Studies on the Simultaneous Synthesis of Dimethyl Carbonate and Poly(ethylene terephthalate): I. Catalytic Activity of Metal Acetate in Transesterification of Ethylene Carbonate with Dimethyl Terephthalate

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.

Simultaneous Synthesis of Dimethyl Carbonate and Poly（ethylene terephthalate） Using Alkali Metals as Catalysts

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%.

Enzymatic Synthesis and Characterization of Novel Amphiphilic Triblock Copolymer Poly(p-dioxanone-co-5-benzyloxytrimethylene carbonate)-block-poly(ethylene glycol)

Novel amphiphilic triblock copolymer poly（p-dioxanone-co-5-benzyloxytrimethylene carbonate）-block-poly（ethylene glycol）-block-poly（p-dioxanone-co-5-benzyloxytrimethylene carbonate） （p（PDO-co-BTMC）-b-PEG-b-p（PDO-co-BTMC）） was successfully synthesized using immobilized porcine pancreas lipase on porous silica particles （IPPL） as the catalyst for the fLrSt time. 1H NMR, 13C NMR and GPC analysis were used to confirm the structures of resulting copolymers. The molecular weight （Mn） of the copolymer with feed ratio of 69：20：11 （BTMC： PDO： PEG ） was 31300 g/mol and the polydispersity was 1.85, while the Mn decreased to 25000 g/mol and polydispersity of 1.93 with the feed ratio of 50：40：10.

In-situ Polymerization-modification Process and Foaming of Poly（ethylene terephthalate）

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.

Transesterification of Ethylene Carbonate with Dimethyl Terephthalate over Various Metal Acetate Catalysts

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%.

Isothermal Crystallization Behavior of Poly (ethylene terephthalate)/Carbon Black Masterbatch

Poly(ethylene terephthalate) (PET)/carbon black (CB) masterbatch was prepared by melt blending using a separate feeding technique and its homogeneous dispersion morphology was confirmed by transmission electron microscope (TEM). The Avrami and Hoffman-Lauritzen secondary nucleation theories were employed to analyze the effect of high CB content on crystallization kinetics of PET, providing theoretical support for the development of masterbatch with high content of functional components. The Avrami exponents,average values of n,for PET and PET/CB masterbatch are both greater than 3, which indicates three-dimensional growth of crystals. In addition,no significant evidence for regime transition of PET is found applying Hoffman-Lauritzen secondary nucleation theory,though such observations have been reported previously in the literature. Furthermore,appropriate U* value for PET is determined to be 12 800 J/mol. For PET/CB masterbatch,a transition from regime I to regime II around 225℃ is observed with appropriate U* value (12 800 J/mol) . This phenomenon is consistent with a transition point in plot of G versus Tc . The fold surface free energy σe (100. 3 mJ/m 2) of PET is much greater than that of PET/CB masterbatch (48. 3 mJ/m 2) ,which indicates heterogeneous nucleation effect of CB particles.

Polyvinyl acetate/poly(amide-12-b-ethylene oxide) blend membranes for carbon dioxide separation

In this paper,blend membranes from polyvinyl acetate(PVAc)and block copolymer poly(amide-12-b-ethylene oxide)(Pebax1074)are prepared by solution casting and solvent evaporation method.Although they are homogeneous on a macro-scale,the observations from DSC and SEM indicate micro-phase separation for PVAc/Pebax1074 blend membranes.With the increase of Pebax1074 content,gas permeabilities of CO2,H2,N2and CH4all increase greatly.PVAc/Pebax1074 blend membranes with high PVAc content are appropriate for CO2/CH4separation.The temperature dependence of gas permeability is divided into rubbery region and glassy region.The activation energies of permeation in rubbery region are smaller than those in glassy region,and they all decrease with increasing Pebax1074 content.For N2,H2and CH4,their gas permeation properties are mainly influenced by the dual-mode sorption and hydrostatic pressure effect.But for CO2,its permeability increases with the increase of pressure due to CO2-induced plasticization effect,which is more obvious for PVAc/Pebax1074 blend membranes with high PVAc content.

