CN105289333A - 包含氨基酸活动载体的膜 - Google Patents

包含氨基酸活动载体的膜 Download PDF

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CN105289333A
CN105289333A CN201510661874.6A CN201510661874A CN105289333A CN 105289333 A CN105289333 A CN 105289333A CN 201510661874 A CN201510661874 A CN 201510661874A CN 105289333 A CN105289333 A CN 105289333A
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heterocyclic amino
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G·W·伊格
E·J·普雷斯曼
S·M·米勒
C·奥尔森
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General Electric Co
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Abstract

一方面，本发明提供可用于制备气体分离膜的可固化组合物。可固化组合物包含聚乙烯醇、脂族聚胺、聚缩水甘油醚和C2至C4杂环氨基酸的盐。另一方面，本发明提供一种组合物，所述组合物包括包含衍生自聚缩水甘油醚的结构单元的交联聚乙烯醇、聚胺和C2至C4杂环氨基酸的盐。组合物可用于制备气体分离膜，其中盐形式的C2至C4杂环氨基酸作为二氧化碳的活动载体。

Description

包含氨基酸活动载体的膜
技术领域
本发明涉及一种可固化组合物，所述可固化组合物包含聚乙烯醇和杂环氨基酸的盐。本公开还涉及一种由经固化组合物制成的制品，所述经固化组合物包含聚乙烯醇和杂环氨基酸的盐.另外，本公开涉及制备经固化组合物和制品的方法。
背景技术
由于能量成本增加，分离气体的膜技术在减小环境影响和工业过程成本中起重要作用。气体分离膜提供超过其他气体分离技术的许多益处.常规技术，如空气低温蒸馏、冷凝以从气体混合物除去可冷凝的有机蒸气以及胺吸收以从天然气除去酸性气体(如二氧化碳)，需要在要分离的气体混合物中有气至液相变化.相变给分离成本增加显著能量成本。另一方面，膜气体分离不需要此相变.
另外，气体分离膜单元小于其他类型装置，如胺汽提装置，因此具有相对较小足迹。小足迹在环境(如海上气处理平台)中重要。在膜系统中缺少机械复杂性是另一个优点。
目前，气体分离膜在工业上广泛用于氢分离，例如在氨装置中氢/氮分离和在石油化工应用中氢/烃分离.其他工业气体分离技术包括从空气分离氮，从天然气除去CO2和水，和从空气和/或氮流除去有机蒸气。用于气体分离的最广泛使用的膜材料为聚合物材料，尤其用作膜的材料，因为其成本相对较低，并且处理容易.
气体分离膜过程的效率在很大程度上由膜的传输性质(如透过性)和对混合物中具体气体的选择性决定。膜应理想显示高选择性和高透过性。然而，对于大多数膜，选择性和透过性成相反关系.因此，随着选择性增加，透过性降低，反之亦然.
刚性聚合物材料可用于能够从天然气流除去CO2的膜，并且在某些情况下由于高CO2扩散选择性已显示高选择性。很多此类膜的关键限制是，在高分压CO2或高级烃污染物存在下，膜的分离性质可退化到不可用的水平。另外，少量存在于天然气中的高级脂族烃和芳族烃高度溶于所用聚合物膜材料，并且可浓缩于聚合物膜材料并使聚合物膜材料塑化，从而降低膜的扩散选择性.由于膜分离性质可能受经历气体分离过程的主要气体中相对低含量杂质存在的负面影响，因此可能需要严格和耗费巨大的预处理。
因此，需要进一步改善气体分离膜的膜性能和性质，和构成它们的相应聚合物组合物.具体地讲，需要进一步改善，以提供容易构成为膜，在气体分离条件下显示优良性能稳定性，并且对一种或多种工业相关气体显示高选择性和高透过性的聚合物组合物.本发明提供这些和与气体分离相关的其他挑战的另外解决方法.
发明内容
一方面，本发明提供一种可固化组合物，所述可固化组合物包含聚乙烯醇、脂族聚胺、聚缩水甘油醚和C2至C4杂环氨基酸的盐.
