CN110452323A - A kind of butyl rubber and preparation method thereof - Google Patents
A kind of butyl rubber and preparation method thereof Download PDFInfo
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- CN110452323A CN110452323A CN201910800903.0A CN201910800903A CN110452323A CN 110452323 A CN110452323 A CN 110452323A CN 201910800903 A CN201910800903 A CN 201910800903A CN 110452323 A CN110452323 A CN 110452323A
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- 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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Abstract
The present invention provides a kind of preparation methods of butyl rubber, during the preparation process, phenolic compound and monoolefine are added into reaction raw materials.Method provided by the invention has further widened the range for the stabilizer that butyl rubber synthesis can select, by introducing phenolic compound as slurry stabilizer, so that polymeric reaction product is evenly dispersed in the reaction system, effectively improve mass transfer, the heat transfer of system, monoolefine is as molecular weight regulator, molecular weight distribution more effectively is broadened, improves processing performance.
Description
Technical field
The invention belongs to field of rubber technology, and in particular to a kind of butyl rubber and preparation method thereof.
Background technique
Butyl rubber (IIR) is one kind of synthetic rubber, is synthesized by isobutene and a small amount of isoprene.With goodization
Stability and thermal stability are learned, most outstanding is air-tightness and watertightness.It is only the 1/ of natural rubber to the transmitance of air
7, the 1/5 of butadiene-styrene rubber, and be then the 1/200 of natural rubber to the transmitance of steam, the 1/140 of butadiene-styrene rubber.Therefore main
For manufacturing the various rubber products such as the various inner tubes of a tyre, steam pipe, curing bag, dam bottom and washer.Butyl rubber curingprocess rate
Slowly and the mutual viscosity of other rubber is poor that weak disadvantage is acted between reinforcing agent, limits the usage of butyl rubber, In
Synthesis phase more effectively improves its processing performance by the way that molecular weight distribution is adjusted.
The polymerization of butyl rubber is to react to carry out with carbonium ion, when polymerization temperature is higher than -85 DEG C, in slurry system
The easy aggregation of particle is blocking, influences system mass-and heat-transfer, causes serious kiss-coating and blocking, leads to polymeric kettle cleaning during shutdown, sternly
Ghost image rings the polymerization reaction continuous operation period and butyl rubber yield declines, and production cost increases.
Therefore, discharge heat of polymerization is carried out in a low temperature of constant rapidly with controlling reaction, keeps the stability of system, is improved
Butyl rubber polymerization system mass-and heat-transfer problem becomes those skilled in the art's problem urgently to be resolved.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of butyl rubber and preparation method thereof, this hair
The preparation method of bright offer is effectively improved mass transfer and heat transfer in butyl rubber preparation process, and can effectively widen butyl rubber
Molecular weight distribution, improve processing performance.
The present invention provides a kind of preparation methods of butyl rubber, during the preparation process, phenols are added into reaction raw materials
Compound and monoolefine.
Preferably, the phenolic compound is selected from p-methyl phenol, ortho-methyl phenol, 2,6- di-t-butyl -4- methylbenzene
One of phenol, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenol) are a variety of.
Preferably, the monoolefine is selected from ethylene, propylene, 1- butylene, 1- amylene, 1- hexene, 1- heptene, 2- methyl-1-
One of butylene and 2- methyl-2-butene are a variety of.
Preferably, comprising the following steps:
A) isomonoolefin, conjugated diene, solvent, phenolic compound and monoolefine are mixed, obtain reactant solution；
B) major catalyst, co-catalyst and solvent are mixed, obtain catalyst solution；
C catalyst solution is mixed with reactant solution), is reacted, butyl rubber is obtained.
Preferably, the carbon atom number of the isomonoolefin is 4~16；The carbon atom number of the conjugated diene be 4~
14；
The molar ratio of the conjugated diene and monoolefine is (0.01~0.1): 1；The isomonoolefin is molten in reactant
Mass content in liquid is 5wt%~30wt%.
Preferably, mass content of the phenolic compound in reactant solution is 1~3000mg/Kg.
