Elongation-induced phase separation of poly(vinyl alcohol)/poly(acrylic-acid) blends as studied by C CP/MAS NMR and wide-angle X-ray diffraction

The membrane samples of poly(vinyl alcohol)/poly(acrylic-acid) (PVA/PAA) blend with different draw ratios were studied by both ¹³C CP/MAS NMR and wide-angle X-ray diffraction (WAXD) measurements. Phase separation induced by elongation of the sample was observed and the change of the phase structure with draw ratio was found to be dependent on the composition of the blend samples.     

Preparation and characterization of crosslinked polyimide–poly(dimethylsiloxane)s

Crosslinked polyimide–poly(dimethylsiloxane)s with theoretical content of the siloxane phase up to 60 wt% were prepared. The starting materials were p-aminophenyltrimethoxysilane terminated polyamic acids with number average molecular weight of 10,000 g mol⁻¹, based on 4,4′-oxydiphthalic anhydride and 4,4′-oxydianiline and dimethoxydimethylsilane. The structure of the prepared polymeric materials was analyzed using ²⁹Si and ¹³C NMR solid-state spectroscopy. Their thermal and mechanical properties, chemical resistance and density were evaluated. The influence of the basic catalysts employed (ammonium hydroxide) on the course of the reaction and properties of the materials was also studied.     

Synthesis of amphiphilic microspheres by suspension copolymerization of styrene and poly(ethylene oxide) macromonomer

Amphiphilic microspheres, ranging in size from 3 to 35 μm, were prepared by suspension copolymerization of styrene with poly(ethylene oxide) vinylbenzyl (PEO–VB) macromonomer by changing polymerization conditions. It was found that an increase in the amount of dispersant and the PEO–VB concentration resulted in decreases of the size and size distribution of amphiphilic microspheres. The morphology, size, and size distribution of amphiphilic microspheres were characterized by scanning electron microscopy. The structure of copolymer was confirmed by infrared spectroscopy, differential scanning calorimetry, elemental analysis, and X‐ray photoelectron spectroscopy. The content of the hydroxyl groups localized in the microspheres ranged from 0.05 to 0.2 mmol/g. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 333–339, 2001     

Preparation and characterization of biocompatible poly(L‐lactic acid)/gelatin blend membrane

Poly(L ‐lactic acid) (PLLA)/gelatin blend membranes were prepared by solution casting method and using dimethyl sulfoxide (DMSO) as a cosolvent. Scanning electron microscopy measurement indicated that when the amounts of gelatin in PLLA/gelatin blend membranes are less than 5%, the sizes of phase separation of gelatin are in range of several hundred nanometers. These benefit in retaining the strength of PLLA membranes. X‐ray diffraction analysis revealed that the semicrystalline PLLA became amorphous and the melt temperature of crystalline PLLA changes from 56 to 38°C after it was processed in DMSO solvent. When the content of gelatin is less than 5%, the films not only retain a good mechanical property but also improve the hydrophilicity of PLLA. The molecular motion of PLLA in blend films were also investigated by solid state ¹³C CP/MAS NMR. On the basis of the result of relaxation times, it was found that the molecular motion of PLLA100 and PLLA/gelatin blends increased when compared with that of original PLLA. It was further verified that semicrystalline PLLA became amorphous. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 269–276, 2006     

