PS-b-P4VP的合成及其薄膜的微相分离形貌

通过原子转移自由基聚合（ATRP）方法制备了聚苯乙烯-b-聚（4-乙烯基吡啶）二嵌段共聚物（PS-b-P4VP）,使用核磁共振（1H NMR）和凝胶渗透色谱（GPC）对嵌段共聚物进行了表征。将PS-b-P4VP/三氯甲烷溶液旋涂成膜,使用原子力显微镜（AFM）观察热处理条件对薄膜微相分离形貌的影响。结果表明,PS-b-P4VP薄膜会发生微相分离,形成以PS链段为分散相、P4VP链段为连续相基体的纳米尺度微相分离形貌。热处理条件的改变使薄膜呈现不同程度的微相分离形貌结构,提高热处理温度以及延长热处理时间均有利于促进嵌段共聚物的微相分离,使微相分离程度加大。在150℃、24 h的热处理条件下,PS-b-P4VP薄膜形成了PS微相区以规则的柱状形态在薄膜表面突起的微相分离形貌,且分布均匀,界面清晰。     

三嵌段共聚物PS-b-PEG-b-PS与聚苯乙烯共混薄膜的表面形貌与性能研究

使用原子转移自由基聚合(ATRP)制备三嵌段共聚物PS-b-PEG-b-PS.通过红外光谱、核磁共振氢谱(1H-NMR)和凝胶渗透色谱(GPC)对嵌段共聚物结构及分子量进行表征.将嵌段共聚物与聚苯乙烯溶液共混成膜,使用原子力显微镜(AFM)和接触角测试仪(CA)对不同含量嵌段共聚物共混膜的表面形貌和性能进行了分析表征.PEG链段与PS链段在共混膜中发生了微相分离,由于PEG链段对PS链段的热力学排斥作用以及PS的硬链段特性,PS不能在PEG微区上方形成覆盖,因而在薄膜表面形成大量孔洞,PEG微相区位于孔洞底部.随嵌段共聚物含量增加,孔洞(PEG微区)尺寸增大.当嵌段共聚物含量增加10％以后,孔洞内出现PS微相区,导致形成“胞状”结构.嵌段共聚物含量增加使得共混薄膜的亲水性和表面张力增大.     

PS-b-PEO-b-PS三嵌段共聚物的结晶形态和微相分离(I)PEO含量及分子量的影响

采用偏光显微镜和透射电镜研究了 PS-b-PEO-b-PS三嵌段共聚物的结晶形态和微相分离 ,重点讨论了 PEO含量和分子量的影响。实验发现 ,当共聚物中的 PEO分子量低至 60 0 0、含量低至 4 2 %时 ,均有球晶生成 ,且随着 PEO含量的升高 ,球晶形态变得更加完善。 TEM结果显示 ,当 PEO分子量为1 0 0 0 0、含量分别为 93%和 91 %时 ,形成以 PEO为连续相、PS为分散相的微相分离结构 ;但当 PEO含量降低到 77%时 ,发生了相反转 ,PEO变为分散相 ,PS变为连续相。当 PEO分子量为 60 0 0 ,含量为 4 2 %时 ,形成了以 PS为连续相、PEO为分散相的微相分离结构。所有的分散相都有球形或近似球形的形貌。在 PEO的分子量为 2 0 0 0、含量为 1 8%、34 %时 ,发现了层状微相分离结构。同时我们还发现 ,p H=6.0的磷钨酸水溶液是该类嵌段共聚物的有效染色体系     

