二胺结构对线形缩聚型聚酰亚胺性能的影响

以3,3',4,4'-二苯醚二酐(OPDA)与六种不同结构的二胺在N,N-二甲基乙酰胺中通过逐步聚合,合成了线性缩聚型聚酰胺酸,并通过热关环制备了聚酰亚胺,探讨了二胺结构对其热性能及粘接性能的影响.红外分析表明,固化后的聚酰亚胺已经完全酰亚胺化.差示扫描量热(DSC)结果表明,聚酰亚胺具有较高的玻璃化转变温度,并随着结...     

联苯酐型聚酰亚胺胶粘剂的合成与性能

以联苯二酐和三种含有醚键结构的二胺——4,4'-二氨基二苯醚(4,4'-ODA)、3,4'-二氨基二苯醚(3,4'-ODA)和1,3-二(4-氨基苯氧基)苯(1,3,4-APB)为原料,在N N-二甲基乙酰胺中通过逐步聚合反应,合成了三种含有柔性二胺结构的线性聚酰亚胺。分析了不同的溶剂及含水量对粘接性能的影响。考察了不同的分子结构对聚酰亚胺粘接性能和热性能的影响。通过红外分析,固化后的聚酰亚胺已经完全酰亚胺化;通过热失重分析发现,三种线性聚酰亚胺的热分解温度均在500℃以上,且由4,4'-ODA制得的聚酰亚胺(PI)耐热性能优于其余两种;热机械分析表明,1,3,4-APB具有最小的玻璃化转变温度。     

联苯类三芳胺空穴传输材料的合成及其光电性能研究

以4,4'-二甲基二苯胺和3-甲基二苯胺为原料分别与4,4'-二碘联苯反应合成了N,N,N',N'-四(4-甲基苯基)-1,1'-联苯-4,4'-二胺(S-100)和N,N'-二苯基-N,N'-二(3-甲基苯基)-1,1'-联苯-4,4'-二胺(m-TPD),产品收率为93.3%和94.3%.以S-100和m-TPD作为空穴传输材料,以酞菁氧钛为电荷产生材料制备功能分离型有机光导器件并进行光电性能的测试,结果表明所合成化合物具有优异的空穴传输性能.     

含氟和氧膦的二胺及其聚酰亚胺的合成

从3,5-二(三氟甲基)溴苯出发,经格氏、硝化、还原反应合成了含氟和氧膦的新型二胺单体.然后用常规的二步法,和4,4'-二氨基苯氧醚(ODA)与2,2'-六氟异叉丙基二苯四酸二酐(6FDA)进行共缩聚并经化学酰亚胺化法制备了共缩聚型聚酰亚胺.     

几种可溶性聚酰亚胺的合成与性能表征

以3,5-二硝基溴苯与对甲基苯酚为原料,合成出中间产物3,5-二硝基-4'-甲基-二苯基醚,再用钯/碳还原得到芳香二胺单体3,5-二氨基-4'-甲基-二苯基醚,以此芳香二胺和四种不同芳香二酐为单体,通过低温聚合反应合成了高分子量的聚酰胺酸,热亚胺化的产物在极性强的溶剂中具有较好的溶解性.差示扫描量热(DSC)和热重法(...     

可溶性联苯型聚酰亚胺的合成及表征

选用3,3’,4,4’-联苯四甲酸二酐（BPDA）作为二酐单体，同时选用一种带有侧链的3,3’-二甲基-4,4’-二氨基二苯甲烷（DMMDA）作为二胺单体，采用两步法合成了可溶性的联苯型聚酰亚胺。探讨了单体配比、固含量、反应温度和反应时间等因素对聚酰胺酸黏度的影响，以及化学亚胺化时间对PI亚胺化程度的影响，并确定了聚酰亚胺最佳的合成条件。聚酰胺酸合成过程的最佳单体配比确定为1∶1，固含量为12%，反应温度为20℃，反应时间为8 h，最优条件下的聚酰胺酸特性黏度为1.88 d L/g；聚酰亚胺合成过程的最佳化学亚胺化时间为24 h,在该条件下亚胺化程度为98%。之后，对最优条件下合成的聚酰亚胺进行了一系列的结构和性能表征。结果表明，合成的聚酰亚胺相对分子质量较高（数均分子量（■）和重均分子量（■）分别为14万和21万）且分布较窄，在保持耐热性能和耐溶剂性能的同时，显著提高了成膜性、溶解性等加工性能，是制备耐溶剂纳滤膜的理想材料。     

