Ni-catalyzed carbon–carbon bonds cleavage of mixed polyolefin plastics waste

The inert carbon–carbon(C–C) bonds cleavage is a main bottleneck in the chemical upcycling of recalcitrant polyolefin plastics waste. Here we develop an efficient strategy to catalyze the complete cleavage of C–C bonds in mixed polyolefin plastics over non-noble metal catalysts under mild conditions. The nickelbased catalyst involving Ni_(2)Al_(3) phase enables the direct transformation of mixed polyolefin plastics into natural gas, and the gas carbon yield reaches up to 89.6%. Reaction pathway investigation reveals that natural gas comes from the stepwise catalytic cleavage of C–C bonds in polypropylene, and the catalyst prefers catalytic cleavage of terminal C–C bond in the side-chain with the low energy barrier.Additionally, our developed approach is evaluated by the technical economic analysis for an economically competitive production process.

SUPER POLYOLEFIN BLENDS ACHIEVED VIA DYNAMIC PACKING INJECTION MOLDING:MORPHOLOGY AND PROPERTIES

As a long-term project aimed at developing super polyolefin blends, in this paper we summarize our work on themechanical reinforcement and phase morphology of polyolefin blends achieved by dynamic packing injection molding(DPIM). The main feature of this technology is that the specimen is forced to move repeatedly in the model by two pistonsthat move reversibly with the same frequency during cooling, which results in preferential orientation of the dispersed phaseas well as the matrix. The typical morphology of samples obtained via DPIM is a shear-induced morphology with a core inthe center, an oriented zone surrounding the core and a skin layer in the cross-section areas. Shear-induced phase dissolutionat a higher shear rate but phase separation at low shear rates is evident from AFM examination of LLDPE/PP (50/50) blends.The super polyolefin blends having high modulus (1.9-2.2 GPa), high tensile strength (100-120 MPa) and high impactstrength (6 times as that of pure HDPE) have been prepared by controlling the phase separation, molecular orientation andcrystal morphology.

Application of prodigiosin as a colorant for polyolefines

Serratia marcescens strain 9986 is a producer of prodigiosin used as a dye of polyolefines (polyethylene, ultratene). The biosynthesis of pigment was closely connected with controlled growth parameters. A prodigiosin yield 0.2 - 0.4 mg per l of culture medium in the batch culture under aerobic conditions was obtained. Prodigiosin was extracted from crude biomass treated by 0.1% of sodium dodecyl sulfate (SDS). This novel elaborated stage is necessary for thermostability a dye in polymer. The consumption of prodigiosin preparation is more economical in the technology of the coloration of polyolefines. The elaborated method has been manufactured for dyeing polyethylene by biological pigment-articles of the common use corresponding to the technological standard.

Ionomer Toughened Polyolefine

The morphology and properties of HDPE blends with Zn-SEPDM and GR were studied through SEM and mechanical property test. The results show that as Zn-SEPDM/GR content amounts to 20%, the blend becomes an IPN in structure, and that a rather high impact and tensile strength of HDPE may be obtained after blending. The antistatic effect, the softening point,and HDT of the blend are higher as compared to HDPE/Zn-SEPDM/ZnSt (zinc stearate).The effect of Zn-SEPDM on the compatibility the morphology and properties of IPP blends were studied by DSC, TEM and mechanical properties test. The results show that as Zn-SEPDM content exceeds 20%. Zn-SEPDM in the blend becomes continuous and an abrupt change in impact strength is incurred there from. Owing to the incorporation of ionic groups into EPDM.the strong interactions betWeen the chains make both the impact and the tensile strength of IPP remarkably higher

Diffusion Characteristics and Removal of Cyclohexane in Polyolefin Elastomer Melt

