CN107344982B - Method for producing wide/bimodal molecular weight distribution butyl rubber - Google Patents
Method for producing wide/bimodal molecular weight distribution butyl rubber Download PDFInfo
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- CN107344982B CN107344982B CN201610288408.2A CN201610288408A CN107344982B CN 107344982 B CN107344982 B CN 107344982B CN 201610288408 A CN201610288408 A CN 201610288408A CN 107344982 B CN107344982 B CN 107344982B
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- 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
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- 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
- C08F2400/00—Characteristics for processes of polymerization
- C08F2400/02—Control or adjustment of polymerization parameters
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- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/04—Broad molecular weight distribution, i.e. Mw/Mn > 6
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- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/05—Bimodal or multimodal molecular weight distribution
Abstract
The invention relates to a method for producing wide/bimodal molecular weight distribution butyl rubber, which comprises the following steps: s1, mixing isobutene, isoprene and a diluent to obtain a monomer stream; mixing an initiator and a diluent to obtain an initiator stream; s2, mixing the monomer stream and the initiator stream and feeding the mixture into a first loop reactor zone, and then carrying out polymerization reaction to obtain a first part of butyl rubber slurry; s3, feeding the first butyl rubber slurry into a second loop reactor zone, continuing to perform polymerization reaction to generate a second butyl rubber slurry, and finally obtaining and leading out a butyl rubber slurry with broad/bimodal molecular weight distribution; s4, contacting the led-out butyl rubber slurry with water, and removing unreacted monomers and diluents to obtain rubber particle water; s5, dehydrating and drying the colloidal particle water to obtain the butyl rubber with wide/bimodal molecular weight distribution. The method provided by the invention has the advantages of good heat exchange, mild conditions, good product quality and bimodal distribution.
Description
Technical Field
The invention relates to the field of rubber production, in particular to a method for producing butyl rubber with wide/bimodal molecular weight distribution.
Background
It is well known that the physical properties and processing characteristics of polymers depend on the weight average molecular weight (Mw) and number average molecular weight (Mn). In general, the tensile strength and modulus of the vulcanizate depend on the number average molecular weight. The processability of elastomers depends on Mw and Mw/Mn (molecular weight distribution or MWD).
It has been found that butyl rubber having a broad/bimodal molecular weight distribution exhibits excellent internal mixer mixing characteristics and good resistance to flow (cold flow) under storage conditions. The molecular weight distribution of the butyl rubber also controls the degree of extrudate swell. Butyl rubber with a broad/bimodal molecular weight distribution has an improved green strength compared to rubber with a narrower molecular weight distribution. The increased green strength or unvulcanized compound strength results in improved manufacturing operations (e.g., inner tube manufacturing) and unvulcanized rubber articles having increased strength and less distortion.
Chinese patent CN1427851A discloses a method for preparing butyl rubber with wide molecular weight distribution. The process uses a mixed catalyst system comprising a major amount of a dialkylaluminum halide, a minor amount of a monoalkylaluminum dihalide, and a minor amount of an aluminoxane to produce butyl rubber having a molecular weight distribution of greater than 3.5 and up to 7.6.
At present, there is still a need for a simple and feasible process for preparing butyl rubber with a broad/bimodal molecular weight distribution which is industrially mass producible.
Disclosure of Invention
In view of the above-mentioned prior art, the inventors of the present application conducted extensive and intensive studies in the technical field of rubber production in order to obtain a simple and easy method for preparing a butyl rubber having a broad/bimodal molecular weight distribution, which is industrially mass-producible, and can obtain a butyl rubber having a broad/bimodal molecular weight distribution by employing at least two loop reactors operated in series and controlling the polymerization temperature and time of the two loop reactors, respectively.
The invention provides a method for producing butyl rubber with wide/bimodal molecular weight distribution, which comprises the following steps:
s1, mixing isobutene, isoprene and a diluent to obtain a monomer stream; mixing an initiator and a diluent to obtain an initiator stream;
s2, mixing the monomer stream and the initiator stream and feeding the mixture into a first loop reactor zone, and then carrying out polymerization reaction to obtain a first part of butyl rubber slurry;
s3, feeding the first butyl rubber slurry into the second loop reactor zone, continuing to perform polymerization reaction to generate a second butyl rubber slurry, finally obtaining a butyl rubber slurry with broad/bimodal molecular weight distribution, and leading out from the top of the loop reactor in the second loop reactor zone;
s4, contacting the led-out butyl rubber slurry with water, and removing unreacted monomers and diluents to obtain rubber particle water;
s5, dehydrating and drying the colloidal particle water to obtain butyl rubber with wide/bimodal molecular weight distribution;
wherein the temperature of the polymerization reaction in the step S2 is lower than the temperature of the polymerization reaction in the step S3, and the pressure of the polymerization reaction in the step S2 is higher than the pressure of the polymerization reaction in the step S3.