含螺环结构的二胺及其聚酰亚胺的合成与性能

首先,以双酚A和甲磺酸反应合成出3,3,3',3'-四甲基-6,6'-二羟基-1,1'-螺旋双茚满,然后与2-氯-5-硝基三氟甲苯反应得到3,3,3',3'-四甲基-6,6'-双[4-硝基-2-三氟甲基苯氧基]-1,1'-螺旋双茚满,最后在Pd/C-水合肼还原作用下得到3,3,3',3'-四甲基-6,6'-双[4-氨基-2-三氟甲基苯氧基]-1,1'-螺旋双茚满。采用上述二胺单体分别与1,2,3,4-环丁烷四酸二酐、均苯四甲酸二酐、联苯二酐、3,3',4,4'-二苯醚四酸二酐、3,3',4,4'-二苯酮四酸二酐和六氟二酐通过两步法制备出6种含螺环结构的聚酰亚胺(PI)。采用核磁、红外光谱、X射线衍射、紫外-可见光谱、热重分析、差示扫描量热分析和溶解性测试等手段表征了所得化合物和PI的结构与性能。研究结果表明,这些含螺环的PI主要表现为非晶结构和较大的分子链间距离,且具有良好的溶解性、光学性能和热性能。     

ODA二胺单体双酮酐型聚酰亚胺的合成与性能EI北大核心CSCD

以4,4'-对苯二甲酰二邻苯二甲酸酐(TDPA)为二酐单体,4,4'-二氨基二苯醚(4,4'-ODA)和3,4'-二氨基二苯醚(3,4'-ODA)为二胺单体,采用两步法低温溶液缩聚分别合成了2种聚酰亚胺(PI)。采用红外光谱、X射线衍射、差示扫描量热分析、热重分析、拉伸强度测试等对聚合物的结构与性能进行了表征。研究结果表明,制得的聚酰亚胺均具有良好的成膜性,PI(4,4'-ODA)膜的拉伸强度达到262 MPa,玻璃化转变温度(Tg)为297℃; PI(3,4'-ODA)膜的拉伸强度为149 MPa,Tg为261℃。热分解温度都在520℃以上,具有优良的耐热性能及力学性能。     

ODA二胺单体双酮酐型聚酰亚胺的合成与性能

以4,4'-对苯二甲酰二邻苯二甲酸酐(TDPA)为二酐单体,4,4'-二氨基二苯醚(4,4'-ODA)和3,4'-二氨基二苯醚(3,4'-ODA)为二胺单体,采用两步法低温溶液缩聚分别合成了2种聚酰亚胺(PI)。采用红外光谱、X射线衍射、差示扫描量热分析、热重分析、拉伸强度测试等对聚合物的结构与性能进行了表征。研究结果表明,制得的聚酰亚胺均具有良好的成膜性,PI(4,4'-ODA)膜的拉伸强度达到262 MPa,玻璃化转变温度(Tg)为297℃; PI(3,4'-ODA)膜的拉伸强度为149 MPa,Tg为261℃。热分解温度都在520℃以上,具有优良的耐热性能及力学性能。     

可溶性聚酰亚胺规整多孔膜的形成与控制

选用4种聚合单体:4,4'-六氟亚异丙基一邻苯二甲酸酐(6FDA)、双酚A二酐(BPA-DA)、4,4'-二氨基二苯甲烷(MDA)、3,3'-二甲基-4,4'-二氨基二苯甲烷(DMMDA),采用低温溶液缩聚-化学亚胺化合成了3种可溶性的聚酰亚胺:6FDA-MDA,6FDA-DMMDA,BPADA-DMMDA,利用FI-IR、NMR等对其结构进行了分析表征,测试了它们的溶解性能与热性能.将这3种聚酰亚胺溶于氯仿溶液中,在高湿度环境下浇铸形成规整多孔膜结构;研究了其规整孔结构的拉伸与吹扫特定形变,最后还研究了所得的规整多孔膜的高温热稳定性,发现在350℃仍能保持规整结构的稳定.     

