CN101033275A - Process for preparing polyisobutylene with high reaction activity - Google Patents
Process for preparing polyisobutylene with high reaction activity Download PDFInfo
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Abstract
The invention discloses a method to prepare a Polyisobutene with high reactivity. This method uses AlCl3 to compose catalyst with the organic compounds containing nitrogen, phosphorus and/or oxygen, triggering the polymerization of the mixed C4 fraction of distillate containing isobutylene or isobutene alkanes, preparing the Polyisobutene product, in which, the average molecular weight is 500 to 15000 Dalton, the content of alpha-double bond is more than 50%mol, the better one is more than 70%mol, the best more than 80%mol.
Description
Technical field
The present invention relates to a kind of method that is used for the active polyisobutene of preparation feedback, especially for 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
By iso-butylene (IB) preparation polyisobutene (PIB) is typical cationic polymerization, terminal α-double bond content in the polyisobutene molecular chain is a most important quality standard in the activity polyisobutylene product, the polyisobutene of common terminal α-double bond content below 10% (mole) is referred to as common polyisobutene; When its terminal double link content during, be referred to as high-activity polyisobutylene greater than 70% (mole).The catalyzer that the common polyisobutene of general preparation uses is a Lewis acid, and industrialization is modal to be aluminum chloride (AlCl
3) and BF
3Catalyst system.Utilize AlCl
3Catalyst system is produced polyisobutene output and is accounted for 80%, and this catalyzer is cheap, it is simple to be easy to get, to prepare, and adaptability is good, and toxicity is little.But, industrial AlCl commonly used
3, the synthetic preparation of alkyl aluminum chloride catalysis α-double bond content is lower than 10% common polyisobutene.Adopt HCl/AlCl as BP-Amoco company
3Cause the mixed C that contains iso-butylene with the mixture of varsol
4Isobutene polymerisation in the cut, ExxonMobil company adopts AlCl
3The catalyst system of suspended dispersed in normal hexane causes iso-butylene in polyreaction, and the smart connection in a Jinzhou lubricating oil additive company limited and Japan day stone company adopts AlCl
3Catalysis causes isobutene polymerisation, all is to be used to prepare common polyisobutene.
The high-activity polyisobutylene product is different with above-mentioned these common polyisobutene products.Terminal α-two keys have higher chemical reactivity than internal double bond, and the polyisobutene that terminal α-double bond content is high is the desired further functionalized intermediate polymer of energy.At present, effective initiator system of preparation high-activity polyisobutylene is to contain boron trifluoride (BF
3) initiator system that cooperates with 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).EP671,419 and CN 1,120,049 in propose to adopt the mixed C that contains iso-butylene and 5% above butene-1
4The method of the active polyisobutene of cut building-up reactions, this method must be with mixed C before polyreaction
4Feedstock is carried out the hydrogenation isomerization pre-treatment, common pretreated mixed C
4Butene-1 content in the cut should be less than 5%, and eliminated mixed C basically
4In the cut to disadvantageous alkynes of isobutene polymerisation and diolefine component; Raw material after the process hydrogenation isomerization is handled is at BF
3With carry out cationic polymerization under the initiator system that alcohol, uncle's ether or carboxylic acid cooperate, though can obtain terminal double link content greater than 80% polyisobutene, but in the hydrogenation isomerization pre-treatment step, used catalyzer is the palladium on alumina supporter, reaction pressure is 500～3000KPa, and temperature is 5～100 ℃, causes many, the long flow path of production process like this, reaction conditions requires high, thereby the production cost height.In addition, BF
3Corrodibility is strong, strong toxicity, and costs an arm and a leg.
Summary of the invention
The purpose of this invention is to provide a kind of AlCl cheap and easy to get that adopts
3Catalyzer causes the iso-butylene cationoid polymerisation, and the method for the high-activity polyisobutylene that preparation α-double bond content height and molecular weight are also higher particularly can adopt the mixed C that contains iso-butylene and butene-1
4The active polyisobutene of cut direct polymerization preparation feedback.
Method of the present invention: in liquid phase iso-butylene polymerizable raw material system, adopt AlCl
3Or/and oxygen containing organic compound Synergist S-421 95 is formed composition catalyst, cause isobutene polymerisation with nitrogenous, phosphorus, wherein, Synergist S-421 95 and AlCl
3Proportioning be 0.01～0.5, the catalyzer mole dosage be in the polymer raw the iso-butylene amount 0.02%～2.5%.
