Thermal,mechanical and rheological properties of biodegradable poly(propylene carbonate) and poly(butylene carbonate) blends

Poly(propylene carbonate)(PPC) was melt blended in a batch mixer with poly(butylene carbonate)(PBC) in an effort to improve the toughness of the PPC without compromising its biodegradability and biocompatibility. DMA results showed that the PPC/PBC blends were an immiscible two-phase system. With the increase in PBC content, the PPC/PBC blends showed decreased tensile strength, however, the elongation at break was increased to 230% for the 50/50 PPC/PBC blend. From the tensile strength experiments, the Pukanszky model gave credit to the modest interfacial adhesion between PPC and PBC, although PPC/PBC was immscible. The impact strength increased significantly which indicated the toughening effects of the PBC on PPC. SEM examination showed that cavitation and shear yielding were the major toughening mechanisms in the blends subjected the impact tests. TGA measurements showed that the thermal stability of PPC decreased with the incorporation of PBC. Rheological investigation demonstrated that the addition of PBC reduced the value of storage modulus, loss modulus and complex viscosity of the PPC/PBC blends to some extent. Moreover, the addition of PBC was found to increase the processability of PPC in extrusion. The introduction of PBC provided an efficient and novel toughened method to extend the application area of PPC.     

Synthesis and Properties of Poly(butylene carbonate-co-spirocyclic carbonate)

Poly(butylene carbonateXPBC) has significantly promising applications as a degradable material in the field of polymers, while its poor thermal performance and low crystallization rate are its main defects. To overcome these shortcomings, a series of poly(butylene carbonate-co-spirocyclic carbonateXPBSC) copolymers were synthesized from diphenyl carbonate, 1,4-butanediol and spiroglycol via two-step polycondensation reactions, using magnesium oxide as a catalyst. Differential scanning calorimetry(DSC) results indicated that the glass transition temperature(Tg) values of PBSC copolymers were enhanced from -19℃ to 56℃ with rising the spiroacetal moiety content. Thermogravimetric analysis(TGA) results showed that the resulting PBSCs have a higher thermal stability than that of poly(butylene carbonate). Wide angle X-ray diflraction(WXRD) patterns were characterized to investigate the crystallization behaviour of PBSCs. Tensile testing demonstrated that copolymerization of spiroacetal moieties into PBC chains imparted PBSC with favourable mechanical performance. Typically, PBSC 30 had a tensile modulus of (1735±430) MPa, a tensile strength of (42±5) MPa and an elongation of 504%±36%.     

Thermal,Rheological and Mechanical Properties of Biodegradable Poly(propylene carbonate)/Epoxidized Soybean Oil Blends

Biodegradable poly(propylene carbonate)(PPC)/epoxidized soybean oil(ESO) blends with different component ratios were prepared by melt blending to improve the performance of PPC. The phase morphology, thermal properties, rheological properties and mechanical properties of the blends were investigated in detail. SEM examination revealed good interfacial adhesion between PPC matrix and ESO.According to DSC and DMA, as the content of ESO increased, the glass transition temperature of the PPC compone...     

氯化聚丙撑碳酸酯增容聚丙撑碳酸酯/秸秆粉复合材料的制备及性能

聚丙撑碳酸酯(PPC)是一种新型热塑性生物降解材料,但其热性能及力学性能较差,应用受到限制。以秸秆粉这种农作物副产品作为增强体改性PPC,既可以提高PPC的力学性能同时又可开发利用秸秆资源。氯化聚丙撑碳酸酯(CPPC)是聚丙撑碳酸酯(PPC)经过氯化得到的,对天然纤维表面具有良好的浸润性和粘结性。本文以CPPC为增容剂,通过熔融共混法制备了PPC/秸秆粉复合材料。采用扫描电子显微镜(SEM)、拉伸实验、动态力学性能测试(DMA)及转矩流变仪对复合材料的结构及性能进行了表征,重点考察了CPPC的添加量对复合材料力学和流变性能的影响。结果表明,当CPPC质量分数为1.8%时,可使添加质量分数为30%秸秆粉的PPC复合材料拉伸强度提高38%,模量提高30%。同时,CPPC的引入使复合材料的粘度下降,改善了PPC/秸秆粉复合材料的加工性能。因此,作为增容剂的CPPC为制备高性能PPC/天然纤维复合材料提供了新的解决办法。     

聚碳酸亚丙酯的化学改性

利用温室气体二氧化碳(CO2)与环氧化合物共聚制备具有生物可降解性的脂肪族聚碳酸酯是近年来聚合物科学领域的研究热点之一。其中最受关注的是CO2和环氧丙烷(PO)的交替共聚物-聚碳酸亚丙酯(PPC)。由于PPC的分子间作用力比较弱,致使其热性能和力学性能较差,限制了其规模化生产与应用。三元共聚、嵌段共聚、接枝、扩链、交联和封端等化学方法是调控PPC链结构进而改善其性能的最直接最有效途径。本文对这一研究领域的进展情况进行了综述,探讨了化学改性过程中面临的挑战和问题,指出了未来发展的新趋势,以期促进PPC的开发和应用。     

