聚乙烯催化剂用烷氧基镁载体的研究进展

基于烷氧基镁载体的Ziegler-Natta聚乙烯催化剂具有活性高、氢调性能好等优点,是目前聚烯烃工业中的研究热点。介绍了烷氧基镁载体的发展进程,综述了烷氧基镁载体的制备及改进方法,分析了烷氧基镁载体在催化剂制备过程中的作用,并对开发适用于乙烯聚合的烷氧基镁载体提出了展望。     

Facile access to carboxyl-terminated polybutadiene and polyethylene from cis-polybutadiene rubber

Carboxyl-terminated polybutadiene (CTPB) is a widely used telechelic liquid rubber, which is mainly prepared by anionic or free-radical polymerization of 1,3-butadiene. It is known that the microstructure of liquid polybutadiene rubber largely affects its processability and mechanical properties. However, it is hard to control its microstructure in the free radical or anionic polymerization. In this study, a series of CTPB with high cis-1,4 content has been prepared for the first time via the oxidolysis and selective oxidation of cis-polybutadiene rubber (BR). Hydrogenation of their CC double bonds with p-toluenesulfonyl hydrazide/tri-n-propylamine (TSH/TPA) reagents afforded carboxyl-terminated polyethylenes (CTPE). For comparison, commercial CTPB (FCTPB), prepared by free-radical polymerization of 1,3-butadiene, was also hydrogenated and gave FCTPE with more ethyl branches. Linear CTPE (L-CTPE) was synthesized by ring-opening metathesis polymerization of 1,5-cyclooctadiene in the presence of maleic acid and subsequent hydrogenation. The microstructure of the polymers was established by FT-IR, ¹H NMR, ¹³C NMR, and GPC and their thermal properties were determined by DSC and TGA. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46934.     

Improved compatibility of PET/HDPE blend by using GMA grafted thermoplastic elastomer

ABSTRACT

Herein, graft-modified ethylene-1-octene copolymer (POE-g-GMA) and styrene-butadiene-styrene triblock copolymer (SBS-g-GMA) were found to be excellent reactive compatibilizers for immiscible poly(ethylene terephthalate) (PET)/high-density polyethylene (HDPE) blends via in-situ reaction compatibilization. With increase in compatibilizer amount, uniform phase morphology was observed in all the blends. Thus, exhibiting enhanced mechanical properties, especially, the notched Izod impact strength. In comparison with SBS-g-GMA, compatibilizer POE-g-GMA demonstrated greater impact on the compatibility. The addition of 15% POE-g-GMA produced blends with best mechanical properties. Besides, both POE-g-GMA and SBS-g-GMA enhanced the melt viscosity of PET/HDPE blends.     

核电厂聚乙烯管道设计方法及标准简介

随着聚乙烯管道在三门核电厂、大亚湾核电厂中的试应用成功，大量的新建核电厂及核电厂改造项目均将聚乙烯管道作为海水冷却水管道系统的首选管材，自主研制核电厂聚乙烯管技术标准迫在眉睫。本文介绍了核电聚乙烯管道的发展历史和应用现状，对比了核安全3级聚乙烯管道和非核安全相关聚乙烯管道、城市燃气与给水聚乙烯管道技术标准的设计方法及适用范围，探讨了中国目前聚乙烯管技术标准与核3级聚乙烯管道技术标准的差异与差距，为核电厂聚乙烯管道的设计制造与标准研制提供参考。     

纳米氧化锌/低密度聚乙烯膜中锌向食品的迁移研究

目的研究纳米氧化锌/低密度聚乙烯膜(low density polyethylene film,LDPE)中锌(Zn)向食品的迁移行为,探究其迁移规律。方法选取2种食品模拟物(3%乙酸及超纯水)及真实食品(食用白醋及瓶装水),在3种不同实验温度下(70、40及20℃),研究锌向食品模拟物的迁移规律。采用扫描电子显微镜(scanning electron microscope,SEM)和原子力显微镜(atomic force microscope,AFM)表征纳米ZnO/LDPE膜的表面形貌。结果锌向酸性模拟物中的迁移率远远大于水性模拟物中的迁移率,其中锌向酸性模拟物中的最大迁移率分别为22.7%,20.3%及18.6%(ZL-1,ZL-2及ZL-2#),向水性模拟物中的最大迁移率分别为9.9%,5.7%及4.9%(ZL-1,ZL-2及ZL-2#);锌向酸性食品的迁移量(1.59~5.03 mg/g)同样高于向水性食品的迁移量(2.98~24.60μg/g);随着纳米ZnO的初始含量变大迁移率变小;而偶联剂的加入对锌的迁移有一定的抑制作用。随着纳米ZnO浓度的增加,在薄膜中观察到纳米ZnO的不规则形貌。结论纳米ZnO/LDPE膜不适合在高温下包装食物,且其在酸性食品中的安全隐患高于水性食品。     

