与烷氧基的聚合Phenylacetylene-Based Monodendrons外围团体和氧/氮膜的渗透行为gydF4y2Ba

文摘gydF4y2Ba

Monodendron单体与烷氧基外围组织合成,monodendrons的焦点,终端乙炔与铑催化剂聚合产生相应polydendrons高分子量。polydendrons溶于普通有机溶剂,容易形成膜。氧选择通透性提高在polydendrons space-persistent树突的人群。发现的定义良好的树突和棒状结构对于选择性渗透膜polydendrons是有用的。gydF4y2Ba

1。介绍gydF4y2Ba

聚合物的化学结构和/或形态发挥重要作用的无孔的选择通透性膜。最近,树枝状分子在有机和高分子化学吸引了太多的关注由于其新颖的属性或函数,基于其特定形状和精确定义的三维结构(gydF4y2Ba1gydF4y2Ba- - - - - -gydF4y2Ba3gydF4y2Ba]。树枝状分子的特点是一个定期和fractally-branched树状架构。这个特性提供了一种纳米均质空间的树枝状分子特别适合刚性分子架构。此外,聚合物分子的中心和外围取代基团体可以修改,这可能帮助分子识别(gydF4y2Ba4gydF4y2Ba]。gydF4y2Ba

我们以前合成monodendron单体组成的gydF4y2Ba米gydF4y2Ba有关phenyleneethynylene重复单元与三甲基硅烷基外围组和低聚糖(dimethylsiloxane)链和获得相应的polydendrons单体的聚合使用铑催化剂(Rh) (gydF4y2Ba5gydF4y2Ba,gydF4y2Ba6gydF4y2Ba]。polydendrons机械稳定和优秀的准备自营膜。第一代polydendron (polyTMS1H)膜显示一个氧选择渗透性高于相应的zero-generation保利(苯乙炔)导数(polyTMS0H)。在这项研究中,我们与烷氧基合成polydendrons外围团体如计划所示gydF4y2Ba1gydF4y2Ba因为烷基领域能有更好的气体防护性能的低聚糖(dimethylsiloxane)域将适合研究树突域在气体选择通透性的影响。我们检查了氧气的选择通透性膜与它们的化学结构。gydF4y2Ba

2。实验gydF4y2Ba

2.1。材料gydF4y2Ba

(3,5-Dibromo-1) - 3-hydroxyl-3-methylbutynyl苯是合成如前所述gydF4y2Ba7gydF4y2Ba]。3,5-Dimethoxybenzyl氯(gydF4y2Ba8gydF4y2Ba),3,5-dihexyloxybenzyl酒精(gydF4y2Ba9gydF4y2Ba),3,5-didodecyloxybenzyl酒精(gydF4y2Ba10gydF4y2Ba5-dihexyloxybenzyloxy] 3 5-bis(3)苯甲醇(gydF4y2Ba11gydF4y2Ba),(4-hexyloxyphenyl)乙炔(gydF4y2BaHex0HgydF4y2Ba)[gydF4y2Ba12gydF4y2Ba根据文献合成过程。(Bicyclo [2.2.1] hepta-2 5-diene) chlororhodium(我)二聚体催化剂((Rh (nbd) Cl)gydF4y2Ba_2gydF4y2Ba)(奥德里奇有限公司)、双(三苯基膦)氯化钯(II)(奥德里奇有限公司)gydF4y2BangydF4y2Ba-butyllithium(关东大化工有限公司,公司1.6年的己烷)是使用前未经纯化。其它常规试剂用作接收或由传统方法纯化。gydF4y2Ba

2.2。单体的合成gydF4y2Ba

的一般程序gydF4y2Ba3,5-dialkoxybenzyl氯gydF4y2Ba如下gydF4y2Ba。gydF4y2Ba解决方案3,5-dialkoxybenzyl酒精(5更易),DMF(0.5毫升),和亚硫酰氯(10更易)在氯仿(25毫升)是在室温下搅拌2 h。多余的亚硫酰氯和溶剂蒸发压力降低,然后是残留在乙醚溶解。醚的解决方案是用水洗,然后在无水硫酸钠干燥,过滤,蒸发。3,5-dialkoxybenzyl氯化得到进一步净化。gydF4y2Ba

3,5-Dihexyloxybenzyl氯gydF4y2Ba
收益率94%。红外(KBr;厘米gydF4y2Ba^{−1gydF4y2Ba}):2872 - 2936(碳氢键)。gydF4y2Ba^1gydF4y2BaH NMR (CDClgydF4y2Ba_3gydF4y2Ba,270 MHz;ppm):gydF4y2BaδgydF4y2Ba0.91 (t, 6小时,gydF4y2BaJgydF4y2Ba= 6.8赫兹,CHgydF4y2Ba_3gydF4y2Ba),1.33 (m, 8 h, CHgydF4y2Ba_2gydF4y2Ba),1.44 (m, 4 h, CHgydF4y2Ba_2gydF4y2Ba),1.77 (m, 4 h, CHgydF4y2Ba_2gydF4y2Ba),3.93 (t, 4 h,gydF4y2BaJgydF4y2Ba= 6.5赫兹,CHgydF4y2Ba_2gydF4y2BaO), 4.50 (2 h, CHgydF4y2Ba_2gydF4y2BaCl), 6.39 (t, 1 h,gydF4y2BaJgydF4y2Ba= 2.4赫兹,ArH), 6.51 (d, 2 h,gydF4y2BaJgydF4y2Ba= 2.4赫兹,ArH)。gydF4y2Ba^13gydF4y2BaC NMR (CDClgydF4y2Ba_3gydF4y2Ba;ppm):gydF4y2BaδgydF4y2Ba14.10,22.66,25.68,29.07,31.55,46.46,68.07,101.17,106.78,139.16,160.26。gydF4y2Ba

3,5-Didodecyloxybenzyl氯gydF4y2Ba
收益率76%。红外(KBr;厘米gydF4y2Ba^{−1gydF4y2Ba}):2856 - 2928(碳氢键)。gydF4y2Ba^1gydF4y2BaH NMR (CDClgydF4y2Ba_3gydF4y2Ba,500 MHz;ppm):gydF4y2BaδgydF4y2Ba0.88 (t, 6小时,gydF4y2BaJgydF4y2Ba= 6.5赫兹,CHgydF4y2Ba_3gydF4y2Ba),1.27 (m, 32 h, CHgydF4y2Ba_2gydF4y2Ba),1.44 (m, 4 h, CHgydF4y2Ba_2gydF4y2Ba),1.76 (m, 4 h, CHgydF4y2Ba_2gydF4y2Ba),3.93 (t, 4 h,gydF4y2BaJgydF4y2Ba= 6.5赫兹,CHgydF4y2Ba_2gydF4y2BaO), 4.50 (2 h, CHgydF4y2Ba_2gydF4y2BaCl), 6.40 (t, 1 h,gydF4y2BaJgydF4y2Ba= 2.5赫兹,ArH), 6.51 (d, 2 h,gydF4y2BaJgydF4y2Ba= 2.5赫兹,ArH)。gydF4y2Ba

3,5-Bis (3 5-dihexyloxybenzyloxy)苄基氯gydF4y2Ba
收益率99%。红外(KBr;厘米gydF4y2Ba^{−1gydF4y2Ba}):2868 - 2944(碳氢键)。gydF4y2Ba^1gydF4y2BaH NMR (CDClgydF4y2Ba_3gydF4y2Ba,270 MHz;ppm):gydF4y2BaδgydF4y2Ba0.90 (t, 12 h,gydF4y2BaJgydF4y2Ba= 7.0赫兹,CHgydF4y2Ba_3gydF4y2Ba),1.34 (m, 16 h, CHgydF4y2Ba_2gydF4y2Ba),1.45 (m, 8 h, CHgydF4y2Ba_2gydF4y2Ba),1.76 (m, 8 h, CHgydF4y2Ba_2gydF4y2Ba),3.93 (t, 8 h,gydF4y2BaJgydF4y2Ba= 6.5赫兹,CHgydF4y2Ba_2gydF4y2BaO), 4.50 (2 h, CHgydF4y2Ba_2gydF4y2BaCl), 4.94 (s, 4 h, CHgydF4y2Ba_2gydF4y2BaO), 6.40 (t 2 h,gydF4y2BaJgydF4y2Ba= 2.2赫兹,ArH), 6.51 (d, 4 h,gydF4y2BaJgydF4y2Ba= 2.2赫兹,ArH), 6.55 (t, 1 h,gydF4y2BaJgydF4y2Ba= 2.2赫兹,ArH), 6.62 (d, 2 h,gydF4y2BaJgydF4y2Ba= 2.2赫兹,ArH)。gydF4y2Ba^13gydF4y2BaC NMR (CDClgydF4y2Ba_3gydF4y2Ba;ppm):gydF4y2BaδgydF4y2Ba14.14,22.68,25.79,29.27,31.64,46.35,68.04,70.15,100.75,101.99,105.62,107.53,138.62,139.34,159.88,160.33。gydF4y2Ba

