Syntheses and cofluorescence of complexes of Eu(Ⅲ)/Y(Ⅲ) with terephthalic acid, 2-thenoyltrifluoroacetone and trioctylphosphine oxide

A series of Eu( Ⅲ )/Y( Ⅲ ) complexes of terephthalic acid(TPA) with 2-thenoyltrifluoroacetone(HTTA) and trioctylphosphine oxide(TPPO) were synthesized. Compositions of these complexes are revealed to be Eu2(1-x)Y2x(TPA)(TTA)4- (TPPO)4 or Eu1-xYx(TPA)(TTA)(TPPO)2. Their IR spectra, fluorescent spectra and the thermal and optical stability were studied. The fluorescent excitation spectra of these complexes show more broad excitation bands than those of Eu2(TPA)3(TPPO)4 and Eu(TTA)3(TPPO)2 corresponding to their formations. In addition, both the binuclear complex EuY(TPA)(TTA)4(TPPO)4 and the chain complex Eu0.4Y0.6(TPA)(TTA)(TPPO)2 present higher thermal stability and better optical stability than the mononuclear complex Eu(TTA)3(TPPO)2 does. And their thermal and optical stabilities are preferably interpreted from the binuclear structure together with the chain polynuclear structure of the complexes. The fluorescence enhancement of cofluorescence Y3+ ions to the Eu(Ⅲ) complexes is clear. The optimum content of Y3+ is 0.6 (molar fraction) for the chain complexes Eu1-xYx(TPA)(TTA)- (TPPO)2 and 0.5 for the binuclear complexes Eu2(1-x)Y2x(TPA)(TTA)4(TPPO)4. The formation of polynuclear structure of the complex Eu1-xYx(TPA)(TTA)(TPPO)2 appears to be responsible for the good cofluorescence effect of Y3+ ions.

Syntheses and applications of Eu(Ⅲ) complexes of 2-thienyltrifluoroacetonate, terephthalic acid and phenanthroline as light conversion agents

A series of europium(Ⅲ) complexes of 2-thienyltrifluoroacetonate (HTTA), terephthalic acid (TPA) and phenanthroline (Phen) were synthesized. The new complexes Eu(TPA)(TTA)Phen and Eu2(TPA)(TTA)4Phen2 were characterized by elemental analysis, IR spectrum, scanning electron microscope and thermal stability analysis. The results show that the thermal stability of the Eu( Ⅲ ) complexes increases in the following order: the mononuclear complex Eu(TTA)3Phen, the binuclear complex Eu2(TPA)(TTA)4Phen2, the chain polynuclear complex Eu(TPA)(TTA)Phen. And the formation of the binuclear/polynuclear structure of the new complexes appears to be responsible for the enhancement of their thermal and optical stability. In addition, The fluorescence excitation spectra of these new complexes show more broad excitation bands than that of the complex Eu(TTA)3Phen corresponding to their formation. The enhancement of Eu3+ fluorescence in the new complexes can be observed by the addition of Gd3+. The bright red luminescent plastics can be obtained when the complex EuGd(TPA)(TTA)4Phen2 is added above 0.5% (mass fraction).

Induction of Bladder Lesion by Terephthalic Acid and Its Mechanism

To provide more information for rational evaluation of potential risks of terephthalic acid （TPA）, we studied the effects of TPA on rats＇ bladders in 90 days after TPA exposure. Methods Sprague Dawley rats were subdivided into five groups, ingesting 0 %, 0.04 %, 0.2 %, 1%, and 5 % TPA respectively for a sub-chronic feeding study lasting for 90 days. Urine, serum and samples of brain, liver, lung, kidney, bladder, etc. were collected and analyzed. Results TPA ingesting decreased the value of urinary pH, and increased the contents of Ca^2＋, Zn^2＋, Mg^2＋, Na^＋, K^＋ in urine. The volume of 24 h urine was significantly increased in male rats in the 1% and 5 % TPA groups. Urinary white sediment was found in both sexes, and its formation in male rats seemed more susceptible than that in female rats. Alpha 2u-globulin （AUG） in serum and urine of male rats was markedly increased in a dose-dependent manner. Fifteen cases of hyperplasia （simple or atypical） were determined in the 5 % TPA ingesting group, 14/52 in male rats and 1/23 in female rats. Among them 3 male rats had no stone or calculus. Those with either bladder stones or hyperplasia were accompanied with urinary white sediments. Conclusion White sediment accompanied with elevated urine AUG is the basis of TPA induced urolith formation, and is also associated with TPA induced bladder epithelial cell proliferation. It can act as an early biomarker for the potential toxic effect of TPA.