Preferably, it is 10~20000mg/Kg that the monoolefine, which accounts for isomonoolefin mass content,.
Preferably, the major catalyst is water or hydrogen chloride；
The co-catalyst be lewis acid, as alchlor, ethyl aluminum dichloride, two chlorobutyl aluminium, a chlorine dibutyl aluminium,
One or more of boron trifluoride；
The molar ratio of the co-catalyst and major catalyst is (1~10): 1；
The molar ratio of the co-catalyst and isomonoolefin is (0.0001~0.005): 1.
Preferably, the reaction temperature is -98~-80 DEG C, and the reaction time is 1~20min.
The present invention also provides a kind of butyl rubbers that above-mentioned preparation method is prepared.
Compared with prior art, the present invention provides a kind of preparation methods of butyl rubber, during the preparation process, Xiang Fanying
Phenolic compound and monoolefine are added in raw material.Method provided by the invention has further been widened butyl rubber synthesis and can have been selected
The range for the stabilizer selected, by introducing phenolic compound as slurry stabilizer, so that polymeric reaction product is in reaction system
In it is evenly dispersed, effectively improve mass transfer, the heat transfer of system, monoolefine more effectively broadens point as molecular weight regulator
Son amount distribution, improves processing performance.
Detailed description of the invention
Fig. 1 is the nuclear magnetic spectrogram of butyl rubber prepared by embodiment 1.
Specific embodiment
The present invention provides a kind of preparation methods of butyl rubber, during the preparation process, phenols are added into reaction raw materials
Compound and monoolefine.
During the reaction, phenolic compound is as slurry stabilizer, and monoolefine is as molecular weight regulator.It was preparing
Phenolic compound and monoolefine are introduced in journey, polymerization system dispersity can not only be effectively improved, to enhance polymerization system
Mass transfer and heat transfer, keep butyl rubber evenly dispersed in system, avoid in production process parking of frequently driving, keep product steady
Qualitative raising, while can effectively widen the molecular weight distribution of butyl rubber product, improve the processing performance of butyl rubber.
Wherein, the phenolic compound be selected from p-methyl phenol, ortho-methyl phenol, 2,6- di-tert-butyl-4-methy phenol,
One of 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenol) are a variety of, preferably methylphenol or 2, the tertiary fourth of 6- bis-
Base -4- methylphenol.
The monoolefine is selected from ethylene, propylene, 1- butylene, 1- amylene, 1- hexene, 1- heptene, 2-methyl-1-butene alkene and 2-
One of methyl-2-butene is a variety of, preferably 1- butylene or 1- heptene.
Specifically, the preparation method comprises the following steps:
A) isomonoolefin, conjugated diene, solvent, phenolic compound and monoolefine are mixed, obtain reactant solution；
B) major catalyst, co-catalyst and solvent are mixed, obtain catalyst solution；
C catalyst solution is mixed with reactant solution), is reacted, butyl rubber is obtained.
The present invention first mixes isomonoolefin, solvent, phenolic compound and monoolefine, obtains mixed solution；
Then, conjugated diene is added into above-mentioned mixed solution, is uniformly mixed, obtains reactant solution.
Wherein, the carbon atom number of the isomonoolefin is 4~16, preferably 4~10, more preferably 4~6；
The carbon atom number of the conjugated diene is 4~14, preferably 4~8, more preferably 4~6；
Solvent used in the dissolution monomer is selected from monochloro methane；
The molar ratio of the conjugated diene and monoolefine is (0.01~0.1): 1, preferred (0.01~0.8): 1, more
Preferably (0.01~0.5): 1.
Mass content of the isomonoolefin in reactant solution be 5wt%~30wt%, preferably 5wt%~
25wt%, further preferably 19wt%~20wt%.
Mass content of the phenolic compound in reactant solution be 1~3000mg/Kg, preferably 10~
1000mg/Kg, further preferably 20~100mg/Kg.
