Although the efficiency of poly(ethylene terephthalate)(PET)degradation has been successfully improved by depolymerase engineering,mostly by using Goodfellow-PET(gf-PET)as a substrate,efforts to degrade unpretreated P...Although the efficiency of poly(ethylene terephthalate)(PET)degradation has been successfully improved by depolymerase engineering,mostly by using Goodfellow-PET(gf-PET)as a substrate,efforts to degrade unpretreated PET materials with high crystallinity remain insufficient.Here,we endeavored to improve the degradation capability of a WCCG mutant of leaf-branch compost cutinase(LCC)on a unpretreated PET substrate(crystallinity>40%)by employing iterative saturation mutagenesis.Using this method,we developed a high-throughput screening strategy appropriate for unpretreated substrates.Through extensive screening of residues around the substrate-binding groove,two variants,WCCG-sup1 and WCCG-sup2,showed good depolymerization capabilities with both high-(42%)and low-crystallinity(9%)substrates.The WCCG-sup1 variant completely depolymerized a commercial unpretreated PET product in 36 h at 72℃.In addition to enzyme thermostability and catalytic efficiency,the adsorption of enzymes onto substrates plays an important role in PET degradation.This study provides valuable insights into the structure-function relationship of LCC.展开更多
With the aim to effectively depolymerize polyethylene terephthalate(PET)under mild reaction conditions,PET methanolysis and dimethyl terephthalate(DMT)hydrolysis are integrated in a catalyst system.Firstly,methanolysi...With the aim to effectively depolymerize polyethylene terephthalate(PET)under mild reaction conditions,PET methanolysis and dimethyl terephthalate(DMT)hydrolysis are integrated in a catalyst system.Firstly,methanolysis of PET to DMT is achieved over Cu-Mg-Al oxide catalyst.Next,terephthalic acid(TPA)is prepared by DMT hydrolysis.It is found that hydrolysis of DMT to TPA can be promoted by introducing trace amount of water in this catalyst system.CuO-MgO-4.5Al_2O_(3)catalyst demonstrates the excellent catalytic performance for the depolymerization of PET with high conversion rate and TPA yield(100%and 99.5%,respectively)after reaction at 160℃for 6 h,which provides a new idea for the depolymerization of PET.展开更多
This work proposed a strategy to improve the caking index of polyethylene terephthalate(PET)waste,in which low-temperature pyrolysis treatment(LTPT)was used to depolymerize PET waste.The mechanism of G modification wa...This work proposed a strategy to improve the caking index of polyethylene terephthalate(PET)waste,in which low-temperature pyrolysis treatment(LTPT)was used to depolymerize PET waste.The mechanism of G modification was revealed combining thermogravimetric(TG)analysis,Fourier transform infrared spectroscopy,pyrolysis-gas chromatography with mass spectrometric detection,and solid-state 13C nuclear magnetic resonance spectroscopy.Furthermore,crucible coking experiments were also conducted using industrial coal mixture and treated PET with the optimum G(PET300)or raw PET to evaluate the applicability of PET waste in coal-blending coking.According to characterization results of coke reactivity(CR),coke strength after reaction(CSR)indices,TG-related curves,pore volumes,and Raman spectra of the resultant cokes,LTPT could greatly increase the G of PET,and the optimum temperature was 300℃.Specifically,compared with the coke obtained from the blend with PET,the CR of the coke produced from the blend with PET300 decreased by 4.9%,whereas the CSR of the increased by 7.4%,suggesting that LTPT could increase the proportion of PET used for coal-blending coking.The improvement in G is attributed to the changes in C-O/C=O ratio,aliphatic H and aromaticity caused by LTPT.展开更多
To enhance the hydrophilicity and antistatic properties of the polyethylene terephthalate(PET)fabric,the lawsone dye was employed in dyeing the PET fabric.It was dissolved in ethanol/deionized water mixture and deioni...To enhance the hydrophilicity and antistatic properties of the polyethylene terephthalate(PET)fabric,the lawsone dye was employed in dyeing the PET fabric.It was dissolved in ethanol/deionized water mixture and deionized water separately,forming different lawsone dye solutions(LDSs).The study investigated how the compounds in the LDS improve the surface properties and color durability of the PET fabric,resulting in increased dye uptake.An infrared dyeing machine was utilized to expedite the reactions between the lawsone dye and the PET fabric.Additionally,the chemical composition of the dyed PET fabric was verified using techniques such as Fourier transform infrared(FTIR)spectroscopy,X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD)and ultraviolet-visible(UV-Vis)spectrophotometry.The K/S value was measured to assess color durability.After dyeing,the PET fabric exhibited high hydrophilicity which improved the hygroscopicity of the PET fabric and thus the conductivity of the PET fabric surface increased,thereby providing an antistatic effect.展开更多
