不同聚合物浓度对聚醚砜微滤膜性能的影响

研究了不同聚合物浓度对浸没沉淀相转化法制备聚醚砜(PES)微滤膜的形态结构、成膜厚度、孔隙率、过滤性能、亲水性的影响。实验结果表明:随聚合物浓度的增加,铸膜液黏度增大,导致铸膜液分相固化时间较短,表面孔隙率逐渐减少,且成膜孔隙率、纯水通量及膜亲水性均在聚合物浓度为14%时呈现最佳值。     

木质素改性多孔酚醛树脂微球的制备研究

本文以苯酚和甲醛为反应单体,采用聚乙烯醇(PVA1788)作分散剂,三乙胺(TEA)作碱催化剂,六次甲基四胺(HMTA)作交联剂,利用水相悬浮缩聚法制备了球形酚醛树脂。在稳定悬浮缩聚体系引入致孔剂,制备多孔的酚醛树脂微球,并对木质素部分替代苯酚制备多孔酚醛树脂微球进行初步探讨。通过实验确定了水相悬浮缩聚法制备酚醛树脂珠体基本合成工艺:先将苯酚、甲醛、三乙胺加入到一定浓度的PVA水溶液,在95～97℃反应40 min后,加入HMTA,继续反应4 h,再用1 mol/L的盐酸溶液调节pH值至2,固化反应1 h,可得到形态规整的珠体;并发现PVA浓度对酚醛树脂珠体粒度影响很大,粒度分布较宽。甲苯致孔得到多孔球形酚醛树脂微球,粒径分布较无致孔剂时窄,孔径在2μ以上;甲苯用量5 g,PVA浓度为0.375%时,得到的粒径在20～80目间的粒子数量达90%;提高甲苯量能增大多孔球形酚醛树脂微球比表面积,但加宽粒径分布;且高甲苯添加量时,PVA浓度对缩聚产物形态影响非常显著,低PVA浓度下易结块,高PVA浓度下得细粉(粒径小于200目)。邻苯二甲酸二丁酯致孔得到外表面光滑内表面多孔的酚醛树脂中空微球,粒径分布也窄,粒径在20～80目间粒子数量占80%以上。木质素替代苯酚制备多孔球形酚醛树脂,木质素能参与反应成球,但球形度稍差,孔径也更小。     

乳液法结合溶胶-凝胶法制备多孔TiO2微球

为了进一步提高二氧化钛（ TiO₂）的反射率,采用乳液法结合溶胶 -凝胶法,以聚乙二醇（PEG）为相分离诱导剂,制备了内部具有不连续多孔结构的 TiO₂微球。考察了 PEG的添加量对 TiO₂微球内部孔径大小的影响。研究结果表明： TiO₂微球内部的孔径随 PEG的用量增加而增大。基于溶胶-凝胶转变和相分离过程,详细介绍了多孔 TiO₂微球的形成机理。当 PEG的添加量为 9.0%时,所制备的多孔 TiO₂微球在近红外区的积分平均反射率为 84.9%,比常见钛白粉提高了 5.4%。     

聚醚砜疏水膜的制备和性能表征

以质量分数15%的聚醚砜(PES)为膜材料,以N,N-二甲基乙酰胺为溶剂,分别以聚乙二醇(PEG400),无机小分子磷酸和有机小分子丙酮为添加剂,研究了添加剂种类及浓度对PES膜性能的影响。结果表明,同种添加剂,随PES分子量增大制得膜的孔隙率增大。不同添加剂,大分子PEG孔隙率随浓度先增大后减小,而磷酸随浓度变化不显著,由接触角测定,发现正面亲水性明显强于反面,抗污染性优于反面。     