Poly(amide-6-b-ethylene oxide)/[Bmim][Tf2N] blend membranes for carbon dioxide separation

Poly（amide-6-b-ethylene oxide）（Pebax1657）/1-butyl-3-methylimidazo-lium bis[trifluoromethyl）sulfonyl]-imide（[Bmim][Tf2N]） blend membranes with different [Bmim][Tf2N] contents were prepared via solution casting and solvent evaporation method. The permeation properties of the blend membranes for CO2, N2,CH4 and H2 were studied, and the physical properties were characterized by differential scanning calorimeter（DSC） and X-ray diffraction（XRD）. Results showed that [Bmim][Tf2N] was dispersed as amorphous phase in the blend membranes, which caused the decrease of Tg（PE） and crystallinity（PA）. With the addition of [Bmim][Tf2N], the CO2 permeability increased and reached up to approximately 286 Barrer at 40 wt%[Bmim][Tf2N], which was nearly double that of pristine Pebax1657 membrane. The increase of CO2 permeability may be attributed to high intrinsic permeability of [Bmim][Tf2N], the increase of fractional free of volume（FFV） and plasticization effect. However, the CO2 permeability reduced firstly when the [Bmim][Tf2N]content was below 10 wt%, which may be due to that the small ions of [Bmim][Tf2N] in the gap of polymer chain inhibited the flexibility of polymer chain; the interaction between Pebax1657 and [Bmim][Tf2N]decreased the content of EO units available for CO2 transport and led to a more compact structure. For Pebax1657/[Bmim][Tf2N] blend membranes, the permeabilities of N2, H2 and CH4decreased with the increase of feed pressure due to the hydrostatic pressure effect, while CO2 permeability increased with the increase of feed pressure for that the CO2-induced plasticization effect was stronger than hydrostatic pressure effect.

Electrical Percolation of Carbon Black Filled Poly (ethylene oxide)Composites in Relation to the Matrix Morphology

The present work studies the electrical conduction performance of carbon black (CB)filled poly(ethylene oxide) (PEO) composites. The addition of CB leads to reduced matrixcrystallinity as the fillers which are partly situated inside the lamellae and hinder the growth of PEOcrystallites. As a result, the electrical percolation behavior is related with the matrix morphology.

Flame Retardant Finishing of Poly(ethylene terephthalate) Fabric with a Carbon Source Containing DOPO Derivative

9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide( DOPO)-based flame retardant( DOPO-DOPC) which contains carbon source was used to improve the flame retardancy of poly( ethylene terephthalate)( PET) fabrics. The prepared DOPODOPC dispersion was applied onto PET fabrics via two kinds of processes,thermosol process and exhaustion process,and in the later using it alone or together with disperse dyes. The flame retardancy of PET fabrics was determined by limiting oxygen index( LOI) and vertical burning test. The results showed that DOPODOPC could obviously improve the flame retardancy of PET fabrics.The PET fabric treated by 60 g/L DOPO-DOPC dispersion via exhaustion process achieved an LOI value of 32. 3%,for example.The flame retardancy and dyeing performances showed that DOPODOPC dispersion could be used together with a part of disperse dyes in one bath. The thermal stability of DOPO-DOPC and the treated PET fabrics were investigated by thermogravimetric analysis( TGA). And the flame retardant mechanism of DOPO-DOPC treated PET fabrics was further investigated by pyrolysis-gas chromatography/mass spectrometry( Py-GC/MS), Fourier transform infrared spectroscopy( FTIR) and scanning electron microscopy( SEM).

Effect of poly(ethylene glycol) molecular weight on CO_2/N_2 separation performance of poly(amide-12-b-ethylene oxide)/poly(ethylene glycol) blend membranes

Membranes from block copolymer poly(amide-12-b-ethylene oxide)(Pebax1074) and its blends with different molecular weight poly(ethylene glycol)(PEG)(200, 400, 600, 1500, 4600 and 8000) were prepared. The thermal properties and structures of Pebax1074/PEG blend membranes were characterized by DSC and SEM, and the gas permeation properties of CO_2 and N_2 were also investigated at different temperatures. For Pebax1074/PEG blend membranes with low molecular weight PEG(MW≤ 600), higher gas permeabilities than Pebax1074 were achieved. The permeability increased with the increase of PEG molecular weight. The addition of low molecular weight PEG resulted in decrease in activation energy of permeation. For Pebax1074/PEG blend membranes with high molecular weight PEG(MW≥ 1500), due to the melt of PEO phase crystals, the gas permeation properties of blend membranes were temperaturedependent, which could be divided into crystalline region, transition region and amorphous region according to two different transition temperatures. PEG molecular weight and operation temperature determined different gas permeation properties of Pebax1074/PEG blend membranes in three regions. The activation energies of permeation in crystalline region were larger than those in amorphous region.

