CN109689731A - 包括具有特勒格碱和螺双茚部分的子单元的具有固有微孔性的聚合物 - Google Patents
包括具有特勒格碱和螺双茚部分的子单元的具有固有微孔性的聚合物 Download PDFInfo
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
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Abstract
一种包含子单元或重复单元的聚合物,所述子单元或重复单元包括借助于连接基团(L)连接在一起的螺双茚部分和特勒格碱部分,其中所述连接基团(L)由式III表示:
Description
技术领域
本发明涉及具有固有微孔性的聚合物,特别是包括子单元的聚合物,所述子单元包括特勒格碱(Troger's base)和螺双茚部分。本发明聚合物具有用于气体和液体分离的膜的特定效用。
背景技术
具有固有微孔性(PIM)的聚合物的特征在于具有刚性和扭曲的大分子结构,从而具有极大的自由体积分数。实例包括聚(1-三甲基硅烷基-1-丙炔)(PTMSP)、聚(4-甲基-2-戊炔)(PMP)和聚苯并二恶烷(PIM-1)。由于其特殊的自由体积,其全都极具渗透性。参见:Baker的《膜技术和应用(Membrane Technology and Applications)》第3版(2012),和《具有固有微孔性的聚合物(Polymers of Intrinsic Microporosity)》《聚合物科学与技术百科全书(Enc.Polymer Sci.&Tech.)》,(2009)-两个都根据John Wiley&Sons Ltd。又参见:WO2005/113121;US2004/01985587;US2013/0146538;US2013/0172433;US2013/0267616;US2014/0251897;US9018270;US 8623928;US8575414;US8056732;US7943543;US7690514和US7410525,其以全文的方式并入本文中。借助于实例,US2014/0251897描述薄层复合膜,其包括具有通过有凹部的单体的界面聚合形成的固有微孔性的网络微孔聚合物(例如螺双茚、双萘、乙桥蒽)的薄选择性层。类似地,US9018270描述用于制备包括PIM薄层的薄膜复合膜的界面聚合技术。在一个实施例中,聚合物包括重复单元,所述重复单元包括特勒格碱部分,例如
还参见D.Xin等人,《用于非均相催化剂的特勒格碱官能化有机纳米多孔聚合物(Troger's base-functionalised organic nanoporous polymer for heterogeneouscatalyst)》,《化学通信(Chem Comm)》(2009)第970-972页,其提供了所谓的特勒格碱纳米多孔聚合物的制备以及其在二乙基锌与芳香族醛的加成反应中作为催化剂的用途的描述。
发明内容
本发明包括具有固有微孔性的聚合物(和共聚物-在本文中统称为“聚合物”)以及制备和使用其的相应方法。本发明聚合物包括具有特勒格碱和螺双茚部分的子单元(和优选重复单元)。特勒格碱部分和螺双茚部分优选通过“连接基团”连接,所述“连接基团”包含具有3到5个碳原子的亚烷基,其中醚或酯官能团提供连接键。以下提供代表性重复单元。
在一优选类的实施例中,本发明包括聚合物,所述聚合物包括子单元(或优选的重复单元),其中所述特勒格碱部分由式I表示
式I:
其中E是包含1到4个环的亚芳基(优选亚苯基);L是与螺双茚部分的连接基团,并且D选自:氢、羟基、腈、硝基、烷基(例如,1到4个碳原子,但优选为甲基)、烷氧基(例如,1到4个碳原子,但优选为甲氧基)、羟烷基(例如,1到4个碳原子,但优选为OH-CH2-);羧酸、磺酸和其相应盐或酯。特勒格碱部分的优选子类由式Ia和Ib表示:
螺双茚部分由式II表示:
其中A独立地选自稠环结构(优选包括1到4个环,例如亚芳基,例如亚苯基)或不存在,并且L是与特勒格碱部分的连接基团。
在优选实施例中,L独立地选自优选包含2到5个碳原子并且包括至少两个选自酯和醚的官能团的亚烷基。举例来说,在一组优选实施例中,L的每个实例独立地由式III表示:
其中Z和Z'独立地选自醚和酯官能团。
在另一个优选实施例中,本发明包括聚合物,所述聚合物包含环氧基官能性螺双茚单体与特勒格碱单体、低聚物、共聚物或被与环氧基反应的成分(例如羟基、羧酸)取代的聚合物的反应产物。
在额外实施例中,本发明包括使用本发明聚合物制备的薄膜、涂层和膜,本发明聚合物包括可用于形成这类薄膜、涂层和膜的网络形式的聚合物。
在优选实施例中,本发明聚合物解决与已知PIM技术相关的缺点中的一个或多个,例如提高的膜耐久性、排斥性、耐污垢性、使得在不同的最终使用条件下更好地维护纳米多孔结构的刚性和尺寸稳定性、对提高选择性所需官能团的更好耐受性、改进的可加工性和制造、更高的玻璃化转变温度、更高的热稳定性、更高的热氧化稳定性、提高的防潮性、提高的耐酸性和耐碱性和耐有机溶剂性。
具体实施方式
