Syntheses, Structure and Property Characterizations of Rare earth- and Transition Metal-based Functional compounds

本论文综合了三年内有关稀土、过渡金属基功能材料的合成、结构分析和性能探索的成果，其中大多数内容以前尚未整理并公开发表。首先是对含甲酸根的稀土复盐RE(HCO2)3(HNO2)(H2CO2)（RE=Rareearth）的系列性研究，首次合成了镥基化合物，Lu(HCO2)3(HNO2)(H2CO2)，同时测试了该系列化合物的激光粉末倍频效应（SHG），并首次从配位化学和晶体学的角度探讨了合成规律和结构性质，指明结构和性能的关系、反应条件的选择和产物的差异。其次是首次用固态反应法合成一种新的Ba磷酸盐——Ba4P2O9，通过化学分析和晶胞大小确定其化学组分比，同时研究其铕掺杂的X射线激发荧光光谱；表...The main contents of this dissertation include the syntheses, crystal structure and physical property characterizations of rare earth- and transition metal-based functional compounds done in the last three years. Most of these have not been published.(1) A new compound, Lu(HCO2)3(HNO2)(H2CO2), with the structure type of RE(HCO2)3(HNO2)(H2CO2)(RE=Y,Tb, Dy,Ho,Er,Yb,Tm、Gd) is synthesized from normal ...学位：工学硕士院系专业：化学化工学院材料科学系_材料学学号：20003600

SYNTHESES OF A-B TYPE BLOCK COPOLYMERS USING 1-PHENYLETHYL DITHIOBENZOATE AS RAFT AGENT

[中文文摘]研究了以双硫酯为链转移剂进行的均聚和嵌段共聚物的合成 .首先合成大分子链转移剂 ,得到分子量可控、多分散性系数较小的均聚物PMMA、PBMA、PEMA、PEA、PBA、PMA、PSt,多分散性系数一般小于 1 30 .在相同的条件下 ,甲基丙烯酸酯类的聚合速度最快 ,苯乙烯其次 ,丙烯酸酯类最慢 .用末端带有双硫酯基团的PSt、PBMA、PBA为链转移剂 ,加入多种第二单体聚合得到实测分子量与理论分子量接近 ,且多分散性系数较小的两嵌段聚合物 .在链转移剂和引发剂的比例为 3∶1～ 6∶1的范围内 ,聚苯乙烯同样可以作为第一嵌段得到和其它酯类单体的两嵌段聚合物 .1 H NMR方法证明了聚合物的末端带有双硫酯基团 .嵌段聚合时必须加入微量的自由基引发剂以形成大分子自由基 ,达到较好的控制聚合效果。[英文文摘]The syntheses of the homopolymers and diblock copolymers by adding dithioester as chain transfer agent. First a series of monomers:methyl methacrylate (MMA), butyl methacrylate (BMA),methyl acrylate (MA),ethyl acrylate (EA),butyl acrylate (BA), and styrene (St) were polymerized in bulk by Reversible Addition\|Fragmentation Chain Transfer (RAFT) polymerization. All of these homopolymers (PMMA、PBMA、PEA、PBA、PMA、PSt)have the controllable polymerization characteristics, the polydispersity index (PDI) is narrow (1108～ 1130) . At the same reaction conditions the rate of polymerization of the methacrylate is the fastest , styrene is slower, acrylate is the slowest . The higher the reaction temperature , the faster the polymerization rate. The effects of the molar ratio of chain transfer agent to initiator on polymerization and the effects of conversion and reaction time on the molar mass characteristics of the prepared block copolymers were discussed. The diblock copolymers have the characteristics of the controlledPliving radical polymerization , that is to say that the real molecular weight of these copolymers is similar to the theoretical molecular2weight , and the polydispersity index is less than 1180. When the molar ratio of ABIN to CTA is ranged from 1∶3 to 1∶6 , the copolymers with PSt as the first block also have characteristics of the controlledPliving radical polymerization. The 1H2NMR spectra of the homopolymer ( PMMA) and copolymer (PMMA2b2PEA) showed that the synthesized polymers have functional groups, dithioester, at the end of these polymers

