CN101062962A - Preparation method of polyisobutylene - Google Patents
Preparation method of polyisobutylene Download PDFInfo
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- CN101062962A CN101062962A CN 200610076695 CN200610076695A CN101062962A CN 101062962 A CN101062962 A CN 101062962A CN 200610076695 CN200610076695 CN 200610076695 CN 200610076695 A CN200610076695 A CN 200610076695A CN 101062962 A CN101062962 A CN 101062962A
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- iso
- butylene
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- titanium tetrachloride
- title complex
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- 229920002367 Polyisobutene Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims description 10
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 51
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 24
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 150000001298 alcohols Chemical class 0.000 claims abstract description 7
- 150000002170 ethers Chemical class 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 15
- 239000004615 ingredient Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000000694 effects Effects 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 239000000178 monomer Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000000710 polymer precipitation Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 238000010538 cationic polymerization reaction Methods 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 3
- -1 alkyl compound Chemical group 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- JUHDUIDUEUEQND-UHFFFAOYSA-N methylium Chemical compound [CH3+] JUHDUIDUEUEQND-UHFFFAOYSA-N 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000010552 living cationic polymerization reaction Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparing method of polyisobutene, which comprises the following steps: adopting alcohols or ethers organic complex in liquid phase isobutene raw material; comprising with titanic chloride as initiated system; triggering isobutene or hydrocarbons mixture with isobutene or isobutene ingredient in mixing light C4 fraction with isobutene; proceeding basic ion polymerization; adopting one step method; preparing high reaction active polyisobutene product with number average molecular weight at 500-6000 Dalton, end-group alpha-double bond content not less than 70% mol and special merit more than 80% mol. This system is cheap and possesses higher active and adaptability, which can simplify process of polymerization reaction.
Description
Technical field
The present invention relates to a kind of method that is used to prepare polyisobutene, particularly with containing the initiator system of titanium tetrachloride, to the hydrocarbon mixture of iso-butylene, iso-butylene or contain the light C of mixing of iso-butylene
4Cut carries out the method that carbon cation polymerization prepares high-activity polyisobutylene under liquid phase.
Background technology
Lewis acid causes the alkene carbon cation polymerization altogether, and to prepare polyisobutene (PIB) be known method.This type of Lewis acid is the halogenide of aluminium, iron, zinc, titanium, tin, mercury or boron normally.Yet, in the carbon cation polymerization reaction process, carbocation active centre less stable, easily take place to a series of side reactions such as monomer chain transfer reaction, intramolecularly alkylated reactions, react wayward, so the polyisobutene end of preparation has chemically active α-double bond content generally about 10% (mole), is referred to as common polyisobutene." high reaction activity " polyisobutene product is different with common polyisobutene product, its terminal α-double bond content 〉=70% (mole), therefore the terminal double link content that improves in the polyisobutene product is a target of studying for a long time, and improves and improve the reactive behavior of polyisobutene emphatically from the research initiator system.
The effective system that is used to prepare high-activity polyisobutylene at present is to contain boron trifluoride (BF
3) with the initiator system of alcohol and/or ether.In public technology, used BF
3The title complex initiator system is normally by BF
3Cooperate and form with the secondary alcohol of 3～20 carbon atoms and/or uncle's ether of 4～20 carbon atoms (at least one tertiary carbon atom links to each other with Sauerstoffatom in the ether).Using the method for this initiator system to describe can be referring to US4605808, in the patents such as US5068490 and DE4033196, can prepare α-terminal double link content greater than 80% polyisobutene.Yet boron trifluoride corrodibility is strong, and costs an arm and a leg.
In public technology, adopt non-BF in addition
3Initiator system, but effect is relatively poor relatively.Disclose a kind of be used to the cause molybdate of iso-butylene cationoid polymerisation or the heteropolyacid of tungstate as US64441110, can prepare vinylidene content greater than 50% polyisobutene.
