Preparation and Cytotoxicity of Novel Aliphatic Polycarbonate Synthesized from Dihydroxyacetone

A new cyclic carbonate, 2,2-ethylenedioxypropane-l,3-diol carbonate (EOPDC), was synthesized through a two-step reaction from dihydroxyacetone dimer, and polymerized in bulk initiated by Sn(Oct)2 to give a high molecular weight polycarbonate. The structure of monomer and the polymer were characterized by FT-1R, ^1H NMR, ^13C NMR. The cytotoxicity of the obtained polycarbonate was investigated by MTT assay.     

新型超支化接枝共聚物的合成

以对氯甲基苯乙烯(CMS)为活性单体,CuCl/2,2′-联吡啶(bpy)为催化体系,利用原子转移自由基聚合(ATRP)方法,制备具有不同支化度的超支化聚对氯甲基苯乙烯(h-PCMS, 4);以4为大分子引发剂,引发第二单体进行聚合,合成了两个以4为核的新型星状多臂共聚物,其结构经¹H NMR, IR和GPC表征。     

RAFT聚合合成一种即含甲酰基又含手性β-蒎烯单元聚合物

设计并合成了一种新型含甲酰基同时又含β-蒎烯单元的新单体2-β-蒎氧基-5-乙烯基苯甲醛(POVB),选择苯基双硫代乙酸1-苯基乙酯(PEPDA)为RAFT试剂、以AIBN为引发剂、在60℃下THF中实现了POVB的"活性"/可控RAFT自由基聚合.单体浓度半对数ln([M]0/[M])与聚合时间符合线性关系,聚合过程呈现一级动力学特征;聚合物分子量(Mn)随单体转化率几乎线性增加,而且整个反应过程中分子量分布(Mw/Mn1.2)保持在较窄的范围.1H-NMR的分析进一步证实了聚合物链的末端精细结构.此外,CD谱结果表明手性单元β-蒎烯基能赋予聚合物以光学活性.     

A new terpyridine tethered polythiophene: Electrosynthesis and characterization

A novel polythiophene bearing a pendant terpyridine moiety has been synthesized by electrochemical polymerization of a new thiophene monomer, namely 4′‐(2,2′:5′,2″‐terthien‐3′‐ethynyl)‐2,2′:6′,2″‐terpyridine (TAT). The insertion of a conjugated ethynyl spacer between the terthiophene and the terpyridine fragments provides for an effective extension of the delocalization of electrons within the structural unit and the polymer as a whole. The synthesis and characterization of the relevant monomer, the electrosynthesis of the corresponding polymer and its electrochemical, UV–visible spectroelectrochemical and IR characterization are described. Finally, a comparison between the electrochemical, spectroscopic, and spectroelectrochemical properties of PTAT and the analogue, saturated‐spacer PTTT (TTT = 4′‐[(2,2′:5′,2″‐terthien‐3′‐yl)methoxy]‐2,2′:6′,2″‐terpyridine) polymer is discussed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis,Characterization, and Photocrosslinking Properties of Poly(4‐Methacrylamidophenyl‐2′,3′‐benzostyryl Ketone)

Abstract

A new methacrylamide monomer, 4‐methacrylamidophenyl‐2′,3′‐benzostyryl ketone (MPBSK) having a free‐radical polymerizable group and a photocrosslinkable functional group, was synthesized by reacting 4‐(2′,3′‐benzocinnamoyl)aniline with methacryloyl chloride in the presence of triethyl amine. The monomer, MPBSK was polymerized in methyl ethyl ketone (MEK) at 70°C using benzoyl peroxide (BPO) as the initiator. The polymer was characterized by UV, IR, ¹H‐NMR, and ¹³C‐NMR spectroscopy. The polymer was found to be soluble in several polar aprotic solvents and in chlorinated solvents but insoluble in aliphatic and aromatic hydrocarbons and in alcohols. The molecular weight data of the polymer as obtained from gel permeation chromatography suggests a higher tendency for chain termination by disproportionation than dimerization. The glass transition temperature of the polymer was determined by differential scanning calorimetry. Thermogravimetric analysis of the polymer carried out in air reveals that it possesses good thermal stability required of a negative photoresist. The photocrosslinking property of the polymer was investigated by irradiating the polymer solution with UV light in the presence and absence of triplet photosensitizers. The effect of the solvent on the rate of photocrosslinking of the polymer was also studied.     