PS—b—PEO—b—PS三嵌段共聚物的结晶形态和微相分离——（Ⅰ）PEO含量及分子量的影响

采用偏光显微镜和透射电镜研究了PS-b-PEO-b-PS三嵌段共聚和折结晶形态和微相分离,重点讨论了PEO含量和分子量的影响,实验发现,当共聚物中的PEO分子量低至6000、含量低于42%时,均有球晶生成,且随着PEO含量的升高,球晶形态变得更加完善,TEM结晶显示,当PEO分子量为1000含量分别为93%和91%时,形成以PEO为连续相,PS为分散相的微相分离结构,但当PEO含理降低到77%时,发生了相反转,PEO变为分散相,PS变为连续相,当PEO分子量为6000,含量为42%时,形成了以PS为连续相,PEO为分散相的微相分离结构,所有的分散相都有球形或近似球形的形貌,在PEO的分子量为2000,含理为18%,34%时,发现了层状微相分离结构,同时我们还发现,pH=6.0的磷钨酸水溶液是该类嵌段共聚物的有效染色体系。     

PS-b-PEO-b-PS三嵌段共聚物的结晶形态与微相分离 (Ⅱ)浇铸溶剂的影响

采用偏光显微镜和透射电镜 ( TEM)研究了 PS-b-PEO-b-PS三嵌段共聚物不同溶剂浇铸成膜的结晶形态和微相分离行为。所采用的溶剂分别为硝基甲烷 (对 PEO选择 )、乙苯 (对 PS选择 )、氯仿 (是PEO和 PS的共溶剂 )。偏光显微镜显示该类共聚物不同溶剂浇铸成膜形成球晶完整性从大到小依次为 :氯仿>硝基甲烷 >乙苯。TEM显示用氯仿溶剂浇铸成膜 ,共聚物的微相分离最为彻底 ;而用硝基甲烷和乙苯浇铸成膜时 ,由于在溶剂中部分链的运动受到限制 ,故在溶剂挥发过程中 ,微相分离程度要降低。当用乙苯选择性溶剂时 ,伸展的 PS链有利于体系微相分离 ,但塌陷的 PEO紧密线团使微相分离受限 ;而用硝基甲烷选择性溶剂时 ,塌陷的 PS线团使微相分离受限 ,但伸展的 PEO链不仅在运动自由度上有利于微相分离 ,而且在溶剂挥发过程中 ,PEO链的结晶焓变会有利于体系微相分离的形成。     

拉曼Mapping成像研究聚苯乙烯/聚甲基丙烯酸甲酯共混体系的相态结构

利用拉曼光谱成像技术研究了聚苯乙烯/聚甲基丙烯酸甲酯（PS/PMMA）共混薄膜体系及其增容体系（增容剂为PS-b-PMMA嵌段共聚物）的相态结构及化学成分分布。实验结果表明,拉曼Mapping成像技术不仅可以得到PS/PMMA共混体系化学成分的精确分布图,同时也可以获取共混体系中分散相、界面相和连续相的分子指纹光谱。研究发现,共混体系中分散相和连续相组分分布与体系的组成紧密相关,当PS/PMMA质量比30/70时,分散相为PS,连续相为PMMA;当PS/PMMA质量比为50/50时,分散相为PS,但PS分子链仍存在于PMMA连续相中;当PS/PMMA质量比为70/30时,分散相为PMMA,连续相为PS。当增容剂PS-b-PMMA加入到PS/PMMA共混体系中后,分散相粒径减小、分布更加均匀、共混体系相容性指数（N_c）增大,说明PS/PMMA共混体系由完全不相容体系趋向变成半相容性体系,这是因为增容剂能增加PS和PMMA之间的相互作用,降低了体系的相分离程度,改善了共混体系的相容性。     

