CN115322173B - 一种多功能受阻胺类光稳定剂及其制备方法 - Google Patents
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Abstract
本发明公开了一种多功能受阻胺类光稳定剂及其制备方法,其制备方法由以下步骤组成:步骤S1:以N‑正丁基‑2,2,6,6‑四甲基‑4‑哌啶胺和2,4,6‑三氯‑1,3,5‑三嗪为原料,经亲核取代合成2‑氯‑4,6‑二‑[N‑正丁基‑N‑(2,2,6,6‑四甲基‑4‑哌啶基)氨基]‑1,3,5‑三嗪;步骤S2:经取代反应合成2‑(2’,4’‑二羟基苯)‑4,6‑二[N‑正丁基‑N‑(2,2,6,6‑四甲基‑4‑哌啶基)氨基]‑1,3,5‑三嗪;步骤S3:将2‑(2’,4’‑二羟基苯)‑4,6‑二[N‑正丁基‑N‑(2,2,6,6‑四甲基‑4‑哌啶基)氨基]‑1,3,5‑三嗪和1‑氯己烷经醚化反应得到多功能受阻胺类光稳定剂UH;本发明通过在三嗪结构光稳定剂基础上引入内氢键结构并对一个羟基进行醚化,使得制备得到的化合物具有紫外线吸收和自由基捕获两种功能的同时还能使其与不同材料具有较好的相容性。
Description
技术领域
本发明属于光稳定剂领域,尤其涉及一种多功能受阻胺类光稳定剂及其制备方法。
背景技术
聚合物材料使用和加工过程中,难免会因光、氧、热等原因造成不同程度的老化,为了防止材料在加工和使用期间过早的老化而缩短使用寿命,人们研究出了一系列具有不同功能的防老化助剂,光稳定剂为其中一种重要的助剂。
受阻胺光稳定剂(HALS)是目前使用最为广泛,市场占有率最高的一类光稳定剂。随着人们对受阻胺光稳定剂研究的开展与深入,如何开发出具有优良性能的新型光稳定剂成为越来越棘手的问题。无论是单体型还是聚合型,市场上常见的HALS已经代表了很多结构上的可能性,于是人们开始尝试引入新的官能团。由受阻胺光稳定剂的作用机理我们可知,其光稳定性能在于受阻胺基,官能团的作用在此显得尤为突出。所以,通过引入具有其他功能的官能团,在不影响受阻胺作用的基础上,借由分子内的自协同效应,既开发了新的结构类型,又兼具新的功能受阻胺光稳定剂,成为了目前HALS开发的主要趋势之一。
发明内容
本发明的目的是提供一种多功能受阻胺类光稳定剂及其制备方法,以解决现有技术中多功能光稳定剂与不同聚合物相容性较差的问题。
本发明采用以下技术方案:一种多功能受阻胺类光稳定剂,结构式如下:
一种多功能受阻胺类光稳定剂的制备方法,反应方程式如下:
进一步地,由以下步骤组成:
步骤S1:以N-正丁基-2,2,6,6-四甲基-4-哌啶胺和2,4,6-三氯-1,3,5-三嗪为原料,经亲核取代合成2-氯-4,6-二-[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪;
步骤S2:将2-氯-4,6-二-[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪和间苯二酚为原料,经取代反应合成2-(2’,4’-二羟基苯)-4,6-二[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪;
步骤S3:将2-(2’,4’-二羟基苯)-4,6-二[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪和1-氯己烷经醚化反应得到多功能受阻胺类光稳定剂UH。
进一步地,步骤S1中:N-正丁基-2,2,6,6-四甲基-4-哌啶胺和2,4,6-三氯-1,3,5-三嗪的摩尔比为2:1;
步骤S2中:2-氯-4,6-二-[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪和间苯二酚的摩尔比为1:1.1-1.3;
步骤S3中:2-(2’,4’-二羟基苯)-4,6-二[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪和1-氯己烷的摩尔比为1:1.1-1.4。
进一步地,步骤S1中:
反应溶剂为甲苯,催化剂为10-30%的氢氧化钠/氢氧化钾水溶液,反应条件为60-90℃;反应时间为6-14h;
N-正丁基-2,2,6,6-四甲基-4-哌啶胺、2,4,6-三氯-1,3,5-三嗪、氢氧化钠/氢氧化钾的摩尔比为2-2.4:1:2-2.5。