Electrocatalytic valorization of disused poly(ethylene terephthalate)(PET)plastics into value-added chemicals emerges as a potential approach to address plastic pollution and resources upgrading,but it faces challenge...Electrocatalytic valorization of disused poly(ethylene terephthalate)(PET)plastics into value-added chemicals emerges as a potential approach to address plastic pollution and resources upgrading,but it faces challenges in the development of efficient catalysts for PET-derived ethylene glycol(EG)electrooxidation.Herein,we proposed pyramid arrays on sheet Fe-doped NiO/FeNi_(3)(SPA-NiFeO_(x)/FeNi_(3))heterostructure,which is derived from the pyrolysis of MOF-on-MOF heterostructure growth triggered by graphene quantum dots(GQDs).Such SPA-NiFeO_(x)/FeNi_(3)exhibits superior catalytic performance on the electrooxidation of EG(EGOR)from PET hydrolysate,with a formic acid(FA)selectivity of 91.5%and a Faradaic efficiency of 92%.The ligand effect of GQDs in both the catalyst design and improved electrocatalytic performance was studied with combined spectroscopy analysis and theoretical calculations,which revealed that such spatially separated NiFeO_(x)and FeNi_(3)components by GQDs possess more active sites to anticipate in electrocatalytic EGOR,and the large sp2 domains in GQDs possess a strong electron-withdrawing ability to reduce the electron density of bonded Ni and Fe,resulting in high-valenced Ni^(δ+)/Fe^(δ+)in FeNi_(3)and Ni(2+δ)in NiO,respectively.Furthermore,the coordination number of Ni and Fe centers was lowered due to the steric effect of GQDs.Therefore,the adsorption of EG on Ni^(δ+)for cascade dehydrogenation and C–C bond cleavage led to adsorbed FA that transferred to adjacent Fe for desorption,which was promoted by the enrichment of OH−on nearby Ni^((2+δ))sites,along with optimized Gibbs free energy change in the multistep reaction pathway.This work provides an efficient multi-active-site catalyst for disused PET plastics valorization,thereby presenting a new approach to enhance the efficiency of PET plastics valorization reactions.展开更多
A novel direct method for preparation of dimethyl carbonate and poly（ethylene terephthalate） from ethylene carbonate and dimethyl terephthalate has been demonstrated in the presence of metal acetate catalysts, lithi...A novel direct method for preparation of dimethyl carbonate and poly（ethylene terephthalate） from ethylene carbonate and dimethyl terephthalate has been demonstrated in the presence of metal acetate catalysts, lithium acetate dihydrate showed highest catalytic activity with 47.9% yield of dimethyl carbonate. This method was a green chemical process.展开更多
Dimethyl carbonate （DMC） and poly（ethylene terephthalate） was simultaneously synthesized by the transesterification of ethylene carbonate （EC） with dimethyl terephthalate （DMT） in this paper. This reaction is ...Dimethyl carbonate （DMC） and poly（ethylene terephthalate） was simultaneously synthesized by the transesterification of ethylene carbonate （EC） with dimethyl terephthalate （DMT） in this paper. This reaction is an excellent green chemical process without poisonous substance. Various alkali metals were used as the catalysts. The results showed alkali metals had catalytic activity in a certain extent. The effect of reaction condition was also studied. When the reaction was carded out under the following conditions： the reaction temperature 250℃, molar ratio of EC to DMT 3 ： 1, reaction time 3h, and catalyst amount 0.004 （molar ratio to DMT）, the yield of DMC was 68.9%.展开更多
The reaction between ethylene carbonate and dimethyl terephthalate was carried out for the simultaneous synthesis of dimethyl carbonate and poly（ethylene terephthalate）, This reaction is an excellent chemical proces...The reaction between ethylene carbonate and dimethyl terephthalate was carried out for the simultaneous synthesis of dimethyl carbonate and poly（ethylene terephthalate）, This reaction is an excellent chemical process that is environmentally friendly and produces no poisonous substance. The metal acetate catalysts used for this reaction are discussed in detail. Lithium acetate dihydrate was found to be a novel and efficient catalyst for this reaction. Compared with other metal acetates, lithium acetate dihydrate can attain a maximum catalytic activity at a lower concentration. When the reaction was carried out under the following conditions： the reaction temperature from 230 to 250 ℃, molar ratio of ethylene carbonate（EC） to dimethyl terephthalate（DMT） 3： 1, reaction time 3 h, and a catalyst amount of 0. 4% （molar fraction to DMT）, the yield of dimethyl carbonate（DMC） was 79. 1%.展开更多
Poly (trimethylene-co-ethylene terephthalate) with various compositions of diol has been synthesized. The crystallization of copolyesters with high comonomer content was observed by both wide-angle X-ray diffraction (...Poly (trimethylene-co-ethylene terephthalate) with various compositions of diol has been synthesized. The crystallization of copolyesters with high comonomer content was observed by both wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). It was found that the copolyesters become less crystallizable with the involvement of the comonomer, the crystals of crystallizable copolyesters come from PTT or PET homopolymers. The glass transition temperature (Tg) of the copolyester increases with increasing PET component in the copolyester, and the relationship between Tg and composition obey both Fox equation and additive law, the former is better in describing this relationship.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 work,a novel alcohol alkali hydrolysis method was explored for the preparation of terephthalic acid(TPA)from waste polyethylene terephthalate(PET).First,a series of single factor experiments on the depolymeriz...In this work,a novel alcohol alkali hydrolysis method was explored for the preparation of terephthalic acid(TPA)from waste polyethylene terephthalate(PET).First,a series of single factor experiments on the depolymerization rate of waste PET bottles and the yield of TPA were conducted to determine the optimized experimental conditions,in terms of reaction time,reaction temperature,dosage of ethylene glycol and sodium bicarbonate,amount of distilled water and stirring rate.Then IR spectra and elemental analysis were carried out for the characterization of obtained product.Under optimal experimental conditions,over 98%PET can be depolymerized into the target product(TPA)and the purity and yield of TPA are over 97%and 94%,respectively.Both the experimental and analytical results support a feasible process for the preparation of TPA from waste PET.It is expected that this alcohol alkali hydrolysis method can promise an effective way for the sustainable recycling of waste PET.展开更多
