Synthesis and Properties of pH and Temperature Responsive Copolymer with Pesudorotaxane Structure

pH and temperature responsive copolymers PNAM4VBCB of N-isopropyl acrylamide(NAM) and complex pseudorotaxane monomer N¹-(4-vinylbenzyl)-1,4-diaminobutane dihydrochloride with cucurbit[6]uril(CB[6]) threaded(4VBCB) were prepared via free-radical polymerization in aqueous solution. The copolymers were characterized by ¹H NMR, Fourier transform infrared(FTIR) spectrometry, elemental analysis, and static light scattering. The thermodynamic properties of the copolymers were studied by thermogravimetric analysis(TGA), and the effects of pH and the concentration of the copolymer on the average hydrodynamic radius(R_h) were studied by dynamic light scattering(DLS). In addition, the thermal sensitivities of the copolymers were studied by DLS and UV-Vis. The experiment data show that CB[6] beads are localized on 1,4-diaminobutane units in the side chains of the copolymer. TGA data show that thermal stability of the copolymers increases with the adding of CB[6] threaded because of the enhanced rigidity and the bulky steric hindrance of 4VBCB in the side chain of PNAM4VBCB. DLS data show that the average hydrodynamic radius of copolymer increases with the increase of the copolymer concentration and has a jump with adjusting pH due to the existing of the small size CB[6] dethreaded from the copolymer with increasing pH. Both pH and electrical conductivity curves of the solution of PNAM4VBCB-4 have a jump because CB[6] could dethread from the copolymers with the addition of NaOH. In addition, the copolymers have thermal sensitivity and their phase-change temperatures could be controlled by adjusting the molar ratio of NAM to 4VBCB in the copolymers.     

Synthesis,characterization, and properties of copolymer of acrylamide and complex pseudorotaxane monomer consisting of cucurbit[6]uril with butyl ammonium methacrylate

The novel copolymers of acrylamide (AM) with complex pseudorotaxane monomer (BAMACB) of butyl ammonium methacrylate (BAMA) and cucurbit[6]uril (CB[6]) were prepared via free‐radical polymerization in aqueous solution. The copolymers containing pseudorotaxane (PAM/BAMACB) were characterized by ¹H‐NMR, FTIR, elemental analysis, TGA, and DSC. The glass transition temperature (T_g) of the copolymer PAM/BAMACB are higher than that of the copolymer of acrylamide and butyl ammonium methacrylate (PAM/BAMA) because of the enhanced rigidity and the bulky steric hindrance of BAMACB side chain in PAM/BAMACB. The molecular weights of copolymer PAM/BAMACB were obtained via static light scattering. The hydrodynamic radii of coils or aggregates were investigated by dynamic light scattering. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5999–6008, 2008     

新型磷-钒-氧层状化合物[H2en]2[H3O]6[Co(H2O)2(VO)8(OH)4(PO4)8]的水热合成与晶体结构

金属磷酸盐材料在吸附、离子交换、离子传导和催化剂方面有潜在的应用前景[1～5]. 近年来, 通过水热反应合成了一些A-V-P-O化合物. 在这些化合物中, A一般为碱金属或有机阳离子, 如层状结构的[H2N(C4H8)2NH2][(VO)4(OH)4(PO4)2][6] 和[H2N(C2H4)3NH2][(VO)8(HPO4)3(PO4)4*(OH)2]*2H2O[6], 一维链状结构的 [H2NCH2CH2NH3(VO)(PO4)][7], 手性双螺旋结构的 [(CH3)2NH2]K4[(VO)10(H2O)2(OH)4(PO4)7]*H2O[8]以及具有三维骨架结构的化合物 [H3N(CH2)3NH3K(VO)3(PO4)3][9], [H3N(CH2)3NH3]2[V(H2O)2(VO)6(OH)2(HPO4)3(PO4)5]*3H2O[10]和[H3N(CH2)2NH3][(VO)3(H2O)2(PO4)2(HPO4)4][11].     

One novel multidimensional organic-inorganic hybrid based on polyoxometalates and copper chlorine coordination polymers with 4,4’-bipyridine ligands

One novel organic-inorganic hybrid materials with 4,4’-bipy ligands and copper chlorine coordination polymers as linkers,with new topology,{[Cu^I（4,4’-bipy）]₁₀Cl₂(SiW₁₂O₄₀)₂}·6H₂O（1）（4,4’-bipy = 4,4’-bipyridine）,has been hydrothermally synthesized. The single crystal X-ray structural analysis reveals that the structure of 1 is constructed from classical Keggin anions and[Cu^I（4,4’- bipy）]cations into a novel,three-dimensional（3D） polyoxometalates（POMs）based network.From the topological view,compound 1 is a novel（3.4⁴.5².6³）（3².4⁴.5⁶.6⁹） topology.The electrochemical and photocatalysis properties of 1 have been investigated in details.     