According to the method provided by the invention, two loop reactor zones are adopted, and the polymerization conditions of the two loop reactor zones are controlled, so that the butyl rubber with a high molecular weight part is obtained in the first loop reactor zone, the butyl rubber with a lower molecular weight part is obtained in the second loop reactor zone, and finally the butyl rubber with broad/bimodal molecular weight distribution can be obtained; and the heat exchange is good, the polymerization condition is mild, the product quality is good, the operation period is long, and the production cost is low.
According to a preferred embodiment of the process according to the invention, in step S1, the molar ratio of isobutene to isoprene is from 95:5 to 99.5:0.5, preferably from 97:3 to 99: 1. The initiator is an initiator commonly used in the art, such as at least one selected from the group consisting of a water/aluminum trichloride system and HCl/ethyl aluminum dichloride. The mixing is also carried out in a vessel such as a mixer. The diluent is a diluent commonly used in the art, such as methyl chloride.
According to a preferred embodiment of the process according to the invention, in step S2, the combined mass concentration of isobutene and isoprene in the mixed stream is from 25 to 45%, preferably from 30 to 40%. In the mixed stream, the mass concentration of the initiator is from 0.10 to 0.25%, preferably from 0.15 to 0.20%. ,
according to a preferred embodiment of the process according to the present invention, the first loop reactor zone comprises at least one loop reactor and the second loop reactor zone comprises at least one loop reactor. In the loop reactor of the first and second loop reactor zones, the slurry is driven by an axial flow pump to make a high-speed directional circulating flow. In a particular embodiment, the flow velocity of the stream is above 7m/s, such as 7.0 to 10.0 m/s.
According to a preferred embodiment of the method of the present invention, in step S2, the polymerization temperature is from-98 to-96 ℃ and the pressure is from 0.3 to 0.4 MPaG. The time of the polymerization reaction is 5-10 min.
According to the present invention, the high molecular weight fraction of the first butyl rubber slurry, wherein the weight average molecular weight is not less than 80 ten thousand, is obtained at a lower temperature and a higher pressure by step S2.
According to a preferred embodiment of the method of the present invention, in the step S3, the polymerization temperature is-92 to-90 ℃ and the pressure is 0.1 to 0.2 MPaG. The time of the polymerization reaction is 5-10 min. The polymerization temperature in step S3 is higher and the polymerization pressure is lower, and the polymerization in step S3 produces a second portion of butyl rubber slurry of the low molecular weight fraction. In one particular embodiment, the first portion of the butyl rubber slurry is fed to the second loop reactor zone by a pressure differential.
According to a preferred embodiment of the process according to the invention, the loop reactor in both loop reactor zones is provided with a jacket in which the medium is ethylene. In a specific example, the ethylene entering the jacket is liquid ethylene at-115 ℃ and the ethylene vapor-liquid mixture at-115 ℃ flows out of the jacket. The polymerization temperature in the first loop reactor zone was controlled to be-98 to-96 ℃ and the polymerization temperature in the second loop reactor zone was controlled to be-92 to-90 ℃ by adjusting the amount of liquid ethylene vaporized in the jacket. The material in the first loop reactor zone enters the second loop reactor zone through pressure difference, the material in the loop reactor is continuously circulated at high speed by an axial flow pump, and the generated butyl rubber particles are uniformly suspended in the diluent.
According to a preferred embodiment of the present invention, because the polymerization temperature in step S2 is low, the initiator stream and the monomer stream may be cooled down via a cooler (e.g., the temperature of the initiator stream may be reduced to-95 ℃ and the temperature of the monomer stream may be reduced to-98 ℃) in step S1. In one embodiment, after isobutene, a small amount of isoprene and a diluent methane chloride are uniformly mixed in a mixer according to a certain proportion, the temperature is reduced to 15 ℃ by using low-temperature water, and then low-pressure propylene and low-pressure ethylene are cooled to-98 ℃; the initiator and the diluent methane chloride are uniformly mixed in a mixer according to a certain proportion, and then are cooled to-35 ℃ by low-pressure propylene and then are cooled to-95 ℃ by low-pressure ethylene. The cooled stream is then sent (e.g., pumped) to the first loop reactor zone in step S2.
