A biodegradable blend foaming material of poly(butylene adipate-co-terephthalate)(PBAT)/poly(propylene carbonate)(PPC)was successfully prepared by chemical foaming agent and screw extrusion method.First,PBAT was modif...A biodegradable blend foaming material of poly(butylene adipate-co-terephthalate)(PBAT)/poly(propylene carbonate)(PPC)was successfully prepared by chemical foaming agent and screw extrusion method.First,PBAT was modified by bis(tert-butyl dioxy isopropyl)benzene(BIBP)for chain extension,and then the extended PBAT(E-PBAT)was foamed with PPC using a twin(single)screw extruder.By analyzing the properties of the blends,we found that Young’s modulus increased from 58.8 MPa of E-PBAT to 244.7 MPa of E-PBAT/PPC 50/50.The viscosity of the polymer has a critical influence on the formation of cells.Compared with neat PBAT(N-PBAT),the viscosity of E-PBAT increased by 3396 Pa·s and E-PBAT/PPC 50/50 increased by 8836 Pa·s.Meanwhile,the dynamic mechanical analysis(DMA)results showed that the storage modulus(E’)at room temperature increased from 538 MPa to 1650 MPa.The various phase morphologies(“sea-island”,“quasi-co-continuous”and“cocontinuous”)and crystallinity of the blends affected the spread velocity of gas and further affected the foaming morphology in E-PBAT/PPC foam.Therefore,through the analysis of phase morphology and foaming mechanism,we concluded that the E-PBAT/PPC 70/30 component has both excellent strength and the best foaming performance.展开更多
In this paper, melt blends of poly（propylene carbonate） （PPC） with poly（butylene succinate） （PBS） were characterized by dynamic mechanical analysis （DMA）, differential scanning calorimetry （DSC）, tensile t...In this paper, melt blends of poly（propylene carbonate） （PPC） with poly（butylene succinate） （PBS） were characterized by dynamic mechanical analysis （DMA）, differential scanning calorimetry （DSC）, tensile testing, wide-angle X-ray diffraction （WAXD）, polarized optical microscopy and thermogravimetric analysis （TGA）. The results indicated that the glass transition temperature of PPC in the 90/10 PPC/PBS blend was decreased by about 11 K comparing with that of pure PPC. The presence of 10% PBS was partially miscible with PPC. The 90/10 PPC/PBS blend had better impact and tensile strength than those of the other PPC/PBS blends. The glass transition temperature of PPC in the 80/20, 70/30, and 60/40 PPC/PBS blends was improved by about 4.9 K, 4.2 K, and 13 K comparing with that of pure PPC, respectively; which indicated the immiscibility between PPC and PBS. The DSC results indicated that the crystallization of PBS became more difficult when the PPC content increased. The matrix of PPC hindered the crystallization process of PBS. While the content of PBS was above 20%, significant crystallization-induced phase separation was observed by polarized optical microscopy. It was found from the WAXD analysis that the crystal structure of PBS did not change, and the degree of crystallinity increased with increasing PBS content in the PPC/PBS blends.展开更多
A series of aliphatic biodegradable poly（ether-ester）s based on poly（butylene succinate）（PBS）as hard segment and poly（tetramethylene oxide）（PTMO,M_n=1 000 g/mol） as soft segment were synthesized.The composit...A series of aliphatic biodegradable poly（ether-ester）s based on poly（butylene succinate）（PBS）as hard segment and poly（tetramethylene oxide）（PTMO,M_n=1 000 g/mol） as soft segment were synthesized.The composition dependence of thermal behavior,morphology and mechanical properties was investigated by differential scanning calorimetry（DSC）,atomic force microscopy（AFM）,and tensile testing.The crystallization temperature（T_c） and melting temperature（T_m） of the PBS block within poly（ether-ester）s decrease steadily at first,but decrease sharply with PTMO content above 50 wt%.Two crystallization peaks were detected for PTMO in PBSPTMO60 sample,suggesting the occurrence of fractionated crystallization.The crystallization enthalpies（△H_c） and melting enthalpies（△H_m） of PBS block decrease at first,then increase as PTMO content increases further.AFM has demonstrated that phase-separated morphology transforms from a phase of continuous hard matrix to one of continuous soft matrix containing isolated hard domain as PTMO content is increased.Finally,the results of tensile testing show that the poly（ether-ester）s present the behavior of plastics when PTMO content is below 40 wt%,and of thermoplastic elastomers with PTMO content above 50 wt%.By varying the composition of copolymer,the aliphatic poly（ether-ester）s plastics,or especially biodegradable aliphatic poly（ether-ester）s thermoplastic elastomers can be obtained.展开更多
The main aim of this research was to investigate the synergistic influence of additives and poly（butylene succinate）（PBS） in improving both the mechanical and flame retardant properties of polylactide（PLA） blend...The main aim of this research was to investigate the synergistic influence of additives and poly（butylene succinate）（PBS） in improving both the mechanical and flame retardant properties of polylactide（PLA） blends. Tricresyl phosphate（TCP） and montmorillonite（MMT） were the additives used to improve the mechanical characteristics and fire resistance of PLA. Differential scanning calorimetry（DSC） thermograms revealed that the addition of TCP and MMT significantly affected their thermal behaviors. The results of the mechanical and morphological characterizations were in agreement with the changes in thermal behavior. The impact strength and limiting oxygen index（LOI） value of PLA significantly increased with the presence of PBS. The failure mode of the blends as evidenced by scanning electron microscopy（SEM） changed from brittle to ductile. The addition of TCP and MMT produced excellent anti-dripping and self-extinguishing behaviors of the blends, achieving V-0 rating. For the PLA/PBS blends, the synergistic combination of PBS and additives led to an acceleration of cold crystallization, a significant increment of flexibility and impact toughness, and an improvement of flame retardancy.展开更多
