CN112480095B - 一种双(2,3-环硫丙基)硫醚的制备方法 - Google Patents
一种双(2,3-环硫丙基)硫醚的制备方法 Download PDFInfo
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Abstract
本发明提供了一种双(2,3‑环硫丙基)硫醚的制备方法，包括以下步骤：将环氧氯丙烷、四氢呋喃和硫氢化钠混合，反应，后处理，得到双(2,3‑环氧丙基)硫醚；将所述双(2,3‑环氧丙基)硫醚、硫氰酸钾、甲苯、助剂和去离子水，搅拌混合，反应，得到双(2,3‑环硫丙基)硫醚。该方法简单，且制备的产物产率和纯度较高。该方法制备的双(2,3‑环硫丙基)硫醚制成的树脂镜片具有较高的折射率，还能通过落球实验。
Description
技术领域
本发明属于化合物制备技术领域，尤其涉及一种双(2,3-环硫丙基)硫醚的制备方法。
背景技术
光学树脂材料因其具有质量轻、易染色及不易破碎等优点，被广泛应用于眼镜镜片、光盘基材、光学透镜以及仪器棱镜等领域；近年来，玻璃眼镜片由于重量较重、易破碎及不易加工成型等缺点，严重影响了使用的眼镜佩戴的舒适性和安全性，已经逐步被光学树脂镜片取代。并且光学树脂镜片以其高透光率、轻薄的材料及不易破碎等优点广受消费者喜爱；目前国内市场上，以镜片折射率的高低来评价光学树脂材料的优劣，折射率越高，镜片的越轻越薄。
目前国内市场上大部分的折射率在1.60以下，多以1.56～1.60之间，少见1.67，为了提高折射率，需要引入硫元素是最有效的途径，同时有着色散小、环境稳定性良好等优点。硫元素在聚合物中通常以硫醚、硫酯、砜基等形式存在。但上述形式的硫元素制备的聚合物生产的树脂镜片的折射率仍较低。
发明内容
有鉴于此，本发明的目的在于提供一种双(2,3-环硫丙基)硫醚的制备方法，该方法简单，且产物产率和纯度较高。
本发明提供了一种双(2,3-环硫丙基)硫醚的制备方法，包括以下步骤：
将环氧氯丙烷、四氢呋喃和硫氢化钠混合，反应，后处理，得到双(2,3-环氧丙基)硫醚；
将所述双(2,3-环氧丙基)硫醚、硫氰酸钾、甲苯、助剂和去离子水，搅拌混合，反应，得到双(2,3-环硫丙基)硫醚。
优选地，所述硫化钠、环氧氯丙烷与四氢呋喃的质量比为1:2.5～5:10～20。
优选地，所述环氧氯丙烷、四氢呋喃和硫氢化钠反应的温度为0～10℃，时间为8～24h。
优选地，所述后处理包括：
将环氧氯丙烷、四氢呋喃和硫氢化钠反应产物升温至20～60℃，保温4～8h，然后加入水，分去水相，蒸去溶剂，加入甲苯，萃取水相，甲苯相合并后用去离子水洗涤至中性，硫酸镁干燥，蒸除溶剂后，得到双(2,3-环氧丙基)硫醚。
优选地，所述双(2,3-环氧丙基)硫醚与硫氰酸钾的质量比为1:1.3～1.6。
优选地，所述双(2,3-环氧丙基)硫醚和硫氰酸钾反应的温度为0～30℃，时间为10～30h。
优选地，所述助剂选自碳酸钾；
所述双(2,3-环氧丙基)硫醚与助剂的质量比为1：0.005～0.01。
本发明提供了一种双(2,3-环硫丙基)硫醚的制备方法，包括以下步骤：将环氧氯丙烷、四氢呋喃和硫氢化钠混合，反应，后处理，得到双(2,3-环氧丙基)硫醚；将所述双(2,3-环氧丙基)硫醚、硫氰酸钾、甲苯、助剂和去离子水，搅拌混合，反应，得到双(2,3-环硫丙基)硫醚。该方法简单，且制备的产物产率和纯度较高。该方法制备的双(2,3-环硫丙基)硫醚制成的树脂镜片具有较高的折射率，还能通过落球实验。
附图说明
