Side reactions in the synthesis of triblock copolymers of nylon‐6 with telechelic oligomers

BACKGROUND: The polymerization of hexanelactam (HL) is complicated by numerous side reactions: chain transfer to monomer, termination of the polymer chain, exchange as transamidation and formation of β‐ketoimides and β‐ketoamides. The generation of by‐products and their effect on the anionic polymerization of HL in the bulk in the presence of functionalized tetrahydrofuran oligomers as polymeric activators (PACs) were investigated. RESULTS: In order to consider how side reactions influence the process of HL polymerization, qualitative and quantitative determination of the by‐products obtained and their exhaustion were carried out. An investigation of the polymerization kinetics and the formation of low molecular weight by‐products through the polymerization was performed. The products are further involved in the polymerization process and consumed until an equilibrium level is reached. The mechanism of their generation is discussed. These processes were followed during the first polymerization stage by means of gel permeation chromatography. A mechanism of by‐product formation and consumption is proposed. CONCLUSION: The investigation of the polymerization kinetics and the formation of low molecular weight by‐products through the polymerization has shown that the side reaction yields oligomeric HL‐based products. The products are further involved in the polymerization process and consumed until an equilibrium level is reached. The equilibrium values depend on the HL/PACs ratio. Copyright © 2008 Society of Chemical Industry     

Zur Kinetik der stabilisierten Fällungs-polymerisation eines Kationischen Monomeren in wäßrigen Natriumchlorid-Lösungen

The stabilized free-radical precipitation polymerization of the cationic monomer N-(2-methacryloyloxyethyl)-N,N-dimethylbenzylammonium chloride (MADAMBQ) in aqueous solutions of sodium chloride was studied by reaction calorimetry. Poly(ethylene oxide) was used as stabilizer. The rate of polymerization reaches its maximum immediately after initiation and remains nearly constant up to 50 % conversion followed by a decrease that could be described by a first order kinetics. The particles formed are approximately 1 to 30 μm in diameter and are stable over a period of several months. A model based on the theory of homogeneous particle nucleation is suggested to describe the kinetic course of polymerization, taking into account the rate of polymerization in both phases. With the assumption that the concentration of monomer in the phases is determined by a Nernst distribution law, the kinetics of the early stage of polymerization can be modelled reasonably well. The solution polymerization and the unstabilized precipitation polymerization of MADAMBQ was also studied.     

Side-Chain Metallocene-Containing Polymers by Living and Controlled Polymerizations

This review summarizes recent work on side-chain metallocene-containing polymers prepared by controlled and living polymerizations, which include living anionic polymerization (LAP), ring-opening metathesis polymerization (ROMP) and controlled radical polymerization (CRP) such as atom transfer radical polymerization (ATRP), reversible addition fragmentation chain transfer polymerization (RAFT), and nitroxide-mediated polymerization (NMP). The majority of efforts in the field are focused on side-chain ferrocene-containing polymers, while cobaltocenium-containing polymers have recently started to draw attention. Future direction on the development of other metallocene-containing polymers is discussed.     

Polymerization of p-cresyl glycidyl ether catalyzed by imidazoles I. The influence of the imidazole concentration,the reaction temperature,and the presence of isopropanol on the polymerization

The polymerization of p-cresyl glycidyl ether catalyzed by imidazoles has been investigated as a model reaction for the polymerization of technical epoxy resins. The dependence of oligomer yield on time, temperature, and imidazole concentration, the distribution of the polymerization degrees, and the influence of isopropanol have been studied. The reaction rate and the average degree of polymerization are affected by the presence or absence of a secondary nitrogen on the imidazole, i.e., different results are obtained when 2-ethyl, 4-methyl imidazole (EMI) or 1-methyl imidazole (1-MIA) are used. 1-MIA seems to be “precursor” of the catalyst rather than a catalyst by itself. The comparisons of CGE polymerizations catalyzed by 1-MIA in the absence and presence of isopropanol show only quantitative differences: The polymerization in the presence of isopropanol is faster, and the average degree of polymerization is shifted to higher values. The activation energies of CGE polymerizations catalyzed by different imidazoles have been determined.     