The diffusion coefficient of volatiles in polymer solutions is a crucial parameter to describe the mass transfer efficiency and ability of volatiles.In this research,polyolefin elastomer(POE)was used as a polymer,and cyclohexane was used as a volatile.A gravimetric analysis was applied to measure the diffusion coefficient of cyclohexane in POE.The devolatilization rate of the POE-cyclohexane system under different conditions was measured.The effects of temperature,film sample thickness,and initial concentration of volatiles on the devolatilization rate were discussed.Based on the devolatilization rate data,the average diffusion coefficient of cyclohexane in POE was obtained by fitting with a mathematical model.The experimental results indicate that the devolatilization rate increased with increasing temperature and initial concentration of volatiles,but it decreased with increasing sample thickness.As the thickness increased,the overall diffusion resistance increased.As the temperature increased,the molecular movement increased,resulting in the increase of average diffusion coefficient.The relationship between the diffusion coefficient of the POE-cyclohexane system and temperature follows the Arrhenius law.The diffusion activation energy E=6201.73 J/mol,and the pre-exponential factor of the diffusion coefficient D0=2.64×10^(-10) m^(2)/s.This work can provide basic data for exploring the devolatilization of POE polymers and serves as a useful reference for enhancing the effect of devolatilization.

A METHOD TO QUANTIFY CRAZING DEFORMATION BY TENSILE TESTS FOR POLYSTYRENE/POLYOLEFIN ELASTOMER IMMISCIBLE BLENDS

A method to quantify crazing deformations by tensile tests for polystyrene （PS） and polyolefin elastomer （POE） blends was investigated. The toughness of PS/POE blends, reflected by the Charpy impact strength, increased with the content of POE. SEM micrographs showed the poor compatibility between PS and POE. In simple tensile tests, it is very easy to achieve the ratio of crazing deformation, i.e. K by measuring the size changes of samples. The K values decreased with increasing the content of POE, and the deformations of PS/POE blends were dominated by crazing. The plots of the change of volume （△V） against longitudinal variation （△I） showed a linear relationship, and the slope of lines decreased with the content of POE. Measuring samples at the tensile velocities of 5 mm/min, 50 mm/min, and 500 mm/min respectively, the K values kept unchanged for each PS/POE blends.

UNUSUAL CRYSTALLIZATION AND MELTING PROCESSES OF AN OPTICALLY ACTIVE POLYOLEFIN:ISOTACTIC POLY((S)-4-METHYL-HEXENE-1)

Polyolefins that bear a chiral side chain(typically an isobutyl group)experience a so-called macromolecularamplification of chirality:the chiral side-chain induces a slight preference for either tg or tg(?) main chain conformation.Thisslight conformational bias is amplified cooperatively along the chain,and results in preferred chirality of the main chainhelical conformations.As a result,these polymers display a liquid-crystal(LC)phase both in solution and,in the melt as atransient phase on the way to crystallization.The existence of two processes(melt-LC and LC-crystal transitions)results inunconventional behaviors that were first analyzed by Pino and collaborators back in 1975.These polymers also offer a meansto test the structural consequences of recently introduced crystallization schemes.These schemes postulate the formation of atransient liquid-crystal phase as a general scheme for polymer crystallization.

FILLED POLYOLEFIN COMPOSITES PREPARED FROM IN-SITU POLYMERIZATION VIA A CATALYST-SUPPORTED APPROACH——Ⅰ.MORPHOLOGY OF PE IN CARBON BLACK(CB)/PE IN-SITU COMPOSITES

The morphology of PE in the in-situ CB/PE composites prepared from in-situ polymerization via a catalyst-supported approach was studied by DSC. It is found that both the melting peak temperature and crystallinity of the PE shelldecrease as filler level increases. The unexpected phenomena are ascribed to the strong interaction between PE and CB andthe very high specific area of CB. It is suggested that the lamellar thickness should be well correlated to the PE shell thickness. A two-layer PE model is successfully used to explain the experiment results.

