CN116396188B - 一种聚氨酯的降解方法 - Google Patents
一种聚氨酯的降解方法 Download PDFInfo
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Abstract
本发明公开了一种新型的聚氨酯降解方法,其是以甲醇同时作为溶剂和醇解剂,碱性离子液体为催化剂,在60‑80℃条件下进行聚酯型聚氨酯的降解,降解产物经过滤分离后,所得滤液经蒸馏、萃取等操作可分别回收甲醇、催化剂以及醇解产物,而过滤所得固体产物主要为异氰酸酯及其衍生物。本发明采用甲醇为溶剂和醇解剂,其价格低廉且沸点低,不仅有利于降低聚氨酯醇解反应的原料成本,更关键的是,其无需添加其它物质,可以实现醇解剂和醇解产物的分离提纯,提高醇解产物的经济价值,因而具有广阔的应用前景。
Description
技术领域
本发明属于聚氨酯降解技术领域,具体涉及一种以甲醇为醇解剂、碱性离子液体为催化剂降解聚酯型聚氨酯弹性体的方法。
背景技术
聚氨酯,全称聚氨基甲酸酯(PU),是由异氰酸酯(-NCO)和多元醇(-OH)发生缩聚反应生成的分子主链上含有重复氨基甲酸酯基团(-NHCOO-)的高聚物统称。聚氨酯材料因其具有易加工、物理性能优异、耐老化和耐腐蚀等优点受到市场的广泛欢迎,现已成为使用最多的高分子材料之一。随着聚氨酯生产消费规模的扩展,废旧聚氨酯的回收利用也越来越受到人们的重视。
目前已有的聚氨酯降解方法可分为水解法、碱解法、胺解法、加氢裂解法和醇解法,其中醇解法研究最多且已实现规模化生产。现有的聚氨酯醇解工艺基本上使用多元醇(乙二醇、丁二醇、甘油等)为醇解剂,反应中还需要添加助醇解剂(乙醇胺、三乙胺等含胺类物质),且反应结束后醇解产物和醇解剂混合在一起,成分复杂,难以分离,胺含量高,再利用只能用于制备低端的聚氨酯产品。
相比之下,甲醇价格低廉、活性高,作为溶剂和醇解剂可以使聚氨酯醇解反应在相对低温下高效进行;且甲醇沸点低,易于蒸馏分离,最关键的是,甲醇只含有一个官能团,完成醇解反应后自动封闭,不会再次反应生成结构复杂的物质。
离子液体具有结构稳定、蒸汽压低、安全环保等特性,以碱性离子液体为催化剂仅需少量添加便可使醇解反应高效进行,无需再添加任何助醇解剂,不会污染醇解产物,且碱性离子液体与醇解产物不互溶,反应结束后催化剂通过简单处理即可实现再生。
发明内容
现有聚氨酯降解回收工艺往往存在能耗高、设备投资高、降解产物再利用价值低等问题,为了解决这些问题,本发明提出以碱性离子液体为聚氨酯醇解催化剂的新降解方法,其可以在相对温和的反应条件下实现聚氨酯废料的高效醇解,且醇解产物结构明确、分离方便、纯度高,催化剂经简单处理即可实现重复使用。
为实现上述目的,本发明采用如下技术方案:
一种聚氨酯的降解方法,其是以甲醇为溶剂和醇解剂,碱性离子液体为催化剂,在不添加其他物质的条件下,对聚酯型聚氨酯进行催化降解,然后经过滤分离,所得固体产物为异氰酸酯及其衍生物,所得滤液经蒸馏、萃取后分别回收甲醇、催化剂和醇解产物。
进一步地,所述甲醇的用量为聚酯型聚氨酯质量的10~15倍。
进一步地,所述碱性离子液体的用量为聚酯型聚氨酯质量的20%~50%。
进一步地,所述碱性离子液体为式(I)、式(II)中的任意一种:
,其中,n=1、2、3。
进一步地,所述催化降解的温度为60℃~80℃,时间为1h~3h。
如图1所示,在碱性离子液体的作用下,聚氨酯分子上的N-H键、CO-O酯键以及甲醇分子中的O-H键发生选择性断裂,促使聚氨酯醇解为异氰酸酯、己二酸二甲酯及1,4-丁二醇。
