CN110483671A - A kind of butyl rubber and its production technology - Google Patents
A kind of butyl rubber and its production technology Download PDFInfo
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- CN110483671A CN110483671A CN201910795172.5A CN201910795172A CN110483671A CN 110483671 A CN110483671 A CN 110483671A CN 201910795172 A CN201910795172 A CN 201910795172A CN 110483671 A CN110483671 A CN 110483671A
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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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Abstract
The present invention provides a kind of production technologies of butyl rubber, in process of production, Calixarene Derivatives are added into reaction system.The present invention introduces Calixarene Derivatives as slurry stabilizer in the course of the polymerization process, the presence of the substance can make the evenly dispersed raising slurry dispersion effect of product, inhibit polymerizate conglomeration, to be effectively improved mass transfer and the heat transfer of butyl rubber polymerization system, make process units can be with long period underrun.Meanwhile the molecular weight distribution of product is widened, product Mooney stability increases substantially, and the processing performance of product quality and product is more excellent.
Description
Technical field
The invention belongs to field of rubber technology, and in particular to a kind of butyl rubber and its production technology.
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 realizes work certainly
Since industry metaplasia produces, the structure type of raw material route, production technology and polymeric kettle changes always less, generally uses chloromethanes
Make diluent, alchlor makees catalyst, controls the conversion ratio of the adjustable monomer of dosage of the two.According to product unsaturation
The class requirement of degree, the dosage of isoprene are generally the 1.5%~4.5% of isobutene dosage, and conversion ratio is 60%~
90%.
The polymerization of butyl rubber is to react to carry out with carbonium ion, and reaction temperature is low, and speed is fast, and heat release is concentrated, and poly-
The molecular weight for closing object sharply declines with the raising of temperature.Butyl rubber polymerization simultaneously has the easy kiss-coating of slurry and conglomeration etc. special
Point, reactor kiss-coating will lead to heat-conducting effect variation, and polymerization temperature rise is accelerated, and rubber lump seriously leads to overflow blockage, causes
Polymerization reaction cycle time.Discharge heat of polymerization is carried out in a low temperature of constant rapidly with controlling reaction, is mainly asking in production
Topic.The frequent driving and parking of process units will lead to that the production cost increases, and product quality is caused to fluctuate widely.Therefore, butyl rubber
Glue polymerization system mass-and heat-transfer problem becomes this field problem urgently to be resolved.
Summary of the invention
In view of this, polymerizeing the technical problem to be solved in the present invention is that provide a kind of production technology of butyl rubber
Calixarene Derivatives are introduced in the process as slurry stabilizer, and the presence of the substance can make product evenly dispersed to effectively change
The mass transfer of kind butyl rubber polymerization system and heat transfer, make process units can be with long period underrun.
The present invention provides a kind of production technologies of butyl rubber, in process of production, cup virtue are added into reaction system
Hydrocarbon derivative.
Preferably, the Calixarene Derivatives are selected from 4- tert-butyl p tertButylcalixarene, 4- tert-butyl-calix [6] aromatic hydrocarbons, the tertiary fourth of 4-
One of base cup [8] aromatic hydrocarbons, 4- tert-butyl thia cup [4] aromatic hydrocarbons, 4- tert-butyl oxa- cup [4] aromatic hydrocarbons are a variety of.
Preferably, comprising the following steps:
A) monoolefine, alkadienes, Calixarene Derivatives and solvent are mixed, obtain reactant solution；
B low temperature maturation is carried out after) mixing major catalyst, co-catalyst and solvent, obtains catalyst system；
C) reactant solution and catalyst system are mixed, it is after being reacted, reaction product is dry, obtain rubber.
Preferably, the monoolefine is the isomonoolefin of C4~C16；
The alkadienes is C4~C14 conjugated diene；
The molar ratio of the alkadienes and monoolefine is (0.01~0.1): 1.
Preferably, mass content of the monoolefine in reactant solution is 5~40wt%；
Mass content of the Calixarene Derivatives in reactant solution is 1~1000mg/Kg.
Preferably, the major catalyst is H2O or HCl；
The co-catalyst is lewis acid；
The molar ratio of the co-catalyst and monoolefine is (0.0001~0.005): 1；
The molar ratio of the co-catalyst and major catalyst is (0.005~1): 1.
Preferably, the temperature of the ageing is -80~-95 DEG C, and the time of the ageing is 1~45min.
Preferably, the reaction temperature is -60~-98 DEG C, and the reaction time is 1~20min.
Preferably, step A) in, the solvent is selected from chloromethanes；
Step B) in, the solvent is selected from chloromethanes.
The present invention also provides a kind of butyl rubbers that above-mentioned production technology obtains.
