CN1201800A - Inductive system for activated cation - Google Patents
Inductive system for activated cation Download PDFInfo
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- CN1201800A CN1201800A CN 98102282 CN98102282A CN1201800A CN 1201800 A CN1201800 A CN 1201800A CN 98102282 CN98102282 CN 98102282 CN 98102282 A CN98102282 A CN 98102282A CN 1201800 A CN1201800 A CN 1201800A
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- initiator
- mol
- coinitiator
- nucleophilic reagent
- polymerization
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Abstract
A relatively consistent and stable trigger system with active cations is composed of trigger, cotrigger and nucleophile, and can be used for the high-molecular compounds obtained by C-C unsaturated bond, active cation polymerizing reaction, such as vinyl monomer, to take part in homopolymerization, block copolymerization, star polymerization and graft copolymerization. The influence of the sequence of adding raw materials to the polymerization of polyisobutylene is disclosed. Its advantages includes cheap raw materials, and narrow distribution of molecular weights and excellent properties for products.
Description
The present invention relates to a kind of new initiator system, it is used for the macromolecular compound that the reaction of carbon one carbon unsaturated link(age) living cationic polymerization obtains, more particularly, the present invention relates to a kind of new Organohalogen compounds, the initiator system of the living cationic polymerization that coinitiator, nucleophilic reagent are formed.
For living cationic polymerization, because the high activity of carbonium ion makes polyreaction that various pairs of reactions easily take place, make that the realization of living cationic polymerization is very difficult, in recent years, to the research of its initiator system, realized the living cationic polymerization of different systems.
Up to the present, the living cationic polymerization system of discovery and report mainly contains:
Organo-peroxide/Lewis acid is an initiator system, CH
3Cl or CH
2Cl
2During for solvent, low temperature causes iso-butylene down;
2,4,4-trimethylammonium-2-chloropentane (TMPCl)/TiCl
4Be initiator system, CH
3Cl and methylcyclohexane are solvent, under the low temperature, in the presence of N,N-dimethylacetamide, cause vinylbenzene;
U.S.P5451647 provides a kind of living cationic polymerization, and with organic compound alcohol, ether, ester, perhaps Organohalogen compounds are initiator, a kind of Lewis acid is a coinitiator, 2, the 6-di-tert-butyl pyridine exists down, and polymerization makes homopolymer, multipolymer or segmented copolymer;
The EP0725095 patent provides a kind of living cationic polymerization system, and at initiator, coinitiator and pyridine, or derivatives thereof exists down, initiating polymerization of vinyl monomer.
At present, during the different monomers polymerization, generally adopt different initiator systems, shortage has the initiator system that extensively is suitable for.
The objective of the invention is to overcome weak point of the prior art, and a kind of stable consistent relatively new active cation initiator system is provided, be used to cause vinyl monomer and carry out homopolymerization, block copolymerization, star polymerization, graft copolymerization.
Purpose of the present invention can reach by following measure: inductive system for activated cation is by (1) initiator, by a kind of compound of following general formula representative and composition thereof
R wherein
1, R
2Represent hydrogen atom separately, R
1, R
2, R
3Represent C separately
1～C
8The straight or branched alkyl, R
2Represent five yuan, hexa-atomic saturated or unsaturated ring, R
1And R
2Form five yuan, hexa-atomic saturated or unsaturated ring, X representation hydroxy, ether, ester group, halogen with the carbon atom that links to each other together; (2) coinitiator Lewis acid: SnCl
4, BCl
3, TiCl
4, SbF
5, SeCl
3, ZnCl
2, FeCl
3, VCl
4, AlRnCl
3-n, wherein R represents C
1～C
8Straight or branched alkyl, n are represented 0～3 integer; (3) nucleophilic reagent (claim the proton capture agent again, or electron donor) Lewis base is formed as hexahydropyridine or derivatives thereof, fatty amine, aromatic amine,
Initiator concentration is 1mol/L～10
-5Mol/L, the add-on of initiator is decided by the molecular weight size of polymerization product, and preferable initiator is to dicumyl chlorine;
The concentration of coinitiator is 10mol/L～10
-4Mol/L, the add-on of coinitiator is decided by the add-on of initiator, and preferable coinitiator is TiCl
4
The concentration of nucleophilic reagent is 0.1mol/L～10
-6Mol/L, the add-on of nucleophilic reagent is decided by the water content size and the initiator add-on of system, and preferable nucleophilic reagent is a hexahydropyridine.
