CN103467636A - Production technology of brominated butyl rubber - Google Patents
Production technology of brominated butyl rubber Download PDFInfo
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- CN103467636A CN103467636A CN2013104596546A CN201310459654A CN103467636A CN 103467636 A CN103467636 A CN 103467636A CN 2013104596546 A CN2013104596546 A CN 2013104596546A CN 201310459654 A CN201310459654 A CN 201310459654A CN 103467636 A CN103467636 A CN 103467636A
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- 229920005557 bromobutyl Polymers 0.000 title claims abstract description 29
- 238000005516 engineering process Methods 0.000 title abstract description 6
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000005893 bromination reaction Methods 0.000 claims abstract description 61
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract description 50
- 239000007789 gas Substances 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- 230000031709 bromination Effects 0.000 claims abstract description 18
- 230000035484 reaction time Effects 0.000 claims abstract description 16
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 65
- 229920001971 elastomer Polymers 0.000 claims description 59
- 239000005060 rubber Substances 0.000 claims description 59
- 238000002156 mixing Methods 0.000 claims description 32
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 25
- YFQFTOCCYRNGIY-UHFFFAOYSA-N Br[N] Chemical compound Br[N] YFQFTOCCYRNGIY-UHFFFAOYSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 17
- 238000010092 rubber production Methods 0.000 claims description 13
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 12
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 12
- 239000011344 liquid material Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 239000006200 vaporizer Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- ZJKABZNFELLAQQ-UHFFFAOYSA-N octane Chemical compound CCCCCCCC.CCCCCCCC ZJKABZNFELLAQQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000008016 vaporization Effects 0.000 claims description 2
- 229920005549 butyl rubber Polymers 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- ABXSJIXCMARDGV-UHFFFAOYSA-N [N].[Br] Chemical compound [N].[Br] ABXSJIXCMARDGV-UHFFFAOYSA-N 0.000 abstract 2
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 2
- -1 bromine alkane Chemical class 0.000 abstract 1
- 125000001246 bromo group Chemical group Br* 0.000 abstract 1
- 239000012159 carrier gas Substances 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 10
- 241001441571 Hiodontidae Species 0.000 description 7
- 229910000435 bromine oxide Inorganic materials 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 5
- 238000007259 addition reaction Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000010523 cascade reaction Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 230000005945 translocation Effects 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the technical field of chemistry and chemical engineering and discloses a production technology of brominated butyl rubber. The production technology of the brominated butyl rubber comprises the following steps that firstly, liquid bromine is gasified and becomes a bromine-nitrogen gas mixture in the method that nitrogen is used as carrier gas in a bromine evaporator; secondly, rapid mixture of the bromine-nitrogen gas mixture and butyl rubber is achieved through a bromination mixer so that a bromination reaction can be caused; thirdly, after formed bromination reaction liquid stays in a following-up bromination reaction pipeline for a certain time, the formed bromination reaction liquid and a neutralization solution are rapidly mixed in a neutralization mixer so that a neutralization reaction can be started; fourthly, the reaction process of a formed multiphase mixture is finished in a following-up neutralization reaction pipeline and a neutralization kettle, and tail gas can be recycled after purification. The production technology of the brominated butyl rubber has the advantages that traditional bromine alkane solution feed is replaced by gas phase bromine, the mixture speed of reactants is high, the reaction time is short and can be accurately controlled, the bromination degree of a product can be controlled to the range from 0% to 1.8%, the secondary bromine content is higher than 97%, and the indexes such as the degree of unsaturation and the Mooney viscosity of the obtained product are good.
Description
Technical field
The invention belongs to technical field of chemistry and chemical engineering, be specifically related to a kind of production technique of brominated butyl rubber.
Technical background
Brominated butyl rubber is a kind of important rubber product, in order to overcome the slow problem of conventional butyl rubbers vulcanization rate, the nineteen fifty-three human research has gone out the bromination process of isoprene-isobutylene rubber, the more traditional isoprene-isobutylene rubber of brominated butyl rubber heat-resisting, acid and alkali-resistance, sulfurate activity, and other blend rubbers and regenerability aspect there is obvious advantage, be the main raw material of high grade air tube, the engineering automobiles inner tube of a tyre, tubeless forum air retaining wall.Along with the development of Domestic Automotive Industry, the demand for brominated butyl rubber constantly promotes at present, but China there is no ripe preparation method at present.
