PAA·2HC1—RH体系引发DMDAAC—AM共聚合的动力学研究

合成了二甲基二烯丙基氯化铵—丙烯酰胺共聚物 ,测定了水溶性偶氮化合物 -RH引发体系 (PAA·2HCl-RH)和过硫酸钾 -RH引发体系 (KPS -RH)引发共聚反应时单体DM和AM的竞聚率 ,以及PAA·2HCl-RH体系用于DM -AM共聚时的活化能。结果表明 :PAA·2HCl-RH引发DM -AM共聚时 ,DM和AM的竞聚率分别为 0 .174和 6 .8,活化能为 33.2 5kJ/mol;而KPS -RH引发DM -AM共聚时 ,DM和AM的竞聚率分别为 0 .0 76和 7.1。     

Crystallization behavior of oxyethylene/oxybutylene diblock and triblock copolymers

The crystallization behavior of poly(oxyethylene)-b-poly(oxybutylene) block copolymers with different compositions, morphologies and architectures (E_mB_n diblock copolymers and E_mB_nE_m, B_nE_mB_n triblock copolymers) were investigated and the effect of volume fraction and architecture on the crystallization temperature (T_c) in non-isothermal crystallization was determined. It is found that the E_mB_n diblock copolymers having long E blocks exhibit similar crystallization temperatures, irrespective of volume fraction and morphology, but for the block copolymers with shorter E blocks the crystallization temperature increases with both the volume fraction, φ_E, and the length, m, of the E block. Some block copolymers with extremely low T_c, which fall into the temperature range normally associated with homogenous nucleation, were chosen for time-resolved small-angle X-ray scattering (SAXS) and isothermal crystallization kinetics experiments. The results show that breakout crystallization occurs in all these block copolymers. Therefore, unlike E_mB_n/B_h blends, there is no obvious relationship between T_c and crystallization behavior in neat block copolymers and homogeneous nucleation does not definitely lead to confined crystallization. The values of χ_c/χ_ODT for all the block copolymers with hex and bcc morphology were also calculated. It is found that all the block copolymers have χ_c/χ_ODT<3, in agreement with the previously reported critical value and consistent with their breakout crystallization behavior.     

Grafting poly(t‐butyl acrylate) to poly(allylamine) by inverse microemulsion radical polymerization: From comb‐polymer to amphiphilic shell crosslinked polymer nanocapsule

An interfacial grafting radical polymerization method for amphiphilic comb copolymer and shell crosslinked polymer nanocapsules was reported. Macropolyradicals on a water soluble long chain polyamine were generated with hydrogen peroxide in the water phase and subsequent grafting radical polymerization of a vinylic monomer at the water/oil interface proceeded at 65°C. In the presence of a crosslinker, the resulting graft copolymer formed a defined core‐shell structure with hydrophilic aqueous core functionalized by the polyamine and a hydrophobic crosslinked polymer shell. The structure of the core‐shell material was characterized by NMR, FTIR, DSC, TGA, SEM, TEM, and the mechanism of the graft polymerization is proposed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1905–1911, 2007     

不同分子量聚酯的羟值分析方法

用醋酐／高氯酸／乙酸乙酯法，醋酐吡啶回流法，分别对相对分子质量为１１００－１２０００的聚酯进行了羟值的测定，并用气压渗透法和析出物溶解重滴法进行了核对。结果表明醋酐／高氯酸／乙酸乙酯法对于Ｍ〈５０００的聚酯是适用的，而高分子量的聚酯则必须用醋酐／吡啶回流法，才能获得满意的结果。     

Synthesis of tetramethyl-p-silphenylenesiloxanedimethylsiloxane triblock copolymer by employing living anionic polymerization

Dimethylsiloxane-tetramethyl-p-silphenylenesiloxane-dimethylsiloxane (DMS-TMPS-DMS) triblock copolymer was synthesized by employing living anionic polymerization of hexamethylcyclotrisiloxane (D₃). Two synthetic methods were carried out for the polymerization. One of those methods was the anionic polymerization of D₃ initiated at the silanolate anion which was prepared from the terminal hydroxyl group of silanol-terminated TMPS prepolymer by reaction with n-butyllithium (method 1). The other was the coupling reaction of vinyl-terminated TMPS prepolymer with hydrosilyl-terminated DMS prepolymer obtained from the anionic polymerization of D₃ by using diphenylmethylsilanolate anion as initiator (method 2). In method 1, DMS contents of the copolymers ranged from 25.8 to 72.5 wt% and the values agreed with the ratio of D₃ to TMPS prepolymer. The weight-average molecular weights ranged from 1.36×10⁴ to 19.4×10⁴ and were close to the predicted values calculated from the $\text{M}\text{?}{}_{\mathrm{v}}$ of the TMPS prepolymer and the amount of D₃ added. In the case of method 2, weight-average molecular weights ranged from 19.5×10⁴ to 24.2×10⁴. The high molecular weight copolymer could thus be obtained by method 2. Intrinsic viscosity values of the triblock copolymers agreed with calculated values obtained by considering the copolymer as a binary mixture of these homopolymers. Differential scanning calorimetry and thermogravimetry were carried out on the triblock copolymers. The equilibrium melting temperatures of each of the copolymers were very close to that of poly-TMPS (160°C). The glass transition temperature and heat of fusion were decreased as the DMS content was increased. The thermogravimetric curves for the copolymers indicated that the thermal stability of the triblock copolymer was intermediate between the DMS and TMPS homopolymers.     

