CN108623785A - 一种水性聚氨酯酸性高分子指示剂及其制备方法 - Google Patents
一种水性聚氨酯酸性高分子指示剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种水性聚氨酯酸性高分子指示剂及其制备方法，首先聚合物多元醇与过量异氰酸酯反应，再与指示剂刚果红(CAS:573‑58‑0)反应，将刚果红指示剂接入聚氨酯分子链上，接下来通过扩链反应引亲水基团，最后通过乳化，脱溶剂的方法，制得水性聚氨酯酸性高分子指示剂。制备的水性聚氨酯酸性高分子指示剂具有贮存稳定性好、绿色环保、抗菌、不污染待测试样等特点，且使用方便、可重复使用、应用领域广等优点。
Description
技术领域
本发明涉及酸性指示剂技术领域，尤其涉及的是一种水性聚氨酯酸性高分子 指示剂及其制备方法。
背景技术
小分子指示剂是一类结构较复杂的有机弱酸或有机弱碱，其对应的共轭碱或 共轭酸具有不同的颜色，因而在pH不同的溶液中呈现不同的颜色。小分子指示 剂对测试体系有可能产生污染，具有一定毒副作用，不具有反复使用性等缺点， 使其在很多等领域中的应用受到了限制。
高分子指示剂具无毒，绿色环保，不污染被测溶液等优点，且使用方便，可 反复使用，应用领域广等优点。
水性聚氨酯以其优异综合性能，已被广泛应用于建筑材料、皮革涂饰、织物 涂层、涂料和医疗等领域。目前，水性聚氨酯高分子指示剂已引起人们的广泛关 注。
水性聚氨酯酸性高分子指示剂具有稳定性好、耐腐蚀性、抗菌性、绿色环保、 气密性好、可塑性高、不污染被测溶液等特点。并且使用方便、可以重复使用、 卫生性好等优点。
发明内容
本发明的目的在提供一种水性聚氨酯酸性高分子指示剂的制备方法，实现对 小分子指示剂的替代，且使用方便、重复使用、经济益好、市场潜力大。本发明 是通过以下技术方案实现的；选用小分子刚果红、异氰酸酯、聚合物多元醇、小 分子扩链剂等为原料合成一种水性聚氨酯酸性高分子指示剂。首先聚合物多元醇 与过量异氰酸酯反应，再与指示剂刚果红反应，将刚果红指示剂接入聚氨酯分子 链上，接下来通过扩链反应引亲水基团，最后通过乳化，脱溶剂的方法，制得水 性聚氨酯酸性高分子指示剂。
所述的聚合物多元醇为聚丁二烯二醇、聚氧化丙烯二醇、四氢呋喃-氧化丙烯共聚二醇、聚丁二烯-丙烯腈醇、聚己二酸乙二醇酯二醇、聚碳酸1，6-己二醇酯 二醇、聚己二酸乙二醇－丙二醇酯二醇、聚己二酸一缩二乙二醇酯二醇、聚四氢 呋喃二醇、聚己二酸蓖麻油酯二醇、聚己内酯二醇及其聚己二酸-1，4-丁二醇 酯二醇中的一种或多种。
所述的异氰酸酯为甲苯二异氰酸酯(TDI)、1，6-己二异氰酸酯(HDI)、4，4- 二苯基甲烷二异氰酸酯(MDI)、异佛尔酮二异氰酸酯(IPDI)、1，5-萘二异氰酸酯 (NDI)、多亚甲基多苯基多异氰酸酯(PAPI)、甲基环己基二异氰酸酯(HTDI)、二 环己基甲烷二异氰酸酯(HMDI)中的一种或多种。
所述催化剂选自有机锡类、叔胺类催化剂中的一种或多种。
所述扩链剂选自乙二醇(EG)、一缩二乙二醇(DEG)、一缩二丙二醇(DPG)、1,2- 丙二醇(1,2-PG)、1，4-丁二醇(BDO)、新戊二醇(NPG)，1，6-己二醇(HD)等中的 一种或多种。
所述有机溶剂选自丁酮、环己酮、二氧六环、二甲亚砜、四氢呋喃、二甲基甲酰 胺、甲苯、乙酸乙酯中的一种或多种。
作为本发明的优选方式之一，所述酸性指示剂为刚果红(CAS:573-58-0)。
为实现上述发明目的，本发明采用以下技术方案：
一种水性聚氨酯酸性高分子指示剂的制备方法，其特征在于包括以下操作步骤；