The effect of interpenetrating polymer network formation on polymerization kinetics in an epoxy‐acrylate system

The kinetics of thermally initiated cationic epoxy polymerization and free radical acrylate photopolymerization were studied using photo-differential scanning calorimetry. The reactions of the neat monomers and diluted monomers as well as interpenetrating polymer networks (IPNs) were studied as a function of dilution by the other monomer and temperature. The reaction sequence was also varied to study its effect on the kinetics of formation of the simultaneous IPN's. Both reactions quickly become diffusion controlled. The effects of increasing temperature and dilution on the acrylate polymerization rate profiles are similar, leading to reduced polymerization rate and longer polymerization times. The dilution effect on the epoxy polymerization is similar to that of the acrylate. However, unlike the acrylate reaction the epoxy polymerization rate increases strongly with temperature. The preexistence of one polymer has a significant effect on the polymerization of the second monomer. This effect is larger for the acrylate than for the epoxy polymerization. New kinetic models are needed to capture these complex behaviors.     

Modeling and simulation of semibatch emulsion polymerization

By taking advantage of recent theoretical developments in emulsion polymerization and radical polymerization kinetics at high conversion, a model is developed for simulating seeded semibatch emulsion polymerization. The model is used to calculate the time evolution of the polymerization rate, the monomer conversion, the instantaneous degree of polymerization, the monomer concentration in particles, the average radical number per particle, and the propagation rate coefficient and termination rate coefficient over the whole course of the polymerization. Experimental observations by previous workers, including the existence of steady-state phenomenon and the broad distributions of molecular weight, are reproduced in the results of the simulation. The gel effect on emulsion polymerization and the open-loop stability of the semibatch process are discussed. © 1993 John Wiley & Sons, Inc.     

热硫化氟硅橡胶聚合动力学的研究

采用小型反应器对热硫化氟硅橡胶聚合动力学过程和热力学过程的特点进行了基础性研究。考查了聚合温度和初始引发剂浓度对热硫化氟硅橡胶聚合动力学的影响,并掌握了相关规律。     

非腈复合引发剂用于乙酸乙烯溶液聚合

以生物乙烯法生产的乙酸乙烯为单体、过氧化月桂酰-十二烷基二甲基叔胺为非腈复合引发剂、甲醇为溶剂进行溶液聚合反应的研究。实验考察了反应温度、反应时间、甲醇用量、引发剂用量对反应产物聚合率和聚合度的影响,采用正交试验优化了乙酸乙烯溶液聚合的反应条件,确定反应因素对聚合率和聚合度影响的相对大小。结果表明,最优的乙酸乙烯溶液聚合条件为:反应温度65℃,反应时间3h,甲醇用量10%,引发剂用量0.010%,获得聚乙烯醇产品的聚合度为3776,聚合率为45.29%。直观分析确定影响聚合率的因素主次顺序为引发剂用量> 反应时间> 甲醇用量> 反应温度;影响聚合度的因素主次顺序为甲醇用量 >引发剂用量 >反应温度 >反应时间。     

Effects of long-chain branching on distribution of degree of polymerization

The method of generating functions is used to calculate the number fraction of molecules having any specified degree of polymerization and number of long branches for polymers produced under conditions in which the probabilities of chain propagation and of branching on a monomer unit incorporated in the polymer are both constant; termination by combination is assumed absent. Expressions are given for the moments of degree of polymerization and the first two moments of branch number. It is shown that all moments of degree of polymerization are finite, for this model. An asymptotic expression for the number distribution at very high degrees of polymerization is obtained. The way in which the average number of branches per monomer unit varies with degree of polymerization is studied.     

A novel approach for synthesis of poly(norbornene)‐co‐poly(styrene) block copolymers via metathesis polymerization and free‐radical polymerization

It is successfully realized that block copolymers are synthesized via metathesis polymerization followed by free‐radical polymerization. This method is performed using styrene (St) and norbornene, one block is synthesized using the Grubbs second generation catalyst in the presence of chain transfer agents, and the subsequent polymerization of St is initiated by azo compounds to complete the additional blocks in the copolymers. The use of free‐radical polymerization instead of controlled radical polymerization or ionic polymerization can be potentially superior for industrialization. As a result, the molecular weights of the block copolymers ranging from 10.4 to 54.3 kDa and polydispersity indices ranging from 1.30 to 1.91 are obtained. In principle, this new method can be potentially useful to prepare a broad range of block copolymers with cyclic olefin groups in the main chains, which may be used in some particular applications.     

