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.     

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.     

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.     

Isothermal Crystallization Kinetics and Crystalline Morphologies of Poly(butylene adipate-co-butylene 1,4-cyclohexanedicarboxylate) Copolymers

In this study, the isothermal crystallization kinetics and crystalline morphology of poly(butylene adipate-co-butylene 1,4-cyclohexanedicarboxylate)(PBAC), which refers to a copolyester containing a non-planar ring structure, were investigated by differential scanning calorimetry and polarized optical microscopy, and compared with those of neat poly(butylene 1,4-cyclohexanedicarboxylate)(PBC). The results indicate that the introduction of butylene adipate(BA) unit into PBAC did not change the intrinsical crystallization mechanism. But, the crystallization rate and ability, and equilibrium melting temperature of PBAC copolymers were reduced. All PBC and PBAC copolymers could only form high density of nucleation from melt at given supercooling, while no Maltese cross or ring-banded spherulites could be observed. PBAC copolymers with a high amount of BA unit became amorphous after quenching with liquid nitrogen from melt, while PBC and PBAC copolymers with a low amount of BA unit could still form a large amount of nuclei under the same treatment.     

聚(碳酸丁二醇酯-co-三环癸烷二甲醇碳酸酯)的制备与性能

采用熔融酯交换和缩聚两步法,合成了以1,4-丁二醇、4,8-三环[5.2.1.0(2,6)]癸烷二甲醇和碳酸二苯酯为原料的聚(碳酸丁二醇酯-co-三环癸烷二甲醇碳酸酯)(PBTCx, x为进料中TCD占二元醇总量的百分比)。用1H NMR和13C NMR对PBTCs的微观结构和组成进行了表征。采用GPC、 DSC、 XRD、 TG对PBTCs的分子量、玻璃化转变温度(Tg)、热稳定性等进行了研究。结果表明,PBTCs的Mw为10500~124800 g?mol-1, Mn为6300~73000 g?mol-1, PDI为1.59~1.73; PBTCs呈无定形态、Tg为-3.43 ℃~70.90 ℃, PBTCs表现出比PBC更高的热稳定性。薄膜拉伸试验结果表明,PBTC30(拉伸强度为33.54 MPa,断裂伸长率为275.69%)和PBTC40(拉伸强度为32.13 MPa,断裂伸长率为294.63%)具有较高的强度和韧性,在薄膜材料中具有一定的应用潜力。     

Improvement of thermal stability,crystallinity and degradation of poly(butylene carbonate) by incorporation of bio‐based poly(ethylene sebacate) segment

Multiblock poly(carbonate‐co‐esters) (PBC‐PESe) containing poly(butylene carbonates) (PBC) and bio‐based poly(ethylene sebacate) (PESe) had been synthesized successfully by chain‐extension of dihydroxyl terminated PBC (PBC‐OH) and PESe (PESe‐OH) using 1,6‐hexmethylene diisocyanate as chain extender. The chemical structures, molecular weights, crystallization behaviors, and thermal and degradation properties of the copolymers were all characterized by proton nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, gel permeation chromatography, differential scanning calorimetry, polarized optical microscope, thermogravimetry analysis, water contact angle, and hydrolytic degradation. The resulting copolymers PBC‐PESe all had a sole glass transition temperature (Tg), indicating the two segments, PBC and PESe, were well compatible in the amorphous phase. PESe segment acted a significant role on enhancing the thermal degradation temperature and hydrolytic degradation rate of multiblock copolymers. And the crystallization rate of PBC got dramatically accelerated after PESe segment was incorporated. However, the crystallization mechanism did not change. Furthermore, the mechanical properties of multiblock copolymers could be adjusted by changing the feed composition. Copyright © 2017 John Wiley & Sons, Ltd.     