Synthesis and Crystal Structure of Fe_2BP_3O_12

采用固态反应方法合成了有序的铁基硼磷酸盐Fe2BP3O12,用X射线粉末衍射方法精修了其晶体结构,属三方晶系,空间群为P3,α=8.02703(6)°A,c=7.40168(9)°A,V=413.02(1)°A3,Dx=3.2758(1)(g/Cm3),Z=2,对于55个参数,用188条衍射线及18001个衍射强度全谱数据点精修到R(Ⅰ)=6.35％,R(p)=15.36％,所对应的R(dbw)=10.12％.B原子具有三角形氧配位,P和Fe的氧配位分别是四面体和八面体.Fe的两配位八面体共面形成新结构单元,BO3三角形联接磷氧和铁氧多面体形成三维结构.对比同构的铬硼磷酸盐,此化合物期望具有类似的非线性光学及其它非线性物理性质.Fe2BP3O12 was synthesized by high temperature solid state reactions. Its crystal structure was refined by powder X-ray diffraction methods, belonging to trigonal system with space group P3, α=8.02703(6)°A, c=7.40168(9)°A, v=413.02(l)°A3, Dx=3.2758(l)(g/cm3), Z=2. The full profile refinement resulted to R(Ⅰ)=6.35%, R(p)=15.36% and R(dbw)=10.12% for 55 parameters using 188 reflections and 18001 profile data points. The structure contains [BP3O12]4-poly-anion, built by trigonal planar BO3 sharing the three corner oxygen atom with three PO4 tetrahedra. And Fe2O9 bi-octahedra fused by two face-sharing FeO6 connect with the poly-anions forming three dimensional ordered structure. Compared with its chromium isotypic compound, Cr2BP3O12, which shows NLO property, the title compound may be a potential NLO material.国家自然科学基金委杰出青年基金(20025101);上海市光科技发展基金(022261015);国家科技部863计划(2002AA324070

LIVING FREE-RADICAL POLYMERIZATION IN WATER USING DITHIOESTER AS CHAIN TRANSFER AGENT

[中文文摘]在通常的自由基乳液聚合体系中加入双硫酯链转移剂 Ph C(S) SCH(CH3 ) Ph,研究了 3种酯类单体的活性自由基水相聚合。发现在引发剂与链转移剂的摩尔比为 1∶ 3.3～ 1∶ 4时 ,可得到多分散性系数小 (<1.3) ,实测分子量与理论分子量相近的聚甲基丙烯酸丁酯 (PBMA)、聚丙烯酸丁酯 (PBA)等聚合物 ;聚合物的分子量随时间和转化率的增加而增加 ,具有活性聚合特征 ;醋酸乙烯酯的聚合未得到理想产物。以偶氮二异丁腈 (AIBN)为引发剂时 ,合适乳化剂为 OP- 8(占单体量 10 % ) ;以 (NH4) 2 S2 O8引发时 ,合适乳化剂是十二烷基磺酸钠 (占单体量 2 .4 % )与聚乙烯醇 (PVA,占单体量 1% )的混合乳化体系。油溶性引发剂 AIBN具有较好的控制聚合效果。[英文文摘]Butyl methacryle(BMA), butyl acrylate(BA) and vinyl acetate(VAc) were polymerized by controlled/living radical polymerization in water using reversible addition fragmentation chain transfer(RAFT process). 1 phenylethyl dithiobenzoate (PhC(S)SCH(CH 3)Ph) was selected as dithioester chain transfer agent, 2,2′ azobis(2 cyanopropane)(AIBN) and ammonium peroxysulfate(APS) were used as initiator respectively. The best ratio of chain transfer agent to initiator for controlling polymer molecular weight and molecular weight distribution was 3. 3～ 4. 0. The living character of the RA FT process in water was also indicated by the narrow polydispersity product (1. 1～ 1. 3) , a linear molecular weight conversion profile, the predictab ility of the molecular weight from the ratio of monomer consumed to chaint ransferagent. By contrast, A IBN was more effective than A PS for living radical polymerization in water using reversib leaddition fragmentat on chain tran-sfer, VAc did not polymerize well in this system. The effect s of the ratio of chain transfer agent to in itiator, surfactants and the amount used on the polymer molecular weight and molecular weight dist- ribution were discussed.固体表面物理化学国家重点实验室资助课

Synthesis of A-B Type Block Copolymers Using 1-Phenylethyl Dithiobenzoate as RAFT Agent

