利用ISBS分散纳米P(MMA-St)对聚丙烯增强增韧改性研究

将0.5%~4.0%的P(MMA-St)粉体作为改性剂加入到聚丙烯(PP)中,利用原位气泡拉伸法(ISBS)进行纳米分散。采用力学性能和SEM研究了共聚物粉体用量对PP拉伸强度、冲击强度及弯曲强度的影响。结果表明：利用ISBS方法,可以将P(MMA-St)很好地分散到PP中,P(MMA-St)的加入提高了PP/P(MMA-St)共混物的力学性能,其中拉伸强度提高了7.50 %,缺口冲击强度提高了103.77 %。利用XRD对共混物的结晶形态和行为进行了研究,结果表明纳米共聚物粉体的加入可以诱导β晶型的产生,使得共混物的韧性提高。     

P(MMA-St)/SiO2纳米复合材料的制备及性能研究

采用硅烷偶联剂(KH-570)对纳米二氧化硅(SiO2)进行有机化处理,然后将其与甲基丙烯酸甲酯(MMA)和苯乙烯(St)按一定比例进行原位悬浮聚合,得到甲基丙烯酸甲酯苯乙烯共聚物P(MMA-St)/SiO2纳米复合材料。利用傅里叶红外光谱、凝胶渗透色谱仪、热失重分析仪、透射电子显微镜等对纳米SiO2及复合材料的结构、热稳定性、力学性能及加工流动性进行了分析和表征。结果表明,在保证良好加工性能的前提下,复合材料的热稳定性、力学性能均得到了显著提升,并且纳米SiO2的加入使聚合物相对分子质量增大,相对分子质量分布变窄。     

Steady state multiobjective optimization of continuous copolymerization reactors

The multiobjective nature of optimization problems related to homopolymerizaton and copolymerization processes implies a vector objective formulation for a correct approach. Two copolymerization systems, methyl methacrylate-vinyl acetate (MMA-VA) and styrene-acrylonitrile (ST-AN) are simulated, and some aspects of the steady state optimality of continuous operation are analyzed. The determination of non-inferior sets through the concept of Pareto optimality permits a clear decision on trade-offs related to operating conditions and product specifications.     

Application of GPC in the Study of Stereospecific Block Copolymers

Abstract

Three different techniques involved in the preparation of Stereospecific block copolymers were studied using gel permeation chromatography (GPC). These techniques involved the use of a monofunctional organo-lithium catalyst, a difunctional organolithium catalyst, and a combination of a monofunctional organolithium catalyst and a coupling technique. GPC curves were obtained on the block copolymers using two different column sequences and solvents. The ABA block copolymers studied contained styrene, vinyl toluene, or α-methyl styrene as thermoplastic monomers and butadiene as the elastomeric monomer. The results obtained showed that block copolymers prepared using monomers and catalyst systems free of impurities generally exhibited single peaked GPC curves. In systems where impurities were found to be present, small amounts of A block homopolymer and AB block copolymer were formed. In such cases, the GPC curves were observed to have two or three peaks.     

Synthesis and characterization of novel copolymers with the trimethylsilyl group for deep‐UV photoresists

N‐(4‐Acetoxyphenyl) maleimide (APMI) and three kinds of comonomers bearing a trimethylsilyl group were copolymerized at 60°C in the presence of azobisisobutyronitrile (AIBN) as an initiator in 1,4‐dioxane to obtain the three IP, IIP, and IIIP copolymers. These copolymers were removed from the acetoxy group in a transesterification process into new IVP, VP, and VIP copolymers with a pendant hydroxyl group. Two modified processes were adopted to prepare photoresists using these copolymers. The first process involved mixing the dissolution inhibitor, o‐nitrobenzyl cholate, with the new copolymers. Second, o‐nitrobenzyl cholate was introduced into the copolymers using 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) in dimethylformamide (DMF). The cyclic maleimide structure is responsible for the high thermal stability of these copolymers. After irradiation using deep–UV light and development with aqueous Na₂CO₃ (0.01 wt %), the developed patterns showed positive images and exhibited good adhesion to the silicon wafer without using any adhesion promoter. The resolution of these resists was at least 0.8 μm and an oxygen‐plasma etching rate was 1/5.3 to that of hard‐baked HPR‐204. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2791–2798, 2002; DOI 10.1002/app.10255     

