The effect of composition drift and copolymer microstructure on mechanical bulk properties of styrene-methyl acrylate emulsion copolymers

In order to determine the influence of composition drift and copolymer microstructure on the mechanical bulk properties of styrene -methyl acrylate copolymers, several copolymers were produced by emulsion copolymerization. Three different average compositions were used. By performing the copolymerizations under batch and semicontinuous conditions with two different monomer addition strategies (starved conditions and optimal addition) it was possible to control composition drift and to produce copolymers with different microstructures (chemical composition distributions). All these copolymers were processed in a way that ensured that the original particle structure was lost before the polymers were tested. It was found that composition drift had an influence on the mechanical properties (Young's modulus, maximum stress, elongation at break). This influence could be understood very well on the basis of present knowledge about structure-mechanical properties relationships. In the case of homogeneous copolymers maximum stress and elongation at break are dependent on the molecular weight, and only weakly dependent on the chemical composition, and Young's modulus is independent of chemical composition and molecular weight in the range of compositions investigated, as expected. In the case of heterogeneous copolymers, the influence of copolymer microstructure on Young's modulus, maximum stress and elongation at break is very large. Depending on the extent of control of composition drift during the polymerizations, phase separation was observed in the processed polymers, and the presence of a rubber phase affected the properties profoundly.     

Composition and molecular weight analysis of styrene-acrylic copolymers using thermal field-flow fractionation

Thermal field-flow fractionation coupled with online multiangle light scattering, differential refractive index and quasielastic light scattering (ThFFF-MALS/dRI/QELS) was used to simultaneously determine the molecular weight (MW) and composition of polystyrene-poly(n-butyl acrylate) (PS-PBA) and polystyrene-poly(methyl acrylate) (PS-PMA) copolymers. The online measurement of the normal diffusion coefficient (D) by QELS allowed calculation of the copolymer thermal diffusion coefficient (D(T)) of sample components as they eluted from the ThFFF channel. DT was found to be independent of MW for copolymers with similar compositions and dependent on composition for copolymers with similar MW in a non-selective solvent. By using a solvent that is non-selective to both blocks of the copolymer, it was possible to establish a universal calibration plot of DT versus mole fraction of one of the monomer chemistries comprising the copolymer. PS-PBA and PS-PMA linear diblock polymers were determined to vary in composition from 100/0 to 20/80 wt% PS/acrylate and ranged in MWs between 30 and 360 kDa. The analysis of a PS-PBA miktoarm star copolymer revealed a polydisperse material with a weight percent PBA of 50-75% and MW ranging from 100 to 900 kDa. The presented ThFFF-MALS/dRI/QELS method allowed rapid characterization of polymers with MW and chemical distributions in a single analysis.     

Molecular weight distribution in composition controlled emulsion copolymerization

The effect of different strategies for copolymer composition control on the molecular weight distribution (MWD) and gel fraction in the emulsion copolymerization of methyl methacrylate and butyl acrylate was investigated. Starved and semistarved processes for copolymer composition control were both considered. For gel‐forming systems it was found that the starved process gave more gel and lower molecular weights than the semistarved process. The feasibility of simultaneous control of the copolymer composition and the MWD was assessed. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1100–1109, 2000     

The wettability of polymer films depends on the polymerization conditions

The polymerization conditions have a strong influence on the properties and time-dependent behavior of a sessile water drop on polymer films. For a given copolymer composition, the recipe components of emulsion copolymer films clearly influence the initial static water contact angle. Common emulsifiers such as sodium dodecyl sulfate lead to lower contact angles than poly(ionic liquid) dispersions which are a new class of stabilizers for emulsion polymerization. In contrast to the static contact angle, the time-dependent properties of the water contact angle reflect the particular conditions during the polymerization. It is a general conclusion of this study that waterborne emulsion copolymers show a distinctly different time-dependent behavior of the contact angle than bulk polymers of the same molecular composition regardless of the initial static contact angle.     