Isothermal Crystallization Kinetics and Crystalline Morphologies of Poly(butylene adipate-<Emphasis Type="Italic">co</Emphasis>-butylene 1,4-cyclohexanedicarboxylate) Copolymers

In this study,the isothermal crystallization kinetics and crystalline morphology of poly(butylene adipate-co-butylene 1,4-cyclohexanedicarboxylate) (PBAC),which refers to a copolyester containing a non-planar ring structure,were investigated by differential scanning calorimetry and polarized optical microscopy,and compared with those of neat poly(butylene 1,4-cyclohexanedicarboxylate) (PBC).The results indicate that the introduction ofbutylene adipate (BA) unit into PBAC did not change the intrinsical crystallization mechanism.But,the crystallization rate and ability,and equilibrium melting temperature of PBAC copolymers were reduced.All PBC and PBAC copolymers could only form high density of nucleation from melt at given supercooling,while no Maltese cross or ring-banded spherulites could be observed.PBAC copolymers with a high amount of BA unit became amorphous after quenching with liquid nitrogen from melt,while PBC and PBAC copolymers with a low amount of BA unit could still form a large amount of nuclei under the same treatment.     

二氧化碳/1,2-环氧丁烷/ε-己内酯的三元共聚合和表征

以高聚物负载型双金属负离子配位化合物PBM为催化剂,通过二氧化碳(CO2),1,2-环氧丁烷(BO)与ε-己内酯(CL)的三元开环共聚合反应,得到三元共聚物,脂肪族聚碳酸酯(PBCL).对PBCL进行了FTIR1、H-NMR1、3C-NMR、DSC和WAXD等表征,并考察了反应单体比例及反应时间对共聚物性能的影响.结果表明,由于ε-己内酯开环共聚,引入了易水解的羧酸酯单元,PBCL的降解速度和玻璃化转变温度较二氧化碳-环氧丁烷的二元共聚物(PBC)得到了有效地提高.同时,PBCL相对于聚己内酯(PCL)玻璃化转变温度和降解速度明显改善,且PBCL为非晶结构.     

Properties of biodegradable poly(butylene carbonate) (PBC) composites with fumed silica nanoparticles

Biodegradable poly(butylene carbonate)/fumed silica (PBC/SiO₂) nanocomposites were prepared by melt compounding. The PBC/SiO₂ nanocomposites exhibited a good dispersion of aggregates of SiO₂ in the PBC matrix, and an improvement in mechanical properties. Nanoparticles affect, also, the thermal properties of PBC and especially the crystallization rate, which in all nanocomposites is faster than that of pure PBC. Due to ongoing crystallization and the crystal perfection during heating process, the melting peak of PBC shifted to higher temperature when heating from amorphous state with decreasing heating rate. With increasing cooling rate, the non-isothermal crystallization exotherms became wider and shifted to lower temperature. At a given cooling rate, the crystallization peak temperature of neat PBC was lower than that of its nanocomposite. Non-isothermal crystallization kinetic procedure, the method of Ozawa, was applied to the first deconvoluted DSC peak only by processing the data related to DSC peak. The average value of Ozawa exponent m of pure PBC is 3.04, while the one of its nanocomposite is about 2.98. Moreover, the thermal stability of the nanocomposites was increased. The T _d enhancement of the nanocomposite was remarkable.     

Wide‐angle X‐ray diffraction and differential scanning calorimetry study of the crystallization of poly(ethylene naphthalate), poly(butylene naphthalate), and their copolymers

The crystallization behavior of a series of poly(ethylene‐co‐butylene naphthalate) (PEBN) random copolymers was studied. Wide‐angle X‐ray diffraction (WAXD) patterns showed that the crystallization of these copolymers could occur over the entire range of compositions. This resulted in the formation of poly(ethylene naphthalate) or poly(butylene naphthalate) crystals, depending on the composition of the copolymers. Sharp diffraction peaks were observed, except for 50/50 PEBN. Eutectic behavior was also observed. This showed isodimorphic cocrystallization of the PEBN copolymers. The variation of the enthalpy of fusion of the copolymers with the composition was estimated. The isothermal and nonisothermal crystallization kinetics were studied. The crystallization rates were found to decrease as the comonomer unit content increased. The tensile properties were also measured and were found to decrease as the butylene naphthalate content of the copolymers increased. For initially amorphous specimens, orientation was proved by WAXD patterns after drawing, but no crystalline reflections were observed. However, the fast crystallization of drawn specimens occurred when they were heated above the glass‐transition temperature. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 843–860, 2004     

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.     

