PREPARATION OF POLY （LACTIC ACID） THROUGH THIONYL CHLORIDE ACTIVATED POLYCONDENSATION

A two-step process was used to synthesize the high molecular weight poly (lactic acid) using thionyl chloride as an activator for the polycondensation of prepolymer of lactic acid.The products were characterized by GPC,DSC and 1H-NMR.Poly(L-lactic acid)(PLLA) with molecular weight Mw:32875 was obtained when thionyl chloride was used.while low molecular weight PLLA MW:7350 was yielded without thionyl chloride.Effects of the concentration of thionyl chloride,polymerization time and bases on the molecular weight of poly(lactic acid) were investigated.In DSC scans the glass transition temperatures(Tg)of the resulting polymers varied from 25.3 to 57.6℃.and the Tg of poly(L-lactic acid)was higher than that of poly (D,L0lactic acid)(PDLLA).The melting points of poly(L-lactic acid)and poly (D,L-lactic acid) could not be found unless the polymers were obtained by thionyl chloride activator.     

INVESTIGATION OF THE ATRP OF n-BUTYL METHACRYLATE USING THE Cu(I)/N,N,N′,N″,N″-PENTAMETHYLDIETHYLENETRIAMINE CATALYST SYSTEM

The polymerization of n-butyl methacrylate was investigated using the Atom Transfer Radical Polymerization technique with CuBr and CuCl/N,N,N′,N″,N″-pentamethyldiethylenetriamine catalytic systems. Various combinations of catalyst systems and initiators were utilized in order to optimize the polymerization conditions and to obtain well-defined polymers (i.e. controlled molecular weights and low polydispersities). It has been found that the optimal initiator for this system is a chlorine-based initiator, when the catalyst used is a Cu(I) salt in conjunction with the N,N,N′,N″,N″-pentamethyldiethylenetriamine ligand. Bromine-based initiators tend to result in large amounts of initial termination, leading to polymers with less than ideal chain end functionality, even if CuCl is used as the Cu(I) species to invoke the halogen exchange. Additionally, the effects of the polymerization temperature, copper(1) species and the initiator structure were determined.     

INVESTIGATION OF THE ATRP OF n-BUTYL METHACRYLATE USING THE Cu（I）／N,N,N＇ N＂ N＂-PENTAMETHYLDIETHYLENETRIAMINE CATALYST SYSTEM

The polymerization of n-butyl methacrylate was investigated using the Atom Transfer Radical Polymerization technique with CuBr and CuCl/N,N,N‘,N“,N“-pentamethyldiethylenetriamine catalytic systems. Various combinations of catalyst systems and initiators were utilized in order to optimize the polymerization conditions and to obtain well-defined polymers (i.e. controlled molecular weights and low polydispersities). It has been found that the optimal initiator for this system is a chlorine-based initiator, when the catalyst used is a Cu(I) salt in conjunction with the N,N,N‘,N“,N“-pentamethyldiethylenetriamine ligand. Bromine-based initiators tend to result in large amounts of initial termination, leading to polymers with less than ideal chain end functionality, even if CuCI is used as the Cu(I) species to invoke the halogen exchange. Additionally, the effects of the polymerization temperature, copper(I) species and the initiator structure were determined.     

OPTICALLY ACTIVE AND FLAME-RETARDANT POLY(AMIDE-IMIDE)S BASED ON PHOSPHINE OXIDE MOIETY AND N,N′-(PYROMELLITOYL)BIS-L-AMINO ACID IN THE MAIN CHAIN:SYNTHESIS AND CHARACTERIZATION

