原子转移自由基聚合合成两种功能化高分子
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摘要
本论文通过原子转移自由基聚合合成了两种分布较窄的功能化高分子。
首先,通过原子转移自由基聚合(ATRP)制备端基为8-羟基喹啉基团的聚合物。将5-氯甲基-8-羟基喹啉乙酰化得到5-氯甲基-8-乙酰氧基喹啉,以CuCl/5-氯甲基-8-乙酰氧基喹啉/联吡啶(bpy)为引发体系引发苯乙烯,得到端基为8-羟基喹啉基团的聚苯乙烯。将聚合物水解后与三乙基铝反应得到聚合物金属铝配合物。利用FT-IR,UV-Vis,RF,GPC和1HNMR对上述聚合物和聚合物配合物的结构进行了表征。利用TGA对聚合物和聚合物配合物的热性能进行了研究。进一步以聚合物金属铝配合物作为发光层制作了有机电致发光器件,测试了其电致发光和光致发光性能。结果表明:(1)得到分子量分布较窄的含8-羟基喹啉基团的聚合物:Mn=5923,Mw=7479,D=1.26。(2)聚合物及聚合物金属铝配合物热稳定性较好,聚合物金属铝配合物在二氯甲烷、四氢呋喃等常规溶剂中有较好的溶解度,能很好地成膜。(3)金属铝配合物在400～600nm之间出现一个有一定强度的荧光发射峰,峰值为512nm。(4)聚合物E单独成膜制作器件时,发光很弱;与PVK制成1∶4混合膜,当有PVK空穴传输层时,器件的最大亮度约为280Cd /m~2;而没有PVK空穴传输层时,器件的最大亮度约为150Cd/m~2。
另外,聚甲基丙烯酸丙炔醇酯的侧基为炔基,可以和叠氮化合物1,3-偶极环加成合成1,2,3-三唑五元杂环化合物,是一种很好的“链接”化学中间体。也正是由于甲基丙烯酸丙炔醇酯含有炔基,聚合时容易交联,目前的一些聚合方法转化率和分子量分布并不理想。因此,找到一种合适的聚合体系,以提高单体的转化率和分子量的可控性显得很有意义。本文分别以氯化苄、对甲苯磺酰氯、氯乙酰化7-羟基-4-甲基香豆素、α-溴代异丁酸乙酯为引发剂,用原子转移自由基聚合的方法考察了引发剂对聚合的影响。并分别以对甲基苯磺酰氯/CuCl/联吡啶、α-溴代异丁酸乙酯/CuBr/联吡啶为引发体系,四氢呋喃(THF)为溶剂,成功地实现甲基丙烯酸丙炔醇酯的ATRP。实验结果表明:聚合温度(60~90℃)对聚合结果影响很小,聚合时间延长、单体浓度增大都导致分散系数增大。
In this paper, two polymers with low polydispersion index was synthesized by atom transfer radical polymerization(ATRP) method.
First, 8-hydroxyquinoline-end-capped polystyrene was obtained by ATRP. The initiator, 5-chloromethyl-8-acetoxyquinoline was prepared by acetylation of 5-chloromethyl-8-hydrox -yl quinoline with acetic anhydride under reflux. Styrene was polymerized by ATRP with the initiator system consisting of CuCl/5- chloromethyl- 8-acetoxy-quinoline/2,2′-Bipyridine. The end-capped polystyrene with free 8-hydroxyquinoline group was obtained by hydrolysis in aqueous THF with dilute NaOH solution. The purified polymer was coordinated with the ions of Aluminum, to prepare the polymeric complexes. The chemical structure of the polymer and the polymeric complexes were characterized by FT-IR, UV-Vis, RF, GPC and 1HNMR. The thermal performance of the polymers and the polymeric complexes were studied by thermogravimetry analysis. The electroluminescent device using polymeric complex as emitting element have been fabricated. The photoluminescence of the film and the electroluminescence of the device were investigated. The experimental results indicate:(1) 8-hydroxyquinoline-end-capped polystyrene with low polydispersity index(1.26) is obtained. (2) All polymers have excellent thermal stability under nitrogen atmosphere and initial weight-loss temperature higher than 300℃. The polymeric complexes can dissolve in dichloromethane, tetrahydrofuran and other common organic solvent and this dissolubility will facilitate the device-making procedure.(3) Strong fluorescent emission at 512nm was observed of polymeric complexes when the polymeric complexes were irradiated with ultraviolet rays. The polymeric complexes might be potential photoluminescent or electroluminescent materials with excellent film-forming property. (4) The device using polymeric complex as emitting element and PVK as hole transportation materials at the ratio of 1∶4 has the brightness about 280Cd/m~2.
In addition, Poly(propargyl methacrylate), containing 2-propynyl side group which can undergo 1,3-dipolar cycloaddition reaction with azides acts as a excellent intermediate in“click”chemistry. But the radical polymerization of propargyl methacrylate always obtained a crosslinked product due to crosslinking reaction of propargyl side group even under low percent conversion of monomer. Thus, it is quite significant to find a suitable polymerization system which can enhance the monomer conversion and molecular weight controllability.
In this paper, the effects of reaction conditions on polymerization of propargyl methacrylate(PgMA) by ATRP were studied. Benzyl chloride, tosyl chloride(TsCl), 7-chloroacetoxy-4-methylcoumarin and ethylα-bromoisobutyrate(EBB) was used as initiators, bipyridine as the chelating agent and tetrahydrofuran as solvent. The experiment results indicated that polymerization temperature (60~90℃) has little effect on polymerization, and the prolongation of polymerization time and the increase of monomer concentration will broaden the molecular weight distribution.