Above-mentioned nitrogenous, phosphorus is or/and oxygen containing compound Synergist S-421 95, be to contain oxygen, nitrogenous or contain oxygen, nitrogen simultaneously or contain compound of oxygen, phosphorus and composition thereof simultaneously, be selected from following suitable nucleophilicity compound: alcohols, ketone, ethers, amine, amides, alcamines, pyrrolidinone compounds and phosphate compounds.The preferred C of alcohol compound wherein
1～C
5Alcohol, as: methyl alcohol, ethanol, Virahol, isopropylcarbinol, the trimethyl carbinol, primary isoamyl alcohol; The preferred C of ketone compounds
3～C
6Ketone, as: acetone, butanone, pentanone, pimelinketone; Ether compound is selected from alkyl oxide, as ether, tetrahydrofuran (THF); Aminated compounds preferred alkyl amine is as diethylamine, triethylamine; Amides such as N, dinethylformamide, N,N-dimethylacetamide; The preferred C of alcamine compound
4～C
8Hydramine, as N, N-dimethylethanolamine, N, N-dimethyl propanol amine, N, N-dimethyl butyrate hydramine, N, N-dimethyl hexanol amine.Pyrrolidinone compounds chemical combination 2-Pyrrolidone, 3-pyrrolidone and N-alkyl-substituted derivative thereof are as N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, N-propyl group-2-Pyrrolidone, N-butyl-2-Pyrrolidone, N-methyl-3-pyrrolidone, N-ethyl-3-pyrrolidone, N-propyl group-3-pyrrolidone, N-butyl-3-pyrrolidone.Phosphate compounds is selected from C
1～C
4The phosphoric acid ester of alkyl, as triethyl phosphate, tributyl phosphate.Because the existence of these Synergist S-421 95s, the activity and the reaction probability that can make polyisobutene molecule chain end α-double-bond isomerism turn to the low activity internal double bond reduce, and the proton of regulating in the termination reaction removes reaction, thereby obtain the polyisobutene of high terminal double link content.
The above-mentioned Synergist S-421 95 and the proportioning of aluminum chloride depend primarily on polymerization conversion, polymericular weight and end group α-double bond content, and preferred mol ratio is 0.05-0.30.Catalyzer of the present invention can prepare in advance, also can generate immediately in polymerization system.
Catalyzer usage quantity of the present invention 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 the aluminum chloride composition catalyst is with respect to used monomeric amount.Catalyst levels increases, and the molecular weight of polyisobutene is low, and vice versa.Above-mentioned catalyzer preferable amount is 0.08%～2.0% (mole) of the iso-butylene amount in the polymer raw.Should reduce its consumption to reduce unnecessary isomerization reaction and to reduce cost as far as possible.
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.
Polymerization of the present invention can be carried out under popular response device and processing condition.Polyreaction can be to carry out off and on or continuously.Polymerization temperature is-55 ℃～20 ℃, preferred-50 ℃～10 ℃.Polymerization reaction time is 1～60 minute, and preferred 1～40 minute, 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,, to remove the initiator system resistates of inactivation, use the washing with alcohol deionization with the deionized water wash polymerisate again, after vacuum-drying obtains polymerisate with the ethanol sedimentation washing.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 is by the organic compound Synergist S-421 95 (alcohols, ketone, ethers, amine, amides, alcamines, pyrrolidinone compounds, phosphate compounds) and the AlCl of nitrogenous, oxygen, phosphorus
3Form catalyzer, according to the molecular weight of polyisobutene, regulate catalyst levels, having realized can be directly from pure iso-butylene, mixed C
4Cut prepares the high-activity polyisobutylene product with the hydrocarbon mixture raw material that contains iso-butylene.The number-average molecular weight of high-activity polyisobutylene product is 500～30000, preferred 1000～15000 dalton, and end group α-double bond content is greater than 50%mol, and is more excellent in 70%mol, excellent in especially 80%mol.It is higher active and to the adaptability of raw material, especially for mixed C to experiment showed, that particularly this catalyzer has
4Feedstock does not need the hydrogenation isomerization pretreatment process just can directly use, thereby can simplify reaction process and flow process, reduces production costs.
Embodiment
Be used to illustrate some preferable representative embodiment of the present invention the present invention may be better understood by following, although provided these embodiment, but also should comprise: do not departing under the scope of the invention condition, disclosed method is carried out the apparent various changes of those skilled in the art.