聚乙二醇-聚乙烯醇相变储能纤维的制备及其性能

以聚乙二醇(PEG)为相变物质,聚乙烯醇(PVA)为纤维基体,加入少量丁烷四羧酸(BTCA)作为交联剂,采用干法纺丝制备相变储能纤维,利用原位交联法在纤维拉伸热定形过程中使BTCA与PVA、PEG发生交联,将PEG接枝在PVA上。研究了BTCA、PEG合适的添加量以及最佳热定形温度对PEG保留率的影响,并通过差示扫描量热法、扫描电镜对纤维的热性能和形貌进行了分析。结果表明:当PEG添加量为30%(占PVA质量的百分数)、BTCA添加量为5%(占PVA质量的百分数)时,纤维充分交联,200℃下热处理10 min所得纤维PEG的保留率98%;制得的纤维的相变热焓可达34 J/g,拉伸强度可达3.26 cN/dtex;在升降温循环400次后仍具有良好的储能性。     

球形多孔羟基磷灰石支架的孔结构特征与力学性能

用特殊的高分子微球粘接技术制备成型用模板,通过注浆成型制备出孔结构可控的球形多孔羟基磷灰石(hydroxyapatite,HA)支架.重点研究了HA支架的制备工艺参数对孔结构的影响及孔结构和力学性能之间的关系.结果表明:加入合适粒径的氯化钠(NaCl)填充剂可调节支架的孔隙率和连通性.通过改变高分子微球的尺寸和NaCl晶体的添加量,支架的孔径在100～800 μm范围内、孔隙率在40%～90%范围内实现可控.研究了多孔HA支架的压缩强度(σ)与孔隙率(p)之间的定量关系,为多孔HA支架强度的预测提供了依据.     

静电纺丝法制备多孔超细聚醚砜纤维及其对双酚A的吸附性能

创新性地将静电纺丝法技术和沉浸凝胶方法相结合,制备了多种不同结构的多孔超细聚醚砜(PES)纤维,将多孔超细纤维运用于水溶液中环境激素双酚A(BPA）的吸附,并考查了多孔超细PES纤维对环境激素BPA的吸附机理。结果表明,以聚乙二醇(PEG）为致孔剂得到的多孔超细纤维的孔洞小而分布均匀,以聚乙烯醇(PVA）为致孔剂产生的多孔超细纤维的孔洞大且发生了取向;接收方式对以PVA为致孔剂的多孔超细PES纤维形貌影响大,空气浴中接收到的是多孔超细纤维,水浴中接收到的是中空多孔超细PES纤维;多孔超细PES纤维对环境激素BPA的动态吸附符合伪二阶动力学模型,等温吸附符合Freundlish等温模型。     

溶剂挥发法制备大孔聚合物微球

以乙基纤维素(EC)和具有pH敏感性的聚丙烯酸树脂Ⅳ(PAR)为原料,通过溶剂挥发法制备大孔聚合物微球。聚合物浓度和乳化剂聚乙烯醇(PVA)的浓度影响聚合物微球的粒径大小,聚合物浓度减小或乳化剂浓度增大有利于形成较小的微球。研究了pH和PAR/EC质量比对微球孔结构、比表面积的影响,分析了微球多孔结构形成的机理。溶液的pH可改变PAR的亲疏水性,影响微球的孔结构:酸性环境中得到的微球表面出现致密的大孔,内部是复杂的多孔网络结构,碱性环境中则得到表面无孔的微球。因此,可通过调节溶液PAR/EC质量比和pH来调控微球的孔结构。     

泡沫相相分离制备多孔聚合物微球连续化工艺

采用在泡沫相进行溶剂挥发的方法,连续、高效制备聚甲基丙烯酸甲酯-丙烯酸丁酯[P(MMA-BA)]共聚物多孔微球。采用自制的连续化反应装置,在一定搅拌速率和反应温度下,向反应器连续加料,在出口处连续收集溢出的泡沫并进行消泡、分散,再经洗涤、过滤、干燥得到多孔聚合物微球。重点研究了油相进料速率、反应温度、搅拌速率、聚乙烯醇用量(PVA浓度)对平均泡沫溢出速率、微球收率、微球粒径以及多孔形态的影响规律。结果表明:在反应温度为45℃,搅拌速率为500 r/min,油相溶液进料速率为30 g/min,PVA浓度为1.0%(质量),油相溶液中P(MMA-BA)∶二氯甲烷(DCM)∶正庚烷(HT)=10∶53∶6(质量比)的工艺条件下,聚合物微球的收率高达92%,平均粒径为130μm,P(MMA-BA)微球球形饱满,呈多孔结构。关键词:泡沫;聚合物:多孔微球;制备     

