TW201422672A - Multifunctional hyperbranched organic intercalating agent, method for its manufacture and its use - Google Patents
Multifunctional hyperbranched organic intercalating agent, method for its manufacture and its use Download PDFInfo
- Publication number
- TW201422672A TW201422672A TW101145655A TW101145655A TW201422672A TW 201422672 A TW201422672 A TW 201422672A TW 101145655 A TW101145655 A TW 101145655A TW 101145655 A TW101145655 A TW 101145655A TW 201422672 A TW201422672 A TW 201422672A
- Authority
- TW
- Taiwan
- Prior art keywords
- dianhydride
- hydrophilic
- triamine
- agent
- branched
- Prior art date
Links
Abstract
Description
本發明係關於一種具多官能、高分支形態的有機插層劑及其製法和用途，尤其是一種在不同酸鹼的環境下可形成微胞(micelle)而具有螢光發光特性，並藉其豐富官能基，可將氧化石墨完全脫層的雙性超分支狀高分子有機插層劑。 The present invention relates to an organic intercalation agent having a multi-functional, high-branched morphology, and a preparation method and use thereof, in particular, a micelle can be formed in a different acid-base environment to have a fluorescent luminescence property, and An amphoteric super-branched polymer organic intercalation agent which enriches the functional group and completely detaches the graphite oxide.
本發明亦關於一種利用上述具多官能、高分支形態的有機插層劑製造插層之二維層狀材料的方法及所製成的插層之二維層狀材料。 The present invention also relates to a method for producing an intercalated two-dimensional layered material using the above-described multi-functional, high-branched organic intercalating agent and a two-dimensional layered material of the intercalated layer.
本發明又關於一種具多官能、高分支形態的有機插層劑的應用。 The invention further relates to the use of a multi-functional, high-branched organic intercalant.
日本Toyota研究發展中心於1987年首次公開發表奈米分散黏土/聚醯胺(Nylon)複合材料。有別於傳統之黏土/高分子複合材料，奈米尺寸分散(nanometer scale dispersion)之黏土/高分子奈米複合材料，需克服黏土本質上之親水性(hydrophilic)，與疏水性(hydrophobic)本質之高分子基材間的相容性(compatibility)，因此二維層狀材料之應用首先著重於其改質(modify)。例如：中華民國專利第I230181號揭示一種水性聚胺酯樹脂/黏土奈米級複合材料之製備方法，以六~十八烷基雙胺改質層狀黏土，並與水性聚胺酯樹脂組成物預聚合，經過鏈延伸後成為一安定分散液，即水性PU/黏土奈米複合材料；中華民國專利第 I263628號揭示一種改質型黏土、聚氨酯/黏土奈米複合材料之製法，透過親油性改質劑以及一反應性改質劑(具羥基-OH及胺基-NH結構)，該反應性改質劑具有一官能基可與聚氨酯樹脂反應。 The Japan Research and Development Center of Japan first published the nano-dispersed clay/polyamide (Nylon) composite in 1987. Unlike traditional clay/polymer composites, nanometer scale dispersion clay/polymer nanocomposites need to overcome the inherent hydrophilicity and hydrophobic nature of clay. The compatibility between the polymer substrates, so the application of the two-dimensional layered material first focuses on its modification. For example, the Republic of China Patent No. I230181 discloses a method for preparing an aqueous polyurethane resin/clay nano-composite material, which is modified with a layer of octadecyl bisamine and prepolymerized with an aqueous polyurethane resin composition. After the chain is extended, it becomes a stable dispersion, that is, water-based PU/clay nano composite; Republic of China patent I263628 discloses a process for the preparation of a modified clay, polyurethane/clay nanocomposite, through a lipophilic modifier and a reactive modifier (having a hydroxyl-OH and an amine-NH structure), the reactive modification The agent has a monofunctional group reactive with the polyurethane resin.
另於文獻中報導的層狀矽酸鹽黏土插層改質劑，包括12-胺基十二烷酸(12-aminolauric acid)、十六烷基胺(hexadecylamine)、脂肪族胺(fatty amine)、雙(2-羥基乙基)甲基牛脂烷基氯化銨(bis(2-hydroxyethyl)methyl tallow alkyl ammonium chloride)、十八烷基胺(stearylamine)等胺類或四級銨鹽(quaternary ammonium salt)。此類插層劑具有極性銨鹽官能基，能與層間帶電荷之無機層狀分子離子交換，並改變黏土之親水性成為親有機溶劑之性質，提昇黏土層板對有機單體或高分子之親和性，以利下一步之相容、插層與脫層反應。如中華民國專利公告第I364435號所揭露的有機改質層狀物複合材料之製作方法，指出利用助脫層劑改質層狀物，以製得新型有機改質層狀物複合材料，可與大部分之高分子材料形成良好之相互作用力，據以形成脫層型複合材料。T.J.Pinnavaia於文獻(Chem.Mater.,1995,7,2144.)中報導，烷基銨鹽插層劑之長度與層間距大小有關，適當寬度之插層，可讓環氧樹脂單體進入聚合，並進一步分散層狀無機物達到奈米材料之應用效果。C.C.Chou等亦透過改變不同分子量的聚丙烯醚胺(MW 230~5000)、親水/親油作用力、分子分支結構與四級胺基的 比例等，控制黏土之層間距在20~92 Å，經由臨界分子型態改變機制(critical conformation change mechanism)，並歸納層間距變化與插層劑分子長度為正比關係(Macromolecules,2003,36,2187.)(Macromol.Rapid Commun.,2003,24,492.)。因此，提高插層改質劑之分子量及官能基數目或特性，可以進一步提供二維層狀材料另一種分散及排列狀態，進而達到其有效應用。如美國專利第7,442,728號及第7,125,916號，揭露製備含胺基之曼尼希寡聚物(Amine terminal-Mannich Oligomer)及含胺基之環氧樹脂寡聚物(amine-terminating epoxy oligomers)，利用插層劑與矽氧層狀無機黏土在一酸性環境下進行插層反應，進一步藉由控制酸化程度來達到脫層狀態，並更進一步提昇該複合材料之機械性質、透明度及熱性質等。中華民國專利公開第201144360號(同美國專利公開第20110297044號)則提供一種苯胺寡聚物脫層劑，可製備包含該脫層劑之脫層片狀黏土及其方法。此外，中華民國專利第I280261號(同美國專利第8,168,698號)，藉由聚醚三胺及雙酚A縮水甘油醚形成一結構式為多官能且高分支形態之聚胺有機物，此脫層劑經由插層及置換反應，可使蒙脫土及雲母等無機黏土達到直接脫層的效果，再經萃取離子交換形成無序奈米矽片，開發成為抗菌材料。而美國公開第20100190905號亦提供一高度分支狀有機黏土改質劑，其平均分子量介於 200~30000，含有5~300之羥基(hydroxyl)，0~100的羰基(carbonyl)，有機改質黏土層間距可達3~20 nm，進而有效促進黏土材料與高分子之相容性。 