Structural characterization of reactor blends of polypropylene and ethylene‐propylene rubber

Blends of isotactic polypropylene (PP), ethylene‐propylene rubber copolymer (EPR), and ethylene‐propylene crystalline copolymer (EPC) can be produced through in situ polymerization processes directly in the reactor and blends with different structure and composition can be obtained. In this work we studied the structure of five reactor‐made blends of PP, EPR, and EPC produced by a Ziegler‐Natta catalyst system. The composition of EPR was related to the ratio between ethylene and propylene used in the copolymerization step. The ethylene content in the EPR was in the range of 50–70 mol %. The crystallization behavior of PP and EPC in the blends was influenced by the presence of the rubber, and some specific interactions between the components could be established. By preparative temperature rising elution fractionation (P‐TREF) analysis, the isolation and characterization of crystalline EPC fractions were made. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2155–2162, 2004     

A water‐developable negative photoresist based on the photocrosslinking of N‐phenylamide groups with reduced environmental impact

A water‐developable negative photoresist based on the photocrosslinking of N‐phenylamide groups was prepared by the copolymerization of 4‐styrenesulfonic acid sodium salts (SSS) with N‐phenylmethacrylamide (copolymer A) or p‐hydroxy‐N‐phenylmethacrylamide (copolymer B), and its properties such as solubility changes, photochemical reaction, and photoresist characteristics were studied. The copolymer containing a relatively higher amount of SSS units was soluble in water. Solubility changes of the copolymers in the various buffer solutions of pH 4 ～ 11 and in water upon irradiation were observed by the measurement of insoluble fraction. The copolymers were soluble in water before irradiation, whereas they became insoluble upon irradiation with the UV light of 254 nm. The photochemical reaction of the copolymer studied by the UV and IR absorption spectroscopies indicated that a photo‐Fries rearrangement was favored for copolymer A, whereas a photocrosslinking reaction was predominate for copolymer B. Resist properties of the copolymers were studied by measurement of the normalized thickness and by development of the micropattern. Negative tone images with a resolution of 1 μm were obtained with these materials that have a sensitivity (D) of ～ 1100 mJ/cm² with an aqueous developing process.© 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1172–1180, 2002     

等离子硅刻蚀及其工艺参数的多尺度优化

用CFD-ACE+和CFD-TOPO分别对容性耦合等离子体反应腔室放电和等离子硅刻蚀过程进行仿真,讨论不同射频电压和腔室条件对等离子体特性的影响.结果表明:随着射频电压的升高,离子的通量增大;在低射频电压时,离子通量随腔室压强的升高而减小,而在高射频电压时趋势则相反.用Kriging模型对影响刻蚀形貌的参数(腔室压强和射频电压)进行优化,结果表明该优化方法可以为工艺条件相近的刻蚀机设备的设计提供参考.     

Cold Crystallization of PLLA Studied by Simultaneous SAXS and WAXS

Summary: The cold crystallization process of initially amorphous poly(L ‐lactic acid), PLLA, with two different molecular weights, during a heating at 2 °C/min, was investigated by DSC and time‐resolved simultaneous SAXS and WAXS, using synchrotron radiation. Equatorial scans of the isotropic 2D‐SAXS patterns showed that the average Bragg long period (L_B) of PLLA samples was approximately constant with the development of cold crystallization up to a temperature that corresponded to a melt/re‐crystallization process that took place before the nominal melting peak seen by DSC. L_B values were found to be higher for the high molecular weight material. This was in accordance with the higher melting temperature observed in the high molecular weight PLLA that implied the existence of thicker lamellae. WAXS results showed that the molecular weight did not apparently affect the crystal form and the final degree of crystallinity of PLLA. The Avrami parameters from WAXS and DSC were consistent, showing that the non‐isothermal cold crystallization of the two PLLA samples corresponded mainly to a three‐dimensional growth, although an imperfect crystallization process was involved at early times. The crystallization rate of PLLA, observed both by WAXS and DSC, decreased with increasing molecular weight.

SAXS profiles of PLLA2 as a function of temperature. The inset shows the 2D‐SAXS pattern obtained at 180 °C.     