在一个优选实施例中,本发明聚合物具有固有微孔性。术语“固有微孔性”是指聚合物具有互连分子间空隙的连续网络,所述空隙形成聚合物的组分单体的至少一部分的形状和刚性的直接结果。术语“微孔”是指具有由IUPAC定义的直径小于2nm的空隙的互连系统的材料。优选地,本发明聚合物具有由标准泡点测试(例如ASTM F316-03(2011))测定的0.2nm到20nm的平均孔隙直径。聚合物还具有高表观表面积(例如,如通过Brunauer-Emmett-Teller(BET)方法测定,大于100m2/g,并且更优选大于150m2/g。
在几个实施例中,本发明聚合物是网络共聚物。术语“网络”定义为与不具有共价交联3维网络的“非网络聚合物”或线性聚合物相反的共价交联3维聚合物网络。
使用本发明聚合物制备的膜可以通过常规技术形成,例如浇铸、在多孔载体上原位聚合、浸涂以及随后聚合到多孔载体上等。这类膜可用于基于不同物种横跨膜的传质的相对速率的分离。动力(通常是压力或浓度差)被施加到膜上使得所选物种优先地横穿所述膜。膜可以用于液体(例如水性、有机物)或气相中的特定物种(例如盐、有机物、离子物种)的纯化、分离或吸收。特定地说,本发明膜展现极佳pH和溶剂稳定性,并且因此适用于广泛范围的应用中,包括:气体分离、离子交换、水软化、水净化、例如电子等应用中的超高纯度水生产、包括稀土的金属分离、催化、采矿废水的修复、铀加工、浸析采矿和乳制品、食糖、果汁和药品中液体的加工以及连续发酵/膜渗透蒸发系统中的乙醇生产。在具体实施例中,本发明聚合物包括亲水性官能团,例如在许多应用中提供改进选择性的羧酸。
本发明膜不受具体类型、构造或应用特定限制。举例来说,本发明聚合物可以制成在各种应用中发现效用的平片(膜)、管式和中空纤维状配置,所述应用包括气体分离、渗透蒸发、正渗透(FO)、逆渗透(RO)、纳米过滤(NF)、超滤(UF)、微滤(MF)和压力延迟流体分离。一个优选设计是薄膜复合结构。参见例如WO 2005/113121和US2014/0251897。结合薄膜复合设计,使用熟知技术(例如浸涂、浇铸本发明聚合物的溶液等)在载体上形成本发明聚合物的“薄膜”,并且进行相分离(例如通过骤冷、冷却等)以形成所需孔隙度。可以进一步对所得膜进行加热以促进交联。借助于更具体的实例,复合膜可以包括非编织背衬幅材(例如,PET纱布)的底层(背侧)、具有约25-125μm的典型厚度的多孔载体的中间层以及包含典型地具有小于约1微米(例如0.01微米到1微米,但更通常约0.01到0.1μm)的厚度的薄膜聚合物层的顶层(前侧)。多孔载体通常是孔径足以允许渗透物基本上不受限制通过,但并未大到足以干扰其上所形成的薄膜聚合物层桥接的聚合材料。举例来说,载体的孔径优选地在约0.001到0.5μm范围内。多孔载体的非限制性实例包括由以下所制成的那些载体:聚醚醚酮、聚砜、聚醚砜、聚酰亚胺、聚酰胺、聚醚酰亚胺、聚丙烯腈、交联聚丙烯腈、聚(甲基丙烯酸甲酯)、聚乙烯、聚丙烯和例如聚偏二氟乙烯等各种卤代聚合物。对于大多数应用来说,多孔载体提供强度,但由于其相对较高的孔隙度而几乎无流体流动阻力。
在一个实施例中,本发明包括一种聚合物,所述聚合物包括由以下表示的子单元(并且更优选为重复单元):
其中Z和Z'独立地选自醚和酯官能团。
特勒格碱化合物,例如描述于《应用化学国际版(Angewandte ChemieInternational Edition)》,第50卷,第10期,第2401-2404页,8FEB 2011DOI:10.1002/anie.201007162和Prelog,V.;Wieland,P.(1944).“die Spaltung derBase in optische Antipoden,ein Beitrag zur Stereochemie desdreiwertigen Stickstoffs”,《海尔维提卡化学学报(Helvetica Chimica Acta)》27(1):1127-1134,(1944)中的那些可用于本发明。特勒格碱部分的优选子类由式Ic以及其相应异构体(未图示)表示:
式Ic:
其中G选自:羧酸、磺酸和其相应盐或酯;羟基和氢。
可用于本发明的螺双茚单体可由如上所示的式II表示。优选的环结构由式IIa表示(其中式II的A和A'都不存在):
式IIa:
螺双茚单体可以使用由Chen,W-F.;Lin,H-Y.;Dai,S.A.;《有机化学通讯(OrganicLetters)》,6,14,2341-2343(2004);Faler,G.R.;Lynch,J.C.;美国专利第4,701,566号(1987年10月20日);Ito,M.;Iimuro,S.;美国专利第5,339,783号(1995年3月21日);Curtis,R.F.;Lewis,K.O.;《化学学会杂志(J.Chem.Soc.)》,418-421(1962);Baker,W.;《化学学会杂志》,1678-1681(1934);Fisher,C.H.;Furlong,R.W.;Grant,M.;《美国化学学会杂志(Journal of the American Chemical Society)》58,820-822(1936);Baker,W.;Besly,D.M.;《化学学会杂志》,1421-1424(1939);Baker,W.;Besly,D.M.;《化学学会杂志》,347-353(1938),Ma,X;Swaidan,Y.B.;Zhu,Y.;Litwiller,E.;Jouiad,I.P.;Han,Y.;《大分子(Macromolecules)》,45,3841-3849(2012);Li,S.;Jo,H.J.;Han,S.H.;Park,C.H.;Kim,S.;Budd,P.M.;Lee,Y.M.;《膜科学杂志(Journal of Membrane Science)》,434,137-147(2013)所描述的方法制备。