Proposing to adopt tertiary alkyl compound (A) among US5122572 and the US5169914 is that initiator cooperates the initiator system of forming with Lewis acid (boron trichloride or titanium tetrachloride) for coinitiator, realize the iso-butylene living cationic polymerization, and generate the polyisobutene product of terminal group structure without any exception for uncle's cl radical.Wherein the structure of A is as follows:
R
1, R
2And R
3Be can be identical or different alkyl, aryl or aralkyl, X is ester group, ether or hydroxyl, i is a positive integer.
Therefore, adopt TiCl
4Cause the iso-butylene living cationic polymerization altogether, simply single stage method obtains the high-activity polyisobutylene product, and containing of obtaining after further removing hydrogenchloride, uncle's chlorine end group polyisobutene just can only be obtained high-activity polyisobutylene usually, numerousization flow process, and remove and produce the internal double bond product in the hydrogenchloride process inevitably.
Summary of the invention
The present invention uses the suitable oxygen organic coordination compound that contains to participate in TiCl
4Cause the iso-butylene cationoid polymerisation altogether, reduce generating uncle's chlorine terminal group structure in the polymerization process, promote that β-proton removes reaction generation terminal α-two keys in the carbocation of active centre, thereby develop a kind of TiCl cheap and easy to get that adopts
4Cause the iso-butylene cationoid polymerisation altogether, single stage method obtains the method for high-activity polyisobutylene, and can simplify reaction process, reduces production costs.
Method of the present invention: in liquid phase iso-butylene material system, adopt alcohols or ethers organic coordination compound and titanium tetrachloride to form initiator system, cause isobutene polymerisation, wherein, the mol ratio of title complex and titanium tetrachloride is 0.002～0.5, the titanium tetrachloride mole dosage be in the polymer raw the iso-butylene amount 0.01～0.10.
In above-mentioned alcohols or the ethers oxygenated organic coordination compound, the preferred C of alcohol compound
1～C
5Alcohol, as: methyl alcohol, ethanol, n-propyl alcohol, Virahol; The preferred C of ether compound
3～C
4Ether, as: methyl ethyl ether, ether.Regulate in the iso-butylene cationic polymerization active centre gegenion to the nucleophilicity of carbocation by selecting title complex provided by the invention, thereby can impel polyisobutene molecular chain-end active centre carbocation generation β-H to remove and generate terminal α-two keys, and reduce the reaction probability that α-double-bond isomerism turns to internal double bond, to obtain the polyisobutene of high terminal double link content.
The mole proportion optimization 0.004～0.3 of above-mentioned title complex and titanium tetrachloride.Too high proportioning can cause productive rate to descend, and low excessively proportioning then can't suppress the uncontrollable initiation of water, and it is bimodal to cause product GPC to occur, and more importantly is that the mole proportioning of too high and low excessively title complex and titanium tetrachloride all can hinder the generation of terminal α-two keys.The catalyzer that oxygen-containing organic compound title complex and titanium tetrachloride are formed can prepare in advance, also can generate immediately in polymerization system.
Above-mentioned titanium tetrachloride consumption is to decide according to the molecular weight and the temperature of reaction of polymerisate, and except other factors, the molecular weight of polyisobutene depends on that titanium tetrachloride and title complex are with respect to used monomeric amount.Should reduce titanium tetrachloride and title complex consumption to reduce unnecessary isomerization reaction and to reduce cost as far as possible.The titanium tetrachloride preferable amount is 0.04～0.08 (mole) of the iso-butylene amount in the polymer raw.
Above-mentioned iso-butylene raw material can be the C that the by product of pure iso-butylene, petroleum cracking or the generation of catalytic cracking system ethene contains components such as iso-butylene, butene-1, butene-2 and butane
4Cut, or contain the hydrocarbon mixture of iso-butylene, contain hydrocarbon compound in the mixture, as butane, pentane, hexane or octane-iso, or halohydrocarbon such as methylene dichloride or trichloromethane.
Solvent is the saturated hydrocarbons solvent in the above-mentioned liquid phase iso-butylene polymerizable raw material system, as common: butane, pentane, hexane or octane-iso, or halohydrocarbon such as methylene dichloride or trichloromethane and their mixture thereof.Iso-butylene carries out polyreaction in saturated hydrocarbons solvent polymeric system.
