CN117304123A - 一种防晒剂天来施s的制备方法 - Google Patents
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Abstract
本发明公开了一种防晒剂天来施S的制备方法,以RET、卤代异辛烷为反应原料,使用油水两相体系,在相转移催化剂的作用下进行缩合醚化反应,经过后处理得到。与现有技术相比,本发明的有益效果是:本发明使用油水两相体系,在相转移催化剂的作用下,提高了反应的效率和选择性,且使得产品只溶于有机相中,易于与反应体系分离;本发明的油水两相体系使得反应变得比较温和,避免了高温引起的副反应和对设备的苛刻要求。
Description
技术领域
本发明涉及紫外吸收剂领域,尤其涉及一种防晒剂天来施S的制备方法。
背景技术
三嗪类紫外线吸收剂是近年发展起来的一类新型紫外线吸收剂,它具有较大的分子结构和很高的紫外线吸收效率及抗氧化功能。某些三嗪类紫外吸收剂具有广谱抗紫外效果,即既防UVB段紫外线,又防UVA段紫外线,是紫外线吸收剂的发展方向,例如天来施S,化学名,2,4-二(4-(2-乙基己氧基)-2-羟基苯基)-6-(4-甲氧基苯基)-1,3,5-s-三嗪,CAS号:187393-00-6,其化学结构式如下:
Scheme 1天来施S化学结构式
近年来,国外各大公司,如汽巴、巴斯夫、拜尔、氰特、欧莱雅、伊士曼等一直致力于三嗪类紫外线吸收剂的研究开发。国内在三嗪类紫外线吸收剂领域的研究不多,且产品多为低层次品种。
从国内需求和世界发展趋势来看,加速研制三嗪类紫外线吸收剂,改进三嗪紫外线吸收剂产品的合成工艺,提高产品质量,降低成本,减少污染,便于规模化生产,是我们十分迫切的任务。
三嗪类紫外线吸收剂的作用机理,由苯环上的羟基氢和相邻的氮原子之间,形成的分子内氢键构成了一个鳌合环,当吸收紫外光后,分子发生热振动,氢键断裂鳌合环打开,形成离子型化合物,这个化合物处于不稳定的高能状态,要恢复到原来的低能稳定状态,把多余的能量以其他形式释放出来,鳌合环又闭环,这样周而复始的吸收紫外光起到保护作用,如Scheme 2所示。
天来施S分子中所含有的羟基与三嗪环上的氮原子形成的鳌合六元环具有更高的稳定性,开环所需的能量也较高,因此其需要吸收更靠近较高能量区域的能量,其较一般三嗪类紫外线吸收剂具有更高的摩尔吸光系数;其苯环与三嗪环的结构特点使分子在发生分子内异构化后可以更快地释放能量回复原状,从而以较低的添加量即可达到应用的要求。此外,天来施S还具有低色泽性、高加工温度、较好的相溶性等特点。以上这些优点使得天来施S成为全面防护UVA和UVB波段的广谱高效防晒剂,广泛应用于各类高SPF值防晒产品中。
天来施S目前主要制造商为BASF,国内只有安徽圣诺贝化学科技有限公司于2016年实现工业化量产,商品名为Parsol S(PS)。
天来施S一般以4,6-二(2',4'-二羟基苯基)-2-(4'-甲氧基苯基)-1,3,5-三嗪(RET)和卤代异辛烷为原料,经醚化反应制备。专利US5955060描述了以RET为原料,乙二醇单甲醚为溶剂,先与50%的氢氧化钠形成RET钠盐,再加入溴代异辛烷,于112-114℃反应8h后,用甲苯和己烷混合液萃取,再过硅胶柱,得到的洗脱液经数周结晶得到产品天来施S,收率仅78.4%。该法步骤冗长,反应时间久,选择性和收率低,而且使用硅胶柱提纯产品,劳动强度大,结晶需数周时间,耗时,成本高,不利于工业化生产。专利WO2016/184766,以DMF为溶剂,将RET溶解后,加入碳酸钠和氯代异辛烷,升温至133-143℃,反应至7-8h结束反应,加入仲丁醇和晶种结晶,得天来施S,收率85-87%,纯度96.6-96.8%。该法以水溶液性DMF为反应溶剂,回收困难,结晶使用双溶剂,分离回收溶剂成本高,此外,过高的反应温度不仅增加了设备的制造成本和维护成本,还降低了反应的选择性。同时,缚酸剂碳酸钠的用量是氯代异辛烷的3.5倍当量,这也降低了反应的选择性,使得三醚化产物增多,而且还会产生较多的难以处理的固体废盐,严重污染环境。