聚合物的优选类别包括由式IV表示的子单元(或重复单元):
其中对于给定单元,A和L的每个实例不必相同,并且A、L和D如上所定义。
虽然未图示,但特勒格碱部分的部分或全部氮基团可被(例如低碳数烷基,例如甲基、基等)取代,在所述氮原子上产生阳离子电荷,其与相应阴离子带电物种相关。
本发明聚合物可以使用已知的起始材料和技术制备。特别地说,优选起始材料包括例如特勒格碱低聚物和含有酚羟基或羧酸基的聚合物和螺双茚单体的二缩水甘油醚。
包括缩水甘油醚基的螺双茚单体可使用常见合成技术(例如,使得3,3,3',3'-四甲基-1,1'-螺双茚-6,6'-二醇的环氧化)制备:
下面提供了几种用于制备本发明聚合物的代表性反应途径。
反应路径I:本发明的代表性实例是通过合并3,3,3',3'-四甲基-1,1'-螺双茚-6,6'-二醇的二缩水甘油醚和苯基封端的羟基官能性特勒格碱聚合物,随后任选地B分阶和热固化来制备以产生如以下所描绘的共聚物。
反应途径II:本发明的另一代表性实例是通过合并3,3,3',3'-四甲基-1,1'-螺双茚-6,6'-二醇的二缩水甘油醚和羧酸官能性特勒格碱聚合物,随后任选地B分阶和热固化来制备以产生如以下所描绘的共聚物。
反应途径III:将提供水溶性PIM的本发明的代表性实例是通过合并3,3,3',3'-四甲基-1,1'-螺双茚-6,6'-二醇的二缩水甘油醚和羟基官能性和磺酸酯官能性特勒格碱共聚物,随后任选地B分阶和热固化来制备以产生如以下所描绘的共聚物。特勒格碱PIM的例示性合成涉及在三氟乙酸中缩合2,4-二氨基苯酚二盐酸盐和2,4-二氨基苯磺酸和多聚甲醛,随后将磺酸基转化为磺酸钠基团。与3,3,3',3'-四甲基-1,1'-螺双茚-6,6'-二醇的二缩水甘油醚的共聚可能需要使用非质子溶剂,特别是N,N-二甲基甲酰胺。水性介质中的共聚合可以例如作为乳液进行。
反应途径IV:将提供水溶性PIM的本发明的代表性实例是通过合并3,3,3',3'-四甲基-1,1'-螺双茚-6,6'-二醇的二缩水甘油醚和羟基官能性特勒格碱共聚物,随后任选地B分阶和热固化来制备以产生如以下所描绘的共聚物。季盐结构可用于酚羟基和环氧基的自催化反应,但如果有需要可以加入催化剂。水性介质中的共聚合可以例如作为乳液进行。
反应途径V:本发明的另一代表性实例是通过合并3,3,3',3'-四甲基-1,1'-螺双茚-6,6'-二醇的二缩水甘油醚和羟基官能性特勒格碱聚合物,随后任选地B分阶和热固化来制备以产生如以下所描绘的共聚物。
(1)一种或多种含有环氧树脂的螺环稠环结构的其它代表包括6,6'-二羟基-1,1'-螺双茚-3,3'-二酮的二缩水甘油醚;6,6'-二羟基-1,1'-螺双茚-3-芴-3'-酮的二缩水甘油醚;6,6'-二羟基-1,1'-螺双茚-3,3'-双芴的二缩水甘油醚;5,5'-二甲氧基-6,6'-二羟基-1,1'-螺双茚-3,3'-双芴的二缩水甘油醚;5,5'-二甲氧基-6,6'-二羟基-3,3,3',3'-四甲基-1,1'-螺双茚的二缩水甘油醚;5,4'-二甲氧基-6,6'-二羟基-1,1'-螺双茚的二缩水甘油醚;3,3,3',3'-四甲基-1,1'-螺双茚-4,6,4',6-四醇的四缩水甘油醚;其混合物以及其类似物。
(1)一种或多种含有环氧树脂的螺环稠环结构与(2)一种或多种特勒格碱化合物、低聚物、共聚物和/或含有至少一种环氧化物反应性官能团的聚合物的可固化组合物可特别有利于例如在薄膜复合物中与载体和/或与另一膜层偶合的反应。在这个实施例中,至少一部分环氧基与存在于载体和/或其它膜层上的基团反应以形成共价键。
本发明聚合物可以包括额外重复单元或分支,即通过共聚形成;然而,本发明聚合物优选包含至少50摩尔%、75摩尔%和更优选至少90摩尔%的由式I表示的重复单元(例如50-100摩尔%、75-100摩尔%和90到100摩尔%的本发明单体)。可能的各种异构体结构未在式(例如式I)中示出,但意欲包括在内。
聚合物合成的多种变体可用于改变聚合物的物理和机械特性。这些变体包括所用共聚单体中的结构变化和所用共聚单体的化学计量比的变化。所用共聚单体的结构变化的实例包括加成一个或多个取代基,例如表示式I中的“D”部分和式Ic中的“G”部分以及共聚单体的变体。所用共聚单体的化学计量比的变化包括:所用共聚单体的当量比的变体(可以显著改变分子量和/或交联密度),包括额外的共聚单体。
通过使用较低温度和/或较短固化时间和/或降低的催化剂浓度,可以实现含有螺双茚的环氧基和含有特勒格碱的材料的可共聚混合物的B阶或预聚合。由此形成的B阶(预聚合)产物的固化可接着在稍后的时间或通过升高温度和/或增加固化时间在B阶(预聚合)之后立即实现。
Claims (9)
1.一种聚合物,其包含子单元,所述子单元包含借助于连接基团(L)连接在一起的螺双茚部分和特勒格碱部分,其中所述连接基团(L)由式III表示:
其中Z和Z'独立地选自醚和酯官能团。
2.根据权利要求1所述的聚合物,其中所述特勒格碱部分由式I表示:
其中E是包含1到4个环的亚芳基;L是与螺双茚部分的连接基团,并且D选自:氢、羟基、腈、硝基、烷基、烷氧基、羟烷基;和羧酸、磺酸和
其相应盐或酯。
3.根据权利要求2所述的聚合物,其中所述特勒格碱部分由式Ia和Ib中的至少一种表示:
4.根据权利要求1所述的聚合物,其中所述螺双茚部分由式II表示:
其中A独立地选自包括1到4个环的稠环结构或不存在,并且L独立地选自与特勒格碱部分的连接基团。
5.根据权利要求4所述的聚合物,其中所述螺双茚部分由式IIa表示,其中L独立地选自与特勒格碱部分的连接基团
6.根据权利要求4所述的聚合物,其包括由式IV表示的子单元:
其中D选自:氢、羟基、腈、硝基、烷基、烷氧基、羟烷基;和羧酸、磺酸和其相应盐或酯。
7.根据权利要求1所述的聚合物,其包含重复单元,所述重复单元包含借助于连接基团(L)连接在一起的螺双茚部分和特勒格碱部分。
8.根据权利要求1所述的聚合物,其特征在于如通过ASTM F316-03(2011)测定的平均孔径为0.2到20nm。
9.一种膜,其包含根据权利要求1所述的聚合物。
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4555574A (en) * | 1981-06-19 | 1985-11-26 | Daicel Chemical Industries, Ltd. | Methacrylic ester useful as an optical resolving agent |
CN1500105A (zh) * | 2001-01-12 | 2004-05-26 | ͨ�õ�����˾ | 熔融聚碳酸酯催化剂体系 |
CN1612916A (zh) * | 2001-11-12 | 2005-05-04 | 通用电气公司 | 阻燃树脂组合物和其制备方法 |
CN1703393A (zh) * | 2002-10-01 | 2005-11-30 | 大日本制药株式会社 | 螺环化合物、含有该化合物的药用组合物和该化合物的中间体 |
CN102015969A (zh) * | 2008-03-04 | 2011-04-13 | 马萨诸塞大学 | 固体生物质的催化热解及相关的生物燃料、芳烃化合物和烯烃化合物 |
CN102333593A (zh) * | 2009-02-27 | 2012-01-25 | 赢创奥克森诺有限公司 | 从工艺流富集均相催化剂的方法 |
CN102993017A (zh) * | 2011-09-09 | 2013-03-27 | 财团法人工业技术研究院 | 旋光添加物、液晶配方及其形成方法、以及液晶显示器 |
EP2616493A1 (en) * | 2010-09-15 | 2013-07-24 | University College Cardiff Consultants, Ltd. | Polymerisation method |
Family Cites Families (48)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4701566A (en) | 1986-10-10 | 1987-10-20 | General Electric Company | Method for preparing spirobiindane bisphenols |
US5339783A (en) | 1993-07-07 | 1994-08-23 | Freightliner Corporation | Throttle breakover apparatus |
JP3084292B2 (ja) | 1994-07-28 | 2000-09-04 | ミリポア コーポレイション | 多孔質複合膜と方法 |
GB0115201D0 (en) | 2001-06-21 | 2001-08-15 | Univ Manchester | Organic microporous materials |
GB0317557D0 (en) | 2003-07-26 | 2003-08-27 | Univ Manchester | Microporous polymer material |
GB0411463D0 (en) | 2004-05-22 | 2004-06-23 | Univ Manchester | Thin layer composite membrane |
US7410525B1 (en) | 2005-09-12 | 2008-08-12 | Uop Llc | Mixed matrix membranes incorporating microporous polymers as fillers |
US7485173B1 (en) | 2005-12-15 | 2009-02-03 | Uop Llc | Cross-linkable and cross-linked mixed matrix membranes and methods of making the same |