基于熔喷非织造材料的温度传感器制备及其传感性能

为结合织物的柔软性、舒适度和耐磨性制备低成本、高性能的可穿戴温度传感器,以超声波处理工艺将不同浓度比的聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)和碳纳米管(CNTs)共同负载在聚对苯二甲酸丁二酯(PBT)熔喷非织造材料表面,制备了PEDOT:PSS/CNTs/PBT熔喷非织造材料的温度传感器。借助扫描电子显微镜、X射线衍射仪和傅里叶变换红外光谱仪对温度传感器的微观形貌、化学结构进行表征与分析,并对其热稳定性能、传感性能和力学性能进行测试与研究。结果表明,所制备的温度传感器在25~80℃范围内,灵敏度可达-0.71%/℃,响应时间较快(18 s),线性度较好(R^(2)=0.99),迟滞度低至4.98%,具有良好的重复使用性及长期稳定性,并且在37~38℃的温度范围内感应精度可达0.1℃。所制备的温度传感器能够对环境温度和人体表面温度进行实时稳定监测,具有广阔的应用前景。

高性能PET珠粒泡沫的制备及机理

聚对苯二甲酸乙二醇酯(PET)高温熔体强度低,难以通过超临界二氧化碳(scCO_(2))发泡技术制备高强度、高膨胀率的珠粒泡沫材料。本文建立了一种基于原位熔体增强的发泡新技术,利用聚对苯二甲酸丁二醇酯(PBT)有效负载扩链剂均苯四甲酸二酐(PMDA)得到扩链剂负载母粒(PMDA-MB)。通过PMDA-MB与PET的共混挤出制备了改性PET,有效地延长并支化PET分子链,大幅度地提升了熔体黏度,有效地改善了PET的发泡性能。进一步通过scCO_(2)珠粒发泡技术制备了具有优异的泡孔结构和高膨胀率的PET泡沫材料。结果表明,当PMDA-MB的质量分数为3%、发泡温度为244℃、发泡压力为25 MPa时,所得PET泡沫平均泡孔尺寸为100.8μm,泡孔密度1.91×10^(6)个/cm^(3),膨胀率达15.2,而且该PET珠粒泡沫材料的力学性能优良,拉伸强度达2.54 MPa,压缩强度达4.08 MPa。

长链支化聚对苯二甲酸乙二醇酯的制备及其超临界CO_(2)挤出发泡性能研究

以具有支化结构的多元醇原位聚合改性聚对苯二甲酸乙二醇酯(MPET)为原料,均苯四甲酸二酐(PMDA)为扩链剂,通过反应挤出改性可控制备了不同长链支化程度的聚对苯二甲酸乙二醇酯(PET)。流变测试结果表明长链支化改性MPET熔体黏弹性得到大幅度提升,应变硬化因子也随长链支化程度的增加而增强。在超临界CO_(2)(scCO_(2))挤出发泡过程中,长链支化改性MPET具有优异的挤出可发泡性。采用0.3%(质量分数,下同)PMDA制备得到的MPET-P3具有最佳的挤出发泡性能。当熔体温度为265℃时,其发泡倍率可达14.0倍,泡孔密度为4.81×10^(6)个/cm^(3),平均泡孔直径为153.9μm。

Poly(ethylene carbonate)-based electrolytes with high concentration Li salt for all-solid-state lithium batteries

High-performance solid polymer electrolyte （SPE） has long been desired for the next-generation high energy density and safe rechargeable lithium batteries. A SPE composed of 80 wt% lithium bis（trifluo-romethanesulfonyl）imide （LiTFSI）, 20% poly（ethylene carbonate） （PEC） and a polyamide （PA） fiber membrane backbone was prepared by solution-casting method. This solid electrolyte exhibits quite high ionic conductivity and lithium ion transference number （t＋）, and excellent mechanical strength. The as-prepared solid electrolyte shows good wettability to porous electrodes during cycles, which is beneficial to form ionically conductive phase throughout porous electrodes. All-solid-state LiFePO4lLi cells assembled with the as-prepared solid electrolyte deliver a high initial discharge specific capacity of 125.7 mAh·g^-1 and good cycling stability at 55 ℃ （93.4% retention at 1C after 200 cycles）, and superior cycle performance. Outstanding electrochemical performance can be mainly ascribed to the improved ionic conductivity in the entire porous electrodes due to the good wettability of SPE.

