CN105683228B - 一种具有2,5呋喃二酮、金属盐的1-十八烯导电性聚合物 - Google Patents
一种具有2,5呋喃二酮、金属盐的1-十八烯导电性聚合物 Download PDFInfo
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Abstract
一种酸值大于100的聚合物,其具有结合到至少一个反应活性基团的价金属离子。该聚合物的特性包括4S/cm至200S/cm以上的电导率,这取决于结合金属的浓度和性质,电导率与结合金属的数量、聚合物结合具有+1,+2,+3,+4,或+5价电荷的金属到聚合物的能力、以及结合两种或多种不同金属至聚合物上分离的结合位点的能力成比例。
Description
技术领域
本发明涉及具有2,5呋喃二酮、金属盐的1-十八烯聚合物,并且更具体地涉及具有2,5呋喃二酮、金属盐的1-十八烯聚合物作为导电性聚合物的用途。本发明描述了使用具有2,5呋喃二酮、金属盐的1-十八烯聚合物实现各种功能的方法。
背景技术
1988年以前,所有的碳基聚合物都被专门列为绝缘体。实际上,由于这一特性,塑料已被广泛用于电子工业中。1979年,Diaz和他的同事报道了聚吡咯的导电性能(Diaz,A.F.,Kanazawa,K.K.,和Gardini,G.P.,Electrochemical Polymerization of Pyrrole,JChem Soc Chem Commun,635-6(1979).)。迄今为止,已经开发出了大量的本征导电性聚合物或电活性聚合物。这些聚合物在电子设备领域(Novak,P.,Muller,K.,Santhanam,K.S.V.,和Haas,O.,Electrochemically active polymers for rechargeablebatteries,Chem Rev,97,207(1997));光学器件领域(Potember,R.S.,Hoffman,R.C.,Hu,H.S.,Cocchiaro,J.E.,Viands,C.A.,Murphy,R.A.,和Poehler,T.O.,Conductingorganics and polymers for electronic and optical devices,Polymer,28,574(1987));传感器领域(Nicholas,M.,Fabre,B.,和Simonet,J.,Electrochemical sensingof F-and CI-with a boric ester-functionalized polypyrrole,J Electroanal Chem,5091(2001)),能源储存,医药,电力基础设施领域中具有广阔的应用前景。
本征导电性聚合物
本征导电性聚合物是具有导电特性的聚合有机化合物。通常,这些材料或是半导体,或具有金属导电性。导电聚合物具有由共轭sp2杂化碳键组成的碳骨架。与每一个sp2杂化碳原子相关的价电子存在于相对于与这些杂化碳原子相关的三个σ键垂直的pz轨道中。在这些pz轨道中的电子被称为是离域的,并且当通过氧化“掺杂”该材料时通常具有高迁移率,这是移除部分离域电子的过程。类似地,通过还原共轭碳骨架可以形成本征导电性聚合物。通常,大多数导电性聚合物是通过氧化来“掺杂”以得到“p-型”材料。这个过程类似于硅半导体的掺杂。
迄今为止,这些聚合物制品都存在相同的弊端-较差的加工性和缺乏必需的机械性能。在解决这些限制的尝试中,已经尝试努力转向生产导电聚合物膜和绝缘聚合物的复合材料。例如,绝缘聚合物如聚碳酸酯,与导电聚合物如聚吡咯结合,以生产出导电聚合物复合材料,其具有导电性并且具有更好的机械性能(Wang,H.L.,Toppare,L.,和Fernandez,J.E.,Conducting polymer blends:polythiophene and polypyrrole blends withpolystyrene and poly(bisphenol A carbonate),Macromolecules,23,1053-9(1990))。
使用的其它绝缘聚合物包括聚(苯乙烯磺酸盐)(Otero,T.F.,和Sansinena,J.M.,Influence of synthesis conditions on polypyrrole-poly(styrenesulphonate)composite electroactivity,J Electroanal Chem,412,109-16(1996));聚(氯乙烯)(DePaoli,M.A.,Waltman,R.J.,Diaz,A.F.,和Bargon,J,An electrically conductiveplastic composite derived from polypyrrole and poly(vinylchloride),J PolymSci Polym Chem Ed,23,1687-97(1985));丁腈橡胶(Naoi,K.,和Osaka,T.,Highlyenhanced anion doping-undoping process at the polypyrrole electrode ofregulated morphology prepared with the aid of insulating NBR film,JElectrochem Soc Electrochem Sci Tech,134,2479-83(1987));聚酰亚胺(Iroh,J.O.,和Levine,K.,Electrochemical synthesis of polypyrrole/polyimide conductingcomposite using a polyamic acid precursor,Eur Polym J,38,1547-50(2002));和聚(乙烯醇)(Gangopadhyay,R.,和De,A.,Conducting polymer composites:novelmaterials for gas sensing.Sensors and Actuators B,77,326-9(2001))。报道的其它导电聚合物包括聚苯胺和聚噻吩。
