膦腈碱催化一步合成聚氧化苯乙烯大分子单体及其接枝共聚
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摘要
以4-乙烯基苄醇(VBA)为引发剂,膦腈碱t-BuP4为催化剂,室温下催化氧化苯乙烯(SO)进行开环聚合一步合成聚氧化苯乙烯(PSO)大分子单体. PSO大分子单体与甲基丙烯酸甲酯(MMA)在不同温度下进行自由基共聚合成接枝共聚物.用核磁(~1H-NMR)、凝胶渗透色谱(GPC)、示差扫描量热仪(DSC)等对引发剂和聚合物结构及性能进行表征分析.结果表明成功合成了功能引发剂VBA. t-BuP_4能顺利催化SO聚合一步合成结构可控的PSO大分子单体,大分子单体PSO与MMA可以顺利共聚合成接枝共聚物.GPC和~1H-NMR分析表明:合成的大分子单体中约有4.0%的惰性组分. DSC测得共聚物只有1个玻璃化转变温度,而且与理论计算值相吻合.
Poly(styrene oxide)(PSO)macromonomers were synthesized in one step through the anionic ringopening polymerization(ROP)of styrene oxide(SO)at room temperature,with 1-tert-butyl-4,4,4-tris(dimethyla-as the catalyst,and 4-vinylbenzyl alcohol(VBA)as the functional initiator.The copolymerization of PSO macromonomers and methyl methacrylate(MMA)was carried out at different temperatures through free radical co-polymerization to prepare graft copolymers.The structures and properties of the functional initiator,the obtained macromonomers and the grafted copolymers were characterized by nuclear magnetic resonance spectroscopy(NMR),gel permeation chromatography(GPC)and differential scanning calorimetry(DSC).The results showed that functional initiator VBA was synthesized successfully.Super basedisplayed high catalytic activity for the ring-opening polymerization of SO,resulting in PSO macromonomers with polymerizable vinyl group,controlled molecular weight(Mn=2700–11300 g/mol),and narrow molecular weight distribution(<1.19).NMR measurement confirmed that the copolymerization of PSO macromonomers and MMA was carried out successfully to produce grafted copolymers.With the increase of copolymerization temperature,the conversion of MMA increased(>96%),while the molecular weight of the copolymers decreased and the molecular weight distribution became narrow.The GPC curves of the product for the copolymerization before precipitation were bimodal,the molecular weight of the obtained polymers was low(6200–7800 g/mol)and the molecular weight distribution was wide(6.39–10.41).After precipitation,the GPC curves showed a unimodal signal,the molecular weight became larger(4.33×10~4–5.95×10~4 g/mol)and the molecular weight distribution became narrower(1.46–1.62).Integral calculation of the GPC curves and NMR measurement confirmed that there were about 3.8%–4.6%inert components in the synthesized macromonomers.For the thermal analysis of PSO,PMMA-g-PSO and PMMA,the glass transition temperaturemeasured by DSC showed that the prepared grafted copolymer had only one Tg,which was in good accordance with the theoretical value calculated according to the Fox equation.This result further proved that the graft copolymers were successfully prepared.
Poly(styrene oxide)(PSO)macromonomers were synthesized in one step through the anionic ringopening polymerization(ROP)of styrene oxide(SO)at room temperature,with 1-tert-butyl-4,4,4-tris(dimethyla-as the catalyst,and 4-vinylbenzyl alcohol(VBA)as the functional initiator.The copolymerization of PSO macromonomers and methyl methacrylate(MMA)was carried out at different temperatures through free radical co-polymerization to prepare graft copolymers.The structures and properties of the functional initiator,the obtained macromonomers and the grafted copolymers were characterized by nuclear magnetic resonance spectroscopy(NMR),gel permeation chromatography(GPC)and differential scanning calorimetry(DSC).The results showed that functional initiator VBA was synthesized successfully.Super basedisplayed high catalytic activity for the ring-opening polymerization of SO,resulting in PSO macromonomers with polymerizable vinyl group,controlled molecular weight(Mn=2700–11300 g/mol),and narrow molecular weight distribution(<1.19).NMR measurement confirmed that the copolymerization of PSO macromonomers and MMA was carried out successfully to produce grafted copolymers.With the increase of copolymerization temperature,the conversion of MMA increased(>96%),while the molecular weight of the copolymers decreased and the molecular weight distribution became narrow.The GPC curves of the product for the copolymerization before precipitation were bimodal,the molecular weight of the obtained polymers was low(6200–7800 g/mol)and the molecular weight distribution was wide(6.39–10.41).After precipitation,the GPC curves showed a unimodal signal,the molecular weight became larger(4.33×10~4–5.95×10~4 g/mol)and the molecular weight distribution became narrower(1.46–1.62).Integral calculation of the GPC curves and NMR measurement confirmed that there were about 3.8%–4.6%inert components in the synthesized macromonomers.For the thermal analysis of PSO,PMMA-g-PSO and PMMA,the glass transition temperaturemeasured by DSC showed that the prepared grafted copolymer had only one Tg,which was in good accordance with the theoretical value calculated according to the Fox equation.This result further proved that the graft copolymers were successfully prepared.