The bromination reaction mechanism of isoprene-isobutylene rubber is that simple substance bromine contacts with rubber rapidly the secondary position hydrogen atom on the two keys of rubber is replaced and becomes brominated butyl rubber, and reaction forms hydrogen bromide simultaneously, and unreacted bromine simple substance and hydrogen bromide neutralize finally by alkali lye.The difficult point that butyl rubber bromide composes mainly is that there are contradiction in reaction process characteristic and system performance characteristic.Aspect response characteristic, position conversion to the uncle position by secondary position easily occurs under the environment that the product brominated butyl rubber exists at hydrogen bromide to replace, the simultaneously addition of hydrogen bromide also can make the certain two keys of rubber loss, so the synthetic needs of brominated butyl rubber be swift in response initiations, the rapid neutralization.Aspect the system performance characteristic, the viscosity of the alkane solution of reactant isoprene-isobutylene rubber very high (generally being greater than 70cP), the volume ratio great disparity (being generally 1/10～1/20) of traditional bromine source---bromoalkane solution and isoprene-isobutylene rubber solution, the short mix of reactant is not easy to realize, reacts local microenvironment and is difficult to control; Neutralizer and bromination reaction liquid are immiscible profit system, and the transfer rate of product hydrogen bromide between from the oil solution to the aqueous solution needs further to strengthen, and these factors are all having a strong impact on the quality product of brominated butyl rubber.
Quick initiation based on the brominated butyl rubber building-up reactions, the ultimate principle of Quick stop, the mixed gas that the present invention proposes to using bromo-nitrogen carries out bromination reaction as the bromine source, by traditional liquid liquid system being changed into to the mixing process of gas-liquid system strengthening bromine and isoprene-isobutylene rubber solution, neutralizer and bromination reaction liquid; Use the method for Hi-mixer cascade reaction pipeline strictly to control the reaction times simultaneously, utilize kinetics difference and the time series relation thereof of bromination main reaction and transposition side reaction, reduce the probability of translocation reaction and addition reaction, thereby obtain high performance brominated butyl rubber product.
Summary of the invention
The object of the invention is to the improvement to existing brominated butyl rubber production technology, a kind of brominated butyl rubber production technique in providing.
A kind of brominated butyl rubber production technique, this technique comprises that the bromo-nitrogen mixture of bromine vaporizing system, bromo-nitrogen mixture separate four unit with hybrid reaction, the neutralizer of isoprene-isobutylene rubber solution with bromination reaction liquid hybrid reaction and tail gas, comprise that step is as follows:
(1) nitrogen buffer gas passes in the bromine vaporizer and contacts with bromine, utilizes the volatility of bromine to make the gas mixture of bromo-nitrogen;
(2) bromo-nitrogen mixture body is passed in the bromination mixing tank to the Quick uniform of realizing mixed gas and isoprene-isobutylene rubber solution and mix, start bromination reaction, the bromination reaction liquid of formation reacts in follow-up bromination reaction pipeline;
(3) by bromination reaction liquid and neutralizer in and in mixing tank the liquid Quick uniform mix, start neutralization reaction, the heterogeneous mixed stream of formation reacts in follow-up neutralization reaction pipeline;
(4) the heterogeneous mixed stream that bromination reaction liquid and neutralizer form enters the neutralization reaction still and completes neutralization reaction, product solution carries out aftertreatment from extraction at the bottom of still, tail gas (main component is nitrogen) from and the extraction of still top, can be used for the circulation bromo-nitrogen mixture body of preparation or carry out the emptying processing after purifying.
Described bromination mixing tank and in and mixing tank be selected from microstructure mixing tank, static mixer, venturi mixer or jetting type mixing tank; Service temperature is controlled at 15 ℃～45 ℃.
In described, with still, be stirring tank, service temperature is controlled at 15 ℃～45 ℃.
The massfraction of described isoprene-isobutylene rubber solution is 3%～12%, and solvent is selected from normal hexane, normal heptane or octane, and temperature is controlled at 15 ℃～45 ℃.
In the gas mixture of described bromo-nitrogen, the vapour pressure of bromine is 19kPa～54kPa, and stagnation pressure is 100kPa～300kPa; Mixture temperature is controlled at 15 ℃～45 ℃.
