CN102807640B - Initiation system based on boron trifluoride and method for preparing polyisobutylene using initiation system - Google Patents
Initiation system based on boron trifluoride and method for preparing polyisobutylene using initiation system Download PDFInfo
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Abstract
The invention relates to an initiation system based on boron trifluoride and a method for preparing polyisobutylene using the initiation system. The initiation system is composed of BF3, a proton donor and an electron donor, wherein the proton donor can be selected from water, methanol, ethanol, phenol, orthocresol, aromatic alcohol or aromatic acid compound; and the electron donor is an organic compound containing C3-C10 saturated oxa heterocyclic ether, cyclic amine aza heterocycle or epithio ether heterocycle. Two kinds of polyisobutylene with different molecular weights and narrower molecular weight distribution can be prepared according to needs by using the initiation system and adopting a common tank reactor: (1) medium-molecular-weight polyisobutylene, which has the molecular weight of 5*10<4>-1.5*10<5>, narrower molecular weight distribution and distribution index number (Mw/Mn) of 2.3-3.5; and (2) high-molecular-weight polyisobutylene, which has the molecular weight of 2.0*10<5>-1.5*10<6>, narrower molecular weight distribution and distribution index number (Mw/Mn) of 2.3-3.5. The production process is simple and the production cost is saved.
Description
Technical field
The present invention relates to a kind of based on boron trifluoride (BF
3) initiator system and for the preparation of the method for polyisobutene.Be specifically related to adopt the initiator system being comprised of initiator, boron trifluoride and organic compound part, Isobutylene Initiated carries out cationoid polymerisation in liquid phase, the polyisobutene of molecular weight and high molecular series in preparation.
Background technology
Polyisobutene is a kind of broad-spectrum polymkeric substance, and according to the difference of molecular weight, its range of application is not identical yet.Low-molecular-weight polyisobutylene, its number-average molecular weight (M
n) between 500～5000, mainly as lubricating oil additive, mythimna separata agent, electrical equipment cable insulation wet goods; The weight-average molecular weight of middle molecular weight polyisoprene iso-butylene is conventionally 3 * 10
4～1.5 * 10
5between, mainly as sealing agent, sizing agent, chewing gum base, paraffin modification agent, asphalt modifier etc.; The weight-average molecular weight of high molecular weight polyisobutylene is greater than 2 * 10 conventionally
5, mainly as sealing material, adhesive backers, rubber mixture etc.At present, based on BF
3initiator system is more common for the preparation of polyisobutene technology, the polyisobutene product of preparation through aftertreatment can reach medical or edible rank (referring to Chemical Manufacture and technology, 2008, (02): 15).Existing based on BF
3the initiator system of preparing polyisobutene, is used for preparing low-molecular-weight polyisobutene product, as disclosed with BF in US5286823
3the tertiary ether complex catalysis system Isobutylene Initiated of the secondary alcohol of/3～20 carbon atoms and/or 2～20 carbon atoms is at-40～+ 20 ℃, under 1～20bar condition, occur cationoid polymerisation prepare molecular weight 500～5000, end α-double bond content is higher than the lower molecular weight high-activity polyisobutylene of 80mol%, wherein BF
3and the molar ratio of alcohol or ether is between 0.4～0.95.In order to improve catalyst stability, employing BF is disclosed in CN 1176124C
3, the alcohol of 1～10 carbon atom and the catalyst system that alkyl ether benzene forms, at 0～-30 ℃, prepare lower molecular weight high-activity polyisobutylene, wherein BF
3with the mol ratio of alcohol and alkyl ether benzene be 1.25～2.0.In order to improve the solvability in polymer raw of catalyzer and to reduce fluorine content in polymkeric substance, at US2008/0249268 and CN101287770A, disclose a kind of by (BF
3)
a(L
1)
b(L
2)
c(L
3)
dthe initiator system forming, L
1for " initiator ", be selected from water, uncle C
1～C
5alkanol, secondary C
3～C
5alkanol and uncle C
1～C
5alkanol and/or secondary C
3～C
5the mixture of alkanol and tert-alkyl ether, L
1/ BF
3(mol ratio) is 0.5～3.0; L
2for conditioning agent, be at least one aldehyde and/or ketone, L
2/ BF
3(mol ratio) is 0～0.5; L
3for solubilizing agent, increase the solubleness of catalyzer in raw material, be selected from least 5 carbon atoms tert-alkyl ether, have the alkanol of at least 6 carbon atoms, L
3/ BF
3(mol ratio) is 0～1.0, and the end group α-double bond content of gained low-molecular-weight polyisobutylene is greater than 50mol%.A kind of employing is disclosed in CN1176123C with carbonyl or ester group organic compound part and BF
3form initiator system and cause IB polymerization, prepare molecular weight 300～5000, terminal double link content reaches more than 80% low-molecular-weight high-activity polyisobutene, organic compound part and BF
3mol ratio be 0.5～3.0.Disclosed BF in above-mentioned patent
3the polymerization of initiator system Isobutylene Initiated, all exist serious β-H to remove reaction, cause the interruption reaction of polymer chain, be difficult to improve the molecular weight of polyisobutene, even if (-4～-30 ℃ conventionally), also can only obtain molecular weight and be less than 1.0 * 10 at a lower temperature
4(be conventionally less than 6.0 * 10
3) the end low-molecular-weight polyisobutylene product that contains α-bis-keys.
