CN107344982A - A kind of method for producing wide/double peak molecular weight distribution butyl rubber - Google Patents
A kind of method for producing wide/double peak molecular weight distribution butyl rubber Download PDFInfo
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- CN107344982A CN107344982A CN201610288408.2A CN201610288408A CN107344982A CN 107344982 A CN107344982 A CN 107344982A CN 201610288408 A CN201610288408 A CN 201610288408A CN 107344982 A CN107344982 A CN 107344982A
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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
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Abstract
The present invention relates to a kind of method for producing wide/double peak molecular weight distribution butyl rubber, including：S1, monomer stream is obtained after isobutene, isoprene and diluent are mixed；Initiator stream is obtained after initiator and diluent are mixed；S2, monomer stream and initiator stream are mixed and fed into the first annular-pipe reactor area, then carry out polymerisation, obtains Part I butyl rubber slurry；S3, Part I butyl rubber slurry is sent into the second annular-pipe reactor area, continues polymerisation, Part II butyl rubber slurry is generated, finally gives butyl rubber slurry and the extraction of wide/double peak molecular weight distribution；S4, the butyl rubber slurry of the extraction is contacted with water, remove unreacted monomer and diluent, obtain micelle water；S5, by micelle water through being dehydrated and drying, obtain the butyl rubber of wide/double peak molecular weight distribution.According to method provided by the invention, exchange heat, mild condition, good product quality, in bimodal distribution.
Description
Technical field
The present invention relates to rubber production field, and in particular to a kind of butyl for producing wide/double peak molecular weight distribution
The method of rubber.
Background technology
It is well known that the physical property and processing characteristics of polymer are equal depending on weight average molecular weight (Mw) sum
Molecular weight (Mn).Typically, the tensile strength and modulus for vulcanizing rubber depend on number-average molecular weight.Elastomer
Processing characteristics depend on Mw and Mw/Mn (molecular weight distribution or MWD).
It has been found that the butyl rubber of wide/double peak molecular weight distribution shows excellent mixer mixing characteristic,
And it is fine to move (cold flow) property for anti-current under condition of storage.The molecular weight distribution of butyl rubber also controls extrusion
The degree that thing swells.Butyl rubber with the wide/double peak molecular weight distribution rubber phase narrower with molecular weight distribution
Than its green strength improves.The green strength or rubber unvulcanizate intensity of raising cause production operation (such as
The inner tube of a tyre manufactures) improve, unvulcanized rubber intensity increases and distorted smaller.
Chinese patent CN1427851A discloses a kind of method for the butyl rubber for preparing wide molecular weight distribution.
This method uses hybrid catalyst system (including substantial amounts of aluminum dialkyl monohalide, a small amount of alkyl of dihalide one
Aluminium and micro aikyiaiurnirsoxan beta), the molecular weight distribution of obtained butyl rubber is more than 3.5, up to 7.6.
At present, it is still necessary to simple and easy and can industrialize large-scale production prepares wide/double peak molecular weight distribution fourth
The method of base rubber.
The content of the invention
In view of above-mentioned prior art situation, present inventor has been carried out extensively in the technical field of rubber production
General in-depth study, is desirably to obtain that a kind of simple and easy and can industrialize large-scale production prepares wide/double peak
The method of molecular weight distribution butyl rubber, by using at least two annular-pipe reactor serial operations, and respectively
The polymerization temperature of two annular-pipe reactors of control and time, wide/double peak molecular weight distribution butyl rubber can be obtained
Glue.