已知甲醇沸点为64 ℃、己二酸二甲酯沸点为228 ℃、1,4-丁二醇沸点为228 ℃,从沸点数据可看出,经简单蒸馏即可分离出甲醇;己二酸二甲酯不溶于水,而1,4-丁二醇与离子液体易溶于水,使用水为萃取剂洗去离子液体和1,4-丁二醇可以得到高纯度的己二酸二甲酯;而萃取液减压蒸馏除水后,利用1,4-丁二醇可溶于乙酸乙酯而离子液体不溶于乙酸乙酯的特性,采用乙酸乙酯萃取,并经减压蒸馏,可以回收离子液体并得到高纯度的1,4-丁二醇。所得己二酸二甲酯可作为精细化工品,异氰酸酯和丁二醇可作为原料制备高品质的聚氨酯产品,回收的离子液体催化剂可以用于下一次反应。
本发明的创新点如下:
(1)本发明使用甲醇同时作为溶剂和醇解剂,其价格低廉、反应活性高、沸点低,可实现温和条件下聚氨酯的高效醇解,且醇解产物成分简单,易于分离提纯,所用甲醇还可回收再利用,解决了传统聚氨酯降解工艺难度大、成本高、产物再利用价值低等问题。
(2)本发明使用碱性离子液体作为催化剂,其催化机理为化学键的选择性断裂,因而仅添加少量便可高效催化聚氨酯的醇解。同时,碱性离子液体与醇解产物不互溶,极大方便了醇解产物的分离提纯以及催化剂的回收再利用。
(4)本发明无需使用二乙醇胺、乙二胺等作为助醇解剂或加入其他添加剂,不仅降低了原料成本,也提升了醇解产物的质量,避免胺值过高。
(5)本发明获得的醇解产物为异氰酸酯、己二酸二甲酯、1,4-丁二醇,其保留了珍贵的异氰酸酯结构,经济价值高;而己二酸二甲酯则是精细化工产品。
综上所述,本发明以更低的原料成本,实现了聚氨酯更高价值的醇解回收利用,因此具有良好的应用前景。
附图说明
图1为本发明实现聚氨酯降解的原理图。
具体实施方式
一种聚氨酯的降解方法,其步骤如下:
1)以甲醇为溶剂和醇解剂,碱性离子液体为催化剂,在不添加其他物质的条件下,以聚酯型聚氨酯为底物,于60℃~80℃催化降解1h~3h;此时反应体系仅为固液两相,聚酯型聚氨酯为固相,碱性离子液体溶于甲醇为液相;反应温度超过甲醇的沸点时,使用氮气加压,保证甲醇呈液态;
2)降解反应结束后进行过滤分离;分离出的固体产物为异氰酸酯()及其衍生物,分离出的滤液经蒸馏回收甲醇,得到分离的上下两相液体,上层液体用乙酸乙酯、乙腈、环己烷等萃取回收,获得醇解产物己二酸二甲酯(/>)、1,4-丁二醇(/>),下层液体经去离子水洗出、脱水,获得与醇解产物不相溶的碱性离子液体,可重复利用。
其中,甲醇的用量为聚酯型聚氨酯质量的10~15倍。碱性离子液体的用量为聚酯型聚氨酯质量的20%~50%。
所述碱性离子液体为式(I)、式(II)中的任意一种:
,其中,n=1、2、3。
以下通过具体实施例进一步详细说明本发明的实施过程和产生的有益效果,旨在有助于更好的理解本发明的实质和特点,但不应作为是对本发明实施范围的限定。下述实施例中所使用的实验方法均为常规方法;所用的材料、试剂等均可从商业途径可购得。
实施例1咪唑型碱性离子液体[C4mim]OH的制备:
(1)将N-甲基咪唑(8.2 g,0.1mol)、1-氯丁烷(18.6 g,0.2 mol)依次加入到单口烧瓶中,装上冷凝管并通水,保持反应体系密封,100 ℃冷凝回流反应24 h,可以观察到反应体系由无色变为淡黄色;结束反应,用乙酸乙酯洗涤、减压旋蒸三次以上以除去未反应的原料,然后经100 ℃真空干燥12 h,得到15.8g离子液体[C4mim]Cl,收率90 %。
