agent.
Preferably, the high efficiency deacidification agent comprises: water, surfactant, stearate.
Further preferably, the surfactant comprises: alkyl ester emulsifier and polyol ester emulsifier.
Further preferably, the stearate comprises: the effect of the calcium stearate selected is best through the test and determination of the inventor.
Preferably, the water is used in an amount of 0.5 to 3.0wt% based on the butyl rubber solution.
Preferably, the surfactant is used in an amount of 0.01 to 0.3wt% based on the butyl rubber solution.
Preferably, the stearate is used in an amount of 1.0 to 2.0wt% based on the butyl rubber solution.
Further preferably, the solvent containing butyl rubber used in the step (1) is one or more of n-hexane, n-heptane and n-octane
Further preferably, the halogenating agent in step (1) is Cl2Or Br2。
Further preferably, the alkali liquor in the step (2) is used for neutralizing the unreacted halogen and the hydrogen halide in the reaction liquor to terminate the reaction process, the molar ratio of the added alkali to the halogenating agent is more than 2.2:1, and from the viewpoint of consumption of actual production, the alkali liquor is preferably 2.2-2.8: 1; wherein the alkali solution is one of aqueous solution of sodium hydroxide, potassium hydroxide or ammonia.
Further, the temperature of all the reactions is controlled to be 15-45 ℃.
The invention has the following beneficial effects:
the surface tension of water is reduced by using the surfactant in the high-efficiency deacidification agent, so that the water is promoted to be emulsified and dispersed in an organic phase, and the water and an organic phase reaction solution system are promoted to be fully and uniformly mixed, so that the hydrogen halide generated by the reaction can be quickly extracted and absorbed; meanwhile, stearate is added into the high-efficiency deacidification agent, so that hydrogen halide can be further converted into weak acid stearic acid, and the pH value of a reaction solution system is rapidly increased from about 2 to more than 5, so that the retention time of a reaction product under a strong acid condition is reduced, and the occurrence of an isomerization side reaction is inhibited; the secondary substitution content (the proportion of the secondary to the substituted structure) in the halogenation reaction product can be effectively increased by the above improved optimization.
Description of the drawings
FIG. 1 is a flow chart of a conventional process.
FIG. 2 is a process flow diagram employed in the present invention.
Detailed Description
In the present invention, the butyl rubber is a copolymer obtained by copolymerizing isobutylene and a small amount of isoprene, and the content of isoprene monomer units in the butyl rubber is usually 0.5 to 3.0 mol% based on the total amount of all monomer units of the butyl rubber; there is no particular limitation in the molecular weight of the butyl rubber, as long as the butyl rubber is capable of undergoing halogenation reactions to introduce halogen atoms. In general, the weight average molecular weight of butyl rubber is 30X 104~100×104(ii) a The butyl rubber used in the present invention is commercially available, for example, yanhan IIR1751 manufactured by petrochemical company ltd, china, or can be prepared by a method known in the art; the concentration of butyl rubber is conventional, as long as halogenation is possible, and generally speaking, based on the content of butyl rubber solution,the content of the butyl rubber is 5-30 wt%, if the concentration is higher than 30wt%, the halogenated reagent and the glue solution are mixed unevenly in the reaction process due to too high concentration and large viscosity of the glue solution, the content of the synthesized halogenated butyl rubber is low, the structural proportion is unqualified, and if the concentration is lower than 5%, the viscosity of the halogenated butyl rubber is reduced easily after the reaction due to too low concentration of the glue solution.
Since butyl rubber is a substitution reaction during halogenation, 1mol of halogen (Br) per reaction2/Cl2) Molecules can release 1mol of hydrogen halide (HBr/HCl) and the halogenation reaction speed is very high, if the hydrogen halide in the halogenation reaction product can not be led out and neutralized quickly in time, the hydrogen halide can be collected in the glue solution, and the glue solution forms strong acidity; under strong acid conditions, the molecular structure rearrangement of the halogenated butyl rubber is caused, secondary substitution is transferred to primary substitution, and the molecular structure rearrangement is shown as follows:
to achieve the object of the present invention, the halogenation reaction of the butyl rubber solution with the halogenating agent needs to be carried out in the presence of a highly effective deacidifying agent. In the research of the halogenation reaction of the butyl rubber, the inventor finds that if halogen free radicals occur due to various reasons in the halogenation reaction process, the halogen free radicals are mainly contained in the halogenated butyl rubber as a result of the free radical substitution, and the halogen free radicals can be absorbed, inhibited and eliminated by the presence of the high-efficiency deacidification agent in the halogenation system, so that the content of the primary structures containing the primary halogen atoms in the halogenated butyl rubber in the halogenation reaction process can be obviously reduced.
