玻璃表面聚苯乙烯“刷子”的制备与表征

采用原位活性接枝聚合反应在玻璃表面制备了聚苯乙烯"刷子"层,制备过程包括:将偶联剂3-甲基丙烯酰氧基丙基三甲氧基硅烷接枝到玻璃表面,然后以4-羟基-2,2,6,6-四甲基哌啶氧自由基(HTEMPO.)为自由基捕捉剂,过氧化苯甲酰(BPO)为引发剂,在玻璃表面引发苯乙烯接枝聚合反应,制备了4nm～28nm厚的聚苯乙烯"刷子"。X射线光电子能谱(XPS)表明Si(1s/2p)在99eV、151eV处吸收峰强度随接枝反应时间的延长而逐渐减弱,C(1s)在285eV处的吸收峰强度随接枝时间的延长而增强;椭圆偏振仪结果表明聚苯乙烯层的厚度随聚合时间的延长从4nm增加到28nm。红外光谱(FT-IR)表明在玻璃表面的聚合物为聚苯乙烯。     

阿司匹林表面印迹微球的制备与药物缓释性能评价

采用表面印迹技术,选取γ-氨丙基三甲氧基硅烷(APTS)和甲基丙烯酰氯修饰的硅胶为载体,以阿司匹林(Asp)为模板分子,丙烯酰胺(AM)为功能单体,乙二醇二甲基丙烯酸酯(EDGMA)为交联剂,在乙腈溶液中合成了阿司匹林表面分子印迹聚合物微球(MIPs)和非印迹聚合物微球(NIPs)。通过紫外、红外光谱、扫描电镜、透射电镜、热重分析以及吸附实验进行了表征并进行了药物扩散实验。结果表明,MIPs平衡吸附量可达164.40μmol/g,对苯甲酸(BA)和水杨酸(SA)的分离因子达到3.15和3.32,有很好的热稳定性和选择性吸附能力;MIPs持续释药时间是NIPs的2.6倍,有很好的缓释效果和应用价值。     

RAFT聚合结合“巯基-炔”点击反应制备凹凸棒土杂化粒子

以十二烷基三硫代碳酸酯-2-甲基-丙酸炔丙酯(alkyne-DMP)为链转移剂,通过RAFT聚合合成炔基封端的聚(N-异丙基丙烯酰胺)(alkyne-PNIPAM),以γ-巯丙基三甲氧基硅烷(MTS)修饰凹凸棒土(ATP)制备表面巯基化的ATP-MTS,经"巯基-炔"点击反应制备杂化粒子ATP@PNIPAM。研究了聚合反应动力学,采用傅里叶红外光谱(FT-IR)、X射线光电子能谱(XPS)、热重分析(TGA)和透射电镜(TEM)等手段对杂化粒子进行表征。结果表明:RAFT聚合具有较好的可控性,通过点击反应成功制备了杂化粒子,点击反应进行3 h时,杂化粒子表面PNIPAM的接枝率可达12.6%,且具有明显的温度响应性。     

玻璃表面引发接枝聚合物研究

将氨丙基三乙氧基硅烷化学键合于玻璃片表面,与a-溴代异丁酰溴进行酰胺化反应制备表面引发剂.以甲基丙烯酸甲酯,苯乙烯和r-甲基丙烯酰氧基丙基三甲氧基硅烷为单体,在玻璃表面引发原子转移自由基聚合反应(SP-AT-RP).衰减全反射傅立叶变换红外光谱(ATR/FT-IR),X-射线光电子能谱(XPS)显示PMMA、PS和PS/KH570共聚物(Poly(St-co-KH570))都接枝到玻璃片表面.凝胶渗透色谱(GPC)数据表明游离PMMA与PS的数均分子量随反应时间增加而增大,且分子量分布系数较低.接触角测试表明,改性后玻璃的表面疏水性得到一定程度改善,当KH570体积含量为80％时,水接触角增大到92.5°.     

