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
In order to improve the wettability and biocompatibility of the poly （butylene terephthalate） non-woven （PBTNW）, the method of surface modification is used to graft copolymerization of chitosan （CS） onto the PBT...In order to improve the wettability and biocompatibility of the poly （butylene terephthalate） non-woven （PBTNW）, the method of surface modification is used to graft copolymerization of chitosan （CS） onto the PBTNW under alkylpolyglycoside （APG） inducing. The product is thoroughly characterized with the Fourier transform infrared spectroscopy （FrIR）, the electron spectroscopy for chemical analysis （ESCA）, the thermogravimetric （TG） and the scanning electron microscopy （SEM）. It is found that chitosan is successfully grafted onto PBTNW. In addition, the water contact angles, hemolysis tests and cytotoxicity evaluation tests show an improvement in wettability and biocompatihility as a result of graft copolymerization of chitosan. So the CS-grafted PBTNW exhibits greater superiority than the original PBTNW. The CS-grafted PBTNW can be a candidate for blood filter materials and other medical applications.展开更多
In this article, the transesterification of poly(bisphenol A carbonate) (PC) with butylene terephthalate-caprolactone copolyester at a weight ratio 50/50 (BCL(21)) was thoroughly investigated by proton nuclear magneti...In this article, the transesterification of poly(bisphenol A carbonate) (PC) with butylene terephthalate-caprolactone copolyester at a weight ratio 50/50 (BCL(21)) was thoroughly investigated by proton nuclear magnetic resonance spectroscopy ('H-NMR), in conjunction with a model compound. The 1 H-NMR results of the annealed blend PC/BCL(21) show that the formation of bisphenol A-terephthalate ester units is the same as in the annealed blend of PC with PBT, and the transesterification actually occurs between PC and butylene terephthalate (BT) segments in BCL(21). By comparison with the model compound bisphenol A dibutyrate, the new signal appearing at δ= 2.56 in the 1H-NMR spectrum confirms the existence of bisphenol A caprolactone ester units resulting from the exchange reaction of PC with caprolactone (CL) segments. 1H-NMR analysis of the transesterification rates reveals that the reaction of PC with aromatic and aliphatic segments in BCL(21) proceeds in a random manner. The miscibility of the blend PC/BCL(21) copolyester is favorable for the transesterification of PC with BT segments and CL segments.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
The morphology of polyamide 6/poly(butylene terephthalate)(PA6/PBT, 70/30, W/W) blends filled with pristine Zinc oxide(ZnO) nanoparticles and ZnO surface-modified by γ-glycidoxypropyltrimethoxysilane(K-ZnO) was inves...The morphology of polyamide 6/poly(butylene terephthalate)(PA6/PBT, 70/30, W/W) blends filled with pristine Zinc oxide(ZnO) nanoparticles and ZnO surface-modified by γ-glycidoxypropyltrimethoxysilane(K-ZnO) was investigated. The incorporation of ZnO and K-ZnO by one-step compounding both resulted in a smaller size and narrower distribution of PBT domains and the effect of ZnO was greater than K-ZnO. To reveal the underlying mechanism, two-step compounding in which ZnO or K-ZnO was premixed with PA6 or PBT was conducted and the finest morphology was achieved when mixing PA6 with premixed PBT/ZnO. Transmission electron microscopy(TEM) demonstrated that ZnO was distributed in PBT in all cases and K-ZnO was enriched at the interface except when K-ZnO was premixed with PBT. ZnO and K-ZnO caused a deterioration in the melt rheological properties of PBT, which played a dominating role in the morphological changes. In addition, the interfacial localization of K-ZnO enhanced the dynamic rheological properties of PA6/PBT blends substantially.展开更多
Core-shell structured polyacrylic（named CSSP） impact modifiers consisting of a rubbery poly（n-butyl acrylate） core and a rigid poly（methyl methacrylate） shell with a size of about 353 nm were prepared by seed em...Core-shell structured polyacrylic（named CSSP） impact modifiers consisting of a rubbery poly（n-butyl acrylate） core and a rigid poly（methyl methacrylate） shell with a size of about 353 nm were prepared by seed emulsion polymerization. The CSSP modifiers with different core-shell weight ratios（90/10, 85/15, 80/20, 75/25, 70/30, 65/35 and 60/40） were used to modify the toughness of poly（butylene terephthalate）（PBT） by melt blending. It was found that the polymerization had a very high instantaneous conversion（ 95.7%） and