CN104387550A - 一种含炔基的聚氨酯及其制备方法 - Google Patents
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Abstract
本发明涉及一种含炔基的聚氨酯及其制备方法，属于耐高温材料、阻燃材料技术领域。将液态聚醚二醇与液态二异氰酸酯混合，加热进行加成反应，加入1,4-丁炔二醇，加热进行缩聚反应，反应结束后，得到耐高温含炔基的聚氨酯。本发明具有反应条件温和稳定，重复性好，产率高，周期短等特点，适合扩大性生产；得到的聚合物具有优异的耐高温、力学强度和阻燃等多种性能。
Description
技术领域
本发明涉及一种含炔基的耐高温聚氨酯及其制备方法，属于耐高温材料、阻燃材料技术领域。
背景技术
热塑性聚氨酯弹性体(TPU)是一种介于一般橡胶与塑料之间的弹性材料，其主链上含有重复的氨基甲酸酯链段，大分子主链是由玻璃化温度低于室温的柔性链段和玻璃化温度高于室温的刚性链段嵌段而成的，它具有优异的机械性能，例如高强度、高弹性、高伸长率，因此可制成橡胶、涂料、粘合剂、防水材料等一系列产品，因此被广泛应用于汽车、机械、医疗和航天等领域。但是其作为一种有机高分子材料，在空气中极易燃烧，燃烧时火焰非常剧烈且伴有黑烟，同时具有严重的熔滴现象，其极限氧指数(LOI)仅为18-20之间，具有严重的火灾隐患。因此对TPU的耐热及其阻燃改性是一个十分紧迫的问题。
目前，对TPU耐热和阻燃的改性主要是通过物理共混和合成本质阻燃聚合物材料的方式。物理共混方式就是将添加型阻燃剂分散于聚合物基材中，赋予基材阻燃性能，特点是阻燃剂与基材及基材中的其他组分不发生化学反应，加工工艺简单，应用普遍，但需要改善阻燃剂与基材等组分间的界面相容性，提高阻燃聚合物材料的力学性能，避免阻燃剂迁出。为了有效地解决这些问题，越来越多地研究集中在合成本质阻燃、耐热聚合物材料的方式。通过化学反应将阻燃、耐热基团引入到聚合物分子结构中，使其具有分解温度高、耐热性好、不容易燃烧的性质。
近年来，分子主链含炔基的有机聚合物以其特殊的热稳定性而备受关注。 由于其分子中的C≡C可通过热交联反应或光交联反应使分子间高度交联形成更加稳定的网络结构，因而这类聚合物通常具有较高的热稳定性，可作为耐高温热固化或光固化树脂，成为耐高温材料领域研究的热点。通过分子设计，将含有炔基的二醇作为扩链剂，与聚四氢呋喃醚二醇(PTMG)和4，4-二苯基甲烷二异氰酸酯(MDI)反应，制备出新型的含炔基的聚氨酯(TPU)。
发明内容
本发明的目的是制备一种含炔基的聚氨酯，并提出其制备方法。该聚氨酯是一种新型的含炔基的耐高温聚氨酯材料，同时含有炔基，聚醚，异氰酸酯，在聚合物复合材料中具有阻燃、耐高温、高力学强度的作用。
本发明的目的是通过以下技术方案实现的。
本发明的一种抗熔滴耐高温聚酰亚胺型聚氨酯，其结构式为：
其中Ar是或或中的任意一种；n为B的聚合度，
B为-CH2CH2CH2CH2O-，n＝10-45；
或B为-CH2CH2O-，n＝20-500；
或B为n＝10-70；
D是或
或 或
中的任意一种；
x为聚合度，x＝1-10，y为聚合度，y＝2-15，z为聚合度，z＝2-15，a为聚合度，a＝20-90，b为聚合度，b＝35-150。
本发明的一种含炔基聚氨酯的制备方法，步骤为：
1)将液态无水聚醚二醇与液态二异氰酸酯混合，搅拌，加热进行加成反应，加热温度为50-100℃，加热时间是1-15h；液态无水聚醚二醇与液态二异氰酸酯的摩尔比为0.1-1:1
2)将1,4-丁炔二醇加入步骤1)得到的产物，搅拌，加热进行缩聚反应，加热温度为60-150℃，加热时间是2-24h；1,4-丁炔二醇与步骤1)中液态无水聚醚二醇的摩尔比为0.1-1:1；
3)步骤2)反应结束后得到的产物为含炔基聚氨酯。
