CN113603668A - 2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯、水性聚氨酯及制备方法 - Google Patents

2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯、水性聚氨酯及制备方法 Download PDF

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CN113603668A
CN113603668A CN202111009687.1A CN202111009687A CN113603668A CN 113603668 A CN113603668 A CN 113603668A CN 202111009687 A CN202111009687 A CN 202111009687A CN 113603668 A CN113603668 A CN 113603668A
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parts
waterborne polyurethane
difluoroacetate
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王胜鹏
陈八斤
徐伟明
宋金星
章鹏飞
王小君
于本成
黄又举
杨小波
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Hangzhou Transfar Fine Chemicals Co Ltd
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Abstract

本发明提供了一种2‑溴‑2,2‑二氟乙酸丙酮叉保护甘油单酯、水性聚氨酯及它们的制备方法，涉及印染助剂技术领域。本发明提供的2‑溴‑2,2‑二氟乙酸丙酮叉保护甘油单酯可以作为改性单体用于制备水性聚氨酯，所述2‑溴‑2,2‑二氟乙酸丙酮叉保护甘油单酯C2位的取代基为两个氟原子和一个溴原子，用于水性聚氨酯制备时，在水性聚氨酯结构中引入氟和溴基团，得到的水性聚氨酯具有良好的防潮性能和阻燃性。

Description

2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯、水性聚氨酯及制备 方法
技术领域
本发明涉及印染助剂技术领域，尤其涉及一种2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯、水性聚氨酯及制备方法。
背景技术
印染助剂能赋予织物风格各异的功能，在纺织领域有着不可替代的作用。水性聚氨酯(PU)以水为介质，安全不燃烧，无公害，其保留了传统溶剂型聚氨酯的优良性能，如能赋予织物优良的柔软度、丰满感、会弹性好、爽滑、手感好、抗静电等，因此是一类理想的印染助剂。但现有的水性聚氨酯普遍存在着易吸水回潮，阻燃性差等缺陷。
如中国专利CN101545207A公开了一种纯棉针织物抗其毛起球整理剂及其制备方法，在容器中加入三聚氰胺、异佛尔加热、搅拌，滴加用异丙醇溶解异佛尔二异氰酸酯的混合溶液，再加入催化剂加热混合均匀，冷却后加入异丙醇、封端剂、促进剂及水充分反应后升温至常温，继续搅拌制得水性聚氨酯，直接作为抗起毛起球剂，具有不易使纺织品泛黄、环境友好等优点；但制备的水性聚氨酯仍存在易吸水回潮、阻燃性差的问题。
发明内容
本发明的目的在于提供一种2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯、水性聚氨酯及制备方法，将本发明的2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯作为改性单体用于水性聚氨酯的制备，得到的水性聚氨酯具有良好的防潮性能和阻燃性。
为了实现上述发明目的，本发明提供以下技术方案：
本发明提供了2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯，具有式I所示结构：
Figure BDA0003238428550000011
