CN113861051B - 一种聚氨酯材料及其制备、回收与再生方法 - Google Patents

一种聚氨酯材料及其制备、回收与再生方法 Download PDF

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CN113861051B
CN113861051B CN202111049593.7A CN202111049593A CN113861051B CN 113861051 B CN113861051 B CN 113861051B CN 202111049593 A CN202111049593 A CN 202111049593A CN 113861051 B CN113861051 B CN 113861051B
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CN113861051A (zh
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白静
史子兴
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Shanghai Jiaotong University
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Abstract

本发明提出了一种聚氨酯材料及其制备、回收与再生方法，属于聚氨酯技术领域，将含羟基烯酮胺化合物、二元醇、二异氰酸酯及交联剂按照一定比例混合溶解在有机溶剂中，然后高温除去溶剂并反应成型。本发明通过制备含乙烯酮结构的小分子，与异氰酸酯构建动态反应键，添加到聚氨酯体系，使得聚氨酯具有动态可回收性能，相比于线性或交联结构，具有了二者的优点，在提高了耐溶剂性与力学性能的同时，保持了热塑性。这种方法原料易得、成本较低。得到的聚氨酯弹性体材料力学性能等提高的同时，没有损失热塑性，可再次加工使用。可广泛应用到日常生活和工业生产中。

Description

一种聚氨酯材料及其制备、回收与再生方法
技术领域
本发明涉及聚氨酯技术领域，具体涉及一种聚氨酯材料及其制备、回收与再生方法。
背景技术
聚氨酯弹性体性能介于塑料和橡胶之间，耐油、耐磨、耐低温、耐老化、硬度高、弹性好，作为各种应用中必不可少的一类重要聚合物也得到了广泛的探索。目前已经广泛应用于日常生活中的多个领域，如家居领域、建筑领域、日用品领域、交通领域、家电等领域。尽管PU具有很多优点，但传统设计的PU及其材料因其不可逆的化学键，使得其在自愈性、可再加工性和可回收性等方面存在缺点。大量的使用和消耗，也不利于环境保护，因此，近年来一直在对其回收利用和自愈性进行研究。
CN104558498B聚氨酯弹性体的制备方法公开了将A组份和B组份混合，浇注入模具中，脱模，常温硫化后，即得，该方法综合聚醚多元醇和聚酯多元醇产品的特点，使产品具有两者的优点，同时采用酯醚逐步聚合的方法使得到酯醚共混聚氨酯弹性体的途径简单。但是，该方法制得的聚氨酯弹性体很难回收重复利用，不利于可持续发展。
CN101134843A公开了一种高弹聚氨酯弹性体的制备方法，采用PTMG2000或PPG3000与BDO、催化剂、抗老化剂混合作为聚合物组分，预聚物组分中的异氰酸酯选择MDI、碳化二亚胺改性的MDI以及它们的混合物，制作的高弹弹性体硬度范围窄(邵A80±2)、回弹性能差。
发明内容
为了克服现有技术的不足，本发明的目的在于提供一种聚氨酯材料及其制备、回收与再生方法。该方法可以制备一种可回收利用的聚氨酯材料，并且可以通过向原有成熟合成路线和配方中添加适量功能化小分子而实现聚氨酯材料的回收及再生。普适性强、成本低、合成简单、原料成本低廉。
