Water-Soluble Copolymers. XIX. Copolymers of Acrylamide with Sodium 3-(N-Propyl)acrylamido-3-Methylbutanoate: Synthesis and Characterization

The copolymerization of acrylamide (AM) with sodium 3-(N-propyl)acrylamido-3-methlbutanoate (NaPAMB) has been studied in the range from 40 to 90% AM in the feed. The copolymer compositions have been determined from elemental analysis and ¹³C NMR. Reactivity ratio studies have been performed, and the value of r₁r₂ determined to be 0.36. The molecular weights, as determined by low-angle laser light scattering of the copolymers, were found to decrease sharply with increasing NaPAMB content, and were in the range 0.5–7.0 × 10⁶. The copolymer microstructures, including mean sequence length distributions, were calculated from the reactivity ratios. Knowledge of polymer composition, micro-structure, and molecular weight is utilized for assessment of structure/dilute solution property relationships reported in a subsequent paper in this series.     

Synthesis and Characterization of Water-Soluble Starch-Acrylamide Graft Copolymers

A series of water-soluble starch-polyacrylamide graft copolymers (ST-g-PAM) were prepared by Ce⁴⁺-initiated graft copolym-erizations of acrylamide (AM) onto starch (ST) dissolved in water at 30°C. The copolymers were found to contain 3-33% (wt) of ST. The structure of the copolymers, including the average number of grafts per chain and the efficiency of the initiator, was determined by acid-catalyzed degradation of the ST followed by size exclusion chromatography (SEC) analysis of the PAM chains and was found to be consistent with the presence or absence of free ST in the polymerization product prior to hydrolysis. The average number of grafts per starch molecule was found to be three or less, depending on conditions. The initiator efficiency (6–43%) was shown to decrease with increasing [Ce⁴⁺] and decreasing [AM], and this was found to be qualitatively in accord with the proposed mechanism of initiation and polymerization. The low efficiency was shown to be due, in part, to the low rate of reaction of Ce⁴⁺ compared to the polymerization rate. The copolymers were characterized by ultra-centrifugation, SEC, and viscometry.     

Synthesis and Characterization of Water-Soluble Graft Copolymers from 2, 3-Dihydroxypropylcellulose and Acrylamide

Water-soluble 2,3-dihydroxypropylcellulose-polyacrylamide graft copolymers (DHPC-g-PAM) were prepared by Ce⁴⁺ ion-initiated graft copolymerization of acrylamide (AM) onto 2,3-dihydroxypropylcellulose (DHPC) dissolved in dilute nitric acid at room temperature under argon. The ratios of the concentration of Ce⁴⁺ ion to the concentration of DHPC were shown to affect the number and the length of the polyacrylamide grafts. The average number of grafts per chain was determined by acid-catalyzed degradation of the cellulose backbone and was found to be consistent with the presence or absence of free DHPC in the polymerization product prior to hydrolysis. The average number of grafts per DHPC molecule was found to be 2.7 or less depending on the reaction conditions.     

Synthesis and characterization of a novel mid‐chain macrophotoinitiator of polyacrylonitrile by Ce(IV)/HNO3 redox system

The polymerization of acrylonitrile initiated by cerium(IV) ammonium nitrate in combination with dihydroxy functional photoinitiator namely, 2‐hydroxy‐1‐[4‐(2‐hydroxyethoxy)phenyl]‐2‐methyl propan‐1‐one (HE‐HMPP), Irgacure 2959, has been investigated in aqueous nitric acid. A novel mid‐chain macrophotoinitiator of polyacrylonitrile (PAN) was obtained. The effects of acrylamide (AAm), HE‐HMPP, Ce(IV), and HNO₃ concentrations and temperature on the polymerization rate, monomer conversion, and intrinsic viscosities were investigated. The photodegradation and IR, H NMR, UV, and fluorescence spectroscopic studies revealed that PAN with desired photoinitiator functionality in the middle of the chain was obtained. The obtained PAN was used as prepolymer for photoinduced free radical polymerization of methyl methacrylate (MMA) and AAm to produce block copolymers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5404–5413, 2008     

Water-Soluble Copolymers. XLI. Copolymers of Acrylamide and Sodium 3-Acrylamido-3-methylbutanoate

Copolymers of acrylamide (AM, M ₁) with sodium 3-acrylamido-3-methylbutanoate (NaAMB, M ₂) synthesized in 1 M NaCl (the ABAM2 series) are compared to those synthesized in deionized water (the ABAM1 series). At fixed feed ratios, higher incorporation rates were found for NaAMB with increasing ionic strength of the polymerization solvent. Reactivity ratios calculated by the methods of Kelen-Tüdös changed from r ₁ = 1.23 and r ₂ = 0.50 in deionized water to r ₁ = 1.00 and r ₂ = 0.64 in 1 M NaCl. This change is in accord with a decrease in electrostatic repulsion between the macroradical and unreacted NaAMB. Dilute solution properties, examined as a function of composition and added electrolytes, indicate differences in microstructure for the ABAM1 and ABAM2 copolymers.     

