Solid‐state polymerization of poly(ethylene terephthalate). I. Experimental study of the reaction kinetics and properties

The solid‐state polymerization (SSP) reaction kinetics of poly(ethylene terephthalate) were investigated in connection with the initial precursor intrinsic viscosity (IV; molecular weight). Evaluations were performed with otherwise equivalent precursors melt‐polymerized to IVs of 0.50, 0.56, and 0.64 dL/g. The changes in the molecular weight and other properties were monitored as functions of the reaction times at solid‐state temperatures of 160–230°C. Precursors with higher initial molecular weights exhibited higher rates of SSP than those with lower initial values, as discussed in connection with the levels of crystallinity and the carboxyl and hydroxyl end‐group composition. Activation energies decreased at temperatures above 200°C, and this indicated a change in the SSP reaction mechanism. At temperatures of 200–230°C, similar activation energies were required for the polymerization of all three precursors. Lower temperature polymerizations, from 160 to 200°C, required higher activation energies for all precursors, with the 0.50‐IV material requirement almost twice as high as that calculated for the higher IV precursors. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 197–212, 2003     

Direct ethoxylation of fatty methyl ester over Al-Mg composite oxide catalyst

For the purpose of estimating the reaction mechanism of the direct ethoxylation of a fatty ester in the presence of an Al-Mg composite oxide catalyst, a labeled fatty methyl ester C₁₁H₂₃CO¹⁸OCH₃ containing ¹⁸O isotope was synthesized and directly ethoxylated. The product was evaluated by gas chromatography-mass spectrometry (GC-MS). The GC-MS spectra showed that the ¹⁸O isotope label was present only in the methoxy group at the molecular end of the ethoxylated fatty methyl ester. This supports the reaction mechanism of coordination anionic polymerization where the bond between the acyl and methoxy groups of the fatty methyl ester molecule was broken, caused by the bifunctional effect of the acid-base active sites; an intermediate chemisorption species was formed; and then ethylene oxide was addition-polymerized sequentially, in parallel.     

硅铁复合型絮凝剂的实验研究

研究了硅铁复合型絮凝剂的制备方法和絮凝性能 ,确定了其最佳反应条件 ,所得复合型絮凝剂对江水的除浊性能优于聚合硫酸铁 (PFS)和聚合氯化铝 (PAC)。     

High solids content emulsions. III. Synthesis of concentrated latices by classic emulsion polymerization

Two different methods of producing bi‐ and trimodal latices of a mixture of methyl methacrylate, butyl acrylate, and small amounts of acrylic acid were tested. It is shown that a combination of concentrating blends of seed particles by semibatch reaction, followed by a nucleation of small particles plus a second semibatch phase allowed us to obtain stable latices with solids contents over 65% and viscosities of below 2500 mPa s^?1 with little coagulum formation. The key parameter in determining latex stability, coagulum formation, and viscosity appears to be the the particle size distribution, and especially its modification attributed to secondary nucleation. Because it is not possible to eliminate water‐soluble monomers from the polymerization recipe, secondary (homogeneous) nucleation must be minimized by careful addition of the free‐radical initiator and choice of monomer feed flow rates. The nucleation of the third population in the trimodal latices is best accomplished with a mixed surfactant system because renucleation by anionic surfactant alone leads to detrimental changes in the particle size distribution (PSD) resulting from excessive flocculation of particles. In addition, it was found that the viscosity of the final products was not sensitive to small changes in the ionic strength of the latex, although neutralization to a pH of 6 effectively doubles the final latex viscosity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1916–1934, 2002; DOI 10.1002/app.10513     

原位聚合法研制纳米胶囊相变材料

采用超声波工艺及细乳液原位聚合方法,研制了以聚苯乙烯为囊壁、正十八烷为囊芯的纳米胶囊相变材料;系统探讨了聚合反应各因素如引发剂、链转移剂、表面活性剂以及正十八烷/苯乙烯比等对乳胶粒子的形态、胶囊材料热性能的影响,对所研制的胶囊相变材料进行激光衍射粒度分析、透射电镜及差示扫描量热等表征.实验结果表明,在引发剂AIBN 0.5%(油相质量百分比,下同);链转移荆DD在T0.4%;复合乳化剂(SDS/OP10)总量2%,配比1:1及正十八烷/苯乙烯比=1:1条件下,胶囊呈球形均匀分布,聚苯乙烯囊壁能将正十八烷囊芯很好包裹住,其胶囊Z均直径124nm,相变焓可达124.4kJ·kg-1.     