Polyreaction of the present invention can be to carry out off and on or continuously under popular response device and processing condition; Polymerization temperature is-45 ℃～+ 20 ℃, preferred-40 ℃～0 ℃.Polymerization reaction time is 1～120 minute, and preferred 5～70 minutes, this depended on the performance index of reaction conditions and polymerisate.Polyreaction adds excessive alkaline matter after for some time, as the aqueous solution that contains NaOH, alcohol or ammonia makes the initiator system inactivation and stops polyreaction to reaction solution.
After stopping polymerization, after the evaporation of components such as unreacted monomer and solvent, with the deionized water wash polymerisate to remove the initiator system resistates of inactivation, after vacuum-drying obtains polymerisate.With the molecular weight and the molecular weight distribution of GPC test polymer, characterize and measure the end-group structure (CDCl of polymkeric substance with NMR
3Solvent, the agent of TMS standard).
The inventive method cooperates with titanium tetrachloride by alcohols or ethers oxygenated organic compound and forms initiator system, thereby impel polyisobutene molecular chain-end active centre carbocation generation β-H to remove and generate terminal α-two keys, and reduce activity and the reaction probability that α-double-bond isomerism turns to the low activity internal double bond, obtain the polyisobutene of high terminal α-double bond content.Simultaneously can be according to the molecular weight of polyisobutene, the consumption of control title complex has been realized from pure iso-butylene and is contained the hydrocarbon mixture of iso-butylene or contain the light C of mixing of iso-butylene
4It is 500～6000 that feedstock prepares number-average molecular weight, preferred 1000～6000 dalton and end group α-double bond content 〉=70%mol, more excellent high-activity polyisobutylene product greater than 80%mol.
Embodiment
The present invention may be better understood by following examples, although provided these embodiment, also should comprise: do not departing under the scope of the invention condition, disclosed method is carried out the conspicuous various changes of those skilled in the art.
Embodiment 1
Under the high pure nitrogen protection; the methyl alcohol and the 1.5mmol titanium tetrachloride initiated polymerization that in the monomer solution (isobutylene concentration is 1.5mol/L) of 25mL iso-butylene/hexanes/ch, add 0.15mmol; behind-30 ℃ of reaction 10min; the NaOH/ ethanolic soln termination reaction that adds 1mL 0.1g/L; add ethanol and make polymer precipitation, and repeatedly with washing with alcohol to the clear shape.Monomer conversion is 73%, obtains number-average molecular weight and be 1400, molecular weight distributing index is 1.6, α-double bond content is 70%, uncle's chlorine endgroup content is 30% high-activity polyisobutylene.
Embodiment 2
Under the high pure nitrogen protection; the methyl alcohol and the 1.5mmol titanium tetrachloride initiated polymerization that in the monomer solution (isobutylene concentration is 1.5mol/L) of 25mL iso-butylene/hexanes/ch, add 0.4mmol; after reacting 60min under-30 ℃; the NaOH/ ethanolic soln termination reaction that adds 1mL 0.1g/L; add ethanol and make polymer precipitation, and repeatedly with washing with alcohol to the clear shape.Monomer conversion is 95.7%, obtains number-average molecular weight and be 1400, molecular weight distributing index is 1.5, α-double bond content is 87%, uncle's chlorine endgroup content is 13% high-activity polyisobutylene.
Embodiment 3
Under the high pure nitrogen protection; the Virahol and the 3.0mmol titanium tetrachloride initiated polymerization that in the monomer solution (isobutylene concentration is 1.5mol/L) of 25mL iso-butylene/hexanes/ch, add 0.45mmol; after reacting 60min under-30 ℃; the NaOH/ ethanolic soln termination reaction that adds 1mL 0.1g/L; add ethanol and make polymer precipitation, and repeatedly with washing with alcohol to the clear shape.Monomer conversion is 27.3%, obtains number-average molecular weight and be 1600, molecular weight distributing index is 2.3, α-double bond content is 79%, uncle's chlorine endgroup content is 21% high-activity polyisobutylene.