不同铺设方式的PET工程塑料板材阻燃性能及力学性能

研究了一种基于聚对苯二甲酸乙二酯(PET)、阻燃剂以及碳纤维材料制备的改性PET工程塑料,并对所制材料的阻燃性、力学性能、热导性以及电导性进行检测。结果发现,改性PET工程塑料板材阻燃性较好;力学性能受铺设方式影响,0°铺设方式最优,0°/90°铺设方式优于编织铺设方式;热导率、电导率受铺设方式影响不大,但因加入碳纤维材料,所制得改性PET工程塑料的导热以及导电性能优于纯PET。

碳量子点/聚环氧乙烷固态电解质的制备

针对聚氧化乙烷(PEO)基固态电解质室温电导率较低的问题,通过在PEO中掺杂碳量子点(CQDs)作为填料,制备出不同CQDs含量的PEO基固态电解质,通过差示扫描量热分析技术、X射线衍射技术、扫描电子显微镜(SEM)技术等对其进行表征。结果表明:与PEO基固态电解质相比,掺杂CQDs的PEO基固态电解质的结晶度有明显的下降趋势;通过电化学阻抗测试(EIS)得出,PEO-LITFSI-5%CQDs固态电解质在室温下的离子电导率为2.01×10^(-5) S/cm,与PEO-LiTFSI-0%CQDs室温下的离子电导率相比,有明显的提升。

Enzymatic ring-opening copolymerization of trimethylene carbonate and ethylene ethyl phosphate

Enzymatic ring-opening copolymerization of trimethylene carbonate (TMC) and ethylene ethyl phosphate (EEP) are performed in bulk at 100°C using porcine pancreas lipase (PPL) or candida rugosa lipase (CL) as catalyst. The factors affecting the yield and molecular weights such as catalyst concentration, polymerization time and monomer feed ratio are investigated. The random copolymers obtained have molecular weight ranging from 3200 to 10200. The glass transition temperature (T g) of the copolymers decreases from ?28 to ?41.7°C, with the increase of the EEP content in the feed from zero to 5:10. Degradation tests show that the degradability of the copolymers is improved by introduction of the EEP unit into the copolymer chain.

聚碳酸乙烯撑酯与双端氨基聚乙二醇交联体系固定化酶载体的合成与表征

将聚碳酸乙烯撑酯 (PVCA)与α,ω-双端氨基聚乙二醇 (H2 N-PEG-NH2 )溶于 DMF,于液蜡中进行交联反应制得亲水性固定化酶载体 ,将其与胰蛋白酶进行偶联反应制备了固定化胰蛋白酶 .酶蛋白的比活力及其于载体上的结合量与反应条件有关 ,当 w(PVCA) / w(H2 N-PEG-NH2 )为 0 .5时 ,二者均处于最高值 .此固定化酶酶促反应的最适 p H值和 Km 值均较之溶液酶有显著提高 。

乙酰丙酮盐催化碳酸乙烯酯和丁二酸二甲酯的耦合反应

研究了乙酰丙酮盐催化碳酸乙烯酯（EC）和丁二酸二甲酯（DS）耦合反应合成聚丁二酸乙二酯（PES）预聚体和碳酸二甲酯（DMC）的新工艺。结果表明,乙酰丙酮氧钛对EC和DS耦合反应的催化效果最好。并以乙酰丙酮氧钛为催化剂考察了反应温度、催化剂用量、物料配比、反应时间对耦合反应的影响,得到最佳的工艺条件：反应温度225℃~235℃,n（EC）=0.23 mol,n（DS）=0.1 mol,n（cat）=3.3mol,反应时间3h。在该工艺条件下,DMC收率51.3%,PES预聚体的特性黏数0.1358。