CN116948137A - 一种软硬段阻燃水性聚氨酯的制备方法 - Google Patents
一种软硬段阻燃水性聚氨酯的制备方法 Download PDFInfo
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Abstract
本发明涉及阻燃高分子材料领域，公开了一种软硬段阻燃水性聚氨酯的制备方法，本发明中以含磷聚酯多元醇作为软段、小分子阻燃二醇和端羟基聚丁二烯丙烯腈作为硬段改善其阻燃性；并采用羟基硅油及六亚甲基二异氰酸酯协同调控其手感，解决阻燃单体的加入存在的手感偏硬的问题；制备得到了一种软硬段改性的阻燃水性聚氨酯。本发明制备的软硬段改性的阻燃水性聚氨酯，工艺简单且易于控制，容易实现规模化生产，制得的水性聚氨酯树脂手感柔软且阻燃性能优异，具备阻燃耐久性且对环境污染小，在涂料、油墨、皮革等领域具备潜在的应用价值。
Description
技术领域
本发明涉及阻燃高分子材料领域，更具体地说，它涉及一种软硬段阻燃水性聚氨酯的制备方法。
背景技术
水性聚氨酯由于其突出的环保优势和优良的综合性质使其在涂料、油墨、皮革等领域取得了较为广泛的应用。但由于水性聚氨酯树脂属于易燃材料,燃烧过程中会产生大量的有毒气体并伴随熔滴现象，限制了其应用。因此，开发综合性能较佳的阻燃水性聚氨酯产品也就成为了目前行业研究的重点。
目前改善水性聚氨酯的阻燃性的方法包括添加型阻燃改性和反应型阻燃改性。添加型阻燃改性具有制备工艺简单，成本低的特点，但制备得到的水性聚氨酯阻燃耐久性较差的问题。反应型阻燃改性又可以划分为软段改性、硬段改性及后扩链改性。由于反应型的阻燃水性聚氨酯性能较为稳定，这使得反应型阻燃改性成为了目前阻燃水性聚氨酯研究的主要方向。随着研究的深入，单一的阻燃改性方法越来越不能满足人们的需求，协同使用多种阻燃改性方法开发含有多种阻燃元素的阻燃聚氨酯，也成为了目前研究的热点。
公开号专利CN202110960762.6公布了一种复合阻燃剂、添加型单组份阻燃水性聚氨酯及其制备方法。该专利通过复合阻燃剂和硅溶胶搭配使用进行水性聚氨酯的阻燃，制备工艺简单，但仍存在阻燃耐久性差的问题。
公开号专利CN115505093A公布了一种磷氮硅阻燃水性聚氨酯的制备方法。该专利以阻燃单体含磷聚醚多元醇、含硅多元醇作为软段，三聚氰胺为硬段，通过软硬段共改性制备了一种磷-氮-硅协同作用的阻燃水性聚氨酯。该工艺具备较佳的柔软性及阻燃耐久性，但三聚氰胺的加入会出现分散不均匀的现象，严重影响聚氨酯树脂的外观。
公开号专利CN114591486A公布了一种反应型阻燃水性聚氨酯树脂及其制备方法。该专利以ExolitOP550、三羟甲基氧化磷作为预聚单体进行硬段改性，含氮扩链剂(N-甲基二乙醇胺等)进行后扩链改性，制备得到了一种磷-氮协同作用的阻燃水性聚氨酯。该工艺制备得到是树脂具备较佳的阻燃性，但由于硬段改性的添加量过高使得聚氨酯树脂存在柔软性方面的问题。公开号专利CN113354680A公布了一种生物基反应型阻燃剂、阻燃水性聚氨酯乳液及制备方法。将自制的生物基反应型阻燃剂作为硬段阻燃扩链剂对水性聚氨酯进行硬段改性。制备得到的阻燃水性聚氨酯同样存在柔软性方面的问题。
为了克服以上方法的不足，本专利制备了一种软硬段改性阻燃水性聚氨酯，解决了阻燃耐久性差、阻燃剂分散不均匀以及阻燃性与柔软性无法兼顾的难题，制得的水性聚氨酯树脂手感较为柔软，阻燃性能优异，对环境污染小，在涂料、油墨、皮革等领域具备潜在的应用价值。
发明内容
针对上述问题，本发明的提供了一种软硬段改性阻燃水性聚氨酯的制备方法。此方法制备得到的本征阻燃水性聚氨酯树脂兼顾阻燃性与柔软性，具备优异阻燃耐久性和品质性能，在涂料、油墨、皮革等领域具备潜在的应用价值。
本发明提出的一种软硬段改性阻燃水性聚氨酯的制备方法，包括以下步骤：
步骤一：将含磷阻燃聚酯多元醇、聚醚多元醇、羟基硅油及抗氧化剂1010置于容器中真空脱水45min；