本发明先合成含羟基的乙烯酮分子，再按照一定比例加入到聚氨酯合成体系中替代二醇，合成聚氨酯材料。这种方法得到的聚氨酯材料，分子链上具有动态键，可以在高温下发生断裂，进而实现材料的回收与再生利用。同时可以通过调节羟基乙烯酮小分子的结构和加入的量，对材料的性能进行设计。进一步地，利用其高温下的解聚反应，还可以实现分子链的延长及其结构的再设计，对回收材料的性能进行设计和改进。
本发明的技术方案是这样实现的：
本发明提供一种含羟基烯酮胺结构化合物的制备方法，包括以下步骤：将β-二酮化合物与含有羟基与氨基的化合物按照一定摩尔比混合溶解在有机溶剂中，搅拌反应一定时间后除去溶剂。
作为本发明的进一步改进，所述β-二酮化合物为乙酰丙酮、乙酰乙酸乙酯、乙酰乙酸甲酯、硬脂酰苯甲酰甲烷、二苯甲酰基甲烷、六氟乙酰丙酮、苯甲酰三氟丙酮、1-苯基-1,3-丁二酮、二苯甲酰基甲烷、丙二酸二乙酯、乙酰乙酸叔丁醇酯、N,N-二甲基-3-氧代丁酰胺、N-甲基乙酰基乙酰胺中的至少一种。
作为本发明的进一步改进，所述含有羟基与氨基的化合物选自乙醇胺、5-氨基-1-戊醇、6-氨基-1-己醇、4-氨基-1-丁醇、3-氨基-1-丙醇、二甘醇胺中的至少一种。
作为本发明的进一步改进，所述有机溶剂为四氢呋喃、醇类、醚类、氯仿、二氯甲烷、二甲基亚砜、1，4-二氧六环、N,N’-二甲基甲酰胺、N,N’-二甲基乙酰胺、N-甲基-吡咯烷酮、苯、甲苯或二甲苯中的至少一种。
作为本发明的进一步改进，所述除去溶剂的方法选自旋转蒸发、过滤、减压蒸馏、重结晶中的至少一种。
本发明进一步保护一种上述的制备方法制得的含羟基烯酮胺结构化合物。
本发明进一步保护一种聚氨酯材料的制备方法，步骤如下：将上述含羟基烯酮胺化合物、二元醇、二异氰酸酯及交联剂按照一定比例混合溶解在有机溶剂中，然后高温除去溶剂并反应成型。
作为本发明的进一步改进，所述二元醇选自聚醚二元醇、聚四氢呋喃二元醇、聚己内酯二元醇、以及烷基二元醇中的至少一种。
作为本发明的进一步改进，所述二异氰酸酯选自4,4-二异氰酸酯二环己基甲烷、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、甲苯二异氰酸酯、4，4`-二苯基甲烷二异氰酸酯中的至少一种。
作为本发明的进一步改进，所述有机溶剂选自四氢呋喃、氯仿、二氯甲烷、二甲基亚砜、1，4-二氧六环、N,N’-二甲基甲酰胺、N,N’-二甲基乙酰胺、N-甲基-吡咯烷酮、苯、甲苯或二甲苯中的至少一种。
作为本发明的进一步改进，所述交联剂为三羟基化合物或者三异氰酸酯基化合物，选自甘油、三乙醇胺、三苯基甲烷三异氰酸酯、1,3,5-三(6-异氰酰基己基)-1,3,5-三嗪-2,4,6(1h,3h,5h)-三酮中的至少一种。
作为本发明的进一步改进，所述含羟基烯酮胺化合物：二元醇：二异氰酸酯：交联剂的摩尔比x:y:z:m满足3m＝2(x+y-z)或3m＝2(z-x-y)。
作为本发明的进一步改进，所述高温除去溶剂的温度为40-100℃。
本发明进一步保护一种上述的制备方法制得的聚氨酯材料。
本发明进一步保护一种上述聚氨酯材料的回收与再塑成型方法，包括以下方法：
将上述聚氨酯材料碎片在高温条件下热压，实现再次成型加工；
或者，
将上述聚氨酯材料溶于溶剂中，高温使其发生逆反应，得到均一溶液，将所述溶液烘干反应得到聚氨酯膜。
作为本发明的进一步改进，所述热压条件为温度高于140℃，压力大于5MPa。
作为本发明的进一步改进，所述高温使其发生逆反应的温度为高于140℃。
作为本发明的进一步改进，所述烘干反应温度为40-100℃。
本发明进一步保护一种上述聚氨酯材料的再生方法，包括以下步骤：
(1)将上述聚氨酯材料于溶剂中，并同时加入含有羟基与氨基的化合物，高温解交联，
(2)向步骤(1)得到的溶液中加入二异氰酸酯，然后高温除去溶剂并反应成型。
作为本发明的进一步改进，所述含有羟基与氨基的化合物选自乙醇胺、5-氨基-1-戊醇、6-氨基-1-己醇、4-氨基-1-丁醇、3-氨基-1-丙醇、二甘醇胺中的至少一种。
作为本发明的进一步改进，所述高温解交联温度为高于140℃。
作为本发明的进一步改进，所述溶剂选自二甲基亚砜、N,N’-二甲基甲酰胺、N,N’-二甲基乙酰胺、N-甲基-吡咯烷酮其中的至少一种。
