CN100551938C - The method of one-step synthesis of polyisocrotyl phenol by isobutene - Google Patents
The method of one-step synthesis of polyisocrotyl phenol by isobutene Download PDFInfo
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- CN100551938C CN100551938C CNB2007100563478A CN200710056347A CN100551938C CN 100551938 C CN100551938 C CN 100551938C CN B2007100563478 A CNB2007100563478 A CN B2007100563478A CN 200710056347 A CN200710056347 A CN 200710056347A CN 100551938 C CN100551938 C CN 100551938C
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- phenol
- butylene
- polyisocrotyl
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- isobutene
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Abstract
The present invention relates to the method for one-step synthesis of polyisocrotyl phenol by isobutene,, utilize high-purity isobutylene to react one-step synthesis of polyisocrotyl phenol through polymerization in homogeneous phase being in the presence of the boron trifluoride complex catalyst of the 3rd component with the alkyl phenylate.Wherein used high-purity isobutylene is made by the MTBE cracking, and used boron trifluoride complex catalyst is made up of boron trifluoride, complexometric reagent, and complexometric reagent is by (C
1～C
10Pure) and alkyl ether benzene (C
6H
5～OR) form.Making the intermediates polyisobutene does not need directly to carry out alkylation reaction through handling, and the present invention simplifies technological process, has effectively controlled the generation of reaction process phenomenon of rupture, helps realizing mass-producing and serialization production, and characteristics such as reduce production costs.
Description
Technical field
The present invention relates to a kind of method of synthesizing polyisobutylene base phenol, the method that relates to a kind of one-step synthesis of polyisocrotyl phenol by isobutene specifically, relating in particular to a kind of is that the 3rd monomeric boron trifluoride complex is a catalyzer with alkyl ether benzene, the method for one-step synthesis of polyisocrotyl phenol by isobutene.
Background technology
Polyisobutenyl phenol (polyisobutenylphenols) and Mannich adducts thereof as the 5th generation fuel oil cleaning agent important component, not only can be used as the intermediate of fuel oil additive, and self also can be used alone as fuel oil cleaning agent, settling in removing fuel of internal combustion engine system and oil nozzle, sparking plug, keeping fuel oil thermostability and antioxygen aspect has the incomparable advantage of the 4th generation gasoline cleaning agent.In addition, polyisobutenyl phenol and Mannich adducts thereof also can be used as and stablize abiotic organic materials, with the effect of opposing light, heat, oxygen.
The synthetic of polyisobutenyl phenol is a kind of alkylated reaction of classics, and promptly Fu-Ke reacts (Friedel-Crafts reaction), and the catalyzer that is adopted is a kind of Lewis acid, is alkylating reagent with the polyolefine.
It has been generally acknowledged that; highly active polyisobutene has higher reactive behavior in alkylation process; but the shortcoming of this Fu-Ke alkylated reaction exactly is that alkylate has higher reactive behavior than unreacted initiator; in polyolefine and alkylate cleavage reaction takes place through regular meeting; the complicated often mixture of forming that obtains thus; for most of industrial application, such mixture obviously is inappropriate.For this reason, what need provides a kind of method, and the activity of alkylate is reduced, and reduces the generation of cleavage reaction.In this respect, many good tries have all been made by a lot of enterprises and research institution.
The method of a kind of 2-of preparation alkyl polyisobutenyl phenol and their Mannich adducts is disclosed among the CN1914234A.For avoiding and reduce the generation of cleavage reaction, adopting the polyisobutene that has the phenol of alkyl substituent and contain the 60mol% terminal double link at least on 2-position or 6-position is raw material.
CN200580003894 provides a kind of method of using the polyisobutylene alkylate fortified phenol.This method should be specially adapted to alkylation has alkyl substituent in the 2-position phenol, and this fortified phenol also at random has other substituting group, particularly on the 6-position.In this alkylated reaction, there is not the cleavage reaction of employed polyisobutene or fortified phenol basically.In the method, used the BF that can form complex compound with the alkyl substituted phenol that is used as reactant
3The source is as alkylation catalyst.Mention especially in this patent as not using aromatic oxide in the boron trifluoride System Catalyst as title complex.
Disclose a kind of compositions of additives of Mannich reaction products that comprises polyisobutylene alkylate hydroxyl aromatic compound, aldehyde and have the amine of at least one reactive amino among the CN1902238A, wherein polyisobutene is conventional polyisobutene and high end group vinylidene polyisobutylenes or both blends.