About intermediate molecular weight polyisobutene, conventionally adopt BF
3and the initiator system of alcohol (as Virahol) composition, Isobutylene Initiated carries out cationic polymerization in hexane solvent at-10～-60 ℃ to be prepared.US5910550 discloses a kind of by BF
3in/water, alcohol, ether, organic acid, phenol a kind of (0.3～1, mol ratio) initiator system forming causes the hydrocarbon material polymerization of IB weight fraction 30～70%, prepare medium contents of ethylene (> 50mol%), number-average molecular weight is in the method for 5000～80000 polyisobutene, but the product polyisobutene molecular weight that the method makes is in an embodiment lower, weight-average molecular weight (M
w) be less than 3.5 * 10
4.
Prepare the existing initiator system of high molecular weight polyisobutylene normally by BF
3and alcohol (as Virahol) composition, and need under extremely low temperature (as-104 ℃), carry out polyreaction, could obtain sufficiently high molecular weight.At US 4391959, employing BF is disclosed
3/ C
1～C
10primary alconol or secondary alcohol system (conventionally adopting Virahol) cause IB and in ethene medium, under low temperature, carry out cationoid polymerisation, wherein initiator system is 0.01～0.1% of iso-butylene weight fraction, prepares molecular weight 1.0 * 10
5～3.0 * 10
5polyisobutene, the method polymerization temperature is low, consume energy high, speed of reaction is exceedingly fast, and completes in the several seconds, the exothermic heat of reaction of moment makes ethene evaporation, so high to equipment requirements, need on the transmission steel band of particular design, (wide 50cm, long 16～18m) carry out successive reaction, but polyisobutene has visco-elasticity, to operating process, bring great difficulty; Because rate of polymerization is fast, polymerization exotherm is concentrated greatly, causes reaction process to be difficult to regulation and control, can cause polymer molecular weight to distribute wide, in addition,, in disclosed four embodiment, polymerization temperature is-104 ℃, the molecular weight ranges of synthesized polyisobutene is 183,000～280,000.For improving the problems such as the banded reactor apparatus complexity of transmission and the more difficult control of operation, in DE102005048698.3, EP06120781.7 and CN101287769A, disclose a kind of method that mixture that adopts iso-butylene and inert diluent contacts with catalyzer in the gas space of polymerization unit and prepared high molecular weight polyisobutylene, simplified conversion unit, though can make the polyisobutene product of high molecular, but molecular weight distribution is wide, from embodiment, can find out that molecular weight distributing index is generally between 4.2～6.1.
In sum, at existing BF
3in the initiator system forming with organic compound part, the main and BF of organic compound part wherein
3complexing, reduces BF
3lewis acid, some part, as alcohol or tert-alkyl ether, also plays initiator effect, some part is in order to increase the solvability of complex compound and to play modulator effect.The main technical barrier existing is: catalyzer is unstable, easily layering; The problem that exists β-H to remove while being difficult to solve Isobutylene Initiated polymerization, thus cause being difficult to improve the molecular weight of polyisobutene, therefore at polymerization temperature, higher than-30 ℃ in the situation that, conventionally can only obtain the polyisobutene of lower molecular weight high reaction activity; Production unit for the preparation of middle molecular weight and high molecular weight polyisobutylene is complicated, and high to equipment requirements, as belting, production cost is high, and the molecular weight distribution of gained polyisobutene is wider; The by product C-4-fraction polymerization that is difficult to directly to cause petroleum cracking or catalytic cracking synthesize in the polyisobutene product of molecular weight; Need extremely low polymerization temperature (as-104 ℃, ethene boiling point), could obtain the polyisobutene product of high molecular, consume energy high.Above-mentioned these technical problems, relevant with the Activity and stabill in active centre, also with the chemical structure of the organic coordination compound of selecting and relevant with the synergy of catalyzer.
