聚合物异核交叉弛豫及二维NOE谱

The heteronuclear cross-relaxation rates in polymers were determined by selective and conventional ~(13)C spin-lattice relaxation experiments, the proton-carbon distances were calculated by the theoretical formula, and two-dimensional NOE spectra of the polymers were also measured. The results showed that (1) the measured proton-carbon distances coincide with the distances from molecular models, (2) there is the observable dipolar cross-relaxation effect between the quaternary carbons and their neighboring protons, and (3) the optimum mixing times depend on the relaxation properties of the proton and carbon.     

Measurement of the Rates of Diffusion of Halomethanes into Polymer Films Using ATR-FTIR Spectroscopy

Polymer-modified attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy and FEWS (fibre-optic evanescent wave) spectroscopy have been very successful to date for sensitive detection of organic pollutants in water utilising the mid-infrared (MIR) region of the electromagnetic spectrum (4000-400 cm^?1). This sensing approach involves the use of different polymer films for preconcentration with optimisation of the sensor related to the rate of diffusion of solvent molecules into these polymer films. Compounds such as chloroform, bromoform, bromodichloromethane and dibromochloromethane which are collectively referred to as trihalomethanes (THMs) were analysed in this work. A gaseous phase experimental design was used and from experimental data the rate of diffusion of each of the halomethanes was quantified based on a Fickian type diffusion model. Individual diffusion coefficient values were found to be in the range 3.38 E-10 ± 0.01 E-10 to 4.72 E-08 ± 0.42 E-08 cm² s^?1. Multicomponent effects were observed for mixtures of compounds diffusing into polyisobutylene and ethylene-propylene copolymer.     

Synthesis and application of cinnamate-functionalized rubber for the preparation of UV-curable films

A butyl rubber derivative that can be cured upon exposure to UV light in the absence of additional chemical additives was developed. This polymer was prepared by the reaction of hydroxyl-functionalized butyl rubber with cinnamoyl chloride to provide a cinnamate functionalized rubber. The cinnamate content was varied by starting with derivatives prepared from butyl rubber containing either 2 or 7 mol% isoprene. The kinetics of the cross-linking was studied by UV–visible spectroscopy and it was found to vary according to the film thickness. The changes in gel content and volume swelling ratio with irradiation time were dependent on the cinnamate content. Toxicity studies suggested that the cross-linked materials do not leach toxic molecules. The approach was also applied to obtain cross-linked films of butyl rubber-poly(ethylene oxide) graft copolymers, leading to surfaces that resisted the adhesion and growth of cells. Thus the approach is versatile and is of particular interest when non-leaching coatings of cross-linked butyl rubber are desired for biomedical or other applications.     

Amphiphilic Graft Copolymers of Hydroxypropyl Cellulose Backbone with Nonpolar Polyisobutylene Branches

The novel amphiphilic graft copolymers with hydrophilic hard polar hydroxypropyl cellulose(HPC) backbone and hydrophobic soft nonpolar polyisobutylene(PIB) branches have been successfully synthesized through nucleophilic substitution reaction of living PIB chains carrying oxonium ions with the-OH groups along HPC backbone. The PIB branch length in the graft copolymers could be designed by living cationic polymerization and the grafting density could be adjusted by PIB~+/-OH molar ratio. The living PIB chains carrying oxonium ion were prepared by transformation of allyl bromide end groups in the presence of AgClO_4 and silver nanoparticles(3.2±0.3 nm, 0.7 wt%-1.8 wt%)generated in situ from AgBr. The phase-separation morphology was formed in the graft copolymers due to their incompatibility between backbone and branches. The hydrophilicity on the surface of graft copolymer films could be turned to hydrophobicity by increasing grafting density or/and length of PIB branches. The soft PIB segments in graft copolymers provided an unique surface via self-assembly for anti-protein adsorption against bovine serum albumin. A small amount of Ag nanoparticles in the copolymers contributed to good antibacterial activities against Staphylococcus aureus or Escherichia coli.     