overall conversion（99.7%）. The morphology of the core-shell structure was confirmed by means of transmission electron microscopy. Scanning electron microscopy was used to observe the morphology of the fractured surfaces. Differential scanning calorimeter was used to study the crystallization behaviors of PBT/CSSP blends. The dynamic mechanical analyses of PBT/CSSP blends showed two merged transition peaks of PBT matrix, with the presence of CSSP core-shell structured modifier, that were responsible for the improvement of PBT toughness. The results indicated that the notch impact strength of PBT/CSSP blends with a core-shell weight ratio of 75/25 was almost 8.64 times greater than that of pure PBT, and the mechanical properties agreed well with the SEM observation.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
When the size of the material is smaller than the size of the molecular chain,new nanostructures can be formed by crystallizing polymers in nanoporous alumina.However,the effect of pore wall and geometric constraints ...When the size of the material is smaller than the size of the molecular chain,new nanostructures can be formed by crystallizing polymers in nanoporous alumina.However,the effect of pore wall and geometric constraints on polymer nanostructures remains unclear.In this study,we demonstrate three new restricted nanostructures{upright-,flat-and tilting-ring}in polybutylene terephthalate(PBT)nanorods prepared from nanoporous alumina.The dual effects of geometrical constraints and interfacial interactions on the formation of PBT nanostructures were investigated for the first time by using X-ray diffraction and Cerius^(2) modeling packages.Under weak constraints,the interaction between pore wall and the PBT rings is dominant and the ring plane tends to be parallel to the pore wall and radiate outward to grow the upright-ring crystals.Surprisingly,in strong 2D confinement,a structural formation reversal occurs and geometrical constraints overpower the effect of pore wall.Rings tend to pile up vertically or obliquely along the long axis of the rod,so the flat-and tilting-ring crystals are predominate in the constrained system.In principle,our study of the nanostructure formation based on the geometrical constraints and the pore wall interfacial effects could provide a new route to manipulate the chain assembly at the nanoscale,further improving the performance of polymer nanomaterial.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
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.
文摘In order to improve the wettability and biocompatibility of the poly （butylene terephthalate） non-woven （PBTNW）, the method of surface modification is used to graft copolymerization of chitosan （CS） onto the PBTNW under alkylpolyglycoside （APG） inducing. The product is thoroughly characterized with the Fourier transform infrared spectroscopy （FrIR）, the electron spectroscopy for chemical analysis （ESCA）, the thermogravimetric （TG） and the scanning electron microscopy （SEM）. It is found that chitosan is successfully grafted onto PBTNW. In addition, the water contact angles, hemolysis tests and cytotoxicity evaluation tests show an improvement in wettability and biocompatihility as a result of graft copolymerization of chitosan. So the CS-grafted PBTNW exhibits greater superiority than the original PBTNW. The CS-grafted PBTNW can be a candidate for blood filter materials and other medical applications.
文摘In this article, the transesterification of poly(bisphenol A carbonate) (PC) with butylene terephthalate-caprolactone copolyester at a weight ratio 50/50 (BCL(21)) was thoroughly investigated by proton nuclear magnetic resonance spectroscopy ('H-NMR), in conjunction with a model compound. The 1 H-NMR results of the annealed blend PC/BCL(21) show that the formation of bisphenol A-terephthalate ester units is the same as in the annealed blend of PC with PBT, and the transesterification actually occurs between PC and butylene terephthalate (BT) segments in BCL(21). By comparison with the model compound bisphenol A dibutyrate, the new signal appearing at δ= 2.56 in the 1H-NMR spectrum confirms the existence of bisphenol A caprolactone ester units resulting from the exchange reaction of PC with caprolactone (CL) segments. 1H-NMR analysis of the transesterification rates reveals that the reaction of PC with aromatic and aliphatic segments in BCL(21) proceeds in a random manner. The miscibility of the blend PC/BCL(21) copolyester is favorable for the transesterification of PC with BT segments and CL segments.