<正>Six new optically active and flame-retardant poly(amide-imide)s PAIs 5a-5f containing phosphine oxide moiety as a flame-retardant unit in the main chain were synthesized from direct polycondensation reaction of six chiral N,N′-(pyromellitoyl)-bis-L-amino acid 3a-3f with bis(3-aminophenyl)phenyl phosphine oxide 4 in a medium consisting of N-methyl-2-pyrrolidone(NMP),triphenyl phosphite(TPP),calcium chloride(CaCl_2) and pyridine.The polymerization reactions produced a series of optically active poly(amide-imide)s with good yield and good inherent viscosity of 0.34-0.70 dLg~(-1).The resulted polymers were fully characterized by means of FTIR and ~1H-NMR spectroscopy,gel permeation chromatography(GPC),elemental analyses,inherent viscosity and solubility tests.Thermal properties and flame-retardant behavior of the PAIs 5a-5f were investigated using thermal gravimetric analysis(TGA and DTG) and limiting oxygen index(LOI).Data obtained by thermal analysis(TGA and DTG) revealed that these polymers showed good thermal stability.Furthermore,high char yield in TGA and good LOI values indicated that the resulting polymers were capable of exhibiting good flame retardant properties.N,N′-(pyromellitoyl)-bis-L-amino acids 3a-3f were prepared in quantitative yields by the condensation reaction of pyromellitic dianhydride(1,2,4,5-benzenetetracarboxylicacid-1,2,4,5-dianhydride) 1 with L-alanine 2a,L-valine 2b,L-leucine 2c,L-isoleucine 2d,L-phenyl alanine 2e and L-2-aminobutyric acid 2f in acetic acid solution.     

Aliphatic Hyperbranched Poly（amido amine）s （PAMAMs） ： Preparation and Modification

A series of water soluble aliphatic hyperbranched poly(amido amine)s(PAMAMs) with the same or similar chemical structure of poly(amido amine) dendrimer was successfully synthesized from commercially available AB and Cn types of monomers by one-pot polymerization via the couple-monomer methodology(CMM). The AB type monomer used in this paper was methyl acrylate, and Cn monomers were multi-amino compounds such as ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetraamine (TETA). tetraethylenepentaamine (TEPA) and pentaethylenehexamine (PEHA). The reaction mechanism was investigated by means of the mass spectra of the reaction intermediates. Adjusting the feed ratio of AB to Cn. hyperbranched polymers with different terminal groups and properties were obtained. FTIR, NMR, DSC. and TGA were used to characterize the polymers. It was found that the polymers‘ properties such as solubility, thermal behaviour and encapsulation capability varied with changing the feed ratio of AB to Cn. Benzoyl and palmitoyl groups were introduced into these macromolecules by acidylation to form amphiphilic hyperbranched polymers which have a high capability to encapsulate water soluble dyes such as Congo red. It is expected that the hyperbranched PAMAMs can play an important role in the industrial applications, such as coatings, cross-linking and phase-transferring agents because of their versatility and availability.     

POLYMERIZATION OF N,N′-（PYROMELLITOYL）-BIS-L-LEUCINE DIACID CHLORIDE WITH HYDANTOIN DERIVATIVES BY MICROWAVE IRRADIATION

Facile and rapid polycondensation reactions of N,N′-(pyromellitoyl)-bis-L-leucine diacid chloride 1 with eight different derivatives of hydantoin compounds 2a-h were developed by using a domestic microwave oven in the presence of a small amount of polar organic medium such as o-cresol. The polycondensation reactions proceeded rapidly, compared with the conventional solution polycondensation, and was completed within 7-10 min, producing a series of novel optically active poly(amide-imide)s 3a-h with high yield and inherent viscosity of 0.35-0.65 dL/g. All of the above polymers were fully characterized by FT-IR, elemental analyses, inherent viscosity (ηinh), solubility test and specific rotation. Some structural characterization and physical properties of these optically active poly(amide-imide)s are reported.     

Synthesis and characterization of biodegradable materials： PDLLA-（MAh-Diol）n-PDLLA copolymer

The novel biodegradable copolymer PDLLA-(MAH-Diol)_n-PDLLAwith unsaturated bond was synthesized by copolymerizing lactide and prepolymer, which was prepared by the polycondensation of maleic anhydride and poly(ethylene glycol), using p- toluene sulphonic acid as catalyst. The new copolymer has improved hydrophilicity and fexibility. The structure and properties of the novel polymers were studied by FTIR, NMR, GPC-MALLS and DSC.     