聚2,5-呋喃二甲酸乙二醇酯/聚丁二酸丁二醇酯共混物的制备与表征

通过熔融共混制备了聚2,5-呋喃二甲酸乙二醇酯(PEF)/聚丁二酸丁二醇酯(PBS)共混物,探究了制备PEF/PBS共混物的影响因素,考察了共混温度、共混时间、螺杆转速、共混比例对PEF/PBS共混物力学性能的影响因素,并用示差扫描量热仪、热失重、扫描电子显微镜等技术手段对其热性能和相容性进行了表征。 结果表明,当PBS的含量为15%、共混温度为230 ℃,共混时间为90 s、螺杆转速为150 r/min时,为最佳共混制备条件,此时相容性最好,热性能良好,冲击强度和拉伸强度最大,冲击强度相对纯PEF提高了6倍,拉伸强度提高了近20%,从而大幅提高了PEF的冲击强度,有效地增强了PEF的抗冲击韧性。 这些工作为这一生物基聚酯材料的应用提供了可能。     

利用β-环糊精提高聚碳酸1,2-丙二酯的热稳定性

将聚碳酸1,2-丙二酯与β-环糊精在60℃下固相共混,得到了两者的内含复合物.线性的聚碳酸1,2-丙二酯穿入β-环糊精分子空腔形成准聚轮烷结构,导致聚合物分子链的刚性增大,主链上受热易发生断裂的碳酸酯键由于受到环糊精空腔的保护变得稳定,聚碳酸1,2-丙二酯的热稳定性得到提高.实验结果表明,所得内含复合物的玻璃化转变温度(T_g)提高了5℃,在N_2氛围下10%热失重温度(T_(d-10%))增加了33℃.     

聚碳酸1,2-丙二酯/蒙脱土复合材料的制备与性能

利用阳离子交换法,以十六烷基三甲基溴化铵(HTAB)改性钠基蒙脱土制备了有机改性蒙脱土(OMMT),OMMT的层间距达到了2nm,比普通的钠基蒙脱土增加了0.74nm.采用熔融插层法制备了插层-絮凝型PPC/OMMT复合材料,当复合材料中OMMT含量为5wt%时,复合材料的杨氏模量较纯PPC树脂大幅度提高了61.8%,同时玻璃化温度(Tg)提高了2.4℃,热分解温度提高了32.3℃.因此,OMMT对大幅度提高PPC的杨氏模量具有很大的潜力.     

Preparation, characterization and hydrolytic degradation of poly[p-dioxanone-(butylene succinate)] multiblockcopolymer

A series of poly[p-dioxanone-(butylene succinate)] (PPDOBS) copolymers were prepared from p-dioxanone (PDO), 1,4-butanediol and succinate acids through a two-step process including the initial prepolymer preparation of poly(p-dioxanone)diol (PPDO-OH) and poly(butylene succinate)diol (PBS-OH) and the following copolymerization of the two kinds of prepolymers by coupling with hexamethylene diisocyanate (HDI). The molecular structures of the prepared PPDO-OH, PBS-OH and PPDOBS were characterized by hydrogen nuclear magnetic resonance spectroscopy (¹H NMR). The crystallization of the copolymers was investigated by using differential scanning calorimetry (DSC), polarized optical microscopy (POM) and wide angle X-ray diffraction (WAXD). It has been shown that the crystallization rate and the degree of crystallization increases with the increase of the weight fraction of poly(butylene succinate) (PBS) blocks in the copolymers. In phosphate buffer solution with pH 7.4 at 37 °C for 18 weeks, the hydrolytic degradation behaviors of the copolymers were studied. The changes of retention weight, water absorption, pH value, and surface morphologies with the degradation time showed that the hydrolytic degradation rate of PPDOBS could be controlled by adjusting the weight fraction of poly(p-dioxanone) (PPDO) and PBS blocks in the copolymers. The changes of the thermal properties of PPDOBS during the degradation were also investigated by DSC.     