Preparation of Novel Side-chain Pseudopolyrotaxanes Consisting of Cucurbituril[6] and Polyamine Salts

Pseudorotaxane monomer （VBCB） containing cucurbitutil[6] （CB[6]） and N^1-（4-vinylbenzyl）-1,4-diaminobutane dihydrochloride （VBDADC） is obtained by self-assembly of cucurbituril[6] with VBDADC in water and then polymerized using potassium persulfate （KPS） as initiator to give novel water-soluble side-chain cucurbituril[6]-based pseudopolyrotaxane（PVBCB）. The chemical structures of PVBCB, VBCB and VBDADC are confirmed by ^1H NMR,^13C NMR spectra and elemental analysis. In VBCB, CB[6] is localized aliphatic group of the side chain and the molar ratio of CB[6] to VBDAC is 1：1 .     

Preparation and properties of two new soluble carbazole-containing functional polyacetylenes

Two new functional polyacetylenes bearing carbazole group as pendant,poly {3-[（4-ethynylstyryl）-N-butyl]carba/ole}（P1） and poly{3-[4-（prop-2-ynyloxy）phenyl-N-butyl]carbazole}（P2）,were prepared using[Rh（nbd）Cl)₂-Et₃N as catalyst.The polymers were soluble in common organic solvents such as CHCl₃ and THK Their structures and properties were characterized and evaluated with FTIR,¹H NMR,UV,TGA,GPC,and CV,respectively.The results show that the polymers possess high thermal stability and well hole-injection property.     

侧链含卤素基团聚芳醚酮的合成及性能

通过分子设计, 合成了新型含碘基苯基的双酚单体4-碘苯基对苯二酚(I-Ph-HQ), 利用上述单体与含氟双酚单体(3-三氟甲基)苯基对苯二酚和氟酮通过亲核取代缩聚反应合成了一系列侧链含卤素基团的聚芳醚酮共聚物(PEEK-CF₃-I). 通过FTIR和 ¹H NMR等测试手段, 表征了共聚物的化学结构. 研究了所合成的PEEK-CF₃-I共聚物的介电性能、热性能和机械性能, 探讨了共聚物中含碘侧基和含氟侧基含量的变化及对材料各项性能的影响. 研究表明, 共聚物中含碘侧基含量的增加能够显著提升共聚物的玻璃化转变温度, 其中共聚物材料PEEK-CF₃-I-10%的玻璃化转变温度为153 ℃, 同时材料依然能够保持优异的机械性能和较低的介电常数.     

含侧链盘状苯并菲和棒状偶氮苯的二嵌段液晶共聚物的可控合成及其光物理性质

分别通过可逆加成-断裂链转移（RAFT）聚合和原子转移自由基聚合（ATRP）结合叠氮-端炔基大分子点击反应,制备了一系列不同聚合度和不同嵌段比例的基于侧链苯并菲TP盘状液晶基元和偶氮苯Azo棒状液晶基元的盘棒杂化二嵌段共聚物。采用核磁共振氢谱（¹H NMR）、凝胶渗透色谱（GPC）、差示扫描量热分析（DSC）和正交偏光分析（POM）对盘棒杂化二嵌段共聚物的组成结构、相对分子质量和液晶相行为进行了表征。偶氮苯嵌段较短的共聚物P（TP₆）₄₀-b-P（Azo）₁₀,主要表现出占优势嵌段TP盘状液晶聚合物的热转变温度与相行为。而偶氮苯嵌段较长的共聚物P（TP₆）₁₀-b-P（Azo）₄₀和P（TP₆）₄₀-b-P（Azo）₄₀则更多体现出类似Azo棒状侧链液晶聚合物的相行为和光响应特性。小角/广角X射线散射（SAXS/WAXS）分析证实了Azo嵌段较长的嵌段共聚物薄膜尤其经退火处理后呈现层状结构,倾向于平行基底取向排布的苯并菲诱导偶氮苯平躺沿着平行基底方向排列而显著减少了光吸收,经紫外及可见光的辐照后光吸收显著增大,其中盘状嵌段较长的P（TP₆）₄₀-b-P（Azo）₄₀对比响应增幅尤其明显。这种盘棒杂化二嵌段共聚物薄膜所表现出的特殊光物理性质及其快速光响应-回复特性,加深了对其相互作用的理解,可望为设计合成新的光响应材料提供参考依据。     