The monoolefine account for isomonoolefin mass content be 10~20000mg/Kg, preferably 100~5000mg/Kg, into
One step is preferably 1000~2000mg/Kg.
The present invention mixes major catalyst, co-catalyst and solvent, obtains catalyst solution；
The major catalyst is water or hydrogen chloride；
The co-catalyst be lewis acid, as alchlor, ethyl aluminum dichloride, two chlorobutyl aluminium, a chlorine dibutyl aluminium,
One or more of boron trifluoride, preferably lewis acid；
It is described dissolution major catalyst, co-catalyst solvent be selected from one of monochloro methane, methylene chloride, n-hexane or
It is several, preferred monochloro methane.
The molar ratio of the co-catalyst and major catalyst is (1~10): 1, preferred (1~5): 1, preferred (2~
5):1；
The molar ratio of the co-catalyst and isomonoolefin be (0.0001~0.005): 1 preferably (0.0001~
0.002): 1, more preferably (0.0005~0.001): 1.
Catalyst solution is mixed with reactant solution, is reacted, the reaction temperature is -98~-80 DEG C, preferably
- 85~-98 DEG C, preferred -92~-97.5 DEG C；The reaction time be 1~20min, preferred 5~15min, it is more excellent
6~10min of choosing.
Alcohol compound is added into the above-mentioned reaction paste reacted and terminates reaction, the alcohols material is first
Alcohol or ethyl alcohol, preferably ethanol solution, the volume fraction of ethanol water preferably 35%~45%.
After reaction paste is removed solvent, butyl rubber is obtained.There is no special for method of the present invention to the removal solvent
Different limitation, the known method of those skilled in the art.
The present invention also provides a kind of butyl rubbers being prepared using above-mentioned preparation method.
Method provided by the invention has further widened the range for the stabilizer that butyl rubber synthesis can select, and passes through
Phenolic compound is introduced as slurry stabilizer, so that polymeric reaction product is evenly dispersed in the reaction system, is effectively improved
The mass transfer of system, heat transfer, monoolefine more effectively broaden molecular weight distribution as molecular weight regulator, improve processability
Energy.
For a further understanding of the present invention, below with reference to embodiment to butyl rubber provided by the invention and preparation method thereof
It is illustrated, protection scope of the present invention is not limited by the following examples.
Embodiment 1
At -70 DEG C, the 1- heptene of 2, the 6- di-tert-butyl-4-methy phenol and 0.75g that weigh 0.1g is added to
In the monochloro methane of 99.15g, it is configured to monochloro methane solution, it is therefore an objective to convenient for 2,6- di-tert-butyl-4-methy phenol and 1- heptan
The solution is cooled to -95 DEG C, obtains 2,6- di-tert-butyl-4-methy phenol and 1- heptene by the addition of alkene after stirring 30min
Solution.
At -70 DEG C, weigh 0.1g20% Dichloroethyl aluminum solutions, the monochloro methane that is added to 5g0.05wt%HCl it is molten
It is uniformly mixed in liquid, obtains catalyst solution, after being aged 30min at -92 DEG C, cool the temperature to -95 DEG C.
Temperature of reactor is -95 DEG C, sequentially adds 2, the 6- bis- of the isobutene of 11.25g, the monochloro methane of 63.75g, 2g
Tert-butyl-4-methyl-Phenol and 1- heptene solution, then addition 0.5g isoprene, which is uniformly mixed, obtains reactant solution.Stirring
After 15min, above-mentioned catalyst solution is added.
Catalyst system is added in reactant solution in -95 DEG C of reaction 10min, obtains being in granular form evenly dispersed slurry
Material.
1g ethyl alcohol is added and terminates reaction, by obtained reaction product at 40 DEG C, is dried in vacuo 48h, yield 87% will
Obtained product carries out nmr analysis (being the nuclear magnetic spectrogram of butyl rubber prepared by embodiment 1 referring to Fig. 1, Fig. 1), gel infiltration
Chromatograph test, gained butyl rubber degree of unsaturation 1.72mol%, weight average molecular weight 21000, molecular weight distribution 5.9, rubber
300% stretches surely for 7.2Mpa, tensile strength 17.5Mpa.