本发明提供了上述方案所述2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯的制备方法，包括以下步骤：将2-溴-2,2-二氟乙酸酯、丙酮缩甘油和碱性催化剂混合，进行酯交换反应，得到具有式I所示结构的2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯；
所述2-溴-2,2-二氟乙酸酯和丙酮缩甘油的摩尔比为1:1～5。
优选的，所述碱性催化剂包括氢氧化物、碳酸盐、碳酸氢盐、氢化钠和醇钠中的一种或多种。
优选的，所述2-溴-2,2-二氟乙酸酯为2-溴-2,2-二氟乙酸甲酯或2-溴-2,2-二氟乙酸乙酯。
优选的，所述2-溴-2,2-二氟乙酸酯与碱性催化剂的质量比为1:0.01～0.2。
优选的，所述酯交换反应的温度为80～140℃。
优选的，所述酯交换反应的时间为5～25h。
本发明提供了上述方案所述2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯或上述方案所述制备方法制备得到的2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯在制备水性聚氨酯中的应用。
本发明提供了一种水性聚氨酯，以质量份数计，制备原料包括以下组分：
15～40份多异氰酸酯单体、45～65份聚合物多元醇、5～25份含氟改性单体、固体路易斯酸催化剂、0.5～8份小分子扩链剂、3～10份离子型亲水扩链剂、＞0且≤12份的电性中和剂和水；所述含氟改性单体与固体路易斯酸的质量比为1:0.005～0.05；所述含氟改性单体为上述方案所述的2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯。
本发明提供了上述方案所述水性聚氨酯的制备方法，包括以下步骤：
(1)将部分多异氰酸酯、含氟改性单体和固体路易斯酸催化剂混合，进行第一亲核加成反应，得到NCO封端的氟化预聚物；
(2)将聚合物多元醇和剩余的多异氰酸酯混合，进行第二亲核加成反应，向所得反应产物中加入所述NCO封端的氟化预聚物、小分子扩链剂和离子型亲水扩链剂进行扩链反应，向得到的扩链反应产物中加入催化剂，进行第三亲核加成反应，得到氟化改性聚氨酯预聚体；
(3)向所述氟化改性聚氨酯预聚体中加入电性中和剂进行中和反应，然后加入水进行乳化分散，得到水性聚氨酯。
本发明提供了一种2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯，具有式I所示结构：
Figure BDA0003238428550000031
本发明提供的2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯中，C2位的取代基为两个氟原子和一个溴原子，使得其作为改性单体具有一定疏水性的同时，可进一步提高改性单体防潮阻燃性能。在用于水性聚氨酯的制备时，在水性聚氨酯结构中引入氟和溴基团，得到的水性聚氨酯因含有氟原子和溴原子而具有良好的防潮性能和阻燃性能。
附图说明
图1为实施例1制备得到的2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯的核磁氢谱；
图2为实施例1制备得到的2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯的核磁氟谱。
具体实施方式
本发明提供了一种2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯，具有式I所示结构：
Figure BDA0003238428550000032
本发明提供了上述方案所述2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯的制备方法，包括以下步骤：将2-溴-2,2-二氟乙酸酯、丙酮缩甘油和碱性催化剂混合进行酯交换反应，得到具有式I所述结构的2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯；
所述2-溴-2,2-二氟乙酸酯和丙酮缩甘油的摩尔比为1:1～5。
在本发明中，未经特殊说明，所用原料均为本领域熟知的市售商品。