Synthesis of polysilanes bearing pendant carbosilyl groups and Si-NMR probe on the tacticity using side chain silicon atoms

New functional polysilanes [R₂R¹Si(CH₂)₂SiH]_n (R=Me, R¹=H (1); R=R¹=Et (2); R=Me, R¹=Ph (3)) bearing carbosilyl side chains have been synthesized by catalytic dehydropolymerization of precursor carbosilanes R₂R¹SiCH₂CH₂SiH₃ using Cp₂TiCl₂–BuLi as a catalyst. These polymers are characterized by ¹H, ¹³C, ²⁹Si, {¹H–²⁹Si} HSQC NMR spectroscopy, GPC and TGA. Attempts to delineate the tacticity from the analysis of deconvoluted ²⁹Si{¹H}-NMR signals associated with the side chain silicon atoms reveal that the triad concentration ratio follows a Bernoullian statistical model for polymers 1 and 2 only.     

Studies on molecular weight distribution of carbon fiber polymer precursors synthesized using mixed solvents

The molecular weight distributions were estimated for carbon fiber polymer precursors such as poly（acrylonitrile-co -itaconic acid） synthesized by semi batch solution polymerization in mixed solvents media with the azonitrile compounds as initiator under the different ratios of solvent and non solvent from 0.75 to 2.5 in weight.The copolymer was characterized by using Fourier transform infrared spectroscopy（FTIR） and nuclear magnetic resonance（¹H-NMR） analyses.The molecular weight distributions were evaluated by M_v/M_n ratios estimated from viscosity and osmotic measurements,and M_w/M_n estimated from size exclusion chromatography.The molecular weight distributions of these polymers as determined from M_v/M_n and M_w/M_n are 2.9 to 3.2 and 2.0 to 2.5 respectively.The molecular distributions were close to a narrow distribution of 2.0 when the solvent/non-solvent ratio was varied between 1.4 and 2.0.Intrinsic viscosity[?]as a function of molecular weight of poly（acrylonitrile-co-itaconic acid） was evaluated by means of low angle laser light scattering with size exclusion chromatography（SEC-LALLS） and viscometry with SEC（SEC-VISCO）.The relationship between[?]and M_w for poly（acrylonitrile-co-itaconic acid） in DMF at 50℃was[?]= 1.1×10^-5M_w^0.79,where[?]is obtained in dL/g.     

A supramolecular bottlebrush polymer assembled on the basis of cucurbit[8]uril-encapsulation-enhanced donor-acceptor interaction

A supramolecular bottlebrush polymer has been constructed in water through the self-assembly of a rigid electron-deficient building block and an electron-rich monomer which bears two tetraethylene glycol chains, driven by CB[8]-encapsulation-enhanced donor-acceptor interaction. The as-formed supramolecular bottlebrush polymer has been characterized by ¹H NMR titration experiment, UV-vis spectroscopy, DLS and 2D ¹H NMR DOSY.     

Two New Alkaline Metal Borates with Supramolecular Framework Constructed from 1D {B5}/{B6} Helical Chains

Two new alkaline metal borates containing 1D{B5}/{B6}oxoboron helical chains,namely Na0.5[B5O8(OH)2]0.5[B5O6(OH)2]0.5·0.5H3O(1)and NaKCs[B6O9(OH)3](2)were synthesized under solvothermal conditions.Compound 1 contains the interesting alternative left-and right-handed helical{[B5O8(OH)2][B5O6(OH)2]}2-({B5}-1 and{B5}-2)1D chains and compound 2 possesses the similar[B6O11(OH)3]7-({B6})chains.Their 1D chains are further assembled into 2D layers and 3D supramolecular frameworks through O-H…O hydrogen bonds.In addition,the UV cutoff edge of compounds 1 and 2 is both below 190 nm.     