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%）.
文摘The morphology of polyamide 6/poly(butylene terephthalate)(PA6/PBT, 70/30, W/W) blends filled with pristine Zinc oxide(ZnO) nanoparticles and ZnO surface-modified by γ-glycidoxypropyltrimethoxysilane(K-ZnO) was investigated. The incorporation of ZnO and K-ZnO by one-step compounding both resulted in a smaller size and narrower distribution of PBT domains and the effect of ZnO was greater than K-ZnO. To reveal the underlying mechanism, two-step compounding in which ZnO or K-ZnO was premixed with PA6 or PBT was conducted and the finest morphology was achieved when mixing PA6 with premixed PBT/ZnO. Transmission electron microscopy(TEM) demonstrated that ZnO was distributed in PBT in all cases and K-ZnO was enriched at the interface except when K-ZnO was premixed with PBT. ZnO and K-ZnO caused a deterioration in the melt rheological properties of PBT, which played a dominating role in the morphological changes. In addition, the interfacial localization of K-ZnO enhanced the dynamic rheological properties of PA6/PBT blends substantially.
基金financially supported by Program for Changjiang Scholars and Innovative Research Team in University-IRT13060Key Lab for Micro-and Nano-Scale Boron Nitride Materials in Hebei Province
文摘Core-shell structured polyacrylic（named CSSP） impact modifiers consisting of a rubbery poly（n-butyl acrylate） core and a rigid poly（methyl methacrylate） shell with a size of about 353 nm were prepared by seed emulsion polymerization. The CSSP modifiers with different core-shell weight ratios（90/10, 85/15, 80/20, 75/25, 70/30, 65/35 and 60/40） were used to modify the toughness of poly（butylene terephthalate）（PBT） by melt blending. It was found that the polymerization had a very high instantaneous conversion（ 95.7%） and overall conversion（99.7%）. The morphology of the core-shell structure was confirmed by means of transmission electron microscopy. Scanning electron microscopy was used to observe the morphology of the fractured surfaces. Differential scanning calorimeter was used to study the crystallization behaviors of PBT/CSSP blends. The dynamic mechanical analyses of PBT/CSSP blends showed two merged transition peaks of PBT matrix, with the presence of CSSP core-shell structured modifier, that were responsible for the improvement of PBT toughness. The results indicated that the notch impact strength of PBT/CSSP blends with a core-shell weight ratio of 75/25 was almost 8.64 times greater than that of pure PBT, and the mechanical properties agreed well with the SEM observation.
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 Natural Science Foundation of Shenzhen University(Nos.827-000150 and 860-000002110375).
文摘When the size of the material is smaller than the size of the molecular chain,new nanostructures can be formed by crystallizing polymers in nanoporous alumina.However,the effect of pore wall and geometric constraints on polymer nanostructures remains unclear.In this study,we demonstrate three new restricted nanostructures{upright-,flat-and tilting-ring}in polybutylene terephthalate(PBT)nanorods prepared from nanoporous alumina.The dual effects of geometrical constraints and interfacial interactions on the formation of PBT nanostructures were investigated for the first time by using X-ray diffraction and Cerius^(2) modeling packages.Under weak constraints,the interaction between pore wall and the PBT rings is dominant and the ring plane tends to be parallel to the pore wall and radiate outward to grow the upright-ring crystals.Surprisingly,in strong 2D confinement,a structural formation reversal occurs and geometrical constraints overpower the effect of pore wall.Rings tend to pile up vertically or obliquely along the long axis of the rod,so the flat-and tilting-ring crystals are predominate in the constrained system.In principle,our study of the nanostructure formation based on the geometrical constraints and the pore wall interfacial effects could provide a new route to manipulate the chain assembly at the nanoscale,further improving the performance of polymer nanomaterial.
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.
