ABS树脂形态结构及力学性能的研究

ABS树脂具有优良的抗冲击性、耐热性和耐化学药品性，还具有易加工性、制品尺寸稳定性等特点，广泛应用于工业领域。ABS树脂的制备方法有许多种，目前应用最为广泛的是乳液接枝ABS共聚物一本体SAN掺混法。首先采用乳液聚合方法合成聚丁二烯胶乳，然后将其作为种子进行苯乙烯和丙烯睛的接枝共聚反应生成ABS接枝共聚物；采用本体法制备SAN树脂；最后将ABS接枝共聚物（冲击改性剂）和SAN树脂共混制得ABS树脂。由此看来，ABS接枝共聚物的合成是控制ABS树脂性能的关键。目前国产ABS树脂普遍存在的问题是ABS接枝共聚物的增韧效率低。影响其增韧效率的因素包括共聚单体的组成、橡胶相的组成及结构、橡胶与树脂之间的界面结合力等。因此为提高ABS冲击改性剂的增韧效率，拓宽ABS树脂的应用领域，应合理地控制ABS冲击改性剂的合成参数。本论文采用种子乳液聚合方法在PB（聚丁二烯）橡胶粒子上接枝共聚苯乙烯和丙烯睛合成ABS接枝共聚物，将其作为冲击改性剂与SAN树脂共混制备ABS树脂，对ABS树脂形态结构及力学性能进行了研究。主要研究内容和结论如下：1、研究ABS接枝共聚物中PB／SAN组成、TDDM（叔十二碳硫醇）链转移剂和CHP（过氧化氢异丙苯）用量、单体加料方式及引发剂类型对SAN在PB橡胶粒子上接枝度的影响。sAN在PB橡胶粒子上的接枝度随PB和TDDM含量的增加而降低；随CHP用量的增加先增加后降低；随单体滴加时间的延长而增加，但过分延长时间则对接枝度影响很小；与AIBN（偶氮二异丁睛）和K25208（过硫酸钾）相比，采用氧化一还原引发体系得到的接枝度较高。2、研究ABS接枝共聚物的力学性能。DMA结果表明，随着PB含量的增加，ABS接枝共聚物的储能模量降低，橡胶相的玻璃化转变温度向低温移动，内耗峰值增加。拉伸试验结果表明，当体系中没有TDDM时，不同橡胶含量的ABS接枝共聚物均没有发生明显的应变软化；当加入适量的TDDM后，材料发生应变软化，且随着TDDM用量的增加，材料的屈服应力提高。3、研究ABS接枝共聚物对ABS树脂形态结构及力学性能的影响。ABS接枝共聚物中PB／SAN组成及TDDM链转移剂用量影响ABs树脂中橡胶粒子的内部形态及橡胶粒子在基体中的分散。在合成ABS接枝共聚物的过程中，应合理地调节PB／SAN组成及TDDM的用量以使ABS接枝共聚物达到最大的增韧效率。4、研究ABS树脂在不同应变速率下的断裂行为及形变机理。结果表明，橡胶含量及应变速率影响ABS树脂的力学性能，但没有改变ABS树脂的形变机理。ABS树脂的形变机理包括银纹、橡胶粒子的空洞化及基体的剪切屈服，其中占主导地位的是橡胶粒子的空洞化及基体的剪切屈服。

Morphological, mechanical and thermal properties of nylon 6/ABS blends using glycidyl methacrylate-methyl methacrylate copolymers

Nylon6 is an attractive polymer for engineering applications because it has reactive functionality through amine and carboxyl end groups that are capable of reacting. For this reason, it has been used a lot in polymeric blends. Blends of nylon6/ABS (acrylonitrile-butadiene-styrene) were produced using glycidyl methacrylate-methyl methacrylate (GMA-MMA) copolymers as compatibilizer. The binary blends were immiscible and exhibited poor mechanical properties that stemmed from the unfavorable interactions among their molecular segments. This produced an unstable coarse phase morphology and weak interfaces between the phases in the solid state. The presence of the copolymer in the blends clearly led to a more efficient dispersion of the ABS phase and consequently optimized Izod impact properties. However, the compatibilized blend showed poor toughness at room temperature and failed in a brittle manner at subambient temperatures. © 2005 Springer Science + Business Media, Inc.