Preparation of Poly(amic acid) and Polyimide via Microwave-Assisted Polycondensation of Aromatic Dianhydrides and Diamines

Summary: A copolycondesation-type poly (amic acid) (PAA) was synthesized using pyromellitic dianhydride (PMDA) and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) as dianhydride monomers, and 4,4′-oxydianiline (ODA) as a diamine monomer under microwave irradiation in dimethylformamide (DMF). PAA was then converted into a polyimide (PI) by an imidization. The structure and performance of the polymer were characterized by Fourier-transform infrared (FT-IR) spectroscopy, Proton nuclear magnetic resonance (¹H NMR) spectrometry, viscosity, X-ray diffraction (XRD), and thermogravimetric (TG) analyses. The results showed that under microwave irradiation, the intrinsic viscosity and the yield of PAA were increases, and the reaction time was shortened. The FT-IR spectra of the polymer revealed characteristic peaks for PI around 1778^– and 1723 cm^–1. TG curves indicated that the obtained PI began to lose weight at 535 °C, and its 10% thermal decomposition temperature under N₂ was 587 °C.     

主链型聚氨酯光动力高分子的合成与表征

合成了一种主链含推拉电子型偶氮苯基团的聚氨酯光动力高分子 .对聚合物的结构、热性能及光学性能进行了表征 .此聚合物为主链含假芪型偶氮生色团的无定形高分子 .用 4 88nmAr+ 激光对聚合物薄膜进行光加工 ,得到了规则的正弦表面起伏光栅 ,其起伏深度大于 2 0 0nm .光栅的一级衍射效率可达 2 4 % .     

POLYBINAPHTHYLS INCORPORATING (R)-2,2’-BINAPHTHO-20-CROWN-6 AND NAPHTHYL MOITIES

Chiral polymer was synthesized by the polymerization of （R）-6,6＇-bistributylstannyl-2,2＇-binaphtho-20-crown-6 （M-1） with 1,4-dibromo-2,3-bisbutoxy-naphthyl （M-2） by Pd（PPhs）4 catalyzed Stille coupling reaction. Both monomer and polymer were analyzed by NMR, MS, FT-IR, UV, polarimetry, DSC-TGA, CD, fluorescent spectroscopy and GPC. The major difference between monomer and polymer is that a long wavelength Cotton Effect was observed for the polymer due to its more extended conjugation in the repeating unit and a highly rigid backbone in the polymer chain. Polymer has strong blue fluorescence due to the efficient energy migration from the extended n-electronic structure of the repeating unit of the polymer to the chiral binaphthyl core and is expected to have potential application in the materials of fluorescent sensors and chiral chromatographic packing for resolution ofracemic amino acid.     

SYNTHESIS AND ANIONIC POLYMERIZATION OF 2-METHYL-2-METHOXY CARBONYL-5-METHYLENE-1, 3-DIOXOLAN-4-ONE

A new cyclic monomer, 2-methyl-2-methocycarbonyl-5-methylene 1,3-dioxlan-4-one,wassynthesized successfully. The monomer and intermediate were characterized by ~1H NMR,~(13)C NMR, INEPT (Intensive Nuclei Enhanced by Polarization Transfer) technique, IR andelemental analysis. Anionic polymerization of the monomer was carried out in anhydrous THF at.70℃, and 9-fluorenyllithium was used as initiator. The polymer strucure was determined byIR, NMR and elemental analysis. Molecular weight of the polymer was estimated by viscositymeasurement in DMSO at 30℃.     

Synthesis and polymerization of 5‐(methacrylamido)tetrazole,a water‐soluble acidic monomer

The reaction of methacryloyl chloride with 5‐aminotetrazole gave the polymerizable methacrylamide derivative 5‐(methacrylamido)tetrazole ( 4 ) in one step. The monomer had an acidic tetrazole group with a pK_a value of 4.50 ± 0.01 in water methanol (2:1). Radical polymerization proceeded smoothly in dimethyl formamide or, after the conversion of monomer 4 into sodium salt 4‐Na , even in water. A superabsorbent polymer gel was obtained by the copolymerization of 4‐Na and 0.08 mol % N,N′‐methylenebisacrylamide. Its water absorbency was about 200 g of water/g of polymer, although the extractable sol content of the gel turned out to be high. The consumption of 4‐Na and acrylamide (as a model compound for the crosslinker) during a radical polymerization at 57 °C in D₂O was followed by ¹H NMR spectroscopy. Fitting the changes in the monomer concentration to the integrated form of the copolymerization equation gave the reactivity ratios r _4‐Na = 1.10 ± 0.05 and r_acrylamide = 0.45 ± 0.02, which did not differ much from those of an ideal copolymerization. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4333–4343, 2002     

A2和B3型单体缩聚合成超支化偶氮聚氨酯研究

通过双官能度异氰酸酯基单体MDI(A2)与三官能度羟基偶氮单体(B3)的缩聚反应,得到了超支化偶氮聚氨酯,利用核磁共振、热分析、紫外-可见光谱、红外光谱、GPC等方法对其结构和性能等进行了详细表征.该聚合物在干涉的p偏振Ar+激光照射下,可得到周期性规则的正弦波形表面起伏光栅.     