(4-Bromo-1) - 3 5-dimethoxybenzyloxy苯gydF4y2Ba
的混合物4-bromophenol(13克,74更易),3,5-dimethoxybenzyl氯(15克,81更易),KgydF4y2Ba_2gydF4y2Ba有限公司gydF4y2Ba_3gydF4y2Ba(22 g、0.16摩尔)和18-crown-6 (3.0 g,更易与11日)丙酮(200毫升)回流18 h。去除溶剂后,残渣用二氯甲烷提取。有机层用盐水洗净,然后在无水硫酸钠干燥,过滤,蒸发。原油产品是由硅胶柱分离纯化与二氯甲烷/正己烷(1/1 v / v)作为洗脱液给4-bromo-1 - (3 5-dimethoxybenzyloxy)苯(19 g, 58更易)。收益率78%;议员75°C。薄层色谱(二氯甲烷/正己烷(1/1 v / v)):gydF4y2Ba= 0.14。红外(KBr;厘米gydF4y2Ba^{−1gydF4y2Ba}):2844 - 2944(碳氢键)。gydF4y2Ba^1gydF4y2BaH NMR (CDClgydF4y2Ba_3gydF4y2Ba,270 MHz;ppm):gydF4y2BaδgydF4y2Ba3.77 (s, 6 h, CHgydF4y2Ba_3gydF4y2Ba),4.96 (2 h, CHgydF4y2Ba_2gydF4y2Ba),6.41 (t, 1 h,gydF4y2BaJgydF4y2Ba= 2.4赫兹,ArH), 6.55 (d, 2 h,gydF4y2BaJgydF4y2Ba= 2.4赫兹,ArH), 6.83 (d, 2 h,gydF4y2BaJgydF4y2Ba= 8.9赫兹,ArH), 7.36 (d, 2 h,gydF4y2BaJgydF4y2Ba= 8.9赫兹,ArH)。gydF4y2Ba^13gydF4y2BaC NMR (CDClgydF4y2Ba_3gydF4y2Ba;ppm):gydF4y2BaδgydF4y2Ba55.36,70.10,99.80,105.05,113.04,116.58,132.13,138.78,157.57,160.85。gydF4y2Ba

1 - (3,5-Dimethoxybenzyloxy) 4 - (3-hydroxyl-3-methylbutynyl)苯gydF4y2Ba
2-Methyl-3-butyn-2-ol(10毫升,0.10摩尔)加入三乙胺溶液(110毫升)4-bromo-1 - (3 5-dimethoxybenzyloxy)苯(18 g, 55更易)双(三苯基膦)氯化钯(II)(0.14克,0.2更易)、三苯基膦(0.72克,2.7更易)和铜(I)碘(0.34克,1.8更易)在氮气气氛。解决方案是激起了18 h在90°C。冷却后,混合物被处理水4 N盐酸,用二氯甲烷提取,用盐水洗净。有机层是在无水硫酸钠干燥,和溶剂被减少的压力。原油产品是由硅胶柱分离纯化与二氯甲烷作为洗脱液给1 - (3,5-dimethoxybenzyloxy) 4 - (3-hydroxyl-3-methylbutynyl)苯(5.5 g,更易与17日)。收益率31%。薄层色谱(二氯甲烷):gydF4y2Ba= 0.15。红外(KBr;厘米gydF4y2Ba^{−1gydF4y2Ba}):3324(-哦),2848 - 2988(碳氢键),2228 (CgydF4y2Ba≡gydF4y2BaC)。gydF4y2Ba^1gydF4y2BaH NMR (CDClgydF4y2Ba_3gydF4y2Ba,270 MHz;ppm):gydF4y2BaδgydF4y2Ba1.61 (s, 6 h, CHgydF4y2Ba_3gydF4y2Ba),2.11 (1 h, -哦),3.79 (s, 6 h, CHgydF4y2Ba_3gydF4y2Ba),4.99 (2 h, CHgydF4y2Ba_2gydF4y2Ba),6.41 (t, 1 h,gydF4y2BaJgydF4y2Ba= 2.2赫兹,ArH), 6.56 (d, 2 h,gydF4y2BaJgydF4y2Ba= 2.2赫兹,ArH), 6.88 (d, 2 h,gydF4y2BaJgydF4y2Ba= 8.9赫兹,ArH), 7.34 (d, 2 h,gydF4y2BaJgydF4y2Ba= 8.9赫兹,ArH)。gydF4y2Ba^13gydF4y2BaC NMR (CDClgydF4y2Ba_3gydF4y2Ba;ppm):gydF4y2BaδgydF4y2Ba31.61,55.36,65.61,69.89,81.89,92.45,99.82,105.08,114.69,115.03,132.94,138.81,158.44,160.82。gydF4y2Ba

[4 - (3 5-Dimethoxybenzyloxy)苯基]乙炔(gydF4y2BaMG0PAgydF4y2Ba)gydF4y2Ba
氢化钠(2.0克,50更易)添加到甲苯溶液(65毫升)的1 - (3,5-dimethoxybenzyloxy) 4 - (3-hydroxyl-3-methylbutynyl)苯(5.5 g,更易与17日)。的解决方案是回流2 h在氮气氛。冷却后,混合物被处理水,用二氯甲烷提取,用盐水洗净。有机层是在无水硫酸钠干燥,和溶剂被减少的压力。原油产品是由硅胶柱分离纯化与二氯甲烷作为洗脱液gydF4y2BaMG0PAgydF4y2Ba(1.1克,4.3更易)。收益率25%;议员60°C。薄层色谱(己烷):gydF4y2Ba= 0.75。红外(KBr;厘米gydF4y2Ba^{−1gydF4y2Ba}):3296 (gydF4y2Ba≡gydF4y2Ba碳氢键),2848 - 2988(碳氢键),2112 (CgydF4y2Ba≡gydF4y2BaC)。gydF4y2Ba^1gydF4y2BaH NMR (CDClgydF4y2Ba_3gydF4y2Ba,270 MHz;ppm):gydF4y2BaδgydF4y2Ba3.00 (1 h, CgydF4y2Ba≡gydF4y2Ba碳氢键),3.78 (s, 6 h, CHgydF4y2Ba_3gydF4y2Ba),4.98 (2 h, CHgydF4y2Ba_2gydF4y2Ba),6.40 (t, 1 h,gydF4y2BaJgydF4y2Ba= 1.9赫兹,ArH), 6.55 (d, 2 h,gydF4y2BaJgydF4y2Ba= 1.9赫兹,ArH), 6.89 (d, 2 h,gydF4y2BaJgydF4y2Ba= 8.9赫兹,ArH), 7.41 (d, 2 h,gydF4y2BaJgydF4y2Ba= 8.9赫兹,ArH)。gydF4y2Ba^13gydF4y2BaC NMR (CDClgydF4y2Ba_3gydF4y2Ba;ppm):gydF4y2BaδgydF4y2Ba55.32,69.87,75.96,83.53,99.80,105.04,114.31,114.70,133.43,138.71,158.79,160.81。gydF4y2Ba

(4-Bromo-1) - 3 5-didodecyloxybenzyloxy苯gydF4y2Ba
的混合物4-bromophenol (1.9 g,更易与11日),3,5-didodecyloxybenzyl氯(6.0克,12更易),KgydF4y2Ba_2gydF4y2Ba有限公司gydF4y2Ba_3gydF4y2Ba(3.3 g,更易与24日),18-crown-6(3.2克,12更易)丙酮(60毫升)回流87 h。混合物在相同的方式工作如上所述,和原油产品是由硅胶柱分离纯化与二氯甲烷/正己烷(1/2 v / v)作为洗脱液给4-bromo-1 - (3 5-didodecyloxybenzyloxy)苯(5.3克,8.3更易)。收益率76%。薄层色谱(二氯甲烷/正己烷(1/2 v / v)):gydF4y2Ba= 0.90。红外(KBr;厘米gydF4y2Ba^{−1gydF4y2Ba}):2856 - 2928(碳氢键)。gydF4y2Ba^1gydF4y2BaH NMR (CDClgydF4y2Ba_3gydF4y2Ba,500 MHz;ppm):gydF4y2BaδgydF4y2Ba0.88 (t, 6小时,gydF4y2BaJgydF4y2Ba= 6.8赫兹,CHgydF4y2Ba_3gydF4y2Ba),1.26 (m, 32 h, CHgydF4y2Ba_2gydF4y2Ba),1.43 (m, 4 h, CHgydF4y2Ba_2gydF4y2Ba),1.76 (m, 4 h, CHgydF4y2Ba_2gydF4y2Ba),3.92 (t, 4 h,gydF4y2BaJgydF4y2Ba= 6.8赫兹,CHgydF4y2Ba_2gydF4y2BaO), 4.95 (2 h, CHgydF4y2Ba_2gydF4y2BaO), 6.40 (t, 1 h,gydF4y2BaJgydF4y2Ba= 2.3赫兹,ArH), 6.52 (d, 2 h,gydF4y2BaJgydF4y2Ba= 2.3赫兹,ArH), 6.84 (d, 2 h,gydF4y2BaJgydF4y2Ba= 8.8赫兹,ArH), 7.36 (d, 2 h,gydF4y2BaJgydF4y2Ba= 8.8赫兹,ArH)。gydF4y2Ba