Non-thermal plasmas under atmospheric pressure are of great interest in polymer surface processing because of their convenience, effectiveness and low cost. In this paper, the treatment of Polyethylene terephthalate (...Non-thermal plasmas under atmospheric pressure are of great interest in polymer surface processing because of their convenience, effectiveness and low cost. In this paper, the treatment of Polyethylene terephthalate (PET) film surface for improving hydrophilicity using the non-thermal plasma generated by atmospheric pressure glow discharge (APGD) in air is conducted. The discharge characteristics of APGD are shown by measurement of their electrical discharge parameters and observation of light-emission phenomena, and the surface properties of PET before and after the APGD treatment are studied using contact angle measurement, x-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). It is found that the APGD is homogeneous and stable in the whole gas gap, which differs from the commonly filamentary dielectric barrier discharge (DBD). A short time (several seconds) APGD treatment can modify the surface characteristics of PET film markedly and uniformly. After 10 s APGD treatment, the展开更多
The aluminum oxide(AlOx)coatings were deposited on poly(ethylene terephthalate)(PET)surface by reactive magnetron sputtering for improving its barrier property.With O2 flux increasing,three modes including metallic mo...The aluminum oxide(AlOx)coatings were deposited on poly(ethylene terephthalate)(PET)surface by reactive magnetron sputtering for improving its barrier property.With O2 flux increasing,three modes including metallic mode,transition mode and oxide mode exist in sputtering.The properties of the aluminum oxide(AlOx)coatings prepared at different modes were discussed.Also,the influences of oxygen flux on the stoichiometry,structure,gas permeation of the coatings were investigated.The chemical composition of AlOx films fabricated in transition mode is different as oxygen flux varies slightly,and the gas barrier property is better as the stoichiometry is closer to 1.5 with oxygen flux increasing.The coating uniformity,roughness and particle size depend remarkably upon oxygen flux.The coatings deposited at oxide mode have a good barrier performance to oxygen and water,and the permeability to oxygen decreases by sixty times and water vapor ten times compared with uncoated展开更多
Stannous-acetylacetonate was prepared efficiently and characterized by ^1H NMR and FT-IR. Its catalytic activity for poly（trimethylene terephthalate） （PTT） synthesis was investigated. By this catalyst, the degree ...Stannous-acetylacetonate was prepared efficiently and characterized by ^1H NMR and FT-IR. Its catalytic activity for poly（trimethylene terephthalate） （PTT） synthesis was investigated. By this catalyst, the degree of esterification of pure terephthalic acid was up to 91.7% after reaction at 260 ℃ for 2 h, while the intrinsic viscosity and content of terminal carboxyl groups of the corresponding PTT polymerized at 260 ℃, 60 Pa for 2 h was 0.8816 dL/g and 17 mol/t,respectively. Stannous-acetylacetonate was more active and promising than tetrabutyl titanate and stannous octoate for PTT synthesis.展开更多
Most of traditional linear poly(ethylene terephthalate)(PET)resins of relatively low molecular mass and narrow molecular mass distribution have low melt strength at foaming temperatures,which are not enough to support...Most of traditional linear poly(ethylene terephthalate)(PET)resins of relatively low molecular mass and narrow molecular mass distribution have low melt strength at foaming temperatures,which are not enough to support and keep cells.An in-situ polymerization-modification process with esterification and polycondensation stages was performed in a 2 L batch stirred reactor using pyromellitic dianhydride(PMDA)or pentaerythritol(PENTA)as modifying monomers to obtain PETs with high melt strength.The influence of amounts of modifying monomers on the properties of modified PET was investigated.It was found that the selected modifying monomers could effectively introduce branched structures into the modified PETs and improve their melt strength.With increasing the amount of the modifying monomer,the melt strength of the modified PET increased.But when the amount of PENTA reached 0.35%or PMDA reached 0.9%,crosslinking phenomenon was observed in the modified PET.Supercritical carbon dioxide(ScCO2)was employed as physical foaming agent to evaluate the foaming ability of modified PETs.The modified PETs had good foaming properties at 14 MPa of CO2pressure with foaming temperature ranging from 265°C to 280°C.SEM micrographs demonstrated that both modified PET foams had homogeneous cellular structures,with cell diameter ranging from 35μm to 49μm for PENTA modified PETs and38μm to 57μm for PMDA modified ones.Correspondingly,the cell density had a range of 3.5×107cells·cm 3to 7×106cells·cm 3for the former and 2.8×107cells·cm 3to 5.8×106cells·cm 3for the latter.展开更多