Also reported in the literature as layered citrate clay intercalation modifiers, including 12-aminolauric acid, hexadecylamine, fatty amine An amine or a quaternary ammonium such as bis(2-hydroxyethyl)methyl tallow alkyl ammonium chloride or stearylamine Salt). The intercalant has a polar ammonium salt functional group, can ion exchange with the interlayer charged charged layered molecule, and change the hydrophilicity of the clay to become an organic solvent, and enhance the clay layer to the organic monomer or polymer. Affinity to facilitate the next compatibility, intercalation and delamination reactions. For example, the method for preparing an organically modified layered composite material disclosed in the Patent Publication No. I364435 of the Republic of China states that the use of a delaminating agent to modify the layered material to obtain a novel organically modified layered composite material can be Most of the polymer materials form a good interaction force to form a delaminated composite. TJ Pinnavaia reports in the literature (Chem. Mater., 1995, 7, 2144.) that the length of the alkylammonium salt intercalant is related to the size of the interlayer spacing, and the intercalation of the appropriate width allows the epoxy resin monomer to enter the polymerization. And further dispersing the layered inorganic material to achieve the application effect of the nano material. C.C.Chou et al. also changed the molecular weight of polyetheretheramine (MW 230~5000), hydrophilic/lipophilic force, molecular branching structure and quaternary amine group Proportion, etc., control the layer spacing of clay between 20 and 92 Å, through the critical conformation change mechanism, and the variation of the layer spacing is proportional to the length of the intercalating agent molecule (Macromolecules, 2003, 36, 2187). .) (Macromol. Rapid Commun., 2003, 24, 492.). Therefore, by increasing the molecular weight of the intercalation modifier and the number or characteristics of the functional groups, another dispersing and arranging state of the two-dimensional layered material can be further provided, thereby achieving its effective application. The preparation of amine-containing Amine terminal-Mannich Oligomers and amine-terminating epoxy oligomers is disclosed, for example, in U.S. Patent Nos. 7,442,728 and 7,125,916. The intercalation agent and the bismuth oxide layered inorganic clay are intercalated in an acidic environment, and the delamination state is further controlled by controlling the degree of acidification, and the mechanical properties, transparency and thermal properties of the composite material are further improved. The Republic of China Patent Publication No. 201144360 (the same as U.S. Patent Publication No. 20110297044) provides an aniline oligomer delaminating agent for preparing a delaminated sheet-like clay comprising the delaminating agent and a method therefor. In addition, the Republic of China Patent No. I280261 (same as U.S. Patent No. 8,168,698) forms a polyamine organic compound having a polyfunctional and highly branched form by a polyether triamine and a bisphenol A glycidyl ether. Through the intercalation and displacement reaction, the inorganic clay such as montmorillonite and mica can be directly delaminated, and then the extracted ion exchange can be used to form an unordered nanosheet, which is developed into an antibacterial material. U.S. Patent No. 20100190905 also provides a highly branched organic clay modifier having an average molecular weight between 200~30000, containing 5~300 hydroxyl groups, 0~100 carbonyl, organically modified clay layer spacing up to 3~20 nm, which effectively promotes the compatibility of clay materials with polymers.
本發明則提出一種製備新穎的雙性超分支狀高分子之方法，作為有機改質化插層劑及以其於二維層狀材料進行插層，進而形成無序脫層化混成材料，尤其是關於石墨烯(graphene)薄片混成二維材料，該插層劑係以聚醚三胺及二酸酐聚合形成，結構上具有醯胺酸(amic acid)、醯亞胺(amide)及豐富外圍胺基，在不同酸鹼的環境下可形成微胞(micelle)與特殊螢光發光特性；藉由該插層劑之豐富官能基與結構，可將氧化石墨完全脫層，並可應用於其他二維層狀材料之脫層化，包括陽離子型水滑石、陰離子型矽酸鹽黏土與有機官能化之層狀石墨碳材等。 The invention provides a method for preparing a novel amphiphilic super-branched polymer, which is used as an organic modified intercalation agent and intercalated in a two-dimensional layered material to form a disordered delamination hybrid material, in particular It is a two-dimensional material of graphene mixed with a polyether triamine and a dianhydride. The structure has amic acid, amide and rich peripheral amines. Base, in the environment of different acid and alkali can form microcapsules (micelle) and special fluorescent luminescence properties; through the rich functional groups and structures of the intercalation agent, the graphite oxide can be completely delaminated, and can be applied to other two The delamination of the stratified material includes cationic hydrotalcite, anionic silicate clay and organofunctionalized layered graphite carbon.
本發明之一目的在於提供一種具多官能、高分支形態的有機插層劑及其製法和用途。 It is an object of the present invention to provide an organic intercalant having a polyfunctional, high branched form, a process for its preparation and use.
為達上述目的，本發明提供一種製造多官能、高分支形態的有機插層劑的方法，包括一合成步驟，其係利用具有聚醚基鏈段之親水性三胺類與雙官能基二酸酐(di-anhydride)進行合成反應，以形成一具聚 醯胺酸(polyamic acid)與聚醯亞胺(polyimide)結構之A2B3型超分支狀高分子插層劑。 To achieve the above object, the present invention provides a process for producing a polyfunctional, high-branched organic intercalant comprising a synthetic step utilizing a hydrophilic triamine having a polyether-based segment and a difunctional dianhydride. A di-anhydride is subjected to a synthesis reaction to form an A 2 B 3 type super-branched polymer intercalation agent having a polyamic acid and a polyimide structure.
上述具有聚醚基鏈段之親水性三胺類係聚氧化丙烯三胺(poly(oxypropylene)triamine)，其具有如下之結構：
其中a=4~5、16~17或27~28。 Where a=4~5, 16~17 or 27~28.
市面上可使用之具有聚醚基鏈段之親水性三胺類包括Jeffamine® T-403、T-3000或T-5000之化合物。 Hydrophilic triamines having a polyether-based segment which can be used in the market include compounds of Jeffamine ® T-403, T-3000 or T-5000.
