CN103242495B - 一种含有聚酰胺链段的两嵌段共聚物的制备方法 - Google Patents
一种含有聚酰胺链段的两嵌段共聚物的制备方法 Download PDFInfo
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Abstract
本发明公开了一种含有聚酰胺链段的两嵌段共聚物的制备方法,通过配制可控缩聚体系,进行可控缩聚反应制备端基为TEMPO基团的聚酰胺POBE,然后以POBE为大分子TEMPO试剂调控苯乙烯的“活性”/可控自由基聚合,制备了一段为聚酰胺、一段为聚苯乙烯的两嵌段共聚物;再将POBE与通过ATRP制备的聚甲基丙烯酸甲酯进行大分子间反应,制备了一段为聚酰胺、一段为聚甲基丙烯酸甲酯的两嵌段共聚物。本发明充分利用了TEMPO基团在可控缩聚反应中表现为“惰性”基团的现象,先通过可控缩聚反应制备聚酰胺,而后通过TEMPO在活性自由基聚合中的作用,制备两嵌段共聚物,合成步骤较少,操作性强,方便,快捷。
Description
技术领域
本发明涉及两嵌段共聚物的制备领域,具体涉及一种含有聚酰胺链段的两嵌段共聚物的制备方法。
背景技术
嵌段共聚物在微观尺寸上分为两相,呈微相分离结构,这种微区与那些能观察到的不相容的聚合物混合物的区域相比小很多,使得其表现出超分子结构行为。嵌段共聚物表现出来的微相分离的现象, 使得嵌段共聚在聚合物化学改性或聚合改性中占有重要的地位。
“活性”/可控自由基聚合(LRP)以其可用于聚合的单体种类丰富、相对于其他活性聚合来说,聚合条件温和且具有很强的分子设计能力引起人们越来越多的关注。通过LRP可以很方便地在聚合物链上引入多种功能性基团,制备多种拓扑结构的聚合物。
通过缩聚制备的聚酰胺具有良好的机械加工性能、热稳定性等优点,使其在人们的日常生活使用的材料中占有重要的一席。而通过可控缩聚可以制备相对分子量可控、相对分子量分布较窄的聚酰胺。
若将LRP与可控缩聚结合起来,可以制备一段为聚酰胺一段为聚乙烯基类的两嵌段共聚物,这样就为制备满足特定要求的两嵌段共聚物提供了一种新思路。结合可控缩聚和LRP的方法,制备一段为聚酰胺一段为聚乙烯基类的嵌段共聚物的工作已有报道(参见:Masukawa, T.; Yokoyama, A.; Yokozawa, T., Synthesis of Well-Defined Polybenzamide- block-Polystyrene by Combination of Chain-Growth Condensation Polymerization and RAFT Polymerization. Macromol. Rapid Commun. 2009, 30 (16), 1413-1418.)。然而,该体系通过分批次加入单体方法可控的制备对甲基-N-辛基苯胺封端的聚酰胺,而后以之作Z基团,通过多步骤的反应制备RAFT试剂,并用来进行苯乙烯的RAFT聚合。此路线,合成步骤较多,多次涉及了大分子反应,这无疑增加了制备一段为聚酰胺、一段为聚乙烯基类的两嵌段共聚物的难度。
发明内容
本发明的目的是提供一种含有聚酰胺链段的两嵌段共聚物的制备方法,首先合成一种双官能团的小分子引发剂,而后进行可控缩聚和LRP制备了一段为聚酰胺一段为聚乙烯基类的两嵌段共聚物,合成步骤较少,操作性强。
为解决上述技术问题,实现上述技术效果,本发明采用了以下技术方案:
一种含有聚酰胺链段的两嵌段共聚物的制备方法,包括以下步骤:
步骤1)配制可控缩聚体系,包括单体、引发剂、碱和溶剂;
步骤2)进行可控缩聚反应,制备端基为TEMPO基团的聚酰胺POBE;
步骤3)以POBE为大分子TEMPO试剂调控苯乙烯的“活性”/可控自由基聚合,制备了一段为聚酰胺、一段为聚苯乙烯的两嵌段共聚物;
步骤4) POBE与通过ATRP制备的聚甲基丙烯酸甲酯进行大分子间反应,制备了一段为聚酰胺、一段为聚甲基丙烯酸甲酯的两嵌段共聚物。