[中文文摘]研究了以双硫酯为链转移剂进行的均聚和嵌段共聚物的合成。首先合成大分子链转移剂 ,得到分子量可控、多分散性系数 ( PDI)较小 ( <1 .30 )的均聚物。用末端带有双硫酯基团的 PSt,PBMA和 PBA为链转移剂 ,加入第二单体聚合得到分子量可控、且 PDI较小的两嵌段聚合物。嵌段聚合时必须加入微量的自由基引发剂以形成大分子自由基 ,达到较好的控制聚合效果。[英文文摘]The synthesis of homopolymers and diblock copolymers by adding dithioester as chain transfer agent were performed. A series of monomers were polymerized by Reversible Addition-Fragmentation Chain Transfer(RAFT) polymerization. All of these homopolymers have the controlled polymerization characteristics, PDI is narrow(1.08~1.30). The effect of the molar ratio of chain transfer agent to initiator on polymerization was discussed. The diblock copolymers were gotten by addition of the secong monomer. These copolymers have the characteristics of the controlled/living radical polymerization

Studies on Syntheses and Formation of Borophosphates under Room Temperature and Ambient Pressure

在常温常压条件下直接合成了硼磷酸盐NaCd(H2O)2[BP2O8·]0.8H2O(Hexagonal,P6122,a=0.97130(14)nm,c=1.6136(3)nm,V=1.31836(40)nm3,Z=6)和NaZn(H2O)2[BP2O8]·H2O(Hexagonal,P6122,a=0.95404(2)nm,c=1.47780(3)nm,V=1.16488(5)nm3,Z=6)。用粉末XRD表征了合成产物。用扫描电镜观察了不同温度下形成的产物的形态。通过实时XRD监测方法研究了常温常压下硼磷酸盐NaZn(H2O)2[BP2O8·]H2O的形成过程。NaCd(H2O)2·0.8H2O and NaZn(H2O)2·H2O have been synthesized under room temper-ature and ambient pressure. The two borophosphates were characterized by powder X-ray diffraction. Their morphology were observed by SEM. The formation procedure of NaZn(H2O)2·H2O was studied by in situ powder X-ray diffraction.国家自然科学基金委杰出青年基金(No.20025101);; 国家自然科学基金委重点基金(50332050);; 上海市光科技发展基金(No.022261015);; 国家科技部863计划课题(No.2002AA324070)

New Indium(III) Phosphate CsIn[PO_3(OH)]_2 with a New Type of Structure

水热法合成了新结构类型化合物CsIn[PO3(OH)]2,并通过单晶X--射线衍射表征结构。标题化合物空间群为P121/c1(No.14),晶体学参数为:Mr=439.69,mP56,a=0.53286(6)nm,b=0.91653(7)nm,c=1.47839(14)nm,β=93.849(9)°,V=0.7204(1)nm3,Z=4,Dx=4.054g·cm-3,μ=8.713mm-1,F(000)=800,R1=0.0325,wR2=0.0874。在该化合物中,2个InO6八面体和4个PO4四面体形成交连的六元环柱,并沿a轴方向形成近六方密堆积并连接成Cs+离子占据的十二元环结构隧道,六元环和十二元环连接构筑了三维网络结构。与类似化学计量比化合物Na2In2[PO3(OH)]4·H2O比较,标题化合物中十二元环的形成明显取决于隧道阳离子的大小,其拓扑构造可看作扩展的6,3-网格连接,化合物RbIn[PO3(OH)]2与之同构。A cesium indium hydrated phosphate, CsIn2, was synthesized under mild hydrothermal conditions, and the crystal structures were characterized by single crystal X-ray diffraction method. CsIn2 has a new type of crystal structure. Crystallographic data are as following: Mr=439.69, monoclinic, mP56, P1 21/c 1 (No.14) , a=0.532 86(6) nm, b=0.916 53(7) nm, c=1.478 39(14) nm, β=93.849(9)°, V=0.720 4(1) nm3, Z=4, Dx=4.054 g·cm-3, μ=8.713 mm-1, F(000)=800, R1=0.032 5, wR2=0.087 4 for 116 variables and 1 502 contributing unique reflections. The structure is characterized by 6-membered column with cross-section formed by two InO6 octahedra and four PO4 tetrahedra. The condensation of the column forms an almost hexagonal close-packing array along a axis, resulting in close packing of 12-membered-ring channels occupied by Cs+ cations. The connections of the columns and channels result in a three-dimensional network structure. The formation of the 12-membered ring in these structures seems clearly governed by the cation size by comparing to Na2In24·H2O with the similar stoichiometry. The topological construction of the title structure can be considered as an augmented 6,3-net. RbIn2 is isotypic to the Cs compound. CSD: 391266.国家自然科学基金资助项目(No.50332050);; 国家杰出青年基金资助项目(No.20025101);; 国家科技部“863”计划(No.2002AA324070);; 上海市科委光科技项目(No.D11161015)资