图1为本发明实施例1提供的方法制备的双(2,3-环硫丙基)硫醚气质色谱图。
具体实施方式
本发明提供了一种双(2,3-环硫丙基)硫醚的制备方法，包括以下步骤：
将环氧氯丙烷、四氢呋喃和硫氢化钠混合，反应，后处理，得到双(2,3-环氧丙基)硫醚；
将所述双(2,3-环氧丙基)硫醚、硫氰酸钾、甲苯、助剂和去离子水，搅拌混合，反应，得到双(2,3-环硫丙基)硫醚。
本发明将环氧氯丙烷、四氢呋喃和硫氢化钠混合，反应，后处理，得到双(2,3-环氧丙基)硫醚。在本发明中，所述硫化钠、环氧氯丙烷与四氢呋喃的质量比优选为1:2.5～5:10～20，更优选为1:3～5:13～15。具体实施例中，所述硫化钠、环氧氯丙烷与四氢呋喃的质量比为1:3:13；或1:5:15。
在本发明中，所述环氧氯丙烷、四氢呋喃和硫氢化钠反应的温度为0～10℃，时间为8～24h。具体实施例中，所述环氧氯丙烷、四氢呋喃和硫氢化钠反应的温度为0℃；反应的时间为12h或8h。
在本发明中，所述后处理包括：
将环氧氯丙烷、四氢呋喃和硫氢化钠反应产物升温至20～60℃，保温3～8h，然后加入水，分去水相，蒸去溶剂，加入甲苯，萃取水相，甲苯相合并后用去离子水洗涤至中性，硫酸镁干燥，蒸除溶剂后，得到双(2,3-环氧丙基)硫醚。
本发明优选将反应产物升温至30～50℃，保温3～4h。
得到双(2,3-环氧丙基)硫醚后，本发明将所述双(2,3-环氧丙基)硫醚、硫氰酸钾、甲苯、助剂和去离子水，搅拌混合，反应，得到双(2,3-环硫丙基)硫醚。
在本发明中，所述双(2,3-环氧丙基)硫醚与硫氰酸钾的质量比为1:1.3～1.6。具体实施例中，所述双(2,3-环氧丙基)硫醚与硫氰酸钾的质量比为1:1.3；或1:1.5。
所述双(2,3-环氧丙基)硫醚和硫氰酸钾反应的温度为0～30℃，时间为10～30h。具体实施例中，所述双(2,3-环氧丙基)硫醚和硫氰酸钾反应的温度为14℃；或20℃；时间为15h或20h。
所述助剂选自碳酸钾；
所述双(2,3-环氧丙基)硫醚与助剂的质量比为1：0.005～0.01。
本发明采用上述制备方法制备的产品制成一种树脂镜片，以重量份数计，包括以下组分：
双(2,3-环硫丙基)硫醚80～90份，硫醇6.5～10份，多异氰酸酯3～10份，引发剂0.001～0.005份，脱模剂0.05～0.1份，UV329 1～1.5份，调色剂1～5.5ppm；
所述调色剂优选包括蓝色剂和/或红色剂；所述蓝色剂的浓度为3ppm～3.5ppm；红色剂的浓度为1ppm～2ppm。
所述多硫醇优选选自甲二硫醇、1,2-乙二硫醇、1,1-丙二硫醇、1,2-丙二硫醇、1,3-丙二硫醇、2,2’-硫代双(乙硫醇)、1，6-二巯基己烷、2,3-二(2-巯基乙基硫代)-3-丙基-1-硫醇、季戊四醇四(3-巯基丙酸)酯、4-巯基甲基-1,8-二巯基-3,6-二硫代辛烷、2,2-二(巯基甲基)-1,3-丙基二硫醇、二(2-巯基乙基)硫化物、四(巯基甲基)甲烷、2-(2-巯基乙基硫代)丙基-1,3-二硫醇、2-(2,3-二(2-巯基乙基硫代)丙基硫代)乙烷硫醇、二(2,3-二巯基丙醇)硫化物、二(2,3-二巯基丙醇)二硫化物和1,2-二(2-巯基乙基硫代)-3-巯基丙烷中的一种或多种；更优选为2,2’-硫代双(乙硫醇)。
所述异氰酸酯优选选自4,4-二环己基甲烷二异氰酸酯、降冰片烷二异氰酸酯、、异佛尔酮二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯、亚甲基双环己基二异氰酸酯和间苯二甲基二异氰酸酯中的一种或多种；更优选为六亚甲基二异氰酸酯；
