新型PVC热稳定剂—三（羟基乙硫醇）锑的合成

研究了一种充醇锑类热稳定剂－三（羟基乙硫醇）锑的合成及其应用,实验时以三氧化二锑和巯基乙醇为原料,采用一步法直接化合生成三（羟基乙硫醇）锑。此外,探讨了反就耦葩应物配比、反应时间等因素对产率的影响。实验结果表明：以二甲苯作为带水剂尖物Ｓb２Ｏ３与６ＨＳＣＨ２ＣＨ２ＯＨ的量比为１：１．２,加热回流１．０h,得产品的收率为 ９３．８％;三（羟基乙硫醇）锑为 黄色液体,其折光率Ｄn＾２０为１．４４７９;当     

PVC热稳定剂五（巯基乙酸异辛酯）锑的合成及其性质

以焦锑酸钠与巯基乙酸异辛酯为原料，用一步法合成了五（巯基乙酸异辛酯）锑，并用红外光谱对产品进行了分析，实验结果表明，当焦锑酸钠与巯基乙酸异辛酯的量比为1．2：1．0时，以甲苯为溶剂，加热回流3．5h，即可得到目标产物五（巯基乙酸异辛酯）锑，其收率为92．8％；当五（巯基乙酸异辛酯）锑在PVC中加添加量为2．5％时，PVC的热稳定时间为40min(20℃时）；当其与硬脂酸钡复配时，表现出协同作用。     

Synthesis and characterization of mibolerone

A simple and effective route for the synthesis of mibolerone was described starting from the estr-5(10)-en-3,17-dione in four steps with the overall yield of 47.0 %.Thus,two methods for key intermediate methylnorandrost were investigated:one(method A)starting from estr-4-en-3,17-dione underwent 3-keto group protected with ethyl orthoformate to give 3-ethoxy-3,5-dien-estr-17-one,the other(method B)from estr-5(10)-en-3,17-dione and protected 3-keto group to give 3,3-dimethoxy-estr-5(10)-7-one in a mild acidic condition.Then,two intermediates were subsequently reacted with methyllithium followed by a mild hydrolytic procedure and gave methylnorandrost with total yield 25.0% and 86.0 %,respectively.In the preparation of 6-dehydrogenation product of methylnorandrost,two procedures(method C and method D)were investigated:one was the protected 17α-methyl-17β-hydroxy 3,5-enol ethers estrendiene brominated and the resulting 6-bromo-19-methylnortestosterone was then immediately dehydrohaloenated to give 6-dehydro-19-methylnortestosterone,the total yield only reaches 36.0%;the other was directly dehydrogenated with chloranil and the yield reaches 75.6% under the optimum conditions:in refluxing tetrahydrofuran,the molar ratio of methylnorandrost to chloranil is 0.66 and reaction time of 5 h.The titled compound and intermediates were characterized by 1H and 13C NMR,IRMS and elemental analysis.     

Synthesis and Characterization of Poly （L-lactide-co-glycolide）

Poly （ l- lactide- co-glycolide ） （ PLGA ） with different compositions was prepared using stannous octaoate as catalyst by bulk ring-opening copolymerization of l-lactide and glycolide. The structure and properties of the PLGA copolymers were cbaracterized by means of attenuated total reflectance-Fourier transform infrared （ATR-FTIR）, ^1H NMR, differential scanning calorimeter （ DSC and X-ray diffraction （XRD） methods, The experimented results indicate that the synthetic conditions and the composition of copolymers have art obvious influence on the structure of PLGA copolymers, The degradation rate of eopolymers increased with the increasing of the glycolide component in the copolymers.     