Rapid production of a plasmid DNA encoding a malaria vaccine candidate via amino-functionalized poly(GMA-co-EDMA) monolith

Malaria is a global health problem; an effective vaccine is urgently needed. Due to the relative poverty and lack of infrastructure in malaria endemic areas, DNA-based vaccines that are stable at ambient temperatures and easy to formulate have great potential. While attention has been focused mainly on antigen selection, vector design and efficacy assessment, the development of a rapid and commercially viable process to manufacture DNA is generally overlooked. We report here a continuous purification technique employing an optimized stationary adsorbent to allow high-vaccine recovery, low-processing time, and, hence, high-productivity. A 40.0 mL monolithic stationary phase was synthesized and functionalized with amino groups from 2-Chloro-N,N- diethylethylamine hydrochloride for anion-exchange isolation of a plasmid DNA (pDNA) that encodes a malaria vaccine candidate, VR1020-PyMSP4/5. Physical characterization of the monolithic polymer showed a macroporous material with a modal pore diameter of 750 nm. The final vaccine product isolated after 3 min elution was homogeneous supercoiled plasmid with gDNA, RNA and protein levels in keeping with clinical regulatory standards. Toxicological studies of the pVR1020-PyMSP4/5 showed a minimum endotoxin level of 0.28 EU/m.g pDNA. This cost-effective technique is cGMP compatible and highly scalable for the production of DNA-based vaccines in commercial quantities, when such vaccines prove to be effective against malaria. © 2008 American Institute of Chemical Engineers.

A thermal expulsion approach to homogeneous large-volume methacrylate monolith preparation; enabling large-scale rapid purification of biomolecules

Numerous efforts have been dedicated to the synthesis of large-volume methacrylate monoliths for large-scale biomolecules purification but most were obstructed by the enormous release of exotherms during preparation, thereby introducing structural heterogeneity in the monolith pore system. A significant radial temperature gradient develops along the monolith thickness, reaching a terminal temperature that supersedes the maximum temperature required for structurally homogenous monoliths preparation. The enormous heat build-up is perceived to encompass the heat associated with initiator decomposition and the heat released from free radical-monomer and monomer-monomer interactions. The heat resulting from the initiator decomposition was expelled along with some gaseous fumes before commencing polymerization in a gradual addition fashion. Characteristics of 80 mL monolith prepared using this technique was compared with that of a similar monolith synthesized in a bulk polymerization mode. An extra similarity in the radial temperature profiles was observed for the monolith synthesized via the heat expulsion technique. A maximum radial temperature gradient of only 4.3°C was recorded at the center and 2.1°C at the monolith peripheral for the combined heat expulsion and gradual addition technique. The comparable radial temperature distributions obtained birthed identical pore size distributions at different radial points along the monolith thickness.

Morphology of Nylon 6/Acrylonitrile-Butadiene-Styrene Blends Compatibilized by a Methyl Methacrylate/Maleic Anhydride Copolymer

The morphologies of nylon 6/acrylonitrile-butadiene-styrene blends compatibilized with a methyl methacrylate/maleic anhydride copolymer, with 3-20 wt % maleic anhydride, were examined by transmission electron microscopy. Some staining techniques were employed for identifying the various phases. The binary blends were immiscible and exhibited poor mechanical properties that stemmed from the unfavorable interactions among their molecular segments. This produced an unstable and coarse phase morphology and weak interfaces among the phases in the solid state. The presence of the copolymer in the blends clearly led to a more efficient dispersion of the acrylonitrile-butadiene-styrene phase and consequently optimized Izod impact properties. © 2003 Wiley Periodicals, Inc.

Effect of compatibilizer in acrylonitrile-butadiene-styrene toughened nylon 6 blends: Ductile-brittle transition temperature

The ductile-brittle transition temperatures were determined for compatibilized nylon 6/acrylonitrile-butadiene-styrene (PA6/ABS) copolymer blends. The compatibilizers used for those blends were methyl methacrylate-co-maleic anhydride (MMA-MAH) and MMA-co-glycidyl methacrylate (MMA-GMA). The ductile-brittle transition temperatures were found to be lower for blends compatibilized through maleate modified acrylic polymers. At room temperature, the PA6/ABS binary blend was essentially brittle whereas the ternary blends with MMA-MAH compatibilizer were supertough and showed a ductile-brittle transition temperature at -10°C. The blends compatibilized with maleated copolymer exhibited impact strengths of up to 800 J/m. However, the blends compatibilized with MMA-GMA showed poor toughness at room temperature and failed in a brittle manner at subambient temperatures.