步骤二：降温至70℃，向容器中加入异佛尔酮二异酸酯及六亚甲基二异氰酸酯进行预聚反应，逐步升温至85℃反应2h；
步骤三：降温至60℃，向容器中依次加入1，4-丁二醇、二羟甲基丙酸、三羟甲基丙烷及催化剂，并分别滴加小分子阻燃二醇和端羟基聚丁二烯丙烯腈进行扩链反应，在反应过程中加入适量丙酮调节粘度，逐步升温至70℃反应3h；
步骤四：降温到40℃加入KH-550，反应时间为10min；冰水浴降温至25℃加入三乙胺，反应时间5min，即可得到阻燃的预聚体；
步骤五：将阻燃的预聚体进行高速分散并加入乙二胺和去离子水即可得到乳液；
步骤六：将得到的乳液在70℃边抽丙酮边熟化2h，得到最终的阻燃水性聚氨酯乳液。
步骤七：将阻燃水性聚氨酯乳液置于四氟乙烯模具中，常温固化即可制备得到阻燃水性聚氨酯胶膜。
进一步地：步骤一中，含磷阻燃聚酯多元醇为无卤阻燃型聚酯二元醇BY3009T，添加量为多元醇总量的40％～50％。
进一步地：步骤一中，聚醚多元醇相对分子质量为2000～3000。
进一步地：步骤一中，羟基硅油为双端羟基封端的硅油，相对分子质量为2000～3000，添加量为多元醇总量的10％～15％。
进一步地：步骤二中，异佛尔酮二异酸酯及六亚甲基二异氰酸酯的质量比为(1：1)～(3：1)。
进一步地：步骤三中，端羟基聚丁二烯丙烯腈羟值为0.40～0.75mmol/g，添加量为2％～10％。
进一步地：步骤三中，小分子阻燃二醇为BY3010和FRC-6的一种或两种组合，添加量为多元醇总量的2％～10％。
进一步地：步骤五中，分散工艺为：将阻燃的预聚体在3500r/min的转速下分散30s加入水溶液；然后降速至1800r/min，加入质量分数为15％的乙二胺水溶液及消泡剂，分散15min；最后降速至600r/min滴加消泡剂分散5min。
本发明的有益效果在于：本发明以含磷聚酯多元醇作为软段、小分子阻燃二醇和端羟基聚丁二烯丙烯腈作为硬段进行阻燃改性，结合羟基硅油及六亚甲基二异氰酸酯调控其手感，通过一步预聚体法制备得到了一种软硬段改性的阻燃水性聚氨酯。此方法制备得到的本征阻燃水性聚氨酯树脂兼顾阻燃性与柔软性，具备优异阻燃耐久性和品质性能，在涂料、油墨、皮革等领域具备潜在的应用价值。
附图说明
图1是本发明软硬段改性阻燃水性聚氨酯的测试数据表格示意图。
具体实施方式
现在将参考示例实施方式讨论本文描述的主题。应该理解，讨论这些实施方式是为了使得本领域技术人员能够更好地理解从而实现本文描述的主题。可以在不脱离本说明书内容的保护范围的情况下，对所讨论的元素的功能和排列进行改变。各个示例可以根据需要，省略、替代或者添加各种过程或组件。另外，相对一些示例所描述的特征在其他例子中也可以进行组合。
实施例1
在本实施例中提出了一种软硬段改性阻燃水性聚氨酯的制备方法，制备步骤如下：
步骤一：将31g聚四氢呋喃醚二醇(分子质量为2000)、15g双端羟基封端的硅油、50gBY3009T和0.96g抗氧化剂加入容器中，在105℃真空条件下脱水45min。
步骤二：降温至70℃，向容器中加入21.15g异佛尔酮二异酸酯及7.05g六亚甲基二异氰酸酯，升温至85℃，持续反应2h。
步骤三：降温至60℃，向容器中依次加入0.41g的1，4-丁二醇、2.8g的二羟甲基丙酸、0.41g的三羟甲基丙烷及0.14g的催化剂，并滴加4g的阻燃二醇BY3010、2.5g的端羟基聚丁二烯丙烯腈进行扩链反应，在反应过程中加入适量丙酮调节粘度；逐步升温至70℃反应3h；
步骤四：降温至40℃加入0.82g的KH-550反应10min，冰水浴降温至25℃加入1.69g的三乙胺反应5min即可得到阻燃的预聚体；
步骤五：将阻燃的预聚体在3500r/min的转速下分散30s加入水溶液320.6g；然后降速至1800r/min，加入0.59g的乙二胺及适量消泡剂分散15min，最后降速至600r/min滴加消泡剂分散5min即可得到乳液；