Heparin‐immobilized poly(2‐hydroxyethylmethacrylate)‐based microspheres

Poly(2‐hydroxyethylmethacrylate) (PHEMA)‐based microspheres (150–200 µm in diameter) were produced by a modified suspension polymerization of different type of comonomers—namely, acrylic acid, dimethylaminoethyl‐methacrylate, and methylmethacrylate. These microspheres were activated with cyanogen bromide (CNBr) at pH 11.5, and heparin molecules were then immobilized through covalent bonds. The amount of immobilized heparin was controlled by changing the initial concentration of CNBr and heparin. The increase in the initial concentrations of both CNBr and heparin caused an increase in the amount of heparin immobilized onto microspheres for all polymer surfaces. The maximum heparin immobilization was observed on the PHEMA homopolymer microspheres (180 mg/g). The plain and heparin‐immobilized microspheres were contacted with blood in in vitro systems and in ex vivo animal experiments. Loss of the blood cells and clotting times were followed. Anticoagulant effect of the immobilized heparin was clearly observed with blood coagulation experiments. Loss of cells in the blood contacting with heparin‐immobilized microspheres was significantly lower than those observed with the plain microspheres. Bovine serum albumin adsorption onto the microspheres containing heparin on their surfaces was also studied. High albumin adsorption values (up to 127 mg/g) were observed in which the heparin‐immobilized PHEMA microspheres were used. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 655–662, 1999     

In situ immobilization of alkaline protease during inverse suspension polymerization of polyacrylamide and poly(acrylamide-co-methacrylic acid) hydrogel beads

We report the in situ immobilization of alkaline protease in highly porous polyacrylamide and poly(acrylamide-co-methacrylic acid) hydrogel beads synthesized by inverse suspension polymerization using ammonium persulfate, N,N,N′,N′,-tetraethylmethylenediamine as the redox initiator. The influences of reaction variables on the polymerization, conversion, enzymatic activity, water absorption, and LCST properties were studied in detail. Evaluation of the enzymatic activities on various substrates was carried out for potential applications in the detergent industry. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2273–2291, 1999     

Highly isotactic poly(vinyl alcohol) derived from tert-butyl vinyl ether. Part IV. Some physical properties, structure and hydrogen bonding of highly isotactic poly(vinyl alcohol) films

Some basic physical properties, structure and hydrogen bonding have been characterized for different stereoregular PVA films including highly isotactic PVAs (HI-PVAs), which were recently succeeded in synthesis, as functions of the mm fraction by using different analytical methods. The melting temperature, degree of crystallinity, and ¹³C spin-lattice relaxation time of the crystalline component are found to have their own clear minima at the mm fraction of about 0.4-0.5. This fact suggests that structural disordering associated with the decrease in crystallinity may be most strongly induced at this mm fraction. The formation of the new crystal form of PVA has been reconfirmed for HI-PVAs with the mm fractions higher than about 0.55 by FTIR spectroscopy and the structure and hydrogen bonding have been investigated in detail by solid-state ¹³C NMR spectroscopy. It is found that all OH groups are allowed to form successive intramolecular hydrogen bonding along the respective chains in the crystalline region for HI-PVAs with the mm fractions higher than about 0.7. Since these chains should contain some amount of r units even in the crystalline region, a slightly helical structure with a considerably long period may be adopted by them as an energetically stable state. On the basis of the line shape analysis of the CP/MAS ¹³C NMR spectra of the crystalline components, structural causes of the appearance of the minima of the physical values described above are also discussed in relation to the introduction of disordered units mainly associated with hydrogen bonding to the syndiotactic or isotactic sequences forming successive intermolecular or intramolecular hydrogen bonding, respectively.     

Modeling of solid-state polymerization of poly(ethylene terephthalate)

A mathematical model for solid-state polymerization of poly(ethylene terephthalate) was developed. The effects of temperature and chain entanglement on chain mobility were considered to estimate the rate constants of chemical reactions. The diffusivities of volatile byproducts could be determined using the free volume theory.^13,14 The model predictions were validated with experimental data reported in the literature. In addition, assuming that the concentration profiles of volatile byproducts in spherical particles are described by a sinusoidal function, the mass transfer rate of the byproducts at a given time could be derived as an ordinary differential equation that can be easily treated. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:837–846, 1998     

Solid-state C NMR investigation of the structure and hydrogen bonding for stereoregular poly(vinyl alcohol) films in the hydrated state