SYNTHESIS AND POLYMERIZATION OF 2-OXO-3-METHYLENE-5, 6-DIPHENYL-1,4-DIOXAN

A new cyclic monomer, 2-oxo-3-methylene-5, 6-diphenyl-1, 4-dioxan, was synthesized. Thestructure of the intermediates and the monomer were determined by IR,~1H NMR,~(13)C NMR andelemental analysis. This new monomer is different from other cyclic monomers in this series,it isa solid (mp 108--109℃)and not very reactive, but still can undergo free radical ring-openingpolymerization. The free radical polymerization was carried out at 130℃. The structure of theresulting polymer was discussed and charaterized by IR, ~1H NMR, ~(13)C NMR and elementalanalysis. The molecular weight of the polymer was estimated by viscosity determination.     

4,4'-二(4-烯丙氧基苯甲酸)联苯酯的合成及其液晶性能

以3-溴丙烯、4-羟基苯甲酸和4,4'-二羟基联苯为主要原料,经Williamson醚化、羧酸酰化和酯化反应合成了一种新的液晶单体--4,4'-二(4-烯丙氧基苯甲酸)联苯酯(1),用~1H NMR,~(13)C NMR,FT-IR,DSC,TGA和POM对其分子结构和液晶性能进行了表征.结果表明1呈现向列相,具有较高的熔点、液晶清亮点和较宽的液晶相温度范围.     

Synthesis of Poly[2‐decyloxy‐5‐(4′‐tert‐butylphenyl)‐1,4‐phenylenevinylene] as a Light Emitting Material

In this study, a new electroluminescent poly(2‐decyloxy‐5‐(4′‐tert‐butylphenyl)‐1,4‐phenylene‐vinylene) (designated as DBP‐PPV) with no tolane‐bis–benzyl (TBB) structure defect was prepared by dehydrohalogenation of 1,4‐bisbromomethyl‐2‐decyloxy‐5‐(4′‐tert‐butyl‐phenyl) benzene (as monomer). The monomer bearing decyloxy and 4′‐tert‐butylphenyl substituents was synthesized via alkylation, bromination and Suzuki coupling reactions. The two asymmetric substituents of the monomer can suppress the formation of TBB defect during polymerization process and make the resultant polymer be soluble in common organic solvents. The structure and properties of DBP‐PPV were examined by ¹H‐NMR, FT‐IR, UV/Vis, TGA and photoluminescence (PL) analyses. Moreover, with the DBP‐PPV acting as a light‐emitting polymer, a device with sequential lamination of ITO/PEDOT/DBP‐PPV/Ca/Ag was fabricated. The electroluminescence (EL) spectrum of the device showed a maximum emission at around 546 nm, corresponding to a yellowish‐green light. The device showed a turn‐on voltage of about 8.4 V and a maximum luminescence efficiency of 0.11 cd/A at an applied voltage of 12 V.     

Synthesis and characterization of a novel reactive ladderlike 4,4′‐phenylene ether‐bridged polyvinylsiloxane

A novel soluble, reactive ladderlike 4,4′‐phenylene ether‐bridged polyvinylsiloxane (L) was synthesized successfully for the first time by a stepwise coupling polymerization (SCP) including hydrolysis and polycondensation. The monomer, 4,4′‐bis(vinyldimethoxysilyl)phenylene ether (M), was synthesized by Grignard reaction. The structures of the monomer and the polymer were characterized by infrared spectrometry (IR), nuclear magnetic resonance (¹H NMR, ¹³C NMR, ²⁹Si NMR), mass spectrometry (MS), differential scanning calorimetry (DSC), X‐ray diffraction (XRD), and gel permeation chromatography (GPC). It is proposed from the characterization data that the polymer possesses an ordered ladderlike structure. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2702–2710, 2000     

Synthesis and characterization of polybenzoxazine containing phosphorus

The novel benzoxazine monomer containing phosphorus has been synthesized based on multifunctional amine route from bis(4-aminophenyl)phenylphosphate,p-cresol and formaldehyde.Subsequently,the benzoxazine monomer was thermo-cured into polybenzoxazine containing phosphorus.The chemical structures were identified by nuclear magnetic resonance(NMR),Fourier transform infrared spectroscopy(FT-IR).The curing reaction was monitored by differential scanning calorimetry(DSC) and FT-IR.The thermal and flame-retardant properties of obtained polybenzoxazine were evaluated by dynamic mechanical thermal analysis(DMA),thermal gravimetric analysis(TGA) and oxygen index meter, respectively.The results show that the novel polybenzoxazine has high limiting oxygen index(38.1) and glass transition temperature(232℃).     