上述雙官能基二酸酐係選自於由4,4'-氧代雙苯酐(4,4'-oxydiphthalic dianhydride(ODPA))、均苯四甲酸二酐(pyromellitic dianhydride(PMDA))、3,3',4,4'-二苯酮四甲酸二酐(3,3',4,4'-Benzophenone tetracarboxilic dianhydride(BTDA))、3,3',4,4'-聯苯四羧酸二酐(3,3',4,4'-Biphenyl tetracarboxylic dianhydride(BPDA))以及4,4-六氟異丙基鄰苯二甲酸酐(hexafluoroisopropylidene diphthalic dianhydride(6FDA))所組成之
群組。上述4,4'-氧代雙苯酐(4,4'-oxydiphthalic dianhydride(ODPA))，具有如下之結構：
其中，該具有聚醚基鏈段之親水性三胺類與雙官能基二酸酐於合成反應中的莫耳比為0.7：1~2：1。 Wherein, the molar ratio of the hydrophilic triamine having a polyether-based segment to the difunctional dianhydride in the synthesis reaction is 0.7:1 to 2:1.
其中，該具有聚醚基鏈段之親水性三胺類與雙官能基二酸酐的合成係在低於室溫下的溫度進行以避免反應太迅速造成膠凝化，較佳的是在冰浴(0℃)下為佳，緩慢進料，整體濃度為0.05~0.09 M。所述之整體濃度係指具有聚醚基鏈段之親水性三胺類與雙官能基二酸酐二者於溶劑中的濃度。 Wherein the synthesis of the hydrophilic triamine having a polyether-based segment and the difunctional dianhydride is carried out at a temperature lower than room temperature to prevent the reaction from being too rapid to cause gelation, preferably in an ice bath. (0 ° C) is better, slowly feeding, the overall concentration is 0.05 ~ 0.09 M. The overall concentration refers to the concentration of both hydrophilic triamines and difunctional dianhydrides having a polyether-based segment in a solvent.
較佳的是，在與該具有聚醚基鏈段之親水性三胺類合成之前，該雙官能基二酸酐單體係經一預處理步驟以降低水解程度，該預處理步驟係包括使用熱環化法(如：抽真空加熱170℃持續6小時)或化學環化法(如：利用觸媒吡啶與脫水劑醋酸酐作用環化後並抽真空除之)。 Preferably, the difunctional dianhydride single system undergoes a pretreatment step to reduce the degree of hydrolysis prior to synthesis with the hydrophilic triamine having a polyether-based segment, the pretreatment step including the use of heat The cyclization method (for example, heating at 170 ° C for 6 hours) or chemical cyclization (for example, cyclization with catalytic pyridine and dehydrating agent acetic anhydride and vacuuming).
其中，於該合成步驟中，係令該具有聚醚基鏈段之親水性三胺類與雙官能基二酸酐於一溶劑中進行該合成反應，所述之溶劑為無水之N,N-二甲基乙醯胺(N,N-Dimethylacetamide；DMAc)。 Wherein, in the synthesizing step, the hydrophilic triamine having a polyether-based segment and the difunctional dianhydride are subjected to the synthesis reaction in a solvent, wherein the solvent is anhydrous N, N-di N,N-Dimethylacetamide (DMAc).
其中，本發明所提供之製造多官能、高分支形態的有機插層劑的方法，尚於該合成步驟後包含一去除溶劑步驟，其係包括利用減壓蒸餾除去溶劑，置入真空烘箱中，於60℃下乾燥24小時，以移除殘留溶劑，所獲得之A2B3型超分支狀高分子插層劑為橘黃色之超分支狀聚醯胺酸(hyperbranched polyamic acid；HBPAA)。 The method for producing a polyfunctional, high-branched organic intercalation agent provided by the present invention further comprises a solvent removal step after the synthesizing step, which comprises removing the solvent by distillation under reduced pressure and placing it in a vacuum oven. After drying at 60 ° C for 24 hours to remove residual solvent, the obtained A 2 B 3 type super-branched polymer intercalating agent was orange-brown hyperbranched polyamic acid (HBPAA).
其中，本發明所提供之製造多官能、高分支形態的有機插層劑的方法，尚於該合成步驟後包含一去除溶劑步驟，其係包括使用熱醯胺化(thermal imidization)方式，通氮氣下將溫度升到150℃進行迴流反應24小時，透過減壓蒸餾除去溶劑後置入真空烘箱中，於60℃下乾燥6小時，以移除殘留溶劑，所獲得之A2B3型超分支狀高分子插層劑為深黃色之超分支狀聚醯亞胺(hyperbranched polyimide；HBPI)。 The method for producing a polyfunctional, high-branched organic intercalation agent provided by the present invention further comprises a solvent removal step after the synthesizing step, which comprises using a thermal imidization method to pass nitrogen gas. The temperature was raised to 150 ° C for refluxing for 24 hours, the solvent was removed by distillation under reduced pressure, placed in a vacuum oven, and dried at 60 ° C for 6 hours to remove residual solvent, and the obtained A 2 B 3 type super-branched The polymer intercalating agent is a deep yellow hyperbranched polyimide (HBPI).
本發明亦提供一種由上述方法所製成的插層劑。 The present invention also provides an intercalation agent prepared by the above method.
其中，該插層劑的NH2當量數利用胺滴定量測，其介於8.32~18.32 mequiv/g；GPC分子量(MW)係介於5000~7500 g/mol；分子量分布的指數(polydispersity index；PDI)係介於2.0~3.8。 Wherein, the NH 2 equivalent number of the intercalant is determined by amine titration, which is between 8.32 and 18.32 mequiv/g; the GPC molecular weight (M W ) is between 5000 and 7500 g/mol; the molecular weight distribution index (polydispersity index) ;PDI) is between 2.0 and 3.8.
其中，該插層劑係於不同環境(pH值)能形成粒徑大小介於5~400 nm的微胞型態。 The intercalating agent is capable of forming a microcell type with a particle size ranging from 5 to 400 nm in different environments (pH values).
本發明之另一目的在於提供一種利用上述具多官能、高分支形態的有機插層劑改質二維層狀材料的方法及所改質之二維層狀材料，藉 由上述具有聚醚基鏈段之親水性三胺類及雙官能基二酸酐反應形成之插層劑，於二維層狀材料混合而進行插層反應，並在插層劑和二維層狀材料以一定比例混合時達到脫層效果，形成無序分散狀態之二維層狀材料。 Another object of the present invention is to provide a method for modifying a two-dimensional layered material by using the above-mentioned multi-functional, high-branched organic intercalation agent and a modified two-dimensional layered material. An intercalation agent formed by reacting the above-mentioned hydrophilic triamine having a polyether-based segment and a difunctional dianhydride, and intercalating the two-dimensional layered material, and intercalating the agent and two-dimensional layer When the materials are mixed in a certain ratio, the delamination effect is achieved, and a two-dimensional layered material in a disorderly dispersed state is formed.