1 - (3,5-Didodecyloxybenzyloxy) 4 - (3-hydroxyl-3-methylbutynyl)苯gydF4y2Ba
2-Methyl-3-butyn-2-ol(1.2毫升,更易与12日)加入三乙胺溶液(12毫升)4-bromo-1 - (3 5-didodecyloxybenzyloxy)苯(4.0克,6.3更易)双(三苯基膦)氯化钯(II)(1.6毫克,0.0022更易)、三苯基膦(2.8毫克,0.010更易)和铜(I)碘(1.5毫克,0.0077更易)在氮气气氛。的解决方案是激起了24小时在90°C。混合物在相同的方式工作如上所述,和原油产品是由硅胶柱分离纯化与二氯甲烷/正己烷(1/2 v / v)作为洗脱液给1 - (3,5-didodecyloxybenzyloxy) 4 - (3-hydroxyl-3-methylbutynyl)苯(1.6克,2.5更易)。收益率40%。红外(KBr;厘米gydF4y2Ba^{−1gydF4y2Ba}):3324(-哦),2856 - 2928(碳氢键),2240 (CgydF4y2Ba≡gydF4y2BaC)。gydF4y2Ba^1gydF4y2BaH NMR (CDClgydF4y2Ba_3gydF4y2Ba,500 MHz;ppm):gydF4y2BaδgydF4y2Ba0.88 (t, 6小时,gydF4y2BaJgydF4y2Ba= 6.5赫兹,CHgydF4y2Ba_3gydF4y2Ba),1.26 (m, 32 h, CHgydF4y2Ba_2gydF4y2Ba),1.42 (m, 4 h, CHgydF4y2Ba_2gydF4y2Ba),1.60 (s, 6 h, CHgydF4y2Ba_3gydF4y2Ba),1.76 (m, 4 h, CHgydF4y2Ba_2gydF4y2Ba),2.04 (1 h, -哦),3.92 (t, 4 h,gydF4y2BaJgydF4y2Ba= 6.5赫兹,CHgydF4y2Ba_2gydF4y2BaO), 4.98 (2 h, CHgydF4y2Ba_2gydF4y2BaO), 6.40 (t, 1 h,gydF4y2BaJgydF4y2Ba= 2.0赫兹,ArH), 6.53 (d, 2 h,gydF4y2BaJgydF4y2Ba= 2.0赫兹,ArH), 6.88 (d, 2 h,gydF4y2BaJgydF4y2Ba= 8.5赫兹,ArH), 7.34 (d, 2 h,gydF4y2BaJgydF4y2Ba= 8.5赫兹,ArH)。gydF4y2Ba^13gydF4y2BaC NMR (CDClgydF4y2Ba_3gydF4y2Ba;ppm):gydF4y2BaδgydF4y2Ba14.18,22.67,26.03,29.23,29.34,29.38,29.56,29.58,29.62,29.65,31.56,31.91,65.63,68.07,70.01,81.96,92.44,100.79,105.60,114.80,115.05,133.04,138.75,158.70,160.53。gydF4y2Ba

[4 - (3 5-Didodecyloxybenzyloxy)苯基]乙炔(gydF4y2BaDG0PAgydF4y2Ba)gydF4y2Ba
催化氢化钠的添加了甲苯溶液(12毫升)的1 - (3,5-didodecyloxybenzyloxy) 4 - (3-hydroxyl-3-methylbutynyl)苯(0.90克,1.4更易)。解决方案是回流3 h在氮气氛。混合物在相同的方式工作如上所述,和原油产品是由硅胶柱分离纯化与二氯甲烷/正己烷(1/1 v / v)和己烷作为洗脱液gydF4y2BaDG0PAgydF4y2Ba(0.45克,0.78更易)。收益率55%。薄层色谱(二氯甲烷/正己烷(1/1 v / v)):gydF4y2Ba= 0.71。红外(KBr;厘米gydF4y2Ba^{−1gydF4y2Ba}):3328 (gydF4y2Ba≡gydF4y2Ba碳氢键),2856 - 2924(碳氢键),2112 (CgydF4y2Ba≡gydF4y2BaC)。gydF4y2Ba^1gydF4y2BaH NMR (CDClgydF4y2Ba_3gydF4y2Ba,500 MHz;ppm):gydF4y2BaδgydF4y2Ba0.88 (t, 6小时,gydF4y2BaJgydF4y2Ba= 7.0赫兹,CHgydF4y2Ba_3gydF4y2Ba),1.26 (m, 32 h, CHgydF4y2Ba_2gydF4y2Ba),1.43 (m, 4 h, CHgydF4y2Ba_2gydF4y2Ba),1.76 (m, 4 h, CHgydF4y2Ba_2gydF4y2Ba),2.99 (1 h, CgydF4y2Ba≡gydF4y2Ba碳氢键),3.92 (t, 4 h,gydF4y2BaJgydF4y2Ba= 6.5赫兹,CHgydF4y2Ba_2gydF4y2BaO), 4.98 (2 h, CHgydF4y2Ba_2gydF4y2BaO), 6.40 (t, 1 h,gydF4y2BaJgydF4y2Ba= 2.0赫兹,ArH), 6.53 (d, 2 h,gydF4y2BaJgydF4y2Ba= 2.0赫兹,ArH), 6.90 (d, 2 h,gydF4y2BaJgydF4y2Ba= 8.5赫兹,ArH), 7.41 (d, 2 h,gydF4y2BaJgydF4y2Ba= 8.5赫兹,ArH)。gydF4y2Ba^13gydF4y2BaC NMR (CDClgydF4y2Ba_3gydF4y2Ba;ppm):gydF4y2BaδgydF4y2Ba14.11,22.68,26.03,29.23,29.34,29.38,29.56,29.59,29.63,29.65,31.91,68.06,70.02,75.81,83.60,100.78,105.56,114.38,114.83,133.56,138.66,159.06,160.53。gydF4y2Ba

(4-Iodo-1) - 3 5-dihexyloxybenzyloxy苯gydF4y2Ba
的混合物4-iodophenol (18 g 80更易),3,5-dihexyloxybenzyl氯(29克,88更易),KgydF4y2Ba_2gydF4y2Ba有限公司gydF4y2Ba_3gydF4y2Ba(24 g, 18更易)和18-crown-6 (23 g 88更易)丙酮(530毫升)回流8 h。混合物在相同的方式工作如上所述,和原油产品是由硅胶柱分离纯化与二氯甲烷/正己烷(1/3 v / v)作为洗脱液给4-iodo-1 - (3 5-dihexyloxybenzyloxy)苯(37克,73更易)。收益率91%。薄层色谱(二氯甲烷/正己烷(v / v) 1/3):gydF4y2Ba= 0.40。红外(KBr;厘米gydF4y2Ba^{−1gydF4y2Ba}):2872 - 2936(碳氢键)。gydF4y2Ba^1gydF4y2BaH NMR (CDClgydF4y2Ba_3gydF4y2Ba,270 MHz;ppm):gydF4y2BaδgydF4y2Ba0.90 (t, 6小时,gydF4y2BaJgydF4y2Ba= 6.8赫兹,CHgydF4y2Ba_3gydF4y2Ba),1.32 (m, 8 h, CHgydF4y2Ba_2gydF4y2Ba),1.44 (m, 4 h, CHgydF4y2Ba_2gydF4y2Ba),1.76 (m, 4 h, CHgydF4y2Ba_2gydF4y2Ba),3.92 (t, 4 h,gydF4y2BaJgydF4y2Ba= 6.8赫兹,CHgydF4y2Ba_2gydF4y2BaO), 4.94 (2 h, CHgydF4y2Ba_2gydF4y2BaO), 6.39 (t, 1 h,gydF4y2BaJgydF4y2Ba= 2.2赫兹,ArH), 6.52 (d, 2 h,gydF4y2BaJgydF4y2Ba= 2.2赫兹,ArH), 6.73 (d, 2 h,gydF4y2BaJgydF4y2Ba= 9.3赫兹,ArH), 7.53 (d, 2 h,gydF4y2BaJgydF4y2Ba= 9.3赫兹,ArH)。gydF4y2Ba^13gydF4y2BaC NMR (CDClgydF4y2Ba_3gydF4y2Ba;ppm):gydF4y2BaδgydF4y2Ba14.13,22.68,25.79,29.27,31.64,68.07,70.08,82.99,100.72,105.48,117.22,138.07,138.57,158.43,160.39。gydF4y2Ba