在本发明中，所述2-溴-2,2-二氟乙酸酯优选为2-溴-2,2-二氟乙酸甲酯或2-溴-2,2-二氟乙酸乙酯。所述碱性催化剂优选包括氢氧化物、碳酸盐、碳酸氢盐、氢化钠和醇钠中的一种或多种，更优选包括碱金属氢氧化物、碱金属碳酸盐、碱金属碳酸氢盐、氢化钠、甲醇钠和乙醇钠中的一种或多种。在本发明中，所述碱金属氢氧化物优选为氢氧化钠和/或氢氧化钾；所述碱金属碳酸盐优选为碳酸钠和/或碳酸钾；所述碱金属碳酸氢盐优选为碳酸氢钠和/或碳酸氢钾。当所述碱性催化剂包括上述物质中的多种时，各碱性催化剂的质量优选相等。
在本发明中，所述2-溴-2,2-二氟乙酸酯和丙酮缩甘油的摩尔比为1:1～5，优选为1:2～4，进一步优选为1:2.5～3.5。在本发明中，当所述丙酮缩甘油的摩尔用量大于2-溴-2,2-二氟乙酸酯时，所述丙酮缩甘油还可以起到溶剂的作用，有利于酯交换反应的充分进行。
在本发明中，所述2-溴-2,2-二氟乙酸酯与碱性催化剂的质量比优选为1:0.01～0.2，更优选为1:0.05～0.15，进一步优选为1:0.08～0.12。
本发明对2-溴-2,2-二氟乙酸酯、丙酮缩甘油和碱性催化剂混合的过程没有特殊要求，采用本领域熟知的混合过程，能够将各原料混匀即可。
在本发明中，所述酯交换反应的温度优选为80～140℃，更优选为90～130℃，进一步优选为100～120℃；所述酯交换反应的时间优选为5～25h，更优选为10～20h，进一步优选为13～16h。在本发明中，所述酯交换反应优选在搅拌条件下进行，本发明对所述搅拌的速率没有特殊要求，采用本领域熟知的搅拌速率即可。
在本发明的实施例中，所述酯交换反应的方程式如式(1)所示：
Figure BDA0003238428550000041
完成所述酯交换反应后，本发明优选对得到的酯交换反应产物进行减压蒸馏，收集104～106℃/25mmHg条件下的馏分，得到具有式I所示结构的2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯。
本发明提供的制备方法操作简单、过程环保、产物收率高。
本发明提供了上述方案所述2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯或上述方案所述制备方法制备得到的2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯在制备水性聚氨酯中的应用。所述2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯优选作为制备水性聚氨酯的改性单体使用。2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯C2位的取代基为两个氟原子和一个溴原子，使得改性助剂单体具有一定疏水性的同时，可进一步提高改性助剂单体防潮阻燃性能。在用于水性聚氨酯的制备时，在水性聚氨酯结构中引入氟和溴基团，得到的水性聚氨酯因含有氟原子和溴原子而具有良好的防潮性能和阻燃性能。
本发明提供了一种水性聚氨酯，以质量份数计，制备原料优选包括以下组分：15～40份多异氰酸酯单体、45～65份聚合物多元醇、5～25份含氟改性单体、固体路易斯酸催化剂、0.5～8份小分子扩链剂、3～10份离子型亲水扩链剂、＞0且≤12份的电性中和剂和水；所述含氟改性单体与固体路易斯酸的质量比为1:0.005～0.05；所述含氟改性单体为上述方案所述的2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯。
以质量份数计，本发明提供的水性聚氨酯的制备原料包括15～40份多异氰酸酯单体，优选为20～35份，更优选为25～30份。在本发明中，所述多异氰酸酯单体优选为脂肪族、脂环族、芳香族或芳脂族的多异氰酸酯；所述多异氰酸酯单体的官能度≥2。本发明对所述脂肪族、脂环族、芳香族或芳脂族的多异氰酸酯的具体种类没有特殊要求，采用本领域熟知的脂肪族、脂环族、芳香族或芳脂族的多异氰酸酯即可。在本发明中，所述多异氰酸酯具体的可以为六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯或二环己基甲烷二异氰酸酯。