為達上述目的，本發明提供一種利用上述插層劑改質二維層狀材料的方法，包括將上述插層劑與一無機酸或鹼中和而離子化，以形成一離子化之雙性多官能基樹枝狀型態有機高分子；再使該離子化之雙性多官能基樹枝狀型態有機高分子於水相中形成微胞；將該離子化之雙性多官能基樹枝狀型態有機高分子與待處理之二維層狀材料混合進行插層反應以獲得改質之二維層狀材料。 In order to achieve the above object, the present invention provides a method for modifying a two-dimensional layered material by using the above intercalating agent, comprising neutralizing the intercalating agent with an inorganic acid or a base to form an ionized bisexuality. a polyfunctional dendritic organic polymer; the ionized amphoteric polyfunctional dendritic organic polymer is then formed into a microcell in an aqueous phase; the ionized amphoteric polyfunctional dendrimer The organic polymer is mixed with the two-dimensional layered material to be processed to carry out an intercalation reaction to obtain a modified two-dimensional layered material.
上述無機酸可為鹽酸、硝酸、磷酸、硫酸或任何具相同效果的酸；上述無機鹼可為鹼金屬或鹼土金屬之氫氧化物或氯化物，或任何具相同效果的鹼。 The above inorganic acid may be hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid or any acid having the same effect; the above inorganic base may be a hydroxide or chloride of an alkali metal or an alkaline earth metal, or any base having the same effect.
上述離子化之雙性多官能基樹枝狀型態有機高分子的離子化官能基數、化學鍵結型式、分子大小等，可以根據欲插層物特性來進行調整，以達到其作用。 The ionization functional group number, the chemical bonding type, the molecular size, and the like of the ionized amphiphilic dendritic organic polymer can be adjusted according to the properties of the intercalation layer to achieve its effect.
其中，該待處理之二維層狀材料與離子化之雙性多官能基樹枝狀型態有機高分子的莫耳比為1：1~1：9。 The molar ratio of the two-dimensional layered material to be treated to the ionized amphoteric polyfunctional dendritic organic polymer is from 1:1 to 1:9.
上述將該離子化之雙性多官能基樹枝狀型態有機高分子與待處理之二維層狀材料混合係使用非質子極性親水共溶劑，其可為N,N-二甲基乙醯胺(N,N-Dimethylacetamide；DMAc)、二甲基甲醯胺(dimethylfomamide；DMF)二甲基亞碸(dimethylsulfoxide；DMSO)或N-甲基吡咯烷酮(1-methyl-2-pyrrolidone；NMP)等。 The above-mentioned ionized amphiphilic dendritic organic polymer and the two-dimensional layered material to be treated are mixed with an aprotic polar hydrophilic cosolvent, which may be N,N-dimethylacetamide. (N, N-Dimethylacetamide; DMAc), dimethylfomamide (DMF) dimethylsulfoxide (DMSO) or N-methyl-2-pyrrolidone (NMP).
上述待處理之二維層狀材料可為氧化石墨、蒙脫土、雲母、高嶺土、蛭石、水滑石(layered double hydroxides，LDH)或任何可脫層的二維層狀材料，其中較佳的二維層狀材料為氧化石墨、蒙脫土與水滑石。 The two-dimensional layered material to be treated may be graphite oxide, montmorillonite, mica, kaolin, vermiculite, layered double hydroxides (LDH) or any delaminable two-dimensional layered material, of which preferred The two-dimensional layered material is graphite oxide, montmorillonite and hydrotalcite.
該氧化石墨係利用高純度之石墨粉末為原料，以最常見之Hummers-Offeman方法進行氧化所獲得者。 The graphite oxide is obtained by using high-purity graphite powder as a raw material and oxidizing by the most common Hummers-Offeman method.
此外，由試驗結果發現，本發明之超分支狀聚醯胺酸(HBPAA)插層於氧化石墨，於重量比1：3時可有效達到無序脫層化；超分支狀聚醯亞胺(HBPI)插層於氧化石墨，於重量比1：7時可有效達到無序脫層化。 In addition, it was found from the test results that the super-branched polylysine (HBPAA) of the present invention is intercalated in graphite oxide, and can effectively achieve disordered delamination at a weight ratio of 1:3; super-branched polyimine ( HBPI) intercalated in graphite oxide to effectively achieve disordered delamination at a weight ratio of 1:7.
上述無序脫層化之二維層狀材料，如氧化石墨烯(graphene oxide)，可透過習知的有效還原方法，還原為單層化之石墨烯(graphene)材料。如文獻(Nanoscale,2011,3,3132.)或(J.Phys.Chem.C 2011,115,11327)所報導。可進一步應用於熱或電傳導性材料包括：電極、電子 元件、電晶體、導電薄膜、鋰電池材料、超級電容及複合材料等，製備電化學電池、燃料電池、軟性基板、顯示面板、太陽能板等光電產品。 The above-mentioned disordered delaminated two-dimensional layered material, such as graphene oxide, can be reduced to a single-layered graphene material by a conventional effective reduction method. As reported in the literature ( Nanoscale , 2011 , 3, 3132.) or ( J. Phys . Chem . C 2011 , 115 , 11327). It can be further applied to thermal or electrical conductive materials including: electrodes, electronic components, transistors, conductive films, lithium battery materials, super capacitors and composite materials, etc., to prepare electrochemical cells, fuel cells, flexible substrates, display panels, solar panels And other optoelectronic products.
本發明亦提供一種由上述方法所改質之二維層狀材料。 The present invention also provides a two-dimensional layered material modified by the above method.
本發明之又一目的在於提供一種具多官能、高分支形態的有機插層劑的應用，藉由此高分支形態有機插層劑，在不同酸鹼的環境下可形成奈米微胞，於鹼性環境下還具有螢光特性，可作為奈米容器、分子自組裝、藥物輸送與藥物追蹤劑的應用。 Another object of the present invention is to provide an organic intercalation agent having a multi-functional, high-branched morphology, whereby a high-branched organic intercalation agent can form nano-cells in different acid-base environments. It also has fluorescent properties in an alkaline environment and can be used as a nano container, molecular self-assembly, drug delivery and drug tracking agent.