步骤六：将得到的乳液逐步升温至70℃，边抽丙酮边熟化2h，得到最终的阻燃水性聚氨酯乳液。
步骤七：将阻燃水性聚氨酯乳液置于四氟乙烯模具中温固化48h、60℃烘干2h、120℃烘干30min即可制备得到阻燃水性聚氨酯胶膜。
实施例2
在本实施例中提出了一种软硬段改性阻燃水性聚氨酯的制备方法，制备步骤如下：
步骤一：将34g聚四氢呋喃醚二醇(分子质量为2000)、15g双端羟基封端的硅油、45gBY3009T和0.94g抗氧化剂加入容器中，在105℃真空条件下脱水45min。
步骤二：降温至70℃，向容器中加入21g异佛尔酮二异酸酯及7g六亚甲基二异氰酸酯，升温至85℃，持续反应2h。
步骤三：降温至60℃，向容器中依次加入0.37g的1，4-丁二醇、1.9g的二羟甲基丙酸、0.37g的三羟甲基丙烷及0.14g的催化剂，并滴加6g的阻燃二醇BY3010、2g的端羟基聚丁二烯丙烯腈进行扩链反应，在反应过程中加入适量丙酮调节粘度；逐步升温至70℃反应3h；
步骤四：降温至40℃加入0.8g的KH-550反应10min，冰水浴降温至25℃加入1.15g的三乙胺反应5min即可得到阻燃的预聚体；
步骤五：将阻燃的预聚体在3500r/min的转速下分散30s加入水溶液315.4g；然后降速至1800r/min，加入0.59g的乙二胺及适量消泡剂分散15min，最后降速至600r/min滴加消泡剂分散5min即可得到乳液；
步骤六：将得到的乳液逐步升温至70℃，边抽丙酮边熟化2h，得到最终的阻燃水性聚氨酯乳液。
步骤七：将阻燃水性聚氨酯乳液置于四氟乙烯模具中温固化48h、60℃烘干2h、120℃烘干30min即可制备得到阻燃水性聚氨酯胶膜。
实施例3
在本实施例中提出了一种软硬段改性阻燃水性聚氨酯的制备方法，制备步骤如下：
步骤一：将39g聚四氢呋喃醚二醇(分子质量为2000)、15g双端羟基封端的硅油、40gBY3009T和0.94g抗氧化剂加入容器中，在105℃真空条件下脱水45min。
步骤二：降温至70℃，向容器中加入21.3g异佛尔酮二异酸酯及7.1g六亚甲基二异氰酸酯，升温至85℃，持续反应2h。
步骤三：降温至60℃，向容器中依次加入0.4g的1，4-丁二醇、2.0g的二羟甲基丙酸、0.4g的三羟甲基丙烷及0.14g的催化剂，并滴加6g的阻燃二醇BY3010、2g的端羟基聚丁二烯丙烯腈进行扩链反应，在反应过程中加入适量丙酮调节粘度；逐步升温至70℃反应3h；
步骤四：降温至40℃加入0.8g的KH-550反应10min，冰水浴降温至25℃加入1.21g的三乙胺反应5min即可得到阻燃的预聚体；
步骤五：将阻燃的预聚体在3500r/min的转速下分散30s加入水溶液316.9g；然后降速至1800r/min，加入0.6g的乙二胺及适量消泡剂分散15min；最后降速至600r/min滴加消泡剂分散5min即可得到乳液；
步骤六：将得到的乳液逐步升温至70℃，边抽丙酮边熟化2h，得到最终的阻燃水性聚氨酯乳液。
步骤七：将阻燃水性聚氨酯乳液置于四氟乙烯模具中温固化48h、60℃烘干2h、120℃烘干30min即可制备得到阻燃水性聚氨酯胶膜。
对比例
在本对比例中提供了一种水性聚氨酯的制备方法，制备步骤如下：
一种软硬段改性阻燃水性聚氨酯的制备方法，制备步骤如下：
步骤一：将115g聚四氢呋喃醚二醇(分子质量为2000)和1.15g抗氧化剂加入容器中，在105℃真空条件下脱水45min。
步骤二：降温至70℃，向容器中加入24g异佛尔酮二异酸酯及8g六亚甲基二异氰酸酯，升温至85℃，持续反应2h。
步骤三：降温至60℃，向容器中依次加入0.5g的1，4-丁二醇、5.7g的二羟甲基丙酸、0.5g的三羟甲基丙烷及0.16g的催化剂，在反应过程中加入适量丙酮调节粘度，逐步升温至70℃反应3h；
步骤四：降温至40℃加入0.92g的KH-550反应10min，冰水浴降温至25℃加入3.44g的三乙胺反应5min即可得到阻燃的预聚体；