Synthesis and Characterization of Poly(p-phenylene benzobisoxazole)/Poly(pyridobisimidazole) Block Copolymers

Poly(p-phenylene benzobisoxazole)/poly(pyridobisimidazole) block copolymers (PBO-b-PIPD) were prepared by introducing poly(pyridobisimidazole) (PIPD) moieties into the main chains of poly(p-phenylene benzobisoxazole) (PBO) in order to enhance its photostability. PBO and copolymer fibers were directly prepared from the polymerization solutions by dry-jet wet-spinning. Chemical structures and molecular chains arrangement of the block copolymers were characterized by Fourier transform infrared (FTIR) spectroscopy, solid-state ¹³C-NMR and wide angle X-ray diffraction (WAXD). Thermal stability of the copolymers was investigated by thermogravimetric analysis (TGA) in nitrogen. Thin films of PBO and copolymers were cast from methanesulfonic acid (MSA) solutions. Both the films and fibers were exposed to UV light to determine their photostability. Changes in the chemical structures and surface morphologies of the films were characterized by FTIR spectra and scanning electronic microscopy (SEM), respectively. After UV light exposure, the retention of strength for copolymer fibers is improved compared to PBO fibers. The results revealed that copolymers suffered less photodegradation in comparison with homopolymer. The mechanism for the improved photostability of the copolymers was discussed.     

水溶性席夫碱型锰配合物的合成、表征及其模拟超氧化物歧化酶活性研究

以水杨醛为母体, 与胺类化合物缩合形成席夫碱配体, 用分子自组装法合成了一系列水溶性席夫碱型金属锰单核、双核配合物. 通过元素分析、红外光谱对配合物进行了表征, 采用邻苯三酚自氧化法测定了配合物的超氧化物歧化酶(SOD)活性. 结果表明, 这些水溶性锰配合物具有良好的SOD活性.     

Water-Soluble Copolymers. XX. Copolymers of Acrylamide with Sodium 3-(N-Propyl)Acrylamido-3-Methylbutanoate: Solution Properties

Dilute solution properties of copolymers of acrylamide (AM) with sodium 3-(N-propyl)acrylamido-3-methylbutanoate (NaPAMB) of known molecular weight have been studied as a function of composition, temperature, time, pH, and added electrolytes. Phase separation and potentiometric studies have also been performed. The AM-NaPAMB copolymers possess lower molecular weights and solution viscosities than the AM-NaAMB copolymers. In addition, the AM-NaPAMB polymers exhibit moderate viscosity-temperature coefficients and poor salt tolerance. These polymers undergo phase separation in the presence of divalent cations as a function of temperature. The observed properties can be related to the steric and hydrophobic effects caused by the presence of the n-propyl substituent at the amide nitrogen.     

Synthesis and Characterization of Palladium(II) and Platinum(II) Complexes Containing Water-Soluble Hybrid Phosphine-Phosphonate Ligands

Water-soluble phosphonate-functionalized triaryl phosphine ligands Na(2)[Ph(2)P(4-C(6)H(4)PO(3))].1.5H(2)O (4a), Na(2)[Ph(2)P(3-C(6)H(4)PO(3))].2H(2)O (4b), and Na(2)[Ph(2)P(2-C(6)H(4)PO(3))].2H(2)O (4c), were prepared in 54-56% yields by the transesterification and hydrolysis of the appropriate phosphonic acid diethyl ester precursors. The solubilities of 4a-c in water are compared and the spectroscopic properties studied in detail. The crystal structure of Na(2)[Ph(2)P(4-C(6)H(4)PO(3))(H(2)O)(3)(CH(3)OH)].CH(3)OH (monoclinic, P2(1)/n, a = 6.4457(8) ?, b = 8.1226(8) ?, c = 46.351(3) ?, beta = 92.902(8) degrees, Z = 4) shows a dimeric association via two bridging water molecules and four sodium ions. Reaction of 4a with PtCl(2)(PPh(3))(2) in a biphasic H(2)O/CH(2)Cl(2) mixture gives cis- and trans-Na(4)[PtCl(2){Ph(2)P(4-C(6)H(4)PO(3))}(2)]. 3H(2)O. Palladium dichloride and 4a in H(2)O/benzene catalyzes the carbonylation of benzyl chloride to give phenylacetic acid (91%).     