MICROMOLDING ON CURVED SURFACES WITH THERMOPLASTICS

Microstructures were produced on curved surfaces and micro-protrusions by using direct micromolding with fourthermoplastic polymers. This method is simpler and more convenient than micromolding with liquid prepolymer or using theμTM method. By repeated molding, crossed structures were produced with a stamp prepared only with lines. The processingvariables including the softening temperature of the polymers and heating time were discussed. The result shows that theoptimal molding temperature is preferably slightly higher than the melting temperature of the thermoplastic polymers, atwhich polymers are in the critical states of being melted. This method can be applied to many polymers except those with high softening temperatures or high rate of shrinkage upon temperature change.     

Synthesis and Properties of Polyurethane Resins from Liquefied Benzylated Wood

In this paper, polyurethane resins were synthesized from liquefied benzylated wood and TDI (toluene diisocyanate)-TMP (trihydromethylene propane) prepolymer. And the relation between microphase structure and properties of PU samples were also studied. The results indicated that coatings obtained had good mechanical and thermal properties. The amount of the curing agent has great effect on the degree of phase segregation. In addition, with increased the curing agent amount, the thermal stabilities were also improved.     

Iron-mediated AGET ATRP of styrene and methyl methacrylate using ascorbic acid sodium salt as reducing agent

Atom transfer radical polymerization of styrene(St) and methyl methacrylate(MMA) in bulk and in different solvents using activators generated by electron transfer(AGET ATRP) were investigated in the presence of a limited amount of air using FeCl3·6H2O as the catalyst, ascorbic acid sodium salt(AsAc-Na) as the reducing agent, and a cheap and commercially available tetrabutylammonium bromide(TBABr) as the ligand. It was found that polymerization in THF resulted in shorter induction period than that in bulk and in toluene for AGET ATRP of St, while referring to AGET ATRP of MMA, polymerization in THF showed three advantages compared with that in bulk and toluene: 1) shortening the induction period, 2) enhancing the polymerization rate and 3) having better controllability. The living features of the obtained polymers were verified by chain end analysis and chain-extension experiments.     

Y型三苯胺生色分子的二阶极化率

通过Knoevenagel反应合成了3个Y型三苯胺生色分子N,N-二{4-[2-(2-苯并噻唑基)乙烯基]苯基}苯胺(BBtVPA)、N,N-二{4-[1-(2-苯并噻唑基)-1,3-丁二烯-4-基]苯基}苯胺(BBtBPA)和N,N-二{4-[1-(2-二氰基甲叉-3-氰基-5,5-二甲基-2,5-二氢-4-呋喃基)-1,3-丁二烯-4-基]苯基}苯胺(BCfBPA), 以及4个一维偶极分子4-[2-(2-苯丙噻唑基)乙烯基]-N,N-二苯基苯胺(BtVPA)、1-(2-苯并噻唑基)-4-[4-(N,N-二苯基)氨基]苯基-1,3-丁二烯(BtAPB)、1-[(2-二氰基甲叉-3-氰基-5,5-二甲基-2,5-二氢)-4-呋喃基]-4-[4-(N,N-二苯基氨基)]苯基-1,3-丁二烯(CfAPB)和4-[2-(2-二氰基甲叉-3-氰基-5,5-二甲基-2,5-二氢呋喃-4-基)乙烯基]-N,N-二苯基苯胺(CfVPA). 测定了生色分子的紫外吸收和荧光性质, 在二氯甲烷中, Y型分子BBtVPA, BBtBPA和BCfBPA的最大吸收波长分别为425, 443和613 nm, 比偶极分子红移了约30 nm, Y型分子BBtVPA和BBtBPA的最大荧光发射峰分别位于516和558 nm, 比偶极分子稍有红移. 根据双能级模型理论, 用溶致变色法测定了生色分子的二阶非线性极化率(β), Y型分子BBtVPA, BBtBPA和BCfBPA的β0分别为40×10-30, 64×10-30和238×10-30 esu, 比相应的偶极分子分别提高了0.9~2.8倍. 结果表明, 提高吸电子基团强度, 增大共轭体系有助于获得更大的β值.     

A rapid and sensitive analysis of diphenylarsinic acid in water by gas chromatography/mass spectrometry.