Macropolyhedral boron-containing cluster chemistry. Aspects of the S2B16H16 system. Preparation, structure, NMR spectroscopy and isomerism

Thermolysis of [arachno-4-SB₈H₁₂] (1) in boiling cyclohexane gives two isomers 2 and 3 of 18-vertex [S₂B₁₆H₁₆], together with known 12-vertex [closo-1-SB₁₁H₁₁] (4) and known 11-vertex [nido-7-SB₁₀H₁₂] (5). Compounds 2 and 3 are characterised by single-crystal X-ray diffraction analyses and single- and double-resonance ¹¹B- and ¹H-NMR spectroscopy. The [n-S₂B₁₆H₁₆] isomer 2 takes the form of nido ten-vertex: nido ten-vertex [anti-B₁₈H₂₂] with the 9 and 9′ positions occupied by S vertices, whereas the [iso-S₂B₁₆H₁₆] isomer 3 takes the form of a nido 11-vertex {SB₁₀} subcluster fused via a common two-boron edge to a nido-type {B₈} subcluster that is additionally linked exo to the {SB₁₀} subcluster by a bridging S atom that is held endo to the {B₈} unit. Isomer 2 is readily deprotonated and its monoanion 6 is characterised by NMR spectroscopy and by a single-crystal X-ray diffraction analysis of its [tmndH]⁺[n-S₂B₁₆H₁₅] salt 6b; deprotonation has occurred from an open-face B---H---B bridging site.     

Novel phosphorus-silicon synergistic flame retardants:Synthesis and characterization

Three novel flame retardants containing both phosphorus and silicon elements in their structures,including[（1,1,3,3- tetramethyl-1,3-disiloxanediyl）di-2,1-ethanediyl]bis（diphenylphosphine oxide）（FR-1）,[（2,4,6,8-tetramethylcyclotetra-siloxane -2,4,6,8-tetrayl）tetra-2,1-ethanediyl]tetrakis[diphenylphosphine oxide]（FR-2） and 1,3,5,7,9,11,13,15-octakis（di-phenylphosphine oxide-2,1-ethanediyl）pentacyclo[9.5.1.1^3,9.l^5,15.1^7,13]octasiloxane（FR-3） were synthesized by a convenient pathway from the reaction of diphenylphosphine oxide（DPPO） and vinyl-terminated siloxanes under the catalysis of triethylborane. The chemical structures of the target compounds were confirmed by nuclear magnetic resonance(¹H NMR,¹³C NMR,²⁹Si NMR and ³¹P NMR),matrix-assisted laser desorption/ionization time-of-flight mass spectrometry（MALDI-TOF-MS） and Fourier transform infrared（FT IR） measurements.Thermogravimetric analysis（TGA） results indicated that the new flame retardants possessed good thermal stability both in nitrogen and in air.FR-3 containing polyhedral oligosilsesquioxanes（POSS） moiety exhibited the best thermal properties with a 10%weight loss temperature>400℃ and a residual weight ratio>39%at 700℃ .     

Synthesis, characterization of new Rh---Co mixed-metal clusters and reactions of clusters containing [Rh2Co2C2] core with 1-alkynes and/or carbon monoxide

Six new cluster derivatives [Rh₂Co₂(CO)₆(μ-CO)₄(μ₄,η²-HCCR)] (R=FeCp₂ 1, CH₂OH 2, (CH₃O)C₁₀H₆CH(CH₃)COOCH₂CCH 3) and [RhCo₃(CO)₆(μ-CO)₄(μ₄,η²-HCCR)] (R=FeCp₂ 4, CH₂OH 5, (CH₃O)C₁₀H₆CH(CH₃)COOCH₂CCH 6) were obtained by the reactions of [Rh₂Co₂(CO)₁₂] and [RhCo₃(CO)₁₂] with substituted 1-alkyne ligands HCCR [R=FeCp₂ 7, CH₂OH 8, (CH₃O)C₁₀H₆CH(CH₃) COOCH₂CCH 9] in n-hexane at room temperature, respectively. Alkynes insert into the Co---Co bond of the tetranuclear clusters to give butterfly clusters. [Rh₂Co₂(CO)₆(μ-CO)₄(μ₄,η²-HCCFeCp₂)] (1) was characterized by a single-crystal X-ray diffraction analysis. Reactions of 1, 2 with 7, 8 and ambient pressure of carbon monoxide at 25 °C gave two known cluster complexes [Co₂(CO)₆(μ₂, η²-HCCR)] (R=FeCp₂ 10, CH₂OH 11), respectively. All clusters were characterized by element analysis, IR and ¹H-NMR spectroscopy.     

Lower Critical Solution Temperature Properties of N‐Isopropylacrylamide‐Based Pseudopolyrotaxanes by Complexation with Cucurbituril[6]

Pseudopolyrotaxanes 4a and 5a are synthesized by two paths: a) directly from the pseudorotaxane, and b) by complexing with cucurbituril (CB[6]) in water at room temperature after the polymerization. Free radical copolymerization with CB[6] (un)complexed monomer and N‐isopropylacrylamide (NIPAAM) is carried out using a redox initiator in aqueous media at room temperature. The properties of pesudorotaxanes ( 4a and 5a ) and polymers ( 4 and 5 ) are investigated by TGA, DSC, and turbidity measurements. The lower critical solution temperatures of the NIPAAM‐containing copolymers and CB[6] are significantly higher than those of pure NIPAAM copolymers. The pseudopolyrotaxanes 4a and 5a have a higher thermal stability, as a result of threading of the CB[6] rings onto the polymer side groups.