原子转移自由基聚合法在硅橡胶表面接枝聚甲基丙烯酸甲酯EI北大核心CSCD

采用表面引发原子转移自由基聚合(SI-ATRP)在室温硫化硅橡胶表面接枝聚甲基丙烯酸甲酯(PMMA)。通过衰减全反射傅立叶变换红外光谱(FT-IR/ATR)、X射线光电子能谱(XPS)、接触角和扫描电子显微镜(SEM)对改性前后硅橡胶表面结构、表面形貌及表面润湿性进行表征。结果表明,在硅橡胶表面成功接枝了PMMA;随着聚合时间的延长,单位面积上的接枝量逐渐增大,当聚合时间为16h时,接枝量达到3.75mg/cm2;接触角从108.8°下降到71.7°;表面自由能从17.7mN/m增大到32.0mN/m。     

原子转移自由基聚合法在硅橡胶表面接枝聚甲基丙烯酸甲酯

采用表面引发原子转移自由基聚合(SI-ATRP)在室温硫化硅橡胶表面接枝聚甲基丙烯酸甲酯(PMMA)。通过衰减全反射傅立叶变换红外光谱(FT-IR/ATR)、X射线光电子能谱(XPS)、接触角和扫描电子显微镜(SEM)对改性前后硅橡胶表面结构、表面形貌及表面润湿性进行表征。结果表明,在硅橡胶表面成功接枝了PMMA;随着聚合时间的延长,单位面积上的接枝量逐渐增大,当聚合时间为16h时,接枝量达到3.75mg/cm2;接触角从108.8°下降到71.7°;表面自由能从17.7mN/m增大到32.0mN/m。     

基于原子转移自由基聚合法制备多壁碳纳米管/Ag复合材料

在多壁碳纳米管(MWNT)表面键接可用于原子转移自由基聚合(ATRP)的引发剂,并以此引发甲基丙烯酸缩水甘油酯(GMA)在MWNT表面的ATRP.利用红外光谱(FT-IR)、核磁共振(<'1>H-NMR)和透射电镜(TEM)对接枝聚合物MWNT的结构和外观形貌进行了研究.接枝在MWNT表面的PGMA与过量的乙二胺发生开...     

SBA-15介孔硅片胺基修饰及其CO_2吸附

以3-氨基丙基三乙氧基硅烷(APTS)和N-[3-(二甲氧基甲硅烷基)丙基]乙二胺(TPED)为表面胺基修饰剂,通过化学接枝法制备了胺基修饰的SBA-15介孔硅片(SBA-15-EHP)吸附剂。采用SEM、全自动气体吸附仪、XRD、TGA等测试手段对胺基修饰的SBA-15-EHP进行表征,研究了胺基修饰的SBA-15-EHP的表面形貌,孔隙结构,晶体结构,SBA-15-EHP表面胺基的接枝量及CO_2的吸附特性。结果表明,在常压、35℃下,TPED修饰的SBA-15-EHP的CO_2吸附能力优于APTS修饰的SBA-15-EHP,最大的CO_2吸附容量为53.0mg/g,这是由于胺基与CO_2发生酸碱反应形成盐类的可逆化学吸附过程所致。     

DMF/SiO2有机溶胶的制备与表征

采用3-(2,3-环氧丙氧)丙基甲基三甲氧基硅烷(CG-560)对硅溶胶进行接枝改性后,与适量的N,N-二甲基甲酰胺(DMF)混合均匀,除去混合液中水分,制备DMF/SiO有机溶胶.探讨了不同硅烷用量对表面接枝的影响,并用傅里叶红外光谱(FT-IR)、透射电镜(TEM)对有机溶胶进行分析表征.研究结果表明:添加适量的硅烷可以对硅溶胶表面羟基实现最大接枝改性,有机溶胶为无色透明液体,有机溶胶粒子呈球形,粒径约20nm,粒度分布均匀.     

