CN1631880A - Carbazole dithioformate RAFT reagent and preparation method and application thereof - Google Patents
Carbazole dithioformate RAFT reagent and preparation method and application thereof Download PDFInfo
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- CN1631880A CN1631880A CN 200410072591 CN200410072591A CN1631880A CN 1631880 A CN1631880 A CN 1631880A CN 200410072591 CN200410072591 CN 200410072591 CN 200410072591 A CN200410072591 A CN 200410072591A CN 1631880 A CN1631880 A CN 1631880A
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Abstract
Disclosed is a RAFT and its preparing method and its application, belongs to the technology to polymerize active free radical; the structure general fomulor 1 RAFT is shown in the righ figure; dissolve carbazole and strong alkali into the reagent, after a while, add carbon disulfide reaction, then disulfide diN-carbazole generated by adding iodine, add azo diisobutyronitrile and azo-bis-iso-heptonitrile seperately to make N-carbazole. The reagent has good ability to control the polymerization of free radical of conjugate monomer of styrene and methyl methacrylate. Its advantages include, friendly condition for polymerizing the reagent, can be easily controlled, has high productivity, since it is solid, it can be purificated by recrystallization, which avoids complex purification course of chromatographic column, can be store stably for long period.
Description
Technical field
The present invention relates to a kind of carbazole dithioformate RAFT reagent and preparation method and application, belong to living radical polymerization technique.
Background technology
From the seventies in 20th century, the high molecular scholar just begins to be devoted to Study on Living Radical Polymerization.But the real breakthrough of Study on Living Radical Polymerization is to wait at the grand row in big Tianjin of nineteen eighty-two to propose the Iniferter notion, and is applied to living polymerization.This method has realized making Study on Living Radical Polymerization enter a new developmental stage to free radical activity and to the control of transfer reaction from chemical terms.The nineties, realized nitroxyl free radical (TEMPO) in succession
[1], atom transferred free radical (ATRP)
[2]With reversible addition-cracking chain transfer free radical (Reversibleaddition-fragmentation chain trans-fer, RAFT)
[3]The isoreactivity polymerization system.
The RAFT polymerization mechanism is Rizzardo patent (WO9801478) in 1998
[3]In at first propose.Compare with other active free radical polymerization, the RAFT polymerization technique can be the same with common free crowd reacts in being lower than 80 ℃ environment, and the suitable monomers scope is broader, and the RAFT polymerization more is applicable to environmental friendliness polymerization processs such as suspension polymerization and letex polymerization.
Can the key that the RAFT polymerization successfully realizes be find a kind of suitable compound as chain-transfer agent, is called RAFT reagent.At present, this class active chain transfer agent commonly used is the dithioesters derivative.
The dithioesters class RAFT reagent of having reported mainly is based on phenyl ring, pyrroles and alkane
[3,4], make two sulfuric acid based on the many grignard reactions of dithioesters class RAFT reagent of phenyl ring and alkane by halogeno-benzene, then with the alkene addition, the building-up process complexity, severe reaction conditions, productive rate is lower.Product is heavy-gravity liquid normally, generally separates by column chromatography, separates purification difficult.Poor stability is even can not preserve for a long time under the low temperature.This is the difficult point of RAFT polyreaction.The reference that relates to relevant RAFT reagent:
[1].Georges?M?K，Veregin?R?P.[J].Macromolecules，1993，26：2987～2990
[2].Wang?J?S，Matyjaszewski?K.[J].Am?Chem?Soc，1995，117：5614～5617
[3].Le?T?P.Polymerization?with?Living?Characteristics?PCT?Int?Appl，WO9801478Al.98-01-15
[4].Mc?CORMICK，CharlesL，Polymerization?process?with?living?Characteristics?andpolymers?made?therefrom?PCT?Int?APPL，WO?9931144?AL.03-8-14
Summary of the invention
A kind of carbazole dithioformate RAFT reagent and preparation method and application have been the object of the present invention is to provide.This kind RAFT reagent building-up process is simple, separates and purifies easily, and product can be preserved for a long time, and vinylbenzene and methyl methacrylate equiconjugate alkene are had controllability preferably.
The present invention is achieved by the following technical solutions: a kind of carbazole dithioformate RAFT reagent, and its general structure is:
R is
Or
Above-mentioned carbazole dithioformate RAFT reagent preparation method comprises following process:
1, the preparation of over cure two N-carbazole sulfo-formyls:
Carbazole and sodium hydroxide, yellow soda ash, sodium, potassium hydroxide, salt of wormwood or potassium in molar ratio 1: (1～4), be dissolved in tetrahydrofuran (THF), DMF or the acetone, in 10～60 ℃ of reactions 2～10 hours, press the mol ratio 1 of carbazole and dithiocarbonic anhydride then: (1～4) adds dithiocarbonic anhydride, in 10～42 ℃, reacted again 1～4 hour, press carbazole and iodine mol ratio 1: (1～3) adds iodine, reacts 0.5～3 hour down in 20～50 ℃, makes over cure two N-carbazole sulfo-formyls.