Stannous oxalate was prepared efficiently and characterized by XRD and FT-IR. It exhibited higher catalytic activity and had profitable effect than tetrabutyl titanate and stannous octoate for the synthesis of polytri...Stannous oxalate was prepared efficiently and characterized by XRD and FT-IR. It exhibited higher catalytic activity and had profitable effect than tetrabutyl titanate and stannous octoate for the synthesis of polytrimethylene terephthalate （PTT） via esterification-route. Over this catalyst, the degree of esterification of pure terephthalic acid was up to 94.4% at 260 ℃ after 1.5 h,while the intrinsic viscosity and content of terminal carboxyl groups of the corresponding PTT polyester, polymerized at 260 ℃,60 Pa for 2 h, was 0.8950 dL/g and 15 mol/t, respectively. Stannous oxalate was a promising catalyst for the synthesis of PTT polyester.展开更多
In order to develop a more economical pretreatment method for electroless nickel plating, a dielectric barrier discharge （DBD） plasma at atmospheric pressure was used to improve the hydrophilicity and adhesion of po...In order to develop a more economical pretreatment method for electroless nickel plating, a dielectric barrier discharge （DBD） plasma at atmospheric pressure was used to improve the hydrophilicity and adhesion of poly （ethylene terephthalate） （PET） nonwoven fabric. The properties of the PET nonwoven fabric including its liquid absorptive capacity （WA）, aging behavior, surface chemical composition, morphology of the surface, adhesion strength, surface electrical resistivity and electromagnetic interference （EMI）- shielding effectiveness （SE） were studied. The liquid absorptive capacity （WA） increased due to the incorporation of oxygen-containing and nitrogen-containing functional groups on the surface of PET nonwoven fabric after DBD airplasma treatment. The surface morphology of the nonwoven fibers became rougher after plasma treatment. Therefore, the surface was more prone to absorb tin sensitizer and palladium catalyst to form an active layer for the deposition of electroless nickel. SEM and X-ray diffraction （XRD） measurements indicated that a uniform coating of nickel was formed on the PET nonwoven fabric. The average EMI-SE of Ni-plating of PET nonwoven fabric maintained a relatively stable value （38.2 dB to 37.3 dB） in a frequency range of 50 MHz to 1500 MHz. It is concluded that DBD is feasible for pretreatment of nonwoven fabric for electroless nickel plating to prepare functional material with good EMI-SE properties.展开更多
One-step reaction compatibilized microfibrillar reinforced iPP/PET blends （CMRB） were successfully prepared through a ＂slit extrusion-hot stretching-quenching＂ process. Crystallization behavior and morphology of C...One-step reaction compatibilized microfibrillar reinforced iPP/PET blends （CMRB） were successfully prepared through a ＂slit extrusion-hot stretching-quenching＂ process. Crystallization behavior and morphology of CMRB were systematically investigated. Scanning electronic microscopy （SEM） observations showed blurry interface of compatibilized common blend （CCB）. The crystallization behavior of neat iPP, CCB, microfibrillar reinforced iPP/PET blend （MRB） and CMRB was investigated by differential scanning calorimetry （DSC） and polarized optical microscopy （POM）. The increase of crystallization temperature and crystallization rate during nonisothermal crystallization process indicated both PET particles and mierofibrils could serve as nucleating agents and PET microfibrils exhibited higher heterogeneous nucleation ability, which were also vividly revealed by results of POM. Compared with MRB sample, CMRB sample has lower crystallization temperature due to existence of PET microfibrils with smaller aspect ratio and wider distribution. In addition, since in situ compatibilizer tends to stay in the interphase, it could also hinder the diffusion ofiPP molecules to the surface of PET phase, leading to decrease of crystallization rate. Two-dimensional wide-angle X-ray diffi：action （2D-WAXD） was preformed to characterize the crystalline structure of the samples by injection molding, and it was found that well-developed PET microfibrils contained in MRB sample promoted formation of t-phase of/PP.展开更多
With the increasing application of electric and electronic devices in space and nuclear power stations, the polymeric insulation materials are inevitably exposed to various kinds of environments. Accordingly, it becom...With the increasing application of electric and electronic devices in space and nuclear power stations, the polymeric insulation materials are inevitably exposed to various kinds of environments. Accordingly, it becomes necessary to investigate the effects of the radiation and air pressure on insulation materials. This paper describes the effects of gamma-ray irradiation and reduced pressure on dielectric breakdown of polybutylene naphthalate (PBN) and polybutylene terephthalate (PBT) by applying a DC pulse voltage. Both PBN and PBT were irradiated in air up to 100 kGy and then up to 1 000 kGy with a dose rate of 10 kGy/h by using a60Co gamma-source. The effects of total dose and reduced pressure on the time to dielectric breakdown and discharge quantity were discussed. Obtained results show that, while increasing the total dose, the discharge quantity decreased with PBN, but increased with PBT. With decreasing the air pressure, the discharge quantity increased with PBN, but decreased with PBT. With increasing the total dose, the time to dielectric breakdown increased with PBN, but decreased with PBT. With decreasing the air pressure, the time to dielectric breakdown increased with both PBN and PBT. The experimental results suggest that the chemical structure of polybutylene polymers plays a main role in the result of radiation reaction, which is related to cross-linking and degradation reaction.展开更多