Mixed solvent is CH
3Cl or CH
2Cl
2Mix with any hexane in hexanaphthene, normal hexane, the methylcyclohexane, with the mixed solvent of volume ratio preparation in 40: 60, preferable mixed solvent is CH
3Cl: the mixed solvent of hexanaphthene=40: 60 (V/V), mixed solvent add-on are 1～50 times of polymerization single polymerization monomer volume number;
Terminator: methyl alcohol or alcoholic acid hydrochloric acid soln;
Monomer mainly contains the organic compound of vinyl, can be aliphatics, contain the compound of classes such as aromatic nucleus, ethers, conjugated diolefine, as iso-butylene, vinylbenzene, indenes, vinyl ethers, isoprene etc.
Living cationic polymerization technology is under normal pressure; temperature of reaction 0～-90 ℃ are under the exsiccant nitrogen protection, in the purified reaction vessel of drying; add mixed solvent, initiator, coinitiator Lewis acid and nucleophilic reagent Lewis base successively; elder generation's ageing 10～60 minutes adds vinyl monomer, reacts after 1 hour; add terminator; in a large amount of solution of solution impouring after the termination, the product precipitation is separated out, and filters after drying.
In synthesis technique, different order of addition(of ingredients) are influential to the polyisobutene polymerization, order of addition(of ingredients) is mixed solvent, initiator, coinitiator, nucleophilic reagent, monomer once adds simultaneously, or initiator, coinitiator, nucleophilic reagent add ageing 10～60 minutes earlier, add monomer again and carry out polyreaction, the molecular weight distribution of products obtained therefrom is narrower
Inductive system for activated cation accompanying drawing (is example with the linear polymer)
Chain initiation:
1. carbonium ion forms:
2. the formation of monomer positive ion:
Chain termination:
Wherein RX represents initiator, and MtXn represents coinitiator, and C=C represents vinyl monomer, and n represents 1～6 integer.
The present invention will now be further detailed embodiment:
Embodiment 1: the living cationic polymerization of iso-butylene
At normal pressure, temperature of reaction-70～-75 ℃ under the drying nitrogen protection, in the dry reaction container, add CH
3Cl and normal hexane add 3 * 10 successively with the mixed solvent 1L of volume ratio preparation in 40: 60
-3Mol/L to dicumyl chlorine, 6 * 10
-2The TiCl of mol/L
4, 1.2 * 10
-3Mol/L hexahydropyridine, ageing be after 15 minutes, adds the 1.14mol/L iso-butylene, react 1 hour, and the methyl alcohol that adds 5%HCl stops, and in a large amount of ethanolic soln of the solution impouring after the termination, precipitation is separated out product, the filtration after drying.
Polyisobutene product number-average molecular weight is 10500, and molecular weight distribution is 1.12.
Embodiment 2: identical with embodiment 1 synthesis technique, solvent is CH
3Cl and 40: 60 mixed solvent of hexanaphthene volume ratio are with 3 * 10
-3Mol/L TMPCl (2,4,4-trimethylammonium-2-chloropentane) is an initiator, 4.8 * 10
-2Mol/L TiCl
4Be coinitiator, 4.11 * 10
-3The mol/L hexahydropyridine is a nucleophilic reagent, 0.81mol/L styrene monomer concentration, and polymerization ℃ is carried out, polystyrene products number-average molecular weight 19400, molecular weight distribution 1.48 in temperature of reaction-70～-80.
Embodiment 3: identical with embodiment 1 synthesis technique, solvent is CH
2Cl
2With the volume ratio of hexanaphthene be 40: 60 mixed solvent, with 10
-3Mol/L TMPCl, 2 * 10
-2Mol/L TiCl
4, 4 * 10
-3The mol/L hexahydropyridine, 6.6 * 10
-1Mol/L indenes, temperature of reaction-75～-80 ℃ carry out polymerization.