引文
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29Qiao Z Y,Du F S,Zhang R,Liang D H,Li Z C.Macromolecules,2010,43(15):6485-6494
2Feng C,Li Y J,Yang D,Hu J H,Zhang X H,Huang X Y.Chem Soc Rev,2011,40(3):1282-1295
3Zeigler D F,Mazzio K A,Luscombe C K.Macromolecules,2014,47(15):5019-5028
4Liang X Y,Liu Y J,Huang J,Wei L H,Wang G W.Polym Chem,201,6(3):6466-6475
5Sun F X,Lu G L,Feng C,Li Y J,Huang X Y.Polym Chem,2017,8(2):431-440
6Rooney T R,Monyatsi O,Hutchinson R A.Macromolecules,2017,50(3):784-795
7Schiefer D,Hanselmann R,Sommer M.Polym Chem,2017,8(30):4368-4377
8Li H,Miao H,Gao Y,Li H M,Chen D Y.Polym Chem,2016,7(27):4476-4485
9Sato E,Zetterlund P B,Yamada B.Macromolecules,2004,37(7):2363-2370
10Schreur-Piet I,Heuts J P A.Polym Chem,2017,8(43):6654-6664
11Vandenbergh J,Junkers T.Macromolecules,2013,46(9):3324-3331
12Teo Y C,Xia Y.Macromolecules,2015,48(16):5656-5662
13Zhao N,Ren C L,Li H K,Li Y X,Liu S F,Li Z B.Angew Chem Int Ed,2017,129(56):13167-13170
14Li H K,Zhao N,Ren C L,Liu S F,Li Z B.Polym Chem,2017,8(47):7369-7374
15Hu X,Zhang Y J,Cui G P,Zhu N,Guo K.Macromol Rapid Commun,2017,38(21):1700399
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17Chen J L,Li M S,He W J,Tao Y H,Wang X H.Macromolecules,2017,50(23):9128-9134
18Wang J,Li B X,Xin D H,Hu R R,Zhao Z J,Qin A J,Tang B Z.Polym Chem,2017,8(17):2713-2722
19Hong M,Tang X Y,Newell B S,Chen E Y X.Macromolecules,2017,50(21):8469-8479
20Zhang H X,Hu S Y,Zhao J P,Zhang G Z.Macromolecules,2017,50(11):4198-4205
21Zhang J,Liu Q,Ren H J,Zhang N J,Li P F,Yang K.J Mole Struc,2017,1148:421-428
22Yang H J,Xu J B,Pispas S,Zhang G Z.Macromolecules,2012,45(8):3312-3317
23Zhang Guangzhao(张广照).Acta Polymerica Sinica(高分子学报),2018,(6):668-673
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25Yang H J,Bai T,Xue X Q,Huang W Y,Chen J H,Qian X L,Zhang G Z,Jiang B B.Polymer,2015,72:63-68
26Yang H J,Sun A B,Chai C Q,Huang W Y,Xue X Q,Chen J,Jiang B B.Polymer,2017,121:256-261
27Hong M,Chen E Y.Angew Chem Int Ed,2016,128(13):4188-4193
28Wang D,Hadjichristidis N.Chem Commun,2017,53(6):1196-1199
29Qiao Z Y,Du F S,Zhang R,Liang D H,Li Z C.Macromolecules,2010,43(15):6485-6494