水溶性有机膦盐的合成与表征

高产率地合成了三苯基磷间磺酸铵[MPA,(C6H5)2P(m-C6H4SO3^-NH4 )]和两种季膦盐[MPAE,(C6H5)2P^ (m-C6H4SO3^-)CH2CO2Et],[TPEI,(Ph3CH2CO2Et)I^-],初步研究了其理化性质。     

水溶性氧杂酰胺类化合物的合成及表征

以二甘醇为原料, 经氧化得到的二甘酸, 通过氯代或缩合反应得到中间体酰氯和酸酐, 二烷基胺在吡啶催化下与酰氯或酸酐发生胺解反应, 合成出系列水溶性氧杂单酰胺及氧杂双酰胺, 包括N,N-二烷基-3-氧杂-戊酰胺酸系列和N,N,N'N'-四烷基-3-氧杂-戊二酰胺系列(烷基包括甲基、乙基和丙基). 用IR和¹H NMR对合成的目标产物进行了表征.     

Synthesis of Water-Soluble Chemically Degradable Polymers from Glutaraldehyde and N-Vinylpyrrolidone-Allylamine Copolymers

Water-soluble chemically degradable copolymers of N-vinylpyrrolidone with allylamine, containing azomethine links between the polymeric chains, were prepared. The composition and molecular-weight characteristics of the polymers were determined.     

L-丙交酯与环氧氯丙烷共聚物的合成与表征

以系列烷基铝为催化剂,制得丙交酯与环氧氯丙烷的共聚物。分别考察了Al(Oct)_3、Sn(Oct)_2·4Al(Oct)_3、Al(Oct)_3·0.5H_2O、AlEt_3、AlEt_3·0.5H_2O催化下聚合的情况,结果表明:认为在烷基铝的催化下,丙交酯和环氧氯丙烷可以共聚,其中部分水解烷基铝催化效果较好。聚合反应的最佳温度为100℃。在此温度下,随着反应时间的增加,共聚物的分子量和产率皆提高。环氧氯丙烷用量增加,聚合物的产率和分子量呈下降趋势。用~1H-NMR、GPC、DSC对产物进行测试和表征。     

Synthesis of a Rare Water-Soluble Silver(II)/Porphyrin and Its Multifunctional Therapeutic Effect on Methicillin-Resistant Staphylococcus aureus

Porphyrin derivatives are popular photodynamic therapy (PDT) agents; however, their typical insolubility in water has made it challenging to separate cells of organisms in a liquid water environment. Herein, a novel water-soluble 5,10,15,20-tetrakis(4-methoxyphenyl-3-sulfonatophenyl) porphyrin (TMPPS) was synthesized with 95% yield by modifying the traditional sulfonation route. The reaction of TMPPS with AgNO₃ afforded AgTMPPS an unusual Ag(II) oxidation state (97% yield). The free base and Ag(II) complex were characterized by matrix-assisted laser desorption ionization-mass spectroscopy, and ¹H nuclear magnetic resonance, Fourier-transform infrared, UV-vis, fluorescence, and X-ray photolectron spectroscopies. Upon 460 nm laser irradiation, AgTMPPS generated a large amount of ¹O₂, whereas no ⦁OH was detected. Antibacterial experiments on methicillin-resistant Staphylococcus aureus (MRSA) revealed that the combined action of Ag^Ⅱ ions and PDT could endow AgTMPPS with a 100% bactericidal ratio for highly concentrated MRSA (10⁸ CFU/mL) at a very low dosage (4 μM) under laser irradiation at 360 J/cm². Another PDT response was demonstrated by photocatalytically oxidizing 1,4-dihydronicotinamide adenine dinucleotide to NAD⁺ with AgTMPPS. The structural features of the TMPPS and AgTMPPS molecules were investigated by density functional theory quantum chemical calculations to demonstrate the efficient chemical and photodynamical effects of AgTMPPS for non-invasive antibacterial therapy.     