The structure and hydrogen bonding of the hydrated stereoregular poly(vinyl alcohol) (PVA) films have been investigated by high-resolution solid-state ¹³C NMR spectroscopy. It is found by the ¹³C spin-lattice relaxation analysis that there exist three components with different T_1C values assigned to the crystalline, less mobile and mobile components for the hydrated syndiotactic PVA (S-PVA) and highly isotactic PVA (HI-PVA) films. The line shape analysis indicates that the probability of intramolecular hydrogen bonding is appreciably increased in the crystalline region for the S-PVA films by the hydration but a slightly helical structure, which is probably allowed by the formation of the successive intramolecular hydrogen bondings along the chains in the crystalline region, seems not to undergo any significant change by the hydration for HI-PVA. This fact indicates that intramolecular hydrogen bonding is more stable in the hydrated state in the crystalline region. As for the less mobile component, the line shape of the CH resonance line for the hydrated S-PVA or HI-PVA films is found to be very similar to that of the corresponding crystalline component, probably being due to the successive formation of intermolecular or intramolecular hydrogen bonding in the interfacial region, which mainly contributes to the less mobile component, for the S-PVA or HI-PVA films even in the hydrated state. The mole fractions of the mm, mr and rr sequences are also estimated for the mobile component that is produced in each stereoregular PVA sample by swelling with water and it is concluded that no prominent preferential partitioning of the mm, mr and rr sequences occurs in the crystalline and noncrystalline regions for the PVA films with different tacticities.     

悬浮聚合法制取不同分子量级别的聚甲基丙烯酸甲酯

采用粉状MgCO3 作为分散剂 ,悬浮聚合制取了分子量从 2 4× 10 4 ～ 2 5 4× 10 4 的聚甲基丙烯酸甲酯。考察了温度、引发剂种类和浓度、分子量调节剂、转化率对聚合物分子量的影响规律 ,用粘度法测量了聚合物聚甲基丙烯酸甲酯 (PMMA)的分子量。结果表明 :温度的升高、引发剂浓度的增大、分子量调节剂的加入都会导致分子量的减小 ,随着转化率的提高 ,聚合物的分子量增大。在同等条件下 ,引发剂过氧化苯甲酰 (BPO)聚合所得的分子量较偶氮二异丁腈 (AIBN)高。通过实验 ,得到了满足作者需求的分子量 (96× 10 4 ～ 10 0× 10 4 )的聚合物的聚合条件为 :分散剂MgCO3 用量 1% ,单体∶水相 =1∶2 5 (质量比 ) ,引发剂BPO浓度 0 5 % ,反应温度 70℃ ,反应时间 3h。     

2‐Hydroxypropylmethacrylate based mono‐ and bifunctional gel beads prepared by suspension polymerization

Spherical and swellable gel beads in the size range 35–200 µm were prepared by suspension polymerization of 2‐hydroxypropylmethacrylate (HPMA). In the proposed method, a mixture of cyclohexanol and octanol was used as a diluent phase dispersed in an aqueous medium including poly(vinyl pyrrolidone) (PVP) as the stabilizer. The polymerization was initiated within the organic phase including the monomer and the crosslinker (ethylene glycol dimethacrylate) by an oil soluble initiator benzoyl peroxide. Spherical and swellable gel beads carrying both hydroxyl and carboxyl functional groups were also prepared by suspension copolymerization of HPMA and a water soluble comonomer (methacrylic acid). For this purpose, the suspension polymerization method proposed for HPMA was modified by using poly(vinyl alcohol) as a stabilizer instead of PVP. The effect of initiator concentration, polymerization temperature, monomer/diluent ratio, crosslinker concentration, stirring rate on yield, average size, size distribution, and carboxyl content of the HPMA based gel beads, were investigated. The swelling characteristics of the gel beads were defined. © 2000 Society of Chemical Industry     

聚亚苯基硅氧烷交联网络的热性能

用Si—H/Si—OR缩聚的方法制备了含可交联乙烯基的聚亚苯基硅氧烷-二甲基硅氧烷共聚物(PTMPS-DMS),用硅氢加成、BPO热交联两种方法进行交联得到交联网络,并用热重分析(TG)、300℃恒温热分析和DSC等方法对其热性能进行了研究。结果表明,交联方法对PTMPS-DMS交联网络的热稳定性影响很大,BPO热交联网络的热稳定性远远高于硅氢加成交联网络,两种交联网络在空气中的5%热失重温度分别是480℃和368℃,Tg则没有显著差异,分别是-55℃和-49℃。H2PtCl6能显著降低PTMPS-DMS及其交联网络在空气中的热稳定性。     

