Graft copolymers of starch and poly(ethyl acrylate) dilution effects

Graft copolymerization of ethyl acrylate onto starch initiated by ceric ion in an aqueous medium was studied at 29°C. It was found that the grafting frequencies and molecular weights of grafted poly(ethyl acrylate) changed from 2 graft polymer molecules per 10⁴ anhydroglucose units (AGU) and 3.03 · 10⁵ to 34 and 6.80 · 10⁵, respectively, when the starch content was varied from 1.0 wt.-% to 0.2 wt.-%. The influence of dilution of ceric ion on the extent and rate of graft polymerization of ethyl acrylate onto starch was also examined.     

Preparation of poly(lactic acid) and modified starch composites

In this article, the pretreatment before extrusion between the PLA and the modified starch was researched. The research on the composites of PLA and the modified starch focused on improving its compatibility and mechanical properties. The pretreatment samples were characterized by solid ¹³C-NMR and the chemical titration of the carboxyl end (–COOH) groups in PLA. The results illuminated that the pretreatment reaction was successful and the –COOH in PLA had reacted with the –OH in modified starch. The compatibility of the composites was determined by differential scanning calorimetry and scanning electron microscopy. The results showed that pretreatment could improve the compatibility of the composites. The mechanical properties of the composites were also enhanced. This approach is identified as a reasonable method to produce commercial PLA/modified starch composites with economical feasibility.     

Interpenetrating polymer networks from castor oil based polyurethanes and poly(ethyl acrylate)

Polyurethanes were obtained by the reaction of hydroxyl groups of castor oil with hexamethylene diisocyanate, isophorone diisocyanate or diphenylmethane diisocyanate using an NCO/OH ratio of 1.6. These polyurethanes were swollen in ethyl acrylate monomer and subsequently polymerized by radical polymerization initiated with benzoyl peroxide in the presence of the crosslinking agent ethylene glycol dimethacrylate. A series of interpenetrating polymer networks (PU/PEA IPNs) were obtained as tough films by casting in glass moulds. The characteristics of these films were determined: resistance to chemical reagents, thermal behaviour (DSC, TGA), tensile strength, Young's modulus, elongation at break (%) and Shore A hardness. The morphology was determined by scanning electron microscopy, and the dielectric properties such as electrical conductivity, dielectric constant (ε′), dielectric loss (ε″) and loss tangent (tan δ) were studied.     

Biodegradable polymer blends of poly(3-hydroxybutyrate) and starch acetate

The thermal behaviour and phase morphology of poly(3-hydroxybutyrate) (PHB) and starch acetate (SA) blends have been studied by differential scanning calorimetry, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy and polarizing optical microscopy. PHB/SA blends were immiscible. The melting temperatures of PHB in the blends showed some shift with increase of SA content. The melting enthalpy of the PHB phase in the blend was close to the value for pure PHB. The glass transition temperatures of PHB in the blends remained constant at 9°C. The FTIR absorptions of hydroxyl groups of SA and carbonyl groups of PHB in the blends were found to be independent of the second component at 3470cm^-1 and 1724cm^-1, respectively. The crystallization of PHB was affected by the addition of the SA component both from the melt on cooling and from the glassy state on heating. The temperature and enthalpy of non-isothermal crystallization of PHB in the blends were much lower than those of pure PHB. The crystalline morphology of PHB crystallized from the melt under isothermal conditions varied with SA content. The cold crystallization peaks of PHB in the blends shifted to higher temperatures compared with that of pure PHB. ©1997 SCI     

Interpenetrating polymer networks from caster oil-based-polyurethanes and poly(ethyl acrylate). VII

Liquid prepolyurethanes were synthesized from castor oil and toluene-2, 4-diisocyanate (TDI) under different experimental conditions and varying NCO/OH ratios. All these prepolyurethanes were subsequently reacted with ethyl acrylate/ethylene glycol dimethacrylate mixtures by radical polymerization using benzoyl peroxide as initiator to obtain interpenetrating polymer networks (IPNs) by transfer molding. The novel polyurethane/poly(ethyl acrylate) IPNs are found to be tough films. These IPNs are characterized in terms of their resistance to chemical reagents, thermal behavior (DSC, TGA), mechanical behavior including tensile strength, Young's modulus, and elongation. The dielectric properties, namely electrical conductivity (σ), dielectric constant (ε′), dielectric loss (ε″), and loss tangent (tan δ) were computed. The mechanothermal behavior was analyzed by dynamic mechanical spectroscopy. The morphological behavior was studied by scanning electron microscopy.     