Polyindene product number-average molecular weight 25700, molecular weight distribution 1.60.
Embodiment 4～9: different order of addition(of ingredients) are to the influence of isobutene polymerisation.
Polymerization technique and embodiment 1 basically identical, polymerization result is listed in table 1
The different order of addition(of ingredients) of table 1 are to the influence of isobutene polymerisation
| Embodiment No | Order of addition(of ingredients) | Number-average molecular weight (Mn) | Molecular weight distribution (Mn/Mw) |
| 4 | DiCumCl and TiCl 4Add ageing after 15 minutes, add 6HPY and IB again | 1000 | 1.81 |
| 5 | 6HPY and TiCl 4, add ageing after 15 minutes, add DiCumCl and IB again | 1020 | 1.91 |
| 6 | DiCumCl，TiCl 4, 6HPY and IB add simultaneously | 10500 | 1.12 |
| 7 | DiCumCl，TiCl 4Add ageing after 15 minutes with 6HPY, add IB again | 13640 | 1.23 |
| 8 | DiCumCl and TiCl 4Add ageing after 15 minutes, add 6HPY and IB again | 7800 | 1.24 |
| 9 | 6HPY and TiCl 4Add ageing after 15 minutes, add IB and DiCumCl again | 3350 | 2.56 |
Annotate: at first add solvent, in system, add component afterwards successively.DiCumCl-is to dicumyl chlorine; The 6HPY-hexahydropyridine, the IB-iso-butylene.
Embodiment 10: identical with embodiment 1 synthesis technique, solvent is CH
2Cl
2With normal hexane be 40: 60 mixed solvent with volume ratio, with 3 * 10
-3Mol/L DiCumCl (to dicumyl chlorine) is an initiator, 4.8 * 10
-2Mol/L TiCl
4Be coinitiator, 2.1 * 10
-2The mol/L pentanoic is a nucleophilic reagent, and isobutylene concentration is 1.14mol/L, temperature of reaction-80 ℃.
Polyisobutene product number-average molecular weight is 68140, molecular weight distribution 1.64.
From top embodiment 1～10, provided by the invention as can be seen to dicumyl chlorine and TiCl
4, the initiator system of nucleophilic reagent, the reinforced in certain sequence cation activity polymerization technique that carries out can be realized the living cationic polymerization of multiple vinyl monomer, the molecular weight distribution of its product is 1.12～1.9.
In the time of the present patent application patent, applied for that again this initiator system is used for the synthesis technique of polyolefinic living cationic polymerization, the patent No. is 98102283.9.
The present invention has following advantage compared to existing technology:
1. the invention provides stable, relatively consistent initiator system, be used for vinyl monomer homopolymerization, copolymerization, block copolymerization, star polymerization, graft copolymerization.
2. use dicumyl chlorine, TiCl4, hexahydropyridine initiator system, the resulting polymers narrow molecular weight distribution.
3. the present invention utilizes common chemical reagent to make the raw material technology of initator, coinitiator, nucleopilic reagent and mixed solvent, for the industrialization of various types of olefins compound activity cationic polymerization technique provides advantage.
4. the present invention is domestic raw material with the hexahydropyridine or derivatives thereof, low price, and 20 yuan/500ml, and the U.S. adopts 2,6-di-tert-butyl pyridine, and price is more expensive, and 200 dollars/5ml, domestic without producing, need import.
Claims (6)
1. the initiator system that is used for the polyolefine living cationic polymerization, it is characterized in that by
(1) initiator is by a kind of compound or its mixture of following general formula representative
R wherein
1, R
2Represent hydrogen atom separately, R
1, R
2, R
3Represent C separately
1～C
8The straight or branched alkyl, R
2Represent five yuan, hexa-atomic saturated or unsaturated ring, R
1And R
2Form five yuan, hexa-atomic saturated or unsaturated ring, X representation hydroxy, ether, ester group, halogen with the carbon atom that links to each other together;
(2) coinitiator Lewis acid: SnCl
4, BCl
3, TiCl
4, SbF
5, SeCl
3, ZnCl
2, FeCl
3, VCl
4, AlRnCl
3-n, wherein R represents C
1～C
8Straight or branched alkyl, n are represented 0～3 integer;
(3) nucleophilic reagent: hexahydropyridine or derivatives thereof, fatty amine, aromatic amine are formed,
Initiator, coinitiator, nucleophilic reagent mole number respectively are 1mol/L～10
-5Mol/L, 10mol/L～10
-4Mol/L, 0.1mol/L～10
-6Mol/L in synthesis technique, behind the adding solvent, carries out polymerization by certain order of addition(of ingredients) earlier again.
