VISCOMETRIC STUDY OF POLY(METHYL METHACRYLATE) AND POLYSTYRENE BLENDS IN DIFFERENT SOLVENTS

The intermolecular interaction between poly(methyl methacrylate) (PMMA) and polystyrene (PS) intetrahydrofuran (THF) and N,N'-dimethyl formamide (DMF) solvents was studied at 28℃ using a dilute solution viscometrymethod. Solvent is believed to play a key role in characterizing the viscosity behavior of the polymer solution. The intrinsicviscosity and viscosity interaction parameter were experimentally measured for the binary (solvent/polymer) and for theternary systems in two solvents. The compatibility of the polymer mixture was discussed in terms of the sign of △b_m. Theresults show that the compatibility of PMMA/PS blend in DMF is larger than that in THF.     

THE SYNTHESIS AND CHARACTERIZATION OF Ba-CROSSLINKED POLYMER ANTI-RADIATION MATERIALS

Crosslinked poly(methyl methacrylate) and polystyrene with barium dimethacrylate [Ba(MA)_2] as crosslinking agent have been synthesized. The relationship between X-ray absorbability and the content of Ba(MA)_2 in polymers was investigated. TGA and DSC results indicated that the crosslinked polymers containing barium dimethacrylate have a much better heat stability than pure PMMA or PS. The mechanical properties of the polymers containing barium are improved in comparison with the pure PMMA.     

Poly(2-acetoxyethyl methacrylate)/polystyrene latex interpenetrating polymer networks with well-defined phase-separated structure

A series of poly(2-acetoxyethyl methacrylate)/polystyrene(PAEMA/PS) latex interpenetrating polymer networks(LIPNs) were prepared by seeded soap-free emulsion polymerization of styrene on the crosslinked PAEMA seed particles using an oil-soluble initiator.These PAEMA/PS LIPNs showed a well-defined phase-separated structure with PS phase dispersing in continuous PAEMA phase.The domain size of PS phase was found to depend on the crosslinking degree of PAEMA seed particles and the amount of second-stage styrene monomer.     

SURFACE REARRANGEMENTS OF OXYGEN PLASMA TREATED POLYSTYRENE： SURFACE DYNAMICS AND HUMIDITY EFFECT

The time evolution of oxygen plasma treated polystyrene(PS)surfaces was investigated upon storing them in theair under controlled humidity conditions.The methods of water contact angle,X-ray photoelectron spectroscopy(XPS),sumfrequency generation(SFG)vibrational spectroscopy,and atomic force microscopy(AFM)were used to infer the surfaceproperties and structure.Chemical groups containing oxygen were formed on the PS surface with the plasma treatment,demonstrated by water contact angle and XPS.The surface polarity decayed markedly on time,as assessed by steady increasein the water contact angle as a function of storage time,from zero to around 60°.The observed decay is interpreted as arisingfrom surface rearrangement processes to burying polar groups away from the uppermost layer of the surfaces,which is incontact with air.On the other hand,XPS results show that the chemical composition in the first 3 nm surface layer isunaffected by the surface aging,and the depth profile of oxygen is essentially the same with time.A possible change of PSsurface roughness was examined by AFM,and it showed that the increase of water contact angle during surface aging couldnot be attributed to surface roughness.Thus,it is concluded that surface aging is attributable to surface reorganization andthe motion of oxygen containing groups is confined within the XPS probing depth.SFG spectroscopy,which is intrinsicallyinterface-specific,was used to detect the chemical structure of PS surface at the molecular level after various aging times.The results are interpreted as follows.During the aging of the plasma treated PS surfaces,the oxygen containing groupsundergo reorientation processes toward the polymer bulk and/or parallel to the surface,while the CH_2 moiety stands up onthe PS surface.Our results indicate that the surface configuration changes do not require large length scale segmentalmotions or migration of macromolecules.Motions that are responsible for surface configuration changes could be relativelysmall rotational motions.The aging behaviors under different relative humidity conditions were shown to be similar from18% to 91%,whereas the kinetics of surface polarity decays were faster in higher relative humidity.Here,the surfacerearrangement of polystyrene films that were previously treated by oxygen plasma and aged,and was investigated in terms ofcontact angle after the water immersion.The contact angles of the water-immersed samples were found to change andapproach the initial values before the immersion asymptotically.     

Synthesis of Polymer-bound Sensitizers and their Applications in the Preparation of Previtamin D3 from Tachysterol

Two kinds of polymer-bound photosensitizers were synthesized, in which anthracene acts as sensitizer moiety,polystyrene (PS) and poly(methyl methylacrylate) (PMMA) serve as solid phase supports, respectively. The photoisomerization of tachysterol to previtamin D3 was carried out with these polymer-bound photosensitizers in ethanol and toluene solutions. The experiment results demonstrate that these solid phase photosensitizers are efficient for the photoisomerization with good recycle property and can be simply separated from the reaction mixtures by filtration.     