WO02/26840 has described a kind of method for preparing polyisobutenyl phenol, in the presence of Lewis dialkylaminobenzoic acid catalyzer, uses the polyisobutylene alkylate aromatic hydroxy compound.For preventing the generation of cleavage reaction in the alkylation process, wherein the polyisobutene of 35mol% has two keys in the β position at least.
Polyisobutenyl phenol synthetic traditional technology is to be raw material with pure iso-butylene or hybrid C 4 cut, at first make polyisobutene through cationoid polymerisation, high-activity polyisobutene or contain a certain proportion of polyisobutene that has two keys in the β position particularly, and then be raw material with their wherein a kind of or their mixture, carry out alkylated reaction with phenol or alkylphenol and prepare polyisobutenyl phenol, the shortcoming of this technology is must carry out reaction terminating to this link of isobutene polymerisation before the alkylated reaction, denitrating catalyst, operations such as desolventizing, complex process, long flow path, production cost is higher.
Summary of the invention
The objective of the invention is to overcome the problem that prior art exists, providing a kind of is being in the presence of the 3rd monomeric boron trifluoride complex catalyzer with alkyl ether benzene, the method of one-step synthesis of polyisocrotyl phenol by isobutene, to simplify technological process, the reaction conditions gentleness, the final residual content of iso-butylene can effectively be avoided the generation of cleavage reaction in the alkylation process simultaneously less than 1wt%.
For easy clear for the purpose of, below some notions that just will relate to, now be defined as follows:
(1) isobutene conversion * * mol%=* * iso-butylene of polyisobutene/100 molar part of molar part;
(2) the end group double bond content * * mol%=* * polyisobutene of polyisobutene/100 molfractions of the two keys of the end group vinylidene of molfraction;
Realize that technical scheme of the present invention is:
A kind of method of one-step synthesis of polyisocrotyl phenol by isobutene, form by following steps:
(1) being that the hexane solution of the iso-butylene more than the 98wt% adds in the reactor with purity, when treating that material is reduced to-29 ℃, is benchmark with iso-butylene 100 weight parts, stirs down the BF with 0.1 weight part
3Complex compound catalyst adds in 3 hours in the reactor in batches equably, and the controlled polymerization temperature is-20～-10 ℃, and reaction pressure is 0.01～0.2MPa.When homopolymerization proceeds to isobutene conversion is 90mol% when above, and obtaining number-average molecular weight is 750～1000, and molecular weight distribution is 1.05～2.0, the polyisobutene of the low-molecular-weight high-activity that end group double bond content 90mol% is above, then,
(2) polyisobutene that in 1 hour step (1) is obtained adds in the 2-alkyl substituted phenol with its equimolar amount, simultaneously,
(3) in reactive system, add an amount of BF
3Complex compound catalyst keeps temperature of reaction at 10～20 ℃, and continuously stirring 12 hours promptly gets 2-alkyl polyisobutenyl phenol; The mol ratio of 2-alkyl substituted phenol and iso-butylene consumption is 1: 12～1: 20 in the reaction, BF
3The mol ratio of complex compound catalyst and 2-alkyl substituted phenol consumption is 5: 100;
The BF that above step (1), (3) are mentioned
3Complex compound catalyst is made up of boron trifluoride and complexometric reagent, and described complexometric reagent is by C
1～C
10Pure and mild alkyl ether benzene C
6H
15～OR forms, and R is a methyl in the formula, ethyl or butyl; Said C
1～C
10Alcohol and alkyl ether benzene C
6H
15-OR mol ratio is 2～10, BF
3With the mol ratio of complexometric reagent be 0.5～0.8.
The method of above-mentioned a kind of one-step synthesis of polyisocrotyl phenol by isobutene, its alkyl substituted phenol are to be selected from 2-methylphenol, 2-ethylphenol or 2-tert.-butyl phenol.
Isobutene conversion is more than the 98mol% before the method for above-mentioned a kind of one-step synthesis of polyisocrotyl phenol by isobutene, its alkylation reaction.
The method of above-mentioned a kind of one-step synthesis of polyisocrotyl phenol by isobutene, the iso-butylene that the used raw material of its polyreaction obtains for the MTBE cracking, its purity 〉=99.9wt%.
With the method for above-mentioned a kind of one-step synthesis of polyisocrotyl phenol by isobutene, iso-butylene that it is remaining and solvent change recycle by distilling back.
