CN103641974A - 一种水性聚氨酯乳液的制备方法及其制备的水性聚氨酯乳液 - Google Patents
一种水性聚氨酯乳液的制备方法及其制备的水性聚氨酯乳液 Download PDFInfo
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Abstract
本发明提供一种水性聚氨酯乳液的制备方法，先将废弃聚氨酯纤维进行醇解，得到分子量为5000-10000的羟基封端的聚氨酯和多元醇的混合物，不经分离，再经预聚、扩链、乳化，一步得到水性聚氨酯乳液；所述废弃聚氨酯纤维优选自经干法纺丝或湿法纺丝得到的废弃聚醚型聚氨酯纤维和/或聚碳酸酯型聚氨酯纤维；更优选的，所述废弃聚氨酯纤维为软段比例在85%以上的废弃聚四氢呋喃二醇型聚氨酯纤维和/或聚碳酸酯二醇型的聚氨酯纤维；最优选的，所述废弃聚氨酯纤维为软段比例在85%以上的废弃聚四氢呋喃二醇型聚氨酯纤维。本发明为废弃的高端聚氨酯纤维找到了一个更合理、附加值更好的再生利用方法。
Description
技术领域
本发明属于高分子材料领域，具体涉及一种利用废弃聚氨酯纤维制备水性聚氨酯乳液的方法及其制备的水性聚氨酯乳液。
背景技术
聚氨酯纤维是将聚氨酯溶于有机溶剂如二甲基甲酰胺、二甲基乙酰胺或二甲基亚砜中，得到纺丝溶液，经干法纺丝或湿法纺丝成纤，再通过含有脂肪二胺扩链剂的水溶液，得到具有弹性的高分子合成纤维。其具有非常优良的弹性和物理机械性能，在纺织、生物医药等领域得到了广泛的应用。相应的，聚氨酯纤维的产量也成倍增长。随之而来的，却是大量废弃聚氨酯纤维的产生。这些废弃物的处理，如果只采用填埋和焚烧的方法进行简单的处理，不仅浪费了大量的资源，也造成环境污染。
现有技术中出现了对聚氨酯纤维进行再利用的方法。如中国发明专利申请（公开号CN1526863A）记载了一种聚氨酯纤维废弃物再生利用方法，该方法是将干纺聚氨酯纤维废弃物、湿纺聚氨酯纤维废弃物、熔纺聚氨酯纤维废弃物在醇解剂或醇解剂与催化剂的作用下，在120～240℃的温度范围内降解成低聚物液体，并经分离提纯后得到多元醇；该多元醇再与异氰酸酯和扩链剂反应合成新的聚氨酯薄膜、泡沫或纤维。但是该方法制备的聚氨酯都是较低端的固态产品。
水性聚氨酯乳液是聚氨酯中的高端产品。在人类环保意识日益重视的今天，对以水为介质的聚氨酯乳液的发展越来越来越受到重视，因为以水为溶剂，无毒、无污染的，并且价格低廉。水性聚氨酯因其特有的优良特性，已经广泛应用于制革、纺织、涂料、印刷、和建筑业，并随着人们的逐渐研究开发，逐渐向其他应用领域渗透。因此，对水性聚氨酯乳液的需求日益旺盛。
目前水性聚氨酯乳液生产面临的主要问题有二个。一方面是合成水性聚氨酯乳液的原料比较特殊，相对油性聚氨酯（溶剂型聚氨酯）而言，成本相对高，造成水性聚氨酯乳液生产成本高，市场消化压力大；另一方面是水性聚氨酯合成技术。众所周知，尽管水性聚氨酯具有环保、清洁的优势，却因为水本身表面张力大，与聚氨酯相容性差。将合成的聚氨酯分散于水中，还存在种种技术难题。由于溶剂型聚氨酯对环境的破坏性，国家已经制定相关政策，限制溶剂型聚氨酯及下游产业（如制革业）的发展。因而水性聚氨酯是溶剂型聚氨酯的最佳替代方案。同时国内的水性聚氨酯研究已成为世界水性聚氨酯研究的一个重要组成部分。相关产业得到了国家和政府的大力扶持与政策引导，使得中国内地已经成为世界上水性聚氨酯的主要产地之一。