A SLOW RELAXATION MODE OF POLYMER CHAINS IN A SEMIDILUTE SOLUTION

Dust-free semidilute and concentrated polystyrene(PS)solutions in different solvents were prepared by slow evaporation and in situ anionic polymerization,which removes the effects of troublesome artifacts such as dust contamination and concentration gradient.The dynamics was reexamined by a combination of static and dynamic laser light scattering.In benzene and toluene(good solvents for PS),only one fast diffusive mode of polymer chains can be observed when the concentration(c)is up to 20%,which is attri...     

Studies on partial compatibility of PP and PS

<正>Blends of polystyrene(PS) and polypropylene(PP) were prepared through melt compounding.With an increase of PS content up to 30 wt%,the tensile strength of PP/PS blends increased from 37.4 MPa to 42.2 MPa,although the blends were widely regarded as immiscible.The DSC results showed that there's slight decrease in melting temperature of PP, showing insufficient evidence for partial compatibility between PP and PS.Almost no variation of distinct characterization peaks were observed in FTIR spectra of PS/PP blends compared with those of neat PP and PS,indicating there is no chemical interactions between PP and PS.Since the morphology investigation showed a droplet structure as PS content was up to 30 wt%,the improvement of tensile strength could be simply considered as due to the reinforcing effect of dispersed rigid PS particles on the PP,combining with partial compatibility between them as evaluated by change of C_p at glass transition for both PS and PP.More interestingly,DSC and DMA results showed that the blending of PS and PP could lead to a substantial decrease of the glass transition temperature(T_g) of PP,and increase of T_g of PS.The annealing experiment was carried out to understand the change of T_g in PP/PS blends.It is believed that the compressive stress generated by the contracting PP should be the dominant mechanism for the T_g elevation of PS.On the other hand,the T_g decrease of PP is likely owing to the creation of a large amount free interface of PP and the dilatation of the PP phase resulting from the corresponding tension exerted by PS during cooling.     

Polystyrene-based blend nanorods with gradient composition distribution

The polystyrene-based polymer blends, partially miscible poly(bisphenol A carbonate)/polystyrene (PC/PS) and completely miscible poly(2,6-dimethylphenylene oxide)/polystyrene (PPO/PS), in nanorods with gradient composition distribution were discussed. The polymer blend nanorods were prepared by infiltrating the polymer blends into nanopores of anodic aluminum oxide (AAO) templates via capillary action. Their morphology was investigated by micro-Fourier transform infrared spectroscopy (micro-FTIR) and nano-thermal analysis (nano-TA) with spatial resolution. The composition gradient of polymer blends in the nanopores is governed by the difference of viscosity and miscibility between the two polymers in the blends and the pore diameter. The capillary wetting of porous AAO templates by polymer blends offers a unique method to fabricate functional nanostructured materials with gradient composition distribution for the potential application to nanodevices.     

Preparation of POE/PS blends with fine particle sizes by diffusion and subsequent polymerization of styrene in POE pellets

Ethylene-α-octene copolymer(POE)/polystyrene(PS) blend pellets with fine particle sizes were prepared by diffusion and subsequent polymerization of styrene in POE pellets through a one-pot procedure.The effects of the amounts of styrene and BPO on PS content,monomer efficiency and monomer conversion were investigated.The blend pellets were characterized by Micro-FTIR and FESEM,showing homogeneous diametrical distributions of PS and particle size.After melt-processing into rods,the average particle sizes are almost doubled,but still in submicron scale.Compared to neat POE rods,the blend rods with PS content higher than 15% exhibit improved tensile modulus and tensile strength without significantly losing ductility,being attributed to the small sizes,complex nature of particles and the existence of POE-g-PS copolymer that result in good interfacial adhesion.POE/PS pellets were compared with the previously reported PP/PS pellets,and the differences between the two systems are attributed to the different morphology of the two matrices: POE is completely amorphous at the diffusion and polymerization temperature,while i PP is semicrystalline.Without efficient impediment of the crystal lamellae in POE pellets,styrene diffuses easily in POE pellets.     