DE102006001770A1 (de) | 2006-01-12 | 2007-07-26 | Gkss-Forschungszentrum Geesthacht Gmbh | Protonenleitende Polymermembran |
US20070209505A1 (en) | 2006-03-10 | 2007-09-13 | Chunqing Liu | High Flux Mixed Matrix Membranes for Separations |
GB2437519B (en) | 2006-04-28 | 2010-04-21 | Imp Innovations Ltd | Method for separation |
US7943543B1 (en) | 2006-09-29 | 2011-05-17 | Uop Llc | Ionic liquid-solid-polymer mixed matrix membranes for gas separations |
US7758751B1 (en) | 2006-11-29 | 2010-07-20 | Uop Llc | UV-cross-linked membranes from polymers of intrinsic microporosity for liquid separations |
US8048198B2 (en) | 2007-11-08 | 2011-11-01 | Uop Llc | High performance mixed matrix membranes incorporating at least two kinds of molecular sieves |
US20090155464A1 (en) | 2007-12-12 | 2009-06-18 | Chunqing Liu | Molecular Sieve/Polymer Mixed Matrix Membranes |
WO2010048694A1 (en) | 2008-10-27 | 2010-05-06 | National Research Council Of Canada | Ladder polymers with intrinsic microporosity and process for production thereof |
EP2191891A1 (de) | 2008-11-27 | 2010-06-02 | Gkss-Forschungszentrum Geesthacht Gmbh | Herstellung von Polymeren mit inhärenter Mikroporosität |
CN105289305B (zh) | 2009-01-13 | 2018-03-30 | Ams技术Int(2012)有限公司 | 用于将金属离子与液体加工流分离的溶剂和酸稳定膜、装置和方法 |
US8613362B2 (en) | 2009-03-27 | 2013-12-24 | Uop Llc | Polymer membranes derived from aromatic polyimide membranes |
US8132677B2 (en) | 2009-03-27 | 2012-03-13 | Uop Llc | Polymer membranes prepared from aromatic polyimide membranes by thermal treating and UV crosslinking |
WO2010124359A1 (en) | 2009-04-30 | 2010-11-04 | National Research Council Of Canada | Carboxylated polymers of intrinsic microporosity (pims) with tunable gas transport properties |
WO2011057384A1 (en) | 2009-11-12 | 2011-05-19 | National Research Council Of Canada | Polymers of intrinsic microporosity containing tetrazole groups |
WO2011130818A1 (en) | 2010-04-20 | 2011-10-27 | Parker Filtration B.V. | Process for synthesizing polymers with intrinsic microporosity |
GB201012083D0 (en) | 2010-07-19 | 2010-09-01 | Imp Innovations Ltd | Thin film composite membranes for separation |
GB201015401D0 (en) * | 2010-09-15 | 2010-10-27 | Univ Cardiff | Polymers, their method of manufacture and use thereof |