A rapid and sensitive analytical method using pentafluorothiophenol (PFTP) derivatization was applied to detect diphenylarsinic acid (DPAA) in water. In this study, the optimum derivatization conditions, such as acid concentration, reaction time and reaction temperature, were investigated to develop a suitable procedure for DPAA determination. After extracting the derivatives into benzene, the determination was carried out by gas chromatography/mass spectrometry (GC/MS) with selected ion monitoring (SIM). The detection limit of the method was 9.4 microg/l, and the overall recoveries obtained from real environmental samples were 88.9 - 104.7% and coefficient variations were 5.1 - 13.9%.     

Effect of prepolymer molecular weight on solid state polymerization of poly(bisphenol a carbonate) with nitrogen as a sweep fluid

The effect of prepolymer molecular weight on the solid‐state polymerization (SSP) of poly(bisphenol A carbonate) was investigated using nitrogen (N₂) as a sweep fluid. Prepolymers with different number–average molecular weights, 3800 and 2400 g/mol, were synthesized using melt transesterification. SSP of the two prepolymers then was carried out at reaction temperatures in the range 120–190 °C, with a prepolymer particle size in the range 20–45 μm and a N₂ flow rate of 1600 mL/min. The glass transition temperature (T_g), number–average molecular weight (M_n), and percent crystallinity were measured at various times during each SSP. The phenyl‐to‐phenolic end‐group ratio of the prepolymers and the solid‐state synthesized polymers was determined using 125.76 MHz ¹³C and 500.13 MHz ¹H nuclear magnetic resonance (NMR) spectroscopy. At each reaction temperature, SSP of the higher‐molecular‐weight prepolymer (M_n = 3800 g/mol) always resulted in higher‐molecular‐weight polymers, compared with the polymers synthesized using the lower molecular weight prepolymer (M_n = 2400 g/mol). Both the crystallinity and the lamellar thickness of the polymers synthesized from the lower‐molecular‐weight prepolymer were significantly higher than for those synthesized from the higher‐molecular‐weight prepolymer. Higher crystallinity and lamellar thickness may lower the reaction rate by reducing chain‐end mobility, effectively reducing the rate constant for the reaction of end groups. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4959–4969, 2008     

Rigid-rod polymers with polysiloxane side chains. 2. Synthesis and characterization of aromatic polybenzobisoxazoles with polysiloxane side chains and composite formation with polysiloxane matrices

Aromatic polybenzobisoxazoles, having polydimethylsiloxane side chains (SCPBOs), were prepared using terephthaloyl chloride-terminated polydimethylsiloxane macromonomers and 3,3′-bis(trimethylsiloxy)-4,4′-bis(trimethylsilylamino)biphenyl for the purpose of dispersing rigid-rod molecules in silicone matrices for molecular reinforcement. The degree of polymerization of the side chain was varied from 7.8 to 45.4, and a small amount of (3-butenyloxy)terephthaloyl chloride was copolymerized to give the polymers a functionality that can be linked to the matrices. For all the SCPBOs, the WAXD pattern showed only diffuse reflections, suggesting limited structural regularity, although the polymers were optically anisotropic. No melting transition was observed below the side chain decomposition temperature, 350°C. A polydimethylsiloxane/polybenzobisoxazole composite elastomer was obtained first curing the polysiloxane matrix containing the prepolymer of the SCPBO, followed by in situ thermal ring closure of the prepolymer. Some reinforcement was observed, but the presence of plasticizing effect by the unbound SCPBO was suggested at the same time. © 1995 John Wiley & Sons, Inc.     

聚氨酯/苯丙杂化乳液的合成、表征和特性及其在复膜胶中的应用

由聚氨酯(PU)预聚物、丙烯酸丁酯和苯乙烯单体的乳液聚合制备了聚氨酯-苯乙烯-丙烯酸酯(PUSA)杂化乳液,1H NMR显示所得的PU预聚物由烯烃基团封端。 TEM表明,其粒径约为150 nm,且为颜色深浅不同的两部分所组成。 随着PU含量的降低,杂化乳液的热稳定性增加。 DSC分析表明,所得杂化乳液有单一的Tg值,且处于聚氨酯和聚苯丙(PSA)乳液Tg值的中间。 当将得到的杂化乳液用于纸塑和塑塑复合时,其剥离强度分别为14.1 N/2.5 cm和12.2 N/2.5 cm。     