Biodegradable poly(propylene carbonate)/layered double hydroxide composite films with enhanced gas barrier and mechanical properties

Relatively well crystallized and high aspect ratio Mg-Al layered double hydroxides(LDHs) were prepared by coprecipitation process in aqueous solution and further rehydrated to an organic modified LDH(OLDH) in the presence of surfactant. The intercalated structure and high aspect ratio of OLDH were verified by X-ray diffraction(XRD) and scanning electron microscopy(SEM). A series of poly(propylene carbonate)(PPC)/OLDH composite films with different contents of OLDH were prepared via a melt-blending method. Their cross section morphologies, gas barrier properties and tensile strength were investigated as a function of OLDH contents. SEM results show that OLDH platelets are well dispersed within the composites and oriented parallel to the composite sheet plane. The gas barrier properties and tensile strength are obviously enhanced upon the incorporation of OLDH. Particularly, PPC/2%OLDH film exhibits the best barrier properties among all the composite films. Compared with pure PPC, the oxygen permeability coefficient(OP) and water vapor permeability coefficient(WVP) is reduced by 54% and 17% respectively with 2% OLDH addition. Furthermore, the tensile strength of PPC/2%OLDH is 83% higher than that of pure PPC with only small lose of elongation at break. Therefore, PPC/OLDH composite films show great potential application in packaging materials due to its biodegradable properties, superior oxygen and moisture barrier characteristics.     

Effect of poly(vinyl acetate) (PVAc) on thermal behavior and mechanical properties of poly(3-hydroxybutyrate)/poly(propylene carbonate) (PHB/PPC) blends

To assess the compatibility of blends of synthetic poly(propylene carbonate) (PPC), with a natural bacterial poly(3-hydroxybutyrate) (PHB), a simple casting procedure of blend was used. poly(3-hydroxybutyrate)/poly(propylene carbonate) blends are found to be incompatible according to DSC and DMA analysis. In order to improve the compatibility and mechanical properties of PHB/PPC blends, poly(vinyl acetate) (PVAc) was added as a compatibilizer. The effects of PVAc on the thermal behavior, morphology, and mechanical properties of 70PHB/30PPC blend were investigated. The results show that the melting point and the crystallization temperature of PHB in blends decrease with the increase of PVAc content in blends, the loss factor changes from two separate peaks of 70PHB/30PPC blend to one peak of 70PHB/30PPC/12PVAc blend. It is also found that adding PVAc into 70PHB/30PPC blend can decrease the size of dispersed phase from morphology analysis. The result of tensile properties shows that PVAc can increase the tensile strength and Young’s modulus of 70PHB/30PPC blend, and both the elongation at break and the tensile toughness increase significantly with PVAc added into 70PHB/30PPC.     

Fully biodegradable blends of poly(butylene succinate) and poly(butylene carbonate): Miscibility, thermal properties, crystallization behavior and mechanical properties

Fully biodegradable poly(butylene succinate) (PBS) and poly(butylene carbonate) (PBC) blends were prepared by melt blending. Miscibility, thermal properties, crystallization behavior and mechanical properties of PBS/PBC blends were investigated by scanning electron microscopy (SEM), phase contrast optical microscopy (PCOM), differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD) and mechanical properties tests. The SEM and PCOM results indicated that PBS was immiscible with PBC. The WAXD results showed that the crystal structures of both PBS and PBC were not changed by blending and the two components crystallized separately in the blends. The isothermal crystallization data showed that the crystallization rate of PBS increased with the increase of PBC content in the blends. The impact strength of PBS was improved significantly by blending with PBC. When the PBC content was 40%, the impact strength of PBS was increased by nearly 9 times.     

不同催化剂作用下聚乳酸/聚碳酸亚丙酯的酯交换反应

选用辛酸亚锡[Sn(Oct)₂]和钛酸四丁酯(TBT)作为聚乳酸(PLA)/聚碳酸亚丙酯(PPC)的酯交换反应催化剂, 研究了溶液条件下单一催化剂及复合催化剂对PLA/PPC酯交换反应的催化作用. 通过对反应产物的分子结构、 热力学及流变学行为进行分析, 结果发现, 无论在单一催化剂还是复合催化剂作用下, PLA与PPC分子间均发生了酯交换反应, 同时伴随着断链反应. 其中, 当Sn(Oct)₂作为单一催化剂或Sn(Oct)₂/TBT作为复合催化剂时, 样品更倾向发生断链反应而非显著的酯交换反应. 进一步分析纯样品在催化剂Sn(Oct)₂或TBT作用下的反应情况, 结果发现, PPC在反应最初阶段以高分子量的分子链断链为主, 且会发生明显的解拉链降解, 从而导致PLA/PPC在等质量比时酯交换反应程度不高, 这为今后更好地研究PLA/PPC酯交换反应提供了思路.     