Binary biodegradable polymers films, poly(butylene adipate-co-terephthalate)(PBAT) and poly(glycolic acid)(PGA), were prepared through batch melt mixing to obtain Film Ⅰ and Film Ⅱ under two different processing con...Binary biodegradable polymers films, poly(butylene adipate-co-terephthalate)(PBAT) and poly(glycolic acid)(PGA), were prepared through batch melt mixing to obtain Film Ⅰ and Film Ⅱ under two different processing conditions. PGA crystals played a major role in enhancing the mechanical and barrier properties of the films. For Film Ⅰ, there were initial PGA crystals before the film blowing process, the PGA molecular chain further crystallized, forming the oriented crystallization of PGA. Moreover, the Xcand crystalline size in Film Ⅰ were higher than those in Film Ⅱ. Compared with the different processing methods, Film Ⅰ has excellent mechanical and oxygen barrier properties due to the crystallization and orientation. The tensile strength reached 45.0 MPa, and tear strength exceeded 138.2 kN/m, while the elongation at break was as high as 750% for PBAT/PGA 85/15 in Film Ⅰ. The WVTR, WVP coefficients, and OP coefficients of PBAT/PGA films were decreased obviously with increasing the PGA content both in Film Ⅰ and Film Ⅱ. Moreover, the barrier properties of oxygen in Film Ⅰ were better than that in Film Ⅱ. This work reveals a feasible processing technique by introducing of initial crystallization of PGA to blow PBAT/PGA films with excellent mechanical and barrier properties.展开更多
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 biocompatibi...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.展开更多
The effect of PBS on the morphological features of PVDF has been investigated by optical and atomic force microscopies under various conditions. It was found that neat PVDF forms large γform spherulites with extraord...The effect of PBS on the morphological features of PVDF has been investigated by optical and atomic force microscopies under various conditions. It was found that neat PVDF forms large γform spherulites with extraordinarily weak birefringence at 170℃. Adding 30% PBS makes PVDF exhibit intrigued flower-like spherulitic morphology. The growth mechanism was explained by the decrease of the supercooling and the materials dissipation. Increasing the PBS content to 70% favors the formation of ring banded spherulites. Temperature dependent experiments verify the α→γ phase transition occurs from the junction sites of the ot and y crystals, while starts from the centers of α spherulites in the blends. Ring banded structures could be observed in neat PVDF, 70/30 blend and 30/70 blend when crystallized at 155℃, without γ crystals. The band period of PVDF α spherulites increases with crystallization temperature as well as the amount of PBS content. At 140℃, spherulites in neat PVDF lose their ring banded feature, while coarse spherulites consisting of evident lamellar bundles could be found in 30/70 blend.展开更多
The effects of crystallization temperature and blend ratio on the polymorphic crystal structures of poly（butylene adipate） （PBA） in poly（butylene succinate） （PBS）/poly（butylene adipate） （PBS/PBA） blends we...The effects of crystallization temperature and blend ratio on the polymorphic crystal structures of poly（butylene adipate） （PBA） in poly（butylene succinate） （PBS）/poly（butylene adipate） （PBS/PBA） blends were studied by means of differential scanning calorimetry （DSC）, wide-angle X-ray diffraction （XRD） and atomic force microscopy （AFM）. It was revealed that the polymorphism of PBA can be regulated by the blend ratio even in a non-isothermal crystallization process. The results demonstrate that high temperature favors fiat-on α crystals, while low temperature contributes to edge-on β crystals. It was also found that the effect of blend ratio on the crystallization mechanism of PBA is well coincident with that of the crystallization temperature. The increment of PBS content in the PBS/PBA blend gives rise to more β-form crystals of PBA. For those PBS/PBA blends with low PBA content, the interlamellar phase segregation of PBA makes its molecular chains so difficult to diffuse from one isolated microdomain to another that high crystallization temperature and sufficiently long crystallization time will be required if the PBA α-type crystals are targeted.展开更多
Poly(glycolic acid)(PGA)is derived from glycolide obtained by fermenting pineapples or sugarcane,which has excellent gas barrier properties and a small carbon footprint.PGA is a potential substitute for the current al...Poly(glycolic acid)(PGA)is derived from glycolide obtained by fermenting pineapples or sugarcane,which has excellent gas barrier properties and a small carbon footprint.PGA is a potential substitute for the current aluminum-plastic composite films used in high barrier packaging applications.However,its poor ductility and narrow processing window limit its application in food packaging.Herein,poly(butylene succinate-co-butylene adipate)(PBSA)was used to fabricate PGA/PBSA blend films through an in situ fibrillation technique and blown film extrusion.Under the elongational flow field used during the extrusion process,a unique hierarchical structure based on the PBSA nanofibrils and interfacially oriented PGA crystals was obtained.This structure enhances the strength,ductility and gas barrier properties of the PGA/PBSA blend film.In addition,an epoxy chain extender(ADR4468)was used as a compatibilizer to further enhance the interfacial adhesion between PGA and PBSA.70PGA/0.7ADR exhibited a very low oxygen permeability(2.34×10^(-4)Barrer)with significantly high elongating at break(604.4%),tensile strength(47.4 MPa),and transparency,which were superior to those of petroleum-based polymers.Thus,the 70PGA/0.7ADR blown films could satisfy the requirements for most instant foods such as coffee,peanuts,and fresh meat.展开更多
The concern with environmental preservation is a very current and relevant topic. Regarding polymers, the search for potentially ecofriendly matters has been the subject of scientific research. In this context, this w...The concern with environmental preservation is a very current and relevant topic. Regarding polymers, the search for potentially ecofriendly matters has been the subject of scientific research. In this context, this work aimed to study the effect of adding nanocellulose (nCE) with 1, 3, and 5 wt.% on poly(butylene adipate-co-butylene terephthalate) (PBAT). Thermal, structural, relaxometric, and rheological assessments were carried out. Quantitative evaluation of PBAT copolymer by high field NMR revealed 56.4 and 43.6 m.% of the butylene adipate and butylene terephthalate segments, respectively. WAXD measurement on the deconvoluted diffraction patterns identified that nCE was a mixing of Cellulose I and Cellulose II polymorph structures. At any composition, nanocellulose interfered with the PBAT crystallisation process. Also, a series of new PBAT crystallographic planes appeared as a function of nanocellulose content. PBAT hydrogen molecular relaxation varied randomly with nanocellulose content and had a strong effect on the hydrogen relaxation. PBAT cold crystallisation and melting temperatures (T<sub>cc</sub> and T<sub>m</sub>) were almost unchangeable. Although T<sub>cc</sub> did not change during polymer solidification from PBAT molten state, the sample’s degree of crystallinity varied with composition through the transcrystallization phenomenon. Nanocomposite thermal stability decreased possibly owing to the catalytic action of sulfonated amorphous cellulose chains. For the sample with 3 wt.% of nanocellulose, the highest values of complex viscosity and storage modulus were achieved.展开更多