2, the preparation of carbazole dithioformate RAFT reagent:
1) preparation of the two bamic acid isopropyl cyanide esters of N-carbazole:
In above-mentioned over cure two N-carbazole sulfo-formyls in molar ratio 1: the ratio of (1～3) adds Diisopropyl azodicarboxylate, in 50～70 ℃ of reactions 20～60 hours, with the deionized water repetitive scrubbing repeatedly, obtains the thick product of yellow solid.Purify through recrystallization, make target product.
2) preparation of the two different heptonitrile esters of bamic acid of N-carbazole:
In above-mentioned over cure two N-carbazole sulfo-formyls in molar ratio 1: (1～3) adds 2,2'-Azobis(2,4-dimethylvaleronitrile), in 50～70 ℃ of reactions 20～60 hours, with the deionized water repetitive scrubbing repeatedly, obtains the thick product of yellow solid.Purify through recrystallization, make target product.
The application of above-mentioned carbazole dithioformate RAFT reagent:
At vinylbenzene, methyl methacrylate, butyl acrylate in the radical polymerization of vinylformic acid or acrylamide, adds above-mentioned RAFT reagent and can make the polymkeric substance of specifying molecular weight and narrow molecular weight distributions.
In sum, compare with other dithioesters class RAFT reagent, major advantage of the present invention is: the hydrogen that links to each other with nitrogen on the carbazole is more active, can generate carbazole salt with the highly basic reaction, the reaction conditions gentleness, and control easily, raw material is easy to get, the yield height.
The two thiocarboxylics of carbazole are solid, are easy to purify by recrystallization, have avoided complicated chromatographic column purification process, and the yield height, have reduced the purification operations difficulty of product.The two thiocarboxylics of solid carbazole are easy to long-time stable the preservation.It is active that the two thiocarboxylics of carbazole have higher addition fracture, and vinylbenzene and the monomeric radical polymerization of methyl methacrylate equiconjugate type are had controllability preferably, can make the polymkeric substance of specifying molecular weight and narrow molecular weight distributions.So the synthetic carbazole dithioformate RAFT reagent has an enormous advantage than the RAFT reagent tool of other type among the present invention, and bigger industrial prospect is arranged.
Specific implementation method
Example 1:
In the round-bottomed flask of 100ml, add 3.34g (0.02mol) carbazole and 40ml tetrahydrofuran solvent, add the sodium Metal 99.5 that 0.46g (0.02mol) chops up again.Under nitrogen protection, reaction is 10 hours in 10 ℃ water-bath, and stopped reaction filters unreacted sodium.Add 1.52g (0.02mol) dithiocarbonic anhydride again, reacted 4 hours down in 10 ℃.Make the two bamic acid sodium of N-carbazole.Add 2.54g (0.02mol) iodine then,, make over cure two N-carbazole sulfo-formyls in 20 ℃ of reactions 3 hours.
Example 2:
In the round-bottomed flask of 100ml, add 3.34g (0.02mol) carbazole and 40ml acetone solvent, add 3.2g (0.08mol) sodium hydroxide again.Under nitrogen protection, reaction is 2 hours in 64 ℃ water-bath, and stopped reaction filters unreacted sodium hydroxide.Add 6.08g (0.08mol) dithiocarbonic anhydride again, reacted 1 hour down in 42 ℃.Obtain the two bamic acid sodium of N-carbazole.Add 7.62g (0.06mol) iodine then,, make over cure two N-carbazole sulfo-formyls in 50 ℃ of reactions 0.5 hour.
Example 3:
In the round-bottomed flask of 100ml, add 3.34g (0.02mol) carbazole and 40ml DMF solvent, add the yellow soda ash of 3.18g (0.03mol) again.Under nitrogen protection, reaction is 5 hours in 55 ℃ water-bath, and stopped reaction filters unreacted yellow soda ash.Add 3.04g (0.04mol) dithiocarbonic anhydride again, reacted 2 hours down in 38 ℃.Make the two bamic acid sodium of N-carbazole.Add 2.54g (0.02mol) iodine then, be warming up to 50 ℃ of reactions 2 hours then, obtain over cure two N-carbazole sulfo-formyls.
Example 4:
In the round-bottomed flask of 100ml, add 3.34g (0.02mol) carbazole and 40ml tetrahydrofuran solvent, add 1.17g (0.03mol) potassium again.Under nitrogen protection, reaction is 5 hours in 55 ℃ water-bath, and stopped reaction filters unreacted potassium.Add 3.04g (0.04mol) dithiocarbonic anhydride again, reacted 2 hours down in 38 ℃.Make the two bamic acid potassium of N-carbazole.Add 2.54g (0.02mol) iodine then, reacted 2 hours down, make over cure two N-carbazole sulfo-formyls in 50 ℃.