二氧化碳-环氧乙烷-氧化环己烯三元共聚物的制备与性能

采用稀土三元催化剂实现了二氧化碳、氧化环己烯与环氧乙烷的三元共聚,当环氧乙烷和氧化环己烯等摩尔投料时催化活性达到690 g/(mol Zn h),所得三元共聚物的数均分子量达到7.9×104,远程异核多量子相关核磁谱证明所得共聚物主要是无规三元共聚物,其中环氧乙烷-二氧化碳结构单元与氧化环己烯-二氧化碳结构单元相连的全交替结构占26.9%.二氧化碳-氧化环己烯共聚物的脆性导致其熔体加工十分困难,引入环氧乙烷为第三单体进行三元共聚,实现了二氧化碳-氧化环己烯共聚物的增韧,解决了其熔体加工难题,而且改变环氧单体比率能够调节三元共聚物的耐温性能和力学性能,当环氧乙烷与氧化环己烯等摩尔投料时,所得三元共聚物在20℃下的杨氏模量达到(900±17)MPa,拉伸强度为(38±2)MPa,断裂伸长率为(26.3±9.2)%.     

Synergistic Effect of Nucleation and Compatibilization on the Polylactide and Poly(butylene adipate-co-terephthalate) Blend Films

Polylactide(PLA) films blended with 10 wt% poly(butylene adipate-co-terephthalate)(PBAT) were prepared by using a twin screw extruder in the presence of the nucleating agent of titanium dioxide(TiO_2) and the compatibilizers of toluene diisocyanate(TDI) and PLA-grafted-maleic anhydride(PLA-g-MA). The synergistic effect of the nucleation and compatibilization on the properties and crystallization behavior of the PLA/PBAT(PLB) films was explored. The results showed that the addition of TiO_2 significantly enhanced the tensile strength and the impact tensile resistance of the PLB films while slightly decreased its thermal stability. In addition, the compatibilizers of TDI and PLA-g-MA in the system not only affected the crystallinity and cold crystallization process of the PLB films, but also increased the mechanical properties of them due to the improvement of the interfacial interaction between PLA and PBAT revealed by the morphological measurement. The synergistic effects of the nucleating agent and the compatibilizer afforded the blend films with increased tensile strength and impact tensile toughness, improved cold crystallization property and X_c.     

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。     

Structure-activity correlations of calcined Mg-Al hydrocalcites for aliphatic polycarbonate synthesis <Emphasis Type="Italic">via</Emphasis> transesterification process

Mg-Al mixed oxides with different Mg/Al molar ratio were prepared by thermal decomposition of hydrotalcitelike precursors at 500 °C for 5.0 h and used as catalysts for the transesterification of diphenyl carbonate with 1,4-butanediol to synthesize high-molecular-weight poly(butylene carbonate) (PBC). The structure-activity correlations of these catalysts in this transesterification process were discussed by means of various characterization techniques. It was found that the chain growth for the formation of PBC can only be obtained through connecting ―OH and ―OC(C)OC₆H₅ end-group upon removing the generated phenol, and the sample with Mg/Al molar ratio of 4.0 exhibited the best catalytic performance, giving PBC with M _w of 1.64 × 10⁵ g/mol at 210 °C for 3.0 h. This excellent activity depended mainly on the specific surface area and basicity rather than pore structure or crystallite size of MgO.