Summary of the invention
The invention provides a kind of based on BF
3the initiator system of (A component) and for the preparation of the method for polyisobutene, adopt two kinds of protophobe and electron donors that effect is different, by the polymerization of proton Isobutylene Initiated, negative ion part in protophobe acts synergistically with electron donor, the Electronic Performance of adjusting gegenion and sterically hindered, to solving prior art problem.Thereby regulate initiating activity and the stability in active centre, improve the controllability of polymerization process, reduce the probability that polymer active end of the chain β-H removes reaction, improve molecular weight and reduce molecular weight distribution, and can realize the common tank reactor of employing and prepare middle molecular weight and two serial polyisobutene products of high molecular at the temperature suitably improving.
Provided by the invention based on BF
3initiator system, by BF
3(component A), protophobe (B component), electron donor (component C) form, and wherein protophobe is one or more in water, methyl alcohol, ethanol, phenol, ortho-cresol, aromatic alcohol or aminobenzoic acids, and electron donor is for containing C
3～C
10oxa-ring, nitrogen heterocyclic or sulphur heterocyclic organic compounds in one or more, in initiator system, BF
3with the molar ratio of protophobe be 5～200, BF
3with the molar ratio of electron donor be 0.8～30.
In initiator system of the present invention, protophobe (B component) Main Function, for proton is provided in initiated polymerization, improves efficiency of initiation, thereby reduce active chain end β-H, removes reaction, improves the utilization ratio of catalyzer and the controllability of polymerization.In protophobe of the present invention, aromatic alcohol compound is one or more in phenylcarbinol, methylbenzyl alcohol, ethylbenzene methyl alcohol, propylbenzene methyl alcohol, butylbenzene methyl alcohol preferably; Aromatic acid compound is one or more in phenylformic acid, tolyl acid or ethyl benzoate preferably.When making water, methyl alcohol, ethanol, phenol, ortho-cresol as protophobe, need to introduce containing oxygen, nitrogen or sulfurheterocyclic compound electron donor, i.e. component C, stabilizing active center, reduces chain interruption reaction effectively, thereby improves molecular weight.
In initiator system of the present invention, electron donor (component C) Main Function is for participating in the formation in active centre, and stabilizing active center, reduces the side reaction odds such as chain transfer, thereby improves molecular weight, reduces molecular weight distribution.Oxygen helerocyclics in described component C is preferably from tetrahydrofuran (THF), 2-methyltetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, 2, one or more in 5-diethyl tetrahydrofuran (THF), hexamethylene ether or dioxane; Nitrogen heterocyclic in described component C is one or more in Pyrrolidine, N-methyl Pyrrolidine, 2-methyl Pyrrolidine, piperidines, N-methyl piperidine, pipecoline, lupetidine or 2,2,6,6-tetramethyl piperidine preferably; Sulfurheterocyclic compound in described component C is one or more in tetramethylene sulfide, 2-methyl tetramethylene sulfide, 3-methyl tetramethylene sulfide or tetrahydric thiapyran preferably.
Initiator system of the present invention can pass through BF
3react in advance to prepare with B component and component C, or each component in initiator system is directly joined in polymer raw system.When each component directly joins initiated polymerization in polymerization system in proportion, addition sequence is preferably: first C component is added in polymer raw system, then add BF
3with the mixture Isobutylene Initiated polymerization of B component, or first B and C component are directly added in polymer raw, then add BF
3isobutylene Initiated polymerization, or first B component is added in polymer raw system, then adds BF
3mixture Isobutylene Initiated polymerization with component C.Each component in described initiator system, can directly be used, and uses after also can adopting solvent cut.
Described initiator system can configure with organic solvent diluting, and organic solvent is common polarity or non-polar solvent, can be selected from any one or multiple mixture in alkane, naphthenic hydrocarbon, alkene, halohydrocarbon.
