Improving the thermal and mechanical properties of poly(propylene carbonate) by incorporating functionalized graphite oxide

Poly(propylene carbonate) (PPC) is a new biodegradable aliphatic polycarbonate. However, the poor thermal stability, low glass transition temperatures (T_g), and relatively low mechanical property have limited its applications. To improve the thermal and mechanical properties of PPC, functionalized graphite oxide (MGO) was synthesized and mixed with PPC by a solution intercalation method to produce MGO/PPC composites. A uniform structure of MGO/PPC composites was confirmed by X‐ray diffraction and scanning electron microscope. The thermal and mechanical properties of MGO/PPC composites were investigated by thermal gravimetric analysis, differential scanning calorimetric, dynamic mechanical analysis, and electronic tensile tester. Due to the nanometer‐sized dispersion of layered graphite in polymer matrix, MGO/PPC composites exhibit improved thermal and mechanical properties than pure PPC. When the MGO content is 3.0 wt %, the MGO/PPC composites shows the best thermal and mechanical properties. These results indicate that nanocomposition is an efficient and convenient method to improve the properties of PPC. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

双(三氯甲基)碳酸酯的合成

介绍双（三氯甲基）碳酸酯的合成机理及３种合成方法：溶剂法,非溶剂法,循环法。     

CO_2/环氧丙烷共聚合成聚碳酸亚丙酯多元醇

利用双金属氰化物作为催化剂,催化CO2/环氧丙烷调节共聚制备聚碳酸亚丙酯多元醇(PPC),详细考察了催化剂用量、相对分子质量调节剂及其用量、CO2用量等对聚合的影响.研究发现PPC的相对分子质量与相对分子质量调节剂的用量成线性关系,可以根据需要合成具有规定相对分子质量的PPC树脂.最后提出聚合过程中碳酸丙烯酯可能按照解拉链的方式生成.     

Orientation microstructure and properties of poly(propylene carbonate)/poly(butylene succinate) blend films

The blends of high molecular weight poly(propylene carbonate) (PPC) and poly(butylene succinate) (PBS) were melt blended using triphenylmethane triisocyanate (TTI) as a reactive coupling agent. TTI also serves as a compatibilizer for the blends of PPC and PBS. The blend containing 0.36 wt % TTI showed that the optimal mechanical properties were, therefore, calendared into films with different degrees of orientation. The calendering condition, degree of orientation, morphologies, mechanical properties, crystallization, and thermal behaviors of the films were investigated using wide‐angle X‐ray diffraction, scanning electron microscopy, tensile testing, and differential scanning calorimetry (DSC) techniques. The result showed that the as‐made films exhibited obvious orientation in machine direction (MD). Both tensile strength in MD and the tear strength in transverse direction (TD) increased with increasing the degree of orientation. The orientation of the film also increased the crystallinity and improved the thermal properties of the PPC/PBS blend films. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

碳酸双（三氯甲酯）的合成和应用

综述了碳酸双（三氯甲酯）（ＢＴＣ）的制法、性质及其应用。     

A water dispersed Titanium dioxide/poly(carbonate urethane) nanocomposite for protecting cultural heritage: Preparation and properties

A water dispersed Titanium dioxide/poly(carbonate urethane) nanocomposite was prepared by means of cold mixing of single components via sonication. The work was aimed at achieving a new material with properties suitable for eco-sustainable applications in cultural heritage as protective coating. The nanocomposite water dispersion prepared was subsequently deposited on Petri dish and, after water casting at room temperature, homogeneous, transparent, colourless film samples were obtained. TGA, DSC, DMTA, ATR-FTIR, FESEM and WAXS techniques were then applied in order to investigate the thermal and visco-elastic behaviours along with morphology and structure of the nanocomposite. Moreover, through methylorange decomposition, an azoic dye representative of environmental pollution, a photocatalytic test was set up on nanocomposite film samples assessing that the 1% (wt/wt) content of Titanium dioxide nanoparticles was able to confer self-cleaning ability. Interrelationships among structure, properties and uses in conservation of this kind of nanomaterial were appraised.     

