CN114957573A - 一种含有硝基苄二硫醚和邻硝基苄酯嵌段可降解聚苯乙烯的合成方法 - Google Patents
一种含有硝基苄二硫醚和邻硝基苄酯嵌段可降解聚苯乙烯的合成方法 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,且公开了一种含有硝基苄二硫醚和邻硝基苄酯嵌段可降解聚苯乙烯的合成方法,包括步骤:合成烯基封端中间单体M‑CH=CH2;2‑硝基‑1,3‑二苄醇的醇羟基官能团与4‑溴丁酸的羧酸官能团发生脱水缩合反应,得到溴基化中间单体M‑Br,其溴基官能团化与2‑硝基‑1,4‑苄二硫醇的巯基官能团发生加成消除聚合反应,得到巯基封端聚合物P‑CH2SH,聚合物P‑CH2SH的巯基官能团与中间单体M‑CH=CH2的烯基官能团发生加成聚合反应,得到大分子引发剂P,以其为链转移剂,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和邻硝基苄酯的聚苯乙烯。
Description
技术领域
本发明涉及可降解聚苯乙烯合成技术领域,具体为一种含有硝基苄二硫醚和邻硝基苄酯嵌段可降解聚苯乙烯的合成方法。
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;邻硝基苄基类的物质被光照射后,邻位上的硝基电子分布发生变化,生成一种异恶唑环类似物的活跃中间产物,最后经分子内的电荷重新排列,化学键重新组合,得到硝基邻位上的取代基变成醛基的光解产物;
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2-硝基-1,3-二苄醇的结构和制备方法;
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,本发明提供一种含有硝基苄二硫醚和邻硝基苄酯嵌段可降解聚苯乙烯的合成方法。
(二)技术方案
为实现上述目的,本发明提供如下技术方案:
一种含有硝基苄二硫醚和邻硝基苄酯嵌段可降解聚苯乙烯的合成方法,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和邻硝基苄酯的大分子引发剂P;
步骤Step2,将2份的苯乙烯、0.1-0.8份的大分子引发剂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,大分子引发剂P的的合成方法如下:
步骤Step1-1,以4-氯甲基苯乙烯和二硫化碳为主要原料合成烯基封端中间单体M-CH=CH2;
步骤Step1-2,2-硝基-1,3-二苄醇的醇羟基官能团与4-溴丁酸的羧酸官能团发生脱水缩合反应,得到溴基化中间单体M-Br;
步骤Step1-3,中间单体M-Br的溴基官能团化与2-硝基-1,4-苄二硫醇的巯基官能团发生加成消除聚合反应,得到巯基封端聚合物P-CH2SH;
步骤Step1-4,聚合物P-CH2SH的巯基官能团与中间单体M-CH=CH2的烯基官能团发生加成聚合反应,得到大分子引发剂P。
优选的,所述步骤Step1-1,烯基封端中间单体M-CH=CH2的合成过程采用催化剂四丁基溴化铵。
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80-100℃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:以4-氯甲基苯乙烯和二硫化碳为主要原料合成烯基封端中间单体M-CH=CH2,2-硝基-1,3-二苄醇的醇羟基官能团与4-溴丁酸的羧酸官能团发生脱水缩合反应,得到溴基化中间单体M-Br,中间单体M-Br的溴基官能团化与2-硝基-1,4-苄二硫醇的巯基官能团发生加成消除聚合反应,得到巯基封端聚合物P-CH2SH,聚合物P-CH2SH的巯基官能团与中间单体M-CH=CH2的烯基官能团发生加成聚合反应,得到大分子引发剂P,以大分子引发剂P为链转移剂,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和邻硝基苄酯的聚苯乙烯,并且渗透凝胶色谱(GPC)的测试结果证明利用该主链上的紫外光光降解基团可以实现聚苯乙烯的降解。
附图说明
图1为合成烯基封端的中间单体M-CH=CH2的反应式;
图2为合成溴基化中间单体M-Br的反应式;
图3为合成巯基封端聚合物P-CH2SH的反应式;
图4为合成大分子引发剂P的反应式;
图5为主链上含有硝基苄二硫醚和邻硝基苄酯嵌段可降解聚苯乙烯的结构式。
具体实施方式
实施例1:
烯基封端中间单体M-CH=CH2的合成:
将10mL质量含量为33%的NaOH水溶液和1.27g二硫化碳CS2加入到50mL平底烧瓶中,常温下磁力搅拌,加入112mg四丁基溴化铵催化剂搅拌1h,然后加入2.55g4-氯甲基苯乙烯反应24h,分出二硫化碳CS2相,水相用二硫化碳CS2萃取之后合并二硫化碳CS2相,水洗、无水硫酸钠干燥、过滤,减压蒸馏除去二硫化碳CS2、产物用色谱柱进一步提纯,得到中间单体M-CH=CH2;