According to a preferred embodiment of the method of the present invention, said step S4 is performed in a degassing vessel. The degassing kettle is heated by low-pressure steam, and the temperature of the kettle is controlled by the flow of the steam. Preferably, the degassing vessel is operated at a temperature of from 70 to 75 ℃ and a pressure of from-60 to-50 KPaG, with a residence time of from 1.0 to 2.0 h.
According to the process of the present invention, the butyl rubber slurry may also be mixed with a terminating agent to terminate the polymerization reaction prior to entering the degassing vessel. The terminating agent is triethylene glycol, and the dosage of the terminating agent is 4-6 times of the addition amount of the initiator.
According to a preferred embodiment of the process of the present invention, in step S5, the weight average molecular weight of the butyl rubber is not less than 65 ten thousand, preferably not less than 70 ten thousand. The butyl rubber has a molecular weight distribution (Mw/Mn) of at least 5.0, preferably from 5.0 to 10.0.
According to a specific embodiment of the present invention, the method comprises the steps of:
step S1, uniformly mixing isobutene, a small amount of isoprene and a diluent, namely methane chloride, in a mixer according to a certain proportion, cooling to-98 ℃ through a cooler, uniformly mixing an initiator and the diluent, namely the methane chloride, in the mixer according to a certain proportion, and cooling to-95 ℃ through the cooler;
step S2, pumping the cooled isobutene, a small amount of isoprene, an initiator and a diluent into a first loop reactor, and carrying out polymerization reaction at a temperature of-98 to-96 ℃ and a pressure of 0.3 to 0.4MPaG for 5 to 10 minutes to obtain a first butyl rubber slurry with a high molecular weight part;
step S3, delivering the first butyl rubber slurry obtained in the step S2 into a second loop reactor through pressure difference, carrying out polymerization reaction at the temperature of-92 to-90 ℃ and under the pressure of 0.1 to 0.2MPaG for 5 to 10 minutes, producing second butyl rubber slurry with low molecular weight part, finally obtaining butyl rubber slurry with broad/bimodal molecular weight distribution, and overflowing from the top of the loop reactor;
step S4, feeding the obtained butyl rubber slurry with broad/bimodal molecular weight distribution into a degassing kettle, removing a diluent, namely methyl chloride, in the degassing kettle by using hot water, and removing unreacted monomers to obtain colloidal particle water;
and step S5, extruding, dehydrating, drying and briquetting the obtained colloidal particle water to obtain the qualified butyl rubber.
The invention adopts two loop reactors connected in series to produce the butyl rubber with wide/bimodal molecular weight distribution, the heat exchange coefficient is larger, the polymerization temperature is uniform, the product quality is good, the material flow rate is larger, the slurry viscosity is reduced, the glue hanging speed of the material on the inner wall of the reactor is reduced, and therefore, the production period of the reactor is longer. On the other hand, the reactor has simple structure, easy industrial mass production and low cost.
Drawings
FIG. 1 shows a schematic of a molecular weight distribution according to one embodiment of the present invention.
Detailed Description
The invention is further described with reference to specific examples, which are not intended to be limiting.