Embodiment 2
At -70 DEG C, the 1- heptene of the p-methyl phenol and 0.75g that weigh 0.1g is added to the monochloro methane of 99.15g
In, it is configured to monochloro methane solution, it is therefore an objective to convenient for the addition of p-methyl phenol and 1- heptene, after stirring 30min, by the solution
- 95 DEG C are cooled to, p-methyl phenol and 1- heptene solution are obtained.
At -70 DEG C, weigh 0.1g20% Dichloroethyl aluminum solutions, the monochloro methane that is added to 5g0.05wt%HCl it is molten
It is uniformly mixed in liquid, obtains catalyst solution, after being aged 30min at -92 DEG C, cool the temperature to -95 DEG C.
Temperature of reactor be -95 DEG C, sequentially add the isobutene of 11.25g, the monochloro methane of 63.75g, 2g to methyl
Phenol and 1- heptene solution, then addition 0.5g isoprene, which is uniformly mixed, obtains reactant solution.After stirring 15min, it is added
Above-mentioned catalyst solution.
Catalyst system is added in reactant solution in -95 DEG C of reaction 10min, obtains being in granular form evenly dispersed slurry
Material.
1g ethyl alcohol is added and terminates reaction, by obtained reaction product at 40 DEG C, is dried in vacuo 48h, yield 84% will
Obtained product carries out nmr analysis, gel permeation chromatograph test, and gained butyl rubber degree of unsaturation 1.70mol%, weight is
Molecular weight 18500, molecular weight distribution 5.7, rubber 300% are stretched surely for 7.0Mpa, tensile strength 17.0Mpa.
Embodiment 3
At -70 DEG C, the 1- butylene of 2, the 6- di-tert-butyl-4-methy phenol and 0.75g that weigh 0.1g is added to
In the monochloro methane of 99.15g, it is configured to monochloro methane solution, it is therefore an objective to be convenient for 2,6- di-tert-butyl-4-methy phenol and 1- fourth
The solution is cooled to -95 DEG C, obtains 2,6- di-tert-butyl-4-methy phenol and 1- butylene by the addition of alkene after stirring 30min
Solution.
At -70 DEG C, weigh 0.1g20% Dichloroethyl aluminum solutions, the monochloro methane that is added to 5g0.05wt%HCl it is molten
It is uniformly mixed in liquid, obtains catalyst solution, after being aged 30min at -92 DEG C, cool the temperature to -95 DEG C.
Temperature of reactor is -95 DEG C, sequentially adds 2, the 6- bis- of the isobutene of 11.25g, the monochloro methane of 63.75g, 2g
Tert-butyl-4-methyl-Phenol and 1- butylene solution, then addition 0.5g isoprene, which is uniformly mixed, obtains reactant solution.Stirring
After 15min, above-mentioned catalyst solution is added.
Catalyst system is added in reactant solution in -95 DEG C of reaction 10min, obtains being in granular form evenly dispersed slurry
Material.
1g ethyl alcohol is added and terminates reaction, by obtained reaction product at 40 DEG C, is dried in vacuo 48h, yield 80% will
Obtained product carries out nmr analysis, gel permeation chromatograph test, and gained butyl rubber degree of unsaturation 1.68mol%, weight is
Molecular weight 18000, molecular weight distribution 5.5, rubber 300% are stretched surely for 6.8Mpa, tensile strength 16.7Mpa.
Embodiment 4
At -70 DEG C, the 1- heptene of 2, the 6- di-tert-butyl-4-methy phenol and 1g that weigh 0.1g is added to 98.9g's
In monochloro methane, be configured to monochloro methane solution, it is therefore an objective to convenient for 2,6- di-tert-butyl-4-methy phenol and 1- heptene plus
Enter, after stirring 30min, which is cooled to -95 DEG C, obtains 2,6- di-tert-butyl-4-methy phenol and 1- heptene solution.