进一步的,步骤1)中所述单体为4-(辛基氨基)苯甲酸乙酯,所述引发剂为4-(6-(4-(苯甲酸乙酯基)氧基)己烷基氧基)-2,2,6,6-四甲基氧化哌啶醇,所述碱为双(三甲基硅基)氨基锂,所述溶剂为四氢呋喃,步骤2)中反应温度为-10~30 ℃。
进一步的,步骤2)、步骤3)和步骤4)中聚酰胺的数均分子量为2000~20000 g/mol,聚合物分散性指数M w/M n<1.5。
进一步的,步骤3)中反应温度为100~140 ℃,一段为聚酰胺、一段为聚苯乙烯的两嵌段共聚物的数均分子量为4000~150000 g/mol,聚合物分散性指数M w/M n<1.5。
进一步的,步骤4)中聚甲基丙烯酸甲酯的聚合体系为:单体为甲基丙烯酸甲酯,引发剂为2-溴代异丁酸乙酯,催化剂为溴化亚铜,配体为N, N, N′, N′′, N′′-五甲基二亚乙基三胺,聚合反应温度为50~80 ℃,聚甲基丙烯酸甲酯的数均分子量为3000~130000 g/mol,聚合物分散性指数M w /M n <1.5;大分子间反应溶剂为甲苯,大分子间反应温度为40~60 ℃;一段为聚酰胺、一段为聚甲基丙烯酸甲酯的两嵌段共聚物的数均分子量为5000~150000 g/mol,聚合物分散性指数M w/M n<1.5。
本发明的有益效果为:
本发明充分利用了TEMPO基团在可控缩聚反应中表现为“惰性”基团的现象,先通过可控缩聚制备聚酰胺,而后通过TEMPO在“活性”/可控自由基聚合中的作用,制备两嵌段共聚物,合成步骤较少,操作性强,方便,快捷。
附图说明
图1为POBE的相对分子量及其分布与单体和引发剂的初始摩尔比的关系曲线;
图2为POBE的相对分子量及其分布与反应时间的关系曲线;
图3为POBE以及POBE-b-PSt的GPC流出曲线(POBE: M n,GPC = 3080 g/mol, M w/M n = 1.17; POBE-b-PSt: a (M n,GPC = 11640 g/mol, M w/M n = 1.23), b (M n,GPC = 15070 g/mol, M w/M n = 1.36));
图4为POBE以及POBE-b-PSt的核磁图谱(1H NMR,以CDCl3为溶剂,TMS作内标; POBE: M n,GPC = 3080 g/mol, M w/M n = 1.17; POBE-b-PSt: M n,GPC = 11640 g/mol, M w/M n = 1.23);
图5为POBE与POBE-b-PMMA的GPC流出曲线。POBE: M n,GPC = 3080 g/mol, M w/M n = 1.17; PMMA: M n,GPC = 7850 g/mol, M w/M n = 1.21; POBE-b-PMMA: M n,GPC = 9750 g/mol, M w/M n = 1.25;
图6为POBE-b-PMMA的核磁图谱(1H NMR)( M n,GPC = 9750 g/mol, M w/M n = 1.25)。
具体实施方案
以下结合具体实施例对本发明作进一步详细的描述。
所用的化学试剂:4-羟基-2,2,6,6-四甲基氧化哌啶醇(HTEMPO),99%;甲醇,工业级;正己烷,AR;1,6-二溴己烷,99 %;4-氨基苯甲酸乙酯,98 %;1-溴辛烷,98 %;双(三甲基硅基)氨基锂(LiHMDS),1 M in THF;四氢呋喃,AR;2-溴代异丁酸乙酯(EBiB),98 %;N, N, N' ,N" ,N"-五甲基二乙基三胺(PMDETA),98 %;溴化亚铜(CuBr),AR;苯乙烯(St),AR;甲基丙烯酸甲酯(MMA),AR;甲苯,AR;过氧化二苯甲酰(BPO),AR。
测试仪器:Waters 1515型凝胶渗透色谱仪;INOVA 400MHz核磁仪。
测定条件:HR1, HR3和HR4三柱串联使用,示差检测器,流动相为四氢呋喃(1mL/min),柱温30 ℃,用聚苯乙烯或聚甲基丙烯酸甲酯标样做校正标样进行校正。1H NMR在INOVA 400MHz核磁仪上以TMS为内标测定。
步骤1)端基含有TEMPO基团的聚酰胺POBE的制备:
取HTEMPO (8.60 g, 50 mmol),1,6-二溴己烷(24.4 g, 100 mmol),溶解在THF(25 mL)中,然后将四辛基溴化铵(0.25 g),氢氧化钠水(40 %, 25 mL)溶液加入混合液,接着加热至回流,搅拌12 h。分液,水洗,用无水硫酸镁干燥后,蒸去溶剂,用THF/石油醚=1/20的比例柱层析,得红色液体(BHO-TEMPO)9.88 g,收率59 %;
取BHO-HTEMPO(8.37 g, 25 mmol),4-羟基苯甲酸乙酯(4.98 g, 30 mmol),溶解在丙酮(50 mL)溶液中,然后将无水碳酸钾(3.45 g, 25 mmol)、催化量的碘化钾加入混合液,加热至回流,反应10 h。冷却至室温,抽滤,滤液旋蒸,用乙酸乙酯/石油醚=1/10的比例柱层析,得微红色固体4-(6-(4-(苯甲酸乙酯基)氧基)己烷基氧基)-2,2,6,6-四甲基氧化哌啶醇(EHT) 5.41 g,收率89 %;
取4-氨基苯甲酸乙酯(3.30 g, 20 mmol),1-溴辛烷(1.93 g, 10 mmol),溶解在干燥的DMF(50 mL)中,然后温度升至80 °C,搅拌过夜。冷却至室温,将反应液倒入水中沉淀,抽滤,固体用50 %乙醇水溶液冲洗,得到的固体用无水乙醇重结晶,得到白色晶体的单体4-(辛基氨基)苯甲酸乙酯(OBE)1.42 g,收率51.3 %;
制备POBE的优选方案:单体OBE (277.4mg, 1mmol),引发剂EHT(21.0mg, 0.05mmol),和THF(0.5 mL)搅拌30分钟。用注射器向装有单体和引发剂的烧瓶中加入LiHMDS (1.0M, in THF, 1.5mL, 1.5mmol)。在0 ℃下反应至预设时间后,加入1 mL饱和氯化铵水溶液以终止反应。反应液用二氯甲烷萃取,用1M的氢氧化钠水洗,然后水洗至中性,用无水硫酸镁干燥,蒸去溶剂得到淡黄色油状物POBE。
参见图1所示,在不同的单体和引发剂的初始摩尔比条件下,通过可控缩聚制备的聚合物的相对分子量随单体和引发剂的初始摩尔比的增加而增加且呈线性关系,其相对分子量与理论值吻合较好,并且相对分子量分布较窄。
参见图2所示,在聚合体系中,聚合物的相对分子量随着聚合反应时间的延长而增长,并且聚合物的相对分子量分布比较窄,聚合物的相对分子量与反应时间成线性关系。
步骤2)一段为聚酰胺、一段为聚苯乙烯两嵌段共聚物的制备:
制备一段为聚酰胺、一段为聚苯乙烯两嵌段共聚物的优选方案:POBE(0.05 g, 1.62×10-5 mol), St (0.1688 g, 1.62×10-3 mol)和BPO(0.0019 g, 8.10×10-6 mol)加入到5 mL安培瓶中,将此安培瓶通氩气20分钟以排除其中的氧气,封口,并放入130 ℃的油浴中聚合。在预定的反应时间之后,将其取出放入冰水中,打开封口,将反应液溶于2 mL THF中,溶液在约150 mL甲醇中沉淀,抽滤,真空干燥即可得所需聚合物。
参见图3所示,通过GPC测试,可以发现聚合物的相对分子量随聚合反应时间的延长而增长。为了进一步证明成功制备了一段为聚酰胺、一段为聚苯乙烯的两嵌段共聚物,我们对这两种聚合物进行了核磁分析,参见图4所示,与TEMPO基团相邻的一个苯乙烯链段中叔碳上氢的特征峰在4.8 ppm左右,聚酰胺链段端基的亚甲基上的氢的特征峰在4.3 ppm左右,并且,两个峰的积分比约为1:2。这些证据证明了制备一段为聚酰胺、一段为聚苯乙烯两嵌段共聚物的设想是成功的。
步骤3)一段为聚酰胺、一段为聚甲基丙烯酸甲酯的两嵌段共聚物的制备:
制备一段为聚酰胺、一段为聚甲基丙烯酸甲酯的两嵌段共聚物的优选方案:MMA (2 g, 20 mmol), EBiB (0.0195 g, 0.1 mmol), CuBr (0.0144 g, 0.1 mmol)和PMDETA (0.0520 g, 0.3 mmol) 加入到5 mL安培瓶中,将此安培瓶通氩气20分钟以排除其中的氧气,封口,并放入60 ℃的油浴中聚合。在预定的反应时间之后,将其取出放入冰水中冷却,打开封口,将反应液溶于2 mL THF中,溶液在约150 mL正己烷中沉淀,抽滤,真空干燥即可得聚合物PMMA;