The molecular weight and the distribution of the product are measured by gel permeation chromatography. Gel permeation chromatography from Waters2414, USA, was used. The mobile phase is tetrahydrofuran, the temperature is 25 deg.C, the sample concentration is 0.3%, the sample amount is 50 μ L, the elution time is 40min, and the flow rate is 1 mL/min-1。
Example 1
Two loop reactors having a diameter of 100mm and a length of 26m were cooled to-98 ℃ by means of ethylene in a jacket. Feeding into the first loop reactor a diluent, methyl chloride, polymerized monomers, isobutylene and isoprene, and an initiator, HCl/ethyl aluminum dichloride, wherein the mass concentration of isobutylene and isoprene in the mixed feed is 35%, the mass concentration of initiator in the mixed feed is 0.15%, and the molar ratio of isobutylene to isoprene is 97.7: 2.3. the polymerization temperature is controlled to be-98 to-97 ℃ by utilizing the ethylene in the jacket of the loop reactor, when the pressure of the reactor reaches 0.3MPaG, an axial flow pump of the loop reactor is started, and the flow rate of the material is controlled to be 9 m/s. After the retention time of the materials in the reactor reaches 7min, the butyl rubber slurry obtained by polymerization enters a second loop reactor for continuous polymerization, the polymerization temperature is-92 to-91 ℃, the pressure is 0.2MPaG, the flow rate of the materials is 9m/s, and the retention time is 5 min. The polymerized butyl rubber slurry overflowed from the top of the second loop reactor into the degassing vessel. Controlling the operation temperature of the degassing kettle to be 73 ℃, the pressure to be-50 KPaG and the retention time to be 1.2h by using low-pressure steam to obtain colloidal particle water which does not contain methane chloride and unreacted monomers, and extruding, dehydrating, drying and briquetting the colloidal particle water to obtain a butyl rubber product.
The Mw of the butyl rubber obtained by the polymerization in the first loop reactor was determined to be 950,000 and Mn to be 400,000, and the Mw of the butyl rubber finally obtained was determined to be 790,000, Mn to 120,000, and Mw/Mn to 6.6.
The molecular weight distribution curve of the finally obtained butyl rubber is shown in FIG. 1, and a remarkable bimodal distribution is shown.
Example 2
Two loop reactors having a diameter of 100mm and a length of 26m were cooled to-98 ℃ by means of ethylene in a jacket. To the first loop reactor was added the diluent methyl chloride, the polymeric monomers isobutylene and isoprene, and the initiator HCl/ethyl aluminum dichloride, wherein the mass concentration of isobutylene and isoprene in the mixed feed was 37%, the mass concentration of initiator in the mixed feed was 0.17%, and the molar ratio of isobutylene to isoprene was 98.0: 2.0. the polymerization temperature is controlled to be-97 to-96 ℃ by utilizing the ethylene in the jacket of the loop reactor, and when the pressure of the reactor reaches 0.3MPaG, an axial flow pump of the loop reactor is started, and the flow rate of the material is controlled to be 10 m/s. The residence time of the material in the reactor was 5 min. And the butyl rubber slurry obtained by polymerization enters a second loop reactor for continuous polymerization, the polymerization temperature is-92 to-91 ℃, the pressure is 0.2MPaG, the flow rate of the material is 10m/s, and the retention time is 5 min. The polymerized butyl rubber slurry overflowed from the top of the second loop reactor into the degassing vessel. Controlling the operation temperature of the degassing kettle to be 70 ℃, the pressure to be-60 KPaG and the retention time to be 1.5h by using low-pressure steam to obtain colloidal particle water which does not contain methane chloride and unreacted monomers, and extruding, dehydrating, drying and briquetting the colloidal particle water to obtain a butyl rubber product.
The butyl rubber obtained by the polymerization in the first loop reactor was determined to have Mw 830,000 and Mn 350,000, and the final butyl rubber had Mw 730,000, Mn 143,000 and Mw/Mn 5.1, with a bimodal distribution of molecular weight.
Example 3
Two loop reactors having a diameter of 100mm and a length of 26m were cooled to-98 ℃ by means of ethylene in a jacket. Feeding into the first loop reactor a diluent, methyl chloride, polymerized monomers, isobutylene and isoprene, and an initiator, HCl/ethyl aluminum dichloride, wherein the mass concentration of isobutylene and isoprene in the mixed feed is 30%, the mass concentration of the initiator in the mixed feed is 0.10%, and the molar ratio of isobutylene to isoprene is 98.5: 1.5. the polymerization temperature is controlled to be-98 to-97 ℃ by utilizing the ethylene in the jacket of the loop reactor, when the pressure of the reactor reaches 0.4MPaG, an axial flow pump of the loop reactor is started, and the flow rate of the material is controlled to be 7 m/s. After the material stays in the reactor for 10min, the butyl rubber slurry obtained by polymerization enters a second loop reactor for continuous polymerization, the polymerization temperature is-91 to-90 ℃, the pressure is 0.2MPaG, the flow rate of the material is 7m/s, and the stay time is 10 min. The polymerized butyl rubber slurry overflowed from the top of the second loop reactor into the degassing vessel. Controlling the operation temperature of the degassing kettle to be 70 ℃, the pressure to be-55 KPaG and the retention time to be 2.0h by using low-pressure steam to obtain colloidal particle water which does not contain methane chloride and unreacted monomers, and extruding, dehydrating, drying and briquetting the colloidal particle water to obtain a butyl rubber product.