聚酰亚胺渗透汽化膜的研究(Ⅱ)聚酰亚胺化学结构对膜渗透汽化性能的影响

以2种二酐、3种二胺为单体，制备了6种不同分子结构的聚酰亚胺(PI)均质膜．测定了这几种膜的物理性质和渗透汽化性能，并讨论了聚酰亚胺刚性和分子结构对均质膜渗透汽化性能的影响．     

均苯型聚酰亚胺耐溶剂纳滤膜的制备

两步法制备一种均苯型聚酰亚胺耐溶剂纳滤膜,重点研究热亚胺化进程对膜性能的影响.选用热亚胺化程序为200℃保持2.5h,250℃保持2 h,300℃保持2h.测试结果表明耐溶剂纳滤膜在大部分测试溶剂中有较好的稳定性,膜的几种纯溶剂通量均保持较高水平的同时对结晶紫和依来络蓝黑R水溶液的截留率分别达到99.8％和97.9％.     

荷电纳滤膜对化机浆混合废水的纳滤效果

在制备一种荷正电纳滤膜的基础上研究了制备过程影响成膜性能的几个因素，并探讨了该纳滤膜对化机浆混合废水的纳滤效果。研究发现，与一般聚丙烯腈纳滤膜比较，荷正电聚丙烯腈纳滤膜更有利于提高化机浆混合废水色度，CODCr,BOD5的去除率和钠截留率。     

Impact of monoolein on aquaporin1-based supported lipid bilayer membranes

Abstract

Aquaporin (AQP) based biomimetic membranes have attracted considerable attention for their potential water purification applications. In this paper, AQP1 incorporated biomimetic membranes were prepared and characterized. The morphology and structure of the biomimetic membranes were characterized by in situ atomic force microscopy (AFM), infrared absorption spectroscopy, fluorescence microscopy, and contact angle measurements. The nanofiltration performance of the AQP1 incorporated membranes was investigated at 4 bar by using 2 g l^?1 NaCl as feed solution. Lipid mobility plays an important role in the performance of the AQP1 incorporated supported lipid bilayer (SLB) membranes. We demonstrated that the lipid mobility is successfully tuned by the addition of monoolein (MO). Through in situ AFM and fluorescence recovery after photo-bleaching (FRAP) measurements, the membrane morphology and the molecular mobility were studied. The lipid mobility increased in the sequence DPPC < DPPC/MO (R_MO = 5/5) < DOPC/MO (R_MO = 5/5) < DOPC, which is consistent with the flux increment and salt rejection. This study may provide some useful insights for improving the water purification performance of biomimetic membranes.     

BDAF-PMDA型聚酰亚胺炭膜的制备及其气体分离性能的研究

以2,2-双[4-(4-氨基苯氧基苯基)]六氟丙烷(BDAF)为二胺单体,均苯四酸二酐(PMDA)为二酐单体,采用两步法制备了BDAF-PMDA型聚酰亚胺,进一步高温热解制备炭膜.采用红外、热重、X射线衍射分析其结构变化,并测试炭膜对纯组分及混合气体的渗透性能和分离选择性.结果表明,BDAF-PMDA型炭膜具有较高的气体渗透性,在CO2/H2体系中可优先渗透CO2.提高炭化温度,炭膜孔径减小,气体的渗透性能降低,选择性提高,并使得BDAF-PMDA型炭膜的分离机理由表面扩散为主逐渐变为表面扩散和分子筛分共同控制.     

Impact of monoolein on aquaporin1-based supported lipid bilayer membranes

Aquaporin (AQP) based biomimetic membranes have attracted considerable attention for their potential water purification applications. In this paper, AQP1 incorporated biomimetic membranes were prepared and characterized. The morphology and structure of the biomimetic membranes were characterized by in situ atomic force microscopy (AFM), infrared absorption spectroscopy, fluorescence microscopy, and contact angle measurements. The nanofiltration performance of the AQP1 incorporated membranes was investigated at 4 bar by using 2 g l⁻¹ NaCl as feed solution. Lipid mobility plays an important role in the performance of the AQP1 incorporated supported lipid bilayer (SLB) membranes. We demonstrated that the lipid mobility is successfully tuned by the addition of monoolein (MO). Through in situ AFM and fluorescence recovery after photo-bleaching (FRAP) measurements, the membrane morphology and the molecular mobility were studied. The lipid mobility increased in the sequence DPPC < DPPC/MO (R_MO = 5/5) < DOPC/MO (R_MO = 5/5) < DOPC, which is consistent with the flux increment and salt rejection. This study may provide some useful insights for improving the water purification performance of biomimetic membranes.     

