N,N-二乙基丙烯酰胺与N,N-二甲基丙烯酰胺嵌段共聚物的可控合成及温敏性研究
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摘要
采用B(C6F5)3催化的基团转移聚合(GTP)法,精确合成了聚(N,N-二乙基丙烯酰胺)(PDEAAm)与聚(N,N-二甲基丙烯酰胺)(PDMAAm)的均聚物及无规、二嵌段、三嵌段和五嵌段共聚物.共聚物的聚合度均约为100,分散性指数在1.19～1.26之间.利用可控温紫外可见光谱仪(UV-Vis)测定聚合物水溶液的浊点温度(Tcp),通过Tcp分析与线-球相变有关的温敏性能,利用变温核磁(NMR)及动态光散射粒度仪(DLS)测定聚合物在水溶液中的相变行为.结果表明,对于无规共聚物,随着DMAAm比例增加,Tcp从38.5°C增加到68.0°C,当DMAAm比例> 75%时,没有观察到相转变现象.对于二嵌段共聚物,随着DMAAm比例的增加,Tcp从34.5°C增加到44.5°C,并且当PDEAAm和PDMAAm链段比例为10/90时共聚物没有相转变现象.对于三嵌段和五嵌段共聚物,只有两端为PDEAAm链段的共聚物表现出相转变现象,三嵌段和五嵌段共聚物的Tcp分别为51.5和55.0°C.
The thermoresponsive property of poly(N,N-diethylacrylamide)(PDEAAm) and its copolymer with N,N-dimethylacrylamide(DMAAm) has been studied using various types of the copolymers. The group transfer polymerization(GTP) of N,N-diethylacrylamide(DEAAm) and N,N-dimethylacrylamide(DMAAm) was carried out using tris(pentafluorophenyl borane(B(C6 F5)3) as the organocatalyst and triethyl((1-methoxy-2-methylprop-1-en-1-yl)o-xy)silane(SKAEt) as the initiator to produce the random, di-, tri-, and penta-block copolymers along with the homopolymers of PDEAAm and PDMAAm. The polymerization degrees(PDs) of homopolymers were25, 50, 100, 200, 300, and 500 for PDEAAm, 25, 50, and 100 for PDMAAm and those of all copolymers was 100,and their dispersity was in the range of 1.05–1.26. The monomer compositions(m/n) in the copolymers were90/10, 75/25, 70/30, 65/35, 60/40, 55/45, 50/50, 25/75, and 10/90 for the random copolymer of PDEAAmm-rPDMAAmn and 90/10, 75/25, 50/50, 25/75, and 10/90 for the di-block copolymer of PDEAAmm-b-PDMAAmn.The monomer compositions in the tri-block copolymer were PDEAAm25-b-PDMAAm50-b-PDEAAm25 and PDMAAm25-b-PDEAAm50-b-PDMAAm25, and those in the penta-block copolymer were PDEAAm20-bPDMAAm25-b-PDEAAm50-b-PDMAAm25-b-PDEAAm20 and PDMAAm20-b-PDEAAm20-b-PDMAAm20-bPDEAAm20-b-PDMAAm20. The thermoresponsive property concerning with a coil-globule phase transition was estimated using the temperature of cloud point(Tcp) of aqueous polymer solutions, i.e., the lower critical solution temperature(LCST). The Tcp of PDEAAm increased with the increasing PD from 36.5 °C to 29.5 °C. For PDEAAmm-r-PDMAAmn, the Tcp increased with the increasing DMAAm unit from 38.5 °C to 68.0 °C and none of the Tcps was observed for the copolymers with the m/n ratios of 25/75 and 10/90. For PDEAAmm-bPDMAAmn, the Tcp increased with the increasing segment length of PDMAAm from 34.5 °C to 44.5 °C and no phase transition was observed for PDEAAm10-b-PDMAAm90. For the tri-and penta-block copolymers, which consist of the PDMAAm segment at both copolymer ends, PDEAAm25-b-PDMAAm50-b-PDEAAm25 and PDEAAm20-b-PDMAAm25-b-PDEAAm50-b-PDMAAm25-b-PDEAAm20 only exhibited the phase transition, such as the Tcps of 51.5 and 55.0 °C, respectively. These phase transition behaviors were confirmed by nuclear magnetic resonance spectroscopy(NMR) and dynamic light scattering(DLS) measurements. The hydrodynamic radius(Rh) of PDEAAm25-b-PDMAAm50-b-PDEAAm25 and PDEAAm20-b-PDMAAm20-b-PDEAAm20-bPDMAAm20-b-PDEAAm20 surged from lower temperature of 45 °C to higher temperature of 75 °C.