HIGH VISCOUS STRESS OF ORIENTED POLYOLEFINS UNDER UNIAXIAL TENSILE DEFORMATION

In this communication, by means of stress relaxation experiments, the viscous stress at various strains during tensile deformation of oriented polyolefin samples including high density polyethylene （HDPE）, linear low density polyethylene （LLDPE） and isotactic polypropylene （iPP）, has been determined. The viscous stress in the oriented samples takes up to 50%-70% of the total stress, which is unusually high compared with their isotropic counterparts. The unusual high viscous stress was discussed based on mainly the existence of shish structure in oriented polyolefins, which could enhance the inter-lamella coupling significantly.

A Greener Approach for Synthesis of Functionalized Polyolefins by Introducing Reactive Functionality into Ethylene Copolymers

Recent successful examples for synthesis of new polyolefins containing (polar) functionalities by adopting the approaches by controlled incorporation of reactive functionalities (and the subsequent introduction of polar functionalities under mild conditions) by coordination polymerization in the presence of transition metal complex catalysts have been described. Related methods (such as direct copolymerization of olefin with polar monomer using living radical or coordination insertion methods) have also been demonstrated for comparison. Our recent efforts for precise synthesis of polyolefins containing polar functionalities by efficient incorporation of reactive functionality by copolymerization of ethylene with nonconjugateddiene (1,7-octadiene, vinylcyclohexene etc.) or divinyl-biphenyl using nonbridged half-titanocene [ex. Cp’TiCl2(O-2,6-iPr2C6H3), Cp’ = C5Me5, tBuC5H4 etc.] catalysts have been introduced.

Rolling Circle Amplification on Biotin-Streptavidin Complexes Immobilized to Activated Cyclic Polyolefin Surfaces

Cyclic polyolefin (COP) is an inexpensive hydrophobic material with low auto-fluorescence, high light transmittance and thermal stability, broad chemical resistance and no non-specific protein binding. Here, the hydrophobic alkane COP was modified to have carbonyl functionalities through oxygen plasma and chemical etching treatments to increase usefulness for chemical and biochemical applications. Then, biotin-hydrazide was used to create biotinylated surfaces that bound streptavidin. A biotinylated target oligonucleotide was subsequently bound to the immobilized biotin-streptavidin and ligation mediated rolling circle amplification-based (L-RCA) SNP detection was demonstrated.

Development Scenario of China Polyolefin Industry in 2009 and Its Prospect During Twelfth Five-year-plan Period

The development situation of the polyolefin industry during the first four years of the Elevemth Five-year-plan was reviewed.Domestic supply and demand of polyolefins at the period of the Twelfth Five-year-plan were analyzed and predicted.It was pointed out that production capacity of polyolefin in China will be increased significantly and market demand will keep a steady growth.Large-scale industrial equipment of polyolefin will be developed to meet the increasing demand.

Beyond Conventional Degradation:Catalytic Solutions for Polyolefin Upcycling

Polyolefins(POs,i.e.,polyethylenes,ethylene/α-olefin copolymers,and polypropylenes)are the most ubiquitous synthetic macromolecular materials in modern life.Their widespread use and low recovery rate after extensive usage have caused significant resource waste and environmental concerns.Chemical recycling of POs provides an efficient approach to unravelling the polymer chain to various chemicals.However,conventional chemical recycling methods,including pyrolysis,hydrocracking,and oxidation,require high-energy input(typically>500℃)and/or the use of environmentally unfriendly chemicals,leading to complex product distribution.In this minireview,based on recent representative works,we summarize and highlight catalytic strategies addressing these issues in PO recycling from two perspectives:(1)employing advanced catalysts or technique designs to overcome the challenges in conventional chemical deconstruction approaches;and(2)developing novel tandem/cascade catalytic systems for highly selective PO upcycling under relatively mild conditions.We hope that this minireview will help researchers better understand the state of the art of PO chemical recycling and inspire more innovative and efficient ideas for this fast-developing field.