发泡调节剂聚合工艺的研究

研究了单体组合、分步聚合及加料顺序对乳液聚合法合成发泡调节剂聚合工艺和流变性的影响，确定了按MMA-St、MMA-Mz和St-AN的三种单体组合和三步聚合工艺。     

DSC analysis of ethylene/1-butene copolymers obtained with different ziegler–natta catalysts

The crystallization and melting behaviour of two sets of ethylene/1-butene copolymers have been analysed by DSC. The samples, with comonomer content in the range from 0 to 21.5 mol%, were obtained by industrial processes using both Mg/Ti-based catalyst systems. The composition dependences of melting and crystallization temperatures were found to be strictly affected by the catalyst type. Moreover, logarithmic plots of the melting and crystallization enthalpy as a function of the ethylene content (mol%) in the copolymers fitted linear relationships whose slopes have been related to the critical sequence length of crystallizable ethylene units, depending on the catalytic system. These results are compared with those reported in the literature for ethylene/1-butene copolymers synthesized by other catalysts and are accounted for by a different distribution of the comonomer units in the macromolecules of the two sets of samples.     

Dynamic mechanical study of molecular dynamics in ethylene-norbornene copolymers

Dynamic mechanical studies of molecular dynamics have been performed for two ethylene-norbornene copolymers. The analysis of data indicates the existence of three relaxation processes: a primary (α) and two secondary (β and γ) ones. It was found that the secondary processes β and γ are connected with the local motions of ethylene and norbornene groups, respectively and that their rates follow the Arrhenius relation. Moreover, the β process was recognized as the Johari-Goldstein process acting as the precursor of the cooperative structural α-relaxation. Contrary to γ and β processes, the motional rate of α-one follows the Vogel-Fulcher-Tammann equation indicating the cooperative nature of motions involved in this process. An increase in norbornene content in copolymer slows down the molecular dynamics of both norbornene fragments and whole chains, and in consequence shifts these relaxation processes into higher temperatures. Using the Havriliak-Negami formalism the motional parameters for the processes mentioned above were estimated.     

Morphologies and structures in poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide-<Emphasis Type="Italic">b</Emphasis>-ethylene oxide) copolymers determined by crystallization,microphase separation,and vitrification

Morphologies and structures determined by crystallization of the blocks, microphase separation of the copolymers, and vitrification of PLLA block in poly(l-lactide-b-ethylene oxide) (PLLA-b-PEO) copolymers were investigated using microscopic techniques and synchrotron small angle X-ray scattering. The PLLA-b-PEO copolymer films were crystallized from two different annealing processes: melt crystallization (process A) or crystallized from glass state of PLLA block after quenching from melt state (process B). The relationship between the crystalline morphology and microstructure of the copolymers were explored using SAXS. The morphology and phase structure are predominated by crystallization of PLLA block, and greatly influenced by microphase separation of the copolymers. In process B, lozenge-shape and truncated lozenge-shaped PLLA crystals of nanometer scale can be observed. The crystalline morphology is markedly affected by the microstructure formed during the annealing process. Star-shaped morphologies stacked with PLLA single crystals were observed.     

Preparation and characterization of conducting copolymer films from 5-aminoquinoline and aniline

Conducting copolymer films from 5-aminoquinoline and aniline (abbreviated PAq-An) were prepared by anodic polymerization of different molar ratios of the corresponding monomers in MeCN using cyclic voltammetry and potential step methods. Ellipsometric measurements on the different copolymers indicated that the thickness increases linearly with the anodic charge but with different efficiencies. The electroactivity of the copolymers is attributed to polyaniline in the films and increases as the ratio of aniline in the polymerization solution increases. The copolymer PAq-An(1:5) shows even better electroactivity than polyaniline films prepared under the same conditions due to the higher polymerization efficiency and stability of the former films. Analysis of the spectroelectrochemical measurements in acid solutions showed that the redox peaks of the copolymer PAq-An(1:5) are composed of two consecutive redox processes. Models for the redox processes are proposed to analyse the spectroelectrochemical transient behaviour of the copolymer.     