步骤五：将阻燃的预聚体在3500r/min的转速下分散30s加入水溶液370.1g；然后降速至1800r/min，加入0.67g的乙二胺及适量消泡剂分散15min；最后降速至600r/min滴加消泡剂分散5min即可得到乳液；
步骤六：将得到的乳液逐步升温至70℃，边抽丙酮边熟化2h，得到最终的阻燃水性聚氨酯乳液。
步骤七：将阻燃水性聚氨酯乳液置于四氟乙烯模具中温固化48h、60℃烘干2h、120℃烘干30min即可制备得到阻燃水性聚氨酯胶膜。
将实施例1、2和3及对比例制备的水性聚氨酯进行柔软性、力学性能及阻燃测试，测试结果如附图1所示。
从附图1中表格数据可以看出，本发明制备得到的软硬段改性阻燃水性聚氨酯较对比例的断裂强力略有降低，但在阻燃性能方面具有较大程度的提高。此外，从硬度值及断裂伸长率的对比可以看出，羟基硅油以及六亚甲基二异氰酸酯的加入明显改善了树脂的柔软度，使得阻燃树脂具备阻燃性的同时兼顾柔软度。
尽管本发明的实施方案已公开如上，但其并不仅仅限于说明书和实施方式中所列运用，它完全可以被适用于各种适合本发明的领域，因此本发明不限于上述实施例。本领域技术人员根据本发明的原理，不脱离本发明的范畴所做出的改进和修改都应该在本发明的保护范围内。
Claims (8)
1.一种软硬段阻燃水性聚氨酯的制备方法，其特征在于，包括以下步骤：
步骤一：将含磷阻燃聚酯多元醇、聚醚多元醇、羟基硅油及抗氧化剂1010置于容器中真空脱水45min；
步骤二：降温至70℃，向容器中加入异佛尔酮二异酸酯及六亚甲基二异氰酸酯进行预聚反应，逐步升温至85℃反应2h；
步骤三：降温至60℃，向容器中依次加入1，4-丁二醇、二羟甲基丙酸、三羟甲基丙烷及催化剂，并分别滴加小分子阻燃二醇和端羟基聚丁二烯丙烯腈进行扩链反应，在反应过程中加入适量丙酮调节粘度，逐步升温至70℃反应3h；
步骤四：降温到40℃加入KH-550，反应时间为10min；冰水浴降温至25℃加入三乙胺，反应时间5min，即可得到阻燃的预聚体；
步骤五：将阻燃的预聚体进行高速分散并加入乙二胺和去离子水即可得到乳液；
步骤六：将得到的乳液在70℃边抽丙酮边熟化2h，得到最终的阻燃水性聚氨酯乳液。
步骤七：将阻燃水性聚氨酯乳液置于四氟乙烯模具中，常温固化即可制备得到阻燃水性聚氨酯胶膜。
2.根据权利要求1所述的一种软硬段阻燃水性聚氨酯的制备方法，其特征在于，步骤一中，含磷阻燃聚酯多元醇为无卤阻燃型聚酯二元醇BY3009T，添加量为多元醇总量的40％～50％。
3.根据权利要求1所述的一种软硬段阻燃水性聚氨酯的制备方法，其特征在于，步骤一中，聚醚多元醇相对分子质量为2000～3000。
4.根据权利要求1所述的一种软硬段阻燃水性聚氨酯的制备方法，其特征在于，步骤一中，羟基硅油为双端羟基封端的硅油，相对分子质量为2000～3000，添加量为多元醇总量的10％～15％。
5.根据权利要求1所述的一种软硬段阻燃水性聚氨酯的制备方法，其特征在于，步骤二中，异佛尔酮二异酸酯及六亚甲基二异氰酸酯的质量比为(1：1)～(3：1)。
6.根据权利要求1所述的一种软硬段阻燃水性聚氨酯的制备方法，其特征在于，步骤三中，端羟基聚丁二烯丙烯腈羟值为0.40～0.75mmol/g，添加量为2％～10％。
7.根据权利要求1所述的一种软硬段阻燃水性聚氨酯的制备方法，其特征在于，步骤三中，小分子阻燃二醇为BY3010和FRC-6的一种或两种组合，添加量为多元醇总量的2％～10％。
8.根据权利要求1所述的一种软硬段阻燃水性聚氨酯的制备方法，其特征在于，步骤五中，分散工艺为：将阻燃的预聚体在3500r/min的转速下分散30s加入水溶液；然后降速至1800r/min，加入质量分数为15％的乙二胺水溶液及消泡剂，分散15min；最后降速至600r/min滴加消泡剂分散5min。
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