Compared with prior art, the present invention provides a kind of production technologies of butyl rubber, in process of production, Xiang Fanying
Calixarene Derivatives are added in system.The present invention introduces Calixarene Derivatives as slurry stabilizer, the object in the course of the polymerization process
The presence of matter can make the evenly dispersed raising slurry dispersion effect of product, inhibit polymerizate conglomeration, to be effectively improved butyl
The mass transfer of rubber polymers system and heat transfer make process units can be with long period underrun.Meanwhile the molecular weight distribution of product
Widen, product Mooney stability increases substantially, and the processing performance of product quality and product is more excellent.
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 production technologies of butyl rubber, in process of production, cup virtue are added into reaction system
Hydrocarbon derivative.
The present invention introduces Calixarene Derivatives as slurry stabilizer in the course of the polymerization process, and the presence of the substance can make to produce
Evenly dispersed mass transfer and the heat transfer to be effectively improved butyl rubber polymerization system of object, makes process units can be with long period underload
Operation, meanwhile, the molecular weight distribution of product is widened, and product Mooney stability increases substantially, the processing of product quality and product
Performance is more excellent.
Wherein, the Calixarene Derivatives are selected from 4- tert-butyl p tertButylcalixarene, 4- tert-butyl-calix [6] aromatic hydrocarbons, 4- tert-butyl
Cup [8] aromatic hydrocarbons, 4- tert-butyl thia cup [4] aromatic hydrocarbons, one of 4- tert-butyl oxa- cup [4] aromatic hydrocarbons or a variety of, preferably pair
Tert-butyl p tertButylcalixarene, to tert-butyl thia cup [4] aromatic hydrocarbons, to tert-butyl-calix [6] aromatic hydrocarbons or to tert-butyl-calix [8] aromatic hydrocarbons.
The production technology of butyl rubber provided by the invention, comprising the following steps:
A) monoolefine, alkadienes, Calixarene Derivatives and solvent are mixed, obtain reactant solution；
B low temperature maturation is carried out after) mixing major catalyst, co-catalyst and solvent, obtains catalyst system；
C) reactant solution and catalyst system are mixed, it is after being reacted, reaction product is dry, obtain rubber.
The present invention mixes monoolefine, alkadienes, Calixarene Derivatives and solvent, obtains reactant solution.
Specifically, the present invention mixes monoolefine, alkadienes and solvent, monomer solution is obtained；
The monoolefine is the isomonoolefin of C4~C16, the preferably isomonoolefin of C4~C10, more preferably C4~C6
Isomonoolefin.In certain specific embodiments of the invention, the monoolefine is selected from isobutene.
The alkadienes is C4~C14 conjugated diene, and preferably C4~C8 conjugated diene, more preferably C4~C6 is total
Yoke alkadienes.In certain specific embodiments of the invention, the alkadienes is selected from isoprene.
The molar ratio of the alkadienes and monoolefine is (0.01~0.1): 1, preferred (0.01~0.8): 1, more preferably
(0.01~0.5): 1.
In the present invention, the mixed temperature is -50~-90 DEG C, preferably -65~-85 DEG C.
Calixarene Derivatives mixing is added after obtaining monomer solution, in Xiang Suoshu monomer solution, obtains reactant solution.
Mass content of the monoolefine in reactant solution be 5~40wt%, preferred 10~40wt%, more preferably
25~38wt%；
Mass content of the Calixarene Derivatives in reactant solution be 1~1000mg/Kg, preferred 10~
100mg/Kg, preferred 20~50mg/Kg.
The mixed temperature is -50~-90 DEG C, preferably -60~-70 DEG C.
Low temperature maturation is carried out after major catalyst, co-catalyst and solvent are mixed, obtains catalyst system；
The major catalyst is H2O or HCl；
The co-catalyst is lewis acid, preferably alchlor, ethyl aluminum dichloride, aluminium diethyl monochloride, two neoprenes
Base aluminium, a chlorine dibutyl aluminium, boron trifluoride, in titanium tetrachloride, one or more, the more preferably ethyl aluminum dichloride of sesquialter aluminium；
The molar ratio of the co-catalyst and monoolefine is (0.0001~0.005): 1, preferably (0.0001~
0.002): 1, more preferably (0.0005~0.001): 1；
The molar ratio of the co-catalyst and major catalyst is (0.005~1): 1, preferred (0.01~1): 1, more preferably
(0.1~0.2): 1.
The temperature of the ageing is -80~-95 DEG C, preferably -88~-95 DEG C, -92~-95 DEG C preferred, described
The time of ageing is 1~45min, preferably 5~30min, more preferably 10~30min.
There is no specifically limited for preparation sequence of the present invention to the reactant solution and catalyst system.
Then, reactant solution and catalyst system are mixed, it is after being reacted, reaction product is dry, obtain rubber.