首先,通过原子转移自由基聚合(ATRP)制备端基为8-羟基喹啉基团的聚合物。将5-氯甲基-8-羟基喹啉乙酰化得到5-氯甲基-8-乙酰氧基喹啉,以CuCl/5-氯甲基-8-乙酰氧基喹啉/联吡啶(bpy)为引发体系引发苯乙烯,得到端基为8-羟基喹啉基团的聚苯乙烯。将聚合物水解后与三乙基铝反应得到聚合物金属铝配合物。利用FT-IR,UV-Vis,RF,GPC和1HNMR对上述聚合物和聚合物配合物的结构进行了表征。利用TGA对聚合物和聚合物配合物的热性能进行了研究。进一步以聚合物金属铝配合物作为发光层制作了有机电致发光器件,测试了其电致发光和光致发光性能。结果表明:(1)得到分子量分布较窄的含8-羟基喹啉基团的聚合物:Mn=5923,Mw=7479,D=1.26。(2)聚合物及聚合物金属铝配合物热稳定性较好,聚合物金属铝配合物在二氯甲烷、四氢呋喃等常规溶剂中有较好的溶解度,能很好地成膜。(3)金属铝配合物在400～600nm之间出现一个有一定强度的荧光发射峰,峰值为512nm。(4)聚合物E单独成膜制作器件时,发光很弱;与PVK制成1∶4混合膜,当有PVK空穴传输层时,器件的最大亮度约为280Cd /m~2;而没有PVK空穴传输层时,器件的最大亮度约为150Cd/m~2。
另外,聚甲基丙烯酸丙炔醇酯的侧基为炔基,可以和叠氮化合物1,3-偶极环加成合成1,2,3-三唑五元杂环化合物,是一种很好的“链接”化学中间体。也正是由于甲基丙烯酸丙炔醇酯含有炔基,聚合时容易交联,目前的一些聚合方法转化率和分子量分布并不理想。因此,找到一种合适的聚合体系,以提高单体的转化率和分子量的可控性显得很有意义。本文分别以氯化苄、对甲苯磺酰氯、氯乙酰化7-羟基-4-甲基香豆素、α-溴代异丁酸乙酯为引发剂,用原子转移自由基聚合的方法考察了引发剂对聚合的影响。并分别以对甲基苯磺酰氯/CuCl/联吡啶、α-溴代异丁酸乙酯/CuBr/联吡啶为引发体系,四氢呋喃(THF)为溶剂,成功地实现甲基丙烯酸丙炔醇酯的ATRP。实验结果表明:聚合温度(60~90℃)对聚合结果影响很小,聚合时间延长、单体浓度增大都导致分散系数增大。
In this paper, two polymers with low polydispersion index was synthesized by atom transfer radical polymerization(ATRP) method.
First, 8-hydroxyquinoline-end-capped polystyrene was obtained by ATRP. The initiator, 5-chloromethyl-8-acetoxyquinoline was prepared by acetylation of 5-chloromethyl-8-hydrox -yl quinoline with acetic anhydride under reflux. Styrene was polymerized by ATRP with the initiator system consisting of CuCl/5- chloromethyl- 8-acetoxy-quinoline/2,2′-Bipyridine. The end-capped polystyrene with free 8-hydroxyquinoline group was obtained by hydrolysis in aqueous THF with dilute NaOH solution. The purified polymer was coordinated with the ions of Aluminum, to prepare the polymeric complexes. The chemical structure of the polymer and the polymeric complexes were characterized by FT-IR, UV-Vis, RF, GPC and 1HNMR. The thermal performance of the polymers and the polymeric complexes were studied by thermogravimetry analysis. The electroluminescent device using polymeric complex as emitting element have been fabricated. The photoluminescence of the film and the electroluminescence of the device were investigated. The experimental results indicate:(1) 8-hydroxyquinoline-end-capped polystyrene with low polydispersity index(1.26) is obtained. (2) All polymers have excellent thermal stability under nitrogen atmosphere and initial weight-loss temperature higher than 300℃. The polymeric complexes can dissolve in dichloromethane, tetrahydrofuran and other common organic solvent and this dissolubility will facilitate the device-making procedure.(3) Strong fluorescent emission at 512nm was observed of polymeric complexes when the polymeric complexes were irradiated with ultraviolet rays. The polymeric complexes might be potential photoluminescent or electroluminescent materials with excellent film-forming property. (4) The device using polymeric complex as emitting element and PVK as hole transportation materials at the ratio of 1∶4 has the brightness about 280Cd/m~2.
In addition, Poly(propargyl methacrylate), containing 2-propynyl side group which can undergo 1,3-dipolar cycloaddition reaction with azides acts as a excellent intermediate in“click”chemistry. But the radical polymerization of propargyl methacrylate always obtained a crosslinked product due to crosslinking reaction of propargyl side group even under low percent conversion of monomer. Thus, it is quite significant to find a suitable polymerization system which can enhance the monomer conversion and molecular weight controllability.
In this paper, the effects of reaction conditions on polymerization of propargyl methacrylate(PgMA) by ATRP were studied. Benzyl chloride, tosyl chloride(TsCl), 7-chloroacetoxy-4-methylcoumarin and ethylα-bromoisobutyrate(EBB) was used as initiators, bipyridine as the chelating agent and tetrahydrofuran as solvent. The experiment results indicated that polymerization temperature (60~90℃) has little effect on polymerization, and the prolongation of polymerization time and the increase of monomer concentration will broaden the molecular weight distribution.
引文
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[2] Wang J. S., Matyjaszewski K. Control1ed/"Living" Radical Polymerization. Atom Transfer Radical Polymerization in the Presence of Transition-Metal Complexes[J]. Journal of the American Chemical Society, 1995, 117: 5614~5615
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