熔融酯交换法合成异山梨醇型聚碳酸酯

以碳酸二苯酯和异山梨醇为原料,通过熔融酯交换合成了异山梨醇型聚碳酸酯。考察了催化剂的种类及其用量、温度、压力以及原料配比对产品性能的影响。采用傅立叶变换红外光谱仪、热重分析仪和凝胶渗透色谱仪分别对产物的结构、热稳定性和分子量进行了表征。结果表明,以四乙基氢氧化铵(TEAH)为催化剂,催化剂用量为4.75×10~(–4) mol/mol异山梨醇,原料配比1∶1,缩聚温度245℃,预聚压力0.03 MPa,合成产品的特性黏度为34.61 m L/g,数均分子量为12 219,透明度良好,具有较高的热稳定性。     

Sustainable and biodegradable poly(butylene succinate-co-terephthalate)/poly(propylene carbonate) blown films with enhanced compatibility,mechanical, and barrier properties

In this study, a novel environment-friendly PBST/PPC-based blown film was prepared using maleic anhydride (MA) as a reactive compatibilizer to enhance the compatibility between poly(butylene succinate-co-terephthalate) (PBST) and poly(propylene carbonate) (PPC). Results of rheological testing and gel permeation chromatography (GPC) indicated that MA reacted with PBST/PPC during melt-blending extrusion. Morphological analysis of the cryo-fractured surfaces of PBST/PPC blend showed significantly improved compatibility between PBST and PPC with the addition of MA. Moreover, the Young's modulus, tensile strength, breaking strain, and tear strength of PBST/PPC/MA blown films increased with an increase in MA content. In comparison to PBST/MA blown film without PPC, the barrier property of PBST/PPC/MA blown films was improved. In addition, in vitro cell experiments showed that the PBST/PPC/MA blown film was suitable for the growth of mouse fibroblast (L929) cells. In vitro ecotoxicity testing on mung bean plant showed that the extracts from the PBST/PPC/MA blown film had no negative effects on the development of mung bean plant. Furthermore, degradability testing in soil also proved that the PBST/PPC/MA blown film had good biodegradability. Thus, the PBST/PPC/MA blown film can be used in fields, such as food packaging and agricultural mulch film.     

Preparation and properties of biodegradable thermoplastic starch/poly(hydroxy butyrate) blends

The vital differences using three types of thermoplastic starches (TPS), including potato starch, corn starch, and soluble potato starch, with two different gelatinization degrees to blend with poly(hydroxy butyrate) (PHB) are thoroughly discussed in this study. For blends containing a certain amount of PHB, thermal stability remains in a certain degree. In all cases of this study, mechanical properties of TPS blended with PHB confer higher performance than those of pristine TPS. In particular, a significant increase on tensile strength and tear strength is observed for TPS (potato starch) blended with PHB at low gelatinization degree. A suitable degree of gelatinization of starch is critical to achieve optimum performance. The investigation on the morphological observation partly features the supporting evidence of the above findings. The assessment of biodegradability indicates that the values of water absorption and weight loss increase with increasing treatment period and glycerol content, but decrease with increasing amount of PHB content. Among three types of starches investigated, the TPS (soluble starch)/PHB blend gives the highest level of water absorption and weight loss. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2371–2379, 2006     

三光气法合成取代苯异氰酸酯

以三光气和取代苯胺为原料,合成10种取代苯异氰酸酯。并且对原料的摩尔比、反应溶剂和引发剂等因素对收率的影响进行了研究,研究表明,当三光气与苯胺的摩尔比为1∶2,引发剂为三乙胺,溶剂为甲苯、1,2-二氯乙烷或者乙酸乙酯,反应时间为3.5~5.5 h的情况下,取代苯异氰酸酯产率为69.7%~92.4%。     