另一方面，本发明提供一种经固化组合物，所述经固化组合物包含衍生自聚乙烯醇的结构单元、脂族聚胺、衍生自聚缩水甘油醚的结构单元和C2至C4杂环氨基酸的盐.
另一方面，本发明提供一种经固化组合物，所述经固化组合物包含衍生自聚乙烯醇的结构单元、聚烯丙胺、衍生自乙二醇二缩水甘油醚的结构单元和脯氨酸的盐。
通过参考以下详细说明，本发明的这些和其他特征、方面和优点可变得更容易理解。
具体实施方式
在以下说明书和权利要求书中引用了一些词语，这些词语限定具有以下含义。
除非本文另外清楚地指明，单数形式“一”和“所述”包括复数讨论对象.
“任选”或“任选地”意味随后描述的事件或情况可发生或可不发生，并且此描述包括事件发生的情况和不发生的情况.
本文所用术语“溶剂”可以指单一溶剂或溶剂的混合物。
如在整个说明书和权利要求中所用，可用近似语言修饰任何定量表达，这些表达可容许改变，而不引起所涉及的基本功能的改变.因此，由词语例如“约”修饰的数值不限于所指定的精确值。在某些情况下，近似语言对于测定数值可相当于仪器的精确度.类似地，“不含”可与一个项目结合使用，可包括非基本量或微量，尽管仍可认为是不含所修饰项目。
如前提到，在一个实施方案中，本发明提供一种经固化组合物，所述经固化组合物包含衍生自聚乙烯醇的结构单元、脂族聚胺、衍生自聚缩水甘油醚的结构单元和C2-C4杂环氨基酸的盐.
在一个实施方案中，聚乙烯醇具有约1,000克/摩尔至约2,000,000克/摩尔的重均分子量.在另一个实施方案中，聚乙烯醇具有约30,000克/摩尔至约200,000克/摩尔的重均分子量.在另一个实施方案中，聚乙烯醇具有约50,000克/摩尔至约175,000克/摩尔的重均分子量.
在一个实施方案中，聚乙烯醇以基于组合物总重量约10％重量至约70％重量存在。在另一个实施方案中，聚乙烯醇以基于组合物总重量约35％重量至约50％重量存在.
在一个实施方案中，聚乙烯醇可以为聚乙烯醇与其他聚合物的混合物或共聚物.本文所用术语“共聚物”包括嵌段共聚物、无规共聚物和接枝共聚物.形成所用聚乙烯醇的混合物或共聚物的聚合物的非限制实例包括乙烯基聚合物、聚环氧烷(如聚环氧乙烷)、丙烯酸类聚合物(如聚丙烯酰胺)、乙烯胺等。乙烯基聚合物和共聚物的实例包括但不限于聚乙烯胺、聚烯丙胺、聚二烯丙基胺、聚甲基二烯丙基胺、聚二甲基二烯丙基胺、聚甲基烯丙基胺、聚乙烯基乙酰胺、聚乙酸乙烯酯、聚(3-乙烯基苯胺)、聚(4-乙烯基苯胺)、聚(3-乙烯基苯甲酸)、聚(4-乙烯基苯甲酸)、聚乙烯基硼酸频哪醇酯、聚乙烯基硼酸二烷基酯、聚乙烯基己内酰胺、聚乙烯基环己醇、聚氧化乙烯基环己烷、聚(2-乙烯基-1，3-二氧杂环戊烷)、聚(4-乙烯基-1，3-二氧杂环戊烷)、聚碳酸亚乙烯酯、聚硫代碳酸亚乙烯酯、聚二硫代碳酸亚乙烯酯、聚三硫代碳酸亚乙烯酯、聚(N-乙烯基甲酰胺)、聚(1-乙烯基咪唑)、聚乙烯基异氰酸酯、聚2-丙烯基异氰酸酯、聚(乙烯基环氧乙烷)、聚(乙烯基苯基硼酸)、聚乙烯基膦酸、聚(1-乙烯基-2-吡咯烷酮)、聚乙烯基磺酸、聚乙烯基苯甲醛、聚乙烯基唑啉及衍生自一种或多种前述聚合物的水解产物.