In initiator system of the present invention, by adopting two kinds of protophobe and electron donors that effect is different, and make BF
3particular combination with protophobe (B component), electron donor (component C), by the polymerization of proton Isobutylene Initiated, negative ion part in protophobe acts synergistically with electron donor, the solvability of initiator system in polymerization system and having good stability, form homogeneous system, in storage process, do not occur layering or separate out phenomenon, initiator system activity is high.BF
3with the molar ratio of B component preferably 7～170, BF
3with the molar ratio of component C preferably 1.0～25.
Adopt the method for molecular weight and high molecular weight polyisobutylene in initiator system Isobutylene Initiated polymerization of the present invention preparation, in common tank reactor, described initiator system is joined to Isobutylene Initiated polymerization in the polymer raw that contains isobutylene monomer, monomer concentration can regulate between mass polymerization at 1mol/L, and wherein the consumption of initiator system is (with BF
3meter) and in polymer raw iso-butylene molar ratio is 0.03%～0.45%, and polymerization temperature-100～0 ℃, prepares weight-average molecular weight 5 * 10
4～1.5 * 10
6between middle molecular weight and high molecular weight polyisobutylene, molecular weight distribution is narrower, the dispersion index (M of middle molecular weight polyisoprene iso-butylene
w/ M
n) in 2.3～3.5 scopes, the dispersion index of high molecular weight polyisobutylene is between 2.5～3.5.
The above-mentioned polymer raw that contains iso-butylene is liquid-phase pure iso-butylene, iso-butylene and inert solvent mixed liquid or the C that contains iso-butylene
4cut, preferably with iso-butylene inert solvent mixed liquid or containing the light C of iso-butylene
4cut is raw material.C
4cut is the hydrocarbon mixture forming containing components such as iso-butylene, 1-butylene, 2-butylene and butane that petroleum cracking or catalytic cracking produce.Organic solvent used in inert solvent in polymer raw and initiator system, can be identical, also can be different, and preferably from conventional straight or branched or the C of ring-type
1～C
20alkene, alkane, naphthenic hydrocarbon or halohydrocarbon in any one or its mixture, more preferably from C
2～C
4alkene, C
1～C
12alkane, naphthenic hydrocarbon or halohydrocarbon in one or more.More specifically, described alkene is butene-1 and butene-2; Described alkane or naphthenic hydrocarbon are preferably from ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, sherwood oil, hexanaphthene, methylcyclohexane and their isomer; Described halohydrocarbon is preferably from monochloro methane, methylene dichloride, trichloromethane, monochlorethane, ethylene dichloride, trichloroethane, chloropropane, chlorobutane, methylene fluoride, trifluoromethane, tetrafluoromethane, C2H4F2 C2H4F2, Halothane, Tetrafluoroethane, pentafluoride ethane, hexafluoroethane, difluoropropane, trifluoro propane, tetrafluoropropane, pentafluoropropane, HFC-236fa, fluorine butane etc.
Polyreaction of the present invention can be carried out under common processing condition and conventional reactor.General pressure carries out under barometric point, in polymerization process, due to gasification or the liquefaction of reaction system self, may make maintenance certain pressure in reactor.Generally speaking, pressure is very little on the molecular weight and molecualr weight distribution impact of final product.Polymerization temperature more preferably-95～-10 ℃.
The usage quantity of initiator system of the present invention is to determine according to the molecular weight of polymerisate and temperature of reaction, should reduce its consumption to reduce polymerisate generation isomerization reaction probability and to reduce production costs as far as possible, and its consumption is (with BF
3meter) be preferably 0.04%～0.40% (mol ratio) of iso-butylene amount in polymer raw.
Initiator system of the present invention is Isobutylene Initiated polymerization under popular response device and technique.Polyreaction can be intermittence or continuous carrying out.Polymerization reaction time is 1～40min, preferred 1～20min, and this depends primarily on polymeric reaction condition and process costs and product performance index.Polymerization process is generally under protection of inert gas, and after polymerization completes, by add excesses of basic material in system, as the aqueous solution that contains NaOH, KOH, alcohol or ammonia makes initiator system inactivation to reaction solution, and stops polyreaction.Stop after polymerization, deviate from unreacted monomer and solvent (can Recovery and recycle utilization), ethanol or water repetitive scrubbing for polymerisate, and be dried to constant weight.Gel permeation chromatography for molecular weight and molecualr weight distribution (GPC) the method test of polymerisate, tetrahydrofuran (THF) is moving phase, at 30 ℃ of constant temperature, records.