迄今尚未见有利用废弃聚氨酯纤维再生制备水性聚氨酯乳液的报道。
发明内容
针对现有技术的不足，本发明所要解决的问题在于提供一种以废弃聚氨酯纤维为原料，无需分离，一步法制备的水性聚氨酯乳液的方法。该方法不仅能够充分发挥聚氨酯纤维材料的优越性能和价值，而且可以有效降低水性聚氨酯制造与生产成本，对促进水性聚氨酯技术发展和市场推广有着极其重要的意义。
为了实现上述发明目的，本发明采用了如下的技术方案：
一种水性聚氨酯乳液的制备方法，先将废弃聚氨酯纤维进行醇解，得到分子量为5000-10000的羟基封端的聚氨酯和多元醇的混合物，不经分离，再经预聚、扩链、乳化，一步得到水性聚氨酯乳液；
优选的，所述废弃聚氨酯纤维选自经干法纺丝或湿法纺丝得到的废弃聚醚型聚氨酯纤维和/或聚碳酸酯型聚氨酯纤维；更优选的，所述废弃聚氨酯纤维为软段比例在85%以上的废弃聚四氢呋喃二醇型聚氨酯纤维和/或聚碳酸酯二醇型的聚氨酯纤维；最优选的，所述废弃聚氨酯纤维为软段比例在85%以上的废弃聚四氢呋喃二醇型聚氨酯纤维。
优选的，本发明所述制备方法的原料组成为：
废弃聚氨酯纤维：50-200份，
醇解催化剂：0.05-0.1份，
醇解剂：50-100份，
扩链剂：7-10份，
分子量2000-4000的聚酯多元醇或聚醚多元醇：50-200份，
异氰酸酯：70-200份，
酸碱中和剂：8-20份，
去离子水：500-3000份。
优选的，所述醇解剂和扩链剂各自独立地由选自二羟甲基丙酸或二羟甲基丁酸中的一种，和分子量小于400的低分子量二元醇组成；更优选的，所述醇解剂和扩链剂组成相同；
其中，所述二羟甲基丁酸优选为2,2-二羟甲基丁酸、二羟甲基丙酸；
所述分子量小于400的低分子量二元醇优选自乙二醇、二乙二醇、1,4-丁二醇、1,3-丁二醇、新戊二醇、1,6-己二醇、甲基丙二醇、三甲基戊二醇、羟基新戊酸羟基新戊酯、2-丁基-2-乙基-1,3-丙二醇、分子量小于400的聚酯或聚醚中的一种或几种。
优选的，所述异氰酸酯选自甲苯二异氰酸酯、异氟尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯或苯二亚甲基二异氰酸酯中的一种或几种。
优选的，所述醇解催化剂选自有机金属催化剂、叔胺类催化剂和有机锡类催化剂中的一种或几种；更优选为有机金属类催化剂。
优选的，本发明所述的制备方法，具体步骤包括：
I.废弃聚氨酯纤维的降解
将所述重量份的废弃聚氨酯纤维和醇解催化剂，以及部分的醇解剂、扩链剂和分子量2000-4000的聚酯多元醇或聚醚多元醇混合，搅拌，控制温度为95-120℃，充氮气，反应2-4小时，至料液透明，粘度下降至1200-1700cPs/90℃为止；
II.水性聚氨酯乳液的制备
待步骤I得到的料液降温至50℃以下，加入所述重量份的异氰酸酯以及剩余重量份的醇解剂和分子量2000-4000的聚酯多元醇或聚醚多元醇，控制温度70-75℃，反应2-3小时；然后加入剩余重量份的扩链剂，75-80℃反应2.5-3小时；物料温度降至40-50℃，加入所述重量份的中和剂，调pH至6～8，搅拌2-3分钟；最后快速搅拌下缓缓加入所述重量份的去离子水，即得所述水性聚氨酯乳液。