1 - [4 - (3 5-Dihexyloxybenzyloxy)苯基]2-trimethylsilylacetylenegydF4y2Ba
Trimethylsilylacetylene(19毫升,0.14摩尔)添加到三乙胺溶液(140毫升)4-iodo-1 - (3 5-dihexyloxybenzyloxy)苯(36克,70更易)双(三苯基膦)氯化钯(II)(84毫克,0.12更易)、三苯基膦(87毫克,0.33更易)和铜(I)碘(46毫克,0.24更易)在氮气气氛。解决方案是搅拌10 h 60°C。混合物在相同的方式工作如上所述,和原油产品是由硅胶柱分离纯化与二氯甲烷/正己烷(1/2 v / v)作为洗脱液给1 - [4 - (3 5-dihexyloxybenzyloxy)苯基]2-trimethylsilylacetylene(25克,53岁更易)。收益率76%。红外(KBr;厘米gydF4y2Ba^{−1gydF4y2Ba}):2872 - 2964(碳氢键),2160 (CgydF4y2Ba≡gydF4y2BaC)。gydF4y2Ba^1gydF4y2BaH NMR (CDClgydF4y2Ba_3gydF4y2Ba,270 MHz;ppm):gydF4y2BaδgydF4y2Ba0.24 (9 h, Si (CHgydF4y2Ba_3gydF4y2Ba)gydF4y2Ba_3gydF4y2Ba),0.91 (t, 6小时,gydF4y2BaJgydF4y2Ba= 6.8赫兹,CHgydF4y2Ba_3gydF4y2Ba),1.33 (m, 8 h, CHgydF4y2Ba_2gydF4y2Ba),1.45 (m, 4 h, CHgydF4y2Ba_2gydF4y2Ba),1.76 (m, 4 h, CHgydF4y2Ba_2gydF4y2Ba),3.93 (t, 4 h,gydF4y2BaJgydF4y2Ba= 6.5赫兹,CHgydF4y2Ba_2gydF4y2BaO), 4.98 (2 h, CHgydF4y2Ba_2gydF4y2BaO), 6.40 (t, 1 h,gydF4y2BaJgydF4y2Ba= 2.4赫兹,ArH), 6.53 (d, 2 h,gydF4y2BaJgydF4y2Ba= 2.4赫兹,ArH), 6.88 (d, 2 h,gydF4y2BaJgydF4y2Ba= 8.9赫兹,ArH), 7.39 (d, 2 h,gydF4y2BaJgydF4y2Ba= 8.9赫兹,ArH)。gydF4y2Ba^13gydF4y2BaC NMR (CDClgydF4y2Ba_3gydF4y2Ba;ppm):gydF4y2BaδgydF4y2Ba0.17,14.14,22.68,25.79,29.26,31.64,68.05,69.97,92.46,100.71,105.07,105.49,114.64,115.39,133.33,138.58,158.69,160.35。gydF4y2Ba

[4 - (3 5-Dihexyloxybenzyloxy)苯基]乙炔(gydF4y2BaHG0PAgydF4y2Ba)gydF4y2Ba
的混合1 - [4 - (3 5-dihexyloxybenzyloxy)苯基]2-trimethylsilylacetylene (4.8 g, 10更易)和KgydF4y2Ba_2gydF4y2Ba有限公司gydF4y2Ba_3gydF4y2Ba(0.14克,1.0更易)甲醇(200毫升)在室温下搅拌20 h。去除溶剂后,残渣用二氯甲烷提取。有机层用盐水洗净,然后在无水硫酸钠干燥,过滤,蒸发。原油产品是由硅胶柱分离纯化与二氯甲烷/正己烷(1/4 v / v)作为洗脱液gydF4y2BaHG0PAgydF4y2Ba(3.5克,8.4更易)。收益率84%。薄层色谱(二氯甲烷/正己烷(1/4 v / v)):gydF4y2Ba= 0.76。红外(KBr;厘米gydF4y2Ba^{−1gydF4y2Ba}):3332 (gydF4y2Ba≡gydF4y2Ba碳氢键),2860 - 2932(碳氢键),2160 (CgydF4y2Ba≡gydF4y2BaC)。gydF4y2Ba^1gydF4y2BaH NMR (CDClgydF4y2Ba_3gydF4y2Ba,270 MHz;ppm):gydF4y2BaδgydF4y2Ba0.90 (t, 6小时,gydF4y2BaJgydF4y2Ba= 6.8赫兹,CHgydF4y2Ba_3gydF4y2Ba),1.33 (m, 8 h, CHgydF4y2Ba_2gydF4y2Ba),1.44 (m, 4 h, CHgydF4y2Ba_2gydF4y2Ba),1.76 (m, 4 h, CHgydF4y2Ba_2gydF4y2Ba),2.99 (1 h, CgydF4y2Ba≡gydF4y2Ba碳氢键),3.93 (t, 4 h,gydF4y2BaJgydF4y2Ba= 6.6赫兹,CHgydF4y2Ba_2gydF4y2BaO), 4.96 (2 h, CHgydF4y2Ba_2gydF4y2BaO), 6.40 (t, 1 h,gydF4y2BaJgydF4y2Ba= 2.2赫兹,ArH), 6.53 (d, 2 h,gydF4y2BaJgydF4y2Ba= 2.2赫兹,ArH), 6.89 (d, 2 h,gydF4y2BaJgydF4y2Ba= 8.9赫兹,ArH), 7.41 (d, 2 h,gydF4y2BaJgydF4y2Ba= 8.9赫兹,ArH)。gydF4y2Ba^13gydF4y2BaC NMR (CDClgydF4y2Ba_3gydF4y2Ba;ppm):gydF4y2BaδgydF4y2Ba14.13,22.68,25.79,29.27,31.64,68.08,70.04,75.82,83.60,100.75,105.53,114.31,114.77,133.47,138.57,158.92,160.39。gydF4y2Ba

4-Iodo-1 - [3, 5-bis (3 5-dihexyloxybenzyloxy) benzyloxy] ben-zenegydF4y2Ba
的混合物4-iodophenol (3.7 g,更易与17日),3,5-bis (3 5-dihexyloxybenzyloxy)氯化苄(13 g,更易与17日),KgydF4y2Ba_2gydF4y2Ba有限公司gydF4y2Ba_3gydF4y2Ba34 (4.7 g,更易与),18-crown-6(0.56克,2.1更易)丙酮(130毫升)回流115 h。混合物在相同的方式工作如上所述,和原油产品是由硅胶柱纯化分离乙酸乙酯/己烷(1/8 v / v)作为洗脱液给4-iodo-1 - [3, 5-bis (3 5-dihexyloxybenzyloxy) benzyloxy]苯(11 g, 12更易)。收益率72%。薄层色谱(乙酸乙酯/己烷(1/8 v / v)):gydF4y2Ba= 0.64。红外(KBr;厘米gydF4y2Ba^{−1gydF4y2Ba}):2864 - 2936(碳氢键)。gydF4y2Ba^1gydF4y2BaH NMR (CDClgydF4y2Ba_3gydF4y2Ba,270 MHz;ppm):gydF4y2BaδgydF4y2Ba0.90 (t, 12 h,gydF4y2BaJgydF4y2Ba= 6.9赫兹,CHgydF4y2Ba_3gydF4y2Ba),1.33 (m, 16 h, CHgydF4y2Ba_2gydF4y2Ba),1.45 (m, 8 h, CHgydF4y2Ba_2gydF4y2Ba),1.76 (m, 8 h, CHgydF4y2Ba_2gydF4y2Ba),3.93 (t, 8 h,gydF4y2BaJgydF4y2Ba= 6.6赫兹,CHgydF4y2Ba_2gydF4y2BaO), 4.94 (s, 4 h, CHgydF4y2Ba_2gydF4y2BaO), 4.95 (2 h, CHgydF4y2Ba_2gydF4y2BaO), 6.40 (t 2 h,gydF4y2BaJgydF4y2Ba= 2.2赫兹,ArH), 6.54 (d, 4 h,gydF4y2BaJgydF4y2Ba= 2.2赫兹,ArH), 6.55 (t, 1 h,gydF4y2BaJgydF4y2Ba= 2.2赫兹,ArH), 6.62 (d, 2 h,gydF4y2BaJgydF4y2Ba= 2.2赫兹,ArH), 6.71 (d, 2 h,gydF4y2BaJgydF4y2Ba= 9.0赫兹,ArH), 7.53 (d, 2 h,gydF4y2BaJgydF4y2Ba= 9.0赫兹,ArH)。gydF4y2Ba^13gydF4y2BaC NMR (CDClgydF4y2Ba_3gydF4y2Ba;ppm):gydF4y2BaδgydF4y2Ba14.15,22.69,25.80,29.28,31.64,68.05,69.93,70.13,83.07,100.69,101.50,105.62,106.11,117.20,138.07,138.70,138.75,158.31,159.97,160.32。gydF4y2Ba