     

Synthesis, characterization and antitumor activity of some arylantimony triphenylgermanylpropionates and crystal structures of Ph3GeCH(Ph)CH2CO2SbPh4 and [Ph3GeCH2CH(CH3)CO2]2Sb(4-ClC6H4)3

A series of novel arylantimony(V) triphenylgermanylpropionates with the formula (Ph₃GeCHR¹CHR²CO₂)_nSbAr_(5−n) (R¹=H, Ph; R²=H, CH₃; n=1, 2) were synthesized and characterized by elemental analysis, IR, ¹H-NMR, ¹³C-NMR and mass spectroscopy. The crystal structures of Ph₃GeCH(Ph)CH₂CO₂SbPh₄ and [Ph₃GeCH₂CH(CH₃)CO₂]₂Sb(4-ClC₆H₄)₃ were determined by X-ray diffraction. The in vitro antitumor activities of some selected compounds against five cancer cells are reported.     

Synthesis and characterization of an acrylate polymer containing chlorine-1,3-dioxalane groups in side chains

Poly[2-（4-chlorophenyl）-1,3-dioxolan-4-yl]methyl acrylate,poly（CPhDMA）,was synthesized with radical polymerization process using 2,2′-azobisisobutyronitrile as radical initiator in 1,4-dioxane at 60℃.The structure of poly（CPhDMA） was confirmed by means of UV-Vis,FT-IR,¹H-NMR,and ¹³C-NMR spectral techniques.The molecular weight distribution values of the polymer were determined with gel permeation chromatography（GPC）.The number-average molecular weight（M_n）,weight-average molecular weight（M_W） and polydispersity index（PDI） values of poly（CPhDMA） were determined to be 10300,21600 and 2.097,respectively.The thermal degradation kinetics of the polymer was investigated by using TG/DTG-DTA and DSC analyses at different heating rates in dynamic nitrogen atmosphere.The apparent activation energy values obtained by Flynn-Wall-Ozawa and Friedman methods were found to be 91.68 and 85.23 kJ mol^-1,respectively,for thermal decomposition of poly（CPhDMA）.Also,the thermal degradation activation energy value of poly（CPhDMA） was calculated by using the Kissinger method based on the DTG,DTA and DSC data.Then the mechanism function of it was determined by master plots method.Finally,electrical and optical properties of poly（CPhDMA） were determined by four-point probe and UV-Vis techniques,respectively.     

Copolymerization of poly(propylene oxide) methacrylate macromonomer with styrene

Graft copolymers of styrene and poly(propylene oxide) were prepared by reaction between styrene and a poly(propylene oxide) methacrylate macromonomer. The graft copolymers were characterized by i.r., GPC and ¹H-NMR and mechanical properties were examined. The effect of zinc chloride on the copolymerization was evaluated. The results showed a decrease in the incorporation of macromonomer in the graft copolymer when zinc chloride was added to the system. This effect has been attributed to interaction among chains of poly(propylene oxide) and the zinc chloride.     

[2-(N,N-Dimethylaminomethyl)ferrocenyl] as a ligand towards mercury

The diorganomercurial bis[2-(N,N-dimethylaminomethyl)ferrocenyl]mercury(II), (FcN)₂Hg (3), can be obtained by the symmetrisation of the heteroleptic (FcN)HgCl (2) with Na₂S₂O₃ or in the transmetallation reaction of 2 with (FcN)Li. By crystallisation only the crystals of rac-(FcN)₂Hg were obtained. X-ray diffraction analysis revealed linear coordinated mercury atom with two η¹-bonded FcN ligands. Additionally, weak chelate interactions exist between mercury and nitrogen atoms of the ---CH₂NMe₂ side chains. According to the ¹H-NMR findings, these interactions are not preserved in solution. Diorganomercurial 3 appears in solution as a mixture of two diastereomers with rac/meso-(FcN)₂Hg ratio of 1:1. This diastereomeric ratio in solution remains constant within a wide temperature range and in different solvents. The NMR spectroscopic data of the heteroleptic organomercurials [(FcN)HgCl]₂·H₂O (1) and (FcN)HgCl (2) indicate the chelate-free structure of this compounds in solution within the studied temperature interval (−80 to 90 °C).