铈离子-氨基复合引发N-异丙基丙烯酰胺表面接枝聚合

将硅片用“Piranha”溶液浸蚀处理，使其表面富含羟基，然后用3-氨基丙基-三乙氧基硅烷（APTES）进行表面修饰，得到硅片表面APTES单分子层，利用APTES分子上的氨基与Ce＾4＋组成复合引发聚合体系，引发N-异丙基丙烯酰胺（NIPAm）单体进行硅表面接枝聚合。采用表面接触角测定（CA）、X-射线光电子能谱分析...     

Preparation of poly(N-isopropylacrylamide) brush grafted silica particles via surface-initiated atom transfer radical polymerization used for aqueous chromatography

Thermoresponsive poly(N-isopropylacrylamide) (PNIPAAm) brushes were densely grafted onto silica surface via surface-initiated atom transfer radical polymerization (SI-ATRP). The grafting reaction started from the surfaces of 2-bromoisobutyrate-functionalized silica particles in 2-propanol aqueous solution at ambient temperature using CuCl/CuCl₂/N,N,N′,N′,N″-pentamethyldiethylenetriamine (PMDETA) as the catalytic system. Based on thermogravimetric analysis (TGA) results, the grafting amount and grafting density of PNIPAM chains on the surface of silica were calculated to be 1.29 mg/m² and 0.0215 chains/nm², respectively. The gel permeation chromatography (GPC) result showed the relatively narrow molecular weight distribution (M_w/M_n=1.21) of the grafted PNIPAAm. The modified silica particles were applied as high-performance liquid chromatography (HPLC) packing materials to successfully separate three aromatic compounds using water as mobile phase by changing column temperature. Temperature-dependent hydrophilic/hydrophobic property alteration of PNIPAAm brushes grafted on silica particles was determined with chromatographic interaction between stationary phase and analytes. Retention time was prolonged and resolution was improved with increasing temperature. Baseline separation with high resolution at relatively low temperatures was observed, demonstrating dense PNIPAAm brushes were grafted on silica surfaces.     

Nucleation of polystyrene latex particles in the presence of gamma-methacryloxypropyltrimethoxysilane: functionalized silica particles

Silica/polystyrene nanocomposite particles with different morphologies were synthesized through emulsion polymerization of styrene in the presence of silica particles previously modified by gamma-methacryloxypropyltrimethoxysilane (MPS). Grafting of the silane molecule was performed by direct addition of MPS to the aqueous silica suspension in the presence of an anionic surfactant under basic conditions. The MPS grafting density on the silica surface was determined using the depletion method and plotted against the initial MPS concentration. The influence of the MPS grafting density, the silica particles size and concentration and the nature of the surfactant on the polymerization kinetics and the particles morphology was investigated. When the polymerization was performed in the presence of an anionic surfactant, transmission electron microscopy images showed the formation of polymer spheres around silica for MPS grafting densities lower than typically 1 micromole x m(-2) while the conversion versus time curves indicated a strong acceleration effect under such conditions. In contrast, polymerizations performed in the presence of a larger amount of MPS moieties or in the presence of a non ionic emulsifier resulted in the formation of "excentered" core-shell morphologies and lower polymerization rates. The paper identifies the parameters that allow to control particles morphology and polymerization kinetics and describes the mechanism of formation of the nanocomposite colloids.     