已经报道了的能量存储设备包括由导电聚合物和液体或固体电解质构成的电极。在固态器件中,将电解质层夹在中间,或融合或浸渍于两个电极之间的基质中。通过使用掺杂剂阴离子或阳离子来电化学掺杂导电聚合物来增强存储设备的性能。在这些设备中,导电聚合物用作电子导体,而电解质基质用作离子导体。对这些设备所报道的主要缺点是掺杂离子到聚合物电极的扩散率相对较低,导致了较高程度的内部电阻和设备性能的降低。
也报道了新型离子导电聚合物和电子导电聚合物的复合材料(Berthier,C.M.,Friend,R.H.,Novel composites of an ionic conducting polymer and an electronicconducting polymer,美国专利4,681,822)。这些复合材料由互相穿插的连续电子导电材料和连续离子导电材料的网络组成。电子导电材料包括聚乙炔、聚亚苯基、聚苯二苯基亚乙烯基或取代的聚乙炔,它们与连续的离子导电材料紧密地混合,电子导电材料定义为“离子盐和聚合物溶解剂复合物的混合物,使得离子导电材料具有超过其正常熔点的上升熔点”。使用的离子盐限于例如AsF6 -、PF6 -、BF4 -和ClO4 -的多原子阴离子和碱金属阳离子。此外,为了更有效,这些离子盐必须与能够溶剂化离子盐的聚合物溶解剂进行混合,例如聚环氧烷。此外,电子导电聚合物必须含有能够形成“p-型”或“n-型”材料的共轭碳-碳双键。相对于相关导电聚合物/液体-固体电解质设备,这些复合材料的主要优点是提高了掺杂物离子的离子扩散率,并因此提高了固态能量存储设备的性能。
纳米粒子复合材料
已经报道了大量有机化合物/金属纳米粒子复合导电材料。Yang等人报道了聚吡咯/银导电纳米管的合成(Yang,X.,Li,L.,Yan,F.,Fabrication of Polypyrrole/AgComposite Nanotubes via In Situ Reduction of AgNO3 on Polypyrrole Nanotubes,Chemistry Letters,39(2):118(2009))。Meftah等人报道了镍纳米颗粒/聚苯胺复合薄膜的合成和它们在电子、电催化剂和光电子中的用途(Meftah,A.M.,Saion,E.,Abd,M.,Mohd,M.B.,Zainuddin,H.B.,Absorbance of Nickel Nanoparticles/Polyaniline CompositeFilms,Prepared by Radiation Technique,Solid State Science and Technology,17(2),167-174(2009))。在美国专利申请2009/0272949A1中,Buttry公开了一种生产用导电聚合物包裹的金属氧化物纳米颗粒的方法,其适合作为锂离子电池的阴极或作为催化材料使用(Buttry,D.A.,Method for Producing Metal Oxide Nanoparticles Encapsulatedwith Conducting Polymer,美国专利公开号US 2009/0272949A2,2009)。在美国专利申请2010/0038599A1中,Holliday公开了由至少一个共价连接到共轭导电聚合物的半导体和/或光子吸收剂组成的化合物(Holliday,B.J.,Polymerizable Semiconductors,PolymersThereof,and Methods of Making and Using Same,美国专利公开号US 2010/0038599A1,2010)。在各种情况下,如所见的本征导电聚合物,在这些纳米复合材料体系中报道的聚合物都包含离域在多个共轭碳原子的共轭双键系统或电子系统。
含金属聚合物
1979年,Dawans和Morel在美国专利4,150,067中报道了包括络合到过渡金属原子的饱和碳原子骨架的有机金属聚合物的发展。为了获得这些有机金属材料,聚合物必须含有氟代羧酸基以及配位稳定所需的过渡金属。这些发明人指出:“...对制备这样一种聚合物感兴趣,聚合物包括能够提高金属的催化活性同时保持所述金属牢固地结合到聚合物载体的基团,为了避免催化复合物在反应过程中释放到培养基中..,现已发现,含有易得的氟代羧酸基团的聚合物可以用作金属衍生物的载体,并且特别导致形成了可用于各种反应的非常活跃的催化剂(Dawans,F.,Morel,D.,Metal-Containing Polymers,TheirManufacture and Use,美国专利号4,150,067(1979))。因此,这些发明人教导的理念不同于,羧酸基团可以单独充分地强烈地将金属结合到聚合物载体上,从而避免在随后的反应中释放。
具有2,5呋喃二酮的1-十八烯聚合物在导电聚合物中的用途
由于观察到氧化乙烯单元提供了金属阳离子的有效溶剂化,广泛报道了基于聚(环氧乙烷)(PEO)的固体聚合物电解质(Armand,M.B.In Polymer Electrolytes Reviews;McCallum,J.R.,Vincent,C.,Eds.;Elsevier Applied Science:London,1987;Vol.1,pl..;Gray,F.M.Polymer Electrolytes;The Royal Society of Chemistry:Cambridge,(1997))。由于PEO的高结晶性倾向,在室温下观察到了盐复合物的低导电性,从而限制了它在固态电化学设备中的用途。为了克服这一缺陷,聚(乙二醇)单甲醚(PEGME)接枝到如聚丙烯酸酯和马来酸酐共聚物的聚合物的侧链上。Tang和同事们描述了多功能梳状聚合物电解质的合成和性能,其使用聚(乙二醇)单甲醚(PEGME)作为金属结合侧链和聚(马来酸酐-交替-1-十八烯)(PMAO)作为骨架合成((Tang,Z-l.,Qi,L.,Gao,G-t.,Sun,M.,Dong,S-j.Sythesis and Properties of Multifunctional Comblike Polymer Electrolytes,Journal of Functional Polymers,21(1):36-43,(2008))。