STRUCTURAL CHARACTERIZATION OF POLY(ϵ-CAPROLACTONE) AND POLY(ϵ-CAPROLACTONE-b-ISOBUTYLENE-b-ϵ-CAPROLACTONE) BLOCK COPOLYMERS BY MALDI-TOF MASS SPECTROMETRY

Poly(?-caprolactone)(PC1) and PC1-polyisobutylene-PC1 (PC1-PIB-PC1) block copolymers were synthesized in anhydrous toluene by in situ conversion of 2-methyl-1-propanol (2M1P) and α,ω-dihydroxy PIB, respectively, to the corresponding aluminum alkoxide by reaction with a stoichiometric amount of triethylaluminum (TEA) followed by the addition of e-caprolactone. Structural characterization of 2M1P-initiated PCl by gel permeation chromatography (GPC) and matrix-assisted laser desorption ionization–time of flight (MALDI-TOF) mass spectrometry (MS) demonstrated the presence of cyclic oligomers, which are produced by intramolecular transesterification reactions that become significant at high monomer conversions. A minor fraction of chains bearing carboxylic acid termini was also observed in the MALDI-TOF mass spectrum; however, carboxylic acid chain ends could not be detected by ¹³C NMR analysis. Thus, the likely origin of the carboxylic acid termini is fragmentation of the initiator residue from the chain end during MALDI-TOF analysis. For PCl-PIB-PCl block copolymers, two different α,ω-telechelic PIB diols were used as macroinitiators, one derived from allyl and one from isopropenyl terminated PIB. Terminal olefins were converted to primary alcohols via regioselective hydroboration followed by alkaline hydrogen peroxide oxidation. After reaction with ?-caprolactone, formation of a block copolymer was evidenced by a shift of the polymer peak to lower elution volume in GPC analysis. Block copolymers possessed molecular weight distributions ≤1.4, and molecular weights of the PCl blocks calculated from GPC were in excellent agreement with those found using MALDI-TOF MS. Structural analysis indicated that the PCl end blocks were severed from the crude block copolymer during MS analysis, for both allyl- and isopropenyl-derived materials. For allyl-derived materials the PCl blocks were found to predominantly carry a C₂ residue at the point of detachment of the PIB block; however, the isopropenyl-derived block copolymers showed a complex mixture of different residues suggesting a complex fragmentation mechanism during loss of the PIB block.     

Poly(vinyl alcohol)-based Amphiphilic Copolymer Aggregates as Drug Carrying Nanoparticles

A series of amphiphilic polyisobutylene-block-poly(vinyl alcohol) (PIB-b-PVA) copolymers of constant PIB and varying PVA block length was synthesized by living carbocationic polymerization and their solution behavior was studied. The synthesis involved the preparation of polyisobutylene-b-poly(tert.-butyl vinyl ether) followed by hydrolysis with hydrogen bromide. The copolymers were characterized by gel permeation chromatography, ¹H-NMR, and MALDI-TOF MS methods. The micellization behavior of the copolymers was investigated in aqueous media by direct dissolution and dialysis using static and dynamic light scattering. The critical micelle concentration, micelle size, aggregation number, and micelle shape were determined. The ability of the aggregates as drug carrying nanodevices was also investigated by doping them with indomethacin. UV-Vis measurements showed that the solubility of indomethacine increased significantly. Our findings suggest that the solubility is largely dependent upon the block segment ratios.     