為達上述目的，本發明提供一種上述具多官能、高分支形態的有機插層劑應用於奈米容器、分子自組裝、藥物輸送與藥物追蹤劑的用途，該插層劑於酸性或鹼性環境形成粒徑大小係介於5~400 nm的奈米微胞型態。 In order to achieve the above object, the present invention provides the use of the above-mentioned multi-functional, high-branched organic intercalation agent for nano container, molecular self-assembly, drug delivery and drug tracking agent, the intercalant is acidic or alkaline. The environment forms a nanopore type with a particle size ranging from 5 to 400 nm.
本發明所述之多官能、高分支形態的有機插層劑於不同環境(酸或鹼)可有效形成奈米微胞型態，並於鹼性環境下觀察到具有螢光效應(吸收波長位於~360 nm)，尤其是超分支聚醯胺酸結構者。因為其豐富的官能基以及特殊的分子結構可應用於藥物輸送、藥物追蹤劑、奈米容器和分子自組裝的應用。 The polyfunctional, high-branched organic intercalation agent of the present invention can effectively form a nanopore type in different environments (acid or alkali), and has a fluorescent effect observed under an alkaline environment (the absorption wavelength is located ~360 nm), especially for super-branched poly-proline structures. Because of its rich functional groups and special molecular structure, it can be applied to drug delivery, drug tracking agents, nano containers and molecular self-assembly applications.
「二維層狀材料」係如蒙脫土、合成氟化雲母及水滑石等材料，可經由有機插層改質劑(intercalating agent)之離子交換反應，允許單體之進出並將層間距由10 Å增加至約20~30 Å。 "Two-dimensional layered materials" are materials such as montmorillonite, synthetic fluorinated mica and hydrotalcite, which can be exchanged by an intercalating agent to allow monomer to enter and exit and to separate the layers. 10 Å increases to approximately 20~30 Å.
「插層(intercalation)狀態」係指層板間以固定距離之有序排列分散存在，即層與層之間***有機分子，並阻止層與層之間的作用力與再堆疊。 "Intercalation state" means that the layers are dispersed in an ordered arrangement at a fixed distance, that is, organic molecules are interposed between the layers, and the forces and re-stacking between the layers are prevented.
「脫層(exfoliation)狀態」係指每單一層以不規則之距離及方向存在，通常可藉有機插層改質劑提高相當層間距，增加無機層板與有機高分子之親和性後，再經由聚合反應、混煉加工或再分散機制而得到所謂的有機/無機高分子奈米複合材料。 "Exfoliation state" means that each single layer exists in an irregular distance and direction. Usually, an organic intercalation modifier can be used to increase the interlayer spacing and increase the affinity of the inorganic laminate to the organic polymer. A so-called organic/inorganic polymer nanocomposite is obtained via a polymerization reaction, a kneading process or a redispersion mechanism.
「A2B3型」中的A2單體係指雙官能基二酸酐，而B3單體係指具有聚醚基鏈段之親水性三胺類。 "A 2 B 3 type" refers to a monomer A 2 is a bifunctional acid anhydride, and the monomer B 3 means a group having a hydrophilic polyether segments of triamines.
以下則舉出數較佳實施例說明本發明的製造過程，並由比較例了解相對製造條件及結果。 Hereinafter, preferred embodiments will be described to illustrate the manufacturing process of the present invention, and comparative examples will be given to the relative manufacturing conditions and results.
本發明實施例及比較例使用之原料包括：(1)聚醚二胺(poly(propylene glycol)diamine)購自於Huntsman Chemical Co.或
Aldrich Chemical Co.，商標名Jeffamine® T-403，平均分子量440，結構式如下：
其中a=4~5。 Where a=4~5.
雙官能基二酸酐為4,4’-Oxydiphthalic dianhydride(ODPA)，具有如下之結構：
步驟(a)：多官能、高分支形態的有機插層劑(超分支狀聚醯胺酸及超分支狀聚醯亞胺)之合成：採用一階段合成法，使用500 ml圓底雙頸瓶，架好後通入氮氣10分鐘。三胺類T-403(7.09克，0.0161莫耳)與預處理過之雙官能基二酸酐ODPA(5克，0.0161莫耳)的莫耳比為1：1，以無水DMAc為 溶劑，先加入三胺類和部分DMAc(100 ml)於雙頸瓶，在室溫下攪拌混合；待三胺類全部溶解後，再將雙官能基二酸酐和部分DMAc(260 ml)溶解後，將溶液使用進料管慢慢滴入雙頸瓶，並在冰浴下進行反應，避免反應太迅速造成凝膠化，整體濃度為0.09 M。進料完畢後，反應2~3小時即可得到超分支聚醯胺酸高分子溶液，即多官能、高分支形態的有機插層劑。 Step (a): Synthesis of a multi-functional, high-branched organic intercalant (hyperbranched poly-proline and super-branched polyimine): using a one-stage synthesis using a 500 ml round bottom flask After the rack is set, nitrogen is introduced for 10 minutes. The molar ratio of triamine T-403 (7.09 g, 0.0161 mol) to the pretreated difunctional dianhydride ODPA (5 g, 0.0161 mol) was 1:1, with anhydrous DMAc as Solvent, first add triamine and part of DMAc (100 ml) in a double-necked flask, stir and mix at room temperature; after all the triamines are dissolved, difunctional dianhydride and part of DMAc (260 ml) are dissolved. The solution was slowly dropped into a double-necked flask using a feed tube, and the reaction was carried out in an ice bath to prevent the reaction from being too rapid to cause gelation, and the overall concentration was 0.09 M. After the feed is completed, the reaction can be carried out for 2 to 3 hours to obtain a super-branched polyaminic acid polymer solution, that is, a polyfunctional, high-branched organic intercalation agent.
將超分支聚醯胺酸高分子溶液均分一半，其中一半利用減壓蒸餾除去溶劑，置入真空烘箱中，於60℃下乾燥6小時，以移除殘留溶劑，取得產物為橘黃色之超分支狀聚醯胺酸(hyperbranched polyamic acid-11，簡稱HBPAA-11)。 The super-branched polyaminic acid polymer solution was divided into half, and half of the solvent was distilled off under reduced pressure, placed in a vacuum oven, and dried at 60 ° C for 6 hours to remove residual solvent to obtain an orange-yellow product. Branched polyamic acid (HBPAA-11).