聚醚环氧化合物的合成及其改性环氧树脂的研究

本文采用原料易得、价廉而分子量较大的聚醚树脂合成相应的聚醚环氧化合物及其胺的预反应物,研究其对环氧树脂的改性效果,用红外光谱、差热分析和透视电镜研究其相结构。     

CHEMILUMINESCENT DIPHENYLACETALDEHYDE OXIDATION BY MITOCHONDRIA IS PROMOTED BY CYTOCHROMES and LEADS TO OXIDATIVE INJURY OF THE ORGANELLE

Plant and animal mitochondria promote the aerobic oxidation of diphenylacetaldehyde (DPAA). This process is accompanied by chemiluminescence and rotenone-insensitive oxygen uptake. Tn rat liver and potato tubers, mitochondrial swelling is concurrently detected. Light emission and oxygen consumption decreased (about 50%) in cytochrome c-depleted mitochondria. A model system–cytochrome c or b5/dihexadecylphosphate liposomes–was also able to oxidize DPAA with parallel reduction of the cytochrome. Reduction of respiratory complex I or I plus II by addition of rotenone or antimycin A, respectively, did not prevent DPAA oxidation. However, when all cytochrome was reduced by addition of cyanide, aldehyde oxidation was completely suppressed. Altogether these data indicate that respiratory cytochromes are responsible for DPAA oxidation with production of excited species and consequent mitochondrial permeabilization.     

Synthesis of poly(urethane‐imide) using aromatic secondary amine‐blocked polyurethane prepolymer

A set of poly(urethane‐imide)s were prepared using blocked Polyurethane (PU) prepolymer and pyromellitic dianhydride (PMDA). The PU prepolymer was prepared by the reaction of polyether glycol and 2,4‐tolylene diisocyanate, and end capped with N‐methyl aniline. The PU prepolymer was reacted with PMDA until the evolution of carbon dioxide ceased. The effect of tertiary amine catalysts, organo tin catalysts, solvents, and reaction temperature were studied and compared with the poly(urethane‐imide) prepared using phenol‐blocked PU prepolymer. N‐methyl aniline blocked PU prepolymer gave a higher molecular weight poly(urethane‐imide) at a lower reaction temperature in a shorter time. Amine catalysts were found to be more efficient than organo tin catalysts. The reaction was favorable in particular with N‐ethylmorpholine and diazabicyclo(2.2.2)octane (DABCO) as catalysts, and dimethylpropylene urea as a reaction medium. The poly(urethane‐imide)s were characterized by FTIR, GPC, TGA, and DSC analyses. The molecular weight decreased with an increase in reaction temperature. The thermal stability of the PU was found to increase by the introduction of imide component. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4032–4037, 2000     

Studies on molecular composite. I. Processing of molecular composites using a precursor polymer for poly(p‐phenylene benzobisthiazole)

The blending of a precursor polymer for poly(p‐phenylene benzobisthiazole) (PBZT) with various matrix polymers was attempted, followed by heat conversion of the PBZT precursor polymer to obtain molecular composites consisting of PBZT and the matrix polymers. A higher concentration of mixed solution using organic solvent and milder conditions to remove the solvent could be applied to blend the polymers using the precursor polymer in place of rodlike PBZT. The dispersibility of PBZT in the matrix polymer in the blended materials obtained depended on the ability to form intermolecular hydrogen bridges between the PBZT precursor and the matrix polymer. In particular, the blended material, obtained using a nonthermoplastic aromatic polyamide as the matrix polymer having a molecular structure similar to that of the PBZT prepolymer, was transparent and showed excellent reinforcing efficiency of PBZT. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 189–197, 1999     

The Development of Polybenzimidazole Composites as Ablative Heat Shields

Abstract

The excellent high-temperature mechanical properties and other desirable characteristics of polybenzimidazole (PBI) polymer systems make these systems attractive candidates for development as ablative heat-shield materials. This paper describes the formulation of several new low-density polybenzimidazole composites. The proposed structure of the basic linear PBI prepolymer and of several highly cross-linked PBI polymers are presented. The cross-linked PBI's were obtained either thermally (by postcuring to a high temperature) or chemically (by the use of either preoxidized polyfunctional amines or triphenyl trimeasate as a comonomer in the polymerization).