Saad和同事们报道了包含聚(氯乙烯)(PVC)、极性增塑剂和1-十八烯和马来酸酐的共聚物的聚(氯乙烯)(PVC)组合物的电性能(Saad,A.L.G.,Hassan,A.M.,Gad,E.A.M.Electrical Properties of Poly(vinylchloride)Compositions,Journal ofApplied Polymer Science,49(10):1725-31(1993))。
Kim和同事报道了导电性聚合物-由聚碳酸酯和丙烯腈-丁二烯-苯乙烯共聚物组成的填料复合材料,其中聚碳酸酯和丙烯腈-丁二烯-苯乙烯共聚物的比率范围为4:6至6:4(Kim,W.和Lee,Y.,Electrically Conductive Polymer/Filler Composites,国际专利申请号:PCT/KR2011/010189,公开号WO20122012115344)。
此外,已经报道了含有金属结合配体例如咪唑的聚合物Langmuir-Blodgett膜,其从通过组胺与聚(马来酸酐-交替-1-十八烯)的反应得到的聚合物形成(Jeong,H.,Lee,B-J.,Cho,W.J.,Ha,C-S.,Polymeric Langmuir-Blodgett Films Containing Imidazole-coordinatedMetal Complexes,Polymer,41(14):5525-5529(2000);Jung,S-B.,Yoo,S-Y.,Kwon,Y-S.,Characterization of Metal-ion Complexes of IMI-O Polymer LBFilms,J.Kor.Phys.Soc.,37(4):378-308(2000);Yoo,S-Y.,Shin,H-K.,Jeong,H.,Park,J-C,Kwon,Y-S.,Structure Analysis of Langmuir and Langmuir-Blodgett Films withMetal Complexes,Mol.Cryst.and Liq.Cryst.,337:357-360(1999))。也已经报道了使用由其它如4-氨基吡啶、4-氨基甲基吡啶或聚酰亚胺的含氮金属结合配体组成的类似膜(Nagel,J.,Ulrich,O.,Langmuir-Blodgett Layers from Polymer-metal Complexs:Behavior of Monolayers and Preparation of Multilayers,Polymer,36(2):381-386(1995);Bruckner-Lea,C,Petelenz,D.,Janata,Use of Poly(octadeclene-maleicanhydride)for Interfacing Bilayer Membrane Supports in Sensor Applications,J.,Microchimica Acta 100:169-185(1990)。
疏水性和酸值
参照含羧酸官能团的聚合物材料,将酸值定义为中和1g聚合物所需的氢氧化钾的毫克数。因此,它代表了羧酸基团与聚合物的摩尔比,并且反映了聚合物或树脂的极性酸含量。酸值越大,羧酸基团的数量越多,分子的极性越强。
参照聚(1-十八烯-马来酸酐),Suzuki,Y在美国专利5298568中描述了改性烯烃树脂,其通过用碱中和可以溶解于水中并且具有至少30的酸值。这些树脂从“具有至少6个碳原子的α-烯烃和具有至少一种改性剂的马来酸酐中获得,所述至少一种改性剂具有选自包括羟基、氨基、氮丙啶基和巯基的类别中的至少一个功能基团”。此外,Suzuki教导为了获得所需的水溶性,“改性的烯烃树脂的酸值至少为30,优选为80或更多。具有小于30酸值的改性树脂几乎不表现碱可溶性和水的相容性”。
Suzuki教导具有低酸值(小于30)的树脂不溶于水,而那些酸值大于30的树脂是水溶性的。Suzuki的教导远离在本发明中描述的酸值大于100的聚合物,因为本发明中所描述的聚合物是不溶于水的,并且具有疏水性。由Suzuki所公开的树脂能够结合的金属有限。Suzuki公开了他的树脂结合价态小于2的过渡金属化合物。本发明所描述的聚合物能够结合价态小于1的金属化合物。
Koide等人在日本专利05-202234中描述了由具有烯属不饱和二元酸或其酸酐是螯合剂的α、β烯属不饱和单体组成的共聚物树脂。Koide描述的酸值为20至100的树脂是疏水性的,而那些具有更大酸值的树脂是亲水性的。在本发明中详述的聚合物是不溶于水的,而疏水螯合剂具有大于100的酸值。此外,Koide所描述的试剂螯合了钠、钾和镁。本发明中所公开的聚合物不结合钠、钾或镁。因此,Koide的教导了远离基于乙烯的、不溶于水的、具有大于100酸值的能够结合金属的疏水性聚合物。
目前导电聚合物的局限性
目前,所有导电聚合物具有以下的一个或多个缺陷:加工性差,缺乏必需的机械性能和较高的内电阻以及由于聚合物含有掺杂离子受限的设备性能。此外,所有导电聚合物在结构上要求共轭多重键体系或氟代羧酸官能团和配位稳定的过渡金属。因此,现有技术的教导远离导电聚合物,例如具有2,5-呋喃二酮,金属盐的1-十八烯聚合物,其不包含共轭多重键体系、氟代羧酸官能团或配位稳定的过渡金属。
此外,具有2,5-呋喃二酮的1-十八烯聚合物作为导电聚合物成分的用途仅限于作为骨架或支撑体。这些观察表明具有2,5-呋喃二酮的1-十八烯聚合物作为骨架或支撑体的用途,金属结合官能团对于本领域的技术人员来说是预料不到的或不是显而易见的。
综上所述,在文献中没有预料到本文所描述的聚合物的特性,因为无需共轭多重键体系或氟代羧酸官能团和配位稳定的过渡金属就可以得到导电性。这样,聚合物作为导体以描述的方式进行使用是预料不到的,构成了对于聚合物的新的和预料不到的应用,并且以新的、预料不到的方式发挥功能。