Hygrotermal effects evaluation using the losipescu shear test for glare laminates

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Chromatographic techniques for the determination of free phenol in foundry resins

Phenol is a toxic compound present in a wide variety of foundry resins. Its quantification is important for the characterization of the resins as well as for the evaluation of free contaminants present in foundry wastes. Two chromatographic methods, liquid chromatography with ultraviolet detection (LC-UV) and gas chromatography with flame ionization detection (GC-FID), for the analysis of free phenol in several foundry resins, after a simple extraction procedure (30 min), were developed. Both chromatographic methods were suitable for the determination of phenol in the studied furanic and phenolic resins, showing good selectivity, accuracy (recovery 99–100%; relative deviations <5%), and precision (coefficients of variation <6%). The used ASTM reference method was only found to be useful in the analysis of phenolic resins, while the LC and GC methods were applicable for all the studied resins. The developed methods reduce the time of analysis from 3.5 hours to about 30 min and can readily be used in routine quality control laboratories.

Experimental studies on comparison of microwave curing and thermal curing of epoxy resins used for alternative mould materials

In this present work attempts have been made to study the glass transition temperature of alternative mould materials by using both microwave heating and conventional oven heating. In this present work three epoxy resins, namely R2512, R2515 and R2516, which are commonly used for making injection moulds have been used in combination with two hardeners H2403 and H2409. The magnetron microwave generator used in this research is operating at a frequency of 2.45 GHz with a hollow rectangular waveguide. In order to distinguish the effects between the microwave and conventional heating, a number of experiments were performed to test their mechanical properties such as tensile and flexural strengths. Additionally, differential scanning calorimeter technique was implemented to measure the glass transition temperature on both microwave and conventional heating. This study provided necessary evidences to establish that microwave heated mould materials resulted with higher glass transition temperature than the conventional heating. Finally, attempts were also made to study the microstructure of microwave-cured materials by using a scanning electron microscope in order to analyze the morphology of cured specimens.

Fumaric acid monoethyl ester-functionalized poly(D,L-Lactide)/N-vinyl-2- pyrrolidone Resins for the preparation of tissue engineering scaffolds by stereolithography

Polymer networks were prepared by photocross-linking fumaric acid monoethyl ester (FAME) functionalized, three-armed poly(D,L-lactide) oligomers using Af-vinyl-2-pyrrolidone (NVP) as diluent and comonomer. The use of NVP together with FAME-functionalized oligomers resulted in copolymerization at high rates, and networks with gel contents in excess of 90 were obtained. The hydrophilicity of the poly(D,L-lactide) networks increases with increasing amounts of NVP, networks containing 50 wt of NVP absorbed 40 of water. As the amount of NVP was increased from 30 to 50 wt , the Young's modulus after equilibration in water decreased from 0.8 to 0.2 GPa, as opposed to an increase from 1.5 to 2.1 GPa in the dry state. Mouse preosteoblasts readily adhered and spread onto all prepared networks. Using stereolithography, porous structures with a well-defined gyroid architecture were prepared from these novel materials. This allows the preparation of tissue engineering scaffolds with optimized pore architecture and tunable material properties.

Designed biodegradable hydrogel structures prepared by stereolithography using poly(ethylene glycol)/poly(D,L-lactide)-based resins

Designed three-dimensional biodegradable poly(ethylene glycol)/poly(D,L-lactide) hydrogel structures were prepared for the first time by stereolithography at high resolutions. A photopolymerisable aqueous resin comprising PDLLA-PEG-PDLLA-based macromer, visible light photo-initiator, dye and inhibitor in DMSO/water was used to build the structures. Porous and non-porous hydrogels with well-defined architectures and good mechanical properties were prepared. Porous hydrogel structures with a gyroid pore network architecture showed narrow pore size distributions, excellent pore interconnectivity and good mechanical properties. The structures showed good cell seeding characteristics, and human mesenchymal stem cells adhered and proliferated well on these materials.