The mixed aqueous solution that described neutralizer is sodium hydroxide and Sodium Pyrosulfite, wherein the massfraction of sodium hydroxide is 0.1%～6%, and the massfraction of Sodium Pyrosulfite is 0.05%～3%, and temperature is controlled at 15 ℃～45 ℃.
In the bromination reaction pipeline, the reaction times of material is controlled at 0.2min～2min, and in bromo-nitrogen mixture, the mass ratio of bromine simple substance and isoprene-isobutylene rubber is 0.01～0.065.
The reaction times of material is controlled at 0.1min～1min in the neutralization reaction pipeline, in bromo-nitrogen mixture in bromine simple substance and neutralizer the mass ratio of sodium hydroxide be less than 1.0～1.8.
In and more than in still, reaction times of liquid material is controlled at 10min.
Beneficial effect of the present invention is: (1) is usingd bromo-nitrogen mixture and is replaced traditional brombutyl rubber solutions as raw material, utilizes the mixing process between gas-liquid system strengthening bromine simple substance and isoprene-isobutylene rubber solution, neutralizer and bromination reaction liquid; (2) use the method for Hi-mixer cascade reaction pipeline strictly to control the reaction times, reduce the probability of translocation reaction and addition reaction.These characteristics make novel process can obtain efficiently high-quality brominated butyl rubber product.Adopt new technology, product bromination degree can regulate and control in 0%～1.8% scope, secondary position bromine content is greater than 97%, and the rubber degree of unsaturation reduces by 0%～0.9% before and after reaction, and mooney viscosity reduces by 0～10 before and after reaction.
The accompanying drawing explanation
Fig. 1 is the brominated butyl rubber production technological process;
Wherein label is: V-bromine vaporizer; R1-bromination mixing tank; R2-in and mixing tank; R3-in and still; P1-bromination reaction pipeline; P2-neutralization reaction pipeline; C-gas treating system; 1-nitrogen; 2-bromine; 3-bromo-nitrogen mixture body; 4-isoprene-isobutylene rubber solution; 5-neutralizer (mixing solutions of sodium hydroxide and Sodium Pyrosulfite); 6-liquid product; 7-tail gas.
Embodiment
Below by example, the present invention is further described, but content not thereby limiting the invention.
Implementation process is specially the described assembling reactive system by Fig. 1, nitrogen is passed into to the bromine vaporizer and form bromo-nitrogen mixture body, the alkane solution of bromo-nitrogen mixture and isoprene-isobutylene rubber mixed being incorporated in the bromination reaction pipeline in the bromination mixing tank carried out bromination reaction, until during bromination reaction liquid enters He after mixing tank, passing into neutralizer, neutralizer and bromination reaction liquid react certain hour in the neutralization reaction pipeline, finally all materials enter in and in still and retain certain hour, in and the gas that obtains of still top emptying or return to the nitrogen delivery system after the parlkaline adsorption column.Reaction product adds stablizer from the liquid-phase outlet collection, through boiling water treating, after opening refining, makes solid sample, sample bromination degree and brothers position ratio by nuclear-magnetism measure, degree of unsaturation measures by the mooney viscosity instrument by titrimetry, mooney viscosity.Result of implementation is as follows:
Embodiment 1:
Pass into nitrogen at the bromine evaporator inlet, obtaining temperature is 15 ℃, pressure is 100kPa, bromine vapor is pressed as the gas mixture of 19kPa, after mixing, the isoprene-isobutylene rubber hexane solution that is 15 ℃ of massfractions 3% with temperature by this gas mixture (a kind of microstructure mixing tank) in a micro-channel mixer flows into bromination reaction pipeline (bromine/isoprene-isobutylene rubber mass ratio is 0.04), the neutralizer that it is 25 ℃ at another Microtraps hole mixing tank (a kind of microstructure mixing tank) with temperature that material reacts after 1min in the bromination reaction pipeline mixes that (massfraction of sodium hydroxide is 1.1%, the massfraction of Sodium Pyrosulfite is 0.5%, bromine/sodium hydroxide mass ratio is 1.60), during material reacts after 1min and flows in the neutralization reaction pipeline and still (18 ℃ of temperature), liquid material in and still in the reaction times be 10min.Product isoprene-isobutylene rubber bromination degree is 1.33%, secondary position bromine content 98.1%, degree of unsaturation is 1.20%(initial rubber degree of unsaturation 1.9%), mooney viscosity 33(initial rubber Mooney 40).