而现有技术中所公开的化合物满足各自的具体的目的和要求,上述专利和现有技术没有描述具有2,5-呋喃二酮、金属盐的1-十八烯聚合物的导电聚合物,允许用作导电聚合物而无需共轭多重键体系或氟代羧酸官能团,配位稳定的过渡金属,或金属结合的均聚物组分。
在这方面,根据本发明的具有2,5-呋喃二酮、金属盐的1-十八烯聚合物的导电聚合物基本上背离了传统的概念和现有技术描述的化合物,并且这样做能够提供独特的传输电子的导电性聚合化合物。
因此,可以理解的是,持续存在着对于新的和改进的具有2,5-呋喃二酮、金属盐的1-十八烯聚合物的导体聚合物的需求,其能够用于传输电子。在这方面,本发明实质上满足了这一需求。
发明简述
本发明提供了具有2,5-呋喃二酮、金属盐的1-十八烯聚合物,由1-十八烯、具有2,5-呋喃二酮的聚合物、钠盐制成,如前文所述((Laurino,J.P.,美国专利7,964,688)或由本领域的技术人员熟知的方法制备,其具有新的导电性聚合物特性。这些特性包括但不限于4S/cm至200S/cm以上的电导率,这取决于结合的金属的浓度和性质,电导率与结合到聚合物的金属的数量、聚合物结合具有+1,+2,+3,+4或+5价电荷的金属到聚合物的能力、以及结合两种或多种不同金属至聚合物上的分离的结合位点的能力成比例。
聚合物的基本特征
如本文所述,聚合物含有大量直接结合到提供亲水性金属结合特性的聚合物骨架的羧酸酯基团。聚合物还含有不溶于水的疏水性脂肪族聚合物骨架。这些聚合物提供了特定的、选择性的和快速的金属离子的络合,从而产生了导电聚合物材料。
电导率的比较
各种导电聚合物的电导率在下表中给出:
*如Kumar,D.,Sharma,R.C.,Eur.Polym.J.,34(8):1053-1060(1998)中报道的
具有2,5-呋喃二酮、金属盐的1-十八烯聚合物的电导率读数通过使用用于制备导电聚合物的最低浓度的金属盐溶液来得到。当用于制备导电的具有2,5-呋喃二酮、金属盐的1-十八烯聚合物的金属盐溶液的浓度增加时,得到的导电率也增加。
本文所述的聚合物具有若干有利的潜在用途。该聚合物可用作电能的导电材料。术语“导电材料”是选自用于导电的结构组中的至少一种结构,该组材料包括但不限于薄膜、电线、电极、纳米线、纤维、细丝、油墨、印刷电路和印刷产品。
该聚合物也可用作“电子元件”,其包括但不限于电容器、开关、注塑制品、温度计、螺线管、光伏电池、显示器、导电胶、包括电池、半导体、生物传感器的能量存储电池以及用于测量电阻抗的装置。当在能量存储装置中使用时,所述能量存储装置的至少一个电池使用本文所述的聚合物。能量存储电池由与至少一个电池相连的至少两个电极构成。
此外,由于先前已经报道了过渡金属作为细菌和病毒的消毒剂的用途(McDevitt,C.A.,Ogunniyi,A.D.,Valkov,E.,Lawrence,M.C.,Kobe,B.,McEwan,A.G.,Paton,J.C.,AMolecular Mechanism for Bacterial Susceptibility to Zinc,PLoS Pathog.7(11)2011;Thurman,R.B.,Gerba,C.P.,Bitton,G.,The Molecular Mechanisms of Copper andSilver Ion Disinfection of Bacteria and Viruses,Crit.Rev.inEnviron.Control.18(4):295-315(1989);Molteni,C.,Abicht,H.K.,Solioz,M.,Killingof Bacteria by Copper Surfaces Involves Dissolved Copper,Appl.Environ.Microbiol.,76(12):4099-4101(2010)),这些独特的金属键合聚合物可作为抗菌和抗病毒“屏蔽材料”的成分,其包括但不限于绷带、长袍、手套、缝合线、手术帘、服装、床上用品以及包括片材、屏幕、箱包、口罩、头罩、空气过滤器、房间隔断、地板和注模塑料的屏蔽元件。
长期以来,在提供保护屏障以免受各种辐射源方面,铅被认为是非常有效的材料(A Guide to the Use of Lead for Radiation Shielding,Apublication of the LeadIndustries Association,Inc.,Madison Avenue,纽约)。因此,这些独特的铅-结合的和其它金属-结合的聚合物可以作为“辐射屏蔽”的组件,其包括但不限于衣服、手套、屏幕、房间隔板、隔音材料、床单、寝具、长袍、袋子、口罩、头罩、空气过滤器、房间隔断、地板和注塑塑料。
类似地,这些聚合物也可被用作“防污材料”,其包括但不限于抗真菌剂、抗霉菌剂、抗藻剂和防污剂(Kheybari,S.,Samadi,N.,Hosseini,S.V.,Fazeli,A.,Fazeli,M.R.,Synthesis and Antimicrobial Effects of Silver Nanoparticles Produced byChemical Reduction Method,Daru,18(3):168-172(2010);Schiff,K.,Diehl,D.,Valkirs,A.,Copper Emissions from Antifouling Paint on Recreational Vehicles,Marine Pollution Bulletin,48(3-4):371-377(2004))。
这些聚合物可用于制备“照相材料”,其包括但不限于含有聚合物螯合金属的感光材料,例如银、铂、钯和金(Arentz,D.,Photography in Platinum and Palladium,Platinum Metals Review,49(4):190-195(2005);Sun,Y.,Xia,Y.,Shape-ControlledSynthesis of Gold and Solver Nanoparticles,Science,298,2176(2002))。