作为本发明的进一步改进，所述二异氰酸酯选自4,4-二异氰酸酯二环己基甲烷、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、甲苯二异氰酸酯、4，4`-二苯基甲烷二异氰酸酯中的至少一种。
作为本发明的进一步改进，所述高温除去溶剂并反应成型的温度为40-100℃。
本发明具有如下有益效果：本发明通过制备含乙烯酮结构的小分子，与异氰酸酯构建动态反应键，添加到聚氨酯体系，使得聚氨酯具有动态可回收性能，相比于线性或交联结构，具有了二者的优点，在提高了耐溶剂性与力学性能的同时，保持了热塑性。这种方法原料易得、成本较低。得到的聚氨酯弹性体材料力学性能等提高的同时，没有损失热塑性，可再次加工使用。可广泛应用到日常生活和工业生产中。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。
图1为实施例1中的制备的4-((2-羟基乙基)氨基)戊-3-烯-2-酮的核磁图；
图2为实施例2中的制备的3-((2-羟乙基)氨基)丁-2-烯酸乙酯的核磁图；
图3为实施例3-5中不同4-((2-羟基乙基)氨基)戊-3-烯-2-酮含量的聚氨酯应力-应变曲线图；
图4为实施例6-10制得的再生的新的聚氨酯的应力-应变曲线图。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
将1.001克乙酰丙酮和0.61克乙醇胺溶解在5mL四氢呋喃中，45℃反应12小时。旋蒸除去溶剂，真空烘箱40℃干燥12小时，制得的4-((2-羟基乙基)氨基)戊-3-烯-2-酮。图1是制得的4-((2-羟基乙基)氨基)戊-3-烯-2-酮的核磁图。
实施例2
将1.3014克乙酰乙酸乙酯和0.61克乙醇胺溶解在5mL乙醇中，45℃反应12小时。旋蒸除去溶剂，真空烘箱40℃干燥12小时，制得3-((2-羟乙基)氨基)丁-2-烯酸乙酯。图2是制得的3-((2-羟乙基)氨基)丁-2-烯酸乙酯的核磁图。
实施例3
将PTMEG 4克、IPDI 1.02克和三乙醇胺0.03克溶解在20ml四氢呋喃中，50℃加热24小时，100℃除去溶剂，反应成型。
实施例4
将PTMEG 2克、实施例1制得的4-((2-羟基乙基)氨基)戊-3-烯-2-酮(含量为实施例3中PTMEG总量的50％)0.2864克、IPDI 1.02克和三乙醇胺0.03克溶解在20ml四氢呋喃中，50℃加热24小时，100℃除去溶剂，反应成型。
实施例5
将PTMEG 3克、实施例1制得的4-((2-羟基乙基)氨基)戊-3-烯-2-酮(含量为实施例3中PTMEG总量的25％)0.1432克、IPDI 1.02克和三乙醇胺0.03克溶解在20ml四氢呋喃中，50℃加热24小时，100℃除去溶剂，反应成型。
实施例6
将PTMEG 3.4克、实施例1制得的4-((2-羟基乙基)氨基)戊-3-烯-2-酮(含量为实施例3中PTMEG总量的15％)0.086克、IPDI 1.02克和三乙醇胺0.03克溶解在20ml四氢呋喃中，50℃加热24小时，100℃除去溶剂，反应成型。
图3是实施例3-6中不同4-((2-羟基乙基)氨基)戊-3-烯-2-酮含量的聚氨酯应力-应变曲线图。
实施例7
将2克实施例4中制得的聚氨酯材料和0.3克乙醇胺加入到20ml DMAc中，160℃加热20分钟，得到均一溶液，将上述均一溶液与0.826克HDI进行反应，100℃除去溶剂，反应成型，得到新的聚氨酯。
实施例8
将2克实施例4中制得的聚氨酯材料和0.3克乙醇胺加入到20ml DMAc中，160℃加热20分钟，得到均一溶液，将上述均一溶液与1.229克MDI进行反应，100℃除去溶剂，反应成型，得到新的聚氨酯。
实施例9
将2克实施例4中制得的聚氨酯材料和0.3克乙醇胺加入到20ml DMAc中，160℃加热20分钟，得到均一溶液，将上述均一溶液与0.855克TDI进行反应，100℃除去溶剂，反应成型，得到新的聚氨酯。