Poly(butylene adipate-co-terephthalate)(PBAT)is a promising biodegradable flexible polymer but suffers from slow crystallization rate,making it less attractive for some applications like the injection-molded products ...Poly(butylene adipate-co-terephthalate)(PBAT)is a promising biodegradable flexible polymer but suffers from slow crystallization rate,making it less attractive for some applications like the injection-molded products in comparison with low-density polyethylene(LDPE).This work aimed to accelerate the crystallization of PBAT by adding a self-assembly nucleating agent octamethylenedicarboxylic dibenzoylhydrazide(OMBH).PBAT/OMBH composites with various OMBH contents(0 wt%,0.5 wt%,0.7 wt%,1 wt%,2 wt%,3 wt%and 5 wt%)were prepared through melt-mixing.The effect of OMBH on the crystallization behavior,morphologies and mechanical properties of PBAT was investigated.The highest nucleation efficiency value of 59.6%was achieved for PBAT with 0.7 wt%OMBH,much higher than that of 22.7%for PBAT with 0.7 wt%talc.Atomic force microscopy results showed that OMBH formed fine fibers and induced the formation of transcrystalline layers of PBAT.Fourier transform infrared spectroscopy(FTIR)combined with two-dimensional correlation spectra suggested that the intermolecular dipole-dipole N—H…O=C interactions but not hydrogen bond between OMBH and PBAT promoted the crystallization of PBAT in the initial period of crystallization.The presence of OMBH did not change the crystal form of PBAT but had positive contribution in enhancing its crystallinity and mechanical properties.This work is essential for preparing PBAT with high crystallization rate,enhancing its potential applications in injection-molded products.展开更多
Mg-A1 mixed oxides with different Mg/A1 molar ratio were prepared by thermal decomposition of hydrotalcite- like precursors at 500 ℃ for 5.0 h and used as catalysts for the transesterification of diphenyl carbonate w...Mg-A1 mixed oxides with different Mg/A1 molar ratio were prepared by thermal decomposition of hydrotalcite- like precursors at 500 ℃ 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/A1 molar ratio of 4.0 exhibited the best catalytic performance, giving PBC with Mw of 1.64 × 105 g/mol at 210℃ 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.展开更多
Poly(butylene adipate-co-terephthalate) (PBAT) is currently the largest commercial biodegradable plastics with good toughness and film forming properties, whereas, the inferior barrier and mechanical properties hinder...Poly(butylene adipate-co-terephthalate) (PBAT) is currently the largest commercial biodegradable plastics with good toughness and film forming properties, whereas, the inferior barrier and mechanical properties hinder its applications. Biodegradable poly(propylene carbonate) (PPC) with excellent barrier properties and high strength is a natural choice to address above issue. However, it is challenging to improve the compatibility of these two polymers. Herein, we prepared a reactive compatibilizer with double bond side group through terpolymerization of CO_(2)/propylene oxide/glycidyl methacrylate to enhance the properties of PBAT/PPC blends. Upon addition of 1 wt% compatibilizer, the PBAT/PPC blends (75/25, W/W) showed an increased water vapor barrier property changed from 424 g·m^(−2)·d^(−1) to 204 g·m^(−2)·d^(−1) compared to the control sample. Moreover, the tensile strength and elongation at break increased from 24.7 MPa to 30.3 MPa and from 858% to 1142%, respectively. The PBAT/PPC composite also displayed excellent biodegradability under composting conditions, as confirmed by the significantly decreased molecular weight. The present work provides an efficient way to barrier biodegradable film from PBAT of practical utilization.展开更多
A cross-linkable comonomer containing a diacetylene group,named dimethyl 4,4＇-（buta-l,3-diyne-l,4-diyl）dibenzoate（DA） was synthesized and copolymerized with dimethyl succinate and 1,4-butanediol to prepare a seri...A cross-linkable comonomer containing a diacetylene group,named dimethyl 4,4＇-（buta-l,3-diyne-l,4-diyl）dibenzoate（DA） was synthesized and copolymerized with dimethyl succinate and 1,4-butanediol to prepare a series of slightly cross-linked PBS copolyesters（PBDASx）.The chemical structure,crystallization and Theological behaviours of PBDASx were well investigated.Compared to neat PBS,PBDASx showed the greatly increased crystallization rate because of the promoting nucleation of the cross-linking domains,and the XRD results indicated that it had no influence on crystallization structure of PBS.The rheological behaviours indicate that PBDASx possessed higher viscosity than neat PBS even at high shear rate and temperature.PBDAS0.3 exhibited better comprehensive properties than neat PBS,which will widen applications of PBS.展开更多
Rare earth （Nd, Y, La, Dy） stearates have been synthesized and used as single component catalysts for the polycondensation of dimethyl terephthalate, adipic acid and 1,4-butanediol for the first time preparing biode...Rare earth （Nd, Y, La, Dy） stearates have been synthesized and used as single component catalysts for the polycondensation of dimethyl terephthalate, adipic acid and 1,4-butanediol for the first time preparing biodegradable poly（butylene adipate-co-terephthalate） （PBAT） with high molecular weight, The microstructures of PBAT were characterized by ^1H NMR spectra. The PBAT exhibits good mechanical properties such as high tensile strength （ca. 20 MPa） and long break elongation （〉700%）.展开更多
