Impact of Die Materials on the Effect of New Polymer Processing Aids for Sharkskin Properties

Flows of polymeric liquids undergo instabilities whose origins are quite different from those of Newtonian flows, due to their elastic character and the complexity of the fluid/solid boundary condition. One of these instabilities is well known as “shark-skin” which damages the surface appearance and properties of polymer extrudate while processing in blowmolding or piping, while it can be suppressed by employing various methods including coating the die surface and/or adding Polymer Processing Aid’s (PPA) to the polymer. In this article, the effect of various die materials on the properties of Polyethylene glycol (PEG) as a new type of PPA for suppressing the sharkskin phenomenon has been studied.

Achieving high dielectric energy-storage properties through a phase coexistence design and viscous polymer process in BNT-based ceramics

In the last few decades,dielectric capacitors have gotten a lot of attention because they can store more power and charge and discharge very quickly.But it has a low energy-storage density(Wrec),efficiency(h),and temperature stability.By adding Pb(Mg1/3Nb2/3)O3(PMN)and(Bi0$1Sr0.85)TiO3(BST)to a nonstoichiometric(Bi0$51Na0.5)TiO3(BNT)matrix,the goal is to change the phase transition properties and make the material more relaxor ferroelectric(RFE)by lowering the remnant polarization Pr and keeping the maximum polarization Pmax.A viscous polymer process(VPP)is used to improve the electric breakdown strength,which is also a key part of being able to store energy.By working together,ceramics with the formula 0.79[0.85BNT-0.15PMN]-0.21BST(BP-0.21BST)are made.The phase structure has been changed from a rhombohedral phase to a rhombohedral-tetragonal coexisted phase.This is beneficial for RFE properties and gives a Wrec of 6.45 J/cm^(3) and a h of 90%at 400 kV/cm.Also,the energy-storage property is very temperature stable between 30 and 150C.These results show that process optimization and composition design can be used to improve the energy storage properties,and that the dielectric ceramic materials made can be used in high-powder pulse dielectric capacitors.

Empirical correction of kinetic model for polymer thermal reaction process based on first order reaction kinetics

Based on the theory of first-order reaction kinetics,a thermal reaction kinetic model in integral form has been derive.To make the model more applicable,the effects of time and the conversion degree on the reaction rate parameters were considered.Two types of undetermined functions were used to compensate for the intrinsic variation of the reaction rate,and two types of correction methods are provided.The model was explained and verified using published experimental data of different polymer thermal reaction systems,and its effectiveness and wide adaptability were confirmed.For the given kinetic model,only one parameter needs to be determined.The proposed empirical model is expected to be used in the numerical simulation of polymer thermal reaction process.

Polymerization Process and Morphology of Polyurethane/Vinyl Ester Resin Interpenetrating Polymer Networks

A series of polyurethane （PU）/vinyl ester resin （VER） simultaneous IPNs （interpenetrating polymer networks） with different component ratios and comonomers types introduced to VER were synthesized and the polymerization processes were traced by Fourier transform infrared spectroscopy （FTIR） to study the kinetics of IPNs and hydrogen bonding action within multi-component. Furthermore, the relationship of polymerization process with morphology was investigated in detail for the first time by the morphological information given by chemical action between two networks besides physical entanglement, atomic force microscope （AFM） observation and dynamic mechanical analysis （DMA）. The results indicated that the degree of hydrogen bonding （Xb,UT,%）, calculated from functional group conversional rate and fine structures gained from FT-IR spectra of two networks, were affected by PU/VER weight ratios and comonomer types of VER. The relationship of formation kinetics and morphology showed that the change of Xb,UT （%） values exhibited excellent consistency with that of phase sizes observed by AFM and detected by DMA.

THE PROCESS OF THE EMULSIFIER-FREE POLYMERIZATION IN THE PRESENCE OF BARIUM SULFATE POWDER

The process of emulsifier-free copolymerization of the Styrene-Butyl Acrylate-K_sS_sO_s-water in the presence of Barium Sulfate(BS)powder was investigated under varied conditions within the range of BS powder quantity,initiator concentration and reaction temperature.Experimental results showed that the rate of polymerization is proportional to 0.3-power of the BS quantity and 1.3-power of the initiator concentration.There is a linear relationship of 2/3-power for the conversion and time.A process for the polymerization is propose to explain the experimental results.

THE NEAR-CRITICAL AND SUPER-CRITICAL ASYMPTOTIC BEHAVIOR IN THE THERMODYNAMIC LIMIT OF REVERSIBLE RANDOM POLYMERIZATION PROCESSES

In this paper, the near-critical and super-critical asymptotic behavior of a reversible Markov process as a chemical model for polymerization was studied. The results of the present paper, together with an analysis of the sub-critical stage, establish the existence of three distinct stages (sub-critical, near-critical and super-critical stages) of polymerization (in the thermodynamic limit as N --> +infinity,),depending on the value of strength of the fragmentation reaction. These three stages correspond to the size of the largest length of polymers of size N to be itself of order log N, Nm/m+1 (m greater than or equal to 2, m not equal 4n, n greater than or equal to 1) and N, respectively.