Synthesis and adsorption properties for Au（Ⅲ） of alkoxycarbonyl thiourea resin

A novel alkoxycarbonyl thiourea resin（ATR） was synthesized by monomer polymerization of oxydiethane-2,1-diyl dicarbonisothiocyanatidate and polyethylene polyamine, and characterized by FT-IR. The adsorption properties of ATR were investigated by batch test. The adsorption capacities for Au（Ⅲ）, Ag（Ⅰ）, Cu（Ⅱ）, Zn（Ⅱ, Fe（Ⅲ）, Ca（ Ⅱ ） and Mg（ Ⅱ ） are 4.65, 4.40, 0.40, 0.90, 0.86, 0.0080 and 0.016 mmol/g, respectively, when the adsorption condition is as follows： contact time 24 h, temperature 30 ℃, initial concentration of Au（Ⅲ） 5.08 mmol/L and that of other metals 0.10 mol/L, and concentration of acid 1.0 mol/L. The adsorption capacity for Au（Ⅲ） increases with the increase of contact time, temperature and initial concentration of Au（Ⅲ）. The capacity after five adsorption-desorption cycles remains 90% that of the first time, and the separation factors of ATR for binary metal ion solutions are larger than 995, indicating that ATR is of good regeneration property and selectivity. XPS results show that the functional atoms of ATR supply electrons for Au and coordinate with Au during the adsorption.     

Synthesis of P（St-BA-MAA-SPAA） nano-latex and its application in high anti-corrisive coating

A novel zinc-rich pigment based on P（St-BA-MAA-SPAA） nano-latex was obtained, which is suitable for the use in hot alkali liquid medium. The nano-latex was synthesized by active emulsifier latex polymerization method with monomers of styrene （St）, butylacrylate （BA）, methylacrylic acid（MAA） in the presence of active emulsifier 3-sulfopropylacrylate（SPAA）. The synthesis condition and properties of the latex were investigated. And the anti-corrosive property of the resultant zinc-rich coating was studied. The results show that the nano-latex is self-stabilized and has a narrow particle diameter distribution, the average diameter of the latex particles is 71 nm. Zinc powders can be evenly dispersed in the nano-latex, which indicates that the P（St-BA-MAA-SPAA） nano latex can be used as the binder of zinc-rich coating. The resultant zinc-rich coating is able to resist the invasion of hot alkali solution（the temperature is 95 ℃ and the pH value is 14） for 480 h and the exposure time in salt spray is 1 200 h. Moreover, the coating shows good thermal conductivity and static electricity properties, its thermal conductivity and electric resistivity are 21-37 W/（m.K） and 6.7 × 10^5-3.5 × 10^6 Ωcm, respectively.     

Synthesis and fluorescence properties of Tb（Ⅲ） complexes with pyridine-2,6-dicarboxylic acid derivatives

Two novel ligands named 4-styrylpyridine-2,6-dicarboxylic acid （4-SPDA） and 4-（4-（2-（2, 6-dicarboxypyridin-4-yl）- vinyl）styryl）pyridine-2,6-dicarboxylic acid（DSPDA） and their complexes with Tb（Ⅲ） were synthesized and characterized by infrared spectrometry, 1H nuclear magnetic resonance, elemental analysis and gas chromatograph-mass spectrometry. The ligand synthetic route was optimized. The fluorescence properties of the complex in solid state, in different kind of solvents and in solutions with different pH values were investigated in detail. The results show that the yields of DSPDA and 4-SPDA reach over 78% by Wittig-Horner reaction and other eight pyridine-2, 6-dicarboxylic acid derivatives with different substituents on pyridine ring, and their complexes with Tb（Ⅲ） are also obtained. The fluorescence intensities of the complexes with electron-donating groups are more intense than those of the complexes with electron-withdrawing groups on pyridine ring; fluorescence intensities of the complexes are the strongest in neutral solution （pH=7）, and the less the dipole moment of solvent molecule is, the stronger the fluorescence intensity is. It is found that the two ligands （4-APDA and DSPDA） are the good sensitizers for Tb（Ⅲ） ion.     

Synthesis and structural characterization of macroporous bioactive glass

Porous sol-gel glass of CaO-SiO2-P2O5 system with macropores larger than 100 μm was prepared by adding stearic acid as pore former when the sintering was carried out at 700 ℃ for 3 h. The sol-gel porous glass shows an amorphous structure. The diameter of the pore created by pore former varies from 100 to 300 μm, and macroporous glass has a narrow and small pore size distribution in mesoporous scale. The porosity and pore size ofmacroporous bioactive glass can be controlled.     