以所述多异氰酸酯单体的质量份数为基准，本发明提供的水性聚氨酯的制备原料包括45～65份聚合物多元醇，优选为48～62份，更优选为51～58份。在本发明中，所述聚合物多元醇的摩尔质量优选为500～4000g/mol，更优选为1000～3000g/mol；所述聚合物多元醇的官能度优选≥2。本发明对所述聚合物多元醇的具体种类没有特殊要求，具体的可以为聚己二酸己二醇酯二醇、聚己二酸丁二醇酯二醇、聚己二酸乙二醇酯二醇、聚己二酸新戊二醇酯二醇、聚己二酸一缩二乙二醇酯二醇、聚己内酯二醇、聚碳酸己二醇酯二醇、聚乙二醇、聚丙二醇或聚四氢呋喃醚二醇。
以所述多异氰酸酯单体的质量份数为基准，本发明提供的水性聚氨酯的制备原料包括5～25份含氟改性单体，优选为8～22份，更优选为10～18份。在本发明中，所述含氟改性单体为上述方案所述的2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯。
本发明提供的水性聚氨酯的制备原料包括固体路易斯酸催化剂，所述含氟改性单体与固体路易斯酸催化剂的质量比优选为1:0.005～0.05，更优选为1:0.01～0.04，进一步优选为1:0.02～0.03。在本发明中，所述固体路易斯酸催化剂优选为四氯化锆、三氯化铝或二氯化锌。
以所述多异氰酸酯单体的质量份数为基准，本发明提供的水性聚氨酯的制备原料包括0.5～8份小分子扩链剂，优选为1～7份，更优选为3～5份。在本发明中，所述小分子扩链剂优选为多羟基化合物小分子扩链剂，其摩尔质量小于400g/mol，官能度优选为2到4。在本发明中，所述小分子扩链剂具体的可以为乙二醇、1,4-丁二醇、新戊二醇、一缩二乙二醇、3-甲基戊二醇、丙二醇、2-甲基丙二醇、1,6-己二醇或三羟甲基丙烷。
以所述多异氰酸酯单体的质量份数为基准，本发明提供的水性聚氨酯的制备原料包括3～10份离子型亲水扩链剂，优选为4～8份，更优选为5～6份。在本发明中，所述离子型亲水扩链剂优选为具有羟基或胺基的离子型或潜在离子型亲水扩链剂，官能度优选为2到4。在本发明对所述离子型亲水扩链剂的具体种类没有特殊要求，本领域熟知的符合上述条件的离子型亲水扩链剂均可，具体的可以为N-甲基二乙醇胺、二羟甲基丙酸、二羟甲基丁酸、乙二胺基乙基磺酸钠、1,4-二羟基丁烷-2-磺酸钠或α,ω-聚丙二醇-二胺-磺丙基钠盐。
以所述多异氰酸酯单体的质量份数为基准，本发明提供的水性聚氨酯的制备原料包括＞0且≤12份的电性中和剂，优选为2～10份，更优选为4～8份。本发明对所述电性中和剂的具体种类没有特殊要求，采用本领域熟知的电性中和剂即可，具体的可以为硫酸二甲醚、冰醋酸、三乙胺、三乙醇胺、二甲基乙醇胺、二异丙基乙基胺或氢氧化钠。
本发明提供的水性聚氨酯的制备原料包括水。本发明对所述水的用量没有特殊要求，优选根据水性聚氨酯的固含量确定。在本发明中，所述水性聚氨酯的固含量优选为30～40％。
在本发明中，所述水性聚氨酯的制备方法优选包括以下步骤：
(1)将部分多异氰酸酯、含氟改性单体和固体路易斯酸催化剂混合，进行第一亲核加成反应，得到NCO封端的氟化预聚物；
(2)将聚合物多元醇和剩余的多异氰酸酯混合，进行第二亲核加成反应，向所得反应产物中加入所述NCO封端的氟化预聚物、小分子扩链剂和离子型亲水扩链剂进行扩链反应，向得到的扩链反应产物中加入催化剂，进行第三亲核加成反应，得到氟化改性聚氨酯预聚体；
(3)向所述氟化改性聚氨酯预聚体中加入电性中和剂进行中和反应，然后加入水进行乳化分散，得到水性聚氨酯。
本发明将部分多异氰酸酯、与含氟改性单体和固体路易斯酸催化剂混合，进行第一亲核加成反应，得到NCO基团封端的氟化预聚物。
在本发明中，所述部分多异氰酸酯优选为异氰酸酯总质量的20％～65％，更优选为30～55％，进一步优选为40～50％。在本发明中，所述第一亲核加成反应的温度优选为50～70℃，更优选为55～65℃；所述第一亲核加成反应的时间优选为1～2h；所述第一亲核加成反应优选在氮气保护下进行。本发明在所述第一亲核加成反应过程中，含氟改性单体在固体路易斯酸催化剂的作用下脱保护，多异氰酸酯的-NCO基团与含氟改性单体(即2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯)脱保护后的-OH基团发生亲核加成反应，得到NCO封端的氟化预聚物。
得到NCO封端的氟化预聚物后，本发明将聚合物多元醇和剩余的多异氰酸酯混合，进行第二亲核加成反应，向所得第二亲核加成反应产物中加入所述NCO封端的氟化预聚物、小分子扩链剂和离子型亲水扩链剂进行扩链反应，向扩链反应产物中加入催化剂，进行第三亲核加成反应，得到氟化改性聚氨酯预聚体。