1 - {4 - [3,5-Bis (3 5-dihexyloxybenzyloxy) benzyloxy]苯基}2-trimethylsilylacetylenegydF4y2Ba
Trimethylsilylacetylene(1.4毫升,10更易)加入三乙胺溶液(10毫升)4-iodo-1 - [3, 5-bis (3 5-dihexyloxybenzyloxy) benzyloxy]苯(4.6克,5.0更易)双(三苯基膦)氯化钯(II)(10毫克,0.015更易)、三苯基膦(4.2毫克,0.016更易)和铜(I)碘(17毫克,0.090更易)在氮气气氛。解决方案是激起了14 h在75°C。混合物在相同的方式工作如上所述,和原油产品是由硅胶柱分离纯化与二氯甲烷/正己烷(1/2 v / v)作为洗脱液给1 - {4 - [3,5-bis (3 5-dihexyloxybenzyloxy) benzyloxy]苯基}2-trimethylsilylacetylene(3.5克,4.0更易)。收益率79%。红外(KBr;厘米gydF4y2Ba^{−1gydF4y2Ba}):2864 - 2936(碳氢键),2160 (CgydF4y2Ba≡gydF4y2BaC)。gydF4y2Ba^1gydF4y2BaH NMR (CDClgydF4y2Ba_3gydF4y2Ba,500 MHz;ppm):gydF4y2BaδgydF4y2Ba0.24 (9 h, Si (CHgydF4y2Ba_3gydF4y2Ba)gydF4y2Ba_3gydF4y2Ba),0.90 (t, 12 h,gydF4y2BaJgydF4y2Ba= 7.0赫兹,CHgydF4y2Ba_3gydF4y2Ba),1.33 (m, 16 h, CHgydF4y2Ba_2gydF4y2Ba),1.45 (m, 8 h, CHgydF4y2Ba_2gydF4y2Ba),1.76 (m, 8 h, CHgydF4y2Ba_2gydF4y2Ba),3.93 (t, 8 h,gydF4y2BaJgydF4y2Ba= 6.8赫兹,CHgydF4y2Ba_2gydF4y2BaO), 4.94 (s, 4 h, CHgydF4y2Ba_2gydF4y2BaO), 4.99 (2 h, CHgydF4y2Ba_2gydF4y2BaO), 6.40 (t 2 h,gydF4y2BaJgydF4y2Ba= 2.2赫兹,ArH), 6.54 (d, 4 h,gydF4y2BaJgydF4y2Ba= 2.2赫兹,ArH), 6.56 (t, 1 h,gydF4y2BaJgydF4y2Ba= 2.2赫兹,ArH), 6.63 (d, 2 h,gydF4y2BaJgydF4y2Ba= 2.2赫兹,ArH), 6.86 (d, 2 h,gydF4y2BaJgydF4y2Ba= 9.0赫兹,ArH), 7.38 (d, 2 h,gydF4y2BaJgydF4y2Ba= 9.0赫兹,ArH)。gydF4y2Ba^13gydF4y2BaC NMR (CDClgydF4y2Ba_3gydF4y2Ba;ppm):gydF4y2BaδgydF4y2Ba0.04,14.03,22.59,25.72,29.21,31.57,68.05,69.85,70.15,92.53,100.79,101.60,105.11,105.69,106.22,114.72,115.55,133.44,138.86,138.92,158.76,160.13,160.49。gydF4y2Ba

{4 - [3,5-Bis (3 5-dihexyloxybenzyloxy) benzyloxy]苯基}acety-lene (gydF4y2BaHG1PAgydF4y2Ba)gydF4y2Ba
的混合1 - {4 - [3,5-bis (3 5-dihexyloxybenzyloxy) benzyloxy]苯基}2-trimethylsilylacetylene(3.5克,4.0更易)和KgydF4y2Ba_2gydF4y2Ba有限公司gydF4y2Ba_3gydF4y2Ba(78毫克,0.57更易)在甲醇/乙醚(160毫升/ 50毫升)是24小时在室温下搅拌。混合物在相同的方式工作如上所述,和原油产品是由硅胶柱分离纯化与二氯甲烷/正己烷(1/1 v / v)作为洗脱液gydF4y2BaHG1PAgydF4y2Ba(2.3克,2.8更易)。收益率69%。薄层色谱(二氯甲烷/正己烷(1/1 v / v)):gydF4y2Ba= 0.43。红外(KBr;厘米gydF4y2Ba^{−1gydF4y2Ba}):3296 (gydF4y2Ba≡gydF4y2Ba碳氢键),2864 - 2940(碳氢键),2112 (CgydF4y2Ba≡gydF4y2BaC)。gydF4y2Ba^1gydF4y2BaH NMR (CDClgydF4y2Ba_3gydF4y2Ba,270 MHz;ppm):gydF4y2BaδgydF4y2Ba0.90 (t, 12 h,gydF4y2BaJgydF4y2Ba= 6.5赫兹,CHgydF4y2Ba_3gydF4y2Ba),1.33 (m, 16 h, CHgydF4y2Ba_2gydF4y2Ba),1.45 (m, 8 h, CHgydF4y2Ba_2gydF4y2Ba),1.76 (m, 8 h, CHgydF4y2Ba_2gydF4y2Ba),2.99 (1 h, CgydF4y2Ba≡gydF4y2Ba碳氢键),3.93 (t, 8 h,gydF4y2BaJgydF4y2Ba= 6.5赫兹,CHgydF4y2Ba_2gydF4y2BaO), 4.94 (s, 4 h, CHgydF4y2Ba_2gydF4y2BaO), 4.99 (2 h, CHgydF4y2Ba_2gydF4y2BaO), 6.40 (t 2 h,gydF4y2BaJgydF4y2Ba= 2.2赫兹,ArH), 6.54 (d, 4 h,gydF4y2BaJgydF4y2Ba= 2.2赫兹,ArH), 6.56 (t, 1 h,gydF4y2BaJgydF4y2Ba= 2.2赫兹,ArH), 6.64 (d, 2 h,gydF4y2BaJgydF4y2Ba= 2.2赫兹,ArH), 6.88 (d, 2 h,gydF4y2BaJgydF4y2Ba= 8.8赫兹,ArH), 7.41 (d, 2 h,gydF4y2BaJgydF4y2Ba= 8.8赫兹,ArH)。gydF4y2Ba^13gydF4y2BaC NMR (CDClgydF4y2Ba_3gydF4y2Ba;ppm):gydF4y2BaδgydF4y2Ba14.16,22.70,25.81,29.29,31.66,68.06,69.90,70.15,75.86,83.58,100.72,101.54,105.63,106.16,114.36,114.77,133.47,138.72,138.77,158.82,159.99,160.35。gydF4y2Ba