Preparation and application of antimony mono (isooctyl thioglycolate) di(n-dodecanethiol)

ＡｎｔｉｍｏｎｙｍｅｒｃａｐｔｉｄｅｉｓａｎｅｗｔｙｐｅｏｆｈｅａｔｓｔａｂｉｌｉｚｅｒｆｏｒＰＶＣ,ｗｈｉｃｈｈａｓｔｈｅｆｏｌｏｗｉｎｇｃｈａｒａｃｔｅｒｉｓｔｉｃｓ：ｈｉｇｈｅｆｆｉｃｉｅｎｃｙ,ｎｏｎｔｏｘｉｃｏｒｈａｒｍｆｕｌｅｓ,ｌｏｗ...     

Synthesis and thermal stability of antimony tris (thioethyl stearate) for PVC

ＰＶＣｉｓｉｎｔｒｉｎｓｉｃａｌｌｙｕｎｓｔａｂｌｅｂｅｃａｕｓｅｏｆｍｏｌｅｃｕｌａｒｄｅｆｅｃｔｓｉｎｓｏｍｅｏｆｔｈｅｐｏｌｙｍｅｒｃｈａｉｎｓ ,ａｎｄｗｈｅｎｓｕｂｊｅｃｔ ｅｄｔｏｈｅａｔｔｈｅｙｉｎｉｔｉａｔｅａｓｅｌｆ ａｃｃｅｌｅｒａｔｉｎｇｄｅｈｙｄｒｏｃｈｌｏｒｉ ｎａｔｉｏｎｒｅａｃｔｉｏｎ .ＳｔａｂｉｌｉｚｅｒｓｎｅｕｔｒａｌｉｚｅｔｈｅＨＣｌｐｒｏｄｕｃｅｄａｎｄｉｎｔｒｏｄｕｃｅｎｕｃｌｅｏｐｈｉｌｉｃｓｕｂｓｔｉｔｕｔｉｏｎｒｅａｃｔｉｏｎｓｔｈａｔｐｒｅ ｖｅｎｔｆｕ…     

SYNTHESIS，PROPERTY AND HEAT STABILITY FO RPOLYVINYLCHLORIDSOFANTIMONYTRIS（MERCAPTOACIDESTER）

ＳＹＮＴＨＥＳＩＳ，ＰＲＯＰＥＲＴＹＡＮＤＨＥＡＴＳＴＡＢＩＬＩＴＹＦＯＲＰＯＬＹＶＩＮＹＬＣＨＬＯＲＩＤＳＯＦＡＮＴＩＭＯＮＹＴＲＩＳ（ＭＥＲＣＡＰＴＯＡＣＩＤＥＳＴＥＲ）ＳＹＮＴＨＥＳＩＳ，ＰＲＯＰＥＲＴＹＡＮＤＨＥＡＴＳＴＡＢＩＬＩＴＹＦＯＲＰ...     

有机锑高效PVC热稳定剂的合成

为开发有机锑类高效ＰＶＣ热稳定剂,以三氧化二锑与自制的十二烷基硫醇为原料,合成了三（十二烷基硫醇）锑,。产率可达８７．８％;以三氧化二锑与自制的巯基乙酸异辛酯为原料,合成了三锑,产率可达９３．８％,通过正交实验对反应条件进行了优化。对两产物中间产品进行了分析鉴定。结果与文献值相符。     

Synthesis of lanthanum tris (mono-i-octyl phthalate) and its thermal stability for polyvinyl chloride

ＰＶＣｉｓｕｎｓｔａｂｌｅｂｅｃａｕｓｅｏｆｍｏｌｅｃｕｌａｒｄｅｆｅｃｔｓｉｎｓｏｍｅｏｆｔｈｅｐｏｌｙｍｅｒｃｈａｉｎｓ ,ａｎｄａｓｅｌｆ ａｃｃｅｌｅ ｒａｔｉｎｇｄｅｈｙｄｒｏｃｈｌｏｒｉｎａｔｉｏｎｗｈｅｎｓｕｂｊｅｃｔｅｄｔｏｈｅａｔ;ｓｔａｂｉｌｉｚｅｒｓｎｅｕｔｒａｌｉｚｅｔｈｅＨＣｌｐｒｏｄｕｃｅｄａｎｄｉｎｔｒｏ ｄｕｃｅｎｕｃｌｅｏｐｈｉｌｉｃｓｕｂｓｔｉｔｕｔｉｏｎｒｅａｃｔｉｏｎｓｔｈａｔｐｒｅ ｖｅｎｔｆｕｒｔｈｅｒｄｅｇｒａｄａｔｉｏｎ .Ｓｏｍｅｒａｒｅｅａｒｔｈｃｏｍ …     