步驟(b)：二維層狀材料-氧化石墨的合成 Step (b): Synthesis of two-dimensional layered material - graphite oxide
氧化石墨的合成係採用高純度之石墨粉末當原料，粒徑<20 μm，Aldrich公司製造；其氧化的方法是以最常見之Hummers-Offeman方法為之(J.Am.Chem.Soc.,1958,80,1339.)。石墨粉末40克及硝酸鈉50克混入2300 ml濃硫酸中並以冰浴方式處理，過錳酸鉀300克慢慢加入其中，並攪拌控制讓此混合物之溫度不要超過20℃，混合物於35℃下攪拌30分鐘後再以去離子水稀釋至5200 ml，之後於98℃攪拌15分鐘，反應終止藉由加入含3 wt%之雙氧水並於10℃下攪拌，接下來以去離子水多次清洗離心直到泥狀物清洗後之去離子水 pH值接近7.0為止，最後在藉由真空乾燥，條件為溫度100℃，乾燥時間48小時，可以得到改質氧化石墨粉體。 The synthesis of graphite oxide is based on high-purity graphite powder as raw material, particle size <20 μm, manufactured by Aldrich; its oxidation method is based on the most common Hummers-Offeman method ( J.Am.Chem.Soc. , 1958). , 80, 1339.). 40 grams of graphite powder and 50 grams of sodium nitrate are mixed into 2300 ml of concentrated sulfuric acid and treated in an ice bath. 300 g of potassium permanganate is slowly added thereto, and the temperature of the mixture is not more than 20 ° C, and the mixture is at 35 ° C. After stirring for 30 minutes, it was diluted with deionized water to 5200 ml, then stirred at 98 ° C for 15 minutes. The reaction was terminated by adding 3 wt% of hydrogen peroxide and stirring at 10 ° C, followed by multiple washings with deionized water. After centrifugation until the pH of the deionized water after the washing of the sludge was close to 7.0, finally, the modified graphite oxide powder was obtained by vacuum drying under the conditions of a temperature of 100 ° C and a drying time of 48 hours.
步驟(c)：超分支狀高分子/氧化石墨之插層 Step (c): intercalation of super-branched polymer/graphite oxide
取1克氧化石墨與HBPAA-11，依重量比1/1、1/2、1/3、1/5、1/7至1/9等，進行氧化石墨插層化改質。乃以20 ml之DMAc為溶劑，先溶解超分支狀高分子於瓶中，在室溫下攪拌，並導入適當比例之中和離子，使得該超分支狀高分子形成奈米微胞型態(5~400 nm)。等其全部溶解後，再將預膨潤於熱水之氧化石墨(水20 ml)加入，兩者持續攪拌分散24小時。改質分散後之漿料過濾除去溶劑，置入真空烘箱中，於60℃下乾燥6小時，以移除殘留溶劑，取得粉狀產物。將其樣品進行FTIR、XRD、TEM、SEM等分析。 1 g of graphite oxide and HBPAA-11 were used, and the graphite oxide intercalation was modified according to the weight ratio of 1/1, 1/2, 1/3, 1/5, 1/7 to 1/9, and the like. Using 20 ml of DMAc as a solvent, the super-branched polymer is first dissolved in a bottle, stirred at room temperature, and an appropriate ratio of ions is introduced, so that the super-branched polymer forms a nanopore type ( 5~400 nm). After all of them were dissolved, oxidized graphite (20 ml of water) pre-swelled in hot water was added, and the mixture was continuously stirred and dispersed for 24 hours. The slurry after the modified dispersion was filtered to remove the solvent, placed in a vacuum oven, and dried at 60 ° C for 6 hours to remove the residual solvent to obtain a powdery product. The samples were subjected to analysis by FTIR, XRD, TEM, SEM, and the like.
步驟(a)：改變T-403與ODPA的莫耳比為2：1(簡稱HBPAA-21)。 Step (a): Change the molar ratio of T-403 to ODPA to 2:1 (HBPAA-21 for short).
步驟(b)：同實施例1。 Step (b): Same as Example 1.
步驟(c)：同實施例1，其不同之處在於該插層劑以本實施例步驟(a)者取代之。 Step (c): Same as Example 1, except that the intercalant was replaced by the step (a) of the present example.
步驟(a)：改變T-403與ODPA的莫耳比為2.2：3(簡稱HBPAA-23)。 Step (a): Change the molar ratio of T-403 to ODPA to 2.2:3 (HBPAA-23 for short).
步驟(b)：同實施例1。 Step (b): Same as Example 1.
步驟(c)：同實施例1，其不同之處在於該插層劑以本實施例步驟(a)者取代之。 Step (c): Same as Example 1, except that the intercalant was replaced by the step (a) of the present example.
步驟(a)：將上述實施例1、實施例2及比較例中，步驟(a)所合成之另一半超分支聚醯胺酸溶液(HBPAA-11、HBPAA-21及HBPAA-23)，使用熱醯胺化方式進行環化，將溫度升到150℃進行迴流，在通氮氣下反應24小時，完成熟化後，利用減壓蒸餾裝置除去大部分溶劑，置入真空烘箱中，於60℃下乾燥6小時，以移除殘留溶劑，可得產物為深黃色之超分支狀聚醯亞胺(hyperbranched polyimide-11，簡稱HBPI-11、HBPI-21及HBPI-23)。 Step (a): In the above-mentioned Example 1, Example 2 and Comparative Example, the other half of the super-branched polyaminic acid solution (HBPAA-11, HBPAA-21 and HBPAA-23) synthesized in the step (a) was used. The cyclization was carried out by thermal hydrazylation, the temperature was raised to 150 ° C, refluxed, and reacted under nitrogen for 24 hours. After completion of aging, most of the solvent was removed by a vacuum distillation apparatus and placed in a vacuum oven at 60 ° C. After drying for 6 hours to remove residual solvent, the product was obtained as a dark yellow hyperbranched polyimide-11 (HBPI-11, HBPI-21 and HBPI-23).
步驟(b)：同實施例1。 Step (b): Same as Example 1.
步驟(c)：同實施例1，其不同之處在於該插層劑以本實施例步驟(a)者取代之。 Step (c): Same as Example 1, except that the intercalant was replaced by the step (a) of the present example.