超高分子量PET的固相聚合

本文采用分段固相聚合的方法合成了特性粘度达1.5以上的超高分子量PET树脂。研究了聚合温度、聚合时间、聚合体颗粒度、搅拌速度、真空度等对固相聚合速度的影响,初步探讨了固相聚合机理,确立了较佳的工艺路线,为纺制高强PET纤维打下了基础。     

Ultrasound‐assisted emulsion polymerization of methyl methacrylate and styrene

In this article, we report on the effect of using ultrasound during emulsion polymerization. This work differs somewhat from that previously reported in that ultrasound is used in conjunction with conventional initiators. The aim is to observe the changes in the nature of polymerization and the synthesized polymer. In this work, reaction conditions and compositions typical of conventional emulsion polymerization are used. Azo‐bisisobutyronitrile and potassium per sulfate are the initiators used. The initial indication is that the rate of polymerization and the final conversion are higher when ultrasound is introduced into the polymerization system. This effect is more pronounced at lower temperatures (50°C) and low initiator concentrations (0.01%). At higher temperatures (70°C) the polymerization rate is seemingly unaffected by the use of ultrasound. The final product in all the experiments is a latex. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 101–104, 2000     

Multiple active site Monte Carlo model for heterogeneous Ziegler‐Natta propylene polymerization

In this study, the kinetics of propylene polymerization catalyzed with the fourth heterogeneous Ziegler‐Natta catalyst is studied. More than one type of active site is present in the propylene polymerization based on an analysis of the GPC curves. A multiple active site kinetic model (MSmodel) is proposed by using Monte Carlo technique. Good agreements in the polymerization kinetics are achieved for fitting the kinetic profiles with the MSmodel. In addition, the MSmodel is used to describe the dynamic evolutions of the active sites and their effects on the propylene polymerization. The simulated results indicate that different types of active sites have different polymerization kinetics and the site type can affect the propylene polymerization kinetics. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

希夫碱催化剂催化丙交酯本体开环聚合

合成了希夫碱催化剂,并成功地催化丙交酯本体开环聚合。结果表明,希夫碱催化剂催化合成聚乳酸可达到较高的转化率（高于95％）。研究了单体与催化剂物质的量比、聚合时间及聚合温度对该催化剂催化丙交酯本体开环聚合反应的转化率及所得聚乳酸相对分子质量的影响。当单体与催化剂物质的量比为400,聚合时间24h,聚合温度140℃时,可得到黏均相对分子质量Mq=8．439×10^4的聚乳酸。     

Reactant partitioning in free-radical heterophase polymerization: The case of inverse microemulsion polymerization of acrylamide

Conversion curves have been determined at 60°C for the polymerization of acrylamide in percolating inverse microemulsions. Ammonium peroxo-disulphate (APS) and dibenzoyl peroxide (DBP) were used as initiators of free-radical polymerization in the presence or absence of potassium nitrosodisulphonate (Fremy's salt, FS). The percolation decreases the rate of polymerization of acrylamide initiated by APS. The polymerization is inhibited by FS. After an inhibition period, retardation of acrylamide polymerization is more pronounced in non-percolating microemulsions. No inhibition periods were observed for DBP-initiated polymerization of acrylamide. The percolation shortens the time interval of the ‘slow’ polymerization of acrylamide, but the rates of rapid acrylamide polymerization above 10% conversion are the same for percolating and for non-percolating inverse microemulsions. The polymer particle diameter is a function of acrylamide/water weight ratio and of [water]/[AOT] (AOT: bis(2-ethylhexyl)-sulphosuccinate sodium salt) molar ratio. No effect of the initiator's nature either in the presence or in the absence of FS was found. The results are interpreted on the basis of initiator and/or nitroxide radical partitioning between oil and water phases of the inverse microemulsion, and are discussed with respect to the mechanism of acrylamide polymerization and polymer particle formation proposed for non-percolating inverse microemulsions.     