For the present invention, the high-efficiency deacidification agent comprises: water, surfactant, stearate; wherein, the surface active agent can use alkyl ester emulsifier, polyol ester emulsifier, etc.; as the stearate, magnesium stearate, zinc stearate, calcium stearate, aluminum stearate, lithium stearate, etc. can be used, and calcium stearate is most effective, and therefore calcium stearate is used in the following examples.
For the invention, the halogenation reagent can be molecular chlorine or molecular bromine, the halogenation reagent can be directly used or can be prepared into a solution for use, wherein the molar ratio of halogen to the double bond of the butyl rubber is 0.1-1.1: 1, and the halogenation reaction is carried out for 2-5 min.
For the purposes of the present invention, the solvent of the alkane solution is n-hexane, n-heptane or n-octane.
In the present invention, the halogenated butyl rubber is obtained by post-treating the halogenated butyl rubber solution to terminate the reaction and recover the halogenated butyl rubber, and the halogenated butyl rubber is usually an alkaline aqueous solution, preferably one of sodium hydroxide, potassium hydroxide or ammonia aqueous solution, and the molar ratio of the halogenated butyl rubber to the halogen is more than 2.2:1, and in order to save the use amount of the alkali liquor, the molar ratio is preferably 2.2-2.8: 1.
The reaction flow of the invention is optimized to the traditional process flow (the traditional process flow is shown in figure 1, and the flow of the invention is shown in figure 2).
Example 1
Preparing a butyl rubber n-hexane solution with the concentration of 5.0wt% by using butyl rubber, adding a high-efficiency deacidification agent into the butyl rubber n-hexane solution until the concentration of the high-efficiency deacidification agent is 1.51wt% (0.5 wt% of water, 0.01wt% of T-60 and 1.0wt% of calcium stearate), and fully stirring to obtain a uniform emulsion; chlorine is introduced into the emulsion for chlorination reaction, and Cl2The molar ratio of the double bonds in the butyl rubber is 0.8:1, the reaction time is 5min, and the temperature is 15 ℃; then quickly adding sodium hydroxide aqueous solution into the reaction system to control sodium hydroxide and Cl2The molar ratio of the addition amount is 2.3:1, the reaction temperature is 15 ℃, and the mixture is stirred and stood; taking out the alkane solution of the chlorinated butyl rubber at the upper layer, washing, adding a stabilizer, drying, and measuring the substitution condition of chlorine by adopting nuclear magnetism.
Example 2
Preparing a butyl rubber n-hexane solution with the concentration of 10.0wt% by using butyl rubber, adding a high-efficiency deacidification agent into the butyl rubber n-hexane solution until the concentration of the high-efficiency deacidification agent is 3.6wt% (2.0 wt% of water, 0.1wt% of T-60 and 1.5wt% of calcium stearate), and fully stirring to obtain the productHomogenizing the emulsion; adding Cl with the concentration of 16wt% into the emulsion2In which Cl is present2The molar ratio of the double bonds in the butyl rubber is 0.81:1, the reaction time is 4min, and the temperature is 25 ℃; then quickly adding sodium hydroxide aqueous solution into the reaction system to control sodium hydroxide and Cl2The molar ratio of the addition amount is 2.2:1, the reaction temperature is 25 ℃, and the mixture is stirred and stood; taking out the alkane solution of the chlorinated butyl rubber at the upper layer, washing, adding a stabilizer, drying, and measuring the substitution condition of chlorine by adopting nuclear magnetism.