利用KH560和纳米SiO2采用“一步法”反应挤出增黏PET

以KH560（3-缩水甘油基氧基丙基三甲氧基硅烷）和纳米SiO₂颗粒复配作为扩链剂，采用“一步法”反应挤出增黏聚对苯二甲酸乙二醇酯（PET）。KH560和SiO₂的添加量均为PET质量分数的2.5%时，增黏效果最好。并且在PET不干燥的情况下，KH560和SiO₂复配也可增加PET的黏度，可用作PET的扩链剂和防水解剂。经透射电镜观察，发现SiO₂在PET中的分散状况良好。用FTIR研究了KH560、SiO₂、PET三者之间的反应机理。用TGA分析了SiO₂的接枝率，发现接枝率高达72.0%。用DSC对PET/纳米SiO₂复合材料的结晶行为进行了研究，并讨论了结晶行为对力学性能的影响。当KH560和SiO₂的添加量均为PET质量分数的2.5%时，结晶度最低，综合力学性能最好。     

木质素与高密度聚乙烯共热解特性研究

生物质与塑料共热解是一种非常有效的生物质利用方法之一,但由于生物质结构的复杂性,共热解过程的机理尚不明晰。木质素是生物质的主要组分之一,本文通过热重-质谱联用仪和裂解器-气相色谱质谱仪研究其与高密度聚乙烯共热解过程,获取共热解特性及热解产物分布特性,以揭示共热解过程机制。结果显示,木质素与高密度聚乙烯共热解过程存在协同效应,使得热解失重速率加快,热解固体残渣含量减少。共热解过程有利于CH₄、H₂O、CO和C₂H₄的生成,抑制CO₂的生成。同时,酚类、醇类和糖类等含氧化合物产量减少,烷烃和烯烃类化合物产量增加。结果表明,共热解过程会发生氢转移现象,氢与木质素衍生热解产物结合发生反应,从而抑制含氧化合物的生成,促进烷烃类和烯烃类化合物生成。     

Synthesis and two-step sintering behavior of solution derived corundum abrasives with plate-like grains

Corundum abrasives with plate-like grains were fabricated by a two-step sintering technique using the solution-based process with the addition of the ternary compound additive Na₃AlF₆-CaO-SiO₂. The two-step sintering method showed obvious advantages over conventional sintering methods in promoting sample densification, suppressing grain growth, and homogenizing the microstructure of the corundum abrasives. The sample doped with 2.5?wt% Na₃AlF₆ and 4?wt% CaO + SiO₂ in the molar ratio of 1:1 possessed a relative density of 99.3%, average grain size of 0.54?µm, and single-particle compressive strength of 49?N. The introduction of seeds reduced the temperature of θ- to α-Al₂O₃ phase transformation. The relationship between the microstructure and the mechanical properties of the abrasives was also discussed.     

Fabrication of fullerene decorated by iron compound and its effect on the thermal stability and flammability for high-density polyethylene

Fullerene decorated by iron compound (C₆₀-Fe) is fabricated via solution reaction and characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), wide-angle X-ray diffraction (XRD), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). Upon incorporating C₆₀-Fe into high-density polyethylene (HDPE) matrix by melt blending, the thermal and thermo-oxidative stability of HDPE are considerably increased, the oxidative induction time (OIT) is dramatically extend. When the concentration of C₆₀-Fe reached 5 wt%, the onset degradation temperature in air increased from 352°C to 422°C, and the OIT dramatically delayed from 4.5 to 47.8 minutes. Moreover, from microscale combustion calorimetry (MCC), C₆₀-Fe can reduce the peak heat release rate (PHRR), heat release capacity (HRC), and total heat release (THR) values of the composites, all of which are very important parameters for evaluating the fire retardancy of a polymeric material.     

高密度聚乙烯/铅硼复合材料屏蔽性能和力学性能研究

研究了高密度聚乙烯/铅硼复合材料的屏蔽性能和力学性能，通过屏蔽仿真比较了密度及碳化硼（B4C）含量对屏蔽性能的影响，通过试验比较了B4C含量对屏蔽性能、弯曲强度及冲击强度的影响。仿真结果表明,随聚乙烯/铅硼复合材料密度升高，快中子屏蔽性能下降，热中子屏蔽性能和γ屏蔽性能提高；保持聚乙烯/铅硼复合材料密度不变，随B4C含量的提高，中子屏蔽性能提高而γ屏蔽性能下降;实验数据表明,随B4C含量的升高，高密度聚乙烯/铅硼材料的快中子屏蔽性能、热中子屏蔽性能升高，γ屏蔽系数下降，冲击强度和弯曲强度下降明显，屏蔽性能测试结果和仿真结果规律性相符；综合仿真结果和实验数据表明，含B4C 2 %左右的高密度聚乙烯/铅硼复合材料同时具有较好的屏蔽性能和力学性能。