Embodiment 1
Under the high pure nitrogen protection, be the C of 45wt% to 25mL IB content
4Add 0.012mmolN in the mixture, N-dimethylethanolamine and 0.15mmolAlCl
3Initiated polymerization, 0 ℃ down behind the reaction 30min, add the NaOH/ ethanolic soln termination reaction of 1mL 0.1g/L, add ethanol and make polymer precipitation, and repeatedly with washing with alcohol to the clear shape.Monomer conversion is 57%, obtains number-average molecular weight and be 5900, α-double bond content is 54% activity polyisobutylene product.
Embodiment 2
Under high pure nitrogen protection, to 35mL IB content 1 8% liquid C
4Add 0.086mmolN-N-methyl-2-2-pyrrolidone N-and 0.43mmolAlCl in the mixture
3Initiated polymerization ,-45 ℃ down behind the reaction 30min, add the NaOH/ ethanolic soln termination reaction of 1mL 0.1g/L, add ethanol and make polymer precipitation, and repeatedly with washing with alcohol to the clear shape.Monomer conversion is 38%, obtains number-average molecular weight and be 11900, molecular weight distributing index is 2.6, α-double bond content is 72% high-activity polyisobutylene.
Embodiment 3
Under high pure nitrogen protection, to 35ml IB content 15% liquid C
4Add 0.066mmol triethylamine and 0.54mmolAlCl in the mixture
3Initiated polymerization ,-40 ℃ down behind the reaction 30min, add the NaOH/ ethanolic soln termination reaction of 1mL 0.1g/L, add ethanol and make polymer precipitation, and repeatedly with washing with alcohol to the clear shape.Monomer conversion is 49%, obtains number-average molecular weight and be 4300, α-double bond content is 85% high-activity polyisobutylene.
Embodiment 4
Under high pure nitrogen protection, in being 25% hexane, 25ml IB content adds 0.084mmolN, N-dimethylethanolamine and 0.28mmolAlCl
3Initiated polymerization.-28 ℃ down behind the reaction 20min, add the NaOH/ ethanolic soln termination reaction of 1mL0.1g/L, add ethanol and make polymer precipitation, and repeatedly with washing with alcohol to the clear shape.Monomer conversion is 44%, obtains number-average molecular weight and be 4100, α-double bond content is 84% high-activity polyisobutylene.
Embodiment 5
Under high pure nitrogen protection and condition, to 35mL IB content 18% liquid C
4Add 0.09mmol Virahol and 0.43mmolAlCl in the mixture
3Initiated polymerization ,-50 ℃ down behind the reaction 10min, add the NaOH/ ethanolic soln termination reaction of 1mL 0.1g/L, add ethanol and make polymer precipitation, and repeatedly with washing with alcohol to the clear shape.Monomer conversion is 91%, obtains number-average molecular weight and be 9200, α-double bond content is 55% activity polyisobutylene.
Embodiment 6
Under high pure nitrogen protection and condition, to 35mL IB content 22% liquid C
4Add 0.09mmol tetrahydrofuran (THF) and 0.45mmolAlCl in the mixture
3Initiated polymerization ,-40 ℃ down behind the reaction 10min, add the NaOH/ ethanolic soln termination reaction of 1mL 0.1g/L, add ethanol and make polymer precipitation, and repeatedly with washing with alcohol to the clear shape.Monomer conversion is 89%, obtains number-average molecular weight and be 12700, molecular weight distributing index 2.5, α-double bond content are 72% high-activity polyisobutylene.
Embodiment 7
Under high pure nitrogen protection and condition, to 35mL IB content 18% liquid C
4Add 0.74mmol Virahol and 1.6mmolAlCl in the mixture
3Initiated polymerization ,-50 ℃ down behind the reaction 40min, add the NaOH/ ethanolic soln termination reaction of 1mL0.1g/L, add ethanol and make polymer precipitation, and repeatedly with washing with alcohol to the clear shape, monomer conversion is 61%.
Implement Comparative Examples
Under the high pure nitrogen protection, be the C of 18wt% to 25mL IB content
4Add 0.15mmolAlCl in the mixture
3Initiated polymerization, 0 ℃ down behind the reaction 30min, add the NaOH/ ethanolic soln termination reaction of 1mL 0.1g/L, add ethanol and make polymer precipitation, and repeatedly with washing with alcohol to the clear shape.Monomer conversion is 95%, obtains number-average molecular weight and be 6400, α-double bond content is 10% common polyisobutene.