Grafting of ion-imprinted polymers on the surface of silica gel particles through covalently surface-bound initiators: a selective sorbent for uranyl ion

A new ion imprinted polymer coated silica gel sorbent has been prepared using the radical "grafting from" polymerization method through surface-bound azo initiators for selective uranyl uptake. The introduction of azo initiator onto the silica surface was achieved by the reaction of surface amino groups with 4,4'-azobis(4-cyanopentanoic acid chloride). The grafting step was then carried out in a stirred solution of initiator-modified silica particles in the presence of uranyl ion and functional and cross-linking monomers. The prepared sorbent was characterized using FT-IR spectroscopy, scanning electron microscopy (SEM), elemental analysis (EA), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and BET adsorption isotherm analysis. The influence of the uranyl concentration, pH, and flow rate of solution on the grafted polymer affinity has been investigated. Maximum uptake of uranyl ion was observed at a pH 3.0. The rebinding behavior of the sorbent has been successfully described by the Langmuir-Freundlich isotherm. The dynamic column capacity of sorbent and enrichment factor for uranyl ion were 52.9 +/- 3.4 micromol g(-1) and 52, respectively. It was found that imprinting results in increased affinity of the sorbent toward uranyl ion over strong competitor metal ions such as Fe(III) and Th(IV). The sorbent was repeatedly used and regenerated for 3 months without any significant decrease in polymer binding affinities. Finally the sorbent was applied to the preconcentration and determination of uranyl ion in real water samples.     

Fumed silica/polymer hybrid nanoparticles prepared by redox-initiated graft polymerization in emulsions

Hybrid particles comprising aggregated fumed silica nanoparticles as the core and hydrophobic polymers existing around the nanoparticles were prepared by ‘grafting from’ polymerization in emulsions. The emulsion polymerization employed cetyltrimethylammonium bromide (CTAB) as a cationic surfactant and sodium dodecyl sulfate (SDS) as an anionic surfactant, respectively, to stabilize the emulsion polymerization. The polymerization was initiated by the redox reaction between ceric ion Ce(IV) and the amine groups on the surfaces of aminated fumed silica nanoparticles that were modified by 3-aminopropyltriethoxysilane. Infrared spectroscopy and thermogravimetric analysis demonstrated that both poly(methyl methacrylate) (PMMA) and polystyrene (PS) were successfully grafted onto the fumed silica surface. The type of surfactant greatly affected the grafting ratio, monomer-to-polymer conversion, and morphology of the product. When CTAB was used as the surfactant, both the grafting ratio and monomer-to-polymer conversion were lower than when SDS was used, but transmission electron microscopy and light scattering analysis indicated that most of the resultant particles were sub-100 nm hybrid nanoparticles with a non-spherical shape and particles sizes of 75–90 and 57–85 nm for PMMA and PS-grafted fumed silica, respectively. Whereas, when SDS was used as the surfactant, the particles agglomerated to form large irregular clusters or even networks, possibly due to the electrostatic attractions between SDS and Ce(IV) and/or the aminated fumed silica nanoparticles in aqueous solution.     

In situ polymerization of l-Lactide in the presence of fumed silica

Chemiorheology, i.e. rheological changes during the polymerization, of a biosourced monomer, i.e. l-Lactide, containing fumed silica have been studied. For that purpose, the reaction was proceeded in situ between the plates of a dynamic rheometer. The polymerization kinetics was followed from the variation of the complex shear modulus versus reaction time. Moreover, at temperatures lower than the crystallization temperature, it was possible to follow the crystallization process while the polymerization takes place. Adding fumed silica particles into the monomer leads to the formation of a physical (percolated) network from particle–particle interactions, i.e. silica, in the l-Lactide probably hydrophilic interactions. The gel-like structure was kept while the polymerization as long as the strain remains low indicating that the silica particle network remains weak. Furthermore, the mechanism of the break down of the gel structure under large deformation as well as the recovery was discussed. It seems that the non-linearity effect of the nanocomposites stems in the silica inter-particle interactions. It was found that silica particles do not have any effect on the temperature of crystallization – molar mass relation but could act as nucleating agent.In situ polymerization of l-Lactide in the presence of 5 wt.% of modified fumed silica was carried out in a reactor. It was found that fumed hydrophilic silica leaded to a microcomposite with highly dense agglomerates in the polymer matrix whereas with a less hydrophilic silica it was possible to decrease the size of the agglomerates increasing the dispersion. The finest dispersion state was achieved with the “initiating” functionalized silica leading to a “grafting from” polymerization of the l-Lactide. Such functionalized silica leads to a nanoscale dispersion in a one-step bulk polymerization with only a few small agglomerates.     