(1)- 3-Hydroxyl-3-methylbutynyl 3 5-bis (4-hexyloxyphenyl)乙炔基苯gydF4y2Ba
三乙胺(40毫升)解决方案的4 - (2 - (3 5-dibromophenyl)乙炔基)1 - (3-hydroxyl-3-methylbutynyl)苯(11 g, 35更易),gydF4y2BaHex0HgydF4y2Ba(14 g、70更易)、双(三苯基膦)氯化钯(II)(0.23克,0.33更易)、三苯基膦(0.47克,1.8更易)和铜(I)碘(0.24克,1.3更易)激起了16 h在95°C下氮气氛。混合物在相同的方式工作如上所述,和原油产品是由硅胶柱分离纯化与二氯甲烷作为洗脱液给1 - (3-hydroxyl-3-methylbutynyl) 3, 5-bis (4-hexyloxyphenyl)乙炔基苯。(12 g,更易与21日)。收益率60%。薄层色谱(二氯甲烷):gydF4y2Ba= 0.34。红外(KBr;厘米gydF4y2Ba^{−1gydF4y2Ba}):3464(-哦),2960(碳氢键),2212 (CgydF4y2Ba≡gydF4y2BaC)。gydF4y2Ba^1gydF4y2BaH NMR (CDClgydF4y2Ba_3gydF4y2Ba,500 MHz;ppm):gydF4y2BaδgydF4y2Ba0.91 (t, 6小时,gydF4y2BaJgydF4y2Ba= 7.0赫兹,CHgydF4y2Ba_3gydF4y2Ba),1.35 (m, 8 h, CHgydF4y2Ba_2gydF4y2Ba),1.46 (m, 4 h, CHgydF4y2Ba_2gydF4y2Ba),1.62 (s, 6 h, CHgydF4y2Ba_3gydF4y2Ba),1.79 (m, 4 h, CHgydF4y2Ba_2gydF4y2Ba),2.01 (1 h,哦),3.97 (t, 4 h,gydF4y2BaJgydF4y2Ba= 6.7赫兹,CHgydF4y2Ba_2gydF4y2BaO), 6.87 (d, 4 h,gydF4y2BaJgydF4y2Ba= 8.8赫兹,ArH), 7.44 (d, 4 h,gydF4y2BaJgydF4y2Ba= 8.8赫兹,ArH), 7.48 (d, 2 h,gydF4y2BaJgydF4y2Ba= 2.0赫兹,ArH), 7.57 (t, 1 h,gydF4y2BaJgydF4y2Ba= 2.0赫兹,ArH)。gydF4y2Ba^13gydF4y2BaC NMR (CDClgydF4y2Ba_3gydF4y2Ba;ppm):gydF4y2BaδgydF4y2Ba14.03,22.59,25.68,29.14,31.41,31.56,65.58,68.10,80.87,86.52,90.59,94.62,114.58,123.28,124.25,133.11,133.35,133.58,133.74,159.46。gydF4y2Ba

{3,5-Bis [(4-hexyloxyphenyl)乙炔基]苯基}乙炔(gydF4y2BaHex1HgydF4y2Ba)gydF4y2Ba
(1)- 3-Hydroxyl-3-methylbutynyl 3 5-bis ((4-hexyloxyphenyl)乙炔基)苯(12 g,更易)被允许与氢化钠反应如上所述相同的方式。原油产品是由硅胶柱分离纯化与二氯甲烷和正己烷作为洗脱液gydF4y2BaHex1HgydF4y2Ba(9.0 g, 18更易)。收益率82%。薄层色谱(二氯甲烷):gydF4y2Ba= 0.93。红外(生理盐水;厘米gydF4y2Ba^{−1gydF4y2Ba}):3308 (gydF4y2Ba≡gydF4y2Ba碳氢键),2932(碳氢键),2208 (CgydF4y2Ba≡gydF4y2BaC)。gydF4y2Ba^1gydF4y2BaH NMR (CDClgydF4y2Ba_3gydF4y2Ba,500 MHz;ppm):gydF4y2BaδgydF4y2Ba0.91 (t, 6小时,gydF4y2BaJgydF4y2Ba= 7.0赫兹,CHgydF4y2Ba_3gydF4y2Ba),1.35 (m, 8 h, CHgydF4y2Ba_2gydF4y2Ba),1.43 (m, 4 h, CHgydF4y2Ba_2gydF4y2Ba),1.78 (m, 4 h, CHgydF4y2Ba_2gydF4y2Ba),3.09 (1 h, CgydF4y2Ba≡gydF4y2Ba碳氢键),3.97 (t, 4 h,gydF4y2BaJgydF4y2Ba= 6.8赫兹,CHgydF4y2Ba_2gydF4y2BaO), 6.87 (d, 4 h,gydF4y2BaJgydF4y2Ba= 9.0赫兹,ArH), 7.44 (d, 4 h,gydF4y2BaJgydF4y2Ba= 9.0赫兹,ArH), 7.55 (d, 2 h,gydF4y2BaJgydF4y2Ba= 1.5赫兹,ArH), 7.62 (t, 1 h,gydF4y2BaJgydF4y2Ba= 1.5赫兹,ArH)。gydF4y2Ba^13gydF4y2BaC NMR (CDClgydF4y2Ba_3gydF4y2Ba;ppm):gydF4y2BaδgydF4y2Ba14.03,22.59,25.69,29.14,31.57,68.11,78.03,82.21,86.39,90.75,114.52,114.59,122.68,124.37,133.14,133.99,134.31,159.51。gydF4y2Ba

2.3。聚合gydF4y2Ba

适量的单体(通常,0.5 - -1.0 g)被放置在一个Schlenk管配备了三方活塞,磁力搅拌棒橡胶隔膜,能经受考验。管被放置在真空下,其次是氮反冲。新鲜蒸馏溶剂被转移到管,和单体溶解和搅拌。确定数量的(Rh (nbd) Cl)gydF4y2Ba_2gydF4y2Ba和三乙胺溶解在溶剂被加入到搅拌单体的解决方案。详细的聚合条件列在下表中gydF4y2Ba1gydF4y2Ba。反应溶液被注入甲醇或甲醇/苯(3/2 v / v)产生聚合物沉淀。被沉淀的沉淀剂,然后在真空干燥给一个黄色的聚合物。gydF4y2Ba

2.4。膜制备gydF4y2Ba

5 wt % (w / v)聚合物溶液在氯仿或甲苯是聚四氟乙烯板,在室温下,溶剂蒸发。产生的固体膜脱离表并在真空干燥24小时。膜的厚度(L) 70 - 160gydF4y2BaμgydF4y2Bam。gydF4y2Ba

2.5。氧气和氮气渗透率的测量gydF4y2Ba

氧和氮渗透系数(gydF4y2Ba和gydF4y2Ba:厘米gydF4y2Ba^3gydF4y2Ba(STP)厘米厘米gydF4y2Ba^{−2gydF4y2Ba}年代gydF4y2Ba^{−1gydF4y2Ba}cmHggydF4y2Ba^{−1gydF4y2Ba})和氧气分离系数(gydF4y2BaαgydF4y2Ba=gydF4y2Ba/gydF4y2Ba通过气相色谱法测定)使用YANACO GTR-10根据(gydF4y2Ba13gydF4y2Ba]。gydF4y2Ba

2.6。其他测量gydF4y2Ba

红外光谱测量与日立270 - 30光谱仪红外。核磁共振(gydF4y2Ba^1gydF4y2BaH,gydF4y2Ba^13gydF4y2BaC)光谱测量,瓦里安统一500 sw (500 MHz)或JEOL gsx - 270 (270 MHz)谱仪。平均分子量(gydF4y2Ba和gydF4y2Ba)被耦合评价凝胶渗透色谱法和低角度激光光散射(GPC-LALLS)在40°C在四氢呋喃洗脱液使用Tosoh液相色谱仪仪器与sd - 8000, CCPD, c0 - 8010 ls - 8000 ri - 8011和PP8010。光学光谱测量与JASCO乌兰巴托v - 550 ds紫外可见光谱仪。广角x射线散射测量进行使用Rigaku Geigerflex graphite-monochromatized铜KgydF4y2BaαgydF4y2Ba辐射,提供40 kV和20 mA。gydF4y2Ba

3所示。结果与讨论gydF4y2Ba

3.1。Monodendron单体的聚合gydF4y2Ba

由Rh monodendron单体的聚合催化剂,(Rh (nbd) Cl)gydF4y2Ba_2gydF4y2Ba在三乙胺的助催化剂。聚合混合物被沉淀净化成甲醇或甲醇/苯(9/1-4/3 v / v)产生相应的polydendrons黄色粉末。众所周知,Rh催化剂可以选择性地促进种乙炔聚合(gydF4y2Ba14gydF4y2Ba- - - - - -gydF4y2Ba19gydF4y2Ba]。此外,我们之前已经证明gydF4y2BaTMS1HgydF4y2Ba,gydF4y2BaPMDS1H,gydF4y2Ba和gydF4y2BaNMTS1HgydF4y2Ba在终端乙炔聚合组的焦点gydF4y2Ba7gydF4y2Ba]。相同的系统促进聚合催化剂gydF4y2BaHG1PAgydF4y2Ba和gydF4y2BaHex1HgydF4y2Ba产生相应的聚合物如表所示gydF4y2Ba1gydF4y2Ba。gydF4y2BaHG0PAgydF4y2Ba和gydF4y2BaDG0PAgydF4y2Ba给高可溶性聚合物具有高聚合度(gydF4y2BaDPgydF4y2Ba> 10gydF4y2Ba^3gydF4y2Ba)尽管较大的外围组织相比,gydF4y2BaMG0PAgydF4y2Ba。聚合度的产量和polydendrons(即。保利(gydF4y2BaHG1PAgydF4y2Ba)和聚(gydF4y2BaHex1HgydF4y2Ba)类似于相应的zero-generation聚合物(例如保利(gydF4y2BaHG0PAgydF4y2Ba)和聚(gydF4y2BaHex1HgydF4y2Ba),因为第一代树枝石不太拥挤的影响聚合能力。gydF4y2Ba

