CN115028760B - 一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子链转移剂的可降解聚苯乙烯合成方法 - Google Patents
一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子链转移剂的可降解聚苯乙烯合成方法 Download PDFInfo
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Abstract
本发明涉及可降解聚苯乙烯合成技术领域,且公开了一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子链转移剂的可降解聚苯乙烯合成方法,通过双(2‑甲基丙酸)三硫代碳酸酯的羧基官能团与4‑吡啶甲醇的醇羟基官能团发生脱水缩合反应,得到吡啶化中间单体M1,中间单体M1的吡啶官能团与3‑溴丙烯的溴官能团发生烷基化反应,得到烯基化中间单体M2,中间单体M2的烯基官能团与2‑硝基‑1,4‑苄二硫醇的巯基官能团发生加成聚合反应,得到大分子链转移剂P,以大分子链转移剂P为大分子链转移剂,进行苯乙烯的自由基聚合反应,制备得到主链上含有紫外光光降解基团硝基苄二硫醚、可见光光降解基团不对称烷基吡啶鎓酯的聚苯乙烯。
Description
技术领域
本发明涉及可降解聚苯乙烯合成技术领域,具体为一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子链转移剂的可降解聚苯乙烯合成方法。
背景技术
聚苯乙烯(PS)是由苯乙烯单体通过聚合而形成的线性高分子,由于聚苯乙烯物理机械性能良好,能适应多种加工方式且性价比较高,因此,此类制品在我们的日常生活中随处可见,聚苯乙烯塑料被应用于一次性快餐饭盒、电子器件如仪表外壳、建筑板材等制品中,虽然聚苯乙烯拥有很多的优点,但在自然条件下不易降解,废弃后易造成环境污染。聚苯乙烯难以降解的主要原因是其主链由稳定性高的碳碳键构成,在自然条件下不易断裂。如果在聚苯乙烯主链引入易断裂的化学键,使聚苯乙烯在特定条件下降解成为低聚物,低聚物进一步被微生物生物分解,就可以实现聚苯乙烯的降解。
研究发现:2-硝基-1,4-苄二硫醚类物质在紫外光照条件下,硝基被异构化后,苯环上a位上的氢均可以产生自由基,导致物质会按照两种方式进行降解,一是与硝基邻位上的取代基变成醛基,生成邻亚硝基苯甲醛类的产物,另一种是硝基间位上的取代基变成醛基;不对称烷基吡啶鎓酯结构是类可见光光裂解基团,其在可见光触发下可以通过与联吡啶钌/抗坏血酸之间发生间接电子转移过程实现C-O键断裂;
本发明引用下述参考文献:中国科学技术大学的硕士学位论文《可光、化学降解聚苯乙烯的合成与性能研究》公开了双(2-甲基丙酸)三硫代碳酸酯的结构和制备方法;
温州大学的硕士学位论文《光敏性2-硝基-1-4-苄二硫醇在高分子合成中的应用及其光降解机理研究》公开了2-硝基-1,4-苄二硫醇的结构和制备方法。
发明内容
(一)解决的技术问题
针对现有技术聚苯乙烯在自然条件下不易降解,废弃后易造成环境污染的不足,本发明提供一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子链转移剂的可降解聚苯乙烯合成方法。
(二)技术方案
为实现上述目的,本发明提供如下技术方案:
一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子链转移剂的可降解聚苯乙烯合成方法,包括以下步骤:
步骤Step1,合成主链上合有紫外光光降解基团硝基苄二硫醚、可见光光降解基团吡啶鎓酯的大分子链转移剂P;