A new zinc coordination polymer, [Zn2（bpp）（tpa）2H2O] 1 （bpp=1,3-bis（4-pyridyl）-propane and tpa=terephthalate） has been hydrothermally synthesized and characterized by elemental analysis, IR and single-crystal ...A new zinc coordination polymer, [Zn2（bpp）（tpa）2H2O] 1 （bpp=1,3-bis（4-pyridyl）-propane and tpa=terephthalate） has been hydrothermally synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. X-ray crystal structure analysis reveals that complex 1 crystallizes in monoclinic, space group P2/c with a=18.348（2）, b=10.9080（14）, c=13.7924（18）, β=98.156（2）°, V=2732.5（6）3 , Z=4, C29H24N2O9Zn2 , Mr=675.24, Z=4, F（000）=1376, Dc=1.641 mg/m3 , μ=1.815 mm-1 , the final R=0.0443 and wR=0.0769 for 2715 observed reflections （I〉2σ（I））. The title complex exhibits a two-dimensional （4, 4） sheet structure which is further stacked through face-to-face π-π interactions between the monodentately coordinated pyridine ring of bpp ligand and the phenyl ring of terephthalate ligand to form a 3-dimensional supramolecular structure. Thermogravimetric analyses show that the host framework of the complex is thermally stable up to ca. 400 ℃.展开更多
文摘Although the efficiency of poly(ethylene terephthalate)(PET)degradation has been successfully improved by depolymerase engineering,mostly by using Goodfellow-PET(gf-PET)as a substrate,efforts to degrade unpretreated PET materials with high crystallinity remain insufficient.Here,we endeavored to improve the degradation capability of a WCCG mutant of leaf-branch compost cutinase(LCC)on a unpretreated PET substrate(crystallinity>40%)by employing iterative saturation mutagenesis.Using this method,we developed a high-throughput screening strategy appropriate for unpretreated substrates.Through extensive screening of residues around the substrate-binding groove,two variants,WCCG-sup1 and WCCG-sup2,showed good depolymerization capabilities with both high-(42%)and low-crystallinity(9%)substrates.The WCCG-sup1 variant completely depolymerized a commercial unpretreated PET product in 36 h at 72℃.In addition to enzyme thermostability and catalytic efficiency,the adsorption of enzymes onto substrates plays an important role in PET degradation.This study provides valuable insights into the structure-function relationship of LCC.
文摘With the aim to effectively depolymerize polyethylene terephthalate(PET)under mild reaction conditions,PET methanolysis and dimethyl terephthalate(DMT)hydrolysis are integrated in a catalyst system.Firstly,methanolysis of PET to DMT is achieved over Cu-Mg-Al oxide catalyst.Next,terephthalic acid(TPA)is prepared by DMT hydrolysis.It is found that hydrolysis of DMT to TPA can be promoted by introducing trace amount of water in this catalyst system.CuO-MgO-4.5Al_2O_(3)catalyst demonstrates the excellent catalytic performance for the depolymerization of PET with high conversion rate and TPA yield(100%and 99.5%,respectively)after reaction at 160℃for 6 h,which provides a new idea for the depolymerization of PET.
基金supported by the National Natural Science Foundation of China(22308006,22278001)the Natural Science Foundation of Anhui Provincial Education Department(KJ2021A0407).
文摘This work proposed a strategy to improve the caking index of polyethylene terephthalate(PET)waste,in which low-temperature pyrolysis treatment(LTPT)was used to depolymerize PET waste.The mechanism of G modification was revealed combining thermogravimetric(TG)analysis,Fourier transform infrared spectroscopy,pyrolysis-gas chromatography with mass spectrometric detection,and solid-state 13C nuclear magnetic resonance spectroscopy.Furthermore,crucible coking experiments were also conducted using industrial coal mixture and treated PET with the optimum G(PET300)or raw PET to evaluate the applicability of PET waste in coal-blending coking.According to characterization results of coke reactivity(CR),coke strength after reaction(CSR)indices,TG-related curves,pore volumes,and Raman spectra of the resultant cokes,LTPT could greatly increase the G of PET,and the optimum temperature was 300℃.Specifically,compared with the coke obtained from the blend with PET,the CR of the coke produced from the blend with PET300 decreased by 4.9%,whereas the CSR of the increased by 7.4%,suggesting that LTPT could increase the proportion of PET used for coal-blending coking.The improvement in G is attributed to the changes in C-O/C=O ratio,aliphatic H and aromaticity caused by LTPT.
文摘To enhance the hydrophilicity and antistatic properties of the polyethylene terephthalate(PET)fabric,the lawsone dye was employed in dyeing the PET fabric.It was dissolved in ethanol/deionized water mixture and deionized water separately,forming different lawsone dye solutions(LDSs).The study investigated how the compounds in the LDS improve the surface properties and color durability of the PET fabric,resulting in increased dye uptake.An infrared dyeing machine was utilized to expedite the reactions between the lawsone dye and the PET fabric.Additionally,the chemical composition of the dyed PET fabric was verified using techniques such as Fourier transform infrared(FTIR)spectroscopy,X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD)and ultraviolet-visible(UV-Vis)spectrophotometry.The K/S value was measured to assess color durability.After dyeing,the PET fabric exhibited high hydrophilicity which improved the hygroscopicity of the PET fabric and thus the conductivity of the PET fabric surface increased,thereby providing an antistatic effect.