Synthesis of porous poly(hydroxamic acid) from poly(ethyl acrylate-co-divinylbenzene)

Summary Porous poly(hydroxamic acid) resins were prepared by suspension polymerization of poly(ethyl acrylate-co-divinylbenzene) followed by the reaction with hydroxylamine via nucleophilic substitution. Various degree of dilution and crosslinking ratio were applied to obtain suitable material for use as a chelating polymer. The effects of degree of dilution and crosslinking ratio on the surface morphology, hydroxamic acid group content, and apparent density were investigated in detail.     

Nanoparticles of alkylglyceryl dextran and poly(ethyl cyanoacrylate) for applications in drug delivery: Preparation and characterization

Toward the development of drug carriers that are capable of crossing biological membranes, controlled emulsion polymerization has been utilized to produce nanoparticulate carriers from the combination of poly(alkyl cyanoacrylate) and alkylglyceryl dextran to a molecular structure designed to combine the nonimmunogenic and stabilizing properties of dextran with the demonstrated permeation enhancing ability of alkylglycerols. To this aim, a systematic series of alkylglyceryl dextrans have been synthesized and functionalized with ethyl or butyl cyanoacrylates to form stable polymeric nanocarriers (100–500?nm). Results of investigations into their capability to act as controlled-release devices and their cytotoxicity against bEnd3 cells are reported.     

PBTA/TPS共混物的结构、性能和断裂行为

将热塑性淀粉(TPS)与聚(对苯二甲酸丁二醇酯-己二酸丁二醇酯)(PBAT)挤出共混并注塑成型,制备了可完全生物降解的TPS/PBAT复合材料制品。采用扫描电子显微镜研究了注塑复合材料的层次结构与微观形态,测试了不同组分复合材料的性能和应力应变行为。结果表明：TPS在PBAT中呈皮芯结构分布,随含量增加逐渐由芯层向皮层分布。当含量为45%时,芯层到皮层形成均匀的以纤维为主的分散相形态,提高了复合材料的力学性能。加入TPS后会改变复合材料的形变行为,由类似半结晶聚合物的应力应变行为转变为屈服-冷拉行为。     

Dynamic mechanical behavior of chlorosubstituted derivatives of poly(ethyl methacrylate) and poly(ethyl acrylate)

A freely oscillating torsional pendulum was used in the investigation of the influence of trichloroethyl, tetrachloroethyl, trichloromethoxyethyl, and trichloroethoxyethyl side groups on the molecular mobility in the glassy state and on the glass transition temperature of poly(meth)acrylates. All the polymers under study, which may be used as fire retardants, exhibit a simple relaxation behavior. While the parameters of the low-temperature and secondary relaxation process in the glassy state are not noticeably affected by the substituents used, the glass transition temperature T_g, increases with rising polarity and volume of side chains. The increase is larger in the series of polyacrylates, so that differences in the softening temperatures of polymethacrylates and polyacrylates having the same side chains decrease considerably with growing substitution.     

Conducting polymer composites: Polypyrrole and poly(vinyl chloride-vinyl acetate) copolymer

Composites of a polypyrrole (PPy) and poly(vinyl chloride-vinyl acetate) copolymer (PVC-PVA) were prepared both chemically and electrochemically. An insulating polymer was retained in the blend and the thermal stability of the polymer was enhanced by polymerizing pyrrole into the host matrix in both cases. The composites prepared electrochemically gave the best results in terms of conductivity and air stability. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 667–671, 1997     

High-resolution thermogravimetric analysis of polyurethane/poly(ethyl methacrylate) interpenetrating polymer networks