Example 3
Preparing a butyl rubber n-hexane solution with the concentration of 20.0wt% by using butyl rubber, adding a high-efficiency deacidification agent into the butyl rubber n-hexane solution until the concentration of the high-efficiency deacidification agent is 3.6wt% (2.0 wt% of water, 0.1wt% of potassium hexadecyl phosphate and 1.5wt% of calcium stearate), and fully stirring to obtain a uniform emulsion; adding Br to the emulsion at a concentration of 5.0wt%2The n-hexane solution of (A) is subjected to bromination reaction, wherein Br is2The molar ratio of the double bonds in the butyl rubber is 1.1:1, the reaction time is 4min, and the temperature is 25 ℃; then quickly adding sodium hydroxide aqueous solution into the reaction system to control sodium hydroxide and Br2The molar ratio of the addition amount is 2.3:1, the reaction temperature is 25 ℃, and the mixture is stirred and stood; taking out the alkane solution of the brominated butyl rubber at the upper layer, washing, adding a stabilizer, and measuring the substitution condition of bromine by adopting nuclear magnetism after drying.
Example 4
Preparing a butyl rubber n-hexane solution with the concentration of 20.0wt% by using butyl rubber, adding a high-efficiency deacidification agent into the butyl rubber n-hexane solution until the concentration of the high-efficiency deacidification agent is 3.6wt% (2.0 wt% of water, 0.1wt% of T-80 and 1.5wt% of calcium stearate), and fully stirring to obtain a uniform emulsion; adding liquid bromine into the emulsion to carry out bromination reaction, wherein Br is2The molar ratio of the double bonds in the butyl rubber is 0.5:1, the reaction time is 3min, and the temperature is 15 ℃; then quickly adding sodium hydroxide aqueous solution into the reaction system to control sodium hydroxide and Br2The molar ratio of the addition amount is 2.8:1, the reaction temperature is 15 ℃, and the mixture is stirred and stood; taking out alkane solution of upper brominated butyl rubber, washing, adding stabilizer, drying, and measuring bromine by nuclear magnetismAnd (4) substitution.
Example 5
Preparing a butyl rubber n-heptane solution with the concentration of 30.0wt% by using butyl rubber, adding a high-efficiency deacidification agent into the butyl rubber n-heptane solution until the concentration of the high-efficiency deacidification agent is 5.3wt% (3.0 wt% of water, 0.3wt% of potassium hexadecyl phosphate and 2.0wt% of calcium stearate), and fully stirring to obtain a uniform emulsion; br was added to the emulsion at a concentration of 4.8wt%2Is subjected to a bromination reaction in an n-heptane solution of (1), wherein Br is present2The molar ratio of the double bonds in the butyl rubber is 0.7:1, the reaction time is 2min, and the temperature is 45 ℃; then quickly adding sodium hydroxide aqueous solution into the reaction system to control sodium hydroxide and Br2The molar ratio of the addition amount is 2.2:1, the reaction temperature is 45 ℃, and the mixture is stirred and stood; taking out the alkane solution of the brominated butyl rubber at the upper layer, washing, adding a stabilizer, and measuring the substitution condition of bromine by adopting nuclear magnetism after drying.
Example 6
Preparing a butyl rubber n-octane solution with the concentration of 5.0wt% by using butyl rubber, adding a high-efficiency deacidification agent into the butyl rubber n-octane solution until the concentration of the high-efficiency deacidification agent is 1.51wt% (0.5 wt% of water, 0.01wt% of T-60 and 1.0wt% of calcium stearate), and fully stirring to obtain a uniform emulsion; br was added to the emulsion at a concentration of 5.2wt%2In the presence of a catalyst, with Br2The molar ratio of the double bonds in the butyl rubber is 0.75:1, the reaction time is 2min, and the temperature is 45 ℃; then quickly adding sodium hydroxide aqueous solution into the reaction system to control sodium hydroxide and Br2The molar ratio of the addition amount is 2.3:1, the reaction temperature is 45 ℃, and the mixture is stirred and stood; taking out the alkane solution of the brominated butyl rubber at the upper layer, washing, adding a stabilizer, and measuring the substitution condition of bromine by adopting nuclear magnetism after drying.
Example 7
Preparing a butyl rubber n-hexane solution with the concentration of 10.0wt% by using butyl rubber with the unsaturation degree of 1.9%, adding a high-efficiency deacidification agent into the butyl rubber n-hexane solution until the concentration of the high-efficiency deacidification agent is 1.51wt% (0.5 wt% of water, 0.01wt% of T-60 and 1.0wt% of calcium stearate), and fully stirring to obtain a uniform emulsion; brominating liquid bromine in emulsion, where Br2With double bonds in butyl rubberThe molar ratio is 0.1:1, the reaction time is 3min, and the temperature is 25 ℃; then quickly adding an aqueous solution of ammonia into the reaction system to control ammonia and Br2The molar ratio of the addition amount is 2.7:1, the reaction temperature is 25 ℃, and the mixture is stirred and stood; taking out the alkane solution of the brominated butyl rubber at the upper layer, washing, adding a stabilizer, and measuring the substitution condition of bromine by adopting nuclear magnetism after drying.
