嵌段共聚物的改性研究及其在胶黏剂中的应用

论述了嵌段共聚物SBS／SIS（苯乙烯-丁二烯-苯乙烯／苯乙烯-异戊二烯-苯乙烯）的结构、结构对性能的影响及其在胶黏剂中的应用概况,重点介绍了它们的各种改性方法、改性机理及其改性后的效果。将各种化学改性方法和共混改性方法结合起来运用,有条件时进一步使用电子束或紫外光改性,是其重要的发展趋势。     

PE-b-PEO嵌段共聚物的合成及其芳烃/烷烃渗透汽化分离性能

采用阴离子聚合方法合成了具有不同环氧乙烷聚合度的聚丁二烯-b-聚环氧乙烷嵌段共聚物(PB-b-PEO嵌段共聚物),然后催化加氢得到聚乙烯-b-聚环氧乙烷嵌段共聚物(PE-b-PEO嵌段共聚物),使用凝胶渗透色谱仪(GPC)、核磁共振氢谱(1H-NMR)对共聚物进行了分析,结果表明所得聚合物具有预定的结构。通过熔融压片的方法制备PE-b-PEO嵌段共聚物均质膜,考察了PE-b-PEO嵌段共聚物分子链中聚环氧乙烷的聚合度对渗透汽化分离性能的影响。     

嵌段共聚物的表面活性行为及其应用

综述了嵌段共聚物在选择性溶剂中的胶束性质和在气/液界面、液/液界面以及固/液界面的界面行为 ,并介绍了嵌段共聚物胶束在药物输送、分离和释放等方面的应用。     

嵌段共聚物PAN-b-PZDMA的合成及表征

使用原子转移自由基聚合法(ATRP)设计合成了大分子引发剂PAN-Br,通过引发甲基丙烯酸锌单体聚合制备得到黏均相对分子质量(简称黏均分子量,下同)分别为7 507、8 517、9 905的嵌段共聚物聚丙烯腈-b-聚甲基丙烯酸锌(PAN-b-PZDMA),利用1HNMR和FTIR确认了大分子引发剂和嵌段共聚物的分子结构。TGA和DSC测试结果显示,ZDMA链段抑制了聚丙烯腈的环化反应,提高了聚合物的热性能。     

The Adsorption of a Polystyrene-b-Polyisoprene Block Copolymer at the n-Hexadecane/Air Interface

Surface-tension measurements were used to investigate the surface adsorption and micellisation of a polystyrene-b-polyisoprene block copolymer in n-hexadecane which is a selectively bad solvent for polystyrene. Measurements were made over a range of concentrations (1.29–2.88)x10^?4 mol dm^?3 and temperatures 25–40°C. The block copolymer was found to be positively adsorbed at the n-hexadecane/air interface. The linearity of plots of γ against In c just below the critical micelle concentration (c.m.c.) indicated an approximately constant surface concentration. The area per block copolymer molecule at the surface had an average value of 4.1 nm². A plot of In (c.m.c.) against T^?1 gave a value for the standard enthalpy of micellisation of -41.9.3.0 kJ per mole of copolymer chains. The standard entropy contribution (-TΔSΔ) to the standard free energy of micellisation was found to be 19.7.3.0 kJ mol^?1. These thermodynamic values are in good agreement with results obtained earlier for this system by light scattering and calorimetry.     

含氟嵌段聚酰亚胺共聚物的制备及其介电常数计算

通过顺序加料法制备了一系列不同氟含量聚酰亚胺,FT-IR、1H-NMR及GPC测试结果表明,所制备的聚合物为嵌段共聚物.Lorenz和Vogel介电常数计算公式主要用于均聚物介电常数的计算,通过对上述两计算公式进行相应变形处理,使之适用于计算嵌段共聚物的理论介电常数,并将其运用到所合成的嵌段型含氟聚酰亚胺模板聚合物的介电常数计算中,计算结果显示,Lorenz和Vogel介电常数变形公式计算所得的模板聚合物的介电常数与聚合物介电常数实测值具有较好的吻合性,能够有效指导低介电常数嵌段聚酰亚胺的设计与合成.     