这些聚合物也可用于制备“治疗组合物”,其包括但不限于抗癌治疗、抗炎治疗、抗感染治疗、抗糖尿病药物化合物和化妆品制剂。它们也可以用于制备膳食补充剂、诊断剂、牙科填料和植入物(Warra,A.A.,Transition Metal Complexes and Their Applicationin Drugs and Cosmetics-A Review,J.Chem.Pharm.Res.,3(4):951-958(2011))。
这些聚合物也可分别用于制备螯合肥料和无机杀虫剂,或“肥料材料”和“农药材料”。肥料材料包括铁、锰、锌、铜和镍。已经研发出螯合肥料以增加例如铁、锰、锌、铜和镍的微量营养素的利用率。由于这些微量营养素容易氧化或在土壤中沉淀,非螯合金属的利用率不是很有效(Liu,G.,Hanlon,E.,Li,Y.Understanding and Applying ChelatedFertilizers Effectively Based on Soil pH.,Document HS 1208,University ofFlorida,Horticultural Sciences Department,Florida Cooperative ExtensionService,Institute of Food and Agricultural Sciences,2012年11月;Sekhon,B.S.,Chelates for Micronutrient Nutrition among Crops.Resonance,8(7):46-53(2003))。
铜、镉、钴、镍、铅、锌、铁,锰和其他金属是常见的农药成分(Gimeno-Garcia,E,Andreu,V.,Boluda,R.,Heavy Metals Incidence in the Application of InorganicFertilizers and Pesticides to Rice Farming Soils,Environmental Pollution,92(1):19-25(1996))。农药材料包括铜、镉、钴、镍、铅、锌、铁和锰。
这些聚合物也可用作“催化剂材料”。许多研究者已经对铂-多元酸、钯多元酸、铑金属-聚合物和其它过渡金属-聚合物催化剂的用途进行了报道。
在本文中使用时,术语“催化剂材料”包括过渡金属(Mayer,A.B.R.,Mark,J.E.,和Hausner,S.N.,Collodial platinum-polyacid nanocatalyst systems,Angew.Makromol.Chem.,259:45-53(1998);Mayer,A.B.R.,Mark,J.E.,和Hausner,S.N.Palladium nanocatalysts protected by polyacids.J.Appl.Poly.Sci.,70(6):1209-1219(1998);Banavali,R.,Deetz,M.J.,和Schultz,A.K.Transition MetalCatalysts,The Power of Functional Resins in Organic Synthesis(eds.J.Tulla-Puche和F.Albericio),Wiley-VCH Verlag GmbH&Co.KGaA,Weinheim,Germany(2009))和非过渡金属。非过渡金属例如可以是铝和铅。过渡金属例如可以是钪、钛、钒、铬、锰、铁、钴、镍、铜、锌、钇、锆、铌、钼、锝、钌、铑、钯、银、镉、铪、钽、钨、锇、铱、铂、金、汞、镥或铼。
鉴于在现有领域中目前存在的已知类型的导电聚合物所固有的上述缺点,本发明提供了改进的具有2,5-呋喃二酮、金属盐的1-十八烯聚合物的导电聚合物。因此,本发明总的目的是提供一种具有现有技术的优点且不具有部分或全部缺点的新型导电聚合物。
为了实现此目的,本发明提供了一种包含脂肪族聚合物骨架的导电聚合物。骨架是疏水的、脂肪族的、饱和的碳原子结构。每个重复单元上存在两个直接结合到聚合物骨架上的金属羧酸基团。
为了随后的详细的说明书可以更好地理解,而且为了本发明对本领域的贡献可以更好地理解,本文已经相当广泛地概述了本发明更重要的特征。当然将在下文中描述本发明存在的附加特征,并且这将形成所附权利要求书的主题。
在这方面,在详细地解释本发明的至少一个实施方案之前,应当理解的是,本发明的应用方面不限于下面描述或附图中示出的结构详情和部件的布置。本发明可以是其他实施方案并以不同的方式实践和实施。此外,应该理解的是,本文所采用的措辞和术语是为了目的和描述,且不应该被视为是限制。
本领域技术人员将理解的是,本发明所基于的理念可容易地用作设计其它制剂的基础和用于执行本发明若干目的的方法。因此,重要的是,权利要求书被认为包括这些等效的制剂,只要它们不脱离本发明的精神和范围。
本发明提供了新型和改进的具有2,5-呋喃二酮、金属盐的1-十八烯聚合物的导电聚合物,以及使用具有2,5-呋喃二酮、金属盐的1-十八烯聚合物的导电聚合物的方法,其具有现有技术的导电聚合物的优点但没有其部分或全部缺点。
有利地,改进的具有2,5-呋喃二酮、金属盐的1-十八烯聚合物的导电聚合物和使用方法可以容易地和有效地制造、销售和再生产。
本发明提供了新型和改进的具有2,5-呋喃二酮、金属盐的1-十八烯聚合物的导电聚合物和使用方法,在材料和劳动力方面,制造成本低,从而可以低价格销售给消费大众,从而使得这种新型和改进的具有2,5-呋喃二酮、金属盐的1-十八烯聚合物的导电聚合物和使用方法,对消费大众来说是经济可购的。
本发明还提供了新型和改进的具有2,5-呋喃二酮、金属盐的1-十八烯聚合物的导电聚合物和用于能量存储和传输的使用方法。
本发明还提供了新型和改进的具有2,5-呋喃二酮、金属盐的1-十八烯聚合物的导电聚合物和用作抗细菌、抗真菌、抗霉菌(anti-mold)、抗病毒、抗霉菌(anti-mildew)、抗藻剂和防污剂的使用方法。
这些与本发明的其它的目的以及表征本发明的新颖性的各种特征一起,特别是在附加的并形成本发明一部分的权利要求书中指出。为更好地理解本发明、其操作优点和通过其使用所达到的具体目的,参考附图和描述性内容,其中存在本发明示出的优选实施方式。
附图说明