离子化对SBS/聚(苯乙烯-甲基丙烯酸甲酯)热塑性互穿聚合物网络结构与力学性能影响的研究

采用原子转移自由基聚合（ATRP）法合成了聚（苯乙烯一甲基丙烯酸甲酯）[P（St—MMA）]，采用两步法制备了SBS／P（St—MMA）热塑性互穿聚合物网络（TIPN）。在双螺杆挤出机上通过熔融挤出方法对SBS／P（St—MMA）直接进行水解，制备了含有离子键的SBS／P（St—MMA）TIPN。离子化后TIPN的拉伸强度明显增加，在离子化程度为25％时达到最大，断裂伸长率明显下降。TIPN的中PB和PS嵌段的Tg均明显增加，PS嵌段增加更加明显，提高20℃；弹性模量E’均明显提高。     

A block copolymer nanotemplate for mechanically tunable polarized emission from a conjugated polymer

A polymer blend system consisting of polystyrene grafted onto poly (p-phenylene ethynylene) (PS-g-PPE) and poly (styrene-block-isoprene-block-styrene) triblock copolymer (SIS) yields highly polarized emission due to the unidirectional alignment of the PPE molecules. During the roll casting, the triblock copolymer microphase separates and creates unidirectionally aligned PS cylindrical microdomains in the rubbery PI matrix. PPE, a fluorescent conjugated polymer, was grafted with polystyrene (PS) side chains that enabled sequestration and alignment of these rigid backbone emitter molecules into the PS microdomains of the SIS triblock copolymer. Deforming the thermoplastic elastomer in a direction perpendicular to the orientation direction of the cylinders causes rotation of the PS cylinders and the PPE emitter molecules and affords tunable polarized emission due to re-orientation of the PPE containing PS cylinders as well as film thinning from Poisson effect.     

EVA／木质素薄膜的制备与性能研究

研究了经造粒、吹塑成膜的乙烯醋酸乙烯酯共聚物（EVA）／木质素共混物的结构、热性能以及力学性能。热重分析表明木质素与EVA共混物的热稳定性比单一组分的高；差示扫描量热分析表明木质素与EVA的相容性好；傅里叶红外光谱分析表明木质素与EVA之间存在分子间氢键相互作用；扫描电子显微分析表明木质素含量对共混物形貌有明显的影响；力学性能测试表明木质素含量在30％（质量分数，下同）以内，共混物薄膜仍具有较好的力学性能，随着木质素含量的增加，共混物力学性能降低。     

Graft Copolymerization of Acrylamide onto Oil Palm Empty Fruit Bunch (OPEFB) Fiber

Grafting of acrylamide (AAm) onto oil palm empty fruits bunch fiber using hydrogen peroxide as initiator and methyl acrylate as comonomer was investigated. The amount of comonomer needed to make grafting of acrylamide possible was determined. The percentage of poly(acrylamide) and the comonomer in the final graft copolymer was estimated by elemental analysis. Results obtained indicated that methyl acrylate facilitated the incorporation of acrylamide monomer onto OPEFB. The reactivity ratios for both monomers were determined by using Fineman–Ross plot. The effects of reaction temperature and period as well as amount of the initiator, solvent, monomer and comonomer on the percentage of grafting at fixed amount of comonomer (11 mmol) were studied. Maximum percentage of grafting was achieved when the amount of initiator and solvent 3.98×10⁻³ mol and 50 mL respectively. The optimum reaction temperature was 50 ^○C and the reaction period was 90 min. Highest percentage of grafting was 232% when 25.6 mmol of acrylamide was used under these optimum conditions. The presence of functional group in the grafted polymer is characterized by infrared spectroscopy and the surface morphology is observed by scanning electron microscopy. Thermoanalytic investigation on OPEFB and OPEFB-g-PAAM were carried out to evaluate the thermal stability and respective activation energy of the materials.     

ABS／PVC共混改性的研究

考察了PVC含量对ABS/PVC共混体系性能的影响。为了进一步提高共混体系的性能，在体系中分别加入CPE、MBS做为第三组分。通过性能比较，发现MBS可有效提高共混体系的综合性能。为了增加共混体系的阻燃性能，加入助阻燃剂Sb2O3，结果表明共混体系的阻燃性能有了很大提高。