(1)将酸性指示剂刚果红5～2000mg用10～20g有机溶剂溶解，得到酸性指示 剂刚果红溶液。
(2)在干燥N2的保护下，将真空脱水后的聚合物多元醇30～100g加入250ml 三颈烧瓶中，加入异氰酸酯30～80g，升温至60～100℃反应2～3h。再加入酸 性指示剂刚果红溶液，在60～100℃反应2～3h得到预聚物。
(3)向预聚物中加入亲水扩链剂5～20g、小分子二元醇0～15g、催化剂0～0.2g、有机溶剂30～100g、反应3～6h后，降温至30℃左右，加入150～300g去离子 水高速乳化，在80～110℃，减压脱溶剂，过滤得到固含量为20～45％的水性 聚氨酯酸性高分子指示剂乳液。
其中，步骤(1)和步骤(3)所述有机溶剂为丙酮、丁酮、环己酮、四氢呋喃、 二甲亚砜、二甲基甲酰胺、甲苯、二氧六环、乙酸乙酯中的一种或多种。
本发明中所述的小分子指示剂为刚果红(CAS:573-58-0)，有如下结构及其在酸性条件下的结构：
水性聚氨酯酸性高分子指示剂是高分子指示剂的重要分支，是通过化学键 合的方式将小分子指示剂引入到聚氨酯的主链形成水性聚氨酯高分子指示剂，具 有稳定性好环保等优点。
本发明是通过逐步聚合，将刚果红接入聚氨酯主链形成聚氨酯基刚果红指 示剂，实现对小分子指示剂的替代，制备的水性聚氨酯酸性高分子指示剂具有贮 存稳定性好、绿色环保、抗菌、不污染待测试样等特点，且使用方便、可重复使 用、应用领域广等优点。
附图说明
图1是实施例1制备的水性聚氨酯刚果红指示剂的红外光谱示意图。
具体实施方式
实施例1
本实施例中，将1g刚果红溶解于20g的N,N-二甲基甲酰胺中，得到刚果红的 N,N-二甲基甲酰胺的溶液。在N2的保护下，向装备有温度计、搅拌器、回流冷 凝器的250ml烧瓶内，加入50g聚氧化丙烯二醇(Mn＝1000)，110℃，0.1MPa 条件下，脱水处理2h。然后加入33g异佛尔酮二异氰酸酯和0.02g二月桂酸 二丁基锡，升温至90℃反应2.5h，加入刚果红的N,N-二甲基甲酰胺溶液110 ℃反应3h。降温至70℃，加入9g 1，2-丙二醇-3-磺酸钠和2g乙二醇下反应2 小时。300g去离子水，高速分散30min。升温80℃，0.6MPa下脱有机溶剂， 过滤制得水性聚氨酯刚果红指示剂。
本实施例制得的水性聚氨酯刚果红指示剂变色范围为3.5到5.2，碱态为红色， 酸态为蓝紫色，固含量24.4％。红外光谱示意图如图1。
实施例2
本实施例中，将1.5g刚果红溶解于20g的四氢呋喃溶液中，得到刚果红的四氢 呋喃溶液。向装备有温度计、搅拌器、回流冷凝器的250ml烧瓶内，加入50g聚 四氢呋喃二醇(Mn＝1000)，110℃，0.1MPa条件下，脱水处理1.5h。加入27g 甲苯二异氰酸酯和0.02g辛酸亚锡，升温至80℃反应3h，加入刚果红的四氢呋 喃溶液110℃反应3h。降温至70℃，加入10gl，4-丁二醇-2-磺酸钠和3g 1,4- 丁二醇下反应2h。300g去离子水，高速分散30min。升温80℃，0.6MPa下 脱有机溶剂，过滤制得水性聚氨酯刚果红指示剂。
本实施例制得的水性聚氨酯刚果红指示剂变色范围为3.5到5.2，碱态为红色， 酸态为蓝紫色，固含量22.4％。
实施例3
本实施例中，将2.0g刚果红溶解于20g的四氢呋喃溶液中，得到刚果红的四氢 呋喃溶液。向装备有温度计、搅拌器、回流冷凝器的250ml烧瓶内，加入50g聚 己内酯二醇(Mn＝1000)，110℃，0.1MPa条件下，脱水处理1.5h。加入37.5g 4，4-二苯基甲烷二异氰酸酯和0.02g辛酸亚锡，升温至80℃反应3h，加入刚 果红的四氢呋喃溶液110℃反应3h。温度为。降温至70℃，加入10g l，4- 丁二醇-2-磺酸钠和3g一缩二乙二醇下反应2h。150g去离子水，高速分散30 min。升温80℃，0.6MPa下脱有机溶剂，过滤制得水性聚氨酯刚果红指示剂。 本实施例制得的水性聚氨酯刚果红指示剂变色范围为3.5到5.2，碱态为红色， 酸态为蓝紫色，固含量40.6％。