Spontaneous generation of amphiphilic block copolymer micelles with multiple morphologies through interfacial Instabilities

We introduce a method for the formation of block copolymer micelles through interfacial instabilities of emulsion droplets. Amphiphilic polystyrene-block-poly(ethylene oxide) (PS-PEO) copolymers are first dissolved in chloroform; this solution is then emulsified in water and chloroform is extracted by evaporation. As the droplets shrink, the organic solvent/water interface becomes unstable, spontaneously generating a new interface and leading to dispersion of the copolymer as micellar aggregates in the aqueous phase. Depending on the composition of the copolymer, spherical or cylindrical micelles are formed, and the method is shown to be general to polymers with several different hydrophobic blocks: poly(1,4-butadiene), poly(-caprolactone), and poly(methyl methacrylate). Using this method, hydrophobic species dissolved or suspended in the organic phase along with the amphiphilic copolymer can be incorporated into the resulting micelles. For example, addition of PS homopolymer, or a PS-PEO copolymer of different composition and molecular weight, allows the diameter and morphology of wormlike micelles to be tuned, while addition of hydrophobically coated iron oxide nanoparticles enables the preparation of magnetically loaded spherical and wormlike micelles.     

低分子量结晶性丙交酯/乙交酯与己内酯/乙交酯共聚物热转变温度的组成与分子量依赖性

以1,4-丁二醇为引发剂、辛酸亚锡为催化剂,通过L-丙交酯(LLA)、乙交酯(GA)、ε-己内酯(CL)的开环共聚,制得了低分子量的端羟基结晶性LLA/GA共聚物(PLLGA)和CL/GA共聚物(PCG),分别以FTIR1、H-NMR、GPC、DSC对其微结构和热转变温度进行了表征,重点考察了其热转变温度的组成、分子量依赖性.结果表明,利用辛酸亚锡/二元醇引发开环聚合,通过改变单体配比和单体/引发剂配比,可方便地调控共聚物的组成和分子量;通过改变共聚物的组成和分子量,可在较宽的范围内调节共聚物的热转变温度,并得到了玻璃化温度和熔点与组成、分子量之间定量的经验关系式.     

聚合物驱蚊剂的慢释放研究

本文研究了丙烯酸酯共聚物载体对驱蚊剂N,N-二乙基间甲苯酰胺(DETA)慢释放行为的控制,探讨了单体配比、共聚物分子量以及DETA含量对释放速率的影响。结果表明。增加亲水性单体丙烯酸(AA),可提高DETA的释放速率;降低共聚物数均分子量,会减少DETA的释放量;剂型中DETA含量与释放量存在线性正比关系,但DETA的含量增加并不导致释放有效时间的线性增加。本文还就共聚物膜的透湿性和碱溶性作了研究,亲水性单体AA的增加同样导致透湿性和碱溶性的增加。制备的聚合物驱蚊剂经现场应用试验,表明具有良好的长效驱蚊特性。     

聚(丙烯酰胺-丙烯酸十八酯)的合成及其增稠性能

共聚合;聚(丙烯酰胺-丙烯酸十八酯)的合成及其增稠性能     

Ethylene–vinyl acetate semi-batch emulsion copolymerization: Use of factorial experiments for improved process understanding

A good working knowledge of the mechanism and an appreciation of the effects the process variables have on the properties of interest are required for optimization and control of polymerization processes. Despite the importance of ethylene-vinyl acetate emulsion copolymers, limited kinetic information is available. Results from a series of factorial experiments are presented here which examine the emulsion polymerization of ethylene with vinyl acetate. Copolymers of up to 32 wt % ethylene have been produced at an ethylene pressure of 500 psig and a temperature of 20°C. The effects of the process variables on the rate of polymerization, copolymer composition, particle size and number, molecular weight averages, and gel content are discussed. The kinetic results obtained suggest process improvements for the production of homogeneous copolymer. Mechanistically, the locus of polymerization has been verified as the polymer particles and little water phase polymerization was observed. © 1993 John Wiley & Sons, Inc.     