Soap‐free emulsion copolymerization of perfluoroalkyl acrylates in the presence of a reactive surfactant

Soap‐free emulsion copolymerization of perfluoroalkyl acrylate (FA)/methyl methacrylate (MMA)/n‐butyl acrylate (n‐BA) was carried out in the presence of sodium 2‐acrylamide‐2‐methyl propanesulfonate (AMPSNa) as a reactive surfactant and potassium persulfate (KPS) as an initiator. An analysis of the effects of concentration of AMPSNa, KPS, FA as well as polymerization temperature on the kinetic features (rate of polymerization) and colloidal characteristics (mean particle diameter, particle disperse index, particle numbers, and surface charge density) was followed. NMR, FTIR, AFM, and fluorine‐selective electrode analysis were used to characterize the composition and morphology of the FA copolymers. Both AFM analysis and contact angle measurements strongly implied that the fluorinated segments migrated to the outmost surface and created films with lower surface energy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2438–2444, 2007     

Synthesis of copolymers of tert‐butyl vinyl ether with maleic and citraconic anhydrides

In the present study, the effects of charge‐transfer complex formation and intramolecular fragmentation (side‐chain lactonization) in radical copolymerization of tert‐butyl vinyl ether (t‐BVE) with anhydrides of maleic (MA) and citraconic (CA) acids and the structure–thermal behavior relationships of the resulting copolymers were examined using the ¹H‐NMR, FTIR, DSC, and TGA analysis methods. It was shown that copolymerization under the chosen conditions proceeded through intramolecular fragmentation with the formation of γ‐lactone units. Side‐chain fragmentation of t‐BVE–MA and t‐BVE–CA copolymers also was confirmed by TGA and DSC analysis. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2455–2463, 2006 2006     

One‐step synthesis and ring‐opening polymerization of novel macrocyclic(arylene multisulfide) oligomers

A series of macrocyclic(arylene multisulfide) oligomers were synthesized under high dilution conditions by reacting diphenyl ether/diphenyl/diphenyl disulfide/diphenyl methane with dichloro disulfide in the presence of a trace amount of iron powder by a one‐step reaction. From MALDI‐TOF mass spectra, it was established that the repeating units of the cyclization ranged from two to seven and the unit of macrocyclic(arylene multisulfide) oligomers had one to seven sulfur atoms. The macrocyclic oligomers readily underwent ring‐opening polymerization in the melt, resulting in linear, high molecular weight polymultisulfides. DSC thermograms demonstrated that the four polymultisulfides, derived from the macrocyclic(arylene multisulfide) oligomers, are amorphous in nature. The macrocyclic(arylene multisulfide) oligomers and polymers were analyzed by MALDI‐TOF‐MS, IR, HPLC, NMR, DSC, and TGA methods. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 735–741, 2004     

Biobased thermosets from the free‐radical copolymerization of conjugated linseed oil

New polymeric thermosets were prepared through the bulk free‐radical copolymerization of 100% conjugated linseed oil, acrylonitrile, and divinylbenzene. Under the appropriate reaction conditions and with the appropriate curing sequence, 61–96 wt % of the oil was incorporated into the crosslinked thermosets. The resulting yellow, transparent thermosets varied from being soft and flexible to being hard and brittle. Dynamic mechanical analysis and thermogravimetric analysis showed that these thermosets had good mechanical properties and thermal stability. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 979–985, 2007     

Gas Hold‐Up in Stirred Tank Reactors in the Presence of Inorganic Electrolytes

Gas hold‐up (?_G) in air‐aqueous electrolyte solutions in stirred tank reactors (STR) is correlated using a relative gas dispersion parameter, N/N_cd and a surface tension factor (STF), (c/z)(dδ/dc)². For electrolyte concentration below transition concentration (c_t) a single correlation in the form of ?_G = f(N/N_cd, vvm, STF) shows good agreement with gas hold‐up data over a wide range of system and operating conditions. Above ct no effect of STF on gas hold‐up is observed and the correlation obtained is of the form ?_G = f(N/N_cd, vvm). Data available in the literature on large STR show good fit with the proposed correlation.     

Effect of Co2+, Ni2+, Cu2+, or Zn2+ on properties of polyaniline nanoparticles

Uniform polyaniline (PANI) nanoparticles with typical sizes of about 50 nm were electropolymerized on indium tin oxide surfaces in the presence of Co²⁺, Ni²⁺, Cu²⁺, or Zn²⁺. According to shaping theory, we first suggest the reason forming PANI spherical particles. Their conductivity, UV‐vis spectra, FTIR spectra, X‐ray diffraction, and thermogravimetric analysis were investigated. The conductivities and crystallinity of PANI doped with these ions are higher than those of PANI doped with HCl (PANI/HCl). Both UV‐vis absorption spectra and FTIR spectra indicate the interactions between Co²⁺, Ni²⁺, Cu²⁺, or Zn²⁺ and PANI chains. TG analysis also shows that the thermal stability of PANI doped by Co²⁺, Ni²⁺, Cu²⁺, or Zn²⁺ is lower than that of PANI/HCl. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007