Embodiment 2:
Pass into nitrogen at the bromine evaporator inlet, obtaining temperature is 15 ℃, pressure is 300kPa, bromine vapor is pressed as the gas mixture of 19kPa, after mixing in a micro-channel mixer, the isoprene-isobutylene rubber hexane solution that is 15 ℃ of massfractions 5% with temperature by this gas mixture flows into bromination reaction pipeline (bromine/isoprene-isobutylene rubber mass ratio is 0.041), material reacts after 1min and flows into neutralizer that another micro-channel mixer is 15 ℃ with temperature and mix that (massfraction of sodium hydroxide is 1.1% in the bromination reaction pipeline, the massfraction of Sodium Pyrosulfite is 0.5%, bromine/sodium hydroxide mass ratio is 1.8), during material reacts after 0.1min and flows in the neutralization reaction pipeline and still (15 ℃ of temperature, the pressure normal pressure), liquid material in and still in the reaction times be 11min.Product isoprene-isobutylene rubber bromination degree is 1.21%, secondary position bromine content 99.4%, degree of unsaturation is 1.31%(initial rubber degree of unsaturation 1.9%), mooney viscosity 32(initial rubber Mooney 40).
Embodiment 3:
Pass into nitrogen at the bromine evaporator inlet, obtaining temperature is 25 ℃, pressure is 200kPa, bromine vapor is pressed as the gas mixture of 29kPa, after mixing in a Microtraps hole mixing tank, the isoprene-isobutylene rubber hexane solution that is 25 ℃ of massfractions 5% with temperature by this gas mixture flows into bromination reaction pipeline (bromine/isoprene-isobutylene rubber mass ratio is 0.038), material reacts after 2min and flows into neutralizer that another Microtraps hole mixing tank is 25 ℃ with temperature and mix that (massfraction of sodium hydroxide is 1.1% in the bromination reaction pipeline, the massfraction of Sodium Pyrosulfite is 0.5%, bromine/sodium hydroxide mass ratio is 1.57), during material reacts after 0.1min and flows in the neutralization reaction pipeline and still (25 ℃ of temperature, the pressure normal pressure), liquid material in and still in the reaction times be 11min.Product isoprene-isobutylene rubber bromination degree is 1.41%, secondary position bromine content 99.0%, degree of unsaturation is 1.14%(initial rubber degree of unsaturation 1.9%), mooney viscosity 30(initial rubber Mooney 40).
Embodiment 4:
Pass into nitrogen at the bromine evaporator inlet, obtaining temperature is 25 ℃, pressure is 200kPa, bromine vapor is pressed as the gas mixture of 29kPa, after mixing in jet mixer, the isoprene-isobutylene rubber hexane solution that is 25 ℃ of massfractions 5% with temperature by this gas mixture flows into bromination reaction pipeline (bromine/isoprene-isobutylene rubber mass ratio is 0.01), material reacts after 2min and flows into neutralizer that another jet mixer is 25 ℃ with temperature and mix that (massfraction of sodium hydroxide is 0.1% in the bromination reaction pipeline, the massfraction of Sodium Pyrosulfite is 0.05%, bromine/sodium hydroxide mass ratio is 1.0), during material reacts after 0.3min and flows in the neutralization reaction pipeline and still (25 ℃ of temperature, the pressure normal pressure), liquid material in and still in the reaction times be 10min.Product isoprene-isobutylene rubber bromination degree is 0.38%, secondary position bromine content 99.7%, degree of unsaturation is 1.58%(initial rubber degree of unsaturation 1.9%), mooney viscosity 37(initial rubber Mooney 40).