High-temperature resins based on aromatic amine-terminated bisaspartimides

Various 4,4′-bis{N²-[4-(4-aminophenoxy)phenyl]aspartimido}diphenylmethane (APADM)-type precursors were synthesized by Michael-type reaction of an aromatic bismaleimide (1mol) with an aromatic diamine (2 mol) in an aprotic solvent. The structures of these materials were characterized by using Fourier-transform infrared (FT-IR), ¹H nuclear magnetic resonance (NMR) and ¹³C-NMR; their curing behaviors and thermal stabilities were evaluated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The thermal polymerization of APADM by heating it above its melting temperature produced a tough polymer. From these preimidized precursors, graphite-fiber laminates were prepared and their mechanical properties evaluated. To elucidate the thermal curing mechanism and the structure of the polymer, a model compound, N-[4-(4′-aminobenzyl) phenyl] aspartimidobenzene was synthesized. The gas-chromatographic mass spectra of these compounds has suggested a mechanism for their decomposition. The structure of the polymer also was studied by using FT-IR and ¹H-NMR.     

Hydrogen‐bonding‐aided synthesis of novel ladderlike organobridged polysiloxane containing side‐chain naphthyl groups

With a hydrogen‐bonding template, a novel soluble aryl amide‐bridged ladderlike polysiloxane, containing naphthyl as the side‐chain group, has been successfully synthesized via a stepwise coupling polymerization. It is proposed that the monomer, N,N′‐di(3‐naphthyldiethoxylsilyl‐propyl)‐[4,4′‐oxybis(benzyl amide)], prepared by Grignard and hydrosilylation reactions, undergoes self‐assembly first via amido hydrogen bonding and then via hydrolysis, followed by condensation under controlled reaction conditions to yield a high molecular weight, soluble, dark yellow polymer. The analytical results (Fourier transform infrared, ¹H NMR, ²⁹Si NMR, X‐ray diffraction, differential scanning calorimetry, and vapor pressure osmometry) show that the polymer possesses an ordered ladderlike architecture. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 636–644, 2003     

偶氮苯侧链共聚硅氧烷的合成及液晶行为的研究

以苯酚、十一烯酸、正溴己烷、对硝基苯酚和二氯亚砜为主要原料 ,通过取代、还原、重氮化和偶合等反应 ,合成了一种新的液晶单体 4 己氧基 4′ 十一烯 [1 0 ] 酰氧基偶氮苯 ,并与聚 (甲基氢硅氧烷 )通过硅氢加成生成一种新的高分子液晶 .通过1 H NMR和IR对单体和聚合物的结构进行了表征 ,并证实了聚合物的硅氢化程度近于完全 .通过DSC和热台偏光显微镜 (POM)对单体和聚合物的液晶行为进行了研究 ,证明了都具有液晶性     

POLYBINAPHTHYLS INCORPORATING (R)-20,''-BINAPHTHO-20-CROWN-6AND NAPHTHYL MOITIES

Chiral polymer was synthesized by the polymerization of (R)-6,6'-bistributylstannyl-2,2'-binaphtho-20-crown-6(M-1) with 1,4-dibromo-2,3-bisbutoxy-naphthyl (M-2) by Pd(PPh3)4 catalyzed Stille coupling reaction. Both monomer and polymer were analyzed by NMR, MS, FT-IR, UV, polarimetry, DSC-TGA, CD, fluorescent spectroscopy and GPC. The major difference between monomer and polymer is that a long wavelength Cotton Effect was observed for the polymer due to its more extended conjugation in the repeating unit and a highly rigid backbone in the polymer chain. Polymer has strong blue fluorescence due to the efficient energy migration from the extended π-electronic structure of the repeating unit of the polymer to the chiral binaphthyl core and is expected to have potential application in the materials of fluorescent sensors and chiral chromatographic packing for resolution ofracemic amino acid.