纳米SiO2改性聚乙烯醇超滤膜的研究

以聚乙烯醇(PVA)为基膜材料,聚乙二醇(PEG)为添加剂,通过相转化法制备了纳米SiO2/聚乙烯醇膜。考察了PEG的分子量、纳米SiO2的加入量和PEG加入量对PVA膜性能的影响。结果表明,经纳米SiO2改性的PVA膜的性能有了显著的提高,膜的水通量随着PEG分子量和PEG加入量的增大而增大,随着纳米SiO2加入量的增大而减小。     

聚乙二醇修饰的高分子磁性微球的合成及表征

利用显微摄相、红外光谱、激光粒度分析等手段对所合成的聚乙二醇(PEG)修饰的四氧化三铁/聚乙烯醇(PVA)磁性高分子微球的形貌、结构组成、磁响应性、酸碱稳定性以及温度稳定性进行了表征. 结果表明, 所合成高分子磁性微球的粒度分布较窄,具有超顺磁性和较强的磁响应性. 微球被PEG有效功能化,在三相相转移催化和生物技术领域中具有良好的应用前景.     

Preparation of biodegradable polymer microspheres encapsulating protein with micron sizes

Biodegradable polymer poly-D,L -lactide-polyethylene glycol (PLA-PEG) was synthesized with stannous octoate (SnOc₂) as catalyst by a cationic ring-opening polymerization. The molecular weight of PLA-PEG is the highest at a content of 0.1% SnOc₂. The PLA-PEG microspheres carrying protein were prepared by a solvent evaporation composite emulsion technique with a narrow size range (1–2 μm). The sizes of PLA-PEG microspheres increased with the increase of the molecular weight of PLA-PEG. The PEG in PLA-PEG (10%) significantly improved the size control of the microspheres of the PLA family as a drug carrier matrix. Polyvinyl alcohol (PVA) aqueous solution was used as dispersion medium for microsphere preparation. The concentration of the PVA solution can affect the size of the PLA-PEG microspheres. The differential scanning calorimetry data showed that the PLA-PEG microspheres can efficiently encapsulate the protein and that the crystalline of the microspheres carrying protein was lower than that of the nonprotein-loading microspheres. The amount of protein carried in the PLA-PEG microspheres was related to the nature of the protein itself. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 583–590, 1997     

The preparation and forming mechanism of the red blood cell‐shaped microspheres via electrospraying

This article successfully prepared the red blood cell‐shaped microspheres via electrospraying. The polymer solution was comprised of polyether sulfone (PES) and dimethyl sulfoxide (DMSO), and the hydrophilic polyethylene glycol (PEG) was added to regulate and control the structure of the microspheres. When the solution concentration was 7.6 wt % and PES/PEG proportion was 10 : 5 while preparing microspheres, the shape and diameter of the microspheres was the most similar to that of erythrocyte. The results suggested that the forming mechanism of the red blood cell‐shaped microspheres be related to two aspects. One is that the microspheres had relatively weak mechanical strength because of the sponge pores internal nanostructure. The other is that the existence of residual solvents and water within the microspheres would dissolve the gel phase PES and then further weaken mechanical strength of the outer layer of the microspheres, which caused the structural changes on the top layer of the spheres, that is, the top layer collapsed, and the microspheres finally turned into the red blood cell‐shaped microspheres. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Electrosprayed porous microspheres for the removal of endocrine disruptors