步骤1)中液态无水聚醚二醇为聚四氢呋喃醚二醇、聚乙二醇或聚环氧乙烷-四氢呋喃醚二醇中的一种。聚四氢呋喃醚二醇的数均分子量为1000±50、1400±50、1800±50、2000±50或3000±100。聚乙二醇的数均分子量为1000±50、1400±50、2000±200、4000±400和6000±500；8000±500、10000±1500或20000±1500。聚环氧乙烷-四氢呋喃醚二醇的数均分子量为1800-6200。
步骤1)中液态二异氰酸酯为：4，4’-二苯基甲烷二异氰酸酯、甲苯-2,4- 二异氰酸酯或甲苯-2,6-二异氰酸酯中的一种。
步骤1)中液态4，4’-二苯基甲烷二异氰酸酯的制备方法为：将固体4，4’-二苯基甲烷二异氰酸酯加入到反应容器中，加热使其融化；加热温度为30-100℃。
步骤1)中液态无水聚醚二醇的制备方法为：将聚醚二醇在高温的真空烘箱中，真空条件下除去水分；真空烘箱的温度为100-120℃，除水时间0.5-20h；真空度小于-0.02MPa。
有益效果
本发明的反应条件温和稳定，重复性好，产率高、周期短等特点，适合扩大性生产；经过测试得知炔基改性提高了极限氧指数的值，并且还提高了聚氨酯在UL-94垂直燃烧的等级。此外，炔基改性还降低了聚氨酯的总的热释放量和热释放速率峰值。
附图说明
红外光谱采用NICOLET 6700 IR型红外光谱仪测定；热失重(TG)采用NETZSCH 209 F1热重分析仪测定，氮气气氛，升温速率10℃/min；极限氧指数(流变科学有限公司)依照GB/T 2406.2-2009测试；UL-94垂直燃烧试验依照UL94-09进行，标准样品尺寸125×12.5×3.2mm3；测试结果如表1所示。
图1为实施例1制备的炔基的聚氨酯的FT-IR谱图；
图2为实施例1制备的含炔基的聚氨酯的热失重曲线图，纵坐标为质量损失百分比；
图3为实施例1制备的含炔基的聚氨酯的热释放速率曲线图，其纵坐标表示热释放速率，单位为KW/m2；
图4为实施例1制备的含炔基的聚氨酯的总的热释放曲线图，其纵坐标表示总的热释放量，单位为MJ/m2。
表1含炔基的聚氨酯的UL-94垂直燃烧、极限氧指数和力学强度
具体实施方式
下面通过实施例对本发明作进一步说明，但实施例并不限制本发明的保护范围。
实施例1
制备MDI：PTMG：1,4-丁炔二醇的摩尔比例为2:1:1的含炔基的聚氨酯，称为PU211，PTMG数据分子量为2000；
原料为：MDI为50.0g，PTMG为200.0g，1,4-丁炔二醇为8.6g，
1)将200.0g PTMG在120℃高温的真空烘箱中，真空条件下除去水分2h；
2)将50.0g固体MDI加入到反应容器中，在50℃条件下使其融化；
3)将步骤1)得到的200.0g液态PTMG中加入步骤2)得到的50.0g液态MDI中，真空条件下搅拌，在80℃条件下进行加成反应，1h，解除真空；
4)将8.6g 1,4-丁炔二醇加入到步骤3)得到的产物中，搅拌，70℃条件下进行扩链反应24h，得到含炔基的聚氨酯TPU211。
上述步骤3和4的反应路线如下：
表1
Claims (9)
1.一种含炔基的聚氨酯，其特征在于：其结构式为：
其中Ar是或或中的任意一种；n为B的聚合度，
B为-CH2CH2CH2CH2O-，n＝10-45；
或B为-CH2CH2O-，n＝20-500；
或B为n＝10-70；
D是或或或中的任意一种；
x为聚合度，x＝1-10，y为聚合度，y＝2-15，z为聚合度，z＝2-15，a为聚合度，a＝20-90，b为聚合度，b＝35-150。
2.一种含炔基聚氨酯的制备方法，其特征在于步骤为：
1)将液态无水聚醚二醇与液态二异氰酸酯混合，搅拌，加热进行加成反应，加热温度为50-100℃，加热时间是1-15h；液态无水聚醚二醇与液态二异氰酸酯的摩尔比为0.1-1:1
