Hi

It is possible to polymerize this monomer , witg Maghnite-H or Montmorillonite,in bulk at RT.

Pr M.Belbachir

Thank you for your feedback,

I will have a look into the suggested initiator. Could you eleborate a bit about the procedure or supply a literature reference, Mohamed?

Regarding Michels question:

I tried to polymerize vinylbenzyl imidazolium chloride (quaternization of vinylbenzyl chlorid with methyl imidazole). I have a nmr and I will post it tomorrow. Thank you.

I am mostly interested to understand the process of this paticular radical polymerization in more detail, so papers and book recommendations are very welcomed.

Best regards

Judith

Hi, you can see this paper. It help you possoibly.

Thermoresponsive poly(ionic liquid): Controllable RAFT synthesis, thermoresponse, and application in dispersion RAFT polymerization

DOI: 10.1002/pola.27929

http://onlinelibrary.wiley.com/wol1/doi/10.1002/pola.27929/full

Most probably you still have quite a lot of inhibitor in your monomer and that's why it is not polymerising properly. Try also using a more aggressive radical starter.

Dear Michel,

I followed the follwing procedure:

4,9 g VBMIM Cl in DMF(80 wt%) mixed then 2 wt% AIBN (recristallized) dissolved in DMF added and cooked with a cooler under Nitrogen @ 80°C 16 hrs overnight --> precipitation not sucessfull

Repeat:

4,9 g VBMIM Cl in DMF (80 wt%) mixed then 1 wt% AIBN (recristallized) dissolved in DMF added and cooked with a cooler under Nitrogen @ 80°C 16 hrs overnight --> precipitation not sucessfull

4,9 g VBMIM Cl in DMF (80 wt%) mixed then 1 wt% BPO dissolved in DMF added and cooked with a cooler @ 80°C 16 hrs overnight --> precipitation not sucessfull

4,9 g VBMIM Cl in Chlorofom (80 wt%) mixed then 1 wt% AIBN dissolved in Chloroform added and cooked with a cooler @ 80°C 16 hrs overnight --> precipitation not sucessfull

4,9 g VBMIM Cl in DMF (70 wt%) mixed then 1 wt% AIBN (recristallized) dissolved in DMF added and cooked with a cooler under Nitrogen @ 80°C 72 hrs --> geled product not dissolveable in water/MeOH/EtOH/EtAc/MeCN/DMF/Acetone/Tolene

0,5 g  VBMIM Tf2N in DMF (70 wt%) mixed then 1 wt% AIBN (recristallized) dissolved in DMF added and cooked with a cooler under Nitrogen @ 80°C 72 hrs --> precipitation but very mucilaginous --> not film forming

0,5 g VBMIM Tf2N in DMF (70 wt%) mixed then 1 wt% AIBN (recristallized) dissolved in DMF added, Freeze thaw cycles and Polymerization in an anionic line under Argon @ 80°C 16hrs overnight --> no precipitation

Do you want the NMR of all the starting products? for the geled I tried solid state NMR but no success. The sucess of the polymerization I checked by looking at the IR in the process and by precipitation.

Dear Boyan,

I calculated the amount of Inhibitor and the amount of initiator was definitly exeeding the inhibitor amount.

I had a look into transfer constants of solvents and DMF is less qualified compared to Chloroform. But I also found that the polymerization of Methyl styrene works best, in bulk (without solvent) and lower amount of Initiator. So maybe that was the problem? Because the Molecular weight that I achieved was too low for precipitation? Do you think the stabilization of the benzyl radical was negativly contributing to the result?

I believe the 1-vinyl-3-benzylimidazolium is meant and it is also clear how it was synthesized. The question is rather the purification and if the monomer has not at least partially already polymerized and how much of the stabilizer is stuck into it. Chloroform should indeed be better than DMF and molecular weight will have an effect on solubility, how about making an MS before we jump to conclusions?

@Michael: yes, you are right, I missed this one...so it's the 1-(4-vinyl-benzil)-3-methylimidazolium chloride....

An interesting alternative is redox polymerization. For this purpose you must solve half of your monomer in water together with 1 weight% of potassiumperoxodisulfate or ammoniumperoxodisulfate and the other half also in water together with 1 weight% of ascorbic adic. Then you can pour both halves together and polymerization takes place at room temperature.

A complete different strategy would be to polymerize first the chloromethyl styrene (vinyl benzylchloride) optionally in presence of comonomers like styrene in a conventional manner and to make afterwards the reaction with the alkylimidazole.

Dear Scientist,

thank you very much for all the valubale contributions, espacially the detailed reply of Mr. Shaplov,

Please find attached some H-NMR.

I tried the following monomer procedure:

VB-Cl + 1-methylImidazole (without solvent) first combined at 0°C, then slow heat up to 60°C and stirring overnight.

The next day evaporation of solvents and inhibitor in a high vacuum pump (10-7 mbar) @ 60°C

or extraction with Diethylether --> removal of Diethylether by Rotary evaporator.

To dry out residual solvents zeolithes with 3 Angström used

I once run VB-Cl over a column and the tried to quaternize but it polymerized before the quaternization.

Monomers were kept in a deep freezer @-18 °C

I will have a read on the suggested papers.

Thank you very much for the contributions.

Best regards

Judith

I forgot to add: regarding the remark of AIBN, I did recrystalize it.

First top - 6 th bottom:

• First NMR VBMIM BF4 after polymerization
• 2nd VBMIM Tf2N after polymerization --> was gelly
• 3rd VB-Cl after Column
• 4th VBMIM Cl after polymerization
• 5th VBMIM Cl before polymerization
• 6th VB-Cl fresh from the bottle (sigma aldrich)

[names appear in an mouse over effect]

No it is not a mixture:

http://www.sigmaaldrich.com/catalog/product/aldrich/436887?lang=de®ion=DE&gclid=Cj0KEQiA4qSzBRCq1-iLhZ6Vsc0BEiQA1qt-zlEGNUh1mNWAXEuO-ycY5vLOzux1GGOkB9Nqei-VzYgaApyf8P8HAQ

inhibitor: 500 ppm tert-butylcatechol