Biodegradable poly（butylene succinate） （PBS） and layered double hydroxide （LDH） nanocomposites were prepared via melt blending in a twin-screw extruder. The morphology and dispersion of LDH nanoparticles within ...Biodegradable poly（butylene succinate） （PBS） and layered double hydroxide （LDH） nanocomposites were prepared via melt blending in a twin-screw extruder. The morphology and dispersion of LDH nanoparticles within PBS matrix were characterized by transmission electron microscopy （TEM）, which showed that LDH nanoparticles were found to be well distributed at the nanometer level. The nonisothermal crystallization behavior of nanocomposites was extensively studied using differential scanning calorimetry （DSC） technique at various cooling rates. The crystallization rate of PBS was accelerated by the addition of LDH due to its heterogeneous nucleation effect; however, the crystallization mechanism and crystal structure of PBS remained almost unchanged. In kinetics analysis of nonisothermal crystallization, the Ozawa approach failed to describe the crystallization behavior of PBS/LDH nanocomposites, whereas both the modified Avrami model and the Mo method well represented the crystallization behavior of nanocomposites. The effective activation energy was estimated as a function of the relative degree of crystallinity using the isoeonversional analysis. The subsequent melting behavior of PBS and PBS/LDH nanocomposites was observed to be dependent on the cooling rate. The POM showed that the small and less perfect crystals were formed in nanocomposites.展开更多
Differential scanning calorimetry（DSC） has been widely applied to study crystallization and melting of materials. However, for polymeric lamellar crystals, the melting thermogram during heating process usually exhib...Differential scanning calorimetry（DSC） has been widely applied to study crystallization and melting of materials. However, for polymeric lamellar crystals, the melting thermogram during heating process usually exhibits a broad endothermic peak or even multiple endotherms, which may result from changes of metastability via recrystallization process. Sometimes, the recrystallization exotherm cannot be observed due to its overlapping with the melting endotherm. In this work, we employed a step heating procedure consisting of successive heating and temperature holding stages to measure the metastability of isothermally crystallized poly（butylene succinate）（PBS） crystals. With this approach we could gain the fraction of crystals melted at different temperature ranges and quantitatively detect the melting-recrystallization behavior. The melting-recrystallization behavior depends on the polymer chain structure and the crystallization temperature. For instance, PBS block copolymer hardly shows recrystallization behavior while PBS oligomer and high molecular weight PBS homopolymer demonstrate remarkable melting-recrystallization phenomenon. High molecular weight PBS isothermally crystallized in the low temperature range shows multiple melting-recrystallization while those isothermally crystallized at elevated temperatures do not exhibit observable recrystallization behavior. Furthermore, the melting endotherms were fitted via the melting kinetics equations. The original isothermally crystallized lamellae demonstrate quite different melting kinetics from the recrystallized lamellar crystals that melt at the highest temperature range, which is attributed to the different degrees of stabilization. Finally, the mechanism of melting-recrystallization is briefly discussed. We propose that apparent meltrecrystallization phenomenon be observed when melting of preformed lamellar crystals and recrystallization of thicker lamellae have similar free energy barrier.展开更多
The pyrolysis of poly(ethylene terephthalate)(PET)/poly(butylene terephthalate)(PBT)catalyzed by five alkaline earth metal-based minerals/wastes,namely calcined dolomite,calcite,magnesite,calcium carbide slag(CCS),and...The pyrolysis of poly(ethylene terephthalate)(PET)/poly(butylene terephthalate)(PBT)catalyzed by five alkaline earth metal-based minerals/wastes,namely calcined dolomite,calcite,magnesite,calcium carbide slag(CCS),and ophicalcitum,was conducted by a pyrolyzer-gas chromatography-mass spectrometer(Py-GC-MS)with the objective of recovering benzenes-enriched oil.Compared with magnesium-based catalysts and pure CaO,the calcium-based catalysts with calcium hydroxide as the main component performed better catalytic effect,which could simultaneously promote the hydrolysis of ester products and the decarboxylation of aromatic acids after hydrolysis.For PET,the addition of solid base catalysts at 600℃promoted the complete degradation of aromatic acids and aryl esters,which accounted for 32.6%and 30.7%of the pyrolysis oil,respectively.The content of benzene in oil increased from 8.8%to 31.7%–78.8%.For PBT,the addition of solid base catalysts at 600℃completely decomposed the aromatic acids,which accounted for 67.1%of the pyrolysis oil,and the content of benzene in oil increased from 12.3%to 34.5%–81.0%.During the deoxygenation of polyester pyrolysis products,increasing temperature was more effective for the decomposition/conversion of acetone and tetrahydrofuran,while increasing the alkalinity of the reaction environment contributed to the rapid decrease in acetaldehyde and aryl ketone contents.展开更多
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 rin...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.展开更多
基金financially supported by the National Key Research and Development Program of China(No.2016YFC0501402)Science and Technology Services Network Program of Chinese Science Academy(STS Project)(No.KFJSTS-ZDTP-082)Chinese Academy of Sciences(Changchun Branch)(Nos.2020SYHZ0002 and No.2020SYHZ0047)。
文摘A biodegradable blend foaming material of poly(butylene adipate-co-terephthalate)(PBAT)/poly(propylene carbonate)(PPC)was successfully prepared by chemical foaming agent and screw extrusion method.First,PBAT was modified by bis(tert-butyl dioxy isopropyl)benzene(BIBP)for chain extension,and then the extended PBAT(E-PBAT)was foamed with PPC using a twin(single)screw extruder.By analyzing the properties of the blends,we found that Young’s modulus increased from 58.8 MPa of E-PBAT to 244.7 MPa of E-PBAT/PPC 50/50.The viscosity of the polymer has a critical influence on the formation of cells.Compared with neat PBAT(N-PBAT),the viscosity of E-PBAT increased by 3396 Pa·s and E-PBAT/PPC 50/50 increased by 8836 Pa·s.Meanwhile,the dynamic mechanical analysis(DMA)results showed that the storage modulus(E’)at room temperature increased from 538 MPa to 1650 MPa.The various phase morphologies(“sea-island”,“quasi-co-continuous”and“cocontinuous”)and crystallinity of the blends affected the spread velocity of gas and further affected the foaming morphology in E-PBAT/PPC foam.Therefore,through the analysis of phase morphology and foaming mechanism,we concluded that the E-PBAT/PPC 70/30 component has both excellent strength and the best foaming performance.