优选的，本发明所述的制备方法中，所述醇解剂、扩链剂和分子量2000-4000的聚酯多元醇或聚醚多元醇各自独立地在所述步骤I和II的重量份分配比例是1-2：2-3；
更优选的，所述醇解剂、扩链剂和分子量2000-4000的聚酯多元醇或聚醚多元醇在所述步骤I和II的重量份分配比例是1：1。
本发明的另一个目的在于提供通过上述制备方法制备的水性聚氨酯乳液。
本发明还有一个目的，在于提供所述的水性聚氨酯乳液在制备水性聚氨酯革用树脂、水性聚氨酯胶粘剂、水性聚氨酯漆或水性聚氨酯复合材料中的应用。
另外，本发明还有一个目的，在于提供废弃聚氨酯纤维在制备本发明所述的水性聚氨酯乳液中的应用。优选的，所述废弃聚氨酯纤维选自经干法纺丝或湿法纺丝得到的废弃聚醚型聚氨酯纤维和/或聚碳酸酯型聚氨酯纤维；更优选的，所述废弃聚氨酯纤维为软段比例在85%以上的废弃聚四氢呋喃二醇型聚氨酯纤维和/或聚碳酸酯二醇型的聚氨酯纤维。
本发明所述的醇解催化剂，选自有机金属催化剂、叔胺类催化剂、有机锡催化剂或它们的混合物。其中，有机金属催化剂可以选自醋酸钾、醋酸锌和醋酸钠中的一种或几种；叔胺类催化剂可以选自三亚乙基二胺、三乙胺和三乙醇胺中的一种或几种；有机锡类催化剂可以选自二丁基锡二月桂酸酯和/或辛酸亚锡。
本发明所述废弃聚氨酯纤维醇解时，充入的惰性气体，可以选自氮气、氩气或氦气，优选为氮气。
本发明所述的酸碱中和剂，是为了中和所述醇解剂和扩链剂中的二羟甲基丙酸或二羟甲基丁酸，可以选择有机或无机的中和剂。有机中和剂可以选自三乙胺、二乙醇胺等。无机中和剂可以选自氢氧化钠/钾、碳酸氢钠/钾等。为了控制终产品水性聚氨酯乳液中的无机金属离子的量，本发明优选有机碱性中和剂。
本发明所述的制备方法，在步骤II反应结束后，加入酸碱中和剂之前，根据物料粘度，可以加入适量丙酮以降低粘度。
本发明所述粘度以布拉班德（Brabender）粘度计或旋转粘度计测定。
利用本发明所述制备方法，对废弃的聚氨酯纤维进行降解，得到粘度为1200-1700cPs/90℃的羟基封端的聚氨酯和多元醇（包括聚醚多元醇、聚酯多元醇）的混合物；再与多元醇与异氰酸酯预聚体、扩链剂等进行反应，无需添加表面活性剂助溶，即可均匀地分布在水中进行乳化。
具体实施方式
下面结合实施例，对本发明作详细说明。
下列实施例中，所用的各种原料，如没有特殊的说明，都可以通过市售的途径购买到。
实施例1一种水性聚氨酯乳液
各原料配比（单位：g）如下：
其中，废弃聚氨酯纤维为经干法纺丝得到的、软段比例在90%的废弃聚四氢呋喃二醇型聚氨酯纤维。
通过如下步骤制备：
1.将所述废弃聚氨酯纤维60g进行清洁、干燥。备用。
2.在四孔圆底烧瓶内，投入PTMEG100g、醇解催化剂0.05g、BDO5g和DMBA7g，控制温度为95-120℃，同时充氮并搅拌均匀，将清洁干燥好的废弃的聚氨酯纤维60g加入反应瓶内；保温反应2小时，待料液清透及粘度明显下降至1200-1500cPs/90℃为止；
3.待物料温度降至50℃以下，把PTMEG50g，BDO4.5g，TMP1.25g投入反应瓶内并搅拌均匀后，再加入TDI75g，控制70-75℃反应2小时；加入剩余的DMBA7.3g，75℃反应2.5小时，降至45℃左右加入TEA13g中和，搅拌2-3分钟，然后快速搅拌下，缓缓加入去离子水600g进行乳化，即得异氰酸酯指数为1.28，固含量为35%的高耐水解、稳定性好的水性聚氨酯乳液。