Scheme 2天来施S吸收紫外线作用机制
因此,仍需继续探索新的制备方法,以适应业界对防晒剂天来施S的需求。
发明内容
为了解决上述背景技术中提到的问题,本发明提供一种防晒剂天来施S的制备方法,以RET、卤代异辛烷为反应原料,使用油水两相体系,在相转移催化剂的作用下进行缩合醚化反应得到。
优选的,所述油水两相体系中油相溶剂选自甲苯、苯、环己烷、正辛烷中的任意一种。
优选的,所述相转移催化剂选自四丁基溴化铵、苄基三乙基氯化铵、四乙基对甲苯磺酸铵、十四烷基三甲基氯化铵中的任意一种。
优选的,所述缩合醚化反应时,还加入了缚酸剂。
优选的,所述缚酸剂选自氢氧化钠、氢氧化钾、三乙胺中的任意一种或几种。
优选的,所述卤代异辛烷为氯代异辛烷、溴代异辛烷中的任意一种。
优选的,所述RET、卤代异辛烷的摩尔比为1:(3-4)。
与现有技术相比,本发明的有益效果是:
1.本发明使用油水两相体系,在相转移催化剂的作用下,提高了反应的效率和选择性,且使得产品只溶于有机相中,易于与反应体系分离;本发明的油水两相体系使得反应变得比较温和,避免了高温引起的副反应和对设备的苛刻要求。
2.本发明使用甲苯、苯、环己烷、正辛烷等作为反应的有机相溶剂,使得溶剂与产品分离,以及溶剂回收变得非常容易,大大简化了操作,节省了制造成本。
3.本发明采用两相醚化反应,选择性大大提高,使得结晶采用单一溶剂即能获得高品质的产品,从而使得溶剂回收更加方便,大大降低了溶剂回收的成本。
4.本发明采用加晶种诱导结晶的方式,不仅提高了产品的品质,而且使得结晶时间大大减少,缩短了产品的生产周期,降低了产品的制造成本。
5.本发明具有三废少,绿色环保,操作简单,易于控制和易于实现工业化生产的特点,制备得到的防晒剂天来施S颜色浅、质量好、市场竞争力强,易于工业化推广。
具体实施方式
除非另有说明,以下本发明中使用的原料和试剂均为市售商品,或者可以通过已知方法制备。
其中,4,6-二(2',4'-二羟基苯基)-2-(4'-甲氧基苯基)-1,3,5-三嗪(RET)的制备:参考CN112321520A,一锅法合成双-乙基己氧苯酚甲氧苯基三嗪的工艺制备方法。
实施例1
将84.74g RET(QLC 95.2%,0.2mol)加入到反应釜中,加入28.0g氢氧化钠水溶液(氢氧化钠含量0.21mol)和540g水,升温至釜温80-85℃,搅拌至RET完全溶解;然后加入300g甲苯和1.3g四丁基溴化铵(0.0040mol),升温至回流,开始滴加104.07g氯代异辛烷(0.7mol),5h滴加完毕,滴加结束,继续保温反应,保温反应0.5h后开始取样;反应至天来施S之HPLC纯度达最大(92~95%)时停止反应,降温至40-45℃,静置分液,油相常压蒸馏回收甲苯,馏底加入500g仲丁醇,升温至60℃全溶,自然降温至50℃加入天来施S晶种,自然降温至40℃育晶1h,冷至6℃保温1h,过滤,滤饼烘干,得成品天来施S110.4g,HPLC纯度99.54%,收率88.0%。
实施例2