PP/PS共混熔纺中相结构沿纺程的梯度演变

将聚丙烯(PP)/聚苯乙烯(PS)按质量比92∶8进行共混纺丝,以自制的纺程取样器对PP/PS熔融纺丝进行纺程取样,利用冷冻超薄切片机获得纺程各点取样纤维的横截面和纵剖面,扫描电子显微镜观察纤维中PS分散相的形貌,研究了共混熔融纺丝中梯度结构沿纺程的演变及其梯度结构的形成机理。结果表明:PS分散相数目沿纤维径向呈现内密外疏的梯度分布,这一差异沿着纺程不断增大;PS分散相在纺程0~60 cm发生形变,纺丝速度为125~500 m/min下PS分散相直径逐渐减小,当纺丝速度达到1 000 m/min时,PS分散相直径在纺程0~20 cm减小,在纺程20~60 cm增加,PS分散相液滴在此区域发生了明显的聚并,在纤维表层各个纺丝速度下分散相都呈现不同程度的聚并现象;在PP/PS共混纤维中呈现中心层分散相液滴形变程度大表层形变程度小的梯度差异,但高速纺丝会弱化这一差异。     

四官能度过氧化物JWEB50引发的PS-b-PMMA合成与表征

引言嵌段共聚物是具有两种或两种以上不同链段的聚合物,不同链段间存在的化学键限制了聚合物的相分离程度,易形成微相分离结构[1],而嵌段共聚物能作为聚合物共混体系的相容剂,只需加入少量     

复配对有机硅整理剂成膜形态与应用性能的影响

采用原子力显微镜(AFM)和接触角滴定技术,研究了N-β-氨乙基-γ-氨丙基聚二甲基硅氧烷(ASO)和侧链聚醚/环氧基聚硅氧烷(CGF)溶剂共混组装膜(ASO/CGF)和乳液共混组装膜(AS/CGF)的微观表面形貌、亲疏水性能和其在纯棉织物上的应用性能。结果表明,ASO/CGF膜和AS/CGF膜均存在明显的相分离,其膜的分散相由CGF中聚醚链段吸水团聚堆积而成,连续相为聚二甲基硅氧烷链段(PDMS)。因受到乳胶粒子的限制,AS/CGF膜的相分离特征较ASO/CGF膜明显减小,膜的粗糙度也随之减小,亲水性增加。整理剂的组装膜性能数据可在一定程度反映整理剂的应用性能,对实际应用具有指导和借鉴意义。     

聚氯乙烯-聚丙烯酸嵌段共聚物改性的pH响应性聚氯乙烯超滤膜

为了改进聚氯乙烯(PVC)超滤膜的渗透和抗生物污染特性,采用单电子转移-蜕化转移活性自由基聚合制备了聚丙烯酸-b-聚氯乙烯-b-聚丙烯酸三嵌段共聚物(PAA-b-PVC-b-PAA),并采用非溶剂诱导相转移法制备了PAA-b-PVC-b-PAA改性的PVC超滤膜。发现PAA-b-PVC-b-PAA具有微相分离特性,对应PVC和PAA嵌段的玻璃化温度分别为80和108oC。PAA-b-PVC-b-PAA的引入使膜的指状结构增大。由于PAA-b-PVC-b-PAA共聚物在膜表面的富集,共混物超滤膜的水通量随着PAA链长的增长而增大。随着pH值变化,PAA链段的荷电性和构象变化,使共混物超滤膜的渗透行为具有可逆pH响应性,pH值由2.3增大到11.6时,水通量明显下降;在强酸性和碱性条件下,PAA链段与牛血清蛋白存在强的电荷排斥作用,通量和抗污染性较好。     