实施例2一种水性聚氨酯乳液
各原料配比（单位：g）
其中，废弃聚氨酯纤维为经干法纺丝得到的、软段比例在87%的废弃聚碳酸酯二醇型聚氨酯纤维。
通过如下步骤制备：
1.将废弃聚氨酯纤维50g进行清洁、干燥。备用。
2.在四孔圆底烧瓶内，投入多元醇PBA120g、醇解催化剂0.05g、HDO6g、DMBA4.7g，控制温度为95-120℃，同时充氮并搅拌均匀，及将清洁干燥好的废弃聚氨酯纤维50g，加入反应瓶内；保温反应2小时，待料液清透及粘度明显下降至1200-1500cPs/90℃为止。
3.待物料温度降至50℃以下，把剩余的多元醇PBA45g、HDO4.5g和TMP1.25g投入反应瓶内并搅拌均匀后，再加入HDI72g，控制70-75℃反应2小时；加入剩余的DMBA7g，75℃反应2.5小时，加入适量丙酮降粘；待物料温度降至45℃左右加入TEA10g，搅拌2-3分钟；然后快速搅拌下，缓缓加入去离子水630g进行乳化，即得异氰酸酯指数为1.32，固含量为30%的高耐水解、耐黄变的水性聚氨酯乳液。
5.耐黄变测试
实施例3一种水性聚氨酯乳液
各原料配比（单位：kg）
其中，废弃聚氨酯纤维为经干法纺丝得到的、软段比例在90%的废弃聚碳酸酯二醇型聚氨酯纤维。
通过如下步骤制备：
1.将废弃聚氨酯纤维200kg进行清洁、干燥。备用。
2.在反应釜内，投入PTMEG75kg、醇解催化剂0.1kg和BDO6kg、DMPA4.7g，控制温度为95-120℃，同时充氮并搅拌均匀，及将清洁干燥好的废弃聚氨酯纤维200kg，加入反应瓶内；保温反应4小时，待料液清透及粘度明显下降至1200-1500cPs/90℃为止。
3.待物料温度降至50℃以下，把剩余的PTMEG100kg、BDO19kg投入反应瓶内并搅拌均匀后，再加入异氟尔酮二异氰酸酯200kg，控制70-75℃反应3小时；加入剩余的DMPA5.3kg，75℃反应3小时；待物料温度降至45℃左右加入TEA20kg，搅拌2-3分钟；然后快速搅拌下，缓缓加入去离子水3000kg进行乳化，固含量为25%的高耐水解、高性能的水性聚氨酯乳液。
试验例1实施例1-3制备的水性聚氨酯乳液的性能测定
1.耐水解性：以耐碱性测试耐水解性能
试验方法：
1）将实施例1-3制备得到的水性聚氨酯乳液分别在玻璃板上涂膜，厚度为0.70mm，100℃±2℃烘箱内烘干。
2）将步骤1得到的膜片切割成100mm×20mm的方块，每个实施例样品取3块。
3）在温度为23℃±2℃，相对湿度45%～55%的条件下，将2块试样浸泡在10%NaOH水溶液中，放置24h后用镊子将试样取出，并用水冲洗干净，在100℃±2℃烘箱内烘干后，观察试片表面侵蚀龟裂情形或测试试样的拉伸强度负荷，与未浸泡试片进行对比判定。
2.测试结果：见表1-3。
表1实施例1制备的水性聚氨酯乳液耐水解测试结果
| 试片序号 | 浸泡前（kgf/2mm） | 浸泡后（kgf/2mm） | 表明侵蚀 | 备注 |
| 1 | 19.8 | - | ||
| 2 | 19.2 | 无 | 耐水解优 | |
| 3 | 19.0 | 无 | 耐水解优 |