两步法LDPE/HSS表面光接枝的研究

采用两步表面光接枝方法研究了乙烯基苯磺酸(HSS)在低密度聚乙烯(LDPE)膜表面的接枝聚合,使LDPE膜表面有效强酸化．探讨了各反应条件对表面接枝的影响规律,利用称量法、表面水接触角测定法、红外光谱分析、扫描电镜观察等手段对表面接枝膜进行了表征。     

偶联剂改性纳米硅溶胶的接枝率及稳定性

为改善纳米硅溶胶与有机物间的亲和性及分散稳定性,用硅烷偶联剂对碱性纳米硅溶胶进行表面接枝改性。分析了偶联剂用量、反应温度和反应时间对接枝率、分散稳定性及微观形貌的影响。结果表明,偶联剂KH560更适合做碱性纳米硅溶胶的表面改性剂,且制备的改性纳米硅溶胶表面可接枝KH560;从接枝率变化梯度来看,KH560用量对接枝率影响最大,当KH560含量为12.5%、反应时间为5h、反应温度为60℃时,改性接枝率及Zeta电位绝对值最高,分别为7.37%和55.6mV。     

细乳液聚合制备纳米二氧化硅-丙烯酸酯复合乳液的研究

采用硅溶胶和丙烯酸酯单体通过细乳液聚合制备纳米二氧化硅/丙烯酸酯复合高分子乳液。考察了聚合过程中硅溶胶量对于单体转化率和聚合物粒子粒径的影响,并用GPC、XPS表征所得的复合乳液。实验结果表明:二氧化硅的引入提高了聚合反应速率,增加聚合物的分子量并使分子量分布变窄;在复合乳液粒子中,二氧化硅主要以分散相分布在连续的丙烯酸酯相内部;复合乳液的力学性能明显优于不含二氧化硅的纯丙烯酸酯聚合物乳液。     

利用开环聚合和原子转移自由基聚合在纳米二氧化硅表面接枝聚合物

利用硅烷偶联剂KH-550处理纳米二氧化硅(SiO_2)表面,得到氨基化的SiO_2,再通过溴异丁酸缩水甘油酯与氨基的开环反应,在SiO_2表面同时键接了开环聚合(ROP)的引发剂-OH和原子转移自由基聚合(ATRP)的引发剂-Br(SNPs-fOH/Br)。以SNPs-f-OH/Br为引发剂,分别进行ROP和ATRP,在纳米SiO_2表面接枝了聚己内酯(PCL)和聚苯乙烯(PS)混合聚合物刷(Mixed brush)。采用红外光谱、透射电镜、热失重、凝胶渗透色谱等方法对所得到的复合粒子进行了表征和测试。研究结果表明,混合聚合物刷成功接枝到了纳米SiO_2表面,通过控制聚合时间可以控制2种接枝聚合物的相对分子质量。本方法为纳米粒子表面接枝混合聚合物刷提供了一种简便的方法。     

Improvement of thermal stability of UV curable pressure sensitive adhesive by surface modified silica nanoparticles

Pressure sensitive adhesives (PSAs) with higher thermal stability were successfully prepared by forming composite with the silica nanoparticles modified via reaction with 3-methacryloxypropyltrimethoxysilane. The acrylic copolymer was synthesized as a base resin for PSAs by solution polymerization of 2-EHA, EA, and AA with AIBN as an initiator. The acrylic copolymer was further modified with GMA to have the vinyl groups available for UV curing. The peel strength decreased with the increase of gel content which was dependent on both silica content and UV dose. Thermal stability of the composite PSAs was improved noticeably with increasing silica content and UV dose mainly due to the strong and extensive interfacial bonding between the organic polymer matrix and silica.