Thermal degradation of a series of polyurethane/poly(ethyl methacrylate) interpenetrating polymer networks and their constituent networks were studied by three modes of thermogravimetric analysis: the conventional method, the constant reaction rate method, and the dynamic rate technique. The best understanding of the degradation mechanism was achieved by the last method, which allows much better resolution of overlapping events. In addition, the weight losses correspond well with the results obtained from the constant reaction rate analysis, but are achieved in shorter times. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 287–295, 1998     

Biodegradable polymer blends of poly(L‐lactic acid) and gelatinized starch

Gelatinized starches were prepared with various content of glycerol and were investigated in terms of the effect of the glycerol addition on characteristics of starch and its blends. Poly (L‐lactic acid) (PLA) with various ratios of linear/star shaped PLA and starch gelatinized with various ratios of water/glycerol were melt‐blended by using twin screw mixer. The blends were characterized by DSC thermal analysis, tensile test and morphological analysis. Gelatinization of starch was found to lead to destruction or diminution of hydrogen bonding in granules and a decrease of crystallinity of starch. DSC data showed that starch played a role as a nucleating agent and glycerol as plasticizer contributed to an improvement in crystallinity in PLA blends. When the content of starch increased, the size of spherulites in PLA blends was smaller and less regular. In the case of PLA/pure starch blends, the voids appeared, which were formed by the separation of starch particles from the matrix. But for PLA/gelainized starch blends, these voids were not observed. In the case of blends with linear PLA and starch gelatinized with water/glycerol ratio of 100/40, the greatest superiority of mechanical properties was shown and the toughness was improved compared with PLA/pure starch blends.     

可降解材料聚(己二酸二甲基硅基酯)的合成及表征

以己二酸和二甲基-二乙酰氧基硅烷为单体,采用熔融缩聚法合成了聚(己二酸二甲基硅基酯),并通过1H-核磁共振、差示扫描量热法、热重分析、凝胶渗透色谱对聚合物进行了表征。结果表明,聚(己二酸二甲基硅基酯)的重均分子量为4 021,分子量分布指数为2.10,玻璃化转变温度为-42.186℃,热稳定性较好,其在四氢呋喃水溶液中不稳定,随着放置时间的延长,降解速率变缓。     

可降解材料聚(二甲基硅基草酸酯)的合成及表征

以草酸与二甲基-二乙酰氧基硅烷为单体,采用熔融缩聚法合成了聚(二甲基硅基草酸酯),并通过~1H-核磁共振、差示扫描量热法、热重分析、凝胶渗透色谱对聚合物进行了表征.结果表明,聚(二甲基硅基草酸酯)的特性黏数为0.173 mL/g、数均分子量为28 496、分子量分布指数为1.38,其主链中存在结晶区,且热稳定性高.     

Recycling of poly(ethylene terephthalate) as polymer‐polymer composites

Microfibrillar reinforced composites (MFC) comprising an isotropic matrix from a lower melting polymer reinforced by microfibrils of a higher melting polymer were manufactured under industrially relevant conditions and processed via injection molding. Low density polyethylene (LDPE) (matrix) and recycled poly(ethylene terephthalate) (PET) (reinforcing material) from bottles were melt blended (in 30/70 and 50/50 PET/LDPE wt ratio) and extruded, followed by continuous drawing, pelletizing and injection molding of dogbone samples. Samples of each stage of MFC manufacturing and processing were characterized by means of scanning electron microscopy (SEM), wide‐angle X‐ray scattering (WAXS), dynamic mechanical thermal analysis (DMTA), and mechanical testing. SEM and WAXS showed that the extruded blend is isotropic but becomes highly oriented after drawing, being converted into a polymer‐polymer composite upon injection molding at temperatures below the melting temperature of PET. This MFC is characterized by an isotropic LDPE matrix reinforced by randomly distributed PET microfibrils, as concluded from the WAXS patterns and SEM observations. The MFC dogbone samples show impressive mechanical properties—the elastic modulus is about 10 times higher than that of LDPE and about three times higher than reinforced LDPE with glass spheres, approaching the modulus of LDPE reinforced with 30 wt% short‐glass fibers (GF). The tensile strength is at least two times higher than that of LDPE or of reinforced LDPE with glass spheres, approaching that of reinforced LDPE with 30 wt% GF. The impact strength of LDPE increases by 50% after reinforcement with PET. It is concluded that: (i) the MFC approach can be applied in industrially relevant conditions using various blend partners, and (ii) the MFC concept represents an attractive alternative for recycling of PET as well as other polymers.     