苯酚对Pluronic嵌段共聚物F127胶束化以及胶束增溶蒽的影响

通过紫外 -可见光谱、荧光光谱和黏度等技术测定在苯酚存在下 ,Pluronic嵌段共聚物F12 7水溶液的临界胶束浓度 (CMC)以及胶束结构的变化 ,考察苯酚浓度cph对胶束增溶蒽的影响。实验结果发现F12 7的CMC随cph的增高先增大 ,在cph>3 0× 10 -6 后减小 ,胶束特性黏度[η]则先减小再增大 ,胶束内核中PO成分逐渐增大 ,在cph>3 0× 10 -6 后胶束内核几乎完全由PO构成。蒽与胶束的K1/N值先急剧下降 ,同样在cph>3 0× 10 -6 后转而逐渐增大。结合苯酚对水结构的影响 ,以及与PEO嵌段上醚氧原子的氢键相互作用解释了上述实验现象。     

Preparation of the Sulfonamide Containing Block Copolymer as Polymeric Sorbent for Removal of Mercury from Aqueous Solutions

A new sulfonamide containing polymeric sorbent for the removal of mercury ions from waste waters was prepared starting from poly(glycidyl methacrylate)-b-poly(ethylene glycol)-b-poly(glycidyl methacrylate) (PGMA- b -PEG- b -PGMA) triblock copolymer prepared by using the ATRP method. Epoxy groups on the block copolymer were functionalized with amino groups. Ammonia-functionalized PGMA- b -PEG- b -PGMA was treated with excess of benzenesulfonyl chloride to obtain a sulfonamide-based polymeric sorbent. The sulfonamide containing the polymeric sorbent with a 3.5 mmol · g^?1 total nitrogen content is able to selectively sorb mercury from aqueous solutions. The mercury sorption capacity of the resin is around 3.12 mmol g^?1 under non-buffered conditions. Experiments performed in identical conditions with several metal ions revealed that Cd(II), Pb(II), Zn(II), Fe(III), and Fe(II) also were extractable in quantities (0–0.45 mmol/g). The sorbed mercury can be eluted by repeated treatment with 4 M HNO₃ without hydrolysis of the sulfonamide groups.     

有机硅改性聚氨酯的研究进展

有机硅改性聚氨酯聚合物是一类很有应用前景的性能优异的新型高分子材料。综述了有机硅改性聚氨酯的合成方法、结构特点和性能 ,探讨了相分离及其对材料的影响和增加相容性的途径 ,并简要介绍了其应用。     

Compatibility Studies and Characterisation of a PVC/NR Blend System Using NR/PU Block Copolymer

Summary Polyvinyl chloride (PVC) has been blended with masticated natural rubber (NR₅) in the presence of a compatibiliser. A block copolymer of NR and polyurethane (PU) based on propylene glycol (PG) and toluene diisocyanate (TDI) was used as the compatibiliser. Compatibilising effect of this block copolymer on PVC/NR₅ (90/10) blend system was investigated by solution viscometry and optical microscopy. Testing and analysis of the blends showed that the mechanical and morphological properties are functions of compatibiliser concentration. Incorporation of 10 parts of NR₅ into PVC caused deterioration of tensile properties of the latter, which were recovered on the addition of 1.5 weight per cent of the compatibiliser. Besides, the tensile impact strength of PVC gets improved greatly. This was attributed to the enhanced interfacial adhesion between PVC and NR caused by the compatibiliser. The modification at the interface leads to finer and uniform distribution of NR domains in the PVC matrix.     

Thermodynamics of Surfactants, Block Copolymers and Their Mixtures in Water: The Role of the Isothermal Calorimetry

The thermodynamics of conventional surfactants, block copolymers and their mixtures in water was described to the light of the enthalpy function. The two methodologies, i.e. the van’t Hoff approach and the isothermal calorimetry, used to determine the enthalpy of micellization of pure surfactants and block copolymers were described. The van’t Hoff method was critically discussed. The aqueous copolymer+surfactant mixtures were analyzed by means of the isothermal titration calorimetry and the enthalpy of transfer of the copolymer from the water to the aqueous surfactant solutions. Thermodynamic models were presented to show the procedure to extract straightforward molecular insights from the bulk properties.     