(2)准确取离子液体[C4mim]Cl(8.7g,0.05mol)溶于100mL甲醇,采用交换量为0.1mol的强碱性氯型离子离子交换树脂进行离子交换,直至用硝酸酸化的硝酸银溶液检测没有沉淀产生,然后减压蒸馏脱去甲醇,得到红色透明状液体,即为碱性离子液体[C4mim]OH。
通过将所用1-氯丁烷替换为等摩尔量的1-氯戊烷、1-氯己烷,可制备获得咪唑型碱性离子液体[C5mim]OH、[C6mim]OH。
实施例2哌啶型碱性离子液体[C4mpip]OH的制备:
(1)将N-甲基哌啶(9.9 g,0.1mol)、1-氯丁烷(18.6 g,0.2 mol)依次加入到单口烧瓶中,装上冷凝管并通水,保持反应体系密封,100 ℃冷凝回流反应24 h;结束反应后产物呈黄色透明液体状,使用乙酸乙酯洗涤、减压旋蒸三次以上以除去未反应的原料,然后经100 ℃真空干燥12 h,得到17.3 g离子液体[C4mpip]OH,收率90 %。
(2)准确取离子液体[C4mpip]OH(9.6 g,0.05mol)溶于100mL甲醇,采用交换量为0.1mol的强碱性氯型离子离子交换树脂进行离子交换,直至用硝酸酸化的硝酸银溶液检测没有沉淀产生,然后减压蒸馏脱去甲醇,得到红色透明状液体,即为碱性离子液体[C4mpip]OH。
通过将所用1-氯丁烷替换为等摩尔量的1-氯戊烷、1-氯己烷,可制备获得哌啶型碱性离子液体[C5mpip]OH、[C6mpip]OH。
应用实施例离子液体催化聚氨酯醇解反应:
取离子液体0.50 g、聚氨酯1.00 g、甲醇10.0 g加入压力反应釜中,氮气充压1.0MPa,80 ℃保温反应3 h。反应结束后将反应釜置于冷水中降温,待其冷却至室温后打开压力釜,观察到反应体系呈悬浊液;过滤得到异氰酸酯和淡黄色透明反应液,反应液于50 ℃减压脱甲醇,得到分离的上下两相液体,上层液体即为己二酸二甲酯,用乙酸乙酯萃取提纯;而离子液体催化剂则在下层液体中,用去离子水洗出、脱水后即可再次使用。
表1为不同碳链制备的碱性离子液体在80 ℃下降解聚氨酯3 h所得己二酸二甲酯(DMA)收率的对比情况。
表1
从表1的数据可看出,相同反应条件下,碳链越短,碱性离子液体的催化性能越强,且碳链相同时,咪唑型离子液体[Bmim]OH的催化性能优于哌啶型离子液体[Cmpip]OH。
表2为碱性离子液体[Bmim]OH与其它常用离子液体在80 ℃下降解聚氨酯3 h所得己二酸二甲酯(DMA)收率的对比情况。
表2
从表2数据可看出,相同反应条件下,碱性离子液体的催化性能优于酸性离子液体,而中性离子液体不能催化聚氨酯醇解。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (4)
1.一种聚氨酯的降解方法,其特征在于,以甲醇为溶剂和醇解剂,碱性离子液体为催化剂,对聚酯型聚氨酯进行催化降解,然后经过滤分离,所得固体产物为异氰酸酯及其衍生物,所得滤液经蒸馏、萃取后分别回收甲醇、催化剂和醇解产物;
所述碱性离子液体为式(I)、式(II)中的任意一种:
,其中,n=1、2、3。
2.根据权利要求1所述的聚氨酯的降解方法,其特征在于,所述甲醇的用量为聚酯型聚氨酯质量的10~15倍。
3.根据权利要求1所述的聚氨酯的降解方法,其特征在于,所述碱性离子液体的用量为聚酯型聚氨酯质量的20%~50%。
4.根据权利要求1所述的聚氨酯的降解方法,其特征在于,所述催化降解的温度为60℃~80℃,时间为1h~3h。
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