A NOVEL TITANIUM COMPLEX WITH LINKED β-DIKETONATO-INDENYL LIGAND FOR CATALYTIC SYNDIOSPECIFIC POLYMERIZATION OF STYRENE

A novel ligand (3), in which the indenyl group is linked to a β-diketone moiety through a three-carbon bridge, andits titanium complex (4) were synthesized. The titanium complex was employed as a metallocene analog with co-catalystmethylaluminoxane (MAO) in catalytic syndiospecific polymerization of styrene to give highly syndiotactic polystyrene(s-PS, 96%-97%). Polymerization temperature (T_p) strongly influenced the catalytic activity and syndiotacticity of theproduced PS. The activities of catalyst 4 increase from 1.84×10~6 to 3.26×10~6 gPS/molTi·h with the increase of T_p from60℃ to 80℃ and the syndiotacticities of the produced s-PS also increase slightly. Then, both the catalytic activity and thesyndiotacticity of PS decrease at T_p of 90℃.     

静电纺丝法制备三维聚二甲基硅氧烷纳米通道

利用静电纺丝技术构建了新型三维纳米通道系统。 在不同质量分数的聚苯乙烯（PS：Mw=1.3×105）溶液中加入一定量十二烷基磺酸钠（SDS）,于不同电压下进行静电纺丝。 所得纤维在90 ℃加热粘连后,形成三维聚苯乙烯纳米网络模板,然后于聚二甲基硅氧烷(PDMS)预聚体（含10%交联剂）灌注进入上述模板并交联形成网络复合材料,再用二硫化碳超声除去聚苯乙烯纤维。 采用扫描电子显微镜、透射电子显微镜对纤维模板形貌和纳米通道进行了表征。 结果表明,质量分数为10%的PS溶液加入0.5%SDS,在20 kV电压下进行静电纺丝,得到直径为150 nm的纤维。 SDS的加入对纺丝纤维具有平滑作用,使得粘连的纤维模板更易去除,形成的三维纳米通道直径约160 nm,与纤维模板直径一致。 该类型纳米通道可以应用于医学药物载体、纳流控芯片等众多领域。     

交联网络和浓溶液中高分子链运动的NMR研究 Ⅱ质子自旋-自旋弛豫与凝胶和浓溶液体系中高分子链段运动

用自旋－自旋弛豫时间考察了线型聚苯乙烯溶液与溶胀交联聚丙烯酰胺－丙烯酸凝胶的质子弛豫行为。发现在溶胀交联体系中，不论交联度高低，聚丙烯酰胺－丙烯酸质子的弛豫时间弛豫都呈现出双指数衰减特征；而在线型溶液体系中，聚苯乙烯质子的弛豫时间弛豫符合单指数衰减特征。说明在线性聚苯乙烯溶液中，高分子的链段运动是一种均匀行为，而在溶胀交联聚丙烯酰胺－丙烯酸体系中，不论交联度高低，高分子链段运动始终存在快慢不同的两部分。     

Model filled polymers. IX. Synthesis of uniformly crosslinked polystyrene microbeads

Monodisperse sized crosslinked polystyrene (PS) beads prepared by reaction of styrene (S) and divinylbenzene (DVB), in batch emulsion copolymerization in the absence of emulsifiers, are not uniformly crosslinked, because DVB is more reactive than S. For copolymerization of 1 to 10 mol % DVB and S, within each crosslinked PS microbead, the crosslink density varies by a factor exceeding two and decreases with increased conversion. A semicontinuous copolymerization, involving incremental additions of DVB, produces uniformly crosslinked PS beads. For both copolymerization techniques, T_g correlates well with crosslink density and PS beads are spherical and monodisperse in size. © 1992 John Wiley & Sons, Inc.     

交联网络和浓溶液中高分子链运动的NMR研究Ⅲ.质子自旋-晶格弛豫时间与凝胶和浓溶液体系中高分子链段的运动

用自旋－晶格弛豫时间（Ｔ１）研究了溶胀的交联聚丙烯酰胺－丙烯酸网络和线型聚苯乙烯溶液中质子的弛豫行为。交联网络中，随着交联度增大，Ｔ１ＣＨ／Ｔ１ＣＨ２的值由１．１７逐渐趋近于１；而线型聚苯乙烯溶液中，Ｔ１ＣＨ／Ｔ１ＣＨ２的值由最稀浓度下的１．７过渡到１。说明在交联网络中，交联度很低时，链段的运动已经相当受约束；但交联度很大时，充分溶胀的交联网络中链段运动仍有一定自由度。而在线型高分子浓溶液中，链段的运动严重受阻，导致自旋扩散效应非常完全，彻底平均掉了各质子间Ｔ１时间的差异。     

A rheological study of latex polystyrene-based model systems

Latex two-phased polystyrene blends have been produced by three different mixing routes. Polystyrene (PS) and lightly crosslinked polystyrene (XPS) latices were either mixed, or else used as seeds in two-stage polymerizations. This resulted in different microstructures by each of the procedures, leading to different rheological behaviors. Latex PS/XPS systems flow at every composition studied. Activation energies are independent of XPS content, and of the same order of magnitude as PS. Power-law relaxation has been observed for the physically blended system in the terminal region. This has been attributed to the formation of a “continuous” XPS network in the range 60–100% XPS.     