表2实施例2制备的水性聚氨酯乳液耐水解测试结果
| 试片序号 | 浸泡前（kgf/2mm） | 浸泡后（kgf/2mm） | 表明侵蚀 | 备注 |
| 1 | 22.7 | - | ||
| 2 | 20.7 | 无 | 耐水解优 | |
| 3 | 19.8 | 无 | 耐水解优 |
表3实施例3制备的水性聚氨酯乳液耐水解测试结果
| 试片序号 | 浸泡前（kgf/2mm） | 浸泡后（kgf/2mm） | 表明侵蚀 | 备注 |
| 1 | 34.5 | - | ||
| 2 | 33.5 | 无 | 耐水解优、力学性能优 | |
| 3 | 33.0 | 无 | 耐水解优、力学性能优 |
3.稳定性
取实施例1-3制备的水性聚氨酯乳液各100克，密封好。置于离心机下高速转动，30分钟后目视样品有无分层现象。
结果：3个样品均无分层。满足6个月稳定储存期要求。
4.耐黄变性
1）试验装置：紫外线光源照射箱
2）样品制备：将实施例1-3制备得到的水性聚氨酯乳液分别在玻璃板上涂膜，厚度为0.70mm，100℃±2℃烘箱内烘干，然后切割成60mm×90mm的方块。
3）试验方法：将样品夹入夹具中，试片一半暴露，一半以样品夹盖住；将试片连同样品夹放入紫外线灯箱内进行测试。灯泡紫外线光源30W；照射距离250mm；试验箱温度50℃±1℃；照射时间4h。暴露后取出，按GB/T250-1995进行判定。
结果：所有样品达到4级以上。
上述测试结果表明，实施例1-3制备的水性聚氨酯乳液具有高耐水解、耐黄变及稳定好的性能特点。
总之，本发明提供了一种以废弃聚氨酯纤维为原料、一步法制备水性聚氨酯乳液的方法，以及通过该方法制备的水性聚氨酯乳液。不仅为废弃的高端聚氨酯纤维找到一个更合理、附加值更好的再生利用方法；而且能够有效地控制水性聚氨酯制造与生产成本，对促进水性聚氨酯技术发展和市场推广有着极其重要的意义。
Claims (10)
1.一种水性聚氨酯乳液的制备方法，其特征在于，先将废弃聚氨酯纤维进行醇解，得到分子量为5000-10000的羟基封端的聚氨酯和多元醇的混合物，不经分离，再经预聚、扩链、乳化，一步得到水性聚氨酯乳液；
所述废弃聚氨酯纤维优选自经干法纺丝或湿法纺丝得到的废弃聚醚型聚氨酯纤维和/或聚碳酸酯型聚氨酯纤维；更优选的，所述废弃聚氨酯纤维为软段比例在85%以上的废弃聚四氢呋喃二醇型聚氨酯纤维和/或聚碳酸酯二醇型的聚氨酯纤维；最优选的，所述废弃聚氨酯纤维为软段比例在85%以上的废弃聚四氢呋喃二醇型聚氨酯纤维。
2.根据权利要求1所述的制备方法，其特征在于：所述制备方法的原料组成为：
废弃聚氨酯纤维：50-200份，
醇解催化剂：0.05-0.1份，
醇解剂：50-100份，
扩链剂：7-10份，
分子量2000-4000的聚酯多元醇或聚醚多元醇：50-200份，
异氰酸酯：70-200份，
酸碱中和剂：8-20份，
去离子水：500-3000份。
3.根据权利要求2所述的制备方法，其特征在于：所述醇解剂和扩链剂各自独立地由选自二羟甲基丙酸或二羟甲基丁酸中的一种，和分子量小于400的低分子量二元醇组成；优选的，所述醇解剂和扩链剂组成相同；
其中，所述二羟甲基丁酸优选为2,2-二羟甲基丁酸；