Preparation of Functionalized Organometallic Metal–Metal Bonded Dimers Used in the Synthesis of Photodegradable Polymers

This review describes the synthesis of functional dimeric metal carbonyl complexes and their subsequent polymerization to afford polymers containing metal–metal bonds in the main chain. Such polymers are photodegradable because the metal–metal bonds are cleavable by visible light. The functionalization of the dimeric complexes and their polymerization is challenging due to the reactivity of the M–M bond, and therefore many standard synthesis and polymerization methods cannot be used. Various polymerization methods are discussed including ring-opening metathesis polymerization, acyclic diene metathesis polymerization, ring-opening polymerization, traditional step polymerization, and copper-catalyzed step polymerization using click chemistry.     

无外加表面活性剂的苯乙烯悬浮聚合

针对传统悬浮聚合制备聚苯乙烯颗粒粒径分布宽、有效粒子收率低的问题,采用过硫酸铵/磷酸钙复合分散剂体系,在无外加表面活性剂情况进行苯乙烯悬浮聚合,制备了聚苯乙烯珠粒。通过对聚合稳定性、聚苯乙烯珠粒粒径及分布的测定与分析,考察了磷酸钙、过硫酸铵的用量及比例对悬浮聚合的影响,并分析了过硫酸胺对悬浮聚合的分散稳定机理。结果表明,当过硫酸铵和磷酸钙的用量分别为单体质量的0.01%和1.00%时,悬浮聚合体系稳定,得到的粒子透明性好,平均粒径为1.35 mm,粒径分布窄;通过改变过硫酸铵和磷酸钙的用量,可以调节聚苯乙烯珠粒的平均粒径。     

Einfluß des stofftransportes bei der polymerisation von äthylen und 1-okten mit Ziegler-Katalysatoren

The polymerization of ethylene and 1-octene with supported Ziegler-catalysts was investigated with regard to the influence of mass transport of monomers on the kinetics, molecular weight and molecular weight distribution. In the case of the polymerization of ethylene, it was found that for certain conditions of reaction the mass transport of ethylene can influence the kinetics of polymerization respectively the catalyst efficiency strongly. The molecular weight and molecular weight distribution of the polyethylene formed are practically not affected by the conversion as well as particle size of catalyst and polymer. The molecular weight distribution however is affected by the concentration of the catalyst. The polymerization process of ethylene in suspension is distinguished by chemical and physical processes. A continuous chain initiation, for example, is based on the continuous reduction of the catalyst particles to small pieces during the course of polymerization. An apparent chain termination respectively catalyst deactivation can occur when catalyst particles are encapsulated within the growing polymer particles. The polymerization of 1 -octene for similar conditions of reaction gave polymers which were solved completely in the system used. The molecular weight distribution of the polymer formed nevertheless was very broad. This indicates that the mass transport of the monomers through the solid phase of polymer cannot be the main reason for the broad molecular weight distribution of the polymers which are produced by heterogeneous Ziegler-catalysts in suspension.     

Photoinduzierte Polymerisation von Methylmethacrylat in Gegenwart von niederund hochmolekularen Chinoxalinderivaten

The photoinduced polymerization of methyl methacrylate in presence of 2,3-diphenylquinoxaline and 6-acrylamido-2,3-diphenylquinoxaline polymers is investigated. As photoexcited quinoxaline molecules are capable of hydrogen abstraction, which can be followed by hydrogen transfer, the formation of starting radicals in the considered system is referred to a hydrogen transfer from a H-donor to monomer molecules with monohydroquinoxaline radicals as transferring reagent. The polymerization mechanism based on this reaction is confirmed by endgroup analysis of the polymers and by the polymerization kinetics.     

反应型乳化剂对苯丙微皂乳液聚合及性能的影响

采用不同结构类型的反应型乳化剂应用于苯丙微皂乳液的聚合,讨论了聚合方式、乳化剂的结构类型和用量等对乳液聚合及性能的影响。借助DSC、粒径分布仪、FT-IR、拉力机、TEM等仪器及分析技术对制得的苯丙乳液的性能进行表征分析,发现通过半连续核壳乳液聚合方式,采用合适的反应型乳化剂复配体系,可以制备出综合性能优异,粒径小于100 nm的苯丙微皂乳液。