Syntheses and Co-Fluorescence of Complexes of Eu (III)/Gd (III) with Thienyltrifluoroacetonate, Terephthalic Acid and Phenanthroline

A series of complexes of europium (III)/gadolinium (III) with 2-thienyltrifluoroacetonate (HTTA), terephthalic acid (TPA) and phenanthroline (Phen) were synthesized by coprecipitation. The resulting complexes including Eu2(TPA)(TTA)4Phen2, Eu1.4Gd0.6(TPA)(TTA)4Phen2, Eu1.0Gd1.0(TPA)(TTA)4Phen2 and Eu0.8Gd1.2(TPA)(TTA)4Phen2 were characterized by elemental analysis, IR spectroscopy and thermal stability analysis. The results of analysis indicate that the complexes obtained have similar binuclear structure with each other. The thermal stability analysis indicates that the complexes Eu2(TPA)(TTA)4Phen2and Eu1.0Gd1.0(TPA)(TTA)4Phen2 possess good thermal stability, which melt at ~241°C and decompose at ~370°C - 430°C corresponding to the formation of the complexes. The fluorescence spectra of Eu2(1-x)Gd2x(TPA)(TTA)4Phen2 (x = 0 - 1) complex powders and their doped silica gels were studied. The co-fluorescence effect of Gd3+ ions in complex powders is different from that of their doped silica gels. The optimum concentration of Gd3+ for complex powders and their doped silica gels is 0.5 and 0.3 (molar fraction), respectively. The co-fluorescence distinction of Gd3+ ions for complex powders and their doped silica gels is preferably interpreted from the proposed binuclear structure together with monomolecular compositions of the complexes for the first time. Both intermolecular energy transfer and intra molecular energy transfer in cross binuclear monomolecular EuGd(TPA)(TTA)4Phen2 are thought to be responsible for the co-fluorescence effect of the complex powders;yet only the latter is thought to be responsible for the co-fluorescence effect in silica gels, for the complex molecules in this case are isolated from each other.

S_2O_8^(2-)／ZnO催化废聚酯醇解制备对苯二甲酸二辛酯

制备了S_2O_8^(2-)/ZnO固体超强酸催化剂,并用于催化废聚酯醇解合成对苯二甲酸二辛酯(DOTP)。用XRD、SEM、XPS、FT-IR等对S_2O_8^(2-)/ZnO的结构和性能进行了表征,考察了固体超强酸制备条件对其催化性能的影响。结果表明,673K焙烧5h所得超强酸S_2O_8^(2-)/ZnO催化性能稳定,废聚酯与异辛醇在210～220℃反应3h,DOTP收率可达91．6%以上。

2,5-二羟基对苯二甲酸Tb(Ⅲ)配位聚合物的合成与表征

采用溶剂热法合成了一个配位聚合物{[Ln2(H2-DHBDC)3(H2O)4](H2O)2}n(H2-DHBDC=2,5-二羟基对苯二甲酸)。利用X-射线单晶衍射(SCXRD)、元素分析(EA)、红外光谱(FTIR)、热重分析(TG)和荧光分光光度法(FS)等对其结构和性质进行了分析与表征。结果表明:晶体属于单斜晶系,P-1空间群,晶胞参数a=1.0640(8)nm,b=1.1239(9)nm,c=1.5232(12)nm,α=99.351(11)°,β=99.511(11)°,γ=92.482(12)°,V=1768(2)nm3,Z=2。八个氧原子在铽离子周围形成一个变形的三角十二面体配位环境,金属离子通过与配体连接形成具有一定孔道的三维结构。荧光分析测试表明,配合物具有较好的荧光性。