本发明提供的可固化组合物包含脂族聚胺，所述脂族聚胺可在跨含固化形式的制剂的膜的CO2传输中作为固定载体.在一个实施方案中，聚胺包含仲胺基.聚胺可包括氨基聚糖(如透明质酸盐(hylaronate))、软骨素、4-硫酸软骨素、6-硫酸软骨素、皮肤素、硫酸皮肤素、甲壳质、脱乙酰壳多糖、胞壁质(murien)、N-乙酰基乳糖胺、壳二糖、角质素、硫酸角质素、肝素、硫酸乙酰肝素等。聚胺的非限制实例包括聚乙烯胺；聚烯丙胺，如聚二烯丙基胺、聚二甲基二烯丙基胺、聚三烯丙基胺和聚甲基烯丙基胺；聚乙烯基甲酰胺；和聚乙烯基乙酰胺。在一个实施方案中，聚胺包括至少一种选自聚烯丙胺、聚乙烯胺、聚二烯丙基胺、乙烯胺-乙烯醇共聚物、聚乙烯亚胺和乙亚胺-环氧乙烷共聚物的物质。在一个实施方案中，聚胺为聚烯丙胺。
在一个实施方案中，聚胺以基于组合物总重量约1％重量至约50％重量存在.在另一个实施方案中，聚胺以基于组合物总重量约5％重量至约20％重量存在。
本发明提供的可固化组合物包含聚缩水甘油醚。在一个实施方案中，聚缩水甘油醚包括至少一种选自甘油二缩水甘油醚、甘油三缩水甘油醚、三羟甲基丙烷三缩水甘油醚、三羟甲基丙烷二缩水甘油醚、乙二醇二缩水甘油醚、双酚-A二缩水甘油醚、二乙二醇二缩水甘油醚、三乙二醇二缩水甘油醚和丙二醇二缩水甘油醚的组分.在一个实施方案中，聚缩水甘油醚为二缩水甘油醚.在另一个实施方案中，二缩水甘油醚为乙二醇二缩水甘油醚。
在一个实施方案中，聚缩水甘油醚以基于组合物总重量约5％重量至约40％重量存在.在另一个实施方案中，聚缩水甘油醚以基于组合物总重量约10％重量至约20％重量存在.
在本发明提供的经固化组合物中，聚乙烯醇由聚缩水甘油醚交联.在此实施方案中，经交联的聚乙烯醇包含衍生自聚缩水甘油醚的结构单元。
如上提到，本发明提供的可固化组合物包含C2至C4杂环氨基酸的盐。在另一个实施方案中，杂环氨基酸的盐包含至少一种选自锂、钾、钠、钙和镁的金属阳离子.在另一个实施方案中，金属阳离子包括钾.
C2至C4杂环氨基酸的非限制实例包括L-脯氨酸、D-脯氨酸、外消旋脯氨酸、2-吡咯甲酸、2-吡咯烷甲酸、3-吡咯烷甲酸、2-氮杂环丁烷甲酸、3-氮杂环丁烷甲酸、2-氮丙啶甲酸.在一个实施方案中，C2至C4杂环氨基酸的盐为L-脯氨酸.
在一个实施方案中，杂环氨基酸的盐以基于组合物总重量约10％重量至约50％重量存在。在另一个实施方案中，杂环氨基酸的盐以基于组合物总重量约15％重量至约30％重量存在。
在一个实施方案中，可固化组合物基本不含甲醛或甲醛相当物。术语“甲醛相当物”是指容易转化成甲醛的化合物(如二甲氧基甲烷、二乙酰氧基甲烷、二氧杂环戊烷等)和甲醛与聚胺的产物(如聚缩醛胺).