Synthesis of lanthanum tris (mono- i -octyl phthalate) and its thermal stability for polyvinyl chloride

A novel type of thermal stabilizer—lanthanum tris (mono-i-octyl phthalate) (LTMP) was synthesized by double-decomposition reaction of sodium mono-i-octyl phthalate with lanthanum chloride at 60 °C. Sodium mono-i-octyl phthalate was prepared by sodium hydrate and mono-i-octyl phthalate prepared by reaction of isooctyl alcohol and phthalic anhydride in the presence of sulfuric acid catalyst at 110 °C. The yield of lanthanum tris (mono-i-octyl phthalate) is about 84.5%. Its thermal stabilities were measured by heat-ageing oven test when incorporated into PVC. The experimental results show that the heat stability time is about 40min at 190 °C when adding 3phr (per hundred resin) to PVC. The thermal stability of this product is better than that of Ca-Zn complex and basic lead salt stabilizers, and equal to that of dibutyltin diaurate. Foundation item: The Key Program of 9^th Five-Year Plan of China(No. 96-119-04-03-05) Biography of the first author: LIU You-nian, associate professor, born in Oct. 1964, majoring in fine chemical engineering & separation processes.     

二亚磷酸二(对叔丁基苯基)季戊四醇酯的合成

以亚磷酸三乙酯、季戊四醇、对叔丁基苯酚为原料,无水碳酸钾为催化剂,采用酯交换法合成了二亚磷酸二（对叔丁基苯基）季戊四醇酯。实验探讨了反应温度、反应时间、催化剂、催化剂用量、物料配比等因素的影响,确定了最佳工艺条件：第一步的反应温度是120～130℃,反应时间为2h,第二步的反应温度为160～170℃,反应时间为3h,无水碳酸钾为催化剂,物料配比n（季戊四醇）：n（亚磷酸三乙酯）：n（对叔丁基苯酚）为1：2．05：2,催化剂的用量为0．5g,产品的收率在97％以上。通过元素分析、红外分析对产品进行了表征。     

二亚磷酸二(2,6-二叔丁基对甲酚)季戊四醇酯的合成

以亚磷酸三乙酯、季戊四醇和2,6-二叔丁基对甲酚为原料合成了抗氧剂二亚磷酸二（2,6-二叔丁基对甲酚）季戊四醇酯。探讨了物料配比、催化剂的种类及用量、反应时间等反应条件对产率的影响,并通过正交试验法确定了最佳工艺条件。实验结果表明：催化剂为无水碳酸钾,其用量为0.6 g;物料配比（n（季戊四醇）∶n（亚磷酸三乙酯）∶n（2,6-二叔丁基苯酚））为1.0∶2.12∶2.04;反应Ⅰ温度为130~140℃,反应Ⅰ时间为2 h,反应Ⅱ温度为170~180℃,反应Ⅱ时间为4 h。在最佳工艺条件下所制得的产品为白色粉末状固体,熔点为67~69℃,产率为87%左右。此外,通过元素分析、红外光谱分析对产品进行了物性和结构表征。     

微波法合成树枝状纳米硫化锑

以氯化锑、硫脲为原料,采用微波法合成树枝状硫化锑纳米材料。用X射线粉末衍射（XRD）、扫描电子显微镜（SEM）和X射线能谱（EDS）等对Sb2S3晶体的物相及形貌进行分析表征。结果表明制备出的是正交相Sb2S3,长度可达数十微米。并给出树枝状硫化锑纳米材料的可能的形成机理。     

新型聚芳酰胺酰亚胺的合成与表征

基于新型邻二苯基取代偏苯三酸酐合成了粘度在0.39～1.43系列聚芳酰胺酰亚胺,新型无定型聚合物在极性非质子溶剂DMAC,NMP,DMF,DMSO等中有良好的溶解性. 其玻璃化转变温度在284～336℃. 5 %热失重温度大于468℃.