所述分子量小于400的低分子量二元醇优选自乙二醇、二乙二醇、1,4-丁二醇、1,3-丁二醇、新戊二醇、1,6-己二醇、甲基丙二醇、三甲基戊二醇、羟基新戊酸羟基新戊酯、2-丁基-2-乙基-1,3-丙二醇、分子量小于400的聚酯或聚醚中的一种或几种。
4.根据权利要求2所述的制备方法，其特征在于，所述异氰酸酯选自甲苯二异氰酸酯、异氟尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯或苯二亚甲基二异氰酸酯中的一种或几种。
5.根据权利要求2所述的制备方法，其特征在于，所述醇解催化剂选自有机金属催化剂、叔胺类催化剂和有机锡类催化剂中的一种或几种；优选有机金属类催化剂。
6.根据权利要求2至5中任一项所述的制备方法，其特征在于，具体步骤包括：
I.废弃聚氨酯纤维的降解
将所述重量份的废弃聚氨酯纤维和醇解催化剂，以及部分的醇解剂、扩链剂和分子量2000-4000的聚酯多元醇或聚醚多元醇混合，搅拌，控制温度为95-120℃，充惰性气体，反应2-4小时，至料液透明，粘度下降至1200-1700cPs/90℃为止；
II.水性聚氨酯乳液的制备
待步骤I得到的料液降温至50℃以下，加入所述重量份的异氰酸酯以及剩余重量份的醇解剂和分子量2000-4000的聚酯多元醇或聚醚多元醇，控制温度70-75℃，反应2-3小时；然后加入剩余重量份的扩链剂，75-80℃反应2.5-3小时；物料温度降至40-50℃，加入所述重量份的中和剂，调pH至6～8，搅拌2-3分钟；最后快速搅拌下缓缓加入所述重量份的去离子水，即得所述水性聚氨酯乳液。
7.根据权利要求6所述的制备方法，其特征在于：所述醇解剂、扩链剂和分子量2000-4000的聚酯多元醇或聚醚多元醇各自独立地在所述步骤I和II的重量份分配比例是1-2：2-3；
优选的，所述醇解剂、扩链剂和分子量2000-4000的聚酯多元醇或聚醚多元醇在所述步骤I和II的重量份分配比例是1：1。
8.权利要求1至7中任一项所述的制备方法制备的水性聚氨酯乳液。
9.权利要求8所述的水性聚氨酯乳液在制备水性聚氨酯革用树脂、水性聚氨酯胶粘剂、水性聚氨酯漆或水性聚氨酯复合材料中的应用。
10.废弃聚氨酯纤维在制备权利要求8所述的水性聚氨酯乳液中的应用；
所述废弃聚氨酯纤维优选自经干法纺丝或湿法纺丝得到的废弃聚醚型聚氨酯纤维和/或聚碳酸酯型聚氨酯纤维；更优选的，所述废弃聚氨酯纤维为软段质量比例在85%以上的废弃聚四氢呋喃二醇型聚氨酯纤维和/或聚碳酸酯二醇型的聚氨酯纤维。
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| CN112029148A (zh) * | 2020-08-31 | 2020-12-04 | 浙江工业大学 | 一种使用乳液体系回收废弃聚氨酯泡沫中聚醚多元醇的方法 |
| CN112063013A (zh) * | 2020-08-31 | 2020-12-11 | 浙江工业大学 | 一种聚氨酯泡沫降解回收后亲水改性制备水性聚氨酯的方法 |
| TWI797953B (zh) * | 2022-01-07 | 2023-04-01 | 國立臺灣大學 | 一種非光氣法聚氨酯製程及其中間產物 |
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