The invention provides a kind of method for the butyl rubber for producing wide/double peak molecular weight distribution, including following step
Suddenly：
S1, monomer stream is obtained after isobutene, isoprene and diluent are mixed；By initiator and dilution
Initiator stream is obtained after agent mixing；
S2, monomer stream and initiator stream are mixed and fed into the first annular-pipe reactor area, then carried out
Polymerisation, obtain Part I butyl rubber slurry；
S3, Part I butyl rubber slurry is sent into the second annular-pipe reactor area, continues polymerisation,
Part II butyl rubber slurry is generated, finally gives the butyl rubber slurry of wide/double peak molecular weight distribution, and
Annular-pipe reactor Base top contact from the second annular-pipe reactor area；
S4, the butyl rubber slurry of the extraction is contacted with water, remove unreacted monomer and diluent, obtain
To micelle water；
S5, by micelle water through being dehydrated and drying, obtain the butyl rubber of wide/double peak molecular weight distribution；
Wherein, the temperature of the polymerisation in step S2 is less than the temperature of the polymerisation in step S3, step
The pressure of polymerisation in rapid S2 is higher than the pressure of the polymerisation in step S3.
According to method provided by the invention, using Liang Ge annular-pipe reactors area, and two annular-pipe reactors are controlled
The polymerizing condition in area, the butyl rubber of high molecular weight moieties is obtained in the first annular-pipe reactor area, in the second ring
Pipe reactor area obtains the butyl rubber of lower molecular weight part, can finally obtain with wide/double peak molecular weight
The butyl rubber of distribution；And exchange heat, polymerizing condition is gentle, good product quality, cycle of operation length, production
Cost is low.
According to the method for the invention preferred embodiment, in step sl, isobutene and isoamyl two
The mol ratio of alkene is 95:5 to 99.5:0.5, preferably 97:3 to 99:1.The initiator is commonly used in the art
Initiator, such as be selected from water/at least one of alchlor system and HCl/ ethyl aluminum dichlorides.The mixing
Also carried out in the container of such as blender.The diluent is diluent conventional in the art, such as a chloromethane
Alkane.
According to the method for the invention preferred embodiment, in step s 2, stream upon mixing
In, isobutene and the total mass concentration of isoprene are 25 to 45%, preferably 30 to 40%.Mixing
In stream afterwards, the mass concentration of initiator is 0.10 to 0.25%, preferably 0.15 to 0.20%.,
According to the method for the invention preferred embodiment, the first annular-pipe reactor area is included extremely
A few annular-pipe reactor, the second annular-pipe reactor area includes at least one annular-pipe reactor.Described
In the annular-pipe reactor in the first and second annular-pipe reactor areas, slurry is done under the promotion of axial-flow pump to be oriented at a high speed
Circulate.In a specific embodiment, the flow velocity of logistics is more than 7m/s, such as 7.0 to 10.0m/s.
According to the method for the invention preferred embodiment, in step s 2, the temperature of polymerisation
For -98 to -96 DEG C, pressure 0.3 to 0.4MPaG.The time of the polymerisation is 5-10min.
According to the present invention, by step S2, under lower temperature and elevated pressures, obtained HMW portion
The Part I butyl rubber slurry divided, wherein weight average molecular weight are not less than 800,000.
According to the method for the invention preferred embodiment, in the step S3, polymerisation
Temperature is -92 to -90 DEG C, and pressure is 0.1 to 0.2MPaG.The time of the polymerisation is 5-10min.
The temperature of polymerisation in step S3 is higher, and polymerization pressure is relatively low, the polymerisation life in step S3
Into the Part II butyl rubber slurry of low molecular weight part.In a specific embodiment, described first
Part butyl rubber slurry, the second annular-pipe reactor area is sent into by pressure difference.
According to the method for the invention preferred embodiment, in described Liang Ge annular-pipe reactors area
Chuck is all carried in annular-pipe reactor, medium is ethene in chuck.In a specific embodiment, enter
The ethene of chuck is -115 DEG C of liquid ethylene, and what is flowed out from chuck is -115 DEG C of ethene gas-liquid mixture.
By the liquid ethylene evaporating capacity adjusted in chuck control the polymerization temperature in the first annular-pipe reactor area for -98 to
- 96 DEG C, the polymerization temperature in the second annular-pipe reactor area is -92 to -90 DEG C.In first annular-pipe reactor area
Material is entered in second annular-pipe reactor area by pressure difference, and the material in annular-pipe reactor is made using axial-flow pump
Continuous high speed is circulated, and the butyl rubber particle of generation is uniformly suspended in diluent.