进行第二亲核加成反应前，本发明优选先将聚合物多元醇进行真空脱水；所述真空脱水的温度优选为105～120℃，更优选为110～115℃；所述真空脱水的时间优选为1～2h。在本发明中，将聚合物多元醇和剩余的多异氰酸酯混合的温度优选为55～75℃。在本发明中，所述第二亲核加成反应的温度优选为60～90℃，更优选为70～80℃；所述第二亲核加成反应的保温时间优选为1～2h。本发明在所述第二亲核加成反应过程中，多异氰酸酯的-NCO基团与聚合物多元醇的-OH基团发生亲核加成反应，得到NCO封端的聚氨酯预聚物。
完成第二亲核加成反应后，本发明向所得反应产物中加入NCO封端的氟化预聚物、小分子扩链剂和离子型亲水扩链剂进行扩链反应，向得到的扩链反应产物中加入催化剂，进行第三亲核加成反应，得到氟化改性聚氨酯预聚体。
在本发明中，所述扩链反应的温度优选为60～90℃，更优选为70～80℃；所述扩链反应的时间优选为1～1.5h。
本发明对所述催化剂的种类没有特殊要求，采用本领域熟知的用于水性聚氨酯制备的催化剂即可。在本发明的实施例中，所述催化剂为有机铋催化剂。在本发明中，所述催化剂的用量优选为扩链反应产物质量的0.05～0.1％，更优选为0.07～0.08％。
在本发明中，所述第三亲核加成反应的温度优选为60～75℃，更优选为70～75℃；所述第三亲核加成反应的时间优选为2～3h。本发明在所述第三亲核加成反应过程中，继续进行-NCO基团与-OH基团的亲核加成反应，形成得到NCO封端的氟化改性聚氨酯预聚体。
本发明在所述扩链反应前和第三亲核加成反应前，优选根据具体实验情况加入丙酮溶剂来降低反应体系粘度，溶剂用量为当前反应物质量的5～30％，此为本领域公知常识。
完成第三亲核加成反应后，本发明向所述氟化改性聚氨酯预聚体中加入电性中和剂进行中和反应，然后加入水进行乳化分散，得到水性聚氨酯。
在本发明中，所述中和反应的温度优选为30～40℃，更优选为33～38℃；所述中和反应的时间优选为5～20min。在本发明中，所述水优选为去离子水，所述水的用量优选为保证最终水性聚氨酯乳液(脱除丙酮溶剂后)固含量为30～40％。在本发明中，所述乳化分散优选在高速搅拌条件下进行，搅拌速率优选为800～2000rpm。
完成所述乳化分散后，所得乳化液即为水性聚氨酯，或者本领域技术人员可以根据需求向所得乳化液中加入二元胺扩链剂进行后扩链反应，得到水性聚氨酯乳液。
本发明对所述二元胺扩链剂的具体种类没有特殊要求，采用本领域熟知的二元胺扩链剂即可。在本发明中，所述二元胺扩链剂的摩尔用量为剩余NCO摩尔量的60％以下。在本发明中，所述后扩链反应的时间优选为5～10min。
下面结合实施例对本发明提供的2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯、水性聚氨酯及制备方法进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。
实施例1
在装有温度计、回流冷凝管、分水器和搅拌器的1L反应容器中加入203克2-溴-2,2-二氟乙酸乙酯、260克丙酮缩甘油、3.2克甲醇钠，在115℃下反应12小时，将所得反应产物进行减压蒸馏收集104～106℃/25mmHg条件下的馏分，得到具有式I所示结构的2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯285.5克，收率98.8％，纯度为99.5％。
Figure BDA0003238428550000091
对实施例1制备得到的2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯进行核磁分析，结果如图1～图2所示，其中图1为核磁氢谱，图2为核磁氟谱。由图1～图2可知，本发明实施例1制备得到的2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯与预期结构相符。
核磁表征数据：
1H NMR(500MHz,CDCl3)δ4.43-4.30(m,3H),4.12(ddd,J＝10.3,4.4,1.7Hz,1H),3.87-3.81(m,1H),1.44(s,3H),1.38(s,3H).
19F NMR(471MHz,CDCl3)δ-60.81.