Embodiment 5:
Pass into nitrogen at the bromine evaporator inlet, obtaining temperature is 25 ℃, pressure is 300kPa, bromine vapor is pressed as the gas mixture of 29kPa, after mixing in a Microtraps hole mixing tank, the isoprene-isobutylene rubber hexane solution that is 25 ℃ of massfractions 12% with temperature by this gas mixture flows into bromination reaction pipeline (bromine/isoprene-isobutylene rubber mass ratio is 0.026), material reacts after 0.2min neutralizer that to flow in a static mixer be 25 ℃ with temperature and mixes that (massfraction of sodium hydroxide is 6% in the bromination reaction pipeline, the massfraction of Sodium Pyrosulfite is 3%, bromine/sodium hydroxide mass ratio is 1.71), during material reacts after 0.22min and flows in the neutralization reaction pipeline and still (25 ℃ of temperature, the pressure normal pressure), liquid material in and still in the reaction times be 15min.Product isoprene-isobutylene rubber bromination degree is 0.32%, secondary position bromine content 100%, degree of unsaturation is 1.82%(initial rubber degree of unsaturation 1.9%), mooney viscosity 39(initial rubber Mooney 40).
Embodiment 6:
Pass into nitrogen at the bromine evaporator inlet, obtaining temperature is 45 ℃, pressure is 100kPa, bromine vapor is pressed as the gas mixture of 54kPa, after mixing in a venturi mixer, the isoprene-isobutylene rubber n-heptane solution that is 45 ℃ of massfractions 6% with temperature by this gas mixture flows into bromination reaction pipeline (bromine/isoprene-isobutylene rubber mass ratio is 0.065), material reacts after 2min neutralizer that to flow in another venturi mixer be 45 ℃ with temperature and mixes that (massfraction of sodium hydroxide is 0.5% in the bromination reaction pipeline, the massfraction of Sodium Pyrosulfite is 0.25%, bromine/sodium hydroxide mass ratio is 1.41), during material reacts after 0.12min and flows in the neutralization reaction pipeline and still (25 ℃ of temperature, the pressure normal pressure), liquid material in and still in the reaction times be 10min.Product isoprene-isobutylene rubber bromination degree is 1.8%, secondary position bromine content 97.1%, degree of unsaturation is 1.02%(initial rubber degree of unsaturation 1.9%), mooney viscosity 40(initial rubber Mooney 50).
Embodiment 7:
Pass into nitrogen at the bromine evaporator inlet, obtaining temperature is 45 ℃, pressure is 300kPa, bromine vapor is pressed as the gas mixture of 54kPa, after mixing in a jet mixer, the isoprene-isobutylene rubber octane solution that is 45 ℃ of massfractions 5.6% with temperature by this gas mixture flows into bromination reaction pipeline (bromine/isoprene-isobutylene rubber mass ratio is 0.039), material reacts after 1.1min neutralizer that to flow in another jet mixer be 25 ℃ with temperature and mixes that (massfraction of sodium hydroxide is 0.5% in the bromination reaction pipeline, the massfraction of Sodium Pyrosulfite is 0.25%, bromine/sodium hydroxide mass ratio is 1.4), during material reacts after 1min and flows in the neutralization reaction pipeline and still (35 ℃ of temperature, the pressure normal pressure), liquid material in and still in the reaction times be 10min.Product isoprene-isobutylene rubber bromination degree is 1.35%, secondary position bromine content 97.4%, degree of unsaturation is 1.12%(initial rubber degree of unsaturation 1.9%), mooney viscosity 42(initial rubber Mooney 50).
Claims (9)
1. a brominated butyl rubber production technique, it is characterized in that, this technique comprises that the bromo-nitrogen mixture of bromine vaporizing system, bromo-nitrogen mixture separate four unit with hybrid reaction, the neutralizer of isoprene-isobutylene rubber solution with bromination reaction liquid hybrid reaction and tail gas, comprise that step is as follows:
(1) nitrogen buffer gas passes in the bromine vaporizer and contacts with bromine, utilizes the volatility of bromine to make the gas mixture of bromo-nitrogen;
(2) bromo-nitrogen mixture body is passed in the bromination mixing tank to the Quick uniform of realizing mixed gas and isoprene-isobutylene rubber solution and mix, start bromination reaction, the bromination reaction liquid of formation reacts in follow-up bromination reaction pipeline;
(3) by bromination reaction liquid and neutralizer in and in mixing tank the liquid Quick uniform mix, start neutralization reaction, the heterogeneous mixed stream of formation reacts in follow-up neutralization reaction pipeline;
(4) the heterogeneous mixed stream that bromination reaction liquid and neutralizer form enters the neutralization reaction still and completes neutralization reaction, product solution carries out aftertreatment from extraction at the bottom of still, tail gas from and the extraction of still top, can be used for the circulation bromo-nitrogen mixture body of preparation or carry out the emptying processing after purifying.