According to a preferred embodiment of the present invention, because the polymerization temperature in step S2 is relatively low, therefore,
In step sl, the initiator stream and monomer stream can cool (such as initiator stream through cooler
Temperature can be down to -95 DEG C, and the temperature of monomer stream can be down to -98 DEG C).In a specific embodiment, isobutyl
After alkene, a small amount of isoprene and diluent monochloro methane are well mixed in a mixer by a certain percentage, first use
Water at low temperature is down to 15 DEG C, then is cooled to -98 DEG C with low pressure propylene and low pressure ethylene；Initiator and the chlorine of diluent one
After methane is well mixed in a mixer by a certain percentage, -35 DEG C first are cooled to low pressure propylene, then use low pressure
Ethene is cooled to -95 DEG C.Then, in step s 2, then by the stream after cooling it is sent into (being such as pumped into pump)
First annular-pipe reactor area.
According to the method for the invention preferred embodiment, the step S4 is carried out in the kettle that deaerates.
Degassing kettle is heated with low-pressure steam, and kettle temperature is controlled by steam flow.It is preferred that the operation temperature of degassing kettle is 70
To 75 DEG C, pressure is -60 to -50KPaG, and the residence time is 1.0 to 2.0h.
According to method of the present invention, butyl rubber slurry can also be first with terminating before the kettle that deaerates is entered
Agent is mixed to terminate polymerisation.The terminator is triethylene glycol, and its dosage is the 4-6 of initiator addition
Times.
According to the method for the invention preferred embodiment, in step s 5, the butyl rubber
Weight average molecular weight is not less than 650,000, preferably not less than 700,000.The molecular weight distribution of the butyl rubber
(Mw/Mn) it is at least 5.0, preferably 5.0-10.0.
According to the specific embodiment of the present invention, methods described comprises the steps of：
Step S1, isobutene, a small amount of isoprene and diluent monochloro methane are by a certain percentage in a mixer
After well mixed, -98 DEG C are cooled to through cooler, initiator and diluent monochloro methane are by a certain percentage mixed
After being well mixed in clutch, -95 DEG C are cooled to through cooler；
Step S2, isobutene, a small amount of isoprene, initiator and diluent after cooling are with being pumped into first
In annular-pipe reactor, polymerisation occurs under -98 to -96 DEG C of temperature, pressure 0.3 to 0.4MPaG, gathers
The conjunction time is 5-10 minutes, obtains the first butyl rubber slurry of high molecular weight moieties；
Step S3, the first butyl rubber slurry that step S2 is obtained are sent to the second ring canal reaction by pressure difference
In device, polymerisation occurs under -92 to -90 DEG C of temperature, pressure 0.1 to 0.2MPaG, polymerization time is
5-10 minutes, the second butyl rubber slurry of low molecular weight part is produced, finally give wide/double peak molecular weight point
The butyl rubber slurry of cloth, and go out from the top overflow of annular-pipe reactor；
Step S4, the butyl rubber slurry of obtained wide/double peak molecular weight distribution is sent into degassing kettle, deaerated
Using hot water removing diluent monochloro methane in kettle, and unreacted monomer is removed, obtain micelle water；
Step S5, obtained micelle water obtain qualified butyl rubber through extrusion dehydration and drying, briquetting again.
The present invention is using the butyl rubber of two annular-pipe reactor series connection production wide/double peak molecular weight distributions, heat exchange
Coefficient is larger, and polymerization temperature is uniform, good product quality, and material flow is larger so that and Slurry Viscosity declines,
Kiss-coating speed of the material on reactor wall reduces, and therefore, the production cycle of reactor is longer.The opposing party
Face, structure of reactor is simple, is easy to industrialization large-scale production, and cost is low.
Brief description of the drawings
Fig. 1 shows molecular weight distribution schematic diagram according to an embodiment of the invention.
Embodiment
With reference to specific embodiment, the present invention will be further described, but does not form and the present invention is appointed
What is limited.
Molecular weight product and its measure of distribution are determined using gel permeation chromatography.Using the U.S.