A simple method for creating nanoporous block-copolymer thin films

We introduce a simple method to create block copolymer films with controlled porosity. We show that the pore structure can be varied over a broad range of length scales not obtainable in homopolymer blend films. The morphology is a random two phase kinetically trapped structure that is not limited by the equilibrium block copolymer structure. The morphology is obtained through blending homopolymer poly(4-vinylpyridine) (P4VP) with block copolymer polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) and then removing the homopolymer P4VP by washing with ethanol. The structure obtained prior to washing (which templates the nanoporous structure) is stabilized in the kinetically trapped morphology during spincoating and is not obtainable from either homopolymer blends or the pure block copolymer. When PS/P4VP blend solutions in tetrahydrofuran were spincoated at 25% relative humidity, continuous films with raised P4VP nanodomains were formed due to a preferential affinity of the spinning solvent for polystyrene. In a similar manner, when PS-b-P4VP/P4VP block copolymer/homopolymer solutions were spincoated, the P4VP homopolymer was solubilized in the P4VP block domains during spincoating, suppressing macro-phase separation. The film morphology is generated at the air surface and then propagates through the film, resulting in P4VP nanodomains oriented vertically to the substrate. In the resulting films, the size of P4VP nanodomains were varied by increasing the amount of P4VP homopolymer. The subsequent extraction of P4VP homopolymer from the PS-b-P4VP/P4VP blend films in ethanol resulted in nanopores with a distribution of length scales. The morphology of these materials makes the films potentially suitable for a range of applications such as anti-reflective coatings, nanoporous membranes and low-k materials. An illustrative example of an anti-reflective coating will be presented.     

High-throughput preparation of complex multi-scale patterns from block copolymer/homopolymer blend films

A simple, straightforward process for fabricating multi-scale micro- and nanostructured patterns from polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP)/poly(methyl methacrylate) (PMMA) homopolymer in a preferential solvent for PS and PMMA is demonstrated. When the PS-b-P2VP/PMMA blend films were spin-coated onto a silicon wafer, PS-b-P2VP micellar arrays consisting of a PS corona and a P2VP core were formed, while the PMMA macrodomains were isolated, due to the macrophase separation caused by the incompatibility between block copolymer micelles and PMMA homopolymer during the spin-coating process. With an increase of PMMA composition, the size of PMMA macrodomains increased. Moreover, the P2VP blocks have a strong interaction with a native oxide of the surface of the silicon wafer, so that the P2VP wetting layer was first formed during spin-coating, and PS nanoclusters were observed on the PMMA macrodomains beneath. Whereas when a silicon surface was modified with a PS brush layer, the PS nanoclusters underlying PMMA domains were not formed. The multi-scale patterns prepared from copolymer micelle/homopolymer blend films are used as templates for the fabrication of gold nanoparticle arrays by incorporating the gold precursor into the P2VP chains. The combination of nanostructures prepared from block copolymer micellar arrays and macrostructures induced by incompatibility between the copolymer and the homopolymer leads to the formation of complex, multi-scale surface patterns by a simple casting process.     

Solvent annealing assisted self-assembly of hydrogen-bonded interpolymer complexes of AB block copolymer/C homopolymer in thin film

A simple process of solvent annealing has been shown to produce ordered self-assembly structures of poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP)/poly(4,4′-oxydiphenylenepyromellitamic acid) (POAA) block copolymer/homopolymer blends in thin film, where POAA chains selectively interact with P4VP blocks by strong interpolymer hydrogen-bonding. By simply exposing the thin film to benzene/NMP (0.97/0.03, in volume) vapor mixture, ordered microphase-separated structures with PS spherical microdomains distributed within P4VP/POAA complexes matrix were obtained. The formation of the microphase-separated structures could be attributed to the substantial mobility of PS blocks and P4VP/POAA complexes and enhanced repulsion between them under the benzene/NMP mixture vapor. When the volume ratio of benzene to NMP increased to 0.98/0.02, the increasing benzene in the mixture vapor induced the adhesive collision of spherical microphase-separated structures to form long “pearl necklaces”. With increasing volume ratio of benzene to NMP to 0.99/0.01, an ordered “pearl necklace” array oriented parallel to the film surface formed. The self-assembly structures were studied by FTIR spectroscopy, atomic force microscopy (AFM), and transmission electron microscopy (TEM). Finally, possible mechanism of self-assembly and formation of microphase morphology was proposed.     