Embodiment 4
Under the high pure nitrogen protection; the ether and the 2.0mmol titanium tetrachloride initiated polymerization that in the monomer solution (isobutylene concentration is 1.5mol/L) of 25mL iso-butylene/hexanes/ch, add 0.2mmol; behind-30 ℃ of reaction 60min; the NaOH/ ethanolic soln termination reaction that adds 1mL 0.1g/L; add ethanol and make polymer precipitation, and repeatedly with washing with alcohol to the clear shape.Monomer conversion is 81.1%, obtains number-average molecular weight and be 2000, molecular weight distributing index is 2.4, α-double bond content is 73%, β-internal double bond content is 10%, uncle's chlorine endgroup content is 17% high-activity polyisobutylene.
Embodiment 5
Under the high pure nitrogen protection, mix light C to 35mL
4The methyl alcohol and the 10.6mmol titanium tetrachloride initiated polymerization that add 0.05mmol in the cut (isobutylene concentration is 5.1mol/L), behind-35 ℃ of reaction 120min, the NaOH/ ethanolic soln termination reaction that adds 3mL0.1g/L, add ethanol and make polymer precipitation, and repeatedly with washing with alcohol to the clear shape.Monomer conversion is 14%, obtains molecular-weight average and be 5800, α-double bond content is 70%, uncle's chlorine endgroup content is 30% high-activity polyisobutylene.
Claims (7)
1, a kind of preparation method of polyisobutene, it is characterized in that: in liquid phase iso-butylene polymerizable raw material system, adopt alcohols or ethers organic coordination compound and titanium tetrachloride to form initiator system, cause isobutene polymerisation, wherein, the mol ratio of title complex and titanium tetrachloride is 0.002～0.5, the titanium tetrachloride mole dosage be in the polymer raw the iso-butylene amount 0.01～0.10.
2, preparation method according to claim 1 is characterized in that, the alcohols title complex is selected from C
1～C
3Alcohol; The ethers title complex is selected from C
3～C
4Ether.
3, preparation method according to claim 1 is characterized in that, the alcohols title complex is selected from methyl alcohol, ethanol, n-propyl alcohol, Virahol; The ethers title complex is selected from: methyl ethyl ether, ether.
4, preparation method according to claim 1 is characterized in that, the mole proportioning of title complex and titanium tetrachloride is 0.004-0.30.
5, preparation method according to claim 1 is characterized in that, the titanium tetrachloride mole dosage be in the polymer raw iso-butylene amount 0.04～0.08.
6, preparation method according to claim 1 is characterized in that, polymerization temperature is-40 ℃～0 ℃.
7, preparation method according to claim 1 is characterized in that, the iso-butylene raw material is pure iso-butylene, or contains the hydrocarbon mixture of iso-butylene, or contains the light C of mixing of iso-butylene
4Cut.
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| CNB2006100766957A CN100506855C (en) | 2006-04-29 | 2006-04-29 | Preparation method of polyisobutylene |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464736A (en) * | 2010-11-19 | 2012-05-23 | 北京化工大学 | Process method for preparing polyisobutene and polymerization device |
| CN103965383A (en) * | 2013-02-01 | 2014-08-06 | 北京化工大学 | Preparation method for polyisobutylene with high reaction activity |
| CN113661185B (en) * | 2019-08-19 | 2023-12-29 | 株式会社Lg化学 | Organoborate catalyst, process for producing isobutylene oligomer using the same, and isobutylene oligomer produced thereby |
-
2006
- 2006-04-29 CN CNB2006100766957A patent/CN100506855C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464736A (en) * | 2010-11-19 | 2012-05-23 | 北京化工大学 | Process method for preparing polyisobutene and polymerization device |
| CN102464736B (en) * | 2010-11-19 | 2013-07-24 | 北京化工大学 | Process method for preparing polyisobutene and polymerization device |
| CN103965383A (en) * | 2013-02-01 | 2014-08-06 | 北京化工大学 | Preparation method for polyisobutylene with high reaction activity |
| CN113661185B (en) * | 2019-08-19 | 2023-12-29 | 株式会社Lg化学 | Organoborate catalyst, process for producing isobutylene oligomer using the same, and isobutylene oligomer produced thereby |
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| Publication number | Publication date |
|---|---|
| CN100506855C (en) | 2009-07-01 |
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