进一步地,步骤S2中:
反应溶剂为氯苯/邻二氯苯,催化剂为无水三氯化铝,反应条件为60-90℃;反应时间为4-12h;
2-氯-4,6-二-[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪、间苯二酚、无水三氯化铝的摩尔比为1:1.1-1.3:1-1.2。
进一步地,步骤S3中:
反应溶剂为DMF,催化剂为氢氧化钠/氢氧化钾,反应温度为80-120℃;反应时间为6-10h;
2-(2’,4’-二羟基苯)-4,6-二[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪、1-氯己烷、氢氧化钠/氢氧化钾的摩尔比为1:1.1-1.4:1-1.3。
本发明的有益效果是:本发明采用间苯二酚、1-氯己烷作为取代基,对2-氯-4,6-二-[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪进行修饰,通过在三嗪结构光稳定剂基础上引入内氢键结构并对一个羟基进行醚化,使得制备得到的化合物具有紫外线吸收和自由基捕获两种功能的同时还能使其与不同材料具有较好的相容性,解决了现有技术中多功能光稳定剂与不同聚合物相容性较差的难题,具有一剂多用优势的同时具有更好的相容性;本发明以2-氯-4,6-二-[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪为原料,接入间苯二酚后构成内氢键结构,以1-氯己烷作为取代基修饰得到,该化合物具有内氢键和受阻胺结构,导致其具有紫外线吸收和自由基捕获的双重功能,同时通过醚化一个羟基使其在不同材料中具有良好的相容性,在塑料制品的防老化领域具有重要应用前景。
附图说明
图1为本发明中2-氯-4,6-二-[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪的结构表征图;
图1(a)为2-氯-4,6-二-[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪的高分辨质谱;
图1(b)为2-氯-4,6-二-[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪的核磁共振氢谱;
图2为本发明中2-(2’,4’-二羟基苯)-4,6-二[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪的结构表征图;
图2(a)为2-(2’,4’-二羟基苯)-4,6-二[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪的高分辨质谱;
图2(b)为2-(2’,4’-二羟基苯)-4,6-二[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪核磁共振氢谱;
图3为本发明中多功能受阻胺类光稳定剂,即化合物UH的结构表征图;
图3(a)为多功能受阻胺类光稳定剂的高分辨质谱;
图3(b)为多功能受阻胺类光稳定剂核磁共振氢谱;
图4为不同老化时间掺杂化合物UH的薄膜和空白的PE薄膜老化对比图;
图5为老化后的聚乙烯薄膜力学性能测试图;
图5(a)为不同老化时间与薄膜的拉伸强度保留率的关系;
图5(b)为不同老化时间与薄膜的断裂伸长率保留率的关系。
具体实施方式
下面结合附图和具体实施方式对本发明进行详细说明。
本发明公开了一种多功能受阻胺类光稳定剂,结构式如下:
本发明还公开了一种多功能受阻胺类光稳定剂的制备方法,反应方程式如下:
一种多功能受阻胺类光稳定剂的制备方法,由以下步骤组成:
步骤S1:以N-正丁基-2,2,6,6-四甲基-4-哌啶胺和2,4,6-三氯-1,3,5-三嗪为原料,经亲核取代合成2-氯-4,6-二-[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪;
步骤S2:将2-氯-4,6-二-[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪和间苯二酚为原料,经取代反应合成2-(2’,4’-二羟基苯)-4,6-二[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪;