Rubbed films of isomeric poly(4-vinylpyridine) and poly(2-vinylpyridine): surface morphology, molecular orientation, and liquid crystal alignability

Films of poly(4-vinylpyridine) (P4VP) and poly(2-vinylpyridine) (P2VP) were characterized before and after they were rubbed with a rayon velvet, and their liquid crystal (LC) aligning abilities were investigated. Atomic force microscopy images showed that microgrooves developed along the rubbing direction in the surfaces of the rubbed films of both polymers. Retardation and linearly polarized infrared spectroscopy analyses revealed that in both polymers the vinyl backbones are oriented along the rubbing direction, while the pyridine side groups are oriented perpendicular to the rubbing direction; the para-directions of the pyridine rings in the P4VP film have a tilt angle of about 45° in the plane perpendicular to the rubbing direction but the para-directions of the pyridine rings in the P2VP film align nearly in the film surface. These rubbed films were found to induce uniform, homogeneous LC alignment along the rubbing direction. Both LC alignments were, however, found to have low anchoring energies that are due to the inherently weak interactions of the LCs with the film surfaces. Moreover, LC cells prepared using these films were found to have only limited stability. These results lead to the conclusion that the microgrooves generated along the rubbing direction play a critical role in governing the alignment of LCs that weakly interact with the parallel oriented vinyl main chains in competition with the perpendicularly oriented pyridine side groups, despite their dimensions, which are larger than the LC molecules and thus limit their effectiveness. In addition, the zero degree pre-tilting behavior of the LCs on these films was investigated in detail, taking into account both the rubbing-induced orientations of the polymer segments and their anisotropic interactions with the LC molecules.     

Surface morphology evolution of poly(styrene-block-4-vinylpyridine) (PS-b-P4VP)(H) and poly(methyl methacrylate)-dibenzo-18-crown-6-poly(methyl methacrylate) (PMCMA) supramolecular film

Well-ordered nanostructured polymeric supramolecular thin films were fabricated from the supramolecular assembly of poly(styrene-block-4-vinylpyridine) (PS-b-P4VP)(H⁺) and poly(methyl methacrylate)-dibenzo-18-crown-6-poly(methyl methacrylate) (PMCMA). A depression of cylindrical nanodomains was formed by the block of P4VP(H⁺) and PMCMA associates surrounded by PS. The repulsive force aroused from the incompatibility between the block of P4VP(H⁺) and PMCMA was varied through changing the molecule weight (M_w) of PMCMA, the volume fraction of the block of P4VP(H⁺), and annealing the film at high temperature. Increasing the repulsive force led to a change of overall morphology from ordered nanoporous to featureless structures. The effects of solvent nature and evaporation rate on the film morphology were also investigated. Further evolution of surface morphologies from nanoporous to featureless to nanoporous structures was observed upon exposure to carbon bisulfide vapors for different treatment periods. The wettability of the film surface was changed from hydrophilicity to hydrophobicity due to the changes of the film surface microscopic composition.     

Tailoring block copolymer nanoporous thin films with acetic acid as a small guest molecule

Block copolymers offer the fabrication of mesoporous thin films with distinct nanoscale structural features. In this contribution, we present the use of acetic acid (CH₃COOH) as a low‐molecular‐weight guest molecule to tune the supramolecular assembly of poly[styrene‐block‐(4‐vinylpyridine)] (PS‐b‐P4VP), offering a versatile and straightforward method to obtain tailored nanostructured films with controlled topography and pore size. Spin‐coating toluene solutions of PS‐b‐P4VP, with a variable amount of CH₃COOH, leads to micellar thin films, where the micelles contain the carboxylic acid as a guest molecule. The size can be conveniently modified in these films (from 48 to 75 nm) by varying the amount of organic acid in the starting solutions. Subsequent surface reconstruction of micellar films using ethanol leads to ring‐shaped copolymer nanoporous films with modulated diameter. Controlling the micelle reconstruction process, cylindrical porous films are also obtained. Interestingly, changing the type of aliphatic carboxylic acid leads to a modification of the observed film morphology from micelles to out‐of‐plane P4VP cylinders (or lamellae) in a PS matrix. © 2019 Society of Chemical Industry