At -70 DEG C, weigh 0.1g40% Dichloroethyl aluminum solutions, the monochloro methane that is added to 5g0.05wt%HCl it is molten
It is uniformly mixed in liquid, obtains catalyst solution, after being aged 30min at -92 DEG C, cool the temperature to -95 DEG C.
Temperature of reactor is -95 DEG C, sequentially adds 2, the 6- bis- of the isobutene of 11.25g, the monochloro methane of 63.75g, 3g
Tert-butyl-4-methyl-Phenol and 1- heptene solution, then addition 0.5g isoprene, which is uniformly mixed, obtains reactant solution.Stirring
After 15min, above-mentioned catalyst solution is added.
Catalyst system is added in reactant solution in -95 DEG C of reaction 10min, obtains being in granular form evenly dispersed slurry
Material.
1g ethyl alcohol is added and terminates reaction, by obtained reaction product at 40 DEG C, is dried in vacuo 48h, yield 75% will
Obtained product carries out nmr analysis, gel permeation chromatograph test, and gained butyl rubber degree of unsaturation 1.64mol%, weight is
Molecular weight 169000, molecular weight distribution 5.4, rubber 300% are stretched surely for 6.9Mpa, tensile strength 16.7Mpa.
Embodiment 5
At -70 DEG C, the 1- heptene of 2, the 6- di-tert-butyl-4-methy phenol and 0.3g that weigh 0.1g is added to 99.6g
Monochloro methane in, be configured to monochloro methane solution, it is therefore an objective to convenient for 2,6- di-tert-butyl-4-methy phenol and 1- heptene plus
Enter, after stirring 30min, which is cooled to -95 DEG C, obtains 2,6- di-tert-butyl-4-methy phenol and 1- heptene solution.
At -70 DEG C, weigh 0.1g40% Dichloroethyl aluminum solutions, the monochloro methane that is added to 5g0.05wt%HCl it is molten
It is uniformly mixed in liquid, obtains catalyst solution, after being aged 30min at -92 DEG C, cool the temperature to -95 DEG C.
Temperature of reactor is -95 DEG C, sequentially adds 2, the 6- bis- of the isobutene of 11.25g, the monochloro methane of 63.75g, 2g
Tert-butyl-4-methyl-Phenol and 1- heptene solution, then addition 0.5g isoprene, which is uniformly mixed, obtains reactant solution.Stirring
After 15min, above-mentioned catalyst solution is added.
Catalyst system is added in reactant solution in -95 DEG C of reaction 10min, obtains being in granular form evenly dispersed slurry
Material.
1g ethyl alcohol is added and terminates reaction, by obtained reaction product at 40 DEG C, is dried in vacuo 48h, yield 68% will
Obtained product carries out nmr analysis, gel permeation chromatograph test, and gained butyl rubber degree of unsaturation 1.62mol%, weight is
Molecular weight 16000, molecular weight distribution 5.1, rubber 300% are stretched surely for 6.6Mpa, tensile strength 16.2Mpa.
Embodiment 6
At -70 DEG C, the 1- heptene of 2, the 6- di-tert-butyl-4-methy phenol and 0.75g that weigh 0.01g is added to
In the monochloro methane of 99.24g, it is configured to monochloro methane solution, it is therefore an objective to convenient for 2,6- di-tert-butyl-4-methy phenol and 1- heptan
The solution is cooled to -95 DEG C, obtains 2,6- di-tert-butyl-4-methy phenol and 1- heptene by the addition of alkene after stirring 30min
Solution.
At -70 DEG C, weigh 0.1g20% Dichloroethyl aluminum solutions, the monochloro methane that is added to 5g0.05wt%HCl it is molten
It is uniformly mixed in liquid, obtains catalyst solution, after being aged 30min at -92 DEG C, cool the temperature to -95 DEG C.
Temperature of reactor is -95 DEG C, sequentially adds 2, the 6- bis- of the isobutene of 11.25g, the monochloro methane of 63.75g, 2g
Tert-butyl-4-methyl-Phenol and 1- heptene solution, then addition 0.5g isoprene, which is uniformly mixed, obtains reactant solution.Stirring
After 15min, above-mentioned catalyst solution is added.