嵌段共聚物在乳液聚合和分散聚合中的应用

综述了嵌段共聚物在乳液聚合和分散聚合中作为稳定剂应用的进展，主要讨论了共聚物化学组成，比例，分子量，浓度以及胶束形成等因素对聚合体系的影响。     

Synthesis and characterization of a novel polymer electrolyte based on acrylonitrile/N-[4-(aminosulfonyl)phenyl]acrylamide copolymers

<正>Acrylonitrile/N-[4-(aminosulfonyl)phenyl]acrylamide(AN/ASPAA) copolymers were synthesized and used as a host of lithium ion conducting electrolytes.The composition,molecular weight and molecular weight distribution of AN/ASPAA copolymers were determined,and the influence of copolymer composition on the glass temperature of AN/ASPAA copolymers and the ion conductivity of electrolytes were investigated.The molecular weights of AN/ASPAA copolymers were lower than those of AN and ASPAA homopolymers due to the cross-termination reaction.The glass temperatures of AN/ASPAA copolymers increased as the molar fraction of ASPAA units in copolymers increased.The lithium ion conductivities of the polymer electrolytes increased initially as the molar fraction of ASPAA units in copolymers increased,and a maximum conductivity was achieved when the molar fraction of ASPAA in the copolymer was 16.8%.     

强阴离子型丙烯酰胺共聚物P(AM-co-NaAMPS)的结构与性能

在水介质中实施了丙烯酰胺 (AM)与 2 丙烯酰胺基 2 甲基丙磺酸钠 (NaAMPS)的溶液共聚合 ,制备了组成系列变化的强阴离子型共聚物P(AM co NaAMPS) ;通过红外光谱法与元素分析法对共聚物的组成进行了表征 ;稀释外推粘度法测定了共聚物的特性粘数及Huggins常数 ;测定了共聚物纯水溶液及盐水溶液的表观粘度及高温下共聚物盐水溶液的粘度保持率 ;重点考察了共聚物的结构与组成对其各种性能的影响规律 .实验结果表明 ,在聚丙烯酰胺 (PAM)分子主链上引入NaAMPS链节后 ,磺酸根的强阴离子性与庞大侧基的位阻效应 ,赋于共聚物P(AM co NaAMPS)以优良的溶解、增稠、耐温与抗盐性能 ,且这些性能随共聚物的结构与组成的改变发生规律性的变化 .     

聚苯乙烯大单体与丙烯酸丁酯接枝共聚物的微观分相与表面性能研究

研究了以大单体技术合成的不同侧链长度的苯乙烯与丙烯酸丁酯的接枝共聚物的侧链长度对其微观分相与表面性能的影响,发现仅当聚苯乙烯侧链分子量大于5900时,才可能发生部分微观相分离,分离后对其表面性能影响不明显。临界表面张力r_c虽有差异,但色散力部分y_s^D的计算值却较一致,与所用参照液无关。实验证实,接枝共聚物的表面几乎全被低表面能的聚丙烯酸丁酯骨架所复盖,呈现出明显的表面富集现象。     

开环易位聚合合成瓶刷聚合物

瓶刷聚合物是一类具有独特侧链结构的梳形聚合物。功能性瓶刷聚合物在光子晶体、表面活性剂、医药载体、防污涂层以及智能材料等领域具有良好的应用价值。通过开环易位聚合合成瓶刷聚合物的方法具有合成步骤简单、聚合物接枝密度高和侧链组成均一等优点,在控制聚合物组成、分子量和分散性等方面具有显著优势。本文基于开环易位聚合,简述了合成瓶刷均聚物以及嵌段型、混合型和核-壳型三种类型的瓶刷共聚物的方法,并介绍了合成精确结构的瓶刷聚合物的新进展。     

嵌段共聚物微胶束行为的研究Ⅱ．动态激光光散射法研究聚（苯乙烯－异戊二烯）二嵌段共聚物在选择性溶剂中微胶束的形成过程

采用动态激光光散射研究聚（苯乙烯－异成二烯）（ＰＳ－ＰＩ）二嵌段共聚物在选择性溶剂二氧六环／甲醇混合体系中微胶束的形成过程。讨论了温度、混合溶剂的组成和共聚物分子量对形成微胶束的影响。并对与体积排斥色谱法得到结果的差异进行了讨论，从而提出临界接触浓度的概念。还就实验测得的分子链尺寸和微胶束尺寸进行理论估算，结果符合Ｆｌｏｒｙ无扰链模型。     