基金This work was supported by the National Natural Science Foundation of China(Nos.270274049 and 220374051).
文摘In this paper, melt blends of poly（propylene carbonate） （PPC） with poly（butylene succinate） （PBS） were characterized by dynamic mechanical analysis （DMA）, differential scanning calorimetry （DSC）, tensile testing, wide-angle X-ray diffraction （WAXD）, polarized optical microscopy and thermogravimetric analysis （TGA）. The results indicated that the glass transition temperature of PPC in the 90/10 PPC/PBS blend was decreased by about 11 K comparing with that of pure PPC. The presence of 10% PBS was partially miscible with PPC. The 90/10 PPC/PBS blend had better impact and tensile strength than those of the other PPC/PBS blends. The glass transition temperature of PPC in the 80/20, 70/30, and 60/40 PPC/PBS blends was improved by about 4.9 K, 4.2 K, and 13 K comparing with that of pure PPC, respectively; which indicated the immiscibility between PPC and PBS. The DSC results indicated that the crystallization of PBS became more difficult when the PPC content increased. The matrix of PPC hindered the crystallization process of PBS. While the content of PBS was above 20%, significant crystallization-induced phase separation was observed by polarized optical microscopy. It was found from the WAXD analysis that the crystal structure of PBS did not change, and the degree of crystallinity increased with increasing PBS content in the PPC/PBS blends.
基金Funded by the National Natural Science Foundation of China(No.50873071)the Teaching and Research Award Program for Outstanding Young Professors in Higher Education Institute,MOE,China
文摘A series of aliphatic biodegradable poly（ether-ester）s based on poly（butylene succinate）（PBS）as hard segment and poly（tetramethylene oxide）（PTMO,M_n=1 000 g/mol） as soft segment were synthesized.The composition dependence of thermal behavior,morphology and mechanical properties was investigated by differential scanning calorimetry（DSC）,atomic force microscopy（AFM）,and tensile testing.The crystallization temperature（T_c） and melting temperature（T_m） of the PBS block within poly（ether-ester）s decrease steadily at first,but decrease sharply with PTMO content above 50 wt%.Two crystallization peaks were detected for PTMO in PBSPTMO60 sample,suggesting the occurrence of fractionated crystallization.The crystallization enthalpies（△H_c） and melting enthalpies（△H_m） of PBS block decrease at first,then increase as PTMO content increases further.AFM has demonstrated that phase-separated morphology transforms from a phase of continuous hard matrix to one of continuous soft matrix containing isolated hard domain as PTMO content is increased.Finally,the results of tensile testing show that the poly（ether-ester）s present the behavior of plastics when PTMO content is below 40 wt%,and of thermoplastic elastomers with PTMO content above 50 wt%.By varying the composition of copolymer,the aliphatic poly（ether-ester）s plastics,or especially biodegradable aliphatic poly（ether-ester）s thermoplastic elastomers can be obtained.
基金financially supported by Prince of Songkla University (No.SCI600593S)the Faculty of Science Research Fund,Prince of Songkla University (No.1-2558-02-006)Development and Promotion of Science and Technology Talents Project (DPST)
文摘The main aim of this research was to investigate the synergistic influence of additives and poly（butylene succinate）（PBS） in improving both the mechanical and flame retardant properties of polylactide（PLA） blends. Tricresyl phosphate（TCP） and montmorillonite（MMT） were the additives used to improve the mechanical characteristics and fire resistance of PLA. Differential scanning calorimetry（DSC） thermograms revealed that the addition of TCP and MMT significantly affected their thermal behaviors. The results of the mechanical and morphological characterizations were in agreement with the changes in thermal behavior. The impact strength and limiting oxygen index（LOI） value of PLA significantly increased with the presence of PBS. The failure mode of the blends as evidenced by scanning electron microscopy（SEM） changed from brittle to ductile. The addition of TCP and MMT produced excellent anti-dripping and self-extinguishing behaviors of the blends, achieving V-0 rating. For the PLA/PBS blends, the synergistic combination of PBS and additives led to an acceleration of cold crystallization, a significant increment of flexibility and impact toughness, and an improvement of flame retardancy.