According to the present invention, the reaction raw materials that is used for polymerization in homogeneous phase in the step (1) is the highly purified iso-butylene of hybrid C 4 or MTBE cracking preparation, preferably the high-purity isobutylene of MTBE cracking preparation (〉=99.9wt%).
According to the present invention, be used for the polyisobutene of alkylated reaction in the step (2), be the polyisobutene of low-molecular-weight high-activity, its number-average molecular weight Mn is 750～1000, molecular weight distributing index (PDI) is 1.05-2.0, two key [the CH-C (=CH of end group vinylidene
2)-CH
3] content is at least the polyisobutene of 90mol% based on the macromolecular sum of polyisobutene.
According to the present invention, what be used in the step (2) that the alkyl substituted phenol of alkylated reaction is suitable for is to have the substituent phenol of branching on the 2-position, this alkyl can be the alkyl of straight chain, also can be the alkyl group of branching or replacement, as 2-methylphenol, 2-ethylphenol or 2-tert.-butyl phenol etc.
According to the present invention, employed BF in step (1) and the step (3)
3The catalyzer of complex system all is to be the BF of the 3rd component with alkyl ether benzene
3Complex compound catalyst is by BF
3Form with complexometric reagent; Complexometric reagent is by C
1～C
10Pure and mild alkyl ether benzene C
6H
5～OR forms.Wherein, R is methyl, ethyl or butyl.Said alcohol and ether mol ratio are 2～10, BF
3With the mol ratio of complexometric reagent be 0.5～0.8.Described catalyzer and high purity polyisobutene all are products of being produced by Jihua Group Co.
The present invention compared with prior art has outstanding substantive distinguishing features and obvious improvement:
(1) to have adopted patent No. ZL02144631.8's be the 3rd monomeric boron trifluoride (BF with alkyl ether benzene in the present invention
3) the complex catalysis system, produce low-molecular-weight high-activity polymerization butylene.Key of the present invention be when isobutene conversion be 90% when above, its polyisobutene does not need to carry out intermediate treatment, under same catalyst system, directly carry out alkylated reaction, that is to say by by highly purified iso-butylene through polymerization in homogeneous phase reaction one-step synthesis polyisobutenyl phenol; Effectively control and when having avoided the prior art polyisobutene to carry out alkylated reaction, cleavage reaction takes place.
(2) the present invention has simplified technological process, the reaction conditions gentleness, and operating process is controlled easily, helps realizing mass-producing and continuous operation, reduces production costs.
(3) the final residual content of iso-butylene is less than 1wt%; Remaining iso-butylene can steam with solvent together by distillating method, and recycles.
Embodiment
Embodiment 1
150ml is contained the hexane solution of 30.52wt% iso-butylene, add in the 500ml there-necked flask, and be placed in the low temperature bath, when treating that material is reduced to-29 ℃, stir down with the BF of syringe with 0.2ml
3Complex compound catalyst, in 3 hours, join in the there-necked flask equably in batches, the controlled polymerization temperature is at-12 ± 2 ℃, reaction pressure is at 0.01～0.2MPa, it is that 90mol% is when above that question response proceeds to isobutene conversion, in 1 hour, it is joined in the fused 2-tert.-butyl phenol of same molar, the catalyzer of adding 5mol% simultaneously is (that is: when being benchmark with 2-tert.-butyl phenol 100 molfractions, add the described catalyzer of 5 molfractions, below roughly the same), keep temperature of reaction about 10～20 ℃, and continuously stirring 12 hours, 2-tertiary butyl polyisobutenyl phenol promptly got.Isobutene conversion 96.2% (wt) before its alkylated reaction, the molecular-weight average of polyisobutene is 900, and molecular weight distribution is 2.1, and the end group double bond content is the 93mol% umber.
Make the 40g product, wherein, 2-tertiary butyl polyisobutenyl phenol is 95.1wt%, and a small amount of 2-tert.-butyl phenol is arranged in addition.
Embodiment 2
Polymeric reaction temperature is controlled at-18 ± 2 ℃, and other conditions are with embodiment 1.
Make the 43g product, wherein, 2-tertiary butyl polyisobutenyl phenol is 94.5wt%, and a small amount of 2-tert.-butyl phenol is arranged in addition.