The thermoresponsive property of poly(N,N-diethylacrylamide)(PDEAAm) and its copolymer with N,N-dimethylacrylamide(DMAAm) has been studied using various types of the copolymers. The group transfer polymerization(GTP) of N,N-diethylacrylamide(DEAAm) and N,N-dimethylacrylamide(DMAAm) was carried out using tris(pentafluorophenyl borane(B(C6 F5)3) as the organocatalyst and triethyl((1-methoxy-2-methylprop-1-en-1-yl)o-xy)silane(SKAEt) as the initiator to produce the random, di-, tri-, and penta-block copolymers along with the homopolymers of PDEAAm and PDMAAm. The polymerization degrees(PDs) of homopolymers were25, 50, 100, 200, 300, and 500 for PDEAAm, 25, 50, and 100 for PDMAAm and those of all copolymers was 100,and their dispersity was in the range of 1.05–1.26. The monomer compositions(m/n) in the copolymers were90/10, 75/25, 70/30, 65/35, 60/40, 55/45, 50/50, 25/75, and 10/90 for the random copolymer of PDEAAmm-rPDMAAmn and 90/10, 75/25, 50/50, 25/75, and 10/90 for the di-block copolymer of PDEAAmm-b-PDMAAmn.The monomer compositions in the tri-block copolymer were PDEAAm25-b-PDMAAm50-b-PDEAAm25 and PDMAAm25-b-PDEAAm50-b-PDMAAm25, and those in the penta-block copolymer were PDEAAm20-bPDMAAm25-b-PDEAAm50-b-PDMAAm25-b-PDEAAm20 and PDMAAm20-b-PDEAAm20-b-PDMAAm20-bPDEAAm20-b-PDMAAm20. The thermoresponsive property concerning with a coil-globule phase transition was estimated using the temperature of cloud point(Tcp) of aqueous polymer solutions, i.e., the lower critical solution temperature(LCST). The Tcp of PDEAAm increased with the increasing PD from 36.5 °C to 29.5 °C. For PDEAAmm-r-PDMAAmn, the Tcp increased with the increasing DMAAm unit from 38.5 °C to 68.0 °C and none of the Tcps was observed for the copolymers with the m/n ratios of 25/75 and 10/90. For PDEAAmm-bPDMAAmn, the Tcp increased with the increasing segment length of PDMAAm from 34.5 °C to 44.5 °C and no phase transition was observed for PDEAAm10-b-PDMAAm90. For the tri-and penta-block copolymers, which consist of the PDMAAm segment at both copolymer ends, PDEAAm25-b-PDMAAm50-b-PDEAAm25 and PDEAAm20-b-PDMAAm25-b-PDEAAm50-b-PDMAAm25-b-PDEAAm20 only exhibited the phase transition, such as the Tcps of 51.5 and 55.0 °C, respectively. These phase transition behaviors were confirmed by nuclear magnetic resonance spectroscopy(NMR) and dynamic light scattering(DLS) measurements. The hydrodynamic radius(Rh) of PDEAAm25-b-PDMAAm50-b-PDEAAm25 and PDEAAm20-b-PDMAAm20-b-PDEAAm20-bPDMAAm20-b-PDEAAm20 surged from lower temperature of 45 °C to higher temperature of 75 °C.
引文
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24Tao X,Deng Y,Shen Z,Ling J.Macromolecules,2014,47(18):6173-6180
2Gil E,Hudson S.Prog Polym Sci,2004,29(12):1173-1222
3Mura S,Nicolas J,Couvreur P.Nat Mater,2013,12(991):991-1003
4Roth P J,Lowe A B.Polym Chem,2017,8(1):10-11
5Scarpa J S,Mueller D D,Klotz I M.J Am Chem Soc,1967,89(24):6024-6030
6Crespy D,Rossi R M.Polym Int,2007,56(12):1461-1468
7Liu R,Fraylich M,Saunders B R.Colloid Polym Sci,2009,287(6):627-643
8Hocine S,Li M H.Soft Matter,2013,9(25):5839-5861
9Saeki S,Kuwahara N,Nakata M,Kaneko M.Polymer,1976,17(8):685-689
10Wei H,Cheng S X,Zhang X Z,Zhuo R X.Prog Polym Sci,2009,34(9):893-910
11Schild H G.Prog Polym Sci,1992,17(2):163-249
12Plamper F A,Ruppel M,Schmalz A,Borisov O,Ballauff M,Müller A H E.Macromolecules,2007,40(23):8361-8366
13Plamper F A,Ballauff M,Müller A H E.J Am Chem Soc,2007,129(47):14538-14539
14Meeussen F,Nies E,Berghmans H,Verbrugghe S,Goethals E,Du Prez F.Polymer,2000,41(24):8597-8602
15Salzinger S,Seemann U B,Plikhta A,Rieger B.Macromolecules,2011,44(15):5920-5927
16Vancoillie G,Frank D,Hoogenboom R.Prog Polym Sci,2014,39(6):1074-1095
17Xia Y,Yin X,Burke N A D,St?ver H D H.Macromolecules,2005,38(14):5937-5943
18Zhang Y,Furyk S,Bergbreiter D E,Cremer P S.J Am Chem Soc,2005,127(41):14505-14510
19Kikuchi S,Chen Y,Kitano K,Takada K,Satoh T,Kakuchi T.Polym Chem,2015,6(38):6845-6856
20Hasegawa A,Naganawa Y,Fushimi M,Ishihara K,Yamamoto H.Org Lett,2006,8(15):3175-3178
21Lessard D G,Ousalem M,Zhu X X.Can J Chem,2001,79(12):1870-1874
22Huber S,Jordan R.Colloid Polym Sci,2007,286(4):395-402
23Sakai N,Jin M,Sato S I,Satoh T,Kakuchi T.Polym Chem,2014,5(3):1057-1062
24Tao X,Deng Y,Shen Z,Ling J.Macromolecules,2014,47(18):6173-6180
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