基金supported by the Science and Technology Development Plan of Jilin Province(Nos.20210203199SF and 20210509017RQ)the Science and Technology Development Program of Yantai of China(No.2022ZDCX015)+2 种基金the Chinese Academy of Sciences(Changchun Branch)(Nos.2021SYHZ0044 and 2021SYHZ0042)Science and Technology Bureau of Changchun City of China(Nos.21SH13 and 21KY01)Development and Reform commission of Jilin Province of China(No.2021C039-2).
文摘Binary biodegradable polymers films, poly(butylene adipate-co-terephthalate)(PBAT) and poly(glycolic acid)(PGA), were prepared through batch melt mixing to obtain Film Ⅰ and Film Ⅱ under two different processing conditions. PGA crystals played a major role in enhancing the mechanical and barrier properties of the films. For Film Ⅰ, there were initial PGA crystals before the film blowing process, the PGA molecular chain further crystallized, forming the oriented crystallization of PGA. Moreover, the Xcand crystalline size in Film Ⅰ were higher than those in Film Ⅱ. Compared with the different processing methods, Film Ⅰ has excellent mechanical and oxygen barrier properties due to the crystallization and orientation. The tensile strength reached 45.0 MPa, and tear strength exceeded 138.2 kN/m, while the elongation at break was as high as 750% for PBAT/PGA 85/15 in Film Ⅰ. The WVTR, WVP coefficients, and OP coefficients of PBAT/PGA films were decreased obviously with increasing the PGA content both in Film Ⅰ and Film Ⅱ. Moreover, the barrier properties of oxygen in Film Ⅰ were better than that in Film Ⅱ. This work reveals a feasible processing technique by introducing of initial crystallization of PGA to blow PBAT/PGA films with excellent mechanical and barrier properties.
基金financially supported by the fund of Science&Technology Bureau of Jilin Province of China(No.20126023)the National High Technology Research and Development Program of China(863 Program)(No.2012AA062904)the National Natural Science Foundation of China(No.51021003)
文摘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.
基金financially supported by the National Natural Science Foundations of China(No.20974011)the program of Introducing Talents of Discipline to Universities(No.B08003)
文摘The effect of PBS on the morphological features of PVDF has been investigated by optical and atomic force microscopies under various conditions. It was found that neat PVDF forms large γform spherulites with extraordinarily weak birefringence at 170℃. Adding 30% PBS makes PVDF exhibit intrigued flower-like spherulitic morphology. The growth mechanism was explained by the decrease of the supercooling and the materials dissipation. Increasing the PBS content to 70% favors the formation of ring banded spherulites. Temperature dependent experiments verify the α→γ phase transition occurs from the junction sites of the ot and y crystals, while starts from the centers of α spherulites in the blends. Ring banded structures could be observed in neat PVDF, 70/30 blend and 30/70 blend when crystallized at 155℃, without γ crystals. The band period of PVDF α spherulites increases with crystallization temperature as well as the amount of PBS content. At 140℃, spherulites in neat PVDF lose their ring banded feature, while coarse spherulites consisting of evident lamellar bundles could be found in 30/70 blend.
基金financially supported by the National Natural Science Foundation of China(Nos.21204045 and 21276151)Natural Science Basic Research Plan in Shaanxi Province of China(No.2011JQ2004)Key Scientific Research Group of Shaanxi Province(No.2013KCT-08)
文摘The effects of crystallization temperature and blend ratio on the polymorphic crystal structures of poly（butylene adipate） （PBA） in poly（butylene succinate） （PBS）/poly（butylene adipate） （PBS/PBA） blends were studied by means of differential scanning calorimetry （DSC）, wide-angle X-ray diffraction （XRD） and atomic force microscopy （AFM）. It was revealed that the polymorphism of PBA can be regulated by the blend ratio even in a non-isothermal crystallization process. The results demonstrate that high temperature favors fiat-on α crystals, while low temperature contributes to edge-on β crystals. It was also found that the effect of blend ratio on the crystallization mechanism of PBA is well coincident with that of the crystallization temperature. The increment of PBS content in the PBS/PBA blend gives rise to more β-form crystals of PBA. For those PBS/PBA blends with low PBA content, the interlamellar phase segregation of PBA makes its molecular chains so difficult to diffuse from one isolated microdomain to another that high crystallization temperature and sufficiently long crystallization time will be required if the PBA α-type crystals are targeted.
基金the National Key Research and Development Program of China(No.2022YFB3704900)the National Natural Science Foundation of China(No.52073004)China National Tobacco Corporation Guizhou Company(No.2023XM24)。
文摘Poly(glycolic acid)(PGA)is derived from glycolide obtained by fermenting pineapples or sugarcane,which has excellent gas barrier properties and a small carbon footprint.PGA is a potential substitute for the current aluminum-plastic composite films used in high barrier packaging applications.However,its poor ductility and narrow processing window limit its application in food packaging.Herein,poly(butylene succinate-co-butylene adipate)(PBSA)was used to fabricate PGA/PBSA blend films through an in situ fibrillation technique and blown film extrusion.Under the elongational flow field used during the extrusion process,a unique hierarchical structure based on the PBSA nanofibrils and interfacially oriented PGA crystals was obtained.This structure enhances the strength,ductility and gas barrier properties of the PGA/PBSA blend film.In addition,an epoxy chain extender(ADR4468)was used as a compatibilizer to further enhance the interfacial adhesion between PGA and PBSA.70PGA/0.7ADR exhibited a very low oxygen permeability(2.34×10^(-4)Barrer)with significantly high elongating at break(604.4%),tensile strength(47.4 MPa),and transparency,which were superior to those of petroleum-based polymers.Thus,the 70PGA/0.7ADR blown films could satisfy the requirements for most instant foods such as coffee,peanuts,and fresh meat.