US8575414B2 (en) | 2010-12-17 | 2013-11-05 | Uop Llc | Membrane system for natural gas upgrading |
US9126185B2 (en) | 2011-09-30 | 2015-09-08 | The United States Of America, As Represented By The Secretary Of The Navy | Porous polymer supported polyoxometalates |
GB201117950D0 (en) | 2011-10-18 | 2011-11-30 | Imp Innovations Ltd | Membranes for separation |
US20130146538A1 (en) | 2011-12-08 | 2013-06-13 | Uop Llc | Blend polymeric membranes comprising tetrazole-functionalized polymer of intrinsic microporosity and polyethylene glycol |
US8814982B2 (en) | 2011-12-08 | 2014-08-26 | Uop Llc | Tetrazole functionalized polymer membranes |
US20130247756A1 (en) | 2012-02-15 | 2013-09-26 | National University Of Singapore | Uv-rearranged pim-1 polymeric membranes and a process of preparing thereof |
WO2014052021A1 (en) | 2012-09-25 | 2014-04-03 | 3M Innovative Properties Company | Polymerizable spirobisindane monomers and polymers prepared therefrom |
US20140255636A1 (en) | 2013-03-06 | 2014-09-11 | Saudi Basic Industries Corporation | Polymeric Membranes |
EP2997056B1 (en) | 2013-05-14 | 2018-03-21 | 3M Innovative Properties Company | Sulfonyl-containing polymeric material with rigid and contorted divinyl crosslinker |
DE102013215726A1 (de) | 2013-08-09 | 2015-02-12 | Zf Friedrichshafen Ag | Drehschwingungsdämpfungsanordnung für den Antriebsstrang eines Fahrzeugs |
KR101582379B1 (ko) | 2013-09-04 | 2016-01-04 | 주식회사 두산 | 디아민계 화합물 및 이를 이용하여 제조된 고분자 |
WO2015077444A1 (en) | 2013-11-20 | 2015-05-28 | King Abdullah University Of Science And Technology | Amine functionalized porous network |
US9238202B2 (en) | 2013-12-12 | 2016-01-19 | Uop Llc | Gas separation membranes from chemically and UV treated polymers of intrinsic microporosity |
KR101704369B1 (ko) | 2013-12-16 | 2017-02-07 | 사빅 글로벌 테크놀러지스 비.브이. | 처리된 혼합 매트릭스 중합 멤브레인들 |
KR20160066046A (ko) | 2013-12-16 | 2016-06-09 | 사빅 글로벌 테크놀러지스 비.브이. | 플라즈마-처리된 중합 멤브레인들 |
WO2015095034A1 (en) | 2013-12-16 | 2015-06-25 | Sabic Global Technologies B.V. | Uv and thermally treated polymeric membranes |
EP3110879A4 (en) | 2014-02-27 | 2017-11-15 | Kyoto University | Crosslinked polymer, method for producing the same, molecular sieve composition and material separation membranes |