Hydrothermal Synthesis and Characterizations of Na_6In_4[P_7O_(24)(OH)_5]·4H_2O

A new sodium indium phosphate Na 6In 4[P 7O 24(OH) 5]·4H 2O was synthesized under a mild hydrothermal condition and its structure was determined by means of single-crystal X-ray diffraction methods. The title compound crystallizes in a hexagonal system, space group P6 3, with a= 0.950 23(5) nm, b=0.950 23(5) nm, c=1.694 2(2) nm, α=90°, β=90°, γ=120°, V=1.324 8(2) nm 3, Z=8, structure refined to R=0.052 8 and wR=0.116 5 for 2 134 independent observed reflections. The three-dimensional network structure consists of helical chains formed by apex-sharing polyhedra. The connection of the chains results in 4- and 8-polyhedral rings and cages centered by three indium metal connecting oxygen atoms formed by three 4-rings. The three-connected oxygen atom is firstly observed in indium phosphate systems.国家自然科学杰出青年基金 (批准号 :2 0 0 2 5 10 1);; 上海市光科技发展基金 (批准号 :0 2 2 2 610 15 );; 国家科技部“八六三”计划 (批准号 :2 0 0 2 AA3 2 40 70 )资

Low-temperature flux synthesis, crystal structure and Ce-doped luminescence of the first lutetium diphosphate NH4LuP2O7

The first lutetium diphosphate NH4LUP2O7 has been prepared by a two-step, low-temperature self-flux synthesis in the presence of the F-anion, functioning as a mineralizer, which played a significant role in the synthetic process. The crystal structure has been characterized by single-crystal Xray diffraction. The title compound crystallizes in a monoclinic system of the space group P2(1)/c (No. 14), a = 7.651(2) angstrom, b = 10.789(2) angstrom, c = 8.577(2) angstrom, beta = 105.75(3)degrees, V = 681.4(2) angstrom(3), Z = 4, The three-dimensional framework of NH4LUP2O7, composed of LU2P4O14 building units formed by vertex-linking LUO6 and P2O7 goups, is isostructural with compounds of the type KAIP(2)O(7) in the ternary diphosphate(A(I)M(III)P(2)O(7)) system. X-ray-excited luminescence measurements of Ce-activated samples show insteresting scintillation properties with a short decay time of 16 ns at room temperature. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Syntheses of A-B type block copolymers using 1-phenylethyl dithiobenzoate as raft agent

The syntheses of the homopolymers and diblock copolymers by adding dithioester as chain transfer agent. First a series of monomers:methyl methacrylate (MMA), butyl methacrylate (BMA),methyl acrylate (MA),ethyl acrylate(EA),butyl acrylate (BA), and styrene (St) were polymerized in bulk by Reversible Addition-Fragmentation Chain Transfer (RAPT) polymerization. All of these homopolymers (PMMA, PBMA, PEA, PBA, PMA, PSt) have the controllable polymerization characteristics, the polydispersity index (PDI) is narrow (1.08 similar to 1.30). At the same reaction conditions the rate of polymerization of the methacrylate is the fastest, styrene is slower, acrylate is the slowest. The higher the reaction temperature, the faster the polymerization rate, The effects of the molar ratio of chain transfer agent to initiator on polymerization and the effects of conversion and reaction time on the molar mass characteristics of the prepared block copolymers were discussed. The diblock copolymers have the characteristics of the controlled/living radical polymerization, that is to say that the real molecular-weight of these copolymers is similar to the theoretical molecular-weight, and the polydispersity index is less than 1.80, When the molar ratio of ABIN to CTA is ranged from 1:3 to 1:6, the copolymers with PSt as the first block also have characteristics of the controlled/living radical polymerization, The H-1-NMR spectra of the homopolymer (PMMA) and copolymer (PMMA-b-PEA) showed that the synthesized polymers have functional groups, dithioester, at the end of these polymers