步骤S3:将2-(2’,4’-二羟基苯)-4,6-二[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪和1-氯己烷经醚化反应得到多功能受阻胺类光稳定剂UH。
进一步地,步骤S1中:N-正丁基-2,2,6,6-四甲基-4-哌啶胺和2,4,6-三氯-1,3,5-三嗪的摩尔比为2:1;
步骤S2中:2-氯-4,6-二-[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪和间苯二酚的摩尔比为1:1.1-1.3;
步骤S3中:2-(2’,4’-二羟基苯)-4,6-二[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪和1-氯己烷的摩尔比为1:1.1-1.4。
步骤S1中:
反应溶剂为甲苯,催化剂为10-30%的氢氧化钠/氢氧化钾水溶液,反应条件为60-90℃;反应时间为6-14h;
N-正丁基-2,2,6,6-四甲基-4-哌啶胺、2,4,6-三氯-1,3,5-三嗪、氢氧化钠/氢氧化钾的摩尔比为2-2.4:1:2-2.5。
步骤S2中:
反应溶剂为氯苯/邻二氯苯,催化剂为无水三氯化铝,反应条件为60-90℃;反应时间为4-12h;
2-氯-4,6-二-[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪、间苯二酚、无水三氯化铝的摩尔比为1:1.1-1.3:1-1.2。
步骤S3中:
反应溶剂为DMF,催化剂为氢氧化钠/氢氧化钾,反应温度为80-120℃;反应时间为6-10h;
2-(2’,4’-二羟基苯)-4,6-二[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪、1-氯己烷、氢氧化钠/氢氧化钾的摩尔比为1:1.1-1.4:1-1.3。
实施例1
步骤S1:2-氯-4,6-二-[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪的制备
在500mL三口烧瓶中,加入200mL甲醇,将2,4,6-三氯-1,3,5-三嗪(18.44g,100mmol)溶于其中,冰水浴下,缓慢加入N-正丁基-2,2,6,6-四甲基-4-哌啶胺(42.42g,200mmol),并且反应2h;将35%NaOH溶液加至三口瓶中,70℃反应14小时。待反应结束后加水200mL,萃取,分出有机相,无水硫酸钠干燥,脱溶得淡黄色固体,产量约48.8g,产率91%。
将产物2-氯-4,6-二-[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪检测后结果如下:
1H NMR(400MHz,CDCl3)δ5.15(m,2H),3.33(s,4H),1.60(ddd,J=26.5,14.3,9.4Hz,9H),1.30(m,22H),1.18(s,12H),0.94(ddd,J=17.4,10.9,5.4Hz,6H)。MS(ESI),m/z:536.3893[M+H]+。
步骤S2:2-(2’,4’-二羟基苯)-4,6-二[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪的制备
在500ml三口瓶中加入2-氯-4,6-二-[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪(16.0g,30.0mmol)、氯代苯120mL搅拌,冰水浴下加入无水三氯化铝(4.0g,30.0mmol),冰浴搅拌30min后向反应瓶中加入间苯二酚(3.96g,36.0mmol),80℃反应4小时。向反应瓶中缓慢滴加120mL 2%稀盐酸,常压蒸馏回收氯苯水共沸物,升温至100℃。趁热抽滤,粗品分别用稀盐酸、水、二氯甲烷洗涤数次,得白色固体,产量约16.8g,收率为92%。
将产物2-(2’,4’-二羟基苯)-4,6-二[N-正丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪检测后结果如下:
1H NMR(400MHz,MeOD)δ7.46(m,1H),6.38(d,J=6.5Hz,1H),5.45(s,1H),5.24(s,2H),3.59(s,4H),2.05(ddd,J=17.8,15.8,6.8Hz,9H),1.70(s,16H),1.65(s,13H),1.51(dd,J=14.1,6.8Hz,4H),1.10(t,J=7.1Hz,6H)。MS(ESI),m/z:610.4783[M+H]+。
步骤S3:多功能受阻胺类光稳定剂UH的制备
将0.7g(17.5mmol)氢氧化钠固体和100mLDMF加入到三口烧瓶中,加热搅拌溶解,然后加入10.0g(16.4mmol)中间体,升温至80℃,边反应边滴加1-氯己烷(2.9mL,21.3mmol)和DMF(6.0mL)的混合液,2min内滴完,恒温继续,反应6-7h到达终点后,冷却反应液,抽滤得到粗品,水洗后干燥,用DMF结晶得到淡黄色固体,产量约7.96g,收率为70.1%。
将多功能受阻胺类光稳定剂UH检测后结果如下:
1H NMR(400MHz,MeOD)δ7.37–7.26(m,1H),6.25(d,J=7.3Hz,1H),5.43–5.24(m,1H),5.11(s,2H),3.42(dd,J=20.2,8.2Hz,6H),2.05–1.82(m,12H),1.58(s,18H),1.52(d,J=4.9Hz,14H),1.38(dd,J=14.7,7.4Hz,6H),0.97(q,J=7.4Hz,9H)。MS(ESI),m/z:694.5629[M+H]+。
对本实施例制备得到的多功能受阻胺类光稳定剂掺杂在聚乙烯(PE)薄膜中,进行老化性能测试,测试结果如图4左侧所示,图4左侧为添加有化合物UH的薄膜,图4右侧为空白薄膜,由图4可明显看出,未添加的UH的PE薄膜在紫外老化机中老化400h之后出现明显龟裂,而添加光稳定剂UH后的PE薄膜老化800h后也基本上完好无损。
对本实施例制备得到的多功能受阻胺类光稳定剂掺杂在PE薄膜后,对老化后的聚乙烯薄膜力学性能进行测试,测试结果如图5所示,从图5可以看出,在不同的老化时间下,添加有光稳定剂UH的聚乙烯薄膜的拉升强度保留率(图5a)和断裂伸长率保留率(图5b)在不同老化时间后始终优于未添加UH的聚乙烯薄膜。因此,光稳定剂UH确实具有优良的防老化性能。
实施例2
本实施例与实施例1的操作步骤相同,不同的是:
在步骤S1中N-正丁基-2,2,6,6-四甲基-4-哌啶胺的加入量为(46.66g,220mmol),NaOH溶液为25%,最终产量约47.1g,产率88%。
在步骤S2中溶剂氯代苯替换为邻二氯苯,加入无水三氯化铝(4.8g,36.0mmol),稀盐酸为3%稀盐酸,产量约16.4g,收率为90%。
在步骤S3中将1-氯己烷的加入量为(3.1mL,23.0mmol),催化剂氢氧化钠(0.7g,17.5mmol)替换为氢氧化钾(0.98g,17.5mmol),最终产量约为7.83g,产率为69%。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,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 (4)
1.一种多功能受阻胺类光稳定剂,其特征在于,结构式如下:
。
2.一种多功能受阻胺类光稳定剂的制备方法,其特征在于,反应方程式如下:
。
3.根据权利要求2所述的一种多功能受阻胺类光稳定剂的制备方法,其特征在于,
步骤S1中:化合物(1)和化合物(2)的摩尔比为2:1;
步骤S2中:化合物(3)和间苯二酚的摩尔比为1:1.1-1.3;
步骤S3中:化合物(5)和1-氯己烷的摩尔比为1:1.1 -1.4。
4.根据权利要求3所述的一种多功能受阻胺类光稳定剂的制备方法,其特征在于,步骤S2中:
反应溶剂为氯苯/邻二氯苯,催化剂为无水三氯化铝,反应条件为60-90℃;反应时间为4-12h;
化合物(3)、间苯二酚、无水三氯化铝的摩尔比为1:1.1-1.3:1-1.2。
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CN110452223A (zh) * | 2019-07-29 | 2019-11-15 | 宿迁联盛科技股份有限公司 | 一种复合型光稳定剂的制备方法 |
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