Preparation and characterization of poly(propylene carbonate)/exfoliated graphite nanocomposite films with improved thermal stability,mechanical properties and barrier properties

Relatively high aspect ratio exfoliated graphite (EFG) particles with an average size of 7.4 µm and a nanometer sized thickness of 30–50 nm were successfully prepared by thermal treatment at 1050 °C and subsequent ultrasonication for application as a filler to improve the physical properties of eco‐friendly poly(propylene carbonate) (PPC). A series of poly(propylene carbonate)/exfoliated graphite (PPC/EFG) nanocomposite films with different EFG contents were prepared via a solution blending method. The physical properties were strongly dependent upon the chemical and morphological structures originating from the differences in EFG composition. The morphological structures, thermal properties, mechanical properties and barrier properties of the nanocomposite films were investigated as a function of the EFG content. While all of the PPC/EFG nanocomposite films exhibited good dispersion of EFG to some extent, Fourier transform infrared and SEM results revealed that solution blending did not lead to strong interactions between PPC and EFG. As a result, poor dispersion occurred in composite films with a high EFG content. By loading EFG particles, the oxygen permeabilities, moisture permeabilities and water uptake at equilibrium decreased as the EFG content increased. Compared with pure PPC, PPC/EFG nanocomposite films have enhanced molecular ordering. Specifically, the 2% PPC/EFG composite film shows greater molecular ordering than the other composite films, which results in the highest mechanical strength. In future work, the compatibility and dispersion of the PPC matrix polymer and EFG filler particles should be increased by modifying the EFG surface or introducing additives. © 2013 Society of Chemical Industry     

Poly(2,2-dimethyltrimethylene carbonate)-block-poly(dimethylsiloxane)-block-poly(2,2-dimethyltrimethylene carbonate). Synthesis and thermal properties

Lithium salts of hydroxytelechelic poly(dimethylsiloxane) [poly-(DMS)] were used as initiators for the anionic ring-opening polymerization of 2,2-dimethyltrimethylene carbonate (DTC). Triblock copolymers were obtained in high yields. Complexation of the active site in DTC polymerization by the poly(DMS) chain leads to a decrease in polymerization rate. The thermal properties of the copolymers of different compositions were determined. Catalysed thermal degradation of the block copolymers leads to cyclic oligomers D_n and DTC upon ring-closing depolymerization.     

Improved thermal stability and mechanical properties of poly(propylene carbonate) by reactive blending with maleic anhydride

To extend the application of a carbon dioxide sourced environmental friendly polymer: poly (propylene carbonate) (PPC), a small amount of maleic anhydride (MA) was melt blended to end‐cap with PPC to improve its thermal stability and mechanical properties. Thermal and mechanical properties of end‐capped PPC were investigated by TGA, GPC, mechanical test, and DMA. TGA and titration results demonstrate that PPC can be easily end‐capped with MA through simple melt blending. TGA results show that the thermal degradation temperature of PPC could be improved by around 140°C by adding MA. GPC measurement indicates that the molecular weight of PPC can be maintained after blending with MA, where pure PPC experiences a dramatic degradation in molecular weight during melt process. More importantly, the tensile strength of PPC after blending with MA was found to be nearly eight times higher than that of pure PPC. It has approached the mechanical properties of polyolefin polymers, indicating the possibility of replacing polyolefin polymers with PPC for low temperature applications. The method described here could be used to extend the applications of PPC and fight against the well known global warming problem. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Crystallization and melting behavior of blends comprising poly(3‐hydroxy butyrate‐co‐3‐hydroxy valerate) and poly(ethylene oxide)