2,4,6-三吡啶基三嗪-铽、钐配合物的合成、表征及荧光性能研究(英文)

分别以对羟基苯甲酸、对苯二甲酸和2,4,6-三吡啶基三嗪为配体,铽、钐为中心合成了两个系列共10种配合物。对所合成的配合物进行了元素分析、电导率测定、紫外光谱和红外光谱的测试,推测其组成分别为:RE(TPTZ)(NO3)3(C2H5OH)·H2O,RE(TPTZ)2(NO3)3(C2H5OH)·H2O,RE2(TPTZ)(NO3)6(C2H5OH)·2H2O,RE(TPTZ)(C7H5O3)3(C2H5OH)·2H2O和RE2(TPTZ)2(C8H4O4)(NO3)4(C2H5OH)·H2O(RE=Tb,Sm)。硝酸根、芳香酸的氧原子以及TPTZ的主配位点氮原子与稀土离子成键。对羟基苯甲酸的三重态能级及配合物的荧光测试表明,虽然对羟基苯甲酸三重态能级低于Tb3+和Sm3+离子的最低激发态能级,但该配体和具有芳香环的配体TPTZ耦合,能与Tb3+和Sm3+离子形成发光较好的稀土配合物。对苯二甲酸对铽和钐配合物的荧光增强最大,同时,稀土离子浓度高则荧光强度也高,在这两个系列配合物中未见浓度猝灭现象。

铕Ⅲ-对苯二甲酸-2-噻酚甲酰三氟丙酮多核体系的荧光增强及其应用

以对苯二甲酸(TPA)与2-噻酚甲酰三氟丙酮(HTTA)为配体研究了Eu3+在其乙醇溶液中的荧光增强效果。研究结果表明,在pH为6.8的乙醇溶液中,对苯二甲酸与2-噻酚甲酰三氟丙酮混合配体的敏化可使Eu3+荧光强度提高三个多数量级。在三苯基氧化膦(TP-PO)存在的条件下,稀土La3+、Gd3+、Y3+与Eu3+-TPA-TTA-TPPO形成的多核发光体系具有很强的发光效果,据此建立了测定稀土样品中痕量铕的新方法,方法线性范围为4.0×10-8～3.0×10-6mol/L,检出限达6.0×10-10mol/L。用此体系对4个人工合成的稀土混合物样品进行分析,相对误差为1.7%～3.8%,相对标准偏差为1.7%～3.5%。

2,6-二羟基对苯二甲酸的合成及酯化反应研究

以3,5-二羟基苯甲酸为原料,常压下经Koble-Schmitt反应得2,6-二羟基对苯二甲酸（2,6-DHTA）,再经酯化反应得到两种不同的单酯,即2,6-二羟基-4-甲酯基苯甲酸（β-单酯）和2,6-二羟基-l-甲酯基苯甲酸（α酯）.合成2,6-DHTA较佳实验条件：在甲酸钾熔融状态下,m（3,5-二羟基苯甲酸）∶m（甲酸钾）=1∶ 5.46,反应温度180～190℃,反应时间4h,收率87.32％,质量分数为99.62％；β-单酯合成：以2,6-DHTA为原料,甲醇作为酯化试剂和溶剂,反应时间0.75 h,收率76.94％,质量分数为98.76％；β-单酯的合成：以2,6-二羟基对苯二甲酸双甲酯（二酯）为原料,n（NaOH）∶n（二酯）=4∶1,反应温度0～10℃,氢氧化钠浓度0.6 mol/IL,反应时间2h,收率86.14％,质量分数为98.99％.2,6-DHTA、β-单酯和α-单酯经FT-IR、13C-NMR和EI-MS表征确认.