2. a kind of brominated butyl rubber production technique according to claim 1 is characterized in that: described bromination mixing tank and in and mixing tank be selected from microstructure mixing tank, static mixer, venturi mixer or jetting type mixing tank; Service temperature is controlled at 15 ℃～45 ℃.
3. a kind of brominated butyl rubber production technique according to claim 1 is characterized in that: in described and still be stirring tank, service temperature is controlled at 15 ℃～45 ℃.
4. a kind of brominated butyl rubber production technique according to claim 1, it is characterized in that: the massfraction of described isoprene-isobutylene rubber solution is 3%～12%, and solvent is selected from normal hexane, normal heptane or octane, temperature is controlled at 15 ℃～45 ℃.
5. a kind of brominated butyl rubber production technique according to claim 1, it is characterized in that: in the gas mixture of described bromo-nitrogen, the vapour pressure of bromine is 19kPa～54kPa, stagnation pressure is 100kPa～300kPa; Mixture temperature is controlled at 15 ℃～45 ℃.
6. a kind of brominated butyl rubber production technique according to claim 1, it is characterized in that: the mixed aqueous solution that described neutralizer is sodium hydroxide and Sodium Pyrosulfite, wherein the massfraction of sodium hydroxide is 0.1%～6%, the massfraction of Sodium Pyrosulfite is 0.05%～3%, and temperature is controlled at 15 ℃～45 ℃.
7. a kind of brominated butyl rubber production technique according to claim 1 is characterized in that: in the bromination reaction pipeline, the reaction times of material is controlled at 0.2min～2min, and in bromo-nitrogen mixture, the mass ratio of bromine simple substance and isoprene-isobutylene rubber is 0.01～0.065
8. a kind of brominated butyl rubber production technique according to claim 1, it is characterized in that: the reaction times of material is controlled at 0.1min～1min in the neutralization reaction pipeline, in bromo-nitrogen mixture in bromine simple substance and neutralizer the mass ratio of sodium hydroxide be less than 1.0～1.8.
9. a kind of brominated butyl rubber production technique according to claim 1 is characterized in that: in and more than in still, the reaction times of liquid material is controlled at 10min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105218719A (en) * | 2014-06-16 | 2016-01-06 | 中国石油化工股份有限公司 | The method preparing halogenated butyl rubber and the halogenated butyl rubber obtained thus |
| EP3110883B1 (en) * | 2014-02-28 | 2018-10-10 | ExxonMobil Chemical Patents Inc. | Mooney viscosity stable brominated elastomers |
| CN108794307A (en) * | 2018-07-18 | 2018-11-13 | 山东道可化学有限公司 | A kind of micro- reaction system and method for the solvent method synthesis bromo- 3- methylanisoles of 4- |
| CN111141773A (en) * | 2019-12-31 | 2020-05-12 | 湖北亿纬动力有限公司 | Negative plate binder distribution detection method and dyeing device |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3110883B1 (en) * | 2014-02-28 | 2018-10-10 | ExxonMobil Chemical Patents Inc. | Mooney viscosity stable brominated elastomers |
| US10781295B2 (en) | 2014-02-28 | 2020-09-22 | Exxonmobil Chemical Patents Inc. | Mooney viscosity stable brominated elastomers |
| CN105218719A (en) * | 2014-06-16 | 2016-01-06 | 中国石油化工股份有限公司 | The method preparing halogenated butyl rubber and the halogenated butyl rubber obtained thus |
| CN105218719B (en) * | 2014-06-16 | 2017-06-06 | 中国石油化工股份有限公司 | Prepare the method and thus obtained halogenated butyl rubber of halogenated butyl rubber |
| CN108794307A (en) * | 2018-07-18 | 2018-11-13 | 山东道可化学有限公司 | A kind of micro- reaction system and method for the solvent method synthesis bromo- 3- methylanisoles of 4- |
| CN108794307B (en) * | 2018-07-18 | 2022-11-11 | 山东道可化学有限公司 | Micro-reaction system and method for synthesizing 4-bromo-3-methylanisole by solvent method |
| CN111141773A (en) * | 2019-12-31 | 2020-05-12 | 湖北亿纬动力有限公司 | Negative plate binder distribution detection method and dyeing device |
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