Towards Understanding the Chemical Structure Modification of EVA Copolymer upon MAPLE Processing of Thin Films

A series of coatings from poly(ethylene-co-vinyl acetate) (EVA) were obtained using the matrix-assisted pulsed laser evaporation (MAPLE) technique. By changing the process parameters, i.e., laser fluence and EVA co-polymer concentration in the target, coatings with various morphologies and topographies were produced. The evaluation of the film structure was based on an analysis of optical and atomic force microscopy and profilometry measurements. A detailed chemical structure investigation, conducted based on Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) spectra, revealed that although the general structure was preserved, some alterations of ethylene (Et) and vinyl acetate (VAc) blocks took place. The most noticeable change was in the ester group that was transformed into ketone and carboxyl groups; nevertheless, some changes in the aliphatic main chain were also present. The chemical structure changes in EVA coatings took place regardless of the process parameters used. The use of chloroform as a solvent to dissolve the EVA copolymer was indicated as a possible reason of the changes as well as the tendency of EVA macromolecules to form clusters. Nevertheless, due to low level of structure alteration, it has been shown that the MAPLE technique can be successfully used to obtain coatings from polymers with more complex structures, which are soluble in a limited number of solvents.     

Thermal Stabilities and Thermal Degradation Kinetics of a Styrene-Butadiene-Styrene Star Block Copolymer

The thermal and thermo-oxidative degradation behaviors of styrene-butadiene-styrene (SBS) star block copolymer were reported using thermogravimetric analysis (TGA). TGA coupled with Fourier Transform Infrared spectroscopy was used to characterize the degradation volatile of SBS in air atmosphere. The thermal degradation kinetics of SBS in nitrogen and air atmospheres was studied in three steps: (1) the activation energies E _α were estimated by iterative method; (2) the proper form of f(α) was deduced by Popescu method; (3) the results obtained by above steps were used in determination pre-exponential factor A.     

RAFT合成pH和温度响应的双亲水嵌段共聚物

以S-十二烷基-S-′(2-羧基-异丙基)三硫酯(DDATC)为链转移剂,偶氮二异丁腈(AIBN)为引发剂,通过可逆加成-断裂链转移(RAFT)聚合合成了结构明确,窄相对分子质量分布(Mw/Mn=1.27)的聚(N-异丙基丙烯酰胺)-b-聚(N,N-二甲氨基甲基丙烯酸乙酯)(PNIPAm-b-PDMAEMA)双亲水两嵌段共聚物。共聚物的结构通过红外光谱、核磁共振氢谱和凝胶渗透色谱表征。采用透光率法、稳态荧光光谱法、电位滴定和动态光散射考察了PNIPAm-b-PDMAEMA在水中对温度和pH敏感的胶束化行为。结果表明,PNIPAm-b-PDMAEMA具有温度响应性,其水溶液的低临界溶液温度(LCST)为32.3℃,溶液温度高于LCST后发生温度诱导的胶束化,胶束的流体力学半径(Rh)为50 nm左右,Rh随温度升高而稍微增大;PNIPAm-b-PDMAEMA水溶液表现出明显的pH敏感性,25℃时两嵌段共聚物pH诱导胶束化的临界pH=9.8,溶液pH高于临界pH后发生pH诱导的胶束化,胶束的Rh约为31 nm(pH=11.0)。     

Fabrication of Highly Ordered Polymeric Nanodot and Nanowire Arrays Templated by Supramolecular Assembly Block Copolymer Nanoporous Thin Films