超分支狀高分子分為聚醯胺酸及超分支狀聚醯亞胺兩系列，第一圖說明實施例中樹枝狀高分子結構及官能基特性差異。實施例與比較例中的原料組成比例、凝膠滲透層析法(GPC)所測定之分子量及分佈、胺滴定當量與熱性質等則列於表一。 The super-branched polymer is divided into two series of poly-proline and super-branched polyimine. The first figure illustrates the difference in dendrimer structure and functional group characteristics in the examples. The composition ratio of the raw materials in the examples and the comparative examples, the molecular weight and distribution measured by gel permeation chromatography (GPC), the amine titration equivalent and the thermal properties are shown in Table 1.
第二圖為實施例中所述超分支狀高分子微胞之穿透式電子顯微鏡(TEM)照片。第三圖為此超分支狀高分子微胞之螢光光譜吸收圖，可以發現於鹼性環境下具有螢光效應(吸收波長位於~360 nm)，尤其是超分支聚醯胺酸結構者。 The second figure is a transmission electron microscope (TEM) photograph of the super-branched polymer micelles in the examples. The third figure shows the fluorescence absorption spectrum of the super-branched polymer micelles, which can be found to have a fluorescent effect in an alkaline environment (absorption wavelength is ~360 nm), especially for super-branched poly-proline structures.
透過結構上具有醯胺酸、醯亞胺及豐富外圍胺基之雙性超分支狀高分子微胞，作為有機改質化插層劑製備二維層狀之無序脫層化混成材料，乃透過分子間/內強氫鍵、樹枝狀三維立體特性、醯胺酸或醯亞胺鍵結、中和離子化官能基作用力與親/疏水作用力等來有效達成，尤其是氧化石墨烯薄片混成材料，其機制如第四圖所示。 A two-dimensional layered disordered delamination hybrid material is prepared as an organically modified intercalating agent by a bimodal super-branched polymer microcell having a structure of proline, samarium and a rich peripheral amine group. It is effectively achieved by intermolecular/internal strong hydrogen bonding, dendritic three-dimensional characteristics, proline or sulfhydryl bond bonding, neutralization of ionizing functional groups and pro-/hydrophobic forces, especially graphene oxide sheets. The structure of the mixed material is shown in the fourth figure.
請參看表二與第五圖，其係以X光繞射(X-ray Diffraction，XRD)分析各實施例步驟(c)之插層及脫層結果，由於氧化石墨表面含有豐富含氧官能基，熱分析無法判斷其混成效果，故以氮元素分析來觀察比較，如第五圖所示。當於一定比例下，XRD之波峰呈現不明顯(featureless)，表示已經有部分脫層而可能達到無序狀態。 Please refer to Tables 2 and 5 for X-ray Diffraction (XRD) analysis of the intercalation and delamination results of step (c) of each example, since the surface of the graphite oxide is rich in oxygen-containing functional groups. Thermal analysis cannot judge the mixing effect, so the nitrogen element analysis is used to observe and compare, as shown in the fifth figure. When at a certain ratio, the peak of XRD is not characteristic, indicating that there has been partial delamination and may reach a disordered state.
第六圖以TEM觀察水分散之單層氧化石墨烯及其電子衍射(SAED)分析來佐證，很明顯可看到清晰六點內環(1110)與六點外環(2110)；此為文獻中所指出之單層石墨材料證據(ACS Nano.,2011,5,1253.)(Solid State Commun.2007,143,101.)(ACS Nano.,2010,4,3169.)。而透過環氧樹脂包埋切片亦可同樣獲得脫層化無序分散之單層氧化石墨烯確實證據，如第七圖所示。 The sixth figure is confirmed by TEM observation of water-dispersed single-layer graphene oxide and its electron diffraction (SAED) analysis. It is obvious that the clear six-point inner ring (1110) and six-point outer ring (2110) can be seen; Evidence for single-layer graphite materials as noted ( ACS Nano. , 2011, 5, 1253.) (Solution State Commun. 2007, 143, 101.) ( ACS Nano. , 2010, 4, 3169.). The evidence of delamination-distributed monolayer graphene oxide can also be obtained by embedding the slice by epoxy resin, as shown in the seventh figure.
第八圖則比較拉曼光譜。其中ID/IG值越大代表其結構缺陷越大，而2700 cm-1附近的2D峰的強度、形狀和波峰位置，可以判斷石墨烯的層數，圖中發現2D峰隨著超分支狀高分子量增加，其2D峰亦有所偏移，根據相關文獻證實隨著石墨層數越少，其2D峰會往低波數偏移，我們在圖譜上亦可看到此趨勢(Chem.Rev.,2010,110,132.)(J.Mater.Chem.,2009,19,2457)。 The eighth graph compares Raman spectra. The larger the I D /I G value is, the larger the structural defect is, and the intensity, shape and peak position of the 2D peak near 2700 cm -1 can determine the number of graphene layers. The 2D peak is found along with the hyperbranche The high molecular weight increases, and the 2D peak also shifts. According to the related literature, as the number of graphite layers decreases, the 2D peak shifts to a low wave number. We can also see this trend on the map ( Chem.Rev . , 2010, 110, 132.) ( J. Mater. Chem. , 2009, 19, 2457).
以上敘述以及範例僅為說明和示範本發明之技術，使所屬技術領域中具有通常知識者能夠輕易了解並據以實施本發明。除了在此所述之外，本發明還有很多實施例和適用範圍，以及很多改變、修飾以及等效的範圍都能明顯地從本發明和以上並未脫離本發明實質或範疇的敘述中得知或獲得合理的建議，故以上敘述並未限制本發明之範疇，或排除其他實施例、適用範圍、改變、修飾以及等效的範圍，本發明僅藉由在此所附之申請專利範圍以及其等效範圍作為限制。 The above description and examples are merely illustrative of the techniques of the invention, and are in the In addition to the various embodiments and the scope of the invention, and the scope of the invention, and the scope of the invention, The above description does not limit the scope of the invention, or the scope of the invention, the scope of the invention, the scope of the invention, Its equivalent range is limited.
第一圖係樹枝狀高分子之合成示意圖。 The first picture is a schematic diagram of the synthesis of dendrimers.
第二圖係超分支狀高分子微胞之穿透式電子顯微鏡(TEM)照片及其結構示意圖。 The second figure is a transmission electron microscope (TEM) photograph of a super-branched polymer microcell and a schematic diagram thereof.
第三圖係雙性多官能基樹枝狀高分子微胞溶液在不同酸鹼環境下之螢光光譜圖。 The third picture is the fluorescence spectrum of the amphiphilic polyfunctional dendrimer cell solution in different acid and alkali environments.
第四圖係透過雙性多官能基樹枝狀型態有機高分子脫層氧化石墨示意圖。 The fourth figure is a schematic diagram of delamination of graphite oxide by an amphoteric polyfunctional dendritic organic polymer.