文摘The concern with environmental preservation is a very current and relevant topic. Regarding polymers, the search for potentially ecofriendly matters has been the subject of scientific research. In this context, this work aimed to study the effect of adding nanocellulose (nCE) with 1, 3, and 5 wt.% on poly(butylene adipate-co-butylene terephthalate) (PBAT). Thermal, structural, relaxometric, and rheological assessments were carried out. Quantitative evaluation of PBAT copolymer by high field NMR revealed 56.4 and 43.6 m.% of the butylene adipate and butylene terephthalate segments, respectively. WAXD measurement on the deconvoluted diffraction patterns identified that nCE was a mixing of Cellulose I and Cellulose II polymorph structures. At any composition, nanocellulose interfered with the PBAT crystallisation process. Also, a series of new PBAT crystallographic planes appeared as a function of nanocellulose content. PBAT hydrogen molecular relaxation varied randomly with nanocellulose content and had a strong effect on the hydrogen relaxation. PBAT cold crystallisation and melting temperatures (T<sub>cc</sub> and T<sub>m</sub>) were almost unchangeable. Although T<sub>cc</sub> did not change during polymer solidification from PBAT molten state, the sample’s degree of crystallinity varied with composition through the transcrystallization phenomenon. Nanocomposite thermal stability decreased possibly owing to the catalytic action of sulfonated amorphous cellulose chains. For the sample with 3 wt.% of nanocellulose, the highest values of complex viscosity and storage modulus were achieved.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.52073261 and U1704162).
文摘Poly(butylene adipate-co-terephthalate)(PBAT)is a promising biodegradable flexible polymer but suffers from slow crystallization rate,making it less attractive for some applications like the injection-molded products in comparison with low-density polyethylene(LDPE).This work aimed to accelerate the crystallization of PBAT by adding a self-assembly nucleating agent octamethylenedicarboxylic dibenzoylhydrazide(OMBH).PBAT/OMBH composites with various OMBH contents(0 wt%,0.5 wt%,0.7 wt%,1 wt%,2 wt%,3 wt%and 5 wt%)were prepared through melt-mixing.The effect of OMBH on the crystallization behavior,morphologies and mechanical properties of PBAT was investigated.The highest nucleation efficiency value of 59.6%was achieved for PBAT with 0.7 wt%OMBH,much higher than that of 22.7%for PBAT with 0.7 wt%talc.Atomic force microscopy results showed that OMBH formed fine fibers and induced the formation of transcrystalline layers of PBAT.Fourier transform infrared spectroscopy(FTIR)combined with two-dimensional correlation spectra suggested that the intermolecular dipole-dipole N—H…O=C interactions but not hydrogen bond between OMBH and PBAT promoted the crystallization of PBAT in the initial period of crystallization.The presence of OMBH did not change the crystal form of PBAT but had positive contribution in enhancing its crystallinity and mechanical properties.This work is essential for preparing PBAT with high crystallization rate,enhancing its potential applications in injection-molded products.
基金financially supported by the National Key Technology Pillar Program(No.2013BAC11B05)Key Research and Innovation Program of Jiangsu Province(No.BE2015055)the Science&Technology Pillar Program in Sichuan Province(No.2016GZ0228)
文摘Mg-A1 mixed oxides with different Mg/A1 molar ratio were prepared by thermal decomposition of hydrotalcite- like precursors at 500 ℃ 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/A1 molar ratio of 4.0 exhibited the best catalytic performance, giving PBC with Mw of 1.64 × 105 g/mol at 210℃ 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.
基金supported by National Key Research and Development Program of China (No. 2021YFD1700700).
文摘Poly(butylene adipate-co-terephthalate) (PBAT) is currently the largest commercial biodegradable plastics with good toughness and film forming properties, whereas, the inferior barrier and mechanical properties hinder its applications. Biodegradable poly(propylene carbonate) (PPC) with excellent barrier properties and high strength is a natural choice to address above issue. However, it is challenging to improve the compatibility of these two polymers. Herein, we prepared a reactive compatibilizer with double bond side group through terpolymerization of CO_(2)/propylene oxide/glycidyl methacrylate to enhance the properties of PBAT/PPC blends. Upon addition of 1 wt% compatibilizer, the PBAT/PPC blends (75/25, W/W) showed an increased water vapor barrier property changed from 424 g·m^(−2)·d^(−1) to 204 g·m^(−2)·d^(−1) compared to the control sample. Moreover, the tensile strength and elongation at break increased from 24.7 MPa to 30.3 MPa and from 858% to 1142%, respectively. The PBAT/PPC composite also displayed excellent biodegradability under composting conditions, as confirmed by the significantly decreased molecular weight. The present work provides an efficient way to barrier biodegradable film from PBAT of practical utilization.
基金supported financially by the National Natural Science Foundation of China (Nos. 21634006 and 51121001)the Program for Changjiang Scholars and Innovative Research Teams in University of China (No. IRT1026)
文摘A cross-linkable comonomer containing a diacetylene group,named dimethyl 4,4＇-（buta-l,3-diyne-l,4-diyl）dibenzoate（DA） was synthesized and copolymerized with dimethyl succinate and 1,4-butanediol to prepare a series of slightly cross-linked PBS copolyesters（PBDASx）.The chemical structure,crystallization and Theological behaviours of PBDASx were well investigated.Compared to neat PBS,PBDASx showed the greatly increased crystallization rate because of the promoting nucleation of the cross-linking domains,and the XRD results indicated that it had no influence on crystallization structure of PBS.The rheological behaviours indicate that PBDASx possessed higher viscosity than neat PBS even at high shear rate and temperature.PBDAS0.3 exhibited better comprehensive properties than neat PBS,which will widen applications of PBS.