当结合下面的详细描述进行考虑时,将更好地理解本发明且除上面阐述的那些之外的目的将变得显而易见。这样的说明要参照附图,其中:
图1是化合物的图,示出了相关的结构和化学式,其中M是金属离子,R′、R"和R"′各自独立地选自烷基、烯基和芳基;n是包括0的亚甲基基团的整数数目;且n′是单体单元的整数数目。
图2是具有2,5-呋喃二酮、金属盐的1-十八烯聚合物的类似物的合成路线图,其中M是金属,R是H,R′、R"和R"′各自独立地选自烷基、烯基和芳基结构;n是包括0的亚甲基基团的整数数目;n′是单体单元的整数数目,并且x和y分别代表金属和多原子离子的数量。
发明详述
参考附图,且特别是图1,体现本发明的原理和理念的新型和改进的具有2,5-呋喃二酮、金属盐的1-十八烯聚合物的导电聚合物的一个优选实施方案将进行说明。本文所述的聚合物包含多个反应活性基团,其为结合到价金属离子的羧酸酯或羧酸基团。术语“价金属离子”是指价金属离子组中的成员,该价金属组包括一价金属离子、二价金属离子、三价金属离子、四价金属离子和五价金属离子。
反应活性基团直接结合到碳骨架上。
本领域技术人员可理解的是,一价金属离子能够与一个反应活性基团结合,二价金属离子能够与两个反应活性基团结合,三价金属离子能够与三个反应活性基团结合,四价金属离子能够与四个反应活性基团结合,且五价金属离子能够与五个反应活性基团结合。
应当理解的是,当用于指一价离子时,“价金属离子”是指该键具有至少一个反应活性基团。同样地,当用于指二价金属离子时,价金属离子是指该键具有至少两个反应活性基团。当用于指三价金属离子时,术语价金属离子是指该键具有至少三个反应活性基团。当用于指四价金属离子时,术语价金属离子是指该键具有至少四个反应活性基团。当用于五价离子时,术语价金属离子是指该键具有至少五个反应活性基团。
用于合成的初始或主要成分通过授权给J.P.Laurino且名称为“螯合化合物聚(1-十八烷基丁二酸酯)和相应酸聚(1-十八烷基-丁二酸)以及使用方法”的美国专利7,964,688中描述的方法合成。具有2,5-呋喃二酮、金属盐的1-十八烯聚合物的导电聚合物可以由聚羧酸制备,如图2所示,且如下所述:
室温下将10克聚羧酸酯添加到金属硝酸盐溶液中。该反应混合物被允许反应5分钟、真空过滤并干燥固体导电聚合物。
还有其他的方法来生产具有2,5-呋喃二酮、金属盐的1-十八烯聚合物的导电聚合物。一种方法是使用相应的聚酯。聚酯随后水解将产生聚羧酸酯,其然后能与金属硝酸盐溶液进行反应。此外,其它可溶性金属盐可用于由聚羧酸酯制备导电聚合物。阅读本发明后,这些反应方案对有机合成或聚合物合成的领域中的技术人员将是显而易见的。
还应当指出的是,聚羧酸酯具有两个不同的结合位点群体。图2中,如果n=0,重复单元上的反应活性基团相距两个碳而重复单元之间的反应活性基团相距四个碳。很显然的是,这两个结合位点具有不同的三维几何形状。此外,该反应性基团必须连接到骨架上,并且不一定需要连接到相邻的碳原子上。因此,可能的是,柔性的聚合物链(多个)能够包围金属,从而提高与金属离子的结合。
图1示出具有2,5-呋喃二酮、金属盐的1-十八烯聚合物的导电聚合物的相关结构和化学式。图1是的化合物的第一结构。
图2示出具有2,5-呋喃二酮、金属盐的1-十八烯聚合物的导电聚合物类似物的合成路线。
考虑到测得的具有2,5-呋喃二酮、金属盐的1-十八烯聚合物的导电聚合物类似物的电导率,本文所述的聚合物具有多种有利用途。聚合物可以用作导电材料,其包括但不限于薄膜、电线、电极、纳米线、纤维、细丝、油墨、印刷电路和印刷产品。
这些聚合物也可用作电子元件装置,其包括但不限于电解电容器、开关、注塑制品、温度计、螺线管、光伏电池、显示器、导电胶、能量存储池、半导体、生物传感器和电阻抗传感器。
此外,这些金属结合的聚合物可用作抗微生物和抗病毒阻挡材料的组分,其包括但不限于绷带、长袍、手套、缝合线、外科帘、服装、床上用品以及包括片材、屏幕、袋子、口罩、头罩、空气过滤器、房间隔断、地板和注塑塑料的屏蔽元件。
这些金属结合的聚合物可用作辐射阻挡材料,其包括但不限于服装、手套、屏幕、房间隔断
同样地,这些金属结合的聚合物也可用作防污材料,其包括但不限制于抗真菌剂、抗霉菌剂、抗藻剂和防污剂。
这些聚合物在抗癌、抗炎、抗感染和抗糖尿病药物化合物的制备和化妆品制备中,也可以用作抗感染和医药材料。
这些聚合物也可用于制备感光材料,该材料包括但不限于含有螯合金属的聚合物的感光材料。
这些聚合物也可用于制备“治疗组合物”,其包括但不限于,抗癌治疗,抗炎治疗,抗感染治疗,消毒剂,抗糖尿病药物的化合物和化妆品制剂。(Warra,A.A.,TransitionMetal Complexes and Their Application in Drugs and Cosmetics-A Review,J.Chem.Pharm.Res.,3(4):951-958(2011))。它们也可用于制备膳食补充剂、诊断剂和牙科填料以及植入物。
此外,这些聚合物也可用于制备肥料和农药材料。
肥料材料例如可以是肥料微量营养素,例如铁、锰、锌、铜或镍。
农药材料例如可以是铜、镉、钴、镍、铅、锌、铁或锰。
最后,这些聚合物也可被用作“催化剂材料”。催化剂材料例如可以是过渡金属或非过渡金属。
非过渡金属例如可以是铝或铅。过渡金属例如可以是钪、钛、钒、铬、锰、铁、钴、镍、铜、锌、钇、锆、铌、钼、锝、钌、铑、钯、银、镉、铪、钽、钨、锇、铱、铂、金、汞、镥或铼。
至于本发明的使用和操作方式,同样应该从上面的说明变得显而易见。因此,将不提供关于使用和操作方式的进一步讨论。
根据以上说明,然后应该认识到的是,用于本发明的部分的包括尺寸、材料、形状、形式、功能和操作方式、组装和使用的最佳尺寸关系,对本领域技术人员来说是容易想到且显而易见的,且附图中示出和说明书中描述的所有等同关系旨在为本发明所涵盖。
因此,上文仅仅例示说明了本发明的原理。此外,由于本领域技术人员将容易想到许多修改和变化,因此并不希望将本发明限于所示和所述的准确结构和操作,因此,可借助的所有适当的修改和等同变化都落入本发明的保护范围内。
Claims (2)
1.一种导电性聚合物,所述聚合物具有以下式:
其具有大于100的酸值,其中M是价过渡金属离子,所述价过渡金属离子连接至至少一个反应活性基团,R',R"和R'"选自烷基、烯基和芳基,n是包括0的亚甲基基团的整数数目,n'是单体单元的整数数目,其中M是由钪、钛、钒、铬、锰、铁、钴、镍、铜、锌、钇、锆、铌、钼、锝、钌、铑、钯、银、镉、铪、钽、钨、锇、铱、铂、金、汞、镥或铼组成的组中的至少一种。
2.根据权利要求1所述的聚合物,其中所述聚合物用作结构化的导电材料,用于导电。
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| US9786834B2 (en) * | 2012-04-12 | 2017-10-10 | Parker-Hannifin Corporation | EAP transducers with improved performance |
| TW201429147A (zh) | 2012-08-16 | 2014-07-16 | 拜耳智慧財產有限公司 | 用於輥軋介電彈性轉換器之電性互連終端 |
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| CN109385049B (zh) * | 2018-11-06 | 2020-12-18 | 湖北省普林标准技术服务有限公司 | 一种防静电改性聚噻吩树脂及其在精密检测仪器上的应用 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51105388A (zh) * | 1975-02-13 | 1976-09-17 | Inst Francais Du Petrole | |
| EP0747343B1 (en) * | 1995-06-09 | 1999-05-06 | Nippon Shokubai Co., Ltd. | Polycarboxylic monomer, polymer of the same, and detergent composition containing the polymer |
| CN101878242B (zh) * | 2007-11-30 | 2013-09-18 | 约瑟夫·劳里诺 | 聚(2-十八烷基丁二酸盐)及相应的酸聚(2-十八烷基丁二酸)的螯合化合物及使用方法 |
Family Cites Families (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2698298A (en) * | 1951-03-15 | 1954-12-28 | Socony Vacuum Oil Co Inc | Lubricating greases containing an acidic copolymer salt |
| US4150067A (en) * | 1975-02-13 | 1979-04-17 | Institut Francais Du Petrole | Metal-containing polymers, their manufacture and use |
| US4362713A (en) * | 1980-07-25 | 1982-12-07 | Johnson & Johnson Products Inc. | Salts of maleic acid copolymers as dental plaque barrier agents |
| DE3336129A1 (de) * | 1983-10-05 | 1985-04-18 | Battelle-Institut E.V., 6000 Frankfurt | Kationenaustauscher-membran fuer elektrodialyse |
| JP2861589B2 (ja) * | 1992-01-24 | 1999-02-24 | 東洋インキ製造株式会社 | 着色用組成物 |
| JP3064015B2 (ja) * | 1995-01-26 | 2000-07-12 | メルク フロスト カナダ アンド カンパニー | プロスタグランジンレセプターdp |
| EP1027709A1 (en) * | 1997-10-15 | 2000-08-16 | The Dow Chemical Company | Electronically-conductive polymers |
| US6323309B1 (en) * | 1997-12-01 | 2001-11-27 | Massachusetts Institute Of Technology | Conducting polymer transition metal hybrid materials and sensors |
| US6241972B1 (en) * | 1999-02-19 | 2001-06-05 | Block Drug Company, Inc. | Oral care formulation for the treatment of sensitivity teeth |
| TWI284639B (en) | 2000-01-24 | 2007-08-01 | Shionogi & Co | A compound having thrombopoietin receptor agonistic effect |
| JP2003295380A (ja) * | 2002-03-29 | 2003-10-15 | Fuji Photo Film Co Ltd | 熱現像画像記録材料 |
| US20060057209A1 (en) * | 2004-09-16 | 2006-03-16 | Predicant Biosciences, Inc. | Methods, compositions and devices, including microfluidic devices, comprising coated hydrophobic surfaces |
| JP4839833B2 (ja) * | 2005-12-27 | 2011-12-21 | Tdk株式会社 | 電極塗料並びにこれを用いて形成された電極及び電気化学素子 |