基金support from the National Natural Science Foundation of China(Grant No.22102140the Natural Science Foundation of Jiangsu Province(Grant No.BK20211602)+1 种基金the Qing Lan Project of Yangzhou Universitythe Postgraduate Research&Practice Innovation Program of Jiangsu Province(Yangzhou University,Grant No.SJCX23_1911).
文摘Electrocatalytic valorization of disused poly(ethylene terephthalate)(PET)plastics into value-added chemicals emerges as a potential approach to address plastic pollution and resources upgrading,but it faces challenges in the development of efficient catalysts for PET-derived ethylene glycol(EG)electrooxidation.Herein,we proposed pyramid arrays on sheet Fe-doped NiO/FeNi_(3)(SPA-NiFeO_(x)/FeNi_(3))heterostructure,which is derived from the pyrolysis of MOF-on-MOF heterostructure growth triggered by graphene quantum dots(GQDs).Such SPA-NiFeO_(x)/FeNi_(3)exhibits superior catalytic performance on the electrooxidation of EG(EGOR)from PET hydrolysate,with a formic acid(FA)selectivity of 91.5%and a Faradaic efficiency of 92%.The ligand effect of GQDs in both the catalyst design and improved electrocatalytic performance was studied with combined spectroscopy analysis and theoretical calculations,which revealed that such spatially separated NiFeO_(x)and FeNi_(3)components by GQDs possess more active sites to anticipate in electrocatalytic EGOR,and the large sp2 domains in GQDs possess a strong electron-withdrawing ability to reduce the electron density of bonded Ni and Fe,resulting in high-valenced Ni^(δ+)/Fe^(δ+)in FeNi_(3)and Ni(2+δ)in NiO,respectively.Furthermore,the coordination number of Ni and Fe centers was lowered due to the steric effect of GQDs.Therefore,the adsorption of EG on Ni^(δ+)for cascade dehydrogenation and C–C bond cleavage led to adsorbed FA that transferred to adjacent Fe for desorption,which was promoted by the enrichment of OH−on nearby Ni^((2+δ))sites,along with optimized Gibbs free energy change in the multistep reaction pathway.This work provides an efficient multi-active-site catalyst for disused PET plastics valorization,thereby presenting a new approach to enhance the efficiency of PET plastics valorization reactions.
文摘A novel direct method for preparation of dimethyl carbonate and poly（ethylene terephthalate） from ethylene carbonate and dimethyl terephthalate has been demonstrated in the presence of metal acetate catalysts, lithium acetate dihydrate showed highest catalytic activity with 47.9% yield of dimethyl carbonate. This method was a green chemical process.
基金the National High Technology Research and Development Program of China(No.2003AA321010).
文摘Dimethyl carbonate （DMC） and poly（ethylene terephthalate） was simultaneously synthesized by the transesterification of ethylene carbonate （EC） with dimethyl terephthalate （DMT） in this paper. This reaction is an excellent green chemical process without poisonous substance. Various alkali metals were used as the catalysts. The results showed alkali metals had catalytic activity in a certain extent. The effect of reaction condition was also studied. When the reaction was carded out under the following conditions： the reaction temperature 250℃, molar ratio of EC to DMT 3 ： 1, reaction time 3h, and catalyst amount 0.004 （molar ratio to DMT）, the yield of DMC was 68.9%.
基金the National High Technology Research and Development Program of China(No 2003AA321010)
文摘The reaction between ethylene carbonate and dimethyl terephthalate was carried out for the simultaneous synthesis of dimethyl carbonate and poly（ethylene terephthalate）, This reaction is an excellent chemical process that is environmentally friendly and produces no poisonous substance. The metal acetate catalysts used for this reaction are discussed in detail. Lithium acetate dihydrate was found to be a novel and efficient catalyst for this reaction. Compared with other metal acetates, lithium acetate dihydrate can attain a maximum catalytic activity at a lower concentration. When the reaction was carried out under the following conditions： the reaction temperature from 230 to 250 ℃, molar ratio of ethylene carbonate（EC） to dimethyl terephthalate（DMT） 3： 1, reaction time 3 h, and a catalyst amount of 0. 4% （molar fraction to DMT）, the yield of dimethyl carbonate（DMC） was 79. 1%.
文摘Poly (trimethylene-co-ethylene terephthalate) with various compositions of diol has been synthesized. The crystallization of copolyesters with high comonomer content was observed by both wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). It was found that the copolyesters become less crystallizable with the involvement of the comonomer, the crystals of crystallizable copolyesters come from PTT or PET homopolymers. The glass transition temperature (Tg) of the copolyester increases with increasing PET component in the copolyester, and the relationship between Tg and composition obey both Fox equation and additive law, the former is better in describing this relationship.
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.
基金Project(2016TP1007)supported by the Hunan Provincial Science and Technology Plan,China
文摘In this work,a novel alcohol alkali hydrolysis method was explored for the preparation of terephthalic acid(TPA)from waste polyethylene terephthalate(PET).First,a series of single factor experiments on the depolymerization rate of waste PET bottles and the yield of TPA were conducted to determine the optimized experimental conditions,in terms of reaction time,reaction temperature,dosage of ethylene glycol and sodium bicarbonate,amount of distilled water and stirring rate.Then IR spectra and elemental analysis were carried out for the characterization of obtained product.Under optimal experimental conditions,over 98%PET can be depolymerized into the target product(TPA)and the purity and yield of TPA are over 97%and 94%,respectively.Both the experimental and analytical results support a feasible process for the preparation of TPA from waste PET.It is expected that this alcohol alkali hydrolysis method can promise an effective way for the sustainable recycling of waste PET.