Comparative example 1
This scheme differs from example 1 in that no high efficiency deacidification agent was used.
Comparative example 2
This scheme differs from example 1 in that the same amount of water is used instead of the high efficiency deacidification agent.
Comparative example 3
The difference between this scheme and example 1 is that the high efficiency deacidification agent used is water instead of calcium stearate.
Comparative example 4
This scheme differs from example 7 in that the same amount of water is used instead of the high efficiency deacidification agent.
The test results measured are shown in table 1 below:
table 1.
As shown in the table, the high-efficiency deacidification agent can obviously improve the secondary substitution content (the proportion of the secondary to the substitution structure), and is superior to the water extraction experimental method in the comparison document; the reason why the effect of the experiment is not good when calcium stearate is not used is that the stearate has the effect of further converting hydrogen halide into weak acid stearic acid and rapidly increasing the pH value of the reaction solution system from about 2 to more than 5, thereby reducing the retention time of the reaction product under the strong acid condition and inhibiting the occurrence of side isomerization reaction; therefore, the high-efficiency deacidification agent adopted by the scheme can effectively improve the secondary substitution content (the proportion of the secondary substitution structure).
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (10)
1. A method for deacidifying a butyl rubber halogenation reaction product comprises the following steps:
(1) reacting a solution comprising butyl rubber with a halogenating agent to obtain a halogenated butyl rubber solution;
(2) adding alkali liquor into the halogenated butyl rubber solution obtained in the step (1), quickly mixing, and stopping reaction;
characterized in that the halogenation reaction in the step (1) is carried out in the presence of a high-efficiency deacidifying agent.
2. The process of deacidifying a butyl rubber halogenation reaction product according to claim 1 wherein said high efficiency deacidifying agent comprises: water, surfactant, stearate.
3. A process for deacidifying a butyl rubber halogenation reaction product according to claim 2 wherein said surfactant comprises: alkyl ester emulsifier and polyol ester emulsifier.
4. A process for deacidifying a butyl rubber halogenation reaction product according to claim 2 wherein said stearate comprises: one or more of magnesium stearate, zinc stearate, calcium stearate, aluminum stearate and lithium stearate.
5. The method for deacidifying butyl rubber halogenation reaction products according to claim 2, wherein the amount of water is 0.5-3.0 wt% based on the butyl rubber solution.
6. The method for deacidifying butyl rubber halogenation reaction products according to claim 5, wherein the amount of the surfactant is 0.01-0.3 wt% based on the butyl rubber solution.
7. The method for deacidifying butyl rubber halogenation reaction products according to claim 6, wherein the amount of said stearate is 1.0-2.0 wt% based on the butyl rubber solution.
8. The butyl rubber halogenation reaction product deacidification method according to claim 1, wherein the solvent containing butyl rubber used in the step (1) is one or more of n-hexane, n-heptane and n-octane.
9. The process for deacidifying reaction product of halogenation of butyl rubber according to claim 1, wherein said halogenating agent in step (1) is Cl2Or Br2。
10. The deacidification method for butyl rubber halogenation reaction products according to claim 1, wherein the molar ratio of the alkali liquor to the halogenating agent in the step (2) is 2.2-2.8: 1; the alkali liquor is one of aqueous solutions of sodium hydroxide, potassium hydroxide or ammonia.
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| CN111875722A (en) * | 2020-08-31 | 2020-11-03 | 山东京博中聚新材料有限公司 | Preparation method of halogenated butyl rubber |
| CN111944076A (en) * | 2020-09-04 | 2020-11-17 | 浙江信汇新材料股份有限公司 | Water washing process of halogenated butyl rubber |
| CN116283547A (en) * | 2023-03-28 | 2023-06-23 | 上海麦克林生化科技股份有限公司 | Process for halogenating aromatic compounds |
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Application publication date: 20200619 |