无水AlCl_3催化PVC/PS反应性增容的研究

以无水AlCl3为催化剂,通过聚氯乙烯(PVC)与聚苯乙烯(PS)之间Friedel-Crafts反应,实现了PVC/PS共混体系的反应性增容,使PVC与PS熔融共混温度由160℃降为140℃;通过预碾磨和加入苯乙烯(St)的方法,提高材料韧性,制备了综合力学性能良好的PVC/PS合金材料.应用FTIR、DSC、SEM和力学性能测试等手段表征了合金材料的结构与性能.结果表明,FTIR出现了1943和838 cm-12个苯环对位被取代的特征吸收峰;DSC在89℃出现了玻璃化转变;SEM证明PVC/PS两相界面粘接性随AlCl3、St的加入越来越好.在PS、AlCl3和St的质量分数分别为6%,0.6%和9%时,实现了对PVC的增强增韧.合金拉伸强度达到60.54MPa,比PVC的49.35 MPa提高了22.7%;缺口冲击强度达到5.3 kJ/m2,比PVC的3.9 kJ/m2提高了35.9%.     

The structure of latex polystyrenes blends: dynamic properties of PS/XPS systems

The dynamic behavior of latex polystyrene/crosslinked polystyrene (PS/XPS) systems has been studied. PS and XPS lattices were either physically blended, or used as seeds in semi-continuous sequential two-stage polymerizations. The Cox–Merz equation is not met by any PS/XPS system. Power-law relaxation has been observed for the physically blended PS–b–XPS system in the terminal region. A two-parameter equation suggested for polymers at the critical gel point fits the experimental data for XPS contents beyond 60%. This has been attributed to the formation of a “continuous” XPS network. This network is able to disrupt upon flow, due to the unique morphology of the XPS phase. It is possible that, for the sequential system with XPS seed particles, such a network may appear at a lower XPS content, due to a PS occlusion effect. A qualitative model is presented for these PS/XPS systems.     

交联核壳结构PBA/PS和PBA/PMMA纳米微球的制备与应用

考察了聚丙烯酸丁酯/聚苯乙烯(PBA/PS)以及聚丙烯酸丁酯/聚甲基丙烯酸甲酯(PBA/PMMA)交联核壳结构纳米高分子微球的制备方法,并对其在尼龙复合材料中的应用进行了初步研究.结果表明,通过交联剂的引入使粒子核层和壳层内部均形成了高度交联的结构,可以限制亲水性较小的聚苯乙烯(PS)壳层向粒子内部迁移的趋势;制备出的微球平均粒径为40~50 nm,粒径分布很窄.采用饥饿态加料方式加入第二单体不仅可以使微球具有较高的产率和凝胶率,而且可以使其具有更理想的核壳结构和更窄的粒径分布.此外,将合成出的PBA/PMMA核壳粒子对尼龙6基体进行复合的结果表明,由于该微球表面与尼龙6基体之间具有较强的界面相互作用且微球具有较大的形变能力,可以在基体中形成良好的分散,在保持材料强度的同时有效地提高了其刚性和韧性.     

Synthesis of submicron-sized peanut-shaped poly(methyl methacrylate)/polystyrene particles by seeded soap-free emulsion polymerization

Submicron-sized peanut-shaped poly(methyl methacrylate)/polystyrene(PMMA/PS) particles were successfully synthesized by seeded soap-free emulsion polymerization of styrene on the spherical crosslinked PMMA seed particles.The obtained peanut-shaped particles showed a novel internal morphology:PS phase formed one domain which linked to the other domain having PMMA core encased by PS shell.     

十二烷基苯磺酸钡存在下负离子聚合控制聚苯乙烯立构规整性研究

以正丁基锂(n-BuLi)为引发剂,环已烷为溶剂,通过添加十二烷基苯磺酸钡/四氢呋喃(SDBB/THF),对苯乙烯负离子聚合进行了研究.该体系可在60℃聚合得到立构规整性聚苯乙烯,其丁酮不溶物含量可达80%左右.13C-NMR表征结果显示其微观序列组成以等规结构为主,三元组mm和等规五元组mmmm含量可达57%和45%;DSC谱图中不仅有聚苯乙烯玻璃化温度(100℃),而且在211℃有一熔融峰.GPC结果表明,实测分子量与设计分子量差别较大,且分子量分布较宽。