2)将1,4-丁炔二醇加入步骤1)得到的产物，搅拌，加热进行缩聚反应，加热温度为60-150℃，加热时间是2-24h；1,4-丁炔二醇与步骤1)中液态无水聚醚二醇的摩尔比为0.1-1:1；
3)步骤2)反应结束后得到的产物为含炔基聚氨酯。
3.根据权利要求2所述的一种含炔基聚氨酯的制备方法，其特征在于：步骤1)中液态无水聚醚二醇为聚四氢呋喃醚二醇、聚乙二醇或聚环氧乙烷-四氢呋喃醚二醇中的一种。
4.根据权利要求3所述的一种含炔基聚氨酯的制备方法，其特征在于：聚四氢呋喃醚二醇的数均分子量为1000±50、1400±50、1800±50、2000±50或3000±100。
5.根据权利要求3所述的一种含炔基聚氨酯的制备方法，其特征在于：聚乙二醇的数均分子量为1000±50、1400±50、2000±200、4000±400和6000±500；8000±500、10000±1500或20000±1500。
6.根据权利要求3所述的一种含炔基聚氨酯的制备方法，其特征在于：聚环氧乙烷-四氢呋喃醚二醇的数均分子量为1800-6200。
7.根据权利要求2所述的一种含炔基聚氨酯的制备方法，其特征在于：步骤1)中液态二异氰酸酯为：4，4’-二苯基甲烷二异氰酸酯、甲苯-2,4-二异氰酸酯或甲苯-2,6-二异氰酸酯中的一种。
8.根据权利要求7所述的一种含炔基聚氨酯的制备方法，其特征在于：步骤1)中液态4，4’-二苯基甲烷二异氰酸酯的制备方法为：将固体4，4’-二苯基甲烷二异氰酸酯加入到反应容器中，加热使其融化；加热温度为30-100℃。
9.根据权利要求2所述的一种含炔基聚氨酯的制备方法，其特征在于：步骤1)中液态无水聚醚二醇的制备方法为：将聚醚二醇在高温的真空烘箱中，真空条件下除去水分；真空烘箱的温度为100-120℃，除水时间0.5-20h；真空度小于-0.02MPa。
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| CN110669203A (zh) * | 2019-09-30 | 2020-01-10 | 湖南大学 | 一种分子内多炔基聚氨酯及聚三唑固化体系 |
| CN110776616A (zh) * | 2019-10-26 | 2020-02-11 | 福建华夏蓝新材料科技有限公司 | 一种高效润湿水性异氰酸酯固化剂 |
| CN114989393A (zh) * | 2022-06-28 | 2022-09-02 | 岳阳凯门水性助剂有限公司 | 聚氨酯缔合型增稠剂及其制备方法和应用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110669203A (zh) * | 2019-09-30 | 2020-01-10 | 湖南大学 | 一种分子内多炔基聚氨酯及聚三唑固化体系 |
| CN110669203B (zh) * | 2019-09-30 | 2021-06-04 | 湖南大学 | 一种分子内多炔基聚氨酯及聚三唑固化体系 |
| CN110776616A (zh) * | 2019-10-26 | 2020-02-11 | 福建华夏蓝新材料科技有限公司 | 一种高效润湿水性异氰酸酯固化剂 |
| CN110776616B (zh) * | 2019-10-26 | 2021-06-22 | 福建华夏蓝新材料科技有限公司 | 一种高效润湿水性异氰酸酯固化剂 |
| CN114989393A (zh) * | 2022-06-28 | 2022-09-02 | 岳阳凯门水性助剂有限公司 | 聚氨酯缔合型增稠剂及其制备方法和应用 |
| CN114989393B (zh) * | 2022-06-28 | 2024-03-26 | 岳阳凯门水性助剂有限公司 | 聚氨酯缔合型增稠剂及其制备方法和应用 |
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