Example 5:
In the round-bottomed flask of 100ml, add 3.34g (0.02mol) carbazole and 40ml DMF solvent, add 4.14g (0.03mol) salt of wormwood again.Under nitrogen protection, reaction is 5 hours in 55 ℃ water-bath, and stopped reaction filters unreacted salt of wormwood.Add 3.04g (0.04mol) dithiocarbonic anhydride again, control reaction temperature was 38 ℃ of reactions 2 hours.Make the two bamic acid potassium of N-carbazole.Add 2.54g (0.02mol) iodine then, be warming up to 50 ℃ of reactions 2 hours then, make over cure two N-carbazole sulfo-formyls.
Example 6:
In the single necked round bottom flask of 100ml, add 3.34g (0.02mol) carbazole and 40ml DMF solvent, add 1.68g (0.03mol) potassium hydroxide again.Under nitrogen protection, reaction is 5 hours in 55 ℃ water-bath, and stopped reaction filters unreacted potassium hydroxide.Add 3.04g (0.04mol) dithiocarbonic anhydride again, reacted 2 hours down in 38 ℃.Make the two bamic acid sodium of N-carbazole.Add 2.54g (0.02mol) iodine then, reacted 2 hours down, make over cure two N-carbazole sulfo-formyls in 50 ℃.
Example 7:
To example 6, add 3.28g (0.02mol) Diisopropyl azodicarboxylate at above-mentioned example 1, reacted 60 hours down in 50 ℃.With the reactant cool to room temperature, the deionized water repetitive scrubbing repeatedly obtains the yellow solid product.Through the sherwood oil recrystallization, obtain the two bamic acid isopropyl cyanide esters of yellow N-carbazole.Productive rate 75%.
1H-nmr (CDCL
3), d (ppm): δ=2.031 (m, 6H) δ=8.342～8.314 (2H, doublet), δ=7.999～7.975 (m, 2H), δ=7.475～7.257 (s, 4H).IR:3054cm
-1Place's absorption band is the stretching vibration peak of the c h bond that links to each other with carbazole group, 2924cm
-1Place's absorption band is the stretching vibration of the c h bond on the methyl, 2229cm
-1Place's absorption band is a CN triple-linked stretching vibration peak, 1039cm
-1Place's absorption band is the stretching vibration of the two keys of C=S.
Example 8:
To example 6, add 13.12g (0.08mol) Diisopropyl azodicarboxylate at above-mentioned example 1, reacted 60 hours down in 70 ℃.With the reactant cool to room temperature, the deionized water repetitive scrubbing repeatedly obtains the yellow solid product.Through the sherwood oil recrystallization, make the two bamic acid isopropyl cyanide esters of pure yellow N-carbazole.Productive rate 70%.Structural analysis is with example 7.
Example 9:
To example 6, add 4.92g (0.03mol) Diisopropyl azodicarboxylate at above-mentioned example 1, reacted 50 hours down in 60 ℃.With the reactant cool to room temperature, the deionized water repetitive scrubbing repeatedly obtains the yellow solid product.The sherwood oil recrystallization makes the two bamic acid isopropyl cyanide esters of pure yellow N-carbazole.Productive rate 72%.Structural analysis is with example 7.
Example 10:
To example 6, add 4.96g (0.02mol) 2,2'-Azobis(2,4-dimethylvaleronitrile) at above-mentioned example 1, reacted 60 hours down in 50 ℃.With the reactant cool to room temperature, the deionized water repetitive scrubbing repeatedly obtains the yellow solid product.Through the sherwood oil recrystallization, make the two different heptonitrile esters of bamic acid of pure yellow N-carbazole.Productive rate 65%.
Example 11:
To example 6, add 19.84g (0.08mol) 2,2'-Azobis(2,4-dimethylvaleronitrile) at above-mentioned example 1, reacted 60 hours down in 70 ℃.With the reactant cool to room temperature, the deionized water repetitive scrubbing repeatedly obtains the yellow solid product.Through the sherwood oil recrystallization, make the two different heptonitrile esters of bamic acid of pure yellow N-carbazole.Productive rate 70%.
Example 12:
To example 6, add 7.44g (0.03mol) 2,2'-Azobis(2,4-dimethylvaleronitrile) at above-mentioned example 1, reacted 50 hours down in 60 ℃.With the reactant cool to room temperature, the deionized water repetitive scrubbing repeatedly obtains the yellow solid product.The sherwood oil recrystallization makes the two different heptonitrile esters of bamic acid of pure yellow N-carbazole.Productive rate 60%.