N,N′-二(2-羟基苯甲酰基)-1,3-苯二甲酰肼和N,N′-二(2-羟基苯甲酰基)-1,4-苯二甲酰肼的合成与热稳定性研究

以自制的水杨酰肼(4)、间苯二甲酰氯(5)为原料,以DMF为溶剂、三乙胺作缚酸剂,间苯二甲酰氯(5)与水杨酰肼(4)摩尔分数为1.00/2.75,于90℃反应9 h,合成了N,N′-二(2-羟基苯甲酰基)-1,3-苯二甲酰肼(7),产品的收率达到79.3%.在相同的条件下,采用对苯二甲酰氯(6)为原料,合成了N,N′-二(2-羟基苯甲酰基)-1,4-苯二甲酰肼(8),收率达到了80.2%.其结构经1H NMR和MS等技术得到确证.并进行了热重分析和针对PVC应用研究,发现其具有良好的热稳定作用.

2-氨基对苯二甲酸双核铜配合物的合成与晶体结构

合成了一种新的铜配合物[Cu2(μ-2-atp)(phen)4].2ClO4(2-atp为2-氨基对苯二甲酸,phen为邻菲咯啉),利用红外光谱和X射线单晶衍射表征了产物的结构,利用元素分析测定了其元素组成,利用热重分析考察了其热分解行为.结果表明,标题化合物属于三斜晶系,P-1空间群,晶胞参数为:a=0.971 0(9)nm,b=1.187 8(1)nm,c=1.234 9(1)nm,α=70.104 0(1)°,β=68.699 0(1)°,γ=86.719 0(1)°,V=1.244 1(2)nm3,Z=1,Dc=1.635g/cm3,μ=1.041mm-1,F(000)=623,R1=0.058 4,wR2=0.129 3.该化合物具有双核铜结构,通过强烈的π-π堆积作用形成二维超分子结构.

精对苯二甲酸生产废水处理与CO_(2)协同利用技术的实践与展望

在全球变暖的严峻形势和我国“双碳”目标的大背景下,本文提出了“化工废水处理与CO_(2)协同利用”概念,选择精对苯二甲酸(PTA)生产废水处理与CO_(2)协同利用生产微藻生物质,开展了实验室研究和为期124天的中试试验。实验结果表明,实现了PTA生产废水COD去除率达到92%以上,对CO_(2)(体积分数10%)捕集率达到93%以上,CO_(2)捕集强度为9~11kg/t废水。产生的剩余生物质通过热裂解处理,生物质热裂解率>95%。通过闭环的碳转化,利用体系处理,利用废水、气体和固体中的碳,实现了从“无用碳”到“可用碳”的转化,为化工企业的碳中和目标提供了新的思路。

快速溶剂萃取-层析柱净化-气相色谱质谱法测定土壤中对苯二甲酸二(2-乙基己基)酯含量

以快速溶剂萃取-层析柱净化-气相色谱质谱法测定土壤中对苯二甲酸二(2-乙基己基)酯的含量。风干土壤样品经ASE-350快速溶剂萃取仪萃取,萃取液用层析柱净化,旋转蒸发仪蒸干,氮吹仪浓缩后,用全扫描(SCAN)采集气相色谱-质谱法分析测定土壤中的对苯二甲酸二(2-乙基己基)酯含量。该方法检出限为0.03 mg/kg,加标回收率为75.0%~116.0%,相对标准偏差为0.55%~6.55%(n=6)。该方法具有萃取效果好、灵敏度高、重现性好、前处理操作简便及净化效果好等优点,可用于测定土壤中对苯二甲酸二(2-乙基己基)酯的含量。

羟甲基苯基次膦酸阻燃共聚酯的合成与性能

合成了一种新型有机磷阻燃剂——羟甲基苯基次膦酸(HMPPA)及HMPPA改性的阻燃共聚酯,研究了其阻燃性能,并与商品化产品——羧乙基苯基次膦酸(CEPPA)阻燃单体及其改性的阻燃共聚酯进行了对比,测试表明,阻燃单体HMPPA的热稳定性比CEPPA高,相同磷含量的HMPPA阻燃共聚酯比CEPPA阻燃共聚酯熔点高,热稳定性好,阻燃性高,HMPPA阻燃共聚酯具有良好的可纺性。

