RAFT Polymerization of Acrylamide Polyhedral Oligometic Silsesquioxane in Supercritical CO2+

doi:10.7503/cjcu20150377

Abstract

Abstract:

Polyacrylamide(PAM) isobutyl-polyhedral oligometic silsesquioxane(POSS)(PAMPOSS) homopolymer and PAMPOSS-b-PMMA(polymethyl methacrylate) block copolymers were prepared via reversible addition-fragmentation transfer(RAFT) polymerization using benzenecarbodithioic acid 1,1-dimethylethyl ester as the RAFT agent in supercritical CO₂. The products were characterized. The results show that polymerization reaction in supercritical CO₂ is well controlleded. Both of PAMPOSS and PAMPOSS-b-PMMA have high degree of polymerization(DP) and low polydispersity index(PDI). It can be also found that the polymerization of AM-POSS is a homogeneous reaction, and the solubility of POSS containing polymers in supercritical CO₂ is effected by the crystallinity of POSS.

Key words: Supercritical CO2, Polyhedral oligometic silsesquioxane(POSS), Benzenecarbodithioic acid 1, 1-dimethylethyl ester(TTBT), Reversible addition fragmentation transfer(RAFT) polymerization

CLC Number:

O631

TrendMD:

CHENG Long, BIAN Zhongxuan, DING Minyuan, ZHAO Meng, LI Hui. RAFT Polymerization of Acrylamide Polyhedral Oligometic Silsesquioxane in Supercritical CO₂⁺[J]. Chem. J. Chinese Universities, 2015, 36(10): 2067.

Figures/Tables 11

Scheme 1 Synthesis of polymers PAMPOSS and PAMPOSS-b-PMMA

Fig.1 1H NMR spectrum of AM-POSS^Peaks a—i are the same as compound AM-POSS in Scheme 1.

Fig.2 FTIR spectrum of AM-POSS

Table 1 Conversion and molecular weight of PAMPOSS

Time/h	Conversion of monomer(%)	ln([M₀]/[M])	10^-3M_n,NMR	10^-3M_n,th	10^-3M_n,GPC	PDI
12	32.1	0.39	5.57	5.96	2.32	1.12
24	44.9	0.60	8.35	8.34	3.20	1.11
36	63.4	1.01	12.06	11.77	5.12	1.13
48	72.6	1.29	13.92	13.47	6.60	1.30
72	83.3	1.79	15.78	15.47	8.34	1.36

Fig.3 1H NMR spectra of PAMPOSS(a) and PAMPOSS-b-PMMA(b)

Fig.4 Dependence of Mn on AM-POSS conversion(c)

Table 2 Effect of pressure on conversion and molecular weight of PAMPOSS*

Pressure/MPa	Conversion of monomer(%)	10^-3M_n,NMR	10^-3M_n,th	10^-3 M_n,GPC	PDI
20	72.6	13.92	13.47	6.60	1.30
25	71.4	13.74	13.25	6.45	1.26
30	70.1	13.56	13.01	6.23	1.20

Fig.5 Reaction kinetics curve of PAMPOSS

Fig.6 FTIR spectra of PAMPOSS(a) and PAMPOSS-b-PMMA(b)

Table 3 Molecular weight of PAMPOSS and PAMPOSS-b-PMMA

Structure	10^-3M_n,NMR	10^-3M_n,th	10^-3M_n,GPC	PDI
PAMPOSS	13.92	13.47	6.60	1.30
PAMPOSS-b-PMMA	443.60	450.30	480.20	1.35

Fig.7 GPC spectra of PAMPOSS homopolymer(a) and PAMPOSS-b-PMMA block copolymer(b)