The present invention catalyst system is added under reaction temperature in reactant solution to be mixed, reacts, and product slurry is obtained；
Wherein, the reaction temperature is -60~-98 DEG C, -80~-98 DEG C preferred, -90~-97.5 DEG C preferred,
The reaction time is 1~20min, preferred 2~15min, preferred 5~10min.
Then, alcohol compound is added in Xiang Suoshu product slurry and terminates reaction, obtain final product；The alcohols material
For methanol or ethyl alcohol.
Finally, product slurry is dried and removed into vacuum drying oven solvent, obtains rubber.
The present invention also provides a kind of butyl rubbers being prepared using above-mentioned production technology.
Butyl rubber is polymerized to typical cationic polymerization, and reaction speed is fast, and heat release is not easy to control, the molecule of polymer
Amount sharply declines with the raising of temperature；Butyl rubber polymerization simultaneously has the characteristics that the easy kiss-coating of slurry and conglomeration, and kiss-coating can be led
Heat-conducting effect is caused to be deteriorated, polymerization temperature rise is accelerated.Temperature rise causes polymerization temperature to increase, and two problems of kiss-coating will lead to product quality
It is unstable.The present invention introduces Calixarene Derivatives as slurry stabilizer in the course of the polymerization process, and the presence of the substance can make to produce
The evenly dispersed raising slurry dispersion effect of object inhibits polymerizate conglomeration, to be effectively improved the biography of butyl rubber polymerization system
Matter and heat transfer make process units can be with long period underrun.Meanwhile the molecular weight distribution of product is widened, product Mooney is steady
Qualitative to increase substantially, the processing performance of product quality and product is more excellent.
For a further understanding of the present invention, below with reference to embodiment to butyl rubber provided by the invention and its production technology
It is illustrated, protection scope of the present invention is not limited by the following examples.
Embodiment 1
It at -70 DEG C, weighs 22.5g isobutene and is added in the monochloro methane of 127.5g, 1g isoprene is then added
It is uniformly mixed and obtains monomer solution.
2g is weighed to reactant solution is obtained in tert-butyl p tertButylcalixarene addition monomer solution, which is cooled to -95
℃。
At -70 DEG C, the monochloro methane that weighs 0.2g20% Dichloroethyl aluminum solutions, be added to 10g0.025wt%HCl
It is uniformly mixed in solution, obtains catalyst system, after being aged 30min at -88 DEG C, cool the temperature to -95 DEG C.
Catalyst system is added in reactant solution in -95 DEG C of reaction 20min, obtains being in granular form evenly dispersed slurry
Material.
2g ethyl alcohol is added and terminates reaction, slurry to removing solvent in a vacuum drying oven is obtained into butyl rubber.Referring to figure
The nuclear magnetic spectrogram of 1, Fig. 1 butyl rubber prepared for embodiment 1.
Obtained butyl rubber is subjected to nmr analysis, Mooney viscosity analysis, GPC test, gained butyl rubber is unsaturated
1.74mol% is spent, 125 DEG C of Mooney viscosity ML (1+8) are 51, weight average molecular weight 18000, molecular weight distribution 4.2.
Embodiment 2
It at -70 DEG C, weighs 20g isobutene and is added in the monochloro methane of 113.5g, 1.3g isoprene is then added
It is uniformly mixed and obtains monomer solution.
2.5g is weighed to reactant solution is obtained in tert-butyl thia cup [4] aromatic hydrocarbons addition monomer solution, which is dropped
Temperature is to -97 DEG C.
At -70 DEG C, weigh 0.15g20% Dichloroethyl aluminum solutions, the monochloro methane that is added to 6g0.02wt%HCl it is molten
It is uniformly mixed in liquid, obtains catalyst system, after being aged 20min at -90 DEG C, cool the temperature to -97 DEG C.
Catalyst system is added in reactant solution in -97 DEG C of reaction 10min, obtains being in granular form evenly dispersed slurry
Material.
2g ethyl alcohol is added and terminates reaction, slurry to removing solvent in a vacuum drying oven is obtained into butyl rubber.
Obtained butyl rubber is subjected to nmr analysis, Mooney viscosity analysis, GPC test, gained butyl rubber is unsaturated
1.71mol% is spent, 125 DEG C of Mooney viscosity ML (1+8) are 49, weight average molecular weight 17500, molecular weight distribution 4.0.
Embodiment 3
It at -85 DEG C, weighs 40g isobutene and is added in the monochloro methane of 110g, the mixing of 2g isoprene is then added
Uniformly obtain monomer solution.
3g is weighed to reactant solution is obtained in tert-butyl-calix [6] aromatic hydrocarbons addition monomer solution, which is cooled to -90
℃。
At -85 DEG C, the monochloro methane that weighs 0.3g20% Dichloroethyl aluminum solutions, be added to 12g 0.02wt%HCl
It is uniformly mixed in solution, obtains catalyst system, be aged 30min at -90 DEG C.