基金Project supported by the National Natural Science Foundation of China （No. 20434020）, the Major State Basic Research Development Program （No. 2005CB623802）, and China Postdoctor Science Foundation （No. 20060390334）.
文摘Rare earth （Nd, Y, La, Dy） stearates have been synthesized and used as single component catalysts for the polycondensation of dimethyl terephthalate, adipic acid and 1,4-butanediol for the first time preparing biodegradable poly（butylene adipate-co-terephthalate） （PBAT） with high molecular weight, The microstructures of PBAT were characterized by ^1H NMR spectra. The PBAT exhibits good mechanical properties such as high tensile strength （ca. 20 MPa） and long break elongation （〉700%）.
基金supported by the National High Technology Research and Development Program of China (863 Program No. 2009AA03Z319)the National Natural Science Foundation of China (Nos. 30870633, 31000427)the Fundamental Research Funds for the Central Universities (DUT12JB09)
文摘Biodegradable poly（butylene succinate） （PBS） and layered double hydroxide （LDH） nanocomposites were prepared via melt blending in a twin-screw extruder. The morphology and dispersion of LDH nanoparticles within PBS matrix were characterized by transmission electron microscopy （TEM）, which showed that LDH nanoparticles were found to be well distributed at the nanometer level. The nonisothermal crystallization behavior of nanocomposites was extensively studied using differential scanning calorimetry （DSC） technique at various cooling rates. The crystallization rate of PBS was accelerated by the addition of LDH due to its heterogeneous nucleation effect; however, the crystallization mechanism and crystal structure of PBS remained almost unchanged. In kinetics analysis of nonisothermal crystallization, the Ozawa approach failed to describe the crystallization behavior of PBS/LDH nanocomposites, whereas both the modified Avrami model and the Mo method well represented the crystallization behavior of nanocomposites. The effective activation energy was estimated as a function of the relative degree of crystallinity using the isoeonversional analysis. The subsequent melting behavior of PBS and PBS/LDH nanocomposites was observed to be dependent on the cooling rate. The POM showed that the small and less perfect crystals were formed in nanocomposites.
基金financially supported by the National Natural Science Foundation of China(No.21374054)the SinoGerman Center for Research Promotion and the National Basic Research Program of China(No.2014CB932202)
文摘Differential scanning calorimetry（DSC） has been widely applied to study crystallization and melting of materials. However, for polymeric lamellar crystals, the melting thermogram during heating process usually exhibits a broad endothermic peak or even multiple endotherms, which may result from changes of metastability via recrystallization process. Sometimes, the recrystallization exotherm cannot be observed due to its overlapping with the melting endotherm. In this work, we employed a step heating procedure consisting of successive heating and temperature holding stages to measure the metastability of isothermally crystallized poly（butylene succinate）（PBS） crystals. With this approach we could gain the fraction of crystals melted at different temperature ranges and quantitatively detect the melting-recrystallization behavior. The melting-recrystallization behavior depends on the polymer chain structure and the crystallization temperature. For instance, PBS block copolymer hardly shows recrystallization behavior while PBS oligomer and high molecular weight PBS homopolymer demonstrate remarkable melting-recrystallization phenomenon. High molecular weight PBS isothermally crystallized in the low temperature range shows multiple melting-recrystallization while those isothermally crystallized at elevated temperatures do not exhibit observable recrystallization behavior. Furthermore, the melting endotherms were fitted via the melting kinetics equations. The original isothermally crystallized lamellae demonstrate quite different melting kinetics from the recrystallized lamellar crystals that melt at the highest temperature range, which is attributed to the different degrees of stabilization. Finally, the mechanism of melting-recrystallization is briefly discussed. We propose that apparent meltrecrystallization phenomenon be observed when melting of preformed lamellar crystals and recrystallization of thicker lamellae have similar free energy barrier.
基金would like to gratefully acknowledge the National Key Research and Development Program(No.2018YFC1901300)the Key Research and Development Program of Zhejiang Province(No.2020C03084).
文摘The pyrolysis of poly(ethylene terephthalate)(PET)/poly(butylene terephthalate)(PBT)catalyzed by five alkaline earth metal-based minerals/wastes,namely calcined dolomite,calcite,magnesite,calcium carbide slag(CCS),and ophicalcitum,was conducted by a pyrolyzer-gas chromatography-mass spectrometer(Py-GC-MS)with the objective of recovering benzenes-enriched oil.Compared with magnesium-based catalysts and pure CaO,the calcium-based catalysts with calcium hydroxide as the main component performed better catalytic effect,which could simultaneously promote the hydrolysis of ester products and the decarboxylation of aromatic acids after hydrolysis.For PET,the addition of solid base catalysts at 600℃promoted the complete degradation of aromatic acids and aryl esters,which accounted for 32.6%and 30.7%of the pyrolysis oil,respectively.The content of benzene in oil increased from 8.8%to 31.7%–78.8%.For PBT,the addition of solid base catalysts at 600℃completely decomposed the aromatic acids,which accounted for 67.1%of the pyrolysis oil,and the content of benzene in oil increased from 12.3%to 34.5%–81.0%.During the deoxygenation of polyester pyrolysis products,increasing temperature was more effective for the decomposition/conversion of acetone and tetrahydrofuran,while increasing the alkalinity of the reaction environment contributed to the rapid decrease in acetaldehyde and aryl ketone contents.
基金financially supported by the National Natural Science Foundation of China(No.51503217)Zhejiang Province Public Welfare Project(No.2017C31081)+1 种基金the Open Project Program of MOE Key Laboratory of Macromolecular Synthesis and Functionalization,Zhejiang University(No.2016MSF001)Youth Innovation Promotion Association CAS(No.2017339)
文摘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.