Preparation and characterization of poly(methyl methacrylate) beads

The phase behavior of Poly(ethylene terephthalate)/Poly(ethylene‐2,6‐naphthalate)/Poly(ethylene terephthalate‐co‐ethylene‐2,6‐naphthalate) (PET/PEN/P(ET‐co‐EN)) ternary blends in molten state was evaluated from differential scanning calorimetry (DSC) and NMR results as well as optical microscopic observations. Copolymer of ethylene terephthalate and ethylene‐2,6‐naphthalate was prepared by a condensation polymerization, which was a random copolymer with an intrinsic viscosity (IV) of 0.3 dL/g. The phase diagram of the ternary blends revealed that the miscibility of ternary blends in molten state was dependent on the fraction of P(ET‐co‐EN) in the blends and holding time of the blends at high temperatures above 280°C. With increase in the holding time, the fraction of copolymer in the blends necessary to induce the immiscible to miscible transition decreased. For the blends with longer holding time at 280°C, the phase diagram in molten state was irreversible against the temperature, although a reversibility was found for the blends with short holding time of 1 min at 280°C. The irreversibility of phase behavior was not explained simply by the increase of copolymer content produced during heat treatment. Complex irreversible physical and chemical interactions between components and change of phase structure of the blend in the molten state might influence on the irreversibility. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Solid state polymerization of bis(trichlorophenoxo) cobalt(ii) complex to give poly(dichlorophenylene oxide)

Synthesis of four-coordinated (tetrahedral) trichlorophenol cobalt(II) complex with neutral ligand pyridine was achieved from the aqueous solution and its characterization was performed by UV-visible, IR spectral and CHN analysis. Solid state thermal polymerization of the complex was accomplished first at constant temperature employing different time intervals and secondly at constant decomposition time. The poly(dichlorophenylene oxide)s so synthesized were characterized by IR, ¹H NMR and ¹³C NMR spectral analysis, T_g determination, as well as measurement of molecular weight by a viscometric method.     

Mechanical properties, morphology and molecular characteristics of poly(ethylene terephthalate) toughened by natural rubber

The melt blending of poly(ethylene terephthalate) (PET) and natural rubber (NR) in a twin-screw extruder is studied. Parameters affecting the blend properties such as the amounts of the NR in the blends and screw speeds are investigated. Increased toughness of the PET/NR blend was found as the amount of NR was increased. The impact strength of the PET/NR (80/20 wt%) blend using a screw speed of 100 rpm, increased up to seven-fold when compared to that of pure PET. The morphology of the blend was investigated by SEM. The molecular characteristic was evaluated by spectroscopic technique. The toughening effect of NR on the PET might come from the possible interaction between the two phases, which was clearly evidenced by solid-state CP/MAS ¹³C NMR data. The data revealed an increase in the cross polarization time (T_D) of the carbonyl carbon and a decrease of the relaxation of the carbonyl groups in the PET/NR blend. This should come from the interaction between the carbonyl group of PET with some abnormal groups such as hydroxyl function in the NR, resulting in an improvement of the compatibility of the studied blends.     