References 25

[1]	Zheng H. Z., Li Z. H., Yun G., Wei A. Z., Polym. Chem., 2014, 5, 4534—4541
[2]	Zhang W. A., Muller A. H. E., Prog. Polym. Sci., 2013, 38(8), 1121—1162
[3]	Kannan R. Y., Salacinski H. J., Butler P. E., Acc. Chem. Res., 2005, 38(11),879—884
[4]	Lin Y. C., Kuo S. W., Polym. Chem., 2012, 4, 882—891
[5]	Li Y. W., Hao S., Feng X. Y., Yue K., Lin Z. W., Zhu X. L., Fu Q., Zhang Z. B., Cheng S. Z. D., Zhang W. B., Polym. Chem., 2015, 6, 827—837
[6]	Raus V., Cadova E., Starovoytova L., Janata M., Macromolecules, 2014, 47, 7311—7320
[7]	Li Y. W., Dong X. H., Guo K., Wang Z., Chen Z., Wesdemiotis C., Quirk R. P., Zhang W. B., Cheng S. Z. D., ACS. Macro. Lett., 2012, 1, 834—839
[8]	Franczyk A., He H., Burdynska J., Hui C. M., Matyjaszewski K., Marciniec B., ACS. Macro. Lett., 2014, 3, 799—802
[9]	Wang C. M., Zhang X. Q., Zhao Y., Han B. X., Wang D. J., Chem. J. Chinese Universities, 2010, 31(6), 1252—1256
	(王长明, 张秀芹, 赵莹, 韩布兴, 王笃金. 高等学校化学学报,2010, 31(6), 1252—1256)
[10]	Yu H. Q., Zhang Y., Wu B., Yang N. N., Yang X. N., Liu X. J., Chem. Res. Chinese Universities, 2011, 27(5), 850—853
[11]	Zhang J.C., Supercritical Fluid Extraction, Chemical Industry Press, Beijing, 2000, 149—151
	(张镜澄. 超临界流体萃取, 北京: 化学工业出版社, 2000, 149—151)
[12]	Liu X. W., Li H., Zhao Z., Miu X. R., Han Z. W., Chem. J. Chinese Universities, 2013, 34(6), 1536—1541
	(刘小伟, 李慧, 赵镇, 缪夏然, 韩哲文. 高等学校化学学报,2013, 34(6), 1536—1541)
[13]	Villarroya S., Thurecht K.J., Heise A., Howdle S. M.,Chem. Commun., 2007, (37), 3805—3813
[14]	Zhou J. X., Villarroya S., Wang W. X., Wyatt M. F., Duxbury C. J., Thurecht K. J., Howdle S. M., Macromolecules, 2006, 39(16), 5352—5358
[15]	Duxbury C. J., Wang W. X., De G. M., Heise A., Howdle S. M., J. Am. Chem. Soc., 2005, 127(8), 2384—2385
[16]	Chong Y. K., Krstina J., Le T. T., Moad G., Postma A., Rizzardo E., Thang S. H., Macromolecules, 2003, 36, 2256—2272
[17]	Chiefari J., Mayadunne R. A., Moad C. L., Moad G., Rizzardo E., Postma A., Skidmore M. A., Thang S. H., Macromolecules, 2003, 36, 2273—2283
[18]	Johnston-Hall G., Stenzel M. H., Davis T. P., Barner-Kowollik C., Monteiro M. J., Macromolecules, 2007, 40, 2730—2736
[19]	Loiseau J., Doeerr N., Suau J. M., Egraz J. B., Llauro M. F., Ladaviere C., Claverie J., Macromolecules, 2003, 36, 3066—3077
[20]	Favier A., Ladaviere C., Charreyre M.T., Pichot C., Macromolecules, 2004, 37, 2026—2034
[21]	Xia J. H., Johnson T., Gaynor S. G., Matyjaszewski K., De Simone J., Macromolecules, 1999, 32, 4802—4805
[22]	Zhang Z. B., Shi Z. Q., Han X., Holdcrof S., Macromolecules, 2007, 40, 2295—2298
[23]	Woods H. M., Nouvel C., Licence P., Irvine D. J., Howdle S. M., Macromolecules, 2005, 38, 3271—3282
[24]	Jennings J., Beija M., Richez A. P., Cooper S. D., Mignot P. E., Thurecht K. J., Jack K. S., Howdle S. M., J. Am. Chem. Soc., 2012, 134(10), 4772—4781
[25]	Seifert D., Kipping M., Adler H. P., KucklinD., Macromol. Symp., 2007, 254, 386—391

RAFT Polymerization of Acrylamide Polyhedral Oligometic Silsesquioxane in Supercritical CO₂⁺

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