文摘Non-thermal plasmas under atmospheric pressure are of great interest in polymer surface processing because of their convenience, effectiveness and low cost. In this paper, the treatment of Polyethylene terephthalate (PET) film surface for improving hydrophilicity using the non-thermal plasma generated by atmospheric pressure glow discharge (APGD) in air is conducted. The discharge characteristics of APGD are shown by measurement of their electrical discharge parameters and observation of light-emission phenomena, and the surface properties of PET before and after the APGD treatment are studied using contact angle measurement, x-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). It is found that the APGD is homogeneous and stable in the whole gas gap, which differs from the commonly filamentary dielectric barrier discharge (DBD). A short time (several seconds) APGD treatment can modify the surface characteristics of PET film markedly and uniformly. After 10 s APGD treatment, the
基金Key Projects in the National Science&Technology Pillar Program during the Eleventh Five-year Plan Period(2006BAD05A05)
文摘The aluminum oxide(AlOx)coatings were deposited on poly(ethylene terephthalate)(PET)surface by reactive magnetron sputtering for improving its barrier property.With O2 flux increasing,three modes including metallic mode,transition mode and oxide mode exist in sputtering.The properties of the aluminum oxide(AlOx)coatings prepared at different modes were discussed.Also,the influences of oxygen flux on the stoichiometry,structure,gas permeation of the coatings were investigated.The chemical composition of AlOx films fabricated in transition mode is different as oxygen flux varies slightly,and the gas barrier property is better as the stoichiometry is closer to 1.5 with oxygen flux increasing.The coating uniformity,roughness and particle size depend remarkably upon oxygen flux.The coatings deposited at oxide mode have a good barrier performance to oxygen and water,and the permeability to oxygen decreases by sixty times and water vapor ten times compared with uncoated
文摘Stannous-acetylacetonate was prepared efficiently and characterized by ^1H NMR and FT-IR. Its catalytic activity for poly（trimethylene terephthalate） （PTT） synthesis was investigated. By this catalyst, the degree of esterification of pure terephthalic acid was up to 91.7% after reaction at 260 ℃ for 2 h, while the intrinsic viscosity and content of terminal carboxyl groups of the corresponding PTT polymerized at 260 ℃, 60 Pa for 2 h was 0.8816 dL/g and 17 mol/t,respectively. Stannous-acetylacetonate was more active and promising than tetrabutyl titanate and stannous octoate for PTT synthesis.
基金Supported by the National Natural Science Foundation of China（21176070） the National High Technology Research and Development Program of China（2012AA040211）+2 种基金 the Joint Research Project of Yangtze River Delta（12195810900） the Specialized Research Fund for the Doctoral Program of Higher Education（20120074120019） the Fundamental Research Funds for the Central Universities
文摘Most of traditional linear poly(ethylene terephthalate)(PET)resins of relatively low molecular mass and narrow molecular mass distribution have low melt strength at foaming temperatures,which are not enough to support and keep cells.An in-situ polymerization-modification process with esterification and polycondensation stages was performed in a 2 L batch stirred reactor using pyromellitic dianhydride(PMDA)or pentaerythritol(PENTA)as modifying monomers to obtain PETs with high melt strength.The influence of amounts of modifying monomers on the properties of modified PET was investigated.It was found that the selected modifying monomers could effectively introduce branched structures into the modified PETs and improve their melt strength.With increasing the amount of the modifying monomer,the melt strength of the modified PET increased.But when the amount of PENTA reached 0.35%or PMDA reached 0.9%,crosslinking phenomenon was observed in the modified PET.Supercritical carbon dioxide(ScCO2)was employed as physical foaming agent to evaluate the foaming ability of modified PETs.The modified PETs had good foaming properties at 14 MPa of CO2pressure with foaming temperature ranging from 265°C to 280°C.SEM micrographs demonstrated that both modified PET foams had homogeneous cellular structures,with cell diameter ranging from 35μm to 49μm for PENTA modified PETs and38μm to 57μm for PMDA modified ones.Correspondingly,the cell density had a range of 3.5×107cells·cm 3to 7×106cells·cm 3for the former and 2.8×107cells·cm 3to 5.8×106cells·cm 3for the latter.
文摘Stannous oxalate was prepared efficiently and characterized by XRD and FT-IR. It exhibited higher catalytic activity and had profitable effect than tetrabutyl titanate and stannous octoate for the synthesis of polytrimethylene terephthalate （PTT） via esterification-route. Over this catalyst, the degree of esterification of pure terephthalic acid was up to 94.4% at 260 ℃ after 1.5 h,while the intrinsic viscosity and content of terminal carboxyl groups of the corresponding PTT polyester, polymerized at 260 ℃,60 Pa for 2 h, was 0.8950 dL/g and 15 mol/t, respectively. Stannous oxalate was a promising catalyst for the synthesis of PTT polyester.