Catalyst system is added in reactant solution in -90 DEG C of reaction 20min, obtains being in granular form evenly dispersed slurry
Material.
2g ethyl alcohol is added and terminates reaction, slurry to removing solvent in a vacuum drying oven is obtained into butyl rubber.
Obtained butyl rubber is subjected to nmr analysis, Mooney viscosity analysis, GPC test, gained butyl rubber is unsaturated
1.6mol% is spent, 125 DEG C of Mooney viscosity ML (1+8) are 52, weight average molecular weight 15000, molecular weight distribution 3.9.
Embodiment 4
It at -80 DEG C, weighs 15g isobutene and is added in the monochloro methane of 135g, it is mixed that 1.5g isoprene is then added
It closes and uniformly obtains monomer solution.
It weighs 2g tert-butyl-calix [8] aromatic hydrocarbons is added in monomer solution and obtain reactant solution, which is cooled to-
97.5℃。
At -80 DEG C, weigh 0.15g20% Dichloroethyl aluminum solutions, the monochloro methane that is added to 8g0.02wt%HCl it is molten
It is uniformly mixed in liquid, obtains catalyst system, after being aged 10min at -90 DEG C, cool the temperature to -97.5 DEG C.
Catalyst system is added in reactant solution in -97.5 DEG C of reaction 15min, obtains being in granular form evenly dispersed slurry
Material.
2g ethyl alcohol is added and terminates reaction, slurry to removing solvent in a vacuum drying oven is obtained into butyl rubber.
Obtained butyl rubber is subjected to nmr analysis, Mooney viscosity analysis, GPC test, gained butyl rubber is unsaturated
1.69mol% is spent, 125 DEG C of Mooney viscosity ML (1+8) are 48, weight average molecular weight 21000, molecular weight distribution 3.7.
Comparative example 1
With embodiment 1, rest materials proportion is also identical for process flow and step, and difference is that not adding calixarenes derives
Object.Product conglomeration sticks on agitating paddle and kettle wall.
Product conglomeration sticks on agitating paddle and kettle wall.
Nmr analysis, Mooney viscosity analysis, GPC test, gained butyl rubber are carried out to the above-mentioned butyl rubber product of preparation
Glue degree of unsaturation 1.50%, 125 DEG C of Mooney viscosity ML (1+8) are 45, weight average molecular weight 10000, molecular weight distribution 3.5.
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 production technology of butyl rubber, which is characterized in that in process of production, calixarenes is added into reaction system and spreads out
Biology.
2. production technology according to claim 1, which is characterized in that the Calixarene Derivatives are selected from 4- tert-butyl-calix
[4] aromatic hydrocarbons, 4- tert-butyl-calix [6] aromatic hydrocarbons, 4- tert-butyl-calix [8] aromatic hydrocarbons, 4- tert-butyl thia cup [4] aromatic hydrocarbons, 4- tert-butyl oxygen
One of miscellaneous cup [4] aromatic hydrocarbons is a variety of.
3. production technology according to claim 1, which comprises the following steps:
A) monoolefine, alkadienes, Calixarene Derivatives and solvent are mixed, obtain reactant solution；
B low temperature maturation is carried out after) mixing major catalyst, co-catalyst and solvent, obtains catalyst system；
C) reactant solution and catalyst system are mixed, it is after being reacted, reaction product is dry, obtain rubber.
4. production technology according to claim 3, which is characterized in that the monoolefine is the isomonoolefin of C4~C16；
The alkadienes is C4~C14 conjugated diene；
The molar ratio of the alkadienes and monoolefine is (0.01~0.1): 1.
5. production technology according to claim 3, which is characterized in that quality of the monoolefine in reactant solution contains
Amount is 5~40wt%；
Mass content of the Calixarene Derivatives in reactant solution is 1~1000mg/Kg.
6. production technology according to claim 3, which is characterized in that the major catalyst is H2O or HCl；
The co-catalyst is lewis acid；
The molar ratio of the co-catalyst and monoolefine is (0.0001~0.005): 1；
The molar ratio of the co-catalyst and major catalyst is (0.005~1): 1.
7. production technology according to claim 3, which is characterized in that the temperature of the ageing is -80~-95 DEG C, described
The time of ageing is 1~45min.
8. production technology according to claim 3, which is characterized in that the reaction temperature is -60~-98 DEG C, described anti-
It is 1~20min between seasonable.
9. production technology according to claim 3, which is characterized in that step A) in, the solvent is selected from chloromethanes；
Step B) in, the solvent is selected from chloromethanes.
10. a kind of butyl rubber that the production technology as described in claim 1~8 any one obtains.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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