EP3271414A1 (en) | 2015-03-17 | 2018-01-24 | Dow Global Technologies LLC | Polymers of intrinsic microporosity |
WO2016161367A1 (en) | 2015-04-03 | 2016-10-06 | The Regents Of The University Of California | Polymeric materials for electrochemical cells and ion separation processes |
WO2016195977A1 (en) | 2015-05-29 | 2016-12-08 | Dow Global Technologies Llc | Isatin copolymers having intrinsic microporosity |
US10189948B2 (en) | 2015-06-24 | 2019-01-29 | Dow Global Technologies Llc | Isatin copolymers having intrinsic microporosity |
US20190153154A1 (en) | 2015-08-20 | 2019-05-23 | Auckland Uniservices Limited | Polymers of intrinsic microporosity (pims) containing locked spirobisindane structures and methods of synthesis of pims polymers |
WO2017091357A1 (en) | 2015-11-24 | 2017-06-01 | Dow Global Technologies Llc | Troger's base polymers having intrinsic microporosity |
-
2017
- 2017-07-31 WO PCT/US2017/044605 patent/WO2018057119A1/en unknown
- 2017-07-31 CN CN201780056063.0A patent/CN109689731A/zh active Pending
- 2017-07-31 US US15/571,080 patent/US10472467B2/en not_active Expired - Fee Related
- 2017-07-31 EP EP17752523.5A patent/EP3515968A1/en not_active Withdrawn
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4555574A (en) * | 1981-06-19 | 1985-11-26 | Daicel Chemical Industries, Ltd. | Methacrylic ester useful as an optical resolving agent |
CN1500105A (zh) * | 2001-01-12 | 2004-05-26 | ͨ�õ�����˾ | 熔融聚碳酸酯催化剂体系 |
CN1612916A (zh) * | 2001-11-12 | 2005-05-04 | 通用电气公司 | 阻燃树脂组合物和其制备方法 |
CN1703393A (zh) * | 2002-10-01 | 2005-11-30 | 大日本制药株式会社 | 螺环化合物、含有该化合物的药用组合物和该化合物的中间体 |
CN102015969A (zh) * | 2008-03-04 | 2011-04-13 | 马萨诸塞大学 | 固体生物质的催化热解及相关的生物燃料、芳烃化合物和烯烃化合物 |
CN102333593A (zh) * | 2009-02-27 | 2012-01-25 | 赢创奥克森诺有限公司 | 从工艺流富集均相催化剂的方法 |
EP2616493A1 (en) * | 2010-09-15 | 2013-07-24 | University College Cardiff Consultants, Ltd. | Polymerisation method |
CN102993017A (zh) * | 2011-09-09 | 2013-03-27 | 财团法人工业技术研究院 | 旋光添加物、液晶配方及其形成方法、以及液晶显示器 |
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WO2018057119A1 (en) | 2018-03-29 |
US20190211151A1 (en) | 2019-07-11 |
US10472467B2 (en) | 2019-11-12 |
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