The gel permeation chromatograph of Waters2414 companies.Mobile phase is tetrahydrofuran, and temperature is 25 DEG C, and sample is dense
Spend for 0.3%, sample size is 50 μ L, elution time 40min, flow velocity 1mLmin-1。
Embodiment 1
By a diameter of 100mm, length is that 26m two annular-pipe reactors are cooled to by the ethene in chuck
-98℃.Diluent monochloro methane, polymerized monomer isobutene and isoamyl two are added into first annular-pipe reactor
Alkene and initiator HCl/ ethyl aluminum dichlorides, the wherein quality of isobutene and isoprene in mixed feeding are dense
Spend for 35%, mass concentration of the initiator in mixed feeding is 0.15%, and isobutene and isoprene rub
You are than being 97.7：2.3.It is -98~-97 DEG C to control polymerization temperature using the ethene in annular-pipe reactor chuck, when
After reactor pressure reaches 0.3MPaG, the axial-flow pump of annular-pipe reactor is opened, the flow velocity of control material is
9m/s.After the residence time of material in the reactor reaches 7min, it polymerize obtained butyl rubber slurry and enters the
Two annular-pipe reactors continue to polymerize, and polymerization temperature is -92~-91 DEG C, pressure 0.2MPaG, material
Flow velocity be 9m/s, residence time 5min.Butyl rubber slurry after polymerization is from second annular-pipe reactor
Top overflow enter degassing kettle.The operation temperature that degassing kettle is controlled using low low-pressure steam is 73 DEG C, pressure
For -50KPaG, residence time 1.2h, the micelle water without monochloro methane and unreacted monomer, glue are obtained
Grain water obtains butyl rubber product through extrusion dehydration and drying, briquetting.
After measured, first annular-pipe reactor polymerize the Mw=950 of obtained butyl rubber, and 000,
Mn=400,000, the Mw=790 of the butyl rubber finally given, 000, Mn=120,000, Mw/Mn=6.6.
The molecular weight distribution curve of the butyl rubber finally given is shown in Fig. 1, shows obvious bimodal distribution.
Embodiment 2
By a diameter of 100mm, length is that 26m two annular-pipe reactors are cooled to by the ethene in chuck
-98℃.Diluent monochloro methane, polymerized monomer isobutene and isoamyl two are added into first annular-pipe reactor
Alkene and initiator HCl/ ethyl aluminum dichlorides, the wherein quality of isobutene and isoprene in mixed feeding are dense
Spend for 37%, mass concentration of the initiator in mixed feeding is 0.17%, and isobutene and isoprene rub
You are than being 98.0：2.0.It is -97~-96 DEG C to control polymerization temperature using the ethene in annular-pipe reactor chuck, when
After reactor pressure reaches 0.3MPaG, the axial-flow pump of annular-pipe reactor is opened, the flow velocity of control material is
10m/s.After the residence time of material in the reactor reaches 5min.It polymerize obtained butyl rubber slurry to enter
Second annular-pipe reactor continues to polymerize, and polymerization temperature is -92~-91 DEG C, pressure 0.2MPaG, thing
The flow velocity of material is 10m/s, residence time 5min.Butyl rubber slurry after polymerization is anti-from second endless tube
The top overflow of device is answered to enter degassing kettle.Using low low-pressure steam control degassing kettle operation temperature for 70 DEG C,
Pressure is -60KPaG, residence time 1.5h, obtains the micelle water without monochloro methane and unreacted monomer,
Micelle water obtains butyl rubber product through extrusion dehydration and drying, briquetting.
After measured, first annular-pipe reactor polymerize the Mw=830 of obtained butyl rubber, and 000,
Mn=350,000, the Mw=730 of the butyl rubber finally given, 000, Mn=143,000, Mw/Mn=5.1,
Molecular weight distribution is in bimodal distribution.
