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Electronic Supplementary Information (ESI) for

Design, Synthesis and Self-Assembly Manipulating of Polymerized

Ionic Liquids Contained Imidazolium Based on “Jacketing” Effect

Liang Weng

a

, Jiao-Jiao Yan

a

, He-Lou Xie

a

*, Gun-Qun Zhong

a

, Si-Qi Zhu

a

,

Hai-Liang Zhang

a

*, Er-Qiang Chen

b a

Key Laboratory of Special Functional Polymer Materials of Hunan Province, Key

Laboratory of Advanced Functional Polymer Materials of Colleges and Universities of Hunan Province and Key Lab of Environment-friendly Chemistry and Application in Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan

411105, Hunan Province, China b

Key Laboratory of Polymer Chemistry and Physics of the Ministry of Education,

College of Chemistry and Molecular Engineering, Peking University, Beijing 100871,

China

*

To whom the correspondence should be addressed.

E-mail: [email protected]

(HLX) and [email protected]

(HLZ)

The preparation of momomer and polymer

The monomer 2,5-bis{[6-(4- -butoxy-4´-oxy phenyl) hexyl] oxycarbonyl} styrene(M2) and the corresponding polymer (P2) was synthesized as shown in Scheme S1

1

Scheme S1

. Synthetic route of the monomerM2 and the corresponding polymerP2.

The Synthesis of 4-Butoxyphenol.

The hydroquinone 20.05g (0.18mol) and n-butyl bromide 22.01g (0.17mol), K

2

CO

3

50.02g (0.36mol), and together with 200 ml DMF were added to a 500 ml round bottom flask and refluxed for 24h. After the reaction, the reaction mixture was cooled and filtered, the filter residue was washed with a small quantity of DMF. The filtrate was collected and precipitated into ice water 3 times. After filtering, the filter residue was dissolved with little dichloromethane and purified by column chromatography (dichloromethane). By removing the solvent with rotate vaporizing apparatus, the product was recrystalled into petroleum ether, then filtered and dried in a vacuum oven gave a white needle crystal. Yield: 70.25%.

1

H NMR (CDCl

3

)

δ

(ppm): 7.46-7.40(d, 4H, Ar-

H

), 4.36-4.34(s, 1H, -O

H

),

3.92-3.88(t, 2H, -OC

H

2

-), 1.77-1.69(m, 2H, -OCH

2

C

H

2

-), 1.52-1.43(m, 2H,

-C

H

2

CH

3

), 0.98-0.90(t, 3H, -C

H

3

).

The Synthesis of

ω-(4´-Butoxy phenyl-4-yloxy)-1-Bromo-Hexane.

The

1,6-dibromohexane 18.02g (73.77mmol), 4-Butoxyphenol 2.52g (15.18mmol), KOH

1.26g (22.50mmol), and together with 60 ml acetone were added to a 250 ml round bottom flask and heated to 80 o

C for 8 h. After the reaction, the reaction mixture was

2

cooled and filtered, the filter residue was washed with a small quantity of acetone.

The filtrate was collected and removed much solvent with rotate vaporizing apparatus.The product was purified by column chromatography (petroleum ether: dichloromethane = 2:1), then removed the solvent with rotate vaporizing apparatus, and dried in a vacuum oven gave a white solid. Yield: 30.21%.

1

H NMR (CDCl

3

)

δ

(ppm): 6.83-6.82 (d, 4H, Ar-

H

), 3.92-3.88(t, 4H, -OC

H

2

-), 3.45-3.39 (t, 2H, -C

H

2

Br),

1.93-1.43(m, 12H, -C

H

2

-), 0.99-0.94(t, 3H, -C

H

3

).

Synthesis of monomer 2,5-bis{[6-(4-butoxy-4´-oxy phenyl) hexyl] oxycarbonyl} styrene (M2).

Vinyl p-biphthalic acid 0.47g (2.44mmol), potassium hydrogen carbonate 0.74g(7.40mmol) and dry acetonitrile (40mL) were input a 250mL three-neck round bottom flask and stirred at room temperature for 30 min to form potassium salt. The ω-(4´-Butoxy phenyl-4-yloxy)-1-Bromo-Hexane 2.00g(6.08mmol) and little nitrobenzene in acetonitrile (40mL) were added to the flask, then the resulting mixture was heated to 80ºC for 24h. After the reaction, the reaction mixture was cooled and filtered, and the filter residue was washed with a small quantity of dichloromethane. The residual liquid was purified by column chromatography

( dichloromethane ), then removed the solvent with rotate vaporizing apparatus, and dried in a vacuum oven gave a white solid. Yield: 43.12%.

1

H NMR (CDCl

3

)

δ

(ppm):

8.24 (s, 1H, Ar-

H

), 7.86 (d, 2H, Ar-

H

), 7.45-7.38(d, 1H, -C

H

=), 6.82-6.80(d, 8H,

Ar-

H

), 5.75-5.39(d, 2H, =C

H

2

), 4.40-4.31(t, 4H, -COOC

H

2

-), 3.92-3.88(t, 8H,

-OC

H

2

-),

δ=

2.15-1.45(m, 24H, -C

H

2

-), 1.00-0.94(t, 6H, -C

H

3

)

3

Synthesis of polymer Poly(2,5-bis{[6-(4-butoxy-4´-oxy phenyl) hexyl] oxycarbonyl} styrene) (P2).

The polymer without ionic groups was synthetized by conventional radical polymerization. A typical polymerization procedure was carried out as follows. M2(0.20g, 0.29mmol)and AIBN (0.476mg) were dissolved in DMF

(0.372 mL) and degassed through three freeze−pump−thaw cycles, the tube was sealed off under vacuum. Polymerization was carried out at 70ºC for 8h. The reaction mixture was diluted with dichloromethane, and then reprecipitated in methanol. By filtering, the polymer was dried in a vacuum oven.Yield:75%. (GPC results: M n

=88000g mol

-1

, M w

/ M n

=2.23)

Figure S1.

1

H NMR spectra of M2 and P2.

4

Figure S2.

GPC trace of P2.

Figure S3.

TGA thermograms of P2 at a ramp rate of 10 ºC/min in nitrogen flow.

Figure S4.

DSC thermograms of P2 upon the second heating.

5

Figure S5.

Representative textures of P2 at 80

°

C (200 × magnification) with PLM.

6

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