实施例2
在装有温度计、回流冷凝管、分水器和搅拌器的1L反应容器中加入189克2-溴-2,2-二氟乙酸甲酯、260克丙酮缩甘油、1.89克氢氧化钾，在125℃下反应8小时，然后将所得反应产物进行减压蒸馏收集104～106℃/25mmHg条件下的馏分，得到2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯283.3克，收率98.0％，纯度为99.5％。
实施例3
在装有温度计、回流冷凝管、分水器和搅拌器的1L反应容器中加入189克2-溴-2,2-二氟乙酸甲酯、660克丙酮缩甘油、3.2克碳酸氢钾、3.2克碳酸钾，在80℃下反应25小时，将所得反应产物进行减压蒸馏收集104～106℃/25mmHg条件下的馏分，得到2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯282.1克，收率97.6％，纯度为99.4％。
实施例4
在装有温度计、回流冷凝管、分水器和搅拌器的1L反应容器中加入203克2-溴-2,2-二氟乙酸乙酯、350克丙酮缩甘油、3.2克氢氧化钠、3.2克碳酸钠、3.2克碳酸氢钠，在140℃下反应5小时，将所得反应产物进行减压蒸馏收集104～106℃/25mmHg条件下的馏分，得到2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯280.1克，收率96.9％，纯度为99.3％。
实施例5
在装有温度计、回流冷凝管、分水器和搅拌器的1L反应容器中加入189克2-溴-2,2-二氟乙酸甲酯、350克丙酮缩甘油、5.2克氢化钠，在110℃下反应10小时，将所得反应产物进行减压蒸馏收集104～106℃/25mmHg条件下的馏分，得到2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯284.1克，收率98.3％，纯度为99.6％。
对实施例2～5制备得到的2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯进行核磁分析，结果显示本发明实施例2～5制备得到的2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯与预期结构相符。
应用例1
a)加入15g甲苯二异氰酸酯、0.05g四氯化锆和10g 2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯，通入氮气保护，在50℃下搅拌反应1h，得到异氰酸酯NCO基团封端的氟化预聚物；
b)将58g聚丙二醇(Mn＝2000)升温在105℃下真空脱水1h，降温到55℃后，加入11g甲苯二异氰酸酯，在80℃下保温反应1h；再加入上述a)得到的NCO封端的氟化预聚物；然后向体系中加入3g新戊二醇、5g二羟甲基丙酸、10g丙酮，在80℃下扩链反应1h；再向体系中加入0.08g有机铋催化剂、8g丙酮，在75℃下反应2h；降温到30℃，加入3.5g三乙胺反应5min；在2000rpm的高速搅拌下加入234g去离子水乳化分散，减压脱去丙酮，得到含固量为30％的水性聚氨酯。
对比应用例1
与应用例1的不同之处在于对比应用例1未使用2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯。具体的制备过程如下：
58g将聚丙二醇(Mn＝2000，)升温在105℃下真空脱水1h，降温到55℃后，26g加入甲苯二异氰酸酯，在80℃下保温反应1h；然后向体系中加入5g新戊二醇、5g二羟甲基丙酸、10g丙酮，在80℃下反应1h；再向体系中加入0.08g有机铋催化剂、8g丙酮，在75℃下反应2h；降温到30℃，加入3.5g三乙胺反应5min；在2000rpm的高速搅拌下加入234g去离子水乳化分散，减压脱去丙酮，得到含固量为30％的水性聚氨酯。
性能测试：
(1)吸水率测试
a)聚氨酯胶膜制备
先将水性聚氨酯倒入聚四氟乙烯板成膜器中，保证没有气泡，先室温干燥48h，再于60℃干燥48h，最后在80℃干燥24h，即得到水性聚氨酯胶膜。
b)吸水率测试
将水性聚氨酯胶膜裁制成大小为2cm×2cm试样，称重，记作初始质量m0；然后将样品完全浸入去离子水中浸泡24h，之后将样品取出，用滤纸擦除浸泡试样表面水分，然后称重，记作吸水后质量m1；聚氨酯胶膜试样吸水率W由式(2)计算得到，测试三个试样取平均值。
Figure BDA0003238428550000111
(2)阻燃性能测试
采用国家标准《GB/T 5455-2014纺织品燃烧性能垂直方向损毁长度、阻燃和续燃时间的测定》测定聚氨酯胶膜的氧指数。
对应用例1和对比应用例1制备的水性聚氨酯进行耐水性能和阻燃性能测试，测试结果见表1。
表1 应用例1和对比应用例1制备的水性聚氨酯的性能
吸水率/％ 氧指数
应用例1 10％ 25％
对比应用例1 25％ 17％