Realizing the vast technological potential of patternable block copolymers requires both the precise controlling of the orientation and long-range ordering, which is still a challenging topic so far. Recently, we have demonstrated that ordered nanoporous thin film can be fabricated from a simple supramolecular assembly approach. Here we will extend this approach and provide a general route to fabricate large areas of highly ordered polymeric nanodot and nanowire arrays. We revealed that under a mixture solvent annealing atmosphere, a near-defect-free nanoporous thin film over large areas can be achieved. Under the direction of interpolymer hydrogen bonding and capillary action of nanopores, this ordered porous nanotemplate can be properly filled with phenolic resin precursor, followed by curation and pyrolysis at middle temperature to remove the nanotemplate, a perfect ordered polymer nanodot arrays replication was obtained. The orientation of the supramolecular assembly thin films can be readily re-aligned parallel to the substrate upon exposure to chloroform vapor, so this facile nanotemplate replica method can be further extend to generate large areas of polymeric nanowire arrays. Thus, we achieved a successful sub-30 nm patterns nanotemplates transfer methodology for fabricating polymeric nanopattern arrays with highly ordered structure and tunable morphologies.     

Preparation and Characterization of Copolymer Micelles Formed by Poly(ethylene glycol)-Polylactide Block Copolymers as Novel Drug Carriers

Diblock copolymer poly(ethylene glycol) methyl ether-polylactide (MePEG-PLA) micelles were prepared by dialysis against water. Indomethacin (IMC) as a model drug was entrapped into the micelles by dialysis method. The critical micelle concentration (CMC) of the prepared micelles in distilled water investigated by fluorescence spectroscopy was 0.0051 mg/mL which is lower than that of common low molecular weight surfactants. The diameters of MePEG-PLA micelles and IMC loaded MePEG-PLA micelles in number-averaged scale measured by dynamic light scattering were 52.4 and 53.7 nm respectively. Transmission electron microscope and scanning electron microscope observation showed that the appearance of MePEG-PLA micelles was in a spherical shape. The content of IMC incorporated in the core portion of the micelles was 18 wt.%. The effects of the synthesis method of the copolymer on the polydispersity of the micelles and the yield of the micelles formation were discussed.     

聚(对苯二甲酸-1,3-丁二醇酯/对苯二甲酸-1,4-丁二醇酯)/PEG嵌段共聚物的合成及性能研究

用熔融缩聚法合成了一系列聚(对苯二甲酸-1,3-丁二醇酯/对苯二甲酸-1,4-丁二醇酯)/聚乙二醇的嵌段共聚物。用FT-IR,1H-NMR,DSC,TGA,水降解测试等方法表征了材料的结构与性能。FT-IR和1H-NMR分析表明合成得到的共聚物为预期产物;DSC分析显示,共聚聚酯随着1,3-丁二醇在共聚物中比例的增大,熔点(Tm)逐渐降低,由158.24℃下降至104.19℃,玻璃化温度(Tg)逐渐升高,由4.86℃升至24.56℃,合成得到的共聚酯趋向于无定形态;TGA分析表明1,3-丁二醇在共聚酯中比例增大会使聚酯的热稳定性下降,但合成得到的共聚酯依然具有较好的热稳定性,初始分解温度大于310℃,不需要在反应过程中添加热稳定剂;水降解测试结果表明共聚物随1,3-丁二醇比例的增加,降解速率大幅提升。     

Fundamental Understanding in Rolling Ball Tack of Tackified Block Copolymer Adhesives

In the pressure sensitive adhesive (PSA) industry, rolling ball tack is a very common tack test, which is simple, inexpensive and easy to operate. This work attempts to search for key parameter(s), which will affect the rolling ball tack of a PSA based on a blend of styrene-isoprene-styrene triblock copolymer(SIS) and hydrocarbon tackifier(s). We want to better understand whether this particular PSA performance is controlled by the surface or bulk properties of the adhesive.