3.2。Polydendrons结构gydF4y2Ba

乙炔聚合monodendrons的终端组的焦点是通过红外和确认gydF4y2Ba核磁共振;例如,在红外和gydF4y2Ba核磁共振光谱聚gydF4y2BaHex1HgydF4y2Ba),峰值可转让的终端乙炔群monodendrongydF4y2BaHex1HgydF4y2Ba,也就是3308年gydF4y2Ba(的伸缩振动gydF4y2Ba≡gydF4y2Ba红外光谱和碳氢键)gydF4y2BaδgydF4y2Ba3.09 (1 h,gydF4y2Ba≡gydF4y2Ba碳氢键)gydF4y2Ba核磁共振,完全消失了。可见吸收最大值(gydF4y2Ba)polydendrons显著增加由于树突结构的建筑,也就是说,聚gydF4y2BaHex0HgydF4y2Ba聚()(400海里)gydF4y2BaHex1HgydF4y2Ba)(455海里)和聚gydF4y2BaHG0PAgydF4y2Ba聚()(400海里)gydF4y2BaHG1PAgydF4y2Ba)(441海里)。一个红移已经报道了一些gydF4y2Ba昊图公司gydF4y2Ba- - -gydF4y2Ba元gydF4y2Ba取代聚(苯乙炔)相比,简单的或gydF4y2Ba帕拉gydF4y2Ba取代聚(苯乙炔)[gydF4y2Ba20.gydF4y2Ba- - - - - -gydF4y2Ba24gydF4y2Ba]。这红移表明发达gydF4y2BaπgydF4y2Ba主链的共轭polydendrons,表明取代基位阻和排斥笨重的gydF4y2Ba米gydF4y2Ba-安置形成扩展的主链结构。这导致一个高度扭曲的二面角主链和附加的苯基环之间被轻度或中度扭曲中和主链的单键。可见吸收最大值(gydF4y2BaλgydF4y2Ba_{马克斯gydF4y2Ba})的第一代polydendrons显著增加是由于的笨重的取代基的影响gydF4y2Ba米gydF4y2Ba-安置与相应的zero-generation聚合物聚(相比gydF4y2BaHG0PAgydF4y2Ba)和聚(gydF4y2BaHex1HgydF4y2Ba)。gydF4y2Ba

广角x射线散射(蜡)的聚gydF4y2BaHG0PAgydF4y2Ba)和聚(gydF4y2BaHG1PAgydF4y2Ba州(表)是衡量电影gydF4y2Ba2gydF4y2Ba)。尖锐的峰出现在2gydF4y2BaθgydF4y2Ba= 3−4°,归因于这些锋利的结晶峰(100)反射pseudohexagonal晶格的棒状分子(gydF4y2Ba7gydF4y2Ba,gydF4y2Ba25gydF4y2Ba]。的晶面间的gydF4y2Ba生成聚合物的间距增加而增加,而很少密度下降。这些数据表明,增加gydF4y2Ba间距有关增加立柱直径的一代。聚合物的立柱直径估计gydF4y2Ba间距仅略小于分子建模。(分子建模进行完全的假设扩展为侧链构象monodendrons和扭曲gydF4y2Ba独联体gydF4y2Ba-transoid主链构象(二面角= 130度),如[gydF4y2Ba7gydF4y2Ba]。)立柱直径差异值估计gydF4y2Ba间距和从分子建模表明,柔性烷基链作为外围群体略微弯曲和/或列相互重叠的外围组织的一部分。gydF4y2Ba

3.3。氧气Polydendron膜的选择通透性gydF4y2Ba

聚合物溶于常见的有机溶剂,如氯仿、甲苯、四氢呋喃。聚合物聚gydF4y2BaHG0PAgydF4y2Ba),聚(gydF4y2BaHex0HgydF4y2Ba)和聚(gydF4y2BaHex1HgydF4y2Ba)表现出良好的成膜能力取决于他们的聚合度,并成立了一个橙色由于自营的电影gydF4y2BaπgydF4y2Ba共轭主链发色团的溶液浇铸法。gydF4y2Ba

氧和氮渗透测量使用空气作为原料气在298 K和76 cmHg使用聚gydF4y2BaHG0PAgydF4y2Ba),聚(gydF4y2BaHex0HgydF4y2Ba)和聚(gydF4y2BaHex1HgydF4y2Ba)膜。图gydF4y2Ba1gydF4y2Ba显示氧气渗透系数之间的关系(gydF4y2Ba)和氧气分离系数(gydF4y2BaαgydF4y2Ba=gydF4y2Ba/gydF4y2Ba)polydendron膜zero-generation聚合物(聚gydF4y2BaTMS0HgydF4y2Ba),聚(gydF4y2BaPMDS0HgydF4y2Ba)和聚(gydF4y2BaNMTS0HgydF4y2Ba)膜。氧气的渗透系数(gydF4y2Ba)的膜由第一代polydendrons小于相应的zero-generation保利(苯乙炔)导数。看来,这种行为是由于僵硬的低流动性和拥挤的树突结构。zero-generation保利(苯乙炔)衍生品展示氧气渗透系数之间的平衡和氧气分离系数。然而,氧气与三甲基硅烷基polydendrons集团的选择通透性,聚gydF4y2BaTMS1HgydF4y2Ba),显示了良好的性能相比,相应zero-generation保利(苯乙炔)衍生品。相比之下,polydendrons与低聚糖(dimethylsiloxane)外围组织(即。保利(gydF4y2BaPMDS1HgydF4y2Ba)表现出类似的趋势,相应的zero-generation保利(苯乙炔)衍生品。另一方面,聚合物和polydendrons与烷氧基外围组织表现出较低的氧渗透系数由于烷基域,气体防护性能优于低聚糖(dimethylsiloxane)域。但聚氧选择通透性gydF4y2BaHex1HgydF4y2Ba)之间的趋势显示了良好的性能相比,聚乙烯和聚gydF4y2BaHex0HgydF4y2Ba)。这些结果表明,space-persistency由于僵硬和拥挤的树突结构中扮演重要角色的高性能氧选择通透性,而外围组的效果类似于相应zero-generation保利(苯乙炔)衍生品。gydF4y2Ba

4所示。结论gydF4y2Ba

monodendron与烷氧基苯乙炔单体组成的外围组织成功与Rh催化剂聚合,(Rh (nbd) Cl)gydF4y2Ba_2gydF4y2Ba与高分子量,产生相应的polydendrons,尽管庞大的树突残渣和外围组织。polydendrons被捏造自营膜,膜由第一代的polydendron,聚gydF4y2BaHex1HgydF4y2Ba),显示一个氧选择渗透性高于相应的zero-generation保利(苯乙炔)衍生品。gydF4y2Ba