Effect of the present invention: provide a kind of stable based on BF
3the initiator system that (component A), protophobe (B component), electron donor (component C) form, the protophobe (B component) of wherein selecting can be for providing proton in initiated polymerization, improved efficiency of initiation, thereby reduce active chain end β-H, remove reaction, improve the utilization ratio of catalyzer and the controllability of polymerization; Electron donor (component C) is for participating in the formation in active centre, and stabilizing active center, reduces the side reactions such as chain transfer and occur, thereby improves molecular weight, reduces molecular weight distribution; Initiator system of the present invention adopts two kinds of organic compound (protophobe and electron donor) that effect is different, passes through BF
3particular combination and synergy with protophobe (B component), electron donor (component C), the Electronic Performance of adjusting gegenion and sterically hindered, increased solvability and the stability of initiator system in described solvent and polymer raw, form homogeneous system, in storage process, there is not layering or separate out phenomenon, initiator system activity is high, and consumption is low.With initiator system of the present invention, can realize in common tank reactor (can be with interior tubulation) and carry out cationoid polymerisation, can prepare as required two serial polyisobutene of middle molecular weight and high molecular, wherein:
(1) molecular weight polyisoprene iso-butylene in, its weight-average molecular weight 5 * 10
4～1.5 * 10
5, molecular weight distribution is narrower, dispersion index (M
w/ M
n) between 2.3～3.5;
(2) directly utilize and mix light C
4cut is polymer raw ,-37 ℃ of left and right, carries out Polymerization of Ib, and the molecular weight of product can reach 1.2 * 10
5, be obviously better than prior art;
(3) ,-40 ℃ of left and right, by regulating suitable B and C component, can synthesize molecular weight up to 2.3 * 10
5high molecular weight polyisobutylene, be obviously better than prior art;
(4) high molecular weight polyisobutylene, its weight-average molecular weight is 2.0 * 10
5～1.5 * 10
6scope, molecular weight distribution is narrower, and dispersion index is between 2.5～3.5;
(5) initiator system of the present invention also has advantages of stability in storage, in placement, within several days, even after some months, still can keep initiating activity;
(6) production technique is simple, can save production cost.
Embodiment
By below for illustrating that some representative example of the present invention can better understand the present invention, although provided these embodiment, also should comprise: do not departing under scope of the invention condition, for a person skilled in the art apparent various change.
Embodiment 1
At-40 ℃ and under high pure nitrogen protection, add 20mL to contain the solution ([IB]=2mol/L) of iso-butylene (IB) and normal hexane, then add by BF
3, H
2the initiator system solution that O, tetrahydrofuran (THF) (THF), normal hexane and methylene dichloride form, makes BF
3/ H
2o=9.7 (mol ratio), BF
3/ THF=1.3 (mol ratio), BF
3/ IB=2.9 * 10
-3(mol ratio).After polymerization 10min, add the NaOH/C of 3mL 0.1g/L
2h
5oH solution termination reaction.Polymerisate precipitates with ethanol, and with deionized water, ethanol repetitive scrubbing, is finally placed in 40 ℃ of vacuum drying ovens and is dried to constant weight.Weight-average molecular weight (the M of polyisobutene
w) be 9.5 * 10
4, molecular weight distribution (M
w/ M
n) be 2.4.
Embodiment 2
At-42 ℃ and under high pure nitrogen protection, add 20mL to contain the solution ([IB]=2mol/L) of iso-butylene (IB) and normal hexane, then add by BF
3, the initiator system that forms of methyl alcohol, tetrahydrofuran (THF), make BF
3/ methyl alcohol=9 (mol ratio), BF
3/ tetrahydrofuran (THF)=20 (mol ratio), BF
3/ IB=1.6 * 10
-3(mol ratio).After polymerization 10min, termination reaction and post-treating method are with embodiment 1.Polyisobutene yield is 26%, M
wbe 8.5 * 10
4, M
w/ M
nbe 2.7.
Embodiment 3
At-37 ℃ and under high pure nitrogen protection, add 20mL to contain the solution ([IB]=2mol/L) of iso-butylene (IB) and normal hexane, adopt and add initiator system with the method described in embodiment 1, make BF
3/ phenol=160 (mol ratio), BF
3/ tetrahydrofuran (THF)=8 (mol ratio), BF
3/ IB=2.8 * 10
-3(mol ratio).After polymerization 10min, termination reaction and post-treating method are with embodiment 1.Polyisobutene yield is 69%, M
wbe 7.8 * 10
4, M
w/ M
nbe 3.5.