A new macroinitiator for the synthesis of triblock copolymers PA12‐b‐PDMS‐b‐PA12

A new PDMS macroinitiator is proposed for the anionic ring‐opening polymerization of lactams. This α,ω‐dicarbamoyloxy caprolactam PDMS macroinitiator was readily obtained in quantitative yield, by an original synthesis scheme in two steps, which involved the scarcely reported reaction of isocyanates with silanol groups. It was then shown that this bifunctional macroinitiator enabled to synthesize triblock copolymers PA12‐b‐PDMS‐b‐PA12 by polymerization of lauryl lactam (LL) at high temperature (200°C) in inert atmosphere under conditions compatible with reactive extrusion processes. Another related high molar weight α,ω‐diacyllactam PDMS macroinitiator was also successfully used in the polymerization of LL under the same conditions, therefore overcoming the limitations formerly reported for this type of macroinitiators during the polymerization ε‐caprolactam (ε‐CL) at a much lower temperature (80°C). Triblock copolymers with a wide range of PA12 /molar weights (M_n: ～ 10,800–250,000 Da) were eventually obtained by using both types of macroinitiators. DMTA and DSC analyses showed that their thermal properties were strongly dependent upon their respective contents in soft and hard blocks. Such triblock copolymers already appear very promising for the highly effective in situ compatibilization of PA12/PDMS blends as shown by recent complementary results obtained in our laboratory. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 2818–2831, 2006     

Effect of synthesis conditions on the rheological properties of styrene butyl acrylate copolymers

The chemical and physical properties of synthetic polymers depend strongly on the polymerization process. This fact is even more determinant when dealing with copolymers. Styrene/butyl acrylate copolymers were synthesized using an emulsion copolymerization process. The amount of initiator, emulsifier, and transfer agent were varied in a systematic way in order to establish the relationship between polymerization conditions and rheological properties of the molten copolymers. Rheological and molecular weight results show that the different polymerization conditions have important effects on the properties of the final copolymers mainly through the development of different sequence distributions of the monomeric units in the copolymer chain. These results have been interpreted in terms of the kinetic mechanisms that explain the emulsion copolymerization processes. Furthermore, the rheological characterization is used as an additional tool in establishing the different structure of the resulting copolymers.     

Kinetics of the melt – Form II phase transition in isotactic random butene-1/ethylene copolymers

The kinetics of formation of the Form II mesophase from the melt has been investigated as a function of the concentration of ethylene chain defects in isotactic random butene-1/ethylene copolymers, using standard and fast scanning chip calorimetry. Presence of ethylene co-units in the butene-1 chain leads to a distinct reduction of the melt – Form II phase transformation rate which has been quantified by evaluation of the critical cooling rate to suppress ordering, and by isothermal analysis of half-times of Form II mesophase formation. For the first time, the temperature-dependence of the rate of Form II mesophase formation has been evaluated for butene-1/ethylene random copolymers and the butene-1 homopolymer. This study needs to be considered as a complementary addendum to former work about the Form II to Form I polymorphic transformation in isotactic random butene-1/ethylene copolymers.     

PVF_2/P(MMA-St)共混体系的结晶性能和相容性的研究

用示差量热法(DSC)、动态力学分析法(DMA)和悬浮法测密度法研究了聚偏氟乙烯(PVF_2)/甲基丙烯酸甲酯与苯乙烯的无规共聚物[P(MMA-St)]的共混体系的相容性和结晶性能。结果发现PVF_2/P(MMA-St)共混体系是部分相容体系,其结晶性能随共混物中P(MMA-St)的含量而变化,并就模压成型的热历史对该共混体系相容性的影响进行了讨论。     

End‐functional polymers,thiocarbonylthio group removal/transformation and reversible addition–fragmentation–chain transfer (RAFT) polymerization

This review focuses on processes for thiocarbonylthio group removal/transformation of polymers synthesized by radical polymerization with reversible addition‐fragmentation‐chain transfer (RAFT). A variety of processes have now been reported in this context. These include reactions with nucleophiles, radical‐induced reactions, thermolysis, electrocyclic reactions and ‘click’ processes. We also consider the use of RAFT‐synthesized polymers in the construction of block or graft copolymers, functional nanoparticles and biopolymer conjugates where transformation of the thiocarbonylthio group is an integral part of the process. This includes the use of RAFT‐synthesized polymers in other forms of radical polymerization such as atom transfer radical polymerization or nitroxide‐mediated polymerization, and the ‘switching’ of thiocarbonylthio groups to enable control over polymerization of a wider range of monomers in the RAFT process. With each process we provide information on the scope and, where known, indicate the mechanism, advantages and limitations. Copyright © 2011 Society of Chemical Industry     