以上所述的具体实施例，对本发明的目的、技术方案和有益效果进行了进一 步详细说明，所应理解的是，以上所述仅为本发明的具体实施例而已，并不用于 限制本发明，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进 等，均应包含在本发明的保护范围之内。
Claims (4)
1.一种水性聚氨酯酸性高分子指示剂的制备方法，其特征在于：包括以下操作步骤：
(1)将酸性指示剂刚果红5～2000mg用10～20g有机溶剂溶解，得到酸性指示剂刚果红溶液。
(2)在干燥N2的保护下，将减压脱水后的聚合物多元醇30～100g加入250ml三颈烧瓶中，加入异氰酸酯30～80g，升温至60～100℃反应2～3h。再加入酸性指示剂刚果红溶液混合均匀，在60～100℃反应2～3h得到预聚物。
(3)向预聚物中加入亲水扩链剂5～20g、小分子二元醇0～15g、催化剂0～0.2g、有机溶剂30～100g、反应3～6h后，降温至30℃左右，加入150～300g去离子水高速乳化，在80～110℃，减压脱溶剂，过滤得到固含量为20～45％的水性聚氨酯酸性高分子指示剂乳液。
其中，步骤(1)和步骤(3)所述有机溶剂为丙酮、丁酮、环己酮、四氢呋喃、二甲亚砜、N,N-二甲基甲酰胺、甲苯、二氧六环、乙酸乙酯中的一种或多种。
步骤(2)中所述的聚合物多元醇为聚丁二烯二醇、聚氧化丙烯二醇、四氢呋喃-氧化丙烯共聚二醇、聚丁二烯-丙烯腈醇、聚己二酸乙二醇酯二醇、聚碳酸1，6-己二醇酯二醇、聚己二酸乙二醇-丙二醇酯二醇、聚己二酸一缩二乙二醇酯二醇、聚四氢呋喃二醇、聚己二酸蓖麻油酯二醇、聚己内酯二醇及其聚己二酸-1，4-丁二醇酯二醇中的一种或多种。
步骤(3)中所述的异氰酸酯为甲苯二异氰酸酯(TDI)、1，6-己二异氰酸酯(HDI)、4，4-二苯基甲烷二异氰酸酯(MDI)、异佛尔酮二异氰酸酯(IPDI)、1，5-萘二异氰酸酯(NDI)、多亚甲基多苯基多异氰酸酯(PAPI)、甲基环己基二异氰酸酯(HTDI)、二环己基甲烷二异氰酸酯(HMDI)中的一种或多种。
步骤(3)中所述的亲水扩链剂为1，2-丙二醇-3-磺酸钠、l，4-丁二醇-2-磺酸钠、乙二胺基乙磺酸钠等以及其同系物、衍生物和异构体中的一种或两种。
步骤(3)中所述的小分子二元醇为乙二醇(EG)、一缩二乙二醇(DEG)、一缩二丙二醇(DPG)、1,2-丙二醇(1,2-PG)、1，4-丁二醇(BDO)、新戊二醇(NPG)，1，6-己二醇(HD)等中的一种或多种。
步骤(3)中所述的催化剂为有机锡类、叔胺类催化剂中的一种或多种。
2.根据权利要求1所述的一种水性聚氨酯酸性高分子指示剂，其特征在于，所述指示剂为刚果红(CAS:573-58-0)。刚果红有如下结构及其在酸性条件下的结构。
3.根据权利要求1所述的一种水性聚氨酯酸性高分子指示剂,其特征在于：所述步骤(2)中，聚合物多元醇加热至100～120℃，真空度≤0.1MPa条件下，脱水处理2h，然后再加入异氰酸酯。
4.根据权利要求1所述的一种水性聚氨酯酸性高分子指示剂的制备方法,其特征在于：所述步骤(3)中加入有机锡类催化剂按重量计，占总重量的0.01～0.05％。
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