所述引发剂优选选自三丁基氧化膦；
所述紫外吸收剂优选选自UV-P、UV-O、UV-9、UV-531、UVP-327、UV-324、UV-326、UV-329、UV-329、UV-541、UV-1157、纳米二氧化钛、纳米氧化锌和纳米氧化锆中的一种或多种，更优选为UV-329；
所述脱模剂优选选自磷酸二丁酯。
本发明将硫醇、多异氰酸酯、引发剂、脱模剂和UV329混合均匀后，再加入双(2,3-环硫丙基)硫醚和调色剂混匀，5℃～10℃保温，进行真空搅拌脱泡，1～2小时后预聚物浇注于模具中。
程序升温：一固程序升温：20℃保温2～3小时，4～6小时内由20℃升至45℃，3～5小时内由45℃升至80℃，3～5小时内由80℃升至100℃，100℃保温1～3小时，1～3小时内100℃降至60℃，二固程序升温：1～5小时内由60℃升至120℃，120℃保温1～3小时，1～3小时内由120℃降至60℃，得到树脂镜片。
为了进一步说明本发明，下面结合实施例对本发明提供的一种双(2,3-环硫丙基)硫醚的制备方法进行详细地描述，但不能将它们理解为对本发明保护范围的限定。
实施例1
步骤1、将环氧氯丙烷、四氢呋喃按照一定比例混合加入反应容器中，降温至0℃下搅拌，滴加硫化钠溶液，反应12小时，其中，硫化钠、环氧氯丙烷与四氢呋喃的质量比为1:3:13；
步骤2、滴加完成后，升温至30℃下保温4小时，然后加入水，分去水相，蒸去溶剂，加入甲苯，萃取水相，甲苯相合并后用去离子水洗涤至中性，硫酸镁干燥，蒸除溶剂后，得到双(2,3-环氧丙基)硫醚。
步骤3、将步骤2得到的双(2,3-环氧丙基)硫醚中加入硫氰酸钾、甲苯、碳酸钾和去离子水，搅拌混合，20℃下搅拌20小时，过滤后切去水相，减压浓缩后得到双(2,3-环硫丙基)硫醚，其中，所加入的双(2,3-环氧丙基)硫醚与硫氰酸钾、碳酸钾、甲苯及去离子水的质量比为1g:1.3g:0.01g 0.5g:5ml。
图1为本发明实施例1制备的双(2,3-环氧丙基)硫醚的气质液相谱图；对图1分析如表1所示：
表1气质液相色谱图的分析结果
| 序号 | 时间(min) | 峰面积(％) | 备注 |
| 1 | 6.099 | 0.758 | |
| 2 | 7.836 | 0.34 | |
| 3 | 11.773 | 9.124 | |
| 4 | 11.933 | 0.494 | |
| 5 | 12.908 | 4.912 | |
| 6 | 13.099 | 0.711 | |
| 7 | 13.481 | 0.667 | |
| 8 | 13.699 | 81.495 | 产品 |
| 9 | 14.381 | 0.151 | |
| 10 | 15.090 | 0.125 |
本发明实施例1制备的双(2,3-环硫丙基)硫醚的收率为80％，纯度为81.5％。
将2,2’-硫代双(乙硫醇)7g，六亚甲基二异氰酸酯8g、引发剂0.002g、脱模剂0.051g和UV329为1.2g混合均匀后，再加入双(2,3-环硫丙基)硫醚85g和蓝色剂的浓度为3ppm，红色剂的浓度为1ppm，进一步混匀，8℃保温，进行真空搅拌脱泡1.5小时后预聚物浇注于模具中。
一固程序升温：20℃保温2小时，4小时内由20℃升至45℃，5小时内45℃升至80℃，3小时内由80℃升至100℃，100℃保温2小时，2小时内由100℃降至60℃，二固程序升温：1小时内由60℃升至120℃，120℃保温2小时，2小时内由120℃降至60℃，得到树脂镜片。树脂镜片的性能检测如下表2所示：
表2实施例1～2制备的树脂镜片的性能测试结果
