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江苏省光伏科学与工程协同创新中心 常州大学材料科学与工程学院 常州 213164
李坚,E-mail:lijian@cczu.edu.cn Jian Li,E-mail:lijian@cczu.edu.cn
纸质出版日期:2016-11,
收稿日期:2016-3-1,
修回日期:2016-4-1,
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刘新, 孙仪琳, 李坚, 任强, 汪称意. 多臂聚丙烯酸丁酯-
Xin Liu, Yi-lin Sun, Jian Li, Qiang Ren, Cheng-yi Wang. Synthesis and Characterization of Multi-arm Poly(butyl acrylate)-
刘新, 孙仪琳, 李坚, 任强, 汪称意. 多臂聚丙烯酸丁酯-
Xin Liu, Yi-lin Sun, Jian Li, Qiang Ren, Cheng-yi Wang. Synthesis and Characterization of Multi-arm Poly(butyl acrylate)-
采用电子转移再生催化剂原子转移自由基聚合(ARGET ATRP)制备了端羟基聚丙烯酸丁酯-
b
-聚甲基丙烯酸甲酯嵌段共聚物(HO-PBA-
b
-PMMA),在此基础上,与六亚甲基二异氰酸酯三聚体(N3390)反应,合成了多臂聚丙烯酸丁酯
-b
-聚甲基丙烯酸甲酯嵌段共聚物.通过凝胶渗透色谱(GPC)、核磁共振仪(
1
H-NMR)、傅里叶变换红外光谱计(FTIR)对聚合物的结构进行了表征,利用原子力显微镜(AFM)观察了其形貌,采用动态热机械分析仪(DMA)和万能拉伸机研究了聚合物的热性能、力学性能及多臂嵌段共聚物对PMMA的增韧性能.结果表明:成功制备了端羟基聚丙烯酸丁酯
-b
-聚甲基丙烯酸甲酯,以及多臂聚丙烯酸丁酯-
b-
聚甲基丙烯酸甲酯嵌段共聚物.在异氰酸酯基/羟基(NCO/OH)摩尔比为1.2/1时,制得的多臂嵌段共聚物相对分子质量最大,Mark-Houwink参数α值最小,表明此时三臂嵌段共聚物最多.多臂嵌段聚合物的拉伸强度和断裂伸长率比线型聚合物均有明显提高,且在NCO/OH摩尔比为1.2/1时达到最大,分别为7.6 MPa和73%.多臂嵌段聚合物具有更高的玻璃化转变温度(
T
g
).通过原子力显微镜(AFM)表明,多臂聚丙烯酸丁酯
-b-
聚甲基丙烯酸甲酯嵌段共聚物形成了以聚丙烯酸丁酯链段为核,聚甲基丙烯酸甲酯为壳的核壳结构.具有核壳结构的多臂聚丙烯酸丁酯
-b
-聚甲基丙烯酸甲酯嵌段共聚物对聚甲基丙烯酸甲酯有明显的增韧作用.
Hydroxyl-terminated poly(butyl acrylate)-
b
-poly(methyl methacrylate) block copolymer was synthesized
via
atom transfer radical polymerization with activators regenerated by electron transfer (ARGET ATRP) using 4-hydroxybutyl 2-bromo-2-methylpropanoate as an initiator
copper (Ⅱ) bromide (CuBr
2
) as a catalyst
pentamethyldiethylene triamine (PMDETA) as a ligand
and stannous octoate (Sn(EH)
2
) as a reducing agent.Then multi-arm poly(butyl acrylate)-
b
-poly(methyl methacrylate) block copolymers were prepared
via
the reaction between hydroxyl-terminated poly(butyl acrylate)-
b
-poly(methyl methacrylate) block copolymer and hexamethylene diisocyanate trimer (N3390) using dibutyltin dilaurate as a catalytic agent.The structures of the copolymers obtained were characterized by gel permeation chromatography (GPC)
1
H nuclear magnetic resonance (
1
H-NMR)
and Fourier transform infrared spectrometer (FTIR).The morphologies of the linear and multi-arm polymers were observed by atomic force microscopy (AFM).Mechanical and thermodynamic properties of the hydroxyl-terminated poly(butyl acrylate)-
b
-poly(methyl methacrylate) block copolymer and the multi-arm block copolymers were investigated by universal tensile machine and dynamic mechanical analyser (DMA)
respectively.The results showed that the hydroxyl-terminated block copolymer and the multi-arm block copolymers were successfully synthesized.When the molar ratio of NCO/OH reached 1.2/1
maximal amount of three-arm block copolymers was obtained.The tensile strength and the elongation at break of the multi-arm copolymers were higher than those of the linear copolymers
and these values achieved maximum with NCO/OH of 1.2/1.In this case
multi-arm block copolymer showed tensile strength of 7.6 MPa and elongation at break of 73%
respectively.Compared with the linear block copolymer
the glass transition temperature (
T
g
) of the multi-arm block copolymer was higher.Atomic force microscopy (AFM) indicated that the multi-arm block copolymer possessed distinct core-shell structure with PBA as the core and PMMA as the shell.And the multi-arm block copolymer with core-shell structure could be used as a toughening agent for poly(methyl methacrylate).
多臂嵌段丙烯酸酯增韧
Multi-armBlock copolymerAcrylateToughening
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