Embodiment 3
By a diameter of 100mm, length is that 26m two annular-pipe reactors are cooled to by the ethene in chuck
-98℃.Diluent monochloro methane, polymerized monomer isobutene and isoamyl two are added into first annular-pipe reactor
Alkene and initiator HCl/ ethyl aluminum dichlorides, the wherein quality of isobutene and isoprene in mixed feeding are dense
Spend for 30%, mass concentration of the initiator in mixed feeding is 0.10%, and isobutene and isoprene rub
You are than being 98.5：1.5.It is -98~-97 DEG C to control polymerization temperature using the ethene in annular-pipe reactor chuck, when
After reactor pressure reaches 0.4MPaG, the axial-flow pump of annular-pipe reactor is opened, the flow velocity of control material is
7m/s.After the residence time of material in the reactor reaches 10min, the butyl rubber slurry for polymerizeing to obtain enters
Second annular-pipe reactor continues to polymerize, and polymerization temperature is -91~-90 DEG C, pressure 0.2MPaG, thing
The flow velocity of material is 7m/s, residence time 10min.Butyl rubber slurry after polymerization is anti-from second endless tube
The top overflow of device is answered to enter degassing kettle.Using low low-pressure steam control degassing kettle operation temperature for 70 DEG C,
Pressure is -55KPaG, residence time 2.0h, obtains the micelle water without monochloro methane and unreacted monomer,
Micelle water obtains butyl rubber product through extrusion dehydration and drying, briquetting.
After measured, first annular-pipe reactor polymerize the Mw=910 of obtained butyl rubber, and 000,
Mn=360,000, the Mw=760 of the butyl rubber finally given, 000, Mn=77,500, Mw/Mn=9.8,
Molecular weight distribution is in bimodal distribution.
Embodiment 4
By a diameter of 100mm, length is that 26m two annular-pipe reactors are cooled to by the ethene in chuck
-98℃.Diluent monochloro methane, polymerized monomer isobutene and isoamyl two are added into first annular-pipe reactor
Alkene and initiator HCl/ ethyl aluminum dichlorides, the wherein quality of isobutene and isoprene in mixed feeding are dense
Spend for 33%, mass concentration of the initiator in mixed feeding is 0.20%, and isobutene and isoprene rub
You are than being 97.0：3.0.It is -97~-96 DEG C to control polymerization temperature using the ethene in annular-pipe reactor chuck, when
After reactor pressure reaches 0.3MPaG, the axial-flow pump of annular-pipe reactor is opened, the flow velocity of control material is
8m/s.After the residence time of material in the reactor reaches 8min, it polymerize obtained butyl rubber slurry and enters the
Two annular-pipe reactors continue to polymerize, and polymerization temperature is -91~-90 DEG C, pressure 0.1MPaG, material
Flow velocity be 7m/s, residence time 8min.Butyl rubber slurry after polymerization is from second from ring canal reaction
The top overflow of device enters degassing kettle.The operation temperature of degassing kettle is controlled to be 72 DEG C, press using low low-pressure steam
Power is -50KPaG, residence time 1.8h, obtains the micelle water without monochloro methane and unreacted monomer,
Micelle water obtains butyl rubber product through extrusion dehydration and drying, briquetting.
After measured, first annular-pipe reactor polymerize the Mw=850 of obtained butyl rubber, and 000,
Mn=380,000, the Mw=690 of the butyl rubber finally given, 000, Mn=95,500, Mw/Mn=7.2,
Molecular weight distribution is in bimodal distribution.
Embodiment 5
By a diameter of 100mm, length is that 26m two annular-pipe reactors are cooled to by the ethene in chuck
-98℃.Diluent monochloro methane, polymerized monomer isobutene and isoamyl two are added into first annular-pipe reactor
Alkene and initiator HCl/ ethyl aluminum dichlorides, the wherein quality of isobutene and isoprene in mixed feeding are dense
Spend for 40%, mass concentration of the initiator in mixed feeding is 0.20%, and isobutene and isoprene rub
You are than being 99：1.It is -97~-96 DEG C to control polymerization temperature using the ethene in annular-pipe reactor chuck, when anti-
After answering device pressure to reach 0.3MPaG, the axial-flow pump of annular-pipe reactor is opened, the flow velocity of control material is 9m/s.