Catalyst system is added in reactant solution in -95 DEG C of reaction 10min, is obtained in spherical evenly dispersed slurry.
1g ethyl alcohol is added and terminates reaction, by obtained reaction product at 40 DEG C, is dried in vacuo 48h, yield 80% will
Obtained product carries out nmr analysis, gel permeation chromatograph test, and gained butyl rubber degree of unsaturation 1.66mol%, weight is
Molecular weight 20000, molecular weight distribution 5.8, rubber 300% are stretched surely for 7.1Mpa, tensile strength 17.6Mpa.
Embodiment 7
At -70 DEG C, the 1- heptene of 2, the 6- di-tert-butyl-4-methy phenol and 0.75g that weigh 0.5g is added to
In the monochloro methane of 98.75g, it is configured to monochloro methane solution, it is therefore an objective to convenient for 2,6- di-tert-butyl-4-methy phenol and 1- heptan
The solution is cooled to -95 DEG C, obtains 2,6- di-tert-butyl-4-methy phenol and 1- heptene by the addition of alkene after stirring 30min
Solution.
At -70 DEG C, weigh 0.1g20% Dichloroethyl aluminum solutions, the monochloro methane that is added to 5g0.05wt%HCl it is molten
It is uniformly mixed in liquid, obtains catalyst solution, after being aged 30min at -92 DEG C, cool the temperature to -95 DEG C.
Temperature of reactor is -95 DEG C, sequentially adds 2, the 6- bis- of the isobutene of 11.25g, the monochloro methane of 63.75g, 2g
Tert-butyl-4-methyl-Phenol and 1- heptene solution, then addition 0.5g isoprene, which is uniformly mixed, obtains reactant solution.Stirring
After 15min, above-mentioned catalyst solution is added.
Catalyst system is added in reactant solution in -95 DEG C of reaction 10min, obtains being in granular form evenly dispersed slurry
Material.
1g ethyl alcohol is added and terminates reaction, by obtained reaction product at 40 DEG C, is dried in vacuo 48h, yield 55% will
Obtained product carries out nmr analysis, gel permeation chromatograph test, and gained butyl rubber degree of unsaturation 1.68mol%, weight is
Molecular weight 18000, molecular weight distribution 5.5, rubber 300% are stretched surely for 7.0Mpa, tensile strength 17.2Mpa.
Comparative example 1
Process flow and step are with embodiment 1, the difference from embodiment 1 is that 2 are not added, 6- di-t-butyl -4- methyl
Phenol and 1- heptene.Reaction sticks on agitating paddle and kettle wall product conglomeration takes place.
Nmr analysis, gel permeation chromatography test are carried out to the above-mentioned butyl rubber product of preparation, gained butyl rubber is not
Saturation degree 1.50mol%, weight average molecular weight 13000, molecular weight distribution 4.1, rubber 300% are stretched surely for 6.3Mpa, tensile strength
For 16.1Mpa.
Comparative example 2
Process flow and step are with embodiment 1, the difference from embodiment 1 is that not adding 1- heptene.Reactive polymeric product
It is in granular form in diluent, reduces the kiss-coating phenomenon in reaction.
Nmr analysis, gel permeation chromatography test are carried out to the above-mentioned butyl rubber product of preparation, gained butyl rubber is not
Saturation degree 1.60mol%, weight average molecular weight 14500, molecular weight distribution 4.0, rubber 300% are stretched surely for 76.5Mpa, tensile strength
For 16.0Mpa.
Comparative example 3
Process flow and step are with embodiment 1, the difference from embodiment 1 is that 2 are not added, 6- di-t-butyl -4- methyl
Phenol.Reaction sticks on agitating paddle and kettle wall product conglomeration takes place.
Nmr analysis, gel permeation chromatography test are carried out to the above-mentioned butyl rubber product of preparation, gained butyl rubber is not
Saturation degree 1.58mol%, weight average molecular weight 16000, molecular weight distribution 5.6, rubber 300% are stretched surely for 7.1Mpa, tensile strength
For 16.9Mpa.