Preparation and characterization of novel poly(glycidyl methacrylate) beads carrying amidoxime groups

Poly(glycidyl methacrylate) (PGMA) beads with an average size of 350 μm were synthesized by suspension polymerization technique. The PGMA beads were first modified with iminodiacetonitrile (IDAN). Then, the IDAN‐modified beads were subsequently modified by hydroxylamine. The IDAN modification and the conversion of the nitrile groups to amidoxime were followed by FT‐IR spectroscopy. The surface morphology and thermal behavior of the PGMA and its modified forms were also characterized by scanning electron microscopy and thermogravimetric analysis techniques, further confirming modification and amidoximation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

CP/MAS C NMR analysis of the structure and hydrogen bonding of melt-crystallized poly(vinyl alcohol) films

The structure and hydrogen bonding of the melt-crystallized atactic poly(vinyl alcohol) (A-PVA) films, which were carefully prepared without significant thermal degradation, have been characterized by CP/MAS ¹³C NMR spectroscopy. The ¹³C spin-lattice relaxation analysis has revealed that there exist three components with different T_1C values, the crystalline, less mobile noncrystalline and mobile noncrystalline components, in good accord with the results for different PVA samples previously reported. It should be noted that the T_1C values of the crystalline and noncrystalline components are appreciably smaller for the melt-crystallized films than those for the un-annealed and annealed samples prepared by casting from the aqueous solution. The ¹³C NMR spectra of the crystalline and noncrystalline components are separately recorded by using the difference in T_1C and their CH lines are successfully resolved into three and seven constituent lines by the least-squares curve fitting, respectively. Moreover, the statistical analysis of the integrated intensities of the constituent lines thus obtained enables to determine the probability f_a for the formation of intramolecular hydrogen bonding in the successive two OH groups along each chain and another probability f_t of the trans conformation for the crystalline and noncrystalline components. It is found that the f_a value is relatively larger for the melt-crystallized films than those for the un-annealed and annealed samples. On the basis of these results, the features of the melt-crystallization and the resulting crystalline-noncrystalline structure are discussed by particularly considering effects of intra- and inter-molecular hydrogen bonding on the crystallization.     

Inverse suspension polymerization of sodium acrylate: Synthesis and characterization

Crosslinked Poly(acrylic acid) was synthesized by inverse suspension polymerization. This process was investigated to determine the influence of different parameters like temperature, stirring speed, solution pH, and crosslinker concentration and to obtain the best control of the kinetics. An aqueous phase containing partially neutralized acrylic acid, crosslinking agent, and initiator agent was dispersed in an organic phase and stabilized by a surfactant. The inverse suspension was carried out in heptane as the organic phase with a different ratio of neutralization of the monomer, different crosslinker concentrations, and several stirring speeds. The polymerization was initiated by potassium persulfate (K₂S₂O₈) with N‐N′‐methylenebisacrylamide (MBA_C) as the crosslinker and sorbitan monooleate as the surfactant. The influence of several parameters on the bead size and the swelling capacity was investigated. Particle diameters ranged from 10 to 130 μm. The kinetic results obtained by differential scanning calorimetry showed that conversion and polymerization rates are a function of the solution pH, and they fell when the concentration of the crosslinking agent was higher than 7.5% in the mass of MBA_C. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2621–2630, 2000     

P(MMA-DBMEA)乳液聚合研究

甲基丙烯酸甲酯 ( MMA)在无皂乳化剂条件下 ,加入少量的功能性单体 N,N一二甲基 ,N-丁基 ,N-甲基丙烯酰氧乙基溴化铵 ( DBMEA) ,合成了稳定的 P( MMA-DBMEA)共聚物乳液 .该共聚物乳胶粒呈现单分散分布。同时用 NMR研究了共聚物 ,并对 P( MMA-DBMEA)聚合物13 C进行了全归属。     

用CP/MAS~(13)C NMR研究壳聚糖的分子运动

用固体交叉极化/魔角旋转(CP/MAS)13CNMR测定了壳聚糖、热失水壳聚糖和戊二醛交联壳聚糖在固态下不同峰位13C的弛豫时间,对不同样品的不同峰位碳弛豫时间的大小进行了解释,并根据弛豫时间的测定值对这3种不同壳聚糖样品的分子运动状态进行了描述。结果表明,壳聚糖受热失去吸附水以后,所有位置碳的弛豫时间均有所延长,以C2,6的弛豫时间延长幅度最大,分子运动受阻;壳聚糖用戊二醛交联以后,所有13C信号的线宽均大幅度增加,而弛豫时间显著降低,分子运动加剧。