Claims (8)
1, a kind of preparation method of high-activity polyisobutylene is characterized in that: in liquid phase iso-butylene polymerizable raw material system, adopt AlCl
3Or/and oxygen containing organic compound Synergist S-421 95 is formed catalyzer, cause isobutene polymerisation, wherein Synergist S-421 95 and AlCl with nitrogenous, phosphorus
3The mole proportioning be 0.01～0.5, the catalyzer mole dosage be in the polymer raw the iso-butylene amount 0.05%～2.5%.
2, preparation method according to claim 1 is characterized in that, Synergist S-421 95 is selected from alcohols, ketone, ethers, amine, amides, alcamines, pyrrolidinone compounds, phosphate compounds.
3, preparation method according to claim 2 is characterized in that, alcohol compound is selected from C
1～C
5Alcohol; Ketone compounds is selected from C
3～C
6Ketone; Ether compound is selected from alkyl oxide; Aminated compounds is selected from alkylamine; Amides is selected from N, dinethylformamide, N,N-dimethylacetamide; Alcamine compound is selected from C
4～C
8Hydramine; Pyrrolidones is selected from 2-Pyrrolidone, 3-pyrrolidone and N-alkyl-substituted derivative thereof; Phosphate compounds is selected from C
1～C
4The phosphoric acid ester of alkyl.
4, preparation method according to claim 1 is characterized in that, Synergist S-421 95 and AlCl
3The mole proportioning be 0.05-0.30.
5, preparation method according to claim 1 is characterized in that, the catalyzer mole dosage be in the polymer raw iso-butylene amount 0.08%～2.0%.
6, 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.
7, preparation method according to claim 1 is characterized in that, polymerization temperature is-50 ℃～10 ℃.
8, preparation method according to claim 1 is characterized in that, polymerization reaction time is 1～40 minute.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613427B (en) * | 2008-06-27 | 2011-04-20 | 北京化工大学 | Method for preparing polyisobutylene with high reaction activity |
| CN101613423B (en) * | 2008-06-27 | 2011-05-18 | 北京化工大学 | Initiation system used for synthesizing polyisobutylene with high reaction activity |
| CN102464736A (en) * | 2010-11-19 | 2012-05-23 | 北京化工大学 | Process method for preparing polyisobutene and polymerization device |
| CN104152176A (en) * | 2013-05-14 | 2014-11-19 | 中国石油天然气股份有限公司 | Method for preparing poly-alpha-alkene synthetic oil from coal-based raw materials |
| CN105149005A (en) * | 2015-10-08 | 2015-12-16 | 山东鸿瑞新材料科技有限公司 | Aluminum trichloride catalyst system and method for producing low-molecular-weight polyisobutene with same |
| CN106905453A (en) * | 2017-03-20 | 2017-06-30 | 山东成泰化工有限公司 | It is a kind of for the composite catalyst of high molecular weight polyisobutylene, preparation method and polymerization technique in synthesis |
| CN108602913A (en) * | 2016-02-16 | 2018-09-28 | 巴斯夫欧洲公司 | The method for preparing highly reactive isobutylene homo or copolymer |
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2006
- 2006-03-07 CN CNB2006100567366A patent/CN100572403C/en active Active
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613427B (en) * | 2008-06-27 | 2011-04-20 | 北京化工大学 | Method for preparing polyisobutylene with high reaction activity |
| CN101613423B (en) * | 2008-06-27 | 2011-05-18 | 北京化工大学 | Initiation system used for synthesizing polyisobutylene with high reaction activity |
| 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 |
| CN104152176A (en) * | 2013-05-14 | 2014-11-19 | 中国石油天然气股份有限公司 | Method for preparing poly-alpha-alkene synthetic oil from coal-based raw materials |
| CN104152176B (en) * | 2013-05-14 | 2016-03-09 | 中国石油天然气股份有限公司 | A kind of method adopting coal-based feedstocks to prepare poly alpha olefine synthetic oil |
| CN105149005A (en) * | 2015-10-08 | 2015-12-16 | 山东鸿瑞新材料科技有限公司 | Aluminum trichloride catalyst system and method for producing low-molecular-weight polyisobutene with same |
| CN108602913A (en) * | 2016-02-16 | 2018-09-28 | 巴斯夫欧洲公司 | The method for preparing highly reactive isobutylene homo or copolymer |
| CN108602913B (en) * | 2016-02-16 | 2022-07-08 | 巴斯夫欧洲公司 | Method for producing highly reactive isobutene homo-or copolymers |
| CN106905453A (en) * | 2017-03-20 | 2017-06-30 | 山东成泰化工有限公司 | It is a kind of for the composite catalyst of high molecular weight polyisobutylene, preparation method and polymerization technique in synthesis |
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