H2O/TiCl4/ED 体系引发异丁烯控制正离子聚合中的影响因素研究

在亲核试剂(ED)如吡啶(Py)、N,N-二甲基乙酰胺(DMA)或三乙胺(TEA)存在下,由引发剂H2O和共引发剂TiCl4组成引发体系,在二氯甲烷/正己烷混合溶剂中进行异丁烯(IB)正离子聚合,考察了溶剂极性、聚合温度及异丁烯浓度对聚合反应转化率、产物分子量和分子量分布的影响.试验结果表明,随聚合体系溶剂极性增大,聚合速率加快,相近转化率时聚合产物的分子量分布变窄.随着聚合温度降低,聚合速率明显提高,聚合物的分子量增加,活化能为负值,活性链端发生链转移或链终止等副反应的几率减小,当聚合温度为-60℃时,可以抑制活性链端的β-H脱除反应和链转移副反应,并得到大分子链末端全部为叔氯基团的聚异丁烯(PIB).当[IB]0≤2.5mol/L时,随[IB]0增加,聚合转化率有所增加,聚合产物的GPC谱图均为单峰分布,分子量增大,而分子量分布基本保持不变,对于加入Py的聚合体系,分子量分布指数在1.33~1.45范围内,对于加入TEA的聚合体系,分子量分布指数在1.47~1.60范围内,并求出在加入Py和TEA的聚合体系中活性链向单体的链转移常数CM分别为5.5×10-4和6.6×10-4.     

Melt fracture of polyisobutylenes

The processability of different grades of polyisobutylene (PIB) was investigated using a capillary rheometer. Direct focus was given to the occurrence of melt fracture phenomena, such as sharkskin and gross melt fracture (GMF). The influence of molecular weight (MW) of PIB, temperature and die entrance angle on melt fracture was examined in detail. Due to their highly elastic nature, high MW PIBs were found to exhibit gross melt fracture instability even at low shear rates, rendering their processing an impossible task. An increase in temperature resulted in postponing both instabilities (sharkskin and gross) to higher shear rates, thus making their processing easier. Finally, decreasing the entrance angle below a critical value resulted in postponing the onset of GMF to higher shear rates.     

聚谷氨酸苄酯-g-(聚四氢呋喃-b-聚异丁烯)共聚物的微观结构与形态

通过可控/活性离子聚合方法设计合成一系列不同共聚组成的聚谷氨酸苄酯-g-(聚四氢呋喃-b-聚异丁烯)的新型嵌段接枝共聚物,即PBLG-g-(PTHF-b-PIB),研究共聚物中支链(PTHF-b-PIB)长度及接枝密度对主链PBLG玻璃化转变温度、α-螺旋二级结构及其转变的影响,研究支链中PTHF链段长度对其双端受限的玻璃化转变及凝聚态结构的影响.结果表明:PBLG-g-(PTHF-b-PIB)共聚物中刚性主链保持α-螺旋二级结构;随着支链长度增加或接枝密度增加,主链PBLG的α-螺旋二级结构特征峰逐渐减弱,玻璃化转变温度逐渐提高,α-螺旋结构发生转变的焓值逐渐增大;在确定接枝密度的情况下,随着支链中PTHF链段长度增加,共聚物中双端受限的PTHF链段结晶逐渐增强,结晶熔融温度及熔融焓均增加;在确定支链中PTHF链段长度的情况下,随着接枝密度增大,支链间链段相互排斥,PTHF链段结晶逐渐减弱.     

含氮试剂对p-DCC/AlCl_3引发异丁烯正离子聚合的影响

以对-二枯基氯(DCC)/AlCl3体系引发异丁烯在二氯甲烷(CH2Cl2)正己烷(Hex)(40/60,V/V)混合溶剂中进行正离子聚合,探讨了DCC用量、含氮试剂2,6-二叔丁基吡啶(DtBP)和三苯胺(TPA)对异丁烯正离子聚合转化率、产物分子量及其分布的影响.结果表明,DCC和体系中微量水均可与AlCl3产生竞争络合,形成两种活性中心并引起相继的竞争引发,聚合产物的GPC谱图呈双峰分布,分子量分布宽;增加DCC用量有利于DCC与AlCl3的络合,致使链增长反应主要通过DCC与AlCl3络合形成的活性中心引发,但聚合产物分子量相对较低,分子量分布较宽;使用DtBP,可有效地抑制微量水引发及活性链向单体的转移反应,使分子量分布明显变窄,基本实现DCC的控制引发;采用DtBP与TPA共同调节聚合反应,可使聚合产物分子量分布变窄的同时,进一步提高分子量,从而得到相对较高分子量(Mw=103200)和单峰分子量分布(Mw/Mn=2.09)的聚异丁烯产物.