Example 13:
In the four-hole bottle of 100ml, add 40g vinylbenzene, 0.063g Diisopropyl azodicarboxylate, the two bamic acid isopropyl cyanide esters of 0.64gN-carbazole, logical nitrogen protection.Under stirring action, reaction is 10 hours in 70 ℃ water-bath.Obtain polystyrene through petroleum ether precipitation then, vacuum drying oven is dried to constant weight and weighs, and calculating transformation efficiency is 40%, and GPC records number-average molecular weight and molecular weight distribution is respectively 7342 and 1.12.
Example 14:
In the four-hole bottle of 100ml, add the 40g methyl methacrylate, 0.031g Diisopropyl azodicarboxylate, the two bamic acid isopropyl cyanide esters of 0.64gN-carbazole, logical nitrogen protection.Under stirring action, reaction is 6 hours in 70 ℃ water-bath.Obtain polymethylmethacrylate through petroleum ether precipitation then, vacuum drying oven is dried to constant weight and weighs, and calculating transformation efficiency is 55%, and GPC records number-average molecular weight and molecular weight distribution is respectively 1158 and 1.22.
Claims (5)
1, a kind of carbazole dithioformate RAFT reagent, its structure is:
2, a kind of carbazole dithioformate RAFT reagent, its structure is:
3, the preparation method of the described carbazole dithioformate RAFT reagent of a kind of claim 1 is characterized in that comprising following process:
Carbazole and sodium hydroxide, yellow soda ash, sodium, potassium hydroxide, salt of wormwood or potassium in molar ratio 1: (1～4), be dissolved in tetrahydrofuran (THF), in DMF or the acetone, reacted 2～10 hours down in 10～60 ℃, press the mol ratio 1 of carbazole and dithiocarbonic anhydride then: (1～4) adds dithiocarbonic anhydride, under 10～42 ℃, reacted again 1～4 hour, press carbazole and iodine mol ratio 1: (1～3) adds iodine, in 20～50 ℃ of following solution reactions 0.5～3 hour, press carbazole and Diisopropyl azodicarboxylate mol ratio 1 again: (1～3) adds Diisopropyl azodicarboxylate, reacted 20～60 hours down in 50～70 ℃, with the deionized water repetitive scrubbing repeatedly, obtain the thick product of yellow solid, purify through recrystallization, make target product.
4, the preparation method of the described carbazole dithioformate RAFT reagent of a kind of claim 2 is characterized in that comprising following process:
Carbazole and sodium hydroxide, yellow soda ash, sodium, potassium hydroxide, salt of wormwood or potassium in molar ratio 1: (1～4), be dissolved in tetrahydrofuran (THF), in DMF or the acetone, reacted 2～10 hours down in 10～60 ℃, press the mol ratio 1 of carbazole and dithiocarbonic anhydride then: (1～4) adds dithiocarbonic anhydride, under 10～42 ℃, reacted again 1～4 hour, press carbazole and iodine mol ratio 1: (1～3) adds iodine, reacted 0.5～3 hour down in 20～50 ℃, press carbazole and 2,2'-Azobis(2,4-dimethylvaleronitrile) mol ratio 1 again: (1～3) adds 2,2'-Azobis(2,4-dimethylvaleronitrile), reacted 20～60 hours down in 50～70 ℃, with the deionized water repetitive scrubbing repeatedly, obtain the thick product of yellow solid, purify through recrystallization, make target product.
5, the application of claim 1 or 2 described carbazole dithioformate RAFT reagents, it is characterized in that at vinylbenzene, methyl methacrylate, butyl acrylate, in the radical polymerization of vinylformic acid or acrylamide, add above-mentioned RAFT reagent and can make the polymkeric substance of specifying molecular weight and narrow molecular weight distributions.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106046221A (en) * | 2016-05-23 | 2016-10-26 | 北京化工大学 | Catalyst for reversible-dormant free radical polymerization and polymerization method |
| CN107922344A (en) * | 2015-06-12 | 2018-04-17 | 联邦科学与工业研究组织 | general RAFT agent |
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2004
- 2004-11-01 CN CN 200410072591 patent/CN1631880A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107922344A (en) * | 2015-06-12 | 2018-04-17 | 联邦科学与工业研究组织 | general RAFT agent |
| EP3307716A4 (en) * | 2015-06-12 | 2018-12-26 | Commonwealth Scientific and Industrial Research Organisation | Versatile raft agent |
| CN106046221A (en) * | 2016-05-23 | 2016-10-26 | 北京化工大学 | Catalyst for reversible-dormant free radical polymerization and polymerization method |
| CN106046221B (en) * | 2016-05-23 | 2018-06-26 | 北京化工大学 | The catalyst and polymerization of a kind of reversible-suspend mode free radical polymerization |
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