Continuous emulsion polymerization of vinyl acetate. II Operation in a single Couette–Taylor vortex flow reactor using sodium lauryl sulfate as emulsifier

Continuous emulsion polymerizations of vinyl acetate were conducted at 50°C in a single continuous Couette–Taylor vortex flow reactor (CCTVFR) using sodium lauryl sulfate as emulsifier and potassium persulfate as initiator. The polymerization can be carried out very smoothly and stably, but the steady‐state monomer conversion attained in a CCTVFR is not as high as that in a plug flow reactor (PFR), but only slightly higher than that in a continuous stirred tank reactor (CSTR), even if the Taylor number is adjusted to an optimum value. Also, the effects of operating variables, such as the emulsifier, initiator, and monomer concentrations in the feed and the mean residence time on the kinetic behaviors were almost the same as those observed in a CSTR. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2755–2762, 2002     

淤浆法HDPE装置低聚物不能结片原因探析

分析了淤浆法HDPE装置低聚物不能结片的原因,并提出了相应的工艺处理措施。     

Comparison of RAFT polymerization of methyl methacrylate in conventional emulsion and miniemulsion systems

In this study, we have conducted the reversible addition-fragmentation chain transfer (RAFT) polymerization of methyl methacrylate (MMA) in two heterogeneous systems, i.e. conventional emulsion and miniemulsion, with identical reaction conditions. The main objective is to compare the living character in both systems according to the nucleation mechanism, the latex stability, the particle sizes and particle size distributions of latexes, the molecular weights and molecular weight distributions (or polydispersity index, PDI) of PMMA, and the kinetics of the RAFT polymerization. The RAFT agent used in both systems was 2-cyanoprop-2-yl dithiobenzoate (CPDB). The effects of an oil-soluble initiator 2,2′-azobisisobutyronitrile (AIBN) and a water-soluble initiator kalium persulfate (KPS) on the RAFT/emulsion and RAFT/miniemulsion polymerizations were investigated. Methyl-β-cyclodextrin (Me-β-CD) was used as a solubilizer. The average molecular weights and molecular weight distributions (PDIs) of dried PMMA samples were characterized by gel permeation chromatography (GPC). The experimental results showed that the RAFT/miniemulsion polymerization of MMA exhibited better living character than that of RAFT/emulsion polymerization under the conditions of our experiment. The PDI of PMMA in RAFT/miniemulsion polymerization was decreased with the addition of Me-β-CD. However, Me-β-CD did not have influence on the PDI of PMMA prepared in RAFT/emulsion polymerization.     

一种多官能团乳化剂在羧基丁苯胶乳合成中的应用

试验发现：一种阴离子型兼具非离子性的乳化剂A用于羧基丁苯胶乳聚合体系，可显著提高胶乳的质量，其质量分数即使下降到原配方乳化剂标准用量的25％，也能制备出合格的胶乳；与使用SDS的聚合体系相比，使用乳化剂A的聚合体系的聚合反应及产物质量重复性好，胶乳的钙离子稳定性显著提高。分析发现，乳化剂用量的大小会导致聚合反应机理的差异，从而影响聚合反应及产物质量；在酸性条件下，乳化剂本 身的稳定性也是造成这种差异的原因之一。应用试验结果表明：用乳化剂A代替SDS并在一定范围内改变其用量，不会影响胶乳的应用性能。     

气相法聚乙烯高效催化剂的进展

综述了国内外气相法聚乙烯高效催化剂研究进展概况,以及各种新型高效催化剂制备技术和性能,并对开发我国新型高效推化剂提出了看法。