The Mw of the butyl rubber obtained by the polymerization in the first loop reactor was 910,000, Mn was 360,000, the Mw of the butyl rubber obtained was 760,000, Mn was 77,500, Mw/Mn was 9.8, and the molecular weight distribution was bimodal.
Example 4
Two loop reactors having a diameter of 100mm and a length of 26m were cooled to-98 ℃ by means of ethylene in a jacket. To the first loop reactor was added the diluent methyl chloride, the polymeric monomers isobutylene and isoprene, and the initiator HCl/ethyl aluminum dichloride, wherein the mass concentration of isobutylene and isoprene in the mixed feed was 33%, the mass concentration of initiator in the mixed feed was 0.20%, and the molar ratio of isobutylene to isoprene was 97.0: 3.0. the polymerization temperature is controlled to be-97 to-96 ℃ by utilizing the ethylene in the jacket of the loop reactor, and when the pressure of the reactor reaches 0.3MPaG, an axial flow pump of the loop reactor is started, and the flow rate of the material is controlled to be 8 m/s. After the material stays in the reactor for 8min, the butyl rubber slurry obtained by polymerization enters a second loop reactor for continuous polymerization, the polymerization temperature is-91 to-90 ℃, the pressure is 0.1MPaG, the flow rate of the material is 7m/s, and the stay time is 8 min. The polymerized butyl rubber slurry overflowed the second from the top of the loop reactor into the degassing vessel. Controlling the operation temperature of the degassing kettle to be 72 ℃, the pressure to be-50 KPaG and the retention time to be 1.8h by using low-pressure steam to obtain colloidal particle water which does not contain methane chloride and unreacted monomers, and extruding, dehydrating, drying and briquetting the colloidal particle water to obtain a butyl rubber product.
The butyl rubber obtained by the polymerization in the first loop reactor was measured to have Mw of 850,000 and Mn of 380,000, and the final butyl rubber was measured to have Mw of 690,000, Mn of 95,500 and Mw/Mn of 7.2, with a bimodal distribution of molecular weight.
Example 5
Two loop reactors having a diameter of 100mm and a length of 26m were cooled to-98 ℃ by means of ethylene in a jacket. Feeding into the first loop reactor a diluent, methyl chloride, polymerized monomers, isobutylene and isoprene, and an initiator, HCl/ethyl aluminum dichloride, wherein the mass concentration of isobutylene and isoprene in the mixed feed is 40%, the mass concentration of initiator in the mixed feed is 0.20%, and the molar ratio of isobutylene to isoprene is 99: 1. the polymerization temperature is controlled to be-97 to-96 ℃ by utilizing the ethylene in the jacket of the loop reactor, and when the pressure of the reactor reaches 0.3MPaG, an axial flow pump of the loop reactor is started, and the flow rate of the material is controlled to be 9 m/s. After the material stays in the reactor for 9min, the butyl rubber slurry obtained by polymerization enters a second loop reactor for continuous polymerization, the polymerization temperature is-92 to-91 ℃, the pressure is 0.2MPaG, the flow rate of the material is 9m/s, and the stay time is 9 min. The polymerized butyl rubber slurry overflowed from the top of the second loop reactor into the degassing vessel. Controlling the operation temperature of the degassing kettle to be 75 ℃, the pressure to be-50 KPaG and the retention time to be 1.0h by using low-pressure steam to obtain colloidal particle water which does not contain methane chloride and unreacted monomers, and extruding, dehydrating, drying and briquetting the colloidal particle water to obtain a butyl rubber product.
The butyl rubber obtained by the polymerization in the first loop reactor was determined to have Mw 820,000 and Mn 390,000, and the final butyl rubber had Mw 700,000, Mn 86,400 and Mw/Mn 8.1, with a bimodal distribution of molecular weight.