基金supported by National Natural Science Foundation of China (No.50833003)
文摘In order to develop a more economical pretreatment method for electroless nickel plating, a dielectric barrier discharge （DBD） plasma at atmospheric pressure was used to improve the hydrophilicity and adhesion of poly （ethylene terephthalate） （PET） nonwoven fabric. The properties of the PET nonwoven fabric including its liquid absorptive capacity （WA）, aging behavior, surface chemical composition, morphology of the surface, adhesion strength, surface electrical resistivity and electromagnetic interference （EMI）- shielding effectiveness （SE） were studied. The liquid absorptive capacity （WA） increased due to the incorporation of oxygen-containing and nitrogen-containing functional groups on the surface of PET nonwoven fabric after DBD airplasma treatment. The surface morphology of the nonwoven fibers became rougher after plasma treatment. Therefore, the surface was more prone to absorb tin sensitizer and palladium catalyst to form an active layer for the deposition of electroless nickel. SEM and X-ray diffraction （XRD） measurements indicated that a uniform coating of nickel was formed on the PET nonwoven fabric. The average EMI-SE of Ni-plating of PET nonwoven fabric maintained a relatively stable value （38.2 dB to 37.3 dB） in a frequency range of 50 MHz to 1500 MHz. It is concluded that DBD is feasible for pretreatment of nonwoven fabric for electroless nickel plating to prepare functional material with good EMI-SE properties.
基金financially supported by National Natural Science Foundation of China(No.20776087)National Programs for High Technology Research and Development of China(No.2008AA03Z510)
文摘One-step reaction compatibilized microfibrillar reinforced iPP/PET blends （CMRB） were successfully prepared through a ＂slit extrusion-hot stretching-quenching＂ process. Crystallization behavior and morphology of CMRB were systematically investigated. Scanning electronic microscopy （SEM） observations showed blurry interface of compatibilized common blend （CCB）. The crystallization behavior of neat iPP, CCB, microfibrillar reinforced iPP/PET blend （MRB） and CMRB was investigated by differential scanning calorimetry （DSC） and polarized optical microscopy （POM）. The increase of crystallization temperature and crystallization rate during nonisothermal crystallization process indicated both PET particles and mierofibrils could serve as nucleating agents and PET microfibrils exhibited higher heterogeneous nucleation ability, which were also vividly revealed by results of POM. Compared with MRB sample, CMRB sample has lower crystallization temperature due to existence of PET microfibrils with smaller aspect ratio and wider distribution. In addition, since in situ compatibilizer tends to stay in the interphase, it could also hinder the diffusion ofiPP molecules to the surface of PET phase, leading to decrease of crystallization rate. Two-dimensional wide-angle X-ray diffi：action （2D-WAXD） was preformed to characterize the crystalline structure of the samples by injection molding, and it was found that well-developed PET microfibrils contained in MRB sample promoted formation of t-phase of/PP.
基金Supported bythe Doctoral Foundation of Education Ministry of China (No.20040056037) .
文摘With the increasing application of electric and electronic devices in space and nuclear power stations, the polymeric insulation materials are inevitably exposed to various kinds of environments. Accordingly, it becomes necessary to investigate the effects of the radiation and air pressure on insulation materials. This paper describes the effects of gamma-ray irradiation and reduced pressure on dielectric breakdown of polybutylene naphthalate (PBN) and polybutylene terephthalate (PBT) by applying a DC pulse voltage. Both PBN and PBT were irradiated in air up to 100 kGy and then up to 1 000 kGy with a dose rate of 10 kGy/h by using a60Co gamma-source. The effects of total dose and reduced pressure on the time to dielectric breakdown and discharge quantity were discussed. Obtained results show that, while increasing the total dose, the discharge quantity decreased with PBN, but increased with PBT. With decreasing the air pressure, the discharge quantity increased with PBN, but decreased with PBT. With increasing the total dose, the time to dielectric breakdown increased with PBN, but decreased with PBT. With decreasing the air pressure, the time to dielectric breakdown increased with both PBN and PBT. The experimental results suggest that the chemical structure of polybutylene polymers plays a main role in the result of radiation reaction, which is related to cross-linking and degradation reaction.
基金supported by the Education Office of Anhui Province (No. 2011SQRL080)
文摘A new zinc coordination polymer, [Zn2（bpp）（tpa）2H2O] 1 （bpp=1,3-bis（4-pyridyl）-propane and tpa=terephthalate） has been hydrothermally synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. X-ray crystal structure analysis reveals that complex 1 crystallizes in monoclinic, space group P2/c with a=18.348（2）, b=10.9080（14）, c=13.7924（18）, β=98.156（2）°, V=2732.5（6）3 , Z=4, C29H24N2O9Zn2 , Mr=675.24, Z=4, F（000）=1376, Dc=1.641 mg/m3 , μ=1.815 mm-1 , the final R=0.0443 and wR=0.0769 for 2715 observed reflections （I〉2σ（I））. The title complex exhibits a two-dimensional （4, 4） sheet structure which is further stacked through face-to-face π-π interactions between the monodentately coordinated pyridine ring of bpp ligand and the phenyl ring of terephthalate ligand to form a 3-dimensional supramolecular structure. Thermogravimetric analyses show that the host framework of the complex is thermally stable up to ca. 400 ℃.