Blends of poly(3‐hydroxy butyrate‐co‐3‐hydroxy valerate) (PHBV) and poly(ethylene oxide) (PEO) were prepared by casting from chloroform solutions. Crystallization kinetics and melting behavior of blends have been studied by differential scanning calorimetry and optical polarizing microscopy. Experimental results reveal that the constituents are miscible in the amorphous state. They form separated crystal structures in the solid state. Crystallization behavior of the blends was studied under isothermal and nonisothermal conditions. Owing to the large difference in melting temperatures, the constituents crystallize consecutively in blends; however, the process is affected by the respective second component. PHBV crystallizes from the amorphous mixture of the constituents, at temperatures where the PEO remains in the molten state. PEO, on the other hand, is surrounded during its crystallization process by crystalline PHBV regions. The degree of crystallinity in the blends stays constant for PHBV and decreases slightly for PEO, with ascending PHBV content. The rate of crystallization of PHBV decreases in blends as compared to the neat polymer. The opposite behavior is observed for PEO. Nonisothermal crystallization is discussed in terms of a quasi‐isothermal approach. Qualitatively, the results show the same tendencies as under isothermal conditions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2776–2783, 2006     

Partially miscible poly(lactic acid)‐ blend‐poly(propylene carbonate) filled with carbon black as conductive polymer composite

BACKGROUND: Conductive polymer composites (CPCs) can be obtained by filling polymer matrices with electrically conductive particles, and have a wide variety of potential applications. In the work reported, the biodegradable polymer poly(lactic acid) (PLA) as a partially miscible blend with poly(propylene carbonate) (PPC) was used as a polymer matrix. Carbon black (CB) was used as the conducting filler. RESULTS: Fourier transform infrared spectroscopy revealed interactions between matrix and CB filler; this interaction was stronger in PPC‐blend‐CB than in PLA‐blend‐CB composites. A rheology study showed that low‐viscosity PPC could improve the fluidity of the CPCs, but decrease that of CB. With increasing CB content, the enforcement effect, storage modulus and glass transition temperature increased, but the elongation at break decreased. CPCs exhibited the lowest electrical percolation thresholds of 1.39 vol.% CB when the content of PPC in PLA‐blend‐PPC was 40 wt%. The conductivity of CPCs containing 5.33 vol.% CB and 40 wt% PPC reached 1.57 S cm^?1. Scanning electron microscopy revealed that CB exhibits a preference for dispersion in the low‐viscosity phase (PPC) of the multiphase matrix. CONCLUSION: In the presence of CB, partially miscible PLA‐blend‐PPC could form multi‐percolation CPCs. Moreover, the combination of PLA and PPC with CB broadens novel application of both renewable polymers and CPCs. Copyright © 2008 Society of Chemical Industry     

Studies on the blends of CO2 copolymer. IV. Natural rubber/poly(propylene carbonate) systems

The blends of a carbon dioxide copolymer, poly(propylene carbonate)(PPC) with natural rubber (NR), were prepared and their mechanical properties and morphology were studied. The optimum formulation blend was obtained by orthogonal experiments. The tensile strength of the blend containing 30 phr PPC was 18.9 MPa, with an elongation at break of 755%. The factors such as PPC and dicumyl peroxide content, PPC molecular weight, sulfur content, curing time, and curing temperature responsible for controlling the mechanical properties were discussed. Transverse electron micrographs showed a two‐phase structure for this blend. Gel content data revealed that PPC was crosslinked. The phase stability of PPC in the blend improved because of the interpenetrating new work structure. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2140–2144, 2002     

Miscibility,morphology and mechanical properties of rubber‐modified biodegradable poly(ester‐urethanes)