2. initiator system according to claim 1 is characterized in that initiator is to dicumyl chlorine.
3. initiator system according to claim 1 is characterized in that coinitiator is TiCl
4
4. initiator system according to claim 1 is characterized in that nucleophilic reagent is hexahydropyridine, pentanoic.
5. initiator system according to claim 1, the consumption that it is characterized in that initiator is 3 * 10
-3Mol/L, the coinitiator consumption is 4 * 10
-2Mol/L, the nucleophilic reagent consumption is 1.8 * 10
-3Mol/L.
6. initiator system according to claim 1, it is characterized in that in polymerization technique, order of addition(of ingredients) be initiator, coinitiator, nucleophilic reagent, monomer once adding simultaneously or initiator, coinitiator, nucleophilic reagent add ageing 10～60 minutes earlier, add monomer again and carry out polyreaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98102282A CN1062568C (en) | 1998-06-19 | 1998-06-19 | Inductive system for activated cation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98102282A CN1062568C (en) | 1998-06-19 | 1998-06-19 | Inductive system for activated cation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1201800A true CN1201800A (en) | 1998-12-16 |
| CN1062568C CN1062568C (en) | 2001-02-28 |
Family
ID=5217248
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98102282A Expired - Lifetime CN1062568C (en) | 1998-06-19 | 1998-06-19 | Inductive system for activated cation |
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|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453565C (en) * | 2002-04-05 | 2009-01-21 | 巴斯福股份公司 | Polyisobutenamines |
| CN101955558B (en) * | 2009-07-15 | 2013-03-13 | 北京化工大学 | Initiating system for preparing high-reaction activity polyisobutene and copolymer of polyisobutene |
| CN103897086A (en) * | 2014-03-05 | 2014-07-02 | 北京石油化工学院 | Preparation method of poly(isobutene-co-p-methylstyrene) random copolymer |
| CN109694453A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of preparation method of block copolymer and a kind of monovinylarene-isomonoolefin-monovinylarene block copolymers |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69223515T2 (en) * | 1991-07-15 | 1998-06-25 | Exxon Chemical Patents Inc | LIVING CARBOXATIONAL POLYMERIZATION PROCESS |
| US5708103A (en) * | 1995-02-01 | 1998-01-13 | Kuraray Co., Ltd. | Process for producing a polymer of vinylic compounds |
-
1998
- 1998-06-19 CN CN98102282A patent/CN1062568C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453565C (en) * | 2002-04-05 | 2009-01-21 | 巴斯福股份公司 | Polyisobutenamines |
| CN101955558B (en) * | 2009-07-15 | 2013-03-13 | 北京化工大学 | Initiating system for preparing high-reaction activity polyisobutene and copolymer of polyisobutene |
| CN103897086A (en) * | 2014-03-05 | 2014-07-02 | 北京石油化工学院 | Preparation method of poly(isobutene-co-p-methylstyrene) random copolymer |
| CN109694453A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of preparation method of block copolymer and a kind of monovinylarene-isomonoolefin-monovinylarene block copolymers |
| CN109694453B (en) * | 2017-10-20 | 2021-08-03 | 中国石油化工股份有限公司 | Preparation method of block copolymer and monovinylarene-isomonoolefin-monovinylarene block copolymer |
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| Publication number | Publication date |
|---|---|
| CN1062568C (en) | 2001-02-28 |
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Assignee: Rongtai Industry Co., Ltd., Guangdong Assignor: Beijing Petro-Chemical Industry College Contract record no.: 2010440001554 Denomination of invention: Inductive system for activated cation Granted publication date: 20010228 License type: Exclusive License Open date: 19981216 Record date: 20101229 |
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Granted publication date: 20010228 |
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