SUBCRITICAL ASYMPTOTIC BEHAVIOR IN THE MODIFIED LUSHNIKOV PROCESS OF POLYMERIZATION

We consider a modified Lnshnikov process as a model of a chemical polymer ization anf study the asymptotic behavior (in the thermodynamic limit;as N →∞)of a particular probability distribution on the set of N-dimensional vectors,tile kth component of which is the number of k-mers.The study study establisles the existence of three stages (subcritical,near-critical and supercritical stages)of polymerization,dependenting upon the ratio of association and dissociation rates of f polymers.The present paper concentrates on the analysis of tile subcritical stage.In the sibcritical.stages we show that tile size of the largest length of polymers of stize N is of the order.log N as N →+∞.

Supporting Processes of Syndiospecific Metallocene Catalyst for Polymerization of Propylene

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长碳链尼龙研究进展

介绍了长碳链尼龙熔融缩聚法和溶液缩聚法工艺技术的研究状况,分析总结了相关研究思路和工艺路线。概述了近年来长碳链尼龙在增强、增韧及阻燃改性方面的研究进展。分析了长碳链尼龙的市场现况,涵盖了国内外主要的生产厂家,并对长碳链尼龙的改性研究未来趋势进行了展望。

宽分布聚乙烯管材树脂结构与性能差异性

本文采用高温凝胶渗透色谱(GPC)、差示扫描量热仪(DSC)、万能拉伸试验机、冲击试验机和动态力学分析仪(DMA)等研究了Hostalen(两釜串联)和Hostalen ACP(三釜串联)淤浆聚合工艺制备的宽分布聚乙烯管材树脂GC1和GC2结构与性能的差异性。结果表明,三釜串联生产的GC2平均分子量更大,分子量分布更宽,高分子量级分(重均分子量M_(W)>10^(6))相对含量更高且共聚单体的含量更高。同时,GC2还具有更高的拉伸强度和冲击强度,耐蠕变性能更优异,高剪切速率下具有更好的加工流动性。

生物可降解聚酯酰胺的合成、结构性能及其纺织材料在医疗卫生领域的应用

从单体原料出发系统介绍了聚酯酰胺(PEAs)的结构和性能,综述了其主要聚合方法,梳理并剖析其纺织材料在医疗卫生领域的应用进展,指出PEAs要在环境保护领域及医疗卫生领域占据重要位置,仍需要在原料选择、制备工艺与性能等多个方面展开探索。

新型复合膜制备工艺研究

以间苯二胺(MPD)为水相单体,均苯三甲酰氯(TMC)为油相单体,采用低温界面聚合方法在聚砜超滤底膜表面制备聚酰胺反渗透膜,无需传统烘箱热处理,考察了界面聚合过程中反应温度、水浴温度及时间对膜性能的影响。结果表明,水相温度为35℃、油相温度为50℃,90℃条件下水浴后处理1 min制备得到的膜性能最佳。该复合膜在25℃、1.05 MPa条件下,以1500 mg/L的NaCl溶液为进料液进行性能测试,截留率为99.5%,水通量为70 L/(m^(2)·h),获得良好的分离效果。本研究提供低温界面聚合制备反渗透膜工艺的探索,可运用于海水淡化等领域。

国产环保型填充油在溶聚丁苯橡胶中的应用研究

考察了中国石化济南分公司200#环保型橡胶填充油作为溶聚丁苯橡胶(SSBR)填充油及加工过程操作油的应用效果,并与德国汉圣公司V500填充油进行对比实验,探讨了200#填充油替代V500填充油的可行性。实验结果表明,200#填充油赋予橡胶更低的混炼胶门尼黏度、略优的加工性能、较高的加工安全性和较快的硫化速率,更优的动态性能,抗湿滑性提高9%,滚动阻力降低6%。200#填充油在SSBR中的应用效果略优于V500填充油,完全满足高性能SSBR使用要求。

丙烯等规配位聚合催化剂及电容器膜基材iPP的制备技术研究进展

生产包括电容器膜基材iPP在内高端聚丙烯的关键技术是丙烯高等规聚合的高活性催化剂和先进聚合工艺。本文详细介绍了丙烯聚合催化剂的发展历程,包括高效Ziegler-Natta催化剂、茂金属催化剂和非茂金属催化剂,指出了在合成电容器基材iPP方面此三类催化剂的优缺点。阐述了烯烃聚合催化剂的近期发展动态:产生了在催化剂结构/组成中引入强吸电子基团有利于提高催化剂活性和聚烯烃分子量的新理论,发展了新一代烯烃聚合催化剂包括内外给电子体于同一分子的丙烯聚合催化剂和全杂环金属有机催化剂,提出了制备嵌端共聚烯烃的可逆“络合-断开”配位聚合新方法。基于丙烯聚合先进工艺,结合高端电容器膜基材iPP技术指标的严苛要求,分析了聚丙烯粉料和粒料中灰分产生的主要因素,建立了在聚丙烯粉料灭活之前进入复合有机溶剂洗涤工序的生产方法,制备合格的高端电容器膜基材i PP。