After above embodiments introduce phenolic compound and monoolefine in the reaction system, polymerizate can be made in diluent
In be in granular form, reduce the kiss-coating phenomenon in reaction, while effectively having adjusted molecular chain conformation.Improve adding for product
Work performance.
The present invention provides a kind of preparation methods of butyl rubber, introduce phenolic compound and monoene during the preparation process
Hydrocarbon effectively changes the mass-and heat-transfer of reaction system, guarantees butyl rubber continuous production, frequent start-stop in production process can be exempted from by keeping away
Vehicle keeps stable product quality good.Molecular chain conformation is effectively had adjusted simultaneously, improves the processing performance of product.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of butyl rubber, which is characterized in that during the preparation process, phenols chemical combination is added into reaction raw materials
Object and monoolefine.
2. the method according to claim 1, wherein the phenolic compound is selected from p-methyl phenol, adjacent methyl
One of phenol, 2,6 di tert butyl 4 methyl phenol, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenol) are more
Kind.
3. preparation method according to claim 1, which is characterized in that the monoolefine be selected from ethylene, propylene, 1- butylene,
One of 1- amylene, 1- hexene, 1- heptene, 2-methyl-1-butene alkene and 2- methyl-2-butene are a variety of.
4. preparation method according to claim 1, which comprises the following steps:
A) isomonoolefin, conjugated diene, solvent, phenolic compound and monoolefine are mixed, obtain reactant solution；
B) major catalyst, co-catalyst and solvent are mixed, obtain catalyst solution；
C catalyst solution is mixed with reactant solution), is reacted, butyl rubber is obtained.
5. the preparation method according to claim 4, which is characterized in that the carbon atom number of the isomonoolefin is 4~16；
The carbon atom number of the conjugated diene is 4~14；
The molar ratio of the conjugated diene and monoolefine is (0.01~0.1): 1；The isomonoolefin is in reactant solution
Mass content be 5wt%~30wt%.
6. the preparation method according to claim 4, which is characterized in that matter of the phenolic compound in reactant solution
Amount content is 1~3000mg/Kg.
7. butyl rubber preparation method according to claim 4, which is characterized in that the monoolefine accounts for isomonoolefin quality
Content is 10~20000mg/Kg.
8. butyl rubber preparation method according to claim 4, which is characterized in that the major catalyst is water or chlorination
Hydrogen；
The co-catalyst is lewis acid, such as alchlor, ethyl aluminum dichloride, two chlorobutyl aluminium, a chlorine dibutyl aluminium, trifluoro
Change one or more of boron；
The molar ratio of the co-catalyst and major catalyst is (1~10): 1；
The molar ratio of the co-catalyst and isomonoolefin is (0.0001~0.005): 1.
9. butyl rubber preparation method according to claim 4, which is characterized in that the reaction temperature is -98~-80
DEG C, the reaction time is 1~20min.
10. a kind of butyl rubber that preparation method as claimed in any one of claims 1 to 9 wherein is prepared.
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| CN110878132A (en) * | 2019-12-23 | 2020-03-13 | 山东京博中聚新材料有限公司 | Production process of butyl rubber |
| CN111019032A (en) * | 2019-12-23 | 2020-04-17 | 山东京博中聚新材料有限公司 | Production process of butyl rubber |
| CN116217773A (en) * | 2023-03-29 | 2023-06-06 | 山东京博中聚新材料有限公司 | Butyl rubber with wide molecular weight distribution and synthetic method thereof |
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| CN110878132A (en) * | 2019-12-23 | 2020-03-13 | 山东京博中聚新材料有限公司 | Production process of butyl rubber |
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| CN116217773A (en) * | 2023-03-29 | 2023-06-06 | 山东京博中聚新材料有限公司 | Butyl rubber with wide molecular weight distribution and synthetic method thereof |
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| CN110452323B (en) | 2022-03-22 |
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