After the residence time of material in the reactor reaches 9min, the butyl rubber slurry for polymerizeing to obtain enters second ring
Pipe reactor continues to polymerize, and polymerization temperature is -92~-91 DEG C, pressure 0.2MPaG, the flow velocity of material
For 9m/s, residence time 9min.Butyl rubber slurry after polymerization is from the top of second annular-pipe reactor
Overflow enters degassing kettle.The operation temperature that the kettle that deaerates is controlled using low low-pressure steam is 75 DEG C, pressure is
- 50KPaG, residence time 1.0h, obtain the micelle water without monochloro methane and unreacted monomer, micelle
Water obtains butyl rubber product through extrusion dehydration and drying, briquetting.
After measured, first annular-pipe reactor polymerize the Mw=820 of obtained butyl rubber, and 000,
Mn=390,000, the Mw=700 of the butyl rubber finally given, 000, Mn=86,400, Mw/Mn=8.1,
Molecular weight distribution is in bimodal distribution.
By data above it is known that according to method provided by the invention, exchanging heat, polymerization temperature is uniform,
Good product quality, and material flow is larger so that Slurry Viscosity declines, extension of the material on reactor wall
Glue speed reduces, and therefore, the production cycle of reactor is longer.On the other hand, the technique of methods described it is simple,
Apparatus structure is simple, is easy to industrialization large-scale production, and cost is low.
Any numerical value mentioned in the present invention, if between any minimum and any of the highest value simply
There is the interval of two units, then include all values of one unit of each increase from minimum to peak.
If for example, state a kind of amount of component, or the value of the state-variable such as temperature, pressure, time is 50-90,
In this manual it means that specifically listing 51-89,52-88 ... and 69-71 and 70-71
Deng numerical value.Can be with due regard to one single with 0.1,0.01,0.001 or 0.0001 for the value of non-integer
Position.This is only some special examples indicated.In this application, in a similar manner, cited minimum
The combination that is possible to of numerical value between peak is considered to disclose.
It should be noted that embodiment described above is only used for explaining the present invention, do not form to the present invention
Any restrictions.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein institute
Word is descriptive and explanatory vocabulary, rather than limited vocabulary.It can be weighed by regulation in the present invention
Profit modifies in the range of requiring to the present invention, and to this in without departing substantially from scope and spirit of the present invention
Invention is revised.Although the present invention described in it is related to specific method, material and embodiment,
It is not meant to that the present invention is limited to wherein disclosed particular case, on the contrary, the present invention can be extended to other all tools
There are the methods and applications of identical function.
Claims (10)
1. a kind of method for the butyl rubber for producing wide/double peak molecular weight distribution, comprises the following steps：
S1, monomer stream is obtained after isobutene, isoprene and diluent are mixed；By initiator and dilution
Initiator stream is obtained after agent mixing；
S2, monomer stream and initiator stream are mixed and fed into the first annular-pipe reactor area, then carried out
Polymerisation, obtain Part I butyl rubber slurry；
S3, Part I butyl rubber slurry is sent into the second annular-pipe reactor area, continues polymerisation,
Part II butyl rubber slurry is generated, finally gives the butyl rubber slurry of wide/double peak molecular weight distribution, and
Annular-pipe reactor Base top contact from the second annular-pipe reactor area；
S4, the butyl rubber slurry of the extraction is contacted with water, remove unreacted monomer and diluent, obtain
To micelle water；
S5, by micelle water through being dehydrated and drying, obtain the butyl rubber of wide/double peak molecular weight distribution；
Wherein, the temperature of the polymerisation in step S2 is less than the temperature of the polymerisation in step S3, step
The pressure of polymerisation in rapid S2 is higher than the pressure of the polymerisation in step S3.
2. according to the method for claim 1, it is characterised in that in the step S2, polymerization is anti-
The temperature answered is -98 to -96 DEG C, and for pressure 0.3 to 0.4MPaG, and/or in the step S3, polymerization is anti-
The temperature answered is -92 to -90 DEG C, and pressure is 0.1 to 0.2MPaG.