Preparation and properties of biodegradable poly(propylene carbonate)/starch composites

Biodegradable composites of poly(propylene carbonate) (PPC) reinforced with unmodified cornstarch were compounded in a batch mixer followed by compression molding. The effects of reinforcement on the morphology, static and dynamic mechanical properties, as well as thermal properties of PPC/starch composites, were investigated. Tensile tests showed that incorporation of starch improves the stiffness and tensile strength of composites significantly. Scanning electron microscopic examination revealed the existence of good interfacial adhesion between the fillers and PPC matrix. Moreover, experimental results indicated that the starch addition leads to a significant improvement in the thermal stability of the composites. This paper demonstrates that the incorporation of low‐cost and biodegradable cornstarch into PPC provided a practical way to produce completely biodegradable and cost‐competitive composites with good mechanical properties. Polym. Eng. Sci. 44:2134–2140, 2004. © 2004 Society of Plastics Engineers.     

丙烯酸接枝淀粉基可降解紫外光固化高吸水性树脂的制备与性能

以丙烯酸接枝淀粉为基体,不饱和聚酯酰胺脲树脂为交联剂制备出一种可降解高吸水性树脂,该树脂不加任何光引发剂即可紫外光固化成膜。研究了树脂的吸水速率及交联剂的加入量、光固化时间对产品吸水率的影响。结果表明,该高吸水性树脂对不同溶液均具有较好的吸收能力,吸水速度较快,在蒸馏水、自来水、0.9%NaCl溶液、0.9%KCl溶液中的吸水率分别为905,3501,00,120 g/g;10 min内对蒸馏水的吸收倍率达200 g。该高吸水性树脂的降解从表面开始,逐渐向里面降解。     

Glass-rubber transition behavior and compatibility of polymer pairs: Poly(ethyl acrylate) and poly(methyl methacrylate)

A series of interpenetrating polymer networks were prepared containing PMMA and PEA as their two components. Corresponding telomer mixtures and random copolymers were also prepared for comparison purposes. The glass-rubber transition studies were made via shear modulus and dilatometric measurements. The results indicate one very broad transition for the IPN's rather than two transitions expected for incompatible polymer pairs. An interpretation based on the compatibility or near-compatibility of the PEA/PMMA pair is offered.     

Synthesis and characterization of sequential interpenetrating polymer networks of novolac resin and poly(ethyl acrylate)

Interpenetrating polymer networks (IPN) of Novolac/poly(ethyl acrylate) have been prepared via in situ sequential technique of IPN formation. Both full and semi IPNs were characterized with respect to their mechanical properties that is, ultimate tensile strength (UTS), percentage elongation at break, modulus, and toughness. Physical properties of these were evaluated in terms of hardness, specific gravity, and crosslink density. Thermal behavior was studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The morphological features were observed by an optical microscope. There was a gradual decrease in modulus and UTS, with consequent increases in elongation at break and toughness for both types of IPNs with increasing proportions of PEA. An inward shift and lowering (with respect to pure phenolic resin) of the glass transition temperatures of the IPNs with increasing proportions of PEA were observed, thus, indicating a plasticizing influence of PEA on the rigid, brittle, and hard matrix of crosslinked phenolic resin. The TGA thermograms exhibit two‐step degradation patterns. An apparent increase in thermal stability at the initial stages, particularly, at lower temperature regions, was followed by a substantial decrease in thermal stability at the higher temperature region under study. As expected, a gradual decrease in specific gravity and hardness values was observed with increase in PEA incorporation in the IPNs. A steady decrease in crosslink densities with increase in PEA incorporation was quite evident. The surface morphology as revealed by optical microscope clearly indicates two‐phase structures in all the full and semi IPNs, irrespective of acrylic content. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006