Polyethersulfone (PES) porous microspheres were prepared via electrospraying technique, and then were used for the removal of endocrine disrupters from aqueous solutions. The surface and the internal structures of electrosprayed microspheres were characterized by scanning electron microscopy (SEM) and the results showed that they were porous. The electrosprayed porous PES microspheres can remove biphenyl A and biphenyl effectively. At the same time, they showed larger adsorption capacity and fast kinetics of uptaking target species than PES injected spheres reported in the earlier publications. The hydrophilicity and porosity of electrosprayed microspheres can be controlled by changing the amount of hydrophilic polyethylene glycol (PEG), which influences the adsorption properties of the microspheres. The results showed that electrosprayed porous PES microspheres have the potential to be used in the environmental application. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Development of polylactide microspheres for protein encapsulation and delivery

The development of injectable microparticles for protein delivery is a major challenge. We demonstrated the possibility of entrapping human serum albumin (HSA) and thrombin (Thr) in poly(ethylene glycol) (PEG)‐coated, monodisperse, biodegradable microspheres with a mean diameter of about 10 μm. In our earlier studies, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis was used to characterize the surface of PEG‐coated, taxol‐loaded poly(lactic acid) (PLA) microspheres. An analysis by DRIFTS revealed that PEG was incorporated well on the PLA microsphere surface. An emulsion of protein (in water) and PLA dissolved in an acetone–dichloromethane (or acetone–chloroform) mixture were poured into an aqueous solution of PEG [or poly(vinyl alcohol) (PVA)] with stirring with a high‐speed homogenizer for the formation of microparticles. HSA recovery in microspheres ranged from 13 to 40%, depending on the solvent and emulsification systems used for the preparation. PLA dissolved in a dichloromethane/acetone system and albumin loaded via a PEG emulsification solution (PLA–PEG–HSA) showed maximum drug recovery (39.5%) and drug content (9.9%). Scanning electron microscopy revealed that PEG‐coated microspheres had less surface micropores than PVA‐based preparations. The drug‐release behavior of microspheres suspended in phosphate‐buffered saline exhibited a biphasic pattern. An initial burst release (30%) followed by a constant slow release for 20 days was observed for HSA and Thr from PLA–PEG microspheres. PEG‐coated PLA microspheres show great potential for protein‐based drug delivery. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1285–1295, 2002     

Porous Electrospun PES/PEG Ultrafine Fibers for the Removal of Endocrine Disruptors

In this work, porous polyethersulfone (PES)/polyethylene glycol (PEG) ultrafine fibers were prepared via electrospinning technique, and then were used to removing endocrine disrupters from their aqueous solutions. The surface and the internal structures of PES/PEG ultrafine fibers were characterized by scanning electron microscopy (SEM) and the result showed that they were both porous. The porous electrospun PES/PEG ultrafine fibers can remove endocrine disrupters such as biphenyl A (BPA) and biphenyl (BP) effectively. Compared with pure PES ultrafine fibers, PES/PEG ultrafine fibers showed larger adsorption capacity and faster kinetics of uptaking target species. The hydrophilic properties and the porosity of porous PES/PEG ultrafine fibers can be controlled by adding hydrophilic materials such as polyethylene glycol (PEG), which can improve the adsorption properties of porous PES/PEG ultrafine fibers significantly. The results showed that porous electrospun PES/PEG ultrafine fibers had the potential to be used in environmental application and water treatment.     

Effects of different porous fillers on interfacial properties of poly (vinyl alcohol) hybrid films

Poly(vinyl alcohol) (PVA)-based hybrids have demonstrated broad liquid separation applications but separation performances are constrained by the compatibility between fillers and polymer, and thus it is essential to study the interfacial properties of these hybrids. In this work, PVA hybrids with four different porous fillers have been fabricated and characterized with Fourier transform infrared, X-ray diffraction, Scanning electron microscope, swelling and contact angle tests. Swelling results show that PVA has a degree of swelling (DS) of 79% in water but the swelling is compressed after adding fillers and the DS for PVA hybrids has decreased by 19%, 17%, 15%, and 9% for 30 wt% loading of ZIF-8, UiO-66, Hβ and ZSM-5, respectively. For methanol and its 10 wt% aqueous solution, similar swelling results are obtained due to mutual interactions among the filler, polymer and test liquids. Based on water and glycerol contact angle results, the surface energy of PVA is estimated to be 40.56 Nm⁻¹ and it drops to 27.39 Nm⁻¹ after adding less hydrophilic ZIF-8 or rise to 48.56 Nm⁻¹ after introducing more hydrophilic ZSM-5. The high-film hydrophilicity and then large surface energy have rendered methanol/water sorption selectivity of PVA hybrids decrease to some extent or vice versa.     