Rheological,thermal and mechanical properties of biodegradable poly(propylene carbonate)/polylactide/Poly(1,2-propylene glycol adipate) blown films

Poly(propylene carbonate)(PPC) was blended with polylactide(PLA) and poly(1,2-propylene glycol adipate)(PPA) using a twin screw extruder. Then the PPC/PLA/PPA films were prepared using the blown film technique. DMA results showed that PPA could act as a plasticizer and improve the miscibility between PPC and PLA. Crystal morphology displayed that blending PLA with the amorphous PPC led to a decrease of the spherulite size of PLA. The results of mechanical tests indicated that PPC-rich films showed high elongation at break and PLA-rich films showed high tear strength and good optical properties. The content of PPC and PLA significantly affected the physical properties of the films. With increasing PPC content, the melt strengths of the PPC/PLA/PPA films were enhanced. These findings contributed to the biodegradable materials application for designing and manufacturing polymer packaging.     

水辅助加工法制备聚丙撑碳酸酯/淀粉共混物

分别采用普通熔融共混法和水辅助加工法,制备了具有不同共混形态的聚丙撑碳酸酯(PPC)/淀粉共混物,并研究了淀粉分散形态对共混物的玻璃化转变温度(Tg)、流变以及力学性能的影响。研究结果表明,采用普通熔融共混法时,淀粉未发生糊化,并以原颗粒状分散于基体中;而采用水辅助加工法时,淀粉发生糊化,并在挤出过程中原位形成纤维结构。当淀粉以纤维形式分散于PPC基体中时,其与PPC间的界面接触面积显著增加,二者的相互作用增强,PPC/淀粉共混物的Tg、储能模量以及复合黏度显著提高。力学性能测试结果表明,当淀粉质量分数为30%,采用水辅助加工法制备的PPC/淀粉共混物的拉伸模量相比于纯PPC提高了67.7%。     

Miscibility and Crystallization in Binary Crystalline Blends of Poly(butylene terephthalate) with Poly(butylene terephthalate-e-caprolactone)

Poly(butylene terephthalate)/poly(butylene terephthalate-e-caprolactone) is a new A/AxB1-x binary crystalline blend with intra-molecular repulsion interaction. Using the mean-field binary interaction model, the value of interaction parameter between the butylene terephthalate and caprolactone structural unit was first reported to be 0.305. This blend exhibited different crystallization behavior from a typical homopolymer/copolymer blend, which was carefully investigated by di?erential scanning calorimetry. It was found that poly(butylene terephthalate-e-caprolactone) copolymers have a great effect on the pure poly(butylene terephthalate) chain mobility and poly(butylene terephthalate) crystalline lattice packing. In the meantime, the crystallization of butylene terephthalate segments in copolymers was restricted by the previously formed poly(butylene terephthalate) crystallites. The two constituents for blending can not form a co-crystal in the range of composition even if they have the same butylene terephthalate unit. It can be concluded that longersegments in a copolymer would be beneficial for the formation of a co-crystal in blends.     

线性聚酯酰胺对聚碳酸亚丙酯的改性

通过己内酯和氨基己酸开环、缩合反应制备了酯段含量为81%的线性聚酯酰胺（PEA）,并用熔融共混的方法制备了PEA/聚碳酸亚丙酯（PPC）共混物,考察了PEA的引入对共混体系相容性、热力学稳定性和机械性能的影响。 结果表明,PEA与PPC之间有较好的相容性,共混物的热力学稳定性比PPC有显著提高,当PEA质量分数为3%时,共混体系的起始分解温度（T-5%）和最大分解速率时的温度（Tmax）比PPC分别提高了52.7%和46.4%。 通过调节PEA的含量可以使共混体系同时达到增强和增韧的效果。     

生物可降解聚丁二酸/甲基丁二酸丁二酯系列共聚物的合成和表征

摘要合成了一系列聚丁二酸/甲基丁二酸丁二醇共聚酯(PBSM), 利用DSC, ¹H NMR和X射线衍射等方法对共聚物组成、 热学性能、 结晶性能、 等温结晶行为进行了研究. 结果表明, 引入甲基丁二酸共聚单元较为显著地改变了聚丁二酸丁二酯(PBS)的热学性能, 利用Hoffman\|Weeks方程得到的共聚物平衡熔点随共聚物的组分含量增加而降低, 玻璃化转变温度亦有所降低, 熔点则符合无规共聚物的Flory方程. 此外, 利用Avrami方程分别研究了均聚物PBS及共聚物PBSM-20的等温结晶行为, 结果表明, 在所研究的温度范围内, 聚酯结晶速率随温度升高而降低, PBS和PBSM\-20的Avrami指数分别介于2.8~3.0和2.7~3.0之间, 结晶方式为三维生长异相成核, 而X射线衍射测试结果表明晶体结构几乎不变.     