Embodiment 3
150ml is contained the hexane solution of 30.52wt% iso-butylene, add in the 500ml there-necked flask, and be placed in the low temperature bath, when treating that material is reduced to-29 ℃, stir down with the BF of syringe with 0.2ml
3Complex compound catalyst, in 3 hours, join in the there-necked flask equably in batches, the controlled polymerization temperature is at-12 ± 2 ℃, reaction pressure is at 0.01～0.2MPa, it is that 90mol% joined it in 1 hour in the fused 2-methylphenol of same molar when above that question response proceeds to isobutene conversion, and adds the 5mol% catalyzer, keeps temperature of reaction about 10～20 ℃, and continuously stirring 12 hours, promptly get 2-methyl polyisobutenyl phenol.Isobutene conversion 96.2% (wt) before its alkylated reaction, the molecular-weight average of polyisobutene is 950, molecular weight distribution is 2.1, end group double bond content 95mol%
Make the 39g product, wherein, 2-methyl polyisobutenyl phenol content is 95.1wt%, and a small amount of 2-methylphenol is arranged in addition.
Embodiment 4
150ml is contained the hexane solution of 30.52wt% iso-butylene, add in the 500ml there-necked flask, and be placed in the low temperature bath, when treating that material is reduced to-29 ℃, stir down with the BF of syringe with 0.2ml
3Complex compound catalyst, in 3 hours, join in the there-necked flask equably in batches, the controlled polymerization temperature is at-12 ± 2 ℃, reaction pressure is at 0.01～0.2MPa, it is that 90mol% joined it in 1 hour in the fused 2-ethylphenol of same molar when above that question response proceeds to isobutene conversion, and adds the 5mol% catalyzer, keeps temperature of reaction about 10～20 ℃, and continuously stirring 12 hours, promptly get 2-ethyl polyisobutenyl phenol.Isobutene conversion 96.2% (wt) before its alkylated reaction, the molecular-weight average of polyisobutene is 1000, molecular weight distribution is 2.1, end group double bond content 90mol%.
Make the 39.5g product, wherein, 2-ethyl polyisobutenyl phenol content is 96.1wt%, and a small amount of 2-ethylphenol is arranged in addition.
Embodiment 5
150ml is contained the hexane solution of 30.52wt% iso-butylene, add in the 500ml there-necked flask, and be placed in the low temperature bath, when treating that material is reduced to-29 ℃, stir down with the BF of syringe with 0.2ml
3Complex compound catalyst, in 3 hours, join in the flask it equably in batches, make polymerization temperature be controlled at-12 ± 2 ℃, reaction pressure is at 0.01～0.2MPa, it is that 90mol% is when above that question response proceeds to isobutene conversion, in 1 hour, polyisobutene is slowly joined in the 100ml toluene solution that is dissolved with the 100g2-tert.-butyl phenol, when being benchmark with 2-tert.-butyl phenol 100 molar part, add the catalyzer of 5mol%, keeping temperature of reaction is about 10 ℃, and continuously stirring 12 hours, promptly get 2-tertiary butyl polyisobutenyl phenol.Isobutene conversion 97.3wt% before its alkylated reaction, the molecular-weight average of polyisobutene is 900, molecular weight distribution is 2.1, end group double bond content 92mol%.
Make the 39g product, wherein, 2-tertiary butyl polyisobutenyl phenol content is 95.3wt%, and a small amount of 2-tert.-butyl phenol is arranged in addition.
Comparative example (according to the CN200580003894 preparation method)
In the 1L four-hole boiling flask of agitator, thermometer is housed, the 2-tert.-butyl phenol of 100g is dissolved in the toluene of 100ml.Subsequently with the BF of 3g
3Complex compound catalyst (Jihua Group Co's product) dropwise adds under 0～5 ℃, and will be dissolved in 330g polyisobutene (the Mn=1000 dalton in the 120ml normal hexane subsequently, Mw/Mn=2.0) under 0～10 ℃ temperature, dropwise add, and stirred 2 hours, stop this reaction with 100ml methyl alcohol then, and with 1L washed with methanol twice, and in 160 ℃, the rotatory evaporator of 0.05Pa, concentrate.
Make the 320g product, wherein, 2-tertiary butyl polyisobutenyl phenol content is 95.0wt%, and more 2-tert.-butyl phenol is arranged.