直接酯化合成聚对苯二甲酸乙二醇酯单体的反应精馏工艺模拟

为开发聚对苯二甲酸乙二醇酯聚酯单体新的生产工艺,利用剩余曲线图,对反应精馏直接酯化合成的可行性进行了分析。利用Aspen Plus软件,就现行的多釜串联酯化反应工艺和反应精馏塔合成工艺进行了模拟比较。讨论了酯化反应精馏塔操作参数、回流比、进料位置、塔顶馏出率等对反应的转化率和选择性的影响。结果表明。反应精馏工艺比传统的多釜串联工艺具有较高的酯化率和选择性,同时简化了流程。

对苯二甲酸单异辛酯的合成

以对苯二甲酸、氯化亚砜、异辛醇为原料 ,经过酰化、酯化两步合成了对苯二甲酸单异辛酯 ,收率 4 0 .4 % ,纯度 99.0 %。

一种新型共聚型阻燃剂的合成及性能测试

合成了一种新型有机磷阻燃剂———羟甲基苯基次膦酸(HMPPA),通过红外光谱、核磁共振、及质谱等进行了结构表征,合成了HMPPA改性的阻燃共聚酯,研究了其阻燃性能,并与商品化产品———羧乙基苯基次膦酸(CEPPA)阻燃单体及其改性的阻燃共聚酯作了比较,测试表明阻燃单体HMPPA的热稳定性比CEPPA高,HMPPA阻燃共聚酯阻燃性优于CEPPA阻燃共聚,HMPPA为CEPPA的良好改进产品。

离聚物Surlyn对聚对苯二甲酸乙二醇酯/聚萘二甲酸乙二醇酯共混物结晶性能和力学性能的影响

利用差示扫描热法(DSC)和偏光显微镜(POM)研究了乙烯-甲基丙烯酸离子键聚合物Surlyn对聚对苯二甲酸乙二醇酯(PET)/聚萘二甲酸乙二醇酯(PEN)共混物的结晶性能和力学性能的影响。研究结果表明,Surlyn对PET/PEN共混物具有化学成核作用。适量添加Surlyn,能促进PET/PEN共混物的成核结晶,明显提高结晶速度、结晶温度和结晶度,减小球晶尺寸,提高球晶均匀性,并有助于改善PET和PEN相容性,从而提高PET/PEN共混材料的拉伸强度、弯曲强度、弯曲模量和缺口冲击强度等力学性能。本研究体系Surlyn的最佳用量为2 phr。

新型反应型阻燃剂对羧苯基苯基次膦酸的合成与热稳定性分析

以苯基二氯化膦与甲苯在无水AlCl_3催化下发生Friedel-Crafts反应,所得中间产物经氧化制成对羧苯基苯基次膦酸(CPPPA),产物收率10.3%～30.8%。结果表明,CPPPA起始分解温度与2-羧乙基苯基次膦酸(CEPPA)接近;其5%,10%,50%分解温度均明显于高CEPPA;CPPPA成碳率高于CEPPA,CPPPA可作聚酯永久阻燃剂。

磷系阻燃剂/硼酸锌复合阻燃PET的制备及性能研究

在聚对苯二甲酸乙二醇酯（PET）的酯化过程中添加含磷共聚型阻燃剂2-羧乙基苯基次膦酸（CEP-PA）（其中磷质量分数相对PET为0.6％）和硼酸锌（ZB）（相对PET质量分数为0.05％ ～0.2％）分别作为主阻燃剂和助阻燃剂制备复合阻燃PET,研究了阻燃PET的热性能、燃烧性能和燃烧前后的成炭形貌.结果表明：与纯PET比较,单独添加质量分数为0.05％ ～0.2％的ZB时制备的阻燃PET,其热性能变化不明显,极限氧指数（LOI）提高到27％,残炭量提高,抑烟效果比较明显,抗熔滴性能得到改善;在PET中共同添加ZB和CEPPA所制得的复合阻燃PET的热降解残炭率最高为14.4％,LOI进一步提高到29％,燃烧残炭表面致密,综合阻燃性能更好.