硅胶载体的制备及在聚烯烃催化剂领域中的应用

催化剂及催化技术的发展是聚烯烃产业技术进步的核心。硅胶作为聚烯烃催化剂常用的载体材料,在催化剂的合成及聚烯烃树脂的制备领域发挥着重要的作用。近年来,关于硅胶负载聚烯烃催化剂的研究已陆续发表。本文综述了硅胶载体的结构、制备方法以及硅胶载体与聚烯烃催化剂(Ziegler-Natta催化剂、茂金属催化剂、后过渡金属催化剂及铬基催化剂)负载化的研究进展,并介绍了催化剂的制备机理、优点及应用。

动态化学交联聚烯烃类弹性体研究进展

聚烯烃类弹性体是由乙烯与丙烯或其他高碳α-烯烃共聚而成的高端聚烯烃材料,具有出色的化学稳定性、耐候性和电绝缘性,广泛应用于光伏、汽车、电缆等领域。通过动态化学交联可在保证其加工性的前提下,进一步提高其力学性能与热稳定性,拓展应用范围。综述了动态化学交联聚烯烃弹性体的制备工艺,包括一步法直接交联和功能化后再交联(多步法)。详细介绍了后功能化、乙烯与功能化单体共聚等功能化方法。讨论了动态化学交联聚烯烃类弹性体的表征手段及其链结构、聚集态结构和性能之间的关系。展望了动态交联聚烯烃类弹性体的未来发展。为动态化学交联聚烯烃类弹性体的可控制备、构效关系研究以及高值应用提供理论指导与技术支持,推动高端聚烯烃材料的创新和发展。

POE溶液聚合反应器内混合与反应过程的CFD研究

聚烯烃弹性体(POE)具有优异的性能而应用广泛,其工业生产通常采用溶液聚合方法。POE反应介质流变行为复杂,受温度、剪切速率、聚合物浓度等诸多因素影响。同时,反应介质的流变行为是决定混合效果的重要因素,进而影响反应进程。由于反应、流变和流场的相互作用,POE溶液聚合反应器的设计和生产过程控制面临着挑战。基于实测的动力学和流变数据,针对POE溶液聚合反应器建立了一个耦合计算流体力学(CFD)模型,综合考虑了流动、混合效率、反应动力学和流变特性等方面的影响,探究了不同工艺条件(搅拌转速、停留时间、进料温度)对速度场、温度场、浓度场、流变特性等参数的影响规律,为优化实际工业过程提供参考。

高通量技术在非均相聚丙烯催化剂制备中的应用研究

考察了催化剂高通量合成系统(HT-Posycat)在非均相Ziegler-Natta催化剂制备中各种加料计量工具的准确性和平行性。实验结果表明,使用高黏液体重力加料系统代替注射泵有效降低了小剂量液体的计量误差;使用缓冲瓶代替12通分流阀,有效降低了气泡对蠕动泵计量准确性的影响;合理设置各种计量设备的参数,可使小剂量反应原料计量误差小于0.5%,有效提高了HT-Posycat的实验平行性,催化剂产量的相对偏差可低于2.3%;增大滤头管径和更换滤材,在不影响催化剂产量及实验平行性的同时,有效缩短抽滤用时9h,进一步提高了HT-Posycat的工作效率。

聚丁烯-1与聚烯烃弹性体共混物的结构与性能

采用熔融共混法制备了聚丁烯-1(PB-1)与丙烯基聚烯烃弹性体(POE)共混物。利用共聚焦显微拉曼系统、拉伸仪以及DSC,WAXD,SAXS等方法研究了材料的相形态、拉伸机械性能、结晶与熔融行为、晶体结构、长周期及长周期与共混物组成的关系。实验结果表明,PB-1和POE为不相容体系,所研究的共混物中均具有明显的分相结构,随着PB-1质量分数(wPB-1)的增加,PB-1由分散相变为连续相,且经历了相反转过程;POE的加入没有改变PB-1的晶型,对PB-1晶体的熔融行为影响不大;受相形态影响,当wPB-1较低时,双重结晶峰出现,且结晶温度较共混前发生显著降低;当POE为连续相时,材料的断裂伸长率高、模量低,当PB-1为连续相时,材料的模量较高,且随着wPB-1的增加明显升高。