Claims (6)
1, a kind of method of one-step synthesis of polyisocrotyl phenol by isobutene, form by following steps:
(1) being that the hexane solution of the iso-butylene more than the 98wt% adds in the reactor with purity, when treating that material is reduced to-29 ℃, is benchmark with iso-butylene 100 weight parts, stirs down the BF with 0.1 weight part
3Complex compound catalyst adds in three hours in the reactor in batches equably, and the controlled polymerization temperature is-20～-10 ℃, and reaction pressure is 0.01～0.2MPa; When homopolymerization proceeds to isobutene conversion is 90mol% when above, and obtaining molecular-weight average is 750～1000, and molecular weight distribution is 1.05～2.0, the polyisobutene of the low-molecular-weight high-activity that end group double bond content 90mol% is above; Then,
(2) polyisobutene that in 1 hour step (1) is obtained adds in the 2-alkyl substituted phenol with its equimolar amount; Simultaneously,
(3) in reactive system, add an amount of BF
3Complex compound catalyst keeps temperature of reaction at 10～20 ℃, and continuously stirring 12 hours promptly gets 2-alkyl polyisobutenyl phenol, and the mol ratio of 2-alkyl substituted phenol and iso-butylene consumption is 1: 12～1: 20 in the reaction, BF
3The mol ratio of complex compound catalyst and 2-alkyl substituted phenol consumption is 5mol%;
The BF that mentions in above-mentioned steps (1), (3)
3Complex compound catalyst is made up of boron trifluoride and complexometric reagent, and complexometric reagent wherein is by C
1～C
10Pure and mild alkyl ether benzene C
6H
5_ OR forms, and R is methyl, ethyl or butyl in the formula; C
1～C
10Alcohol and alkyl ether benzene C
6H
5The mol ratio of _ OR is 2～10, BF
3With the mol ratio of complexometric reagent be 0.5～0.8.
2, the method for a kind of one-step synthesis of polyisocrotyl phenol by isobutene according to claim 1, its described 2-alkyl substituted phenol is selected from 2-methylphenol, 2-ethylphenol or 2-tert.-butyl phenol.
3, isobutene conversion is more than the 98mol% before the method for a kind of one-step synthesis of polyisocrotyl phenol by isobutene according to claim 1, its alkylation reaction.
4, the method for a kind of one-step synthesis of polyisocrotyl phenol by isobutene according to claim 1, its polyreaction raw material iso-butylene are the iso-butylene of its purity 〉=99.9wt% of hybrid C 4 or MTBE cracking preparation.
5, the method for a kind of one-step synthesis of polyisocrotyl phenol by isobutene according to claim 2, the iso-butylene that the used raw material iso-butylene of its polyreaction obtains for the MTBE cracking, its purity 〉=99.9wt%.
6, the method for a kind of one-step synthesis of polyisocrotyl phenol by isobutene according to claim 1, iso-butylene that it is remaining and hexane are by the distillation recycle and reuse.
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| CNB2007100563478A CN100551938C (en) | 2007-11-22 | 2007-11-22 | The method of one-step synthesis of polyisocrotyl phenol by isobutene |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5300701A (en) * | 1992-12-28 | 1994-04-05 | Chevron Research And Technology Company | Process for the preparation of polyisobutyl hydroxyaromatics |
| US20030187171A1 (en) * | 2000-09-28 | 2003-10-02 | Arno Lange | Method for producing polyisobutylphenols |
| CN1902238A (en) * | 2003-11-04 | 2007-01-24 | 卢布里佐尔公司 | Alkylated hydroxyaromatic compound from conventional and high vinylidene polyisobutylenes and compositions and processes thereof |
| CN1914234A (en) * | 2004-02-02 | 2007-02-14 | 巴斯福股份公司 | Method for producing polyisobutenylphenols |
-
2007
- 2007-11-22 CN CNB2007100563478A patent/CN100551938C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5300701A (en) * | 1992-12-28 | 1994-04-05 | Chevron Research And Technology Company | Process for the preparation of polyisobutyl hydroxyaromatics |
| US20030187171A1 (en) * | 2000-09-28 | 2003-10-02 | Arno Lange | Method for producing polyisobutylphenols |
| CN1902238A (en) * | 2003-11-04 | 2007-01-24 | 卢布里佐尔公司 | Alkylated hydroxyaromatic compound from conventional and high vinylidene polyisobutylenes and compositions and processes thereof |
| CN1914234A (en) * | 2004-02-02 | 2007-02-14 | 巴斯福股份公司 | Method for producing polyisobutenylphenols |
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