第五圖係X-光繞射儀(XRD)圖譜及氮含量分析圖。 The fifth picture is an X-ray diffraction (XRD) pattern and a nitrogen content analysis chart.
第六圖係TEM觀察水分散之單層氧化石墨烯及其電子衍射(SAED)分析圖。 The sixth figure is a TEM observation of water-dispersed single-layer graphene oxide and its electron diffraction (SAED) analysis.
第七圖係TEM觀察包埋於環氧樹脂中的單層氧化石墨烯。 The seventh figure is a TEM observation of a single layer of graphene oxide embedded in an epoxy resin.
第八圖係單層氧化石墨烯之拉曼(Raman)光譜圖。 The eighth figure is a Raman spectrum of a single layer of graphene oxide.
Claims (12)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW101145655A TWI473835B (en) | 2012-12-05 | 2012-12-05 | Multifunctional hyperbranched organic intercalating agent, method for its manufacture and its use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW101145655A TWI473835B (en) | 2012-12-05 | 2012-12-05 | Multifunctional hyperbranched organic intercalating agent, method for its manufacture and its use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201422672A true TW201422672A (en) | 2014-06-16 |
| TWI473835B TWI473835B (en) | 2015-02-21 |
Family
ID=51393800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW101145655A TWI473835B (en) | 2012-12-05 | 2012-12-05 | Multifunctional hyperbranched organic intercalating agent, method for its manufacture and its use |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI473835B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105932202A (en) * | 2016-06-08 | 2016-09-07 | 广东工业大学 | Porous hyperbranched polyester graphite oxide membrane, and preparation method and application thereof |
| CN112300389A (en) * | 2020-11-09 | 2021-02-02 | 黑龙江省科学院高技术研究院 | Synthetic method of hydrophilic polyimide film with zwitterionic structure |
| CN114920927A (en) * | 2022-05-27 | 2022-08-19 | 浙江华特新材料有限公司 | Polyamide wax and preparation method and application thereof |
-
2012
- 2012-12-05 TW TW101145655A patent/TWI473835B/en active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105932202A (en) * | 2016-06-08 | 2016-09-07 | 广东工业大学 | Porous hyperbranched polyester graphite oxide membrane, and preparation method and application thereof |
| CN105932202B (en) * | 2016-06-08 | 2018-09-07 | 广东工业大学 | A kind of porous hyper-branched polyester graphite oxide film and its preparation method and application |
| CN112300389A (en) * | 2020-11-09 | 2021-02-02 | 黑龙江省科学院高技术研究院 | Synthetic method of hydrophilic polyimide film with zwitterionic structure |
| CN114920927A (en) * | 2022-05-27 | 2022-08-19 | 浙江华特新材料有限公司 | Polyamide wax and preparation method and application thereof |
| CN114920927B (en) * | 2022-05-27 | 2024-03-22 | 浙江华特新材料有限公司 | Polyamide wax and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI473835B (en) | 2015-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9040604B2 (en) | Multifunctional hyperbranched organic intercalating agent, method for its manufacture and its use | |
| Sun et al. | Modified nano Fe2O3-epoxy composite with enhanced mechanical properties | |
| Chen et al. | Preparation of polyetherimide nanocomposites with improved thermal, mechanical and dielectric properties | |
| US11052355B2 (en) | Gas separation membrane containing heteromorphous shaped silica nanoparticles | |
| Lu et al. | Preparation and properties of in situ amino-functionalized graphene oxide/polyimide composite films | |
| US7645828B2 (en) | Monodisperse silica spheres containing polyamine and process for producing the same | |
| JP6156363B2 (en) | Fine carbon dispersion composition and polyimide-fine carbon composite using the same | |
| Mallakpour et al. | Modification of Mg/Al-layered double hydroxide with L-aspartic acid containing dicarboxylic acid and its application in the enhancement of the thermal stability of chiral poly (amide-imide) | |
| Lu et al. | In situ polymerization and performance of alicyclic polyimide/graphene oxide nanocomposites derived from 6FAPB and CBDA | |
| TW201803808A (en) | Method for manufacturing gas separation membrane | |
| JP5870720B2 (en) | Carbon nanotube dispersant made of polyamic acid | |
| US20150274538A1 (en) | Core-shell silica nanoparticles, method for manufacturing the same, method for manufacturing hollow silica nanoparticles therefrom, and hollow silica nanoparticles manufactured thereby | |
| Dinari et al. | In situ thermal synthesis of novel polyimide nanocomposite films containing organo-modified layered double hydroxide: morphological, thermal and mechanical properties | |
| Toiserkani | Fabrication and characterization of poly (benzimidazole-amide)/functionalized titania nanocomposites containing phthalimide and benzimidazole pendent groups | |
| Mallakpour et al. | Novel nanocomposites based on reactive organoclay of l-tyrosine and amine end-capped poly (amide–imide): Synthesis and characterization | |
| TWI473835B (en) | Multifunctional hyperbranched organic intercalating agent, method for its manufacture and its use | |
| Wu et al. | Green preparation of high-yield and large-size hydrophilic boron nitride nanosheets by tannic acid-assisted aqueous ball milling for thermal management | |
| WO2014058014A1 (en) | Organic-inorganic hybrid silica nanoparticle and production method thereof | |
| Kurose et al. | Compatibilized polyimide (R-BAPS)/BAPS-modified clay nanocomposites with improved dispersion and properties | |
| Mallakpour et al. | Chiral poly (amide-imide)/organoclay nanocomposites derived from pyromellitoyl-bis-l-isoleucine and benzimidazole containing diamine: synthesis, nanostructure, and properties | |
| Mallakpour et al. | Ultrasonic assisted organo-modification of mesoporous SBA-15 with N-trimellitylimido-l-methionine and preparation of the poly (amide–imide)/SBA nanocomposites | |
| Mallakpour et al. | Investigating the nanostructure and thermal properties of chiral poly (amide-imide)/Al2O3 compatibilized with 3-aminopropyltriethoxysilane | |
| Dinari et al. | Thermal, mechanical and optical transport properties of nanocomposite materials based on triethoxysilane-terminated polyimide and TiO 2 nanoparticles | |
| JP2011074278A (en) | Polyamic acid solution, polyimide using the same, and method for producing them | |
| Mallakpour et al. | The nanocomposites of zinc oxide/L‐amino acid‐based chiral poly (ester‐imide) via an ultrasonic route: Synthesis, characterization, and thermal properties |