溴基化中间单体M-Br的合成:
称取546mg2-硝基-1,3-二苄醇溶解于100mL甲苯溶液中,油浴然后加入1g4-溴丁酸和15mg对甲苯磺酸,油浴升温至120℃反应24h,反应结束后,水洗收集产物在无水硫酸钠中干燥后,旋蒸除去甲苯溶剂,产物用溶解于四氢呋喃中,然后加入石油醚析出产物,过滤得到中间单体M-Br;
巯基封端聚合物P-CH2SH的合成:
称取430mg2-硝基-1,4-苄二硫醇于含有6mL四氢呋喃的50mL的圆底烧瓶中,之后加入404mg三乙胺催化剂、480mg中间单体M-Br,在磁力搅拌下于60℃反应24h,旋蒸除去四氢呋喃溶剂,将产物溶解于二氯甲烷中、沉淀在环己烷中,之后于40℃真空干燥24h,得到聚合物P-CH2SH;
大分子引发剂P的合成:
称取460mg聚合物P-CH2SH于含有6mL四氢呋喃的50mL圆底烧瓶中,加入50mg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343mg中间单体M-CH=CH2,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,得到大分子引发剂P
可降解聚苯乙烯的合成:
将2g苯乙烯、376mg大分子引发剂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100℃下进行聚合反应4h,得到可降解聚苯乙烯;
称取样品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),之后于紫外光(365nm,2W)下辐照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°C,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;
光照前渗透凝胶色谱(GPC)的测试结果为:数均分子量Mn=21673g/moL,重均分子量Mw=30559,PDI=Mw/Mn=1.41;
光照后渗透凝胶色谱(GPC)的测试结果为:数均分子量Mn=11083g/moL;
由此可知,含有硝基苄二硫醚和邻硝基苄酯嵌段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2g苯乙烯、125mg大分子引发剂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80℃下进行聚合反应4h,得到可降解聚苯乙烯;
其中,大分子引发剂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2g苯乙烯、752mg大分子引发剂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,大分子引发剂P采用实施例1的制备方法制备得到。
Claims (4)
1.一种含有硝基苄二硫醚和邻硝基苄酯嵌段可降解聚苯乙烯的合成方法,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和邻硝基苄酯的大分子引发剂P;
步骤Step2,将2份的苯乙烯、0.1-0.8份的大分子引发剂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。
2.根据权利要求1所述的一种含有硝基苄二硫醚和邻硝基苄酯嵌段可降解聚苯乙烯的合成方法,其特征在于,所述步骤Step1,大分子引发剂P的的合成方法如下:
步骤Step1-1,以4-氯甲基苯乙烯和二硫化碳为主要原料合成烯基封端中间单体M-CH=CH2;
步骤Step1-2,2-硝基-1,3-二苄醇的醇羟基官能团与4-溴丁酸的羧酸官能团发生脱水缩合反应,得到溴基化中间单体M-Br;
步骤Step1-3,中间单体M-Br的溴基官能团化与2-硝基-1,4-苄二硫醇的巯基官能团发生加成消除聚合反应,得到巯基封端聚合物P-CH2SH;
步骤Step1-4,聚合物P-CH2SH的巯基官能团与中间单体M-CH=CH2的烯基官能团发生加成聚合反应,得到大分子引发剂P。
3.根据权利要求2所述的一种含有硝基苄二硫醚和邻硝基苄酯嵌段可降解聚苯乙烯的合成方法,其特征在于,所述步骤Step1-1,烯基封端中间单体M-CH=CH2的合成过程采用催化剂四丁基溴化铵。
4.根据权利要求1-3任一项所述的一种含有硝基苄二硫醚和邻硝基苄酯嵌段可降解聚苯乙烯的合成方法,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80-100℃下进行聚合反应得到可降解聚苯乙烯。
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