确认gydF4y2Ba

这部分工作是支持科学研究补助金(B)(没有。20310052)从jsp和向井亚纪科学技术基金会。gydF4y2Ba

引用gydF4y2Ba

1. k .井上“功能侧基,超支化聚合物和明星,”gydF4y2Ba高分子科学的进展gydF4y2Ba,25卷,不。4、453 - 571年,2000页。gydF4y2Ba视图:gydF4y2Ba出版商的网站gydF4y2Ba|gydF4y2Ba谷歌学术搜索gydF4y2Ba
2. d . a . Tomalia和j . m . j .邻”,发现树枝状分子、树枝状聚合物:一个简短的历史的角度来看,“gydF4y2Ba高分子科学杂志》的一部分gydF4y2Ba,40卷,不。16,2719 - 2728年,2002页。gydF4y2Ba视图:gydF4y2Ba出版商的网站gydF4y2Ba|gydF4y2Ba谷歌学术搜索gydF4y2Ba
3. j·m·j .邻“树枝状分子和其他树枝状大分子:从构建块在纳米科学和纳米技术功能组件,”gydF4y2Ba高分子科学杂志》的一部分gydF4y2Ba第41卷。。23日,第3725 - 3713页,2003年。gydF4y2Ba视图:gydF4y2Ba出版商的网站gydF4y2Ba|gydF4y2Ba谷歌学术搜索gydF4y2Ba
4. t .青木和t .金子,”新的大分子结构选择性渗透membranes-gas选择性渗透膜从树枝状分子、拆分渗透膜单手螺旋聚合物,”gydF4y2Ba聚合物杂志gydF4y2Ba,37卷,不。10日,717 - 735年,2005页。gydF4y2Ba视图:gydF4y2Ba出版商的网站gydF4y2Ba|gydF4y2Ba谷歌学术搜索gydF4y2Ba
5. 崛江t, t, m .浅野t .青木和e . Oikawa“Polydendron:树突苯乙炔单体的聚合,gydF4y2Ba大分子gydF4y2Ba,30卷,不。10日,3118 - 3121年,1997页。gydF4y2Ba视图:gydF4y2Ba出版商的网站gydF4y2Ba|gydF4y2Ba谷歌学术搜索gydF4y2Ba
6. t . Kaneko k .山本m .浅野m . Teraguchi和t .青木“合成聚(苯乙炔)的polydendrons phenyleneethynylene组成的重复单元,和氧/氮膜的渗透行为,”gydF4y2Ba《膜科学gydF4y2Ba,卷278,不。1 - 2、365 - 372年,2006页。gydF4y2Ba视图:gydF4y2Ba出版商的网站gydF4y2Ba|gydF4y2Ba谷歌学术搜索gydF4y2Ba
7. 山本t Kaneko m .浅野k, t .青木“聚合phenylacetylene-based monodendrons和结构相应的polydendrons,”gydF4y2Ba聚合物杂志gydF4y2Ba,33卷,不。11日,第890 - 879页,2001年。gydF4y2Ba视图:gydF4y2Ba谷歌学术搜索gydF4y2Ba
8. w·g . Chen, y, l . Ren j .董和z,“白藜芦醇类似物的合成和抗炎活动”,gydF4y2Ba化学和制药公告gydF4y2Ba,53卷,不。12日,第1590 - 1587页,2005年。gydF4y2Ba视图:gydF4y2Ba谷歌学术搜索gydF4y2Ba
9. 总督k Sivanandan s . v . Aathimanikandan c . g .参数c·j·巴丁和s . Thayumanavan“探索每一层在树枝石,”gydF4y2Ba美国化学学会杂志》上gydF4y2Ba,卷127,不。7,2020 - 2021年,2005页。gydF4y2Ba视图:gydF4y2Ba出版商的网站gydF4y2Ba|gydF4y2Ba谷歌学术搜索gydF4y2Ba
10. j·f·埃克特,j . f . Nicoud j . f . Nierengarten et al .,“Fullerene-oligophenylenevinylene混合动力车:合成、电子属性和公司在光伏设备,“gydF4y2Ba美国化学学会杂志》上gydF4y2Ba,卷122,不。31日,第7479 - 7467页,2000年。gydF4y2Ba视图:gydF4y2Ba出版商的网站gydF4y2Ba|gydF4y2Ba谷歌学术搜索gydF4y2Ba
11. o .傻瓜,k .混合m .建筑师o . Morikawa h . Konishi,“一个新的光刻胶基于杯[4]resorcinarene树形分子,”gydF4y2Ba化学材料gydF4y2Ba,11卷,不。2、427 - 432年,1999页。gydF4y2Ba视图:gydF4y2Ba谷歌学术搜索gydF4y2Ba
12. s . Gandon p . Mison m .巴氏et al .,“热聚合arylacetylenes: 1。单功能的模型化合物的研究”,gydF4y2Ba聚合物gydF4y2Ba,38卷,不。6,1439 - 1447年,1997页。gydF4y2Ba视图:gydF4y2Ba谷歌学术搜索gydF4y2Ba
13. t .青木h . Nakahara y, sessue Hayakawa m . Kokai和e . Oikawa”Trimethylsilyl-group包含polyphenylacetylenes氧气和乙醇选择性渗透膜,“gydF4y2Ba高分子科学杂志》的一部分gydF4y2Ba,32卷,不。5,849 - 858年,1994页。gydF4y2Ba视图:gydF4y2Ba谷歌学术搜索gydF4y2Ba
14. m . Tabata w·杨,k .横田”的聚合m-chlorophenylacetylene发起(Rh(降)CI),“gydF4y2Ba聚合物杂志gydF4y2Ba,22卷,不。12日,第1107 - 1105页,1990年。gydF4y2Ba视图:gydF4y2Ba谷歌学术搜索gydF4y2Ba
15. m . Tabata w·杨,k .横田,“h - nmr、紫外线的研究Rh复合物作为苯乙炔:有规立构的聚合催化剂配体和溶剂对其催化剂活性的影响,“gydF4y2Ba高分子科学杂志》的一部分gydF4y2Ba,32卷,不。6,1113 - 1120年,1994页。gydF4y2Ba视图:gydF4y2Ba出版商的网站gydF4y2Ba|gydF4y2Ba谷歌学术搜索gydF4y2Ba
16. 岸本y . p . Eckerle t Miyatake et al .,”控制的苯乙炔聚合organorhodium(我)复合物:机制和多基因的结构,“gydF4y2Ba美国化学学会杂志》上gydF4y2Ba,卷121,不。51岁,12035 - 12044年,1999页。gydF4y2Ba视图:gydF4y2Ba谷歌学术搜索gydF4y2Ba
17. y三角和t .此外,“活的苯乙炔聚合小说铑催化剂。定量起始和引入官能团在启动链端,”gydF4y2Ba大分子gydF4y2Ba没有,卷。31日。21日,第7573 - 7572页,1998年。gydF4y2Ba视图:gydF4y2Ba谷歌学术搜索gydF4y2Ba
18. y三角,k . Kanki m .宅一生和t .此外,”生活的苯乙炔聚合rhodium-based三元催化剂,(二烯)Rh (I)复杂/ vinyllithium /磷配体。催化剂组分的影响。”gydF4y2Ba高分子化学与物理gydF4y2Ba,卷201,不。17日,第2244 - 2239页,2000年。gydF4y2Ba视图:gydF4y2Ba谷歌学术搜索gydF4y2Ba
19. m .宅一生y三角,t .此外,“生活的苯乙炔聚合单独的铑配合物。”gydF4y2Ba大分子gydF4y2Ba,33卷,不。18日,第6639 - 6636页,2000年。gydF4y2Ba视图:gydF4y2Ba出版商的网站gydF4y2Ba|gydF4y2Ba谷歌学术搜索gydF4y2Ba
20. t .此外,t . Higashimura聚乙炔与取代基:他们的合成和性质,”gydF4y2Ba高分子科学的进步gydF4y2Ba卷,81年,第165 - 121页,1986年。gydF4y2Ba视图:gydF4y2Ba谷歌学术搜索gydF4y2Ba
21. j . Kunzler诉Percec,“生活的芳基取代乙炔聚合MoCl,”gydF4y2Ba高分子科学杂志》的一部分gydF4y2Ba,28卷,不。5,1221 - 1236年,1990页。gydF4y2Ba视图:gydF4y2Ba出版商的网站gydF4y2Ba|gydF4y2Ba谷歌学术搜索gydF4y2Ba
22. h . Nishide t Kaneko r后藤和e . Tsuchida“聚乙炔衍生物与chain-sided含苯氧基的galvinoxyl激进分子,”gydF4y2Ba分子晶体和液体晶体gydF4y2Ba卷,233年,第96 - 89页,1993年。gydF4y2Ba视图:gydF4y2Ba谷歌学术搜索gydF4y2Ba
23. y三浦、m .松本和y Ushitani,“合成聚(ethynylbenzene)吊坠硝基氧自由基的rhodium-catalyzed聚合ethynylphenyl硝基氧,”gydF4y2Ba大分子gydF4y2Ba,26卷,不。10日,2628 - 2630年,1993页。gydF4y2Ba视图:gydF4y2Ba谷歌学术搜索gydF4y2Ba
24. r·r·施洛克罗,j·c·李,n . c。扎内蒂和w·m·戴维斯,“生活聚合(o -(三甲基硅烷基)苯基)乙炔的钼酰亚胺的烷叉复合物,”gydF4y2Ba美国化学学会杂志》上gydF4y2Ba,卷118,不。16,3883 - 3895年,1996页。gydF4y2Ba视图:gydF4y2Ba出版商的网站gydF4y2Ba|gydF4y2Ba谷歌学术搜索gydF4y2Ba
25. m . Tabata h . Takamura Yokota k . et al .,“Pressure-induced cis反式异构化的聚(o-methoxyphenylacetylene)聚合Rh复杂的催化剂。ramam、x射线和ESR研究。”gydF4y2Ba大分子gydF4y2Ba,27卷,不。21日,第6236 - 6234页,1994年。gydF4y2Ba视图:gydF4y2Ba谷歌学术搜索gydF4y2Ba

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版权©2012金子隆等。这是一个开放分布式下文章gydF4y2Ba知识共享归属许可gydF4y2Ba,它允许无限制的使用、分配和复制在任何媒介,提供最初的工作是正确引用。gydF4y2Ba