聚碳酸丙烯酯中碳酸丙烯酯含量的测定

建立了气相色谱分析聚碳酸丙烯酯中碳酸丙烯酯含量的方法,该方法操作简单,准确度高,可满足工业检测需求.     

聚丙撑碳酸酯的辐射效应

研究了室温条件下聚丙撑碳酸酯(PPC)在钴-60和电子加速器辐照过程中的响应行为。结果表明,聚丙撑碳酸酯是一种辐射裂解型聚合物,其分子量随着辐射剂量的增加而减小。1mm厚PPC片材在室温和N2气保护条件下,其裂解G值为Gs,γ-ray=10.81;Gs,EB=4.9。不同的裂解G值表明,O2气在聚丙撑碳酸酯的辐射裂解过程中有重要影响。红外光谱研究表明,辐射后聚丙撑碳酸酯在3474cm-1处的峰宽峰高增加,表明其裂解后端—OH基增加。由于裂解作用,辐射后聚丙撑碳酸酯的抗张强度和断裂伸长率均下降。在通常的辐射消毒剂量范围内(25~50kGy),PPC的保留抗张强度大于23MPa,断裂伸长率大于4%,裂解后试样的力学性能依然能够满足实际应用需要,因此PPC可以经受辐射消毒。     

Thermal,Mechanical and Rheological Properties of Eco-friendly Poly（propylene carbonate）/Poly（1,2-propylene succinate） Blends

In order to improve the flexibility of poly（propylene carbonate） （PPC）, poly（1,2-propylene succinate） （PPSu） was used to plasticize PPC in a batch mixer. The effects of PPSu on the miscibility, thermal stability, mechanical and theological properties of the blends were investigated. PPC was partially miscible with PPSu. It was demonstrated that PPSu decreased the glass transition temperature and melt viscosity of PPC, as shown in the DSC and rheological curves. With the increase in PPSu content, the PPC/PPSu blends showed decreased tensile strength, however, the elongation at break was increased to 1100% for the 70/30 PPC/PPSu blend. The introduction of PPSu provided an efficient and novel plasticization method to extend the application area of PPC.     

聚碳酸1,2-丙二酯/聚琥珀酸丁二酯/邻苯二甲酸二烯丙酯共混体系的研究

采用熔融共混的方法制备了聚碳酸1,2-丙二酯(PPC)/聚琥珀酸丁二酯(PBS)共混物和PPC/PBS/DAOP(邻苯二甲酸二烯丙酯)增塑共混物,对共混物的相容性、热性能、结晶性和物理机械性能进行了初步研究.研究结果表明PPC/PBS共混物为不相容体系,PPC对PBS的结晶度影响很小;PBS的加入提高了共混物的起始热分解温度(Td-5%),当共混物中PBS含量从10%增加到90%时,共混物的Td-5%可分别增加15℃到59℃.DAOP对PPC/PBS共混物有增塑作用,当PPC/PBS/DAOP的比例从30/70/0变化到30/70/30时,共混物玻璃化转变温度(Tg)下降了36.9℃.与PPC/PBS共混物相比,组成优化的DAOP增塑共混物PPC/PBS/DAOP(PPC/PBS/DAOP=30/70/5)的断裂伸长率和断裂能最大可提高31倍和34倍,分别达到655.1%和3.4 J/mm2,因此引入DAOP尽管使共混材料的热稳定性有所下降,但拓宽了PPC/PBS共混材料的使用温度窗口.     

Thermal and weathering degradation of poly(propylene carbonate)

High molecular-weight poly(propylene carbonate) (PPC) can remain intact upon storage in ambient air or in water for 8 months once the catalyst is completely removed. Catalyst-free pure PPC is also thermally stable below 180 °C. At 200 °C, degradation occurs, mainly due to attack of the chain-ended hydroxyl group onto a carbonate linkage, through which the molecular weight distribution is broadened by simultaneous formation of low and high molecular weight fractions. Incomplete removal of hydrogen peroxide generated during the catalyst preparation results in a prepared polymer that contains a substantial amount of polymer chains grown biaxially from hydrogen peroxide, which gives rise to more severe thermal degradation. Experiments conducted in a weathering chamber at high temperature (63 °C) and high humidity (50%) revealed another degradation process involving chain scission through an attack of water molecules onto the carbonate linkage, which progressively and temporally lowers molecular weight.