步骤Step2,可降解聚苯乙烯的合成:将1份的苯乙烯、0.1-0.5份的大分子链转移剂P和偶氮二异丁腈AIBN溶解于N,N-二甲基甲酰胺中,加入聚合管,经过冷冻-抽真空-通氮气解冻后,在真空条件下封管进行聚合反应得到可降解聚苯乙烯。
优选的,所述步骤Step1,大分子链转移剂P的合成方法如下:
步骤Step1-1,双(2-甲基丙酸)三硫代碳酸酯的羧基官能团与4-吡啶甲醇的醇羟基官能团发生脱水缩合反应,得到吡啶化中间单体M1;
步骤Step1-2,中间单体M1的吡啶官能团与3-溴丙烯的溴官能团发生烷基化反应,得到烯基化中间单体M2;
步骤Step1-3,中间单体M2的烯基官能团与2-硝基-1,4-苄二硫醇的巯基官能团发生加成聚合反应,得到大分子链转移剂P。
优选的,所述步骤Step1-3,大分子链转移剂P的合成过程采用催化剂三乙胺。
优选的,所述步骤Step2,偶氮二异丁腈AIBN的用量为(8-16)×10-4份。
优选的,所述步骤Step2,经过三次冷冻-抽真空-通氮气解冻后,在真空条件下封管,在90-100℃下进行聚合反应得到可降解聚苯乙烯。
(三)有益的技术效果
与现有技术相比,本发明具备以下有益的技术效果:
本发明通过:双(2-甲基丙酸)三硫代碳酸酯的羧基官能团与4-吡啶甲醇的醇羟基官能团发生脱水缩合反应,得到吡啶化中间单体M1,中间单体M1的吡啶官能团与3-溴丙烯的溴官能团发生烷基化反应,得到烯基化中间单体M2,中间单体M2的烯基官能团与2-硝基-1,4-苄二硫醇的巯基官能团发生加成聚合反应,得到大分子链转移剂P,以大分子链转移剂P为大分子链转移剂,进行苯乙烯的自由基聚合反应,制备得到主链上合有紫外光光降解基团硝基苄二硫醚、可见光光降解基团不对称烷基吡啶鎓酯的聚苯乙烯,并且渗透凝胶色谱(GPC)的测试结果证明利用该主链上的光降解基团可以实现聚苯乙烯的降解。
附图说明
图1为合成吡啶化中间单体M1的反应式;
图2为合成烯基化中间单体M2的反应式;
图3为合成大分子链转移剂P的反应式;
图4为主链上含有紫外光光降解基团硝基苄二硫醚、可见光光降解基团吡啶鎓酯嵌段聚苯乙烯的结构式。
具体实施方式
实施例1:
吡啶化中间单体M1的合成:
取564mg双(2-甲基丙酸)三硫代碳酸酯、436mg4-吡啶甲醇和100mg4-二甲氨基吡啶溶解在100mL二氯甲烷中,室温条件下搅拌24h,反应完毕之后依次用饱和碳酸氢钠以及饱和氯化钠溶液洗涤,有机相用无水硫酸镁干燥,收集有机相旋蒸,得到吡啶化中间单体M1;
烯基化中间单体M2的合成:
称取650mg中间单体M1溶于10mL二甲基亚砜,之后加入339mg3-溴丙烯,将反应体系置于85℃油浴中反应24h,反应液在二氯甲烷中沉淀,得到中间单体M2;
大分子链转移剂P的合成:
称取181mg2-硝基-1,4-苄二硫醇于含有6mL四氢呋喃的50mL圆底烧瓶中,加入8.5mg三乙胺催化剂,在室温条件下,用磁力搅拌,然后向恒压滴液漏斗中加入593mg中间单体M2,加入2mL的四氢呋喃稀释,将其逐滴滴加到上述圆底烧瓶中,反应24h,将产物旋蒸,除去大部分的溶剂,再将其沉淀在乙醚中,如此溶解、沉淀反复2-3次,将产物于真空干燥箱中40℃下干燥24h,得到大分子链转移剂P;
可降解聚苯乙烯的合成:
将1g苯乙烯、341mg大分子链转移剂P和0.82mg偶氮二异丁腈AIBN溶解于1mL的N,N-二甲基甲酰胺中,加入1mL的聚合管,经过三次冷冻-抽真空-通氮气解冻后,在真空条件下封管,在100℃下进行聚合反应4h,得到可降解聚苯乙烯。