Preparation of sodium alginate/poly(vinyl alcohol) blend microspheres for controlled release applications

Sodium alginate (NaAlg)/poly (vinyl alcohol) (PVA) blend microspheres (MS) were prepared by water-in-oil (w/o) emulsion method. These polymer microspheres were crosslinked with glutaraldehyde and loaded with metformin hydrochloride (MHC). The microspheres were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and X-ray diffraction (XRD) analysis to confirm the molecular dispersion of the drug, thermal stability, morphological properties, and crystallinity of the polymer matrix before and after blending. SEM of the microspheres suggested the formation of microspheres in spherical structure. Drug release data were analyzed using an empirical equation to understand the nature of drug transport through polymeric matrices. The controlled release (CR) characteristics of the polymer matrices was investigated in pH 7.4 media and from the results it was obtained that the drug was released in controlled manner up to 10 h. The physico-chemical properties of the microspheres were studied by calculating drug entrapment efficiency and drug release kinetics. Percent of encapsulation efficiency (% EE) decreased with increase in crosslinking agent (GA) and PVA content in the microspheres. The optimum % EE (80%) was observed in case of MS containing 40% of PVA with 15% MHC. The release profiles indicate that the release of MHC decreases with increasing the PVA/NaAlg (w/w) and drug/polymer ratio. At the end of 10 h, the highest release of MHC was found to be 96% for MS containing PVA/NaAlg (40 : 60) and 15 wt % drug loaded. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

复乳液滴模板法结合溶剂去除法制备P(MMA-MAA)超大孔聚合物微球

以聚(甲基丙烯酸甲酯-甲基丙烯酸)[P(MMA-MAA)]为主要微球材质,两亲性聚(乳酸-聚乙二醇)二嵌段共聚物(PELA)为辅助材质,通过复乳液滴模板法结合溶剂去除法,制备了微米尺度贯穿孔道结构的超大孔P(MMA- MAA)微球,考察了油相中材质浓度、内水相盐浓度、复乳演变时间等对微球形态及孔道结构的影响,分析了微球表面孔隙的演变机理. 在P(MMA-MAA)浓度100 g/L和PELA浓度30~40 g/L、外水相PVA浓度25 g/L、内水相NaCl浓度1~5 g/L、乳液熟化时间0~30 min的条件下,可制备出形态较好的超大孔微球,微球的表面孔径可达数微米,孔隙率最高可达95%. 超大孔微球形成后,对其骨架进行共价交联,可形成刚性微球骨架.     

膜乳化法与复乳法结合制备粒径均一的载溶菌酶微胶囊

采用微孔膜乳化法与复乳法结合制备粒径均一可控的以聚乳酸和聚(乳酸-羟基乙酸)共聚物为膜材的载溶菌酶微胶囊,粒径分布系数CV(Coefficient of Variation)为14.04%,远低于机械搅拌法制备的微囊的CV(76.54%). 分别加入内水相添加剂PVA, PEG400, HP-b-CD,使溶菌酶的包埋率从无添加剂时的68.1%分别增大到86.6%, 89.0%和94.1%. 添加剂降低了溶菌酶的突释. PEG400, PEG6000, HP-b-CD的加入降低了溶菌酶的释放速率,而PVP或PVA的加入则加快了溶菌酶的释放. 溶菌酶在油水界面上的吸附变性是失活的主要原因. 在酶液中加入PEG400, PEG6000, PVP, HP-b-CD可有效地避免由于油水界面造成的溶菌酶活性的损失.