Embodiment 4
At-39 ℃ and under high pure nitrogen protection, add 20mL to contain the solution ([IB]=2mol/L) of iso-butylene and normal hexane, adopt and add initiator system with the method described in embodiment 1, make BF
3/ phenylcarbinol=88 (mol ratio), BF
3/ THF=9 (mol ratio), BF
3/ IB=1.9 * 10
-3(mol ratio).After polymerization 2min, termination reaction and post-treating method are with embodiment 1.Polyisobutene yield is 67%, M
wbe 1.3 * 10
5, M
w/ M
nbe 2.7.
Embodiment 5
At-43 ℃ and under high pure nitrogen protection, add 20mL to contain the solution ([IB]=1mol/L) of iso-butylene and normal hexane, adopt and add initiator system with the method described in embodiment 1, make BF
3/ phenylcarbinol=88 (mol ratio), BF
3/ tetrahydrofuran (THF)=9 (mol ratio), BF
3/ IB=1.9 * 10
-3(mol ratio).After polymerization 10min, termination reaction and post-treating method are with embodiment 1.Polyisobutene yield is 64%, weight-average molecular weight (M
w) be 1.1 * 10
5, M
w/ M
nbe 2.3.
Embodiment 6
At-41 ℃ and under high pure nitrogen protection, add 20mL to contain the solution ([IB]=2mol/L) of iso-butylene (IB) and normal hexane, adopt and add initiator system with the method described in embodiment 1, make BF
3/ methyl alcohol=93 (mol ratio), BF
3/ Pyrrolidine=9 (mol ratio), BF
3/ IB=2.1 * 10
-3(mol ratio).After polymerization 15min, termination reaction and post-treating method are with embodiment 1.Polyisobutene yield is 31%, M
wbe 2.3 * 10
5, M
w/ M
nbe 2.5.
Embodiment 7
At-40 ℃ and under high pure nitrogen protection, add 20mL to contain the solution ([IB]=2mol/L) of iso-butylene (IB) and normal hexane, adopt and add initiator system with the method described in embodiment 1, make BF
3/ phenylcarbinol=113 (mol ratio), BF
3/ Pyrrolidine=11 (mol ratio), BF
3/ IB=2.6 * 10
-3(mol ratio).After polymerization 15min, termination reaction and post-treating method are with embodiment 1.Polyisobutene yield is 58%, M
wbe 2.1 * 10
5, M
w/ M
nbe 3.5.
Embodiment 8
At-37 ℃ and under high pure nitrogen protection, add 20mL to contain alkane and the light C of olefin
4cut ([IB]=2.7mol/L), adopts and adds initiator system with the method described in embodiment 1, makes BF
3/ H
2o=17 (mol ratio), BF
3/ tetrahydrofuran (THF)=2 (mol ratio), BF
3/ IB=3.7 * 10
-3(mol ratio).After polymerization 10min, termination reaction and post-treating method are with embodiment 1.Polyisobutene yield is 34%, M
wbe 1.2 * 10
5, M
w/ M
nbe 2.8.
Embodiment 9
At-90 ℃ and under high pure nitrogen protection, add 20mL to contain the solution ([IB]=1mol/L) of iso-butylene (IB) and normal hexane, adopt and add initiator system with the method described in embodiment 1, make BF
3/ phenylcarbinol=88 (mol ratio), BF
3/ Pyrrolidine=9 (mol ratio), BF
3/ IB=0.6 * 10
-3(mol ratio).After polymerization 10min, termination reaction and post-treating method are with embodiment 1.Polyisobutene yield is 51%, weight-average molecular weight (M
w) be 1.22 * 10
6, molecular weight distribution is 3.4.
Embodiment 10
At-76 ℃ and under high pure nitrogen protection, add 20mL to contain the solution ([IB]=1mol/L) of iso-butylene (IB) and normal hexane, adopt and add initiator system with the method described in embodiment 1, make BF
3/ methyl alcohol=100 (mol ratio), BF
3/ tetramethylene sulfide=9 (mol ratio), BF
3/ IB=4.0 * 10
-3(mol ratio).After polymerization 10min, termination reaction and post-treating method are with embodiment 1.Polyisobutene yield is 33%, M
wbe 4.6 * 10
5, M
w/ M
nbe 3.3.