在另一个实施方案中，本发明提供一种经固化组合物，所述经固化组合物包含交联聚乙烯醇、脂族聚胺、衍生自聚缩水甘油醚的结构单元和杂环氨基酸的盐.本文试验部分提供制备本发明的经固化组合物的充分指导。本领域的技术人员应了解，本文试验部分中说明的实施方案公开在交联聚乙烯醇与膜的其他组分、脂族聚胺和C2至C4杂环氨基酸的盐配制之前聚乙烯醇组分与聚缩水甘油醚的交联。本文提供的可固化组合物代表其中在与脂族聚胺、聚缩水甘油醚和C2至C4杂环氨基酸的盐配制之前聚乙烯醇不与聚缩水甘油醚交联的变型.这些“可固化组合物”在聚乙烯醇和/或脂族聚胺上包含一种或多种在未固化制剂暴露于一种或多种热能、电磁辐射或化学固化剂时与聚缩水甘油醚反应的反应基。
在一个实施方案中，本发明提供一种由经固化组合物制成的制品，所述经固化组合物包含交联聚乙烯醇、脂族聚胺、衍生自聚缩水甘油醚的结构单元和杂环氨基酸的盐。在一个实施方案中，制品为膜。本发明的膜可根据所需用途制成任何所需形状，如中空的纤维、管、薄膜、片等.可通过制造膜的已知技术制造膜，如刀流延、浸流延等。
在一个实施方案中，本发明的膜可用作气体分离膜.在另一个实施方案中，将本发明的膜在多孔载体上布置为薄膜.多孔载体包括但不限于玻璃、陶瓷和多孔有机聚合物(如多孔聚醚砜和多孔聚四氟乙烯).可用作多孔载体的适合多孔有机聚合物的实例包括聚砜、聚醚砜、聚苯甲腈、聚酰胺砜、聚酰胺苯甲腈、聚硫醚砜、聚苯并咪唑、聚酰亚胺、聚酰胺酰亚胺、聚醚酰亚胺、聚亚苯基、聚苯醚、聚偏二氟乙烯、聚四氟乙烯、乙烯-四氟乙烯共聚物、四氟乙烯-异丙基·乙烯基醚共聚物、聚丙烯腈、多糖、纤维素和纤维素酯和醚。在一个实施方案中，本发明提供一种膜，所述膜包含布置在多孔聚四氟乙烯载体上的本发明的经固化组合物。
在一个实施方案中，本发明的经固化组合物可作为无孔膜用于从含二氧化碳的气流分离二氧化碳.例如，通过使物流接触膜的一侧(第一侧)，并在膜的对应面抽取包含二氧化碳浓化流的透过物，从气态进料流除去二氧化碳。在一个实施方案中，本发明的膜对二氧化碳为高度选择性.在一个实施方案中，膜具有至少约75的二氧化碳选择性，至少约6000GPU的二氧化碳透过性，并且在环境温度至约200℃热稳定。
实施例
以下实施例说明本发明的方法和实施方案.除非另外说明，所有成分均可购自以下一般化学供应商：AlphaAesar，Inc.(WardHill，Massachusetts)，SigmaAldrich(St.Louis，Missouri)，SpectrumChemicalMfg.Corp.(Gardena，California)等.
制备聚乙烯醇和乙二醇二缩水甘油醚的水溶液(PVA/EGDGE)
在装配有机械搅拌器和冷水冷凝器的带有氮打泡器的250毫升3颈圆底烧瓶中，将聚乙烯醇粉末(Mw＝89-98K，8.35克)加入到0.190摩尔KOH，随后加入约45.6克水。将混合物加热到聚乙烯醇溶解。在约80℃加入乙二醇二缩水甘油醚(EDGE，6.42g，0.03686mol)，同时机械搅拌溶液.在氮气下，在连续搅拌下将所得混合物在80℃加热约16-24小时.