3. method according to claim 1 or 2, it is characterised in that in step sl, isobutene
Mol ratio with isoprene is 95:5 to 99.5:0.5, preferably 97:3 to 99:1；And/or the initiation
Agent is selected from least one of water/alchlor and HCl/ ethyl aluminum dichlorides.
4. according to the method any one of claim 1-3, it is characterised in that in step s 2,
In stream upon mixing, isobutene and the total mass concentration of isoprene are 25 to 45%, preferably 30
To 40%；And/or the mass concentration of initiator is 0.10 to 0.25%, preferably 0.15 to 0.20%.
5. according to the method any one of claim 1-4, it is characterised in that in step s 2,
The time of the polymerisation is 5-10min；And/or in step s3, the time of the polymerisation is
5-10min。
6. according to the method any one of claim 1-5, it is characterised in that the step S4 exists
Carried out in degassing kettle, the operation temperature for the kettle that preferably deaerates is 70 to 75 DEG C, and pressure is -60 to -50KPa, is stopped
It is 1.0 to 2.0h to stay the time.
7. according to the method any one of claim 1-6, it is characterised in that first endless tube is anti-
Ying Qi areas include at least one annular-pipe reactor, and it is anti-that the second annular-pipe reactor area includes at least one endless tube
Answer device.
8. according to the method any one of claim 1-7, it is characterised in that in first endless tube
In the annular-pipe reactor in reactor zone and the second annular-pipe reactor area, the flow velocity of logistics is more than 7m/s, excellent
7.0 are elected as to 10.0m/s.
9. according to the method any one of claim 1-8, it is characterised in that in step s 2,
The weight average molecular weight of butyl rubber in first butyl rubber slurry is not less than 800,000；And/or in step
In rapid S5, the weight average molecular weight of the butyl rubber is not less than 650,000, preferably not less than 700,000.
10. according to the method any one of claim 1-9, it is characterised in that in step s 5,
The molecular weight distribution of the butyl rubber is at least 5.0, preferably 5.0-10.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610288408.2A CN107344982B (en) | 2016-05-04 | 2016-05-04 | Method for producing wide/bimodal molecular weight distribution butyl rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610288408.2A CN107344982B (en) | 2016-05-04 | 2016-05-04 | Method for producing wide/bimodal molecular weight distribution butyl rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107344982A true CN107344982A (en) | 2017-11-14 |
| CN107344982B CN107344982B (en) | 2020-05-12 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111635474A (en) * | 2020-06-23 | 2020-09-08 | 北京化工大学 | Synthesis method and synthesis system of butyl rubber |
| CN112011018A (en) * | 2019-05-31 | 2020-12-01 | 中国石油天然气股份有限公司 | Method for preparing bimodal distribution star-shaped branched butyl rubber by slurry method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1427851A (en) * | 2000-05-05 | 2003-07-02 | 拜尔公司 | Process for preparation of butyl rubber having broad molecular weight distribution |
| CN101130585A (en) * | 2006-08-25 | 2008-02-27 | 北京化工大学 | Method for preparing isobutylene isoprene rubber |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1427851A (en) * | 2000-05-05 | 2003-07-02 | 拜尔公司 | Process for preparation of butyl rubber having broad molecular weight distribution |
| CN101130585A (en) * | 2006-08-25 | 2008-02-27 | 北京化工大学 | Method for preparing isobutylene isoprene rubber |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112011018A (en) * | 2019-05-31 | 2020-12-01 | 中国石油天然气股份有限公司 | Method for preparing bimodal distribution star-shaped branched butyl rubber by slurry method |
| CN112011018B (en) * | 2019-05-31 | 2022-11-04 | 中国石油天然气股份有限公司 | Method for preparing bimodal distribution star-shaped branched butyl rubber by slurry method |
| CN111635474A (en) * | 2020-06-23 | 2020-09-08 | 北京化工大学 | Synthesis method and synthesis system of butyl rubber |
| CN111635474B (en) * | 2020-06-23 | 2021-12-28 | 北京化工大学 | Synthesis method and synthesis system of butyl rubber |
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