取摩尔比为[POBE]0/[PMMA]0/ [CuBr]0/ [PMDETA]0 = 1.1:1:1:3,甲苯作溶剂,加入到5 mL安培瓶中,将此安培瓶通氩气20分钟以排除其中的氧气,封口,并放入60 ℃的油浴中反应。在预定的反应时间之后,将其取出放入冰水中冷却,打开封口,将反应液溶于2 mL THF中,溶液在约150 mL甲醇中沉淀,抽滤,真空干燥即可得所需聚合物。
我们通过可控缩聚和ATRP技术制备了端基含有TEMPO基团的POBE (M n,GPC = 3080 g/mol, M w/M n = 1.17)和端基为碳溴键的PMMA (M n,GPC = 7850 g/mol, M w/M n = 1.21)。接着,将摩尔比为1.1:1的两种聚合物溶解在甲苯中,以CuBr和PMDETA为催化体系,在60 ℃进行反应至预设的反应时间后冷却至室温,倒入甲醇中沉淀,得到的聚合物用GPC表征其相对分子量和分子量分布,所得聚合物的GPC流出曲线参见图5所示。从图中可以看出,反应后的聚合物的分子量增至M n,GPC = 9750 g/mol,但聚合物的分子量分布仍保持较窄(1.25)。这说明两种大分子之间的反应成功地进行。为了进一步证明成功制备了一段为聚酰胺一段为聚甲基丙烯酸甲酯的嵌段共聚物,我们对大分子反应后聚合物进行了核磁表征。参见图6所示,POBE中苯环的特征峰与溶剂CDCl3的特征峰有部分重叠。此外,TEMPO上的叔碳上的氢的特征峰在4.05 ppm左右(图中b位置),与TEMPO基团相邻的PMMA链段上亚甲基上的氢的特征峰在2.45 ppm左右(图中a位置),并且两个峰的面积积分的比为1:2。这说明TEMPO基团成功的通过捕捉自由基形成碳氧键,连接到了PMMA的端基上。这些证据证明了制备一段为聚酰胺、一段为聚甲基丙烯酸甲酯嵌段共聚物的设想是成功的。
以上所述仅为本发明的优选实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (1)
1.一种含有聚酰胺链段的两嵌段共聚物的制备方法,其特征在于,包括以下步骤:
步骤1)配制可控缩聚体系,包括单体、引发剂、碱和溶剂;
步骤2)进行可控缩聚反应,制备端基为TEMPO基团的聚酰胺POBE;
步骤3)以POBE为大分子TEMPO试剂调控苯乙烯的“活性”/可控自由基聚合,制备了一段为聚酰胺、一段为聚苯乙烯的两嵌段共聚物;
步骤4) POBE与通过ATRP制备的聚甲基丙烯酸甲酯进行大分子间反应,制备了一段为聚酰胺、一段为聚甲基丙烯酸甲酯的两嵌段共聚物;
步骤1)中所述单体为4-(辛基氨基)苯甲酸乙酯,所述引发剂为4-(6-(4-(苯甲酸乙酯基)氧基)己烷基氧基)-2,2,6,6-四甲基氧化哌啶醇,所述碱为双(三甲基硅基)氨基锂,所述溶剂为四氢呋喃;
步骤2)、步骤3)和步骤4)中聚酰胺的数均分子量为2000~20000 g/mol,聚合物分散性指数M w/M n<1.5;
步骤2)中反应温度为-10~30 ℃;
步骤3)中反应温度为100~140 ℃,一段为聚酰胺、一段为聚苯乙烯的两嵌段共聚物的数均分子量为4000~150000 g/mol,聚合物分散性指数M w/M n<1.5;
步骤4)中聚甲基丙烯酸甲酯的聚合体系为:单体为甲基丙烯酸甲酯,引发剂为2-溴代异丁酸乙酯,催化剂为溴化亚铜,配体为N, N, N′, N′′, N′′-五甲基二亚乙基三胺,聚合反应温度为50~80 ℃,聚甲基丙烯酸甲酯的数均分子量为3000~130000 g/mol,聚合物分散性指数M w /M n <1.5;大分子间反应溶剂为甲苯,大分子间反应温度为40~60 ℃;一段为聚酰胺、一段为聚甲基丙烯酸甲酯的两嵌段共聚物的数均分子量为5000~150000 g/mol,聚合物分散性指数M w/M n<1.5。
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