Photoenzymatic RAFT Emulsion Polymerization with Oxygen Tolerance

Photoenzymatic reversible addition-fragmenatation chain transfer(RAFT) emulsion polymerization, surfactant-free or ab initio, of various monomers is reported with oxygen tolerance. In surfactant-free emulsion polymerizatoin, poly(N,N-dimethylacrylamide)s were used as stabilizer blocks for emulsion polymerization of methyl acrylate, n-butyl acrylate and styrene, producing well-defined amphiphilic block copolymers, including those with an ultrahigh molecular weight, at quantitative conversions. The controlled character of surfactant-free emulsion polymerization was confirmed by kinetic studies, chain extension studies and GPC analyses. Temporal control was demonstrated by light ON/OFF experiments. In ab initio emulsion polymerization of methyl acrylate and methyl methacrylate, low-dispersity hydrophobic polymers were synthesized with predictable molecular weights. This study extends the monomer scope suitable for photoenzymatic RAFT polymerization from hydrophilic to hydrophobic monomers and demonstrates that oxygen-tolerance can be equally achieved for emulsion polymerization with excellent RAFT control.     

从乙烯与丙烯酸二茂铁甲酰氧基乙酯共聚物制备碳纳米材料

使用乙烯和丙烯酸二茂铁甲酰氧基乙酯(FcEA)为单体,合成了乙烯与丙烯酸二茂铁基乙酯共聚物[P(E-co-FcEA)].以P(E-co-FcEA)作为前驱体,通过改变裂解条件,自催化制得系列碳纳米材料.     

Study of pH-sensitive copolymer/phospholipid complexes using the langmuir balance technique: effect of anchoring sequence and copolymer molecular weight

The behavior of three copolymers of N-isopropylacrylamide (NIPAM), methacrylic acid (MAA), and hydrophobic moiety was studied at phospholipid monolayer/subphase interfaces. The hydrophobic moieties, N-terminal dioctadecylamine (DODA) and random octadecylacrylate (ODA), were used as anchoring groups. The interactions between a 1,2-distearoyl-sn-glycero-3-phosphatidylcholine (DSPC) monolayer and the copolymers were studied using the Langmuir balance technique. The effect of subphase pH, distribution of anchors along the copolymer chain, and copolymer molecular weight on the nature of the interactions between the copolymer chains and the DSPC monolayer were investigated. A first-order kinetics model was used to analyze the copolymers adsorption at the DSPC monolayer/subphase interface and allowed the interaction area between the copolymer chains and the DSPC monolayer, A(x), to be determined. The interaction area appears to depend on the subphase pH and the copolymer molecular weight. On decreasing pH, the interaction area of high molecular weight copolymers increases significantly; this is consistent with the copolymer chain phase transition from an extended coil to a collapsed globule while pH is lowered. In the latter conformation, strong hydrophobic attractive interactions between the copolymer chains and the hydrophobic part of the DSPC monolayer favor the copolymer intercalation, which could eventually provoke the phospholipidic layer destabilization or rupture.     

Polymer characterization by interaction chromatography

Liquid chromatography (LC) is a powerful tool for the characterization of synthetic polymers, that are inherently heterogeneous in molecular weight, chain architecture, chemical composition, and microstructure. Of different versions of the LC methods, size exclusion chromatography (SEC) is most commonly used for the molecular weight distribution analysis. SEC separates the polymer molecules according to the size of a polymer chain, a well‐defined function of molecular weight for linear homopolymers. The same, however, cannot be said of nonlinear polymers or copolymers. Hence, SEC is ill suited for and inefficient in separating the molecules in terms of chemical heterogeneity, such as differences in chemical composition of copolymers, tacticity, and functionality. For these purposes, another chromatographic method called interaction chromatography (IC) is found as a better tool because its separation mechanism is sensitive to the chemical nature of the molecules. The IC separation utilizes the enthalpic interactions to vary adsorption or partition of solute molecules to the stationary phase. Thus, it is used to separate polymers in terms of their chemical composition distribution or functionality. Further, the IC method has been shown to give rise to much higher resolution over SEC in separating polymers by molecular weight. We present here our recent progress in polymer characterization with this method. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1591‐1607, 2005