实施例2
步骤1、将环氧氯丙烷、四氢呋喃按照一定比例混合加入反应容器中，降温至0℃下搅拌，滴加硫化钠溶液，反应8小时，其中，硫化钠、环氧氯丙烷与四氢呋喃的质量比为1:5:15；
步骤2、滴加完成后，升温至50℃下保温3小时，然后加入水，分去水相，蒸去溶剂，加入甲苯，萃取水相，甲苯相合并后用去离子水洗涤至中性，硫酸镁干燥，蒸除溶剂后，得到双(2,3-环氧丙基)硫醚。
步骤3、将步骤2得到的双(2,3-环氧丙基)硫醚中加入硫氰酸钾、甲苯、碳酸钾和去离子水，搅拌混合，14℃下搅拌15小时，过滤后切去水相，减压浓缩后得到双(2,3-环硫丙基)硫醚，其中，所加入的双(2,3-环氧丙基)硫醚与硫氰酸钾、碳酸钾、甲苯及去离子水的质量比为1g:1.5g:0.02g：0.6g:7ml。
本发明实施例2制备的双(2,3-环硫丙基)硫醚的收率为79％，纯度为81.7％。
将2,2’-硫代双(乙硫醇)6.5g，六亚甲基二异氰酸酯5g、引发剂0.0015g、脱模剂0.06g和UV329为1.5g混合均匀后，再加入双(2,3-环硫丙基)硫醚88.5g和蓝色剂的浓度为3.2ppm，红色剂的浓度为1.5ppm，进一步混匀，8℃保温，进行真空搅拌脱泡1小时后预聚物浇注于模具中。
一固程序升温：20℃保温3小时，6小时内由20℃升至45℃，3小时内由45℃升至80℃，3小时内由80℃升至100℃，100℃保温3小时，1小时内由100℃降至60℃，二固程序升温：2小时内由60℃升至120℃，120℃保温2.5小时，1小时内由120℃降至60℃，得到树脂镜片。树脂镜片的性能检测结果如表2所示。
以上实施例产品用于生产树脂镜片时，树脂镜片的折光率均达到1.76，保证较高折射率的同时可通过落球实验(FDA)，球重32g，高度127cm。
由以上实施例可知，本发明提供了一种双(2,3-环硫丙基)硫醚的制备方法，包括以下步骤：将环氧氯丙烷、四氢呋喃和硫氢化钠混合，反应，后处理，得到双(2,3-环氧丙基)硫醚；将所述双(2,3-环氧丙基)硫醚、硫氰酸钾、甲苯、助剂和去离子水，搅拌混合，反应，得到双(2,3-环硫丙基)硫醚。该方法简单，且制备的产物产率和纯度较高。该方法制备的双(2,3-环硫丙基)硫醚制成的树脂镜片具有较高的折射率，还能通过落球实验。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (1)
1.一种双(2,3-环硫丙基)硫醚的制备方法，包括以下步骤：
将环氧氯丙烷、四氢呋喃和硫化钠混合，反应，后处理；所述硫化钠、环氧氯丙烷与四氢呋喃的质量比为1:2.5～5:10～20；所述环氧氯丙烷、四氢呋喃和硫化钠反应的温度为0～10℃，时间为8～24h；
所述后处理包括：
将环氧氯丙烷、四氢呋喃和硫化钠反应产物升温至20～60℃，保温4～8h，然后加入水，分去水相，蒸去溶剂，加入甲苯，萃取水相，甲苯相合并后用去离子水洗涤至中性，硫酸镁干燥，蒸除溶剂后，得到双(2,3-环氧丙基)硫醚；
将所述双(2,3-环氧丙基)硫醚、硫氰酸钾、甲苯、助剂和去离子水，搅拌混合，反应，得到双(2,3-环硫丙基)硫醚；
所述双(2,3-环氧丙基)硫醚与硫氰酸钾的质量比为1:1.3～1.6；
所述双(2,3-环氧丙基)硫醚和硫氰酸钾反应的温度为0～30℃，时间为10～30h；
所述助剂选自碳酸钾；所述双(2,3-环氧丙基)硫醚与助剂的质量比为1：0.005～0.01。
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