化学亚胺化和热亚胺化合成超支化聚酰亚胺

以三(4-氨基苯基)胺(TAPA)为三胺单体、均苯四甲酸二酐(PMDA)为二酐单体,采用A2+B3的方式,分别通过化学亚胺化和热亚胺法化制得了氨基封端超支化聚酰亚胺(AM-HBPI)和酐基封端超支化聚酰亚胺(AD-HBPI),然后采用红外(FT-IR)、核磁共振(1H-NMR)、X射线衍射(XRD)、溶解性和热失重分析(TGA)等对合成的超支化聚酰亚胺(HBPI)进行了测试和表征,并将两种方法所得HBPI进行了对比。结果表明,化学亚胺化和热亚胺化均能制得AM-HBPI和AD-HBPI,它们结晶度低,分子链间距比线性聚酰亚胺小;化学亚胺化AM-HBPI和AD-HBPI的溶解性比对应的热亚胺化HBPI好;所得的AM-HBPI和AD-HBPI的10%的失重温度分别为580℃和550℃,800℃时的质量保持率分别为62%和45%。     

Molecularly imprinted polyimide nanofibers prepared by electrospinning

An estrone imprinted polyimide nanofiber mat was prepared by using an electrospinning method. The diamine monomer-template complex was synthesized by the reaction of the diamine monomer having an isocyanate group and estrone (template) having a phenol moiety, in which the template was attached to the monomer via a thermally reversible urethane bond. A poly(amic acid) was synthesized by polymerization of the diamines (1:19 mole ratio of the diamine monomer-template complex to 4,4′-oxydianiline) and pyromellitic dianhydride in N,N-dimethylformamide and the reaction solution was used for electrospinning. The poly(amic acid) fibers were thermally imidized and then heated in 1,4-dioxane in the presence of water to remove the template molecules. The imprinted polyimide nanofibers showed the specific recognition ability and fast kinetic adsorption for estrone.     

Phosphonium Modification Leads to Ultrapermeable Antibacterial Polyamide Composite Membranes with Unreduced Thickness

Water transport rate in network membranes is inversely correlated to thickness, thus superior permeance is achievable with ultrathin membranes prepared by complicated methods circumventing nanofilm weakness and defects. Conferring ultrahigh permeance to easily prepared thicker membranes remains challenging. Here, a tetrakis(hydroxymethyl) phosphonium chloride (THPC) monomer is discovered that enables straightforward modification of polyamide composite membranes. Water permeance of the modified membrane is ≈6 times improved, give rising to permeability (permeance × thickness) one magnitude higher than state-of-the-art polymer nanofiltration membranes. Meanwhile, the membrane exhibits good rejection (R_Na2SO4 = 98%) and antibacterial properties under crossflow conditions. THPC modification not only improves membrane hydrophilicity, but also creates additional angstrom-scale channels in polyamide membranes for unimpeded transport of water. This unique mechanism provides a paradigm shift in facile preparation of ultrapermeable membranes with unreduced thickness for clean water and desalination.     

双(4-氨基苯氧基)二甲基硅烷及其聚酰亚胺合成

为了改善聚酰亚胺的加工性能,以对氨基酚和二氯二甲基硅烷为原料合成了一种含硅二胺活性单体双(4-氨基苯氧基)二甲基硅烷(简写APMSI),采用不同配比的APMSI和4,4’-二氨基二苯醚(ODA)混和胺与均苯四甲酸二酐(PMDA)共缩聚制得含硅聚酰亚胺.采用傅立叶变换红外光谱(FTIR)、核磁共振谱(1H和13C)、熔点测定仪对对乙酰氨基酚、双(4-氨基苯氧基)二甲基硅烷(APMSI)的结构进行了表征,其总产率达到67%.采用傅立叶变换红外光谱仪(FTIR)、差热分析仪(DTA)、热重分析仪(TG)和溶解实验分别对纯聚酰亚胺和含硅聚酰亚胺的结构、热性能和溶解性进行了表征.结果表明,含硅聚酰亚胺较纯聚酰亚胺耐热性低,但随含硅二胺单体增多而升高;其玻璃化转变温度随含硅二胺单体增多而大幅下降;其溶解性相对于纯聚酰亚胺有大幅提高.