Mechanistic transformations involving living and controlled/living polymerization methods

This review is prepared on the occasion of the 50th anniversary of the historic discovery of living anionic polymerization by Michael Szwarc. This process enabled preparation, with good control of polymer architecture, of well-defined polymers such as block and graft copolymers, star polymers, macrocycles, and functional polymers. Transformation reactions provide a facile route to synthesis of block copolymers that cannot be made by a single polymerization mode. A variety of transformation reactions involving step-growth, conventional and controlled free radical, cationic, anionic, group transfer, activated monomer Ziegler–Natta and metathesis reactions are known. In this article, transformation reactions involving living and controlled/living polymerization methods are reviewed. Other possibilities of combining different polymerization methods namely, macromonomer technique, coupling reactions, dual polymerizations and click chemistry are described. Preparation of star and miktoarm-star block copolymers by using mechanistic transformations is also presented.     

Synthesis of block copolymers by combination of ATRP and photoiniferter processes

BACKGROUND: Block copolymers of monomers polymerizing by different mechanisms can be prepared by the transformation approach. A wide range of combinations of different polymerization modes has been reported in the literature. In this work, the transformation approach was further extended to the preparation of block copolymers by combining atom transfer radical polymerization (ATRP) and photoiniferter processes. RESULTS: Photoactive morpholine‐4‐dithiocarbamate‐terminated polystyrene (MDC‐PS‐MDC) was prepared by the reaction of dibrominated polystyrene, obtained by ATRP, with morpholine‐4‐dithiocarbamate sodium salt in dimethylformamide. The structure of MDC‐PS‐MDC was confirmed by ¹H NMR and UV‐visible spectral analysis. The ability of MDC‐PS‐MDC to act as a photoiniferter for the block copolymerization of methyl acrylate was examined. The polymerization shows a ‘living’ character at up to 25% conversion and produces well‐defined polymers with molecular weights close to those predicted from theory and relatively narrow polydispersities (M_w/M_n ≈ 1.40). CONCLUSION: It is demonstrated that the end groups of polymers obtained by ATRP can be converted into morpholino‐4‐dithiocarbamate groups which act as photoiniferters. In this way, the desired mechanistic transformation between two controlled free radical polymerization methods can be achieved. Copyright © 2008 Society of Chemical Industry     

Liquid-crystalline copolymers of bibenzoate and terephthalate units

Summary The effect on the mesophase behaviour of the substitution of mesogenic bibenzoate groups by non-mesogenic terephthalate units is studied. Time-resolved synchrotron X-ray and DSC experiments indicate that copolymers with an amount of terephthalate units as high as 29 mol% exhibit liquid crystalline properties, and a smectic mesophase is obtained on cooling, which further experiences a transformation into a three-dimensional crystal. The two transitions are rather sharp and well defined, in contrast to other similar copolymers.     

DSC study of transitions involved in thermal treatment of foamable mixtures of PE and EVA copolymer with azodicarbonamide

The transitions and reactions involved in the thermal processing of binary mixtures of polyethylene and poly(ethylene‐co‐vinyl acetate) copolymers with different concentrations of a foaming agent (azodicarbonamide) were studied using differential scanning calorimetry (DSC). The effect of ZnO as a kicker also was discussed. The temperature at the maximum rate and the heat evolved were measured for all the processes—melting, transitions, and reactions—all the mixtures prepared were measured and compared. Azodicarbonamide decomposed differently depending on the polymeric matrix. These data can be very useful for the plastic processing industry. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2015–2025, 2006     

丙烯腈嵌段共聚物的合成及其自组装研究进展

综述了含聚丙烯腈(PAN)嵌段共聚物的合成方法及其在溶液中的自组装技术。对常用的活性自由基聚合方法,如原子转移自由基聚合(ATRP)、可逆加成断裂链转移(RAFT)聚合、氮氧自由基聚合(NMP)以及钴调介自由基聚合(CMRP)等方面的研究进行了总结,同时对PAN类嵌段共聚物在溶液中的自组装技术进行了概括。最后提出了现有技术存在的问题,并对其今后发展方向进行了展望。