Biodegradable, lactic acid based amorphous poly(ester‐urethane)s (PEU) were modified with poly(L‐lactic acid‐co‐ϵ‐caprolactone‐urethane) elastomer (P[LA/CL]U) by melt blending. The phase separation of P(LA/CL)U elastomer with three different ϵ‐caprolactone (CL) compositions (CL content 30, 50, and 70 mol %) and the mechanical properties of the resulting impact‐modified linear and branched PEU were investigated. The amounts of P(LA/CL)U elastomer in the PEU blends were 10, 15, 20, and 30 wt %. Dynamic mechanical thermal analysis (DMTA) of the blends with P(LA50/CL50)U and P(LA30/CL70)U elastomers revealed separate glass transition temperatures for rubber and matrix, indicating phase separation. No phase separation was found for P(LA70/CL30)U elastomer. The effect of mixing rate and temperature during processing on composite properties was tested by blending P(LA30/CL70)U rubber with PEU under various processing conditions. Impact modification studies were also made with two P(LA30/CL70)U elastomers having different amounts of functional groups. The influence of end‐functionalization and cross‐linking on mechanical properties was investigated in blends containing PEU and 15 wt % of these elastomers. Scanning electron microscopy (SEM) showed the morphology to change dramatically with increase in the degree of cross‐linking in the rubber. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1074–1084, 2000     

聚碳酸亚酯多元醇在涂料中的应用

介绍了新型环保涂料中间体材料──聚碳酸亚酯多元醇的生产合成与应用,揭示了其在水性工业涂料中的功用。介绍了国内研发和生产该材料的企业或单位,对其未来市场需求作了重点说明和分析。     

Synthesis and thermal properties of poly(urethane‐imide)

The synthesis and thermal properties of thermoplastic poly(urethane‐imide) (PUI) resins were studied. Model reaction studies on the reactions of 4,4′‐diphenylcarbamatodiphenylmethane and 4,4′‐diisocyanatodiphenylmethane with phthalic anhydride were performed. We found that the reaction of anhydrides with urethane groups could take place under certain reaction conditions. According to the model reaction studies, N‐2‐methyl‐pyrrolidone was employed as a solvent, and no catalyst was used in the polymerization. To restrain the side reaction of anhydrides with urethane groups, we adopted a two‐step chain‐extending procedure in a chain‐extending reaction. The inherent viscosity of PUI was 0.83–0.99 dL/g. The prepared polymers not only exhibited improved solubility in organic solvents but also formed flexible films. Thermogravimetric analysis showed that PUI exhibited a two‐step thermal weight‐loss pattern. The first step of the thermal degradation of PUI was attributed to the thermooxidizing cleavage of weak and labile linkage, such as urethane groups, isopropylidene, and methylene, except for imide rings. The polymer inherent viscosity decreased sharply during the first step of thermal degradation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 773–781, 2001     

Solvent effects on the miscibility of poly(methyl methacrylate)/poly(bisphenol a carbonate) blends

Blends of atactic or syndiotactic poly(methyl methacrylate) (designated as aPMMA or sPMMA) and poly(bisphenol A carbonate) (PC) were prepared from solution casting. Tetrahydrofuran (THF) and chloroform were used as solvent. Experimental results indicated that the as‐cast blends from THF were quite different from the chloroform‐cast ones. After film preparation, THF‐cast blends did not show any visible phase separation. However, chloroform‐cast blends formed a phase‐separated structure. The as‐cast PC from either solvent was not completely amorphous, and had a melting point at 239–242°C, indicating a certain degree of crystallinity. In contrast, the quenched samples of aPMMA/PC blends prepared from the two solvents behaved virtually the same. They both showed aPMMA dissolves better in PC, but PC solubility in aPMMA is very little. Using sPMMA instead of aPMMA to blend with PC, different results were obtained. The quenched sPMMA/PC blends cast from THF showed only one T_g. However, immiscibility (i.e., two T_gs) was found in the same blend system when cast from chloroform. THF was believed to cause the observation of single T_g due to the following kinetic reason. sPMMA and PC were still trapped together even after THF removal in a homogeneous, but nonequilibrium state below the glass transition. Therefore, the quenched sPMMA/PC blends were not truly thermodynamically miscible. From the results of aPMMA or sPMMA with PC, increasing syndiotacticity seemed to improve the miscibility between PMMA and PC. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2842–2850, 2001