制备聚乙烯醇和甲醛的水溶液(PVA/KOH/CH2O)
将聚乙烯醇粉末(Mw＝89-98K，7.34克)和44.8克水加入到装配有机械搅拌器和冷水冷凝器和氮入口管的250毫升3颈圆底烧瓶中。在机械搅拌下将溶液在约80℃加热到溶解.向以上溶液加入氢氧化钾丸粒(4.05克，0.072mol)和37％甲醛溶液(6.83克CH2O，0.084mol)。在氮气下，在连续搅拌下将溶液在约80℃加热16-24小时。
制备氨基酸-钾盐溶液
将1-脯氨酸(3.412克，0.0296mol)和6.48克水加入到含磁性搅拌棒的4克(15mL)管形瓶。加入氢氧化钾(1.959克，0.0349mol)，继续搅拌，直到溶解.
制备聚烯丙胺溶液
将聚烯丙胺盐酸盐(Mw＝60K，3.424克，0.0370mol聚合物重复单元，MW＝92.65克/mol)与2.89克KOH溶于64.98克甲醇，并在室温搅拌过夜。将溶液过滤，以除去沉淀的副产物KCl.在旋转式蒸发器上在真空中除去溶剂，得到1.86克聚烯丙胺。然后在19.25克水中溶解聚烯丙胺。
实施例1-5
制备氨基酸-钾盐溶液和PVA/EGDGE水溶液的混合物
在机械搅拌下，将氨基酸-钾盐的溶液经约1分钟加入到PVA/EGDGE(与EDGE交联的PVA)的溶液，同时使温度保持在约80℃。用2克水清洗含氨基酸-钾盐溶液的管形瓶，也加入清洗液，以制备PVA/EGDGE/氨基酸-钾盐水溶液。
制备聚烯丙胺-PVA/EGDGE/氨基酸-钾盐水溶液的混合物
在机械搅拌下，经约1分钟将如上制备的聚烯丙胺溶液加入到PVA/EGDGE/氨基酸-钾盐水溶液。用5克水清洗含聚烯丙胺溶液的烧瓶，也加入清洗液.将所得溶液在约80℃温度搅拌另外10分钟，以制备含聚烯丙胺、与乙二醇二缩水甘油醚交联的聚乙烯醇(PVA/EGDGE)和氨基酸-钾盐的含水涂料制剂.
膜流延步骤A
将包括聚烯丙胺-PVA/EGDGE-氨基酸-钾盐水溶液的溶液(实施例1-5)在约3100转/分钟离心约10分钟，同时冷却。使用流延刀，使离心的溶液在0.8英寸/秒在膨体聚四氟乙烯(ePTFE)载体上流延，以形成流延膜.使流延膜在室温干燥约18小时，以除去大部分水.在规定时间结束时，将经干燥的流延膜在马弗炉中在约120℃温度加热约6小时。
膜流延步骤B
将包括聚烯丙胺-PVA/EGDGE-氨基酸-钾盐水溶液的溶液(实施例1-5)在约3100转/分钟离心约10分钟，同时冷却.使用流延刀，使离心的溶液在0.8英寸/秒速率在ePTFE载体上流延，以形成流延膜.使流延膜在室温干燥约18小时，以除去大部分水.在规定时间结束时，将经干燥的流延膜在马弗炉中在约120℃温度加热约6小时。将约12份SnapsilRTV230A/B(MomentivePerformanceMaterials，Waterford，NYUSA)溶于约20份己烷，并用刮刀在膜表面上流延成1密耳厚度涂层.在膜试验和评价之前，使涂层在室温固化过夜.
性能检测步骤
将实施例1-5的膜独立固定在具有8.7平方厘米活性膜面积的试验单元中，并用含5.01％O2、16.99％CO2和79.0％N2的气体混合物在进料侧加压.通过试验单元的气体流速为约80标准立方厘米/分钟.用氩气流在80标准立方厘米/分钟的流速吹扫膜的透过物侧.进料和透过物均通过使去离子水泵抽入试验单元上游的在110℃加热的1升钢容器湿润。也将试验单元和所有气体管线加热到110℃。通过比较CO2和N2峰的积分面积，用气体(Agilent3000MicroGC)测定透过物气体组成.在不同条件下，用以下公式测定膜透过量(permeance)、透过性(permeability)和选择性.试验结果在表1中给出.