水中构筑物表面生物膜形成物理化学过程

水中构筑物表面生物膜的形成会加速构筑物的腐蚀,严重影响其使用效率和寿命;成熟后的生物膜老化脱落或受水力剪切作用进入主体水中,会造成水体二次污染,对动植物生长和人类生活造成重大影响。生物膜的形成是由单个细菌黏附到表面开始的,经过可逆黏附到不可逆黏附的过渡后,细菌分泌的胞外聚合物(extracellular polymeric substances, EPSs)会加速表面微菌落的形成,再通过细菌间的群体感应(quorum sensing,QS)使细菌启动表型和基因型变化,最终促使成熟生物膜的形成。本文综述了生物膜形成的不同阶段所涉及的物理化学过程(薄膜形成阶段、细菌黏附阶段、胞外聚合物膜阶段、群体感应调节生物膜阶段和生物膜成熟与表征),分析总结了本领域各方向的最新研究进展,归纳并阐明了水中构筑物表面生物膜形成的机理和影响因素,为生物膜防控、清除和利用等相关研究领域提供了理论依据。

微反应器内阳离子聚合研究进展

阳离子聚合是制备高分子材料的重要方法之一。因阳离子聚合反应活性高、可控性差,采用传统的方式对其进行深入研究难度往往很大。微反应器技术因其优异的过程控制能力在阳离子聚合研究中表现出得天独厚的优势。本文介绍了微反应器内传统阳离子聚合和活性阳离子聚合的研究进展,论述了微反应器对提高异丁烯、乙烯基醚类单体阳离子聚合反应可控性、反应效率以及机理研究的重要作用,探讨了阳离子聚合体系和装备理性设计的方向。

丁烯基弹性体的制备与性能

采用自制的负载钛系催化剂催化丁烯-1与己烯-1进行本体聚合制备了丁烯基弹性体,开展了聚合工艺优化研究,通过核磁共振波谱和差示扫描量热表征了共聚物的结构,考察了共聚物的物理机械性能。结果表明,最佳聚合工艺条件:n(单体)/n(催化剂)为20000~25000,n(三乙基铝)/n(负载钛系催化剂)为250~300,聚合温度为45℃,聚合时间为4 h,氢气压力为0.10~0.15 MPa;共聚物含有丁烯-1与己烯-1的无规共聚结构且无固定熔点;随着共聚单体己烯-1用量的增加,共聚物的拉伸强度和弹性模量均减小,当加入己烯-1质量分数为20%时,共聚物的断裂标称应变达到534%。

低缠结超高相对分子质量聚乙烯的制备及表征

为解决传统Ziegler-Natta催化剂(简称Z-N催化剂)制备的超高相对分子质量聚乙烯(UHMWPE)缠结程度较高、加工困难等问题,以MgCl_(2)、TiCl_(4)、异辛醇、正硅酸四乙酯(或邻苯二甲酸二己酯)为主要原料,采用化学反应法制备了氯化镁负载型Z-N催化剂cat1(或cat2)。分别以cat1、cat2为主催化剂、三乙基铝为助催化剂,采用淤浆聚合工艺制备了低缠结UHMWPE,测定了cat1、cat2的粒径分布和金属元素质量分数,考察了聚合温度、时间对催化剂催化活性和UHMWPE的黏均相对分子质量(M_(v))的影响,并使用流变分析法和DSC热力学退火法对UHMWPE的缠结程度进行了表征。结果表明,制备的cat1、cat2与设计相符,在聚合反应温度分别为65和70℃、反应5 h时,cat1、cat2催化活性分别达到27700、37700 g PE/g cat,制备的UHMWPE的Mv分别为6.01×10^(6)、5.03×10^(6),起始储能模量分别为0.21、0.13 MPa,缠结程度低于商品化UHMWPE。

聚己二酸对苯二甲酸丁二醇酯(PBAT)一步法聚合工艺分析

本研究以PET材料为基础,采用酯交换法制备预聚体中间产物,再通过一步法聚合工艺对中间产物进行催化反应以获得聚己二酸对苯二甲酸丁二醇酯(PBAT)。通过对产物的表征显示,本次成功合成了PBAT这一组分,且热稳定性相对较为优良。在此基础上,进一步对其力学性能进行分析,结果显示,本次制备的PBAT材料在主要性能指标上明显优于传统模式下制备的PBAT,与市售材料基本相同,表明本研究一步法聚合工艺较具可行性,具有潜在的应用价值。

高分子量聚丙烯腈聚合工艺研究进展

聚丙烯腈是制备高性能碳纤维的重要前驱体材料,其分子量对最终碳纤维的力学性能有着决定性的影响,而不同的聚合工艺会影响聚丙烯腈的分子量。针对不同聚合方法选择的共聚单体和引发剂,结合其聚合工艺特点和产物特性,对高分子量聚丙烯腈的制备方法进行分析,发现合适的共聚单体和引发剂是制备高分子量聚丙烯腈的必要条件。混合溶剂沉淀聚合是制备碳纤维用聚丙烯腈前驱体过程中较具潜力的方法。