| US7446087B2 (en) * | 2006-05-05 | 2008-11-04 | Johnson & Johnson Consumer Companies, Inc. | Compositions comprising low-DP polymerized surfactants and methods of use thereof |
| US7943554B2 (en) * | 2006-06-26 | 2011-05-17 | Bp Exploration Operating Company Limited | Wellbore fluid comprising at least one polymer containing pendant alkyl groups |
| US7785498B2 (en) * | 2007-07-19 | 2010-08-31 | Nanotek Instruments, Inc. | Method of producing conducting polymer-transition metal electro-catalyst composition and electrodes for fuel cells |
| KR100935168B1 (ko) * | 2007-09-21 | 2010-01-06 | 삼성전기주식회사 | 비수계 전도성 나노잉크 조성물 |
| WO2009050203A1 (en) * | 2007-10-15 | 2009-04-23 | Revolymer Limited | Solvent-free synthesis of amphiphilic polymeric material |
| US8420757B1 (en) | 2007-11-30 | 2013-04-16 | Joseph P. Laurino | Chelating compound and the corresponding acid |
| US8519075B2 (en) * | 2007-11-30 | 2013-08-27 | Joseph P. Laurino | Polycarbonate resin, and method of use of, poly (2-octadecyl-butanedioic acid) and the salts and esters thereof |
| GB0801836D0 (en) * | 2008-01-31 | 2008-03-05 | Glaxo Group Ltd | Novel composition |
| CN102144279A (zh) * | 2008-09-03 | 2011-08-03 | 爱默蕾大学 | 量子点、制造量子点的方法以及使用量子点的方法 |
| JP5979158B2 (ja) * | 2012-01-20 | 2016-08-24 | 東洋インキScホールディングス株式会社 | 水蒸気バリア樹脂、水蒸気バリアコート剤、水蒸気バリア膜、および水蒸気バリア積層体 |
| US10858467B2 (en) * | 2013-10-28 | 2020-12-08 | Joseph Laurino | Conducting polymer, 1-octadecene, polymer with 2,5 furnadione, metal salts |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51105388A (zh) * | 1975-02-13 | 1976-09-17 | Inst Francais Du Petrole | |
| EP0747343B1 (en) * | 1995-06-09 | 1999-05-06 | Nippon Shokubai Co., Ltd. | Polycarboxylic monomer, polymer of the same, and detergent composition containing the polymer |
| CN101878242B (zh) * | 2007-11-30 | 2013-09-18 | 约瑟夫·劳里诺 | 聚(2-十八烷基丁二酸盐)及相应的酸聚(2-十八烷基丁二酸)的螯合化合物及使用方法 |
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| CA2926219A1 (en) | 2015-05-07 |
| US11254769B1 (en) | 2022-02-22 |
| US11254770B1 (en) | 2022-02-22 |
| US11254767B1 (en) | 2022-02-22 |
| KR101946696B1 (ko) | 2019-02-11 |
| WO2015066015A1 (en) | 2015-05-07 |
| EA201690878A1 (ru) | 2016-08-31 |
| US10858468B1 (en) | 2020-12-08 |
| AU2014342516B2 (en) | 2018-06-28 |
| EP3063190A4 (en) | 2017-06-21 |
| US20150119529A1 (en) | 2015-04-30 |
| CN105683228A (zh) | 2016-06-15 |
| US10865265B1 (en) | 2020-12-15 |
| MX2016005525A (es) | 2016-10-26 |
| EA035307B1 (ru) | 2020-05-27 |
| US11254768B1 (en) | 2022-02-22 |
| KR20160105772A (ko) | 2016-09-07 |
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