表1中，吸水率越低，说明耐水性、防水性能越好；氧指数越高，阻燃性能越好。由表1的结果可知，氟化改性聚氨酯的耐水性和阻燃性能明显优于未进行氟化改性样品，说明本发明将C2取代基设计为两个氟原子和一个溴原子，使得改性助剂单体具有一定疏水性的同时，可进一步提高改性助剂单体防潮阻燃性能，用于水性聚氨酯的制备，得到的水性聚氨酯具有良好的防潮性能和阻燃性。
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 (10)

1.2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯，具有式I所示结构：
Figure FDA0003238428540000011
2.权利要求1所述2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯的制备方法，包括以下步骤：将2-溴-2,2-二氟乙酸酯、丙酮缩甘油和碱性催化剂混合，进行酯交换反应，得到具有式I所示结构的2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯；
所述2-溴-2,2-二氟乙酸酯和丙酮缩甘油的摩尔比为1:1～5。
3.根据权利要求2所述的制备方法，其特征在于，所述碱性催化剂包括氢氧化物、碳酸盐、碳酸氢盐、氢化钠和醇钠中的一种或多种。
4.根据权利要求2所述的制备方法，其特征在于，所述2-溴-2,2-二氟乙酸酯为2-溴-2,2-二氟乙酸甲酯或2-溴-2,2-二氟乙酸乙酯。
5.根据权利要求2或3所述的制备方法，其特征在于，所述2-溴-2,2-二氟乙酸酯与碱性催化剂的质量比为1:0.01～0.2。
6.根据权利要求2所述的制备方法，其特征在于，所述酯交换反应的温度为80～140℃。
7.根据权利要求6所述的制备方法，其特征在于，所述酯交换反应的时间为5～25h。
8.权利要求1所述2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯或权利要求2～8任一项所述制备方法制备得到的2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯在制备水性聚氨酯中的应用。
9.一种水性聚氨酯，其特征在于，以质量份数计，制备原料包括以下组分：
15～40份多异氰酸酯单体、45～65份聚合物多元醇、5～25份含氟改性单体、固体路易斯酸催化剂、0.5～8份小分子扩链剂、3～10份离子型亲水扩链剂、＞0且≤12份的电性中和剂和水；所述含氟改性单体与固体路易斯酸催化剂的质量比为1:0.005～0.05；所述含氟改性单体为权利要求1所述的2-溴-2,2-二氟乙酸丙酮叉保护甘油单酯。
10.权利要求9所述水性聚氨酯的制备方法，包括以下步骤：
(1)将部分多异氰酸酯、含氟改性单体和固体路易斯酸催化剂混合，进行第一亲核加成反应，得到NCO封端的氟化预聚物；
(2)将聚合物多元醇和剩余的多异氰酸酯混合，进行第二亲核加成反应，向所得反应产物中加入所述NCO封端的氟化预聚物、小分子扩链剂和离子型亲水扩链剂进行扩链反应，向得到的扩链反应产物中加入催化剂，进行第三亲核加成反应，得到氟化改性聚氨酯预聚体；
(3)向所述氟化改性聚氨酯预聚体中加入电性中和剂进行中和反应，然后加入水进行乳化分散，得到水性聚氨酯。
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US20130344438A1 (en) * 2012-06-26 2013-12-26 Rohm And Haas Electronic Materials Llc Photoacid generator, photoresist, coated substrate, and method of forming an electronic device
CN112608236A (zh) * 2020-07-28 2021-04-06 杭州传化精细化工有限公司 一种2-卤代-2,2-二氟乙酸炔酯的制备方法

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US20130344438A1 (en) * 2012-06-26 2013-12-26 Rohm And Haas Electronic Materials Llc Photoacid generator, photoresist, coated substrate, and method of forming an electronic device
CN112608236A (zh) * 2020-07-28 2021-04-06 杭州传化精细化工有限公司 一种2-卤代-2,2-二氟乙酸炔酯的制备方法

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