通量
其中：
ΔPy(进料-吹扫)＝([进料气体压力(bar)x湿进料组分y浓度]-[吹扫气体压力(bar)x湿吹扫组分y浓度])
透过性＝透过量(y)x膜厚度
表1给出利用上述流延方法A的固定于ePTFE(QM102)载体上的膜的组成。
表2给出利用上述膜试验方法的固定于ePTFE(QM102)载体上的膜组合物的性能特征.
实施例1-5的膜中使用的制剂用乙二醇二缩水甘油醚作为PVA交联剂。这些膜显示小环杂环氨基酸活动载体的杰出性能(表2).因此，具有4个环碳的活动载体(实施例1-实施例5)显示极佳的膜性能.由于提供其中使用较小活动载体产生杰出CO2分离膜性能的膜，因此本发明非常有利。
前述实施例仅为说明性，只用于举例说明本发明的一些特征。附加权利要求旨在要求本发明与表达一样广泛，本文提出的实施例为从各种所有可能实施方案选择的实施方案的说明。因此，申请人的意图是附加权利要求不受用于说明本发明特征的实施例的选择限制。如权利要求书中所用，词语“包括”及其语法变体在逻辑上也对向并且包括变化和不同范围的短语，例如但不限于“基本由...组成”和“由...组成”.在必要时已提供范围，这些范围包括其间的所有子范围。希望本领域的技术人员能想到这些范围中的变化，并且在未向公众提供时，这些变化应尽可能解释为由附加权利要求覆盖。还应预料，科学技术的进步会使现在由于语言不精确未想到的相当和替代成为可能，这些变化也应尽可能解释为由附加权利要求覆盖。

Claims (10)

1.一种可固化组合物，所述可固化组合物包含：
聚乙烯醇；
脂族聚胺；
聚缩水甘油醚；和
C2至C4杂环氨基酸的盐。
2.权利要求1的组合物，其中脂族聚胺为至少一种选自聚烯丙胺、聚乙烯胺、聚二烯丙基胺、乙烯胺-乙烯醇共聚物、聚乙烯亚胺和乙亚胺-环氧乙烷共聚物的聚胺。
3.权利要求1的组合物，其中聚缩水甘油醚为至少一种选自甘油二缩水甘油醚、甘油三缩水甘油醚、三羟甲基丙烷三缩水甘油醚、三羟甲基丙烷二缩水甘油醚、乙二醇二缩水甘油醚、双酚-A二缩水甘油醚、二乙二醇二缩水甘油醚、三乙二醇二缩水甘油醚和丙二醇二缩水甘油醚的聚缩水甘油醚。
4.权利要求1的组合物，其中杂环氨基酸的盐包含至少一种选自锂、钠、钾、钙和镁的金属阳离子。
5.权利要求1的组合物，其中杂环氨基酸的盐为脯氨酸。
6.权利要求1的组合物，所述组合物不含甲醛或甲醛相当物。
7.权利要求1的组合物，所述组合物包含：
基于组合物总重量约10％重量至约70％重量的聚乙烯醇；
基于组合物总重量约1％重量至约50％重量的聚胺；
基于组合物总重量约5％重量至约40％重量的聚缩水甘油醚；和
基于组合物总重量约10％重量至约50％重量的杂环氨基酸的盐。
8.一种制品，所述制品包括权利要求1的经固化组合物。
9.一种气体分离膜，所述气体分离膜包括在多孔载体上作为薄膜布置的权利要求1的经固化组合物。
10.一种经固化组合物，所述经固化组合物包含：
衍生自聚乙烯醇的结构单元；
脂族聚胺；
衍生自聚缩水甘油醚的结构单元；和
C2至C4杂环氨基酸的盐。
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