实施例10
将2克实施例4中制得的聚氨酯材料和0.3克乙醇胺加入到20ml DMAc中，160℃加热20分钟，得到均一溶液，将上述均一溶液与1.092克IPDI进行反应，100℃除去溶剂，反应成型，得到新的聚氨酯。
实施例11
将2克实施例4中制得的聚氨酯材料和0.3克乙醇胺加入到20ml DMAc中，160℃加热20分钟，得到均一溶液，将上述均一溶液与1.289克HMDI进行反应，100℃除去溶剂，反应成型，得到新的聚氨酯。
图4为实施例7-11制得的回收后的新的聚氨酯的应力-应变曲线图。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (7)

1.一种聚氨酯材料的回收与再生方法，其特征在于，包括以下步骤：
(1)将所述聚氨酯材料溶于溶剂中，并同时加入含有羟基与氨基的化合物，高温解交联；
(2)将步骤(1)得到的溶液中加入二异氰酸酯，然后高温除去溶剂并反应成型；
所述高温解交联温度为高于140℃；
其中，所述聚氨酯材料的制备方法，步骤如下：将含羟基烯酮胺结构 化合物、二元醇、二异氰酸酯及交联剂按照一定比例混合溶解在有机溶剂中，然后高温除去溶剂并反应成型；
所述含羟基烯酮胺结构化合物的制备方法，包括以下步骤：将β-二酮化合物与含有羟基与氨基的化合物按照一定摩尔比混合溶解在有机溶剂中，搅拌反应一定时间后除去溶剂；
所述β-二酮化合物为乙酰丙酮、乙酰乙酸乙酯、乙酰乙酸甲酯、硬脂酰苯甲酰甲烷、二苯甲酰基甲烷、六氟乙酰丙酮、苯甲酰三氟丙酮、1-苯基-1,3-丁二酮、二苯甲酰基甲烷、丙二酸二乙酯、乙酰乙酸叔丁醇酯、N,N-二甲基-3-氧代丁酰胺、N-甲基乙酰基乙酰胺中的至少一种；
所述含有羟基与氨基的化合物选自乙醇胺、5-氨基-1-戊醇、6-氨基-1-己醇、4-氨基-1-丁醇、3-氨基-1-丙醇、二甘醇胺中的至少一种；
所述除去溶剂的方法选自旋转蒸发、过滤、减压蒸馏、重结晶中的至少一种。
2.根据权利要求1所述聚氨酯材料的回收与再生方法，其特征在于，所述二元醇选自聚醚二元醇、聚四氢呋喃二元醇、聚己内酯二元醇、以及烷基二元醇中的至少一种。
3.根据权利要求1所述聚氨酯材料的回收与再生方法，其特征在于，所述二异氰酸酯选自4,4-二异氰酸酯二环己基甲烷、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、甲苯二异氰酸酯、4，4`-二苯基甲烷二异氰酸酯中的至少一种。
4.根据权利要求1所述聚氨酯材料的回收与再生方法，其特征在于，所述聚氨酯材料的回收与再生方法的制备方法中的所述溶剂选自二甲基亚砜、N,N’-二甲基甲酰胺、N,N’-二甲基乙酰胺、N-甲基-吡咯烷酮其中的至少一种；所述聚氨酯材料的制备方法中所述有机溶剂选自四氢呋喃、氯仿、二氯甲烷、二甲基亚砜、1，4-二氧六环、N,N’-二甲基甲酰胺、N,N’-二甲基乙酰胺、N-甲基-吡咯烷酮、苯、甲苯或二甲苯中的至少一种；所述含羟基烯酮胺结构化合物的制备方法中所述有机溶剂为四氢呋喃、醇类、醚类、氯仿、二氯甲烷、二甲基亚砜、1，4-二氧六环、N,N’-二甲基甲酰胺、N,N’-二甲基乙酰胺、N-甲基-吡咯烷酮、苯、甲苯或二甲苯中的至少一种。
5.根据权利要求1所述聚氨酯材料的回收与再生方法，其特征在于，所述交联剂为三羟基化合物或者三异氰酸酯基化合物，选自甘油、三乙醇胺、三苯基甲烷三异氰酸酯、1,3,5-三(6-异氰酰基己基)-1,3,5-三嗪-2,4,6(1h,3h,5h)-三酮中的至少一种。
6.根据权利要求1所述聚氨酯材料的回收与再生方法，其特征在于，所述含羟基烯酮胺结构 化合物：二元醇：二异氰酸酯：交联剂的摩尔比x:y:z:m满足3m＝2(x+y-z)或3m＝2(z-x-y)。
7.根据权利要求1所述聚氨酯材料的回收与再生方法，其特征在于，所述高温除去溶剂的温度为40-100℃。
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