From the above data, it can be seen that the method provided by the present invention has the advantages of good heat exchange, uniform polymerization temperature, good product quality, and large material flow rate, so that the slurry viscosity is reduced, the gum hanging speed of the material on the inner wall of the reactor is reduced, and therefore, the production cycle of the reactor is longer. On the other hand, the method has the advantages of simple process, simple device structure, easy industrial large-scale production and low cost.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (15)
1. A process for producing a broad/bimodal molecular weight distribution butyl rubber comprising the steps of:
s1, mixing isobutene, isoprene and a diluent to obtain a monomer stream; mixing an initiator and a diluent to obtain an initiator stream;
s2, mixing the monomer stream and the initiator stream and feeding the mixture into a first loop reactor zone, and then carrying out polymerization reaction to obtain a first part of butyl rubber slurry;
s3, feeding the first butyl rubber slurry into the second loop reactor zone, continuing to perform polymerization reaction to generate a second butyl rubber slurry, finally obtaining a butyl rubber slurry with broad/bimodal molecular weight distribution, and leading out from the top of the loop reactor in the second loop reactor zone;
s4, contacting the led-out butyl rubber slurry with water, and removing unreacted monomers and diluents to obtain rubber particle water;
s5, dehydrating and drying the colloidal particle water to obtain butyl rubber with wide/bimodal molecular weight distribution;
wherein the temperature of the polymerization reaction in the step S2 is lower than the temperature of the polymerization reaction in the step S3, and the pressure of the polymerization reaction in the step S2 is higher than the pressure of the polymerization reaction in the step S3; in step S1, the molar ratio of isobutylene to isoprene is 95:5 to 99.5: 0.5.
2. The method of claim 1, wherein in step S2, the temperature of the polymerization reaction is-98 to-96 ℃ and the pressure is 0.3 to 0.4MPaG, and/or in step S3, the temperature of the polymerization reaction is-92 to-90 ℃ and the pressure is 0.1 to 0.2 MPaG.
3. The method of claim 1 or 2, wherein in step S1, the initiator is selected from at least one of water/aluminum trichloride and HCl/ethyl aluminum dichloride.
4. The method of claim 3, wherein in step S1, the molar ratio of isobutylene to isoprene is 97:3 to 99: 1.
5. The method of claim 1, wherein in step S2, the combined mass concentration of isobutylene and isoprene in the mixed stream is from 25 to 45%; and/or the mass concentration of the initiator is 0.10 to 0.25%.
6. The method of claim 5, wherein in step S2, the combined mass concentration of isobutylene and isoprene in the mixed stream is 30 to 40%; and/or the mass concentration of the initiator is 0.15 to 0.20%.
7. The method according to claim 1, wherein in step S2, the polymerization reaction time is 5-10 min; and/or, in step S3, the time of the polymerization reaction is 5-10 min.
8. The process according to claim 1, wherein step S4 is carried out in a degassing vessel operated at a temperature of 70 to 75 ℃, a pressure of-60 to-50 KPa and a residence time of 1.0 to 2.0 h.
9. The process according to claim 1, wherein the first loop reactor zone comprises at least one loop reactor and the second loop reactor zone comprises at least one loop reactor.
10. Process according to claim 1, wherein the flow rates of the streams in the loop reactors of the first and second loop reactor zones are both above 7 m/s.
11. Process according to claim 10, wherein the flow rates of the streams in the loop reactors of the first and second loop reactor zones are both 7.0 to 10.0 m/s.
12. The process according to claim 1, wherein in step S2, the weight average molecular weight of the butyl rubber in the first butyl rubber slurry is not less than 80 ten thousand; and/or, in step S5, the weight average molecular weight of the butyl rubber is not less than 65 ten thousand.
13. The method according to claim 12, wherein in step S5, the weight average molecular weight of the butyl rubber is not less than 70 ten thousand.
14. The method of claim 1, wherein in step S5, the butyl rubber has a molecular weight distribution of at least 5.0.
15. The method according to claim 14, wherein in step S5, the butyl rubber has a molecular weight distribution of 5.0-10.0.
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| CA2308257A1 (en) * | 2000-05-05 | 2001-11-05 | Adam A. Gronowski | Process for preparation of butyl rubber having broad molecular weight distribution |
| CN101130585B (en) * | 2006-08-25 | 2010-11-10 | 北京化工大学 | Method for preparing isobutylene isoprene rubber |
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2016
- 2016-05-04 CN CN201610288408.2A patent/CN107344982B/en active Active
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