称取上述样品6mg-10mg之间的质量于2mL的四氢呋喃中,样品完全溶解后,转移至玻璃表面皿上,测试其渗透凝胶色谱(GPC),之后于蓝色LED光(452nm,6W)和紫外光(365nm,2W)下同时辐照10h,再次测试其渗透凝胶色谱(GPC),其具体方法如下:采用高效液相色谱(HPLC)分离单元e2695,以聚苯乙烯作为参比标准,流动相为四氢呋喃,流速设定为1mL/min,柱温设为35℃,流动相需预先通过保护预柱以及规格为7.8*300mm的分离柱,检测器为2414示差检测器;测样时,取5mg待测样于1.0mL的色谱级四氢呋喃中,震荡2min,,加速物质溶解,然后将其经过粉色0.22um的聚四氟乙烯滤头,过滤至2mL的玻璃样品瓶中,除去不溶物和大颗粒的物质,防止阻塞GPC内部的注射针头,最后,将样品瓶上样,测样,其测试结果如下:
光照前渗透凝胶色谱(GPC)的测试结果为:数均分子量Mn=31890g/moL,重均分子量Mw=45603,PDI=Mw/Mn=1.43;
光照后渗透凝胶色谱(GPC)的测试结果为:数均分子量Mn=7986g/moL;
由此可知,实施例1制备的聚苯乙烯具有光降解功能。
实施例2:
可降解聚苯乙烯的合成:
将1g苯乙烯、114mg大分子链转移剂P和1.64mg偶氮二异丁腈AIBN溶解于1mL的N,N-二甲基甲酰胺中,加入1mL的聚合管,经过三次冷冻-抽真空-通氮气解冻后,在真空条件下封管,在90℃下进行聚合反应4h,得到可降解聚苯乙烯;
其中,大分子链转移剂P采用实施例1的制备方法制备得到;
实施例3:
可降解聚苯乙烯的合成:
将1g苯乙烯、511mg大分子链转移剂P和0.82mg偶氮二异丁腈AIBN溶解于1mL的N,N-二甲基甲酰胺中,加入1mL的聚合管,经过三次冷冻-抽真空-通氮气解冻后,在真空条件下封管,在100℃下进行聚合反应4h,得到可降解聚苯乙烯;
其中,大分子链转移剂P采用实施例1的制备方法制备得到。
Claims (4)
1.一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子链转移剂的可降解聚苯乙烯合成方法,其特征在于,包括以下步骤:
步骤Step1,合成主链上含有紫外光光降解基团硝基苄二硫醚、可见光光降解基团吡啶鎓酯的大分子链转移剂P;
步骤Step2,可降解聚苯乙烯的合成:将1重量份的苯乙烯、0.1-0.5重量份的大分子链转移剂P和偶氮二异丁腈AIBN溶解于N, N-二甲基甲酰胺中,加入聚合管,经过冷冻-抽真空-通氮气解冻后,在真空条件下封管进行聚合反应得到可降解聚苯乙烯;
所述大分子链转移剂P的合成方法如下:
步骤Step1-1,双(2-甲基丙酸)三硫代碳酸酯的羧基官能团与4-吡啶甲醇的醇羟基官能团发生脱水缩合反应,得到吡啶化中间单体M1;
步骤Step1-2,中间单体M1的吡啶官能团与3-溴丙烯的溴官能团发生烷基化反应,得到烯基化中间单体M2;
步骤Step1-3,中间单体M2的烯基官能团与2-硝基-1,4-苄二硫醇的巯基官能团发生加成聚合反应,得到大分子链转移剂P。
2.根据权利要求1所述的一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子链转移剂的可降解聚苯乙烯合成方法,其特征在于,所述步骤Step1-3,大分子链转移剂P的合成过程采用催化剂三乙胺。
3.根据权利要求1所述的一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子链转移剂的可降解聚苯乙烯合成方法,其特征在于,所述步骤Step2,偶氮二异丁腈AIBN的用量为(8~16)×10-4重量份。
4.根据权利要求1-3任一项所述的一种基于硝基苄二硫醚和吡啶鎓酯嵌段大分子链转移剂的可降解聚苯乙烯合成方法,其特征在于,所述步骤Step2,经过三次冷冻-抽真空-通氮气解冻后,在真空条件下封管,在90~100℃下进行聚合反应得到可降解聚苯乙烯。
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