Firstly, to test the contribution from the surface properties, we employ a model system of SIS/aliphatic tackifier in 1/1 wt. ratio as the control. Part of the tackifier in this PSA is then replaced by various amounts of low molecular weight diluents with different surface tensions. The idea is to vary the surface properties of the PSA because these low surface tension and low molecular weight diluents tend to migrate to the PSA surface. It is observed that the incorporation of a lower surface tension and a lower molecular weight diluent in the PSA tends to produce a larger increase in rolling ball tack compared with the unmodified PSA. On the other hand, the incorporation of a higher surface tension and a more compatible diluent tends to produce a larger increase in loop, peel and quick stick. Each diluent lowers the shear adhesion failure temperature (SAFT) of the diluent-modified PSA. These observations are explained in terms of tackifier molecular weight, and surface tension and compatibility of the various components (polyisoprene, tackifier, diluent and oil) in the adhesive formulation.

Secondly, to test the contribution from the bulk properties, we derive an equation for rolling ball tack in terms of the bulk viscoelastic behavior of the block copolymer PSA. However, experimental values of rolling ball tack do not follow this equation. Also, with increasing tackifier concentration in SIS, rolling ball tack has very different behavior compared with loop, peel, quick stick and probe tack. The latter set of performance criteria is known to be related to PSA bulk viscoelastic behavior. Therefore, these suggest that rolling ball tack is related more to the surface properties than to the bulk properties of the adhesive based on these results and those of the diluent-modified PSA systems.     

Fundamental Understanding in Rolling Ball Tack of Tackified Block Copolymer Adhesives

In the pressure sensitive adhesive (PSA) industry, rolling ball tack is a very common tack test, which is simple, inexpensive and easy to operate. This work attempts to search for key parameter(s), which will affect the rolling ball tack of a PSA based on a blend of styrene-isoprene-styrene triblock copolymer(SIS) and hydrocarbon tackifier(s). We want to better understand whether this particular PSA performance is controlled by the surface or bulk properties of the adhesive.

Firstly, to test the contribution from the surface properties, we employ a model system of SIS/aliphatic tackifier in 1/1 wt. ratio as the control. Part of the tackifier in this PSA is then replaced by various amounts of low molecular weight diluents with different surface tensions. The idea is to vary the surface properties of the PSA because these low surface tension and low molecular weight diluents tend to migrate to the PSA surface. It is observed that the incorporation of a lower surface tension and a lower molecular weight diluent in the PSA tends to produce a larger increase in rolling ball tack compared with the unmodified PSA. On the other hand, the incorporation of a higher surface tension and a more compatible diluent tends to produce a larger increase in loop, peel and quick stick. Each diluent lowers the shear adhesion failure temperature (SAFT) of the diluent-modified PSA. These observations are explained in terms of tackifier molecular weight, and surface tension and compatibility of the various components (polyisoprene, tackifier, diluent and oil) in the adhesive formulation.

Secondly, to test the contribution from the bulk properties, we derive an equation for rolling ball tack in terms of the bulk viscoelastic behavior of the block copolymer PSA. However, experimental values of rolling ball tack do not follow this equation. Also, with increasing tackifier concentration in SIS, rolling ball tack has very different behavior compared with loop, peel, quick stick and probe tack. The latter set of performance criteria is known to be related to PSA bulk viscoelastic behavior. Therefore, these suggest that rolling ball tack is related more to the surface properties than to the bulk properties of the adhesive based on these results and those of the diluent-modified PSA systems.     

氟碳化合物FC-77在Pluronic嵌段共聚物胶束中包封与缓释

采用乙醇注入法制备FC-77的载药纳米胶束,通过动态光散射、透射电子显微镜表征了载药纳米胶束的粒径和形貌;通过紫外可见光谱研究了FC-77在嵌段共聚物P123中的包封率和释放曲线。结果表明,含1%P123的FC-77载药纳米胶束粒径为270 nm,呈球形分布,包封率为50%6,00 min时的释放量为92.2%。进一步地,通过调节嵌段共聚物的组成、浓度等可以改变载药纳米胶束的粒径和包封率。结果证明,嵌段共聚物胶束体系能作为FC-77载药制剂的载体,并且通过调整嵌段共聚物胶束体系配方,可以得到理想的FC-77药物载体。