Claims (4)
1. one kind based on BF
3initiator system, it is characterized in that, by BF
3, protophobe and electron donor form, described protophobe is one or more in water, methyl alcohol, ethanol, phenol, ortho-cresol, aromatic alcohol or aminobenzoic acids, electron donor is for containing C
3～C
10one or more in saturated oxa-ring cyclic ethers, cyclammonium nitrogen heterocyclic or epithio ether heterocyclic organic compounds, BF
3with the molar ratio of protophobe be 5～200, BF
3with the molar ratio of electron donor be 0.8～30, described aromatic alcohol compounds is selected from one or more in phenylcarbinol, methylbenzyl alcohol, ethylbenzene methyl alcohol, propylbenzene methyl alcohol, butylbenzene methyl alcohol; Aromatic acid compound is selected from one or more in phenylformic acid, tolyl acid or ethyl benzoate; Described oxa-ring cyclic ethers is selected from tetrahydrofuran (THF), 2-methyltetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, 2, one or more in 5-diethyl tetrahydrofuran (THF), hexamethylene ether or dioxane; Cyclammonium nitrogen heterocyclic is selected from one or more in Pyrrolidine, N-methyl Pyrrolidine, 2-methyl Pyrrolidine, piperidines, N-methyl piperidine, pipecoline, lupetidine or 2,2,6,6-tetramethyl piperidine; Epithio ether heterocycle is selected from one or more in tetramethylene sulfide, 2-methyl tetramethylene sulfide, 3-methyl tetramethylene sulfide or tetrahydric thiapyran.
2. initiator system according to claim 1, is characterized in that, BF
3with the molar ratio of protophobe be 7～170, BF
3with the molar ratio of electron donor be 1～25.
3. the initiator system by claim 1 is prepared polyisobutene method, it is characterized in that, described initiator system is joined to initiated polymerization in the polymer raw that contains isobutylene monomer, monomer concentration regulates between mass polymerization at 1mol/L, and wherein the consumption of initiator system is with BF
3meter, BF
3with iso-butylene molar ratio in polymer raw 0.03%～0.45%, polymerization temperature-100～0 ℃, polymerization time is 1～40min, adds terminator to stop polyreaction.
4. according to the method for claim 3, it is characterized in that, the weight-average molecular weight of the polyisobutene of preparation is 5 * 10
4～1.5 * 10
6, molecular weight distributing index reaches 2.3.
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| CN107216414B (en) * | 2016-03-21 | 2020-06-02 | 万华化学集团股份有限公司 | Composite catalyst for synthesizing polyisobutylene as well as preparation method and application of composite catalyst |
| CN109593591B (en) * | 2017-09-30 | 2022-05-17 | 中国石油化工股份有限公司 | Low-viscosity poly-alpha-olefin lubricating oil base oil and preparation method and system thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4849572A (en) * | 1987-12-22 | 1989-07-18 | Exxon Chemical Patents Inc. | Process for preparing polybutenes having enhanced reactivity using boron trifluoride catalysts (PT-647) |
| CN1187208A (en) * | 1995-06-07 | 1998-07-08 | 巴斯福股份公司 | Process for preparing low molecular, highly reactive polyisobutylene |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4849572A (en) * | 1987-12-22 | 1989-07-18 | Exxon Chemical Patents Inc. | Process for preparing polybutenes having enhanced reactivity using boron trifluoride catalysts (PT-647) |
| CN1187208A (en) * | 1995-06-07 | 1998-07-08 | 巴斯福股份公司 | Process for preparing low molecular, highly reactive polyisobutylene |
Non-Patent Citations (2)
| Title |
|---|
| Lai-bao Zhang,et al.SYNTHESIS OF HIGHLY REACTIVE POLYISOBUTYLENES WITH BF3·CYCLOHEXANOL INITIATING SYSTEM.《Chinese Journal of Polymer Science》.2011,第29卷(第3期),360-367. |
| SYNTHESIS OF HIGHLY REACTIVE POLYISOBUTYLENES WITH BF3·CYCLOHEXANOL INITIATING SYSTEM;Lai-bao Zhang,et al;《Chinese Journal of Polymer Science》;20110531;第29卷(第3期);360-367 * |
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