（苯乙烯—丁二烯—环氧乙烷）多嵌段共聚物的合成及表征

α,ω—双羟基聚苯乙烯与α,ω—双羟基聚丁二烯及聚乙二醇为预聚体,以2,4-甲苯二异氰酸酯为偶联剂,聚合得到(苯乙烯-丁二烯-环氧乙烷)多嵌段共聚物。研究了聚合条件的影响。产物分别用热环已烷及水萃取提纯。并用IR、~1HNMR、GPC、动态粘弹谱及透射电子显微镜进行了表征。     

苯乙烯和乙烯基三甲氧基硅烷嵌段共聚物的制备及表征

以苯乙烯(St)为单体,二硫代萘甲酸异丁腈酯(CPDN)为可逆-加成断裂链转移聚合(RAFT)试剂,合成大分子链转移剂,再加入不同质量的乙烯基三甲氧基硅烷(A171),得到嵌段比不同的共聚物P(St-b-A171)。通过核磁共振谱仪1 H-NMR、凝胶渗透色谱GPC、动态力学分析仪DMA和接触角等方法对P(St-b-A171)结构进行了表征。结果表明:随着nSt/nA171嵌段比从1∶0.15增加到1∶0.45,P(St-b-A71)数均分子量从10400增加到14000,PDI指数从1.42增加到1.58;聚合物成膜后接触角由78.4°增加到89.6°。通过以上分析得出结论,RAFT合成嵌段共聚物的嵌段比对P(St-b-A171)性能有较大影响。     

氢键型聚芳醚酮共聚物的合成与表征

氢键型聚芳醚酮共聚物的合成与表征王忠刚，陈天禄，徐纪平（中国科学院长春应用化学研究所长春１３００２２０）关键词氢键，聚芳醚酮，合成，表征高分子链之间的氢键相互作用可以有效地提高聚合物的性能［１，２］．本工作通过共聚反应，在酚酞型聚芳醚酮ＰＥＫ－Ｃ分子...     

Synthesis and Characterization of Styrene-Isoprene Diblock Copolymers

A simple reusable apparatus for the synthesis of up to 40 g quantities of poly(styrene-b-isoprene) diblock copolymers of reasonably low (1.2 to 1.5) polydispersity has been described. The diblock copolymers synthesized were characterized by gel permeation chromatography (GPC), membrane osmometry, viscosimetry, and nuclear magnetic resonance (NMR) spectroscopy. Number-average molecular weights (M _n) calculated from the raw GPC chromatographs of the diblock copolymers using the summation method and M versus elution volume plots for polystyrene and polyisoprene standards agree well with those measured experimentally with osmometry. It is suggested that for polydisperse block copolymers this method is simpler than the use of a universal calibration curve. Mark-Houwink constants K ans a for polyisoprene having 18% (1,2-), 66% (3,4-), and 16% (1,4-) microstructure were found to be 3.2 × 10^?4 dL/g and 0.67, respectively, in THF at 25°C. In toluene at 30°C, K = 2.0 × 10^?4 dL/g and α = 0.7 were obtained. The diblock copolymers had 26% (1,2-), 60% (3,4-), and 14% (1,4-) microstructure in the isoprene segments, and the values of K and a for these copolymers (PS > 50%, M 20.0 × 10³) in THF at 25°C were 9.0 × 10^?5 dL/g and 0.75. For M < 20.0 × 10³ the value of α was 0.5. The experimental values of [η] were found to be lower than those calculated theoretically, presumably due to the polydisperse nature and the biellipsoidal configuration of the diblock copolymers.     

Synthesis and Characterization of PS-PIB-PS Triblock Copolymers

Abstract

Poly(styrene-isobutylene-styrene) (PS-PIB-PS) block copolymers synthesized via living carbocationic polymerization using a di- or tricumyl chloride/TiCl₄/pyridine initiating system in 60/40 (v/v) hexane/methyl chloride cosolvents. The kinetics of formation of the PIB block at ? 80°C were found to be first order in isobutylene (IB) concentration, first order in the concentration of initiating sites, second order in TaiCl₄ concentration, and a negative fractional order with respect to the pyridine concentration. The rate of polymerization was found to decrease with increasing temperature, indicating an equilibrium between dormant, covalent and active, ionized chain ends, and chain-end concentration studies suggested that there was no contribution by free ions to the rate of propagation. Diagnosis of the livingness of the IB polymerization indicated that at high (≥90%) monomer conversion, β-proton elimination becomes important, causing the timing of addition of styrene to be critical. Addition of styrene at an IB reaction time significantly exceeding the time necessary for complete IB consumption resulted in contamination of the product with a substantial amount of homo-PS; conversely, addition at intermediate IB conversion resulted in slow copolymerization between IB and styrene and the formation of a tapered block copolymer. Addition of styrene at an IB conversion of about 90% resulted in well-defined block copolymers which displayed ordered, phase-separated morphologies consisting of cylinders of PS in a continuous phase of PIB. The block copolymers possessed properties consistent with those of physically crosslinked rubbers. Dynamic mechanical spectroscopy revealed two glass transitions with a broad rubbery plateau extending from about 0 to 100°C, and tensile strengths of up to 25 MPa and elongations to 1000% were observed for some samples.