将84.74g RET(QLC 95.2%,0.2mol)加入到反应釜中,加入21.21g三乙胺(0.21mol)和540g水,升温至釜温80-85℃,搅拌至RET完全溶解;然后加入300g苯和0.9g苄基三乙基氯化铵(0.0040mol),升温至回流,开始滴加104.07g氯代异辛烷(0.7mol),5h滴加完毕,滴加结束,继续保温反应,保温反应0.5h后开始取样;反应至天来施S之HPLC纯度达最大(92~95%)时停止反应,降温至40-45℃,静置分液,油相常压蒸馏回收苯,馏底加入500g仲丁醇,升温至60℃全溶,自然降温至50℃加入天来施S晶种,自然降温至40℃育晶1h,冷至6℃保温1h,过滤,滤饼烘干,得成品天来施S113.2g,HPLC纯度99.62%,收率90.3%。
实施例3
将84.74g RET(QLC 95.2%,0.2mol)加入到反应釜中,加入28.0g氢氧化钾水溶液(氢氧化钾含量0.21mol)和540g水,升温至釜温80-85℃,搅拌至RET完全溶解;然后加入300g环己烷和1.2g四乙基对甲苯磺酸铵(0.0040mol),升温至回流,开始滴加104.07g氯代异辛烷(0.7mol),5h滴加完毕,滴加结束,继续保温反应,保温反应0.5h后开始取样;反应至天来施S之HPLC纯度达最大(92~95%)时停止反应,降温至40-45℃,静置分液,油相常压蒸馏回收环己烷,馏底加入500g仲丁醇,升温至60℃全溶,自然降温至50℃加入天来施S晶种,自然降温至40℃育晶1h,冷至6℃保温1h,过滤,滤饼烘干,得成品天来施S122.7g,HPLC纯度99.85%,收率97.8%。
实施例4
将84.74g RET(QLC 95.2%,0.2mol)加入到反应釜中,加入28.0g氢氧化钾水溶液(氢氧化钾含量0.21mol)和540g水,升温至釜温80-85℃,搅拌至RET完全溶解;然后加入300g正辛烷和1.17g十四烷基三甲基氯化铵(0.0040mol),升温至回流,开始滴加104.07g氯代异辛烷(0.7mol),5h滴加完毕,滴加结束,继续保温反应,保温反应0.5h后开始取样;反应至天来施S之HPLC纯度达最大(92~95%)时停止反应,降温至40-45℃,静置分液,油相常压蒸馏回收正辛烷,馏底加入500g仲丁醇,升温至60℃全溶,自然降温至50℃加入天来施S晶种,自然降温至40℃育晶1h,冷至6℃保温1h,过滤,滤饼烘干,得成品天来施S113.9g,HPLC纯度99.34%,收率90.8%。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (7)
1.一种防晒剂天来施S的制备方法,其特征在于,以RET、卤代异辛烷为反应原料,使用油水两相体系,在相转移催化剂的作用下进行缩合醚化反应得到。
2.根据权利要求1所述的一种防晒剂天来施S的制备方法,其特征在于,所述油水两相体系中油相溶剂选自甲苯、苯、环己烷、正辛烷中的任意一种。
3.根据权利要求1所述的一种防晒剂天来施S的制备方法,其特征在于,所述相转移催化剂选自四丁基溴化铵、苄基三乙基氯化铵、四乙基对甲苯磺酸铵、十四烷基三甲基氯化铵中的任意一种。
4.根据权利要求1所述的一种防晒剂天来施S的制备方法,其特征在于,所述缩合醚化反应时,还加入了缚酸剂。
5.根据权利要求1所述的一种防晒剂天来施S的制备方法,其特征在于,所述缚酸剂选自氢氧化钠、氢氧化钾、三乙胺中的任意一种或几种。
6.根据权利要求1所述的一种防晒剂天来施S的制备方法,其特征在于,所述卤代异辛烷为氯代异辛烷、溴代异辛烷中的任意一种。
7.根据权利要求1所述的一种防晒剂天来施S的制备方法,其特征在于,所述RET、卤代异辛烷的摩尔比为1:(3-4)。
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